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WO2010146116A1 - Triazole compounds carrying a sulfur substituent - Google Patents

Triazole compounds carrying a sulfur substituent Download PDF

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Publication number
WO2010146116A1
WO2010146116A1 PCT/EP2010/058541 EP2010058541W WO2010146116A1 WO 2010146116 A1 WO2010146116 A1 WO 2010146116A1 EP 2010058541 W EP2010058541 W EP 2010058541W WO 2010146116 A1 WO2010146116 A1 WO 2010146116A1
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het
compounds
formula
tables
combination
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PCT/EP2010/058541
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French (fr)
Inventor
Sarah Ulmschneider
Jochen Dietz
Jens Renner
Thomas Grote
Wassilios Grammenos
Bernd Müller
Jan Klaas Lohmann
Marianna Vrettou-Schultes
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Basf Se
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Publication of WO2010146116A1 publication Critical patent/WO2010146116A1/en

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    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/10—Antimycotics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P35/00—Antineoplastic agents

Definitions

  • the present invention relates to novel triazole compounds of the formulae I and Il as defined below which carry a sulfur substituent, to agricultural compositions containing them, to their use as fungicides and to intermediate compounds used in the method of producing them.
  • Plant disease damage to ornamental, vegetable, field, cereal, and fruit crops can cause significant reduction in productivity and thereby result in increased costs to the consumer.
  • WO 96/41804, WO 96/16048, WO 97/41107, WO 97/43269 and WO 97/44331 describe sulfurized triazolyl derivatives. The compounds are used for combating harmful fungi.
  • triazole compounds of the general formulae I and II defined below, and by the agriculturally acceptable salts of the compounds I and II.
  • the present invention relates to triazole compounds of the formulae I and Il and to agriculturally useful salts thereof
  • Ar is phenyl which may carry 1 , 2, 3, 4 or 5 substituents R 2 , or is a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2, 3 or 4 substituents R 3 ;
  • Het is a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2, 3 or 4 substituents R 4 ;
  • A is a linear d-Cs-alkylene bridge which may be substituted by 1 , 2, 3 or 4 substituents R 5 ;
  • Y is O, S or NR 6 ;
  • Ar, Het, A and Y are as defined for formulae I and II;
  • # is the attachment point to the remainder of the molecule
  • each R 2 is independently selected from halogen, OH, SH, NO 2 , CN, Ci-C4-alkyl, C1-C4- haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3- Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C1-C4- alkenyloxy, Ci-C4-haloalkenyloxy, Ci-C4-alkynyloxy, Ci-C4-haloalkynyloxy, C3-C8- cycloalkoxy, Cs-Cs-halocycloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C1-C4- alkenylylthio, Ci
  • each R 3 is independently selected from halogen, OH, SH, NO2, CN, Ci-C4-alkyl, C1-C4- haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3- Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C1-C4- alkenyloxy, Ci-C4-haloalkenyloxy, Ci-C4-alkynyloxy, Ci-C4-haloalkynyloxy, C3-C8- cycloalkoxy, Cs-Cs-halocycloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C1-C4- alkenylylthio, Ci-C
  • each R 4 is independently selected from halogen, OH, SH, NO2, CN, Ci-C4-alkyl, C1-C4- haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3- Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C1-C4- alkenyloxy, Ci-C4-haloalkenyloxy, Ci-C4-alkynyloxy, Ci-C4-haloalkynyloxy, C3-C8- cycloalkoxy, Cs-Cs-halocycloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C1-C4- alkenylylthio, Ci-C
  • each R 5 is independently selected from halogen, OH, SH, NR 13 R 14 , Ci-C 4 -alkyl, Ci-C 4 - haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, Ci- C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and Ci-C4-haloalkylthio, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R 15 ; or
  • R 6 is selected from hydrogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C 2 -C 4 - haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, phenyl, phenyl-Ci-C4-alkyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R 11 ; COR 12 , COOR 12 , CONR 13 R 14 and
  • each R 7 is independently selected from halogen, OH, SH, NR 13 R 14 , CN, NO 2 , Ci-C 4 - alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C 2 -C 4 - haloalkynyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and Ci-C 4 - haloalkylthio, where the aliphatic moieties in the above radicals may carry 1 , 2 or
  • R 8 is selected from hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, C1-C10- haloalkoxy, Ci-Cio-aminoalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, phenyl, phenyl-Ci-C4-alkyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R 7 , a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents R 7 , and NR 13 R 14 ;
  • R 9 and R 10 are selected from Ci-Cio-alkyl, Ci-Cio- haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C2-Cio-haloalkynyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, Ci-C 4 - alkoxy-Ci-Cio-alkyl, Ci-C4-alkoxy-Ci-Cio-alkoxy, Ci-Cio-alkylthio, C1-C10- haloalkylthio, C2-Cio-alkenyloxy, C2-Cio-alkenylthio, C2-Cio-alkynyloxy, C2-C10- alkynylthi
  • each R 11 is independently selected from halogen, OH, SH, NR 13 R 14 , CN, NO 2 , CrC 4 - alkyl, Ci-C 4 -haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -alkynyl, C 2 -C 4 - haloalkynyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, Ci-C 4 -alkylthio and CrC 4 - haloalkylthio, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R 15 ; each R 12 is independently selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4- alkenyl, C2-C4-haloalkenyl, Ci-C4-aminoalkyl, phenyl
  • each R 13 is independently selected from hydrogen and Ci-Cs-alkyl
  • each R 14 is independently selected from hydrogen, Ci-Cs-alkyl, phenyl, and phenyl-Ci- C 4 -alkyl;
  • R 13 and R 14 together form a linear C4- or Cs-alkylene bridge or a group -CH2CH2OCH2CH2- or -CH 2 CH 2 NR 17 CH 2 CH 2 -;
  • each R 15 is independently selected from nitro, CN, OH, SH, COR 12 , COOR 12 ,
  • each R 16 is independently selected from nitro, CN, OH, SH, COR 12 , COOR 12 ,
  • each R 17 is independently selected from hydrogen and Ci-C4-alkyl
  • Q is O or S
  • M is a metal cation equivalent or an ammonium cation of formula (NR a R b R c R d ) + , wherein R a , R b , R c and R d , independently of each other, are selected from hydrogen, Ci-Cio-alkyl, phenyl and benzyl, where the phenyl moiety in the 2 last- mentioned radicals may carry 1 , 2 or 3 substituents independently selected from halogen, CN, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and NR 13 R 14 ;
  • n O, 1 or 2;
  • p 1 or 2.
  • the present invention also provides the use of triazole compounds of the formulae I and Il and/or their agriculturally useful salts for controlling harmful fungi.
  • the invention further provides fungicidal compositions comprising these triazole com- pounds of the formulae I and/or Il (and/or also of the formula IV; see below) and/or their agriculturally acceptable salts and suitable carriers. Suitable agriculturally acceptable carriers are described below.
  • the compounds I and Il can exist as one or more stereoisomers.
  • the various stereoi- somers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the compounds of the invention may be present as a mixture of stereoisomers, e.g. a racemate, individual stereoisomers, or as an optically active form.
  • Suitable agriculturally useful salts are 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 the compounds I and II.
  • suitable cations are in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and 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 diisopropylammonium, tetramethylammonium, tetrabutylammo- nium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium and sulfoxonium
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen- sulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and also the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting I or Il with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • C n -Cm indicates the number of carbon atoms possible in each case in the substituent or sub- stitutent moiety in question:
  • Halogen fluorine, chlorine, bromine and iodine
  • C 2 -C 3 - Alkyl is ethyl, n-propyl or isopropyl.
  • Ci-C 2 -Alkyl is methyl or ethyl.
  • CrC 4 -AIkVl is methyl, ethyl, propyl, isopropyl, butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl) or 1 ,1-dimethylethyl (tert-butyl).
  • Ci-C ⁇ -Alkyl is additionally also, for example, 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-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2- methylpropyl.
  • Ci-Cs-Alkyl is additionally also, for example, heptyl, octyl, 2-ethylhexyl and positional isomers thereof.
  • Ci-Cio-Alkyl is additionally also, for example, nonyl, decyl, 2-propylheptyl, 3-propylheptyl and positional isomers thereof.
  • Haloalkyl straight-chain or branched alkyl groups having 1 to 2 (Ci-C 2 -haloalkyl), 1 to 3 (Ci-C 3 -haloalkyl), 1 to 4 (Ci-C 4 -haloalkyl), 1 to 6 (Ci-C 6 -haloalkyl), 1 to 8 (CrC 8 - haloalkyl), 1 to 10 (Ci-Cio-haloalkyl) or 2 to 10 (C 2 -Cio-haloalkyl) carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above: in particular Ci-C 2 -haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoro- methyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl
  • Ci-C 3 -Haloalkyl is additionally, for example, 1 ,1 ,1-trifluoroprop-2-yl, 3,3,3-trifluoropropyl or heptafluoropropyl.
  • CrC 4 - Haloalkyl is additionally, for example, 1-chlorobuty, 2-chlorobutyl, 3-chlorobutyl or 4- chlorobutyl.
  • Ci-Cio-Hydroxyalkyl straight-chain or branched alkyl groups having 1 to 2 (Ci-C 2 - hydroxyalkyl), 1 to 4 (Ci-C 4 -hydroxyalkyl), 2 to 4 (C 2 -C 4 -hydroxyalkyl), 1 to 6 (Ci-C 6 - hydroxyalkyl), 2 to 6 (C 2 -C 6 -hydroxyalkyl), 1 to 8 (Ci-C 8 -hydroxyalkyl), 2 to 8 (C 2 -C 8 - hydroxyalkyl), 1 to 10 (Ci-Cio-hydroxyalkyl) or 2 to 10 (C 2 -Cio-hydroxyalkyl) carbon atoms (as mentioned above), where at least one of the hydrogen atoms is replaced by a hydroxyl group, such as in 2-hydroxyethyl or 3-hydroxypropyl.
  • Haloalkenyl and the haloalkenyl moieties in haloalkenyloxy, haloalkenylcarbonyl and the like unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4 (C 2 - C 4 -haloalkenyl), 2 to 6 (C 2 -C 6 -haloalkenyl), 2 to 8 (C 2 -C 8 -haloalkenyl) or 2 to 10 (C 2 - Cio-haloalkenyl) carbon atoms and a double bond in any position (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example chlorovinyl, chloroallyl and the like;
  • C 3 -C6-cycloalkyl-Ci-C2-alkyl a Ci-C2-alkyl residue, as decribed above, wherein one of the hydrogen atoms is replaced by a C 3 -C6-cycloalkyl group.
  • Examples are cyclopro- pylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropyl-1 -ethyl, cyclobutyl-1 -ethyl, cyclopentyl-1 -ethyl, cyclohexyl-1 -ethyl, cyclopropyl-2-ethyl, cyclobu- tyl-2-ethyl, cyclopentyl-2-ethyl, cyclohexyl-2-ethyl and the like.
  • C 3 -Cio-cycloalkyl-Ci-C4- alkyl is a Ci-C4-alkyl residue, as decribed above, wherein one of the hydrogen atoms is replaced by a C 3 -Cio-cycloalkyl group.
  • Examples are, apart those mentioned above for C 3 -C6-cycloalkyl-Ci-C4-alkyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, cycloheptyl-1 -ethyl, cyclooctyl-1 -ethyl, cyclononyl-1 -ethyl, cyclode- cyl-1 -ethyl, cycloheptyl-2 -ethyl, cyclooctyl-2 -ethyl, cyclononyl-2 -ethyl, cyclodecylmethyl, cyclopropyl-1 -propyl, cyclopropyl-2-propyl, cyclopropyl-3-propyl, cyclobutyl-1 - propyl, cyclobutyl-2-propyl, cyclobutyl-3-prop
  • C3-C6-halocycloalkyl-Ci-C2-alkyl a Ci-C2-alkyl residue, as decribed above, wherein one of the hydrogen atoms is replaced by a Cs-C ⁇ -halocycloalkyl group.
  • Examples are 1- chlorocyclopropylmethyl, 1-chlorocyclobutylmethyl, 1-chlorocyclopentylmethyl, 1- chlorocyclohexylmethyl, 1-chlorocyclopropyl-i -ethyl, 1-chlorocyclobutyl-1 -ethyl, 1- chlorocyclopentyl-1 -ethyl, 1-chlorocyclohexyl-i -ethyl, 1-chlorocyclopropyl-2-ethyl, 1- chlorocyclobutyl-2 -ethyl, 1-chlorocyclopentyl-2-ethyl, 1-chlorocyclohexyl-2-ethyl, 2- chlorocyclopropylmethyl, 2-chlorocyclobutylmethyl, 2-chlorocyclopentylmethyl, 2- chlorocyclohexylmethyl, 2-chlorocyclopropyl-1 -ethyl, 2-chlorocyclobutyl-1 -eth
  • C3-Cio-halocycloalkyl-Ci-C4-alkyl is a Ci-C4-alkyl residue, as decribed above, wherein one of the hydrogen atoms is replaced by a C3-Cio-halocycloalkyl group.
  • Ci-C2-Alkoxy is methoxy or ethoxy.
  • Ci-C 3 - Alkoxy is additionally, for example, n-propoxy or 1-methylethoxy (isopropoxy).
  • C1-C4- Alkoxy is additionally, for example, butoxy, 1-methylpropoxy (sec-butoxy), 2- methylpropoxy (isobutoxy) or 1 ,1-dimethylethoxy (tert-butoxy).
  • Ci-C ⁇ -Alkoxy is additionally, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1- dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1- dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3- dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethyl butoxy, 1 ,1 ,2- trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1-ethyl-1 -methylpropoxy or 1 -ethyl-2- methylpropoxy.
  • Ci-Cs-Alkoxy is additionally, for example, heptyloxy, octyloxy, 2- ethylhexyloxy and positional isomers thereof. Ci-Cio-Alkoxy is additionally, for example, nonyloxy, decyloxy and positional isomers thereof. C2-Cio-Alkoxy is like Ci-Cio-alkoxy with the exception of methoxy.
  • Haloalkoxy an alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, preferably by fluorine.
  • Ci-C2-Haloalkoxy is, for example, OCH 2 F, OCHF 2 , OCF 3 , OCH 2 CI, OCHCI 2 , OCCI 3 , chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2- fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy or OC2F5.
  • Ci-C4-Haloalkoxy is additionally, for example, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C2F5, OCF2- C 2 F 5 , 1-(CH 2 F)-2-fluoroethoxy, 1-(CH 2 CI)-2-chloroethoxy, 1-(CH 2 Br)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy.
  • Ci-C ⁇ -Haloalkoxy is additionally, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-brompentoxy,
  • Alkenyloxy alkenyl as mentioned above which is attached via an oxygen atom, for ex- ample C2-Cio-alkenyloxy, such as 1-ethenyloxy, 1-propenyloxy, 2-propenyloxy, 1- methylethenyloxy, 1-butenyloxy, 2-butenyloxy, 3-butenyloxy, 1-methyl-1-propenyloxy, 2-methyl-1-propenyloxy, 1-methyl-2-propenyloxy, 2-methyl-2-propenyloxy, 1- pentenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy, 1-methyl-1-butenyloxy, 2- methyl-1-butenyloxy, 3-methyl-1-butenyloxy, 1-methyl-2-butenyloxy, 2-methyl-2-butenyloxy, 3-methyl-1-butenyloxy, 1-methyl-2-butenyloxy, 2-methyl-2- butenyloxy, 3-methyl-2-butenyloxy, 1-methyl-3
  • Haloalkenyloxy an alkenyloxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, preferably by fluorine.
  • Alkynyloxy alkynyl as mentioned above which is attached via an oxygen atom, for example C2-Cio-alkynyloxy, such as 2-propynyloxy, 2-butynyloxy, 3-butynyloxy, 1-methyl- 2-propynyloxy, 2-pentynyloxy, 3-pentynyloxy, 4-pentynyloxy, 1-methyl-2-butynyloxy, 1- methyl-3-butynyloxy, 2-methyl-3-butynyloxy, 1 -ethyl-2-propynyloxy, 2-hexynyloxy, 3- hexynyloxy, 4-hexynyloxy, 5-hexynyloxy, 1-methyl-2-pentynyloxy, 1-methyl
  • Haloalkynyloxy an alkynyloxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, preferably by fluorine.
  • Cycloalkoxy cycloalkyl as mentioned above which is attached via an oxygen atom, for example C3-Cio-cycloalkoxy or Cs-Cs-cycloalkoxy, such as cyclopropoxy, cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclononyloxy, cyclodecyloxy and the like;
  • Halocycloalkoxy a cycloalkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, preferably by fluorine.
  • Cycloalkenyloxy cycloalkenyl as mentioned above which is attached via an oxygen atom, for example C3-Cio-cycloalkenyloxy, Cs-Cs-cycloalkenyloxy or, preferably, Cs-C ⁇ - cycloalkenyloxy, such as cyclopent-1-enoxy, cyclopent-2-enoxy, cyclohex-1-enoxy and cyclohex-2-enoxy;
  • Alkoxyalkyl alkyl as defined above having 1 to 10, 1 to 8, 1 to 6 or 1 to 4, in particular 1 to 3, carbon atoms, in which one hydrogen atom is replaced by an alkoxy group having 1 to 8, 1 to 6, 1 to 4 or 1 to 3 carbon atoms, for example methoxymethyl, 2- methoxyethyl, ethoxymethyl, 3-methoxypropyl, 3-ethoxypropyl and the like.
  • Alkoxyalkoxy alkoxy as defined above having 1 to 10, 1 to 8, 1 to 6 or 1 to 4, in particu- lar 1 to 3, carbon atoms, in which one hydrogen atom is replaced by an alkoxy group having 1 to 8, 1 to 6 or in particular 1 to 4 carbon atoms, for example 2-methoxyethoxy, 2-ethoxyethoxy, 3-methoxypropoxy, 3-ethoxypropoxy and the like.
  • Alkylcarbonyl group of the formula R-CO- in which R is an alkyl group as defined above, for example Ci-Cio-alkyl, d-Cs-alkyl, d-C ⁇ -alkyl, Ci-C4-alkyl, Ci-C2-alkyl or C3- C4-alkyl. Examples are acetyl, propionyl and the like. Examples for C3-C4-alkylcarbonyl are propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, sec-butylcarbonyl, isobutylcar- bonyl and tert-butylcarbonyl.
  • Haloalkylcarbonyl group of the formula R-CO- in which R is a haloalkyl group as defined above, for example Ci-Cio-haloalkyl, d-Cs-haloalkyl, d-C ⁇ -haloalkyl, C1-C4- haloalkyl, Ci-C2-haloalkyl or C3-C4-haloalkyl. Examples are difluoromethylcarbonyl, trifluoromethylcarbonyl, 2,2-difluoroethylcarbony, 2,2,3-trifluoroethylcarbonyl and the like.
  • Alkoxycarbonyl group of the formula R-CO- in which R is an alkoxy group as defined above, for example Ci-Cio-alkoxy, Ci-Cs-alkoxy, Ci-C ⁇ -alkoxy, Ci-C4-alkoxy or C1-C2- alkoxy.
  • Ci-C4-alkoxycarbonyl are methoxycarbonyl, ethoxycarbonyl, pro- poxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, isobutoxy- carbonyl and tert-butoxycarbonyl.
  • Haloalkoxycarbonyl group of the formula R-CO- in which R is a haloalkoxy group as defined above, for example Ci-Cio-haloalkoxy, d-Cs-haloalkoxy, d-C ⁇ -haloalkoxy, Ci- C4-haloalkoxy or Ci-C2-haloalkoxy.
  • Ci-C4-haloalkoxycarbonyl are di- fluoromethoxycarbonyl, trifluoromethoxycarbonyl, 2,2-difluoroethoxycarbony, 2,2,3- trifluoroethoxycarbonyl and the like.
  • Alkylaminocarbonyl group of the formula R-NH-CO- in which R is an alkyl group as defined above, for example Ci-Cio-alkyl, Ci-C 8 -alkyl, d-Ce-alkyl, Ci-d-alkyl, C1-C2- alkyl or C3-d-alkyl.
  • Ci-C4-alkylaminocarbonyl are methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, isopropylaminocarbonyl, butylaminocar- bonyl, sec-butylaminocarbonyl, isobutylaminocarbonyl and tert-butylaminocarbonyl.
  • Dialkylaminocarbonyl group of the formula RR'N-CO- in which R and R', independently of each other, are an alkyl group as defined above, for example Ci-Cio-alkyl, Ci-Cs- alkyl, Ci-C 6 -alkyl, Ci-d-alkyl, Ci-C 2 -alkyl or C 3 -C 4 -alkyl.
  • R and R' independently of each other, are an alkyl group as defined above, for example Ci-Cio-alkyl, Ci-Cs- alkyl, Ci-C 6 -alkyl, Ci-d-alkyl, Ci-C 2 -alkyl or C 3 -C 4 -alkyl.
  • Examples for di-(Ci-d-alkyl)- aminocarbonyl are dimethylaminocarbonyl, diethylaminocarbonyl, dipropylaminocar- bonyl, diisopropylaminocarbonyl and dibutyla
  • Aminoalkyl group of the formula R-NH2 in which R is an alkyl group as defined above, for example Ci-Cio-alkyl, Ci-C 8 -alkyl, Ci-C 6 -alkyl, Ci-C 4 -alkyl, Ci-C 2 -alkyl or C 3 -C 4 - alkyl.
  • R is an alkyl group as defined above, for example Ci-Cio-alkyl, Ci-C 8 -alkyl, Ci-C 6 -alkyl, Ci-C 4 -alkyl, Ci-C 2 -alkyl or C 3 -C 4 - alkyl.
  • Examples are aminomethyl, 1- and 2-aminoethyl, 1-, 2- and 3-aminopropyl, 1- and 2-amino1-methylethyl, 1-, 2-, 3- and 4-aminobutyl and the like.
  • Alkylsulfonyl group of the formula R-S(O)2- in which R is an alkyl group as defined above, for example Ci-Cio-alkyl, d-Cs-alkyl, Ci-C6-alkyl, Ci-C4-alkyl or Ci-C2-alkyl.
  • Examples for d-d-alkylsulfonyl are methylsulfonyl, ethylsulfonyl, propylsulfonyl, iso- propylsulfonyl, n-butylsulfonyl, sec-butylsulfonyl, isobutylsulfonyl and tert-butylsulfonyl.
  • Alkylthio alkyl as defined above which is attached via a sulfur atom.
  • Haloalkylthio haloalkyl as defined above which is attached via a sulfur atom.
  • Alkenylthio alkenyl as defined above which is attached via a sulfur atom.
  • Haloalkenylthio haloalkenyl as defined above which is attached via a sulfur atom.
  • Alkynylthio alkynyl as defined above which is attached via a sulfur atom.
  • Haloalkynylthio haloalkynyl as defined above which is attached via a sulfur atom.
  • Cycloalkylthio cycloalkyl as defined above which is attached via a sulfur atom.
  • Aryl is a carbocyclic aromatic monocyclic or polycyclic ring containing 6 to 16 carbon atoms as ring members. Examples are phenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl and azulenyl. Preferably, aryl is phenyl or naphthyl, and especially phenyl.
  • Phenyl-Ci-C4-alkyl Ci-C4-alkyl (as defined above), where a hydrogen atom is replaced by a phenyl group, such as benzyl, phenethyl and the like.
  • Phenyl-Ci-C4-alkoxy Ci-C4-alkoxy (as defined above), where one hydrogen atom is replaced by a phenyl group, such as benzyloxy, phenethyloxy and the like.
  • a seven-membered saturated or partially unsaturated heterocycle which contains one, two or three heteroatoms from the group consisting of oxygen, nitrogen and sulfur as ring members: for example mono- and bicyclic heterocycles having 7 ring members which, in addition to carbon ring members, contain one to three ni- trogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms, for example tetra- and hexahydroazepinyl, such as 2,3,4,5-tetrahydro[1 H]azepin-1-, -2-, -3-, -4-, -5-, -6- or -7-yl, 3,4,5,6-tetrahydro[2H]azepin-2-, -3-, -A-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1 H]azepin-1-, -2-, -3-, -4-, -5-, -6- or -7
  • Linear C2-alkylene divalent unbranched chains having 2 carbon atoms, namely CH 2 CH 2 .
  • Linear C 2 - or C3-alkylene divalent unbranched chains having 2 or 3 carbon atoms, namely CH 2 CH 2 and CH 2 CH 2 CH 2 .
  • Linear d-Cs-alkylene divalent unbranched chains having 1 to 5 carbon atoms, namely CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 and CH 2 CH 2 CH 2 CH 2 CH 2 .
  • C 2 -C5-Alkylene divalent branched or preferably unbranched chains having 2 to 5 carbon atoms, for example CH 2 CH 2 , -CH(CH 3 )-, CH 2 CH 2 CH 2 , CH(CH 3 )CH 2 , CH 2 CH(CH 3 ), CH 2 CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 CH 2 .
  • C4-C5-Alkylene divalent branched or preferably unbranched chains having 4 to 5 carbon atoms, for example CH 2 CH 2 CH 2 CH 2 or CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 .
  • the group -SM is more correctly spoken a group -S " M + , where M + is a metal cation equivalent or an ammonium cation as defined above.
  • M + is a metal cation equivalent or an ammonium cation as defined above.
  • a metal cation equivalent is more correctly spoken 1/a M a+ , where a is the valence of the metal and is in general 1 , 2 or 3.
  • Ar if it is a heterocyclic ring as defined above, is bound via a C-atom to the group Y.
  • Ar is phenyl which may carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2, substituents R 2 , or is a 5- or 6-membered heteroaromatic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heteroaromatic ring may carry 1 , 2, 3 or 4, preferably 1 , 2 or 3, more preferably 1 or 2, substituents R 3 .
  • Ar preferably is phenyl which may carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2, substituents R 2 , or is a 5- or 6-membered heteroaromatic ring containing 1 heteroatom selected from N, O and S and optionally 1 or 2 further nitrogen atoms as ring members, where the heteroaromatic ring may carry 1 , 2, 3 or 4, preferably 1 or 2, substituents R 3 .
  • Suitable 5- or 6-membered heteroaromatic radicals are listed above.
  • pyridyl such as pyridin-2-yl, pyridin-3-yl or pyridin-4-yl
  • pyrimidyl such as 2-pyrimidinyl, 4-pyrimidinyl or 5-pyrimidinyl
  • furyl such as 2-furyl or 3-furyl
  • thienyl such as 2-thienyl or 3-thienyl
  • pyr- rolyl such as 1-pyrrolyl, 2-pyrrolyl or 3-pyrrolyl, especially 2-pyrrolyl or 3-pyrrolyl, pyra- zolyl, such as 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl or 5-pyrazolyl, especially 3-pyrazolyl, 4-pyrazolyl or 5-pyrazolyl, imidazolyl, such as 1-imidazolyl, 2-imidazolyl or 4-imidazolyl, especially 2-imidazolyl or 4-imidazolyl, imidazolyl, such as 1-imidazolyl,
  • the given binding position is relative to the 1 -position of the one ring heteroatom.
  • the given binding position is relative to the 1- and 2-positions of the 2 nitrogen ring atoms, in imidazolyl, it is relative to the 1- and 3-positions of the 2 nitrogen ring atoms, in oxazolyl, it is relative to the 1 -position of the oxygen ring atom and to the 3-position of the nitrogen ring atom, in isoxazolyl, it is relative to the 1- position of the oxygen ring atom and to the 2-position of the nitrogen ring atom, in thiazolyl, it is relative to the 1 -position of the sulfur ring atom and to the 3-position of the nitrogen ring atom, in isothiazolyl, it is relative to the 1 -position of the sulfur ring atom and to the 2-position of the nitrogen ring atom, etc.
  • Ar is phenyl which may carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2, substituents R 2 , or is a 5- or 6-membered heteroaromatic ring selected from pyridyl, such as pyridin-2-yl, pyridin-3-yl or pyridin-4-yl, thienyl, such as 2- or 3-thienyl, and thiazolyl, such as 2-thiazolyl, 4-thiazolyl or 5-thiazolyl.
  • pyridyl such as pyridin-2-yl, pyridin-3-yl or pyridin-4-yl
  • thienyl such as 2- or 3-thienyl
  • thiazolyl such as 2-thiazolyl, 4-thiazolyl or 5-thiazolyl.
  • pyridyl such as pyridin-2-yl, pyridin-3-yl or pyridin-4-yl, and especially to pyridin-2-yl, where the heteroaromatic ring may carry 1 , 2, 3 or 4, preferably 1 ,
  • substituents R 3 2 or 3, more preferably 1 or 2, substituents R 3 .
  • Ar is a 6-membered heteroaromatic ring, this carries preferably O, 1 , 2 or 3, more preferably 0, 1 or 2, substituents R 3 ,where the two or more substituents R 3 may be the same or different.
  • Ar is a 5-membered heteroaromatic ring, this carries preferably 0, 1 or 2 substituents R 3 , where two substituents R 3 may be the same or different.
  • R 2 is preferably selected from halogen, OH, SH, NO 2 , CN, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy-Ci-C 4 -alkyl, Ci-C 4 -alkoxy, Ci-C 4 -alkoxy-Ci-C 4 -alkoxy, and Ci-C 4 - haloalkoxy, more preferably from fluorine, chlorine, bromine, Ci-C 4 -alkyl, Ci-C 4 - haloalkyl, Ci-C 4 -alkoxy and Ci-C 4 -haloalkoxy, even more preferably from fluorine, chlorine, bromine, CH3, CHF2, CF3, OCH3, OCHF2 and OCF3, and in particular from fluorine, chlorine, bromine, CH3, CF3, OCH3 and OCF3.
  • R 3 may be C- or N-bound, but is preferably bound to a C-atom of Ar.
  • R 3 is preferably selected from halogen, OH, SH, NO 2 , CN, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy-Ci-C 4 -alkyl, Ci-C 4 -alkoxy, Ci-C 4 -alkoxy-Ci-C 4 -alkoxy, and CrC 4 - haloalkoxy, more preferably from fluorine, chlorine, bromine, Ci-C 4 -alkyl, CrC 4 - haloalkyl, Ci-C 4 -alkoxy and Ci-C 4 -haloalkoxy, even more preferably from fluorine, chlorine, bromine, CH3, CHF 2 , CF3, OCH3, OCHF 2 and OCF3, and in particular from fluorine, chlorine, bromine, CH3, CF3, OCH3 and OCF3.
  • Ar is selected from following formulae Ar.1 to Ar.50, where in formula Ar.1 , the combination of the variables R 21 , R 22 , R 23 , R 24 and R 25 is selected from the defini- tion given in each line of Table A below.
  • Het is bound via two ring C-atoms to the group Y and the quaternary carbon atom (carrying the ketal group and the triazolylmethyl group).
  • Het is a (divalent) 5- or 6-membered het- eroaromatic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heteroaromatic ring may carry 1 , 2, 3 or 4, preferably 1 or 2, sub- stituents R 4 . More precisely spoken, Het preferably is a 5- or 6-membered heteroaromatic ring containing 1 heteroatom selected from N, O and S and optionally 1 or 2 further nitrogen atoms as ring members, where the heteroaromatic ring may carry 1 , 2, 3 or 4, preferably 1 or 2, substituents R 4 . Suitable 5- or 6-membered heteroaromatic radicals are listed above.
  • pyridylene such as 2,3-pyridylene, 2,4-pyridylene, 2,5-pyridylene, 2,6-pyridylene, 3,4-pyridylene or 3,5- pyridylene
  • pyrimidylene such as 2,4-pyrimidylene, 2,5-pyrimidylene, 4,5-pyrimidylene or 4,6-py ⁇ imidylene
  • furylene such as 2,3-furylene, 2,4-furylene, 2,5-furylene or 3,4- furylene
  • thienyl such as 2,3-thienylene, 2,4-thienylene, 2,5-thienylene or 3,4- thienylene
  • pyrrolyl such as 1 ,2-pyrrolylene, 1 ,3-pyrrolylene, 2,3-pyrrolylene, 2,4- pyrrolylene, 2,5-pyrrolylene or 3,4
  • the given binding positions are to be understood as relative to the 1 -position of the ring heteroatom with the highest priority.
  • the given binding position is relative to the 1 -position of the one ring heteroatom.
  • the given bind- ing position is relative to the 1- and 2-positions of the 2 nitrogen ring atoms, in imida- zolylene, it is relative to the 1- and 3-positions of the 2 nitrogen ring atoms, in oxazolylene, it is relative to the 1 -position of the oxygen ring atom and to the 3-position of the nitrogen ring atom, in isoxazolylene, it is relative to the 1 -position of the oxygen ring atom and to the 2-position of the nitrogen ring atom, in thiazolylene, it is relative to the 1 -position of the sulfur ring atom and to the 3-position of the nitrogen ring atom, in isothiazolylene, it is relative to the 1 -position of the sulfur ring atom and to the 3-position of the nitrogen ring atom
  • pyridylene especially 2,5- or 3,6-pyridylene, thienylene, especially 2,4- or 2,5-thienylene, and thiazolylene, especially 2,4-thiazolylene or 2,5- thiazolylene.
  • pyridylene especially 2,5- or 3,6-pyridylene, thienylene, especially 2,4- or 2,5-thienylene.
  • pyridylene especially to 2,5- or 3,6-pyridylene.
  • Het is a 6-membered heteroaromatic ring, this carries preferably 0, 1 , 2 or 3, more preferably 0, 1 or 2, substituents R 4 ,where the two or more substituents R 4 may be the same or different.
  • Het is a 5-membered heteroaromatic ring, this carries preferably 0, 1 or 2 substituents R 4 , where two substituents R 4 may be the same or different.
  • R 4 may be C- or N-bound, but is preferably bound to a C-atom of Het.
  • R 4 is preferably selected from halogen, OH, SH, NO 2 , CN, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy-Ci-C 4 -alkyl, Ci-C 4 -alkoxy, Ci-C 4 -alkoxy-Ci-C 4 -alkoxy, and CrC 4 - haloalkoxy, more preferably from fluorine, chlorine, bromine, Ci-C4-alkyl, C1-C4- haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, even more preferably from fluorine, chlorine, bromine, CH3, CHF2, CF3, OCH3, OCHF2 and OCF3, particularly preferably from fluorine, chlorine, bromine, CH3, CF3, OCH3 and OCF3, and specifically from fluorine and chlorine.
  • Het is selected from following formulae Het.1 to Het.16, where # is the attachment point to the quaternary carbon atom (which carries the ketale and the tria- zolylmethyl group) and * is the attachment point to the group Y:
  • R 8 is specifically Ci-C4-alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, preferably methyl, or is Ci-C4-alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy or tert-butoxy, preferably methoxy, and is more specifically methyl, and in the group -S(O) 2 R 8 , R 8 is specifically methyl.
  • R 13 is hydrogen and R 14 is selected from hydrogen, Ci-C4-alkyl and phenyl, preferably from hydrogen and Ci-C4-alkyl; or R 13 and R 14 are both Ci-C4-alkyl, preferably methyl or ethyl.
  • M is preferably selected from an alkali metal cation, an earth alkaline metal cation equivalent, a cation equivalent of Cu, Zn, Fe or Ni or an ammonium cation of formula (NR a R b R c R d ) + , wherein one of R a , R b , R c and R d is hydrogen and three of R a , R b , R c and R d , independently of each other, are selected from Ci-Cio-alkyl.
  • M is selected from Li + , Na + , K + , YiMg 2+ , a cation equivalent of Cu, Zn, Fe or Ni and an ammonium cation of formula (NR a R b R c R d ) + , wherein one of R a , R b , R c and R d is hydrogen and three of R a , R b , R c and R d , independently of each other, are selected from C1-C10- alkyl.
  • M is selected from Na + , K + , /4Mg 2+ , /4Cu 2+ , /4Zn 2+ , /4Fe 2+ , /4Ni 2+ , triethylammonium and trimethylammonium.
  • R 1 is selected from hydrogen, methyl, ethyl, propyl, isopropyl, methylcarbonyl, methoxycarbonyl,
  • R 1 is hydrogen, methyl, methylcarbonyl, methoxycarbonyl, Na + or a group of the formula III.
  • Y is preferably O.
  • A is preferably a linear C2- or C3-alkyene bridge, where 1 or 2 hydrogen atoms of the alkylene bridge may be replaced by 1 or 2 substituents R 5 , where each R 5 is independently selected from Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4- alkoxy and Ci-C4-haloalkoxy, and preferably from methyl, ethyl, methoxy, ethoxy and methoxymethoxy, or two substituents R 5 bound on adjacent carbon atoms, together with the carbon atoms to which they are bound, form a cyclopentyl or cyclohexyl ring.
  • A is a linear C2- or C3-alkyene bridge, where 1 hydrogen atom of the alkylene bridge may be replaced by 1 substituent R 5 , where R 5 is Ci-C4-alkyl. Even more preferably, A is a linear C2-alkyene bridge, where 1 hydrogen atom of the al- kylene bridge may be replaced by 1 substituent R 5 , where R 5 is Ci-C4-alkyl and preferably methyl. Specifically, A is -CH(CHs)-CH 2 -.
  • m is preferably 0 or 2 and more preferably 0.
  • Examples for preferred compounds I and Il are compounds of formulae 1.1 to 1.192 and 11.1 to 11.96, where the variables have one of the general or, in particular, one of the preferred meanings given above.
  • Examples of preferred compounds are the individual compounds compiled in the tables 1 to 70992 below. Moreover, the meanings mentioned below for the individual variables in the tables are per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question.
  • Tables 197 to 245 Compounds of the formula 1.1 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A, R 1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.5
  • Tables 295 to 343 Compounds of the formula 1.1 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A, R 1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.7
  • Tables 344 to 392 Compounds of the formula 1.1 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A, R 1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.8
  • Tables 589 to 637 Compounds of the formula 1.1 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A, R 1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.13
  • R 1 and Het is as defined in any of tables 1 to 784 Tables 1569 to 2352
  • R 1 and Het is as defined in any of tables 1 to 784
  • Tables 2353 to 3136 Compounds of the formula 1.4 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of
  • R 1 and Het is as defined in any of tables 1 to 784
  • R 6 and Het is as defined in any of tables 1 to 784
  • R 1 and Het is as defined in any of tables 1 to 784 Tables 5489 to 6272
  • R 1 and Het is as defined in any of tables 1 to 784
  • Tables 6273 to 7056 Compounds of the formula 1.9 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of
  • R 1 and Het is as defined in any of tables 1 to 784
  • Tables 7841 to 8624 Compounds of the formula 1.11 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1 and Het is as defined in any of tables 1 to 784
  • Tables 8625 to 9408 Compounds of the formula 1.12 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1 and Het is as defined in any of tables 1 to 784
  • Tables 12545 to 13328 Compounds of the formula 1.17 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1 and Het is as defined in any of tables 1 to 784
  • Tables 17249 to 18032 Compounds of the formula 1.23 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1 and Het is as defined in any of tables 1 to 784
  • Tables 21 169 to 21952 Compounds of the formula 1.28 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1 and Het is as defined in any of tables 1 to 784
  • Tables 22737 to 23520 Compounds of the formula 1.30 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1 and Het is as defined in any of tables 1 to 784
  • Tables 23521 to 24304 Compounds of the formula 1.31 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1 and Het is as defined in any of tables 1 to 784
  • Tables 27441 to 28224 Compounds of the formula 1.36 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1 and Het is as defined in any of tables 1 to 784
  • Tables 32145 to 32928 Compounds of the formula 1.42 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1 and Het is as defined in any of tables 1 to 784
  • Tables 36065 to 36848 Compounds of the formula 1.47 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1 and Het is as defined in any of tables 1 to 784
  • Tables 37665 to 37680 Compounds of the formula 1.51 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
  • Tables 37697 to 37712 Compounds of the formula 1.53 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
  • Tables 37713 to 37728 Compounds of the formula 1.54 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
  • Tables 37793 to 37808 Compounds of the formula 1.59 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
  • Tables 37889 to 37904 Compounds of the formula 1.65 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
  • Tables 37969 to 37984 Compounds of the formula 1.70 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
  • Tables 38001 to 38016 Compounds of the formula 1.72 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
  • Tables 38017 to 38032 Compounds of the formula 1.73 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
  • Tables 38097 to 38112 Compounds of the formula 1.78 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
  • Tables 38193 to 38208 Compounds of the formula 1.84 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
  • Tables 38273 to 38288 Compounds of the formula 1.89 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
  • Tables 38305 to 38320 Compounds of the formula 1.91 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
  • Tables 38321 to 38336 Compounds of the formula 1.92 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
  • Tables 38401 to 38449 Compounds of the formula 1.97 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R 1 is as defined in any of tables 1 to 49
  • Tables 40838 to 40874 Compounds of the formula 11.1 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A, R 1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.2
  • R 1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.3
  • R 1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.4
  • R 1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.5 Tables 40986 to 41022
  • R 1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.6
  • Tables 41023 to 41059 Compounds of the formula 11.1 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A, R 1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.7
  • R 1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.8
  • Tables 41097 to 41 133 Compounds of the formula 11.1 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A, R 1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.9
  • Tables 41 134 to 41 170 Compounds of the formula 11.1 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A, R 1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.10
  • R 1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.11
  • R 1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.12
  • R 1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.14
  • Tables 41319 to 41355 Compounds of the formula 11.1 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A, R 1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.15
  • R 1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.16
  • R 1a and Het is as defined in any of tables 40800 to 41392 Tables 42577 to 43168
  • R 1a and Het is as defined in any of tables 40800 to 41392 Tables 43169 to 43760
  • R 1a and Het is as defined in any of tables 40800 to 41392
  • R 1a and Het is as defined in any of tables 40800 to 41392
  • R 1a and Het is as defined in any of tables 40800 to 41392
  • R 1a and Het is as defined in any of tables 40800 to 41392 Tables 46129 to 46720
  • Tables 46721 to 47312 Compounds of the formula 11.1 1 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1a and Het is as defined in any of tables 40800 to 41392
  • Tables 47905 to 48496 Compounds of the formula 11.13 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1a and Het is as defined in any of tables 40800 to 41392
  • Tables 48497 to 49088 Compounds of the formula 11.14 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1a and Het is as defined in any of tables 40800 to 41392
  • Tables 51457 to 52048 Compounds of the formula 11.19 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1a and Het is as defined in any of tables 40800 to 41392
  • Tables 55009 to 55600 Compounds of the formula 11.25 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1a and Het is as defined in any of tables 40800 to 41392
  • Tables 57969 to 58560 Compounds of the formula 11.30 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1a and Het is as defined in any of tables 40800 to 41392
  • Tables 59153 to 59744 Compounds of the formula 11.32 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1a and Het is as defined in any of tables 40800 to 41392
  • Tables 59745 to 60336 Compounds of the formula 11.33 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1a and Het is as defined in any of tables 40800 to 41392
  • Tables 62705 to 63296 Compounds of the formula 11.38 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1a and Het is as defined in any of tables 40800 to 41392
  • Tables 66257 to 66848 Compounds of the formula 11.44 in which the combination of R 21 , R 22 , R 23 , R 24 and R 25 for a compound corresponds in each case to one row of Table A and the combination of R 1a and Het is as defined in any of tables 40800 to 41392
  • Tables 69217 to 69253 Compounds of the formula 11.49 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R 1a is as defined in any of tables 40800 to 40837
  • Tables 69291 to 69327 Compounds of the formula 11.51 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R 1a is as defined in any of tables 40800 to 40837 Tables 69328 to 69364 Compounds of the formula 11.52 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R 1a is as defined in any of tables 40800 to 40837 Tables 69365 to 69401 Compounds of the formula 11.53 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R 1a is as defined in any of tables 40800 to 40837 Tables 69402 to 69438
  • radicals Ar.2 to Ar.50 correspond to the radicals listed above as specific embodiments of Ar as groups of formulae Ar.2 to Ar.50
  • radicals Het.1 to Het.16 correspond to the radicals listed above as specific embodiments of Het as groups of formulae Het.1 to Het.16.
  • the radicals Ar.2 to Ar.50 correspond to the radicals listed above as specific embodiments of Ar as groups of formulae Ar.2 to Ar.50.
  • the radicals Het.1 to Het.16 correspond to the radicals listed above as specific embodiments of Het as groups of formulae Het.1 to Het.16.
  • an organolithium base such as n-butyllithium, tert- butyllithium or sec-butyllithium, lithium diisopropyl amide, sodium hydride, sodium amide or potassium tert-butylate mixed with tetramethylethylene diamine (TMEDA), and then the resulting anion is reacted with elemental sulfur.
  • Sulfur is generally used in powdered form.
  • the reaction is generally carried out in an inert solvent, such as ethers, e.g. diethylether, methyl-tert-butylether, tetrahydrofuran or dioxane, dimethoxyethane, liquid ammonia, dimethylsulfoxide or dimethylformamide.
  • the reaction temperature is not very critical and can range, for example, from -70 to +50 0 C, preferably from -70 to 0 0 C.
  • sulfurization can be carried out in the absence of a base by reacting 7 with elemental sulfur in a high-boiling solvent, such as N-methylpyrrolidinone, diox- ane or N,N-dimethylformamide, while heating, e.g. to 160 to 250 0 C.
  • a high-boiling solvent such as N-methylpyrrolidinone, diox- ane or N,N-dimethylformamide
  • the resulting mixture is hydrolyzed, e.g. by the addition of water or an aqueous acid, such as a mineral acid (e.g. dilute sulfuric acid or hydrochloric acid), acetic acid or ammoniumchloride, to give compound I.
  • a high-boiling solvent such as N-methylpyrrolidinone, diox- ane or N
  • the triazole compound IV can be prepared in analogy to known methods, such as described, for example, in EP-A-0065485, as outlined in scheme 2.
  • the compound 1 wherein X is a good leaving group, such as a halogen atom, in particular Cl, Br or I, phenylsulfonyloxy, p-tosyloxy, trifluoroacetyloxy or alkylsulfonyloxy, such as mesyloxy, can be reacted with the [1 ,2,4]-1 H-triazole compound 2, wherein M is a hydrogen atom or a metal atom, in particular an alkali metal atom, such as Li, Na or K.
  • M is a hydrogen atom or a metal atom, in particular an alkali metal atom, such as Li, Na or K.
  • the reaction is suitably carried out in the presence of a base, such as an alkali metal hydride (e.g. sodium hydride, potassium hydride), an alkali metal hydroxide (e.g. sodium hydroxide, potassium hydroxide), an alkali metal carbonate (e.g. sodium carbonate, potassium carbonate, caesium carbonate) or a suitable amine (e.g. triethyl- amine, triethylenediamine, piperidine, pyridine, 4-dimethylaminopyridine, 4- pyrrolidylpyridine).
  • a base such as an alkali metal hydride (e.g. sodium hydride, potassium hydride), an alkali metal hydroxide (e.g. sodium hydroxide, potassium hydroxide), an alkali metal carbonate (e.g. sodium carbonate, potassium carbonate, caesium carbonate) or a suitable amine (e.g. triethyl- amine, triethylenediamine, piperidine
  • the reaction is suitably carried out in a solvent.
  • Suitable solvents are inert versus the reacants and products and are rather polar, for example, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, acetoni- trile, benzonitrile, ethers, such as diethyl ether, dipropyl ether, methyl-tert-butyl ether, tetrahydrofuran or dioxane, and the like, and can be used in combination with other inert, less polar solvents, such as benzene, toluene, the xylenes, chlorobenzene, nitrobenzene, hexane, heptane, petrolether and the like.
  • the reaction temperature is not very critical and can range, for example from 0 to 220 0 C and preferably from 80 to 170 0 C.
  • the reaction is carried out at reflux temperature of the reaction mixture.
  • Compound 1 in turn can be prepared in analogy to known methods, such as described, for example, in EP-A-0065485 or in Synthesis, 1974, I, 23, as outlined in scheme 3 below.
  • the ketone 3 may be reacted with a diol HO-A-OH for several hours preferably in the presence of an azeotrope-forming compound, such as benzene, toluene, xylene, chloroform or tetrachloromethane, which can also serve as reaction solvents.
  • the ketalization reaction is accelerated by the presence of a strong acid, such p-toluoenesulfonic acid.
  • halogenation of the resulting ketale 4 yields ketale 1 , wherein X is a halogen atom, which, if desired, can be converted into a compound 1 , wherein X is a leaving group X other than halogen.
  • the ketone 3 can be obtained in analogy to known methods, such as described, for example, in EP-A-0065485, from the condensation of compounds 5 and 6, wherein X 1 is a group Y-H or Y-M, wherein M is a metal atom, in particular an alkali metal atom, such as Li, Na or K, and X 2 is a good leaving group, such as a halogen atom, such as F, Cl, Br or I, phenylsulfonyloxy, p-tosyloxy, trifluoroacetyloxy or alkylsulfonyloxy, such as mesyloxy, or, vice versa, wherein X 1 is a good leaving group and X 2 is a group Y-H or Y-M, as outlined in scheme 4 below.
  • M is a metal atom, in particular an alkali metal atom, such as Li, Na or K
  • X 2 is a good leaving group, such as a
  • X 1 or X 2 is Y-H
  • the reaction is suitably carried out in the presence of a base, such as an alkali metal hydride (e.g. sodium hydride, potassium hydride), an alkali metal hydroxide (e.g. sodium hydroxide, potassium hydroxide), an alkali metal carbonate (e.g. sodium carbonate, potassium carbonate, caesium carbonate) or a suitable amine (e.g. triethylamine, triethylenediamine, piperidine, pyridine, 4-dimethylaminopyridine, 4-pyrrolidylpyridine).
  • a base such as an alkali metal hydride (e.g. sodium hydride, potassium hydride), an alkali metal hydroxide (e.g. sodium hydroxide, potassium hydroxide), an alkali metal carbonate (e.g. sodium carbonate, potassium carbonate, caesium carbonate) or a suitable amine (e.g. triethylamine,
  • the reaction can be accelerated by the addition of an alkali metal iodide, such as NaI or Kl.
  • the reaction is suitably carried out in a solvent.
  • Suitable sol- vents are inert versus the reacants and products and are rather polar, for example, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, acetonitrile, ben- zonitrile, ethers, such as diethyl ether, dipropyl ether, methyl-tert-butyl ether, tetrahy- drofuran or dioxane, and the like, and can be used in combination with other inert, less polar solvents, such as benzene, toluene, the xylenes, chlorobenzene, nitrobenzene, hexane, heptane, petrolether and the like.
  • the reaction temperature such as benzene, tol
  • This in turn can be prepared from the hydroxyl compound 8 which is reacted with a difunctional derivative 9 of carbonic acid, such as phosgene, a halogenoformic acid diester, a dialkylcarbonic diester or a diphenylcarbonic acid diester and further reaction with the hydroxyl compound 10.
  • Decarboxylation is carried out by heating 7 in substance or in a high-boiling inert solvent, such as diphenylether or ethyleneglycoldimethylether, to a temperature in the range of from 120 to 220°C.
  • compound IV can be prepared in analogy to the method described in EP-A-0065485 as outlined in scheme 6 below by a ketalization reaction of the ketone 11 with a diol HO-A-OH.
  • the ketalization reaction can be carried out under reaction conditions described for scheme 3.
  • the ketone 11 in turn can be prepared in analogy to the method described in EP-A- 0065485 as outlined in scheme 7 below by reacting the compound 12, wherein X is a good leaving group, such as a halogen atom, in particular Cl, Br or I, phenylsulfonyloxy, p-tosyloxy, trifluoroacetyloxy or alkylsulfonyloxy, such as mesyloxy, with the triazole compound 2 under reaction conditions described for the reaction in scheme 2.
  • Compound 12, in turn, can be obtained from the halogenation of the ketone 3.
  • compound IV can be prepared in analogy to the method described in EP-A-0065485 as outlined in scheme 8 below by condensation of compounds 13 and 14, wherein X 1 is a group Y-H or Y-M, wherein M is a metal atom, in particular an alkali metal atom, such as Li, Na or K, and X 2 is a good leaving group, such as a halogen atom, in particular Cl, Br or I, phenylsulfonyloxy, p- tosyloxy, trifluoroacetyloxy or alkylsulfonyloxy, such as mesyloxy, or, vice versa, wherein X 1 is a good leaving group and X 2 is a group Y-H or Y-M, under reaction conditions as described for scheme 4.
  • M is a metal atom, in particular an alkali metal atom, such as Li, Na or K
  • X 2 is a good leaving group, such as a halogen atom, in
  • the carbonic ester 15, in turn, can be prepared under reaction conditions described for the condensation reaction in scheme 5.
  • radicals in the above reactants if inert towards the respective reaction, can be present in the above reaction steps or can be introduced at a later stage, e.g. into compound IV.
  • Suitable bases are, for example, alkali metal hydrides (e.g. sodium hydride, potassium hydride), alkali metal hydroxides (e.g. sodium hydroxide, potassium hydroxide), alkali metal carbonates (e.g. sodium carbonate, potassium carbonate, caesium carbonate), alkali metal alkoxides (e.g. sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide) or organolithium bases (e.g.
  • alkali metal hydrides e.g. sodium hydride, potassium hydride
  • alkali metal hydroxides e.g. sodium hydroxide, potassium hydroxide
  • alkali metal carbonates e.g. sodium carbonate, potassium carbonate, caesium carbonate
  • alkali metal alkoxides e.g. sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium
  • n-butyl lithium, sec-butyl lithium, tert-butyl lithium and lithium diisopropylamine. The reaction is generally carried out in a suitable solvent.
  • suitable solvents are, for example, toluene, N-methylpyrrolidinone, ethers (e.g. diethyl ether, tetrahydrofuran, dioxane, 1 ,2-dimethoxyethane), acetonitrile, N,N-dimethylformamide or dimethylsulfox- ide.
  • compounds of formula I wherein m is 0 and R 1 is Ci-Cio-alkyl, C1-C10- haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C2-Cio-haloalkynyl, C3-C10- cycloalkyl, C3-Cio-halocycloalkyl, phenyl, phenyl-Ci-C4-alkyl, where the phenyl moiety in the 2 last-mentioned radicals may be substituted as described above, and a 5- or 6- membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may be substituted as described above, may be prepared in analogy to the method described in Heterocycles, 23(7), 1645-1649, 1985 by react
  • alkoxide e.g. methoxide, ethoxide
  • pentafluorophenoxide in the presence of a base.
  • bases are, for example, alkali metal hydrides (e.g. sodium hydride, potassium hydride), alkali metal hydroxides (e.g. sodium hydroxide, potassium hydroxide), alkali metal carbonates (e.g. sodium carbonate, potassium carbonate, caesium carbonate), alkali metal alkoxides (e.g. sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide) or organolithium bases (e.g.
  • alkali metal hydrides e.g. sodium hydride, potassium hydride
  • alkali metal hydroxides e.g. sodium hydroxide, potassium hydroxide
  • alkali metal carbonates e.g. sodium carbonate, potassium carbonate, caesium carbonate
  • n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium diisopropylamine The reaction is generally carried out in a suitable solvent.
  • suitable solvents are, for example, toluene, N- methylpyrrolidinone, ethers (e.g. diethyl ether, tetrahydrofuran, dioxane, 1 ,2- dimethoxyethane), acetonitrile, N,N-dimethylformamide or dimethylsulfoxide.
  • Compounds of formula I, wherein m is 0 and R 1 is -SO2R 8 may be prepared in analogy to the method described in DE-A-19620590 by reacting a compound I, wherein m is 0 and R 1 is H, with a compound R 8 -SC"2-W, wherein R 8 has one of the above meanings and W is a good leaving group, such as a halide (e.g. Cl, Br, I), an alkoxide (e.g. methoxide, ethoxide) or pentafluorophenoxide, in the presence of a base.
  • Suitable bases are, for example, alkali metal hydrides (e.g.
  • alkali metal hydroxides e.g. sodium hydroxide, potassium hydroxide
  • alkali metal carbon- ates e.g. sodium carbonate, potassium carbonate, caesium carbonate
  • alkali metal alkoxides e.g. sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide
  • organolithium bases e.g. n-butyl lithium, sec- butyl lithium, tert-butyl lithium, lithium diisopropylamine.
  • Suitable solvents are, for example, toluene, N- methylpyrrolidinone, ethers (e.g. diethyl ether, tetrahydrofuran, dioxane, 1 ,2- dimethoxyethane), acetonitrile, N,N-dimethylformamide or dimethylsulfoxide.
  • Compounds of formula I, wherein m is 0 and R 1 is -CN may be prepared in analogy to the method described in DE-A-19620407 by reacting a compound I, wherein m is 0 and R 1 is H, with a compound CN-W, wherein W is a good leaving group, such as a halide (e.g. Cl, Br, I), in the presence of a base.
  • Suitable bases are, for example, alkali metal hydrides (e.g. sodium hydride, potassium hydride), alkali metal hydroxides (e.g. sodium hydroxide, potassium hydroxide), alkali metal carbonates (e.g.
  • reaction is generally carried out in a suitable solvent.
  • suitable solvents are, for example, toluene, N-methylpyrrolidinone, ethers (e.g. diethyl ether, tetrahydrofuran, dioxane, 1 ,2-dimethoxyethane), acetonitrile, N,N-dimethylformamide or dimethylsulfoxide.
  • Compounds of formula I, wherein m is 0 and R 1 is M may be prepared in analogy to the method described in DE-A-19617282 by reacting a compound I, wherein m is 0 and R 1 is H, with an amine NR a R b R c , wherein R a , R b and R c are as defined above, or with a metal salt, such as sodium hydroxide, potassium hydroxide or copper acetate.
  • a metal salt such as sodium hydroxide, potassium hydroxide or copper acetate.
  • Suitable bases are, for example, alkali metal hydrides (e.g. sodium hydride, potassium hydride), alkali metal hydroxides (e.g. sodium hydroxide, potassium hydroxide), alkali metal carbonates (e.g. sodium carbonate, potassium carbonate, caesium carbonate), alkali metal alkoxides (e.g.
  • organolithium bases e.g. n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium diisopropylamine.
  • the reaction is generally carried out in a suitable solvent. Suitable solvents are, for example, toluene, N-methylpyrrolidinone, ethers (e.g. diethyl ether, tetrahydrofuran, dioxane, 1 ,2-dimethoxyethane), acetonitrile, N,N-dimethylformamide or dimethylsulfoxide.
  • Compounds I, wherein m is 1 or 2 can be prepared from respective compounds I, wherein m is 0, by oxidation.
  • compounds I, wherein m is 2 can be prepared from compounds IV by first deprotonating the triazolyl ring and then reacting with a sulfonyl chloride R 1 S ⁇ 2CI.
  • Compounds I, wherein m is 3, can be prepared from compounds IV by first deprotonating the triazolyl ring and then reacting with sulfuric acid chloride or a sulfuric ester chloride of formula R 1 OS ⁇ 2CI, wherein R 1 is selected from hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-C10- alkynyl, C2-Cio-haloalkynyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, phenyl, phenyl-Ci- C4-alkyl, where the phenyl moiety in the 2 last-mentioned radicals may be substituted as mentioned above, and a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S
  • reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or silica gel.
  • Some of the intermediates and end products may be obtained in the form of colorless or pale brown viscous oils, which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystallization or digestion.
  • a further aspect of the invention relates to compounds of formula IV
  • Ar, Het, A and Y have one of the general or, in particular, one of the preferred meanings given above for compounds I and II.
  • Particularly preferred compounds IV are compounds of formulae IV.1 to IV.48, wherein the combination of R 21 , R 22 , R 23 , R 24 and R 25 corresponds in each case to one row in table A above and Het has in ech case one of the formulae Het.1 to Het.16, and compounds of formulae IV.49 to IV.96, wherein the combination of Het and Ar' corresponds in each case to one row in table B above.
  • the invention further refers to an agricultural composition
  • an agricultural composition comprising at least one compound of formula I, Il and/or IV as defined above or an agriculturally acceptable salt thereof and a liquid or solid carrier.
  • Suitable carriers, as well as auxiliaries and further active compounds which may also be contained in the composition of the invention are defined below.
  • the compounds I and Il as well as IV 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, Per- onosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, 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, Il and IV 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 1 II and IV and compositions thereof, respectively are used for controlling a multitude 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.
  • 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. potatoes), which can be used for the multiplication of the plant. This in- eludes 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.
  • treatment of plant propagation materials with compounds I, Il and IV 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://www.bio.org/speeches/pubs/er/agrLproducts.asp).
  • 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.
  • HPPD hydroxyphenylpyruvate dioxygenase
  • ALS acetolactate synthase
  • WO 00/26390 WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imida- zolinones (see e. g.
  • EPSPS enolpyruvylshikimate-3-phosphate synthase
  • GS glutamine synthetase
  • EP-A 242 236, EP-A 242 246) or oxynil herbicides see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering.
  • 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.
  • plants are also covered that, by the use of recombinant DNA techniques, are 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(bi ) or Cry ⁇ c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp.
  • 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), Cry
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • toxins produced by fungi such Strep- tomycetes 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, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase
  • ion channel blockers such as blockers of sodium
  • 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 capable 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.
  • insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coleoptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).
  • Genetically modified plants capable to synthesize one or more insecticidal proteins are, e.
  • 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 CryiAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).
  • plants are also covered that, by the use of recombinant DNA techniques, are 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 Erwinia 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
  • plants are also covered that, by the use of recombinant DNA techniques, are 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, by the use of recombinant DNA techniques, contain 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).
  • 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, by the use of recombinant DNA techniques, contain 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, Il and IV 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); Altemaria spp. (Alternaria leaf spot) on vegetables, rape ⁇ A. brassicola or brassicae), sugar beets ⁇ A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A.retemata), tomatoes (e. g. A. solanior A.retemata) and wheat; Aphano- myces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A.
  • Botrytis cinerea (teleomorph: Botryotinia fuckeliana: 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. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e.g.
  • Gray leaf spot C. zeae-maydis
  • rice sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice
  • Cladosporium spp. on tomatoes e. g. C. fulvum: leaf mold
  • ce- reals e. g. C. herbarum (black ear) on wheat
  • Cochliobolus anamorph: Helminthosporium of Bipolaris
  • spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C.
  • sa- sakii sheath blight
  • Corynespora cassiicola leaf spots
  • 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.
  • vines e. g. C. liriodendri, teleomorph: Neonectria liriodendr ⁇ .
  • Phellinus punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeo- acremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri), 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. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruciferarum); 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. turcicum); Fusarium (teleomorph: Gib- berella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F.
  • vegetables e. g. E. pisi
  • cucurbits e. g. E. cichoracearum
  • cabbages rape (e. g. E. cruciferarum)
  • Eutypa lata Eu
  • Cladosporium vitis on vines; Macrophomina phaseolina (syn. phaseoli) (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.

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Abstract

The present invention relates to novel triazole compounds of the formulae I and Il as defined below which carry a sulfur substituent, to agricultural compositions containing them, to their use as fungicides and to intermediate compounds used in the method of producing them.

Description

TRIAZOLE COMPOUNDS CARRYING A SULFUR SUBSTITUENT
Description
The present invention relates to novel triazole compounds of the formulae I and Il as defined below which carry a sulfur substituent, to agricultural compositions containing them, to their use as fungicides and to intermediate compounds used in the method of producing them.
The control of plant diseases caused by phythopathogenic fungi is extremely important for achieving high crop efficiency. Plant disease damage to ornamental, vegetable, field, cereal, and fruit crops can cause significant reduction in productivity and thereby result in increased costs to the consumer.
WO 96/41804, WO 96/16048, WO 97/41107, WO 97/43269 and WO 97/44331 describe sulfurized triazolyl derivatives. The compounds are used for combating harmful fungi.
There is a continuous need for new compounds which are more effective, less costly, less toxic, environmentally safer and/or have different modes of action.
Accordingly, it is an object of the present invention to provide compounds having a better fungicidal activity and/or a better crop plant compatibility.
Surprisingly, these objects are achieved by triazole compounds of the general formulae I and II, defined below, and by the agriculturally acceptable salts of the compounds I and II.
Accordingly, the present invention relates to triazole compounds of the formulae I and Il and to agriculturally useful salts thereof
Figure imgf000002_0001
wherein Ar is phenyl which may carry 1 , 2, 3, 4 or 5 substituents R2, or is a 3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2, 3 or 4 substituents R3;
Het is a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2, 3 or 4 substituents R4;
A is a linear d-Cs-alkylene bridge which may be substituted by 1 , 2, 3 or 4 substituents R5;
Y is O, S or NR6;
R1 is selected from hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-C10- haloalkenyl, C2-Cio-alkynyl, C2-Cio-haloalkynyl, C3-Cio-cycloalkyl, C3-C10- halocycloalkyl, phenyl, phenyl-Ci-C4-alkyl, where the phenyl moiety in the 2 last- mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R7, and a 5- or 6- membered saturated, partially unsaturated or aromatic heterocyclic ring contain- ing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents R7; or, in case m is 0, may also be selected from -C(=O)R8, -C(=S)R8, -S(O)2R8, -CN, -P(=Q)R9R10, M and a group of the formula III
Figure imgf000003_0001
wherein
Ar, Het, A and Y are as defined for formulae I and II; and
# is the attachment point to the remainder of the molecule;
R1a is selected from hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-C10- haloalkenyl, C2-Cio-alkynyl, C2-Cio-haloalkynyl, C3-Cio-cycloalkyl, C3-C10- halocycloalkyl, phenyl, phenyl-Ci-C4-alkyl, where the phenyl moiety in the 2 last- mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R7, a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents R7, -C(=O)R8, -C(=S)R8, -S(O)2R8, -CN, -P(=Q)R9R10 and M;
each R2 is independently selected from halogen, OH, SH, NO2, CN, Ci-C4-alkyl, C1-C4- haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3- Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C1-C4- alkenyloxy, Ci-C4-haloalkenyloxy, Ci-C4-alkynyloxy, Ci-C4-haloalkynyloxy, C3-C8- cycloalkoxy, Cs-Cs-halocycloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C1-C4- alkenylylthio, Ci-C4-haloalkynylylthio, phenyl, phenyl-Ci-C4-alkyl, phenyl-Ci-C4- alkoxy, phenoxy, phenylthio, where the phenyl moiety in the 5 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R11; 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximum unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents R11; COR12, COOR12,
CONR13R14, NR13R14 and S(O)PR12, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R15 and where the cycloaliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R16; or
two radicals R2 bound on adjacent carbon ring atoms, together with the carbon ring atoms to which they are bound, form a partly unsaturated or maximum unsaturated 5-, 6- or 7-membered carbocyclic ring or a partly unsaturated or maximum unsaturated 5-, 6- or 7-membered heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members; where the carbocyclic or heterocyclic ring may carry 1 , 2 or 3 substituents R11;
each R3 is independently selected from halogen, OH, SH, NO2, CN, Ci-C4-alkyl, C1-C4- haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3- Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C1-C4- alkenyloxy, Ci-C4-haloalkenyloxy, Ci-C4-alkynyloxy, Ci-C4-haloalkynyloxy, C3-C8- cycloalkoxy, Cs-Cs-halocycloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C1-C4- alkenylylthio, Ci-C4-haloalkynylylthio, phenyl, phenyl-Ci-C4-alkyl, phenyl-Ci-C4- alkoxy, phenoxy, phenylthio, where the phenyl moiety in the 5 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R11; 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximum unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents R11; COR12, COOR12, CONR13R14, NR13R14 and S(O)PR12, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R15 and where the cycloaliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R16; or
two radicals R3 bound on adjacent ring atoms (of the heterocyclic ring Ar), to- gether with the ring atoms to which they are bound, form a partly unsaturated or maximum unsaturated 5-, 6- or 7-membered carbocyclic ring or a partly unsaturated or maximum unsaturated 5-, 6- or 7-membered heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members; where the carbocyclic or heterocyclic ring may carry 1 , 2 or 3 substituents R11;
each R4 is independently selected from halogen, OH, SH, NO2, CN, Ci-C4-alkyl, C1-C4- haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3- Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C1-C4- alkenyloxy, Ci-C4-haloalkenyloxy, Ci-C4-alkynyloxy, Ci-C4-haloalkynyloxy, C3-C8- cycloalkoxy, Cs-Cs-halocycloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, C1-C4- alkenylylthio, Ci-C4-haloalkynylylthio, phenyl, phenyl-Ci-C4-alkyl, phenyl-Ci-C4- alkoxy, phenoxy, phenylthio, where the phenyl moiety in the 5 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R11; 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximum unsaturated heterocyclic ring con- taining 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents R11; COR12, COOR12, CONR13R14, NR13R14 and S(O)PR12, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R15 and where the cycloaliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R16; or
two radicals R4 bound on adjacent ring atoms (of Het), together with the ring atom to which they are bound, form a partly unsaturated or maximum unsaturated 5-, 6- or 7-membered carbocyclic ring or a partly unsaturated or maximum unsaturated 5-, 6- or 7-membered heterocyclic ring containing 1 , 2 or 3 heteroa- toms selected from O, S and N as ring members; where the carbocyclic or heterocyclic ring may carry 1 , 2 or 3 substituents R11;
each R5 is independently selected from halogen, OH, SH, NR13R14, Ci-C4-alkyl, Ci-C4- haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, Ci- C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and Ci-C4-haloalkylthio, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R15; or
two radicals R5 bound on two adjacent carbon atoms, together with the carbon atoms to which they are bound, form a 3-, 4-, 5-, 6- or 7-membered saturated, partly unsaturated or maximum unsaturated carbocyclic ring or a 3-, 4-, 5-, 6- or 7-membered saturated, partly unsaturated or maximum unsaturated heterocyclic ring containing 1 , 2, or 3 heteroatoms selected from O, S and N as ring members, where the carbocyclic or heterocyclic ring may carry 1 , 2 or 3 substituents R11;
R6 is selected from hydrogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4- haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, phenyl, phenyl-Ci-C4-alkyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R11; COR12, COOR12, CONR13R14 and
each R7 is independently selected from halogen, OH, SH, NR13R14, CN, NO2, Ci-C4- alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4- haloalkynyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and Ci-C4- haloalkylthio, where the aliphatic moieties in the above radicals may carry 1 , 2 or
3 substituents R15;
R8 is selected from hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, C1-C10- haloalkoxy, Ci-Cio-aminoalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, phenyl, phenyl-Ci-C4-alkyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R7, a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents R7, and NR13R14;
R9 and R10, independently of each other, are selected from Ci-Cio-alkyl, Ci-Cio- haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C2-Cio-haloalkynyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, Ci-C4- alkoxy-Ci-Cio-alkyl, Ci-C4-alkoxy-Ci-Cio-alkoxy, Ci-Cio-alkylthio, C1-C10- haloalkylthio, C2-Cio-alkenyloxy, C2-Cio-alkenylthio, C2-Cio-alkynyloxy, C2-C10- alkynylthio, C3-Cio-cycloalkoxy, C3-Cio-cycloalkylthio, phenyl, phenyl-Ci-C4-alkyl, phenylthio, phenyl-Ci-C4-alkoxy, and NR13R14;
each R11 is independently selected from halogen, OH, SH, NR13R14, CN, NO2, CrC4- alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4- haloalkynyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and CrC4- haloalkylthio, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R15; each R12 is independently selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4- alkenyl, C2-C4-haloalkenyl, Ci-C4-aminoalkyl, phenyl, phenyl-Ci-C4-alkyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 sub- stituents R11, and a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents R11;
each R13 is independently selected from hydrogen and Ci-Cs-alkyl;
each R14 is independently selected from hydrogen, Ci-Cs-alkyl, phenyl, and phenyl-Ci- C4-alkyl;
or R13 and R14 together form a linear C4- or Cs-alkylene bridge or a group -CH2CH2OCH2CH2- or -CH2CH2NR17CH2CH2-;
each R15 is independently selected from nitro, CN, OH, SH, COR12, COOR12,
CONR13R14; NR13R14, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkoxy, CrC4- haloalkoxy, Cs-Cβ-cycloaloxy, phenyl and phenoxy;
each R16 is independently selected from nitro, CN, OH, SH, COR12, COOR12,
CONR13R14; NR13R14, Ci-C4-alkyl, CrC4-haloalkyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Cβ-cycloaloxy, phenyl and phenoxy;
each R17 is independently selected from hydrogen and Ci-C4-alkyl;
Q is O or S;
M is a metal cation equivalent or an ammonium cation of formula (NRaRbRcRd)+, wherein Ra, Rb, Rc and Rd, independently of each other, are selected from hydrogen, Ci-Cio-alkyl, phenyl and benzyl, where the phenyl moiety in the 2 last- mentioned radicals may carry 1 , 2 or 3 substituents independently selected from halogen, CN, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and NR13R14;
m is O, 1 or 2; and
p is 1 or 2. The present invention also provides the use of triazole compounds of the formulae I and Il and/or their agriculturally useful salts for controlling harmful fungi.
The invention further provides fungicidal compositions comprising these triazole com- pounds of the formulae I and/or Il (and/or also of the formula IV; see below) and/or their agriculturally acceptable salts and suitable carriers. Suitable agriculturally acceptable carriers are described below.
The compounds I and Il can exist as one or more stereoisomers. The various stereoi- somers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. The compounds of the invention may be present as a mixture of stereoisomers, e.g. a racemate, individual stereoisomers, or as an optically active form.
Compounds I and Il can be understood as positional/double bond isomers of each other, at least in case the radicals RVR1a are identical. In case R1 (and of course also R1a) is hydrogen, the respective compounds I and Il are tautomers.
Suitable agriculturally useful salts are 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 the compounds I and II. Thus, suitable cations are in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and 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 diisopropylammonium, tetramethylammonium, tetrabutylammo- nium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulf- oxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen- sulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and also the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting I or Il with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid. In the definitions of the variables given in the formulae 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 sub- stitutent moiety in question:
Halogen: fluorine, chlorine, bromine and iodine;
Alkyl and the alkyl moieties in alkoxy, alkoxyalkyl, alkoxyalkoxy, alkylcarbonyl, alkyl- thiocarbonyl, aminoalkyl, alkylamino, dialkylamino, alkylaminocarbonyl, dialkylamino- carbonyl, alkylthio, alkylsulfonyl and the like: saturated straight-chain or branched hydrocarbon radicals having 1 to 2 (Ci-C2-alkyl), 2 or 3 (C2-C3-alkyl), 1 to 4 (Ci-C4-alkyl), 1 to 6 (d-Ce-alkyl), 1 to 8 (Ci-C8-alkyl) or 1 to 10 (Ci-Cio-alkyl) carbon atoms. C2-C3- Alkyl is ethyl, n-propyl or isopropyl. Ci-C2-Alkyl is methyl or ethyl. CrC4-AIkVl is methyl, ethyl, propyl, isopropyl, butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl) or 1 ,1-dimethylethyl (tert-butyl). Ci-Cβ-Alkyl is additionally also, for example, 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-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2- methylpropyl. Ci-Cs-Alkyl is additionally also, for example, heptyl, octyl, 2-ethylhexyl and positional isomers thereof. Ci-Cio-Alkyl is additionally also, for example, nonyl, decyl, 2-propylheptyl, 3-propylheptyl and positional isomers thereof.
Haloalkyl: straight-chain or branched alkyl groups having 1 to 2 (Ci-C2-haloalkyl), 1 to 3 (Ci-C3-haloalkyl), 1 to 4 (Ci-C4-haloalkyl), 1 to 6 (Ci-C6-haloalkyl), 1 to 8 (CrC8- haloalkyl), 1 to 10 (Ci-Cio-haloalkyl) or 2 to 10 (C2-Cio-haloalkyl) carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above: in particular Ci-C2-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoro- methyl, 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. Ci-C3-Haloalkyl is additionally, for example, 1 ,1 ,1-trifluoroprop-2-yl, 3,3,3-trifluoropropyl or heptafluoropropyl. CrC4- Haloalkyl is additionally, for example, 1-chlorobuty, 2-chlorobutyl, 3-chlorobutyl or 4- chlorobutyl. Ci-Cio-Hydroxyalkyl: straight-chain or branched alkyl groups having 1 to 2 (Ci-C2- hydroxyalkyl), 1 to 4 (Ci-C4-hydroxyalkyl), 2 to 4 (C2-C4-hydroxyalkyl), 1 to 6 (Ci-C6- hydroxyalkyl), 2 to 6 (C2-C6-hydroxyalkyl), 1 to 8 (Ci-C8-hydroxyalkyl), 2 to 8 (C2-C8- hydroxyalkyl), 1 to 10 (Ci-Cio-hydroxyalkyl) or 2 to 10 (C2-Cio-hydroxyalkyl) carbon atoms (as mentioned above), where at least one of the hydrogen atoms is replaced by a hydroxyl group, such as in 2-hydroxyethyl or 3-hydroxypropyl.
Alkenyl and the alkenyl moieties in alkenyloxy, alkenylthio, alkenylcarbonyl and the like: monounsaturated straight-chain or branched hydrocarbon radicals having 2 to 4 (C2- C4-alkenyl), 2 to 6 (C2-C6-alkenyl), 2 to 8 (C2-C8-alkenyl), 3 to 8 (C3-C8-alkenyl), 2 to 10 (C2-Cio-alkenyl) or 3 to 10 (C3-Cio-alkenyl) carbon atoms and a double bond in any position, for example C2-C4-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1- methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1- propenyl, 1-methyl-2-propenyl or 2-methyl-2-propenyl, or, for example, C2-C6-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3- butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2- propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl- 1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2- butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1-dimethyl-2- propenyl, 1 ,2-dimethyl-1-propenyl, 1 ,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl- 2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1- pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2- pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3- pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4- pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1 ,1-dimethyl- 2-butenyl, 1 ,1-dimethyl-3-butenyl, 1 ,2-dimethyl-1-butenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2- dimethyl-3-butenyl, 1 ,3-dimethyl-1-butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3-dimethyl-3- butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3- dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1- ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3- butenyl, 1 ,1 ,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1- propenyl, 1-ethyl-2-methyl-2-propenyl and the like;
Haloalkenyl and the haloalkenyl moieties in haloalkenyloxy, haloalkenylcarbonyl and the like: unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4 (C2- C4-haloalkenyl), 2 to 6 (C2-C6-haloalkenyl), 2 to 8 (C2-C8-haloalkenyl) or 2 to 10 (C2- Cio-haloalkenyl) carbon atoms and a double bond in any position (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example chlorovinyl, chloroallyl and the like;
Alkynyl and the alkynyl moieties in alkynyloxy, alkynylthio, alkynylcarbonyl and the like: straight-chain or branched hydrocarbon groups having 2 to 4 (C2-C4-alkynyl), 2 to 6 (C2-C6-alkynyl), 2 to 8 (C2-C8-alkynyl), 3 to 8 (C3-C8-alkynyl), 2 to 10 (C2-Cio-alkynyl) or 3 to 10 (C3-Cio-alkynyl) carbon atoms and one or two triple bonds in any position, for example C2-C4-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3- butynyl, or 1-methyl-2-propynyl, or, for example, C2-C6-alkynyl, such as ethynyl, 1- propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3- butynyl, 3-methyl-1-butynyl, 1 ,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2- hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1- methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3- methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1 ,1-dimethyl-2-butynyl, 1 ,1-dimethyl-3-butynyl, 1 ,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1- butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2- propynyl and the like;
Haloalkynyl and the haloalkynyl moieties in haloalkynyloxy, haloalkynylcarbonyl and the like: unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4 (C2- C4-haloalkynyl), 2 to 6 (C2-C6-haloalkynyl), 2 to 8 (C2-C8-haloalkynyl) or 2 to 10 (C2-Ci0- haloalkynyl) carbon atoms and one or two triple bonds in any position (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine;
Cycloalkyl and the cycloalkyl moieties in cycloalkoxy, cycloalkylcarbonyl and the like; monocyclic saturated hydrocarbon groups having 3 to 6 (Cs-Cβ-cycloalkyl), 3 to 8 (C3- Cs-cycloalkyl) or 3 to 10 (C3-Cio-cycloalkyl) carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl;
Halocycloalkyl and the halocycloalkyl moieties in halocycloalkoxy, halocycloalkylcar- bonyl and the like: monocyclic saturated hydrocarbon groups having 3 to 6 (C3-C6- halocycloalkyl), 3 to 8 (Cs-Cs-halocycloalkyl) or 3 to 10 (C3-Cio-halocycloalkyl) carbon ring members (as mentioned above) in which some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine; Cycloalkenyl and the cycloalkenyl moieties in cycloalkenyloxy, cycloalkenylcarbonyl and the like; monocyclic monounsaturated hydrocarbon groups having 3 to 6 (C3-C6- cycloalkenyl), 3 to 8 (C3-C8-cycloalkenyl) or 3 to 10 (C3-Cio-cycloalkenyl) carbon ring members, such as cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclohep- tenyl, cyclooctenyl, cyclononenyl and cyclodecenyl;
Halocycloalkenyl and the halocycloalkenyl moieties in halocycloalkenyloxy, halo- cycloalkenylcarbonyl and the like: monocyclic monounsaturated hydrocarbon groups having 3 to 6 (C3-C6-halocycloalkenyl), 3 to 8 (C3-C8-halocycloalkenyl) or 3 to 10 (C3- Cio-halocycloalkenyl) carbon ring members (as mentioned above) in which some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine;
C3-C6-cycloalkyl-Ci-C2-alkyl: a Ci-C2-alkyl residue, as decribed above, wherein one of the hydrogen atoms is replaced by a C3-C6-cycloalkyl group. Examples are cyclopro- pylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropyl-1 -ethyl, cyclobutyl-1 -ethyl, cyclopentyl-1 -ethyl, cyclohexyl-1 -ethyl, cyclopropyl-2-ethyl, cyclobu- tyl-2-ethyl, cyclopentyl-2-ethyl, cyclohexyl-2-ethyl and the like. C3-Cio-cycloalkyl-Ci-C4- alkyl is a Ci-C4-alkyl residue, as decribed above, wherein one of the hydrogen atoms is replaced by a C3-Cio-cycloalkyl group. Examples are, apart those mentioned above for C3-C6-cycloalkyl-Ci-C4-alkyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, cycloheptyl-1 -ethyl, cyclooctyl-1 -ethyl, cyclononyl-1 -ethyl, cyclode- cyl-1 -ethyl, cycloheptyl-2 -ethyl, cyclooctyl-2 -ethyl, cyclononyl-2 -ethyl, cyclodecylmethyl, cyclopropyl-1 -propyl, cyclopropyl-2-propyl, cyclopropyl-3-propyl, cyclobutyl-1 - propyl, cyclobutyl-2-propyl, cyclobutyl-3-propyl, cyclopentyl-1 -propyl, cyclopentyl-2- propyl, cyclopentyl-3-propyl, cyclohexyl-1 -propyl, cyclohexyl-2-propyl, cyclohexyl-3- propyl, cycloheptyl-1 -propyl, cycloheptyl-2-propyl, cycloheptyl-3-propyl, cyclooctyl-1 - propyl, cyclooctyl-2-propyl, cyclooctyl-3-propyl, cyclononyl-1 -propyl, cyclononyl-2- propyl, cyclononyl-3-propyl, cyclodecyl-1 -propyl, cyclodecyl-2-propyl, cyclodecyl-3- propy, cyclopropyl-1 -butyl, cyclopropyl-2-butyl, cyclopropyl-3-butyl, cyclopropyl-4-butyl, cyclobutyl-1 -butyl, cyclobutyl-2-butyl, cyclobutyl-3-butyl, cyclobutyl-4-butyl, cyclopentyl- 1 -butyl, cyclopentyl-2-butyl, cyclopentyl-3-butyl, cyclopentyl-4-butyl, cyclohexyl-1 -butyl, cyclohexyl-2-butyl, cyclohexyl-3-butyl, cyclohexyl-4-butyl, cycloheptyl-1 -butyl, cyclohep- tyl-2-butyl, cycloheptyl-3-butyl, cycloheptyl-4-butyl, cyclooctyl-1 -butyl, cyclooctyl-2- butyl, cyclooctyl-3-butyl, cyclooctyl-4-butyl, cyclononyl-1 -butyl, cyclononyl-2-butyl, cyc- lononyl-3-butyl, cyclononyl-4-butyl, cyclodecyl-1 -butyl, cyclodecyl-2-butyl, cyclodecyl-3- butyl, cyclodecyl-4-butyl, and the like. C3-C6-halocycloalkyl-Ci-C2-alkyl: a Ci-C2-alkyl residue, as decribed above, wherein one of the hydrogen atoms is replaced by a Cs-Cβ-halocycloalkyl group. Examples are 1- chlorocyclopropylmethyl, 1-chlorocyclobutylmethyl, 1-chlorocyclopentylmethyl, 1- chlorocyclohexylmethyl, 1-chlorocyclopropyl-i -ethyl, 1-chlorocyclobutyl-1 -ethyl, 1- chlorocyclopentyl-1 -ethyl, 1-chlorocyclohexyl-i -ethyl, 1-chlorocyclopropyl-2-ethyl, 1- chlorocyclobutyl-2 -ethyl, 1-chlorocyclopentyl-2-ethyl, 1-chlorocyclohexyl-2-ethyl, 2- chlorocyclopropylmethyl, 2-chlorocyclobutylmethyl, 2-chlorocyclopentylmethyl, 2- chlorocyclohexylmethyl, 2-chlorocyclopropyl-1 -ethyl, 2-chlorocyclobutyl-1 -ethyl, 2- chlorocyclopentyl-1 -ethyl, 2-chlorocyclohexyl-1 -ethyl, 2-chlorocyclopropyl-2-ethyl, 2- chlorocyclobutyl-2 -ethyl, 2-chlorocyclopentyl-2-ethyl, 2-chlorocyclohexyl-2-ethyl, 1- fluorocyclopropylmethyl, 1-fluorocyclobutylmethyl, 1-fluorocyclopentylmethyl, 1- fluorocyclohexylmethyl, 1-fluorocyclopropyl-1 -ethyl, 1-fluorocyclobutyl-1 -ethyl, 1- fluorocyclopentyl-1 -ethyl, 1-fluorocyclohexyl-1 -ethyl, 1-fluorocyclopropyl-2-ethyl, 1- fluorocyclobutyl-2 -ethyl, 1-fluorocyclopentyl-2-ethyl, 1-fluorocyclohexyl-2-ethyl, 2- fluorocyclopropylmethyl, 2-fluorocyclobutylmethyl, 2-fluorocyclopentylmethyl, 2- fluorocyclohexylmethyl, 2-fluorocyclopropyl-1 -ethyl, 2-fluorocyclobutyl-1 -ethyl, 2- fluorocyclopentyl-1 -ethyl, 2-fluorocyclohexyl-1 -ethyl, 2-fluorocyclopropyl-2-ethyl, 2- fluorocyclobutyl-2-ethyl, 2-fluorocyclopentyl-2-ethyl, 2-fluorocyclohexyl-2-ethyl, and the like. C3-Cio-halocycloalkyl-Ci-C4-alkyl is a Ci-C4-alkyl residue, as decribed above, wherein one of the hydrogen atoms is replaced by a C3-Cio-halocycloalkyl group.
Alkoxy: an alkyl group attached via oxygen. Ci-C2-Alkoxy is methoxy or ethoxy. Ci-C3- Alkoxy is additionally, for example, n-propoxy or 1-methylethoxy (isopropoxy). C1-C4- Alkoxy is additionally, for example, butoxy, 1-methylpropoxy (sec-butoxy), 2- methylpropoxy (isobutoxy) or 1 ,1-dimethylethoxy (tert-butoxy). Ci-Cβ-Alkoxy is additionally, for example, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1- dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1- dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3- dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethyl butoxy, 1 ,1 ,2- trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1-ethyl-1 -methylpropoxy or 1 -ethyl-2- methylpropoxy. Ci-Cs-Alkoxy is additionally, for example, heptyloxy, octyloxy, 2- ethylhexyloxy and positional isomers thereof. Ci-Cio-Alkoxy is additionally, for example, nonyloxy, decyloxy and positional isomers thereof. C2-Cio-Alkoxy is like Ci-Cio-alkoxy with the exception of methoxy.
Haloalkoxy: an alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, preferably by fluorine. Ci-C2-Haloalkoxy is, for example, OCH2F, OCHF2, OCF3, OCH2CI, OCHCI2, OCCI3, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2- fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy or OC2F5. Ci-C4-Haloalkoxy is additionally, for example, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C2F5, OCF2- C2F5, 1-(CH2F)-2-fluoroethoxy, 1-(CH2CI)-2-chloroethoxy, 1-(CH2Br)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy. Ci-Cβ-Haloalkoxy is additionally, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-brompentoxy,
5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dodecafluorohexoxy.
Alkenyloxy: alkenyl as mentioned above which is attached via an oxygen atom, for ex- ample C2-Cio-alkenyloxy, such as 1-ethenyloxy, 1-propenyloxy, 2-propenyloxy, 1- methylethenyloxy, 1-butenyloxy, 2-butenyloxy, 3-butenyloxy, 1-methyl-1-propenyloxy, 2-methyl-1-propenyloxy, 1-methyl-2-propenyloxy, 2-methyl-2-propenyloxy, 1- pentenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy, 1-methyl-1-butenyloxy, 2- methyl-1-butenyloxy, 3-methyl-1-butenyloxy, 1-methyl-2-butenyloxy, 2-methyl-2- butenyloxy, 3-methyl-2-butenyloxy, 1-methyl-3-butenyloxy, 2-methyl-3-butenyloxy, 3- methyl-3-butenyl, 1 ,1-dimethyl-2-propenyloxy, 1 ,2-dimethyl-1-propenyloxy, 1 ,2- dimethyl-2-propenyloxy, 1-ethyl-1-propenyloxy, 1-ethyl-2-propenyloxy, 1-hexenyloxy, 2-hexenyloxy, 3-hexenyloxy, 4-hexenyloxy, 5-hexenyloxy, 1-methyl-1-pentenyloxy, 2-methyl-1-pentenyloxy, 3-methyl-1-pentenyloxy, 4-methyl-1-pentenyloxy, 1-methyl-2- pentenyloxy, 2-methyl-2-pentenyloxy, 3-methyl-2-pentenyloxy, 4-methyl-2-pentenyloxy, 1-methyl-3-pentenyloxy, 2-methyl-3-pentenyloxy, 3-methyl-3-pentenyloxy, 4-methyl-3- pentenyloxy, 1-methyl-4-pentenyloxy, 2-methyl-4-pentenyloxy, 3-methyl-4-pentenyloxy, 4-methyl-4-pentenyloxy, 1 ,1-dimethyl-2-butenyloxy, 1 ,1-dimethyl-3-butenyloxy, 1 ,2-dimethyl-1 -butenyloxy, 1 ,2-dimethyl-2-butenyloxy, 1 ,2-dimethyl-3-butenyloxy, 1 ,3-dimethyl-1 -butenyloxy, 1 ,3-dimethyl-2-butenyloxy, 1 ,3-dimethyl-3-butenyloxy, 2,2-dimethyl-3-butenyloxy, 2,3-dimethyl-1 -butenyloxy, 2,3-dimethyl-2-butenyloxy, 2,3-dimethyl-3-butenyloxy, 3,3-dimethyl-1 -butenyloxy, 3,3-dimethyl-2-butenyloxy, 1-ethyl-1 -butenyloxy, 1-ethyl-2-butenyloxy, 1-ethyl-3-butenyloxy, 2-ethyl-1 -butenyloxy, 2-ethyl-2-butenyloxy, 2-ethyl-3-butenyloxy, 1 ,1 ,2-trimethyl-2-propenyloxy, 1-ethyl-1- methyl-2-propenyloxy, 1-ethyl-2-methyl-1-propenyloxy and 1-ethyl-2-methyl-2- propenyloxy and the like;
Haloalkenyloxy: an alkenyloxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, preferably by fluorine. Alkynyloxy: alkynyl as mentioned above which is attached via an oxygen atom, for example C2-Cio-alkynyloxy, such as 2-propynyloxy, 2-butynyloxy, 3-butynyloxy, 1-methyl- 2-propynyloxy, 2-pentynyloxy, 3-pentynyloxy, 4-pentynyloxy, 1-methyl-2-butynyloxy, 1- methyl-3-butynyloxy, 2-methyl-3-butynyloxy, 1 -ethyl-2-propynyloxy, 2-hexynyloxy, 3- hexynyloxy, 4-hexynyloxy, 5-hexynyloxy, 1-methyl-2-pentynyloxy, 1-methyl-3- pentynyloxy and the like;
Haloalkynyloxy: an alkynyloxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, preferably by fluorine.
Cycloalkoxy: cycloalkyl as mentioned above which is attached via an oxygen atom, for example C3-Cio-cycloalkoxy or Cs-Cs-cycloalkoxy, such as cyclopropoxy, cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclononyloxy, cyclodecyloxy and the like;
Halocycloalkoxy: a cycloalkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, preferably by fluorine.
Cycloalkenyloxy: cycloalkenyl as mentioned above which is attached via an oxygen atom, for example C3-Cio-cycloalkenyloxy, Cs-Cs-cycloalkenyloxy or, preferably, Cs-Cβ- cycloalkenyloxy, such as cyclopent-1-enoxy, cyclopent-2-enoxy, cyclohex-1-enoxy and cyclohex-2-enoxy;
Alkoxyalkyl: alkyl as defined above having 1 to 10, 1 to 8, 1 to 6 or 1 to 4, in particular 1 to 3, carbon atoms, in which one hydrogen atom is replaced by an alkoxy group having 1 to 8, 1 to 6, 1 to 4 or 1 to 3 carbon atoms, for example methoxymethyl, 2- methoxyethyl, ethoxymethyl, 3-methoxypropyl, 3-ethoxypropyl and the like.
Alkoxyalkoxy: alkoxy as defined above having 1 to 10, 1 to 8, 1 to 6 or 1 to 4, in particu- lar 1 to 3, carbon atoms, in which one hydrogen atom is replaced by an alkoxy group having 1 to 8, 1 to 6 or in particular 1 to 4 carbon atoms, for example 2-methoxyethoxy, 2-ethoxyethoxy, 3-methoxypropoxy, 3-ethoxypropoxy and the like.
Alkylcarbonyl: group of the formula R-CO- in which R is an alkyl group as defined above, for example Ci-Cio-alkyl, d-Cs-alkyl, d-Cε-alkyl, Ci-C4-alkyl, Ci-C2-alkyl or C3- C4-alkyl. Examples are acetyl, propionyl and the like. Examples for C3-C4-alkylcarbonyl are propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, sec-butylcarbonyl, isobutylcar- bonyl and tert-butylcarbonyl. Haloalkylcarbonyl: group of the formula R-CO- in which R is a haloalkyl group as defined above, for example Ci-Cio-haloalkyl, d-Cs-haloalkyl, d-Cβ-haloalkyl, C1-C4- haloalkyl, Ci-C2-haloalkyl or C3-C4-haloalkyl. Examples are difluoromethylcarbonyl, trifluoromethylcarbonyl, 2,2-difluoroethylcarbony, 2,2,3-trifluoroethylcarbonyl and the like.
Alkoxycarbonyl: group of the formula R-CO- in which R is an alkoxy group as defined above, for example Ci-Cio-alkoxy, Ci-Cs-alkoxy, Ci-Cβ-alkoxy, Ci-C4-alkoxy or C1-C2- alkoxy. Examples for Ci-C4-alkoxycarbonyl are methoxycarbonyl, ethoxycarbonyl, pro- poxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl, isobutoxy- carbonyl and tert-butoxycarbonyl.
Haloalkoxycarbonyl: group of the formula R-CO- in which R is a haloalkoxy group as defined above, for example Ci-Cio-haloalkoxy, d-Cs-haloalkoxy, d-Cβ-haloalkoxy, Ci- C4-haloalkoxy or Ci-C2-haloalkoxy. Examples for Ci-C4-haloalkoxycarbonyl are di- fluoromethoxycarbonyl, trifluoromethoxycarbonyl, 2,2-difluoroethoxycarbony, 2,2,3- trifluoroethoxycarbonyl and the like.
Alkylaminocarbonyl: group of the formula R-NH-CO- in which R is an alkyl group as defined above, for example Ci-Cio-alkyl, Ci-C8-alkyl, d-Ce-alkyl, Ci-d-alkyl, C1-C2- alkyl or C3-d-alkyl. Examples for Ci-C4-alkylaminocarbonyl are methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, isopropylaminocarbonyl, butylaminocar- bonyl, sec-butylaminocarbonyl, isobutylaminocarbonyl and tert-butylaminocarbonyl.
Dialkylaminocarbonyl: group of the formula RR'N-CO- in which R and R', independently of each other, are an alkyl group as defined above, for example Ci-Cio-alkyl, Ci-Cs- alkyl, Ci-C6-alkyl, Ci-d-alkyl, Ci-C2-alkyl or C3-C4-alkyl. Examples for di-(Ci-d-alkyl)- aminocarbonyl are dimethylaminocarbonyl, diethylaminocarbonyl, dipropylaminocar- bonyl, diisopropylaminocarbonyl and dibutylaminocarbonyl.
Aminoalkyl: group of the formula R-NH2 in which R is an alkyl group as defined above, for example Ci-Cio-alkyl, Ci-C8-alkyl, Ci-C6-alkyl, Ci-C4-alkyl, Ci-C2-alkyl or C3-C4- alkyl. Examples are aminomethyl, 1- and 2-aminoethyl, 1-, 2- and 3-aminopropyl, 1- and 2-amino1-methylethyl, 1-, 2-, 3- and 4-aminobutyl and the like.
Alkylsulfonyl: group of the formula R-S(O)2- in which R is an alkyl group as defined above, for example Ci-Cio-alkyl, d-Cs-alkyl, Ci-C6-alkyl, Ci-C4-alkyl or Ci-C2-alkyl. Examples for d-d-alkylsulfonyl are methylsulfonyl, ethylsulfonyl, propylsulfonyl, iso- propylsulfonyl, n-butylsulfonyl, sec-butylsulfonyl, isobutylsulfonyl and tert-butylsulfonyl. Alkylthio: alkyl as defined above which is attached via a sulfur atom.
Haloalkylthio: haloalkyl as defined above which is attached via a sulfur atom.
Alkenylthio: alkenyl as defined above which is attached via a sulfur atom.
Haloalkenylthio: haloalkenyl as defined above which is attached via a sulfur atom.
Alkynylthio: alkynyl as defined above which is attached via a sulfur atom.
Haloalkynylthio: haloalkynyl as defined above which is attached via a sulfur atom.
Cycloalkylthio: cycloalkyl as defined above which is attached via a sulfur atom.
Aryl is a carbocyclic aromatic monocyclic or polycyclic ring containing 6 to 16 carbon atoms as ring members. Examples are phenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl and azulenyl. Preferably, aryl is phenyl or naphthyl, and especially phenyl.
Phenyl-Ci-C4-alkyl: Ci-C4-alkyl (as defined above), where a hydrogen atom is replaced by a phenyl group, such as benzyl, phenethyl and the like.
Phenyl-Ci-C4-alkoxy: Ci-C4-alkoxy (as defined above), where one hydrogen atom is replaced by a phenyl group, such as benzyloxy, phenethyloxy and the like.
3-, 4-, 5-, 6- or 7- membered saturated, partially unsaturated or maximum unsaturated carbocyclic radical: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclo- propenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclobutadienyl, cyclopentadienyl, cyclohexadienyl, cycloheptadienyl or cycloheptatrienyl. Formally, phenyl is also included in this definition, but as it is also encompassed in the term aryl, it is not listed here.
3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximum unsaturated heterocycle which contains 1 , 2 or 3 heteroatoms or heteroatom containing groups se- lected from oxygen, nitrogen (as N or NR) and sulfur (as S, SO or SO2) and optionally 1 or 2 groups selected from C(=O) and C(=S) as ring members:
three- or four-membered saturated or partially unsaturated heterocycle (hereinbe- low also referred to as heterocyclyl) which contains one, two or three heteroa- toms from the group consisting of oxygen, nitrogen (as N or NR) and sulfur (as S, SO or SO2) and optionally 1 or 2 groups selected from C(=O) and C(=S) as ring members: for example monocyclic saturated or partially unsaturated heterocycles which, in addition to carbon ring members, contain one to three nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms and optionally 1 or 2 groups selected from C(=O) and C(=S), for example 2-oxiranyl, 2-thiiranyl, 1- or 2-aziridinyl, 1-, 2- or 3-azetidinyl,
five- or six-membered saturated or partially unsaturated heterocycle (hereinbelow also referred to as heterocyclyl) which contains one, two or three heteroatoms from the group consisting of oxygen, nitrogen (as N or NR) and sulfur (as S, SO or SO2) and optionally 1 or 2 groups selected from C(=O) and C(=S) as ring members: for example monocyclic saturated or partially unsaturated heterocycles which, in addition to carbon ring members, contain one to three nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms and optionally 1 or 2 groups selected from C(=O) and C(=S), for example 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 3-tetrahydrofuran-2-onyl, 4-tetrahydrofuran-2-onyl, 5-tetrahydrofuran-2-onyl, 2-tetrahydrofuran-3-onyl, 4-tetrahydrofuran-3-onyl, 5-tetrahydrofuran-3-onyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 3-tetrahydrothien-2-onyl, 4-tetrahydrothien-2-onyl,
5-tetrahydrothien-2-onyl, 2-tetrahydrothien-3-onyl, 4-tetrahydrothien-3-onyl, 5-tetrahydrothien-3-onyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 1 -pyrrolidin-2-onyl, 3-pyrrolidin-2-onyl, 4-pyrrolidin-2-onyl, 5-pyrrolidin-2-onyl, 1 -pyrrolidin-3-onyl, 2-pyrrolidin-3-onyl, 4-pyrrolidin-3-onyl, 5-pyrrolidin-3-onyl, 1-pyrrolidin-2,5-dionyl, 3-pyrrolidin-2,5-dionyl, 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-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 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-hexahydropyτidazinyl, 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;
a seven-membered saturated or partially unsaturated heterocycle which contains one, two or three heteroatoms from the group consisting of oxygen, nitrogen and sulfur as ring members: for example mono- and bicyclic heterocycles having 7 ring members which, in addition to carbon ring members, contain one to three ni- trogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms, for example tetra- and hexahydroazepinyl, such as 2,3,4,5-tetrahydro[1 H]azepin-1-, -2-, -3-, -4-, -5-, -6- or -7-yl, 3,4,5,6-tetrahydro[2H]azepin-2-, -3-, -A-, -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-, -A-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1 H]oxepin-2-, -3-, -A-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1 H]oxepin-2-, -3-, -A-, -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.
a five- or six-membered aromatic (= maximum unsaturated) heterocycle (= het- eroaromatic radical) which contains one, two or three heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur, for example 5-membered heteroaryl which is attached via carbon and contains one to three nitrogen atoms or one or two nitrogen atoms and one sulfur or oxygen atom as ring members, such as 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4- isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4- pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5- thiazolyl, 2-imidazolyl, 4-imidazolyl, 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-oxadiazol-5-yl, 1 ,2,4-thiadiazol-3-yl, 1 ,2,4-thiadiazol-5-yl, 1 ,2,4-triazol-3-yl, 1 ,3,4-oxadiazol-2-yl, 1 ,3,4-thiadiazol-2-yl and 1 ,3,4-triazol-2-yl; 5-membered heteroaryl which is attached via nitrogen and contains one to three nitrogen atoms as ring members, such as pyrrol-1-yl, pyτazol-1-yl, imidazol-1-yl, 1 ,2,3-triazol-1-yl and 1 ,2,4-triazol- 1-yl; 6-membered heteroaryl, which contains one, two or three nitrogen atoms as ring members, such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, 3-pyridazinyl, 4- pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1 ,3,5-triazin-2- yl and 1 ,2,4-triazin-3-yl;
Linear C2-alkylene: divalent unbranched chains having 2 carbon atoms, namely CH2CH2.
Linear C2- or C3-alkylene: divalent unbranched chains having 2 or 3 carbon atoms, namely CH2CH2 and CH2CH2CH2.
Linear d-Cs-alkylene: divalent unbranched chains having 1 to 5 carbon atoms, namely CH2, CH2CH2, CH2CH2CH2, CH2CH2CH2CH2 and CH2CH2CH2CH2CH2.
C2-C5-Alkylene: divalent branched or preferably unbranched chains having 2 to 5 carbon atoms, for example CH2CH2, -CH(CH3)-, CH2CH2CH2, CH(CH3)CH2, CH2CH(CH3), CH2CH2CH2CH2, CH2CH2CH2CH2CH2.
C4-C5-Alkylene: divalent branched or preferably unbranched chains having 4 to 5 carbon atoms, for example CH2CH2CH2CH2 or CH2CH2CH2CH2CH2.
The group -SM is more correctly spoken a group -S"M+, where M+ is a metal cation equivalent or an ammonium cation as defined above. A metal cation equivalent is more correctly spoken 1/a Ma+, where a is the valence of the metal and is in general 1 , 2 or 3.
The statements made below with respect to suitable and preferred features of the compounds according to the invention, especially with respect to their substituents Ar, Het, A, Y, R1, R2, R3, R4, R5, R6, R6a, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, Ra, Rb, Rc, Rd, M, Q and the indices m and p, and to their use, are valid both per se and, in particular, in every possible combination with one another.
Preferably, Ar, if it is a heterocyclic ring as defined above, is bound via a C-atom to the group Y.
In a preferred embodiment of the invention, Ar is phenyl which may carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2, substituents R2, or is a 5- or 6-membered heteroaromatic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heteroaromatic ring may carry 1 , 2, 3 or 4, preferably 1 , 2 or 3, more preferably 1 or 2, substituents R3. More precisely spoken, Ar preferably is phenyl which may carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2, substituents R2, or is a 5- or 6-membered heteroaromatic ring containing 1 heteroatom selected from N, O and S and optionally 1 or 2 further nitrogen atoms as ring members, where the heteroaromatic ring may carry 1 , 2, 3 or 4, preferably 1 or 2, substituents R3. Suitable 5- or 6-membered heteroaromatic radicals are listed above.
Among the above-listed heteroaromatic rings, preference is given to pyridyl, such as pyridin-2-yl, pyridin-3-yl or pyridin-4-yl, pyrimidyl, such as 2-pyrimidinyl, 4-pyrimidinyl or 5-pyrimidinyl, furyl, such as 2-furyl or 3-furyl, thienyl, such as 2-thienyl or 3-thienyl, pyr- rolyl, such as 1-pyrrolyl, 2-pyrrolyl or 3-pyrrolyl, especially 2-pyrrolyl or 3-pyrrolyl, pyra- zolyl, such as 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl or 5-pyrazolyl, especially 3-pyrazolyl, 4-pyrazolyl or 5-pyrazolyl, imidazolyl, such as 1-imidazolyl, 2-imidazolyl or 4-imidazolyl, especially 2-imidazolyl or 4-imidazolyl, oxazolyl, such as 2-oxazolyl, 4-oxazolyl or 5- oxazolyl, isoxazolyl, such as 3-isoxazolyl, 4-isoxazolyl or 5-isoxazolyl, thiazolyl, such as 2-thiazolyl, 4-thiazolyl or 5-thiazolyl, isothiazolyl, such as 3-isothiazolyl, 4-isothiazolyl or 5-isothiazolyl, and triazolyl, such as 1 ,2,4-triazol-1-yl, 1 ,2,4-triazol-3-yl, 1 ,2,4-triazol-4- yl, 1 ,3,4-triazol-1-yl, 1 ,3,4-triazol-2-yl or 1 ,3,4-triazol-3-yl, especially 1 ,2,4-triazol-3-yl or 1 ,3,4-triazol-2-yl. The given binding positions are to be understood as relative to the 1- position of the ring heteroatom with the highest priority. For instance, in rings containg
1 ring heteroatom, the given binding position is relative to the 1 -position of the one ring heteroatom. In pyrazolyl, the given binding position is relative to the 1- and 2-positions of the 2 nitrogen ring atoms, in imidazolyl, it is relative to the 1- and 3-positions of the 2 nitrogen ring atoms, in oxazolyl, it is relative to the 1 -position of the oxygen ring atom and to the 3-position of the nitrogen ring atom, in isoxazolyl, it is relative to the 1- position of the oxygen ring atom and to the 2-position of the nitrogen ring atom, in thiazolyl, it is relative to the 1 -position of the sulfur ring atom and to the 3-position of the nitrogen ring atom, in isothiazolyl, it is relative to the 1 -position of the sulfur ring atom and to the 2-position of the nitrogen ring atom, etc.
More preferably, Ar is phenyl which may carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, more preferably 1 or 2, substituents R2, or is a 5- or 6-membered heteroaromatic ring selected from pyridyl, such as pyridin-2-yl, pyridin-3-yl or pyridin-4-yl, thienyl, such as 2- or 3-thienyl, and thiazolyl, such as 2-thiazolyl, 4-thiazolyl or 5-thiazolyl. Particular pref- erence is given to pyridyl, such as pyridin-2-yl, pyridin-3-yl or pyridin-4-yl, and especially to pyridin-2-yl, where the heteroaromatic ring may carry 1 , 2, 3 or 4, preferably 1 ,
2 or 3, more preferably 1 or 2, substituents R3. In case Ar is a 6-membered heteroaromatic ring, this carries preferably O, 1 , 2 or 3, more preferably 0, 1 or 2, substituents R3,where the two or more substituents R3 may be the same or different. In case Ar is a 5-membered heteroaromatic ring, this carries preferably 0, 1 or 2 substituents R3, where two substituents R3 may be the same or different.
R2 is preferably selected from halogen, OH, SH, NO2, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkoxy, and Ci-C4- haloalkoxy, more preferably from fluorine, chlorine, bromine, Ci-C4-alkyl, Ci-C4- haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, even more preferably from fluorine, chlorine, bromine, CH3, CHF2, CF3, OCH3, OCHF2 and OCF3, and in particular from fluorine, chlorine, bromine, CH3, CF3, OCH3 and OCF3.
R3 may be C- or N-bound, but is preferably bound to a C-atom of Ar.
R3 is preferably selected from halogen, OH, SH, NO2, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkoxy, and CrC4- haloalkoxy, more preferably from fluorine, chlorine, bromine, Ci-C4-alkyl, CrC4- haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, even more preferably from fluorine, chlorine, bromine, CH3, CHF2, CF3, OCH3, OCHF2 and OCF3, and in particular from fluorine, chlorine, bromine, CH3, CF3, OCH3 and OCF3.
Specifically, Ar is selected from following formulae Ar.1 to Ar.50, where in formula Ar.1 , the combination of the variables R21, R22, R23, R24 and R25 is selected from the defini- tion given in each line of Table A below.
Figure imgf000022_0001
Ar 8 Ar 9 Ar 10 Ar 11 Ar I2 Ar 13 Ar 14 Ar 15
Figure imgf000022_0002
Ar 16 Ar 17 Ar 18 Ar 19 Ar2O Ar2I Ar22 Ar23
Figure imgf000023_0001
Ar 24 Ar 25 Ar 26 Ar 27 Ar 28 Ar 29 Ar 30 Ar 31
Figure imgf000023_0002
Ar 32 Ar 33 Ar 34 Ar 35 Ar 36 Ar 37 Ar 38 Ar 39
Figure imgf000023_0003
Ar 40 Ar 41 Ar 42 Ar 43
Figure imgf000023_0004
Ar 44 Ar 45 Ar 46 Ar 47 Ar 48 Ar 49 Ar 50
Table A
Figure imgf000023_0005
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Preferably, Het is bound via two ring C-atoms to the group Y and the quaternary carbon atom (carrying the ketal group and the triazolylmethyl group).
In a preferred embodiment of the invention, Het is a (divalent) 5- or 6-membered het- eroaromatic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heteroaromatic ring may carry 1 , 2, 3 or 4, preferably 1 or 2, sub- stituents R4. More precisely spoken, Het preferably is a 5- or 6-membered heteroaromatic ring containing 1 heteroatom selected from N, O and S and optionally 1 or 2 further nitrogen atoms as ring members, where the heteroaromatic ring may carry 1 , 2, 3 or 4, preferably 1 or 2, substituents R4. Suitable 5- or 6-membered heteroaromatic radicals are listed above.
Among the above-listed heteroaromatic rings, preference is given to pyridylene, such as 2,3-pyridylene, 2,4-pyridylene, 2,5-pyridylene, 2,6-pyridylene, 3,4-pyridylene or 3,5- pyridylene, pyrimidylene, such as 2,4-pyrimidylene, 2,5-pyrimidylene, 4,5-pyrimidylene or 4,6-pyτimidylene, furylene, such as 2,3-furylene, 2,4-furylene, 2,5-furylene or 3,4- furylene, thienyl, such as 2,3-thienylene, 2,4-thienylene, 2,5-thienylene or 3,4- thienylene, pyrrolyl, such as 1 ,2-pyrrolylene, 1 ,3-pyrrolylene, 2,3-pyrrolylene, 2,4- pyrrolylene, 2,5-pyrrolylene or 3,4-pyrrolylene, pyrazolylene, such as 1 ,3-pyrazolylene, 1 ,4-pyrazolylene, 1 ,5-pyrazolylene, 3,4-pyrazolylene or 3,5-pyrazolylene, imida- zolylene, such as 1 ,2-imidazolylene, 1 ,4-imidazolylene, 1 ,5-imidazolylene, 2,4- imidazolylene, 2,5-imidazolylene, or 4,5-imidazolylene, oxazolylene, such as 2,4- oxazolylene or 2,5-oxazolylene, isoxazolyl, such as 3,4-isoxazolylene or 3,5- isoxazolylene, thiazolylene, such as 2,4-thiazolylene or 2,5-thiazolylene, isothia- zolylene, such as 3,4-isothiazolylene or 3,5-isothiazolylene, and triazolylene, such as 1 ,2,3-triazolylene, 1 ,2,4-triazolylene or 1 ,3,4-triazolylene. The given binding positions are to be understood as relative to the 1 -position of the ring heteroatom with the highest priority. For instance, in rings containg 1 ring heteroatom, the given binding position is relative to the 1 -position of the one ring heteroatom. In pyrazolylene, the given bind- ing position is relative to the 1- and 2-positions of the 2 nitrogen ring atoms, in imida- zolylene, it is relative to the 1- and 3-positions of the 2 nitrogen ring atoms, in oxazolylene, it is relative to the 1 -position of the oxygen ring atom and to the 3-position of the nitrogen ring atom, in isoxazolylene, it is relative to the 1 -position of the oxygen ring atom and to the 2-position of the nitrogen ring atom, in thiazolylene, it is relative to the 1 -position of the sulfur ring atom and to the 3-position of the nitrogen ring atom, in isothiazolylene, it is relative to the 1 -position of the sulfur ring atom and to the 2- position of the nitrogen ring atom, etc.
More preference is given to pyridylene, especially 2,5- or 3,6-pyridylene, thienylene, especially 2,4- or 2,5-thienylene, and thiazolylene, especially 2,4-thiazolylene or 2,5- thiazolylene. Even more preference is given to pyridylene, especially 2,5- or 3,6- pyridylene, and thienylene, especially 2,4- or 2,5-thienylene. Particular preference is given to pyridylene, especially to 2,5- or 3,6-pyridylene.
In case Het is a 6-membered heteroaromatic ring, this carries preferably 0, 1 , 2 or 3, more preferably 0, 1 or 2, substituents R4,where the two or more substituents R4 may be the same or different. In case Het is a 5-membered heteroaromatic ring, this carries preferably 0, 1 or 2 substituents R4, where two substituents R4 may be the same or different.
R4 may be C- or N-bound, but is preferably bound to a C-atom of Het.
R4 is preferably selected from halogen, OH, SH, NO2, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkoxy, and CrC4- haloalkoxy, more preferably from fluorine, chlorine, bromine, Ci-C4-alkyl, C1-C4- haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, even more preferably from fluorine, chlorine, bromine, CH3, CHF2, CF3, OCH3, OCHF2 and OCF3, particularly preferably from fluorine, chlorine, bromine, CH3, CF3, OCH3 and OCF3, and specifically from fluorine and chlorine.
Specifically, Het is selected from following formulae Het.1 to Het.16, where # is the attachment point to the quaternary carbon atom (which carries the ketale and the tria- zolylmethyl group) and * is the attachment point to the group Y:
Figure imgf000040_0001
Het.1 Het.2 Het.3 Het.4 Het.5
Figure imgf000040_0002
Het.6 Het.7 Het.8 I Het.9 Het.10
Figure imgf000040_0003
Het.11 Het.12 Het.13 Het.14 Het.15 Het.16
Among the above formulae, preference is given to radicals Het.1 to Het.10.
R8 in the groups -C(=O)R8 and -S(O)2R8 is preferably selected from Ci-C4-alkyl, C1-C2- haloalkyl, Ci-C4-alkoxy, Ci-C2-haloalkoxy, phenyl, phenoxy and NR13R14, more preferably from Ci-C4-alkyl, Ci-C2-haloalkyl, Ci-C4-alkoxy, Ci-C2-haloalkoxy and NR13R14 and even more preferably from Ci-C4-alkyl, Ci-C4-alkoxy and NR13R14. In the group -C(=O)R8, R8 is specifically Ci-C4-alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl, preferably methyl, or is Ci-C4-alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy or tert-butoxy, preferably methoxy, and is more specifically methyl, and in the group -S(O)2R8, R8 is specifically methyl. Preferably, R13 is hydrogen and R14 is selected from hydrogen, Ci-C4-alkyl and phenyl, preferably from hydrogen and Ci-C4-alkyl; or R13 and R14 are both Ci-C4-alkyl, preferably methyl or ethyl. M is preferably selected from an alkali metal cation, an earth alkaline metal cation equivalent, a cation equivalent of Cu, Zn, Fe or Ni or an ammonium cation of formula (NRaRbRcRd)+, wherein one of Ra, Rb, Rc and Rd is hydrogen and three of Ra, Rb, Rc and Rd, independently of each other, are selected from Ci-Cio-alkyl. More preferably, M is selected from Li+, Na+, K+, YiMg2+, a cation equivalent of Cu, Zn, Fe or Ni and an ammonium cation of formula (NRaRbRcRd)+, wherein one of Ra, Rb, Rc and Rd is hydrogen and three of Ra, Rb, Rc and Rd, independently of each other, are selected from C1-C10- alkyl. Even more preferably, M is selected from Na+, K+, /4Mg2+, /4Cu2+, /4Zn2+, /4Fe2+, /4Ni2+, triethylammonium and trimethylammonium.
In the group of formula III, the variables preferably have the same meanings as in the remainder of the molecule I. Thus, the remarks made above as to preferred meanings of the radicals apply to this moiety, too.
R1 is preferably selected from hydrogen, Ci-C4-alkyl, -C(=O)R8, -S(O)2R8, -CN, M and a group of the formula III, where R8 has one of the above general meanings or, in particular, one of the above preferred meanings and M has one of the above general meanings or, in particular, one of the above-given preferred meanings.
R1 is more preferably selected from hydrogen, Ci-C4-alkyl, C3-C4-alkylcarbonyl, Ci-C4- alkoxycarbonyl, -C(=O)N(H)Ci-C4-alkyl, -C(=O)N(Ci-C4-alkyl)2, Ci-C4-alkylsulfonyl, CN, M and a group of the formula III, where M has one of the above general meanings or, in particular, one of the above preferred meanings. In particular, R1 is selected from hydrogen, methyl, ethyl, propyl, isopropyl, methylcarbonyl, methoxycarbonyl,
-C(=O)N(CH3)2, CN, M and a group of the formula III, where M has one of the above general meanings or, in particular, one of the preferred meanings and is preferably an alkaline metal cation or /4 Cu2+. Specifically, R1 is hydrogen, methyl, methylcarbonyl, methoxycarbonyl, Na+ or a group of the formula III.
R1a is preferably selected from hydrogen, Ci-Cio-alkyl, Ci-C4-haloalkyl, phenyl, phenyl- Ci-C4-alkyl, -C(=O)R8 and -S(O)2R8, where R8 has one of the above given general or, in particular, one of the above-given preferred meanings. More preferably, R1a is selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, phenyl, benzyl, -C(=O)R8 and -S(O)2R8, where R8 has one of the above given general or, in particular, one of the above-given preferred meanings, and more preferably from hydrogen, Ci-C4-alkyl, Ci- C4-haloalkyl, -C(=O)R8 and -S(O)2R8, where R8 has one of the above given general or, in particular, one of the above-given preferred meanings. In particular, R1a is hydrogen, Ci-C4-alkyl, preferably methyl, or -C(=O)R8, more particularly hydrogen, Ci-C4-alkyl, preferably methyl, methylcarbonyl or methoxycarbonyl, even more particularly hydrogen or Ci-C4-alkyl, preferably methyl, and is specifically hydrogen.
Y is preferably O.
A is preferably a linear C2- or C3-alkyene bridge, where 1 or 2 hydrogen atoms of the alkylene bridge may be replaced by 1 or 2 substituents R5, where each R5 is independently selected from Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4- alkoxy and Ci-C4-haloalkoxy, and preferably from methyl, ethyl, methoxy, ethoxy and methoxymethoxy, or two substituents R5 bound on adjacent carbon atoms, together with the carbon atoms to which they are bound, form a cyclopentyl or cyclohexyl ring. More preferably, A is a linear C2- or C3-alkyene bridge, where 1 hydrogen atom of the alkylene bridge may be replaced by 1 substituent R5, where R5 is Ci-C4-alkyl. Even more preferably, A is a linear C2-alkyene bridge, where 1 hydrogen atom of the al- kylene bridge may be replaced by 1 substituent R5, where R5 is Ci-C4-alkyl and preferably methyl. Specifically, A is -CH(CHs)-CH2-.
If m is 1 , the oxygen atom is preferably bound via a double bond to the sulfur atom, the radical -S(O)m-R1 thus resulting in a group -S(=O)-R1. If m is 2, the two oxygen atoms are preferably both bound via a double bond to the sulfur atom, the radical -S(O)m-R1 thus resulting in a group -S(=O)2-R1. If m is 3, the radical -S(O)m-R1 is a group -S(=O)2- O-R1.
m is preferably 0 or 2 and more preferably 0.
In a particularly preferred embodiment, in compounds I, m is 0 and R1 is H (or, alternatively, in compounds II, R1a is H).
Particular compounds I/I I are the following:
Examples for preferred compounds I and Il are compounds of formulae 1.1 to 1.192 and 11.1 to 11.96, where the variables have one of the general or, in particular, one of the preferred meanings given above. Examples of preferred compounds are the individual compounds compiled in the tables 1 to 70992 below. Moreover, the meanings mentioned below for the individual variables in the tables are per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question.
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 imgf000053_0002
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000055_0002
Figure imgf000056_0001
Figure imgf000057_0001
R R R R
Figure imgf000057_0002
Figure imgf000058_0001
R R R R
Figure imgf000058_0002
R
Figure imgf000058_0003
Figure imgf000059_0001
R
Figure imgf000059_0002
R
Figure imgf000059_0003
R R
Figure imgf000059_0004
Figure imgf000060_0001
R " R " R " R'd
Figure imgf000060_0002
Table 1
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is H Table 2
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is methyl
Table 3 Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is ethyl
Table 4
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is propyl
Table 5
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is isopropyl
Table 6
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is n-butyl Table 7
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is sec-butyl
Table 8
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is isobutyl
Table 9
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is tert-butyl
Table 10
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is phenyl Table 11
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is benzyl
Table 12 Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is Li+
Table 13
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is Na+
Table 14
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is K+
Table 15
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is V2UQ2+ Table 16
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is 1/4Cu2+
Table 17 Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is 1/4Zn2+
Table 18 Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is Y2Fe2+
Table 19
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is 1/2Ni2+
Table 20
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is NH(CHs)3 +
Table 21
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is NH(C2Hs)3 + Table 22
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is NH(CH2CH2CH2)3 +
Table 23 Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is NH(CH(CH3)2)3 +
Table 24
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is NH(CH2CH2CH2CH2)3 +
Table 25
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is methylcarbonyl
Table 26
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is ethylcarbonyl Table 27
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is propylcarbonyl Table 28
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is isopropylcarbonyl
Table 29 Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is methoxycarbonyl
Table 30
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is ethoxycarbonyl
Table 31
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is propoxycarbonyl
Table 32
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is isopropoxycarbonyl Table 33
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is phenoxycarbonyl
Table 34 Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is methylaminocarbonyl
Table 35
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is ethylaminocarbonyl
Table 36 Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is propylaminocarbonyl
Table 37 Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is isopropylaminocarbonyl
Table 38
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is phenylaminocarbonyl
Table 39
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is methylsulfonyl
Table 40
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is ethylsulfonyl Table 41
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is propylsulfonyl
Table 42 Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is isopropylsulfonyl
Table 43
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is phenylsulfonyl
Table 44
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is methoxysulfonyl
Table 45
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is ethoxysulfonyl Table 46
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is propoxysulfonyl Table 47
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is isopropoxysulfonyl
Table 48 Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is phenoxysulfonyl
Table 49
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A above, Het is a radical of formula Het.1 and R1 is CN
Tables 50 to 98
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.2
Tables 99 to 147
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.3 Tables 148 to 196
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.4
Tables 197 to 245 Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.5
Tables 246 to 294
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.6
Tables 295 to 343 Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.7
Tables 344 to 392 Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.8
Tables 393 to 441
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.9
Tables 442 to 490
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.10
Tables 491 to 539
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.11 Tables 540 to 588
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.12
Tables 589 to 637 Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.13
Tables 638 to 686
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.14
Tables 687 to 735
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.15
Tables 736 to 784
Compounds of the formula 1.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1 is as defined in any of tables 1 to 49 and Het is a radical of formula Het.16 Tables 785 to 1568
Compounds of the formula 1.2 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of
R1 and Het is as defined in any of tables 1 to 784 Tables 1569 to 2352
Compounds of the formula 1.3 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of
R1 and Het is as defined in any of tables 1 to 784
Tables 2353 to 3136 Compounds of the formula 1.4 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of
R1 and Het is as defined in any of tables 1 to 784
Tables 3137 to 3920
Compounds of the formula 1.5 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of
R6 and Het is as defined in any of tables 1 to 784
Tables 3921 to 4704
Compounds of the formula 1.6 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 4705 to 5488
Compounds of the formula 1.7 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of
R1 and Het is as defined in any of tables 1 to 784 Tables 5489 to 6272
Compounds of the formula 1.8 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of
R1 and Het is as defined in any of tables 1 to 784
Tables 6273 to 7056 Compounds of the formula 1.9 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of
R1 and Het is as defined in any of tables 1 to 784
Tables 7057 to 7840
Compounds of the formula 1.10 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 7841 to 8624 Compounds of the formula 1.11 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 8625 to 9408 Compounds of the formula 1.12 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 9409 to 10192
Compounds of the formula 1.13 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 10193 to 10976
Compounds of the formula 1.14 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 10977 to 11760
Compounds of the formula 1.15 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784 Tables 11761 to 12544
Compounds of the formula 1.16 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 12545 to 13328 Compounds of the formula 1.17 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 13329 to 14112
Compounds of the formula 1.18 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 14113 to 14896
Compounds of the formula 1.19 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 14897 to 15680
Compounds of the formula 1.20 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784 Tables 15681 to 16464
Compounds of the formula 1.21 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784 Tables 16465 to 17248
Compounds of the formula 1.22 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 17249 to 18032 Compounds of the formula 1.23 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 18033 to 18816
Compounds of the formula 1.24 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 18817 to 19600
Compounds of the formula 1.25 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 19601 to 20384
Compounds of the formula 1.26 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784 Tables 20485 to 21 168
Compounds of the formula 1.27 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 21 169 to 21952 Compounds of the formula 1.28 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 21953 to 22736
Compounds of the formula 1.29 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 22737 to 23520 Compounds of the formula 1.30 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 23521 to 24304 Compounds of the formula 1.31 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 24305 to 25088
Compounds of the formula 1.32 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 25089 to 25872
Compounds of the formula 1.33 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 25873 to 26656
Compounds of the formula 1.34 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784 Tables 26657 to 27440
Compounds of the formula 1.35 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 27441 to 28224 Compounds of the formula 1.36 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 28225 to 29008
Compounds of the formula 1.37 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 29009 to 29792
Compounds of the formula 1.38 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 29793 to 30576
Compounds of the formula 1.39 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784 Tables 30577 to 31360
Compounds of the formula 1.40 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784 Tables 31361 to 32144
Compounds of the formula 1.41 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 32145 to 32928 Compounds of the formula 1.42 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 32929 to 33712
Compounds of the formula 1.43 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 33713 to 34496
Compounds of the formula 1.44 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 34497 to 35280
Compounds of the formula 1.45 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784 Tables 35281 to 36064
Compounds of the formula 1.46 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 36065 to 36848 Compounds of the formula 1.47 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Tables 36849 to 37632
Compounds of the formula 1.48 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1 and Het is as defined in any of tables 1 to 784
Table 37633 Compounds of the formula 1.49 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is a radical of formula Het.1
Table 37634 Compounds of the formula 1.49 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is a radical of formula Het.2
Table 37635
Compounds of the formula 1.49 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is a radical of formula Het.3
Table 37636
Compounds of the formula 1.49 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is a radical of formula Het.4
Table 37637
Compounds of the formula 1.49 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is a radical of formula Het.5 Table 37638
Compounds of the formula 1.49 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is a radical of formula Het.6
Table 37639 Compounds of the formula 1.49 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is a radical of formula Het.7
Table 37640
Compounds of the formula 1.49 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is a radical of formula Het.8
Table 37641
Compounds of the formula 1.49 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is a radical of formula Het.9
Table 37642
Compounds of the formula 1.49 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is a radical of formula Het.10 Table 37643
Compounds of the formula 1.49 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is a radical of formula Het.1 1 Table 37644
Compounds of the formula 1.49 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is a radical of formula Het.12
Table 37645 Compounds of the formula 1.49 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is a radical of formula Het.13
Table 37646
Compounds of the formula 1.49 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is a radical of formula Het.14
Table 37647
Compounds of the formula 1.49 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is a radical of formula Het.15
Table 37648
Compounds of the formula 1.49 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is a radical of formula Het.16 Tables 37649 to 37664
Compounds of the formula 1.50 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37665 to 37680 Compounds of the formula 1.51 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37681 to 37696
Compounds of the formula 1.52 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37697 to 37712 Compounds of the formula 1.53 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37713 to 37728 Compounds of the formula 1.54 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37729 to 37744
Compounds of the formula 1.55 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37745 to 37760
Compounds of the formula 1.56 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37761 to 37776
Compounds of the formula 1.57 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648 Tables 37777 to 37792
Compounds of the formula 1.58 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37793 to 37808 Compounds of the formula 1.59 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37809 to 37824
Compounds of the formula 1.60 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37825 to 37840
Compounds of the formula 1.61 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37841 to 37856
Compounds of the formula 1.62 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648 Tables 37857 to 378872
Compounds of the formula 1.63 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648 Tables 37873 to 378888
Compounds of the formula 1.64 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37889 to 37904 Compounds of the formula 1.65 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37905 to 37920
Compounds of the formula 1.66 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37921 to 37936
Compounds of the formula 1.67 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37937 to 37952
Compounds of the formula 1.68 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648 Tables 37953 to 37968
Compounds of the formula 1.69 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37969 to 37984 Compounds of the formula 1.70 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 37985 to 38000
Compounds of the formula 1.71 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38001 to 38016 Compounds of the formula 1.72 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38017 to 38032 Compounds of the formula 1.73 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38033 to 38048
Compounds of the formula 1.74 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38049 to 38064
Compounds of the formula 1.75 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38065 to 38080
Compounds of the formula 1.76 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648 Tables 38081 to 38096
Compounds of the formula 1.77 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38097 to 38112 Compounds of the formula 1.78 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38113 to 38128
Compounds of the formula 1.79 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38129 to 38144
Compounds of the formula 1.80 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38145 to 38160
Compounds of the formula 1.81 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648 Tables 38161 to 38176
Compounds of the formula 1.82 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648 Tables 38177 to 38192
Compounds of the formula 1.83 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38193 to 38208 Compounds of the formula 1.84 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38209 to 38224
Compounds of the formula 1.85 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38225 to 38240
Compounds of the formula 1.86 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38241 to 38256
Compounds of the formula 1.87 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648 Tables 38257 to 38272
Compounds of the formula 1.88 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38273 to 38288 Compounds of the formula 1.89 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38289 to 38304
Compounds of the formula 1.90 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38305 to 38320 Compounds of the formula 1.91 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38321 to 38336 Compounds of the formula 1.92 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38337 to 38352
Compounds of the formula 1.93 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38353 to 38368
Compounds of the formula 1.94 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38369 to 38384
Compounds of the formula 1.95 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648 Tables 38385 to 38400
Compounds of the formula 1.96 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and Het is as defined in any of tables 37633 to 37648
Tables 38401 to 38449 Compounds of the formula 1.97 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49
Tables 38450 to 38498
Compounds of the formula 1.98 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49
Tables 38499 to 38547
Compounds of the formula 1.99 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49
Tables 38548 to 38596
Compounds of the formula 1.100 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 38597 to 38645
Compounds of the formula 1.101 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 38646 to 38694
Compounds of the formula 1.102 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 38695 to 38743 Compounds of the formula 1.103 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 38744 to 38792 Compounds of the formula 1.104 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 38793 to 38841
Compounds of the formula 1.105 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49
Tables 38842 to 38890
Compounds of the formula 1.106 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 38891 to 38939
Compounds of the formula 1.107 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 38940 to 38988 Compounds of the formula 1.108 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 38989 to 39037 Compounds of the formula 1.109 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39038 to 39086 Compounds of the formula 1.110 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39087 to 39135 Compounds of the formula 1.11 1 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39136 to 39184 Compounds of the formula 1.112 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39185 to 39233
Compounds of the formula 1.113 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49
Tables 39234 to 39282
Compounds of the formula 1.114 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39283 to 39331
Compounds of the formula 1.115 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39332 to 39380 Compounds of the formula 1.116 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39381 to 39429 Compounds of the formula 1.117 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39430 to 39478
Compounds of the formula 1.118 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49
Tables 39479 to 39527
Compounds of the formula 1.119 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39528 to 39576
Compounds of the formula 1.120 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39577 to 39625
Compounds of the formula 1.121 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39626 to 39674 Compounds of the formula 1.122 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39675 to 39723 Compounds of the formula 1.123 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39724 to 39772
Compounds of the formula 1.124 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49
Tables 39773 to 39821
Compounds of the formula 1.125 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39822 to 39870
Compounds of the formula 1.126 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39871 to 39919 Compounds of the formula 1.127 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39920 to 39968 Compounds of the formula 1.128 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 39969 to 40017 Compounds of the formula 1.129 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 40018 to 40066 Compounds of the formula 1.130 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 40067 to 40115 Compounds of the formula 1.131 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 40116 to 40164
Compounds of the formula 1.132 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49
Tables 40165 to 40213
Compounds of the formula 1.133 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 40214 to 40262
Compounds of the formula 1.134 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 40263 to 4031 1 Compounds of the formula 1.135 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 40312 to 40360 Compounds of the formula 1.136 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 40361 to 40409
Compounds of the formula 1.137 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49
Tables 40410 to 40458
Compounds of the formula 1.138 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 40459 to 40507
Compounds of the formula 1.139 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 40508 to 40556
Compounds of the formula 1.140 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 40557 to 40605 Compounds of the formula 1.141 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 40606 to 40654 Compounds of the formula 1.142 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 40655 to 40703
Compounds of the formula 1.143 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49
Tables 40704 to 40752
Compounds of the formula 1.144 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 40753
Compounds of the formula 1.145 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40754 Compounds of the formula 1.146 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B Tables 40755
Compounds of the formula 1.147 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40756 Compounds of the formula 1.148 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40757
Compounds of the formula 1.149 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40758
Compounds of the formula 1.150 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40759 Compounds of the formula 1.151 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40760
Compounds of the formula 1.152 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40761
Compounds of the formula 1.153 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40762 Compounds of the formula 1.154 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B Tables 40763
Compounds of the formula 1.155 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40764 Compounds of the formula 1.156 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40765
Compounds of the formula 1.157 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40766
Compounds of the formula 1.158 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40767 Compounds of the formula 1.159 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B Tables 40768
Compounds of the formula 1.160 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40769 Compounds of the formula 1.161 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40770
Compounds of the formula 1.162 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40771 Compounds of the formula 1.163 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40772
Compounds of the formula 1.164 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B Tables 40773
Compounds of the formula 1.165 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40774 Compounds of the formula 1.166 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40775
Compounds of the formula 1.167 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 40776
Compounds of the formula 1.168 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40777 Compounds of the formula 1.169 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40778
Compounds of the formula 1.170 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40779
Compounds of the formula 1.171 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40780 Compounds of the formula 1.172 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B Tables 40781
Compounds of the formula 1.173 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40782 Compounds of the formula 1.174 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1 is as defined in any of tables 1 to 49 Tables 40783 Compounds of the formula 1.175 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40784
Compounds of the formula 1.176 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B Tables 40785
Compounds of the formula 1.177 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40786 Compounds of the formula 1.178 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40787
Compounds of the formula 1.179 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40788
Compounds of the formula 1.180 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40789 Compounds of the formula 1.181 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B Tables 40790
Compounds of the formula 1.182 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40791 Compounds of the formula 1.183 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40792
Compounds of the formula 1.184 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40793
Compounds of the formula 1.185 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40794 Compounds of the formula 1.186 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B Tables 40795
Compounds of the formula 1.187 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40796 Compounds of the formula 1.188 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40797
Compounds of the formula 1.189 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B Tables 40798
Compounds of the formula 1.190 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40799 Compounds of the formula 1.191 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Tables 40800
Compounds of the formula 1.192 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B Table 40801
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is H Table 40802 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is methyl Table 40803 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is ethyl Table 40804
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of for- mula Het.1 and R1a is n-propyl Table 40805
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is isopropyl Table 40806
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is n-butyl Table 40807 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is sec-butyl Table 40808 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is isobutyl Table 40809 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is tert-butyl Table 40810
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of for- mula Het.1 and R1a is phenyl Table 4081 1
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is benzyl Table 40812
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is methylcarbonyl Table 40813 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is ethylcarbonyl Table 40814 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is propylcarbonyl Table 40815
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of for- mula Het.1 and R1a is isopropylcarbonyl Table 40816
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is phenylcarbonyl Table 40817
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is methoxycarbonyl Table 40818
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is ethoxycarbonyl Table 40819 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is propoxycarbonyl Table 40820 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is isopropoxycarbonyl Table 40821
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of for- mula Het.1 and R1a is phenoxycarbonyl Table 40822
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is methylaminocarbonyl Table 40823
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is ethylaminocarbonyl Table 40824 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is propylaminocarbonyl Table 40825 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is isopropylaminocarbonyl Table 40826 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is phenylaminocarbonyl Table 40827 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is methylsulfonyl Table 40828 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is ethylsulfonyl Table 40829
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of for- mula Het.1 and R1a is propylsulfonyl Table 40830
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is isopropylsulfonyl Table 40831
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is phenylsulfonyl Table 40832 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is methoxysulfonyl Table 40833 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is ethoxysulfonyl Table 40834
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of for- mula Het.1 and R1a is propoxysulfonyl Table 40835
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is isopropoxysulfonyl Table 40836
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is phenoxysulfonyl Table 40837
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, Het is a radical of formula Het.1 and R1a is CN
Tables 40838 to 40874 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.2
Tables 40875 to 4091 1
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.3
Tables 40912 to 40948
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.4
Tables 40949 to 40985
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.5 Tables 40986 to 41022
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.6
Tables 41023 to 41059 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.7
Tables 41060 to 41096
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.8
Tables 41097 to 41 133 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.9
Tables 41 134 to 41 170 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.10
Tables 41 171 to 41207
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.11
Tables 41208 to 41244
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.12
Tables 41245 to 41281
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.13 Tables 41282 to 41318
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.14
Tables 41319 to 41355 Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.15
Tables 41356 to 41392
Compounds of the formula 11.1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A, R1a is as defined in any of tables 40800 to 40837 and Het is a radical of formula Het.16
Tables 41393 to 41984
Compounds of the formula 11.2 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 41985 to 42576
Compounds of the formula 11.3 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of
R1a and Het is as defined in any of tables 40800 to 41392 Tables 42577 to 43168
Compounds of the formula 11.4 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of
R1a and Het is as defined in any of tables 40800 to 41392 Tables 43169 to 43760
Compounds of the formula 11.5 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of
R1a and Het is as defined in any of tables 40800 to 41392
Tables 43761 to 44352 Compounds of the formula 11.6 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of
R1a and Het is as defined in any of tables 40800 to 41392
Tables 44353 to 44944
Compounds of the formula 11.7 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of
R1a and Het is as defined in any of tables 40800 to 41392
Tables 44945 to 45536
Compounds of the formula 11.8 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 45537to 46128
Compounds of the formula 11.9 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of
R1a and Het is as defined in any of tables 40800 to 41392 Tables 46129 to 46720
Compounds of the formula 11.10 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 46721 to 47312 Compounds of the formula 11.1 1 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 47313 to 47904
Compounds of the formula 11.12 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 47905 to 48496 Compounds of the formula 11.13 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 48497 to 49088 Compounds of the formula 11.14 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 49089 to 49680
Compounds of the formula 11.15 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 49681 to 50272
Compounds of the formula 11.16 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 50273 to 50864
Compounds of the formula 11.17 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392 Tables 50865 to 51456
Compounds of the formula 11.18 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 51457 to 52048 Compounds of the formula 11.19 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 52049 to 52640
Compounds of the formula 11.20 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 52641 to 53232
Compounds of the formula 11.21 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 53233 to 53824
Compounds of the formula 11.22 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392 Tables 53825 to 54416
Compounds of the formula 11.23 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392 Tables 54417 to 55008
Compounds of the formula 11.24 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 55009 to 55600 Compounds of the formula 11.25 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 55601 to 56192
Compounds of the formula 11.26 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 56193 to 56784
Compounds of the formula 11.27 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 56785 to 57376
Compounds of the formula 11.28 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392 Tables 57377 to 57968
Compounds of the formula 11.29 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 57969 to 58560 Compounds of the formula 11.30 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 58561 to 59152
Compounds of the formula 11.31 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 59153 to 59744 Compounds of the formula 11.32 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 59745 to 60336 Compounds of the formula 11.33 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 60337 to 60982
Compounds of the formula 11.34 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 60983 to 61520
Compounds of the formula 11.35 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 61521 to 62112
Compounds of the formula 11.36 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392 Tables 62113 to 62704
Compounds of the formula 11.37 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 62705 to 63296 Compounds of the formula 11.38 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 63297 to 63888
Compounds of the formula 11.39 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 63889 to 64480
Compounds of the formula 11.40 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 4481 to 65072
Compounds of the formula 11.41 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392 Tables 65073 to 65664
Compounds of the formula 11.42 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392 Tables 65665 to 66256
Compounds of the formula 11.43 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 66257 to 66848 Compounds of the formula 11.44 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 66849 to 67440
Compounds of the formula 11.45 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 67441 to 68032
Compounds of the formula 11.46 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 68033 to 68624
Compounds of the formula 11.47 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392 Tables 68625 to 69216
Compounds of the formula 11.48 in which the combination of R21, R22, R23, R24 and R25 for a compound corresponds in each case to one row of Table A and the combination of R1a and Het is as defined in any of tables 40800 to 41392
Tables 69217 to 69253 Compounds of the formula 11.49 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837
Tables 69254 to 69290
Compounds of the formula 11.50 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837
Tables 69291 to 69327 Compounds of the formula 11.51 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69328 to 69364 Compounds of the formula 11.52 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69365 to 69401 Compounds of the formula 11.53 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69402 to 69438
Compounds of the formula 11.54 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69439 to 69475
Compounds of the formula 11.55 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69476 to 69512
Compounds of the formula 11.56 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69513 to 69549 Compounds of the formula 11.57 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69550 to 69586 Compounds of the formula 11.58 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69587 to 69623
Compounds of the formula 11.59 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69624 to 69660
Compounds of the formula 11.60 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69661 to 69697
Compounds of the formula 11.61 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69698 to 69734
Compounds of the formula 11.62 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69735 to 69771 Compounds of the formula 11.63 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69772 to 69808 Compounds of the formula 11.64 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69809 to 69845
Compounds of the formula 11.65 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69846 to 69882
Compounds of the formula 11.66 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69883 to 69919
Compounds of the formula 11.67 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69920 to 69956 Compounds of the formula 11.68 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69957 to 69993 Compounds of the formula 11.69 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 69994 to 70030 Compounds of the formula 11.70 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70031 to 70067 Compounds of the formula 11.71 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70068 to 70104 Compounds of the formula 11.72 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70105 to 70141
Compounds of the formula 11.73 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70142 to 70178
Compounds of the formula 11.74 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70179 to 70215
Compounds of the formula 11.75 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70216 to 70252 Compounds of the formula 11.76 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70253 to 70289 Compounds of the formula 11.77 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70290 to 70326
Compounds of the formula 11.78 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70327 to 70363
Compounds of the formula 11.79 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70364 to 70400
Compounds of the formula II.80 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70401 to 70437
Compounds of the formula 11.81 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70438 to 70474 Compounds of the formula 11.82 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70475 to 7051 1 Compounds of the formula 11.83 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70512 to 70548
Compounds of the formula 11.84 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70549 to 70585
Compounds of the formula 11.85 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70586 to 70622
Compounds of the formula 11.86 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70623 to 70659 Compounds of the formula 11.87 in which the combination of Het and Ar' for a compound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70660 to 70696 Compounds of the formula 11.88 in which the combination of Het and Ar' for a com- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70697 to 70733 Compounds of the formula I 1.89 in which the combination of Het and Ar' for a corn- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70734 to 70770 Compounds of the formula I 1.90 in which the combination of Het and Ar' for a corn- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70771 to 70807 Compounds of the formula I 1.91 in which the combination of Het and Ar' for a corn- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70808 to 70844 Compounds of the formula I 1.92 in which the combination of Het and Ar' for a corn- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70845 to 70881 Compounds of the formula I 1.93 in which the combination of Het and Ar' for a corn- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70882 to 70918
Compounds of the formula I 1.94 in which the combination of Het and Ar' for a corn- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70919 to 70955 Compounds of the formula I 1.95 in which the combination of Het and Ar' for a corn- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837 Tables 70956 to 70992 Compounds of the formula I 1.96 in which the combination of Het and Ar' for a corn- pound corresponds in each case to one row of Table B and R1a is as defined in any of tables 40800 to 40837
Table B
Figure imgf000102_0001
Figure imgf000102_0002
No. Ar' Het
B-44 Ar. 45 Het. 1
B-45 Ar. 46 Het. 1
B-46 Ar. 47 Het. 1
B-47 Ar. 48 Het. 1
B-48 Ar. 49 Het. 1
B-49 Ar. 50 Het. 1
B-50 Ar. 2 Het. 2
B-51 Ar. 3 Het. 2
B-52 Ar. 4 Het. 2
B-53 Ar. 5 Het. 2
B-54 Ar. 6 Het. 2
B-55 Ar. 7 Het. 2
B-56 Ar. 8 Het. 2
B-57 Ar. 9 Het. 2
B-58 Ar. 10 Het. 2
B-59 Ar. 1 1 Het. 2
B-60 Ar. 12 Het. 2
B-61 Ar. 13 Het. 2
B-62 Ar. 14 Het. 2
B-63 Ar. 15 Het. 2
B-64 Ar. 16 Het. 2
B-65 Ar. 17 Het. 2
B-66 Ar. 18 Het. 2
B-67 Ar. 19 Het. 2
B-68 Ar. 20 Het. 2
B-69 Ar. 21 Het. 2
B-70 Ar. 22 Het. 2
B-71 Ar. 23 Het. 2
B-72 Ar. 24 Het. 2
B-73 Ar. 25 Het. 2
B-74 Ar. 26 Het. 2
B-75 Ar. 27 Het. 2
B-76 Ar. 28 Het. 2
B-77 Ar. 29 Het. 2
B-78 Ar. 30 Het. 2
B-79 Ar. 31 Het. 2
B-80 Ar. 32 Het. 2
Figure imgf000103_0001
No. Ar' Het
B-118 Ar. 21 Het .3
B-119 Ar. 22 Het .3
B-120 Ar. 23 Het .3
B-121 Ar. 24 Het .3
B-122 Ar. 25 Het .3
B-123 Ar. 26 Het .3
B-124 Ar. 27 Het .3
B-125 Ar. 28 Het .3
B-126 Ar. 29 Het .3
B-127 Ar. 30 Het .3
B-128 Ar. 31 Het .3
B-129 Ar. 32 Het .3
B-130 Ar. 33 Het .3
B-131 Ar. 34 Het .3
B-132 Ar. 35 Het .3
B-133 Ar. 36 Het .3
B-134 Ar. 37 Het .3
B-135 Ar. 38 Het .3
B-136 Ar. 39 Het .3
B-137 Ar. 40 Het .3
B-138 Ar. 41 Het .3
B-139 Ar. 42 Het .3
B-140 Ar. 43 Het .3
B-141 Ar. 44 Het .3
B-142 Ar. 45 Het .3
B-143 Ar. 46 Het .3
B-144 Ar. 47 Het .3
B-145 Ar. 48 Het .3
B-146 Ar. 49 Het .3
B-147 Ar. 50 Het .3
B-148 Ar. 2 Het .4
B-149 Ar. 3 Het .4
B-150 Ar. 4 Het .4
B-151 Ar. 5 Het .4
B-152 Ar. 6 Het .4
B-153 Ar. 7 Het .4
B-154 Ar. 8 Het .4
Figure imgf000104_0001
No. Ar' Het
B-192 Ar. 46 Het .4
B-193 Ar. 47 Het .4
B-194 Ar. 48 Het .4
B-195 Ar. 49 Het .4
B-196 Ar. 50 Het .4
B-197 Ar. 2 Het .5
B-198 Ar. 3 Het .5
B-199 Ar. 4 Het .5
B-200 Ar. 5 Het .5
B-201 Ar. 6 Het .5
B-202 Ar. 7 Het .5
B-203 Ar. 8 Het .5
B-204 Ar. 9 Het .5
B-205 Ar. 10 Het .5
B-206 Ar. 1 1 Het .5
B-207 Ar. 12 Het .5
B-208 Ar. 13 Het .5
B-209 Ar. 14 Het .5
B-210 Ar. 15 Het .5
B-21 1 Ar. 16 Het .5
B-212 Ar. 17 Het .5
B-213 Ar. 18 Het .5
B-214 Ar. 19 Het .5
B-215 Ar. 20 Het .5
B-216 Ar. 21 Het .5
B-217 Ar. 22 Het .5
B-218 Ar. 23 Het .5
B-219 Ar. 24 Het .5
B-220 Ar. 25 Het .5
B-221 Ar. 26 Het .5
B-222 Ar. 27 Het .5
B-223 Ar. 28 Het .5
B-224 Ar. 29 Het .5
B-225 Ar. 30 Het .5
B-226 Ar. 31 Het .5
B-227 Ar. 32 Het .5
B-228 Ar. 33 Het .5
Figure imgf000105_0001
No. Ar' Het
B-266 Ar. 22 Het. 6
B-267 Ar. 23 Het. 6
B-268 Ar. 24 Het. 6
B-269 Ar. 25 Het. 6
B-270 Ar. 26 Het. 6
B-271 Ar. 27 Het. 6
B-272 Ar. 28 Het. 6
B-273 Ar. 29 Het. 6
B-274 Ar. 30 Het. 6
B-275 Ar. 31 Het. 6
B-276 Ar. 32 Het. 6
B-277 Ar. 33 Het. 6
B-278 Ar. 34 Het. 6
B-279 Ar. 35 Het. 6
B-280 Ar. 36 Het. 6
B-281 Ar. 37 Het. 6
B-282 Ar. 38 Het. 6
B-283 Ar. 39 Het. 6
B-284 Ar. 40 Het. 6
B-285 Ar. 41 Het. 6
B-286 Ar. 42 Het. 6
B-287 Ar. 43 Het. 6
B-288 Ar. 44 Het. 6
B-289 Ar. 45 Het. 6
B-290 Ar. 46 Het. 6
B-291 Ar. 47 Het. 6
B-292 Ar. 48 Het. 6
B-293 Ar. 49 Het. 6
B-294 Ar. 50 Het. 6
B-295 Ar. 2 Het. 7
B-296 Ar. 3 Het. 7
B-297 Ar. 4 Het. 7
B-298 Ar. 5 Het. 7
B-299 Ar. 6 Het. 7
B-300 Ar. 7 Het. 7
B-301 Ar. 8 Het. 7
B-302 Ar. 9 Het. 7
Figure imgf000106_0001
No. Ar' Het
B-340 Ar. 47 Het. 7
B-341 Ar. 48 Het. 7
B-342 Ar. 49 Het. 7
B-343 Ar. 50 Het. 7
B-344 Ar. 2 Het. 8
B-345 Ar. 3 Het. 8
B-346 Ar. 4 Het. 8
B-347 Ar. 5 Het. 8
B-348 Ar. 6 Het. 8
B-349 Ar. 7 Het. 8
B-350 Ar. 8 Het. 8
B-351 Ar. 9 Het. 8
B-352 Ar. 10 Het. 8
B-353 Ar. 1 1 Het. 8
B-354 Ar. 12 Het. 8
B-355 Ar. 13 Het. 8
B-356 Ar. 14 Het. 8
B-357 Ar. 15 Het. 8
B-358 Ar. 16 Het. 8
B-359 Ar. 17 Het. 8
B-360 Ar. 18 Het. 8
B-361 Ar. 19 Het. 8
B-362 Ar. 20 Het. 8
B-363 Ar. 21 Het. 8
B-364 Ar. 22 Het. 8
B-365 Ar. 23 Het. 8
B-366 Ar. 24 Het. 8
B-367 Ar. 25 Het. 8
B-368 Ar. 26 Het. 8
B-369 Ar. 27 Het. 8
B-370 Ar. 28 Het. 8
B-371 Ar. 29 Het. 8
B-372 Ar. 30 Het. 8
B-373 Ar. 31 Het. 8
B-374 Ar. 32 Het. 8
B-375 Ar. 33 Het. 8
B-376 Ar. 34 Het. 8
Figure imgf000107_0001
No. Ar' Het
B-414 Ar. 23 Het. 9
B-415 Ar. 24 Het. 9
B-416 Ar. 25 Het. 9
B-417 Ar. 26 Het. 9
B-418 Ar. 27 Het. 9
B-419 Ar. 28 Het. 9
B-420 Ar. 29 Het. 9
B-421 Ar. 30 Het. 9
B-422 Ar. 31 Het. 9
B-423 Ar. 32 Het. 9
B-424 Ar. 33 Het. 9
B-425 Ar. 34 Het. 9
B-426 Ar. 35 Het. 9
B-427 Ar. 36 Het. 9
B-428 Ar. 37 Het. 9
B-429 Ar. 38 Het. 9
B-430 Ar. 39 Het. 9
B-431 Ar. 40 Het. 9
B-432 Ar. 41 Het. 9
B-433 Ar. 42 Het. 9
B-434 Ar. 43 Het. 9
B-435 Ar. 44 Het. 9
B-436 Ar. 45 Het. 9
B-437 Ar. 46 Het. 9
B-438 Ar. 47 Het. 9
B-439 Ar. 48 Het. 9
B-440 Ar. 49 Het. 9
B-441 Ar. 50 Het. 9
B-442 Ar. 2 Het. 10
B-443 Ar. 3 Het. 10
B-444 Ar. 4 Het. 10
B-445 Ar. 5 Het. 10
B-446 Ar. 6 Het. 10
B-447 Ar. 7 Het. 10
B-448 Ar. 8 Het. 10
B-449 Ar. 9 Het. 10
B-450 Ar. 10 Het. 10
Figure imgf000108_0001
Figure imgf000109_0001
Figure imgf000109_0002
Figure imgf000110_0001
Figure imgf000110_0002
Figure imgf000111_0001
Figure imgf000111_0002
Figure imgf000112_0001
Figure imgf000112_0002
No. Ar' Het
B-766 Ar. 32 Het. 16
B-767 Ar. 33 Het. 16
B-768 Ar. 34 Het. 16
B-769 Ar. 35 Het. 16
B-770 Ar. 36 Het. 16
B-771 Ar. 37 Het. 16
B-772 Ar. 38 Het. 16
B-773 Ar. 39 Het. 16
B-774 Ar. 40 Het. 16
B-775 Ar. 41 Het. 16
B-776 Ar. 42 Het. 16
B-777 Ar. 43 Het. 16
B-778 Ar. 44 Het. 16
B-779 Ar. 45 Het. 16
B-780 Ar. 46 Het. 16
B-781 Ar. 47 Het. 16
B-782 Ar. 48 Het. 16
B-783 Ar. 49 Het. 16
B-784 Ar. 50 Het. 16
Figure imgf000113_0001
The radicals Ar.2 to Ar.50 correspond to the radicals listed above as specific embodiments of Ar as groups of formulae Ar.2 to Ar.50, and the radicals Het.1 to Het.16 correspond to the radicals listed above as specific embodiments of Het as groups of formulae Het.1 to Het.16.
The radicals Ar.2 to Ar.50 correspond to the radicals listed above as specific embodiments of Ar as groups of formulae Ar.2 to Ar.50. The radicals Het.1 to Het.16 correspond to the radicals listed above as specific embodiments of Het as groups of formulae Het.1 to Het.16.
Among the above compounds, preference is given to compounds of formulae 1.1 to I.24, I.49 to I.72, I.97 to 1.120, 1.145 to 1.168; 11.1 to 11.24 and II.49 to II.72. Among these, preference is given to compounds 1.1 to 1.12, 1.49 to 1.60, 1.97 to 1.108, 1.145 to 1.156; 11.1 to 11.12 and II.49 to II.60. Particular preference is given to compounds I.2, I.50, I.98, 1.146, II.2 and II.50. Compounds of formulae I and Il can be prepared by one or more of the following methods and variations as described in schemes 1 to 9 and in the syntheses descriptions below. The variables are as defined above for formulae I and II.
Compounds of formula I, wherein R1 is H and m is 0 (or compounds II, wherein R1a is H), can be prepared by sulfurizing the corresponding triazole derivative IV as outlined in scheme 1. Sulfurization can be carried out in analogy to known processes, for example as described in WO 96/41804. For instance, the triazolyl ring can be first depro- tonated with a strong base, e.g. an organolithium base, such as n-butyllithium, tert- butyllithium or sec-butyllithium, lithium diisopropyl amide, sodium hydride, sodium amide or potassium tert-butylate mixed with tetramethylethylene diamine (TMEDA), and then the resulting anion is reacted with elemental sulfur. Sulfur is generally used in powdered form. The reaction is generally carried out in an inert solvent, such as ethers, e.g. diethylether, methyl-tert-butylether, tetrahydrofuran or dioxane, dimethoxyethane, liquid ammonia, dimethylsulfoxide or dimethylformamide. The reaction temperature is not very critical and can range, for example, from -70 to +50 0C, preferably from -70 to 00C. Alternatively, sulfurization can be carried out in the absence of a base by reacting 7 with elemental sulfur in a high-boiling solvent, such as N-methylpyrrolidinone, diox- ane or N,N-dimethylformamide, while heating, e.g. to 160 to 250 0C. After completion of the reaction, the resulting mixture is hydrolyzed, e.g. by the addition of water or an aqueous acid, such as a mineral acid (e.g. dilute sulfuric acid or hydrochloric acid), acetic acid or ammoniumchloride, to give compound I.
Scheme 1
Figure imgf000114_0001
(RVR1a = H; m = 0)
The triazole compound IV can be prepared in analogy to known methods, such as described, for example, in EP-A-0065485, as outlined in scheme 2. For instance, the compound 1 , wherein X is a good leaving group, such as a halogen atom, in particular Cl, Br or I, phenylsulfonyloxy, p-tosyloxy, trifluoroacetyloxy or alkylsulfonyloxy, such as mesyloxy, can be reacted with the [1 ,2,4]-1 H-triazole compound 2, wherein M is a hydrogen atom or a metal atom, in particular an alkali metal atom, such as Li, Na or K. In case M is H, the reaction is suitably carried out in the presence of a base, such as an alkali metal hydride (e.g. sodium hydride, potassium hydride), an alkali metal hydroxide (e.g. sodium hydroxide, potassium hydroxide), an alkali metal carbonate (e.g. sodium carbonate, potassium carbonate, caesium carbonate) or a suitable amine (e.g. triethyl- amine, triethylenediamine, piperidine, pyridine, 4-dimethylaminopyridine, 4- pyrrolidylpyridine). If X is Cl or Br, the reaction can be accelerated by the addition of an alkali metal iodide, such as NaI or Kl. The reaction is suitably carried out in a solvent. Suitable solvents are inert versus the reacants and products and are rather polar, for example, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, acetoni- trile, benzonitrile, ethers, such as diethyl ether, dipropyl ether, methyl-tert-butyl ether, tetrahydrofuran or dioxane, and the like, and can be used in combination with other inert, less polar solvents, such as benzene, toluene, the xylenes, chlorobenzene, nitrobenzene, hexane, heptane, petrolether and the like. The reaction temperature is not very critical and can range, for example from 0 to 2200C and preferably from 80 to 1700C. Suitably, the reaction is carried out at reflux temperature of the reaction mixture.
Scheme 2
Figure imgf000115_0001
Compound 1 in turn can be prepared in analogy to known methods, such as described, for example, in EP-A-0065485 or in Synthesis, 1974, I, 23, as outlined in scheme 3 below. For instance, the ketone 3 may be reacted with a diol HO-A-OH for several hours preferably in the presence of an azeotrope-forming compound, such as benzene, toluene, xylene, chloroform or tetrachloromethane, which can also serve as reaction solvents. The ketalization reaction is accelerated by the presence of a strong acid, such p-toluoenesulfonic acid. Subsequent halogenation of the resulting ketale 4 yields ketale 1 , wherein X is a halogen atom, which, if desired, can be converted into a compound 1 , wherein X is a leaving group X other than halogen.
Scheme 3
Figure imgf000115_0002
The ketone 3 can be obtained in analogy to known methods, such as described, for example, in EP-A-0065485, from the condensation of compounds 5 and 6, wherein X1 is a group Y-H or Y-M, wherein M is a metal atom, in particular an alkali metal atom, such as Li, Na or K, and X2 is a good leaving group, such as a halogen atom, such as F, Cl, Br or I, phenylsulfonyloxy, p-tosyloxy, trifluoroacetyloxy or alkylsulfonyloxy, such as mesyloxy, or, vice versa, wherein X1 is a good leaving group and X2 is a group Y-H or Y-M, as outlined in scheme 4 below. In case X1 or X2 is Y-H, the reaction is suitably carried out in the presence of a base, such as an alkali metal hydride (e.g. sodium hydride, potassium hydride), an alkali metal hydroxide (e.g. sodium hydroxide, potassium hydroxide), an alkali metal carbonate (e.g. sodium carbonate, potassium carbonate, caesium carbonate) or a suitable amine (e.g. triethylamine, triethylenediamine, piperidine, pyridine, 4-dimethylaminopyridine, 4-pyrrolidylpyridine). If the leaving group X1 or X2 is Cl or Br, the reaction can be accelerated by the addition of an alkali metal iodide, such as NaI or Kl. The reaction is suitably carried out in a solvent. Suitable sol- vents are inert versus the reacants and products and are rather polar, for example, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, acetonitrile, ben- zonitrile, ethers, such as diethyl ether, dipropyl ether, methyl-tert-butyl ether, tetrahy- drofuran or dioxane, and the like, and can be used in combination with other inert, less polar solvents, such as benzene, toluene, the xylenes, chlorobenzene, nitrobenzene, hexane, heptane, petrolether and the like. The reaction temperature is not very critical and can range, for example from 0 to 2200C and preferably from 80 to 1700C. Suitably, the reaction is carried out at reflux temperature of the reaction mixture.
Figure imgf000116_0001
As an alternative to the process described in scheme 4, the ketone 3, wherein Y is O (= 31), can be prepared in analogy to the method described in EP-A-0065485 as outlined in scheme 5 below by decarboxylation of the carbonic ester 7. This in turn can be prepared from the hydroxyl compound 8 which is reacted with a difunctional derivative 9 of carbonic acid, such as phosgene, a halogenoformic acid diester, a dialkylcarbonic diester or a diphenylcarbonic acid diester and further reaction with the hydroxyl compound 10. Decarboxylation is carried out by heating 7 in substance or in a high-boiling inert solvent, such as diphenylether or ethyleneglycoldimethylether, to a temperature in the range of from 120 to 220°C.
Scheme 5
Figure imgf000117_0001
As an alternative to the process described in scheme 2, compound IV can be prepared in analogy to the method described in EP-A-0065485 as outlined in scheme 6 below by a ketalization reaction of the ketone 11 with a diol HO-A-OH. The ketalization reaction can be carried out under reaction conditions described for scheme 3.
Scheme 6
Figure imgf000117_0002
The ketone 11 in turn can be prepared in analogy to the method described in EP-A- 0065485 as outlined in scheme 7 below by reacting the compound 12, wherein X is a good leaving group, such as a halogen atom, in particular Cl, Br or I, phenylsulfonyloxy, p-tosyloxy, trifluoroacetyloxy or alkylsulfonyloxy, such as mesyloxy, with the triazole compound 2 under reaction conditions described for the reaction in scheme 2. Compound 12, in turn, can be obtained from the halogenation of the ketone 3.
Scheme 7
Figure imgf000117_0003
As an alternative to the process described in scheme 2, compound IV can be prepared in analogy to the method described in EP-A-0065485 as outlined in scheme 8 below by condensation of compounds 13 and 14, wherein X1 is a group Y-H or Y-M, wherein M is a metal atom, in particular an alkali metal atom, such as Li, Na or K, and X2 is a good leaving group, such as a halogen atom, in particular Cl, Br or I, phenylsulfonyloxy, p- tosyloxy, trifluoroacetyloxy or alkylsulfonyloxy, such as mesyloxy, or, vice versa, wherein X1 is a good leaving group and X2 is a group Y-H or Y-M, under reaction conditions as described for scheme 4.
Scheme 8
Figure imgf000118_0001
As an alternative to the process described in scheme 2, compounds IV, wherein Y is O ( = IV), can be prepared in analogy to the method described in EP-A-0065485 as outlined in scheme 9 below by decarboxylation of the carbonic ester 15 under reaction conditions as described for scheme 5. The carbonic ester 15, in turn, can be prepared under reaction conditions described for the condensation reaction in scheme 5.
Figure imgf000118_0002
Compounds 5, 6, 8, 9 and 10 used in the above reactions are either commercially available or can be produced by standard methods known to the skilled person.
The radicals in the above reactants, if inert towards the respective reaction, can be present in the above reaction steps or can be introduced at a later stage, e.g. into compound IV.
Compounds of formula I, wherein R1 is different from hydrogen and m is 0, can be prepared from compounds I, wherein R1 = H and m = 0.
Compounds of formula I, wherein m is 0 and R1 is Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2- Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C2-Cio-haloalkynyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, phenyl, phenyl-Ci-C4-alkyl, where the phenyl moiety in the 2 last- mentioned radicals may be substituted as described above, and a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 het- eroatoms selected from N, O and S as ring members, where the heterocyclic ring may be substituted as described above, may be prepared in analogy to the method described in DE-A-19520098 or WO, 96/41804 by reacting a compound I, wherein m is 0 and R1 is H, with a compound R1-LG, where R1 has one of the above meanings and LG is a leaving group, such as a halide (e.g. Cl, Br, I), a tosylate or a mesylate, in the presence of a base. Suitable bases are, for example, alkali metal hydrides (e.g. sodium hydride, potassium hydride), alkali metal hydroxides (e.g. sodium hydroxide, potassium hydroxide), alkali metal carbonates (e.g. sodium carbonate, potassium carbonate, caesium carbonate), alkali metal alkoxides (e.g. sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide) or organolithium bases (e.g. n-butyl lithium, sec-butyl lithium, tert-butyl lithium and lithium diisopropylamine.). The reaction is generally carried out in a suitable solvent. Suitable solvents are, for example, toluene, N-methylpyrrolidinone, ethers (e.g. diethyl ether, tetrahydrofuran, dioxane, 1 ,2-dimethoxyethane), acetonitrile, N,N-dimethylformamide or dimethylsulfox- ide.
Alternatively, compounds of formula I, wherein m is 0 and R1 is Ci-Cio-alkyl, C1-C10- haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C2-Cio-haloalkynyl, C3-C10- cycloalkyl, C3-Cio-halocycloalkyl, phenyl, phenyl-Ci-C4-alkyl, where the phenyl moiety in the 2 last-mentioned radicals may be substituted as described above, and a 5- or 6- membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may be substituted as described above, may be prepared in analogy to the method described in Heterocycles, 23(7), 1645-1649, 1985 by reacting compound IV with a disulfide R1-S-S-R1 in the presence of a strong base under conditions similar to those described for scheme 1.
Compounds of formulae I, wherein m is 0 and R1 is -C(=O)R8 or -C(=S)R8, may be prepared in analogy to the method described in DE-A-19617461 by reacting a compound I, wherein m is 0 and R1 is H, with a compound R8-C(=O)-W, R8-C(=S)-W, R8'-N=C=O or R8'-N=C=S, wherein R8 has one of the above meanings, R8' is Ci-Cio-alkyl or C1-C10- haloalkyl and W is a good leaving group, such as a halide (e.g. Cl, Br, I), an alkoxide (e.g. methoxide, ethoxide) or pentafluorophenoxide, in the presence of a base. Suitable bases are, for example, alkali metal hydrides (e.g. sodium hydride, potassium hydride), alkali metal hydroxides (e.g. sodium hydroxide, potassium hydroxide), alkali metal carbonates (e.g. sodium carbonate, potassium carbonate, caesium carbonate), alkali metal alkoxides (e.g. sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide) or organolithium bases (e.g. n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium diisopropylamine). The reaction is generally carried out in a suitable solvent. Suitable solvents are, for example, toluene, N- methylpyrrolidinone, ethers (e.g. diethyl ether, tetrahydrofuran, dioxane, 1 ,2- dimethoxyethane), acetonitrile, N,N-dimethylformamide or dimethylsulfoxide.
Compounds of formula I, wherein m is 0 and R1 is -SO2R8, may be prepared in analogy to the method described in DE-A-19620590 by reacting a compound I, wherein m is 0 and R1 is H, with a compound R8-SC"2-W, wherein R8 has one of the above meanings and W is a good leaving group, such as a halide (e.g. Cl, Br, I), an alkoxide (e.g. methoxide, ethoxide) or pentafluorophenoxide, in the presence of a base. Suitable bases are, for example, alkali metal hydrides (e.g. sodium hydride, potassium hydride), alkali metal hydroxides (e.g. sodium hydroxide, potassium hydroxide), alkali metal carbon- ates (e.g. sodium carbonate, potassium carbonate, caesium carbonate), alkali metal alkoxides (e.g. sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide) or organolithium bases (e.g. n-butyl lithium, sec- butyl lithium, tert-butyl lithium, lithium diisopropylamine). The reaction is generally carried out in a suitable solvent. Suitable solvents are, for example, toluene, N- methylpyrrolidinone, ethers (e.g. diethyl ether, tetrahydrofuran, dioxane, 1 ,2- dimethoxyethane), acetonitrile, N,N-dimethylformamide or dimethylsulfoxide.
Compounds of formula I, wherein m is 0 and R1 is -CN, may be prepared in analogy to the method described in DE-A-19620407 by reacting a compound I, wherein m is 0 and R1 is H, with a compound CN-W, wherein W is a good leaving group, such as a halide (e.g. Cl, Br, I), in the presence of a base. Suitable bases are, for example, alkali metal hydrides (e.g. sodium hydride, potassium hydride), alkali metal hydroxides (e.g. sodium hydroxide, potassium hydroxide), alkali metal carbonates (e.g. sodium carbonate, potassium carbonate, caesium carbonate), alkali metal alkoxides (e.g. sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide) or organolithium bases (e.g. n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium diisopropylamine). The reaction is generally carried out in a suitable solvent. Suitable solvents are, for example, toluene, N-methylpyrrolidinone, ethers (e.g. diethyl ether, tetrahydrofuran, dioxane, 1 ,2-dimethoxyethane), acetonitrile, N,N-dimethylformamide or dimethylsulfoxide.
Compounds of formula I, wherein m is 0 and R1 is M, may be prepared in analogy to the method described in DE-A-19617282 by reacting a compound I, wherein m is 0 and R1 is H, with an amine NRaRbRc, wherein Ra, Rb and Rc are as defined above, or with a metal salt, such as sodium hydroxide, potassium hydroxide or copper acetate.
Compounds of formula I, wherein m is 0 and R1 is a group of formula III, may be pre- pared in analogy to the method described in WO 97/43269 by reacting a compound I, wherein m is 0 and R1 is H, with a halogen, especially iodine, in the presence of a base. Suitable bases are, for example, alkali metal hydrides (e.g. sodium hydride, potassium hydride), alkali metal hydroxides (e.g. sodium hydroxide, potassium hydroxide), alkali metal carbonates (e.g. sodium carbonate, potassium carbonate, caesium carbonate), alkali metal alkoxides (e.g. sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide) or organolithium bases (e.g. n-butyl lithium, sec-butyl lithium, tert-butyl lithium, lithium diisopropylamine). The reaction is generally carried out in a suitable solvent. Suitable solvents are, for example, toluene, N-methylpyrrolidinone, ethers (e.g. diethyl ether, tetrahydrofuran, dioxane, 1 ,2-dimethoxyethane), acetonitrile, N,N-dimethylformamide or dimethylsulfoxide.
Compounds of formula I, wherein m is 0 and R1 is -P(=Q)R9R10, may be prepared in analogy to the method described in WO 99/05149.
Compounds of formula II, wherein R1a is different from hydrogen, can be prepared by reacting the NR1a group, wherein R1a is H, in analogy to the above-described conversion of compounds I, wherein R1 is H, into compounds, wherein R1 is different from H.
Compounds I, wherein m is 1 or 2, can be prepared from respective compounds I, wherein m is 0, by oxidation. Alternatively, compounds I, wherein m is 2, can be prepared from compounds IV by first deprotonating the triazolyl ring and then reacting with a sulfonyl chloride R1Sθ2CI. Compounds I, wherein m is 3, can be prepared from compounds IV by first deprotonating the triazolyl ring and then reacting with sulfuric acid chloride or a sulfuric ester chloride of formula R1OSθ2CI, wherein R1 is selected from hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-C10- alkynyl, C2-Cio-haloalkynyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, phenyl, phenyl-Ci- C4-alkyl, where the phenyl moiety in the 2 last-mentioned radicals may be substituted as mentioned above, and a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S, wherein the heterocyclic ring may be substituted as mentioned above.
If individual compounds cannot be prepared via the above-described routes, they can be prepared by derivatization of other compounds I and Il or by customary modifications of the synthesis routes described. The reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or silica gel. Some of the intermediates and end products may be obtained in the form of colorless or pale brown viscous oils, which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystallization or digestion.
A further aspect of the invention relates to compounds of formula IV
Figure imgf000122_0001
wherein Ar, Het, A and Y have one of the general or, in particular, one of the preferred meanings given above for compounds I and II.
Compounds IV are on the one side valuable intermediates in the preparation of compounds I and Il (see above schemes), but on the other side show a remarkable fungicidal activity, too.
Particularly preferred compounds IV are compounds of formulae IV.1 to IV.48, wherein the combination of R21, R22, R23, R24 and R25 corresponds in each case to one row in table A above and Het has in ech case one of the formulae Het.1 to Het.16, and compounds of formulae IV.49 to IV.96, wherein the combination of Het and Ar' corresponds in each case to one row in table B above.
Figure imgf000122_0002
Figure imgf000123_0001
Figure imgf000124_0001
Figure imgf000125_0001
Among these, preference is given to compounds IV.1 to IV.24 and IV.49 to 1.72, more preference to compounds IV.1 to IV.12 and I.49 to 1.60, and specific preference to compounds IV.2 and IV.50.
The invention further refers to an agricultural composition comprising at least one compound of formula I, Il and/or IV as defined above or an agriculturally acceptable salt thereof and a liquid or solid carrier. Suitable carriers, as well as auxiliaries and further active compounds which may also be contained in the composition of the invention are defined below.
The compounds I and Il as well as IV 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, Per- onosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, 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, Il and IV 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; 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 I1 II and IV and compositions thereof, respectively are used for controlling a multitude 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. potatoes), which can be used for the multiplication of the plant. This in- eludes 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, Il and IV 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://www.bio.org/speeches/pubs/er/agrLproducts.asp). 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 hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e. g. US 6,222,100, WO 01/82685,
WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imida- zolinones (see e. g. US 6,222,100, WO 01/82685, WO 00/026390, WO 97/41218, WO 98/002526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/014357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate (see e. g. WO 92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e.g. EP-A 242 236, EP-A 242 246) or oxynil herbicides (see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering. 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. Genetic engineering methods have been used to render cultivated plants, such as soybean, cotton, corn, beets and rape, tolerant to herbicides such as glypho- sate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate-tolerant, Monsanto, U.S.A.) and LibertyLink® (glufosinate- tolerant, Bayer CropScience, Germany).
Furthermore, plants are also covered that, by the use of recombinant DNA techniques, are 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(bi ) or Cryθc; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp. or Xenor- habdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Strep- tomycetes 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, ecdysteroid-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); stilben 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 capable 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 tolerance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coleoptera), 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 them are commercially available such as YieldGard® (corn cultivars producing the CryiAb toxin), YieldGard® Plus (corn cultivars producing Cry1 Ab and Cry3Bb1 toxins), Starlink® (corn cultivars producing the Cry9c toxin), Her- culex® RW (corn cultivars producing Cry34Ab1 , Cry35Ab1 and the enzyme Phosphi- nothricin-N-Acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the Cry1 Ac toxin), Bollgard® I (cotton cultivars producing the Cry1 Ac toxin), Bollgard® Il (cotton cultivars producing CryiAc and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin); Bt- Xtra®, NatureGard®, KnockOut®, BiteGard®, Protecta®, Bt 11 (e. g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the CryiAb toxin and PAT enyzme), MIR604 from Syngenta Seeds SAS, France (corn cultivars produc- ing 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 CryiAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).
Furthermore, plants are also covered that, by the use of recombinant DNA techniques, are 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 Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the per- son skilled in the art and are described, e. g., in the publications mentioned above.
Furthermore, plants are also covered that, by the use of recombinant DNA techniques, are 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, by the use of recombinant DNA techniques, contain 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, by the use of recombinant DNA techniques, contain 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, Il and IV 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); Altemaria spp. (Alternaria leaf spot) on vegetables, rape {A. brassicola or brassicae), sugar beets {A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. altemata), tomatoes (e. g. A. solanior A. altemata) and wheat; Aphano- myces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. hordei ou barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (β. zeicola) on corn, e. g. spot blotch (β. 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 fuckeliana: 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. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e.g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. beticola), 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 ce- reals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miy- abeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminicola: 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); Corticium spp., e. g. C. sa- sakii (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 liriodendrϊ. 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 Phaeo- acremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri), 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. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruciferarum); 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. turcicum); Fusarium (teleomorph: Gib- berella) 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. oxy- sporum ou tomatoes, F. solani on soybeans and F. verticillioides on corn; Gaeumanno- myces 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. fujikuroϊ. Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grain- staining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; lsariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (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; Phialophora spp. e. g. on vines (e. g. P. tracheiphila 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); Physoderma 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. halstediiou 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: Tapesia yallundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or , rotbrenner' , anamorph: Phialo- phora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (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, and asparagus (e. g. P. asparagi); Pyrenophora (anamorph: Drechslera) tritici- repentis (tan spot) on wheat or P. feres (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 (Ra mu Ia ria leaf spots, Physiological leaf spots) on barley and R. beticola 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. so/an/ (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; Sarocladium 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. rolfsii or 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) nodorum (Sta- gonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) 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: Leptosphaeria [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 incamata (grey snow mold) on barley or wheat; Uro- cystis 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; Venturia 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. dahliae on strawberries, rape, potatoes and tomatoes.
The compounds I, Il and IV 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, colling 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 Ophio- stoma spp., Ceratocysf/s spp., Aureobasidium pullulans, Sclerophoma spp., Chae- tomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Po- ria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichorma spp., Altemaria 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 compounds I, Il and IV 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, Il and/or IV 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, Il and IV can be present in different crystal modifications whose biological activity may differ. They are likewise subject matter of the present invention.
The compounds I, Il and IV 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 protected 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, Il and/or IV as such or a composition comprising at least one compound I, Il and/or IV prophylactically either at or before planting or transplanting.
The invention also relates to agrochemical compositions comprising a solvent or solid carrier and at least one compound I, Il and/or IV and to the use for controlling harmful fungi.
An agrochemical composition comprises a fungicidally effective amount of a compound I, Il and/or IV. The term "effective amount" denotes an amount of the composition or of the compounds I, Il and/or IV, 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, Il and IV and salts thereof can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The composition type depends on the particular intended purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention. Examples for composition types are suspensions (SC, OD, FS), emulsifiable concentrates (EC), emulsions (EW, EO, ES), pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, DP, DS) or granules (GR, FG, GG, MG), which can be water- soluble or wettable, as well as gel formulations for the treatment of plant propagation materials such as seeds (GF).
Usually the composition types (e. g. SC, OD, FS, EC, WG, SG, WP, SP, SS, WS, GF) are employed diluted. Composition types such as DP, DS, GR, FG, GG and MG are usually used undiluted.
The compositions are prepared in a known manner (cf. US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pp. 8-57 et seq., WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030, GB 2,095,558, US 3,299,566, Klingman: Weed Control as a Science (J. Wiley & Sons, New York, 1961 ), Hance et al.: Weed Control Handbook (8th Ed., Blackwell Scientific, Oxford, 1989) and Mollet, H. and Grubemann, A.: Formulation technology (Wiley VCH Verlag, Weinheim, 2001 ).
The agrochemical compositions may also comprise auxiliaries which are customary in agrochemical compositions. The auxiliaries used depend on the particular application form and active substance, respectively.
Examples for suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and inorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e. g. for seed treatment formulations).
Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols, ketones such as cyclohexanone and gamma-butyrolactone, fatty acid dimethylamides, fatty acids and fatty acid esters and strongly polar solvents, e. g. amines such as N- methylpyrrolidone.
Solid carriers are mineral earths such as silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magne- sium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e. g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
Suitable surfactants (adjuvants, wtters, tackifiers, dispersants or emulsifiers) are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsoulfonic acid (Borresperse® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Morwet® types, Akzo Nobel, U.S.A.), dibutylnaphthalene- sulfonic acid (Nekal® types, BASF, Germany), and fatty acids, alkylsulfonates, alkyl- arylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, furthermore condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxy-ethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearyl- phenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and proteins, denatured proteins, polysaccharides (e. g. methylcellulose), hydrophobically modified starches, polyvinyl alcohols (Mowiol® types, Clariant, Switzerland), polycarboxylates (Sokolan® types, BASF, Germany), polyalkoxylates, polyvinyl- amines (Lupasol® types, BASF, Germany), polyvinylpyrrolidone and the copolymers therof.
Examples for thickeners (i. e. compounds that impart a modified flowability to compositions, i. e. high viscosity under static conditions and low viscosity during agitation) are polysaccharides and organic and anorganic clays such as Xanthan gum (Kelzan®, CP Kelco, U.S.A.), Rhodopol® 23 (Rhodia, France), Veegum® (RT. Vanderbilt, U.S.A.) or Attaclay® (Engelhard Corp., NJ, USA).
Bactericides may be added for preservation and stabilization of the composition. Examples for suitable bactericides are those based on dichlorophene and benzylalcohol hemi formal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and ben- zisothiazolinones (Acticide® MBS from Thor Chemie).
Examples for suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin. Examples for anti-foaming agents are silicone emulsions (such as e. g. Silikon® SRE, Wacker, Germany or Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and mixtures thereof.
Suitable colorants are pigments of low water solubility and water-soluble dyes. Examples to be mentioned und the designations rhodamin B, C. I. pigment red 112, C. I. solvent red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Examples for tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose®, Shin-Etsu, Japan).
Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the compounds I and, if appropriate, further active substances, with at least one solid carrier.
Granules, e. g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magne- sium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e. g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
Examples for composition types are:
1. Composition types for dilution with water
i) Water-soluble concentrates (SL, LS) 10 parts by weight of a compound I according to the invention are dissolved in 90 parts by weight of water or in a water-soluble solvent. As an alternative, wetting agents or other auxiliaries are added. The active substance dissolves upon dilution with water. In this way, a composition having a content of 10% by weight of active substance is obtained. ii) Dispersible concentrates (DC)
20 parts by weight of a compound I according to the invention are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, e. g. polyvinylpyrrolidone. Dilution with water gives a dispersion. The active substance content is 20% by weight.
iii) Emulsifiable concentrates (EC)
15 parts by weight of a compound I according to the invention are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The composition has an active substance content of 15% by weight.
iv) Emulsions (EW, EO, ES) 25 parts by weight of a compound I according to the invention are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifying machine (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The composition has an active substance content of 25% by weight.
v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20 parts by weight of a compound I according to the invention are comminuted with addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. The active substance content in the composition is 20% by weight.
vi) Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of a compound I according to the invention are ground finely with addition of 50 parts by weight of dispersants and wetting agents 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. The composition has an active substance content of 50% by weight.
vii) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS) 75 parts by weight of a compound I according to the invention are ground in a rotor- stator mill with addition of 25 parts by weight of dispersants, wetting agents and silica gel. Dilution with water gives a stable dispersion or solution of the active substance. The active substance content of the composition is 75% by weight.
viii) Gel (GF) In an agitated ball mill, 20 parts by weight of a compound I according to the invention are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance, whereby a composition with 20% (w/w) of active substance is obtained.
2. Composition types to be applied undiluted
ix) Dustable powders (DP, DS) 5 parts by weight of a compound I according to the invention are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable composition having an active substance content of 5% by weight.
x) Granules (GR, FG, GG, MG) 0.5 parts by weight of a compound I according to the invention is ground finely and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spray- drying or the fluidized bed. This gives granules to be applied undiluted having an active substance content of 0.5% by weight.
xi) ULV solutions (UL)
10 parts by weight of a compound I according to the invention are dissolved in 90 parts by weight of an organic solvent, e. g. xylene. This gives a composition to be applied undiluted having an active substance content of 10% by weight.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, 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).
Water-soluble concentrates (LS), 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 for the purposes of treatment of plant propagation materials, particularly seeds. These compositions can be applied to plant propagation materials, particularly seeds, diluted or undiluted. The compositions 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% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying or treating agrochemical compounds and com- positions thereof, respectively, on to plant propagation material, especially seeds, are known in the art, and include dressing, coating, pelleting, dusting, soaking and in- furrow application methods of the propagation material. In a preferred embodiment, the compounds 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.
In a preferred embodiment, a suspension-type (FS) composition is used for seed treatment. Typcially, a FS composition may comprise 1-800 g/l of active substance, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
The active substances can be used as such or in the form of their compositions, e. g. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading, brushing, immersing or pouring. The application forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the active substances according to the invention.
Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active sub- stance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1 % by weight of active substance.
The active substances may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives. 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, 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 seed) 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, e. g., 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, herbicides, bactericides, other fungicides and/or pesticides may be added to the active substances or the compositions comprising them, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
Adjuvants which can be used are in particular organic modified polysiloxanes such as Break Thru S 240®; alcohol alkoxylates such as Atplus 245®, Atplus MBA 1303®, PIu- rafac LF 300® and Lutensol ON 30®; EO/PO block polymers, e. g. Pluronic RPE 2035® and Genapol B®; alcohol ethoxylates such as Lutensol XP 80®; and dioctyl sulfosucci- nate sodium such as Leophen RA®.
The compositions according to the invention can, in the use form as fungicides, also be present together with other active substances, e. g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers, as pre-mix or, if appropriate, not until immediately prior to use (tank mix).
Mixing the compounds I, Il and/or IV 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 active substances, in conjunction with which the compounds according to the invention can be used, is intended to illustrate the possible combinations but does not limit them:
A) strobilurins azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, meto- minostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyribencarb, triflox- ystrobin, 2-(2-(6-(3-chloro-2-methyl-phenoxy)-5-fluoro-pyrimidin-4-yloxy)-phenyl)- 2-methoxyimino-N-methyl-acetamide, 3-methoxy-2-(2-(N-(4-methoxy-phenyl)- cyclopropane-carboximidoylsulfanylmethyl)-phenyl)-acrylic acid methyl ester, methyl (2-chloro-5-[1-(3-methylbenzyloxyimino)ethyl]benzyl)carbamate and 2-(2- (3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2- methoxyimino-N-methyl-acetamide; B) carboxamides - carboxanilides: benalaxyl, benalaxyl-M, benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, flutolanil, furametpyr, isopyrazam, isotianil, kiralaxyl, me- pronil, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, oxycarboxin, pen- thiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4-methyl- thiazole-5-carboxanilide, 2-chloro-N-(1 ,1 ,3-trimethyl-indan-4-yl)-nicotinamide, N- (3',4',5'-trifluorobiphenyl-2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-
4-carboxamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxamide, N-(2-(1 ,3-dimethyl-butyl)-phenyl)-1 ,3-dimethyl-5- fluoro-1 H-pyrazole-4-carboxamide and N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3- dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide; - carboxylic morpholides: dimethomorph, flumorph, pyrimorph; benzoic acid amides: flumetover, fluopicolide, fluopyram, zoxamide, N-(3-Ethyl-
3,5,5-trimethyl-cyclohexyl)-3-formylamino-2-hydroxy-benzamide; other carboxamides: carpropamid, dicyclomet, mandiproamid, oxytetracyclin, silthiofarm and N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide; C) azoles triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenocona- zole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquincona- zole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metcona- zole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadi- menol, triticonazole, uniconazole, 1-(4-chloro-phenyl)-2-([1 ,2,4]triazol-1-yl)- cycloheptanol; imidazoles: cyazofamid, imazalil, pefurazoate, prochloraz, triflumizol; benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole; others: ethaboxam, etridiazole, hymexazole and 2-(4-chloro-phenyl)-N-[4-(3,4-di- methoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;
D) heterocyclic compounds pyridines: fluazinam, pyrifenox, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin- 3-yl]-pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine,
2,3,5,6-tetra-chloro-4-methanesulfonyl-pyridine, 3,4,5-trichloropyridine-2,6-di- carbonitrile, N-(1-(5-bromo-3-chloro-pyridin-2-yl)-ethyl)-2,4-dichloronicotinamide, N-[(5-bromo-3-chloro-pyridin-2-yl)-methyl]-2,4-dichloro-nicotinamide; pyrimidines: bupirimate, cyprodinil, diflumetorim, fenarimol, ferimzone, mepani- pyrim, nitrapyrin, nuarimol, pyrimethanil; piperazines: triforine; pyrroles: fenpiclonil, fludioxonil; morpholines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tride- morph; - piperidines: fenpropidin; dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin; non-aromatic 5-membered heterocycles: famoxadone, fenamidone, flutianil, oc- thilinone, probenazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydro- pyrazole-1-carbothioic acid S-allyl ester; - others: acibenzolar-S-methyl, amisulbrom, anilazin, blasticidin-S, captafol, cap- tan, chinomethionat, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat- methylsulfate, fenoxanil, Folpet, oxolinic acid, piperalin, proquinazid, pyroquilon, quinoxyfen, triazoxide, tricyclazole, 2-butoxy-6-iodo-3-propylchromen-4-one, 5- chloro-1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 5-chloro- 7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine and 5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine;
E) carbamates thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasulpho- carb, metiram, propineb, thiram, zineb, ziram; - carbamates: benthiavalicarb, diethofencarb, iprovalicarb, propamocarb, propamo- carb hydrochlorid, valiphenal and N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-but-2- yl) carbamic acid-(4-fluorophenyl) ester;
F) other active substances guanidines: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate); antibiotics: kasugamycin, kasugamycin hydrochloride-hydrate, streptomycin, pol- yoxine, validamycin A; nitrophenyl derivates: binapacryl, dinobuton, dinocap, nitrthal-isopropyl, tecna- zen, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; sulfur-containing heterocyclyl compounds: dithianon, isoprothiolane; organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, iproben- fos, phosphorous acid and its salts, pyrazophos, tolclofos-methyl; organochlorine compounds: chlorothalonil, dichlofluanid, dichlorophen, flusul- famide, hexachlorobenzene, pencycuron, pentachlorphenole and its salts, phthalide, quintozene, thiophanate-methyl, tolylfluanid, N-(4-chloro-2-nitro- phenyl)-N-ethyl-4-methyl-benzenesulfonamide; - inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; others: biphenyl, bronopol, cyflufenamid, cymoxanil, diphenylamin, metrafenone, mildiomycin, oxin-copper, prohexadione-calcium, spiroxamine, tolylfluanid, N- (cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2- phenyl acetamide, N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl- phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)- 2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5- trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N- ethyl-N-methyl formamidine,
2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazole-1-yl)-acetyl]-piperidin-4-yl}-thiazole-4- carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1-yl)-amide, 2-{1-[2-(5- methyl-S-trifluoromethyl-pyrazole-i-yO-acety^-piperidin^-ylJ-thiazole^-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide, acetic acid 6-tert-butyl- 8-fluoro-2,3-dimethyl-quinolin-4-yl ester and methoxy-acetic acid 6-tert-butyl-8- fluoro-2,3-dimethyl-quinolin-4-yl ester. G) growth regulators abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid , trinexapac-ethyl and uniconazole;
H) herbicides acetamides: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufen- acet, mefenacet, metolachlor, metazachlor, napropamide, naproanilide, pethox- amid, pretilachlor, propachlor, thenylchlor; amino acid derivatives: bilanafos, glyphosate, glufosinate, sulfosate; aryloxyphenoxypropionates: clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P-tefuryl;
Bipyridyls: diquat, paraquat; - (thio)carbamates: asulam, butylate, carbetamide, desmedipham, dimepiperate, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate; cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim; - dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, triflu- ralin; diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oxyfluorfen; hydroxybenzonitriles: bomoxynil, dichlobenil, ioxynil; - imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr; phenoxy acetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-
DB, dichlorprop, MCPA, MCPA-thioethyl, MCPB, Mecoprop; pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate; - pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr; sulfonyl ureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, fluce- tosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfu- ron, mesosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfu- ron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, 1-((2- chloro-6-propyl-imidazo[1 ,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6-dimethoxy-pyrimidin-
2-yl)urea; - triazines: ametryn, atrazine, cyanazine, dimethametryn, ethiozin, hexazinone, metamitron, metribuzin, prometryn, simazine, terbuthylazine, terbutryn, triaziflam; ureas: chlorotoluron, daimuron, diuron, fluometuron, isoproturon, linuron, metha- benzthiazuron,tebuthiuron; other acetolactate synthase inhibitors: bispyribac-sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, ortho-sulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfone, pyroxsulam; others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencar- bazone,benfluresate, benzofenap, bentazone, benzobicyclon, bromacil, bromo- butide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethlyl, chlor- thal, cinmethylin, clomazone, cumyluron, cyprosulfamide, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid, fen- trazamide, flumiclorac-pentyl, flumioxazin, flupoxam, flurochloridone, flurtamone, indanofan, isoxaben, isoxaflutole, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methyl arsonic acid, naptalam, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfo- tole, pyrazoxyfen, pyrazolynate, quinoclamine, saflufenacil, sulcotrione, sulfentra- zone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, 4- hydroxy-3-[2-(2-methoxy-ethoxymethyl)-6-trifluoromethyl-pyridine-3-carbonyl]- bicyclo[3.2.1]oct-3-en-2-one, (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4- trifluoromethyl-3,6-dihydro-2H-pyrimidin-1-yl)-phenoxy]-pyridin-2-yloxy)-acetic a- cid ethyl ester, 6-amino-5-chloro-2-cyclopropyl-pyrimidine-4-carboxylic acid methyl ester, 6-chloro-3-(2-cyclopropyl-6-methyl-phenoxy)-pyridazin-4-ol, 4-amino-3- chloro-6-(4-chloro-phenyl)-5-fluoro-pyridine-2-carboxylic acid, 4-amino-3-chloro-
6-(4-chloro-2-fluoro-3-methoxy-phenyl)-pyridine-2-carboxylic acid methyl ester, and 4-amino-3-chloro-6-(4-chloro-3-dimethylamino-2-fluoro-phenyl)-pyridine-2- carboxylic acid methyl ester. I) insecticides - organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dime- thoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methami- dophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydeme- ton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphami- don, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos, te- trachlorvinphos, terbufos, triazophos, trichlorfon; carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate; - pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cyperme- thrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda- cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau- fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimeflu- thrin; insect growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazu- ron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenu- ron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfeno- zide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxy- carb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat; nicotinic receptor agonists/antagonists compounds: clothianidin, dinotefuran, imi- dacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, 1-(2-chloro- thiazol-5-ylmethyl)-2-nitrimino-3,5-dimethyl-[1 ,3,5]triazinane;
GABA antagonist compounds: endosulfan, ethiprole, fipronil, vaniliprole, pyraflu- prole, pyriprole, 5-amino-1 -(2,6-dichloro-4-methyl-phenyl)-4-sulfinamoyl-
1 H-pyrazole-3-carbothioic acid amide; macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram; mitochondrial electron transport inhibitor (METI) I acaricides: fenazaquin, pyrida- ben, tebufenpyrad, tolfenpyrad, flufenerim;
METI Il and III compounds: acequinocyl, fluacyprim, hydramethylnon;
Uncouplers: chlorfenapyr; - oxidative phosphorylation inhibitors: cyhexatin, diafenthiuron, fenbutatin oxide, propargite; moulting disruptor compounds: cryomazine; mixed function oxidase inhibitors: piperonyl butoxide; sodium channel blockers: indoxacarb, metaflumizone; - others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozine, sulfur, thiocyclam, flubendiamide, chlorantraniliprole, cyazypyr (HGW86), cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron, and pyrifluquina- zon.
The present invention furthermore relates to agrochemical compositions comprising a mixture of at least one compound I, Il and/or IV (component 1 ) and at least one further active substance useful for plant protection, e. g. selected from the groups A) to I) (component 2), in particular one further fungicide, e. g. one or more fungicide from the groups A) to F), as described above, and if desired 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, Il and/or IV and at least one fungicide from groups A) to F), as described above, is more efficient than combating those fungi with individual compounds I, Il or IV or individual fungicides from groups A) to F). By applying compounds I, Il and/or IV together with at least one active substance from groups A) to I) a synergistic effect can be obtained, i.e. more then simple addition of the individual effects is obtained (synergistic mixtures). According to this invention, applying the compounds I, Il and/or IV together with at least one further active substance is to be understood to denote that at least one compound of formula IJI and/or IV and at least one further active substance occur simultaneously at the site of action (i.e. the harmful fungi to be controlled or their habitats such as in- fected plants, plant propagation materials, particularly seeds, surfaces, materials or the soil as well as plants, plant propagation materials, particularly seeds, soil, surfaces, materials or rooms to be protected from fungal attack) in a fungicidally effective amount. This can be obtained by applying the compounds I, Il and/or IV and at least one further active substance simultaneously, either jointly (e. g. as tank-mix) or sper- ately, 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.
In binary mixtures, i.e. compositions according to the invention comprising one compound I, Il or IV (component 1 ) and one further active substance (component 2), e. g. one active substance from groups A) to I), the weight ratio of component 1 and component 2 generally 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 , pref- erably 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 :3 to 3:1.
In ternary mixtures, i.e. compositions according to the invention comprising one compound I (component 1 ) and a first further active substance (component 2) and a second further active substance (component 3), e. g. two active substances from groups A) to I), the weight ratio of component 1 and component 2 depends from the properties of the active substances used, preferably it is in the range of from 1 :50 to 50:1 and particularly in the range of from 1 :10 to 10:1 , and the weight ratio of component 1 and component 3 preferably is in the range of from 1 :50 to 50:1 and particularly in the range of from 1 :10 to 10:1.
The components can be used individually or already partially or completely mixed with one another to prepare the composition according to the invention. It is also possible for them to be packaged and used further as combination composition such as a kit of parts.
In one embodiment of the invention, the kits may include one or more, including all, components that may be used to prepare a subject agrochemical composition. E. g., kits may include one or more fungicide component(s) and/or an adjuvant component and/or an insecticide component and/or a growth regulator component and/or a her- bicde. One or more of the components may already be combined together or pre- formulated. In those embodiments where more than two components are provided in a kit, the components may already be combined together and as such are packaged in a single container such as a vial, bottle, can, pouch, bag or canister. In other embodiments, two or more components of a kit may be packaged separately, i. e., not pre- formulated. As such, kits may include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical composition. In both forms, a component of the kit may be applied separately from or together with the further components or as a component of a combination composition according to the invention for preparing the composition according to the invention.
The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank or a spray plane. Here, the agrochemical composition is made up with water and/or buffer to the desired application concentration, it being possible, if appropriate, to add further auxiliaries, and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 50 to 500 liters of the ready-to-use spray liquor are applied per hectare of agricultural useful area, preferably 100 to 400 liters.
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 and further auxiliaries may be added, if appropriate (tank mix).
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising compounds I, Il and/or IV and/or active substances from the groups A) to I), may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate (tank mix).
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising com- pounds I, Il and/or IV and/or active substances from the groups A) to I), can be applied jointly (e. .g. after tankmix) or consecutively.
Preference is also given to mixtures comprising a compound I, Il and/or IV (component 1 ) and at least one active substance selected from the strobilurines of group A) (com- ponent 2) and particularly selected from azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin.
Preference is also given to mixtures comprising a compound I, Il and/or IV (component 1 ) and at least one active substance selected from the carboxamides of group B)
(component 2) and particularly selected from bixafen, boscalid, sedaxane, fenhexamid, metalaxyl, isopyrazam, mefenoxam, ofurace, dimethomorph, flumorph, fluopicolid (pi- cobenzamid), zoxamide, carpropamid, mandipropamid and N-(3',4',5'-trifluorobiphenyl- 2-yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide.
Preference is given to mixtures comprising a compound of formula I, Il and/or IV (component 1 ) and at least one active substance selected from the azoles of group C) (component 2) and particularly selected from cyproconazole, difenoconazole, epoxi- conazole, fluquinconazole, flusilazole, flutriafol, metconazole, myclobutanil, pencona- zole, propiconazole, prothioconazole, triadimefon, triadimenol, tebuconazole, tetra- conazole, triticonazole, prochloraz, cyazofamid, benomyl, carbendazim and eth- aboxam.
Preference is also given to mixtures comprising a compound I, Il and/or IV (component 1) and at least one active substance selected from the heterocyclic compounds of group D) (component 2) and particularly selected from fluazinam, cyprodinil, fenarimol, mepanipyrim, pyrimethanil, triforine, fludioxonil, dodemorph, fenpropimorph, tride- morph, fenpropidin, iprodione, vinclozolin, famoxadone, fenamidone, probenazole, pro- quinazid, acibenzolar-S-methyl, captafol, folpet, fenoxanil, quinoxyfen and 5-ethyl- 6-octyl-[1 ,2,4]triazolo[1 ,5-a]pyrimidine-7-ylamine.
Preference is also given to mixtures comprising a compound I, Il and/or IV (component 1 ) and at least one active substance selected from the carbamates of group E) (component 2) and particularly selected from mancozeb, metiram, propineb, thiram, iprovali- carb, benthiavalicarb and propamocarb.
Preference is also given to mixtures comprising a compound I, Il and/or IV (component 1 ) and at least one active substance selected from the fungicides given in group F) (component 2) and particularly selected from dithianon, fentin salts, such as fentin ace- tate, fosetyl, fosetyl-aluminium, H3PO3 and salts thereof, chlorthalonil, dichlofluanid, thiophanat-methyl, copper acetate, copper hydroxide, copper oxychloride, copper sulfate, sulfur, cymoxanil, metrafenone and spiroxamine. Accordingly, the present invention furthermore relates to compositions comprising one compound I, Il and/or IV (component 1 ) and one further active substance (component 2), which further active substance is selected from the column "Component 2" of the lines C-1 to C-346 of Table C.
A further embodiment relates to the compositions C-1 to C-346 listed in Table C, where a row of Table C corresponds in each case to a fungicidal composition comprising one of the in the present specification individualized compounds of formula I, Il and/or IV (component 1 ) and the respective further active substance from groups A) to I) (component 2) stated in the row in question. Preferably, the compositions described comprise the active substances in synergistically effective amounts.
Table C: Composition comprising one indiviualized compound I, Il or IV and one further active substance from groups A) to I)
Figure imgf000151_0001
Figure imgf000152_0001
Figure imgf000153_0001
Figure imgf000154_0001
MixComponent 1
Component 2 ture
2-(4-Chloro-phenyl)-N-[4-(3,4-
C-103 one individualized compound I, Il or IV dimethoxy-phenyl)-isoxazol-5- yl]-2-prop-2-ynyloxy-acetamide
C-104 one individualized compound I, Il or IV Fluazinam
C-105 one individualized compound I, Il or IV Pyrifenox
3-[5-(4-Chloro-phenyl)-2,3-
C-106 one individualized compound I, Il or IV dimethyl-isoxazolidin-3-yl]- pyridine
3-[5-(4-Methyl-phenyl)-2,3-dime-
C-107 one individualized compound I, Il or IV thyl-isoxazolidin-3-yl]-pyridine
2,3,5,6-Tetrachloro-4-
C-108 one individualized compound I, Il or IV methanesulfonyl-pyridine
3,4,5-Trichloro-pyridine-2,6-
C-109 one individualized compound I, Il or IV dicarbonitrile
N-(1 -(5-Bromo-3-chloro-pyridin-
C-1 10 one individualized compound I, Il or IV 2-yl)-ethyl)-2,4-dichloro- nicotinamide
N-((5-Bromo-3-chloro-pyridin-2-
C-1 1 1 one individualized compound I, Il or IV yl)-methyl)-2,4-dichloro- nicotinamide
C-1 12 one individualized compound I, Il or IV Bupirimate
C-1 13 one individualized compound I, Il or IV Cyprodinil
C-1 14 one individualized compound I, Il or IV Diflumetorim
C-1 15 one individualized compound I, Il or IV Fenarimol
C-1 16 one individualized compound I, Il or IV Ferimzone
C-1 17 one individualized compound I, Il or IV Mepanipyrim
C-1 18 one individualized compound I, Il or IV Nitrapyrin
C-1 19 one individualized compound I, Il or IV Nuarimol
C-120 one individualized compound I, Il or IV Pyrimethanil
C-121 one individualized compound I, Il or IV Triforine
C-122 one individualized compound I, Il or IV Fenpiclonil
C-123 one individualized compound I, Il or IV Fludioxonil
C-124 one individualized compound I, Il or IV Aldimorph
C-125 one individualized compound I, Il or IV Dodemorph
C-126 one individualized compound I, Il or IV Dodemorph-acetate
C-127 one individualized compound I, Il or IV Fenpropimorph
Figure imgf000156_0001
MixComponent 1
Component 2 ture
2-Butoxy-6-iodo-3-propyl-
C-161 one individualized compound I, Il or IV chromen-4-one
5-Chloro-1 -(4,6-dimethoxy-
C-162 one individualized compound I, Il or IV pyrimidin-2-yl)-2-methyl-1 H- benzoimidazole
5-Chloro-7-(4-methyl-piperidin-1-
C-163 one individualized compound I, Il or IV yl)-6-(2,4,6-trifluoro-phenyl)- [1 ,2,4]triazolo[1 ,5-a]pyrimidine
5-ethyl-6-octyl-[1 ,2,4]triazolo[1 ,5-
C-164 one individualized compound I, Il or IV a]pyrimidine-7-ylamine
C-165 one individualized compound I, Il or IV Ferbam
C-166 one individualized compound I, Il or IV Mancozeb
C-167 one individualized compound I, Il or IV Maneb
C-168 one individualized compound I, Il or IV Metam
C-169 one individualized compound I, Il or IV Methasulphocarb
C-170 one individualized compound I, Il or IV Metiram
C-171 one individualized compound I, Il or IV Propineb
C-172 one individualized compound I, Il or IV Thiram
C-173 one individualized compound I, Il or IV Zineb
C-174 one individualized compound I, Il or IV Zi ram
C-175 one individualized compound I, Il or IV Diethofencarb
C-176 one individualized compound I, Il or IV Benthiavalicarb
C-177 one individualized compound I, Il or IV Iprovalicarb
C-178 one individualized compound I, Il or IV Propamocarb
C-179 one individualized compound I, Il or IV Propamocarb hydrochlorid
C-180 one individualized compound I, Il or IV Valiphenal
N-(1 -(1 -(4-cyanophenyl)ethane-
C-181 one individualized compound I, Il or IV sulfonyl)-but-2-yl) carbamic acid- (4-fluorophenyl) ester
C-182 one individualized compound I, Il or IV Dodine
C-183 one individualized compound I, Il or IV Dodine free base
C-184 one individualized compound I, Il or IV Guazatine
C-185 one individualized compound I, Il or IV Guazatine-acetate
C-186 one individualized compound I, Il or IV lminoctadine
C-187 one individualized compound I, Il or IV Iminoctadine-triacetate
C-188 one individualized compound I, Il or IV Iminoctadine-tris(albesilate) MixComponent 1
Component 2 ture
C-189 one individualized compound I, Il or IV Kasugamycin
Kasugamycin-hydrochloride-
C-190 one individualized compound I, Il or IV hydrate
C-191 one individualized compound I, Il or IV Polyoxine
C-192 one individualized compound I, Il or IV Streptomycin
C-193 one individualized compound I, Il or IV Validamycin A
C-194 one individualized compound I, Il or IV Binapacryl
C-195 one individualized compound I, Il or IV Dicloran
C-196 one individualized compound I, Il or IV Dinobuton
C-197 one individualized compound I, Il or IV Dinocap
C-198 one individualized compound I, Il or IV Nitrothal-isopropyl
C-199 one individualized compound I, Il or IV Tecnazen
C-200 one individualized compound I, Il or IV Fentin salts
C-201 one individualized compound I, Il or IV Dithianon
C-202 one individualized compound I, Il or IV lsoprothiolane
C-203 one individualized compound I, Il or IV Edifenphos
C-204 one individualized compound I, Il or IV Fosetyl, Fosetyl-aluminium
C-205 one individualized compound I, Il or IV lprobenfos
Phosphorous acid (H3PO3) and
C-206 one individualized compound I, Il or IV derivatives
C-207 one individualized compound I, Il or IV Pyrazophos
C-208 one individualized compound I, Il or IV Tolclofos-methyl
C-209 one individualized compound I, Il or IV Chlorothalonil
C-210 one individualized compound I, Il or IV Dichlofluanid
C-21 1 one individualized compound I, Il or IV Dichlorophen
C-212 one individualized compound I, Il or IV Flusulfamide
C-213 one individualized compound I, Il or IV Hexachlorbenzene
C-214 one individualized compound I, Il or IV Pencycuron
C-215 one individualized compound I, Il or IV Pentachlorophenol and salts
C-216 one individualized compound I, Il or IV Phthalide
C-217 one individualized compound I, Il or IV Quintozene
C-218 one individualized compound I, Il or IV Thiophanate Methyl
C-219 one individualized compound I, Il or IV Tolylfluanid
N-(4-chloro-2-nitro-phenyl)-N-
C-220 one individualized compound I, Il or IV ethyl-4-methyl- benzenesulfonamide MixComponent 1
Component 2 ture
C-221 one individualized compound I, Il or IV Bordeaux mixture
C-222 one individualized compound I, Il or IV Copper acetate
C-223 one individualized compound I, Il or IV Copper hydroxide
C-224 one individualized compound I, Il or IV Copper oxychloride
C-225 one individualized compound I, Il or IV basic Copper sulfate
C-226 one individualized compound I, Il or IV Sulfur
C-227 one individualized compound I, Il or IV Biphenyl
C-228 one individualized compound I, Il or IV Bronopol
C-229 one individualized compound I, N or IV Cyflufenamid
C-230 one individualized compound I, Il or IV Cymoxanil
C-231 one individualized compound I, Il or IV Diphenylamin
C-232 one individualized compound I, Il or IV Metrafenone
C-233 one individualized compound I, Il or IV Mildiomycin
C-234 one individualized compound I, Il or IV Oxin-copper
C-235 one individualized compound I, Il or IV Prohexadione calcium
C-236 one individualized compound I, Il or IV Spiroxamine
C-237 one individualized compound I, Il or IV Tolylfluanid
N-(Cyclopropylmethoxyimino-(6- difluoromethoxy-2,3-difluoro-
C-238 one individualized compound I, Il or IV phenyl)-methyl)-2-phenyl acetamide
N'-(4-(4-chloro-3-trifluoromethyl-
C-239 one individualized compound I, Il or IV phenoxy)-2,5-dimethyl-phenyl)- N-ethyl-N-methyl formamidine
N'-(4-(4-fluoro-3-trifluoromethyl-
C-240 one individualized compound I, Il or IV phenoxy)-2,5-dimethyl-phenyl)- N-ethyl-N-methyl formamidine
N'-(2-methyl-5-trifluoromethyl-4- (3-trimethylsilanyl-propoxy)-
C-241 one individualized compound I, Il or IV phenyl)-N-ethyl-N-methyl formamidine
N'-(5-difluoromethyl-2-methyl-4- (3-trimethylsilanyl-propoxy)-
C-242 one individualized compound I, Il or IV phenyl)-N-ethyl-N-methyl formamidine
Figure imgf000160_0001
Figure imgf000161_0001
Figure imgf000162_0001
Figure imgf000163_0001
The active substances referred to as component 2, their preparation and their activity against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by IUPAC nomencla- ture, their preparation and their fungicidal 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).
The mixtures of active substances can be prepared as compositions comprising besides the active ingredients at least one inert ingredient by usual means, e. g. by the means given for the compositions of compounds I, Il and/or IV.
Concerning usual ingredients of such compositions reference is made to the explanations given for the compositions containing compounds I, Il and/or IV.
The mixtures of active substances according to the present invention are suitable as fungicides, as are the compounds of formula I, Il ad IV. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the Ascomycetes, Basidiomycetes, Deuteromycetes and Per- onosporomycetes (syn. Oomycetes ). In addition, it is referred to the explanations regarding the fungicidal activity of the compounds and the compositions containing compounds IJI and/or IV respectively.
The compounds IJI and IV and pharmaceutically acceptable salts thereof are also suitable for treating diseases in men and animals, especially as antimycotics, for treating cancer and for treating virus infections. The term "antimycotic", as distinguished from the term "fungicide", refers to a medicament for combating zoopathogenic or hu- manpathogenic fungi, i.e. for combating fungi in animals, especially in mammals (in- eluding humans) and birds.
Thus, a further aspect of the present invention relates to a medicament comprising at least one compound of the formulae I, Il and/or IV and/or at least one pharmaceutically acceptable salt thereof and a pharmaceutically acceptable carrier.
Suitable pharmaceutically acceptable salts are especially physiologically tolerated salts of the compound I, in particular the acid addition salts with physiologically acceptable acids. Examples of suitable organic and inorganic acids are hydrochloric acid, hydro- bromic acid, phosphoric acid, sulfuric acid, Ci-C4-alkylsulfonic acids, such as methane- sulfonic acid, aromatic sulfonic acids, such as benzenesulfonic acid and toluenesulfo- nic acid, oxalic acid, maleic acid, fumaric acid, lactic acid, tartaric acid, adipic acid and benzoic acid. Further suitable acids are described, for example, in Fortschritte der Arzneimittelforschung, Volume 10, pages 224 ff., Birkhauser Verlag, Basle and Stuttgart, 1966, the entire contents of which is expressly incorporated herein by way of ref- erence.
Suitable carriers are, for example, solvents, carriers, excipients, binders and the like customarily used for pharmaceutical formulations, which are described below in an exemplary manner for individual types of administration.
A further aspect of the present invention relates to the use of compounds IJI and IV or of pharmaceutically acceptable salts thereof for preparing an antimycotic medicament; i.e. for preparing a medicament for the treatment and/or prophylaxis of infections with humanpathogenic and/or zoopathogenic fungi. Another aspect of the present invention relates to the use of compounds of formulae I, Il and/or IV or of pharmaceutically acceptable salts thereof for preparing a medicament for the treatment of cancer. Another aspect of the present invention relates to the use of compounds of formulae IJI and/or IV or of pharmaceutically acceptable salts thereof for preparing a medicament for the treatment or prophylaxis of virus infections. The compounds of formulae IJI and IV and/or their pharmaceutically acceptable salts are suitable for the treatment, inhibiton or control of growth and/or propagation of tumor cells and the disorders associated therewith. Accordingly, they are suitable for cancer therapy in warm-blooded vertebrates, for example mammals and birds, in particular man, but also other mammals, in particular useful and domestic animals, such as dogs, cats, pigs, ruminants (cattle, sheep, goats, bison, etc.), horses and birds, such as chicken, turkey, ducks, geese, guineafowl and the like.
The compounds of formulae I , Il and IV and/or their pharmaceutically acceptable salts are suitable for the therapy of cancer or cancerous disorders of the following organs: breast, lung, intestine, prostate, skin (melanoma), kidney, bladder, mouth, larynx, oesophagus, stomach, ovaries, pancreas, liver and brain or CNS.
The compounds of formulae I , Il and IV and/or their pharmaceutically acceptable salts are suitable for the treatment of virus infections in warm-blooded vertebrates, for example mammals and birds, in particular man, but also other mammals, in particular useful and domestic animals, such as dogs, cats, pigs, ruminants (cattle, sheep, goats, bison, etc.), horses and birds, such as chicken, turkey, ducks, geese, guineafowl and the like. They are suitable for treating virus infections like retrovirus infections such as HIV and HTLV, influenza virus infection, rhinovirus infections, herpes and the like.
The compounds according to the invention can be administered in a customary manner, for example orally, intravenously, intramuscularly or subcutaneously. For oral ad- ministration, the active compound can be mixed, for example, with an inert diluent or with an edible carrier; it can be embedded into a hard or soft gelatin capsule, it can be compressed to tablets or it can be mixed directly with the food/feed. The active compound can be mixed with excipients and administered in the form of indigestible tablets, buccal tablets, pastilles, pills, capsules, suspensions, potions, syrups and the like. Such preparations should contain at least 0.1 % of active compound. The composition of the preparation may, of course, vary. It usually comprises from 2 to 60% by weight of active compound, based on the total weight of the preparation in question (dosage unit). Preferred preparations of the compound I according to the invention comprise from 10 to 1000 mg of active compound per oral dosage unit.
The tablets, pastilles, pills, capsules and the like may furthermore comprise the following components: binders, such as traganth, gum arabic, corn starch or gelatin, excipients, such as dicalcium phosphate, disintegrants, such as corn starch, potato starch, alginic acid and the like, glidants, such as magnesium stearate, sweeteners, such as sucrose, lactose or saccharin, and/or flavors, such as peppermint, vanilla and the like. Capsules may furthermore comprise a liquid carrier. Other substances which modify the properties of the dosage unit may also be used. For example, tablets, pills and capsules may be coated with schellack, sugar or mixtures thereof. In addition to the active compound, syrups or potions may also comprise sugar (or other sweeteners), methyl- or propylparaben as preservative, a colorant and/or a flavor. The components of the active compound preparations must, of course, be pharmaceutically pure and nontoxic at the quantities employed. Furthermore, the active compounds can be formulated as preparations with a controlled release of active compound, for example as delayed-release preparations.
The active compounds can also be administered parenterally or intraperitoneally. Solutions or suspensions of the active compounds or their salts can be prepared with water using suitable wetting agents, such as hydroxypropylcellulose. Dispersions can also be prepared using glycerol, liquid polyethylene glycols and mixtures thereof in oils. Frequently, these preparations furthermore comprise a preservative to prevent the growth of microorganisms.
Preparations intended for injections comprise sterile aqueous solutions and dispersions and also sterile powders for preparing sterile solutions and dispersions. The preparation has to be sufficiently liquid for injection. It has to be stable under the preparation and storage conditions and it has to be protected against contamination by microorganisms. The carrier may be a solvent or a dispersion medium, for example, water, etha- nol, a polyol (for example glycerol, propylene glycol or liquid polyethylene glycol), a mixture thereof and/or a vegetable oil.
The invention is further illustrated by the following, non-limiting examples.
I. Synthesis examples
II. Examples of the action against harmful fungi
The fungicidal action of the compounds of the formulae I and Il was demonstrated by the following experiments:
A) Microtiter tests The active substances were formulated separately as a stock solution in dimethyl sulfoxide (DMSO) at a concentration of 10 000 ppm.
Use example 1 : Activity against the late blight pathogen Phytophthora infestans in the microtiter test
The stock solution was pipetted into a microtiter plate (MTP) and diluted to the stated active substance concentration using a pea juice-based aqueous nutrient medium for fungi. An aqueous zoospore suspension of Phytophthora infestans was then added. The plates were placed in a water vapor-saturated chamber at temperatures of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm on day 7 after the inoculation. The measured parameters were compared to the growth of the active substance-free control variant (= 100 %) and the fungus- and active substance-free blank value to determine the relative growth in % of the pathogens in the individual active substances.
Use example 2: Activity against the rice blast pathogen caused by Pyricularia oryzae in the microtiter test
The stock solution was pipetted into a microtiter plate (MTP) and diluted to the stated active substance concentration using a malt-based aqueous nutrient medium for fungi. An aqueous spore suspension of Pyricularia oryzae was then added. The plates were placed in a water vapor-saturated chamber at temperatures of 18°C. Using an absorption photometer, the microtiter plates were measured at 405 nm on day 7 after the in- oculation. The measured parameters were compared to the growth of the active substance-free control variant (= 100%) and the fungus- and active substance-free blank value to determine the relative growth in % of the pathogens in the individual active substances.
Use example 3: Activity against the Septoria blotch pathogen caused by Septoria tritici in the microtiter test
The stock solution was pipetted into a microtiter plate (MTP) and diluted to the stated active substance concentration using a malt-based aqueous nutrient medium for fungi. An aqueous spore suspension of Septoria tritici was then added. The plates were placed in a water vapor-saturated chamber at temperatures of 18°C. Using an absorption photometer, the microtiter plates were measured at 405 nm on day 7 after the inoculation. The measured parameters were compared to the growth of the active substance-free control variant (= 100%) and the fungus- and active substance-free blank value to determine the relative growth in % of the pathogens in the individual active substances.
B) Greenhouse tests
The active substances were formulated separately or together as a stock solution comprising 25 mg of active substance which was made up to 10 ml using a mixture of acetone and/or dimethyl sulfoxide (DMSO) and the emulsifier Wettol EM 31 (wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols) in a vol- ume ratio of solvent/emulsifier of 99 to 1. This solution was then made up to 100 ml using water. This stock solution was diluted with the solvent/emulsifier/water mixture described to the active substance concentration given below.
Use example 4: Activity against early blight on tomatoes caused by Phytophthora in- festans with protective application
Young seedlings of tomato plants were grown in pots. The plants were sprayed to runoff with an aqueous suspension containing the concentration of active substance stated below. The next day, the treated plants were inoculated with an aqueous suspension of sporangia of Phytophthora infestans. After inoculation, the trial plants were immediately transferred to a humid chamber. After 6 days at 18 to 200C and a relative humidity close to 100%, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
Use example 5: Curative action against Puccinia recondita on wheat (brown rust of wheat)
Leaves of potted wheat seedlings of the cultivar "Kanzler" were dusted with a suspension of spores of brown rust of wheat (Puccinia recondita). The plants were then placed in a chamber with high atmospheric humidity (90 to 95%), at 20-220C, for 24 hours.
During this time, the spores germinated and the germinal tubes penetrated into the leaf tissue. The next day, the infected plants were sprayed to runoff point with an aqueous suspension having the concentration of active substance stated below. After drying of the sprayed suspension, the test plants were returned into the greenhouse and culti- vated at temperatures between 20 and 22°C and at 65 to 70% relative atmospheric humidity for a further 7 days. The extent of the rust development on the leaves was then determined visually. Use example 6: Protective action against Puccinia recondita on wheat (brown rust of wheat)
Leaves of potted wheat seedlings of the cultivar "Kanzler" were sprayed to runoff point with an aqueous suspension having the concentration of active substance stated below. The next day, the treated plants were dusted with a suspension of spores of brown rust of wheat (Puccinia recondita). The plants were then placed in a chamber with high atmospheric humidity (90 to 95%), at 20-220C, for 24 hours. During this time, the spores germinated and the germinal tubes penetrated into the leaf tissue. The next day, the test plants were returned into the greenhouse and cultivated at temperatures between 20 and 22°C and at 65 to 70% relative atmospheric humidity for a further 7 days. The extent of the rust development on the leaves was then determined visually.
Use example 7: Protective action against Blumeria graminis tritici on wheat (mildew of wheat)
Leaves of potted wheat seedlings of the cultivar "Kanzler" were sprayed to runoff point with an aqueous suspension having the concentration of active substance stated below. The next day, the treated plants were dusted with a suspension of spores of mil- dew of wheat (Blumeria graminis tritici). The plants were then returned into the greenhouse and cultivated at temperatures between 20 and 24°C and at 60 to 90% relative atmospheric humidity for a further 7 days. The extent of the mildew development on the leaves was then determined visually.
Use example 8: Protective action against Sphaerotheca fuliginea on cucumber (mildew of cucumber)
Leaves of potted cucumber seedlings (in the germ layer stage) were sprayed to runoff point with an aqueous suspension having the concentration of active substance stated below. The next day, the treated plants were dusted with a suspension of spores of mildew of cucumber (Sphaerotheca fuliginea). The plants were then returned into the greenhouse and cultivated at temperatures between 20 and 24°C and at 60 to 80% relative atmospheric humidity for a further 7 days. The extent of the mildew development on the seed leaves was then determined visually.

Claims

We claim:
1. Triazole compounds of the formulae I and Il
Figure imgf000170_0001
wherein
Ar is phenyl which may carry 1 , 2, 3, 4 or 5 substituents R2, or is a 3-, A-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2, 3 or 4 substituents
R3;
Het is a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2, 3 or 4 substituents R4;
A is a linear d-Cs-alkylene bridge which may be substituted by 1 , 2, 3 or 4 substituents R5;
Y is O, S or NR6;
R1 is selected from hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C2-Cio-haloalkynyl, C3-Cio-cycloalkyl,
C3-Cio-halocycloalkyl, phenyl, phenyl-Ci-C4-alkyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R7, and a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents
R7; or, in case m is 0, may also be selected from -C(=O)R8, -C(=S)R8, -S(O)2R8, -CN, -P(=Q)R9R10, M and a group of the formula III
Figure imgf000171_0001
wherein
Ar, Het, A and Y are as defined for formulae I and II; and # is the attachment point to the remainder of the molecule;
R1a is selected from hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C2-Cio-haloalkynyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, phenyl, phenyl-Ci-C4-alkyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R7, a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents R7, -C(=O)R8, -C(=S)R8, -S(O)2R8, -CN, -P(=Q)R9R10 and M;
each R2 is independently selected from halogen, OH, SH, NO2, CN, Ci-C4-alkyl,
Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4- haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkenyloxy, Ci-C4-haloalkenyloxy, Ci-C4-alkynyloxy, Ci- C4-haloalkynyloxy, Cs-Cs-cycloalkoxy, Cs-Cs-halocycloalkoxy, C1-C4- alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkenylylthio, Ci-C4-haloalkynylylthio, phenyl, phenyl-Ci-C4-alkyl, phenyl-Ci-C4-alkoxy, phenoxy, phenylthio, where the phenyl moiety in the 5 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R11; 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximum unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents R11; COR12, COOR12, CONR13R14, NR13R14 and S(O)PR12, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R15 and where the cycloaliphatic moieties in the above radicals may carry 1 , 2 or 3 substitu- ents R16; or
two radicals R2 bound on adjacent carbon ring atoms, together with the carbon ring atoms to which they are bound, form a partly unsaturated or maximum unsaturated 5-, 6- or 7-membered carbocyclic ring or a partly un- saturated or maximum unsaturated 5-, 6- or 7-membered heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members; where the carbocyclic or heterocyclic ring may carry 1 , 2 or 3 sub- stituents R11;
each R3 is independently selected from halogen, OH, SH, NO2, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4- haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkenyloxy, Ci-C4-haloalkenyloxy, Ci-C4-alkynyloxy, Ci- C4-haloalkynyloxy, Cs-Cs-cycloalkoxy, Cs-Cs-halocycloalkoxy, C1-C4- alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkenylylthio, Ci-C4-haloalkynylylthio, phenyl, phenyl-Ci-C4-alkyl, phenyl-Ci-C4-alkoxy, phenoxy, phenylthio, where the phenyl moiety in the 5 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R11; 3-, 4-, 5-, 6- or 7-membered saturated, partially un- saturated or maximum unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents R11; COR12, COOR12, CONR13R14, NR13R14 and S(O)PR12, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R15 and where the cycloaliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R16; or
two radicals R3 bound on adjacent ring atoms, together with the ring atoms to which they are bound, form a partly unsaturated or maximum unsatu- rated 5-, 6- or 7-membered carbocyclic ring or a partly unsaturated or maximum unsaturated 5-, 6- or 7-membered heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members; where the carbocyclic or heterocyclic ring may carry 1 , 2 or 3 substituents R11;
each R4 is independently selected from halogen, OH, SH, NO2, CN, Ci-C4-alkyl,
Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4- haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C4-alkoxy, C1-C4- haloalkoxy, Ci-C4-alkenyloxy, Ci-C4-haloalkenyloxy, Ci-C4-alkynyloxy, Ci- C4-haloalkynyloxy, Cs-Cs-cycloalkoxy, Cs-Cs-halocycloalkoxy, C1-C4- alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkenylylthio, Ci-C4-haloalkynylylthio, phenyl, phenyl-Ci-C4-alkyl, phenyl-Ci-C4-alkoxy, phenoxy, phenylthio, where the phenyl moiety in the 5 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R11; 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or maximum unsaturated heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents R11; COR12, COOR12, CONR13R14, NR13R14 and S(O)PR12, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R15 and where the cycloaliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R16; or
two radicals R4 bound on adjacent ring atoms, together with the ring atom to which they are bound, form a partly unsaturated or maximum unsatu- rated 5-, 6- or 7-membered carbocyclic ring or a partly unsaturated or maximum unsaturated 5-, 6- or 7-membered heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from O, S and N as ring members; where the carbocyclic or heterocyclic ring may carry 1 , 2 or 3 substituents R11;
each R5 is independently selected from halogen, OH, SH, NR13R14, Ci-C4-alkyl,
Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4- haloalkynyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and C1-C4- haloalkylthio, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R15; or
two radicals R5 bound on two adjacent carbon atoms, together with the carbon atoms to which they are bound, form a 3-, 4-, 5-, 6- or 7-membered saturated, partly unsaturated or maximum unsaturated carbocyclic ring or a 3-, 4-, 5-, 6- or 7-membered saturated, partly unsaturated or maximum un- saturated heterocyclic ring containing 1 , 2, or 3 heteroatoms selected from
O, S and N as ring members, where the carbocyclic or heterocyclic ring may carry 1 , 2 or 3 substituents R11;
R6 is selected from hydrogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, Ci-C4-alkoxy, Ci-C4- haloalkoxy, phenyl, phenyl-Ci-C4-alkyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R11; COR12, COOR12, CONR13R14 and S(O)PR12;
each R7 is independently selected from halogen, OH, SH, NR13R14, CN, NO2, Ci-
C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and Ci- C4-haloalkylthio, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R15; R8 is selected from hydrogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, Ci- Cio-haloalkoxy, Ci-Cio-aminoalkyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, phenyl, phenyl-Ci-C4-alkyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R7, a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents R7, and NR13R14;
R9 and R10, independently of each other, are selected from Ci-Cio-alkyl, Ci-Cio- haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C2-C10- haloalkynyl, C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, Ci-Cio-alkoxy, C1-C10- haloalkoxy, Ci-C4-alkoxy-Ci-Cio-alkyl, Ci-C4-alkoxy-Ci-Cio-alkoxy, C1-C10- alkylthio, Ci-Cio-haloalkylthio, C2-Cio-alkenyloxy, C2-Cio-alkenylthio, C2-C10- alkynyloxy, C2-Cio-alkynylthio, C3-Cio-cycloalkoxy, C3-Cio-cycloalkylthio, phenyl, phenyl-Ci-C4-alkyl, phenylthio, phenyl-Ci-C4-alkoxy, and NR13R14;
each R11 is independently selected from halogen, OH, SH, NR13R14, CN, NO2, Ci-
C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and Ci-
C4-haloalkylthio, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R15;
each R12 is independently selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, Ci-C4-aminoalkyl, phenyl, phenyl-Ci-C4- alkyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R11, and a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents R11;
each R13 is independently selected from hydrogen and Ci-Cs-alkyl;
each R14 is independently selected from hydrogen, Ci-Cs-alkyl, phenyl, and phenyl-Ci-C4-alkyl;
or R13 and R14 together form a linear C4- or Cs-alkylene bridge or a group -CH2CH2OCH2CH2- or -CH2CH2NR17CH2CH2-; each R15 is independently selected from nitro, CN, OH, SH, COR12, COOR12, CONR13R14; NR13R14, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Cβ-cycloaloxy, phenyl and phenoxy;
each R16 is independently selected from nitro, CN, OH, SH, COR12, COOR12,
CONR13R14; NR13R14, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Cβ-cycloaloxy, phenyl and phenoxy;
each R17 is independently selected from hydrogen and Ci-C4-alkyl;
Q is O or S;
M is a metal cation equivalent or an ammonium cation of formula (NRaRbRcRd)+, wherein Ra, Rb, Rc and Rd, independently of each other, are selected from hydrogen, Ci-Cio-alkyl, phenyl and benzyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2 or 3 substituents independently selected from halogen, CN, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and NR13R14;
m is O, 1 or 2; and
p is 1 or 2;
and the agriculturally acceptable salts thereof.
2. The compounds of formulae I and Il as claimed in claim 1 , where Ar is phenyl, which may carry 1 , 2, 3, 4 or 5 substituents R2, or is a 5- or 6-membered het- eroaromatic ring containing 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where the heteroaromatic ring may carry 1 , 2, 3 or 4 substituents
R3.
3. The compounds of formulae I and Il as claimed in claim 2, where Ar is phenyl, which may carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, substituents R2, or is a 5- or 6-membered heteroaromatic ring selected from pyridyl, pyrimidyl, furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl and tria- zolyl, where the heteroaromatic ring may carry 1 , 2, 3 or 4, preferably 1 or 2, substituents R3.
4. The compounds of formulae I and Il as claimed in claim 3, where Ar is phenyl, which may carry 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3, substituents R2, or is a 5- or 6-membered heteroaromatic ring selected from pyridyl, thienyl and thiazolyl and preferably pyridyl, where the heteroaromatic ring may carry 1 , 2, 3 or 4, prefera- bly 1 or 2, substituents R3.
5. The compounds of formulae I and Il as claimed in an of the preceding claims, where Het is a 5- or 6-membered heteroaromatic ring containing 1 , 2 or 3 het- eroatoms selected from N, O and S as ring members, where the heteroaromatic ring may carry 1 , 2, 3 or 4 substituents R4.
6. The compounds of formulae I and Il as claimed in claim 5, where Het is a 5- or 6- membered heteroaromatic ring selected from pyridyl, pyrimidyl, furyl, thienyl, pyr- rolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl and triazolyl, where the heteroaromatic ring may carry 1 , 2, 3 or 4, preferably 1 or 2, substituents R4.
7. The compounds of formulae I and Il as claimed in claim 6, where Het is a 5- or 6- membered heteroaromatic ring selected from pyridyl, thienyl and thiazolyl and is preferably pyridyl, where the heteroaromatic ring may carry 1 , 2, 3 or 4, preferably 1 or 2, substituents R4.
8. The compounds of formulae I and Il as claimed in any of the preceding claims, where R2, R3 and R4, independently of each other and independently of each oc- curence, are selected from halogen, OH, SH, NO2, CN, Ci-C4-alkyl, C1-C4- haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkoxy, and Ci-C4-haloalkoxy, and preferably from hydrogen, fluorine, chlorine, bromine, Ci- C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
9. The compounds of formulae I and Il as claimed in any of the preceding claims, where R8 is selected from Ci-C4-alkyl, Ci-C2-haloalkyl, Ci-C4-alkoxy, C1-C2- haloalkoxy, phenyl, phenoxy and NR13R14, where R13 is hydrogen and R14 is selected from hydrogen, Ci-C4-alkyl and phenyl, or both R13 and R14 are Ci-C4-alkyl.
10. The compounds of formulae I and Il as claimed in any of the preceding claims, where R1 is selected from hydrogen, Ci-C4-alkyl, -C(=O)R8, -S(O)2R8, -CN, M and a group of the formula III and is preferably selected from hydrogen, methyl, ethyl, propyl, isopropyl, -C(=O)CH3, -C(=O)OCH3, -C(=O)N(CH3)2, CN, a group of the formula III, an alkaline metal cation and ΛA Cu2+.
1 1. The compounds of formulae I and Il as claimed in any of the preceding claims, where R1a is selected from hydrogen, Ci-C4-alkyl, -S(O)2R8, and -C(=O)R8.
12. The compounds of formulae I and Il as claimed in any of the preceding claims, where A is a linear C2- or C3-alkyene bridge, where 1 or 2 hydrogen atoms of the alkylene bridge may be replaced by 1 or 2 substituents R5, where each R5 is independently selected from Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C1-C4- alkoxy-Ci-C4-alkoxy and Ci-C4-haloalkoxy, and preferably from methyl, ethyl, methoxy, ethoxy and methoxymethoxy, or two substituents R5 bound on adjacent carbon atoms, together with the carbon atoms to which they are bound, form a cyclopentyl or cyclohexyl ring.
13. The compounds of formulae I and Il as claimed in any of the preceding claims, where Y is O.
14. The compounds of formulae I and Il as claimed in any of the preceding claims, where m is 0.
15. Compounds of formula IV
Figure imgf000177_0001
where Ar, Het, A and Y are as defined in any of claims 1 to 8 and 12 to 14.
16. An agricultural composition comprising at least one compound of formula I, Il and/or IV as defined in any of claims 1 to 15 or an agriculturally acceptable salt thereof and a liquid or solid carrier.
17. The use of a compound of formula 1 , 11 and/or IV as defined in any of claims 1 to 15 for controlling harmful fungi.
18. A method for controlling harmful fungi, wherein the fungi, their habitat or the materials or plants to be protected against fungal attack, or the soil or propagation material are treated with an effective amount of at least compound of formula IJI and/or IV, where compounds I, Il and IV are as defined in any of claims 1 to 15.
19. Seed, comprising at least compound of formula I, Il and/or IV, where compounds 1 , 11 and IV are as defined in any of claims 1 to 15, in an amount of from 0.1 g to
10 kg per 100 kg of seeds.
20. A pharmaceutical composition comprising at least one compound of formula I, Il and/or IV as defined in any of claims 1 to 15 or a pharmaceutically acceptable salt thereof and at least one pharmaceutically acceptable carrier.
21. The use of a compound of formula I, Il and/or IV as defined in any of claims 1 to 15 or a pharmaceutically acceptable salt thereof for preparing a medicament for the treatment of cancer or virus infections or for preparing an antimycotic me- dicament.
22. A method for treating cancer or virus infections or for combating zoopathogenic or humanpathogenic fungi, which comprises treating an individual in need thereof with at least one compound of formula 1 , 11 and/or IV as defined in any of claims 1 to 15, with at least one pharmaceutically acceptable salt thereof or with a pharmaceutical composition as defined in claim 20.
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