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WO2010146115A1 - Triazole compounds carrying a sulfur substituent - Google Patents

Triazole compounds carrying a sulfur substituent Download PDF

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Publication number
WO2010146115A1
WO2010146115A1 PCT/EP2010/058540 EP2010058540W WO2010146115A1 WO 2010146115 A1 WO2010146115 A1 WO 2010146115A1 EP 2010058540 W EP2010058540 W EP 2010058540W WO 2010146115 A1 WO2010146115 A1 WO 2010146115A1
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alkyl
cio
het
phenyl
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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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BASF SE
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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
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/12—Antivirals
    • 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 and to agriculturally useful salts thereof
  • 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 5 ;
  • A is a linear d-Cs-alkylene bridge which may be substituted by 1 , 2, 3 or 4 substituents R 7 ;
  • Y is O, S or NR 8 ;
  • R 1 , R 2 , R 3 and R 4 are selected from hydrogen, halogen, OH, SH, NO 2 , CN, Ci-C 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, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C 4 - alkoxy, Ci-C 4 -haloalkoxy, Ci-C 4 -alkenyloxy, Ci-C 4 -haloalkenyloxy, Ci-C 4 - alkynyloxy, Ci-C 4 -haloalkynyloxy, Cs-Cs-cycloalkoxy, Cs-Cs-halocycloalkoxy, Ci- C 4 - C 4 -
  • R 1 and R 2 or R 3 and R 4 together with the carbon atom to which they are bound, form a partly unsaturated or maximum unsaturated 5-, 6- or 7-membered carbo- cyclic 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 R 9 ;
  • each R 5 is independently selected from halogen, OH, SH, NO 2 , CN, Ci-C 4 -alkyl, CrC 4 - haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -alkynyl, C 2 -C 4 -haloalkynyl, C3- Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, CrC 4 - alkenyloxy, Ci-C 4 -haloalkenyloxy, Ci-C 4 -alkynyloxy, Ci-C 4 -haloalkynyloxy, Cs-Cs- cycloalkoxy, C3-Cs-halocycloalkoxy, Ci-C 4 -alkylthio, Ci-C 4 -haloalkyl
  • Het, A, Y, R 1 , R 2 , R 3 and R 4 are as defined for formulae I and II;
  • # is the attachment point to the remainder of the molecule
  • each R 7 is independently selected from halogen, OH, SH, NR 15 R 16 , Ci-C 4 -alkyl, Ci-C 4 - haloalkyl, C2-C 4 -alkenyl, C2-C 4 -haloalkenyl, C2-C 4 -alkynyl, C2-C 4 -haloalkynyl, Ci- C 4 -alkoxy, Ci-C 4 -haloalkoxy, Ci-C 4 -alkylthio and Ci-C 4 -haloalkylthio, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R 18 ; or
  • R 8 is selected from hydrogen, CN, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, C2-C 4 -alkenyl, C 2 -C 4 - haloalkenyl, C2-C 4 -alkynyl, C2-C 4 -haloalkynyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, phenyl, phenyl-Ci-C 4 -alkyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R 9 ; COR 10 , COOR 10 , CONR 15 R 16 and
  • each R 9 is independently selected from halogen, OH, SH, NR 15 R 16 , CN, NO 2 , Ci-C 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 18 ;
  • each R 10 is independently selected from hydrogen, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, C 2 -C 4 - alkenyl, C 2 -C 4 -haloalkenyl, Ci-C 4 -aminoalkyl, phenyl, phenyl-Ci-C 4 -alkyl, where the phenyl moiety in the 2 last-mentioned radicals may carry 1 , 2, 3, 4 or 5 substituents R 9 , 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 R 9 ;
  • each R 11 is independently selected from halogen, OH, SH, NR 15 R 16 , CN, NO 2 , Ci-C 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 18 ;
  • R 12 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 11 , 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 11 , and NR 15 R 16 ;
  • R 13 and R 14 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, C1-C4- alkoxy-Ci-Cio-alkyl, Ci-Cio-alkylthio, C1-C10- haloalkylthio, C2-Cio-alkenyloxy, C2-Cio-alkenylthio, C2-Cio-alkynyloxy, C2-C10- alkynylthio, C3-Cio-cycloalkoxy, C3-Ciio-cycloal
  • each R 15 is independently selected from hydrogen and Ci-Cs-alkyl
  • each R 16 is independently selected from hydrogen, Ci-Cs-alkyl, phenyl, and phenyl-Ci- C 4 -alkyl;
  • R 15 and R 16 together form a linear C 4 - or Cs-alkylene bridge or a group
  • each R 17 is independently selected from hydrogen and Ci-C 4 -alkyl
  • each R 18 is independently selected from nitro, CN, OH, SH, COR 10 , COOR 10 ,
  • each R 19 is independently selected from nitro, CN, OH, SH, COR 10 , COOR 10 , CONR 15 R 16 ; NR 15 R 16 , Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 - halocycloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy, Cs-C ⁇ -cycloaloxy, phenyl and phenoxy;
  • 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 15 R 16 ;
  • n 0, 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 compounds 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 stereoisomers 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,
  • d-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-do-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-chloro
  • Ci-C3-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, i-chlorocyclobutylmethyl, i-chlorocyclopentylmethyl, 1- chlorocyclohexylmethyl, i-chlorocyclopropyl-i -ethyl, 1-chlorocyclobutyl-i -ethyl, 1- chlorocyclopentyl-1 -ethyl, i-chlorocyclohexyl-i -ethyl, i-chlorocyclopropyl ⁇ -ethyl, 1- chlorocyclobutyl-2 -ethyl, i-chlorocyclopentyl ⁇ -ethyl, i-chlorocyclohexyl ⁇ -ethyl, 2- chlorocyclopropylmethyl, 2-chlorocyclobutylmethyl, 2-chlorocyclopentylmethyl, 2- chlorocyclohexylmethyl, 2-chlorocyclopropyl-1 -ethyl
  • 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.
  • C1-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).
  • d-C ⁇ -Alkoxy is addi- tionally, 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-ethylbutoxy, 1 ,1 ,2- trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1-ethyl-i-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,
  • 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,
  • Ci-C6-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 example C 2 -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-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-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 particular 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, Ci-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, Ci-C6-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, d-Cs-alkyl, Ci-C ⁇ -alkyl, Ci-d-alkyl, C1-C2- alkyl or Cs-d-alkyl.
  • Ci-d-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, d-Ce-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, d-Ce-alkyl, Ci-d-alkyl, Ci-C 2 -alkyl or C 3 -C 4 -alkyl.
  • Examples for di-(Ci-C 4 -alkyl)- aminocarbonyl are dimethylaminocarbonyl, diethylaminocarbonyl, dipropylaminocar- bonyl, diisopropylaminocarbonyl and dibut
  • Aminoalkyl group of the formula R-NH 2 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, C-i-C ⁇ -alkyl, Ci-C 4 -alkyl or Ci-C2-alkyl.
  • Ci-C4-alkylsulfonyl examples include 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-C 4 -alkyl Ci-C 4 -alkyl (as defined above), where a hydrogen atom is replaced by a phenyl group, such as benzyl, phenethyl and the like.
  • Phenyl-Ci-C 4 -alkoxy Ci-C 4 -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 nitrogen 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,
  • 5-membered heteroaryl which is attached via nitrogen and contains one to three nitrogen atoms as ring members, such as pyrrol-1-yl, pyrazol-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 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 car- bon 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.
  • Het is bound via a C-atom to the group Y.
  • Het 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 or 2, substituents R 5 . 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, prefera- bly 1 or 2, substituents R 5 . 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 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 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, in isothiazolyl, it is
  • 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.
  • Het is a 6-membered heteroaromatic ring, this carries preferably 0, 1 , 2 or 3, more preferably 0, 1 or 2, substituents R 5 ,where the two or more substituents R 5 may be the same or different.
  • Het is a 5-membered heteroaromatic ring, this carries preferably 0, 1 or 2 substituents R 5 , where two substituents R 5 may be the same or different.
  • R 5 may be C- or N-bound, but is preferably bound to a C-atom of Het.
  • R 5 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 fluo- rine, chlorine, bromine, CH3, CF3, OCH3 and OCF3.
  • Het is selected from following formulae Het.1 to Het.49
  • radicals Het.1 and Het.4 to Het.42 preference is given to radicals Het.1 and Het.4 to Het.42, more preference to radicals Het.1 and Het.4 to Het.24, and specific preference to Het.1 , Het.8, Het.12, Het.19 and Het.22.
  • R 1 , R 2 , R 3 and R 4 are selected from hydrogen, halogen, OH, SH, NO2, CN, Ci-C4-alkyl, Ci-C 4 - haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkoxy, and Ci- C4-haloalkoxy, more preferably from hydrogen, fluorine, chlorine, bromine, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, even more preferably from hydrogen, fluorine, chlorine, bromine, CH3, CHF2, CF3, OCH3, OCHF2 and OCF3, and in par- ticular from hydrogen, fluorine, chlorine, bromine, CH3, CF3, OCH3 and OCF3.
  • R 1 , R 2 , R 3 and R 4 are hydrogen and the remaining 1 or 2 radicals R 1 , R 2 , R 3 and R 4 are selected from halogen, OH, SH, NO 2 , CN, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy-Ci-C 4 -alkyl, CrC 4 - alkoxy, Ci-C 4 -alkoxy-Ci-C 4 -alkoxy, and Ci-C4-haloalkoxy, more preferably from fluorine, chlorine, bromine, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C 4 - haloalkoxy, even more preferably from fluorine, chlorine, bromine, methyl, ethyl, CHF2, CF3, methoxy, ethoxy, OCHF2 and O
  • R 1 , R 2 , R 3 and R 4 are hydrogen and the remaining radical R 1 , R 2 , R 3 or R 4 is 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- 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, methyl, ethyl, CHF2, CF 3 , methoxy, ethoxy, OCHF2 and OCF 3 , and in particular from fluorine
  • R 1 , R 2 , R 3 and R 4 are hydrogen or R 2 , R 3 and R 4 are hydrogen and R 1 is different from hydrogen and 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, CrC 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, methyl, ethyl, CHF2, CF3, methoxy, ethoxy, OCHF2 and OCF3, particular from fluorine, chlorine, chlorine
  • R 1 , R 2 , R 3 and R 4 is selected from following combinations compiled in Table 1 :
  • R 12 is specifically Ci-C 4 -alkyl, such as methyl, ethyl, propyl, isopropyl, n- butyl, sec-butyl, isobutyl or tert-butyl, preferably methyl, or is Ci-C 4 -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 12 , R 12 is specifically methyl.
  • R 15 is hydrogen and R 16 is selected from hydrogen, d- C4-alkyl and phenyl, preferably from hydrogen and Ci-C4-alkyl; or R 15 and R 16 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 6 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 7 , where each R 7 is independ- ently 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 7 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 7 , where R 7 is Ci-C4-alkyl. Even more preferably, A is a linear C2-alkyene bridge, where 1 hydrogen atom of the alkylene bridge may be replaced by 1 substituent R 7 , where R 7 is Ci-C4-alkyl and preferably methyl. Specifically, A is -CH(CHs)-CH 2 -.
  • m is preferably 0 or 2 and more preferably 0.
  • n 0 and R 6 is H (or, alternatively, in compounds II, R 6a is H).
  • Examples for preferred compounds I and Il are compounds of formulae 1.1 to 1.96 and 11.1 to 11.48, 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 4176 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 148 to 196 Compounds of the formula 1.4 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6 is as defined in any of tables 1 to 49
  • Tables 442 to 490 Compounds of the formula 1.10 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6 is as defined in any of tables 1 to 49
  • Tables 687 to 735 Compounds of the formula 1.15 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6 is as defined in any of tables 1 to 49
  • Tables 785 to 833 Compounds of the formula 1.17 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6 is as defined in any of tables 1 to 49
  • Tables 834 to 882 Compounds of the formula 1.18 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6 is as defined in any of tables 1 to 49
  • Tables 1079 to 1 Compounds of the formula 1.23 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6 is as defined in any of tables 1 to 49
  • Tables 1373 to 1421 Compounds of the formula 1.29 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6 is as defined in any of tables 1 to 49
  • Tables 1618 to 1666 Compounds of the formula 1.34 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6 is as defined in any of tables 1 to 49
  • Tables 1716 to 1764 Compounds of the formula 1.36 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6 is as defined in any of tables 1 to 49
  • Tables 1765 to 1813 Compounds of the formula 1.37 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6 is as defined in any of tables 1 to 49
  • Tables 2010 to 2058 Compounds of the formula 1.42 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6 is as defined in any of tables 1 to 49
  • Tables 2304 to 2352 Compounds of the formula 1.48 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6 is as defined in any of tables 1 to 49
  • Table 2355 Compounds of the formula 1.51 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A
  • Table 2360 Compounds of the formula 1.56 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A
  • Table 2363 Compounds of the formula 1.59 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A
  • Table 2368 Compounds of the formula 1.64 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A
  • Table 2381 Compounds of the formula 1.77 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A
  • Tables 2586 to 2622 Compounds of the formula 11.6 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6a is as defined in any of tables 2401 to 2437
  • Tables 2771 to 2807 Compounds of the formula 11.11 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6a is as defined in any of tables 2401 to 2437
  • Tables 2808 to 2844 Compounds of the formula 11.12 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6a is as defined in any of tables 2401 to 2437
  • Tables 2993 to 3029 Compounds of the formula 11.17 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6a is as defined in any of tables 2401 to 2437
  • Tables 3215 to 3251 Compounds of the formula 11.23 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6a is as defined in any of tables 2401 to 2437
  • Tables 3400 to 3436 Compounds of the formula 11.28 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6a is as defined in any of tables 2401 to 2437
  • Tables 3474 to 3510 Compounds of the formula 11.30 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6a is as defined in any of tables 2401 to 2437
  • Tables 3511 to 3547 Compounds of the formula 11.31 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6a is as defined in any of tables 2401 to 2437
  • Tables 3696 to 3732 Compounds of the formula 11.36 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6a is as defined in any of tables 2401 to 2437
  • Tables 3918 to 3954 Compounds of the formula 11.42 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6a is as defined in any of tables 2401 to 2437
  • Tables 4103 to 4139 Compounds of the formula 11.47 in which the combination of Het, R 1 , R 2 , R 3 and R 4 for a compound corresponds in each case to one row of Table A and R 6a is as defined in any of tables 2401 to 2437
  • the radicals Het.1 to Het.49 correspond to the radicals listed above as specific embodiments of Het as groups of formulae Het.1 to Het.49.
  • 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 solvents 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
  • 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 phenol 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 0 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.
  • the radicals R 1 , R 2 , R 3 , R 4 and R 5 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, cae- sium 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, cae- sium carbonate
  • alkali metal alkoxides e.g. sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide
  • 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 6 is Ci-Cio-alkyl, Ci-Cio- 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, so- dium 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 6 is -SO2R 12 may be prepared in analogy to the method described in DE-A-19620590 by reacting a compound I, wherein m is 0 and R 6 is H, with a compound R 12 -SC"2-W, wherein R 12 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 carbonates e.g. sodium carbonate, potassium carbonate, caesium carbonate
  • alkali metal alkoxides e.g. sodium methoxide, potassium methoxide, sodium ethoxide, po- tassium 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 6 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 6 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 6 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 6 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, po- tassium 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.
  • alkali metal hydrides e.g. sodium hydride, po- tassium 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 6 S ⁇ 2CI.
  • Compounds I, wherein m is 3, can be prepared from com- pounds IV by first deprotonating the triazolyl ring and then reacting with sulfuric acid chloride or a sulfuric ester chloride of formula R 6 OS ⁇ 2CI, wherein R 6 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,
  • 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 sol- ids, they may be purified by recrystallization or digestion.
  • a further aspect of the invention relates to compounds of formula IV
  • Het, A, Y, R 1 , R 2 , R 3 and R 4 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 Het, R 1 , R 2 , R 3 and R 4 corresponds in each case to one row in table A 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 ef- fectiveness 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 cul- tivated 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.
  • leguminous plants such as lentils, peas, alfalfa or soybeans
  • compounds I, Il 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.
  • 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 IJI 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
  • sulfonyl ureas see e. g.
  • EPSPS enolpyruvylshikimate-3-phosphate synthase
  • GS glutamine synthetase
  • 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.
  • 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).
  • 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 Cry9c; 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.
  • Albugo spp. white rust
  • vegetables e. g. A. Candida
  • sunflowers e. g. A. tragopogonis
  • Altemaria spp. Alternaria leaf spot
  • vegetables rape ⁇
  • 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
  • cereals 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.
  • liriodendri Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. 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.
  • 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.
  • stem rot P. phaseoli, teleomorph: Diaporthe phaseolorum
  • Physoderma maydis brown spots
  • Phytophthora spp. wilt, root, leaf, fruit and stem root
  • paprika and cucurbits e. g. P. capsici
  • soybeans e. g. P. megasperma, syn. P. sojae
  • potatoes and tomatoes e. g. P. infestans: late blight
  • broad-leaved trees e. g. P.
  • Plasmodiophora brassicae club root
  • Plasmopara spp. e. g. P. viticola (grapevine downy mildew) on vines and P. halstediiou sunflowers
  • Podosphaera spp. powdery mildew on rosa- ceous 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.
  • Pseudocercosporella herpotrichoides eyespot, teleomorph: Tapesia yallundae
  • Pseudoperonospora downy mildew
  • Pseudopezicula tracheiphila red fire disease or , rotbrenner' , anamorph: Phialo- phora) on vines
  • Puccinia spp. rusts
  • 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 (Ram ularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp.
  • R. solani root and stem rot
  • R. so/an/ sheath blight
  • R. cerealis Rhizoctonia spring blight
  • Rhizopus stolonifer black mold, soft rot
  • Rhynchosporium secalis scald
  • seed 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 soy- beans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Sta- gonospora blotch) on cereals; Uncinula (syn.
  • Erysiphe) necator prowdery mildew, anamorph: Oidium tuckeri
  • Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. miliaria: 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.
  • S. nodorum Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum
  • 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
  • tobacco, pome fruits, vegetables, soybeans and cotton e. g. T. basicola (syn. Chalara elegans); Tilletia spp.
  • 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.
  • Ascomycetes such as Ophio- stoma spp., Cerafocysf/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.
  • Ascomycetes such as Ophio- stoma spp., Cerafocysf/s spp., Aureobasidium pullulans, Sclerophoma spp., Chae- tomium spp., Humicola spp., Petriella spp., Trichurus spp
  • 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.
  • 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 in- gredients), plant vigor [e. g. improved plant growth and/or greener leaves ("greening effect")], quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress.
  • yield e. g. increased biomass and/or increased content of valuable in- gredients
  • plant vigor e. g. improved plant growth and/or greener leaves ("greening effect")
  • quality e. g. improved content or composition of certain ingredients
  • tolerance to abiotic and/or biotic stress e. g. improved content or composition of certain ingredients
  • the compounds of formula I, 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 IJI 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.
  • 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.
  • 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.
  • 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).
  • composition types e. g. SC, OD, FS, EC, WG, SG, WP, SP, SS, WS, GF
  • 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, 4 th Ed., McGraw-Hill, New York, 1963, pp.
  • the agrochemical compositions may also comprise auxiliaries which are customary in agrochemical compositions.
  • auxiliaries depend on the particular application form and active substance, respectively.
  • 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.
  • 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,
  • 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.
  • 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
  • Suitable surfactants 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,
  • aromatic sulfonic acids such as ligninsoulfonic acid (Borresperse
  • methylcellulose 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.
  • thickeners i. e. compounds that impart a modified flowability to compositions, i. e. high viscosity under static conditions and low viscosity during agitation
  • thickeners 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.
  • 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- ziothiazolinones (Acticide ® MBS from Thor Chemie).
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • anti-foaming agents examples include 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. Exam- pies to be mentioned und the designations rhodamin B, C. I. pigment red 1 12, 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.
  • tackifiers or binders examples include 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.
  • 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.
  • ammonium sulfate ammonium phosphate, ammonium nitrate, ureas
  • products of vegetable origin such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • composition types are:
  • Water-soluble concentrates 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.
  • 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.
  • a compound I according to the invention 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.
  • a dispersant e. g. polyvinylpyrrolidone.
  • Dilution with water gives a dispersion.
  • the active substance con- tent is 20% by weight.
  • composition 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.
  • Emulsions 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.
  • a compound I according to the invention 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.
  • 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.
  • a compound I according to the invention 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.
  • composition types to be applied undiluted 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.
  • 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.
  • Granules 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.
  • 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 compositions 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.
  • 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.
  • a suspension-type (FS) composition is used for seed treatment.
  • 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.
  • 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.
  • 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.
  • UUV ultra-low-volume process
  • 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.
  • 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.
  • 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.
  • 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 ® .
  • 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
  • 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).
  • 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).
  • 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-difluor
  • 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)- cyclole
  • 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 -( ⁇ -bromo-S-chloro-pyridin ⁇ -yO-ethyO ⁇ -dichloronicotinamide,
  • 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,
  • (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: bom
  • 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
  • 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.
  • 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.
  • 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).
  • 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).
  • 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 I, Il 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 infected 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.
  • 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.
  • 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 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :3 to 3:1.
  • 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
  • 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.
  • kits may include one or more, including all, components that may be used to prepare a subject agrochemical composition.
  • 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.
  • 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.
  • two or more components of a kit may be packaged separately, i. e., not pre- formulated.
  • 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.
  • 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.
  • 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.
  • 50 to 500 liters of the ready-to-use spray liquor are applied per hectare of agricultural useful area, preferably 100 to 400 liters.
  • 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).
  • 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
  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • component 1 a compound I, Il and/or IV
  • 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 B-1 to B-346 of Table B.
  • a further embodiment relates to the compositions B-1 to B-346 listed in Table B, where a row of Table B 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.
  • the compositions described comprise the active substances in synergistically effective amounts.
  • Table B Composition comprising one indiviualized compound I, Il or IV and one further active substance from groups A) to I) MixComponent 1
  • B-1 10 one individualized compound I, Il or IV 2-yl)-ethyl)-2,4-dichloro- nicotinamide
  • component 2 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 nomenclature, their preparation and their fungicidal activity are also known (cf. Can. J. Plant Sci.
  • 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.
  • compositions containing compounds I, Il and/or IV Concerning usual ingredients of such compositions reference is made to the explana- tions 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, espe- daily 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 I, Il and/or IV respectively.
  • the compounds I, Il 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.
  • 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.
  • 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.
  • 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.
  • 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 I, Il 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 I, Il 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 I, Il 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 man- ner, for example orally, intravenously, intramuscularly or subcutaneously.
  • 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.
  • 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
  • flavors such as peppermint, vanilla and the like.
  • Capsules may furthermore comprise a liquid carrier.
  • syrups or potions may also comprise sugar (or other sweeteners), methyl- or propylparaben as preservative, a colorant and/or a flavor.
  • sugar or other sweeteners
  • methyl- or propylparaben as preservative
  • a colorant or a flavor.
  • the components of the active compound preparations must, of course, be pharmaceutically pure and nontoxic at the quantities employed.
  • 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 intraperitoneal ⁇ .
  • 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 microorgan- isms.
  • 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.
  • 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 active substances were formulated separately as a stock solution in dimethyl sulfoxide (DMSO) at a concentration of 10 000 ppm.
  • DMSO dimethyl sulfoxide
  • 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.
  • the MTPs were measured at 405 nm on day 7 after the inoculation.
  • 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.
  • 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 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 volume 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.
  • DMSO dimethyl sulfoxide
  • Wettol EM 31 wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols
  • 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 20 0 C and a relative humidity close to 100%, the extent of fungal attack on the leaves was visually assessed as % diseased leaf area.
  • Use example 7 Protective action against Blumeria graminis triticiou 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 develop- ment on the seed leaves was then determined visually.

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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 and to agriculturally useful salts thereof
Figure imgf000002_0001
wherein 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 R5;
A is a linear d-Cs-alkylene bridge which may be substituted by 1 , 2, 3 or 4 substituents R7;
Y is O, S or NR8;
R1, R2, R3 and R4, independently of each other, are selected from hydrogen, 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, Ci-C4-haloalkoxy, Ci-C4-alkenyloxy, Ci-C4-haloalkenyloxy, Ci-C4- alkynyloxy, Ci-C4-haloalkynyloxy, Cs-Cs-cycloalkoxy, Cs-Cs-halocycloalkoxy, Ci- 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 R9; 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 R9; COR10, COOR10, CONR15R16, NR15R16 and S(O)PR10, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R18 and where the cycloaliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R19; or
R1 and R2 or R3 and R4, together with the carbon atom to which they are bound, form a partly unsaturated or maximum unsaturated 5-, 6- or 7-membered carbo- cyclic 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 R9;
each R5 is independently selected from halogen, OH, SH, NO2, CN, Ci-C4-alkyl, CrC4- 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, CrC4- alkenyloxy, Ci-C4-haloalkenyloxy, Ci-C4-alkynyloxy, Ci-C4-haloalkynyloxy, Cs-Cs- cycloalkoxy, C3-Cs-halocycloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, CrC4- 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 R9; 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 R9; COR10, COOR10, CONR15R16, NR15R16 and S(O)PR10, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R18 and where the cycloaliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R19; or
two radicals R5 bound on adjacent ring atoms (of Het), together 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 R9;
R6 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 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; or, in case m is O, may also be selected from -C(=O)R12, -C(=S)R12, -S(O)2R12, -CN, -P(=Q)R13R14, M and a group of the formula III
Figure imgf000004_0001
wherein
Het, A, Y, R1, R2, R3 and R4 are as defined for formulae I and II; and
# is the attachment point to the remainder of the molecule;
R6a 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 R11, 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, -C(=O)R12, -C(=S)R12, -S(O)2R12, -CN, - P(=Q)R13R14 and M;
each R7 is independently selected from halogen, OH, SH, NR15R16, 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 R18; or
two radicals R7 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 R9;
R8 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 R9; COR10, COOR10, CONR15R16 and
each R9 is independently selected from halogen, OH, SH, NR15R16, 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 CrC4- haloalkylthio, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R18;
each R10 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 R9, 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 R9;
each R11 is independently selected from halogen, OH, SH, NR15R16, 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 CrC4- haloalkylthio, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R18;
R12 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 R11, 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, and NR15R16;
R13 and R14, 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, C1-C4- alkoxy-Ci-Cio-alkyl,
Figure imgf000006_0001
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 NR15R16;
each R15 is independently selected from hydrogen and Ci-Cs-alkyl;
each R16 is independently selected from hydrogen, Ci-Cs-alkyl, phenyl, and phenyl-Ci- C4-alkyl;
or R15 and R16 together form a linear C4- or Cs-alkylene bridge or a group
-CH2CH2OCH2CH2- or -CH2CH2NR17CH2CH2-;
each R17 is independently selected from hydrogen and Ci-C4-alkyl;
each R18 is independently selected from nitro, CN, OH, SH, COR10, COOR10,
CONR15R16; NR15R16, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkoxy, CrC4- haloalkoxy, Cs-Cβ-cycloaloxy, phenyl and phenoxy;
each R19 is independently selected from nitro, CN, OH, SH, COR10, COOR10, CONR15R16; NR15R16, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Cs-Cβ-cycloaloxy, phenyl and phenoxy;
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 NR15R16;
m is 0, 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 compounds 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 stereoisomers 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 R6/R6a are identical. In case R6 (and of course also R6a) 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 tr i (C 1 -C4-a I ky I ) s u If- 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. d-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-do-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 (C3-C8-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, i-chlorocyclobutylmethyl, i-chlorocyclopentylmethyl, 1- chlorocyclohexylmethyl, i-chlorocyclopropyl-i -ethyl, 1-chlorocyclobutyl-i -ethyl, 1- chlorocyclopentyl-1 -ethyl, i-chlorocyclohexyl-i -ethyl, i-chlorocyclopropyl^-ethyl, 1- chlorocyclobutyl-2 -ethyl, i-chlorocyclopentyl^-ethyl, i-chlorocyclohexyl^-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-i -ethyl, 1-fluorocyclobutyl-i -ethyl, 1- fluorocyclopentyl-1 -ethyl, 1-fluorocyclohexyl-i -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. C1-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). d-Cβ-Alkoxy is addi- tionally, 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-ethylbutoxy, 1 ,1 ,2- trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1-ethyl-i-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 OC2Fs. 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-C6-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 example 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 particular 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, Ci-Cβ-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, Ci-C6-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, d-Cs-alkyl, Ci-Cβ-alkyl, Ci-d-alkyl, C1-C2- alkyl or Cs-d-alkyl. Examples for Ci-d-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, d-Ce-alkyl, Ci-d-alkyl, Ci-C2-alkyl or C3-C4-alkyl. Examples for di-(Ci-C4-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, C-i-Cβ-alkyl, Ci-C4-alkyl or Ci-C2-alkyl. Examples for Ci-C4-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 selected 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 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-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-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1 ,3,5-hexahydrotriazin-2-yl and 1 ,2,4-hexahydrotriazin-3-yl and also the corresponding -ylidene radicals;
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 nitrogen 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, pyrazol-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- 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 car- bon 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 Het, A, Y, R1, R2, R3, R4, R5, R6, R6a, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, 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, Het is bound via a C-atom to the group Y.
In a preferred embodiment of the invention, Het 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 or 2, substituents R5. 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, prefera- bly 1 or 2, substituents R5. 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 preference is given to 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 preference is given to pyridyl, such as pyridin-2-yl, pyridin-3-yl or pyridin-4-yl, and especially to pyridin-2-yl. In case Het is a 6-membered heteroaromatic ring, this carries preferably 0, 1 , 2 or 3, more preferably 0, 1 or 2, substituents R5,where the two or more substituents R5 may be the same or different. In case Het is a 5-membered heteroaromatic ring, this carries preferably 0, 1 or 2 substituents R5, where two substituents R5 may be the same or different.
R5 may be C- or N-bound, but is preferably bound to a C-atom of Het.
R5 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 fluo- rine, chlorine, bromine, CH3, CF3, OCH3 and OCF3.
Specifically, Het is selected from following formulae Het.1 to Het.49
Figure imgf000021_0001
Het 1 Het 2 Het 3 Het 4 Het 5 Het 6 Het 7 Het 8
Figure imgf000021_0002
Het 9 Het 10 Het 11 Het 12 Het 13 Het 14 Het 15 Het 16
Figure imgf000021_0003
Het 17 Het 18 Het 19 Het 20 Het 21 Het 22 Het 23 Het 24
Figure imgf000021_0004
Het 25 Het 26 Het 27 Het 28 Het 29 Het 30 Het 31
Figure imgf000021_0005
32 Het 33 Het 34 Het 35 Het 36 Het 37 et 38
Figure imgf000022_0001
Het 39 Het 40 Het 41 Het 42
Figure imgf000022_0002
Het 43 Het 44 Het 45 Het 46 Het 47 Het 48 Het 49
Among the above formulae, preference is given to radicals Het.1 and Het.4 to Het.42, more preference to radicals Het.1 and Het.4 to Het.24, and specific preference to Het.1 , Het.8, Het.12, Het.19 and Het.22.
In a preferred embodiment of the invention, R1, R2, R3 and R4, independently of each other, are selected from hydrogen, 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 hydrogen, fluorine, chlorine, bromine, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, even more preferably from hydrogen, fluorine, chlorine, bromine, CH3, CHF2, CF3, OCH3, OCHF2 and OCF3, and in par- ticular from hydrogen, fluorine, chlorine, bromine, CH3, CF3, OCH3 and OCF3.
In a more preferred embodiment of the invention, 2, 3 or all 4 of R1, R2, R3 and R4 are hydrogen and the remaining 1 or 2 radicals R1, R2, R3 and R4 are selected from halogen, OH, SH, NO2, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, CrC4- 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, methyl, ethyl, CHF2, CF3, methoxy, ethoxy, OCHF2 and OCF3, and in particular from fluorine, chlorine, bromine, CH3, CF3, OCH3 and OCF3. Even more preferably, 3 or all 4 of R1, R2, R3 and R4 are hydrogen and the remaining radical R1, R2, R3 or R4 is 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, methyl, ethyl, CHF2, CF3, methoxy, ethoxy, OCHF2 and OCF3, and in particular from fluorine, chlorine, bromine, CH3, CF3, OCH3 and OCF3. In particular, R1, R2, R3 and R4 are hydrogen or R2, R3 and R4 are hydrogen and R1 is different from hydrogen and is preferably selected from halogen, OH, SH, NO2, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxy, CrC4- 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, methyl, ethyl, CHF2, CF3, methoxy, ethoxy, OCHF2 and OCF3, particular from fluorine, chlorine, bromine, CH3, CF3, OCH3 and OCF3 and is specifically methyl.
Specifically, the combined meaning of R1, R2, R3 and R4 is selected from following combinations compiled in Table 1 :
Table 1
Figure imgf000023_0001
Figure imgf000024_0001
R12 in the groups -C(=O)R12 and -S(O)2R12 is preferably selected from Ci-C4-alkyl, Ci- C2-haloalkyl, Ci-C4-alkoxy, Ci-C2-haloalkoxy, phenyl, phenoxy and NR15R16, more preferably from Ci-C4-alkyl, Ci-C2-haloalkyl, Ci-C4-alkoxy, Ci-C2-haloalkoxy and NR15R16 and even more preferably from Ci-C4-alkyl, Ci-C4-alkoxy and NR15R16. In the group -C(=O)R12, R12 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)2R12, R12 is specifically methyl. Preferably, R15 is hydrogen and R16 is selected from hydrogen, d- C4-alkyl and phenyl, preferably from hydrogen and Ci-C4-alkyl; or R15 and R16 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.
R6 is preferably selected from hydrogen, Ci-C4-alkyl, -C(=O)R12, -S(O)2R12, -CN, M and a group of the formula III, where R12 has one of the above general meanings or, in par- ticular, 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.
R6 is more preferably selected from hydrogen, Ci-C4-alkyl, C3-C4-alkylcarbonyl, C1-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, R6 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 1/4 Cu2+. Specifically, R6 is hydrogen, methyl, methylcarbonyl, methoxycarbonyl, Na+ or a group of the formula III.
R6a is preferably selected from hydrogen, Ci-Cio-alkyl, Ci-C4-haloalkyl, phenyl, phenyl- Ci-C4-alkyl, -C(=O)R12 and -S(O)2R12, where R12 has one of the above given general or, in particular, one of the above-given preferred meanings. More preferably, R6a is selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, phenyl, benzyl, -C(=O)R12 and -S(O)2R12, where R12 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)R12 and -S(O)2R12, where R12 has one of the above given general or, in particular, one of the above-given preferred meanings. In particular, R6a is hydrogen, Ci-C4-alkyl, preferably methyl, or -C(=O)R12, more particularly hydrogen, C1-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 R7, where each R7 is independ- ently 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 R7 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 R7, where R7 is Ci-C4-alkyl. Even more preferably, A is a linear C2-alkyene bridge, where 1 hydrogen atom of the alkylene bridge may be replaced by 1 substituent R7, where R7 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-R6 thus resulting in a group -S(=O)-R6. 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-R6 thus resulting in a group -S(=O)2-R6. If m is 3, the radical -S(O)m-R6 is a group -S(=O)2- O-R6.
m is preferably 0 or 2 and more preferably 0.
In a particularly preferred embodiment, in compounds I, m is 0 and R6 is H (or, alternatively, in compounds II, R6a is H).
Particular compounds I/I I are the following:
2-{4-methyl-2-[2-methyl-4-(pyridin-2-yloxy)-phenyl]-[1 ,3-dioxolan-2-ylmethyl}-2-H- [1 ,2,4]triazole-3-thiol; 2-{4-methyl-2-[2-methyl-4-(5-trifluoromethyl-pyridin-2-yloxy)-phenyl]-[1 ,3-dioxolan-2- ylmethyl}-2-H-[1 ,2,4]triazole-3-thiol;
2-{4-methyl-2-[4-(5-chloro-3-fluoro-pyridin-2-yloxy)-2-methyl-phenyl]-[1 ,3-dioxolan-2- ylmethyl}-2-H-[1 ,2,4]triazole-3-thiol; 2-{4-methyl-2-[4-(3,5-dichloro-pyridin-2-yloxy)-2-methyl-phenyl]-[1 ,3-dioxolan-2- ylmethyl}-2-H-[1 ,2,4]triazole-3-thiol;
2-{2-[4-(3-chloro-5-trifluoromethyl-pyridin-2-yloxy)-2-methyl-phenyl]-4-methyl-[1 ,3- dioxolan-2-ylmethyl}-2-H-[1 ,2,4]triazole-3-thiol;
2-{2-[4-(5-chloro-3-fluoro-pyridin-2-yloxy)-phenyl]-4-methyl-[1 ,3-dioxolan-2-ylmethyl}-2-
H-[1 ,2,4]triazole-3-thiol.
Examples for preferred compounds I and Il are compounds of formulae 1.1 to 1.96 and 11.1 to 11.48, 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 4176 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 imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000033_0002
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000035_0002
R
Figure imgf000036_0001
R R R
Figure imgf000036_0002
R R
Figure imgf000036_0003
R R R
Figure imgf000036_0004
R RM RM RM
Figure imgf000036_0005
Figure imgf000037_0001
Table 1
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is H
Table 2 Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is methyl
Table 3
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is ethyl Table 4
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is propyl
Table 5
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is isopropyl
Table 6
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is n-butyl
Table 7 Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is sec-butyl
Table 8
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is isobutyl Table 9
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is tert-butyl
Table 10 Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is phenyl
Table 11
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is benzyl Table 12
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is Li+
Table 13
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is Na+
Table 14
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is is K+
Table 15 Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is R6 is YiMg2+
Table 16
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is /4Cu2+ Table 17
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is /4Zn2+
Table 18
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is /4Fe2+
Table 19
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is VzNi2+
Table 20 Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is NH(CH3)3+
Table 21
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is NH(C2H5)3+ Table 22
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is
Figure imgf000039_0001
Table 23
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is NH(CH(CHs)2)3+
Table 24
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is
Figure imgf000039_0002
Table 25
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is methylcarbonyl Table 26
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is ethylcarbonyl
Table 27
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is propylcarbonyl
Table 28
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is isopropylcarbonyl
Table 29 Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is methoxycarbonyl
Table 30
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is ethoxycarbonyl Table 31
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is propoxycarbonyl
Table 32
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is isopropoxycar- bonyl
Table 33
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is phenoxycarbonyl Table 34
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is methylaminocar- bonyl Table 35
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is ethylaminocar- bonyl
Table 36 Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is propylaminocar- bonyl
Table 37
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is isopropylamino- carbonyl
Table 38
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is phenylaminocar- bonyl
Table 39
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is methylsulfonyl
Table 40 Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is ethylsulfonyl
Table 41
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is propylsulfonyl Table 42
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is isopropylsulfonyl
Table 43
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is phenylsulfonyl
Table 44
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is methoxysulfonyl
Table 45 Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is ethoxysulfonyl
Table 46
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is propoxysulfonyl
Table 47
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is isopropoxysul- fonyl Table 48
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is phenoxysulfonyl
Table 49
Compounds of the formula 1.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is CN
Tables 50 to 98
Compounds of the formula 1.2 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49 Tables 99 to 147
Compounds of the formula 1.3 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 148 to 196 Compounds of the formula 1.4 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 197 to 245
Compounds of the formula 1.5 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 246 to 294
Compounds of the formula 1.6 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 295 to 343
Compounds of the formula 1.7 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49 Tables 344 to 392
Compounds of the formula 1.8 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49 Tables 393 to 441
Compounds of the formula 1.9 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 442 to 490 Compounds of the formula 1.10 in which the combination of Het, R1 , R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 491 to 539
Compounds of the formula 1.11 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 540 to 588
Compounds of the formula 1.12 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 589 to 637
Compounds of the formula 1.13 in which the combination of Het, R1 , R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49 Tables 638 to 686
Compounds of the formula 1.14 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 687 to 735 Compounds of the formula 1.15 in which the combination of Het, R1 , R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 736 to 784
Compounds of the formula 1.16 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 785 to 833 Compounds of the formula 1.17 in which the combination of Het, R1 , R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 834 to 882 Compounds of the formula 1.18 in which the combination of Het, R1 , R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 883 to 931
Compounds of the formula 1.19 in which the combination of Het, R1 , R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 932 to 980
Compounds of the formula 1.20 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 981 to 1029
Compounds of the formula 1.21 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49 Tables 1030 to 1078
Compounds of the formula 1.22 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 1079 to 1 127 Compounds of the formula 1.23 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 1128 to 1 176
Compounds of the formula 1.24 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 1177 to 1225
Compounds of the formula 1.25 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 1126 to 1274
Compounds of the formula 1.26 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49 Tables 1275 to 1323
Compounds of the formula 1.27 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49 Tables 1324 to 1372
Compounds of the formula 1.28 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 1373 to 1421 Compounds of the formula 1.29 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 1422 to 1470
Compounds of the formula 1.30 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 1471 to 1519
Compounds of the formula 1.31 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 1520 to 1568
Compounds of the formula 1.32 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49 Tables 1569 to 1617
Compounds of the formula 1.33 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 1618 to 1666 Compounds of the formula 1.34 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 1667 to 1715
Compounds of the formula 1.35 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 1716 to 1764 Compounds of the formula 1.36 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 1765 to 1813 Compounds of the formula 1.37 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 1814 to 1862
Compounds of the formula 1.38 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 1863 to 191 1
Compounds of the formula 1.39 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 1912 to 1960
Compounds of the formula 1.40 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49 Tables 1961 to 2009
Compounds of the formula 1.41 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 2010 to 2058 Compounds of the formula 1.42 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 2059 to 2107
Compounds of the formula 1.43 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 2108 to 2156
Compounds of the formula 1.44 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 2157 to 2205
Compounds of the formula 1.45 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49 Tables 2206 to 2254
Compounds of the formula 1.46 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49 Tables 2255 to 2303
Compounds of the formula 1.47 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Tables 2304 to 2352 Compounds of the formula 1.48 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6 is as defined in any of tables 1 to 49
Table 2353
Compounds of the formula 1.49 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2354
Compounds of the formula 1.50 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2355 Compounds of the formula 1.51 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2356
Compounds of the formula 1.52 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A Table 2357
Compounds of the formula 1.53 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2358
Compounds of the formula 1.54 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2359
Compounds of the formula 1.55 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2360 Compounds of the formula 1.56 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2361
Compounds of the formula 1.57 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A Table 2362
Compounds of the formula 1.58 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2363 Compounds of the formula 1.59 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2364
Compounds of the formula 1.60 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A Table 2365
Compounds of the formula 1.61 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2366
Compounds of the formula 1.62 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2367
Compounds of the formula 1.63 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2368 Compounds of the formula 1.64 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2369
Compounds of the formula 1.65 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A Table 2370
Compounds of the formula 1.66 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2371
Compounds of the formula 1.67 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2372
Compounds of the formula 1.68 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2373 Compounds of the formula 1.69 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2374
Compounds of the formula 1.70 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A Table 2375
Compounds of the formula 1.71 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2376 Compounds of the formula 1.72 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2377
Compounds of the formula 1.73 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A Table 2378
Compounds of the formula 1.74 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2379
Compounds of the formula 1.75 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2380
Compounds of the formula 1.76 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2381 Compounds of the formula 1.77 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2382
Compounds of the formula 1.78 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A Table 2383
Compounds of the formula 1.79 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2384
Compounds of the formula 1.80 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2385
Compounds of the formula 1.81 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2386 Compounds of the formula 1.82 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2387
Compounds of the formula 1.83 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A Table 2388
Compounds of the formula 1.84 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2389 Compounds of the formula 1.85 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2390
Compounds of the formula 1.86 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A Table 2391
Compounds of the formula 1.87 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2392
Compounds of the formula 1.88 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2393
Compounds of the formula 1.89 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2394 Compounds of the formula 1.90 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2395
Compounds of the formula 1.91 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A Table 2396
Compounds of the formula 1.92 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2397
Compounds of the formula 1.93 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2398
Compounds of the formula 1.94 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2399 Compounds of the formula 1.95 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A
Table 2400
Compounds of the formula 1.96 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A Table 2401
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is H
Table 2402 Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is methyl
Table 2403
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is ethyl Table 2404
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is n-propyl
Table 2405
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is isopropyl
Table 2406
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is n-butyl
Table 2407 Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is sec-butyl
Table 2408
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is isobutyl Table 2409
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is tert-butyl
Table 2410
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is phenyl
Table 2411
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is benzyl
Table 2412 Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is methylcarbonyl
Table 2413
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is ethylcarbonyl Table 2414
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is propylcarbonyl
Table 2415 Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is isopropylcar- bonyl
Table 2416
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is phenylcarbonyl
Table 2417
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is methoxycarbonyl
Table 2418 Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is ethoxycarbonyl
Table 2419
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is propoxycarbonyl Table 2420
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is isopropoxycar- bonyl
Table 2421 Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is phenoxycarbonyl
Table 2422
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is methylamino- carbonyl
Table 2423
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is ethylaminocar- bonyl Table 2424
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is propylaminocar- bonyl
Table 2425 Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is isopropylamino- carbonyl
Table 2426 Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is phenylamino- carbonyl
Table 2427
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is methylsulfonyl
Table 2428
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is ethylsulfonyl
Table 2429 Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is propylsulfonyl
Table 2430
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is isopropylsulfonyl Table 2431
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is phenylsulfonyl
Table 2432
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is methoxysulfonyl
Table 2433
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is ethoxysulfonyl
Table 2434 Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is propoxysulfonyl
Table 2435
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is isopropoxysul- fonyl
Table 2436
Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is phenoxysulfonyl
Table 2437 Compounds of the formula 11.1 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is CN
Tables 2438 to 2474
Compounds of the formula II.2 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 2475 to 251 1
Compounds of the formula 11.3 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 2512 to 2548
Compounds of the formula 11.4 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437 Tables 2549 to 2585
Compounds of the formula 11.5 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 2586 to 2622 Compounds of the formula 11.6 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 2623 to 2659
Compounds of the formula 11.7 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 2660 to 2696
Compounds of the formula 11.8 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 2697 to 2733
Compounds of the formula 11.9 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437 Tables 2734 to 2770
Compounds of the formula 11.10 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 2771 to 2807 Compounds of the formula 11.11 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 2808 to 2844 Compounds of the formula 11.12 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 2845 to 2881
Compounds of the formula 11.13 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 2882 to 2918
Compounds of the formula 11.14 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 2919 to 2955
Compounds of the formula 11.15 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437 Tables 2956 to 2992
Compounds of the formula 11.16 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 2993 to 3029 Compounds of the formula 11.17 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3030 to 3066
Compounds of the formula 11.18 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3067 to 3103
Compounds of the formula 11.19 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3104 to 3140
Compounds of the formula 11.20 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437 Tables 3141 to 3177
Compounds of the formula 11.21 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437 Tables 3178 to 3214
Compounds of the formula 11.22 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3215 to 3251 Compounds of the formula 11.23 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3252 to 3288
Compounds of the formula 11.24 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3289 to 3325
Compounds of the formula 11.25 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3326 to 3362
Compounds of the formula 11.26 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437 Tables 3363 to 3399
Compounds of the formula 11.27 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3400 to 3436 Compounds of the formula 11.28 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3437 to 3473
Compounds of the formula 11.29 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3474 to 3510 Compounds of the formula 11.30 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3511 to 3547 Compounds of the formula 11.31 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3548 to 3584
Compounds of the formula 11.32 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3585 to 3621
Compounds of the formula 11.33 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3622 to 3658
Compounds of the formula 11.34 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437 Tables 3659 to 3695
Compounds of the formula 11.35 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3696 to 3732 Compounds of the formula 11.36 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3733 to 3769
Compounds of the formula 11.37 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3770 to 3806
Compounds of the formula 11.38 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3807 to 3843
Compounds of the formula 11.39 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437 Tables 3844 to 3880
Compounds of the formula 11.40 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437 Tables 3881 to 3917
Compounds of the formula 11.41 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3918 to 3954 Compounds of the formula 11.42 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3955 to 3991
Compounds of the formula 11.43 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 3992 to 4028
Compounds of the formula 11.44 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 4029 to 4065
Compounds of the formula 11.45 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437 Tables 4066 to 4102
Compounds of the formula 11.46 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 4103 to 4139 Compounds of the formula 11.47 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Tables 4140 to 4176
Compounds of the formula 11.48 in which the combination of Het, R1, R2, R3 and R4 for a compound corresponds in each case to one row of Table A and R6a is as defined in any of tables 2401 to 2437
Table A
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
The radicals Het.1 to Het.49 correspond to the radicals listed above as specific embodiments of Het as groups of formulae Het.1 to Het.49.
Among the above compounds, preference is given to compounds of formulae 1.1 to 1.24, 1.49 to 1.72 and 11.1 to Il .24. Among these, preference is given to compounds 1.1 , I.2, 1.13, 1.14, I.49, I.50, 1.61 , I.62, 11.1 , II.2, 11.13 and 11.14. More preference is given to compounds 1.1 , I.2, I.49, 1.50, 11.1 and II.2 and even more preference to compounds 1.2, l.50 and II.2.
Compounds of formulae I and Il can be prepared by one or more of the following meth- ods 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 R6 is H and m is 0 (or compounds II, wherein R6a 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 imgf000090_0001
(R6/R6a = 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 imgf000091_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 imgf000092_0001
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 solvents 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.
Scheme 4
Figure imgf000092_0002
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 phenol 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 2200C.
Scheme 5
Figure imgf000093_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 imgf000093_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 imgf000094_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 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 imgf000094_0002
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 imgf000094_0003
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 R1, R2, R3, R4 and R5 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 R6 is different from hydrogen and m is 0, can be pre- pared from compounds I, wherein R6 = H and m = 0.
Compounds of formula I, wherein m is 0 and R6 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 R6 is H, with a compound R6-LG, where R6 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, cae- sium 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 R6 is Ci-Cio-alkyl, Ci-Cio- 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 R6-S-S-R6 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 R6 is -C(=O)R12 or -C(=S)R12, may be prepared in analogy to the method described in DE-A-19617461 by reacting a compound I, wherein m is 0 and R6 is H, with a compound R12-C(=0)-W, R12-C(=S)-W, R12'- N=C=O or R12'-N=C=S, wherein R12 has one of the above meanings, R12' is C1-C10- alkyl or Ci-Cio-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, so- dium 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 R6 is -SO2R12, may be prepared in analogy to the method described in DE-A-19620590 by reacting a compound I, wherein m is 0 and R6 is H, with a compound R12-SC"2-W, wherein R12 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 carbonates (e.g. sodium carbonate, potassium carbonate, caesium carbonate), alkali metal alkoxides (e.g. sodium methoxide, potassium methoxide, sodium ethoxide, po- tassium 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 R6 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 R6 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 R6 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 R6 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 R6 is a group of formula III, may be prepared in analogy to the method described in WO 97/43269 by reacting a compound I, wherein m is 0 and R6 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, po- tassium 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 R6 is -P(=Q)R13R14, may be prepared in analogy to the method described in WO 99/05149.
Compounds of formula II, wherein R6a is different from hydrogen, can be prepared by reacting the NR6a group, wherein R6a is H, in analogy to the above-described conversion of compounds I, wherein R6 is H, into compounds, wherein R6 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 R6Sθ2CI. Compounds I, wherein m is 3, can be prepared from com- pounds IV by first deprotonating the triazolyl ring and then reacting with sulfuric acid chloride or a sulfuric ester chloride of formula R6OSθ2CI, wherein R6 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 sol- ids, they may be purified by recrystallization or digestion.
A further aspect of the invention relates to compounds of formula IV
Figure imgf000098_0001
wherein Het, A, Y, R1, R2, R3 and R4 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 fungi- cidal activity, too.
Particularly preferred compounds IV are compounds of formulae IV.1 to IV.48, wherein the combination of Het, R1, R2, R3 and R4 corresponds in each case to one row in table A above.
Figure imgf000099_0001
Figure imgf000100_0001
Among these, preference is given to compounds IV.1 to IV.24, more preference to compounds IV.1 to IV.12, even more preference to compounds IV.1 and IV.2 and spe- cific preference to compounds IV.2.
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 ef- fectiveness 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 cul- tivated 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, soy- bean, 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 I, Il 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 IJI 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 Cry9c; 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 CryiAc 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®, Bt1 1 (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 producing a modified version of the Cry3A toxin, c.f. WO 03/018810), MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the 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 person 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 cereals, 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 liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier 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. fujikuroi: 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 rosa- ceous 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. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum); Ramularia spp., e. g. R. collo-cygni (Ram ularia 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 soy- beans, 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. miliaria: 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., Cerafocysf/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 /Wucorspp., 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 in- gredients), 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 IJI 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. Exam- pies to be mentioned und the designations rhodamin B, C. I. pigment red 1 12, 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 con- tent 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 compositions 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 ac- cording 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 -(δ-bromo-S-chloro-pyridin^-yO-ethyO^^-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-3-trifluoromethyl-pyrazole-1-yl)-acetyl]-piperidin-4-yl}-thiazole-4-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; - aryloxyphenoxypropionat.es: 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- thai, 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 I, Il 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 infected 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 com- pound 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 , preferably in the range of from 1 :20 to 20:1 , more preferably in the range of from 1 :10 to 10:1 and in particular in the range of from 1 :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 B-1 to B-346 of Table B.
A further embodiment relates to the compositions B-1 to B-346 listed in Table B, where a row of Table B 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 B: Composition comprising one indiviualized compound I, Il or IV and one further active substance from groups A) to I)
Figure imgf000126_0001
MixComponent 1
Component 2 ture
B-23 one individualized compound I, Il or IV Fenhexamid
B-24 one individualized compound I, Il or IV Flutolanil
B-25 one individualized compound I, Il or IV Furametpyr
B-26 one individualized compound I, Il or IV Isopyrazam
B-27 one individualized compound I, Il or IV lsotianil
B-28 one individualized compound I, Il or IV Kiralaxyl
B-29 one individualized compound I, Il or IV Mepronil
B-30 one individualized compound I, Il or IV Metalaxyl
B-31 one individualized compound I, Il or IV Metalaxyl-M
B-32 one individualized compound I, Il or IV Of u race
B-33 one individualized compound I, Il or IV Oxadixyl
B-34 one individualized compound I, Il or IV Oxycarboxin
B-35 one individualized compound I, Il or IV Penthiopyrad
B-36 one individualized compound I, Il or IV Sedaxane
B-37 one individualized compound I, Il or IV Tecloftalam
B-38 one individualized compound I, Il or IV Thifluzamide
B-39 one individualized compound I, Il or IV Tiadinil
2-Amino-4-methyl-thiazole-5-
B-40 one individualized compound I, Il or IV carboxylic acid anilide
2-Chloro-N-(1 ,1 ,3-trimethyl-
B-41 one individualized compound I, Il or IV indan-4-yl)-nicotinamide
N-(3',4',5'-trifluorobiphenyl-2-yl)-
B-42 one individualized compound I, Il or IV 3-difluoromethyl-1-methyl-1 H- pyrazole-4-carboxamide
N-(4'-trifluoromethylthiobiphenyl-
B-43 one individualized compound I, Il or IV 2-yl)-3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxamide
N-(2-(1 ,3-dimethyl-butyl)-
B-44 one individualized compound I, Il or IV phenyl)-1 ,3-dimethyl-5-fluoro- 1 H-pyrazole-4-carboxamide
N-(2-(1 ,3,3-trimethyl-butyl)-
B-45 one individualized compound I, Il or IV phenyl)-1 ,3-dimethyl-5-fluoro- 1 H-pyrazole-4-carboxamide
B-46 one individualized compound I, Il or IV Dimethomorph
B-47 one individualized compound I, Il or IV Flumorph
B-48 one individualized compound I, Il or IV Pyrimorph
Figure imgf000128_0001
Figure imgf000129_0001
MixComponent 1
Component 2 ture
N-(1 -(5-Bromo-3-chloro-pyridin-
B-1 10 one individualized compound I, Il or IV 2-yl)-ethyl)-2,4-dichloro- nicotinamide
N-((5-Bromo-3-chloro-pyridin-2-
B-1 11 one individualized compound I, Il or IV yl)-methyl)-2,4-dichloro- nicotinamide
B-1 12 one individualized compound I, Il or IV Bupirimate
B-1 13 one individualized compound I, Il or IV Cyprodinil
B-1 14 one individualized compound I, Il or IV Diflumetorim
B-1 15 one individualized compound I, Il or IV Fenarimol
B-1 16 one individualized compound I, Il or IV Ferimzone
B-1 17 one individualized compound I, Il or IV Mepanipyrim
B-1 18 one individualized compound I, N or IV Nitrapyrin
B-1 19 one individualized compound I, Il or IV Nuarimol
B-120 one individualized compound I, Il or IV Pyrimethanil
B-121 one individualized compound I, Il or IV Triforine
B-122 one individualized compound I, Il or IV Fenpiclonil
B-123 one individualized compound I, Il or IV Fludioxonil
B-124 one individualized compound I, Il or IV Aldimorph
B-125 one individualized compound I, Il or IV Dodemorph
B-126 one individualized compound I, Il or IV Dodemorph-acetate
B-127 one individualized compound I, Il or IV Fenpropimorph
B-128 one individualized compound I, Il or IV Tridemorph
B-129 one individualized compound I, Il or IV Fenpropidin
B-130 one individualized compound I, Il or IV Fluoroimid
B-131 one individualized compound I, Il or IV lprodione
B-132 one individualized compound I, Il or IV Procymidone
B-133 one individualized compound I, Il or IV Vinclozolin
B-134 one individualized compound I, Il or IV Famoxadone
B-135 one individualized compound I, Il or IV Fenamidone
B-136 one individualized compound I, Il or IV Flutianil
B-137 one individualized compound I, Il or IV Octhilinone
B-138 one individualized compound I, Il or IV Probenazole
5-Amino-2-iso-propyl-4-ortho-
B-139 one individualized compound I, Il or IV tolyl-2,3-dihydro-pyrazole-1 - carbothioic acid S-allyl ester MixComponent 1
Component 2 ture
B-140 one individualized compound I, Il or IV Acibenzolar-S-methyl
B-141 one individualized compound I, Il or IV Amisulbrom
B-142 one individualized compound I, Il or IV Anilazin
B-143 one individualized compound I, Il or IV Blasticidin-S
B-144 one individualized compound I, Il or IV Captafol
B-145 one individualized compound I, N or IV Captan
B-146 one individualized compound I, Il or IV Chinomethionat
B-147 one individualized compound I, Il or IV Dazomet
B-148 one individualized compound I, Il or IV Debacarb
B-149 one individualized compound I, Il or IV Diclomezine
B-150 one individualized compound I, Il or IV Difenzoquat,
B-151 one individualized compound I, Il or IV Difenzoquat-methylsulfate
B-152 one individualized compound I, Il or IV Fenoxanil
B-153 one individualized compound I, Il or IV Folpet
B-154 one individualized compound I, Il or IV Oxolinsaure
B-155 one individualized compound I, Il or IV Piperalin
B-156 one individualized compound I, Il or IV Proquinazid
B-157 one individualized compound I, Il or IV Pyroquilon
B-158 one individualized compound I, Il or IV Quinoxyfen
B-159 one individualized compound I, Il or IV Triazoxid
B-160 one individualized compound I, Il or IV Tricyclazole
2-Butoxy-6-iodo-3-propyl-
B-161 one individualized compound I, Il or IV chromen-4-one
5-Chloro-1 -(4,6-dimethoxy-
B-162 one individualized compound I, Il or IV pyrimidin-2-yl)-2-methyl-1 H- benzoimidazole
5-Chloro-7-(4-methyl-piperidin-1-
B-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-
B-164 one individualized compound I, Il or IV a]pyrimidine-7-ylamine
B-165 one individualized compound I, Il or IV Ferbam
B-166 one individualized compound I, Il or IV Mancozeb
B-167 one individualized compound I, Il or IV Maneb
B-168 one individualized compound I, Il or IV Metam
B-169 one individualized compound I, Il or IV Methasulphocarb MixComponent 1
Component 2 ture
B-170 one individualized compound I, Il or IV Metiram
B-171 one individualized compound I, Il or IV Propineb
B-172 one individualized compound I, Il or IV Thiram
B-173 one individualized compound I, Il or IV Zineb
B-174 one individualized compound I, Il or IV Zi ram
B-175 one individualized compound I, N or IV Diethofencarb
B-176 one individualized compound I, Il or IV Benthiavalicarb
B-177 one individualized compound I, Il or IV Iprovalicarb
B-178 one individualized compound I, Il or IV Propamocarb
B-179 one individualized compound I, Il or IV Propamocarb hydrochlorid
B-180 one individualized compound I, Il or IV Valiphenal
N-(1 -(1 -(4-cyanophenyl)ethane-
B-181 one individualized compound I, Il or IV sulfonyl)-but-2-yl) carbamic acid- (4-fluorophenyl) ester
B-182 one individualized compound I, Il or IV Dodine
B-183 one individualized compound I, Il or IV Dodine free base
B-184 one individualized compound I, Il or IV Guazatine
B-185 one individualized compound I, Il or IV Guazatine-acetate
B-186 one individualized compound I, Il or IV lminoctadine
B-187 one individualized compound I, Il or IV Iminoctadine-triacetate
B-188 one individualized compound I, Il or IV Iminoctadine-tris(albesilate)
B-189 one individualized compound I, Il or IV Kasugamycin
Kasugamycin-hydrochloride-
B-190 one individualized compound I, Il or IV hydrate
B-191 one individualized compound I, Il or IV Polyoxine
B-192 one individualized compound I, Il or IV Streptomycin
B-193 one individualized compound I, Il or IV Validamycin A
B-194 one individualized compound I, Il or IV Binapacryl
B-195 one individualized compound I, Il or IV Dicloran
B-196 one individualized compound I, Il or IV Dinobuton
B-197 one individualized compound I, Il or IV Dinocap
B-198 one individualized compound I, Il or IV Nitrothal-isopropyl
B-199 one individualized compound I, Il or IV Tecnazen
B-200 one individualized compound I, Il or IV Fentin salts
B-201 one individualized compound I, N or IV Dithianon
B-202 one individualized compound I, Il or IV lsoprothiolane
Figure imgf000133_0001
Figure imgf000134_0001
Figure imgf000135_0001
Figure imgf000136_0001
Figure imgf000137_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 nomenclature, 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 explana- tions 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, espe- daily 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 I, Il and/or IV respectively.
The compounds I, Il 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 Stutt- gart, 1966, the entire contents of which is expressly incorporated herein by way of reference.
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 I, Il 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 I, Il 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 I, Il 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 man- ner, for example orally, intravenously, intramuscularly or subcutaneously. For oral administration, 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 intraperitoneal^. 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 microorgan- isms. 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 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 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 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.
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 volume 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 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 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 triticiou 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 develop- ment on the seed leaves was then determined visually.

Claims

We claim:
Triazole compounds of the formulae I and Il
Figure imgf000145_0001
wherein
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 sub- stituents R5;
A is a linear d-Cs-alkylene bridge which may be substituted by 1 , 2, 3 or 4 substituents R7;
Y is O, S or NR8;
R1, R2, R3 and R4, independently of each other, are selected from hydrogen, 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, C3-C8- halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkenyloxy, Ci-C4- haloalkenyloxy, Ci-C4-alkynyloxy, Ci-C4-haloalkynyloxy, Cs-Cs-cycloalkoxy, C3-C8-halocycloalkoxy, Ci-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 R9; 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 R9; COR10, COOR10, CONR15R16, NR15R16 and S(O)PR10, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R18 and where the cycloaliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R19; or R1 and R2 or R3 and R4, together with the carbon 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 R9;
each R5 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 R9; 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 R9; COR10, COOR10, CONR15R16, NR15R16 and S(O)PR10, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R18 and where the cycloaliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R19; or
two radicals R5 bound on adjacent ring atoms, together 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 R9;
R6 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 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; or, in case m is 0, may also be selected from -C(=O)R12, -C(=S)R12, -S(O)2R12, -CN, -P(=Q)R13R14, M and a group of the formula III
Figure imgf000147_0001
wherein
Het, A, Y, R1, R2, R3 and R4 are as defined for formulae I and II; and # is the attachment point to the remainder of the molecule;
R6a 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 R11, 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,
-C(=O)R12, -C(=S)R12, -S(O)2R12, -CN, -P(=Q)R13R14 and M;
each R7 is independently selected from halogen, OH, SH, NR15R16, 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 CrC4- haloalkylthio, where the aliphatic moieties in the above radicals may carry 1 , 2 or 3 substituents R18; or
two radicals R7 bound on two adjacent carbon atoms, together with the car- bon 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 R9;
R8 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, CrC4- 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 R9; COR10, COOR10, CONR15R16 and S(O)PR10;
each R9 is independently selected from halogen, OH, SH, NR15R16, 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 R18;
each R10 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 R9, and a 5- or 6-membered saturated, partially unsaturated or aromatic heterocyclic ring containing 1 , 2 or 3 heteroatoms se- lected from N, O and S as ring members, where the heterocyclic ring may carry 1 , 2 or 3 substituents R9;
each R11 is independently selected from halogen, OH, SH, NR15R16, 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 R18;
R12 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 R11, 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, and NR15R16;
R13 and R14, 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 NR15R16; each R15 is independently selected from hydrogen and Ci-Cs-alkyl;
each R16 is independently selected from hydrogen, Ci-Cs-alkyl, phenyl, and phenyl-Ci-C4-alkyl;
or R15 and R16 together form a linear C4- or Cs-alkylene bridge or a group -CH2CH2OCH2CH2- or -CH2CH2NR17CH2CH2-;
each R17 is independently selected from hydrogen and Ci-C4-alkyl;
each R18 is independently selected from nitro, CN, OH, SH, COR10, COOR10, CONR15R16; NR15R16, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C3-C6-cycloaloxy, phenyl and phenoxy;
each R19 is independently selected from nitro, CN, OH, SH, COR10, COOR10,
CONR15R16; NR15R16, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6- halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, C3-C6-cycloaloxy, phenyl and phenoxy;
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 NR15R16;
m is O, 1 or 2; and
p is 1 or 2;
and the agriculturally acceptable salts thereof.
The compounds of formulae I and Il as claimed in claim 1 , where Het 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 substituents R5.
3. The compounds of formulae I and Il as claimed in claim 2, 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, substitu- ents R5.
4. The compounds of formulae I and Il as claimed in claim 3, 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, prefera- bly 1 or 2, substituents R5.
5. The compounds of formulae I and Il as claimed in any of the preceding claims, where R1, R2, R3 and R4, independently of each other, are selected from hydrogen 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, and preferably from hydrogen, fluorine, chlorine, bromine, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
6. The compounds of formulae I and Il as claimed in any of the preceding claims, where each R5 is independently 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, and preferably from fluorine, chlorine, bromine, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
7. The compounds of formulae I and Il as claimed in any of the preceding claims, where R12 is selected from Ci-C4-alkyl, Ci-C2-haloalkyl, Ci-C4-alkoxy, C1-C2- haloalkoxy, phenyl, phenoxy and NR15R16, where R15 is hydrogen and R16 is selected from hydrogen, Ci-C4-alkyl and phenyl, or both R15 and R16 are Ci-C4-alkyl.
8. The compounds of formulae I and Il as claimed in any of the preceding claims, where R6 is selected from hydrogen, Ci-C4-alkyl, -C(=O)R12, -S(O)2R12, -CN, M and a group of the formula III.
9. The compounds of formulae I and Il as claimed in claim 8, where R6 is 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 V2 Cu2+.
10. The compounds of formulae I and Il as claimed in any of the preceding claims, where R6a is selected from hydrogen, Ci-C4-alkyl, -S(O)2R12, and -C(=O)R12.
1 1. 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 R7, where each R7 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 R7 bound on adjacent carbon atoms, together with the carbon atoms to which they are bound, form a cyclopentyl or cyclohexyl ring.
12. The compounds of formulae I and Il as claimed in any of the preceding claims, where Y is O.
13. The compounds of formulae I and Il as claimed in any of the preceding claims, where m is 0.
14. Compounds of formula IV
Figure imgf000151_0001
where Het, A, Y, R1, R2, R3 and R4 are as defined in any of claims 1 to 6 and 1 1 to 13.
15. An agricultural composition comprising at least one compound of formula I, Il and/or IV as defined in any of claims 1 to 14 or an agriculturally acceptable salt thereof and a liquid or solid carrier.
16. The use of a compound of formula I, Il and/or IV as defined in any of claims 1 to 14 for controlling harmful fungi.
17. 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 14.
18. Seed, comprising at least compound of formula I, Il and/or IV, where compounds I, Il and IV are as defined in any of claims 1 to 14, in an amount of from 0.1 g to
10 kg per 100 kg of seeds.
19. A pharmaceutical composition comprising at least one compound of formula I, Il and/or IV as defined in any of claims 1 to 14 or a pharmaceutically acceptable salt thereof and at least one pharmaceutically acceptable carrier.
20. The use of a compound of formula I, Il and/or IV as defined in any of claims 1 to 14 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.
21. 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 14, with at least one pharmaceutically acceptable salt thereof or with a pharmaceutical composition as defined in claim 19.
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