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WO2018073110A1 - Quinoline compounds as fungicides - Google Patents

Quinoline compounds as fungicides Download PDF

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Publication number
WO2018073110A1
WO2018073110A1 PCT/EP2017/076155 EP2017076155W WO2018073110A1 WO 2018073110 A1 WO2018073110 A1 WO 2018073110A1 EP 2017076155 W EP2017076155 W EP 2017076155W WO 2018073110 A1 WO2018073110 A1 WO 2018073110A1
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alkyl
compounds
alkoxy
halogenalkoxy
phenyl
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French (fr)
Inventor
Bernd Mueller
Erica CAMBEIS
Ana Escribano Cuesta
Jan Klaas Lohmann
Antje Wolf
Nadine RIEDIGER
Marcus Fehr
Thomas Grote
Violeta TERTERYAN-SEISER
Wassilios Grammenos
Christian Winter
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P3/00—Drugs for disorders of the metabolism
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • the present invention relates to quinoline compounds and the N-oxides and the salts thereof for combating phytopathogenic fungi, and to the use and methods for combating phytopathogenic fungi and to seeds coated with at least one such compound.
  • the invention also relates to processes for preparing these compounds, intermediates, processes for preparing such intermediates, and to compositions comprising at least one compound I.
  • the fungicidal activity of the known fungicidal compounds is unsatisfactory. Based on this, it was an object of the present invention to provide compounds having improved activity and/or a broader activity spectrum against phytopathogenic harmful fungi.
  • R 1 is in each case independently selected from halogen, OH, CN, NO2, SH, N H2,
  • R x is Ci-C4-alkyl, Ci-C4-halogenalkyl, unsubstituted aryl or aryl that is substituted by one, two, three, four or five substituents R x1 independently selected from Ci-C4-alkyl, halogen, OH, CN, Ci-C4-halogenalkyl, Ci-C4-alkoxy, and C1-C4- halogenalkoxy;
  • R 1 wherein the aliphatic moieties of R 1 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R 1a which independently of one another are selected from:
  • R 1a halogen, OH, CN, Ci-C 6 -alkoxy, C 3 -C 6 -cycloalkyl, C 3 -C 6 -halogencycloalkyl, Ci-
  • R 1 wherein the cycloalkyi, heteroaryl and aryl moieties of R 1 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R 1 b which independently of one another are selected from:
  • R 1 b halogen, OH, CN, Ci-C 4 -alkyl, Ci-C 4 -alkoxy, Ci-C 4 -halogenalkyl, C 3 -C 6 - cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio; n is O, 1 or 2;
  • R 2 is in each case independently selected from the substituents as defined for R 1 , wherein the possible substituents for R 2 are R 2a and R 2b , respectively, which correspond to R 1a and R 1 b , respectively;
  • R 3 is CH 3 , CH 2 F, CHF 2 and CF 3 ;
  • R 4 wherein the carbocyclic, heterocyclic moieties of R 4 are independently not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R 4b , respectively, which independently of one another are selected from:
  • R b halogen, OH, CN, N0 2 , SH, NH 2 , NH(Ci-C 4 -alkyl), N(Ci-C 4 -alkyl) 2 ,
  • R 5 is H
  • R 6 is H
  • R 7 and R 8 together with the carbon atoms to which they are bound form a phenyl ring; wherein the phenyl carries zero, one, two, three or four substituents (R 78 ) 0 , wherein o is 0, 1 , 2 or 3; and
  • R 78 are independently selected from halogen, OH, CN, N0 2 , SH, NH 2,
  • R 78a halogen, OH, CN, Ci-C 6 -alkoxy, C 3 -C 6 -cycloalkyl, C 3 -C 6 - cycloalkenyl, C3-C6-halogencycloalkyl, C 3 -C6-halogencycloalkenyl, Ci-C 4 -halogenalkoxy, Ci-C6-alkylthio, five- or six-membered het- eroaryl, phenyl and phenoxy, wherein the heterorayl, phenyl and phenoxy group is unsubstituted or carries one, two, three, four or five substituents R 78a' selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and C1-C4- halogenalkoxy; wherein the cyclic, phenyl, heterocyclic and heteroaryl moie
  • alkoxy)phosphoryl five- or six-membered heteroaryl and aryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; wherein the aryl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, C1-C4- halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy; wherein z is as defined above;
  • R Y is Ci-C6-alkyl, Ci-C6-halogenalkyl, C 2 -C6-alkenyl, C 2 -C6-halogenalkenyl, C 2 -C6- alkynyl, C 2 -C6-halogenalkynyl, C 3 -C6-cycloalkyl, C 3 -C6-halogencycloalkyl, phenyl and phenyl-Ci-C6-alkyl; wherein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci- C4-halogenalkoxy; wherein the acyclic moieties of R 9 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R 9a which independently
  • R 9a halogen, OH, CN, Ci-C 6 -alkoxy, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenyl, C 3 -C 6 - halogencycloalkyl, C3-C6-halogencycloalkenyl, Ci-C4-halogenalkoxy, C1-C6- alkylthio, five- or six-membered heteroaryl, phenyl and phenoxy, wherein the heteroaryl, phenyl and phenoxy group is unsubstituted or carries one, two, three, four or five substituents R 9a' selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and C1-C4- halogenalkoxy; wherein the alicyclic, phenyl, heterocyclic and heteroaryl moieties of R 9 are not
  • R 9b halogen, OH, CN, Ci-C 4 -alkyl, Ci-C 4 -alkoxy, Ci-C 4 -halogenalkyl, C 3 -C 6 - cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio; and the N-oxides and the agriculturally acceptable salts thereof.
  • reaction is performed in a range between 0 °C and ambient temperature in the presence of a reactive group and organic base.
  • Suitable base preferably NEt.3, pyridine NaOH, TEBAC, K2CO3, NaCOs or KOH.
  • solvents are THF, DMF, DMSO, MeOH or water (see for example, Journal of Medicinal Chemistry, 1989, 32(6), 1242-1248; European Jour- nal of Medicinal Chemistry, 2009, 44(10), 4034-4043).
  • Compounds of formula I.A.2-1 can be accessed e.g. starting from compounds of the formula I.A.1 via a reduction agent in an organic solvent or water or a mixture of organic solvent and water (see for example WO2009095253, WO2008143263).
  • Reduction agent can be for example NaBhU or NaCNBH3.
  • the reaction is performed in a range between 0°C, room temperature and 60°C in an solvent, such as THF, dichloromethane, acetonitrile, MeOH, EtOH or water or in a mixture of or anic solvent and water.
  • Compounds of formula I.A.1 can be also reduced to I.A.2-1 via hydrogenation by using a metal catalyst in an organic solvent, water or a mix of water and organic solvent (see for example ChemCatChem, 5(10), 2939-2945; 2013; Organic Letters, 17(12), 2878-2881 ; 2015).
  • metal catalyst can be used for example Ru, Ir, and Pd, with or without ligands such as phosphines, phosphates, cyclooctadiene, diamines and imidazoles.
  • the reaction can take place at temperature from 0°C to 100 °C.
  • Preferable organic solvent are methanol, acetone, dichloromethane, 2,2,2-trifluoroethanol or DMF.
  • the reaction can also take place the presence of an acid for example HCO2H, trifluoroacetic acid and acetic acid.
  • sulfuric acid or a sulfonic acid in particular tri- flic acid
  • acid preferably sulfuric acid or a sulfonic acid, in particular tri- flic acid
  • suitable solvents are hydrocarbons, preferably benzene or dichloromethane.
  • the reaction is performed at a temperature from -40°C to 200°C, in particular from -10°C to 120°C, more specifically from 0°C to 100°C, even more specifically from room or ambient temperature (about 23°C) to 80°C.
  • Nitriles of type III are either commercially available or can be prepared by a skilled person from the corresponding halides following literature procedures (see, for example Journal of Organic Chemistry, 76(2), 665-668; 201 1 ; Angewandte Chemie, International Edition, 52(38), 10035- 10039; 2013; WO2004/013094).
  • Alcohols of type II can be prepared as described below.
  • organometallic reagents preferably alkyl Grignard or al- kyl-Lithium reagents
  • ethereal solvents preferably THF
  • alcohols of type II can be prepared from epoxides Va and compounds VI (see below):
  • the metalation reaction may preferably be carried out using Lithium-organic compounds, such as for example n-butyl lithium, sec-butyl lithium or tert-butyl lithium to result in an exchange of halogen by lithium. Also suitable is the reaction with magnesium resulting in the formation of the respective Grignard reagents. A further possibility is the use of other Grignard reagents such as isopropyl-magnesium-bromide instead of Mg.
  • a typical preparation of compounds of type IV can be achieved by reacting compounds of type V with organometallic reagents, preferably alkyl Grignard or alkyl-Lithium reagents, in ethereal solvents, preferably TH F at low temperatures and under inert conditions to furnish compounds of type IV as previously reported see for example WO2012051036; WO201 1042918).
  • organometallic reagents preferably alkyl Grignard or alkyl-Lithium reagents
  • an organic solvent preferably THF or dichloromethane.
  • the reaction is performed in a range between 0 °C and ambient temperature in the presence of an organic base, preferably NEt.3 or pyridine (see e.g. US 20130324506; Tetrahedron: Asymmetry, 17(4), 508-51 1 ; 2006).
  • an activating reagent preferably a carbodiimide
  • an activating reagent preferably a carbodiimide
  • compounds of type VII can be prepared from the corresponding aryl halides of type VI (Hal is halogen, preferably Br or I).
  • aryl halides VIII will react with compounds of type IX in the presence of a transition metal catalyst, preferably a copper(l) salt, in an organic solvent, preferably DMF or DMSO, at elevated temperatures.
  • a transition metal catalyst preferably a copper(l) salt
  • organic solvent preferably DMF or DMSO
  • a base preferably potassium phosphate
  • alcohols of type II can be prepared as follows.
  • a known or commercially available compound of type X can be reacted with an organometallic reagent of type XI, preferably a Gri- gnard or an organolithium reagent, readily prepared by a skilled person.
  • the reaction is performed in a temperature range from -78 °C to room temperature under inert conditions in an ethereal solvent.
  • compounds of the formula I.A.1 can be provided e.g. starting from alkenes of type XII with nitriles of type III in the presence of a acid in an organic solvent (see for example Journal of Heterocyclic Chemistry,1980, 17(7), 1457-63; WO2001070746).
  • a acid in an organic solvent
  • sulfuric acid or a sulfonic acid, in particular triflic acid are used as acid.
  • Most suitable solvents are hydrocarbons, preferably benzene or dichloromethane.
  • Alkenes XII are either commercially available or easily prepared using the methods known by persons who are skilled in the art.
  • alkenes of type XII can be easily prepared form alcohol of type II in the presence of an acid in an organic solvent.
  • sulfuric acid or a sulfonic acid, in particular triflic acid are used as acid.
  • Most suitable solvents are hydrocarbons, preferably benzene or dichloromethane.
  • Compounds I.A.1 can be prepared via intramolecular reaction of amide XIII.
  • the intramolecular cyclization will take place in the presence of a dehydrating agent in an organic solvent (WO 2008143263, Synthetic Communications 2007, 37, 1331-1338.).
  • a dehydrating agent in an organic solvent (WO 2008143263, Synthetic Communications 2007, 37, 1331-1338.).
  • POCIs phosphoryl chloride
  • POCI3/P2O5 H3PO4/P2O5, SnCU or BF 3
  • suitable solvents are hydrocarbons, preferably benzene, toluene or acetonitrile.
  • halogenat- ed solvents can be us enzene.
  • the reaction is performed at temperature from - 40°c to 200 °C, in particular from -10°C to 120°C, more specifically from 0°C to 100°C, even more specifically from room temperature to 100°C.
  • an activating agent preferably a carbodiimide or acid chloride
  • Amines of type XV are either commercially available or easily prepared using the methods known by persons who are skilled in the art. If required, compounds of type amine XV can be synthesized from the correspond nitriles. As described Synlett. 2007, 4 652-654 or Tetrahedron 2012, 68, 2696-2703, nitriles will react with organometallic agents, preferably Grignard or Lithium reagent, in ethereal solvents, preferably THF at low temperature and under inert conditions to furnish compounds of type XV. The synthesis of compounds of type XV can take place in two steps or one pot.
  • organometallic agents preferably Grignard or Lithium reagent
  • amines of type XV can synthesized via formation of the correspond carboxylic azide and quench with water (Journal of the American Chemical Society, 1949, 71 , 2233-7; Journal of the American Chemical Society, 1990, 1 12, 297-304) or via Grignard addition to enamines (Tetrahedron Letters, 1992, 33, 1689-92; US20030216325)
  • Compound of type I.A.1 can be also synthesized via Suzuki coupling of halides of type XVI with a boronic acid XVII (see for example, Journal of Fluorine Chemistry, 2010, 131 , 856-860); wherein R 31 and R 41 together with the groups they are attached to form a tetramethyl-1 ,3,2- dioxaborolane-ring or independently from one another mean hydrogen or Ci-C6-alkyl to yield compounds I.A.1.
  • Compounds of type XVI, wherein Hal is halogen, preferably chloro and bromo can be obtained by transformation of an amide of type XVIII with a halogenating reagent, such as phosphorus oxachloride, phosphorus pentachloride, phosphoric trichloride, phosphorus oxybromide, thionyl chloride or Vilsmeier reagent.
  • a halogenating reagent such as phosphorus oxachloride, phosphorus pentachloride, phosphoric trichloride, phosphorus oxybromide, thionyl chloride or Vilsmeier reagent.
  • the reaction takes place in the presence of an organic solvent, preferably THF, benzene, CCU, or dichloromethane.
  • reaction is performed in a range between 0°C to 180°C (see as reference, Journal of Medicinal Chemistry, 2004, 47, 663- 672; Journal of Organic Chemistry, 1980, 45, 80-89; Bulletin des Societes Chimiques Beiges, 1991 , 100, 169-174).
  • Amides of type XVIII can be prepared from compounds of type XIX, wherein R x is a Ci-C6-alkyl.
  • the reaction takes places in the presence of acid, preferably acetic acid, HCI, triflic acid or a mixture of sodium acetate and acetic acid.
  • acid preferably acetic acid, HCI, triflic acid or a mixture of sodium acetate and acetic acid.
  • the reaction in performed net or in polar solvents, preferably in water, methanol or acetonitrile (see WO2016/156085; Pharmaceutical Chemistry Journal, 2005, 39, 405-408 .
  • compounds of type XVI can be direct synthesized from compounds of type XIX in the presence of a halogenating reagent, such as sulfonyl chloride.
  • a halogenating reagent such as sulfonyl chloride.
  • the reaction takes places neat or in organic solvents, such as chloroform, dichloromethane or acetonitrile, in a range of temperature from 0°C to room temperature (see, Tetrahedrons Letters, 2010, 51 , 4609; Tetrahedron Letters, 1986, 27(24), 274 -6).
  • Compounds of type XIX can also be obtained by the reaction of alcohol II or alkene XII and a Ci-C6-alkyl thiocyanate under acidic conditions, see for example Bioorganic & Medicinal Chemistry Letters, 2013, 23(7), 2181-2186; Pharmaceutical Chemistry Journal, 2005, 39, 405-408.
  • acids are sulfuric acid, HCI or trific acid.
  • the reaction takes place most preferably in water, dichloromethane, toluene or a mixture of solvents, in a range of temperatures from 0°C to 1 10 °C.
  • Amide of type XVIII can be synthesized via ring expansion of oxime XX in the presence of an acid.
  • suitable acids are for example, sulfuric acid, polyphosphoric acid or POCI3.
  • the reaction in performed net or in a polar solvents, preferably in water, methanol or acetonitrile (see Bioorganic & Medicinal Chemistry Letters, 2002, 12(3), 387-390; Medicinal Chemistry Research, 2015, 24(2), 523-532).
  • Oxime of type XX can be easily prepared from ketone of type XXI in the presence of hydroxyl- amine or hydroxylamine hydrochloride in polar solvents such as water, pyridine, ethanol or methanol.
  • polar solvents such as water, pyridine, ethanol or methanol.
  • the reaction can take place in the presence of absence of a base, such as sodium acetate or sodium hydroxide, in a range of temperatures from room temperature to 120 °C (Journal of Organic Chemistry, 2016 81 (1 ), 336-342).
  • Ketone of type XXI are either commercial available or readily prepared by a skilled person.
  • compounds of type I.A.1 can also be obtained intramolecular cyclization of amines of type XXII in the presence of an acid.
  • acids are HCI, trifluoroacetic acid, acetic acid or sulfuric acid.
  • the reaction is preform in dichloromethane, water, ethanol, THF or chloroform, at temperature from room temperature to 120 °C (see, Synthesis, 1995, (5), 592-604; Heterocycles, 1988, 27(10), 2403-12).
  • Amines of type XXII are either commercial available or easily prepared by a skilled person or following the procedures described before.
  • the N-oxides may be prepared from the inventive compounds according to conventional oxidation methods, e. g. by treating compounds I with an organic peracid such as metachloroper- benzoic acid (cf. WO 03/64572 or J. Med. Chem. 38(1 1 ), 1892-903, 1995); or with inorganic oxidizing agents such as hydrogen peroxide (cf. J. Heterocyc. Chem. 18(7), 1305-8, 1981 ) or oxone (cf. J. Am. Chem. Soc. 123(25), 5962-5973, 2001 ).
  • the oxidation may lead to pure mono-N-oxides or to a mixture of different N-oxides, which can be separated by conventional methods such as chromatography.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 ,R 7 , R 8 , R 9 , m, n and o are as defined and preferably defined for formula I.
  • the compounds of formula XIII have fungicidal activity and the details below referring to the compounds I also apply to compounds XIII.
  • C n -C m indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.
  • halogen refers to fluorine, chlorine, bromine and iodine.
  • Ci-C6-alkyl refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, e.g. methyl, ethyl, propyl, 1-methylethyl, butyl, 1 -methylpropyl, 2- methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl,
  • C2-C4-alkyl refers to a straight-chained or branched alkyl group having 2 to 4 carbon atoms, such as ethyl, propyl (n-propyl), 1-methylethyl (iso-propoyl), butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (iso-butyl), 1 ,1 -dimethylethyl (tert. -butyl).
  • Ci-C6-halogenalkyl refers to an alkyl group having 1 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
  • Examples are "Ci-C2-halogenalkyl” groups such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1 -bromoethyl, 1 - fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro- 2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,
  • Ci-C6-hydroxyalkyl refers to an alkyl group having 1 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by OH groups.
  • Ci-C4-alkoxy-Ci-C4-alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C4-alkoxy group (as defined above).
  • Ci-C4-alkoxy-CrC4-alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C6-alkoxy group (as defined above).
  • C2-C6-alkenyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position.
  • Examples are “C2-C4-alkenyl” groups, such as ethenyl, 1 -propenyl, 2-propenyl (allyl), 1 -methylethenyl, 1 -butenyl, 2-butenyl,
  • C2-C6-alkynyl refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and containing at least one triple bond.
  • Examples are "C2-C4- alkynyl” groups, such as ethynyl, prop-1 -ynyl, prop-2-ynyl (propargyl), but-1 -ynyl, but-2-ynyl, but-3-ynyl, 1 -methyl-prop-2-ynyl.
  • Ci-C6-alkoxy refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms which is bonded via an oxygen, at any position in the alkyl group.
  • Examples are “C1-C4- alkoxy” groups, such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1 - methyhpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy.
  • Ci-C6-halogenalkoxy refers to a Ci-C6-alkoxy radical as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as men- tioned above.
  • Ci-C4-halogenalkoxy groups, such as OCH2F, OCHF2, OCF3, OCH2CI, OCHCI2, OCCI3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-tri- fluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloro -, ethoxy, OC2F5, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy,
  • 2,3-difluoro -, propoxy 2 chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bro- mo-'propoxy, 3 bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C2F5, OCF2-C2F5, 1-fluoromethyl-2 -fluoroethoxy, 1 -chloromethyl-2-chloroethoxy, 1 -bromomethyl-2- bromo-'ethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy.
  • C2-C6-alkenyloxy refers to a straight-chain or branched alkenyl group having 2 to 6 carbon atoms which is bonded via an oxygen, at any position in the alkenyl group. Examples are “C2-C4-alkenyloxy” groups.
  • C2-C6-alkynyloxy refers to a straight-chain or branched alkynyl group having 2 to 6 carbon atoms which is bonded via an oxygen, at any position in the alkynyl group. Examples are “C2-C4-alkynyloxy” groups.
  • C3-C6-cycloalkyl refers to monocyclic saturated hydrocarbon radicals having 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. Accordingly, a saturated three-, four-, five-, six-, seven-, eight-, nine or ten-membered carbocyclyl or carbocycle is a "C3-Cio-cycloalkyl".
  • C3-C6-cycloalkenyl refers to a monocyclic partially unsaturated 3-, 4- 5- or 6- membered carbocycle having 3 to 6 carbon ring members and at least one double bond, such as cyclopentenyl, cyclopentadienyl, cyclohexadienyl. Accordingly, a partially unsaturated three-, four-, five-, six-, seven-, eight-, nine or ten-membered carbocyclyl or carbocycle is a "C3-C10- cycloalkenyl".
  • C3-C8-cycloalkyl-CrC4-alkyl refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a cycloalkyl radical having 3 to 8 carbon atoms (as defined above).
  • Ci-Ce-alkylthio refers to straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as defined above) bonded via a sulfur atom. Accordingly, the term “Ci- C6-halogenalkylthio” as used herein refers to straight-chain or branched halogenalkyi group having 1 to 6 carbon atoms (as defined above) bonded through a sulfur atom, at any position in the halogenalkyi group.
  • the number of valence of carbon is 4, that of nitrogen is 3.
  • saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine or ten- membered heterocyclyl or heterocycle, wherein the heterocyclyl or heterocycle contains 1 , 2, 3 or 4 heteroatoms selected from N, O and S is to be understood as meaning both saturated and partially unsaturated heterocycles, wherein the ring member atoms of the heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms independently selected from the group of O, N and S.
  • saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine or ten- membered heterocyclyl or heterocycle, wherein the heterocyclyl or heterocycle contains 1 , 2, 3 or 4 heteroatoms selected from N, O and S is to be understood as meaning both saturated and partially unsaturated heterocycles, wherein the ring member atoms of the heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms independently selected from the group of O, N and
  • a 3- or 4-membered saturated heterocycle which contains 1 or 2 heteroatoms from the group consisting of O, N and S as ring members such as oxirane, aziridine, thiirane, oxetane, azet- idine, thiethane, [1 ,2]dioxetane, [1 ,2]dithietane, [1 ,2]diazetidine; and
  • a 5- or 6-membered saturated or partially unsaturated heterocycle which contains 1 , 2 or 3 het- eroatoms from the group consisting of O, N and S as ring members such as 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl,
  • a 7-membered saturated or partially unsaturated heterocycle such as tetra- and hexahydroaze- pinyl, such as 2,3,4,5-tetrahydro[1 H]azepin-1-,-2-,-3-,-4-,-5-,-6- or-7-yl, 3,4,5,6-tetra- hydro[2H]azepin-2-,-3-,-4-,-5-,-6- or-7-yl, 2,3,4,7-tetrahydro[1 H]azepin-1 -,-2-,-3-,-4-,-5-,-6- or-7- yl, 2,3,6,7-tetrahydro[1 H]azepin-1 -,-2-,-3-,-4-,-5-,-6- or-7-yl, hexahydroazepin-1 -,-2-,-3- or-4-yl, tetra- and hexahydrooxepinyl such as 2,3,4,5-tetrahydro[1 H]
  • 5-or 6-membered heteroaryl refers to aromatic ring systems incuding besides carbon atoms, 1 , 2, 3 or 4 heteroatoms independently selected from the group consisting of N, O and S, for example,
  • a 5-membered heteroaryl such as pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan- 2-yl, furan-3-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1 -yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl
  • a 6-membered heteroaryl such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyri- dazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl.
  • Agriculturally acceptable salts of the inventive compounds encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of said compounds.
  • Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four Ci-C 4 -alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammoni- um, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phos- phonium ions, sulfonium ions, preferably tri(Ci-C 4 -alkyl)sulfonium, and
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C 4 -alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting such inventive compound with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • inventive compounds can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention.
  • the compounds of formula I and their N-oxides may have one or more centers of chirality, in which case they are present as pure enantiomers or pure diastereomers or as enantiomer or diastereomer mixtures. Both, the pure enantiomers or dia- stereomers and their mixtures are subject matter of the present invention.
  • R 1 is in each case independently selected from halogen, OH, CN, N0 2 , SH, NH 2 , NH(Ci-C 4 -alkyl), N(Ci-C 4 -alkyl) 2 , NH-S0 2 -R x , Ci-C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 - alkynyl, Ci-C6-alkoxy, C3-C6-cycloalkyl, five- or six-membered heteroaryl and aryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein
  • R x is Ci-C 4 -alkyl, Ci-C 4 -halogenalkyl, unsubstituted aryl or aryl that is substituted by one, two, three, four or five substituents R x1 independently selected from Ci-C 4 -alkyl, halogen, OH, CN, Ci-C 4 -halogenalkyl, Ci-C 4 -alkoxy, and Ci-C 4 -halogenalkoxy; wherein the acyclic moieties of R 1 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R 1a which independently of one another are selected from:
  • R 1a halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, C1-C4- halogenalkoxy, Ci-C6-alkylthio and phenoxy, wherein the phenyl group is unsubstituted or carries one, two, three, four or five substituents R 11a selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy;
  • R 1 wherein the cycloalkyl, heteroaryl and aryl moieties of R 1 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R 1 b which independently of one another are selected from:
  • R 1 b halogen, OH, CN, Ci-C 4 -alkyl, Ci-C 4 -alkoxy, Ci-C 4 -halogenalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 - halogencycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio.
  • R 1 there can be zero, one, two, three or four R 1 present, namely for m is 0, 1 , 2, 3 or 4.
  • m is 0.
  • m is 1.
  • m is 2.
  • n is 2 or 3. According to one specific embodiment thereof, m is 2, according to a further specific embodiment, m is 3.
  • one R 1 is attached to the 5-position as numbered in formula I above. According to a further embodiment of the invention, one R 1 is attached to the 6-position as numbered in formula I above. According to a further embodiment of the invention, one R 1 is attached to the 7-position as numbered in formula I above. According to a further embodiment of the invention, one R 1 is attached to the 8-position as numbered in formula I above
  • two R 1 are attached in 7, 8-position as numbered in formula I above.
  • R 1 is halogen, in particular Br, F or CI, more specifically F or CI.
  • R 1 is F.
  • R 1 is CI.
  • R 1 is Br.
  • R 1 is OH
  • R 1 is CN. According to a further specific embodiment, R 1 is NO2.
  • R 1 is SH.
  • R 1 is NH2.
  • R 1 is NH(Ci-C4-alkyl) or N(Ci-C4-alkyl)2, in particular Ci-C 2 -alkyl, such as CH 3 or CH2CH3.
  • R 1 is NH-SC>2-R X , wherein R x is Ci-C4-alkyl, C1-C4- halogenalkyl, unsubstituted aryl or aryl that is substituted by one, two, three, four or five substit- uents R x1 independently selected from Ci-C4-alkyl, halogen, OH, CN, Ci-C4-halogenalkyl, C1-C4- alkoxy, and Ci-C4-halogenalkoxy;
  • R 1 is Ci-C6-alkyl, in particular Ci-C4-alkyl, such as CH 3 or CH 2 CH 3 .
  • R 1 is Ci-C6-halogenalkyl, in particular C1-C4- halogenalkyl, such as CF 3 , CHF 2 , CH 2 F, CCI 3 , CHCI2, CH 2 CI, CF3CH2, CCI3CH2 or CF 2 CHF 2 .
  • R 1 is C2-C6-alkynyl or C2-C6-halogenalkynyl, in particular C 2 -C 4 -alkynyl or C 2 -C 4 -halogenalkynyl, such as C ⁇ CH, C ⁇ CCI, C ⁇ CF, CH 2 C ⁇ CH, CH 2 C ⁇ CCI, or CH 2 C ⁇ CF.
  • R 1 is Ci-C6-alkoxy, in particular Ci-C4-alkoxy, more specifically Ci-C2-alkoxy such as OCH 3 or OCH 2 CH 3 .
  • R 1 is Ci-C6-halogenalkoxy, in particular C1-C4- halogenalkoxy, more specifically Ci-C2-halogenalkoxy such as OCF 3 , OCHF2, OCH2F, OCCI 3 , OCHCI2 or OCH2CI, in particular OCF 3 , OCHF 2 , OCCI 3 or OCHCI 2 .
  • R 1 is C 3 -C6-cycloalkyl, in particular cyclopropyl.
  • R 1 is C 3 -C6-cycloalkyl, for example cyclopropyl, substituted by one, two, three or up to the maximum possible number of identical or different groups R 1b as defined and preferably herein.
  • R 1 is C 3 -C6-halogencycloalkyl. In a special embodiment R 1 is fully or partially halogenated cyclopropyl.
  • R 1 is unsubstituted aryl or aryl that is
  • R 1 is unsubstituted phenyl or phenyl that is substituted by one, two, three or four R 1b , as defined herein.
  • R 1 is unsubstituted 5- or 6-membered heteroaryl. According to still a further embodiment, R 1 is 5- or 6-membered heteroaryl that is substituted by one, two or three R 1b , as defined herein.
  • R 1 is in each case independently selected from halogen, OH, CN, N0 2 , SH, NH 2 , NH(CrC 4 -alkyl), N(Ci-C 4 -alkyl) 2 , NH-S0 2 -R x , Ci-C 6 -alkyl, C 2 -C 6 -alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy and C3-C6-cycloalkyl; wherein the acyclic moieties of R 1 are not further substituted or carry one, two, three, four or five identical or different groups R 1a as defined below and wherein the cycloalkyl moieties of R 1 are not further substituted or carry one, two, three, four or five identical or different groups R 1 b as defined below.
  • R 1 is independently selected from halogen, OH, Ci-C6-alkyl, Ci-C6-halogenalkyl, Ci-C6-alkoxy and Ci-C6-halogenalkoxy, in particular independently selected from F, CI, Br, CN, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy.
  • R 1a are the possible substituents for the acyclic moieties of R 1 .
  • R 1a is independently selected from halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy, Ci-C6-alkylthio and phenoxy, wherein the phenyl group is unsubstituted or carries one, two, three, four or five substituents R 11a selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, C1-C4- alkoxy and Ci-C4-halogenalkoxy, in particular selected from halogen, Ci-C2-alkyl, C1-C2- halogenalkyl, Ci-C2-alkoxy and Ci-C2-halogenalkoxy, more specifically selected from halogen, such as F, CI and Br.
  • halogen such as F, CI and Br.
  • R 1a is independently selected from halogen, OH, CN, C1-C2- alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and Ci-C2-halogenalkoxy.
  • R 1a is independently selected from F, CI, OH, CN, Ci-C2-alkoxy, cyclopropyl, 1-F-cyclopropyl, 1-CI- cyclopropyl, 1 ,1-F2-cyclopropyl, 1 ,1-Cl2-cyclopropyl and Ci-C2-halogenalkoxy.
  • R 1a is independently selected from halogen, such as F, CI, Br and I, more specifically F, CI and Br.
  • R 1a is independently selected from OH, C 3 -C6-cycloalkyl, C 3 - C6-halogencycloalkyl and Ci-C2-halogenalkoxy. Specifically, R 1a is independently selected from OH, cyclopropyl and Ci-C2-halogenalkoxy.
  • R 1 b are the possible substituents for the cycloalkyl, heteroaryl and aryl moieties of R 1 .
  • R 1 b according to the invention is independently selected from halogen, OH, CN, Ci-C4-alkyl, Ci- C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy or Ci-C6-alkylthio.
  • R 1 b is independently selected from halogen, OH, CN, Ci- C2-alkyl, Ci-C2-alkoxy, Ci-C2-halogenalkyl, C 3 -C6-cycloalkyl, C 3 -C6-halogencycloalkyl and C1-C2- halogenalkoxy.
  • R 1 b is independently selected from F, CI, Br, OH, CN, CH 3 , OCH 3 , cyclopropyl, 1-F-cyclopropyl, 1-CI-cyclopropyl, 1 ,1-F2-cyclopropyl, 1 ,1-Cl2-cyclopropyl and halogenmethoxy.
  • R 1 b is independently selected from halogen, C1-C2- alkyl, Ci-C2-alkoxy, Ci-C2-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and C1-C2- halogenalkoxy.
  • R 1 b is independently selected from F, CI, Br, CH3, CHF2, CF3, OCH3, cyclopropyl, 1-F-cyclopropyl, 1-CI-cyclopropyl, 1 ,1-F2-cyclopropyl, 1 ,1-Cl2-cyclopropyl and halogenmethoxy, more specifically independently selected from F, CI, Br, CH 3 , CHF 2 , CF 3 , OCH3, cyclopropyl, 1-F-cyclopropyl, 1-CI-cyclopropyl, 1 ,1-F 2 -cyclopropyl, 1 ,1-Cl2-cyclopropyl and OCHF2.
  • R 2 is is in each case independently selected from halogen, OH, CN, N0 2 , SH, NH 2 , NH(Ci-C 4 -alkyl), N(Ci-C 4 -alkyl) 2 , NH-S0 2 -R x , Ci-C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 - alkynyl, Ci-C6-alkoxy, C3-C6-cycloalkyl, five- or six-membered heteroaryl and aryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein R x is Ci-C 4 -alkyl, Ci-C 4 -halogenalkyl, unsubstituted aryl or aryl that is substituted by one, two, three, four or five substituents R x2 independently selected from Ci-C 4 -alkyl, halogen
  • R 2a halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, C1-C4- halogenalkoxy, Ci-C6-alkylthio and phenoxy, wherein the phenyl group is unsubstituted or car- ries one, two, three, four or five substituents R 22a selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy;
  • R 2 wherein the cycloalkyl, heteroaryl and aryl moieties of R 2 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R 2b which independently of one another are selected from:
  • R 2b halogen, OH, CN, Ci-C 4 -alkyl, Ci-C 4 -alkoxy, Ci-C 4 -halogenalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 - halogencycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio.
  • n is 0, 1 or 2.
  • n is 0 or 1 .
  • n 0.
  • n 1
  • n is 2.
  • one R 2 is attached to the 2-position as numbered in formula I above. According to a further embodiment of the invention, one R 2 is attached to the 4-position as numbered in formula I above.
  • two R 2 are attached in 2, 4-position as numbered in formula I above.
  • R 2 is halogen, in particular Br, F or CI, more specifically F or CI.
  • R 2 is F.
  • R 2 is CI
  • R 2 is Br.
  • R 2 is OH
  • R 2 is CN
  • R 2 is NO2.
  • R 2 is SH.
  • R 2 is NH 2 .
  • R 2 is, NH(Ci-C4-alkyl) or N(CrC4-alkyl) 2 , , in particular Ci-C2-alkyl, such as CH3 or CH2CH3.
  • R 2 is NH-S02-R X , wherein R x is Ci-C4-alkyl, C1-C4- halogenalkyl, unsubstituted aryl or aryl that is substituted by one, two, three, four or five substit- uents R x2 independently selected from Ci-C4-alkyl, halogen, OH, CN, Ci-C4-halogenalkyl, C1-C4- alkoxy, and Ci-C4-halogenalkoxy;
  • R 2 is Ci-C6-alkyl, in particular Ci-C4-alkyl, such as CH 3 or CH 2 CH 3 .
  • R 2 is Ci-C6-halogenalkyl, in particular C1-C4- halogenalkyl, such as CF 3 , CHF 2 , CH 2 F, CCI 3 , CHCI 2 ,CH 2 CI, CF 3 CH 2 , CCI 3 CH 2 or CF 2 CHF 2 .
  • R 2 is C 2 -C6-alkynyl or C 2 -C6-halogenalkynyl, in particular C 2 -C 4 -alkynyl or C 2 -C 4 -halogenalkynyl, such as C ⁇ CH, C ⁇ CCI, C ⁇ CF, CH 2 C ⁇ CH, CH 2 C ⁇ CCI, or CH 2 C ⁇ CF.
  • R 2 is Ci-C6-alkoxy, in particular Ci-C 4 -alkoxy, more specifically Ci-C 2 -alkoxy such as OCH 3 or OCH 2 CH 3 .
  • R 2 is Ci-C6-halogenalkoxy, in particular C1-C4- halogenalkoxy, more specifically Ci-C 2 -halogenalkoxy such as OCF 3 , OCHF 2 , OCH 2 F, OCCI 3 , OCHCI 2 or OCH 2 CI, in particular OCF 3 , OCHF 2 , OCCI 3 or OCHCI 2 .
  • R 2 is C 3 -C6-cycloalkyl, in particular cyclopropyl.
  • R 2 is C 3 -C6-cycloalkyl, for example cyclopropyl, substituted by one, two, three or up to the maximum possible number of identical or different groups R 2b as defined and preferably herein.
  • R 2 is C 3 -C6-halogencycloalkyl.
  • R 2 is fully or partially halogenated cyclopropyl.
  • R 2 is unsubstituted aryl or aryl that is
  • R 2 is unsubstituted phenyl or phenyl that is substituted by one, two, three or four R 2b , as defined herein.
  • R 2 is unsubstituted 5- or 6-membered heteroaryl. According to still a further embodiment, R 2 is 5- or 6-membered heteroaryl that is substituted by one, two or three R 2b , as defined herein.
  • R 2 is in each case independently selected from halogen, OH, CN, N0 2 , SH, NH 2, NH(C C 4 -alkyl), N(C C 4 -alkyl) 2 , NH-S0 2 -R*, Ci-C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C6-alkynyl, Ci-C6-alkoxy and C 3 -C6-cycloalkyl; wherein the acyclic moieties of R 2 are not further substituted or carry one, two, three, four or five identical or different groups R 2a as defined below and wherein the cycloalkyl moieties of R 2 are not further substituted or carry one, two, three, four or five identical or different groups R 2b as defined below.
  • R 2 is independently selected from halogen, OH, Ci-C6-alkyl, Ci-C6-halogenalkyl, Ci-C6-alkoxy and Ci-C6-halogenalkoxy, in particular independently selected from F, CI, Br, CN, OH, Ci-C 4 -alkyl, Ci-C 4 -halogenalkyl, Ci-C 4 -alkoxy and Ci-C 4 -halogenalkoxy.
  • R 2a are the possible substituents for the acyclic moieties of R 2 .
  • R 2a is independently selected from halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy, Ci-C6-alkylthio and phenoxy, wherein the phenyl group is unsubstituted or carries one, two, three, four or five substituents R 22a selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, C1-C4- alkoxy and Ci-C4-halogenalkoxy, in particular selected from halogen, Ci-C2-alkyl, C1-C2- halogenalkyl, Ci-C2-alkoxy and Ci-C2-halogenalkoxy, more specifically selected from halogen, such as F, CI and Br.
  • halogen such as F, CI and Br.
  • R 2a is independently selected from halogen, OH, CN , C1-C2- alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and Ci-C2-halogenalkoxy.
  • R 2a is independently selected from F, CI, OH, CN, Ci-C2-alkoxy, cyclopropyl, 1-F-cyclopropyl, 1 -CI- cyclopropyl, 1 ,1 -F2-cyclopropyl, 1 ,1-Cl2-cyclopropyl and Ci-C2-halogenalkoxy.
  • R 2a is independently selected from halogen, such as F, CI, Br and I , more specifically F, CI and Br.
  • R 2a is independently selected from OH , C3-C6-cycloalkyl, C3- C6-halogencycloalkyl and Ci-C2-halogenalkoxy. Specifically, R 2a is independently selected from OH, cyclopropyl, 1 ,1-F 2 -cyclopropyl, 1 ,1-Cl2-cyclopropyl and Ci-C2-halogenalkoxy.
  • R 2b are the possible substituents for the cycloalkyl, heteroaryl and aryl moieties of R 2 .
  • R 2b according to the invention is independently selected from halogen, OH, CN , Ci-C4-alkyl, Ci- C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl Ci-C4-halogenalkoxy or Ci-C6-alkylthio;
  • R 2b is independently selected from halogen, OH, CN, Ci- C2-alkyl, Ci-C2-alkoxy, Ci-C2-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and C1-C2- halogenalkoxy.
  • R 2b is independently selected from F, CI, Br, OH, CN, CH 3 , OCH 3 , cyclopropyl, 1-F-cyclopropyl, 1-CI-cyclopropyl, 1 ,1-F 2 -cyclopropyl, 1 ,1-Cl2-cyclopropyl and halogenmethoxy.
  • R 2b is independently selected from halogen, C1-C2- alkyl, Ci-C2-alkoxy, Ci-C2-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and C1-C2- halogenalkoxy.
  • R 2b is independently selected from F, CI, Br, CH3, CHF2, CF3, OCH3, cyclopropyl, 1 -F-cyclopropyl, 1-CI-cyclopropyl, 1 ,1 -F2-cyclopropyl, 1 ,1 -Cl2-cyclopropyl and halogenmethoxy, more specifically independently selected from F, CI, Br, CH3, CHF2, CF3, OCH3, cyclopropyl, 1 -F-cyclopropyl, 1-CI-cyclopropyl, 1 ,1 -F 2 -cyclopropyl, 1 ,1 -Cl2-cyclopropyl and
  • R 3 is CH3.
  • R 3 is CH 2 F.
  • R 3 is CHF 2 .
  • R 3 is CF3.
  • R 4 is selected from subtituted Ci-C6-alkyl, C2-C6-alkenyl, C2- C6-halogenalkenyl, C2-C6-alkynyl, C2-C6-halogenalkynyl, a saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle or heterocycle.
  • R 4 is OH.
  • R 4 is CN. According to still another embodiment of formula I , R 4 is NO2.
  • R 4 is SH.
  • R 4 is NH2
  • R 4 is NH(Ci-C4-alkyl) or N(Ci-C4-alkyl)2, in particular Ci-C2-alkyl, such as CH3 or CH2CH3.
  • R 4 is NH-S02-R X , such as NH-SO2-C1-C4- alkyl especially NH-SO2-CH3.
  • R 4 is NH-S02-R X , such as NH-SO2-C1-C4- haogenalkyl especially NH-SO2-CF3.
  • R 4 is NH-S02-R X , such as NH-S02-aryl especially NH-S02-phenyl.
  • R 4 is Ci-C6-alkylthio, such as SCH3 or
  • R 4 is C2-C6-alkynyl or C2-C6-halogenalkynyl, in particular C2-C4-alkynyl or C2-C4-halogenalkynyl, such as C CH, C C-CI, CH2- C ⁇ CH, CH 2 -C ⁇ CCI or CH 2 - C ⁇ C-CH 3 .
  • R 4 is Ci-C6-alkoxy, such as OCH 3 , OCH2CH3, OCH 2 CH(CH 3 ) or OC(CH 3 ) 3 .
  • R 4 is Ci-C6-halogenalkoxy, in particular Ci-C4-halogenalkoxy, more specifically Ci-C2-halogenalkoxy such as OCF3, OCHF2, OCH2F, OCCI3, OCHC or OCH2CI, in particular OCF 3 , OCHF2, OCCI 3 or OCHCI 2 .
  • R 4 is C2-C6-alkynyloxy, in particular C2- C4-alkynyloxy, more specifically Ci-C2-alkynyloxy such as OC CH, OChbC CH or ChbOC CH
  • Ci-C6-alkyl moieties of R 4 carry one, two, three or up to the maximum possible number of identical or different groups R 4a , respectively, which independently of one another are selected from:
  • R 4a is in each case independently selected from, S(0) z -Ci-C 6 -alkyl, S(0) z -Ci-C 6 -halogenalkyl, S(0) z -aryl, such as SCH 3 , S0 2 CH 3 , S0 2 Ph.
  • R 4a is in each case independently selected from NH(Ci-C 4 -alkyl), N(Ci-C 4 -alkyl) 2 , NH-S0 2 -R x , such as NH(CH 3 ), N(CH 3 ) 2 , NHS0 2 CH 3 ,
  • R 4a is in each case independently selected from C 3 -C6- cycloalkyl, C 3 -C6-halogencycloalkyl, such as cyclopropyl or fully or partially halogenated cyclo- propyl.
  • R 4a is in each case independently selected from C1-C6- alkoxy, Ci-C 6 -halogenalkoxy, such as OCF 3 , OCHF 2 , OCH 2 F, OCCI 3 , OCHCI 2 or OCH 2 CI, in particular OCF 3 , OCHF 2 , OCCI 3 or OCHCI 2 .
  • R 4a is in each case independently selected from aryl, wherein the aryl is substituted by halogen selected from the group consisting of F, CI, Br, CH 3 , CHF 2 , OCHs, OCHF2, OCF3, CN or SO2CH3.
  • R 4 is unsubstituted 5- or 6-membered heteroaryl.
  • R 4 is 5- or 6-membered heteroaryl substituted by halogen selected from the group consisting of F, CI, Br, CH 3 , CHF 2 , OCH 3 , OCHF 2 , OCF 3 , CN or
  • R 4a is in each case independently selected from halogen, OH, CN, C 3 -C6-cycloalkyl, C 3 -C6-halogencycloalkyl and heterocycle, wherein the heterocy- clocycle is a satureated and contains one N as a ring member.
  • R 4a is in each case independently selected from halogen, OH, CN, Ci-C6-alkoxy, Ci-C6-halogenalkoxy, phenyl, aryl or heteroaryl; wherein the aryl and hteroaryl is substituted by halogen selected from the group consisting of F, CI, Br, CH3, CHF 2 , OCH3, OCHF2, OCF3, CN or SO2CH3.
  • R 4a is in each case independently selected from halogen, phenyl, halogenphenyl and heteroaryl, wherein the halogenphenyl is substituted by halogen selected from the group consisting of F, CI and Br, in particular selected from F and CI.
  • R 4a is in each case independently selected from halogen, CN, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci-C6-alkoxy, Ci-C4-halogenalkoxy, Ci- C6-alkylthio, Ci-C6-halogenalkylthio, phenyl, wherein the phenyl is substituted by halogen selected from the group consisting of F, CI and Br or by Ci-C4-alkyl, Ci-C4-halogenalkyl, C1-C4- alkoxy and Ci-C4-halogenalkoxy.
  • R 4a is in each case independently selected from halogen and phenyl wherein the phenyl is substituted by halogen selected from the group consisting of F, CI and Br, in particular selected from F and CI.
  • R 4 is a partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle, in particular three-, four-, five- or six-membered, wherein the carbocycle is unsubstituted or substituted by substituents R 4b as defined below. According to one embodiment thereof, the carbocycle is unsubstituted.
  • R 4 is a partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle or heterocycle, in particular three-, four-, five- or six-membered, wherein the heterocycle contains one, two, three or four heteroa- toms selected from N, O and S, and wherein the carbocycle and heterocycle are unsubstituted or substituted with substituents R 4b as defined below. According to one embodiment thereof, the carbocycle or heterocycle is unsubstituted.
  • R 4 is a saturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle or heterocycle, in particular three-, four-, five- or six- membered, wherein the heterocycle contains one, two, three or four heteroatoms selected from N, O and S, and wherein the carbocycle and heterocycle are unsubstituted or substituted with substituents R 4b as defined below. According to one embodiment thereof, the carbocycle or het- erocycle is unsubstituted.
  • R 4 is a saturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle, in particular three-, four-, five- or six- membered, wherein the carbocycle is unsubstituted or substituted by substituents R 4b as defined below. According to one embodiment thereof, the carbocycle is unsubstituted.
  • R 4 is a 3-membered saturated carbocycle. According to one embodiment thereof, the carbocycle is unsubstituted, i.e. it does not carry any substituent R 4b . According to still another embodiment of formula I, it is substituted by R 4b .
  • R 4 is a 3-membered saturated carbocycle, which is
  • R 4 is a 3-membered saturated carbocycle, which is substituted by halogen, more specifically by F, such as C3H3F2.
  • R 4 is a 3-membered saturated carbocycle, which is substituted by halogen. More specifically by CI, such as C3H3CI2.
  • R 4 is a 4-membered saturated carbocycle. According to one embodiment thereof, the carbocycle is unsubstituted, i.e. it does not carry any substituent R 4b . According to still another embodiment of formula I, it is substituted by R 4b .
  • R 4 is a 5-membered saturated carbocycle. According to one embodiment thereof, the carbocycle is unsubstituted, i.e. it does not carry any substituent R 4b . According to still another embodiment of formula I, it is substituted by R 4b .
  • R 4 is a 6-membered saturated carbocycle. According to one embodiment thereof, the carbocycle is unsubstituted, i.e. it does not carry any substituent R 4b . According to still another embodiment of formula I, it is substituted by R 4b .
  • R 4 is a partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered heterocycle, in particular three-, four-, five- or six-membered, wherein the heterocycle contains one, two, three or four heteroatoms selected from N, O and S, and wherein the heterocycle is unsubstituted or substituted by substituents R 4b as defined below. According to one embodiment thereof, the heterocycle is unsubstituted.
  • R 4 is a saturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered heterocycle, in particular three-, four-, five- or six- membered, wherein the heterocycle contains one, two, three or four heteroatoms selected from N, O and S, and wherein the heterocycle is unsubstituted or substituted by substituents R 4b as defined below. According to one embodiment thereof, the heterocycle is unsubstituted.
  • the heterocycle contains preferably one, two or three, more specifically one or two heteroatoms selected from N, O and S. More specifically, the hetereocycle contains one heteroatom selected from N, O and S. In particular, the heterocycle contains one or two, in particular one O.
  • R 4 is a 4-membered saturated heterocycle which contains 1 or 2 heteroatoms, in particular 1 heteroatom, from the group consisting of N, O and S, as ring members.
  • the heterocycle contains one O as heteroatom.
  • the formed heterocycle is oxetane.
  • the heterocycle is unsubstituted, i.e. it does not carry any substituent R 4b .
  • R 4b is substituted by R 4b .
  • R 4 is a 5-membered saturated heterocycle which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S, as ring members.
  • the heterocycle contains one O as heteroatom.
  • the heterocycle is unsubstituted, i.e. it does not carry any substituent R 4b .
  • it is substituted by R b .
  • R 4 is a 6-membered saturated heterocycle which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S as ring members.
  • the heterocycle is unsubstituted, i.e. it does not carry any substituent R 4b .
  • R 4b it is substituted by R 4b .
  • said 6-membered saturated heterocycle contains 1 or 2, in particular 1 , heteroatom(s) O.
  • the respective 6-membered heterocycle is unsubstituted, i.e. it does not carry any substituent R 4b .
  • it is substituted by R 4b .
  • R 4b is in each case independently selected from halogen, OH, CN, SH, Ci-C6-alkyl, Ci-C6-halogenalkyl, Ci-C6-alkoxy, Ci-C6-halogenalkoxy, C1-C6- alkylthio and S(0) z -Ci-C6-alkyl.
  • R 4b is in each case independently selected from halogen, Ci-C6-alkoxy, Ci-C6-halogenalkyl, C1-C6- halogenalkoxy and S(0) z -Ci-C6-alkyl.
  • R 4b is in each case independently selected from halogen such as CI, Br, F.
  • R 4b is in each case independently selected from Ci-C6-alkyl, such as methyl and ethyl.
  • R 4b is in each case independently selected from halogen, such as F, CI and Br.
  • R 4b is in each case independently selected from Ci-C6-alkoxy, such as OCH3.
  • R 4b is in each case independently selected from C1-C4- halogenalkoxy, such as OCHF2 and OCF3.
  • R 4b is in each case independently selected from S(0) z -Ci-C6-alkyl such as SO2CH3.
  • R 4 is Ci-C6-alkyl such as CH 3 , C2H5, n- propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl which is substituted by at least one group R 4c , which independently of one another are selected from:
  • R 4 is CH 3 is substituted by at least one group R 4c , which independently of one another are selected from:
  • R 4 is CH2CN.
  • R 4 is CH2OH.
  • R 4 is Ci-C6-alkyl-Ci-C6-halogenalkoxy, in particular Ci-C 4 -alkyl-Ci-C 4 -halogenalkoxy, more specifically Ci-C2-alkyl-Ci-C2-halogenalkoxy such as CH2OCF3, CH2OCHF2, CH2OCH2F, CH2OCCI3, CH2OCHCI2 or CH 2 OCH 2 CI, in particular CH2OCF3, CH 2 OCHF 2 , CH2OCCI3 or CH2OCHCI2.
  • R 4 is Ci-C6-alkyl-Ci-C6- halogenalkylthio, in particular Ci-C 4 -alkyl-Ci-C 4 -halogenalkylthio, more specifically Ci-C2-alkyl- Ci-C 2 -halogenalkylthio such as CH2SCF3, CH 2 SCHF 2 , CH 2 SCH 2 F, CH2SCCI3, CH2SCHCI2 or CH2SCH2CI, in particular CH2SCF3, CH 2 SCHF 2 , CH2SCCI3 or CH2SCHCI2.
  • R 4 is Ci-C6-alkyl-S(0) -Ci-C6-alkyl, wherein alkyl is CH 3 , C2H5, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl.
  • R 4 is Ci-C6-alkyl-S(0)2-Ci-C6-alkyl, wherein alkyl is CH3, C2H5, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl.
  • R 4 is Ci-C6-alkyl-S(0) z -Ci-C6- halogenalkyl, wherein halogenalkyl is CF3 or CHF2 and z is 0, 1 , 2 or 3.
  • R 4 is Ci-C6-alkyl-NH-SC>2-R x wherein R x is Ci-C4-alkyl, Ci-C4-halogenalkyl, unsubstituted aryl or aryl that is substituted by one, two, three, four or five substituents R x2 independently selected from Ci-C4-alkyl, halogen, OH, CN, Ci-C4-halogenalkyl, Ci-C4-alkoxy, or Ci-C4-halogenalkoxy, such as Ch NHSC ⁇ CFs or
  • R 4 is selected from Ci-C6-alkyl which is substituted, a saturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle, in particular three-, four-, five- or six-membered, wherein the carbocycle is unsubstituted or substituted by substituents R 4b as defined below. According to one embodiment thereof, the carbo- cycle is unsubstituted.
  • R 4 is selected from Ci-C6-alkyl, especially CH2 which is substituted by a 3-membered saturated carbocycle. According to one embodiment thereof, the carbocycle is unsubstituted, i.e. it does not carry any substituent R 4b . According to still another embodiment of formula I, it is substituted by R 4b .
  • R 4 is selected from Ci-C6-alkyl, especially CH 2 which is substituted by a 4-membered saturated carbocycle. According to one embodiment thereof, the carbocycle is unsubstituted, i.e. it does not carry any substituent R 4b . According to still another embodiment of formula I, it is substituted by R 4b .
  • R 4 is selected from Ci-C6-alkyl, especially CH2 which is substi- tuted by a 5-membered saturated carbocycle. According to one embodiment thereof, the carbocycle is unsubstituted, i.e. it does not carry any substituent R 4b . According to still another embodiment of formula I, it is substituted by R 4b .
  • R 4 is selected from Ci-C6-alkyl, especially CH 2 which is substituted by a 6-membered saturated carbocycle. According to one embodiment thereof, the carbocycle is unsubstituted, i.e. it does not carry any substituent R 4b . According to still another embodiment of formula I, it is substituted by R 4b .
  • R 4 is Ci-C6-alkyl, especially CH2 substituted by a 4-membered saturated heterocycle which contains 1 or 2 heteroatoms, in particular 1 heteroatom, from the group consisting of N, O and S, as ring members.
  • the heterocycle contains one O as heteroatom.
  • the formed heterocycle is oxetane.
  • the heterocycle is unsubstituted, i.e. it does not carry any substituent R 4b .
  • it is substituted by R 4b .
  • R 4 is Ci-C6-alkyl, especially CH2 substituted by a 5-membered saturated heterocycle which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S, as ring members.
  • the heterocycle contains one O as heteroatom.
  • the heterocycle is unsubstituted, i.e. it does not carry any substituent R 4b .
  • it is substituted by R 4b .
  • R 4 is Ci-C6-alkyl, especially CH2 subsitited by a 6-membered saturated heterocycle which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S as ring members.
  • the heterocycle is unsubstituted, i.e. it does not carry any substituent R 4b .
  • R 4b it is substituted by R 4b .
  • said 6-membered saturated heterocycle contains 1 or 2, in particu- lar 1 , heteroatom(s) O.
  • the respective 6-membered heterocycle is unsubstituted, i.e. it does not carry any substituent R 4b .
  • it is substituted by R 4b .
  • R 4 is Ci-C6-alkyl, especially Chb subsitited by a 5-membered saturated heteroaryl which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S as ring members.
  • the heteroaryl is unsubstituted, i.e. it does not carry any substituent R 4b .
  • R 4b it is substituted by R 4b .
  • R 4 is Ci-C6-alkyl, especially Chb subsitited by a 5-membered saturated heteroaryl which contains one N as ring member.
  • the heteroaryl is unsubstituted, i.e. it does not carry any substituent R 4b . According to still another embodiment of formula I, it is substituted by R 4b .
  • R 4 is Ci-C6-alkyl, especially Chb subsitited by a 5-membered saturated heteroaryl which contains two N as ring members.
  • the heteroaryl is unsubstituted, i.e. it does not carry any substituent R 4b . According to still another embodiment of formula I, it is substituted by R 4b .
  • R 4 is Ci-C6-alkyl, especially Chb subsitited by a 5-membered saturated heteroaryl which contains three N as ring members.
  • the heteroaryl is unsubstituted, i.e. it does not carry any substituent R 4b . According to still another embodiment of formula I, it is substituted by R 4b .
  • said 5-membered saturated heterocycle contains 1 or 2, in particular 1 , heteroatom(s) O.
  • R 4 is Ci-C6-alkyl, especially CH 2 subsitited by a 5-membered saturated heteroaryl which contains one S as ring member.
  • the heteroaryl is unsubstituted, i.e. it does not carry any substituent R 4b . According to still another embodiment of formula I, it is substituted by R 4b .
  • R 4 is Ci-C6-alkyl, especially Chb subsitited by a 5-membered saturated heteroaryl which contains one S and one N as ring members.
  • the heteroaryl is unsubstituted, i.e. it does not carry any substituent R 4b .
  • R 4b it is substituted by R 4b .
  • R 4 is Ci-C6-alkyl, especially CH 2 subsitited by a 5-membered saturated heteroaryl which contains one S and two N as ring mem- bers. According to one embodiment thereof, the heteroaryl is unsubstituted, i.e. it does not carry any substituent R 4b . According to still another embodiment of formula I, it is substituted by R 4b . According to a further specific embodiment of formula I, R 4 is Ci-C6-alkyl, especially Chb subsitited by a 5-membered saturated heteroaryl which contains one oxygen and one N as ring members. According to one embodiment thereof, the heteroaryl is unsubstituted, i.e. it does not carry any substituent R 4b . According to still another embodiment of formula I, it is substituted by R 4b .
  • R 4 is Ci-C6-alkyl, especially CH 2 subsitited by a 5-membered saturated heteroaryl which contains one oxygen and two N as ring members.
  • the heteroaryl is unsubstituted, i.e. it does not carry any substituent R 4b .
  • R 4b it is substituted by R 4b .
  • R 4 is Ci-C6-alkyl, especially Chb subsitited by a 6-membered saturated heteroaryl which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S as ring members.
  • the heteroaryl is unsubstituted, i.e. it does not carry any substituent R 4b .
  • R 4b it is substituted by R 4b .
  • R 4 is Ci-C6-alkyl, especially Chb subsitited by a 6-membered saturated heteroaryl which one N as ring member.
  • the heteroaryl is unsubstituted, i.e. it does not carry any substituent R 4b .
  • R 4b it is substituted by R 4b .
  • R 4 is Ci-C6-alkyl, especially Chb subsitited by a 6-membered saturated heteroaryl which two N as ring members.
  • the heteroaryl is unsubstituted, i.e. it does not carry any substituent R 4b .
  • R 4b it is substituted by R 4b .
  • R 4 is Ci-C6-alkyl, especially Chb subsitited by a 10-membered saturated heteroaryl which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S as ring members.
  • the heteroaryl is unsubstituted, i.e. it does not carry any substituent R 4b .
  • R 4b it is substituted by R 4b .
  • said 10-membered saturated heterocycle contains 1 or 2, in par- ticular 1 , heteroatom(s) N.
  • R 4 is Ci-C6-alkyl, especially CH 2 subsitited by a 10-membered saturated heteroaryl which one N as ring members.
  • the heteroaryl is unsubstituted, i.e. it does not carry any substituent R 4b .
  • R 4b it is substituted by R 4b .
  • R 4 is Chb substituted by a 5-membered heteroaryl such as pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan-2-yl, furan-3-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1 -yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, is
  • R 4 is CH2 substituted by a 6-membered het- eroaryl, such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2- yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl.
  • a 6-membered eroaryl such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2- yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and 1 ,3,5-triazin-2-yl
  • R 4c is in each case independently selected from C1-C6- halogenalkylthio, S(0)-Ci-C 6 -alkyl, S(0) 2 -Ci-C 6 -alkyl, S(0) z -Ci-C 6 -halogenalkyl, S(0) z -aryl, such as SCH 3 , S0 2 CH 3 , S0 2 Ph.
  • R 4c is in each case independently selected from C 3 -C6- cycloalkyl, C 3 -C6-halogencycloalkyl, such as cyclopropyl or fully or partially halogenated cyclo- propyl.
  • R 4c is in each case independently selected C1-C6- halogenalkoxy, such as OCF 3 , OCHF 2 , OCH 2 F, OCCI 3 , OCHCI 2 or OCH 2 CI, in particular OCF 3 , OCHF 2 , OCCIs or OCHCI 2 .
  • R 4 is unsubstituted 5- or 6-membered heteroaryl.
  • R 4 is 5- or 6-membered heteroaryl substituted by halogen selected from the group consisting of F, CI, Br, CH 3 , CHF 2 , OCH 3 , OCHF 2 , OCF 3 , CN or S0 2 CH 3 .
  • R 4c is in each case independently selected from OH, CN, C 3 -C6-cycloalkyl, C 3 -C6-halogencycloalkyl and heterocycle, wherein the heterocycle is a saturated and contains one N as a ring member.
  • R 4 Particularly preferred embodiments of R 4 according to the invention are in Table P4 below, wherein each line of lines P4-1 to P4-101 corresponds to one particular embodiment of the invention, wherein P4-1 to P4-101 are also in any combination with one another a preferred embodiment of the present invention.
  • the connection point to the carbon atom, to which R 4 is bound is marked with "#" in the drawings.
  • R x in the substituent NH-S02-R X is in each case independently selected from Ci-C4-alkyl, C1-C4- halogenalkyl, unsubstituted aryl and aryl that is substituted by one, two, three, four or five substituents R x1 independently selected from Ci-C4-alkyl, halogen, OH, CN, Ci-C4-halogenalkyl, Ci-C4-alkoxy, and Ci-C4-halogenalkoxy;.
  • R x is in each case independently selected from Ci-C4-alkyl and phenyl that is substituted by one, two or three R x1 independently selected from Ci-C4-alkyl, halogen, OH, CN, Ci-C4-halogenalkyl, Ci-C4-alkoxy, and Ci-C4-halogenalkoxy, more specifically R x is in each case independently selected from Ci-C4-alkyl and phenyl that is substituted by one CH3, more specifically S02-R x is the tosyl group ("Ts").
  • R 5 is H.
  • R 6 is H.
  • R 7 and R 8 together with the carbon atoms to which they are bound together with the carbon atoms to which they are bound form a phenyl ring; wherein the phenyl ring carries zero, one, two, three or four substituents (R 78 ) 0 , wherein o is 0, 1 , 2 or 3; and R 78 are independently selected from halogen, OH, CN, N0 2 , SH, NH 2 , NH(Ci-C 4 -alkyl),
  • R 78 wherein the acyclic moieties of R 78 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R 78a which independently of one another are selected from:
  • R 78a halogen, OH, CN, Ci-C 6 -alkoxy, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenyl, C 3 -C 6 - halogencycloalkyl, C3-C6-halogencycloalkenyl, Ci-C 4 -halogenalkoxy, Ci-C6-alkylthio, five- or six- membered heteroaryl, phenyl and phenoxy, wherein the heteroaryl, phenyl and phenoxy group is unsubstituted or carries one, two, three, four or five substituents R 78a' selected from the group consisting of halogen, OH, Ci-C 4 -alkyl, Ci-C 4 -halogenalkyl, Ci-C 4 -alkoxy and Ci-C 4 - halogenalkoxy;
  • R 78 wherein the cyclic, phenyl, heterocyclic and heteroaryl moieties of R 78 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R 78b which independently of one another are selected from:
  • R 78b halogen, OH, CN, Ci-C 4 -alkyl, Ci-C 4 -alkoxy, Ci-C 4 -halogenalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 - halogencycloalkyl, Ci-C 4 -halogenalkoxy and Ci-C6-alkylthio.
  • R 78 there can be zero, one, two or three R 78 present, namely for o is 0, 1 , 2 or 3.
  • o 0.
  • o is 1 .
  • o is 2 or 3. According to one specific embodiment thereof, o is 2, according to a further specific embodiment, o is 3.
  • R 78 is halogen, in particular F, CI, Br or I, more specifically F, CI or Br, in particular F or CI. According to still another embodiment of formula I, R 78 is F.
  • R 78 is CI.
  • R 78 is Br.
  • R 78 is OH.
  • R 78 is CN.
  • R 78 is NO2.
  • R 78 is SH.
  • R 78 is NH2.
  • R 78 is NH-S02-R X such as NH-SO2-CH3, NH-SO2-CH2-CH3, NH-SO2-CF3 or NH-SO2-TS.
  • R 78 is Ci-C6-alkyl, in particular Ci-C 4 -alkyl, such as CH 3 , C2H5, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl., in particular CH 3 .
  • R 78 is Ci-C6-halogenalkyl, in particular C1-C4- halogenalkyl, such as CF 3 , CCI 3 , FCH 2 , CICH 2 , F 2 CH, CI 2 CH, CF 3 CH 2 , CCI 3 CH 2 or CF 2 CHF 2 .
  • R 78 is C 3 -C6-cycloalkyl, in particular cyclopro- pyl.
  • R 78 is C 3 -C6-halogencycloalkyl.
  • R 1 is fully or partially halogenated cyclopropyl.
  • R 78 is C2-C6-alkynyl, in particular C2-C 4 -alkynyl, more specifically C2-C 3 -alkynyl, such as C ⁇ CH.
  • R 78 is C 2 -C6-halogenalkynyl, in particular C 2 -C4- halogenalkynyl, more specifically C2-C3-halogenalkynyl.
  • R 78 is Ci-C6-alkoxy, in particular Ci-C4-alkoxy, more specifically Ci-C2-alkoxy such as OCH3 or OCH2CH3.
  • R 78 is Ci-C6-halogenalkoxy, in particular C1-C4- halogenalkoxy, more specifically Ci-C2-halogenalkoxy such as OCF3, OCHF2, OCH2F, OCCI3, OCHCI2, OCH2CI and OCF2CHF2, in particular OCF 3 , OCHF 2 and OCF 2 CHF 2 .
  • R 78 is C2-C6-alkynyloxy, in particular C2- C4-alkynyloxy, more specifically Ci-C2-alkynyloxy such as OC CH or OChbC CH.
  • R 78 is S(0) z -Ci-C6-alkyl, wherein alkyl is CH3, C2H5, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl and z is 0, 1 , 2 or 3.
  • R 78 is S(0) z -Ci-C6-halogenalkyl, wherein halogenalkyl is CF 3 or CHF 2 and z is 0, 1 , 2 or 3.
  • R 78 is a partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered heterocycle, in particular three-, four-, five- or six-membered, wherein the heterocycle contains one, two, three or four heteroatoms selected from N, O and S, and wherein the heterocycle is unsubstituted or substituted by substituents R 78b as defined below. According to one embodiment thereof, the heterocycle is unsubstituted.
  • R 78 is a saturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered heterocycle, in particular three-, four-, five- or six- membered, wherein the heterocycle contains one, two, three or four heteroatoms selected from N, O and S, and wherein the heterocycle is unsubstituted or substituted by substituents R 78b as defined below. According to one embodiment thereof, the heterocycle is unsubstituted.
  • the heterocycle contains preferably one, two or three, more specifically one or two heteroatoms selected from N, O and S. More specifically, the hetereocycle contains one heteroatom selected from N, O and S. In particular, the heterocycle contains one or two, in particular one O.
  • R 78 is a 4-membered saturated heterocycle which contains 1 or 2 heteroatoms, in particular 1 heteroatom, from the group consisting of N, O and S, as ring members.
  • the heterocycle contains one O as heteroatom.
  • the formed heterocycle is oxetane.
  • the heterocycle is unsubstituted, i.e. it does not carry any substituent R 78b . According to still another embodiment of formula I, it is substituted by R 78b .
  • R 78 is a 5-membered saturated heterocycle which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S, as ring members.
  • the heterocycle contains one O as heteroatom.
  • the heterocycle is unsubstituted, i.e. it does not carry any substituent R 78b .
  • R 78 is substituted by R 78 .
  • R 78 is a 6-membered saturated heterocycle which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S as ring members.
  • the heterocycle is unsubstituted, i.e. it does not carry any substituent R 78b .
  • it is substituted by R 78b .
  • said 6-membered saturated heterocycle contains 1 or 2, in particular 1 , heteroatom(s) O.
  • the respective 6-membered heterocycle is unsubstituted, i.e. it does not carry any substituent R 78b .
  • it is substituted by R 78b .
  • R 78 is phenyl-Ci-C6-alkyl, such as phenyl- CH2, wherein the phenyl moiety in each case is unsubstituted or substituted by one, two or three identical or different groups R 78b which independently of one another are selected from halogen, Ci-C2-alkyl, Ci-C2-alkoxy, Ci-C2-halogenalkyl and Ci-C2-halogenalkoxy, in particular CN, F, CI, Br, CH 3 , OCH3, CHF 2 , CF 3 OCHF 2 , and OCF 3 .
  • R 78 is unsubstituted phenyl or phenyl that is substituted by one, two, three or four R 78b , as defined and preferably herein.
  • R 78 is unsubstituted phenyl or phenyl that is substituted by one, two, three or four R 78b , as defined herein.
  • R 78 is unsubstituted phenyl.
  • R 78 is a 5-membered heteroaryl such as pyrrol-1 -yl, pyrrol-2-yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan-2-yl, furan-3-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4--
  • R 78 is a 6-membered heteroaryl, such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl.
  • R 78 is in each case independently selected from halogen, CN, d-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, d-Ce-alkoxy, d-Ce-halogenalkyl, C2-C6- halogenalkenyl, C2-C6-halogenalkynyl, Ci-C6-halogenalkoxy, C3-C6-alkenyloxy, C3-C6- alkynyloxy, C 3 -C6-cycloalkyl, C 3 -C6-halogencycloalkyl, S(0) z -CrC 6 -alkyl, three-, four-, five- or six-membered saturated or partially unsaturated heterocycle, five- or six-membered heteroaryl and phenyl; wherein the heterocycle or heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the acycl
  • R 78 is in each case independently selected from halogen, CN, Ci-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, d-Ce-alkoxy, Ci-Ce-halogenalkyl, d-d- halogenalkenyl, C2-C6-halogenalkynyl, Ci-C6-halogenalkoxy, C3-C6-alkenyloxy, d-d- alkynyloxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, S(0) z -Ci-C6-alkyl, three-, four-, five- or six-membered saturated or partially unsaturated heterocycle, five- or six-mem bered heteroaryl and phenyl; wherein the heterocycle or heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the acyclic moieties
  • the acyclic and cyclic moieties of R 78 are not further substituted, according to another embodiment, the acyclic moieties of R 78 carry one, two, three or four identical or different groups R 78a as defined and preferably defined herein.
  • R 78 is in each case independently selected from halogen, CN, Ci-Ce-alkyI, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce-alkoxy, d-Ce-halogenalkyl, C2-C6- halogenalkenyl, C2-C6-halogenalkynyl, Ci-C6-halogenalkoxy, C3-C6-alkenyloxy, C3-C6- alkynyloxy, C 3 -C6-cycloalkyl C 3 -C6-halogencycloalkyl, and S(0) z -CrC 6 -alkyl, wherein the acyclic moieties of R 78 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R 78a as defined and preferably defined herein, and wherein the cycloalkyl moieties of R 78 are not further substituted or
  • R 78 is in each case independently selected from halogen, CN, Ci-Ce-alkyI, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-Ce-alkoxy, Ci-C 6 - Ci-C 6 -halogenalkyl, C 2 -C 6 - halogenalkenyl, C2-C6-halogenalkynyl, Ci-C6-halogenalkoxy, C3-C6-alkenyloxy, C3-C6- alkynyloxy, C 3 -C6-cycloalkyl, C 3 -C6-halogencycloalkyl, and S(0) z -Ci-C6-alkyl, wherein the acyclic moieties of R 78 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R 78a as defined and preferably defined herein, and wherein the cyclo
  • the acyclic and cyclic moieties of R 78 are not further substituted, according to another embodiment, the acyclic moieties of R 78 carry one, two, three or four identical or different groups R 78a as defined and preferably defined herein.
  • R 78 is in each case independently selected from halogen, Ci-C6-alkyl and Ci-C6-alkoxy, wherein the acyclic moieties of R 78 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R 78a defined and preferably defined herein.
  • R 78 is in each case independently selected from CN, halogen, Ci-C6-alkyl, Ci-C6-halogenalkyl, Ci-C6-alkoxy and Ci-C6-halogenalkoxy, wherein the acyclic moieties of R 78 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R 78a defined and preferably defined herein.
  • the acyclic and cyclic moieties of R 78 are not further substituted, according to another embodiment, the acyclic moieties of R 78 carry one, two, three or four identical or different groups R 78a as defined and preferably defined herein.
  • R 78a are the possible substituents for the acyclic moieties of R 78 .
  • R 78a is independently selected from halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C3-C6- halogencycloalkyl, C3-C6-halogencycloalkenyl, Ci-C4-halogenalkoxy, Ci-C6-alkylthio, five- or six- membered heteroaryl, phenyl and phenoxy, wherein the heteroaryl, phenyl and phenoxy group is unsubstituted or carries one, two, three, four or five substituents R 78a' selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and C1-C4- halogenalkoxy.
  • R 78a is independently selected from halogen, Ci-C6-alkoxy, C3- C6-cycloalkyl, C3-C6-halogencycloalkyl and Ci-C4-halogenalkoxy. Specifically, R 78a is
  • R 78a is independently halogen, in particular selected from F, CI, Br and I, more specifically F, CI and Br.
  • R 78b are the possible substituents for the cycloalkyi, heterocyclyl, heteroaryl and phenyl moieties of R 78 .
  • R 78b according to the invention is independently selected from halogen, OH, CN, C1-C4- alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, C1-C4- halogenalkoxy and Ci-C6-alkylthio.
  • R 78b is independently selected from halogen, CN, C1-C4- alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl and Ci-C4-halogenalkoxy, in particular halogen, C1-C4- alkyl and Ci-C 4 -alkoxy.
  • R 78b is independently selected from F, CI, CN, CH 3 , OCH 3 and halogenmethoxy.
  • R 7 and R 8 optionally substituted by (R 78 ) 0 , according to the invention are in Table P78 below, wherein each line of lines P78-1 to P78-61 corresponds to one particular embodiment of the invention, wherein P78-1 to P78-61 are also in any combination with one another a preferred embodiment of the present invention.
  • the positions of the heteroaryls marked with "#" represents the connection points (carbon atoms 5' and 6' in formula I) with the remaining skeleton of the compounds of formula I:
  • R Y is Ci-C6-alkyl, Ci-C6-halogenalkyl, C2-C6-alkenyl, C2-C6-halogenalkenyl, C2-C6-alkynyl, C2-C6- halogenalkynyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, phenyl and phenyl-Ci-C6-alkyl;
  • phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN , halogen, OH , Ci-C4-alkyl, Ci-C4-halogenalkyl, C1-C4- alkoxy and Ci-C4-halogenalkoxy;
  • R 9a is the subtituent of the acyclic moieties of R 9 .
  • the acyclic moieties of R 9 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R 9a which independently of one another are selected from halogen, OH , CN , Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C3-C6-halogencycloalkyl, C3-C6- halogencycloalkenyl, Ci-C4-halogenalkoxy, Ci-C6-alkylthio, five- or six-membered heteroaryl, phenyl and phenoxy, wherein the heteroaryl, phenyl and phenoxy group is unsubstituted or carries one, two, three, four or five substituents R 9a' selected from the group consisting of halogen, OH , Ci-C4-al
  • R 9b is the subtituyend of cycloalkyl, phenyl, heterocyclic and heteroaryl moieties of R 9 .
  • the alicyclic, phenyl, heterocyclic and heteroaryl moieties of R 9 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R 9b which independently of one another are selected from halogen, OH , CN , Ci-C4-alkyl, C1-C4- alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy and d-Ce-alkylthio.
  • R 9 is H .
  • R 9 is OH .
  • R 9 is Ci-C6-alkyl, such as CH3, C 2 H5, n- propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl.
  • R 9 is Ci-C6-alkyl, in particular Ci-C4-alkyl, such as CH3, C 2 H5, n-propyl, i-propyl.
  • R 9 is Ci-C6-halogenalkyl, in particular C1-C4- halogenalkyl, such as CF 3 , CCI 3 , FCH 2 , CICH 2 , F 2 CH, CI 2 CH, CF 3 CH 2 , CCI 3 CH 2 or CF 2 CHF 2 .
  • R 9 is C3-C6-cycloalkyl, in particular cyclopropyl.
  • R 9 is C3-C6-halogencycloalkyl.
  • R 9b is fully or partially halogenated cyclopropyl, such as 1 -F-cyclopropyl, 1 -CI- cyclopropyl, 1 ,1 -F 2 -cyclopropyl, 1 ,1-CI 2 -cyclopropyl .
  • R 9 is OR Y , wherein R Y is Ci-C6-alkyl, Ci- C6-halogenalkyl, C 2 -C6-alkenyl, C 2 -C6-halogenalkenyl, C 2 -C6-alkynyl, C 2 -C6-halogenalkynyl, C3- C6-cycloalkyl, C3-C6-halogencycloalkyl, phenyl and phenyl-Ci-C6-alkyl; wherein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and C1-C4- halogenalkoxy;
  • R 9 is OR Y , wherein R Y is Ci-C6-alkyl, in particular Ci-C4-alkyl, more specifically Ci-C 2 -alkyl.
  • R 9 is such as OCH3 or OCH 2 CH3.
  • R 9 is OR Y , wherein R Y is C1-C6- halogenalkyl, in particular Ci-C4-halogenalkyl, more specifically Ci-C 2 -halogenalkyl.
  • R 9 is such as OCF3, OCHF 2 , OCH 2 F, OCCI 3 , OCHCI 2 or OCH 2 CI, in particular OCF 3 , OCHF 2 , OCCI 3 or OCHCI 2 .
  • R 9 is OR Y wherein R Y C 2 -C6-alkenyl, in particular C2-C4-alkenyl, more specifically Ci-C2-alkenyl.
  • R 9 is OR Y , wherein R Y C2-C6-alkynyl, in particular C2-C6-alkynyl, in particular C2-C4-alkynyl, more specifically Ci-C2-alkynyl.
  • R 9 is such as OC ⁇ CH or OCH 2 C ⁇ CH.
  • R 9 is OR Y wherein R Y is C3-C6- halogencycloalkyl.
  • R 1 is fully or partially halogenated cyclopropyl.
  • R 9 is is OR Y , wherein R Y and phenyl; wherein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy.
  • R 9 is is OR Y , wherein R Y phenyl-Ci-C6-alkyl, such as phenyl-Chb, herein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, C1-C4- halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy.
  • R 9 is such as OCH 2 Ph.
  • R 9 is S(0)z-C2-C6-alkenyl such as
  • R 9 is S(0)z-aryl, wherein the aryl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consist- ing of CN, halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and C1-C4- halogenalkoxy.
  • R 9 is such as SPh, SOPh, or S0 2 Ph.
  • R 9 is SC>2-NH(Ci-C6-alkyl), is Ci-C6-alkyl, in particular Ci-C 4 -alkyl, more specifically Ci-C 2 -alkyl.
  • R 9 is such as SO2NHCH3 or SO2NHCH2CH3.
  • R 9 is SC>2-NH(Ci-C6-halogenalkyl), wherein Ci-C6-halogenalkyl, in particular Ci-C4-halogenalkyl, more specifically Ci-C2-halogenalkyl.
  • R 9 is such as SO2NHCF3, SO2NHCHF2, SO2NHCH2F, SO2NHCCI3, SO2NHCHCI2 or S0 2 NHCH 2 CI, in particular SO2NHCF3, SO2NHCHF2, SO2NHCCI3 or SO2NHCHCI2.
  • R 9 is S02-NH-aryl, wherein the aryl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and C1-C4- halogenalkoxy. .
  • R 9 is such as S02NHPh.
  • R 9 is tri-(Ci-C6 alkyl)silyl, in particular C1-C4- alkyl, such as CH 3 . or C 2 H 5 .
  • R 9 is such as OSi(CH 3 ) 3
  • R 9 is di-(Ci-C6 alkoxy)phosphoryl), in particular Ci-C 4 -alkoxy, such as OCH 3 . or OC2H5.
  • R 9 is such as OPO(OCH 3 ) 2 .
  • R 9 is phenyl-Ci-C6-alkyl, such as phenyl- CH2, wherein the phenyl moiety in each case is unsubstituted or substituted by one, two or three identical or different groups R 9b which independently of one another are selected from halogen, Ci-C2-alkyl, Ci-C2-alkoxy, Ci-C2-halogenalkyl and Ci-C2-halogenalkoxy, in particular F, CI, Br, CH 3 , CHF 2 , OCH3, OCHF2, CF 3 and OCF 3 .
  • R 9 is aryl, in particular phenyl, wherein the aryl or phenyl moiety in each case is unsubstituted or substituted by identical or different groups R 9b which independently of one another are selected from halogen, Ci-C2-alkyl, Ci-C2-alkoxy, Ci-C 2 -halogenalkyl and Ci-C 2 -halogenalkoxy, in particular F, CI, Br, CH 3 , CHF 2 , OCH 3 , OCHF 2 , CF3 and OCF3.
  • R 9 is unsubstituted phenyl.
  • R 9 is phenyl, that is substituted by one, two or three, in particular one, halogen, in particular selected from F, CI and Br, more specifically selected from F and CI.
  • R 9 is a 5-membered heteroaryl such as pyr- rol-1 -yl, pyrrol-2-yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan-2-yl, furan-3-yl, pyrazol-1 -yl, pyrazol- 3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1 -yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2- yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isoxazol-4-yl, is
  • R 9 is a 6-membered heteroaryl such as pyri- din-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl.
  • R 9 is in each case independently selected from H, OH, Ci-C 6 -alkyl, Ci-C 6 -halogenalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-C 6 -alkoxy, Ci-C 6 - halogenalkoxy, and C3-C6-cycloalkyl wherein the acyclic moieties of R 9 are unsubstituted or substituted with identical or different groups R 9a as defined and preferably defined herein, and wherein the carbocyclic, phenyl and heteroaryl moieties of R 9 are unsubstituted or substituted with identical or different groups R 9b as defined and preferably defined herein.
  • R 9 is in each case independently selected from H, OH, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy and C3-C6-cycloalkyl, wherein the acyclic moieties of R 9 are unsubstituted or substituted with identical or different groups R 9a as defined and preferably defined herein, and wherein the cycloalkyl moieties of R 9 are unsubstituted or substituted with identical or different groups R 9b as defined and preferably defined herein.
  • R 9 is in each case independently selected from H and OR Y , wherein R Y is most preferably Ci-C6-alkyl, Ci-C6-halogenalkyl, C2-C6-alkenyl, C2-C6-halogenalkenyl, C2-C6-alkynyl, C2-C6-halogenalkynyl, phenyl and phenyl-Ci-C6-alkyl; wherein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, C1-C4- alkoxy and Ci-C4-halogenalkoxy.
  • R 9 is in each case independently selected from H and OR Y , wherein R Y is most preferably C2-C6-alkenyl, C2-C6-alkynyl, phenyl and phenyl- Ci-C6-alkyl; wherein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy.
  • R 9 is in each case independently selected from H, S(0)z-Ci-C 6 -alkyl, S(0) z -Ci-C 6 -halogenalkyl, S(0) z -C 2 -C 6 -alkenyl, S(0) z -C 2 -C 6 -alkynyl, S(0) z aryl, wherein the acyclic moieties of R 9 are unsubstituted or substituted with identical or different groups R 9a as defined and preferably defined herein, and wherein the aryl moieties of R 9 are unsubstituted or substituted with identical or different groups R 9b as defined and preferably defined herein.
  • R 9 is in each case independently selected from H, S0 2 -NH(Ci-C 6 -alkyl), S0 2 -NH(Ci-C 6 -halogenalkyl), S0 2 -NHphenyl i wherein the acyclic moieties of R 9 are unsubstituted or substituted with identical or different groups R 9a as defined and preferably defined herein, and wherein the aryl moieties of R 9 are unsubstituted or substituted with identical or different groups R 9b as defined and preferably defined herein.
  • R 9a are the possible substituents for the acyclic moieties of R 9 .
  • R 9a is independently selected from halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6- cycloalkenyl, C3-C6-halogencycloalkyl, C3-C6-halogencycloalkenyl, Ci-C4-halogenalkoxy, C1-C6- alkylthio, five- or six-membered heteroaryl, phenyl and phenoxy, wherein the heteroaryl, phenyl and phenoxy group is unsubstituted or carries one, two, three, four or five substituents R 9a' se- lected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy or Ci-C4-halogenalkoxy.
  • R 9a is independently selected from halogen, Ci-C6-alkoxy, C3-C6- cycloalkyl, C3-C6-halogencycloalkyl and Ci-C4-halogenalkoxy.
  • R 9a is independently selected from F, CI, Br, I, Ci-C 2 -alkoxy, cyclopropyl, 1 -F-cyclopropyl, 1-CI-cyclopropyl, 1 ,1 -F 2 - cyclopropyl, 1 ,1 -CI 2 -cyclopropyl and Ci-C 2 -halogenalkoxy.
  • R 9a is independently halogen, in particular selected from F, CI, Br and I, more specifically F, CI and Br.
  • R 9b are the possible substituents for the cycloalkyi, heteroaryl and phenyl moieties of R 9 .
  • R 9b according to the invention is independently selected from halogen, OH, CN, Ci-C4-alkyl, C1-C4- alkoxy, Ci-C4-halogenalkyl, C 3 -C6-cycloalkyl, C 3 -C6-halogencycloalkyl, Ci-C4-halogenalkoxy and d-Ce-alkylthio.
  • R 9b is independently selected from halogen, CN, C1-C4- alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl and Ci-C4-halogenalkoxy, in particular halogen, C1-C4- alkyl and Ci-C4-alkoxy.
  • R 9b is independently selected from F, CI, Br, CN, CH3, CHF 2 , CF3, OCHs and halogenmethoxy.
  • R 9 Particularly preferred embodiments of R 9 according to the invention are in Table P13 below, wherein each line of lines P13-1 to P3-50 corresponds to one particular embodiment of the invention, wherein P13-1 to P3-50 are also in any combination with one another a preferred embodiment of the present invention.
  • the connection point to the carbon atom, to which R 9 is bound is marked with "#" in the drawings.
  • Particular embodiments of the compounds I are the following compounds: 1-1.A, 1-1 .B, 1-1.C, I- 1.D; I-2.A, I-2.B, I-2.C, I-2.D; I-3.A, I-3.B, I-3.C, I-3.D; I-4.A, I-4.B, I-4.C, I-4.D that are compiled in the Tables 1-1 to 1-4.
  • Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.
  • Table 1-1 Compounds of the formula 1-1.A, I-2.A, I-3.A, I-4.A in which the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-1.A.1 -1.A-1 to I-1 .A.1-1 .A-513, compounds I-2.A.1-1.A-1 to I-2.A.1 -1.A- 513, compounds I-3.A.1-1 .A-1 to I-3.A.1 -1.A-513 compounds I-4.A.1-1 .A-1 to I-4.A.1-1.A-513).
  • Table 1-2 Compounds of the formula 1-1.B, I-2.B, I-3.B, I-4.B in which the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-1.B.1 -2.A-1 to I-1 .B.1-2.A-513, compounds I-2.B.1-2.A-1 to I-2.B.1 -2.A- 513, compounds I-3.B.1-2.A-1 to I-3.B.1 -2.A-513 compounds I-4.B.1-2.A-1 to I-4.B.1-2.A-513).
  • Table 1-3 Compounds of the formula 1-1 C, I-2C, I-3C, I-4C in which the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds l-1 C.1-3.A-1 to I-1 C.1 -3.A-513, compounds l-2C.1 -3.A-1 to I-2C.1 -3.A- 513, compounds l-3C.1 -3.A-1 to I-3C.1-3.A-513 compounds l-4C.1 -3.A-1 to I-4C.1-3.A-513).
  • Table 1-4 Compounds of the formula 1-1.D, I-2.D, I-3.D, I-4.D in which the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-1.D.1-4.A-1 to I-1.D.1-4.A-513, compounds I-2.D.1 -4.A-1 to I-2.D.1 -4.A- 513, compounds I-3.D.1 -4.A-1 to I-3.D.1 -4.A-513 compounds I-4.D.1-4.A-1 to I-4.D.1-4.A-513).
  • Particular embodiments of the compounds I are the following compounds: I-5.A, 1-15.B, I-5.C, I- 5.D; I-6.A, I-6.B, I-6.C, I-6.D; I-7.A, I-7.B, I-7.C, I-7.D; I-8.A, I-8.B, I-8.C, I-8.D that are compiled in the Tables 1-1 to 1-13, Tables 2-1 to 2-13, Tables 3-1 to 3-13 and Tables 4-1 to 4-13.
  • Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.
  • Table 1-2 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R 9 is CH3 and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -2.A-1 to I-5.A.1-2.A-513, compounds I-6.A.1 -2.A-1 to I- 6.A.1-2.A-513, compounds I-7.A.1-2.A-1 to I-7.A.1 -2.A-513 compounds I-8.A.1-2.A-1 to I-8.A.1 -
  • Table 1-5 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R 9 is CH 2 C ⁇ CH and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -5.A-1 to I-5.A.1 -5.A-513, compounds I-6.A.1- 5. A-1 to I-6.A.1 -5.A-513, compounds I-7.A.1-5.A-1 to I-7.A.1 -5.A-513 compounds I-8.A.1-5.A-1 to I-8.A.1-5.A-513).
  • Table 1-6 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R 9 is C(0)CH 3 and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -6.A-1 to I-5.A.1 -6.A-513, compounds I-6.A.1-
  • Table 1-7 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R 9 is C(0)OCH 3 and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -7.A-1 to I-5.A.1 -7.A-513, compounds I-6.A.1-
  • Table 1-9 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R 9 is CO-N(CH 3 )2 and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1-9.A-1 to I-5.A.1 -9.A-513, compounds I- 6.A.1-9.A-1 to I-6.A.1-9.A-513, compounds I-7.A.1-9.A-1 to I-7.A.1-9.A-513 compounds I-8.A.1-
  • Table 1-1 1 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R 9 is S0 2 NHCH 3 and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -1 1 .A-1 to I-5.A.1-1 1.A-513, compounds I-6.A.1-
  • A-1 to I-6.A.1-1 1.A-513, compounds I-7.A.1-1 1 .A-1 to I-7.A.1 -1 1 .A-513 compounds I-8.A.1-
  • Table 1-12 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R 9 is S0 2 NHPh and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -12.A-1 to I-5.A.1-12.A-513, compounds I-6.A.1-
  • Table 1-13 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R 9 is S0 2 Ph and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -13.A-1 to I-5.A.1-13.A-513, compounds I-6.A.1-
  • Table 2-1 Compounds of the formula I-5.B, I-6.B, I-7.B, I-8.B in which R 9 is H and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-1 .A-1 to I-5.B.2-1.A-513, compounds I-6.B.2-1.A-1 to I- 6.B.2-1.A-513, compounds I-7.B.2-1 .A-1 to I-7.B.2-1.A-513 compounds I-8.B.2-1 .A-1 to I-8.B.2-
  • Table 2-2 Compounds of the formula I-5.B, I-6.B, I-7.B, I-8.B in which R 9 is CH 3 and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-2.A-1 to I-5.B.2-2.A-513, compounds I-6.B.2-2.A-1 to I- 6.B.2-2.A-513, compounds I-7.B.2-2.A-1 to I-7.B.2-2.A-513 compounds I-8.B.2-2.A-1 to I-8.B.2-
  • Table 2-7 Compounds of the formula I-5.B, I-6.B, I-7.B, I-8.B in which R 9 is C(0)OCH 3 and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-7.A-1 to I-5.B.2-7.A-513, compounds I-6.B.2-
  • Table 2-1 1 Compounds of the formula I-5.B, I-6.B, I-7.B, I-8.B in which R 9 is SO2NHCH3 and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-1 1 .A-1 to I-5.B.2-1 1.A-513, compounds I-6.B.2-
  • Table 3-1 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R 9 is H and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-1.A-1 to I-5.C.3-1.A-513, compounds I-6.C.3-1 .A-1 to I- 6.C.3-1 .A-513, compounds I-7.C.3-1.A-1 to I-7.C.3-1.A-513 compounds I-8.C.3-1 .A-1 to I-8.C.3-
  • Table 3-2 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R 9 is CH 3 and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-2.A-1 to I-5.C.3-2.A-513, compounds I-6.C.3-
  • Table 3-5 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R 9 is CH 2 C ⁇ CH and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-5.A-1 to I-5.C.3-5.A-513, compounds I-6.C.3-
  • Table 3-7 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R 9 is C(0)OCH 3 and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-7.A-1 to I-5.C.3-7.A-513, compounds I-6.C.3-
  • Table 3-9 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R 9 is CO-N(CH 3 )2 and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-9.A-1 to I-5.C.3-9.A-513, compounds I- 6.C.3-9.A-1 to I-6.C.3-9.A-513, compounds I-7.C.3-9.A-1 to I-7.C.3-9.A-513 compounds I-8.C.3-
  • Table 3-1 1 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R 9 is S0 2 NHCH 3 and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-1 1 .A-1 to I-5.C.3-1 1.A-513, compounds I- 6.C.3-1 1.A-1 to I-6.C.3-1 1 .A-513, compounds I-7.C.3-1 1.A-1 to I-7.C.3-1 1. A-513 compounds I- 8.C.3-1 1.A-1 to I-8.C.3-1 1 .A-513).
  • Table 3-12 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R 9 is S0 2 NHPh and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-12.A-1 to I-5.C.3-12.A-513, compounds I-6.C.3- 12.A-1 to I-6.C.3-12.A-513, compounds I-7.C.3-12.A-1 to I-7.C.3-12.A-513 compounds I-8.C.3-
  • Table 3-13 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R 9 is S0 2 Ph and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-13.A-1 to I-5.C.3-13.A-513, compounds I-6.C.3-
  • Table 4-1 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R 9 is H and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-1.A-1 to I-5.D.4-1.A-513, compounds I-6.D.4-1 .A-1 to I- 6.D.4-1 .A-513, compounds I-7.D.4-1.A-1 to I-7.D.4-1.A-513 compounds I-8.D.4-1 .A-1 to I-8.D.4-
  • Table 4-2 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R 9 is CH 3 and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-2.A-1 to I-5.D.4-2.A-513, compounds I-6.D.4-
  • Table 4-7 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R 9 is C(0)OCH 3 and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-7.A-1 to I-5.D.4-7.A-513, compounds I-6.D.4-
  • Table 4-9 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R 9 is CO-N(CH 3 )2 and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-9.A-1 to I-5.D.4-9.A-513, compounds I- 6.D.4-9.A-1 to I-6.D.4-9.A-513, compounds I-7.D.4-9.A-1 to I-7.D.4-9.A-513 compounds I-8.D.4-
  • Table 4-1 1 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R 9 is SO2NHCH3 and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-1 1 .A-1 to I-5.D.4-1 1.A-513, compounds I- 6.D.4-1 1.A-1 to I-6.D.4-1 1 .A-513, compounds I-7.D.4-1 1.A-1 to I-7.D.4-1 1. A-513 compounds I-
  • Table 4-12 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R 9 is S0 2 NHPh and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-12.A-1 to I-5.D.4-12.A-513, compounds I-6.D.4- 12.A-1 to I-6.D.4-12.A-513, compounds I-7.D.4-12.A-1 to I-7.D.4-12.A-513 compounds I-8.D.4-
  • Table 4-13 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R 9 is S0 2 Ph and the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-13.A-1 to I-5.D.4-13.A-513, compounds I-6.D.4-
  • Particular embodiments of the compounds I are the following compounds: I-9.A, I-9.B, I-9.C, I-
  • Table 1-1 Compounds of the formula I-9.A, I-10.A, 1-1 1 .A, I-12.A in which the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-9.A.1 -1.A-1 to I-9.A.1-1 .A-513, compounds I-10.A.1 -1.A-1 to I-10.A.1 - 1.A-513, compounds 1-1 1.A.1 -1.A-1 to 1-1 1.A.1 -1.A-513 compounds I-12.A.1-1 .A-1 to I-12.A.1-
  • Table 1-2 Compounds of the formula I-9.B, 1-10. B, 1-1 1 .B, 1-12. B in which the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-9.B.1 -2.A-1 to I-9.B.1-2.A-513, compounds 1-10.B.1 -2.A-1 to I-10.B.1 -
  • Table 1-3 Compounds of the formula I-9.C, 1-10. C, 1-1 1 .C, 1-12. C in which the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-9.C.1-3.A-1 to I-9.C.3-1.A-513, compounds I-10.C.1-3.A-1 to I-10.C.1 -
  • Table 1-4 Compounds of the formula I-9.D, 1-10. D, 1-1 1 .D, 1-12. D in which the meaning for the combination of R 4 and R 78 for each individual compound corresponds in each case to one line of Table A (compounds I-9.D.1-4.A-1 to I-9.D.1-4.A-513, compounds I-10.D.1-4.A-1 to I-10.D.1 -
  • the compounds I and the compositions according to the invention, respectively, are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zy- gomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
  • the compounds I and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g.
  • compounds I and compositions thereof are used for controlling a multi- tude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • field crops such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. pota- toes), which can be used for the multiplication of the plant.
  • vegetative plant material such as cuttings and tubers (e. g. pota- toes)
  • These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
  • treatment of plant propagation materials with compounds I and compositions thereof, respectively is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
  • cultiva plants is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-gmc.org/, see GM crop database therein).
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
  • auxin herbicides
  • herbicides e. bromoxynil or ioxynil herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors.
  • ALS inhibitors e.g. described in Pest Managem. Sci.
  • cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield ® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as ⁇ -endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nema- todes, e. g. Photorhabdus spp.
  • VIP1 , VIP2, VIP3 or VIP3A vegetative insecticidal proteins
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • toxins produced by fungi such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins
  • proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdyster- oid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase
  • ion channel blockers such as blockers of
  • these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins.
  • Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ).
  • Further examples of such toxins or genetically modified plants ca- pable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278,
  • WO 95/34656 EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073.
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above.
  • These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins toler- ance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coelop- tera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).
  • Genetically modified plants capable to synthesize one or more insecticidal proteins are, e.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens.
  • proteins are the so-called "pathogenesis- related proteins" (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the Mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Er- winia amylvora).
  • PR proteins pathogenesis- related proteins
  • plant disease resistance genes e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the Mexican wild potato Solanum bulbocastanum
  • T4-lysozym e. g. potato cultivars capable of synth
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
  • productivity e. g. bio mass production, grain yield, starch content, oil content or protein content
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera ® rape, DOW Agro Sciences, Canada).
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany).
  • a modified amount of substances of content or new substances of content specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany).
  • the compounds I and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:
  • Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassico/a or brassi- cae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. so/an/ or A. alternata), tomatoes (e. g. A. so/anior A. alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A.
  • Botrytis cinerea (teleomorph: Botryotinia fucke/iana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad- leaved trees and evergreens, e. g. C. ⁇ ///77/ ' (Dutch elm disease) on elms; Cercospora spp.
  • Botrytis cinerea teleomorph: Botryotinia fucke/iana: grey mold
  • fruits and berries e. g. strawberries
  • vegetables e. g. lettuce, carrots, celery and cabbages
  • rape flowers, vines, forestry plants and wheat
  • Bremia lactucae
  • Crop cospora leaf spots on corn (e. g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. bet/cola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum. leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helmin- thosporium of Bipolaris) spp.
  • tomatoes e. g. C. fulvum. leaf mold
  • cereals e. g. C. herbarum (black ear) on wheat
  • Cochliobolus anamorph: Helmin-
  • Cortici urn spp. e. g. C. sasak/i (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C.
  • liriodendri Neonectria liriodendri. Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis.
  • barley e. g. D. teres, net blotch
  • wheat e. g. D. tritici-repentis.
  • Drechslera, teleomorph Cochiioboius) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseo/ ⁇ (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M.
  • phaseoli, teleomorph Diaporthe phaseolorum
  • Phy- soderma maydis brown spots
  • Phytophthora spp. wilt, root, leaf, fruit and stem root
  • paprika and cucurbits e. g. P. capsici
  • soybeans e. g. P.
  • Plasmodiophora brassicae club root
  • Plasmopara spp. e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers
  • Podosphaera spp. powdery mildew
  • Puccinia spp. rusts on various plants, e. g. P. tr/t/c/na (brown or leaf rust), P. striiformis (stripe or yellow rust), P. horde/ (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P.
  • kuehn/i range rust on sugar cane and P. asparagion asparagus
  • Pyrenophora anamorph: Drechslera
  • tritici-repentis tan spot
  • P. teres net blotch
  • Pyricularia spp. e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals
  • Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P.
  • Ramularia spp. e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. bet/cola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R.
  • R. solani root and stem rot
  • deformans leaf curl disease
  • T. pruni plum pocket
  • plums Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici(syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U.
  • occulta stem smut
  • Uromyces spp. rust
  • vegetables such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae)
  • Ustilago spp. loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis. corn smut) and sugar cane
  • Venturis spp. scab
  • apples e. g. V. inaequalis
  • pears Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dah/iae on strawberries, rape, potatoes and tomatoes.
  • the compounds I and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
  • protection of materials is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fiber or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria.
  • harmful microorganisms such as fungi and bacteria.
  • Ascomycetes such as Ophiostoma pp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp.
  • the method of treatment according to the invention can also be used in the field of protecting stored products or harvest against attack of fungi and microorganisms.
  • the term "stored products” is understood to denote natural substances of plant or animal origin and their processed forms, which have been taken from the natural life cycle and for which long-term protection is desired.
  • Stored products of crop plant origin such as plants or parts thereof, for example stalks, leafs, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment.
  • stored products are timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood.
  • Stored products of animal origin are hides, leather, furs, hairs and the like.
  • the combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mold.
  • Preferably "stored products” is understood to denote natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms.
  • the compounds I and compositions thereof, respectively, may be used for improving the health of a plant.
  • the invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of compounds I and compositions thereof, respectively.
  • plant health is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress.
  • yield e. g. increased biomass and/or increased content of valuable ingredients
  • plant vigor e. g. improved plant growth and/or greener leaves ("greening effect")
  • quality e. g. improved content or composition of certain ingredients
  • tolerance to abiotic and/or biotic stress e. g. improved content or composition of certain ingredients
  • the compounds of formula I can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.
  • the compounds I are employed as such or in form of compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be pro- tected from fungal attack with a fungicidally effective amount of the active substances.
  • the application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
  • Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting.
  • the invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.
  • An agrochemical composition comprises a fungicidally effective amount of a compound I.
  • the term "effective amount" denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used.
  • compositions e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e. g. SC, OD, FS), emulsifiable concentrates (e. g. EC), emulsions (e. g. EW, EO, ES, ME), capsules (e. g. CS, ZC), pastes, pastilles, wettable powders or dusts (e. g. WP, SP, WS, DP, DS), pressings (e. g.
  • compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6 th Ed. May 2008, CropLife International.
  • compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e. g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e. g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, e. g. cyclohexanone; esters, e. g.
  • mineral oil fractions of medium to high boiling point e. g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydronaphthalene, al
  • lactates carbonates, fatty acid es- ters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e. g. N-methyl pyrroli- done, fatty acid dimethyl amides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e. g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e. g. cellulose, starch; fertilizers, e. g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e. g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e. g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharides e. g. cellulose, star
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective col- loid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sul- fonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyl naphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • Exam- pies of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinyl pyrroli- done, vinyl alcohols, or vinyl acetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinyl amines or polyethylene amines.
  • Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target.
  • Exam- pies are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e. g. xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water- soluble dyes.
  • examples are inorganic colorants (e. g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e. g. alizarin-, azo- and phthalogencyanine colorants).
  • Suitable tackifiers or binders are polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • composition types and their preparation are:
  • a compound I and 5-15 wt% wetting agent e. g. alcohol alkoxylates
  • a water-soluble solvent e. g. alcohols
  • a compound I and 1-10 wt% dispersant e. g. polyvinyl pyrrolidone
  • organic solvent e. g. cyclohexanone
  • emulsifiers e. g. calcium dodecylben- zenesulfonate and castor oil ethoxylate
  • water-insoluble organic solvent e. g. aromatic hydrocarbon
  • Emulsions (EW, EO, ES)
  • emulsifiers e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • water-insoluble organic solvent e. g. aromatic hydrocarbon
  • a compound I In an agitated ball mill, 20-60 wt% of a compound I are comminuted with addition of 2-10 wt% dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate), 0.1- 2 wt% thickener (e. g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e. g. polyvinyl alcohol) is added.
  • dispersants and wetting agents e. g. sodium lignosulfonate and alcohol ethoxylate
  • 0.1- 2 wt% thickener e. g. xanthan gum
  • a compound I 50-80 wt% of a compound I are ground finely with addition of dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water- dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants and wetting agents e. g. sodium lignosulfonate and alcohol ethoxylate
  • wt% of a compound I are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e. g. sodium lignosulfonate), 1 -3 wt% wetting agents (e. g. alcohol ethoxylate) and solid carrier (e. g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants e. g. sodium lignosulfonate
  • 1 -3 wt% wetting agents e. g. alcohol ethoxylate
  • solid carrier e. g. silica gel
  • a compound I In an agitated ball mill, 5-25 wt% of a compound I are comminuted with addition of 3-10 wt% dispersants (e. g. sodium lignosulfonate), 1 -5 wt% thickener (e. g. carboxymethyl cellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
  • dispersants e. g. sodium lignosulfonate
  • 1 -5 wt% thickener e. g. carboxymethyl cellulose
  • wt% of a compound I are added to 5-30 wt% organic solvent blend (e. g. fatty acid dimethyl amide and cyclohexanone), 10-25 wt% surfactant blend (e. g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
  • organic solvent blend e. g. fatty acid dimethyl amide and cyclohexanone
  • surfactant blend e. g. alcohol ethoxylate and arylphenol ethoxylate
  • An oil phase comprising 5-50 wt% of a compound I, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e. g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol). Radical polymerization results in the formation of poly(meth)acrylate microcapsules.
  • an oil phase comprising 5-50 wt% of a compound I according to the in- vention, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), and an isocya- nate monomer (e.
  • g. diphenylmethene-4,4'-diisocyanatae are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol).
  • a protective colloid e. g. polyvinyl alcohol.
  • the addition of a polyamine results in the formation of polyurea microcapsules.
  • the monomers amount to 1 - 10 wt%.
  • the wt% relate to the total CS composition.
  • Dustable powders (DP, DS)
  • a compound I 1 -10 wt% of a compound I are ground finely and mixed intimately with solid carrier (e. g. finely divided kaolin) ad 100 wt%.
  • solid carrier e. g. finely divided kaolin
  • a compound I 0.5-30 wt% of a compound I is ground finely and associated with solid carrier (e. g. silicate) ad 100 wt%.
  • solid carrier e. g. silicate
  • Granulation is achieved by extrusion, spray-drying or fluidized bed.
  • organic solvent e. g. aromatic hydrocarbon
  • compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1 -1 wt% anti-foaming agents, and 0.1 -1 wt% colorants.
  • auxiliaries such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1 -1 wt% anti-foaming agents, and 0.1 -1 wt% colorants.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, more preferably between 1 and 70%, and in particular between 10 and 60%, by weight of active substance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC), and gels (GF) are usually employed.
  • the com- positions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing.
  • Methods for applying compound I and compositions thereof, respectively, onto plant propagation material, especially seeds include dressing, coat- ing, pelleting, dusting, and soaking as well as in-furrow application methods.
  • compound I or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.
  • amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix).
  • pesticides e. g. herbicides, insecticides, fungicides, growth regulators, safeners, biopesticides
  • These agents can be admixed with the compositions ac- cording to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1 .
  • a pesticide is generally a chemical or biological agent (such as pestidal active ingredient, compound, composition, virus, bacterium, antimicrobial or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests.
  • Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease.
  • pesticide includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safen- ers that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
  • the user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the agrochemi- cal composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
  • a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
  • one embodiment of the invention is a kit for preparing a usable pesticidal composition, the kit comprising a) a composition comprising component 1 ) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and optionally a further active component 3) as defined herein.
  • pesticides II e. g. pesticidally-active substances and biopesticides
  • the compounds I in conjunction with which the compounds I can be used, is intended to illustrate the possible combinations but does not limit them:
  • azoxystrobin (A.1 .1 ), coumethoxystrobin (A.1.2), coumoxystrobin (A.1 .3), dimoxystrobin (A.1.4), enestroburin (A.1.5), fenaminstrobin (A.1 .6), fenoxystrobin/flufenoxystrobin (A.1.7), fluoxastrobin (A.1 .8), kresoxim-methyl (A.1 .9), man- destrobin (A.1 .10), metominostrobin (A.1 .1 1 ), orysastrobin (A.1 .12), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystrobin (A.1 .17), 2-(2-(3-(2,6-dichloroph
  • respiration inhibitors diflumetorim (A.4.1 ); nitrophenyl derivates: binapacryl (A.4.2), dinobuton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), meptyldinocap (A.4.6), ferimzone
  • organometal compounds fentin salts, e. g. fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1 ); silthiofam (A.4.12);
  • - C14 demethylase inhibitors triazoles: azaconazole (B.1.1 ), bitertanol (B.1.2), bromu- conazole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), dini- conazole-M (B.1.7), epoxiconazole (B.1 .8), fenbuconazole (B.1 .9), fluquinconazole (B.1.10), flusilazole (B.1.1 1 ), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1 .14), ip- conazole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1 .19), paclobutrazole (B.1.20), penconazo
  • benalaxyl (C.1.1 ), benalaxyl-M (C.1 .2), kiralaxyl (C.1 .3), metalaxyl (C.1 .4), metalaxyl-M (C.1 .5), ofurace (C.1 .6), oxadixyl (C.1 .7);
  • nucleic acid synthesis inhibitors hymexazole (C.2.1 ), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin- 4-amine (C.2.6), 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine (C.2.7), 5-fluoro- 2-(4-chlorophenylmethoxy)pyrimidin-4 amine (C.2.8);
  • tubulin inhibitors benomyl (D.1 .1 ), carbendazim (D.1 .2), fuberidazole (D1.3), thiabendazole (D.1 .4), thiophanate-methyl (D.1 .5), 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyri- dazine (D.1 .6), 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine (D.1 .7), N-eth- yl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]butanamide (D.1.8), N-ethyl-2-[(3-ethynyl-8-methyl- 6-quinolyl)oxy]-2-methylsulfanyl-acetamide (D.1 .9), 2-[(3-ethynyl-8-methyl-
  • diethofencarb (D.2.1 ), ethaboxam (D.2.2), pencycuron (D.2.3), fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriofenone (D.2.7);
  • cyprodinil E.1 .1
  • mepanipyrim E.1.2
  • pyrimethanil E.1.3
  • blasticidin-S (E.2.1 ), kasugamycin (E.2.2), kasugamycin hydro- chloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6);
  • F Signal transduction inhibitors
  • fluoroimid F.1.1
  • iprodione F.1.2
  • procymidone F.1 .3
  • vinclozolin F.1 .4
  • fludioxonil F.1 .5
  • quinoxyfen F.2.1 ;
  • edifenphos G.1.1
  • iprobenfos G.1 .2
  • pyrazophos G.1.3
  • isoprothiolane G.1.4
  • dicloran G.2.1
  • quintozene G.2.2
  • tecnazene G.2.3
  • tolclofos-methyl G.2.4
  • biphenyl G.2.5
  • chloroneb G.2.6
  • etridiazole G.2.7
  • dimethomorph G.3.1
  • flumorph G.3.2
  • mandipropamid G.3.3
  • pyrimorph G.3.4
  • benthiavalicarb G.3.5
  • iprovalicarb G.3.6
  • valifenalate G.3.7
  • propamocarb (G.4.1 );
  • oxathiapiprolin G.5.1
  • 2- ⁇ 3-[2-(1 - ⁇ [3,5-bis(difluoro- methyl-1 H-pyrazol-1 -yl]acetyl ⁇ piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl ⁇ - phenyl methanesulfonate G.5.2
  • 2- ⁇ 3-[2-(1 - ⁇ [3, 5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]- acetyl ⁇ piperidin-4-yl) 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate G.5.3
  • organochlorine compounds anilazine (H.3.1 ), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.1 1 );
  • guanidine H.4.1
  • dodine H.4.2
  • dodine free base H.4.3
  • guazatine H.4.4
  • guazatine-acetate H.4.5
  • iminoctadine H.4.6
  • iminoctadine-triacetate H.4.7
  • iminoctadine-tris(albesilate) H.4.8
  • dithianon H.4.9
  • 2,6-dimethyl-1 H,5H- [1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone H.4.10;
  • - melanin synthesis inhibitors pyroquilon (1.2.1 ), tricyclazole (1.2.2), carpropamid (I.2.3), dicy- clomet (I.2.4), fenoxanil (I.2.5);
  • abscisic acid (M.1.1 ), amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat, chlormequat chloride, choline chloride, cyclanilide, daminozide, dikegulac, dime- thipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gib- berellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat, mepiquat chloride, naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione, prohexadi- one-calcium, prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithio
  • Lipid biosynthesis inhibitors alloxydim, alloxydim-sodium, butroxydim, clethodim,
  • clodinafop clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop- methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop- butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P- methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl,
  • N.2 ALS inhibitors amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethamet- sulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron- methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfu- ron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, met- azosulfuron, metsulfuron, metsulfuron-methyl, nico
  • Photosynthesis inhibitors amicarbazone; chlorotriazine; ametryn, atrazine, chloridazone, cyanazine, desmetryn, dimethametryn,hexazinone, metribuzin, prometon, prometryn, pro- pazine, simazine, simetryn, terbumeton, terbuthylazin, terbutryn, trietazin; chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, sidu- ron, tebuthiuron, thiadiazuron, desmedipham, karbutilat, phenmedipham, phenmedipham- ethyl, bromofenoxim, brom
  • N.4 protoporphyrinogen-IX oxidase inhibitors acifluorfen, acifluorfen-sodium, azafenidin, ben- carbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlor- methoxyfen, cinidon-ethyl, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac- pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fome- safen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, py- raclonil, pyraflufen, pyraflu
  • 6- fluoro-4-trifluoro -, methylphenoxy)-5-methyl-1 H-pyrazole-1 -carboxamide (CAS 452100-03- 7), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl]-1 ,5-dimethyl- 6-thioxo-[1 ,3,5]triazinan-2,4-dione (CAS 451484-50-7), 2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl- 3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1 ,3-dione (CAS 13001 18- 96-0), 1-methyl-6-trifluoro-'methyl-3-(2,2,7-tri-fluoro-3-oxo-4-prop-2-
  • N.5 Bleacher herbicides beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone,
  • norflurazon picolinafen, 4-(3-trifluoromethyhphenoxy)-2-(4-trifluoromethylphen- yl)-"pyrimidine (CAS 180608-33-7); benzobicyclon, benzofenap, bicyclopyrone, clomazone, fenquintrione, isoxaflutole, mesotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate, topramezone; aclonifen, amitrole, flumeturon;
  • N.6 EPSP synthase inhibitors glyphosate, glyphosate-isopropylammonium, glyposate- potassium, glyphosate-trimesium (sulfosate);
  • Glutamine synthase inhibitors bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P, glufosinate-ammonium;
  • Mitosis inhibitors benfluralin, butralin, dinitramine, ethalfluralin, fluchloralin, oryzalin,
  • N.10 VLCFA inhibitors acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, dimethen- amid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, prop- isochlor, thenylchlor, flufenacet, mefenacet, diphenamid, naproanilide, napropamide, napro- pamide-M, fentrazamide, anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, piperophos, pyroxasulfone, isoxazoline compounds of the formulae 11.1 , II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9
  • N.12 Decoupler herbicides dinoseb, dinoterb, DNOC and its salts
  • N.13 Auxinic herbicides 2,4-D and its salts and esters, clacyfos, 2,4-DB and its salts and esters, aminocyclopyrachlor and its salts and esters, aminopyralid and its salts such as amino- pyralid-dimethylammonium, aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, di- chlorprop-P and its salts and esters, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, ha- lauxifen and its salts and esters (CAS 943832-60-8); MCPA and its salts and esters, MCPA- thioethy
  • N.14 Auxin transport inhibitors diflufenzopyr, diflufenzopyr-sodium, naptalam and naptalam- sodium;
  • Acetylcholine esterase (AChE) inhibitors aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; acephate, aza- methiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos,
  • GABA-gated chloride channel antagonists endosulfan, chlordane; ethiprole, fipronil,
  • Sodium channel modulators acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha- cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, del- tamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, fluc
  • Nicotinic acetylcholine receptor allosteric activators spinosad, spinetoram;
  • Chloride channel activators abamectin, emamectin benzoate, ivermectin, lepimectin, mil- bemectin;
  • Juvenile hormone mimics hydroprene, kinoprene, methoprene; fenoxycarb, pyriproxyfen;
  • miscellaneous non-specific (multi-site) inhibitors methyl bromide and other alkyl halides; chloropicrin, sulfuryl fluoride, borax, tartar emetic;
  • Bacillus thuringiensis Bacillus sphaeri- cus and the insecticdal proteins they produce: Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp.
  • israeltaki Bacillus thuringiensis subsp. tenebrionis, the Bt crop proteins: CrylAb, CrylAc, Cry1 Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Ab1 ;
  • Inhibitors of mitochondrial ATP synthase diafenthiuron; azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon;
  • Nicotinic acetylcholine receptor (nAChR) channel blockers bensultap, cartap hydrochloride, thiocyclam, thiosultap sodium;
  • Inhibitors of the chitin biosynthesis type 0 bistrifluron, chlorfluazuron, diflubenzuron, flu- cycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron;
  • Ecdyson receptor agonists methoxyfenozide, tebufenozide, halofenozide, fufenozide, chromafenozide;
  • Octopamin receptor agonists amitraz
  • Mitochondrial complex I electron transport inhibitors fenazaquin, fenpyroximate, pyrimidif- en, pyridaben, tebufenpyrad, tolfenpyrad; rotenone; 0.22 Voltage-dependent sodium channel blockers: indoxacarb, metaflumizone, 2-[2-(4-cyano- phenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazine- carboxamide, N-(3-chloro-2-methylphenyl)-2-[(4-chlorophenyl)-[4-[methyl(methylsulfonyl)- amino]phenyl]methylene]-hydrazinecarboxamide;
  • Inhibitors of the of acetyl CoA carboxylase spirodiclofen, spiromesifen, spirotetramat, spi- ropidion;
  • Mitochondrial complex II electron transport inhibitors cyenopyrafen, cyflumetofen
  • insecticidal active compounds of unknown or uncertain mode of action afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, broflanilide, bromopropylate, chinome- thionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, tioxazafen, 1 1-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-1 1 -en- 10-one, 3-(4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-
  • component 2 The active substances referred to as component 2, their preparation and their activity e. g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available.
  • the compounds described by lUPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968;
  • the present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1 ) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to O) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to K), as described above, and if de- sired one suitable solvent or solid carrier.
  • agrochemical compositions comprising a mixture of at least one compound I (component 1 ) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to O) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to K), as described above, and if de- sired one suitable solvent or solid carrier.
  • Those mixtures are of particular interest, since many of them at the same application rate show higher efficiencies against harmful fungi.
  • the order of application is not essential for working of the present invention.
  • the time between both applications may vary e. g. between 2 hours to 7 days. Also a broader range is possible ranging from 0.25 hour to 30 days, preferably from 0.5 hour to 14 days, particularly from 1 hour to 7 days or from 1.5 hours to 5 days, even more preferred from 2 hours to 1 day.
  • the weight ratio of the component 1 ) and the component 2) generally depends from the properties of the active com- ponents used, usually it is in the range of from 1 :10,000 to 10,000:1 , often it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50: 1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 , even more preferably in the range of from 1 :4 to 4:1 and in particular in the range of from 1 :2 to 2:1 .
  • the weight ratio of the component 1 ) and the component 2) usually is in the range of from 1000:1 to 1 :1 , often in the range of from 100: 1 to 1 :1 , regularly in the range of from 50:1 to 1 :1 , preferably in the range of from 20:1 to 1 :1 , more preferably in the range of from 10:1 to 1 :1 , even more preferably in the range of from 4:1 to 1 :1 and in particular in the range of from 2:1 to 1 :1 .
  • the weight ratio of the component 1 ) and the component 2) usually is in the range of from 1 :1 to 1 :1000, often in the range of from 1 :1 to 1 :100, regularly in the range of from 1 :1 to 1 :50, preferably in the range of from 1 :1 to 1 :20, more preferably in the range of from 1 :1 to 1 :10, even more preferably in the range of from 1 :1 to 1 :4 and in particular in the range of from 1 :1 to 1 :2.
  • the weight ratio of component 1 ) and component 2) depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4:1 , and the weight ratio of component 1 ) and component 3) usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4:1.
  • any further active components are, if desired, added in a ratio of from 20:1 to 1 :20 to the component 1 ).
  • mixtures comprising as component 2) at least one active substance selected from inhibitors of complex III at Q 0 site in group A), more preferably selected from compounds (A.1.1 ), (A.1.4), (A.1.8), (A.1.9), (A.1.10), (A.1 .12), (A.1.13), (A.1 .14), (A.1.17), (A.1 .21 ), (A.1.25), (A.1 .34) and (A.1 .35); particularly selected from (A.1.1 ), (A.1.4), (A.1.8), (A.1 .9), (A.1 .13), (A.1.14), (A.1 .17), (A.1.25), (A.1 .34) and (A.1 .35).
  • mixtures comprising as component 2) at least one active substance selected from inhibitors of complex III at Q, site in group A), more preferably selected from compounds (A.2.1 ), (A.2.3) and (A.2.4); particularly selected from (A.2.3) and (A.2.4).
  • mixtures comprising as component 2) at least one active substance selected from inhibitors of complex II in group A), more preferably selected from compounds (A.3.2), (A.3.3), (A.3.4), (A.3.7), (A.3.9), (A.3.1 1 ), (A.3.12), (A.3.15), (A.3.16), (A.3.17), (A.3.18), (A.3.19), (A.3.20), (A.3.21 ), (A.3.22), (A.3.23), ( (A.3.28), (A.3.31 ), (A.3.32), (A.3.33), (A.3.34), (A.3.35), (A.3.36), (A.3.37), (A.3.38) and (A.3.39); particularly selected from (A.3.2), (A.3.3), (A.3.4), (A.3.7), (A.3.9), (A.3.12), (A.3.15), (A.3.17), (A.3.19), (A.3.22), (A.3.23), (
  • mixtures comprising as component 2) at least one active substance selected from other respiration nhibitors in group A), more preferably selected from compounds (A.4.5) and (A.4.1 1 ); in particular (A.4.1 1 ).
  • mixtures comprising as component 2) at least one active substance selected from C14 demethylase inhibitors in group B), more preferably selected from compounds (B.1 .4), (B.1 .5), (B.1 .8), (B.1 .10), (B.1.1 1 ), (B.1 .12), (B.1.13), (B.1 .17), (B.1.18), (B.1 .21 ), (B.1.22), (B.1.23), (B.1 .25), (B.1.26), (B.1 .29), (B.1.34), (B.1 .37), (B.1.38), (B.1 .43) and (B.1 .46); particularly selected from (B.1.5), (B.1.8), (B.1 .10), (B.1.17), (B.1.22), (B.1.23), (B.1 .25), (B.1.33), (B.1 .34), (B.1.37), (B.1.5), (B
  • mixtures comprising as component 2) at least one active substance selected from Delta 14-reductase inhibitors in group B), more preferably selected from com- pounds (B.2.4), (B.2.5), (B.2.6) and (B.2.8); in particular (B.2.4).
  • mixtures comprising as component 2) at least one active substance selected from phenylamides and acyl amino acid fungicides in group C), more preferably selected from compounds (C.1 .1 ), (C.1 .2), (C.1.4) and (C.1.5); particularly selected from (C.1 .1 ) and (C.1.4).
  • mixtures comprising as component 2) at least one active substance selected from other nucleic acid synthesis inhibitors in group C), more preferably selected from compounds (C.2.6),(C.2.7) and (C.2.8).
  • mixtures comprising as component 2) at least one active substance selected from group D), more preferably selected from compounds (D.1.1 ), (D.1 .2), (D.1.5), (D.2.4) and (D.2.6); particularly selected from (D.1 .2), (D.1.5) and (D.2.6).
  • mixtures comprising as component 2) at least one active substance selected from group E), more preferably selected from compounds (E.1.1 ), (E.1.3), (E.2.2) and (E.2.3); in particular (E.1.3).
  • mixtures comprising as component 2) at least one active substance selected from group H), more preferably selected from compounds (H.2.2), (H.2.3), (H.2.5),
  • mixtures comprising as component 2) at least one active substance selected from group I), more preferably selected from compounds (1.2.2) and (I.2.5).
  • mixtures comprising as component 2) at least one active substance selected from group J), more preferably selected from compounds (J.1 .2), (J.1.5) and (J.1 .8); in particular (J.1.5).
  • mixtures comprising as component 2) at least one active substance selected from group K), more preferably selected from compounds (K.1.41 ), (K.1 .42), (K.1.44), (K.1 .45), (K.1.47) and (K.1.49); particularly selected from (K.1 .41 ), (K.1.44), (K.1 .45), (K.1.47) and (K.1 .49).
  • the mixtures of active substances can be prepared as compositions comprising besides the active ingredients at least one inert ingredient (auxiliary) by usual means, e. g. by the means given for the compositions of compounds I. Concerning usual ingredients of such compositions reference is made to the explanations given for the compositions containing compounds I.
  • HPLC-MS HPLC-column KinetexXB C181,7 ⁇ (50x2,1 mm); eluent: acetonitrile / water +
  • the spray solutions were prepared in several steps:
  • the stock solution were prepared: a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a relation (volume) solvent-emulsifier of 99 to 1 was added to 25 mg of the compound to give a total of 5 ml.
  • Wettol which is based on ethoxylated alkylphenoles
  • This stock solution was diluted with the described solvent-emulsifier-water mixture to the given concentration.
  • Example 1 Preventative fungicidal control of Botrytis cinereaon leaves of green pepper
  • Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below. The next day the plants were inoculated with an aqueous biomalt or DOB media solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 24 ⁇ C and a relative humidity close to 100 % the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
  • Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below. The plants were then cultivated in the greenhouse for 7 days and then inoculated with an aqueous biomalt solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 24°C and a relative humidity close to 100 % the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
  • Example 3 Control of culm rot on pearl millet caused by Fusarium culmorum
  • Pot-grown pearl millet seedlings were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. Seven days later the plants were inoculated with a spore suspension of Fusarium culmorum in an aqueous biomalt or DOB media solution. Then the trial plants were immediately transferred to a humid chamber. After 6 days at 23-25°C and a relative humidity close to 100 % the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.

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Abstract

The present invention relates to compounds I, wherein the variables are defined as given in the description and claims. The invention further relates to uses, processes and intermediates for compounds I.

Description

QUINOLINE COMPOUNDS AS FUNGICIDES
Description
The present invention relates to quinoline compounds and the N-oxides and the salts thereof for combating phytopathogenic fungi, and to the use and methods for combating phytopathogenic fungi and to seeds coated with at least one such compound. The invention also relates to processes for preparing these compounds, intermediates, processes for preparing such intermediates, and to compositions comprising at least one compound I.
In many cases, in particular at low application rates, the fungicidal activity of the known fungicidal compounds is unsatisfactory. Based on this, it was an object of the present invention to provide compounds having improved activity and/or a broader activity spectrum against phytopathogenic harmful fungi.
Surprisingly, this object is achieved by the use of the inventive quinoline compounds of formula I having favorable fungicidal activity against phytopathogenic fungi.
Accordingly, the present inv ula I
Figure imgf000002_0001
Figure imgf000002_0002
R1 is in each case independently selected from halogen, OH, CN, NO2, SH, N H2,
NH(CrC4-alkyl), N(Ci-C4-alkyl)2, NH-S02-Rx, d-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, Ci-C6-alkoxy, C3-C6-cycloalkyl, five- or six-membered heteroaryl and aryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein
Rx is Ci-C4-alkyl, Ci-C4-halogenalkyl, unsubstituted aryl or aryl that is substituted by one, two, three, four or five substituents Rx1 independently selected from Ci-C4-alkyl, halogen, OH, CN, Ci-C4-halogenalkyl, Ci-C4-alkoxy, and C1-C4- halogenalkoxy;
wherein the aliphatic moieties of R1 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R1a which independently of one another are selected from:
R1a halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci-
C4-halogenalkoxy, Ci-C6-alkylthio and phenoxy, wherein the phenyl group is unsubstituted or carries one, two, three, four or five substituents R11a selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci- C4-alkoxy and Ci-C4-halogenalkoxy;
wherein the cycloalkyi, heteroaryl and aryl moieties of R1 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R1 b which independently of one another are selected from:
R1 b halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6- cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio; n is O, 1 or 2;
R2 is in each case independently selected from the substituents as defined for R1 , wherein the possible substituents for R2 are R2a and R2b , respectively, which correspond to R1a and R1 b, respectively;
R3 is CH3, CH2F, CHF2 and CF3; R4 are independently selected from OH, CN , N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4- alkyl)2, NH-S02-Rx, subtituted Ci-C6-alkyl, Ci-C6-alkylthio, C2-C6-alkenyl, C2-C6- halogenalkenyl, C2-C6-alkynyl, C2-C6-halogenalkynyl, Ci-C6-alkoxy, C1-C6- halogenalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6-alkyl), C(=0)NH(Ci-C6-alkyl), C(=0)N(Ci-C6-alkyl)2, CR'=NOR", a saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle or heterocycle, wherein in each case one or two CH2 groups of the carbo- and heterocycle may be replaced by a group independently selected from C(=0) and C(=S),wherein the heterocycle contains independently one, two, three or four heteroatoms selected from N, O and S; and wherein R' and R" are independently selected from H, Ci-C4-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten- membered carbo- and heterocycle, and wherein R' and R" are independently unsubstituted or substituted by R'" which is independently selected from halogen, OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(C C4-alkyl)2, NH-S02-Rx, Ci-C6-alkyl, C C6- halogenalkyl, C2-C6-alkenyl, C2-C6-halogenalkenyl, C2-C6-alkynyl, C2-C6- halogenalkynyl, Ci-C6-alkoxy, Ci-C6-halogenalkoxy, C3-C6-cycloalkyl, C3-C6- halogencycloalkyl and phenyl; wherein the acyclic moieties except for subtituted Ci-C6-alkyl moieties of R4 are independently not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R4a, respectively, which
independently of one another are selected from:
R a halogen, OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2,
NH(C(=0)Ci-C4-alkyl), N(C(=0)Ci-C4-alkyl)2, NH-S02-R*, Ci-C6-alkoxy, C1-C4- halogenalkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl,-S(0)z-Ci-C6-alkyl, S(0)z-Ci-C6-halogenalkyl, S(0)z-aryl, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(Ci-
Ce-alkyl), C(=0)NH(Ci-C6-alkyl), C(=0)N(Ci-C6-alkyl)2, CR'=NOR", a saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle or heterocycle, five-, six- or ten-membered heteroaryl, aryl, phenoxy; wherein in each case one or two CH2 groups of the carbocycle and heterocycle may be replaced by a group independently selected from C(=0) and C(=S); wherein the heterocycle and heteroaryl contain independently one, two, three or four heteroatoms selected from N, O and S; wherein the carbocyclic, heterocyclic, aryl, phenyl and heteroaryl groups are independently unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of halogen, OH, CN, N02, SH,
NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C(=0)Ci-C4-alkyl), N(C(=0)Ci-C4- alkyl)2, NH-S02-Rx, d-C6-alkylthio, Ci-C4-alkyl, C C4-halogenalkyl, C1-C4- alkoxy, CrC4-halogenalkoxy and S(0)z-Ci-C6-alkyl;
wherein the carbocyclic, heterocyclic moieties of R4 are independently not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R4b, respectively, which independently of one another are selected from:
R b halogen, OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2,
NH(C(=0)Ci-C4-alkyl), N(C(=0)Ci-C4-alkyl)2, NH-S02-Rx, Ci-C4-alkyl, C1-C4- alkoxy, CrC4-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, C1-C4- halogenalkoxy, Ci-C6-alkylthio, Ci-C6-halogenalkylthio, S(0)z-CrC6-alkyl, Ci- C4-alkoxy-Ci-C4-alkyl, phenyl and phenoxy, wherein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, C1-C4- alkoxy and Ci-C4-halogenalkoxy; wherein the subtituted Ci-C6-alkyl moieties of R4 carry one, two, three or up to the maximum possible number of identical or different groups R4c, respectively, which independently of one another are selected from:
OH, CN, N02, SH, NH2, NH(C C4-alkyl), N(C C4-alkyl)2, NH(C(=0)C C4- alkyl), N(C(=0)Ci-C4-alkyl)2, NH-S02-Rx, Ci-C4-halogenalkoxy, C3-C6- cycloalkyl, C3-C6-halogencycloalkylS(0)-Ci-C6-alkyl, S(0)2-Ci-C6-alkyl, S(0)z- d-Ce-halogenalkyl, S(0)z-aryl, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6- alkyl), C(=0)NH(Ci-C6-alkyl), C(=0)N(Ci-C6-alkyl)2, CR'=NOR", a saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten- membered carbocycle or heterocycle, five-, six- or ten-membered heteroaryl; wherein in each case one or two CH2 groups of the carbocycle and heterocycle may be replaced by a group independently selected from C(=0) and C(=S); wherein the heterocycle and heteroaryl contain independently one, two, three or four heteroatoms selected from N, O and S; wherein the carbocyclic, heterocyclic, aryl, phenyl and heteroaryl groups are independently unsubsti- tuted or carry one, two, three, four or five substituents selected from the group consisting of halogen, OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4- alkyl)2, NH(C(=0)Ci-C4-alkyl), N(C(=0)Ci-C4-alkyl)2, NH-S02-Rx, Ci-C6- alkylthio, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy, Ci-C4-halogenalkoxy and S(0)z-CrC6-alkyl; z is 0, 1 and 2; and wherein Rx R' and R" is as defined above;
R5 is H;
R6 is H;
and
R7 and R8 together with the carbon atoms to which they are bound form a phenyl ring; wherein the phenyl carries zero, one, two, three or four substituents (R78)0, wherein o is 0, 1 , 2 or 3; and
R78 are independently selected from halogen, OH, CN, N02, SH, NH2,
NH(CrC4-alkyl), N(C C4-alkyl)2, NH(C(=0)C C4-alkyl), N(C(=0)C C4- alkyl)2, NH-S02-Rx, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6-alkyl), C(=0)NH(Ci-C6-alkyl), CR'=NOR", Ci-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, Ci-C6-alkoxy, Ci-C6-halogenalkoxy, C2-C6-alkenyloxy, C2-C6- alkynyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, S(0)z-Ci-C6-alkyl, three- , four-, five- or six-membered saturated or partially unsaturated heterocycle, five- or six-membered heteroaryl and phenyl; wherein the heterocycle or heteroaryl contains one, two or three heteroatoms selected from N , O and S; wherein the heterocycle or heteroaryl contains one, two or three heteroatoms selected from N, O and S; wherein z, R' and R" is as defined above; wherein the acyclic moieties of R78 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R78a which independently of one another are selected from:
R78a halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6- cycloalkenyl, C3-C6-halogencycloalkyl, C3-C6-halogencycloalkenyl, Ci-C4-halogenalkoxy, Ci-C6-alkylthio, five- or six-membered het- eroaryl, phenyl and phenoxy, wherein the heterorayl, phenyl and phenoxy group is unsubstituted or carries one, two, three, four or five substituents R78a' selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and C1-C4- halogenalkoxy; wherein the cyclic, phenyl, heterocyclic and heteroaryl moieties of R78 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R78b which
independently of one another are selected from:
R78b halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio; is in each case independently selected from hydrogen, OH, CH(=0), C(=0)Ci-C6- alkyl, C(=0)C2-C6-alkenyl, C(=0)C2-C6-alkynyl, C(=0)C3-C6-cycloalkyl, C(=0)0(d- Ce-alkyl), C(=0)0(C2-C6-alkenyl), C(=0)0(C2-C6-alkynyl), C(=0)0(C3-C6- cycloalkyl), C(=0)NH(Ci-C6-alkyl), C(=0)NH(C2-C6-alkenyl), C(=0)NH(C2-C6- alkynyl), C(=0)NH(C3-C6-cycloalkyl), C(=0)N(Ci-C6-alkyl)2, C(=0)N(C2-C6- alkenyl)2, C(=0)N(C2-C6-alkynyl)2, C(=0)N(C3-C6-cycloalkyl)2, CH(=S), C(=S)Ci-C6- alkyl, C(=S)C2-C6-alkenyl, C(=S)C2-C6-alkynyl, C(=S)C3-C6-cycloalkyl, C(=S)0(Ci- Ce-alkyl), C(=S)0(C2-C6-alkenyl), C(=S)0(C2-C6-alkynyl), C(=S)0(C3-C6- cycloalkyl), C(=S)NH(Ci-C6-alkyl), C(=S)NH(C2-C6-alkenyl), C(=S)NH(C2-C6- alkynyl), C(=S)NH(C3-C6-cycloalkyl), C(=S)N(C C6-alkyl)2, C(=S)N(C2-C6-alkenyl)2, C(=S)N(C2-C6-alkynyl)2, C(=S)N(C3-C6-cycloalkyl)2, Ci-C6-alkyl, C C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkylC2-C6-alkenyl, C2-C6-halogenalkenyl C2- C6-alkynyl, C2-C6-halogenalkynyl, S(0)z-Ci-C6-alkyl, S(0)z-Ci-C6-halogenalkyl, S(0)z-C2-C6-alkenyl, S(0)z-C2-C6-alkynyl, S(0)zaryl, S02-NH(Ci-C6-alkyl), S02- NH(Ci-C6-halogenalkyl), S02-NH-aryl, tri-(Ci-C6 alkyl)silyl and di-(Ci-C6
alkoxy)phosphoryl), five- or six-membered heteroaryl and aryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; wherein the aryl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, C1-C4- halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy; wherein z is as defined above;
RY is Ci-C6-alkyl, Ci-C6-halogenalkyl, C2-C6-alkenyl, C2-C6-halogenalkenyl, C2-C6- alkynyl, C2-C6-halogenalkynyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, phenyl and phenyl-Ci-C6-alkyl; wherein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci- C4-halogenalkoxy; wherein the acyclic moieties of R9 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R9a which independently of one another are selected from:
R9a halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C3-C6- halogencycloalkyl, C3-C6-halogencycloalkenyl, Ci-C4-halogenalkoxy, C1-C6- alkylthio, five- or six-membered heteroaryl, phenyl and phenoxy, wherein the heteroaryl, phenyl and phenoxy group is unsubstituted or carries one, two, three, four or five substituents R9a' selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and C1-C4- halogenalkoxy; wherein the alicyclic, phenyl, heterocyclic and heteroaryl moieties of R9 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R9b which independently of one another are selected from:
R9b halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6- cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio; and the N-oxides and the agriculturally acceptable salts thereof.
The numbering of the ring members in the compounds of the present invention is as given in formula I above.
Compounds of formula I.A.2, when R9 is not proton, can be accessed e.g. starting from compounds of the formula I.A.2-1 (R9 is proton). A skilled person will realize that compounds of type I.A.2 can be reached via reaction with a reactive group R9-W. Reactive groups are preferably Ci-Cs-alkyl halides, C2-C6-alkenyl halides, C2-C6-alkynyl halides, benzyl halides, aldehydes, ester, acid chlorides, amides, sulfates, silyl halides or phosphates, e.g. carboxylic acid (W = OH), aldehydes (W = H), acid chloride (W = CI), amides (W = NMe2) or phosphates (W =
Figure imgf000007_0001
i.A.2-1
Typically the reaction is performed in a range between 0 °C and ambient temperature in the presence of a reactive group and organic base. Suitable base preferably NEt.3, pyridine NaOH, TEBAC, K2CO3, NaCOs or KOH. Most preferably solvents are THF, DMF, DMSO, MeOH or water (see for example, Journal of Medicinal Chemistry, 1989, 32(6), 1242-1248; European Jour- nal of Medicinal Chemistry, 2009, 44(10), 4034-4043).
Compounds of formula I.A.2-1 can be accessed e.g. starting from compounds of the formula I.A.1 via a reduction agent in an organic solvent or water or a mixture of organic solvent and water (see for example WO2009095253, WO2008143263). Reduction agent can be for example NaBhU or NaCNBH3. Typically the reaction is performed in a range between 0°C, room temperature and 60°C in an solvent, such as THF, dichloromethane, acetonitrile, MeOH, EtOH or water or in a mixture of or anic solvent and water.
Figure imgf000008_0001
I-A.1
Compounds of formula I.A.1 can be also reduced to I.A.2-1 via hydrogenation by using a metal catalyst in an organic solvent, water or a mix of water and organic solvent (see for example ChemCatChem, 5(10), 2939-2945; 2013; Organic Letters, 17(12), 2878-2881 ; 2015). As metal catalyst can be used for example Ru, Ir, and Pd, with or without ligands such as phosphines, phosphates, cyclooctadiene, diamines and imidazoles. The reaction can take place at temperature from 0°C to 100 °C. Preferable organic solvent are methanol, acetone, dichloromethane, 2,2,2-trifluoroethanol or DMF. The reaction can also take place the presence of an acid for example HCO2H, trifluoroacetic acid and acetic acid.
Compounds of the formula I.A.1 can be provided e.g. starting from alcohols of type II with ni- triles of type III in the presence of an acid in an organic solvent (see for example US
2008/0275242 or WO2005/070917). Preferably, sulfuric acid or a sulfonic acid, in particular tri- flic acid, are used as acid. Most suitable solvents are hydrocarbons, preferably benzene or dichloromethane.
Figure imgf000008_0002
II
Depending on the nature of the starting materials, the reaction is performed at a temperature from -40°C to 200°C, in particular from -10°C to 120°C, more specifically from 0°C to 100°C, even more specifically from room or ambient temperature (about 23°C) to 80°C.
Nitriles of type III are either commercially available or can be prepared by a skilled person from the corresponding halides following literature procedures (see, for example Journal of Organic Chemistry, 76(2), 665-668; 201 1 ; Angewandte Chemie, International Edition, 52(38), 10035- 10039; 2013; WO2004/013094).
Alcohols of type II can be prepared as described below. A skilled person will realize that compounds of type IV can be reacted with organometallic reagents, preferably alkyl Grignard or al- kyl-Lithium reagents, in ethereal solvents, preferably THF at low temperatures and under inert conditions to furnish compounds of type I I.
Figure imgf000009_0001
IV
Alternatively, alcohols of type II can be prepared from epoxides Va and compounds VI (see below):
"metallation"
Figure imgf000009_0002
The metalation reaction may preferably be carried out using Lithium-organic compounds, such as for example n-butyl lithium, sec-butyl lithium or tert-butyl lithium to result in an exchange of halogen by lithium. Also suitable is the reaction with magnesium resulting in the formation of the respective Grignard reagents. A further possibility is the use of other Grignard reagents such as isopropyl-magnesium-bromide instead of Mg.
A typical preparation of compounds of type IV can be achieved by reacting compounds of type V with organometallic reagents, preferably alkyl Grignard or alkyl-Lithium reagents, in ethereal solvents, preferably TH F at low temperatures and under inert conditions to furnish compounds of type IV as previously reported see for example WO2012051036; WO201 1042918).
Figure imgf000009_0003
Compounds of type V can be accessed by reacting a carbonyl compound of type VII , preferably a carboxylic acid (X = OH) or an acid chloride (X = CI), with N H(OR')R", wherein R' and R" are selected from Ci-C4-alkyl, most preferably being methyl, in an organic solvent, preferably THF or dichloromethane. Typically the reaction is performed in a range between 0 °C and ambient temperature in the presence of an organic base, preferably NEt.3 or pyridine (see e.g. US 20130324506; Tetrahedron: Asymmetry, 17(4), 508-51 1 ; 2006). If X = OH, the addition of an activating reagent, preferably a carbodiimide, may be preferred (see for example ChemMedChem, 7(12), 2101 -21 12; 2012; 201 1038204; Journal of Organic Chemistry, 76(1 ), 164-169; 201 1 ).
Figure imgf000010_0001
VII
If required, compounds of type VII can be prepared from the corresponding aryl halides of type VI (Hal is halogen, preferably Br or I). As described (Tetrahedron, 68(9), 21 13-2120; 2012; Chemical Communications (Cambridge, United Kingdom), 49(60), 6767-6769; 2013), aryl halides VIII will react with compounds of type IX in the presence of a transition metal catalyst, preferably a copper(l) salt, in an organic solvent, preferably DMF or DMSO, at elevated temperatures. Typically a base, preferably potassium phosphate, is added.
Figure imgf000010_0002
VI
If appropriate, alcohols of type II can be prepared as follows. A known or commercially available compound of type X can be reacted with an organometallic reagent of type XI, preferably a Gri- gnard or an organolithium reagent, readily prepared by a skilled person. Preferably, the reaction is performed in a temperature range from -78 °C to room temperature under inert conditions in an ethereal solvent.
Figure imgf000010_0003
Alternatively, compounds of the formula I.A.1 can be provided e.g. starting from alkenes of type XII with nitriles of type III in the presence of a acid in an organic solvent (see for example Journal of Heterocyclic Chemistry,1980, 17(7), 1457-63; WO2001070746). Preferably, sulfuric acid or a sulfonic acid, in particular triflic acid, are used as acid. Most suitable solvents are hydrocarbons, preferably benzene or dichloromethane.
Figure imgf000011_0001
XII
Alkenes XII are either commercially available or easily prepared using the methods known by persons who are skilled in the art. For example, alkenes of type XII can be easily prepared form alcohol of type II in the presence of an acid in an organic solvent. Preferably, sulfuric acid or a sulfonic acid, in particular triflic acid, are used as acid. Most suitable solvents are hydrocarbons, preferably benzene or dichloromethane.
Figure imgf000011_0002
II XII
Compounds I.A.1 can be prepared via intramolecular reaction of amide XIII. The intramolecular cyclization will take place in the presence of a dehydrating agent in an organic solvent (WO 2008143263, Synthetic Communications 2007, 37, 1331-1338.). Preferably, phosphoryl chloride (POCIs), POCI3/P2O5, H3PO4/P2O5, SnCU or BF3 are used as dehydrating agent. Most suitable solvents are hydrocarbons, preferably benzene, toluene or acetonitrile. Alternatively halogenat- ed solvents can be us enzene.
Figure imgf000011_0003
XIII
Depending on the nature of starting materials, the reaction is performed at temperature from - 40°c to 200 °C, in particular from -10°C to 120°C, more specifically from 0°C to 100°C, even more specifically from room temperature to 100°C.
Amides of type XIII can accessed by reacting a carbonyl of type XIV, preferably a carboxylic acid (X = OH) or an acid chloride (X = CI), with an amines of type XV in an organic solvent, preferably THF or dichloromethane. Typically the reaction is performed in a range between 0°C and room temperature in the presence of an organic base, preferably N(C2H5)3 or pyridine (see e.g. WO 8303968). If X = OH, the addition of an activating agent, preferably a carbodiimide or acid chloride, may be preferred (see for example, Bioorganic & Medicinal Chemistry, 2010, 18, 3088-31 15).
Figure imgf000012_0001
XV
Amines of type XV are either commercially available or easily prepared using the methods known by persons who are skilled in the art. If required, compounds of type amine XV can be synthesized from the correspond nitriles. As described Synlett. 2007, 4 652-654 or Tetrahedron 2012, 68, 2696-2703, nitriles will react with organometallic agents, preferably Grignard or Lithium reagent, in ethereal solvents, preferably THF at low temperature and under inert conditions to furnish compounds of type XV. The synthesis of compounds of type XV can take place in two steps or one pot.
Figure imgf000012_0002
Alternatively, amines of type XV can synthesized via formation of the correspond carboxylic azide and quench with water (Journal of the American Chemical Society, 1949, 71 , 2233-7; Journal of the American Chemical Society, 1990, 1 12, 297-304) or via Grignard addition to enamines (Tetrahedron Letters, 1992, 33, 1689-92; US20030216325)
Compound of type I.A.1 can be also synthesized via Suzuki coupling of halides of type XVI with a boronic acid XVII (see for example, Journal of Fluorine Chemistry, 2010, 131 , 856-860); wherein R31 and R41 together with the groups they are attached to form a tetramethyl-1 ,3,2- dioxaborolane-ring or independently from one another mean hydrogen or Ci-C6-alkyl to yield compounds I.A.1.
Figure imgf000012_0003
Wl χν»
Compounds of type XVI, wherein Hal is halogen, preferably chloro and bromo, can be obtained by transformation of an amide of type XVIII with a halogenating reagent, such as phosphorus oxachloride, phosphorus pentachloride, phosphoric trichloride, phosphorus oxybromide, thionyl chloride or Vilsmeier reagent. The reaction takes place in the presence of an organic solvent, preferably THF, benzene, CCU, or dichloromethane. Typically the reaction is performed in a range between 0°C to 180°C (see as reference, Journal of Medicinal Chemistry, 2004, 47, 663- 672; Journal of Organic Chemistry, 1980, 45, 80-89; Bulletin des Societes Chimiques Beiges, 1991 , 100, 169-174).
Figure imgf000013_0001
Amides of type XVIII can be prepared from compounds of type XIX, wherein Rx is a Ci-C6-alkyl. The reaction takes places in the presence of acid, preferably acetic acid, HCI, triflic acid or a mixture of sodium acetate and acetic acid. Typically the reaction in performed net or in polar solvents, preferably in water, methanol or acetonitrile (see WO2016/156085; Pharmaceutical Chemistry Journal, 2005, 39, 405-408 .
Figure imgf000013_0002
Alternatively, compounds of type XVI can be direct synthesized from compounds of type XIX in the presence of a halogenating reagent, such as sulfonyl chloride. The reaction takes places neat or in organic solvents, such as chloroform, dichloromethane or acetonitrile, in a range of temperature from 0°C to room temperature (see, Tetrahedrons Letters, 2010, 51 , 4609; Tetrahedron Letters, 1986, 27(24), 274 -6).
Figure imgf000013_0003
Compounds of type XIX can also be obtained by the reaction of alcohol II or alkene XII and a Ci-C6-alkyl thiocyanate under acidic conditions, see for example Bioorganic & Medicinal Chemistry Letters, 2013, 23(7), 2181-2186; Pharmaceutical Chemistry Journal, 2005, 39, 405-408. Preferably acids are sulfuric acid, HCI or trific acid. The reaction takes place most preferably in water, dichloromethane, toluene or a mixture of solvents, in a range of temperatures from 0°C to 1 10 °C.
Figure imgf000014_0001
Amide of type XVIII can be synthesized via ring expansion of oxime XX in the presence of an acid. Most suitable acids are for example, sulfuric acid, polyphosphoric acid or POCI3. Typically the reaction in performed net or in a polar solvents, preferably in water, methanol or acetonitrile (see Bioorganic & Medicinal Chemistry Letters, 2002, 12(3), 387-390; Medicinal Chemistry Research, 2015, 24(2), 523-532).
Figure imgf000014_0002
Oxime of type XX can be easily prepared from ketone of type XXI in the presence of hydroxyl- amine or hydroxylamine hydrochloride in polar solvents such as water, pyridine, ethanol or methanol. The reaction can take place in the presence of absence of a base, such as sodium acetate or sodium hydroxide, in a range of temperatures from room temperature to 120 °C (Journal of Organic Chemistry, 2016 81 (1 ), 336-342).
Figure imgf000014_0003
Ketone of type XXI are either commercial available or readily prepared by a skilled person. Alternatively, compounds of type I.A.1 can also be obtained intramolecular cyclization of amines of type XXII in the presence of an acid. Most preferably acids are HCI, trifluoroacetic acid, acetic acid or sulfuric acid. The reaction is preform in dichloromethane, water, ethanol, THF or chloroform, at temperature from room temperature to 120 °C (see, Synthesis, 1995, (5), 592-604; Heterocycles, 1988, 27(10), 2403-12).
Figure imgf000014_0004
Amines of type XXII are either commercial available or easily prepared by a skilled person or following the procedures described before.
The N-oxides may be prepared from the inventive compounds according to conventional oxidation methods, e. g. by treating compounds I with an organic peracid such as metachloroper- benzoic acid (cf. WO 03/64572 or J. Med. Chem. 38(1 1 ), 1892-903, 1995); or with inorganic oxidizing agents such as hydrogen peroxide (cf. J. Heterocyc. Chem. 18(7), 1305-8, 1981 ) or oxone (cf. J. Am. Chem. Soc. 123(25), 5962-5973, 2001 ). The oxidation may lead to pure mono-N-oxides or to a mixture of different N-oxides, which can be separated by conventional methods such as chromatography.
If the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (e. g. under the action of light, acids or bases). Such conversions may also take place after use, e. g. in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.
In the following, the intermediate compounds are further described. A skilled person will readily understand that the preferences for the substituents, also in particular the ones given in the tables below for the respective substituents, given herein in connection with compounds I apply for the intermediates accordingly. Thereby, the substituents in each case have independently of each other or more preferably in combination the meanings as defined herein.
The intermediate compounds of formula XIII are novel. Consequently, one aspect of the present invention relates to compounds of formula XIII:
Figure imgf000015_0001
wherein the substituents R1, R2, R3, R4, R5, R6,R7, R8, R9, m, n and o are as defined and preferably defined for formula I.
The compounds of formula XIII have fungicidal activity and the details below referring to the compounds I also apply to compounds XIII.
In the definitions of the variables given above, collective terms are used which are generally representative for the substituents in question. The term "Cn-Cm" indicates the number of carbon atoms possible in each case in the substituent or substituent moiety in question.
The term "halogen" refers to fluorine, chlorine, bromine and iodine. The term "Ci-C6-alkyl" refers to a straight-chained or branched saturated hydrocarbon group having 1 to 6 carbon atoms, e.g. methyl, ethyl, propyl, 1-methylethyl, butyl, 1 -methylpropyl, 2- methylpropyl, 1 ,1 -dimethylethyl, pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl,
2.2- dimethylpropyl, 1-ethylpropyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl,
1 .3- dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl,
2- ethylbutyl, 1 ,1 ,2-tri methyl propyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl and 1-ethyl-2- methylpropyl. Likewise, the term "C2-C4-alkyl" refers to a straight-chained or branched alkyl group having 2 to 4 carbon atoms, such as ethyl, propyl (n-propyl), 1-methylethyl (iso-propoyl), butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (iso-butyl), 1 ,1 -dimethylethyl (tert. -butyl).
The term "Ci-C6-halogenalkyl" refers to an alkyl group having 1 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above. Examples are "Ci-C2-halogenalkyl" groups such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1 -bromoethyl, 1 - fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro- 2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl or pentafluoroethyl.
The term "Ci-C6-hydroxyalkyl" refers to an alkyl group having 1 or 6 carbon atoms as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by OH groups.
The term "Ci-C4-alkoxy-Ci-C4-alkyl" refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C4-alkoxy group (as defined above). Likewise, the term "Ci-C6-alkoxy-CrC4-alkyl" refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C6-alkoxy group (as defined above).
The term "C2-C6-alkenyl" refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and a double bond in any position. Examples are "C2-C4-alkenyl" groups, such as ethenyl, 1 -propenyl, 2-propenyl (allyl), 1 -methylethenyl, 1 -butenyl, 2-butenyl,
3- butenyl, 1-methyl-1 -propenyl, 2-methyl-1 -propenyl, 1 -methyl-2-propenyl, 2-methyl-2-propenyl. The term "C2-C6-alkynyl" refers to a straight-chain or branched unsaturated hydrocarbon radical having 2 to 6 carbon atoms and containing at least one triple bond. Examples are "C2-C4- alkynyl" groups, such as ethynyl, prop-1 -ynyl, prop-2-ynyl (propargyl), but-1 -ynyl, but-2-ynyl, but-3-ynyl, 1 -methyl-prop-2-ynyl.
The term "Ci-C6-alkoxy" refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms which is bonded via an oxygen, at any position in the alkyl group. Examples are "C1-C4- alkoxy" groups, such as methoxy, ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1 - methyhpropoxy, 2-methylpropoxy or 1 ,1 -dimethylethoxy.
The term "CrC6-halogenalkoxy" refers to a Ci-C6-alkoxy radical as defined above, wherein some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as men- tioned above. Examples are "Ci-C4-halogenalkoxy" groups, such as OCH2F, OCHF2, OCF3, OCH2CI, OCHCI2, OCCI3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-tri- fluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloro-,ethoxy, OC2F5, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy,
2,3-difluoro-,propoxy, 2 chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bro- mo-'propoxy, 3 bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C2F5, OCF2-C2F5, 1-fluoromethyl-2 -fluoroethoxy, 1 -chloromethyl-2-chloroethoxy, 1 -bromomethyl-2- bromo-'ethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy.
The term "C2-C6-alkenyloxy" refers to a straight-chain or branched alkenyl group having 2 to 6 carbon atoms which is bonded via an oxygen, at any position in the alkenyl group. Examples are "C2-C4-alkenyloxy" groups.
The term "C2-C6-alkynyloxy" refers to a straight-chain or branched alkynyl group having 2 to 6 carbon atoms which is bonded via an oxygen, at any position in the alkynyl group. Examples are "C2-C4-alkynyloxy" groups.
The term "C3-C6-cycloalkyl" refers to monocyclic saturated hydrocarbon radicals having 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl. Accordingly, a saturated three-, four-, five-, six-, seven-, eight-, nine or ten-membered carbocyclyl or carbocycle is a "C3-Cio-cycloalkyl".
The term "C3-C6-cycloalkenyl" refers to a monocyclic partially unsaturated 3-, 4- 5- or 6- membered carbocycle having 3 to 6 carbon ring members and at least one double bond, such as cyclopentenyl, cyclopentadienyl, cyclohexadienyl. Accordingly, a partially unsaturated three-, four-, five-, six-, seven-, eight-, nine or ten-membered carbocyclyl or carbocycle is a "C3-C10- cycloalkenyl".
The term "C3-C8-cycloalkyl-CrC4-alkyl" refers to alkyl having 1 to 4 carbon atoms (as defined above), wherein one hydrogen atom of the alkyl radical is replaced by a cycloalkyl radical having 3 to 8 carbon atoms (as defined above).
The term "Ci-Ce-alkylthio" as used herein refers to straight-chain or branched alkyl groups having 1 to 6 carbon atoms (as defined above) bonded via a sulfur atom. Accordingly, the term "Ci- C6-halogenalkylthio" as used herein refers to straight-chain or branched halogenalkyi group having 1 to 6 carbon atoms (as defined above) bonded through a sulfur atom, at any position in the halogenalkyi group.
The term "C(=0)-CrC6-alkyl" refers to a radical which is attached through the carbon atom of the group C(=0) as indicated by the number valence of the carbon atom. The number of valence of carbon is 4, that of nitrogen is 3. Likewise the following terms are to be construed: NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C3-C6-cycloalkyl), N(C3-C6-cycloalkyl)2, C(=0)-N H(Ci-C6- alkyl), C(=0)-N(Ci-C6-alkyl)2.
The term "saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine or ten- membered heterocyclyl or heterocycle, wherein the heterocyclyl or heterocycle contains 1 , 2, 3 or 4 heteroatoms selected from N, O and S" is to be understood as meaning both saturated and partially unsaturated heterocycles, wherein the ring member atoms of the heterocycle include besides carbon atoms 1 , 2, 3 or 4 heteroatoms independently selected from the group of O, N and S. For example:
a 3- or 4-membered saturated heterocycle which contains 1 or 2 heteroatoms from the group consisting of O, N and S as ring members such as oxirane, aziridine, thiirane, oxetane, azet- idine, thiethane, [1 ,2]dioxetane, [1 ,2]dithietane, [1 ,2]diazetidine; and
a 5- or 6-membered saturated or partially unsaturated heterocycle which contains 1 , 2 or 3 het- eroatoms from the group consisting of O, N and S as ring members such as 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl,
5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1 ,2,4-oxadiazolidin-3-yl, 1 ,2,4-oxadiazolidin-5-yl, 1 ,2,4-thiadiazolidin-3-yl, 1 ,2,4-thiadiazolidin-5- yl, 1 ,2,4-triazolidin-3-yl, 1 ,3,4-oxadiazolidin-2-yl, 1 ,3,4-thiadiazolidin-2-yl, 1 ,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-
2- yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-
3- yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2- isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl,
4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3- isothiazolin-4-yl, 4-isoth iazoli n-4-y 1 , 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isoth iazoli n-5-y 1 , 2,3- dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4- yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol- 4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-
4- yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4- yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4- yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 1 ,3-dioxan-5-yl, 2-tetrahydropyranyl, 4- tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1 ,3,5- hexahydrotriazin-2-yl and 1 ,2,4-hexahydrotriazin-3-yl and also the corresponding -ylidene radicals; and
a 7-membered saturated or partially unsaturated heterocycle such as tetra- and hexahydroaze- pinyl, such as 2,3,4,5-tetrahydro[1 H]azepin-1-,-2-,-3-,-4-,-5-,-6- or-7-yl, 3,4,5,6-tetra- hydro[2H]azepin-2-,-3-,-4-,-5-,-6- or-7-yl, 2,3,4,7-tetrahydro[1 H]azepin-1 -,-2-,-3-,-4-,-5-,-6- or-7- yl, 2,3,6,7-tetrahydro[1 H]azepin-1 -,-2-,-3-,-4-,-5-,-6- or-7-yl, hexahydroazepin-1 -,-2-,-3- or-4-yl, tetra- and hexahydrooxepinyl such as 2,3,4,5-tetrahydro[1 H]oxepin-2-,-3-,-4-,-5-,-6- or-7-yl, 2,3,4,7-tetrahydro[1 H]oxepin-2-,-3-,-4-,-5-,-6- or-7-yl, 2,3,6,7-tetrahydro[1 H]oxepin-2-, -3-,-4-,-5- ,-6- or-7-yl, hexahydroazepin-1 -,-2-,-3- or-4-yl, tetra- and hexahydro-1 ,3-diazepinyl, tetra- and hexahydro-1 ,4-diazepinyl, tetra- and hexahydro-1 ,3-oxazepinyl, tetra- and hexahydro-1 ,4- oxazepinyl, tetra- and hexahydro-1 , 3-dioxepinyl, tetra- and hexahydro-1 ,4-dioxepinyl and the corresponding -ylidene radicals.
The term "5-or 6-membered heteroaryl" refers to aromatic ring systems incuding besides carbon atoms, 1 , 2, 3 or 4 heteroatoms independently selected from the group consisting of N, O and S, for example,
a 5-membered heteroaryl such as pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan- 2-yl, furan-3-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1 -yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1 ,2,4-triazolyl-1 -yl, 1 ,2,4-triazol-3-yl 1 ,2,4-triazol-5-yl, 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-oxadiazol-5-yl and 1 ,2,4-thiadiazol-3-yl, 1 ,2,4-thiadiazol-5-yl; or
a 6-membered heteroaryl, such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyri- dazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl.
Agriculturally acceptable salts of the inventive compounds encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of said compounds. Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four Ci-C4-alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammoni- um, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phos- phonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting such inventive compound with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The inventive compounds can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention.
Depending on the substitution pattern, the compounds of formula I and their N-oxides may have one or more centers of chirality, in which case they are present as pure enantiomers or pure diastereomers or as enantiomer or diastereomer mixtures. Both, the pure enantiomers or dia- stereomers and their mixtures are subject matter of the present invention.
In the following, particular embodiments of the inventive compounds are described. Therein, specific meanings of the respective substituents are further detained, wherein the meanings are in each case on their own but also in any combination with one another, particular embodiments of the present invention.
Furthermore, in respect of the variables, generally, the embodiments of the compounds I also apply to the intermediates.
R1 according to the invention is in each case independently selected from halogen, OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH-S02-Rx, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, Ci-C6-alkoxy, C3-C6-cycloalkyl, five- or six-membered heteroaryl and aryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein
Rx is Ci-C4-alkyl, Ci-C4-halogenalkyl, unsubstituted aryl or aryl that is substituted by one, two, three, four or five substituents Rx1 independently selected from Ci-C4-alkyl, halogen, OH, CN, Ci-C4-halogenalkyl, Ci-C4-alkoxy, and Ci-C4-halogenalkoxy; wherein the acyclic moieties of R1 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R1a which independently of one another are selected from:
R1a halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, C1-C4- halogenalkoxy, Ci-C6-alkylthio and phenoxy, wherein the phenyl group is unsubstituted or carries one, two, three, four or five substituents R11a selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy;
wherein the cycloalkyl, heteroaryl and aryl moieties of R1 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R1 b which independently of one another are selected from:
R1 b halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6- halogencycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio.
According to the invention, there can be zero, one, two, three or four R1 present, namely for m is 0, 1 , 2, 3 or 4.
According to one embodiment, m is 0.
According to a further embodiment, m is 1.
According to a further embodiment, m is 2.
According to a further embodiment, m is 2 or 3. According to one specific embodiment thereof, m is 2, according to a further specific embodiment, m is 3.
According to one embodiment of the invention, one R1 is attached to the 5-position as numbered in formula I above. According to a further embodiment of the invention, one R1 is attached to the 6-position as numbered in formula I above. According to a further embodiment of the invention, one R1 is attached to the 7-position as numbered in formula I above. According to a further embodiment of the invention, one R1 is attached to the 8-position as numbered in formula I above
According to a further embodiment of the invention, two R1 are attached in 7, 8-position as numbered in formula I above.
For every R1 that is present in the inventive compounds, the following embodiments and preferences apply independently of the meaning of any other R1 that may be present in the ring. Furthermore, the particular embodiments and preferences given herein for R1 apply independently for each of m=1 , m=2, m=3 and m=4.
According to one specific embodiment, R1 is halogen, in particular Br, F or CI, more specifically F or CI.
According to a further specific embodiment, R1 is F.
According to a further specific embodiment, R1 is CI.
According to a further specific embodiment, R1 is Br.
According to a further specific embodiment, R1 is OH.
According to a further specific embodiment, R1 is CN. According to a further specific embodiment, R1 is NO2.
According to a further specific embodiment, R1 is SH.
According to a further specific embodiment, R1 is NH2.
According to a further specific embodiment R1 is NH(Ci-C4-alkyl) or N(Ci-C4-alkyl)2, in particular Ci-C2-alkyl, such as CH3 or CH2CH3.
According to a further specific embodiment R1 is NH-SC>2-RX, wherein Rx is Ci-C4-alkyl, C1-C4- halogenalkyl, unsubstituted aryl or aryl that is substituted by one, two, three, four or five substit- uents Rx1 independently selected from Ci-C4-alkyl, halogen, OH, CN, Ci-C4-halogenalkyl, C1-C4- alkoxy, and Ci-C4-halogenalkoxy;
According to a further specific embodiment, R1 is Ci-C6-alkyl, in particular Ci-C4-alkyl, such as CH3 or CH2CH3.
According to a further specific embodiment, R1 is Ci-C6-halogenalkyl, in particular C1-C4- halogenalkyl, such as CF3, CHF2, CH2F, CCI3, CHCI2, CH2CI, CF3CH2, CCI3CH2 or CF2CHF2.
According to still a further embodiment, R1 is C2-C6-alkenyl or C2-C6-halogenalkenyl, in particu- lar C2-C4-alkenyl or C2-C4-halogenalkenyl, such as CH=CH2, C(CH3)=CH2, CH=CCI2, CH=CF2, CCI=CCI2, CF=CF2, CH=CH2, CH2CH=CCI2, CH2CH=CF2, CH2CCI=CCI2, CH2CF=CF2,
CCI2CH=CCI2, CF2CH=CF2, CCI2CCI=CCI2, or CF2CF=CF2.
According to still a further embodiment, R1 is C2-C6-alkynyl or C2-C6-halogenalkynyl, in particular C2-C4-alkynyl or C2-C4-halogenalkynyl, such as C≡CH, C≡CCI, C≡CF, CH2C≡CH, CH2C≡CCI, or CH2C≡CF.
According to a further specific embodiment, R1 is Ci-C6-alkoxy, in particular Ci-C4-alkoxy, more specifically Ci-C2-alkoxy such as OCH3 or OCH2CH3.
According to a further specific embodiment, R1 is Ci-C6-halogenalkoxy, in particular C1-C4- halogenalkoxy, more specifically Ci-C2-halogenalkoxy such as OCF3, OCHF2, OCH2F, OCCI3, OCHCI2 or OCH2CI, in particular OCF3, OCHF2, OCCI3 or OCHCI2.
According to a further specific embodiment R1 is C3-C6-cycloalkyl, in particular cyclopropyl.
In a further specific embodiment, R1 is C3-C6-cycloalkyl, for example cyclopropyl, substituted by one, two, three or up to the maximum possible number of identical or different groups R1b as defined and preferably herein.
According to a specific embodiment R1 is C3-C6-halogencycloalkyl. In a special embodiment R1 is fully or partially halogenated cyclopropyl.
According to still a further specific embodiment, R1 is unsubstituted aryl or aryl that is
substituted by one, two, three or four R1b, as defined herein. In particular, R1 is unsubstituted phenyl or phenyl that is substituted by one, two, three or four R1b, as defined herein.
According to still a further specific embodiment, R1 is unsubstituted 5- or 6-membered heteroaryl. According to still a further embodiment, R1 is 5- or 6-membered heteroaryl that is substituted by one, two or three R1b, as defined herein.
According to one further embodiment R1 is in each case independently selected from halogen, OH, CN, N02, SH, NH2, NH(CrC4-alkyl), N(Ci-C4-alkyl)2, NH-S02-Rx, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy and C3-C6-cycloalkyl; wherein the acyclic moieties of R1 are not further substituted or carry one, two, three, four or five identical or different groups R1a as defined below and wherein the cycloalkyl moieties of R1 are not further substituted or carry one, two, three, four or five identical or different groups R1 b as defined below.
According to a further embodiment, R1 is independently selected from halogen, OH, Ci-C6-alkyl, Ci-C6-halogenalkyl, Ci-C6-alkoxy and Ci-C6-halogenalkoxy, in particular independently selected from F, CI, Br, CN, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy.
R1a are the possible substituents for the acyclic moieties of R1.
R1a according to the invention is independently selected from halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy, Ci-C6-alkylthio and phenoxy, wherein the phenyl group is unsubstituted or carries one, two, three, four or five substituents R11a selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, C1-C4- alkoxy and Ci-C4-halogenalkoxy, in particular selected from halogen, Ci-C2-alkyl, C1-C2- halogenalkyl, Ci-C2-alkoxy and Ci-C2-halogenalkoxy, more specifically selected from halogen, such as F, CI and Br.
According to one embodiment R1a is independently selected from halogen, OH, CN, C1-C2- alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and Ci-C2-halogenalkoxy. Specifically, R1a is independently selected from F, CI, OH, CN, Ci-C2-alkoxy, cyclopropyl, 1-F-cyclopropyl, 1-CI- cyclopropyl, 1 ,1-F2-cyclopropyl, 1 ,1-Cl2-cyclopropyl and Ci-C2-halogenalkoxy.
According to one particular embodiment R1a is independently selected from halogen, such as F, CI, Br and I, more specifically F, CI and Br.
According to a further embodiment, R1a is independently selected from OH, C3-C6-cycloalkyl, C3- C6-halogencycloalkyl and Ci-C2-halogenalkoxy. Specifically, R1a is independently selected from OH, cyclopropyl and Ci-C2-halogenalkoxy.
R1 b are the possible substituents for the cycloalkyl, heteroaryl and aryl moieties of R1.
R1 b according to the invention is independently selected from halogen, OH, CN, Ci-C4-alkyl, Ci- C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy or Ci-C6-alkylthio.
According to one embodiment thereof R1 b is independently selected from halogen, OH, CN, Ci- C2-alkyl, Ci-C2-alkoxy, Ci-C2-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and C1-C2- halogenalkoxy. Specifically, R1 b is independently selected from F, CI, Br, OH, CN, CH3, OCH3, cyclopropyl, 1-F-cyclopropyl, 1-CI-cyclopropyl, 1 ,1-F2-cyclopropyl, 1 ,1-Cl2-cyclopropyl and halogenmethoxy.
According to a further embodiment thereof R1 b is independently selected from halogen, C1-C2- alkyl, Ci-C2-alkoxy, Ci-C2-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and C1-C2- halogenalkoxy. Specifically, R1 b is independently selected from F, CI, Br, CH3, CHF2, CF3, OCH3, cyclopropyl, 1-F-cyclopropyl, 1-CI-cyclopropyl, 1 ,1-F2-cyclopropyl, 1 ,1-Cl2-cyclopropyl and halogenmethoxy, more specifically independently selected from F, CI, Br, CH3, CHF2, CF3, OCH3, cyclopropyl, 1-F-cyclopropyl, 1-CI-cyclopropyl, 1 ,1-F2-cyclopropyl, 1 ,1-Cl2-cyclopropyl and OCHF2. Particularly preferred embodiments of (R1)m according to the invention are in Table P1 below, wherein each line of lines P1 -1 to P1-62 corresponds to one particular embodiment of the invention, wherein P1-1 to P1 -62 are also in any combination with one another a preferred embodiment of the present invention. Thereby, for every R1 that is present in the inventive compounds, these specific embodiments and preferences apply independently of the meaning of any other R1 that may be present in the ring:
Table P1 :
Figure imgf000023_0003
Figure imgf000023_0001
Figure imgf000023_0002
R2 according to the invention is is in each case independently selected from halogen, OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH-S02-Rx, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, Ci-C6-alkoxy, C3-C6-cycloalkyl, five- or six-membered heteroaryl and aryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein Rx is Ci-C4-alkyl, Ci-C4-halogenalkyl, unsubstituted aryl or aryl that is substituted by one, two, three, four or five substituents Rx2 independently selected from Ci-C4-alkyl, halogen, OH, CN, C1-C4- halogenalkyi, CrC4-alkoxy, and CrC4-halogenalkoxy; wherein the acyclic moieties of R2 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R2a which independently of one another are selected from:
R2a halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, C1-C4- halogenalkoxy, Ci-C6-alkylthio and phenoxy, wherein the phenyl group is unsubstituted or car- ries one, two, three, four or five substituents R22a selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy;
wherein the cycloalkyl, heteroaryl and aryl moieties of R2 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R2b which independently of one another are selected from:
R2b halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6- halogencycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio.
According to the invention, there can be zero, one or two R2 present, namely for n is 0, 1 or 2. According to one embodiment, n is 0 or 1 .
According to a further embodiment, n is 0.
According to still a further embodiment, n is 1.
According to still a further embodiment, n is 2.
According to one embodiment of the invention, one R2 is attached to the 2-position as numbered in formula I above. According to a further embodiment of the invention, one R2 is attached to the 4-position as numbered in formula I above.
According to a further embodiment of the invention, two R2 are attached in 2, 4-position as numbered in formula I above.
For every R2 that is present in the inventive compounds, the following embodiments and preferences apply independently of the meaning of the other R2 that may be present in the ring. Furthermore, the particular embodiments and preferences given herein for R2 apply inde- pendently for each of n=1 and n=2.
According to one specific embodiment, R2 is halogen, in particular Br, F or CI, more specifically F or CI.
According to a further specific embodiment, R2 is F.
According to a further specific embodiment, R2 is CI.
According to a further specific embodiment, R2 is Br.
According to a further specific embodiment, R2 is OH.
According to a further specific embodiment, R2 is CN.
According to a further specific embodiment, R2 is NO2.
According to a further specific embodiment, R2 is SH.
According to a further specific embodiment, R2 is NH2.
According to a further specific embodiment R2 is, NH(Ci-C4-alkyl) or N(CrC4-alkyl)2, , in particular Ci-C2-alkyl, such as CH3 or CH2CH3.
According to a further specific embodiment R2 is NH-S02-RX, wherein Rx is Ci-C4-alkyl, C1-C4- halogenalkyl, unsubstituted aryl or aryl that is substituted by one, two, three, four or five substit- uents Rx2 independently selected from Ci-C4-alkyl, halogen, OH, CN, Ci-C4-halogenalkyl, C1-C4- alkoxy, and Ci-C4-halogenalkoxy; According to a further specific embodiment, R2 is Ci-C6-alkyl, in particular Ci-C4-alkyl, such as CH3 or CH2CH3.
According to a further specific embodiment, R2 is Ci-C6-halogenalkyl, in particular C1-C4- halogenalkyl, such as CF3, CHF2, CH2F, CCI3, CHCI2,CH2CI, CF3CH2, CCI3CH2 or CF2CHF2. According to still a further embodiment, R2 is C2-C6-alkenyl or C2-C6-halogenalkenyl, in particular C2-C4-alkenyl or C2-C4-halogenalkenyl, such as CH=CH2, CH=CCI2, CH=CF2, CCI=CCI2, CF=CF2, CH=CH2, CH2CH=CCI2, CH2CH=CF2, CH2CCI=CCI2, CH2CF=CF2, CCI2CH=CCI2, CF2CH=CF2, CCI2CCI=CCI2, or CF2CF=CF2.
According to still a further embodiment, R2 is C2-C6-alkynyl or C2-C6-halogenalkynyl, in particular C2-C4-alkynyl or C2-C4-halogenalkynyl, such as C≡CH, C≡CCI, C≡CF, CH2C≡CH, CH2C≡CCI, or CH2C≡CF.
According to a further specific embodiment, R2 is Ci-C6-alkoxy, in particular Ci-C4-alkoxy, more specifically Ci-C2-alkoxy such as OCH3 or OCH2CH3.
According to a further specific embodiment, R2 is Ci-C6-halogenalkoxy, in particular C1-C4- halogenalkoxy, more specifically Ci-C2-halogenalkoxy such as OCF3, OCHF2, OCH2F, OCCI3, OCHCI2 or OCH2CI, in particular OCF3, OCHF2, OCCI3 or OCHCI2.
According to a further specific embodiment R2 is C3-C6-cycloalkyl, in particular cyclopropyl.
In a further specific embodiment, R2 is C3-C6-cycloalkyl, for example cyclopropyl, substituted by one, two, three or up to the maximum possible number of identical or different groups R2b as defined and preferably herein.
According to a specific embodiment R2 is C3-C6-halogencycloalkyl. In a special embodiment R2 is fully or partially halogenated cyclopropyl.
According to still a further specific embodiment, R2 is unsubstituted aryl or aryl that is
substituted by one, two, three or four R2b, as defined herein. In particular, R2 is unsubstituted phenyl or phenyl that is substituted by one, two, three or four R2b, as defined herein.
According to still a further specific embodiment, R2 is unsubstituted 5- or 6-membered heteroaryl. According to still a further embodiment, R2 is 5- or 6-membered heteroaryl that is substituted by one, two or three R2b, as defined herein.
According to one further embodiment R2 is in each case independently selected from halogen, OH, CN, N02, SH, NH2, NH(C C4-alkyl), N(C C4-alkyl)2, NH-S02-R*, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy and C3-C6-cycloalkyl; wherein the acyclic moieties of R2 are not further substituted or carry one, two, three, four or five identical or different groups R2a as defined below and wherein the cycloalkyl moieties of R2 are not further substituted or carry one, two, three, four or five identical or different groups R2b as defined below.
According to a further embodiment, R2 is independently selected from halogen, OH, Ci-C6-alkyl, Ci-C6-halogenalkyl, Ci-C6-alkoxy and Ci-C6-halogenalkoxy, in particular independently selected from F, CI, Br, CN, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy.
R2a are the possible substituents for the acyclic moieties of R2.
R2a according to the invention is independently selected from halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy, Ci-C6-alkylthio and phenoxy, wherein the phenyl group is unsubstituted or carries one, two, three, four or five substituents R22a selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, C1-C4- alkoxy and Ci-C4-halogenalkoxy, in particular selected from halogen, Ci-C2-alkyl, C1-C2- halogenalkyl, Ci-C2-alkoxy and Ci-C2-halogenalkoxy, more specifically selected from halogen, such as F, CI and Br.
According to one embodiment R2a is independently selected from halogen, OH, CN , C1-C2- alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and Ci-C2-halogenalkoxy. Specifically, R2a is independently selected from F, CI, OH, CN, Ci-C2-alkoxy, cyclopropyl, 1-F-cyclopropyl, 1 -CI- cyclopropyl, 1 ,1 -F2-cyclopropyl, 1 ,1-Cl2-cyclopropyl and Ci-C2-halogenalkoxy.
According to one particular embodiment R2a is independently selected from halogen, such as F, CI, Br and I , more specifically F, CI and Br.
According to a further embodiment, R2a is independently selected from OH , C3-C6-cycloalkyl, C3- C6-halogencycloalkyl and Ci-C2-halogenalkoxy. Specifically, R2a is independently selected from OH, cyclopropyl, 1 ,1-F2-cyclopropyl, 1 ,1-Cl2-cyclopropyl and Ci-C2-halogenalkoxy.
R2b are the possible substituents for the cycloalkyl, heteroaryl and aryl moieties of R2.
R2b according to the invention is independently selected from halogen, OH, CN , Ci-C4-alkyl, Ci- C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl Ci-C4-halogenalkoxy or Ci-C6-alkylthio;
According to one embodiment thereof R2b is independently selected from halogen, OH, CN, Ci- C2-alkyl, Ci-C2-alkoxy, Ci-C2-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and C1-C2- halogenalkoxy. Specifically, R2b is independently selected from F, CI, Br, OH, CN, CH3, OCH3, cyclopropyl, 1-F-cyclopropyl, 1-CI-cyclopropyl, 1 ,1-F2-cyclopropyl, 1 ,1-Cl2-cyclopropyl and halogenmethoxy.
According to a further embodiment thereof R2b is independently selected from halogen, C1-C2- alkyl, Ci-C2-alkoxy, Ci-C2-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and C1-C2- halogenalkoxy. Specifically, R2b is independently selected from F, CI, Br, CH3, CHF2, CF3, OCH3, cyclopropyl, 1 -F-cyclopropyl, 1-CI-cyclopropyl, 1 ,1 -F2-cyclopropyl, 1 ,1 -Cl2-cyclopropyl and halogenmethoxy, more specifically independently selected from F, CI, Br, CH3, CHF2, CF3, OCH3, cyclopropyl, 1 -F-cyclopropyl, 1-CI-cyclopropyl, 1 ,1 -F2-cyclopropyl, 1 ,1 -Cl2-cyclopropyl and
Particularly preferred embodiments of (R2)m according to the invention are in Table P2 below, wherein each line of lines P2-1 to P2-32 corresponds to one particular embodiment of the invention, wherein P2-1 to P2-32 are also in any combination with one another a preferred embodi- ment of the present invention. Thereby, for every R2 that is present in the inventive compounds, these specific embodiments and preferences apply independently of the meaning of any other R2 that may be present in the ring:
Figure imgf000026_0001
No. (R2)n No. (R2)n No. (R2)n
P2-7 4-Br P2-17 4-CH2CH3 P2-27 4-OCF3
P2-8 2-0 H P2-18 2-CF3 P2-28 2-OCHF2
P2-9 4-0 H P2-19 4-CF3 P2-29 4-OCHF2
P2-10 2-CN P2-20 2-CHF2 P2-30 2-N H-Ts
P2-1 1 4-CN P2-21 4-CHF2 P2-31 4-N H-Ts
P2-12 2-NO2 P2-22 2-OCH3 P2-32 2,4-F2
P2-13 4-NO2 P2-23 4-OCH3
P2-14 2-CHs P2-24 2-OCH2CH3
P2-15 4-CHs P2-25 4-OCH2CH3
P2-16 2-CH2CH3 P2-26 2-OCF3 According to one embodiment, R3 is CH3.
According to one further embodiment, R3 is CH2F.
According to one further embodiment, R3 is CHF2.
According to one embodiment, R3 is CF3.
R4 is independently selected from OH, CN,-N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH- S02-Rx, subtituted Ci-C6-alkyl, Ci-C6-alkylthio, C2-C6-alkenyl, C2-C6-halogenalkenyl, C2-C6- alkynyl, C2-C6-halogenalkynyl, Ci-C6-alkoxy, Ci-C6-halogenalkoxy, C2-C6-alkenyloxy, C2-C6- alkynyloxy, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6-alkyl), C(=0)NH(Ci-C6-alkyl), C(=0)N(Ci- C6-alkyl)2, CR'=NOR", a saturated or partially unsaturated three-, four-, five-, six-, seven-, eight- , nine-, or ten-membered carbocycle or heterocycle, wherein in each case one or two CH2 groups of the carbo- and heterocycle may be replaced by a group independently selected from C(=0) and C(=S), wherein the heterocycle contain independently one, two, three or four het- eroatoms selected from N, O and S; and wherein R' and R" are independently selected from H, Ci-C4-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbo- and heterocycle, and wherein R' and R" are independently unsubstituted or substituted by R'" which is independently selected from halogen, OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH-S02-Rx, Ci-C6-alkyl, Ci-C6- halogenalkyl, C2-C6-alkenyl, C2-C6-halogenalkenyl, C2-C6-alkynyl, C2-C6-halogenalkynyl, C1-C6- alkoxy, Ci-C6-halogenalkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and phenyl.
According to a further embodiment, R4 is selected from CN, subtituted Ci-C6-alkyl, C2-C6- alkenyl, C2-C6-halogenalkenyl, C2-C6-alkynyl, C2-C6-halogenalkynyl, C3-C6-cycloalkenyl, C3-C6- cycloalkyny, CR'=NOR", a saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle or heterocycle.
According to a further embodiment, R4 is selected from subtituted Ci-C6-alkyl, C2-C6-alkenyl, C2- C6-halogenalkenyl, C2-C6-alkynyl, C2-C6-halogenalkynyl, a saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle or heterocycle.
According to still another embodiment of formula I , R4 is OH.
According to still another embodiment of formula I , R4 is CN. According to still another embodiment of formula I, R4 is NO2.
According to still another embodiment of formula I, R4 is SH.
According to still another embodiment of formula I, R4 is NH2
According to still another embodiment of formula I, R4 is NH(Ci-C4-alkyl) or N(Ci-C4-alkyl)2, in particular Ci-C2-alkyl, such as CH3 or CH2CH3.
According to still another embodiment of formula I, R4 is NH-S02-RX, such as NH-SO2-C1-C4- alkyl especially NH-SO2-CH3.
According to still another embodiment of formula I, R4 is NH-S02-RX, such as NH-SO2-C1-C4- haogenalkyl especially NH-SO2-CF3.
According to still another embodiment of formula I, R4 is NH-S02-RX, such as NH-S02-aryl especially NH-S02-phenyl.
According to still another embodiment of formula I, R4 is Ci-C6-alkylthio, such as SCH3 or
According to still a further embodiment of formula I, R4 is C2-C6-alkenyl, in particular C2-C4-alk- enyl, such as CH=CH2, CH2CH=CH2 or C(CH3)C=CH2.
According to a further specific embodiment of formula I, R4 is C2-C6-halogenalkenyl, in particular C2-C4-halogenalkenyl, more specifically C2-C3-halogenalkenyl such as CH=CHF, CH=CHCI, CH=CF2, CH=CCI2, CF=CF2, CCI=CCI2, CH2CH=CHF, CH2CH=CHCI, CH2CH=CF2,
CH2CH=CCI2, CH2CF=CF2, CH2CCI=CCI2, CF2CF=CF2 or CCI2CCI=CCI2.
According to still a further embodiment of formula I, R4 is C2-C6-alkynyl or C2-C6-halogenalkynyl, in particular C2-C4-alkynyl or C2-C4-halogenalkynyl, such as C CH, C C-CI,
Figure imgf000028_0001
CH2- C≡CH, CH2-C≡CCI or CH2- C≡C-CH3.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkoxy, such as OCH3, OCH2CH3, OCH2CH(CH3) or OC(CH3)3.
According to a further specific embodiment of formula I, R4 is Ci-C6-halogenalkoxy, in particular Ci-C4-halogenalkoxy, more specifically Ci-C2-halogenalkoxy such as OCF3, OCHF2, OCH2F, OCCI3, OCHC or OCH2CI, in particular OCF3, OCHF2, OCCI3 or OCHCI2.
According to a further specific embodiment of formula I, R4 is C2-C6-alkenyloxy, in particular C2- C4-alkenyloxy, more specifically Ci-C2-alkenyloxy such as OCH=CH2, OCH2CH=CH2
OC(CH3)CH=CH2, CH2OCH=CH2, or CH2OCH2CH=CH2.
According to a further specific embodiment of formula I, R4 is C2-C6-alkynyloxy, in particular C2- C4-alkynyloxy, more specifically Ci-C2-alkynyloxy such as OC CH, OChbC CH or ChbOC CH
According to a further specific embodiment of formula I, R4 is CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6-alkyl), C(=0)NH(Ci-C6-alkyl) or C(=0)N(Ci-C6-alkyl)2, wherein alkyl is CH3, C2H5, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl.
According to a further specific embodiment of formula I, R4 is CR'=NOR" such as
C(CH3)=NOCH3, C(CH3)=NOCH2CH3 or C(CH3)=NOCF3. All above mentioned acyclic moieties of R4 except for the substituted Ci-C6-alkyl moieties of R4 carry one, two, three or up to the maximum possible number of identical or different groups R4a, respectively, which independently of one another are selected from:
R a halogen, OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C(=0)Ci-C4-alkyl), N(C(=0)Ci-C4-alkyl)2, NH-S02-Rx, Ci-C6-alkoxy, Ci-C4-halogenalkoxy, C3-C6-cycloalkyl, Cs-Ce-halogencycloalkyl, S(0)z-CrC6-alkyl, S(0)z-Ci-C6-halogenalkyl, S(0)z-aryl, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(C C6-alkyl), C(=0)NH(Ci-C6-alkyl), C(=0)N(Ci-C6-alkyl)2, CR'=NOR", a saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle or heterocycle, five-, six- or ten-membered heteroaryl, aryl, phenoxy; wherein in each case one or two CH2 groups of the carbocycle and heterocycle may be replaced by a group independently selected from C(=0) and C(=S); wherein the heterocycle and heteroaryl contain independently one, two, three or four heteroatoms selected from N, O and S; wherein the carbocyclic, heterocyclic, aryl, phenyl and heteroaryl groups are independently unsubstituted or carry one, two, three, four or five sub- stituents selected from the group consisting of halogen, OH, CN, N02, SH, NH2, NH(Ci- C4-alkyl), N(Ci-C4-alkyl)2, NH(C(=0)Ci-C4-alkyl), N(C(=0)Ci-C4-alkyl)2, NH-S02-R*, Ci-C6- alkylthio, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy, Ci-C4-halogenalkoxy and S(0)z- Ci-C6-alkyl; wherein z is 0, 1 or 2; whein Rx, R', R" and R'" is defined as aboved; According to one preferred embodiment, R4a is in each case independently selected from halogen, OH, CN, N02, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH-S02-Rx, CH(=0), C(=0)Ci-C6- alkyl, C(=0)0(C C6-alkyl), C(=0)NH(C C6-alkyl) or CR'=NOR".
According to one preferred embodiment, R4a is in each case independently selected from OH, CN, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6-alkyl), C(=0)NH(Ci-C6-alkyl) such as CN, CHO, C(0)0(CH3) ,C02NH(CH3) or C02N(CH3)2.
According to one preferred embodiment, R4a is in each case independently selected from, S(0)z-Ci-C6-alkyl, S(0)z-Ci-C6-halogenalkyl, S(0)z-aryl, such as SCH3, S02CH3, S02Ph.
According to one preferred embodiment, R4a is in each case independently selected from NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH-S02-Rx, such as NH(CH3), N(CH3)2, NHS02CH3,
NHS02CF3 or NHS02Ph.
According to one preferred embodiment, R4a is in each case independently selected from C3-C6- cycloalkyl, C3-C6-halogencycloalkyl, such as cyclopropyl or fully or partially halogenated cyclo- propyl.
According to one preferred embodiment, R4a is in each case independently selected from C1-C6- alkoxy, Ci-C6-halogenalkoxy, such as OCF3, OCHF2, OCH2F, OCCI3, OCHCI2 or OCH2CI, in particular OCF3, OCHF2, OCCI3 or OCHCI2.
According to one preferred embodiment, R4a is in each case independently selected from heterocycle, wherein the heterocycle is a satureated, two CH2 groups are replaced by C(=0) and contains one N as a ring member.
According to one preferred embodiment, R4a is in each case independently selected from aryl, wherein the aryl is substituted by halogen selected from the group consisting of F, CI, Br, CH3, CHF2, OCHs, OCHF2, OCF3, CN or SO2CH3.
According to one prefer embodiment, R4 is unsubstituted 5- or 6-membered heteroaryl.
According to still a further embodiment, R4 is 5- or 6-membered heteroaryl substituted by halogen selected from the group consisting of F, CI, Br, CH3, CHF2, OCH3, OCHF2, OCF3, CN or
According to one preferred embodiment, R4a is in each case independently selected from halogen, OH, CN, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and heterocycle, wherein the heterocy- clocycle is a satureated and contains one N as a ring member.
According to one preferred embodiment, R4a is in each case independently selected from halo- gen, OH, CN, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and heterocycle, wherein the heterocycle is a satureated, one CH2 group is replaced by C(=0) and contains one N as a ring member.
According to one preferred embodiment, R4a is in each case independently selected from halogen, OH, CN, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and heterocycle, wherein the heretocy- clocycle is a satureated, two CH2 groups are replaced by C(=0) and contains one N as a ring member.
According to one preferred embodiment, R4a is in each case independently selected from halogen, OH, CN, Ci-C6-alkoxy, Ci-C6-halogenalkoxy, phenyl, aryl or heteroaryl; wherein the aryl and hteroaryl is substituted by halogen selected from the group consisting of F, CI, Br, CH3, CHF2, OCH3, OCHF2, OCF3, CN or SO2CH3. According to one further preferred embodiment, R4a is in each case independently selected from halogen, phenyl, halogenphenyl and heteroaryl, wherein the halogenphenyl is substituted by halogen selected from the group consisting of F, CI and Br, in particular selected from F and CI.
According to one further preferred embodiment, R4a is in each case independently selected from halogen, CN, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci-C6-alkoxy, Ci-C4-halogenalkoxy, Ci- C6-alkylthio, Ci-C6-halogenalkylthio, phenyl, wherein the phenyl is substituted by halogen selected from the group consisting of F, CI and Br or by Ci-C4-alkyl, Ci-C4-halogenalkyl, C1-C4- alkoxy and Ci-C4-halogenalkoxy. According to one further preferred embodiment, R4a is in each case independently selected from halogen and phenyl wherein the phenyl is substituted by halogen selected from the group consisting of F, CI and Br, in particular selected from F and CI.
According to still another embodiment of formula I , R4 is a partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle, in particular three-, four-, five- or six-membered, wherein the carbocycle is unsubstituted or substituted by substituents R4b as defined below. According to one embodiment thereof, the carbocycle is unsubstituted.
According to still another embodiment of formula I , R4 is a partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle or heterocycle, in particular three-, four-, five- or six-membered, wherein the heterocycle contains one, two, three or four heteroa- toms selected from N, O and S, and wherein the carbocycle and heterocycle are unsubstituted or substituted with substituents R4b as defined below. According to one embodiment thereof, the carbocycle or heterocycle is unsubstituted.
According to still a further embodiment, R4 is a saturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle or heterocycle, in particular three-, four-, five- or six- membered, wherein the heterocycle contains one, two, three or four heteroatoms selected from N, O and S, and wherein the carbocycle and heterocycle are unsubstituted or substituted with substituents R4b as defined below. According to one embodiment thereof, the carbocycle or het- erocycle is unsubstituted.
According to still another embodiment of formula I, R4 is a saturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle, in particular three-, four-, five- or six- membered, wherein the carbocycle is unsubstituted or substituted by substituents R4b as defined below. According to one embodiment thereof, the carbocycle is unsubstituted.
According to one embodiment, R4 is a 3-membered saturated carbocycle. According to one embodiment thereof, the carbocycle is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to one embodiment, R4 is a 3-membered saturated carbocycle, which is
unsubstituted such as cyclopropyl.
According to one embodiment, R4 is a 3-membered saturated carbocycle, which is substituted by halogen, more specifically by F, such as C3H3F2.
According to one embodiment, R4 is a 3-membered saturated carbocycle, which is substituted by halogen. More specifically by CI, such as C3H3CI2.
According to one embodiment, R4 is a 4-membered saturated carbocycle. According to one embodiment thereof, the carbocycle is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to one embodiment, R4 is a 5-membered saturated carbocycle. According to one embodiment thereof, the carbocycle is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to one embodiment, R4 is a 6-membered saturated carbocycle. According to one embodiment thereof, the carbocycle is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to still another embodiment of formula I, R4 is a partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered heterocycle, in particular three-, four-, five- or six-membered, wherein the heterocycle contains one, two, three or four heteroatoms selected from N, O and S, and wherein the heterocycle is unsubstituted or substituted by substituents R4b as defined below. According to one embodiment thereof, the heterocycle is unsubstituted.
According to still another embodiment of formula I, R4 is a saturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered heterocycle, in particular three-, four-, five- or six- membered, wherein the heterocycle contains one, two, three or four heteroatoms selected from N, O and S, and wherein the heterocycle is unsubstituted or substituted by substituents R4b as defined below. According to one embodiment thereof, the heterocycle is unsubstituted.
According to still another embodiment of formula I, in the embodiments of R4 described above, the heterocycle contains preferably one, two or three, more specifically one or two heteroatoms selected from N, O and S. More specifically, the hetereocycle contains one heteroatom selected from N, O and S. In particular, the heterocycle contains one or two, in particular one O.
According to one embodiment, R4 is a 4-membered saturated heterocycle which contains 1 or 2 heteroatoms, in particular 1 heteroatom, from the group consisting of N, O and S, as ring members. According to one embodiment, the heterocycle contains one O as heteroatom. For exam- pie, the formed heterocycle is oxetane. According to one embodiment thereof, the heterocycle is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to still another embodiment of formula I, R4 is a 5-membered saturated heterocycle which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S, as ring members. According to one embodiment, the heterocycle contains one O as heteroatom. According to one embodiment thereof, the heterocycle is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R b.
According to still another embodiment of formula I, R4 is a 6-membered saturated heterocycle which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S as ring members. According to one embodiment thereof, the heterocycle is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b. According to one specific embodiment thereof, said 6-membered saturated heterocycle contains 1 or 2, in particular 1 , heteroatom(s) O. According to one embodiment thereof, the respective 6-membered heterocycle is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
All above mentioned carbocyclic and heterocyclic moieties of R4 are independently not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R4b, respectively, which independently of one another are selected from: R halogen, OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C(=0)Ci-C4-alkyl), N(C(=0)Ci-C4-alkyl)2, NH-S02-Rx, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6- cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy, Ci-C6-alkylthio, C1-C6- halogenalkylthio, S(0)z-Ci-C6-alkyl, Ci-C4-alkoxy-Ci-C4-alkyl, phenyl and phenoxy, wherein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4- halogenalkoxy; z is 0, 1 and 2; and wherein Rx is as defined above;
According to one preferred embodiment, R4b is in each case independently selected from halogen, OH, CN, SH, Ci-C6-alkyl, Ci-C6-halogenalkyl, Ci-C6-alkoxy, Ci-C6-halogenalkoxy, C1-C6- alkylthio and S(0)z-Ci-C6-alkyl. According to one further preferred embodiment, R4b is in each case independently selected from halogen, Ci-C6-alkoxy, Ci-C6-halogenalkyl, C1-C6- halogenalkoxy and S(0)z-Ci-C6-alkyl. According to one further particular embodiment, R4b is in each case independently selected from halogen such as CI, Br, F. According to one further particular embodiment, R4b is in each case independently selected from Ci-C6-alkyl, such as methyl and ethyl. According to one further particular embodiment, R4b is in each case independently selected from halogen, such as F, CI and Br. According to one further particular embodiment, R4b is in each case independently selected from Ci-C6-alkoxy, such as OCH3. According to one further particular embodiment, R4b is in each case independently selected from C1-C4- halogenalkoxy, such as OCHF2 and OCF3. According to one further particular embodiment, R4b is in each case independently selected from S(0)z-Ci-C6-alkyl such as SO2CH3.
According to still another embodiment of formula I, R4 is Ci-C6-alkyl such as CH3, C2H5, n- propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl which is substituted by at least one group R4c, which independently of one another are selected from:
OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C(=0)Ci-C4-alkyl), N(C(=0)Ci-C4- alkyl)2, NH-S02-Rx, Ci-C4-halogenalkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, S(0)-Ci- Ce-alkyl, S(0)2-Ci-C6-alkyl, S(0)z-Ci-C6-halogenalkyl, S(0)z-aryl, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6-alkyl), C(=0)NH(Ci-C6-alkyl), C(=0)N(Ci-C6-alkyl)2, CR'=NOR", a saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle or heterocycle, five-, six- or ten-membered heteroaryl; wherein in each case one or two CH2 groups of the carbocycle and heterocycle may be replaced by a group independently selected from C(=0) and C(=S); wherein the heterocycle and heteroaryl contain independently one, two, three or four heteroatoms selected from N, O and S; wherein the carbocyclic, heterocyclic, aryl, phenyl and heteroaryl groups are independently unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of halogen, OH, CN, NO2, SH, NH2, NH(Ci- C4-alkyl), N(Ci-C4-alkyl)2, NH(C(=0)Ci-C4-alkyl), N(C(=0)Ci-C4-alkyl)2, NH-S02-Rx, Ci-C6- alkylthio, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy, Ci-C4-halogenalkoxy and S(0)z-Ci-C6- alkyl; z is 0, 1 and 2; and wherein Rx R' and R" is as defined above;
According to still another embodiment of formula I, R4 is CH3 is substituted by at least one group R4c, which independently of one another are selected from:
OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C(=0)Ci-C4-alkyl), N(C(=0)Ci-C4- alkyl)2, NH-S02-Rx, Ci-C4-halogenalkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, S(0)-Ci- Ce-alkyl, S(0)2-Ci-C6-alkyl, S(0)z-Ci-C6-halogenalkyl, S(0)z-aryl, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6-alkyl), C(=0)NH(Ci-C6-alkyl), C(=0)N(Ci-C6-alkyl)2, CR'=NOR", a saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle or heterocycle, five-, six- or ten-membered heteroaryl; wherein in each case one or two CH2 groups of the carbocycle and heterocycle may be replaced by a group independently selected from C(=0) and C(=S); wherein the heterocycle and heteroaryl contain independently one, two, three or four heteroatoms selected from N, O and S; wherein the carbocyclic, heterocyclic, aryl, phenyl and heteroaryl groups are independently unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of halogen, OH, CN, NO2, SH, NH2, NH(Ci- C4-alkyl), N(Ci-C4-alkyl)2, NH(C(=0)Ci-C4-alkyl), N(C(=0)Ci-C4-alkyl)2, NH-S02-Rx, Ci-C6- alkylthio, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy, Ci-C4-halogenalkoxy and S(0)z-Ci-C6- alkyl. According to still another embodiment of formula I, R4 is C2H5 is substituted by at least one group R4c, which independently of one another are selected from:
OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C(=0)Ci-C4-alkyl), N(C(=0)Ci-C4- alkyl)2, NH-S02-Rx, Ci-C4-halogenalkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, S(0)-Ci- Ce-alkyl, S(0)2-Ci-C6-alkyl, S(0)z-Ci-C6-halogenalkyl, S(0)z-aryl, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6-alkyl), C(=0)NH(Ci-C6-alkyl), C(=0)N(Ci-C6-alkyl)2, CR'=NOR", a saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle or heterocycle, five-, six- or ten-membered heteroaryl; wherein in each case one or two Ch groups of the carbocycle and heterocycle may be replaced by a group independently selected from C(=0) and C(=S); wherein the heterocycle and heteroaryl contain independently one, two, three or four heteroatoms selected from N, O and S; wherein the carbocyclic, heterocyclic, aryl, phenyl and heteroaryl groups are independently unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of halogen, OH, CN, NO2, SH, NH2, NH(Ci- C4-alkyl), N(Ci-C4-alkyl)2, NH(C(=0)Ci-C4-alkyl), N(C(=0)Ci-C4-alkyl)2, NH-S02-Rx, Ci-C6- alkylthio, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy, Ci-C4-halogenalkoxy and S(0)z-Ci-C6- alkyl.
According to still another embodiment of formula I, R4 is CH2CN.
According to still another embodiment of formula I, R4 is CH2OH.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl-Ci-C6-halogenalkoxy, in particular Ci-C4-alkyl-Ci-C4-halogenalkoxy, more specifically Ci-C2-alkyl-Ci-C2-halogenalkoxy such as CH2OCF3, CH2OCHF2, CH2OCH2F, CH2OCCI3, CH2OCHCI2 or CH2OCH2CI, in particular CH2OCF3, CH2OCHF2, CH2OCCI3 or CH2OCHCI2.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl-Ci-C6- halogenalkylthio, in particular Ci-C4-alkyl-Ci-C4-halogenalkylthio, more specifically Ci-C2-alkyl- Ci-C2-halogenalkylthio such as CH2SCF3, CH2SCHF2, CH2SCH2F, CH2SCCI3, CH2SCHCI2 or CH2SCH2CI, in particular CH2SCF3, CH2SCHF2, CH2SCCI3 or CH2SCHCI2.
According to a further specific embodiment of formula I, R4 is Ci-C4-alkyl-CH(=0), CrC4-alkyl- C(=0)CrC6-alkyl, Ci-C4-alkyl-C(=0)0(C C6-alkyl), C C4-alkyl-C(=0)NH(Ci-C6-alkyl) or C C4- alkyl-C(=0)N(Ci-C6-alkyl)2, especially CH2CH(=0), CH2C(=0)Ci-C6-alkyl, CH2C(=0)0(Ci-C6- alkyl), CH2C(=0)NH(Ci-C6-alkyl) or CH2C(=0)N(Ci-C6-alkyl)2 wherein alkyl is CH3, C2H5, n- propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl-NH(Ci-C4-alkyl), C1-C6- alkyl-N(Ci-C4-alkyl)2, Ci-C6-alkyl-NH(C(=0)Ci-C4-alkyl) or Ci-C6-alkyl-N(C(=0)Ci-C4-alkyl)2, wherein alkyl is CH3, C2H5, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl. According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl-S(0) -Ci-C6-alkyl, wherein alkyl is CH3, C2H5, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl-S(0)2-Ci-C6-alkyl, wherein alkyl is CH3, C2H5, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl-S(0)z-Ci-C6- halogenalkyl, wherein halogenalkyl is CF3 or CHF2 and z is 0, 1 , 2 or 3.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl-S(0)z-aryl, wherein the aryl or phenyl moiety in each case is independently unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of halogen, OH, CN, NO2, SH, NH2, NH(CrC4-alkyl), N(C C4-alkyl)2, NH(C(=0)C C4-alkyl), N(C(=0)C C4-alkyl)2, NH-S02-Rx, C C6-alkylthio, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy, Ci-C4-halogenalkoxy and S(0)z-Ci- Ce-alkyl, in particular F, CI, Br, CH3, OCH3, CF3, CHF2, OCHF2, OCF3. According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl-NH-SC>2-Rx wherein Rx is Ci-C4-alkyl, Ci-C4-halogenalkyl, unsubstituted aryl or aryl that is substituted by one, two, three, four or five substituents Rx2 independently selected from Ci-C4-alkyl, halogen, OH, CN, Ci-C4-halogenalkyl, Ci-C4-alkoxy, or Ci-C4-halogenalkoxy, such as Ch NHSC^CFs or
Figure imgf000035_0001
According to still another embodiment of formula I, R4 is selected from Ci-C6-alkyl which is substituted, a saturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle, in particular three-, four-, five- or six-membered, wherein the carbocycle is unsubstituted or substituted by substituents R4b as defined below. According to one embodiment thereof, the carbo- cycle is unsubstituted.
According to one embodiment, R4 is selected from Ci-C6-alkyl, especially CH2 which is substituted by a 3-membered saturated carbocycle. According to one embodiment thereof, the carbocycle is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to one embodiment, R4 is selected from Ci-C6-alkyl, especially CH2 which is substituted by a 4-membered saturated carbocycle. According to one embodiment thereof, the carbocycle is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to one embodiment, R4 is selected from Ci-C6-alkyl, especially CH2 which is substi- tuted by a 5-membered saturated carbocycle. According to one embodiment thereof, the carbocycle is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to one embodiment, R4 is selected from Ci-C6-alkyl, especially CH2 which is substituted by a 6-membered saturated carbocycle. According to one embodiment thereof, the carbocycle is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially CH2 substituted by a 4-membered saturated heterocycle which contains 1 or 2 heteroatoms, in particular 1 heteroatom, from the group consisting of N, O and S, as ring members. According to one embodiment, the heterocycle contains one O as heteroatom. For example, the formed heterocycle is oxetane. According to one embodiment thereof, the heterocycle is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially CH2 substituted by a 5-membered saturated heterocycle which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S, as ring members. According to one embodiment, the heterocycle contains one O as heteroatom. According to one embodiment thereof, the heterocycle is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially CH2 subsitited by a 6-membered saturated heterocycle which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S as ring members. According to one embodiment thereof, the heterocycle is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b. According to one specific embodiment thereof, said 6-membered saturated heterocycle contains 1 or 2, in particu- lar 1 , heteroatom(s) O. According to one embodiment thereof, the respective 6-membered heterocycle is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially Chb substituted by a 5-membered saturated heterocycle which contains one N as ring member and optionally one or two groups Ch are replaced by C(=0).
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially Chb subsitited by a 5-membered saturated heteroaryl which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S as ring members. According to one embodiment thereof, the heteroaryl is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially Chb subsitited by a 5-membered saturated heteroaryl which contains one N as ring member.
According to one embodiment thereof, the heteroaryl is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially Chb subsitited by a 5-membered saturated heteroaryl which contains two N as ring members.
According to one embodiment thereof, the heteroaryl is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially Chb subsitited by a 5-membered saturated heteroaryl which contains three N as ring members.
According to one embodiment thereof, the heteroaryl is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to one specific embodiment thereof, said 5-membered saturated heterocycle contains 1 or 2, in particular 1 , heteroatom(s) O.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially CH2 subsitited by a 5-membered saturated heteroaryl which contains one S as ring member.
According to one embodiment thereof, the heteroaryl is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially Chb subsitited by a 5-membered saturated heteroaryl which contains one S and one N as ring members. According to one embodiment thereof, the heteroaryl is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially CH2 subsitited by a 5-membered saturated heteroaryl which contains one S and two N as ring mem- bers. According to one embodiment thereof, the heteroaryl is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b. According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially Chb subsitited by a 5-membered saturated heteroaryl which contains one oxygen and one N as ring members. According to one embodiment thereof, the heteroaryl is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially CH2 subsitited by a 5-membered saturated heteroaryl which contains one oxygen and two N as ring members. According to one embodiment thereof, the heteroaryl is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially Chb subsitited by a 6-membered saturated heteroaryl which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S as ring members. According to one embodiment thereof, the heteroaryl is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially Chb subsitited by a 6-membered saturated heteroaryl which one N as ring member. According to one embodiment thereof, the heteroaryl is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially Chb subsitited by a 6-membered saturated heteroaryl which two N as ring members. According to one embodiment thereof, the heteroaryl is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially Chb subsitited by a 10-membered saturated heteroaryl which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S as ring members. According to one embodiment thereof, the heteroaryl is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b. According to one specific embodiment thereof, said 10-membered saturated heterocycle contains 1 or 2, in par- ticular 1 , heteroatom(s) N.
According to a further specific embodiment of formula I, R4 is Ci-C6-alkyl, especially CH2 subsitited by a 10-membered saturated heteroaryl which one N as ring members. According to one embodiment thereof, the heteroaryl is unsubstituted, i.e. it does not carry any substituent R4b. According to still another embodiment of formula I, it is substituted by R4b.
According to still another embodiment of formula I, R4 is Chb substituted by a 5-membered heteroaryl such as pyrrol-1-yl, pyrrol-2-yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan-2-yl, furan-3-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1 -yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1 ,2,4-triazolyl- 1-yl, 1 ,2,4-triazol-3-yl 1 ,2,4-triazol-5-yl, 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-oxadiazol-5-yl and 1 ,2,4- thiadiazol-3-yl, 1 ,2,4-thiadiazol-5-yl. According to still another embodiment of formula I, R4 is CH2 substituted by a 6-membered het- eroaryl, such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2- yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl.
According to one preferred embodiment, R4c is in each case independently selected from OH, CN, N02, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C(=0)Ci-C4-alkyl), N(C(=0)Ci-C4-alkyl)2, NH-S02-Rx, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(C C6-alkyl), C(=0)NH(C C6-alkyl) or
CR'=NOR".
According to one preferred embodiment, R4c is in each case independently selected from OH, CN, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6-alkyl), C(=0)NH(Ci-C6-alkyl) such as CN, CHO, C(0)CH3, C(0)0(CH3),C02NH(CH3) or C02N(CH3)2.
According to one preferred embodiment, R4c is in each case independently selected from C1-C6- halogenalkylthio, S(0)-Ci-C6-alkyl, S(0)2-Ci-C6-alkyl, S(0)z-Ci-C6-halogenalkyl, S(0)z-aryl, such as SCH3, S02CH3, S02Ph.
According to one preferred embodiment, R4c is in each case independently selected from NH(CrC4-alkyl), N(C C4-alkyl)2, NH(C(=0)d-C4-alkyl), N(C(=0)C C4-alkyl)2, NH-S02-R*, such as NH(CH3), N(CH3)2 or NHS02CH3, NHS02CF3.
According to one preferred embodiment, R4c is in each case independently selected from C3-C6- cycloalkyl, C3-C6-halogencycloalkyl, such as cyclopropyl or fully or partially halogenated cyclo- propyl.
According to one preferred embodiment, R4c is in each case independently selected C1-C6- halogenalkoxy, such as OCF3, OCHF2, OCH2F, OCCI3, OCHCI2 or OCH2CI, in particular OCF3, OCHF2, OCCIs or OCHCI2.
According to one preferred embodiment, R4c is in each case independently selected from heterocycle, wherein the heterocycle is a satureated, two CH2 groups are replaced by C(=0) and contains one N as a ring member.
According to one prefer embodiment, R4 is unsubstituted 5- or 6-membered heteroaryl.
According to still a further embodiment, R4 is 5- or 6-membered heteroaryl substituted by halogen selected from the group consisting of F, CI, Br, CH3, CHF2, OCH3, OCHF2, OCF3, CN or S02CH3.
According to one preferred embodiment, R4c is in each case independently selected from OH, CN, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and heterocycle, wherein the heterocycle is a saturated and contains one N as a ring member.
According to one preferred embodiment, R4c is in each case independently selected from OH, CN, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and heterocycle, wherein the heterocycle is a saturated, one CH2 group is replaced by C(=0) and contains one N as a ring member.
According to one preferred embodiment, R4c is in each case independently selected from OH, CN, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl and heterocycle, wherein the heretocyclocycle is a saturated, two CH2 groups are replaced by C(=0) and contains one N as a ring member.
Particularly preferred embodiments of R4 according to the invention are in Table P4 below, wherein each line of lines P4-1 to P4-101 corresponds to one particular embodiment of the invention, wherein P4-1 to P4-101 are also in any combination with one another a preferred embodiment of the present invention. The connection point to the carbon atom, to which R4 is bound is marked with "#" in the drawings.
Table P4:
Figure imgf000039_0002
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Particularly preferred embodiments of combinations of R3 and R4 according to the invention are in Table P34 below, wherein each line of lines P34-1 to P34-400 corresponds to one particular embodiment of the invention, wherein P34-1 to P34-400 are also in any combination with one another a preferred embodiment of the present invention. The carbon atom, to which R3 and R4 are bound is marked with * in the drawings.
Table P34:
Figure imgf000042_0003
Figure imgf000042_0002
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Rx in the substituent NH-S02-RX is in each case independently selected from Ci-C4-alkyl, C1-C4- halogenalkyl, unsubstituted aryl and aryl that is substituted by one, two, three, four or five substituents Rx1 independently selected from Ci-C4-alkyl, halogen, OH, CN, Ci-C4-halogenalkyl, Ci-C4-alkoxy, and Ci-C4-halogenalkoxy;. In particular, Rx is in each case independently selected from Ci-C4-alkyl and phenyl that is substituted by one, two or three Rx1 independently selected from Ci-C4-alkyl, halogen, OH, CN, Ci-C4-halogenalkyl, Ci-C4-alkoxy, and Ci-C4-halogenalkoxy, more specifically Rx is in each case independently selected from Ci-C4-alkyl and phenyl that is substituted by one CH3, more specifically S02-Rx is the tosyl group ("Ts").
R5 is H. R6 is H.
R7 and R8 together with the carbon atoms to which they are bound together with the carbon atoms to which they are bound form a phenyl ring; wherein the phenyl ring carries zero, one, two, three or four substituents (R78)0, wherein o is 0, 1 , 2 or 3; and R78 are independently selected from halogen, OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl),
N(Ci-C4-alkyl)2, NH(C(=0)C C4-alkyl), N(C(=0)Ci-C4-alkyl)2, NH-S02-R*, CH(=0), C(=0)d-C6- alkyl, C(=0)0(C C6-alkyl), C(=0)NH(C C6-alkyl), CR'=NOR", Ci-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, Ci-C6-alkoxy, Ci-C6-halogenalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C3-C6- cycloalkyl, C3-C6-cycloalkenyl, S(0)z-Ci-C6-alkyl, three-, four-, five- or six-membered saturated or partially unsaturated heterocycle, five- or six-membered heteroaryl and phenyl; wherein the heterocycle or heteroaryl contains one, two or three heteroatoms selected from N, O and S; wherein the heterocycle or heteroaryl contains one, two or three heteroatoms selected from N, O and S; wherein z is 0, 1 or 2; Rx, R' and R" is as defined above;
wherein the acyclic moieties of R78 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R78a which independently of one another are selected from:
R78a halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C3-C6- halogencycloalkyl, C3-C6-halogencycloalkenyl, Ci-C4-halogenalkoxy, Ci-C6-alkylthio, five- or six- membered heteroaryl, phenyl and phenoxy, wherein the heteroaryl, phenyl and phenoxy group is unsubstituted or carries one, two, three, four or five substituents R78a' selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4- halogenalkoxy;
wherein the cyclic, phenyl, heterocyclic and heteroaryl moieties of R78 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R78b which independently of one another are selected from:
R78b halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6- halogencycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio.
According to the invention, there can be zero, one, two or three R78 present, namely for o is 0, 1 , 2 or 3.
According to one embodiment, o is 0.
According to a further embodiment, o is 1 .
According to a further embodiment, o is 2 or 3. According to one specific embodiment thereof, o is 2, according to a further specific embodiment, o is 3.
For every R78 that is present in the inventive compounds, the following embodiments and preferences apply independently of the meaning of any other R78 that may be present in the ring. Furthermore, the particular embodiments and preferences given herein for R78 apply independently for each of o=1 , o=2 and o=3.
According to one specific embodiment, R78 is halogen, in particular F, CI, Br or I, more specifically F, CI or Br, in particular F or CI. According to still another embodiment of formula I, R78 is F.
According to still another embodiment of formula I, R78 is CI.
According to still another embodiment of formula I, R78 is Br.
According to a further specific embodiment, R78 is OH.
According to a further specific embodiment, R78 is CN.
According to a further specific embodiment, R78 is NO2.
According to still another embodiment of formula I, R78 is SH.
According to still another embodiment of formula I, R78 is NH2.
According to still another embodiment of formula I, R78 is , NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, , NH(C(=0)(Ci-C4-alkyl) or N(C(=0)(Ci-C4-alkyl)2, wherein Ci-C4-alkyl is CH3, C2H5, n-propyl, i- propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl.
According to a further specific embodiment of formula I, R78 is NH-S02-RX such as NH-SO2-CH3, NH-SO2-CH2-CH3, NH-SO2-CF3 or NH-SO2-TS.
According to a further specific embodiment of formula I, R78 is CH(=0), C(=0)CrC6-alkyl, C(=0)0(Ci-C6-alkyl) or C(=0)NH(Ci-C6-alkyl), wherein alkyl is CH3, C2H5, n-propyl, i-propyl, n- butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl.
According to a further specific embodiment of formula I, R78 is CR'=NOR" such as
C(CH3)=NOCH3, C(CH3)=NOCH2CH3 or C(CH3)=NOCF3.
According to a further specific embodiment, R78 is Ci-C6-alkyl, in particular Ci-C4-alkyl, such as CH3, C2H5, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl., in particular CH3.
According to a further specific embodiment, R78 is Ci-C6-halogenalkyl, in particular C1-C4- halogenalkyl, such as CF3, CCI3, FCH2, CICH2, F2CH, CI2CH, CF3CH2, CCI3CH2 or CF2CHF2.
According to still another embodiment of formula I R78 is C3-C6-cycloalkyl, in particular cyclopro- pyl.
According to still another embodiment of formula I, R78 is C3-C6-halogencycloalkyl. In a special embodiment R1 is fully or partially halogenated cyclopropyl.
According to still a further embodiment, R78 is C3-C6-cycloalkyl-C2-C6-alkenyl, in particular C3-C6- cycloalkyl-C2-C4-alkenyl, more specifically C3-C6-cycloalkyl-C2-C3-alkenyl, such as C3H5- CH=CH2.
According to a further specific embodiment, R78 is C2-C6-alkenyl, in particular C2-Cs-alkenyl, such as CH=CH2, CH2CH=CH2, C(CH3)=CH2 or CH2CH=C(CH3)2.
According to a further specific embodiment, R78 is C2-C6-halogenalkenyl, in particular C2-C4- halogenalkenyl, more specifically C2-C3-halogenalkenyl such as CH=CHF, CH=CHCI, CH=CF2, CH=CCI2, CH2CH=CHF, CH2CH=CHCI, CH2CH=CF2, CH2CH=CCI2. CH2CF=CF2,
CH2CCI=CCI2. CF2CF=CF2 or CCI2CCI=CCI2.
According to still a further embodiment, R78 is C2-C6-alkynyl, in particular C2-C4-alkynyl, more specifically C2-C3-alkynyl, such as C≡CH.
According to still a further embodiment, R78 is C2-C6-halogenalkynyl, in particular C2-C4- halogenalkynyl, more specifically C2-C3-halogenalkynyl.
According to a further specific embodiment, R78 is Ci-C6-alkoxy, in particular Ci-C4-alkoxy, more specifically Ci-C2-alkoxy such as OCH3 or OCH2CH3.
According to a further specific embodiment, R78 is Ci-C6-halogenalkoxy, in particular C1-C4- halogenalkoxy, more specifically Ci-C2-halogenalkoxy such as OCF3, OCHF2, OCH2F, OCCI3, OCHCI2, OCH2CI and OCF2CHF2, in particular OCF3, OCHF2 and OCF2CHF2.
According to a further specific embodiment of formula I, R78 is C2-C6-alkenyloxy, in particular C2- C4-alkenyloxy, more specifically Ci-C2-alkenyloxy such as OCH=CH2 or OCH2CH=CH2.
According to a further specific embodiment of formula I, R78 is C2-C6-alkynyloxy, in particular C2- C4-alkynyloxy, more specifically Ci-C2-alkynyloxy such as OC CH or OChbC CH.
According to a further specific embodiment of formula I, R78 is S(0)z-Ci-C6-alkyl, wherein alkyl is CH3, C2H5, n-propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl and z is 0, 1 , 2 or 3.
According to a further specific embodiment of formula I, R78 is S(0)z-Ci-C6-halogenalkyl, wherein halogenalkyl is CF3 or CHF2 and z is 0, 1 , 2 or 3.
According to still another embodiment of formula I, R78 is a partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered heterocycle, in particular three-, four-, five- or six-membered, wherein the heterocycle contains one, two, three or four heteroatoms selected from N, O and S, and wherein the heterocycle is unsubstituted or substituted by substituents R78b as defined below. According to one embodiment thereof, the heterocycle is unsubstituted. According to still another embodiment of formula I, R78 is a saturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered heterocycle, in particular three-, four-, five- or six- membered, wherein the heterocycle contains one, two, three or four heteroatoms selected from N, O and S, and wherein the heterocycle is unsubstituted or substituted by substituents R78b as defined below. According to one embodiment thereof, the heterocycle is unsubstituted.
According to still another embodiment of formula I, in the embodiments of R78 described above, the heterocycle contains preferably one, two or three, more specifically one or two heteroatoms selected from N, O and S. More specifically, the hetereocycle contains one heteroatom selected from N, O and S. In particular, the heterocycle contains one or two, in particular one O.
According to one embodiment, R78 is a 4-membered saturated heterocycle which contains 1 or 2 heteroatoms, in particular 1 heteroatom, from the group consisting of N, O and S, as ring members. According to one embodiment, the heterocycle contains one O as heteroatom. For example, the formed heterocycle is oxetane. According to one embodiment thereof, the heterocycle is unsubstituted, i.e. it does not carry any substituent R78b. According to still another embodiment of formula I, it is substituted by R78b.
According to still another embodiment of formula I, R78 is a 5-membered saturated heterocycle which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S, as ring members. According to one embodiment, the heterocycle contains one O as heteroatom. According to one embodiment thereof, the heterocycle is unsubstituted, i.e. it does not carry any substituent R78b. According to still another embodiment of formula I, it is substituted by R78 . According to still another embodiment of formula I, R78 is a 6-membered saturated heterocycle which contains 1 , 2 or 3, in particular 1 or 2, heteroatoms from the group consisting of N, O and S as ring members. According to one embodiment thereof, the heterocycle is unsubstituted, i.e. it does not carry any substituent R78b. According to still another embodiment of formula I, it is substituted by R78b. According to one specific embodiment thereof, said 6-membered saturated heterocycle contains 1 or 2, in particular 1 , heteroatom(s) O. According to one embodiment thereof, the respective 6-membered heterocycle is unsubstituted, i.e. it does not carry any substituent R78b. According to still another embodiment of formula I, it is substituted by R78b.
According to still another embodiment of formula I, R78 is phenyl-Ci-C6-alkyl, such as phenyl- CH2, wherein the phenyl moiety in each case is unsubstituted or substituted by one, two or three identical or different groups R78b which independently of one another are selected from halogen, Ci-C2-alkyl, Ci-C2-alkoxy, Ci-C2-halogenalkyl and Ci-C2-halogenalkoxy, in particular CN, F, CI, Br, CH3, OCH3, CHF2, CF3 OCHF2, and OCF3.
According to still a further specific embodiment, R78 is unsubstituted phenyl or phenyl that is substituted by one, two, three or four R78b, as defined and preferably herein. In particular, R78 is unsubstituted phenyl or phenyl that is substituted by one, two, three or four R78b, as defined herein. In one embodiment R78 is unsubstituted phenyl.
According to still another embodiment of formula I, R78 is a 5-membered heteroaryl such as pyrrol-1 -yl, pyrrol-2-yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan-2-yl, furan-3-yl, pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1-yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1 ,2,4-triazolyl-1 -yl, 1 ,2,4- triazol-3-yl 1 ,2,4-triazol-5-yl, 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-oxadiazol-5-yl and 1 ,2,4-thiadiazol-3-yl, 1 ,2,4-thiadiazol-5-yl.
According to still another embodiment of formula I, R78 is a 6-membered heteroaryl, such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl.
According to one further embodiment, R78 is in each case independently selected from halogen, CN, d-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, d-Ce-alkoxy, d-Ce-halogenalkyl, C2-C6- halogenalkenyl, C2-C6-halogenalkynyl, Ci-C6-halogenalkoxy, C3-C6-alkenyloxy, C3-C6- alkynyloxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, S(0)z-CrC6-alkyl, three-, four-, five- or six-membered saturated or partially unsaturated heterocycle, five- or six-membered heteroaryl and phenyl; wherein the heterocycle or heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the acyclic moieties of R78 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R78a as defined and preferably defined herein, and wherein the heterocyclic, alicyclic, phenyl and heteroaryl moieties of R78 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R78b as defined and preferably defined herein.
According to one further embodiment, R78 is in each case independently selected from halogen, CN, Ci-Ce-alkyl, C2-Ce-alkenyl, C2-Ce-alkynyl, d-Ce-alkoxy, Ci-Ce-halogenalkyl, d-d- halogenalkenyl, C2-C6-halogenalkynyl, Ci-C6-halogenalkoxy, C3-C6-alkenyloxy, d-d- alkynyloxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, S(0)z-Ci-C6-alkyl, three-, four-, five- or six-membered saturated or partially unsaturated heterocycle, five- or six-mem bered heteroaryl and phenyl; wherein the heterocycle or heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein the acyclic moieties of R78 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R78a as defined and preferably defined herein, and wherein the heterocyclic, alicyclic, phenyl and heteroaryl moieties of R78 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R78b as defined and preferably defined herein. Accordingto one specific embodiment, the acyclic and cyclic moieties of R78 are not further substituted, according to another embodiment, the acyclic moieties of R78 carry one, two, three or four identical or different groups R78a as defined and preferably defined herein.
According to a further embodiment, R78 is in each case independently selected from halogen, CN, Ci-Ce-alkyI, C2-Ce-alkenyl, C2-Ce-alkynyl, Ci-Ce-alkoxy, d-Ce-halogenalkyl, C2-C6- halogenalkenyl, C2-C6-halogenalkynyl, Ci-C6-halogenalkoxy, C3-C6-alkenyloxy, C3-C6- alkynyloxy, C3-C6-cycloalkyl C3-C6-halogencycloalkyl, and S(0)z-CrC6-alkyl, wherein the acyclic moieties of R78 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R78a as defined and preferably defined herein, and wherein the cycloalkyl moieties of R78 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R78b as defined and preferably defined herein.
According to a further embodiment, R78 is in each case independently selected from halogen, CN, Ci-Ce-alkyI, C2-C6-alkenyl, C2-C6-alkynyl, Ci-Ce-alkoxy, Ci-C6- Ci-C6-halogenalkyl, C2-C6- halogenalkenyl, C2-C6-halogenalkynyl, Ci-C6-halogenalkoxy, C3-C6-alkenyloxy, C3-C6- alkynyloxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, and S(0)z-Ci-C6-alkyl, wherein the acyclic moieties of R78 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R78a as defined and preferably defined herein, and wherein the cycloalkyl moieties of R78 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R78b as defined and preferably defined herein. Accordingto one specific embodiment, the acyclic and cyclic moieties of R78 are not further substituted, according to another embodiment, the acyclic moieties of R78 carry one, two, three or four identical or different groups R78a as defined and preferably defined herein.
According to still a further embodiment, R78 is in each case independently selected from halogen, Ci-C6-alkyl and Ci-C6-alkoxy, wherein the acyclic moieties of R78 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R78a defined and preferably defined herein.
According to still a further embodiment, R78 is in each case independently selected from CN, halogen, Ci-C6-alkyl, Ci-C6-halogenalkyl, Ci-C6-alkoxy and Ci-C6-halogenalkoxy, wherein the acyclic moieties of R78 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R78a defined and preferably defined herein. Ac- cordingto one specific embodiment, the acyclic and cyclic moieties of R78 are not further substituted, according to another embodiment, the acyclic moieties of R78 carry one, two, three or four identical or different groups R78a as defined and preferably defined herein. R78a are the possible substituents for the acyclic moieties of R78. R78a is independently selected from halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C3-C6- halogencycloalkyl, C3-C6-halogencycloalkenyl, Ci-C4-halogenalkoxy, Ci-C6-alkylthio, five- or six- membered heteroaryl, phenyl and phenoxy, wherein the heteroaryl, phenyl and phenoxy group is unsubstituted or carries one, two, three, four or five substituents R78a' selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and C1-C4- halogenalkoxy.
According to one embodiment R78a is independently selected from halogen, Ci-C6-alkoxy, C3- C6-cycloalkyl, C3-C6-halogencycloalkyl and Ci-C4-halogenalkoxy. Specifically, R78a is
independently selected from F, CI, Br, I, Ci-C2-alkoxy, cyclopropyl, 1 -F-cyclopropyl, 1-CI- cyclopropyl, 1 ,1 -F2-cyclopropyl, 1 ,1-Cl2-cyclopropyl and Ci-C2-halogenalkoxy.
According to a further embodiment, R78a is independently halogen, in particular selected from F, CI, Br and I, more specifically F, CI and Br.
R78b are the possible substituents for the cycloalkyi, heterocyclyl, heteroaryl and phenyl moieties of R78. R78b according to the invention is independently selected from halogen, OH, CN, C1-C4- alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, C1-C4- halogenalkoxy and Ci-C6-alkylthio.
According to one embodiment thereof R78b is independently selected from halogen, CN, C1-C4- alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl and Ci-C4-halogenalkoxy, in particular halogen, C1-C4- alkyl and Ci-C4-alkoxy. Specifically, R78b is independently selected from F, CI, CN, CH3, OCH3 and halogenmethoxy.
Particularly preferred embodiments of R7 and R8, optionally substituted by (R78)0, according to the invention are in Table P78 below, wherein each line of lines P78-1 to P78-61 corresponds to one particular embodiment of the invention, wherein P78-1 to P78-61 are also in any combination with one another a preferred embodiment of the present invention. Thereby, the positions of the heteroaryls marked with "#" represents the connection points (carbon atoms 5' and 6' in formula I) with the remaining skeleton of the compounds of formula I:
Figure imgf000061_0002
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
R9 is in each case independently selected from hydrogen, OH, CH(=0), C(=0)Ci-C6-alkyl, C(=0)C2-C6-alkenyl, C(=0)C3-C6-cycloalkyl, C(=0)0(Ci-C6-alkyl), C(=0)0(C2-C6-alkenyl), C(=0)0(C2-C6-alkynyl), C(=0)0(C3-C6-cycloalkyl), C(=0)N H(Ci-C6-alkyl), C(=0)NH(C2-C6- alkenyl), C(=0)NH(C2-C6-alkynyl), C(=0)NH(C3-C6-cycloalkyl), C(=0)N(Ci-C6-alkyl)2,
C(=0)N(C2-C6-alkenyl)2, C(=0)N(C2-C6-alkynyl)2, C(=0)N(C3-C6-cycloalkyl)2, CH(=S), C(=S)Ci- Ce-alkyl, C(=S)C2-C6-alkenyl, C(=S)C2-C6-alkynyl, C(=S)C3-C6-cycloalkyl, , C(=S)0(Ci-C6-alkyl), C(=S)0(C2-C6-alkenyl), C(=S)0(C2-C6-alkynyl), C(=S)0(C3-C6-cycloalkyl), C(=S)NH(Ci-C6- alkyl), C(=S)NH(C2-C6-alkenyl), C(=S)N H(C2-C6-alkynyl), C(=S)NH(C3-C6-cycloalkyl),
C(=S)N(Ci-C6-alkyl)2, C(=S)N(C2-C6-alkenyl)2, C(=S)N(C2-C6-alkynyl)2, C(=S)N(C3-C6- cycloalkyl)2, Ci-C6-alkyl, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, C1-C4- alkoxy, Ci-C4-halogenalkoxy, ORY, C2-C6-alkenyl, C2-C6-halogenalkenyl C2-C6-alkynyl, C2-C6- halogenalkynyl, S(0)z-Ci-C6-alkyl, S(0)z-Ci-C6-halogenalkyl, S(0)z-C2-C6-alkenyl, S(0)z-C2-C6- alkynyl, S(0)z-aryl, S02-NH(Ci-C6-alkyl), S02-NH(Ci-C6-halogenalkyl), S02-NH-aryl, tri-(Ci-C6 alkyl)silyl and di-(Ci-C6 alkoxy)phosphoryl), five- or six-membered heteroaryl and aryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; wherein the aryl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN , halogen, OH , Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and C1-C4- halogenalkoxy; wherein z is 0, 1 or 2;
RY is Ci-C6-alkyl, Ci-C6-halogenalkyl, C2-C6-alkenyl, C2-C6-halogenalkenyl, C2-C6-alkynyl, C2-C6- halogenalkynyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, phenyl and phenyl-Ci-C6-alkyl;
wherein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN , halogen, OH , Ci-C4-alkyl, Ci-C4-halogenalkyl, C1-C4- alkoxy and Ci-C4-halogenalkoxy;
R9a is the subtituent of the acyclic moieties of R9. The acyclic moieties of R9 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R9a which independently of one another are selected from halogen, OH , CN , Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C3-C6-halogencycloalkyl, C3-C6- halogencycloalkenyl, Ci-C4-halogenalkoxy, Ci-C6-alkylthio, five- or six-membered heteroaryl, phenyl and phenoxy, wherein the heteroaryl, phenyl and phenoxy group is unsubstituted or carries one, two, three, four or five substituents R9a' selected from the group consisting of halogen, OH , Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy;
R9b is the subtituyend of cycloalkyl, phenyl, heterocyclic and heteroaryl moieties of R9. The alicyclic, phenyl, heterocyclic and heteroaryl moieties of R9 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R9b which independently of one another are selected from halogen, OH , CN , Ci-C4-alkyl, C1-C4- alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy and d-Ce-alkylthio.
According to one embodiment of formula I, R9 is H .
According to still another embodiment of formula I, R9 is OH .
According to a further specific embodiment of formula I, R9 is CH(=0).
According to a further specific embodiment of formula I, R9 is C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6- alkyl), C(=0)N H(Ci-C6-alkyl) or C(=0)N(Ci-C6-alkyl)2, wherein alkyl is CH3, C2H5, n-propyl, i- propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl.
According to a further specific embodiment of formula I, R9 is C(=0)C2-C6-alkenyl, C(=0)0(C2- Ce-alkenyl), C(=0)N H(C2-C6-alkenyl) or C(=0)N(C2-C6-alkenyl)2), wherein alkenyl is CH=CH2, CH2CH=CH2.
According to a further specific embodiment of formula I, R9 is C(=0)C2-C6-alkynyl, C(=0)0(C2- Ce-alkynyl), C(=0) N H(C2-C6-alkynyl) or C(=0)N(C2-C6-alkynyl)2, wherein alkynyl is C≡CH, CH2C≡CH . According to a further specific embodiment of formula I, R9 is C(=0)C3-C6-cycloalkyl,
C(=0)0(C3-C6-cycloalkyl), C(=0)NH(C3-C6-cycloalkyl) or C(=0)N(C3-C6-cycloalkyl)2, wherein cycloalkyl is cyclopropyl (C3H7) or cyclobutyl (C4H9).
According to a further specific embodiment of formula I, R9 is CH(=S).
According to a further specific embodiment of formula I, R9 is C(=S)Ci-C6-alkyl, C(=S)0(Ci-C6- alkyl), C(=S)NH(C C6-alkyl) or C(=S)N(Ci-C6-alkyl)2, wherein alkyl is CH3, C2H5, n-propyl, i- propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl.
According to a further specific embodiment of formula I, R9 is C(=S)C2-C6-alkenyl, C(=S)0(C2- Ce-alkenyl), C(=S)NH(C2-C6-alkenyl) or
Figure imgf000067_0001
wherein alkenyl is CH=CH2 or CH2CH=CH2.
According to a further specific embodiment of formula I, R9 is C(=S)0(C2-C6-alkynyl),
C(=S)NH(C2-C6-alkynyl) or C(=S)N(C2-C6-alkynyl)2, wherein alkynyl is C≡CH or CH2C≡CH.
According to a further specific embodiment of formula I, R9 is C(=S)C3-C6-cycloalkyl,
C(=S)0(C3-C6-cycloalkyl) or C(=S)N(C3-C6-cycloalkyl)2, wherein cycloalkyl is cyclopropyl (C3H7) or cyclobutyl (C4H9).
According to still another embodiment of formula I, R9 is Ci-C6-alkyl, such as CH3, C2H5, n- propyl, i-propyl, n-butyl, i-butyl, tert-butyl, n-pentyl or i-pentyl.
According to still another embodiment of formula I, R9 is Ci-C6-alkyl, in particular Ci-C4-alkyl, such as CH3, C2H5, n-propyl, i-propyl.
According to still another embodiment of formula I, R9 is Ci-C6-halogenalkyl, in particular C1-C4- halogenalkyl, such as CF3, CCI3, FCH2, CICH2, F2CH, CI2CH, CF3CH2, CCI3CH2 or CF2CHF2.
According to still another embodiment of formula I R9 is C3-C6-cycloalkyl, in particular cyclopropyl.
According to still another embodiment of formula I, R9 is C3-C6-halogencycloalkyl. In a special embodiment R9b is fully or partially halogenated cyclopropyl, such as 1 -F-cyclopropyl, 1 -CI- cyclopropyl, 1 ,1 -F2-cyclopropyl, 1 ,1-CI2-cyclopropyl .
According to a further specific embodiment of formula I, R9 is ORY, wherein RY is Ci-C6-alkyl, Ci- C6-halogenalkyl, C2-C6-alkenyl, C2-C6-halogenalkenyl, C2-C6-alkynyl, C2-C6-halogenalkynyl, C3- C6-cycloalkyl, C3-C6-halogencycloalkyl, phenyl and phenyl-Ci-C6-alkyl; wherein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and C1-C4- halogenalkoxy;
According to a further specific embodiment of formula I, R9 is ORY, wherein RY is Ci-C6-alkyl, in particular Ci-C4-alkyl, more specifically Ci-C2-alkyl. R9 is such as OCH3 or OCH2CH3.
According to a further specific embodiment of formula I, R9 is ORY, wherein RY is C1-C6- halogenalkyl, in particular Ci-C4-halogenalkyl, more specifically Ci-C2-halogenalkyl. R9 is such as OCF3, OCHF2, OCH2F, OCCI3, OCHCI2 or OCH2CI, in particular OCF3, OCHF2, OCCI3 or OCHCI2.
According to a further specific embodiment of formula I, R9 is ORY wherein RY C2-C6-alkenyl, in particular C2-C4-alkenyl, more specifically Ci-C2-alkenyl. R9 is such as OCH=CH2, OCH2CH=CH2.
According to a further specific embodiment of formula I, R9 is ORY, wherein RY C2-C6-alkynyl, in particular C2-C6-alkynyl, in particular C2-C4-alkynyl, more specifically Ci-C2-alkynyl. R9 is such as OC≡CH or OCH2C≡CH.
According to still another embodiment of formula I, R9 is ORY wherein RY is C3-C6- halogencycloalkyl. In a special embodiment R1 is fully or partially halogenated cyclopropyl.
According to still another embodiment of formula I, R9 is is ORY, wherein RY and phenyl; wherein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy.
According to still another embodiment of formula I, R9 is is ORY, wherein RY phenyl-Ci-C6-alkyl, such as phenyl-Chb, herein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, C1-C4- halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy. R9 is such as OCH2Ph.
According to still a further embodiment of formula I, R9 is C2-C6-alkenyl, in particular C2-C4-alk- enyl, such as CH=CH2, C(CH3)=CH2, CH2CH=CH2.
According to a further specific embodiment of formula I, R9 is C2-C6-halogenalkenyl, in particular C2-C4-halogenalkenyl, more specifically C2-C3-halogenalkenyl such as CH=CHF, CH=CHCI, CH=CF2, CH=CCI2, CH2CH=CHF, CH2CH=CHCI, CH2CH=CF2, CH2CH=CCI2, CF2CH=CF2, CCI2CH=CCI2, CF2CF=CF2, CCI2CCI=CCI2.
According to still a further embodiment of formula I, R9 is C2-C6-alkynyl or C2-C6-halogenalkynyl, in particular C2-C4-alkynyl or C2-C4-halogenalkynyl, such as C CH, CH2C=CH, C CCI or CH2C≡CCI.
According to still another embodiment of formula I, R9 is S(0)z-Ci-C6-alkyl such as SCH3, S(=0) CH3, S(0)2CH3.
According to still another embodiment of formula I, R9 is S(0)z-Ci-C6-halogenalkyl such as SCFs, S(=0)CF3, S(0)2CF3, SCHF2, S(=0)CHF2, S(0)2CHF2.
According to still another embodiment of formula I, R9 is S(0)z-aryl such as S-phenyl, S(=0) phenyl, S(0)2phenyl, wherein the phenyl group is unsubstituted or carries one, two, three, four or five substituents R78a' selected from the group consisting of halogen, OH, Ci-C4-alkyl, C1-C4- halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy;
According to still another embodiment of formula I, R9 is S(0)z-C2-C6-alkenyl such as
SCH=CH2, S(=0)CH=CH2, S(0)2CH=CH2, SCH2CH=CH2, S(=0)CH2CH=CH2,
S(0)2CH2CH=CH2 .
According to still another embodiment of formula I, R9 is S(0)z-C2-C6-alkynyl such as SC CH, S(=0)C≡CH, S(0)2C≡CH, SCH2C≡CH, S(=0)CH2C≡CH, S(0)2CH2C≡CH.
According to still another embodiment of formula I, R9 is S(0)z-aryl, wherein the aryl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consist- ing of CN, halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and C1-C4- halogenalkoxy. R9 is such as SPh, SOPh, or S02Ph.
According to still another embodiment of formula I , R9 is SC>2-NH(Ci-C6-alkyl), is Ci-C6-alkyl, in particular Ci-C4-alkyl, more specifically Ci-C2-alkyl. R9 is such as SO2NHCH3 or SO2NHCH2CH3. According to still another embodiment of formula I , R9 is SC>2-NH(Ci-C6-halogenalkyl), wherein Ci-C6-halogenalkyl, in particular Ci-C4-halogenalkyl, more specifically Ci-C2-halogenalkyl. R9 is such as SO2NHCF3, SO2NHCHF2, SO2NHCH2F, SO2NHCCI3, SO2NHCHCI2 or S02NHCH2CI, in particular SO2NHCF3, SO2NHCHF2, SO2NHCCI3 or SO2NHCHCI2.
According to still another embodiment of formula I , R9 is S02-NH-aryl, wherein the aryl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and C1-C4- halogenalkoxy. . R9 is such as S02NHPh.
According to still another embodiment of formula I , R9 is tri-(Ci-C6 alkyl)silyl, in particular C1-C4- alkyl, such as CH3. or C2H5. R9 is such as OSi(CH3)3
According to still another embodiment of formula I , R9 is di-(Ci-C6 alkoxy)phosphoryl), in particular Ci-C4-alkoxy, such as OCH3. or OC2H5. R9 is such as OPO(OCH3)2.
According to still another embodiment of formula I , R9 is phenyl-Ci-C6-alkyl, such as phenyl- CH2, wherein the phenyl moiety in each case is unsubstituted or substituted by one, two or three identical or different groups R9b which independently of one another are selected from halogen, Ci-C2-alkyl, Ci-C2-alkoxy, Ci-C2-halogenalkyl and Ci-C2-halogenalkoxy, in particular F, CI, Br, CH3, CHF2, OCH3, OCHF2, CF3 and OCF3.
According to still another embodiment of formula I , R9 is aryl, in particular phenyl, wherein the aryl or phenyl moiety in each case is unsubstituted or substituted by identical or different groups R9b which independently of one another are selected from halogen, Ci-C2-alkyl, Ci-C2-alkoxy, Ci-C2-halogenalkyl and Ci-C2-halogenalkoxy, in particular F, CI, Br, CH3, CHF2, OCH3, OCHF2, CF3 and OCF3. According to one embodiment, R9 is unsubstituted phenyl. According to another embodiment, R9 is phenyl, that is substituted by one, two or three, in particular one, halogen, in particular selected from F, CI and Br, more specifically selected from F and CI.
According to still another embodiment of formula I , R9 is a 5-membered heteroaryl such as pyr- rol-1 -yl, pyrrol-2-yl, pyrrol-3-yl, thien-2-yl, thien-3-yl, furan-2-yl, furan-3-yl, pyrazol-1 -yl, pyrazol- 3-yl, pyrazol-4-yl, pyrazol-5-yl, imidazol-1 -yl, imidazol-2-yl, imidazol-4-yl, imidazol-5-yl, oxazol-2- yl, oxazol-4-yl, oxazol-5-yl, isoxazol-3-yl, isoxazol-4-yl, isoxazol-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, 1 ,2,4-triazolyl-1 -yl, 1 ,2,4-triazol-3-yl 1 ,2,4-triazol-5-yl, 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-oxadiazol-5-yl and 1 ,2,4-thiadiazol-3-yl,
1 ,2,4-thiadiazol-5-yl.
According to still another embodiment of formula I , R9 is a 6-membered heteroaryl such as pyri- din-2-yl, pyridin-3-yl, pyridin-4-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyrazin-2-yl and 1 ,3,5-triazin-2-yl and 1 ,2,4-triazin-3-yl.
According to still another embodiment of formula I , R9 is in each case independently selected from H, OH, Ci-C6-alkyl, Ci-C6-halogenalkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy, Ci-C6- halogenalkoxy, and C3-C6-cycloalkyl wherein the acyclic moieties of R9 are unsubstituted or substituted with identical or different groups R9a as defined and preferably defined herein, and wherein the carbocyclic, phenyl and heteroaryl moieties of R9 are unsubstituted or substituted with identical or different groups R9b as defined and preferably defined herein.
According to still another embodiment of formula I, R9 is in each case independently selected from H, OH, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-alkoxy and C3-C6-cycloalkyl, wherein the acyclic moieties of R9 are unsubstituted or substituted with identical or different groups R9a as defined and preferably defined herein, and wherein the cycloalkyl moieties of R9 are unsubstituted or substituted with identical or different groups R9b as defined and preferably defined herein.
According to still another embodiment of formula I, R9 is in each case independently selected from H and ORY, wherein RY is most preferably Ci-C6-alkyl, Ci-C6-halogenalkyl, C2-C6-alkenyl, C2-C6-halogenalkenyl, C2-C6-alkynyl, C2-C6-halogenalkynyl, phenyl and phenyl-Ci-C6-alkyl; wherein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, C1-C4- alkoxy and Ci-C4-halogenalkoxy.
According to still another embodiment of formula I, R9 is in each case independently selected from H and ORY, wherein RY is most preferably C2-C6-alkenyl, C2-C6-alkynyl, phenyl and phenyl- Ci-C6-alkyl; wherein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy.
According to still another embodiment of formula I, R9 is in each case independently selected from H, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6-alkyl), C(=0)NH(Ci-C6-alkyl),
Figure imgf000070_0001
alkyl)2, C(=0)C2-C6-alkenyl, C(=0)0(C2-C6-alkenyl), C(=0)NH(C2-C6-alkenyl), C(=0)N(C2-C6- alkenyl)2, C(=0)C2-C6-alkynyl, C(=0)0(C2-C6-alkynyl), C(=0)NH(C2-C6-alkynyl), C(=0)N(C2-C6- alkynyl)2C(=0)C3-C6-cycloalkyl, C(=0)0(C3-C6-cycloalkyl), C(=0)NH(C3-C6-cycloalkyl) and C(=0)N(C3-C6-cycloalkyl)2, wherein the acyclic moieties of R9 are unsubstituted or substituted with identical or different groups R9a as defined and preferably defined herein, and wherein the cycloalkyl moieties of R9 are unsubstituted or substituted with identical or different groups R9b as defined and preferably defined herein.
According to still another embodiment of formula I, R9 is in each case independently selected from H, C(=0)Ci-C6-alkyl, C(=0)0(d-C6-alkyl), C(=0)NH(C C6-alkyl), C(=0)N(Ci-C6-alkyl)2, C(=0)C2-C6-alkenyl, C(=0)0(C2-C6-alkenyl), C(=0)NH(C2-C6-alkenyl), C(=0)N(C2-C6-alkenyl)2, wherein the acyclic moieties of R9 are unsubstituted or substituted with identical or different groups R9a as defined and preferably defined herein.
According to still another embodiment of formula I, R9 is in each case independently selected from H, C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6-alkyl), C(=0)NH(Ci-C6-alkyl), C(=0)N(Ci-C6-alkyl)2; wherein the acyclic moieties of R9 are unsubstituted or substituted with identical or different groups R9a as defined and preferably defined herein.
According to still another embodiment of formula I, R9 is in each case independently selected from H, S(0)z-Ci-C6-alkyl, S(0)z-Ci-C6-halogenalkyl, S(0)z-C2-C6-alkenyl, S(0)z-C2-C6-alkynyl, S(0)zaryl, wherein the acyclic moieties of R9 are unsubstituted or substituted with identical or different groups R9a as defined and preferably defined herein, and wherein the aryl moieties of R9 are unsubstituted or substituted with identical or different groups R9b as defined and preferably defined herein.
According to still another embodiment of formula I, R9 is in each case independently selected from H, S02-NH(Ci-C6-alkyl), S02-NH(Ci-C6-halogenalkyl), S02-NHphenyli wherein the acyclic moieties of R9 are unsubstituted or substituted with identical or different groups R9a as defined and preferably defined herein, and wherein the aryl moieties of R9 are unsubstituted or substituted with identical or different groups R9b as defined and preferably defined herein.
According to still another embodiment of formula I, R9 is in each case independently selected from H, Ci-Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6-alkyl), C(=0)NH(Ci-C6-alkyl), C(=0)N(Ci-C6-alkyl)2, S(0)z-Ci-C6-alkyl, S02-NHphenyl and S(0)zaryl; wherein the acyclic moieties of R9 are unsubstituted or substituted with identical or different groups R9a as defined and preferably defined herein, and wherein the aryl moieties of R9 are unsubstituted or substituted with identical or different groups R9b as defined and preferably defined herein.
R9a are the possible substituents for the acyclic moieties of R9. According to one embodiment R9a is independently selected from halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6- cycloalkenyl, C3-C6-halogencycloalkyl, C3-C6-halogencycloalkenyl, Ci-C4-halogenalkoxy, C1-C6- alkylthio, five- or six-membered heteroaryl, phenyl and phenoxy, wherein the heteroaryl, phenyl and phenoxy group is unsubstituted or carries one, two, three, four or five substituents R9a' se- lected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy or Ci-C4-halogenalkoxy.
According to one embodiment R9a is independently selected from halogen, Ci-C6-alkoxy, C3-C6- cycloalkyl, C3-C6-halogencycloalkyl and Ci-C4-halogenalkoxy. Specifically, R9a is independently selected from F, CI, Br, I, Ci-C2-alkoxy, cyclopropyl, 1 -F-cyclopropyl, 1-CI-cyclopropyl, 1 ,1 -F2- cyclopropyl, 1 ,1 -CI2-cyclopropyl and Ci-C2-halogenalkoxy.
According to still another embodiment of formula I, R9a is independently halogen, in particular selected from F, CI, Br and I, more specifically F, CI and Br.
R9b are the possible substituents for the cycloalkyi, heteroaryl and phenyl moieties of R9. R9b according to the invention is independently selected from halogen, OH, CN, Ci-C4-alkyl, C1-C4- alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy and d-Ce-alkylthio.
According to one embodiment thereof R9b is independently selected from halogen, CN, C1-C4- alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl and Ci-C4-halogenalkoxy, in particular halogen, C1-C4- alkyl and Ci-C4-alkoxy. Specifically, R9b is independently selected from F, CI, Br, CN, CH3, CHF2, CF3, OCHs and halogenmethoxy.
Particularly preferred embodiments of R9 according to the invention are in Table P13 below, wherein each line of lines P13-1 to P3-50 corresponds to one particular embodiment of the invention, wherein P13-1 to P3-50 are also in any combination with one another a preferred embodiment of the present invention. The connection point to the carbon atom, to which R9 is bound is marked with "#" in the drawings. Table P9:
Figure imgf000072_0001
Figure imgf000072_0002
Particular embodiments of the compounds I are the following compounds: 1-1.A, 1-1 .B, 1-1.C, I- 1.D; I-2.A, I-2.B, I-2.C, I-2.D; I-3.A, I-3.B, I-3.C, I-3.D; I-4.A, I-4.B, I-4.C, I-4.D that are compiled in the Tables 1-1 to 1-4. Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000074_0002
Figure imgf000075_0001
Table 1-1 Compounds of the formula 1-1.A, I-2.A, I-3.A, I-4.A in which the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-1.A.1 -1.A-1 to I-1 .A.1-1 .A-513, compounds I-2.A.1-1.A-1 to I-2.A.1 -1.A- 513, compounds I-3.A.1-1 .A-1 to I-3.A.1 -1.A-513 compounds I-4.A.1-1 .A-1 to I-4.A.1-1.A-513).
Table 1-2 Compounds of the formula 1-1.B, I-2.B, I-3.B, I-4.B in which the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-1.B.1 -2.A-1 to I-1 .B.1-2.A-513, compounds I-2.B.1-2.A-1 to I-2.B.1 -2.A- 513, compounds I-3.B.1-2.A-1 to I-3.B.1 -2.A-513 compounds I-4.B.1-2.A-1 to I-4.B.1-2.A-513).
Table 1-3 Compounds of the formula 1-1 C, I-2C, I-3C, I-4C in which the meaning for the combination of R4 and R78for each individual compound corresponds in each case to one line of Table A (compounds l-1 C.1-3.A-1 to I-1 C.1 -3.A-513, compounds l-2C.1 -3.A-1 to I-2C.1 -3.A- 513, compounds l-3C.1 -3.A-1 to I-3C.1-3.A-513 compounds l-4C.1 -3.A-1 to I-4C.1-3.A-513).
Table 1-4 Compounds of the formula 1-1.D, I-2.D, I-3.D, I-4.D in which the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-1.D.1-4.A-1 to I-1.D.1-4.A-513, compounds I-2.D.1 -4.A-1 to I-2.D.1 -4.A- 513, compounds I-3.D.1 -4.A-1 to I-3.D.1 -4.A-513 compounds I-4.D.1-4.A-1 to I-4.D.1-4.A-513).
Particular embodiments of the compounds I are the following compounds: I-5.A, 1-15.B, I-5.C, I- 5.D; I-6.A, I-6.B, I-6.C, I-6.D; I-7.A, I-7.B, I-7.C, I-7.D; I-8.A, I-8.B, I-8.C, I-8.D that are compiled in the Tables 1-1 to 1-13, Tables 2-1 to 2-13, Tables 3-1 to 3-13 and Tables 4-1 to 4-13. Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000077_0002
Figure imgf000078_0001
Table 1-1
Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R9 is H and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -1.A-1 to I-5.A.1-1 .A-513, compounds I-6.A.1-1.A-1 to I-6.A.1 -1.A- 513, compounds I-7.A.1-1 .A-1 to I-7.A.1 -1.A-513 compounds I-8.A.1-1 .A-1 to I-8.A.1-1. A-513).
Table 1-2 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R9 is CH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -2.A-1 to I-5.A.1-2.A-513, compounds I-6.A.1 -2.A-1 to I- 6.A.1-2.A-513, compounds I-7.A.1-2.A-1 to I-7.A.1 -2.A-513 compounds I-8.A.1-2.A-1 to I-8.A.1 -
2. A-513).
Table 1-3 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R9 is C2H5 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -3.A-1 to I-5.A.1 -3.A-513, compounds I-6.A.1-
3. A-1 to I-6.A.1 -3.A-513, compounds I-7.A.1-3.A-1 to I-7.A.1 -3.A-513 compounds I-8.A.1-3.A-1 to I-8.A.1-3.A-513).
Table 1-4 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R9 is CH2CH=CH2 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1-4.A-1 to I-5.A.1 -4.A-513, compounds I- 6.A.1-4.A-1 to I-6.A.1-4.A-513, compounds I-7.A.1-4.A-1 to I-7.A.1-4.A-513 compounds I-8.A.1-
4. A-1 to I-8.A.1 -4.A-513).
Table 1-5 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R9 is CH2C≡CH and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -5.A-1 to I-5.A.1 -5.A-513, compounds I-6.A.1- 5. A-1 to I-6.A.1 -5.A-513, compounds I-7.A.1-5.A-1 to I-7.A.1 -5.A-513 compounds I-8.A.1-5.A-1 to I-8.A.1-5.A-513).
Table 1-6 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R9 is C(0)CH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -6.A-1 to I-5.A.1 -6.A-513, compounds I-6.A.1-
6. A-1 to I-6.A.1 -6.A-513, compounds I-7.A.1-6.A-1 to I-7.A.1 -6.A-513 compounds I-8.A.1-6.A-1 to I-8.A.1-6.A-513).
Table 1-7 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R9 is C(0)OCH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -7.A-1 to I-5.A.1 -7.A-513, compounds I-6.A.1-
7. A-1 to I-6.A.1 -7.A-513, compounds I-7.A.1-7.A-1 to I-7.A.1 -7.A-513 compounds I-8.A.1-7.A-1 to I-8.A.1-7.A-513).
Table 1-8 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R9 is C=0-NH(CH3) and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1-8.A-1 to I-5.A.1 -8.A-513, compounds I- 6.A.1-8.A-1 to I-6.A.1-8.A-513, compounds I-7.A.1-8.A-1 to I-7.A.1-8.A-513 compounds I-8.A.1-
8. A-1 to I-8.A.1 -8.A-513).
Table 1-9 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R9 is CO-N(CH3)2 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1-9.A-1 to I-5.A.1 -9.A-513, compounds I- 6.A.1-9.A-1 to I-6.A.1-9.A-513, compounds I-7.A.1-9.A-1 to I-7.A.1-9.A-513 compounds I-8.A.1-
9. A-1 to I-8.A.1 -9.A-513).
Table 1-10 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R9 is S02-CH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -10.A-1 to I-5.A.1-10.A-513, compounds I-6.A.1-
10. A-1 to I-6.A.1-10.A-513, compounds I-7.A.1-10.A-1 to I-7.A.1 -10.A-513 compounds I-8.A.1-
10. A-1 to I-8.A.1-10.A-513).
Table 1-1 1 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R9 is S02NHCH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -1 1 .A-1 to I-5.A.1-1 1.A-513, compounds I-6.A.1-
1 1. A-1 to I-6.A.1-1 1.A-513, compounds I-7.A.1-1 1 .A-1 to I-7.A.1 -1 1 .A-513 compounds I-8.A.1-
1 1. A-1 to I-8.A.1-1 1. A-513).
Table 1-12 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R9 is S02NHPh and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -12.A-1 to I-5.A.1-12.A-513, compounds I-6.A.1-
12. A-1 to I-6.A.1-12.A-513, compounds I-7.A.1-12.A-1 to I-7.A.1 -12.A-513 compounds I-8.A.1-
12. A-1 to I-8.A.1-12.A-513).
Table 1-13 Compounds of the formula I-5.A, I-6.A, I-7.A, I-8.A in which R9 is S02Ph and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.A.1 -13.A-1 to I-5.A.1-13.A-513, compounds I-6.A.1-
13. A-1 to I-6.A.1-13.A-513, compounds I-7.A.1-13.A-1 to I-7.A.1 -13.A-513 compounds I-8.A.1- 13.A-1 to I-8.A.1-13.A-513).
Table 2-1 Compounds of the formula I-5.B, I-6.B, I-7.B, I-8.B in which R9 is H and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-1 .A-1 to I-5.B.2-1.A-513, compounds I-6.B.2-1.A-1 to I- 6.B.2-1.A-513, compounds I-7.B.2-1 .A-1 to I-7.B.2-1.A-513 compounds I-8.B.2-1 .A-1 to I-8.B.2-
1. A-513).
Table 2-2 Compounds of the formula I-5.B, I-6.B, I-7.B, I-8.B in which R9 is CH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-2.A-1 to I-5.B.2-2.A-513, compounds I-6.B.2-2.A-1 to I- 6.B.2-2.A-513, compounds I-7.B.2-2.A-1 to I-7.B.2-2.A-513 compounds I-8.B.2-2.A-1 to I-8.B.2-
2. A-513).
Table 2-3 Compounds of the formula I-5.B, I-6.B, I-7.B, I-8.B in which R9 is C2H5 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-3.A-1 to I-5.B.2-3.A-513, compounds I-6.B.2-
3. A-1 to I-6.B.2-3.A-513, compounds I-7.B.2-3.A-1 to I-7.B.2-3.A-513 compounds I-8.B.2-3.A-1 to I-8.B.2-3.A-513).
Table 2-4 Compounds of the formula I-5.B, I-6.B, I-7.B, I-8.B in which R9 is CH2CH=CH2 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-4.A-1 to I-5.B.2-4.A-513, compounds I- 6.B.2-4.A-1 to I-6.B.2-4.A-513, compounds I-7.B.2-4.A-1 to I-7.B.2-4.A-513 compounds I-8.B.2-
4. A-1 to I-8.B.2-4.A-513).
Table 2-5 Compounds of the formula I-5.B, I-6.B, I-7.B, I-8.B in which R9 is CH2C≡CH and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-5.A-1 to I-5.B.2-5.A-513, compounds I-6.B.2-
5. A-1 to I-6.B.2-5.A-513, compounds I-7.B.2-5.A-1 to I-7.B.2-5.A-513 compounds I-8.B.2-5.A-1 to I-8.B.2-5.A-513).
Table 2-6 Compounds of the formula I-5.B, I-6.B, I-7.B, I-8.B in which R9 is C(0)CH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-6.A-1 to I-5.B.2-6.A-513, compounds I-6.B.2-
6. A-1 to I-6.B.2-6.A-513, compounds I-7.B.2-6.A-1 to I-7.B.2-6.A-513 compounds I-8.B.2-6.A-1 to I-8.B.2-6.A-513).
Table 2-7 Compounds of the formula I-5.B, I-6.B, I-7.B, I-8.B in which R9 is C(0)OCH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-7.A-1 to I-5.B.2-7.A-513, compounds I-6.B.2-
7. A-1 to I-6.B.2-7.A-513, compounds I-7.B.2-7.A-1 to I-7.B.2-7.A-513 compounds I-8.B.2-7.A-1 to I-8.B.2-7.A-513).
Table 2-8 Compounds of the formula I-5.B, I-6.B, I-7.B, I-8.B in which R9 is C=0-NH(CH3) and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-8.A-1 to I-5.B.2-8.A-513, compounds I- 6.B.2-8.A-1 to I-6.B.2-8.A-513, compounds I-7.B.2-8.A-1 to I-7.B.2-8.A-513 compounds I-8.B.2-
8. A-1 to I-8.B.2-8.A-513). Table 2-9 Compounds of the formula 1-5. B, 1-6. B, 1-7. B, 1-8. B in which R9 is CO-N(CH3)2 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-9.A-1 to I-5.B.2-9.A-513, compounds I- 6.B.2-9.A-1 to I-6.B.2-9.A-513, compounds I-7.B.2-9.A-1 to I-7.B.2-9.A-513 compounds I-8.B.2-
9. A-1 to I-8.B.2-9.A-513).
Table 2-10 Compounds of the formula I-5.B, I-6.B, I-7.B, I-8.B in which R9 is S02-CH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-10.A-1 to I-5.B.2-10.A-513, compounds I-6.B.2-
10. A-1 to I-6.B.2-10.A-513, compounds I-7.B.2-10.A-1 to I-7.B.2-10.A-513 compounds I-8.B.2-
10. A-1 to I-8.B.2-10.A-513).
Table 2-1 1 Compounds of the formula I-5.B, I-6.B, I-7.B, I-8.B in which R9 is SO2NHCH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-1 1 .A-1 to I-5.B.2-1 1.A-513, compounds I-6.B.2-
1 1. A-1 to I-6.B.2-1 1.A-513, compounds I-7.B.2-1 1 .A-1 to I-7.B.2-1 1 .A-513 compounds I-8.B.2-
1 1. A-1 to I-8.B.2-1 1.A-513).
Table 2-12 Compounds of the formula I-5.B, I-6.B, I-7.B, I-8.B in which R9 is S02NHPh and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-12.A-1 to I-5.B.2-12.A-513, compounds I-6.B.2-
12. A-1 to I-6.B.2-12.A-513, compounds I-7.B.2-12.A-1 to I-7.B.2-12.A-513 compounds I-8.B.2-
12. A-1 to I-8.B.2-12.A-513).
Table 2-13 Compounds of the formula I-5.B, I-6.B, I-7.B, I-8.B in which R9 is S02Ph and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.B.2-13.A-1 to I-5.B.2-13.A-513, compounds I-6.B.2-
13. A-1 to I-6.B.2-13.A-513, compounds I-7.B.2-13.A-1 to I-7.B.2-13.A-513 compounds I-8.B.2- 13.A-1 to I-8.B.2-13.A-513).
Table 3-1 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R9 is H and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-1.A-1 to I-5.C.3-1.A-513, compounds I-6.C.3-1 .A-1 to I- 6.C.3-1 .A-513, compounds I-7.C.3-1.A-1 to I-7.C.3-1.A-513 compounds I-8.C.3-1 .A-1 to I-8.C.3-
1. A-513).
Table 3-2 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R9 is CH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-2.A-1 to I-5.C.3-2.A-513, compounds I-6.C.3-
2. A-1 to I-6.C.3-2.A-513, compounds I-7.C.3-2.A-1 to I-7.C.3-2.A-513 compounds I-8.C.3-2.A-1 to I-8.C.3-2.A-513).
Table 3-3 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R9 is C2H5 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-3.A-1 to I-5.C.3-3.A-513, compounds I-6.C.3-
3. A-1 to I-6.C.3-3.A-513, compounds I-7.C.3-3.A-1 to I-7.C.3-3.A-513 compounds I-8.C.3-3.A-1 to I-8.C.3-3.A-513).
Table 3-4 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R9 is CH2CH=CH2 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-4.A-1 to I-5.C.3-4.A-513, compounds I- 6.C.3-4.A-1 to I-6.C.3-4.A-513, compounds I-7.C.3-4.A-1 to I-7.C.3-4.A-513 compounds I-8.C.3-
4. A-1 to I-8.C.3-4.A-513).
Table 3-5 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R9 is CH2C≡CH and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-5.A-1 to I-5.C.3-5.A-513, compounds I-6.C.3-
5. A-1 to I-6.C.3-5.A-513, compounds I-7.C.3-5.A-1 to I-7.C.3-5.A-513 compounds I-8.C.3-5.A-1 to I-8.C.3-5.A-513).
Table 3-6 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R9 is C(0)CH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-6.A-1 to I-5.C.3-6.A-513, compounds I-6.C.3-
6. A-1 to I-6.C.3-6.A-513, compounds I-7.C.3-6.A-1 to I-7.C.3-6.A-513 compounds I-8.C.3-6.A-1 to I-8.C.3-6.A-513).
Table 3-7 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R9 is C(0)OCH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-7.A-1 to I-5.C.3-7.A-513, compounds I-6.C.3-
7. A-1 to I-6.C.3-7.A-513, compounds I-7.C.3-7.A-1 to I-7.C.3-7.A-513 compounds I-8.C.3-7.A-1 to I-8.C.3-7.A-513).
Table 3-8 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R9 is C=0-NH(CH3) and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-8.A-1 to I-5.C.3-8.A-513, compounds I- 6.C.3-8.A-1 to I-6.C.3-8.A-513, compounds I-7.C.3-8.A-1 to I-7.C.3-8.A-513 compounds I-8.C.3-
8. A-1 to I-8.C.3-8.A-513).
Table 3-9 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R9 is CO-N(CH3)2 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-9.A-1 to I-5.C.3-9.A-513, compounds I- 6.C.3-9.A-1 to I-6.C.3-9.A-513, compounds I-7.C.3-9.A-1 to I-7.C.3-9.A-513 compounds I-8.C.3-
9. A-1 to I-8.C.3-9.A-513).
Table 3-10 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R9 is S02-CH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-10.A-1 to I-5.C.3-10.A-513, compounds I-6.C.3-
10. A-1 to I-6.C.3-10.A-513, compounds I-7.C.3-10.A-1 to I-7.C.3-10.A-513 compounds I-8.C.3- 10.A-1 to I-8.C.3-10.A-513).
Table 3-1 1 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R9 is S02NHCH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-1 1 .A-1 to I-5.C.3-1 1.A-513, compounds I- 6.C.3-1 1.A-1 to I-6.C.3-1 1 .A-513, compounds I-7.C.3-1 1.A-1 to I-7.C.3-1 1. A-513 compounds I- 8.C.3-1 1.A-1 to I-8.C.3-1 1 .A-513).
Table 3-12 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R9 is S02NHPh and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-12.A-1 to I-5.C.3-12.A-513, compounds I-6.C.3- 12.A-1 to I-6.C.3-12.A-513, compounds I-7.C.3-12.A-1 to I-7.C.3-12.A-513 compounds I-8.C.3-
12. A-1 to I-8.C.3-12.A-513).
Table 3-13 Compounds of the formula I-5.C, I-6.C, I-7.C, I-8.C in which R9 is S02Ph and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.C.3-13.A-1 to I-5.C.3-13.A-513, compounds I-6.C.3-
13. A-1 to I-6.C.3-13.A-513, compounds I-7.C.3-13.A-1 to I-7.C.3-13.A-513 compounds I-8.C.3- 13.A-1 to I-8.C.3-13.A-513).
Table 4-1 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R9 is H and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-1.A-1 to I-5.D.4-1.A-513, compounds I-6.D.4-1 .A-1 to I- 6.D.4-1 .A-513, compounds I-7.D.4-1.A-1 to I-7.D.4-1.A-513 compounds I-8.D.4-1 .A-1 to I-8.D.4-
1. A-513).
Table 4-2 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R9 is CH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-2.A-1 to I-5.D.4-2.A-513, compounds I-6.D.4-
2. A-1 to I-6.D.4-2.A-513, compounds I-7.D.4-2.A-1 to I-7.D.4-2.A-513 compounds I-8.D.4-2.A-1 to I-8.D.4-2.A-513).
Table 4-3 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R9 is C2H5 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-3.A-1 to I-5.D.4-3.A-513, compounds I-6.D.4-
3. A-1 to I-6.D.4-3.A-513, compounds I-7.D.4-3.A-1 to I-7.D.4-3.A-513 compounds I-8.D.4-3.A-1 to I-8.D.4-3.A-513).
Table 4-4 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R9 is CH2CH=CH2 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-4.A-1 to I-5.D.4-4.A-513, compounds I- 6.D.4-4.A-1 to I-6.D.4-4.A-513, compounds I-7.D.4-4.A-1 to I-7.D.4-4.A-513 compounds I-8.D.4-
4. A-1 to I-8.D.4-4.A-513).
Table 4-5 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R9 is CH2C≡CH and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-5.A-1 to I-5.D.4-5.A-513, compounds I-6.D.4-
5. A-1 to I-6.D.4-5.A-513, compounds I-7.D.4-5.A-1 to I-7.D.4-5.A-513 compounds I-8.D.4-5.A-1 to I-8.D.4-5.A-513).
Table 4-6 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R9 is C(0)CH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-6.A-1 to I-5.D.4-6.A-513, compounds I-6.D.4-
6. A-1 to I-6.D.4-6.A-513, compounds I-7.D.4-6.A-1 to I-7.D.4-6.A-513 compounds I-8.D.4-6.A-1 to I-8.D.4-6.A-513).
Table 4-7 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R9 is C(0)OCH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-7.A-1 to I-5.D.4-7.A-513, compounds I-6.D.4-
7. A-1 to I-6.D.4-7.A-513, compounds I-7.D.4-7.A-1 to I-7.D.4-7.A-513 compounds I-8.D.4-7.A-1 to I-8.D.4-7.A-513).
Table 4-8 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R9 is C=0-NH(CH3) and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-8.A-1 to I-5.D.4-8.A-513, compounds I- 6.D.4-8.A-1 to I-6.D.4-8.A-513, compounds I-7.D.4-8.A-1 to I-7.D.4-8.A-513 compounds I-8.D.4-
8. A-1 to I-8.D.4-8.A-513).
Table 4-9 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R9 is CO-N(CH3)2 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-9.A-1 to I-5.D.4-9.A-513, compounds I- 6.D.4-9.A-1 to I-6.D.4-9.A-513, compounds I-7.D.4-9.A-1 to I-7.D.4-9.A-513 compounds I-8.D.4-
9. A-1 to I-8.D.4-9.A-513).
Table 4-10 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R9 is S02-CH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-10.A-1 to I-5.D.4-10.A-513, compounds I-6.D.4-
10. A-1 to I-6.D.4-10.A-513, compounds I-7.D.4-10.A-1 to I-7.D.4-10.A-513 compounds I-8.D.4- 10.A-1 to I-8.D.4-10.A-513).
Table 4-1 1 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R9 is SO2NHCH3 and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-1 1 .A-1 to I-5.D.4-1 1.A-513, compounds I- 6.D.4-1 1.A-1 to I-6.D.4-1 1 .A-513, compounds I-7.D.4-1 1.A-1 to I-7.D.4-1 1. A-513 compounds I-
8. D.4-1 1.A-1 to I-8.D.4-1 1 .A-513).
Table 4-12 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R9 is S02NHPh and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-12.A-1 to I-5.D.4-12.A-513, compounds I-6.D.4- 12.A-1 to I-6.D.4-12.A-513, compounds I-7.D.4-12.A-1 to I-7.D.4-12.A-513 compounds I-8.D.4-
12. A-1 to I-8.D.4-12.A-513).
Table 4-13 Compounds of the formula I-5.D, I-6.D, I-7.D, I-8.D in which R9 is S02Ph and the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-5.D.4-13.A-1 to I-5.D.4-13.A-513, compounds I-6.D.4-
13. A-1 to I-6.D.4-13.A-513, compounds I-7.D.4-13.A-1 to I-7.D.4-13.A-513 compounds I-8.D.4- 13.A-1 to I-8.D.4-13.A-513).
Particular embodiments of the compounds I are the following compounds: I-9.A, I-9.B, I-9.C, I-
9. D; I-10.A, 1-10. B, I-10.C, 1-10. D; 1-1 1. A, 1-1 1 . B, I-1 1 .C, 1-1 1 . D; I-12.A, 1-12. B, I-12.C, I-12.D that are compiled in the Tables 1-1 to 1-4. Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.
Figure imgf000085_0001
Figure imgf000086_0001
Table 1-1 Compounds of the formula I-9.A, I-10.A, 1-1 1 .A, I-12.A in which the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-9.A.1 -1.A-1 to I-9.A.1-1 .A-513, compounds I-10.A.1 -1.A-1 to I-10.A.1 - 1.A-513, compounds 1-1 1.A.1 -1.A-1 to 1-1 1.A.1 -1.A-513 compounds I-12.A.1-1 .A-1 to I-12.A.1-
1. A-513).
Table 1-2 Compounds of the formula I-9.B, 1-10. B, 1-1 1 .B, 1-12. B in which the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-9.B.1 -2.A-1 to I-9.B.1-2.A-513, compounds 1-10.B.1 -2.A-1 to I-10.B.1 -
2. A-513, compounds 1-1 1.B.1 -2.A-1 to 1-1 1.B.1 -2.A-513 compounds I-12.B.1-2.A-1 to 1-12. B.1- 2. A-513).
Table 1-3 Compounds of the formula I-9.C, 1-10. C, 1-1 1 .C, 1-12. C in which the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-9.C.1-3.A-1 to I-9.C.3-1.A-513, compounds I-10.C.1-3.A-1 to I-10.C.1 -
3. A-513, compounds 1-1 1 .C.1 -3.A-1 to 1-1 1.C.1-3.A-513 compounds I-12.C.1 -3.A-1 to I-12.C.1-
3. A-513).
Table 1-4 Compounds of the formula I-9.D, 1-10. D, 1-1 1 .D, 1-12. D in which the meaning for the combination of R4 and R78 for each individual compound corresponds in each case to one line of Table A (compounds I-9.D.1-4.A-1 to I-9.D.1-4.A-513, compounds I-10.D.1-4.A-1 to I-10.D.1 -
4. A-513, compounds 1-1 1 .D.1 -4.A-1 to 1-1 1.D.1-4.A-513 compounds I-12.D.1 -4.A-1 to I-12.D.1- 4.A-513).
Table A
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0001
Figure imgf000103_0001
The compounds I and the compositions according to the invention, respectively, are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zy- gomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
The compounds I and the compositions according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.
Preferably, compounds I and compositions thereof, respectively are used for controlling a multi- tude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. pota- toes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
Preferably, treatment of plant propagation materials with compounds I and compositions thereof, respectively, is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-gmc.org/, see GM crop database therein). Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
Plants that have been modified by breeding, mutagenesis or genetic engineering, e. g. have been rendered tolerant to applications of specific classes of herbicides, such as auxin herbicides such as dicamba or 2,4-D; bleacher herbicides such as hydroxylphenylpyruvate dioxy- genase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones; enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. e. bromoxynil or ioxynil) herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are e. g. described in Pest Managem. Sci. 61 , 2005, 246; 61 , 2005, 258; 61 , 2005, 277; 61 , 2005, 269; 61 , 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1 185; and references quoted therein. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox, or ExpressSun® sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, e. g. tribenuron. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets and rape, tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate-tolerant, Monsanto, U.S.A.), Cul- tivance® (imidazolinone tolerant, BASF SE, Germany) and LibertyLink® (glufosinate-tolerant, Bayer CropScience, Germany).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as δ-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nema- todes, e. g. Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdyster- oid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ). Further examples of such toxins or genetically modified plants ca- pable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278,
WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins toler- ance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coelop- tera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda). Genetically modified plants capable to synthesize one or more insecticidal proteins are, e. g., described in the publications mentioned above, and some of which are commercially available such as YieldGard® (corn cultivars producing the Cry1 Ab toxin), YieldGard® Plus (corn cultivars producing CrylAb and Cry3Bb1 toxins), Starlink® (corn cultivars producing the Cry9c toxin), Herculex® RW (corn cultivars producing Cry34Ab1 , Cry35Ab1 and the enzyme phosphinothri- cin-N-acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the Cry1 Ac toxin), Bollgard® I (cotton cultivars producing the CrylAc toxin), Bollgard® II (cotton cultivars producing CrylAc and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf® (po- tato cultivars producing the Cry3A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Pro- tecta®, Bt1 1 (e. g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the CrylAb toxin and PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the
CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathogenesis- related proteins" (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the Mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Er- winia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above.
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape, DOW Agro Sciences, Canada).
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato, BASF SE, Germany).
The compounds I and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:
Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. Candida) and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassico/a or brassi- cae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. so/an/ or A. alternata), tomatoes (e. g. A. so/anior A. alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. horde/ on barley; Bipolar/s and Drechslera pp. (teleomorph: Cochliobolus spp), e. g. Southern leaf blight (D. maydisj or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e. g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fucke/iana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad- leaved trees and evergreens, e. g. C. ί///77/' (Dutch elm disease) on elms; Cercospora spp. (Cer- cospora leaf spots) on corn (e. g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. bet/cola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum. leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helmin- thosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Giomereiia) spp. (anthracnose) on cotton (e. g. C. gossypil), corn (e. g. C. gramini- <%>/#/Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes. black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Cortici urn spp., e. g. C. sasak/i (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. liriodendri, teleomorph: Neonectria liriodendri. Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis. tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa, Elsinoe spp. on pome fruits (E. pyn), soft fruits (E. veneta: anthracnose) and vines (E. ampelina. anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets {E. betae), vegetables (e. g. E. pisl), such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruel ferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turci- cum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. so/anl( sp. glycines now syn. F. virguliforme ) and F. tucumani- ae and F. brasiliense each causing sudden death syndrome on soybeans, and F. verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and corn; Gibberella spp. on cereals (e. g. G zeae) and rice (e. g. G fujikuror. Bakanae disease); Giomereiia cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; G 'uignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochiioboius) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseo/ή (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco {P. tabacina) and soybeans (e. g. P. manshurica);
Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phia/ophora spp. e. g. on vines (e. g. P. tracheiphi/a and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Phy- soderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P.
megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad- leaved trees (e. g. P. ramorum. sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples; Polymyxa spp., e. g. on cereals, such as barley and wheat {P. graminis) and sugar beets {P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapes/a yal- lundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. hum/71 on hop; Pseudopezicu/a tracheiphi/a (red fire disease or .rotbrenner', anamorph: Phia/ophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. tr/t/c/na (brown or leaf rust), P. striiformis (stripe or yellow rust), P. horde/ (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehn/i (orange rust) on sugar cane and P. asparagion asparagus; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum); Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. bet/cola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sa- rocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. ro/fsiior S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) no- dorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tucker!) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Lepto- sphaeria [syn. Phaeosphaeria] nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici(syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae); Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis. corn smut) and sugar cane; Venturis spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dah/iae on strawberries, rape, potatoes and tomatoes.
The compounds I and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
The term "protection of materials" is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fiber or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria. As to the protection of wood and other materials, the particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma pp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp.,
Chaetomium spp., Hum/cola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coni- ophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Ser- pu/a spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., PeniciHium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucorspp., and in addition in the protection of stored products and harvest the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
The method of treatment according to the invention can also be used in the field of protecting stored products or harvest against attack of fungi and microorganisms. According to the present invention, the term "stored products" is understood to denote natural substances of plant or animal origin and their processed forms, which have been taken from the natural life cycle and for which long-term protection is desired. Stored products of crop plant origin, such as plants or parts thereof, for example stalks, leafs, tubers, seeds, fruits or grains, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment. Also falling under the definition of stored products is timber, whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood. Stored products of animal origin are hides, leather, furs, hairs and the like. The combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mold. Preferably "stored products" is understood to denote natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms.
The compounds I and compositions thereof, respectively, may be used for improving the health of a plant. The invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of compounds I and compositions thereof, respectively.
The term "plant health" is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress. The above identified indicators for the health condition of a plant may be interdependent or may result from each other.
The compounds of formula I can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.
The compounds I are employed as such or in form of compositions by treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be pro- tected from fungal attack with a fungicidally effective amount of the active substances. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
Plant propagation materials may be treated with compounds I as such or a composition comprising at least one compound I prophylactically either at or before planting or transplanting. The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the invention. An agrochemical composition comprises a fungicidally effective amount of a compound I. The term "effective amount" denotes an amount of the composition or of the compounds I, which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used.
The compounds I, their N-oxides and salts can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e. g. SC, OD, FS), emulsifiable concentrates (e. g. EC), emulsions (e. g. EW, EO, ES, ME), capsules (e. g. CS, ZC), pastes, pastilles, wettable powders or dusts (e. g. WP, SP, WS, DP, DS), pressings (e. g. BR, TB, DT), granules (e. g. WG, SG, GR, FG, GG, MG), insecticidal articles (e. g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e. g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e. g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e. g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, e. g. cyclohexanone; esters, e. g. lactates, carbonates, fatty acid es- ters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e. g. N-methyl pyrroli- done, fatty acid dimethyl amides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e. g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e. g. cellulose, starch; fertilizers, e. g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e. g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective col- loid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.). Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sul- fonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyl naphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Exam- pies of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinyl pyrroli- done, vinyl alcohols, or vinyl acetate.
Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinyl amines or polyethylene amines.
Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Exam- pies are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e. g. xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e. g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e. g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e. g. alizarin-, azo- and phthalogencyanine colorants).
Suitable tackifiers or binders are polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for composition types and their preparation are:
i) Water-soluble concentrates (SL, LS)
10-60 wt% of a compound I and 5-15 wt% wetting agent (e. g. alcohol alkoxylates) are dis- solved in water and/or in a water-soluble solvent (e. g. alcohols) ad 100 wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
5-25 wt% of a compound I and 1-10 wt% dispersant (e. g. polyvinyl pyrrolidone) are dissolved in organic solvent (e. g. cyclohexanone) ad 100 wt%. Dilution with water gives a disper- sion.
iii) Emulsifiable concentrates (EC)
15-70 wt% of a compound I and 5-10 wt% emulsifiers (e. g. calcium dodecylben- zenesulfonate and castor oil ethoxylate) are dissolved in water-insoluble organic solvent (e. g. aromatic hydrocarbon) ad 100 wt%. Dilution with water gives an emulsion.
iv) Emulsions (EW, EO, ES)
5-40 wt% of a compound I and 1 -10 wt% emulsifiers (e. g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e. g. aromatic hydrocarbon). This mixture is introduced into water ad 100 wt% by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion. v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of a compound I are comminuted with addition of 2-10 wt% dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate), 0.1- 2 wt% thickener (e. g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e. g. polyvinyl alcohol) is added.
vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of a compound I are ground finely with addition of dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water- dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% of a compound I are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e. g. sodium lignosulfonate), 1 -3 wt% wetting agents (e. g. alcohol ethoxylate) and solid carrier (e. g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the active substance.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of a compound I are comminuted with addition of 3-10 wt% dispersants (e. g. sodium lignosulfonate), 1 -5 wt% thickener (e. g. carboxymethyl cellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
ix) Microemulsion (ME)
5-20 wt% of a compound I are added to 5-30 wt% organic solvent blend (e. g. fatty acid dimethyl amide and cyclohexanone), 10-25 wt% surfactant blend (e. g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
x) Microcapsules (CS)
An oil phase comprising 5-50 wt% of a compound I, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e. g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol). Radical polymerization results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of a compound I according to the in- vention, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), and an isocya- nate monomer (e. g. diphenylmethene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol). The addition of a polyamine (e. g. hexameth- ylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1 - 10 wt%. The wt% relate to the total CS composition.
xi) Dustable powders (DP, DS)
1 -10 wt% of a compound I are ground finely and mixed intimately with solid carrier (e. g. finely divided kaolin) ad 100 wt%.
xii) Granules (GR, FG)
0.5-30 wt% of a compound I is ground finely and associated with solid carrier (e. g. silicate) ad 100 wt%. Granulation is achieved by extrusion, spray-drying or fluidized bed.
xiii) Ultra-low volume liquids (UL)
1 -50 wt% of a compound I are dissolved in organic solvent (e. g. aromatic hydrocarbon) ad 100 wt%.
The compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1 -1 wt% anti-foaming agents, and 0.1 -1 wt% colorants.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, more preferably between 1 and 70%, and in particular between 10 and 60%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
For the purposes of treatment of plant propagation materials, particularly seeds, solutions for seed treatment (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC), and gels (GF) are usually employed. The com- positions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying compound I and compositions thereof, respectively, onto plant propagation material, especially seeds, include dressing, coat- ing, pelleting, dusting, and soaking as well as in-furrow application methods. Preferably, compound I or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting. When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.
When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e. g. herbicides, insecticides, fungicides, growth regulators, safeners, biopesticides) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions ac- cording to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1 .
A pesticide is generally a chemical or biological agent (such as pestidal active ingredient, compound, composition, virus, bacterium, antimicrobial or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests. Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease. The term "pesticide" includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense of against certain pests; safen- ers that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemi- cal composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
Consequently, one embodiment of the invention is a kit for preparing a usable pesticidal composition, the kit comprising a) a composition comprising component 1 ) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and optionally a further active component 3) as defined herein.
Mixing the compounds I or the compositions comprising them in the use form as fungicides with other fungicides results in many cases in an expansion of the fungicidal spectrum of activity being obtained or in a prevention of fungicide resistance development. Furthermore, in many cases, synergistic effects are obtained.
The following list of pesticides II (e. g. pesticidally-active substances and biopesticides), in conjunction with which the compounds I can be used, is intended to illustrate the possible combinations but does not limit them:
A) Respiration inhibitors
- Inhibitors of complex III at Q0 site: azoxystrobin (A.1 .1 ), coumethoxystrobin (A.1.2), coumoxystrobin (A.1 .3), dimoxystrobin (A.1.4), enestroburin (A.1.5), fenaminstrobin (A.1 .6), fenoxystrobin/flufenoxystrobin (A.1.7), fluoxastrobin (A.1 .8), kresoxim-methyl (A.1 .9), man- destrobin (A.1 .10), metominostrobin (A.1 .1 1 ), orysastrobin (A.1 .12), picoxystrobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystrobin (A.1 .17), 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-
2-methoxyimino-N-methyl-acetamide (A.1 .18), pyribencarb (A.1.19), triclopyricarb/chloro- dincarb (A.1.20), famoxadone (A.1 .21 ), fenamidone (A.1.21 ), methyl-/V-[2-[(1 ,4-dimethyl- 5-phenyl-pyrazol-3-yl)oxylmethyl]phenyl]-N-methoxy-carbamate (A.1 .22), 1-[3-chloro- 2-[[1-(4-chlorophenyl)-1 H-pyrazol-3-yl]oxymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1 .23), 1 -[2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-rnethyl-tetrazol-5-one
(A.1 .25), (^2£)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]-oxy-2-methoxyimino-/V,3-dimethyl- pent-3-enamide (A.1.34), (Z,2£)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino- V,3- dimethyl-pent-3-enamide (A.1.35), pyriminostrobin (A.1.36), bifujunzhi (A.1 .37), 2-(ortho- ((2,5-dimethylphenyl-oxymethylen)phenyl)-3-methoxy-acrylic acid methylester (A.1 .38); - inhibitors of complex III at Q, site: cyazofamid (A.2.1 ), amisulbrom (A.2.2),
[(6S,7R,8R)-8-benzyl-3-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-di- oxo-1 ,5-dioxonan-7-yi] 2-methylpropanoate (A.2.3), fenpicoxamid (A.2.4);
- inhibitors of complex II: benodanil (A.3.1 ), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.1 1 ), isopyrazam (A.3.12), mepronil (A.3.13), ox- ycarboxin (A.3.14), penflufen (A.3.15), penthiopyrad (A.3.16), pydiflumetofen (A.3.17), pyra- ziflumid (A.3.18), sedaxane (A.3.19), tecloftalam (A.3.20), thifluzamide (A.3.21 ), inpyrfluxam (A.3.22), /V-[(22)-2-[3-chloro-5-(2-cyclopropylethynyl)-2-pyridyl]-2-isopropoxyimino-ethyl]-3- (difluoromethyl)-1 -methyl-pyrazole-4-carboxamide (A.3.23), fluindapyr (A.3.28)methyl (E)-2- [2-[(5-cyano-2-methyl-phenoxy)methyl]phenyl]-3-methoxy-prop-2-enoate (A.3.30), isoflu- cypram (A.3.31 ), 2-(difluoromethyl)-N-(1 ,1 ,3-trimethyl-indan-4-yl)pyridine-3-carboxamide (A.3.32), 2-(difluoromethyl)-N-[(3R)-1 ,1 ,3-trimethylindan-4-yl]pyridine-3-carboxamide (A.3.33), 2-(difluoromethyl)-N-(3-ethyl-1 ,1-dimethyl-indan-4-yl)pyridine-3-carboxamide (A.3.34), 2-(difluoromethyl)-N-[(3R)-3-ethyl-1 ,1-dimethyl-indan-4-yl]pyridine-3-carboxamide (A.3.35), 2-(difluoromethyl)-N-(1 ,1 -dimethyl-3-propyl-indan-4-yl)pyridine-3-carboxamide (A.3.36), 2-(difluoromethyl)-N-[(3R)-1 ,1 -dimethyl-3-propyl-indan-4-yl]pyridine-3-carboxamide (A.3.37), 2-(difluoromethyl)-N-(3-isobutyl-1 ,1-dimethyl-indan-4-yl)pyridine-3-carboxamide (A.3.38), 2-(difluoromethyl)-N-[(3R)-3-isobutyl-1 ,1-dimethyl-indan-4-yl]pyridine-3- carboxamide (A.3.39);
- other respiration inhibitors: diflumetorim (A.4.1 ); nitrophenyl derivates: binapacryl (A.4.2), dinobuton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), meptyldinocap (A.4.6), ferimzone
(A.4.7); organometal compounds: fentin salts, e. g. fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1 ); silthiofam (A.4.12);
B) Sterol biosynthesis inhibitors (SBI fungicides)
- C14 demethylase inhibitors: triazoles: azaconazole (B.1.1 ), bitertanol (B.1.2), bromu- conazole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), dini- conazole-M (B.1.7), epoxiconazole (B.1 .8), fenbuconazole (B.1 .9), fluquinconazole (B.1.10), flusilazole (B.1.1 1 ), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1 .14), ip- conazole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1 .19), paclobutrazole (B.1.20), penconazole (B.1.21 ), propiconazole (B.1.22), prothioconazole (B.1.23), simeconazole (B.1 .24), tebuconazole (B.1.25), tetraconazole (B.1.26), triadimefon (B.1.27), triadimenol (B.1 .28), triticonazole (B.1 .29), uniconazole (B.1.30), 2-(2,4- difluorophenyl)-1 ,1 -difluoro-3-(tetrazol-1-yl)-1 -[5-[4-(2,2,2-trifluoroethoxy)phenyl]- 2-pyridyl]propan-2-ol (B.1.31 ), 2-(2,4-difluorophenyl)-1 ,1-difluoro-3-(tetrazol-1 -yl)- 1 -[5-[4-(trifluoromethoxy)phenyl]-2-pyridyl]propan-2-ol (B.1.32), ipfentrifluconazole (B.1 .37), mefentrifluconazole (B.1.38), 2-(chloromethyl)-2-methyl-5-(p-tolylmethyl)-1-(1 ,2,4-triazol-1- ylmethyl)cyclopentanol (B.1.43); imidazoles: imazalil (B.1.44), pefurazoate (B.1 .45), prochlo- raz (B.1 .46), triflumizol (B.1.47); pyrimidines, pyridines and piperazines: fenarimol (B.1.49), pyrifenox (B.1 .50), triforine (B.1 .51 ), [3-(4-chloro-2-fluoro-phenyl)-5-(2,4-di- fluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol (B.1 .52);
- Delta 14-reductase inhibitors: aldimorph (B.2.1 ), dodemorph (B.2.2), dodemorph-acetate
(B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spi- roxamine (B.2.8);
- Inhibitors of 3-keto reductase: fenhexamid (B.3.1 );
- Other Sterol biosynthesis inhibitors: chlorphenomizole (B.4.1 );
C) Nucleic acid synthesis inhibitors
- phenylamides or acyl amino acid fungicides: benalaxyl (C.1.1 ), benalaxyl-M (C.1 .2), kiralaxyl (C.1 .3), metalaxyl (C.1 .4), metalaxyl-M (C.1 .5), ofurace (C.1 .6), oxadixyl (C.1 .7);
- other nucleic acid synthesis inhibitors: hymexazole (C.2.1 ), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin- 4-amine (C.2.6), 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine (C.2.7), 5-fluoro- 2-(4-chlorophenylmethoxy)pyrimidin-4 amine (C.2.8);
D) Inhibitors of cell division and cytoskeleton
- tubulin inhibitors: benomyl (D.1 .1 ), carbendazim (D.1 .2), fuberidazole (D1.3), thiabendazole (D.1 .4), thiophanate-methyl (D.1 .5), 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyri- dazine (D.1 .6), 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine (D.1 .7), N-eth- yl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]butanamide (D.1.8), N-ethyl-2-[(3-ethynyl-8-methyl- 6-quinolyl)oxy]-2-methylsulfanyl-acetamide (D.1 .9), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]- N-(2-fluoroethyl)butanamide (D.1 .10), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroeth- yl)-2-methoxy-acetamide (D.1 .1 1 ), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-propyl-butanam- ide (D.1 .12), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methoxy-N-propyl-acetamide (D.1.13), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methylsulfanyl-N-propyl-acetamide (D.1.14),
2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)-2-methylsulfanyl-acetamide (D.1.15), 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine (D.1 .16);
- other cell division inhibitors: diethofencarb (D.2.1 ), ethaboxam (D.2.2), pencycuron (D.2.3), fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriofenone (D.2.7);
E) Inhibitors of amino acid and protein synthesis
- methionine synthesis inhibitors: cyprodinil (E.1 .1 ), mepanipyrim (E.1.2), pyrimethanil (E.1.3);
- protein synthesis inhibitors: blasticidin-S (E.2.1 ), kasugamycin (E.2.2), kasugamycin hydro- chloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6); F) Signal transduction inhibitors
- MAP / histidine kinase inhibitors: fluoroimid (F.1.1 ), iprodione (F.1.2), procymidone (F.1 .3), vinclozolin (F.1 .4), fludioxonil (F.1 .5);
- G protein inhibitors: quinoxyfen (F.2.1 );
G) Lipid and membrane synthesis inhibitors
- Phospholipid biosynthesis inhibitors: edifenphos (G.1.1 ), iprobenfos (G.1 .2), pyrazophos (G.1.3), isoprothiolane (G.1.4);
- lipid peroxidation: dicloran (G.2.1 ), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7);
- phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1 ), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7);
- compounds affecting cell membrane permeability and fatty acides: propamocarb (G.4.1 );
- inhibitors of oxysterol binding protein: oxathiapiprolin (G.5.1 ), 2-{3-[2-(1 -{[3,5-bis(difluoro- methyl-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl}- phenyl methanesulfonate (G.5.2), 2-{3-[2-(1 -{[3, 5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]- acetyl}piperidin-4-yl) 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate (G.5.3), 4-[1-[2-[3-(difluoromethyl)-5-methyl-pyrazol-1-yl]acetyl]-4-piperidyl]-N-te- tralin-1-yl-pyridine-2-carboxamide (G.5.4), 4-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1 -yl]acetyl]- 4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.5), 4-[1 -[2-[3-(difluoromethyl)-5-(tri- fluoromethyl)pyrazol-1 -yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.6), 4-[1-[2-[5-cyclopropyl-3-(difluoromethyl)pyrazol-1 -yl]acetyl]-4-piperidyl]-N-tetralin-1 -yl- pyridine-2-carboxamide (G.5.7), 4-[1 -[2-[5-methyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-pi- peridyl]-N-tetralin-1 -yl-pyridine-2-carboxamide (G.5.8), 4-[1 -[2-[5-(difluoromethyl)-3-(trifluoro- methyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1 -yl-pyridine-2-carboxamide (G.5.9), 4-[1-[2-[3,5-bis(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-car- boxamide (G.5.10), (4-[1 -[2-[5-cyclopropyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]- N-tetralin-1 -yl-pyridine-2-carboxamide (G.5.1 1 );
H) Inhibitors with Multi Site Action
- inorganic active substances: Bordeaux mixture (H.1 .1 ), copper (H.1 .2), copper acetate
(H.1 .3), copper hydroxide (H.1 .4), copper oxychloride (H.1.5), basic copper sulfate (H.1.6), sulfur (H.1 .7);
- thio- and dithiocarbamates: ferbam (H.2.1 ), mancozeb (H.2.2), maneb (H.2.3), metam
(H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9);
- organochlorine compounds: anilazine (H.3.1 ), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.1 1 );
- guanidines and others: guanidine (H.4.1 ), dodine (H.4.2), dodine free base (H.4.3),
guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1 H,5H- [1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone (H.4.10);
I) Cell wall synthesis inhibitors
- inhibitors of glucan synthesis: validamycin (1.1 .1 ), polyoxin B (1.1.2);
- melanin synthesis inhibitors: pyroquilon (1.2.1 ), tricyclazole (1.2.2), carpropamid (I.2.3), dicy- clomet (I.2.4), fenoxanil (I.2.5);
J) Plant defence inducers
- acibenzolar-S-methyl (J.1 .1 ), probenazole (J.1.2), isotianil (J.1.3), tiadinil (J.1.4), prohexadi- one-calcium (J.1.5); phosphonates: fosetyl (J.1.6), fosetyl-aluminum (J.1 .7), phosphorous acid and its salts (J.1 .8), potassium or sodium bicarbonate (J.1.9), 4-cyclopropyl-N-(2,4- dimethoxyphenyl)thiadiazole-5-carboxamide (J.1 .10);
K) Unknown mode of action
- bronopol (K.1.1 ), chinomethionat (K.1 .2), cyflufenamid (K.1 .3), cymoxanil (K.1 .4), dazomet (K.1.5), debacarb (K.1.6), diclocymet (K.1.7), diclomezine (K.1 .8), difenzoquat (K.1 .9), di- fenzoquat-methylsulfate (K.1.10), diphenylamin (K.1 .1 1 ), fenitropan (K.1.12), fenpyrazamine (K.1.13), flumetover (K.1.14), flusulfamide (K.1 .15), flutianil (K.1.16), harpin (K.1 .17), metha- sulfocarb (K.1 .18), nitrapyrin (K.1.19), nitrothal-isopropyl (K.1.20), tolprocarb (K.1.21 ), oxin- copper (K.1.22), proquinazid (K.1.23), tebufloquin (K.1.24), tecloftalam (K.1 .25), triazoxide (K.1.26), N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine (K.1.27), N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-eth- yl-N-methyl formamidine (K.1 .28), N'-[4-[[3-[(4-chlorophenyl)methyl]-1 ,2,4-thiadiazol-5-yl]- oxy]-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine (K.1.29), N'-(5-bromo-6-indan-2-yl- oxy-2-methyl-3-pyridyl)-N-ethyl-N-methyl-formamidine (K.1.30), N'-[5-bromo-6-[1 -(3,5-diflu- orophenyl)ethoxy]-2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1 .31 ), N'-[5-bromo- 6-(4-isopropylcyclohexoxy)-2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.32),
N'-[5-bromo-2-methyl-6-(1-phenylethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.33), N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.34), N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine (K.1.35), 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol- 5-yl]-2-prop-2-ynyloxy-acetamide (K.1 .36), 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin- 3-yl]-pyridine (pyrisoxazole) (K.1 .37), 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3 yl]- pyridine (K.1.38), 5-chloro-1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole (K.1.39), ethyl (Z)-3-amino-2-cyano-3-phenyl-prop-2-enoate (K.1 .40), picarbutrazox (K.1.41 ), pentyl N-[6-[[(Z)-[(1 -methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carba- mate (K.1 .42), but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxy- methyl]-2-pyridyl]carbamate (K.1.43), 2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro- phenyl]propan-2-ol (K.1 .44), 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phen-yl]propan- 2-ol (K.1.45), quinofumelin (K.1 .47), 9-fluoro-2,2-dimethyl-5-(3-quinolyl)- 3H-1 ,4-benzoxazepine (K.1 .49), 2-(6-benzyl-2-pyridyl)quinazoline (K.1.50), 2-[6-(3-fluoro- 4-methoxy-phenyl)-5-methyl-2-pyridyl]quinazoline (K.1.51 ), 3-[(3,4-dichloroisothiazol-
5-yl)methoxy]-1 ,2-benzothiazole 1 ,1 -dioxide (K.1 .52), N'-(2,5-dimethyl-4-phenoxy-phenyl)-N- ethyl-N-methyl-formamidine (K.1 .53), pyrifenamine (K.1.54);
M) Growth regulators
abscisic acid (M.1.1 ), amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat, chlormequat chloride, choline chloride, cyclanilide, daminozide, dikegulac, dime- thipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gib- berellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat, mepiquat chloride, naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione, prohexadi- one-calcium, prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate,
2,3,5-tri-iodobenzoic acid , trinexapac-ethyl and uniconazole;
N) Herbicides from classes N.1 to N.15
N.1 Lipid biosynthesis inhibitors: alloxydim, alloxydim-sodium, butroxydim, clethodim,
clodinafop, clodinafop-propargyl, cycloxydim, cyhalofop, cyhalofop-butyl, diclofop, diclofop- methyl, fenoxaprop, fenoxaprop-ethyl, fenoxaprop-P, fenoxaprop-P-ethyl, fluazifop, fluazifop- butyl, fluazifop-P, fluazifop-P-butyl, haloxyfop, haloxyfop-methyl, haloxyfop-P, haloxyfop-P- methyl, metamifop, pinoxaden, profoxydim, propaquizafop, quizalofop, quizalofop-ethyl, quizalofop-tefuryl, quizalofop-P, quizalofop-P-ethyl, quizalofop-P-tefuryl, sethoxydim, tepra- loxydim, tralkoxydim, 4-(4'-chloro-4-cyclo-,propyl-2'-fluoro[1 ,1 '-biphenyl]-3-yl)-5-hydroxy- 2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS 1312337-72-6); 4-(2',4'-dichloro-4- cyclopropyl[1 ,1 '-biphenyl]-3-yl)-5-hydroxy-2,2,6,6-tetramethyl-2H-pyran-3(6H)-one (CAS 1312337-45-3); 4-(4'-chloro-4-ethyl-2'-fluoro[1 ,1 '-biphenyl]-3-yl)-5-hydroxy-2,2,6,6- tetramethyl-2H-pyran-3(6H)-one (CAS 1033757-93-5); 4-(2',4'-Dichloro-4-ethyl[1 ,1 '- biphenyl]-3-yl)-2,2,6,6-tetramethyl-2H-pyran-3,5(4H,6H)-dione (CAS 1312340-84-3); 5- (acetyloxy)-4-(4'-chloro-4-cyclopropyl-2'-fluoro[1 ,1 '-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6- tetramethyl-2H-pyran-3-one (CAS 1312337-48-6); 5-(acetyloxy)-4-(2',4'-dichloro-4- cyclopropyl- [1 ,1 '-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one; 5- (acetyloxy)-4-(4'-chloro-4-ethyl-2'-fluoro[1 ,1 '-biphenyl]-3-yl)-3,6-dihydro-2,2,6,6-tetramethyl- 2H-pyran-3-one (CAS 1312340-82-1 ); 5-(acetyloxy)-4-(2',4'-dichloro-4-ethyl[1 ,1 '-biphenyl]-3- yl)-3,6-dihydro-2,2,6,6-tetramethyl-2H-pyran-3-one (CAS 1033760-55-2); 4-(4'-chloro-4- cyclopropyl-2'-fluoro[1 ,1 '-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester (CAS 1312337-51 -1 ); 4-(2',4'-dichloro -4-cyclopropyl- [1 ,1 '- biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl es- ter; 4-(4'-chloro-4-ethyl-2'-fluoro[1 ,1 '-biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-
2H-pyran-3-yl carbonic acid methyl ester (CAS 1312340-83-2); 4-(2',4'-dichloro-4-ethyh[1 ,1 '- biphenyl]-3-yl)-5,6-dihydro-2,2,6,6-tetramethyl-5-oxo-2H-pyran-3-yl carbonic acid methyl ester (CAS 1033760-58-5); benfuresate, butylate, cycloate, dalapon, dimepiperate, EPTC, esprocarb, ethofumesate, flupropanate, molinate, orbencarb, pebulate, prosulfocarb, TCA, thiobencarb, tiocarbazil, triallate and vernolate;
N.2 ALS inhibitors: amidosulfuron, azimsulfuron, bensulfuron, bensulfuron-methyl, chlorimuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron, ethamet- sulfuron-methyl, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, flupyrsulfuron- methyl-sodium, foramsulfuron, halosulfuron, halosulfuron-methyl, imazosulfuron, iodosulfu- ron, iodosulfuron-methyl-sodium, iofensulfuron, iofensulfuron-sodium, mesosulfuron, met- azosulfuron, metsulfuron, metsulfuron-methyl, nicosulfuron, orthosulfamuron, oxasulfuron, primisulfuron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron, pyrazosul- furon-ethyl, rimsulfuron, sulfometuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron, thifensulfuron-methyl, triasulfuron, tribenuron, tribenuron-methyl, trifloxysulfuron, triflusulfu- ron, triflusulfuron-methyl, tritosulfuron, imazamethabenz, imazamethabenz-methyl, imaza- mox, imazapic, imazapyr, imazaquin, imazethapyr; cloransulam, cloransulam-methyl, di- closulam, flumetsulam, florasulam, metosulam, penoxsulam, pyrimisulfan and pyroxsulam; bispyribac, bispyribac-sodium, pyribenzoxim, pyriftalid, pyriminobac, pyriminobac-methyl, py- rithiobac, pyrithiobac-sodium, 4-[[[2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]phenyl]methyl]amino]- benzoic acid-1-methyhethyl ester (CAS 420138-41 -6), 4-[[[2-[(4,6-dimethoxy-2- pyrimidinyl)oxy]phenyl]-"methyl]amino]-benzoic acid propyl ester (CAS 420138-40-5), N-(4- bromophenyl)-2-[(4,6-dimethoxy-2-pyrimidinyl)oxy]benzenemethanamine (CAS 420138-01 - 8); flucarbazone, flucarbazone-sodium, propoxycarbazone, propoxycarbazone-sodium, thiencarbazone, thiencarbazone-methyl; triafamone;
N.3 Photosynthesis inhibitors: amicarbazone; chlorotriazine; ametryn, atrazine, chloridazone, cyanazine, desmetryn, dimethametryn,hexazinone, metribuzin, prometon, prometryn, pro- pazine, simazine, simetryn, terbumeton, terbuthylazin, terbutryn, trietazin; chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, fluometuron, isoproturon, isouron, linuron, metamitron, methabenzthiazuron, metobenzuron, metoxuron, monolinuron, neburon, sidu- ron, tebuthiuron, thiadiazuron, desmedipham, karbutilat, phenmedipham, phenmedipham- ethyl, bromofenoxim, bromoxynil and its salts and esters, ioxynil and its salts and esters, bromacil, lenacil, terbacil, bentazon, bentazon-sodium, pyridate, pyridafol, pentanochlor, propanil; diquat, diquat-dibromide, paraquat, paraquat-dichloride, paraquat-dimetilsulfate;
N.4 protoporphyrinogen-IX oxidase inhibitors: acifluorfen, acifluorfen-sodium, azafenidin, ben- carbazone, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlor- methoxyfen, cinidon-ethyl, fluazolate, flufenpyr, flufenpyr-ethyl, flumiclorac, flumiclorac- pentyl, flumioxazin, fluoroglycofen, fluoroglycofen-ethyl, fluthiacet, fluthiacet-methyl, fome- safen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, py- raclonil, pyraflufen, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, tiafenacil, triflu- dimoxazin, ethyl [3-[2-chloro-4-fluoro-5-(1-methyl-6-trifluoromethyl-2,4-dioxo-1 ,2,3,4-te- trahydropyrimidin-3-yl)phenoxy]-2-pyridyloxy]acetate (CAS 353292-31-6), N-ethyl-3-(2,6-di- chloro-4-trifluoro-methylphenoxy)-5-methyl-1 H-pyrazole-1 -carboxamide (CAS 452098-92-9), N tetrahydrofurfuryl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-5-methyl-1 H-pyrazole-1 -car- boxamide (CAS 915396-43-9), N-ethyl-3-(2-chloro-6-fluoro-4-trifluoromethyhphenoxy)-
5- methyl-1 H-pyrazole-1 -carboxamide (CAS 452099-05-7), N tetrahydro->furfuryl-3-(2-chloro-
6- fluoro-4-trifluoro-,methylphenoxy)-5-methyl-1 H-pyrazole-1 -carboxamide (CAS 452100-03- 7), 3-[7-fluoro-3-oxo-4-(prop-2-ynyl)-3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl]-1 ,5-dimethyl- 6-thioxo-[1 ,3,5]triazinan-2,4-dione (CAS 451484-50-7), 2-(2,2,7-trifluoro-3-oxo-4-prop-2-ynyl- 3,4-dihydro-2H-benzo[1 ,4]oxazin-6-yl)-4,5,6,7-tetrahydro-isoindole-1 ,3-dione (CAS 13001 18- 96-0), 1-methyl-6-trifluoro-'methyl-3-(2,2,7-tri-fluoro-3-oxo-4-prop-2-ynyl-3,4-dihydro-2H-ben- zo[1 ,4]oxazin-6-yl)-1 H-pyrimidine-2,4-dione (CAS 13041 13-05-0), methyl (E)-4-[2-chloro- 5-[4-chloro-5-(difluoromethoxy)-1 H-methyl-pyrazol-3-yl]-4-fluoro-phenoxy]-3-methoxy-but- 2-enoate (CAS 948893-00-3), 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1 H-benzimidazol-4-yl]- 1 -methyl-6-(trifluoromethyl)-1 H-pyrimidine-2,4-dione (CAS 212754-02-4);
N.5 Bleacher herbicides: beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone,
norflurazon, picolinafen, 4-(3-trifluoromethyhphenoxy)-2-(4-trifluoromethylphen- yl)-"pyrimidine (CAS 180608-33-7); benzobicyclon, benzofenap, bicyclopyrone, clomazone, fenquintrione, isoxaflutole, mesotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, tolpyralate, topramezone; aclonifen, amitrole, flumeturon;
N.6 EPSP synthase inhibitors: glyphosate, glyphosate-isopropylammonium, glyposate- potassium, glyphosate-trimesium (sulfosate);
N.7 Glutamine synthase inhibitors: bilanaphos (bialaphos), bilanaphos-sodium, glufosinate, glufosinate-P, glufosinate-ammonium;
N.8 DHP synthase inhibitors: asulam;
N.9 Mitosis inhibitors: benfluralin, butralin, dinitramine, ethalfluralin, fluchloralin, oryzalin,
pendimethalin, prodiamine, trifluralin; amiprophos, amiprophos-methyl, butamiphos; chlor- thal, chlorthal-dimethyl, dithiopyr, thiazopyr, propyzamide, tebutam; carbetamide, chlorprop- ham, flamprop, flamprop-isopropyl, flamprop-methyl, flamprop-M-isopropyl, flamprop-M- methyl, propham;
N.10 VLCFA inhibitors: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, dimethen- amid-P, metazachlor, metolachlor, metolachlor-S, pethoxamid, pretilachlor, propachlor, prop- isochlor, thenylchlor, flufenacet, mefenacet, diphenamid, naproanilide, napropamide, napro- pamide-M, fentrazamide, anilofos, cafenstrole, fenoxasulfone, ipfencarbazone, piperophos, pyroxasulfone, isoxazoline compounds of the formulae 11.1 , II.2, II.3, II.4, II.5, II.6, II.7, II.8 and II.9
Figure imgf000123_0001
Figure imgf000123_0002
Figure imgf000123_0003
N.1 1 Cellulose biosynthesis inhibitors: chlorthiamid, dichlobenil, flupoxam, indaziflam, isoxaben, triaziflam, 1 -cyclohexyl-5-pentafluorphenyloxy-14-[1 ,2,4,6]thiatriazin-3-ylamine (CAS
175899-01-1 );
N.12 Decoupler herbicides: dinoseb, dinoterb, DNOC and its salts;
N.13 Auxinic herbicides: 2,4-D and its salts and esters, clacyfos, 2,4-DB and its salts and esters, aminocyclopyrachlor and its salts and esters, aminopyralid and its salts such as amino- pyralid-dimethylammonium, aminopyralid-tris(2-hydroxypropyl)ammonium and its esters, benazolin, benazolin-ethyl, chloramben and its salts and esters, clomeprop, clopyralid and its salts and esters, dicamba and its salts and esters, dichlorprop and its salts and esters, di- chlorprop-P and its salts and esters, fluroxypyr, fluroxypyr-butometyl, fluroxypyr-meptyl, ha- lauxifen and its salts and esters (CAS 943832-60-8); MCPA and its salts and esters, MCPA- thioethyl, MCPB and its salts and esters, mecoprop and its salts and esters, mecoprop-P and its salts and esters, picloram and its salts and esters, quinclorac, quinmerac, TBA (2,3,6) and its salts and esters, triclopyr and its salts and esters, 4-amino-3-chloro-6-(4- chloro-2-fluoro-3-methoxyphenyl)-5-fluoropyridine-2-carboxylic acid, benzyl 4-amino-3- chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-5-fluoropyridine-2-carboxylate (CAS 1390661 - 72-9);
N.14 Auxin transport inhibitors: diflufenzopyr, diflufenzopyr-sodium, naptalam and naptalam- sodium;
N.15 Other herbicides: bromobutide, chlorflurenol, chlorflurenol-methyl, cinmethylin, cumyluron, cyclopyrimorate (CAS 499223-49-3) and its salts and esters, dalapon, dazomet, difenzoquat, difenzoquat-metilsulfate, dimethipin, DSMA, dymron, endothal and its salts, etobenzanid, flurenol, flurenol-butyl, flurprimidol, fosamine, fosamine-ammonium, indanofan, maleic hy- drazide, mefluidide, metam, methiozolin (CAS 403640-27-7), methyl azide, methyl bromide, methyl-dymron, methyl iodide, MSMA, oleic acid, oxaziclomefone, pelargonic acid, pyributi- carb, quinoclamine, tridiphane;
O) Insecticides from classes 0.1 to 0.29
0.1 Acetylcholine esterase (AChE) inhibitors: aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; acephate, aza- methiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosa- lone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, pro- thiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamidothion;
0.2 GABA-gated chloride channel antagonists: endosulfan, chlordane; ethiprole, fipronil,
flufiprole, pyrafluprole, pyriprole;
0.3 Sodium channel modulators: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha- cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, del- tamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imiprothrin, meperfluthrin, metofluthrin, momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin and trans- fluthrin; DDT, methoxychlor; 0.4 Nicotinic acetylcholine receptor agonists (nAChR): acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam;
4,5-dihydro-/V-nitro-1 -(2-oxiranylmethyl)-1 A -imidazol-2-amine, (2£)-1-[(6-chloropyridin-3- y methyl^/V^nitro^-pentylidenehydrazinecarboximidamide; 1-[(6-chloropyridin-3-yl)methyl]- 7-methyl-8-nitro-5-propoxy-1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridine; nicotine; sul- foxaflor, flupyradifurone, triflumezopyrim;
0.5 Nicotinic acetylcholine receptor allosteric activators: spinosad, spinetoram;
0.6 Chloride channel activators: abamectin, emamectin benzoate, ivermectin, lepimectin, mil- bemectin;
0.7 Juvenile hormone mimics: hydroprene, kinoprene, methoprene; fenoxycarb, pyriproxyfen;
0.8 miscellaneous non-specific (multi-site) inhibitors: methyl bromide and other alkyl halides; chloropicrin, sulfuryl fluoride, borax, tartar emetic;
0.9 Chordotonal organ TRPV channel modulators: pymetrozine, flonicamid, flonicamid;
O.10 Mite growth inhibitors: clofentezine, hexythiazox, diflovidazin; etoxazole;
0.1 1 Microbial disruptors of insect midgut membranes: Bacillus thuringiensis, Bacillus sphaeri- cus and the insecticdal proteins they produce: Bacillus thuringiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuringiensis subsp.
kurstaki, Bacillus thuringiensis subsp. tenebrionis, the Bt crop proteins: CrylAb, CrylAc, Cry1 Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Ab1 ;
0.12 Inhibitors of mitochondrial ATP synthase: diafenthiuron; azocyclotin, cyhexatin, fenbutatin oxide, propargite, tetradifon;
0.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient: chlorfenapyr, DNOC, sulfluramid;
0.14 Nicotinic acetylcholine receptor (nAChR) channel blockers: bensultap, cartap hydrochloride, thiocyclam, thiosultap sodium;
0.15 Inhibitors of the chitin biosynthesis type 0: bistrifluron, chlorfluazuron, diflubenzuron, flu- cycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron;
0.16 Inhibitors of the chitin biosynthesis type 1 : buprofezin;
0.17 Moulting disruptors: cyromazine;
0.18 Ecdyson receptor agonists: methoxyfenozide, tebufenozide, halofenozide, fufenozide, chromafenozide;
0.19 Octopamin receptor agonists: amitraz;
O.20 Mitochondrial complex III electron transport inhibitors: hydramethylnon, acequinocyl,
fluacrypyrim, bifenazate;
0.21 Mitochondrial complex I electron transport inhibitors: fenazaquin, fenpyroximate, pyrimidif- en, pyridaben, tebufenpyrad, tolfenpyrad; rotenone; 0.22 Voltage-dependent sodium channel blockers: indoxacarb, metaflumizone, 2-[2-(4-cyano- phenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazine- carboxamide, N-(3-chloro-2-methylphenyl)-2-[(4-chlorophenyl)-[4-[methyl(methylsulfonyl)- amino]phenyl]methylene]-hydrazinecarboxamide;
0.23 Inhibitors of the of acetyl CoA carboxylase: spirodiclofen, spiromesifen, spirotetramat, spi- ropidion;
0.24 Mitochondrial complex IV electron transport inhibitors: aluminium phosphide, calcium
phosphide, phosphine, zinc phosphide, cyanide;
0.25 Mitochondrial complex II electron transport inhibitors: cyenopyrafen, cyflumetofen;
0.26 Ryanodine receptor-modulators: flubendiamide, chlorantraniliprole, cyantraniliprole, cycla- niliprole, tetraniliprole; (R)-3-chloro-N1 -{2-methyl-4-[1 ,2,2,2 -tetrafluoro-l-(trifluoromethyl)- ethyl]phenyl}-N2-(1 -methyl-2-methylsulfonylethyl)phthalamide, (S)-3-chloro-N1-{2-methyl-4- [1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]phenyl}-N2-(1-methyl-2-methylsulfonylethyl)- phthalamide, methyl-2-[3,5-dibromo-2-({[3-bromo-1-(3-chloropyridin-2-yl)-1 H-pyrazol-5-yl]- carbonyl}amino)benzoyl]-1 ,2-dimethylhydrazinecarboxylate; N-[4,6-dichloro-2-[(diethyl- lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole- 3-carboxamide; N-[4-chloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]- 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; N-[4-chloro-2-[(di-2-propyl- lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluorometh- yl)pyrazole-3-carboxamide; N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carba- moyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; N-[4,6-di- bromo-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(tri- fluoromethyl)pyrazole-3-carboxamide; N-[2-(5-amino-1 ,3,4-thiadiazol-2-yl)-4-chloro-6-meth- ylphenyl]-3-bromo-1 -(3-chloro-2-pyridinyl)-1 H-pyrazole-5-carboxamide; 3-chloro-1-(3-chloro- 2-pyridinyl)-N-[2,4-dichloro-6-[[(1-cyano-1 -methylethyl)amino]carbonyl]phenyl]-1 H-pyrazole- 5-carboxamide; 3-bromo-N-[2,4-dichloro-6-(methylcarbamoyl)phenyl]-1-(3,5-dichloro-2-pyri- dyl)-1 H-pyrazole-5-carboxamide; N-[4-chloro-2-[[(1 ,1 -dimethylethyl)amino]carbonyl]-6-meth- ylphenyl]-1 -(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1 H-pyrazole-5-carboxamide; cyhalodi- amide;
0.27: Chordotonal organ Modulators - undefined target site: flonicamid;
0.28. insecticidal active compounds of unknown or uncertain mode of action: afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, broflanilide, bromopropylate, chinome- thionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, tioxazafen, 1 1-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-1 1 -en- 10-one, 3-(4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4.5]dec-3-en-2- one, 1 -[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1 H-1 ,2,4- triazole-5-amine, Bacillus firmus, flupyrimin, fluazaindolizine; 4-[5-(3,5-dichlorophenyl)-5- (trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1-oxothietan-3-yl)benzamide; fluxametamide; 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1 H-pyrazole; 3-(benzoyl- methylamino)-N-[2-bromo-4-[1 ,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]-6-(trifluoro- methyl)phenyl]-2-fluoro-benzamide; 3-(benzoylmethylamino)-2-fluoro-N-[2-iodo-4-[1 ,2,2,2-te- trafluoro-1-(trifluoromethyl)ethyl]-6-(tnfluoromethyl)phenyl]-benzamide; N-[3-[[[2-iodo- 4-[1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbon phenyl]-N-methyl-benzamide; N-[3-[[[2-bromo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]- 6-(trifluoromethyl)phenyl]amino]carbonyl]-2-fluorophenyl]-4-fluoro-N-methyl-benzamide; 4-fluoro-N-[2-fluoro-3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6-(trifluoro- methyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide; 3-fluoro-N-[2-fluoro-3-[[[2-iodo- 4-[1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6(trifluoromethyl)phenyl]amino]carbon yl]-N-methyl-benzamide; 2-chloro-N-[3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)- ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-3-pyridinecarboxamide; 4-cyano-
N-[2-cyano-5-[[2,6-dibromo-4-[1 ,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carba- moyl]phenyl]-2-methyl-benzamide; 4-cyano-3-[(4-cyano-2-methyl-benzoyl)amino]-N-[2,6-di- chloro-4-[1 ,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]-2-fluoro-benzamide;
N-[5-[[2-chloro-6-cyano-4-[1 , 2,2,3, 3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]carba- moyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; N-[5-[[2-bromo-6-chloro-4-[2,2,2-tri- fluoro-1 -hydroxy-1 -(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano- 2-methyl-benzamide; N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)- propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; 4-cyano-N-[2-cy- ano-5-[[2,6-dichloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)propyl]phenyl]carbamoyl]- phenyl]-2-methyl-benzamide; 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1 ,2,2,2-tetrafluoro-
1 - (trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; N-[5-[[2-bromo- 6-chloro-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-
4- cyano-2-methyl-benzamide; 2-(1 ,3-dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]-pyridine;
2- [6-[2-(5-fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; 2-[6-[2-(3-pyridinyl)-5-thi- azolyl]-2-pyridinyl]-pyrimidine; N-methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-car- boxamide; N-methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide; N-ethyl- N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio-propanamide; N-methyl-N-[4-methyl-
2- (3-pyridyl)thiazol-5-yl]-3-methylthio-propanamide; N,2-dimethyl-N-[4-methyl-2-(3-pyridyl)- thiazol-5-yl]-3-methylthio-propanamide; N-ethyl-2-methyl-N-[4-methyl-2-(3-pyridyl)thiazol- 5-yl]-3-methylthio-propanamide; N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-2-methyl-
3- methylthio-propanamide; N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N,2-dimethyl-3-methylthio- propanamide; N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-methyl-3-methylthio-propanamide; N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-3-methylthio-propanamide; 1 -[(6-chloro-3-pyri- dinyl)methyl]-1 ,2,3,5,6,7-hexahydro-5-methoxy-7-methyl-8-nitro-imidazo[1 ,2-a]pyridine; 1 -[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridin-
5- ol; 1 -isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; 1 -(1 ,2-dimethyl- propyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; N,5-dimethyl-N-pyridazin-
4- yl-1 -(2,2,2-trifluoro-1-methyl-ethyl)pyrazole-4-carboxamide; 1-[1 -(1 -cyanocyclopropyl)eth- yl]-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; N-ethyl-1 -(2-fluoro-1 -methyl- propyl)-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; 1 -(1 ,2-dimethylpropyl)-N,5-di- methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; 1-[1 -(1 -cyanocyclopropyl)ethyl]-N,5-di- methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; N-methyl-1-(2-fluoro-1 -methyl-propyl]-
5- methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; 1-(4,4-difluorocyclohexyl)-N-ethyl- 5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; 1-(4,4-difluorocyclohexyl)-N,5-dimethyl- N-pyridazin-4-yl-pyrazole-4-carboxamide, N-(1-methylethyl)-2-(3-pyridinyl)-2H-indazole- 4-carboxamide; N-cyclopropyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide; N-cyclohexyl- 2-(3-pyridinyl)-2H-indazole-4-carboxamide; 2-(3-pyridinyl)-N-(2,2,2-trifluoroethyl)-2H-inda- zole-4-carboxamide; 2-(3-pyridinyl)-N-[(tetrahydro-2-furanyl)methyl]-2H-indazole-5-carbox- amide; methyl 2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazinecarboxylate; N-[(2,2-di- fluorocyclopropyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide; N-(2,2-difluoropropyl)-
2- (3-pyridinyl)-2H-indazole-5-carboxamide; 2-(3-pyridinyl )-N-(2-pyrimidinylmethyl )-2H-in- dazole-5-carboxamide; N-[(5-methyl-2-pyrazinyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-car- boxamide, tyclopyrazoflor; N-[3-chloro-1 -(3-pyridyl)pyrazol-4-yl]-N-ethyl-3-(3,3,3- trifluoropropylsulfinyl)propanamide; N-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-3-[(2,2-di- fluorocyclopropyl)methylsulfanyl]-N-ethyl-propanamide; N-[3-chloro-1 -(3-pyridyl)pyrazol- 4-yl]-3-[(2,2-difluorocyclopropyl)methylsulfinyl]-N-ethyl-propanamide; sarolaner, lotilaner, N- [4-chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-1-methyl-3-(1 ,1 ,2,2,2-pentafluoroethyl)- 4-(trifluoromethyl)-1 A -pyrazole-5-carboxamide; M. UN.22a 2-(3-ethylsulfonyl-2-pyridyl)-3- methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 2-[3-ethylsulfonyl-5-(trifluoromethyl)-2- pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, 4-[5-(3,5-dichlorophenyl)-5-(tri- fluoromethyl)-4A isoxazol-3-yl]-N-[(4 t -2-ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl-benzamide, 4-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(trifluoromethyl)-4 isoxazol-3-yl]-/V-[(4 )-2-ethyl-3-oxo- isoxazolidin-4-yl]-2-methyl-benzamide; N[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-2- methyl-5-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide, /V-[4-chloro-
3- [(1-cyanocyclopropyl)carbamoyl]phenyl]-2-methyl-5-(1 , 1 ,2,2, 2-pentafluoroethyl)-4- (trifluoromethyl)pyrazole-3-carboxamide; acynonapyr; benzpyrimoxan; chloro-/V-(1- cyanocyclopropyl)-5-[1-[2-methyl-5-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazol-3- yl]pyrazol-4-yl]benzamide.
The active substances referred to as component 2, their preparation and their activity e. g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by lUPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968;
EP-A 141 317; EP-A 152 031 ; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941 ; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP-A 1 201 648; EP-A 1 122 244,
JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272;
US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501 ; WO 01/56358; WO 02/22583; WO 02/40431 ; WO 03/10149; WO 03/1 1853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491 ; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721 ; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 10/139271 , WO 1 1/028657, WO 12/168188, WO 07/006670, WO 1 1/77514; WO 13/047749, WO 10/069882, WO 13/047441 , WO 03/16303, WO 09/90181 , WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009, WO 13/24010, WO 13/047441 , WO 13/162072, WO 13/092224, WO 1 1/135833, CN 1907024, CN 1456054, CN 103387541 , CN 1309897, WO 12/84812, CN 1907024, WO 09094442, WO 14/60177, WO 13/1 16251 , WO 08/013622, WO 15/65922, WO 94/01546, EP 2865265, WO 07/129454, WO 12/16551 1 , WO 1 1/081 174, WO 13/47441 ). The present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I (component 1 ) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to O) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to K), as described above, and if de- sired one suitable solvent or solid carrier. Those mixtures are of particular interest, since many of them at the same application rate show higher efficiencies against harmful fungi. Furthermore, combating harmful fungi with a mixture of compounds I and at least one fungicide from groups A) to K), as described above, is more efficient than combating those fungi with individual compounds I or individual fungicides from groups A) to K).
By applying compounds I together with at least one active substance from groups A) to O) a synergistic effect can be obtained, i.e. more then simple addition of the individual effects is obtained (synergistic mixtures).
This can be obtained by applying the compounds I and at least one further active substance simultaneously, either jointly (e. g. as tank-mix) or seperately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further active substance(s). The order of application is not essential for working of the present invention.
When applying compound I and a pesticide II sequentially the time between both applications may vary e. g. between 2 hours to 7 days. Also a broader range is possible ranging from 0.25 hour to 30 days, preferably from 0.5 hour to 14 days, particularly from 1 hour to 7 days or from 1.5 hours to 5 days, even more preferred from 2 hours to 1 day.
In the binary mixtures and compositions according to the invention the weight ratio of the component 1 ) and the component 2) generally depends from the properties of the active com- ponents used, usually it is in the range of from 1 :10,000 to 10,000:1 , often it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50: 1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 , even more preferably in the range of from 1 :4 to 4:1 and in particular in the range of from 1 :2 to 2:1 .
According to further embodiments of the binary mixtures and compositions, the weight ratio of the component 1 ) and the component 2) usually is in the range of from 1000:1 to 1 :1 , often in the range of from 100: 1 to 1 :1 , regularly in the range of from 50:1 to 1 :1 , preferably in the range of from 20:1 to 1 :1 , more preferably in the range of from 10:1 to 1 :1 , even more preferably in the range of from 4:1 to 1 :1 and in particular in the range of from 2:1 to 1 :1 .
According to a further embodiments of the binary mixtures and compositions, the weight ratio of the component 1 ) and the component 2) usually is in the range of from 1 :1 to 1 :1000, often in the range of from 1 :1 to 1 :100, regularly in the range of from 1 :1 to 1 :50, preferably in the range of from 1 :1 to 1 :20, more preferably in the range of from 1 :1 to 1 :10, even more preferably in the range of from 1 :1 to 1 :4 and in particular in the range of from 1 :1 to 1 :2.
In the ternary mixtures, i.e. compositions according to the invention comprising the component 1 ) and component 2) and a compound III (component 3), the weight ratio of component 1 ) and component 2) depends from the properties of the active substances used, usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4:1 , and the weight ratio of component 1 ) and component 3) usually it is in the range of from 1 :100 to 100:1 , regularly in the range of from 1 :50 to 50:1 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :4 to 4:1.
Any further active components are, if desired, added in a ratio of from 20:1 to 1 :20 to the component 1 ).
These ratios are also suitable for inventive mixtures applied by seed treatment.
Preference is also given to mixtures comprising as component 2) at least one active substance selected from inhibitors of complex III at Q0 site in group A), more preferably selected from compounds (A.1.1 ), (A.1.4), (A.1.8), (A.1.9), (A.1.10), (A.1 .12), (A.1.13), (A.1 .14), (A.1.17), (A.1 .21 ), (A.1.25), (A.1 .34) and (A.1 .35); particularly selected from (A.1.1 ), (A.1.4), (A.1.8), (A.1 .9), (A.1 .13), (A.1.14), (A.1 .17), (A.1.25), (A.1 .34) and (A.1 .35).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from inhibitors of complex III at Q, site in group A), more preferably selected from compounds (A.2.1 ), (A.2.3) and (A.2.4); particularly selected from (A.2.3) and (A.2.4).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from inhibitors of complex II in group A), more preferably selected from compounds (A.3.2), (A.3.3), (A.3.4), (A.3.7), (A.3.9), (A.3.1 1 ), (A.3.12), (A.3.15), (A.3.16), (A.3.17), (A.3.18), (A.3.19), (A.3.20), (A.3.21 ), (A.3.22), (A.3.23), ( (A.3.28), (A.3.31 ), (A.3.32), (A.3.33), (A.3.34), (A.3.35), (A.3.36), (A.3.37), (A.3.38) and (A.3.39); particularly selected from (A.3.2), (A.3.3), (A.3.4), (A.3.7), (A.3.9), (A.3.12), (A.3.15), (A.3.17), (A.3.19), (A.3.22), (A.3.23), (A.3.31 ), (A.3.32), (A.3.33), (A.3.34), (A.3.35), (A.3.36), (A.3.37), (A.3.38) and (A.3.39).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from other respiration nhibitors in group A), more preferably selected from compounds (A.4.5) and (A.4.1 1 ); in particular (A.4.1 1 ).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from C14 demethylase inhibitors in group B), more preferably selected from compounds (B.1 .4), (B.1 .5), (B.1 .8), (B.1 .10), (B.1.1 1 ), (B.1 .12), (B.1.13), (B.1 .17), (B.1.18), (B.1 .21 ), (B.1.22), (B.1.23), (B.1 .25), (B.1.26), (B.1 .29), (B.1.34), (B.1 .37), (B.1.38), (B.1 .43) and (B.1 .46); particularly selected from (B.1.5), (B.1.8), (B.1 .10), (B.1.17), (B.1.22), (B.1.23), (B.1 .25), (B.1.33), (B.1 .34), (B.1.37), (B.138), (B.1.43) and (B.1.46).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from Delta 14-reductase inhibitors in group B), more preferably selected from com- pounds (B.2.4), (B.2.5), (B.2.6) and (B.2.8); in particular (B.2.4).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from phenylamides and acyl amino acid fungicides in group C), more preferably selected from compounds (C.1 .1 ), (C.1 .2), (C.1.4) and (C.1.5); particularly selected from (C.1 .1 ) and (C.1.4).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from other nucleic acid synthesis inhibitors in group C), more preferably selected from compounds (C.2.6),(C.2.7) and (C.2.8).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group D), more preferably selected from compounds (D.1.1 ), (D.1 .2), (D.1.5), (D.2.4) and (D.2.6); particularly selected from (D.1 .2), (D.1.5) and (D.2.6).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group E), more preferably selected from compounds (E.1.1 ), (E.1.3), (E.2.2) and (E.2.3); in particular (E.1.3).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group F), more preferably selected from compounds (F.1.2), (F.1.4) and (F.1.5). Preference is also given to mixtures comprising as component 2) at least one active substance selected from group G), more preferably selected from compounds (G.3.1 ), (G.3.3), (G.3.6), (G.5.1 ), (G.5.2), (G.5.3), (G.5.4), (G.5.5), G.5.6), G.5.7), (G.5.8), (G.5.9), (G.5.10) and (G.5.1 1 ); particularly selected from (G.3.1 ), (G.5.1 ), (G.5.2) and (G.5.3).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group H), more preferably selected from compounds (H.2.2), (H.2.3), (H.2.5),
(H.2.7), (H.2.8), (H.3.2), (H.3.4), (H.3.5), (H.4.9) and (H.4.10); particularly selected from (H.2.2), (H.2.5), (H.3.2), (H.4.9) and (H.4.10).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group I), more preferably selected from compounds (1.2.2) and (I.2.5).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group J), more preferably selected from compounds (J.1 .2), (J.1.5) and (J.1 .8); in particular (J.1.5).
Preference is also given to mixtures comprising as component 2) at least one active substance selected from group K), more preferably selected from compounds (K.1.41 ), (K.1 .42), (K.1.44), (K.1 .45), (K.1.47) and (K.1.49); particularly selected from (K.1 .41 ), (K.1.44), (K.1 .45), (K.1.47) and (K.1 .49).
The mixtures of active substances can be prepared as compositions comprising besides the active ingredients at least one inert ingredient (auxiliary) by usual means, e. g. by the means given for the compositions of compounds I. Concerning usual ingredients of such compositions reference is made to the explanations given for the compositions containing compounds I.
I. Synthesis examples
With due modification of the starting compounds, the procedures shown in the synthesis examples below were used to obtain further compounds I. The resulting compounds, together with physical data, are listed in Table I below.
Example 1 Synthesis of 3-(3,3-dichloroallyl)-3-methyl-1-(3-quinolyl)-4H-isoquinoline (LA.1 -1 )
1. Synthesis of 2-(2,2-dichlorocyclopropyl)-1 -phenyl-propan-2-ol
The mixture of 2,2-dichlorocyclopropyl methyl ketone (2.645 g, 18.8 mmol) in THF (100 mL) was added BnMgCI (56.3mL, 56.3 mmol) dropwise at 0 °C under N2, the mixture was stirred for 3 h at 0 °C. The reaction mixture was quenched with aq. NH4CI (50 ml.) and extracted with MTBE (50 ml_), dried over Na2S04 and concentrated, the residue was purified by column
(PE:EtOAc=40:1 ) to give the tittle compound (2.7 g, 60%) as yellow oil.
2. Synthesis of 3-(3,3-dichloroallyl)-3-methyl-1-(3-quinolyl)-4H-isoquinoline (I.A.1 -2)
3,0 g of trifluoromethane sulfonic acid was added dropwise to a mixture of 0,252 g (2 mmol) quinoline-3-carbonitrile and 0,5 g (1 ,6 mmol) 2-(2,2-dichlorocyclopropyl)-1-phenyl-propan-2-ol in 50 ml. dichloroethane at 0 - 5°C. After 12 h at room temperature the reaction mixture was poured onto sodium carbonate solution, the organic layer was separated and the aqueous layer was extracted with dichloromethane. The combined organic extracts were extracted with sodi- urn hydrogen carbonate and water, evaporated and the residue was purified via silica gel column chromatography to yield 0,207 g (34 %) of the title compound as a light yellow oil.
H NMR (CDCIs, δ in ppm): 9,1 (s, 1 H); 8,4 (s, 1 H); 8,2 (d, 2H); 7,9 (d, 1 H); 7,8 (td, 1 H); 7,6 (td, 1 H); 7,3 (m, 3H); 6,1 (t, 1 H); 2,9 (dd, 1 H); 2,8 (dd, 1 H); 2,5 (qd, 2H).
*HPLC-MS: Rt = 0,960 min; M++H=381 ,0
Example 2 Synthesis of 3-[3-(3,3-dichloroallyl)-3-methyl-4H-isoquinolin-1 -yl]-8-fluoro-quinoline
6,0 g of trifluoromethane sulfonic acid was added dropwise to a mixture of 0,591 g (3 mmol) 8- fluoroquinoline-3-carbonitrile and 1 g (4 mmol) 2-(2,2-dichlorocyclopropyl)-1-phenyl-propan-2-ol in 25 ml. dichloroethane at 0 - 5°C. After 12 h at room temperature the reaction mixture was poured onto sodium hydrocarbonate solution, the organic layer was separated and the aqueous layer was extracted with MTBE. The combined organic extracts were extracted with water and a sat. sodium chloride solution, evaporated and the residue was purified via silica gel column chromatography to yield 0,5 g (38 %) of the title compound as a light orange oil.
H NMR (CDCIs, δ in ppm): 9,2 (s, 1 H); 8,4 (s, 1 H); 7,7 (d, 2H); 7,5 (m, 1 H); 7,4 (m, 2H); 7,3- 7,2 (m, 2H); 6,1 (t, 1 H); 2,9 (dd, 1 H); 2,8 (dd, 1 H); 2,5 (qd, 2H).
*HPLC-MS: Rt = 1 ,018 min; M++H=399,29Example 3 Synthesis of 3-[3-(3,3-dichloroallyl)- 2,3-dimethyl-1 ,4-dihydroisoquinolin-1yl]quinoline (I.A.2-2)
. Synthesis of 3-[3-(3,3-dichloroallyl)-3-methyl-2,4-dihydro-1 H-isoquinolin-1-yl]quinoline (I.A.2-
1 )
To a solution of example 2 (0.366 g, 0.917 mmol) in 6 ml. MeOH and 2 ml. acetic acid,
NaBH3CN (0.058 g, 0.917 mmol) at 0 °C. The reaction mixture was allowed to warm to room temperature and stirred overnight. The mixture was diluted with ethyl acetated and poured onto sodium hydrocarbonate solution. The organic layer was separated and the aqueous layer was extracted with ethyl acetate The combined organic extracts were extracted with water and a sat. sodium chloride solution and evaporated to yield 100 mg (25 %) of the title compound as an oil.
*HPLC-MS: Rt = 0,953 and 1 ,039 min; M++H=401 ,0
2. Synthesis of 3-[3-(3,3-dichloroallyl)-2,3-dimethyl-1 ,4-dihydroisoquinolin-1-yl]quinoline (I.A.2- 2) To a solution of 3-[3-(3,3-dichloroallyl)-3-methyl-2,4-dihydro-1 H-isoquinolin-1 -yl]quinoline (100 mg, 0.249 mmol) in 2.5 mL acetonitrile, formaldehyde (10 mL, 2.492 mmol), NaCNBHs (0.047 mg, 0.748 mmol) and .25 mL acetic acid were added. The mixture was stirred at room temperature overnight. The mixture was diluted with ethyl acetated and poured onto 1 M NaOH solution. After the aq. Layer was wahed with a sat. Na2HCC>3 solution, finally the combined organic extracts were extracted with water and a sat. sodium chloride solution. The residue was purified via silica gel column chromatography to yield 0,018 g (14 %) of the title compound as an oil. H NMR (CDCIs, δ in ppm): 8,9 (s, 2H); 8,2 (s, 2H); 7,6 (dd, 2H); 7,4 (q, 2H); 7,2 (s, 4H); 7,2-7,1 (m, 2H); 7.0 (m, 4H); 6,2 (t, 1 H); 5.8 (t, 1 H); 4.8 (s, 1 H); 4.7 (s, 1 H); 3.3 (dd, 2H); 3.1 (dd, 2H); 3.0 (s, 3H); 2.7-2.5 (m, 2H); 2. 6 (s, 3H); 2.5-2.3 (m, 2H); 2.4 (s, 6H).
*HPLC-MS: Rt = 1 ,002, 1 ,013 min; M++H=415,0 Table I:
The positions of the phenyl given as "R7+R8" marked with "#" represents the connection points (carbon atoms 5' and 6' in formula I) with the remaining skeleton of the compounds of formula
Figure imgf000133_0001
I.A.1
No. (R1)m (R2)n R3 R4 R7+R8 1H-NMR (5 in
ppm);
HPLC-MS* (El
(M++H)
Rt [min],
Mp (°C)
I.A.1-1 m=0 n=0 CH3 CI #5' 0,96 min;
M++H=381 ,0;
# *T l)
Figure imgf000134_0001
Figure imgf000135_0001
Figure imgf000136_0001
*HPLC-MS: HPLC-column KinetexXB C181,7μ (50x2,1 mm); eluent: acetonitrile / water +
0.1% TFA (5 gradient from 5:95 to 100 : 0 in 1.5 min at 60°C, flow gradient from 0.8 to 1.0 ml/min in 1.5 min). MS: Quadrupol Electrospray lonisation, 80 V (positive mode).
Figure imgf000137_0001
Figure imgf000137_0002
II. Biological trials
Green House
The spray solutions were prepared in several steps:
The stock solution were prepared: a mixture of acetone and/or dimethylsulfoxide and the wetting agent/emulsifier Wettol, which is based on ethoxylated alkylphenoles, in a relation (volume) solvent-emulsifier of 99 to 1 was added to 25 mg of the compound to give a total of 5 ml.
Water was then added to total volume of 100 ml.
This stock solution was diluted with the described solvent-emulsifier-water mixture to the given concentration.
Example 1 - Preventative fungicidal control of Botrytis cinereaon leaves of green pepper
Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below. The next day the plants were inoculated with an aqueous biomalt or DOB media solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 24· C and a relative humidity close to 100 % the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
In this test, plants which had been treated with 250 ppm of the active substance from examples I.A.1 -1 1 , I.A.1 -12, I.A.1-13, I.A.1-15, I.A.1 -17 and I.A.1-18 respectively, showed up to at most 4 % diseased leaf area compared to 90 % diseased leaf area by untreated plants.
Example 2 - Long lasting control of Botrytis cinerea on leaves of green pepper
Young seedlings of green pepper were grown in pots to the 4 to 5 leaf stage. These plants were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture mentioned in the table below. The plants were then cultivated in the greenhouse for 7 days and then inoculated with an aqueous biomalt solution containing the spore suspension of Botrytis cinerea. Then the plants were immediately transferred to a humid chamber. After 5 days at 22 to 24°C and a relative humidity close to 100 % the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
In this test, plants which had been treated with 250 ppm of the active substance from examples I.A.1 -1 , I.A.1-2, I.A.1 -3, I.A.1-4, I.A.1 -5, I.A.1-6, I.A.1 -7, I.A.1-9, I.A.1 -10, I.A.1 -1 1 , I.A.1 -12, I.A.1 -13, I.A.1 -14, I.A.1 -15, I.A.1 -16, I.A.1-17, I.A.1-18 and I.A.1-19 respectively, showed up to at most 16 % diseased leaf area compared to 90 % diseased leaf area by untreated plants.
Example 3 - Control of culm rot on pearl millet caused by Fusarium culmorum
Pot-grown pearl millet seedlings were sprayed to run-off with an aqueous suspension, containing the concentration of active ingredient or their mixture as described below. Seven days later the plants were inoculated with a spore suspension of Fusarium culmorum in an aqueous biomalt or DOB media solution. Then the trial plants were immediately transferred to a humid chamber. After 6 days at 23-25°C and a relative humidity close to 100 % the extent of fungal attack on the leaves was visually assessed as % diseased leaf area. In this test, plants which had been treated with 250 ppm of the active substance from examples I.A.1 -1 , I.A.1-2, I.A.1 -10, I.A.1 -12, I.A.1 -13, I.A.1 -14, I.A.1 -15, I.A.1 -17, I.A.1 -18 and I.A.1-19 respectively, showed up to at most 14 % diseased leaf area compared to 90 % diseased leaf area by untreated plants.

Claims

Claims
Compounds of the formula I
Figure imgf000139_0001
wherein
A is
Figure imgf000139_0002
m is 0, 1 , 2, 3 or 4;
R1 is in each case independently selected from halogen, OH, CN, NO2, SH, N H2,
NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH-S02-Rx, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, Ci-C6-alkoxy, C3-C6-cycloalkyl, five- or six-membered heteroaryl and aryl; wherein the heteroaryl contains one, two or three heteroatoms selected from N, O and S; and wherein
Rx is Ci-C4-alkyl, Ci-C4-halogenalkyl, unsubstituted aryl or aryl that is substituted by one, two, three, four or five substituents Rx1 independently selected from Ci-C4-alkyl, halogen, OH, CN, Ci-C4-halogenalkyl, Ci-C4-alkoxy, and Ci-C4- halogenalkoxy;
wherein the aliphatic moieties of R1 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R1a which independently of one another are selected from:
R 1a halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci- C4-halogenalkoxy, Ci-C6-alkylthio and phenoxy, wherein the phenyl group is unsubstituted or carries one, two, three, four or five substituents R11a selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci- C4-alkoxy and Ci-C4-halogenalkoxy; wherein the cycloalkyi, heteroaryl and aryl moieties of R1 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R1b which independently of one another are selected from:
R1b halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6- cycloalkyi, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio; n is 0, 1 or 2;
R2 is in each case independently selected from the substituents as defined for R1, wherein the possible substituents for R2 are R2a and R2b , respectively, which correspond to R1a and R1b, respectively;
R3 is CH3, CH2F, CHF2 and CF3;
R4 are independently selected from OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4- alkyl)2, NH-S02-Rx, subtituted Ci-C6-alkyl, Ci-C6-alkylthio, C2-C6-alkenyl, C2-C6- halogenalkenyl, C2-C6-alkynyl, C2-C6-halogenalkynyl, Ci-C6-alkoxy, C1-C6- halogenalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, CH(=0), C(=0)CrC6-alkyl, C(=0)0(CrC6-alkyl), C(=0)NH(C C6-alkyl), C(=0)N(C C6-alkyl)2, CR'=NOR", a saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle or heterocycle, wherein in each case one or two CH2 groups of the carbo- and heterocycle may be replaced by a group independently selected from C(=0) and C(=S),wherein the heterocycle contains independently one, two, three or four heteroatoms selected from N, O and S; and wherein R' and R" are independently selected from H, Ci-C4-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten- membered carbo- and heterocycle, and wherein R' and R" are independently un- substituted or substituted by R'" which is independently selected from halogen, OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH-S02-R*, Ci-C6-alkyl, Ci-C6- halogenalkyl, C2-C6-alkenyl, C2-C6-halogenalkenyl, C2-C6-alkynyl, C2-C6- halogenalkynyl, Ci-C6-alkoxy, Ci-C6-halogenalkoxy, C3-C6-cycloalkyl, C3-C6- halogencycloalkyl and phenyl; wherein the acyclic moieties except for subtituted Ci-C6-alkyl moieties of R4 are independently not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R4a, respectively, which
independently of one another are selected from:
R a halogen, OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2,
NH(C(=0)Ci-C4-alkyl), N(C(=0)Ci-C4-alkyl)2, NH-S02-Rx, Ci-C6-alkoxy, Ci-C4- halogenalkoxy, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl,-S(0)z-Ci-C6-alkyl,
S(0)z-Ci-C6-halogenalkyl, S(0)z-aryl, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(Ci- Ce-alkyl), C(=0)NH(Ci-C6-alkyl), C(=0)N(Ci-C6-alkyl)2, CR'=NOR", a saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten-membered carbocycle or heterocycle, five-, six- or ten-membered heteroaryl, aryl, phenoxy; wherein in each case one or two CH2 groups of the carbocycle and heterocycle may be replaced by a group independently selected from C(=0) and C(=S); wherein the heterocycle and heteroaryl contain independently one, two, three or four heteroatoms selected from N, O and S; wherein the carbocyclic, heterocyclic, aryl, phenyl and heteroaryl groups are independently unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of halogen, OH, CN, NO2, SH,
NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C(=0)C C4-alkyl), N(C(=0)Ci-C4- alkyl)2, NH-S02-Rx, d-C6-alkylthio, Ci-C4-alkyl, C C4-halogenalkyl, Ci-C4- alkoxy, Ci-C4-halogenalkoxy and S(0)z-Ci-C6-alkyl;
wherein the carbocyclic, heterocyclic moieties of R4 are independently not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R4b, respectively, which independently of one another are selected from:
R4b halogen, OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2,
NH(C(=0)CrC4-alkyl), N(C(=0)Ci-C4-alkyl)2, NH-S02-RX, C C4-alkyl, C C4- alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4- halogenalkoxy, Ci-C6-alkylthio, Ci-C6-halogenalkylthio, S(0)z-Ci-C6-alkyl, Ci- C4-alkoxy-Ci-C4-alkyl, phenyl and phenoxy, wherein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4- alkoxy and Ci-C4-halogenalkoxy; wherein the subtituted Ci-C6-alkyl moieties of R4 carry one, two, three or up to the maximum possible number of identical or different groups R4c, respectively, which independently of one another are selected from:
R c OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C(=0)Ci-C4- alkyl), N(C(=0)Ci-C4-alkyl)2, NH-S02-Rx, Ci-C4-halogenalkoxy, C3-C6- cycloalkyl, C3-C6-halogencycloalkylS(0)-Ci-C6-alkyl, S(0)2-Ci-C6-alkyl, S(0)z- d-Ce-halogenalkyl, S(0)z-aryl, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6- alkyl), C(=0)NH(Ci-C6-alkyl), C(=0)N(Ci-C6-alkyl)2, CR'=NOR", a saturated or partially unsaturated three-, four-, five-, six-, seven-, eight-, nine-, or ten- membered carbocycle or heterocycle, five-, six- or ten-membered heteroaryl; wherein in each case one or two CH2 groups of the carbocycle and heterocycle may be replaced by a group independently selected from C(=0) and C(=S); wherein the heterocycle and heteroaryl contain independently one, two, three or four heteroatoms selected from N, O and S; wherein the carbocyclic, heterocyclic, aryl, phenyl and heteroaryl groups are independently unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of halogen, OH, CN, N02, SH, NH2, NH(Ci-C4-alkyl), N(Ci-C4- alkyl)2, NH(C(=0)C C4-alkyl), N(C(=0)C C4-alkyl)2, NH-S02-Rx, Ci-C6- alkylthio, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy, Ci-C4-halogenalkoxy and S(0)z-Ci-C6-alkyl; z is 0, 1 and 2; and wherein Rx R' and R" is as defined above; R5 is H;
R6 is H;
and
R7 and R8 together with the carbon atoms to which they are bound form a phenyl ring; wherein the phenyl carries zero, one, two, three or four substituents (R78)0, wherein o is 0, 1 , 2 or 3; and
R78 are independently selected from halogen, OH, CN, NO2, SH, NH2,
NH(Ci-C4-alkyl), N(Ci-C4-alkyl)2, NH(C(=0)Ci-C4-alkyl), N(C(=0)Ci-C4- alkyl)2, NH-S02-Rx, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6-alkyl), C(=0)NH(Ci-C6-alkyl), CR'=NOR", Ci-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, Ci-C6-alkoxy, Ci-C6-halogenalkoxy, C2-C6-alkenyloxy, C2-C6- alkynyloxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, S(0)z-Ci-C6-alkyl, three- , four-, five- or six-membered saturated or partially unsaturated heterocy- cle, five- or six-membered heteroaryl and phenyl; wherein the heterocycle or heteroaryl contains one, two or three heteroatoms selected from N, O and S; wherein the heterocycle or heteroaryl contains one, two or three heteroatoms selected from N, O and S; wherein z, R' and R" is as defined above; wherein the acyclic moieties of R78 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R78a which independently of one another are selected from:
R78a halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6- cycloalkenyl, C3-C6-halogencycloalkyl, C3-C6-halogencycloalkenyl, Ci-C4-halogenalkoxy, Ci-C6-alkylthio, five- or six-membered het- eroaryl, phenyl and phenoxy, wherein the heterorayl, phenyl and phenoxy group is unsubstituted or carries one, two, three, four or five substituents R78a' selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4- halogenalkoxy; wherein the cyclic, phenyl, heterocyclic and heteroaryl moieties of R78 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R78b which independently of one another are selected from:
R78b halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio;
R9 is in each case independently selected from hydrogen, OH, CH(=0), C(=0)Ci-C6- alkyl, C(=0)C2-C6-alkenyl, C(=0)C2-C6-alkynyl, C(=0)C3-C6-cycloalkyl, C(=0)0(d- Ce-alkyl), C(=0)0(C2-C6-alkenyl), C(=0)0(C2-C6-alkynyl), C(=0)0(C3-C6- cycloalkyl), C(=0)NH(Ci-C6-alkyl), C(=0)NH(C2-C6-alkenyl), C(=0)NH(C2-C6- alkynyl), C(=0)NH(C3-C6-cycloalkyl), C(=0)N(Ci-C6-alkyl)2, C(=0)N(C2-C6- alkenyl)2, C(=0)N(C2-C6-alkynyl)2, C(=0)N(C3-C6-cycloalkyl)2, CH(=S), C(=S)Ci-C6- alkyl, C(=S)C2-C6-alkenyl, C(=S)C2-C6-alkynyl, C(=S)C3-C6-cycloalkyl, C(=S)0(Ci- Ce-alkyl), C(=S)0(C2-C6-alkenyl), C(=S)0(C2-C6-alkynyl), C(=S)0(C3-C6- cycloalkyl), C(=S)NH(Ci-C6-alkyl), C(=S)N H(C2-C6-alkenyl), C(=S)NH(C2-C6- alkynyl), C(=S)NH(C3-C6-cycloalkyl), C(=S)N(Ci-C6-alkyl)2, C(=S)N(C2-C6-alkenyl)2, C(=S)N(C2-C6-alkynyl)2, C(=S)N(C3-C6-cycloalkyl)2, Ci-C6-alkyl, Ci-C4-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkylC2-C6-alkenyl, C2-C6-halogenalkenyl C2- C6-alkynyl, C2-C6-halogenalkynyl, S(0)z-Ci-C6-alkyl, S(0)z-Ci-C6-halogenalkyl, S(0)z-C2-C6-alkenyl, S(0)z-C2-C6-alkynyl, S(0)zaryl, S02-NH(Ci-C6-alkyl), S02- NH(Ci-C6-halogenalkyl), S02-NH-aryl, tri-(Ci-C6 alkyl)silyl and di-(Ci-C6
alkoxy)phosphoryl), five- or six-membered heteroaryl and aryl; wherein the het- eroaryl contains one, two or three heteroatoms selected from N, O and S; wherein the aryl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN , halogen, OH, Ci-C4-alkyl, Ci-C4- halogenalkyl, Ci-C4-alkoxy and Ci-C4-halogenalkoxy; wherein z is as defined above;
RY is Ci-C6-alkyl, Ci-C6-halogenalkyl, C2-C6-alkenyl, C2-C6-halogenalkenyl, C2-C6- alkynyl, C2-C6-halogenalkynyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, phenyl and phenyl-Ci-C6-alkyl; wherein the phenyl groups are unsubstituted or carry one, two, three, four or five substituents selected from the group consisting of CN, halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci- C4-halogenalkoxy; wherein the acyclic moieties of R9 are not further substituted or carry one, two, three or up to the maximum possible number of identical or different groups R9a which independently of one another are selected from:
R9a halogen, OH, CN, Ci-C6-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, C3-C6- halogencycloalkyl, C3-C6-halogencycloalkenyl, Ci-C4-halogenalkoxy, C1-C6- alkylthio, five- or six-membered heteroaryl, phenyl and phenoxy, wherein the heteroaryl, phenyl and phenoxy group is unsubstituted or carries one, two, three, four or five substituents R9a' selected from the group consisting of halogen, OH, Ci-C4-alkyl, Ci-C4-halogenalkyl, Ci-C4-alkoxy and Ci-C4- halogenalkoxy; wherein the alicyclic, phenyl, heterocyclic and heteroaryl moieties of R9 are not further substituted or carry one, two, three, four, five or up to the maximum number of identical or different groups R9b which independently of one another are selected from:
R9b halogen, OH, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-halogenalkyl, C3-C6- cycloalkyl, C3-C6-halogencycloalkyl, Ci-C4-halogenalkoxy and Ci-C6-alkylthio; and the N-oxides and the agriculturally acceptable salts thereof.
The compounds of claim 1 , wherein m is 0.
The compounds of claim 1 or 2, wherein m is 1 or 2 and R1 is halogen.
The compounds of any one of claims 1 to 3, wherein R3 n is 0.
The compounds of any one of claims 1 to 4, wherein R4 is in each case independently selected from CN, C2-C6-alkenyl, C2-C6-halogenalkenyl, C3-C6-cycloalkenyl, C2-C6- alkynyl, C2-C6-halogenalkynyl, C3-C6-cycloalkynyl, CH(=0), C(=0)C C6-alkyl,
C(=0)0(Ci-C6-alkyl), CR'=NOR", C3-C6-halogencycloalkyl, a saturated three-, four-, five- , six-, membered carbocycle or heterocycle, and Ci-C6-alkyl substituted by CN, C1-C4- halogenalkoxy, S(0)z-Ci-C6-alkyl, NH-S02-Rx, NH(Ci-C6-alkyl), N(Ci-C6-alkyl)2, CH(=0), C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6-alkyl), a saturated three-, four-, five-, six-, membered carbocycle or heterocycle or a five- or six-membered heteroaryl.
The compounds of any one of claims 1 to 5, wherein wherein R4 is in each case independently selected from C2-C6-alkenyl, C2-C6-halogenalkenyl, C2-C6-alkynyl, C2-C6- halogenalkynyl, C3-C6-cycloalkyl, C3-C6-halogencycloalkyl, and Ci-C6-alkyl substituted by a five- or six-membered heteroaryl or a carbocycle.
The compounds of any one of claims 1 to 6 of the formula I.A.1 :
Figure imgf000144_0001
Figure imgf000144_0002
wherein R9 is hydrogen, C(=0)Ci-C6-alkyl, C(=0)0(Ci-C6-alkyl), C(=0)NH(Ci-C6-alkyl), S(0)z-Ci-C6-alkyl, S(0)z-aryl, S02-NH(Ci-C6-alkyl), ORY, or Ci-C4-alkyl.
A process for the synthesis of compounds I of claim 1 , comprising the step of:
a) reacting a compound XIII
Figure imgf000145_0001
XIII wherein all substituents are as defined in claim 1 with the proviso that R4 can not be C(=0)0(Ci-C6-alkyl).
10. The intermediate compounds XI as defined in claim 9.
1 1. A composition, comprising one compound of formula I, as defined in any of the claims 1 to 8, an N-oxide or an agriculturally acceptable salt thereof.
12. The composition according to claim 1 1 , comprising additionally a further active substance.
13. A use of a compound of the formula I, as defined in any of the claims 1 to 8, and/or of an agriculturally acceptable salt thereof or of the compositions, as defined in any of the claims 1 1 or 12, for combating phytopathogenic fungi.
14. A method for combating phytopathogenic fungi, comprising treating the fungi or the materials, plants, the soil or seeds to be protected against fungal attack with an effective amount of at least one compound of formula I, as defined in any of the claims 1 to 8 or with a composition, as defined in any of the claims 1 1 or 12.
15. Seed, coated with at least one compound of the formula I, as defined in any of the
claims 1 to 8, and/or an agriculturally acceptable salt thereof or with a composition, as defined in any of the claims 1 1 or 12, in an amount of from 0.1 to 10 kg per 100 kg of seed.
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WO2021204855A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydropyrrolopyrazine derivatives
WO2021204857A1 (en) 2020-04-08 2021-10-14 Syngenta Crop Protection Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
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