WO2007060220A2 - Cyanobenzene compounds for combating animal pests - Google Patents

Cyanobenzene compounds for combating animal pests Download PDF

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Publication number
WO2007060220A2
WO2007060220A2 PCT/EP2006/068880 EP2006068880W WO2007060220A2 WO 2007060220 A2 WO2007060220 A2 WO 2007060220A2 EP 2006068880 W EP2006068880 W EP 2006068880W WO 2007060220 A2 WO2007060220 A2 WO 2007060220A2
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alkyl
crc
alkoxy
group
compounds
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PCT/EP2006/068880
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French (fr)
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WO2007060220A3 (en
Inventor
Matthias Pohlman
Wolfgang Von Deyn
Thomas Schmidt
Florian Kaiser
Douglas D. Anspaugh
Deborah L. Culbertson
Henry Van Tuyl Cotter
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Basf Se
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Priority to US12/094,942 priority Critical patent/US20080300280A1/en
Priority to BRPI0618931A priority patent/BRPI0618931A2/en
Priority to EP06819746A priority patent/EP1956907A2/en
Priority to JP2008541754A priority patent/JP2009517369A/en
Publication of WO2007060220A2 publication Critical patent/WO2007060220A2/en
Publication of WO2007060220A3 publication Critical patent/WO2007060220A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/51—Y being a hydrogen or a carbon atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/04—Sulfonic acids; Derivatives thereof
    • A01N41/06—Sulfonic acid amides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • A01N47/42—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides containing —N=CX2 groups, e.g. isothiourea
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N51/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/15—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings
    • C07C311/16—Sulfonamides having sulfur atoms of sulfonamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/52—Y being a hetero atom
    • C07C311/53—X and Y not being nitrogen atoms, e.g. N-sulfonylcarbamic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/52—Y being a hetero atom
    • C07C311/54—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea
    • C07C311/57—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea having sulfur atoms of the sulfonylurea groups bound to carbon atoms of six-membered aromatic rings
    • C07C311/58—Y being a hetero atom either X or Y, but not both, being nitrogen atoms, e.g. N-sulfonylurea having sulfur atoms of the sulfonylurea groups bound to carbon atoms of six-membered aromatic rings having nitrogen atoms of the sulfonylurea groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/10—Compounds containing sulfur atoms doubly-bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/46—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with hetero atoms directly attached to the ring nitrogen atom
    • C07D207/48—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • C07D231/26—1-Phenyl-3-methyl-5- pyrazolones, unsubstituted or substituted on the phenyl ring
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    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
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    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom

Definitions

  • the present invention relates to a method of combating animal pests by using cyanobenzene compounds and/or agriculturally acceptable salts thereof.
  • the invention also relates to certain cyanobenzene compounds and/or their agriculturally acceptable salts and also to compositions comprising them.
  • Animal pests destroy growing and harvested crops and attack wooden dwelling and commercial structures, causing large economic loss to the food supply and to property. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new agents for combating animal pests. In particular, animal pests such as insects and acaridae are difficult to be effectively controlled.
  • EP 33984 discloses 2-cyanobenzene sulfonamides having aphicidal activity. Their activity, however, is not satisfactory. Similar compounds are described in WO 2005/035486.
  • EP-A-0303863 describes benzenesulfonyl-2-imidazolin-5-one compounds which are useful as herbicides. An activity against animal pests is not mentioned.
  • EP-A-0107624 describes a method for producing sulfonylurea compounds by reacting a sulfonylamidocarbonic diester with an amino-substituted pyrimidine or triazine.
  • the sulfonylurea compounds are said to have a herbicidal activity.
  • the object of the present invention is to provide compounds having a good pesticidal activity, especially against difficult to control insects and acaridae.
  • a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of at least one cyanobenzene compound of the formula I and/or at least one agriculturally acceptable salt thereof:
  • n O, 1 or 2;
  • A is a radical of the formulae
  • A is a N-bound 5-, 6- or 7-membered heterocycle, which is ethylenically unsaturated or aromatic, and which additionally may contain 1 , 2, or 3 further het- eroatoms or heteroatom groups, selected from O, S, SO, SO 2 , N, and NR 12 , and/or 1 , 2 or 3 carbonyl groups as ring members and which may carry 1 , 2, 3 or 4 radicals R 13 ,
  • R 5 is H, OR 5a , NR 5b R 5c , aryl, aryl-C r C 4 -alkyl, heteroaryl, heteroaryl-C r C 4 -alkyl, het- erocyclyl, heterocyclyl-Ci-C 4 -alkyl, Ci-Cio-alkyl, C 3 -Ci 0 -cycloalkyl, CrCi 0 - alkylthio, CrCi 0 -alkylsulfonyl, CrCi O -alkylsulfinyl, wherein the five last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another each selected from the group consisting of cyano, nitro, amino, CrCi 0 -alkoxy, CrCi 0 -alkylthio, CrCi O -alkylsul
  • R 5a is Ci-Ci O -alkyl, C 3 -Ci 0 -cycloalkyl, C 2 -Ci 0 -alkenyl, C 2 -Ci 0 -alkynyl, aryl, aryl- CrC 4 -alkyl, heteroaryl or heteroaryl-CrC 4 -alkyl, heterocyclyl or heterocy- clyl-CrC 4 -alkyl;
  • R 5b , R 5c independently from each other, are selected from hydrogen, CrCi 0 - alkyl, C 3 -Ci 0 -cycloalkyl, C 2 -Ci 0 -alkenyl, C 2 -Ci 0 -alkynyl, aryl, aryl-Ci-C 4 -alkyl, heteroaryl and heteroaryl-CrC 4 -alkyl, heterocyclyl or heterocyclyl-CrC 4 - alkyl;
  • R 5a , R 5b and R 5c may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, C r C 4 -alkoxy, C r C 4 -alkylthio, C r C 4 -alkylsulfinyl, C r C 4 -alkylsulfonyl, C r C 4 - haloalkoxy, CrC 4 -haloalkylthio, (CrC 4 -alkoxy)carbonyl, (CrC 4 -alkyl)amino, di(CrC 4 -alkyl)amino and C 3 -C8-
  • heteroaryl moiety in heteroaryl and heteroaryl-CrC 4 -alkyl of R 5 , R 5a , R 5b and R 5c is 5- or 6 membered and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO 2 , N or NR a , as ring members, R a being hydrogen or Ci-C ⁇ -alkyl;
  • heterocyclyl moiety in heterocyclyl and of R 5 , R 5a , R 5b and R 5c is 3- to 7 membered, is saturated or partly unsaturated and con- tains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO,
  • R b being hydrogen or d-C 6 -alkyl, and additionally may contain 1 , 2 or 3 CO groups as ring members;
  • R 5 , R 5a , R 5b and R 5c may be unsubstituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of halogen, CrC 4 - alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy and CrC 4 -haloalkoxy;
  • R 6 independently has one of the meanings given for R 5 ;
  • R 7 , R 8 independently from each other, are selected from aryl, aryl-Ci-C 4 -alkyl, het- eroaryl, heteroaryl-Ci-C 4 -alkyl, heterocyclyl, heterocyclyl-CrC 4 -alkyl, Ci-Ci O -alkyl, C 3 -Ci 0 -cycloalkyl, C 2 -Ci 0 -alkenyl and C 2 -Ci 0 -alkynyl, wherein the four last- mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another each selected from the group consisting of cyano, nitro, amino, CrCio-alkoxy, CrCio-alkylthio, CrCi 0 - alkylsulfinyl, CrCi ⁇ -alkylsulfonyl, CrCi
  • R 7 and R 8 together with the sulfur atom they are bound to form a saturated or ethyleni- cally unsaturated 5- to 10-membered ring, optionally substituted by 1 , 2, 3 or 4 radicals selected from CrC 5 -alkyl and halogen, wherein the ring may contain, in addition to the sulfur atom, 1 , 2 or 3 heteroatoms and/or heteroatom-containing groups as ring members selected from the group consisting of nitrogen, oxygen, sulfur, CO, SO, SO 2 and N-R 17 ;
  • heteroaryl moiety in heteroaryl and heteroaryl-Ci-C 4 -alkyl of R 7 and R 8 is 5- or 6 membered and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO 2 , N or NR C , as ring members, R c being hydrogen or CrC 6 -alkyl, wherein the heterocyclyl moiety in heterocyclyl and of R 7 and R 8 is 3- to 7-membered, is saturated or partly unsaturated and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO 2 , N or NR d , as ring members, R d being hydrogen or Ci-C ⁇ -alkyl, and additionally may contain 1 , 2 or 3 CO groups as ring members,
  • R 7 and R 8 wherein the carbon atoms of aryl, hetaryl, and heterocyclyl in R 7 and R 8 may be unsubstituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of halogen, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, CrC 4 -alkoxy and CrC 4 -haloalkoxy;
  • aryl is selected from the group consisting of hydrogen, OR 9a , NR 9b R 9c , aryl, aryl-d- C 4 -alkyl, heteroaryl, heteroaryl-Ci-C 4 -alkyl, heterocyclyl, CrCio-alkyl, C 2 -Ci 0 -alkenyl, C 2 -Ci 0 -alkynyl and C 3 -Ci 0 -cycloalkyl, wherein the four last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another each selected from the group consisting of cyano, nitro, amino, Ci-Cio-alkoxy, Ci-Ci 0 -alkylthio, CrCio-alkylsulfinyl, Ci-Ci 0 -alkylsulfonyl, Ci-Cio-haloal
  • R 9a is Ci-Ci ⁇ -alkyl, C 3 -Ci 0 -cycloalkyl, C 2 -Ci 0 -alkenyl, C 2 -Ci 0 -alkynyl, aryl, aryl- CrC 4 -alkyl, heteroaryl or heteroaryl-CrC 4 -alkyl, heterocyclyl or heterocy- clyl-C r C 4 -alkyl,
  • R 9b , R 9c independently from each other, are selected from hydrogen, CrCi 0 - alkyl, C 3 -Ci 0 -cycloalkyl, C 2 -Ci 0 -alkenyl, C 2 -Ci 0 -alkynyl, aryl, aryl-Ci-C 4 -alkyl, heteroaryl and heteroaryl-Ci-C 4 -alkyl, heterocyclyl or heterocyclyl-CrC 4 - alkyl,
  • R 9a , R 9b and R 9c may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, CrC 4 -alkoxy, CrC 4 -alkylthio, CrC 4 -alkylsulfinyl, CrC 4 - alkylsulfonyl, CrC 4 -haloalkoxy, CrC 4 -haloalkylthio, (CrC 4 -alkoxy)carbonyl, (CrC 4 -alkyl)amino, di(CrC 4 -alkyl)amino and C 3 -C8-cycloalkyl, wherein the heteroaryl moiety in heteroaryl and heteroaryl-Ci-C 4 -alkyl of R 9 , R 9a , R 9b and R 9c is 5- or 6-membered and contains 1 , 2, 3 or 4 heteroatoms
  • heterocyclyl moiety in heterocyclyl and heterocyclyl-d-Q-alkyl of R 9 , R 9a , R 9b and R 9c is 3- to 7-membered, is saturated or partly unsaturated and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, se- lected from O, S, SO, SO 2 , N or NR f , as ring members, R f being hydrogen or CrC 6 -alkyl, and additionally may contain 1 , 2 or 3 CO groups as ring members,
  • R 9 , R 9a , R 9b and R 9c may be unsubstituted or may carry 1 , 2 or 3 substitu- ents, independently of one another selected from the group consisting of halogen, d-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy and Ci-C 4 -haloalkoxy;
  • R 9 and R 10 together with the adjacent nitrogen and carbon atoms form a saturated or ethylenically unsaturated 5 to 10-membered ring, optionally substituted by 1 , 2, 3 or 4 radicals selected from CrC 5 -alkyl and halogen, wherein the ring may contain, in addition to the nitrogen and carbon ring members, 1 , 2 or 3 heteroatoms and/or heteroatom groups as ring members selected from the group consisting of nitrogen, oxygen, sulfur, CO, SO, SO 2 and N-R 17 ;
  • R 11 is Ci-Ce-alkyl or C r C 6 -alkoxy
  • R 11 and R 9 together with the adjacent nitrogen and carbon atoms form an ethylenically unsaturated aromatic or non-aromatic 5 to 10-membered ring, optionally substituted by 1 , 2 or 3 CrC 5 -alkyl radicals, wherein the ring may contain, in addition to the nitrogen and carbon ring members, 1 , 2 or 3 heteroatoms and/or heteroatom groups as ring members selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO 2 and N-R 17 ;
  • R 11 and R 10 together with the adjacent nitrogen and carbon atoms form an ethylenically unsaturated aromatic or non-aromatic 5 to 10-membered ring, optionally substituted by 1 , 2 or 3 CrC 5 -alkyl radicals, wherein the ring may contain, in addition to the nitrogen and carbon ring members, 1 , 2 or 3 heteroatoms and/or heteroatom groups as ring members selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO 2 and N-R 17 ;
  • R 12 is hydrogen, d-C 6 -alkyl, Ci-C 4 -alkoxy-Ci-C 4 -alkyl or CrC 6 -alkoxy;
  • each R 13 independently is selected from halogen, cyano, nitro, sulfenylamino, sulfinyl- amino, sulfonylamino, aryl, aryl-Ci-C 4 -alkyl, heteroaryl, heteroaryl-Ci-C 4 -alkyl, heterocyclyl, heterocyclyl-Ci-C 4 -alkyl, CrC 6 -alkyl, C 3 -C 8 -cycloalkyl, CrC 6 -alkoxy, CrC6-alkoxycarbonyl, d-Ce-alkylcarbonyl, (C- ⁇ -C6-alkyl)amino, di(CrC6- alkyl)amino, Ci-C ⁇ -alkylthio, Ci-C ⁇ -alkylsulfinyl or Ci-C 6 -alkylsulfonyl, wherein the ten last-mentioned radicals may be unsubsti
  • heteroaryl moiety in heteroaryl and heteroaryl-Ci-C 4 -alkyl of R 13 is 5- or 6 membered and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO 2 , N or NR 9 , as ring members, R 9 being hydrogen or d-C ⁇ -alkyl,
  • heterocyclyl moiety in heterocyclyl and heterocyclyl-CrC 4 -alkyl of R 13 is 3- to 7-membered and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO 2 , N or NR h , as ring members, R h being hydrogen or CrC 6 -alkyl, and additionally may contain 1 , 2 or 3 CO groups as ring members,
  • carbon atoms of aryl, hetaryl, and heterocyclyl in R 13 may be un- substituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of halogen, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, CrC 4 - alkoxy and CrC 4 -haloalkoxy;
  • R 14 and R 15 independently of one another are selected from the group consisiting of hydrogen, hydroxy, CrC6-alkoxy, amino, Ci-C 4 -alkylamino, di(C-i-C 4 -alkyl)amino, aryl, aryl-Ci-C 4 -alkyl, Ci-C 4 -alkyl, where the alkyl moiety in the two last- mentioned radicals and the aryl moiety in aryl and aryl-Ci-C 4 -alkyl may be par- tially or fully halogenated,
  • heteroaryl ring contains as ring members 1 , 2 or 3 heteroatoms and/or heteroatom groups, selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO 2 and N-R n , wherein R n is hydrogen or Ci-C 4 -alkyl,
  • heterocyclyl or heterocyclyl-CrC 4 -alkyl wherein the heterocyclic ring is saturated or partly unsaturated and contains 1 , 2 or 3 heteroatoms and/or heteroatom groups, selected from the group consisting of nitrogen, oxy- gen, sulfur, SO, SO 2 and N-R 0 , wherein R 0 is hydrogen or d-C 4 -alkyl,
  • carbon atoms of the heterocyclic rings may by unsubstituted or substituted by 1 or 2 radicals selected from halogen or Ci-C 4 -alkyl;
  • R 16 is Ci-C 6 -alkyl, aryl, aryl-Ci-C 4 -alkyl,
  • heteroaryl ring contains as ring members 1 ,2 or 3 heteroatoms and/or heteroatom groups, selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO 2 and N-R k , wherein R k is hydrogen or CrC 4 -alkyl,
  • heterocyclyl or heterocyclyl-CrC 4 -alkyl wherein the heterocyclic ring is saturated or partly unsaturated and contains as ring members 1 , 2 or 3 heteroatoms and/or heteroatom groups, selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO 2 and N-R m , wherein R m is hydrogen or Ci-C 4 - alkyl, and wherein the carbon atoms of the heterocyclic rings may be unsubstituted or substituted by 1 or 2 radicals selected from halogen or d-C 4 -alkyl;
  • R 16 and R 9 together with the adjacent nitrogen and carbon atoms form a saturated or ethylenically unsaturated 5 to 10-membered ring, where the ring may be partially or fully halogenated and/or may be substituted by 1 , 2 or 3 substituents selected from CrC 5 -alkyl and CrC 5 -haloalkyl, wherein the ring may contain, in addition to the nitrogen and carbon ring members, 1 , 2 or 3 heteroatoms and/or heteroatom groups as ring members selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO 2 and N-R 17 ;
  • each R 17 independently is hydrogen, heteroaryl, heteroaryl-Ci-C 4 -alkyl or Ci-C ⁇ -alkyl, where the alkyl moiety in the two last-mentioned radicals may be partially or fully halogenated;
  • the compounds of the formula I and their agriculturally acceptable salts are highly active against animal pest, i.e. harmful arthropodes and nematodes, especially against difficult to control insects and acaridae.
  • the present invention relates to the use of compounds I and/or their salts for combating animal pests.
  • the invention is also related to seed comprising a compound of the formula I or an ag- riculturally useful salt of I, as defined above, in an amount of from 0.1 g to 10 kg per 100 kg of seed.
  • the invention further relates to compounds of the formula (I) and agriculturally acceptable salts thereof,
  • R x and R y are, independently of each other, hydrogen or Ci-C 5 -alkyl and R 10 is H or CrCio-alkyl;
  • R x and R y are, independently of each other, hydrogen or d-C 5 -alkyl and R 10 is H or CrCio-alkyl.
  • the invention also relates to agricultural compositions comprising at least one cyanobenzene derivative of the formula I and/or at least one agriculturally useful salt of I and at least one inert liquid and/or solid agronomically acceptable carrier and, if de- sired, at least one surfactant.
  • the compound I and/or its salt is of course comprised in such an amount that it has a pesticidal action.
  • the compounds of the general formula I may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers.
  • the present invention provides both the pure enantiomes or diastereomers or mixtures thereof.
  • the compounds of the general formula I may also exist in the form of different tautomers, e.g. if one of R 5b or R 5c is H or if X is NR 11 and R 10 is H, but also in other cases.
  • the invention comprises the single tautomers, if separable, as well as the tautomer mix- tures.
  • the compounds of formula I may further exist in the form of different stereoisomers, in particular E/Z-isomers, e.g.
  • the invention comprises single stereoisomers as well as stereoisomer mixtures.
  • Salts of the compounds of the formula I are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality or by reacting an acidic compound of formula I with a suitable base.
  • Suitable agriculturally useful salts are especially the salts of those cations or the acid addition salts of those acids the cations and anions of which do not have any adverse effect on the action of the compounds according to the present invention.
  • Suitable cations are in particular the ions of the alkali metals, preferably lithium, 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 ammonium (NH 4 + ) and substituted ammonium in which one to four of the hydrogen atoms are replaced by CrC 4 -alkyl, Ci-C 4 -hydroxyalkyl, Ci-C 4 -alkoxy, Ci-C 4 -alkoxy-Cr C 4 -alkyl, hydroxy-Ci-C 4 -alkoxy-CrC 4 -alkyl, phenyl or benzyl.
  • substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammo- nium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl- ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl- triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(CrC 4 - alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C 4 -alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of CrC 4 -alkanoic acids, preferably formiate, acetate, propionate and bu- tyrate. They can be formed by reacting the compounds of the formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • Suitable acid addition salts e.g. formed by compounds of formula I containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hy- drochlorids, sulphates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
  • inorganic acids for example hy- drochlorids, sulphates, phosphates, and nitrates
  • salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
  • the organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
  • the prefix C n -C m indicates in each case the possible number of carbon atoms in the group.
  • Halogen will be taken to mean fluoro, chloro, bromo and iodo.
  • partially or fully halogenated will be taken to mean that 1 or more, e.g. 1 , 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by a halogen atom, in particular by fluorine or chlorine.
  • C n -C m -alkyl refers to a branched or unbranched saturated hydrocarbon group having n to m, e.g.
  • 1 to 10 carbon atoms preferably 1 to 6 carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1 ,1-dimethylethyl, pentyl, 1- methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1 ,1- dimethylpropyl, 1 ,2-dimethylpropyl, 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
  • CrC 4 -alkyl means for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1 ,1-dimethylethyl.
  • Ci-C 5 -alkyl additionally means pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1 ,1- dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl and constitutional isomers thereof, d- C 6 -alkyl additionally means hexyl and constitutional isomers thereof.
  • CrC 2 -alkyl means methyl and ethyl.
  • C n -C m -haloalkyl refers to a straight-chain or branched alkyl group having n to m carbon atoms, e.g. 1 to 10 in particular 1 to 6 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, for example CrC 4 -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-fluoro
  • Ci-Cio-haloalkyl in particular comprises CrC 2 -fluoroalkyl, which is synonym with methyl or ethyl, wherein 1 , 2, 3, 4 or 5 hydrogen atoms are substituted by fluorine atoms, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl and pentafluoromethyl.
  • Examples include Cr C 4 -alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobu- toxy and tert-butoxy, further d-C 4 -alkylthio such as methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio further CrC 4 -alkylsulfinyl such as methylsulfinyl, ethyl- sulfinyl, propylsulfinyl, isopropylsulfinyl, and n-butylsulfinyl, and further CrC 4 - alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, and n-butylsulfonyl.
  • Ci-C 2 -fluoroalkoxy and C 1 -C 2 - fluoroalkylthio refer to C 1 -C 2 - fluoroalkyl which is bound to the remainder of the molecule via an oxygen atom or a sulfur atom (or a SO (sulfinyl) or a S(O) 2 (sulfonyl) linkage), respectively.
  • C 2 -C m -alkenyl intends a branched or unbranched unsatu- rated hydrocarbon group having 2 to m, e.g. 2 to 10 or 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 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,
  • C 2 -C m -alkynyl refers to a branched or unbranched unsaturated hydrocarbon group having 2 to m, e.g. 2 to 10 or 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, propynyl, 1-butynyl, 2-butynyl, and the like.
  • Ci-C 4 -alkoxy-Ci-C 4 -alkyl refers to alkyl having 1 to 4 carbon atoms, wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C 4 -alkoxy group.
  • Ci-C 4 -alkylthio-Ci-C 4 -alkyl refers to alkyl having 1 to 4 carbon atoms, wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C 4 -alkylthio group.
  • d-C 6 -alkylcarbonyl refers to a carbonyl group carrying a C r C 6 -alkyl group.
  • Ci-Ci 0 -alkoxycarbonyl or Ci-C 4 -alkoxycarbonyl as used herein refers to a carbonyl group carrying a Ci-Ci O -alkyl group or a Ci-C 4 -alkyl group.
  • Ci-C 4 -alkylcarbonyloxy refers to a carbonyl group which is bound via an oxy- gen atom and which carries a Ci-C 4 -alkyl group.
  • C3-C m -cycloalkyl refers to a monocyclic 3- to m-membered saturated cycloaliphatic radical, for example to a monocyclic 3- to 10-membered or 3- to 8-membered saturated cycloaliphatic radical such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
  • aryl refers to an aromatic hydrocarbon radical such as naphthyl or in particular phenyl.
  • aryl-Ci-C 4 -alkyl refers to an aromatic hydrocarbon radical, which is bound to the remainder of the molecule via a CrC 4 -alkylene group. Examples comprise benzyl, 1-phenylethyl and 2-phenylethyl.
  • non-aromatic heterocyclyl rings examples include azetidinyl, pyrrolidinyl, pyr- rolidinonyl, pyrrolidindionyl, pyrazolinyl, pyrazolinonyl, imidazolinyl, imidazolinonyl, imi- dazolindionyl, pyrrolinyl, pyrrolinonyl, pyrrolindionyl, pyrazolinyl, imidazolinyl, imidazolinonyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3-dioxolanyl, dioxolenyl, thiolanyl, dihy- drothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl,
  • Examples for monocyclic 5- or 6-membered heteroaromatic rings include triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyra- zolyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, isothi- azolyl and isoxazolyl.
  • heterocyclyl-CrC 4 -alkyl and "heteroaryl-Ci-C 4 -alkyl” as used herein refer to a non-aromatic or aromatic heterocyclic radical which is bound to the remainder of the molecule via a CrC 4 -alkylene group, such as methylene, 1 ,2-ethylene, 1 ,2- or 1 ,3- propylene or 1 ,4-butylene.
  • Typical examples for heteroaryl-Ci-C 4 -alkyl are benzyl and 2-phenylethyl. Examples for are cyclopropylmethyl, 2- cyclopropylethyl, cyclopentylmethyl, 2-cyclopentylethyl cyclohexylmethyl and 2- cyclohexylethyl.
  • R 1 is not hydrogen
  • R 1 is selected from halogen, d-C 4 -alkyl, CrC 4 -haloalkyl, Ci-C 4 -alkoxy and Ci-C 4 -haloalkoxy. More preferably, R 1 is selected from CrC 2 -alkyl, d-haloalkyl, CrC 2 - alkoxy and d-haloalkoxy. Even more preferably, R 1 is selected from methyl, methoxy, trifluoromethyl, trichloromethyl, methoxy, trifluoromethoxy, difluoromethoxy, fluoro- methoxy and chlorodifluoromethoxy and in particular from methyl, methoxy, and difluoromethoxy.
  • R 1 is selected from methyl, methoxy, trifluoromethoxy, difluoromethoxy, fluoromethoxy and chlorodifluoromethoxy and more specifically from methyl, methoxy and difluoromethoxy.
  • R 1 is halogen and in particular chlorine.
  • R 1 is selected from Ci-C 4 -alkoxy and Ci-C 4 -haloalkoxy and more specifically from Ci-C 2 -alkoxy, such as methoxy and ethoxy, and d- haloalkoxy, such as trifluoromethoxy, difluoromethoxy, fluoromethoxy and chlorodifluoromethoxy and in particular difluoromethoxy.
  • R 2 , R 3 , and R 4 are preferably selected, independently from each other, from H, CrC 4 - alkyl, CrC 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkoxy and halogen. More preferably R 2 , R 3 and R 4 are selected, independently from each other, from hydrogen, halogen, d- C 4 -alkyl and CrC 4 -haloalkyl, especially from hydrogen, halogen, Ci-C 2 -alkyl, and d- haloalkyl, most preferably, from H, F, Cl, Br, I, CH 3 and CF 3 .
  • two of the radicals R 2 , R 3 or R 4 are hydrogen and the remaining radical is selected from halogen, Ci-C 4 -alkyl and Ci-C 4 -haloalkyl and preferably from halogen. More specifically, R 2 and R 3 are H and R 4 is different from H and is preferably halogen. In another specific embodiment of the invention, all three radicals R 2 , R 3 and R 4 are hydrogen.
  • R 5 and R 6 are not both hydrogen. More preferably, R 5 is not hydrogen.
  • R 5 is OR 5a , NR 5b R 5c , aryl-C r C 4 -alkyl or Ci-Cio-alkyl which may be unsubsti- tuted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from the group consisting of CrCio-alkoxy and phenyl, it being possible for phenyl to be unsubstituted, partially or fully halogenated or carry 1 , 2 or 3 radicals, independently of one another selected from the group consisting of CrC 4 - alkyl, C r C 4 -haloalkyl, C r C 4 -alkoxy and C r C 4 -haloalkoxy, wherein R 5a , R 5b and R 5c are as defined above.
  • R 6 is hydrogen, OR 6a , NR 6b R 6c , aryl-Ci-C 4 -alkyl or C r Ci 0 -alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from the group consisting of Ci-Cio-alkoxy and phenyl, it being possible for phenyl to be unsubstituted, partially or fully halogenated or carry 1 , 2 or 3 radicals, independently of one another selected from the group consist- ing of C r C 4 -alkyl, C r C 4 -haloalkyl, C r C 4 -alkoxy and C r C 4 -haloalkoxy, wherein R 6a , R 6b and R 6c have one of the meanings given above for R 5a , R 5b and R 5c .
  • R 5a , R 5b , R 5c , R 6a , R 6b and R 6c are preferred:
  • R 5a is CrCio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from CrC 4 - alkoxy, or is C 2 -Ci 0 -alkenyl or C 2 -Ci 0 -alkynyl. More preferably, R 5a is CrCio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from CrC 4 -alkoxy. In particular, R 5a is unsubsti- tuted CrCio-alkyl.
  • R 5b and R 5c are, independently from each other, hydrogen, CrCio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from CrC 4 -alkoxy, or are C 2 -CiO- alkenyl or C 2 -Ci 0 -alkynyl. More preferably, R 5b and R 5c are, independently from each other, hydrogen or CrCio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from CrC 4 -alkoxy. In particular, R 5b and R 5c are, independently from each other, hydrogen or unsubstituted CrCio-alkyl. Preferably, at least one of R 5b and R 5c is not hy- drogen.
  • R 6a is CrCio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from CrC 4 - alkoxy, or is C 2 -Ci 0 -alkenyl or C 2 -Ci 0 -alkynyl. More preferably, R 6a is CrCio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from CrC 4 -alkoxy. In particular, R 6a is unsubstituted CrCio-alkyl.
  • R 6b and R 6c are independently from each other, hydrogen, CrCio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from Ci-C 4 -alkoxy, or is C 2 -Cio-alkenyl or C 2 -Cio-alkynyl. More preferably, R 6b and R 6c are, independently from each other, hydrogen or Ci-Cio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from CrC 4 - alkoxy. In particular, R 6b and R 6c are, independently from each other, hydrogen or unsubstituted CrCio-alkyl. Preferably, at least one of R 6b and R 6c is not hydrogen.
  • R 5 is Ci-Cio-alkyl, preferably C r C 6 -alkyl, or a radical OR 5a , and
  • R 6 is a radical OR 6a ,
  • R 5a and R 6a have, independently of each other, one of the meanings of R 5a given above.
  • R 5a and R 6a are, independently of each other, Ci-Cio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals selected from Ci-C 4 -alkoxy, or are C 2 -Cio-alkenyl or C 2 -Cio-alkynyl.
  • R 5a and R 6a are, independently of each other, d-C 6 -alkyl, C 2 -C 6 - alkenyl, C 2 -C 6 -alkynyl, Ci-C 4 -alkoxy-Ci-C 4 -alkyl or CrC 4 -haloalkyl.
  • R 5a and R 6a are, independently of each other, CrC 4 -alkyl, in particular Ci-C 2 -alkyl, C 2 -C 6 -alkenyl, in particular C 2 -C 4 -alkenyl, C 2 -C 6 -alkynyl, in particular C 2 -C 4 -alkynyl, Cr C 4 -alkoxy-Ci-C 4 -alkyl, in particular Ci-C 2 -alkoxy-Ci-C 2 -alkyl, or CrC 4 -haloalkyl, in particular CrC 2 -haloalkyl.
  • R 5a and R 6a are, independently of each other, CrC 4 -alkyl, in particular Ci-C 2 -alkyl.
  • R 5 is Ci-C6-alkyl, which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, CrC 4 -alkoxy, CrC 4 -alkylthio, CrC 4 -alkylsulfinyl, CrC 4 -alkylsulfonyl, d- C 4 -haloalkoxy, CrC 4 -haloalkylthio, (CrC 4 -alkoxy)carbonyl, (Ci-C 4 -alkyl)amino, di(Ci-C 4 -alkyl)amino and Cs-C ⁇ -cycloalkyl, or is phenyl or phenyl-CrC 4 -alkyl, wherein the phenyl group in the two last-mentioned radicals may be unsubstituted or may carry 1 , 2 or 3 substitu
  • CrC 4 -alkyl wherein the phenyl group in the two last-mentioned radicals may be unsubstituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of halogen, Ci-C 4 -alkyl, CrC 4 -haloalkyl, Cr C 4 -alkoxy and Ci-C 4 -haloalkoxy.
  • R 5 is d-Ce-alkyl, Ci-C 4 -alkoxy-C r C 4 -alkyl, C r C 4 -haloalkyl or phenyl-C r C 4 -alkyl, wherein phenyl may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC 4 -alkyl, CrC 4 -haloalkyl, Ci-C 4 -alkoxy and CrC 4 -haloalkoxy; and
  • R 6 is hydrogen, CrC 6 -alkyl, Ci-C 4 -alkoxy-CrC 4 -alkyl, CrC 4 -haloalkyl or phenyl-d-
  • C 4 -alkyl wherein phenyl may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC 4 -alkyl, CrC 4 -haloalkyl, Ci-C 4 -alkoxy and CrC 4 - haloalkoxy.
  • R 5 and R 6 are, independently of each other, CrC ⁇ -alky!, in particular Cr C 4 -alkyl, or phenyl-CrC 4 -alkyl, in particular benzyl. More specifically, R 5 and R 6 are, independently of each other, CrC 6 -alkyl, in particular CrC 4 -alkyl.
  • R 5 is a radical NR 5b R 5c ;
  • R 6 is hydrogen, CrC ⁇ -alky!, which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, Ci-C 4 -alkoxy, CrC 4 -alkylthio, CrC 4 -alkylsulfinyl, CrC 4 - alkylsulfonyl, Ci-C 4 -haloalkoxy, CrC 4 -haloalkylthio, (CrC 4 -alkoxy)carbonyl, (CrC 4 -alkoxy)carbonyl, (Cr
  • R 5b and R 5c are, independently of each other, hydrogen, Ci-Cio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals selected from d-C 4 -alkoxy, or are C 2 -Ci 0 -alkenyl or C 2 -Ci 0 -alkynyl.
  • R 5b and R 5c are, independently of each other, hydrogen, Ci-C ⁇ -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-C 4 -alkoxy-Ci-C 4 -alkyl or Ci-C 4 -haloalkyl.
  • R 5b and R 5c are, independently of each other, hydrogen, Ci-C 4 -alkyl, C 2 -C 6 - alkenyl, in particular C 2 -C 4 -alkenyl, C 2 -C 6 -alkynyl, in particular C 2 -C 4 -alkynyl, CrC 4 - alkoxy-CrC 4 -alkyl, in particular Ci-C 2 -alkoxy-CrC 2 -alkyl, or Ci-C 4 -haloalkyl, in particular Ci-C 2 -haloalkyl.
  • R 5b and R 5c are, independently of each other, hydrogen or CrC 6 -alkyl and more specifically hydrogen or Ci-C 4 -alkyl.
  • At least one of the radicals R 5b and R 5c is not hydrogen.
  • R 6a is CrCio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals selected from Ci-C 4 -alkoxy, or is C 2 -Cio-alkenyl or C 2 -Cio-alkynyl.
  • R 36 b a a is C r C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-C 4 -alkoxy-C r C 4 - alkyl or Ci-C 4 -haloalkyl.
  • R 6a is CrC 4 -alkyl, in particular CrC 2 - alkyl, C 2 -C 6 -alkenyl, in particular C 2 -C 4 -alkenyl, C 2 -C 6 -alkynyl, in particular C 2 -C 4 - alkynyl, Ci-C 4 -alkoxy-CrC 4 -alkyl, in particular Ci-C 2 -alkoxy-CrC 2 -alkyl, or CrC 4 - haloalkyl, in particular CrC 2 -haloalkyl.
  • R 6a is CrC 4 -alkyl, in particular Ci-C 2 -alkyl.
  • R 6 is hydrogen; CrC 6 -alkyl, which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from Ci-C 4 -alkoxy; phenyl- CrC 4 -alkyl, wherein the phenyl group may by unsubstituted or may carry 1 , 2 or 3 sub- stituents, independently of one another selected from the group consisting of halogen,
  • R 6 is hydrogen, CrC ⁇ -alkyl or a radical OR 6a .
  • R 6 is hydrogen, Ci-C 4 -alkyl or a radical OR 6a .
  • the preferred embodiments of R 6a are as defir above.
  • R 7 and R 8 are, independently of each other, aryl, aryl-Ci-C 4 -alkyl, C 2 -C 6 - alkenyl, C 2 -C 6 -alkynyl, CrC 6 -alkyl which may be unsubstituted, partially or fully halo- genated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of Cr C 4 -alkoxy, or R 7 and R 8 , together with the sulfur atom they are bound to, form a 5-, 6- or 7-membered saturated or ethylenically unsaturated ring which may be unsubstituted or may carry 1 , 2, 3 or 4 substituents selected from halogen and CrC 4 -alkyl, and which may contain 1 or 2 carbonyl groups and/or heteroatoms selected from N, O and S and/or heteroatom groups selected from SO
  • R 7 and R 8 are, independently of each other, Ci-C ⁇ -alkyl, C 2 -C 6 - alkenyl, C 2 -C 6 -alkynyl, Ci-C 4 -alkoxy-Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, phenyl or phenyl-d- C 4 -alkyl, wherein phenyl in the last two radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC 4 -alkyl, Ci-C 4 -haloalkyl, CrC 4 -alkoxy and CrC 4 - haloalkoxy, or R 7 and R 8 together form a moiety (CH 2 ) k , wherein k is 4, 5 or 6 and wherein 1 , 2, 3 or 4 hydrogen atoms may be replaced by CrC 4 -alky
  • R 7 and R 8 are, independently of each other, CrC 6 -alkyl, in particular CrC 4 -alkyl, Ci-C 4 -alkoxy-Ci-C 4 -alkyl, in particular Ci-C 2 -alkoxy-CrC 2 -alkyl, Cr C 4 -haloalkyl, phenyl, or phenyl-CrC 4 -alkyl, in particular benzyl, or R 7 and R 8 together form a moiety (CH 2 ) k , wherein k is 4 or 5.
  • R 7 and R 8 are CrC 6 -alkyl, in particular CrC 4 -alkyl, or together form a moiety (CH 2 ) k , wherein k is 4 or 5, in particular 4.
  • A is a radical of the formula NR 10 -CO-R 9 , wherein R 9 and R 10 are as defined above.
  • R 9 is selected from the group consisting of hydrogen, OR 9a , NR 9b R 9c , aryl, aryl-Ci-C 4 -alkyl, CrCio-alkyl, C 2 -Ci 0 -alkenyl and C 2 -Ci 0 -alkynyl, wherein CrCio-alkyl, C 2 -Cio-alkenyl and C 2 -Ci 0 -alkynyl may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals selected from Ci-Cio-alkoxy, and wherein
  • R 9a is CrCio-alkyl, C 3 -Ci 0 -cycloalkyl, C 2 -Ci 0 -alkenyl, C 2 -Ci 0 -alkynyl, aryl, aryl-CrC 4 - alkyl, heteroaryl or heteroaryl-Ci-C 4 -alkyl, heterocyclyl or
  • R 9b , R 9c independently from each other, are selected from hydrogen, d-Cio-alkyl, C 3 - Cio-cycloalkyl, C 2 -Ci 0 -alkenyl, C 2 -Ci 0 -alkynyl, aryl and aryl-CrC 4 -alkyl,
  • R 9 , R 9a , R 9b and R 9c may be unsubstituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of halogen, CrC 4 -alkyl, CrC 4 - haloalkyl, CrC 4 -alkoxy and CrC 4 -haloalkoxy.
  • R 9 and R 10 together with the adjacent nitrogen and carbon atoms form a saturated or ethylenically unsaturated 5 to 10-membered ring, op- tionally substituted by 1 , 2, 3 or 4 radicals selected from CrC 5 -alkyl and halogen, wherein the ring may contain, in addition to the nitrogen and carbon ring members, 1 , 2 or 3 heteroatoms or heteroatom-containing groups as ring members selected from the group consisting of nitrogen, oxygen, sulfur, a group CO, SO, SO 2 or N-R 17 .
  • R 10 is selected from hydrogen, CrC 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, CrC 6 - alkoxy, Ci-C 4 -alkoxy-Ci-C 4 -alkyl, CrC 4 -haloalkyl and acetyl; and
  • R 9 is selected from C r C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-C 4 -alkoxy-Ci-C 4 - alkyl, CrC 4 -haloalkyl, phenyl and phenyl-CrC 4 -alkyl, wherein phenyl in the last two radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents, independently of one another selected from the group consist- ing of Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy and Ci-C 4 -haloalkoxy, or
  • R 10 and R 9 together form a moiety of the (CH 2 ) P , wherein p is 3, 4 or 5 and wherein 1 ,
  • 2, 3 or 4 hydrogen atoms may be replaced by CrC 4 -alkyl or halogen and wherein 1 or 2 non-adjacent CH 2 moieties may be replaced by a carbonyl group, a het- eroatom or a heteroatom group, selected from O, S, SO 2 and N-R # with R # being H or Ci-C 4 -alkyl.
  • R 10 is selected from hydrogen, d-C 4 -alkyl, C 2 -C 6 -alkynyl and CrC 4 -alkoxy and in particular from Ci-C 4 -alkyl;
  • R 9 is selected from CrC 4 -alkyl, C 2 -C 6 -alkenyl, CrC 4 -haloalkyl and phenyl, or
  • R 10 and R 9 together form a moiety of the (CH 2 ) P , wherein p is 3 or 4.
  • R 10 is selected from hydrogen and Ci-C ⁇ -alkyl
  • R 9 is selected from CrC 6 -alkyl and CrC 4 -haloalkyl.
  • R 10 is selected from hydrogen, CrC 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, CrC 6 - alkoxy, Ci-C 4 -alkoxy-CrC 4 -alkyl and CrC 4 -haloalkyl; and
  • R 9 is OR 9a or a radical NR 9b R 9c ,
  • R 9a , R 9b , and R 9c are as defined above.
  • R 9a is Ci-Ci O -alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals selected from Ci-C 4 -alkoxy, or is C 2 -Cio-alkenyl, C 2 -
  • Cio-alkynyl aryl or aryl-Ci-C 4 -alkyl. More preferably, R 9a is Ci-C ⁇ -alkyl, C 2 -C 6 -alkenyl,
  • R 9a is C 2 -C 6 -alkenyl, in particular vinyl or allyl, phenyl or phenyl-CrC 4 - alkyl, in particular benzyl.
  • R 9b and R 9c are, independently of each other, hydrogen, Ci-Cio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals selected from d-C 4 -alkoxy, or are C 2 -Ci 0 -alkenyl, C 2 -Ci 0 -alkynyl, aryl or aryl-CrC 4 - alkyl.
  • R 9b and R 9c are, independently of each other, hydrogen, C 1 -C6- alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-C 4 -alkoxy-CrC 4 -alkyl, Ci-C 4 -haloalkyl, phenyl or phenyl-Ci-C 4 -alkyl. It is preferred that R 9b and R 9c are not both hydrogen. Specifically, one of R 9b and R 9c is hydrogen and the other radical is CrC 6 -alkyl or phenyl.
  • R 10 is selected from hydrogen and CrC 4 -alkyl, more specifi- cally from hydrogen and CrC 2 -alkyl.
  • A is an N-bound 5-, 6- or 7-membered aromatic or non-aromatic unsaturated heterocycle and which additionally may contain 1 , 2, or 3 further heteroatoms or heteroatom groups, selected from O, S, SO, SO 2 , N, and NR 12 , and/or 1 , 2 or 3 carbonyl groups as ring members and which may carry 1 , 2, 3 or 4 radicals R 13 , where R 13 is as defined above.
  • R 13 is as defined above.
  • at least one double bond is positioned ⁇ to the nitrogen atom through which the radical A is bound.
  • the heterocycle contains 1 , 2 or 3 further heteroatoms or heteroatom groups as ring members, it is preferred that these are selected from N and NR 12 .
  • A is an N-bound 5-membered aromatic heterocycle which additionally may contain 1 , 2, or 3 further nitrogen atoms as ring members and which may carry 1 , 2, 3 or 4 radicals R 13 , where R 13 is as defined above.
  • R 13 is independently selected from halogen and Ci-C 4 -alkyl which may be partially or fully halogenated and/or may be substituted by 1 , 2 or 3 radicals selected from OH, Ci-C 4 -alkoxy and Ci-C 4 -alkylcarbonyloxy.
  • A is 1-pyrrolyl, 1-pyrazolyl, 1-imidazolyl or [1 ,2,4]-triazol-1-yl, where the heterocycle may be unsubstituted or may carry 1 , 2 or 3 substituents, specifically 1 substituent, selected from halogen and CrC 4 -alkyl, wherein Ci-C 4 -alkyl may be unsubstituted or may be substituted by hydroxy or acetyloxy.
  • A is 1- pyrrolyl which may be unsubstituted or may carry 1 , 2 or 3 substituents, specifically 1 substituent, selected from halogen and CrC 4 -alkyl, wherein Ci-C 4 -alkyl may be unsub- stituted or may be substituted by hydroxy or acetyloxy.
  • A is a radical of the formula NR 10 -CO-R 9 , wherein R 10 is selected from hydrogen, Ci-C 4 -alkyl, C 2 -C 6 -alkynyl and CrC 4 -alkoxy and R 9 is selected from Ci-C 4 -alkyl, C 2 -C 6 -alkenyl, Ci-C 4 -haloalkyl and phenyl; or A is a radical of the formula NR 10 -CO-R 9 , wherein R 10 and R 9 together form a moiety of the (CH 2 ) P , wherein p is 3 or 4; or
  • A is a radical of the formula NR 10 -CO-OR 9a , wherein R 9a is C r C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-C 4 -alkoxy-CrC 4 -alkyl, Ci-C 4 -haloalkyl, phenyl or phenyl-Ci-C 4 -alkyl and R 10 is hydrogen or Ci-C 4 -alkyl; or
  • A is a radical of the formula NR 10 -CO-R 9 , wherein R 10 is selected from hydrogen, Ci-C 4 -alkyl and C 2 -C 6 -alkynyl; and R 9 is selected from CrC 4 -alkyl, C 2 -C 6 -alkenyl, CrC 4 -haloalkyl and phenyl, or R 10 and R 9 together form a moiety of the (CH 2 ) P , wherein p is 3 or 4; or A is an N-bound 5-membered aromatic heterocycle which additionally may contain 1 , 2, or 3 further nitrogen atoms as ring members and which may carry 1 , 2, 3 or 4 radicals R 13 , where R 13 is as defined above. Preferred embodiments of R 10 , R 9 , R 13 and of the N-bound 5-membered aromatic heterocycle are as defined above.
  • variable m is preferably 2. These compounds are also referred to as compounds Ia. Compounds I, where m is 0 are also referred to as compounds Ib, while compounds I, where m is 1 , are also referred to as compounds Ic.
  • Examples of preferred compounds which are represented by the formulae Ia, Ib and Ic are the individual compounds compiled in the tables 1 to 264 below, where the variable A has the meanings given in one row of table A and the variables R 1 , R 2 , R 3 and R 4 have the meanings given in the respective table.
  • Table 1 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 2 is H, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 2 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 2 is F, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 3 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 2 is Cl, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 4 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 2 is Br, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 5 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 2 is I, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 8 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 2 is CCI 3 ,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 9 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 3 is F, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 10 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 3 is Cl, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 11 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 3 is Br, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 12 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 3 is I, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 13 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 3 is CH 3 ,
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 16 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 4 is F, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 17 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 4 is Cl, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 18 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 4 is Br, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 19 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 4 is I, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 20 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 4 is CH 3 ,
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 21 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 4 is CF 3 ,
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 23 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H5, R 2 is H, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 24 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H 5 , R 2 is F, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 25 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H 5 , R 2 is Cl, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 26 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H5, R 2 is Br, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 27 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H5, R 2 is I, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 28 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H 5 , R 2 is CH 3 ,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 29 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H 5 , R 2 is CF 3 ,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 31 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H 5 , R 3 is F, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 32 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H 5 , R 3 is Cl, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 33 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H 5 , R 3 is Br, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 34 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H 5 , R 3 is I, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 36 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H 5 , R 3 is CF 3 ,
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 38 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H 5 , R 4 is F, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 39 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H5, R 4 is Cl, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 40 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H5, R 4 is Br, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 41 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H 5 , R 4 is I, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 42 Compounds of the formulae Ia, Ib and Ic in which R 1 is C 2 H 5 , R 4 is CH 3 ,
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 45 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 2 is H, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 47 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 2 is Cl, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 48 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 2 is Br, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 50 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 2 is CH 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 51 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 2 is CF 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 52 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 2 is CCI3, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 54 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 3 is Cl, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 55 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 3 is Br, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 57 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 3 is CH 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 58 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 3 is CF 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 59 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 3 is CCI 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 60 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 4 is F, R 2 and
  • R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 61 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 4 is Cl, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 62 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 4 is Br, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 64 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 4 is CH 3 , R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 65 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 4 is CF 3 , R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 66 Compounds of the formulae Ia, Ib and Ic in which R 1 is F, R 4 is CCI3, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 67 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 2 is H, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 68 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 2 is F, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 69 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 2 is Cl, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 70 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 2 is Br, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 72 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 2 is CH 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 73 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 2 is CF 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 74 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 2 is CCI 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 75 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 3 is F, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 76 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 3 is Cl, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 77 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 3 is Br, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 78 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 3 is I, R 2 and
  • R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 79 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 3 is CH 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 80 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 3 is CF 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 81 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 3 is CCI 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 82 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 4 is F, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 83 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 4 is Cl, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 84 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 4 is Br, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 86 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 4 is CH 3 , R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 87 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 4 is CF 3 , R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 88 Compounds of the formulae Ia, Ib and Ic in which R 1 is Cl, R 4 is CCI 3 , R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 89 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 2 is H, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 90 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 2 is F, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 91 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 2 is Cl, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 92 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 2 is Br, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 93 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 2 is I, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 94 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 2 is CH 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 95 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 2 is CF 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 96 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 2 is CCI 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 97 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 3 is F, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 98 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 3 is Cl, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 99 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 3 is Br, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 100 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 3 is I, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 101 Compounds of the formulae Ia, Ib and Ic in which R 1 Br, R 3 is CH 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 102 Compounds of the formulae Ia, Ib and Ic in which R 1 is CH 3 , R 3 is CF 3 ,
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 103 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 3 is CCI 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 104 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 4 is F, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 105 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 4 is Cl, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 106 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 4 is Br, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 107 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 4 is I, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 108 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 4 is CH 3 , R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 109 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 4 is CF 3 , R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 1 10 Compounds of the formulae Ia, Ib and Ic in which R 1 is Br, R 4 is CCI 3 , R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 1 11 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 2 is H, R 3 and
  • R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 1 12 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 2 is F, R 3 and
  • R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 1 13 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 2 is Cl, R 3 and
  • R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 1 14 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 2 is Br, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 1 15 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 2 is I, R 3 and
  • R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 1 16 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 2 is CH 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 1 17 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 2 is CF 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 1 18 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 2 is CCI3, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 1 19 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 3 is F, R 2 and
  • R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 120 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 3 is Cl, R 2 and
  • R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 121 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 3 is Br, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 122 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 3 is I, R 2 and
  • R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 123 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 3 is CH 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 124 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 3 is CF 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 125 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 3 is CCI 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 126 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 4 is F, R 2 and
  • R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 128 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 4 is Br, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 129 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 4 is I, R 2 and
  • R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 130 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 4 is CH 3 , R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 131 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 4 is CF 3 , R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 132 Compounds of the formulae Ia, Ib and Ic in which R 1 is I, R 4 is CCI 3 , R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 133 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 2 is H, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 134 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 2 is F, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 135 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 2 is Cl, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 136 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 2 is Br, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 137 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 2 is I, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 138 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 2 is CH 3 ,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 139 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 2 is CF 3 ,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 140 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 2 is CCI 3 ,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 141 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 3 is F, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 142 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 3 is Cl, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 143 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 3 is Br, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 144 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 3 is I, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 145 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 3 is CH 3 ,
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 146 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 3 is CF 3 ,
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 148 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 4 is F, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 149 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 4 is Cl, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 150 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 4 is Br, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 151 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 4 is I, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 152 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 4 is CH 3 ,
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 153 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 4 is CF 3 ,
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 154 Compounds of the formulae Ia, Ib and Ic in which R 1 is CF 3 , R 4 is CCI 3 ,
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 155 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 2 is H,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 156 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 2 is F, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 158 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 2 is Br,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 159 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 2 is I, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 160 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 2 is CH 3 ,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 161 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 2 is CF 3 ,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • CCI 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 163 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 3 is F, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 164 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 3 is Cl,
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 165 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 3 is Br,
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 166 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 3 is I, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 167 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 3 is CH 3 ,
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 168 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 3 is CF 3 ,
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 169 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 3 is
  • CCI 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 170 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 4 is F, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 172 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 4 is Br,
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 173 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 4 is I, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 175 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCH 3 , R 4 is CF 3 ,
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 180 Compounds of the formulae Ia, Ib and Ic in which R 1 is OC 2 H 5 , R 2 is Br,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 182 Compounds of the formulae Ia, Ib and Ic in which R 1 is OC 2 H5, R 2 is
  • CH 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • CF 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • CCI 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 185 Compounds of the formulae Ia, Ib and Ic in which R 1 is OC 2 H 5 , R 3 is F,
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • CF 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • CCI 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 192 Compounds of the formulae Ia, Ib and Ic in which R 1 is OC 2 H 5 , R 4 is F,
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 195 Compounds of the formulae Ia, Ib and Ic in which R 1 is OC 2 H5, R 4 is I,
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • CH 3 , R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • CCI 3 , R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 199 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 2 is H, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 200 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 2 is F, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 201 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 2 is Cl,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 202 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 2 is Br,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 203 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 2 is I, R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 204 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 2 is CH 3 ,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 205 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 2 is CF 3 ,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 206 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 2 is CCI 3 ,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 207 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 3 is F, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 208 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 3 is Cl,
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 210 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 3 is I, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 211 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 3 is CH 3 ,
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 212 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 3 is CF 3 ,
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 214 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 4 is F, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 216 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 4 is Br,
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 217 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 4 is I, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 220 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCF 3 , R 4 is CCI 3 ,
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 221 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCHF 2 , R 2 is H,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 224 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCHF 2 , R 2 is Br,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 225 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCHF 2 , R 2 is I,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • CH 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • CF 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • CCI 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 229 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCHF 2 , R 3 is F,
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • CF 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • CCI3, R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 237 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCHF 2 , R 4 is Cl,
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • CH 3 , R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • CCI 3 , R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 247 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCCIF 2 , R 2 is I,
  • R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • CH 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • CCI 3 , R 3 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 251 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCCIF 2 , R 3 is F,
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 255 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCCIF 2 , R 3 is
  • CH 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • CF 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • CCI 3 , R 2 and R 4 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 260 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCCIF 2 , R 4 is Br,
  • R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 261 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCCIF 2 , R 4 is I, R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A;
  • Table 262 Compounds of the formulae Ia, Ib and Ic in which R 1 is OCCIF 2 , R 4 is
  • CCI 3 , R 2 and R 3 are H and A for each individual compound corresponds in each case to one row of table A.
  • 2-Cyanobenzene compounds Ia in which A is a radical of the formula NR 10 C(O)-R 9 in which R 9 is aryl, aryl-Ci-C 4 -alkyl, heteroaryl, heteroaryl-Ci-C 4 -alkyl, heterocyclyl, het- erocyclyl-CrC 4 -alkyl, Ci-Cio-alkyl or C 3 -Cio-cycloalkyl and R 10 has the meanings given above may be prepared, for example, by reacting a 2-cyanobenzene sulfonamide (II) with an acyl halide (Ilia), especially an acyl chloride, an acid anhydride (MIb) or a mixed acid anhydride in the presence of an appropriate base, see scheme 1.
  • Appropriate bases include organic bases, for example tertiary amines, such as aliphatic amines, for example trimethylamine, triethylamine or diisopropylethylamine, cycloaliphatic tertiary amines, for example N-methylpiperidine, or aromatic amines, for example pyridine, substituted pyridines such as 2,4,6-collidine, 2,4-lutidine or 4-dimethylaminopyridine.
  • the reaction is usually carried out in a solvent, for example an alkyl cyanide, such as acetonitrile or propionitrile.
  • the compounds of the formula Ia can be prepared analogously to a procedure described in Bull. Chem. Soc. Jpn. 1988, 61 , 3999-4004.
  • the reaction may also be carried out under acidic conditions, e.g. with sulfuric acid as catalyst.
  • a suitable solvent e.g. are polar and inert under the given reaction conditions.
  • suitable solvents include alkyl cyanides such as acetonitrile or propionitrile.
  • the reaction is e.g. analogous to a procedure described in Tetrahedron Letters 2003, 44, 5461-5463 to which reference is made
  • 2-Cyanobenzene compounds Ia in which A is a radical of the formula NR 10 C(O)-R 9 , wherein R 9 is OR 9a in which R 9a has the meanings mentioned above and R 10 has the meanings mentioned above, may be prepared by reacting a 2-cyanobenzene sulfonamide (II) with chloroformates of the formula CIC(O)OR 9a in the presence of suitable bases.
  • suitable bases include those mentioned above, e.g., triethylamine.
  • the reaction is usually carried out in an appropriate solvent such as an alkyl cyanide, for example acetonitrile or propionitrile.
  • the reaction can be carried out analogously to processes known from the prior art, for example in accordance with J. Med. Chem. 2004, 47, 627- 643.
  • 2-Cyanobenzene compounds Ia in which A is a radical of the formula NR 10 -C(O)-R 9 , wherein R 9 and R 10 together with the adjacent nitrogen and carbon atoms form a saturated or ethylenically unsaturated 5- to 10-membered ring as defined above and which may be substituted as described above, may be obtained by reacting a sulfonylhalide (IV), especially a sulfonylchloride, with a cyclic amide (V) in the presence of a strong base such as an organometallic base, for example an alkyllithium compound or aryllith- ium compound, e.g.
  • reaction is usually carried out in a polar organic solvent which is inert under the reaction condi- tions such as ether, for example, dialkyl ether or cyclic ethers such as tetrahydrofuran (THF) or dioxane, see scheme 2.
  • a polar organic solvent which is inert under the reaction condi- tions such as ether, for example, dialkyl ether or cyclic ethers such as tetrahydrofuran (THF) or dioxane, see scheme 2.
  • ether for example, dialkyl ether or cyclic ethers such as tetrahydrofuran (THF) or dioxane
  • THF tetrahydrofuran
  • Hal is halogen, especially chlorine.
  • 2-Cyanobenzene compounds Ia in which A is a radical NR 10 -C(O)-R 9 , wherein R 9 is a radical NR 9b R 9c in which R 9b and R 9c are as defined above and R 10 has the meanings given above may be obtained by reacting a 2-cyanobenzene sulfonamide (II) with an appropriately substituted isocyanate (Vl).
  • the reaction can be performed in analogy to a process described in J. Med. Chem. 1979, 22, 321-325 (see scheme 3).
  • the variables R 1 , R 2 , R 3 , R 4 have the meanings mentioned above and in particular the meanings mentioned as being preferred.
  • Conversion of compounds Ia in which R 9c is H to compounds Ia in which R 9c is different from H may be obtained by alkylating the compounds Ia (where R 9c is H and which are obtainable according to scheme 3) with suitable alkylating agents in the presence of a base.
  • the required reaction conditions are known in the art, for example from J. March, Advanced Organic Synthesis, 3 nd edition, Wiley Interscience, New York, 1985, page 377.
  • 2-Cyanobenzene compounds Ia where A is a radical NR 10 -C(O)-R 9 may be converted by known methods to compounds Ia where A is a radical NR 10 -C(S)-R 9 by treatment with sulfurizing agents.
  • sulfurizing agents are organophosphorus sulfides such as Lawesson reagent, organotin sulfides or phosphorus(V) sulfides, see also J. March, Advanced Organic Synthesis, 3 rd edition, Wiley Interscience, 1985, p. 794 and literature cited therein.
  • the reaction can be carried out in a solvent or in sub- stance.
  • the temperature required for the reaction is generally above room temperature and is in particular in the range from 50 to 200°C.
  • the variables R 1 , R 2 , R 3 and R 4 have the meanings mentioned above and in particular the meanings mentioned as being preferred.
  • the variables R 1 , R 2 , R 3 R 4 , R 5a and R 6a have the meanings mentioned above and in particular the meanings mentioned as being preferred.
  • the variables R 1 , R 2 , R 3 and R 4 have the meanings mentioned above and in particular the meanings mentioned as being preferred.
  • the molar ratio of sulfonamide Il to amine (X) is 1 :1 ,01 to 1 :3.
  • the reaction is usually carried out in an inert organic solvent, such as alkanes, cycloalkanes or aromatic solvents, e.g. toluene.
  • an inert organic solvent such as alkanes, cycloalkanes or aromatic solvents, e.g. toluene.
  • R 1 , R 2 , R 3 and R 4 have the meanings mentioned above and in particular the meanings mentioned as being preferred and R is CrC 6 -alkyl, especially CrC 2 -alkyl, in particular methyl.
  • the reaction is usually carried out in a polar solvent, for example CrC 4 -alkanols such as methanol, ethanol, n-propanol or isopropanol, carboxamides such as N,N-dimethyl formamide, N,N-dimethyl acetamide or N-methylpyrrolidinone.
  • a polar solvent for example CrC 4 -alkanols such as methanol, ethanol, n-propanol or isopropanol, carboxamides such as N,N-dimethyl formamide, N,N-dimethyl acetamide or N-methylpyrrolidinone.
  • Suitable bases are for example those bases mentioned above.
  • the reaction is usually carried out in a polar solvent, for example CrC 4 -alkanols such as methanol, ethanol, n-propanol or isopropanol, carboxamides such as N,N-dimethyl formamide, N,N-dimethyl acetamide or N-methylpyrrolidinone.
  • a polar solvent for example CrC 4 -alkanols such as methanol, ethanol, n-propanol or isopropanol, carboxamides such as N,N-dimethyl formamide, N,N-dimethyl acetamide or N-methylpyrrolidinone.
  • 2-Cyanobenzene compounds Ia wherein A is an N-bound 5-, 6- or 7-membered aromatic or non-aromatic unsaturated heterocycle as defined above, may be prepared by reacting a sulfonamide (II) with a 2,5-dialkoxytetrahydrofuran (XIII) which may be un- substituted or may carry 1 , 2, 3 or 4 radicals R 13 (where R 13 has the meanings men- tioned above), see scheme 10.
  • the reaction is carried out in an acidic solvent such as carboxylic acids, for example Ci-C 4 -carboxylic acids, e.g. acetic acid.
  • the reaction of Il with XIII can be carried out analogously to methods known from the literature, for example, as described in Synthetic Communications 1983, 13, 741-744.
  • R 1 , R 2 , R 3 and R 4 have the meanings mentioned above and in particular the meanings mentioned as being preferred R is Ci-C ⁇ -alkyl, especially CrC 2 -alkyl, in particular methyl.
  • 2-cyanobenzene compounds Ia wherein A is an N-bound 5-, 6- or 7- membered aromatic or non-aromatic unsaturated heterocycle as defined above, may be prepared by reacting a sulfonylchloride (IV) with an appropriate 5-, 6- or 7- membered aromatic or non-aromatic unsaturated N containing heterocycle (XIV) in the presence of an inorganic base, see scheme 1 1.
  • Suitable bases are, for example, alkali metal or alkaline earth metal hydroxides, bicarbonates or carbonates such as lithium hydroxide, lithium bicarbonate or lithium carbonate, sodium hydroxide, sodium bicarbonate or sodium carbonate, potassium hydroxide, potassium bicarbonate or potassium carbonate, calcium hydroxide, calcium bicarbonate or calcium carbonate, or magnesium hydroxide, magnesium bicarbonate or magnesium carbonate.
  • the reaction is carried out under phase transfer catalysis conditions.
  • Suitable for use as phase- transfer catalysts are quaternary ammonium or phosphonium salts.
  • the reaction of IV with XIV can be carried out analogously to methods known from the literature, for example, as described in Can. J. Chem 1985, 63, 896-902.
  • 2-cyanobenzene compounds Ia wherein A is an optionally substituted imidazole may be prepared in analogy to a method described in Indian Journal of Heterocyclic Chemistry 2003, 13, 79-80; 2-cyanobenzene compounds Ia, wherein A is an optionally substituted pyrazole, may be prepared in analogy to a method described in Heterocycles 1988, 27, 2443-2457; or 2-cyanobenzene compounds Ia, wherein A is an optionally substituted triazole may be prepared in analogy to a method described in Bioorganic & Medicinal Chemistry 2004, 2317-2333.
  • the starting material of the formula Il as well as the starting material of the formula IV required for preparing the compounds Ia are known from the literature, for example from WO 2005/035486 cited at the introductory part or they can be prepared in accordance with the literature cited therein.
  • the sulfenylamide compounds of the formula XV may be prepared, for example, by reacting a 2-cyanobenzenesulfenylhalide, (XVI), especially a 2-cyanobenzenesulfenyl- chloride, with ammonia or a primary amine (XVII) by analogy to a process described in Journal of Organic Chemistry 1977, VO. 42, No. 4, pp. 597-600 or in Journal of Medicinal Chemistry 2001 , Vol. 44, No. 13, pp. 2253-2258, see Scheme 12.
  • XVI 2-cyanobenzenesulfenylhalide
  • XVII ammonia or a primary amine
  • the amine XVII is employed in an at least equimolar amount, preferably at least 2-fold molar excess, based on the sulfenylhalide XVI, to bind the hydrogen halide formed. It may be advantageous to employ the primary amine XVII in an up to 6-fold molar excess, based on the sulfenylhalide XVI.
  • the reaction is usually carried out in the presence of a solvent.
  • Suitable solvents are polar solvents which are inert under the reaction conditions, for example CrC 4 -alkanols such as methanol, ethanol, n-propanol or isopropanol, dialkyl ethers such as diethyl ether, diisopropyl ether or methyl tert-butyl ether, cyclic ethers such as dioxane or tet- rahydrofuran, acetonitrile, carboxamides such as N,N-dimethyl formamide, N 1 N- dimethyl acetamide or N-methylpyrrolidinone, water, (provided the sulfenylhalide XVI is sufficiently resistent to hydrolysis under the reaction conditions used) or a mixture thereof.
  • the sulfenylhalide compounds XVI may be prepared, for example by the process as described hereinafter comprising steps a) and b),
  • Suitable reducing agents include (1 ) tris(2- carboxyethyl)phosphine in a mixture of dioxane and water as described in Syn- thetic Communications 2003, Vol. 33, No. 20, pp. 3503-351 1 ; or (2) triphenyl- phosphine with or without the addition of iodine in an aromatic solvent like benzene or toluene as described in Bulletin of the Chemical Society of Japan 1983, Vol. 56, No. 12, pp.
  • the sulfinylamide compounds of the formula XIX can be prepared, for example, by reacting a 2-cyanobenzenesulfinylhalide (XX) with ammonia or a primary amine (XVII) in analogy to a process described in Journal of Organic Chemistry 1983, Vol. 48 pp. 4803-4807, see scheme 14.
  • the variables R 1 , R 2 , R 3 and R 4 have the meanings mentioned above and in particular the meanings mentioned as being preferred and Hal is halogen, in particular chlorine.
  • the amine XVII is employed in an at least equimolar amount, preferably at least 2-fold molar excess, based on the sulfinylhalide XX, to bind the hydrogen halide formed. It may be advantageous to employ the primary amine XVII in an up to 6-fold molar excess, based on the sulfinylhalide XX.
  • the reaction of XVII with XX is usually carried out at a reaction temperature ranging from 0°C to the boiling point of the solvent, preferably from 0 to 30°C.
  • a sulfinylhalide XX with an amine XVII is usually carried out in the presence of a solvent.
  • Suitable solvents are polar solvents which are inert under the reac- tion conditions, for example CrC 4 -alkanols such as methanol, ethanol, n-propanol or isopropanol, dialkyl ethers such as diethyl ether, diisopropyl ether or methyl tert-butyl ether, cyclic ethers such as dioxane or tetrahydrofuran, acetonitrile, carboxamides such as N,N-dimethyl formamide, N,N-dimethyl acetamide or N-methylpyrrolidinone, water, (provided the sulfinylhalide XX is sufficiently resistent to hydrolysis under the reaction conditions used) or a mixture thereof.
  • the sulfinylhalide compounds XX may be prepared for example by the process as described hereinafter, (see scheme 15) comprising steps (a) and (b):
  • 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 on silica gel.
  • Some of the intermediates and end products may be obtained in the form of colorless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystallization or digestion.
  • the compounds of the formula I and their salts are in particular suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes.
  • insects are suitable for controlling insect pests, such as insects from the order of
  • Lepidoptera for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, An- ticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumifer- ana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Gra- pholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis vir
  • Coleoptera (beetles), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufi- manus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cero- toma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12- punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutino
  • Diptera for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chry- somya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophi- lus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia ca- prina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Maye
  • Thysanoptera e.g. Dichromothrips spp., Frankliniella fusca, Frankliniella occi- dentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
  • Hymenoptera e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplo- campa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta,
  • Heteroptera e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysder- cus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiven- tris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor,
  • Homoptera in particular aphids
  • aphids e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis craccivora, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci,
  • Acyrthosiphon pisum Aulacorthum solani, Bemisa tabaci, Bemisa argentifolii, Brachy- caudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus pruni- cola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Em- poasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Mac- rosiphum euphorbiae, Macrosiphon rosae,
  • lsoptera (termites), e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus und Termes natalensis,
  • Orthoptera e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auri- cularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schisto- cerca peregrina, Stauronotus maroccanus and Tachycines asynamorus, and
  • Collembola (springtails), e.g. Onychiurus ssp..
  • Nematodes plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javani- ca, and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, An- guina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursa- phelenchus xylophilus and other Bursaphelenchus species; Ring nematodes
  • arachnids such as acarians ⁇ Acarina
  • Argasidae, Ixodidae and Sarcoptidae such as Amblyomma americanum, Amblyomma variegatum, Argas persi- cus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendi- culatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp.
  • arachnoidea such as acarians ⁇ Acarina
  • Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis.
  • insects preferably sucking or piercing insects such as insects from the genera Thysanoptera, Hymenop- tera, Orthoptera and Homptera, in particular the following species:
  • Thysanoptera Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci, Hymenoptera: Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta,
  • Orthoptera Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricu- laria, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus fe- mur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schisto- cerca peregrina, Stauronotus maroccanus and Tachycines asynamorus ;
  • Homoptera in particular aphids: Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphi
  • Compounds of the formula I are particularly useful for controlling insects of the orders Homoptera and Thysanoptera and more preferably for controlling aphids.
  • the compounds I can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules and directly sprayable solutions.
  • the use form depends on the particular purpose and application method. Formulations and application methods are chosen to ensure in each case a fine and uniform distribution of the compound of the formula I according to the present invention.
  • the formulations are prepared in a known manner, e.g. by extending the active ingredient with solvents and/or carriers, if desired using surfactants, i.e. emulsifiers and dis- persants and other formulation auxiliaries.
  • surfactants i.e. emulsifiers and dis- persants and other formulation auxiliaries.
  • Solvents/carriers which are suitable, are e.g.:
  • solvents such as water, aromatic solvents (for example Solvesso products, xy- lene and the like), paraffins (for example mineral fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexa- none, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diace- tate), alkyl lactates, lactones such as g-butyrolactone, glycols, fatty acid di- methylamides, fatty acids and fatty acid esters, triglycerides, oils of vegetable or animal origin and modified oils such as alkylated plant oils.
  • aromatic solvents for example Solvesso products, xy- lene and the like
  • paraffins for example mineral fractions
  • alcohols for example methanol, butanol, pentanol, benzyl alcohol
  • ketones for example cyclo
  • solvent mixtures may also be used.
  • carriers such as ground natural minerals and ground synthetic minerals, such as silica gels, finely divided silicic acid, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, 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.
  • fertilizers such as, for example, 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 are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylpheny
  • Suitable auxiliaries comprise stabilizers, buffers, antioxidants, biocides, antifoams, thickeners, antifreeze and the like.
  • Suitable thickeners are compounds which confer a pseudoplastic flow behavior to the formulation, i.e. high viscosity at rest and low viscosity in the agitated stage. Mention may be made, in this connection, for example, of cammercial thickeners based on polysaccharides, such as Xanthan Gum ® (Kelzan ® from Kelco), Rhodopol ® 23 (Rhone Poulenc) or Veegum ® (from RT. Vanderbilt), or organic phyllosilicates, such as Atta- clay ® (from Engelhardt).
  • cammercial thickeners based on polysaccharides, such as Xanthan Gum ® (Kelzan ® from Kelco), Rhodopol ® 23 (Rhone Poulenc) or Veegum ® (from RT. Vanderbilt), or organic phyllosilicates, such as Atta- clay ® (from Engelhardt).
  • Antifoam agents suitable for the dispersions according to the invention are, for example, silicone emulsions (such as, for example, Silikon ® SRE, Wacker or Rhodorsil ® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
  • Biocides can be added to stabilize the compositions according to the invention against attack by microorganisms. Suitable biocides are, for example, based on isothiazolones such as the compounds marketed under the trademarks Proxel ® from Avecia (or Arch) or Acticide ® RS from Thor Chemie and Kathon ® MK from Rohm & Haas.
  • Suitable antifreeze agents are organic polyols, for example ethylene glycol, propylene glycol or glycerol. These are usually employed in amounts of not more than 10% by weight, based on the total weight of the active compound composition.
  • the active compound compositions according to the invention may comprise 1 to 5% by weight of buffer, based on the total amount of the formulation prepared, to regulate the pH, the amount and type of the buffer used depending on the chemical properties of the active compound or the active compounds.
  • buffers are alkali metal salts of weak inorganic or organic acids, such as, for example, phosphoric acid, boronic acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.
  • Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are 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, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, etha- nol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
  • 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, for example toluene, x
  • Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients 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, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, 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.
  • the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient.
  • the active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to
  • Soluble concentrates 10 parts by weight of a compound according to the invention are dissolved in water or in a water-soluble solvent.
  • wetters or other auxiliaries are added.
  • the active ingredient dissolves upon dilution with water.
  • DC Dispersible concentrates 20 parts by weight of a compound according to the invention are dissolved in cyclohexanone with addition of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion.
  • a dispersant for example polyvinylpyrrolidone
  • Emulsifiable concentrates 15 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxy- late (in each case 5% strength). Dilution with water gives an emulsion.
  • D Emulsions (EW, EO) 40 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxy- late (in each case 5% strength). This mixture is introduced into water by means of an emulsifier (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.
  • EW EO 40 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxy- late (in each case 5% strength).
  • This mixture is introduced into water by means of an emulsifier (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.
  • a compound according to the invention in an agitated ball mill, 20 parts by weight of a compound according to the invention are milled with addition of dispersant, wetters and water or an organic solvent to give a fine active ingredient suspension. Dilution with water gives a stable suspension of the active ingredient.
  • a compound according to the invention 50 parts by weight of a compound according to the invention are ground finely with addition of dispersants and wetters and made into water-dispersible or wa- ter-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active ingredient.
  • Water-dispersible powders and water-soluble powders (WP, SP) 75 parts by weight of a compound according to the invention are ground in a ro- tor-stator mill with addition of dispersant, wetters and silica gel. Dilution with water gives a stable dispersion or solution with the active ingredient.
  • a compound according to the invention is ground finely and associated with 95.5% carriers.
  • Current methods are extrusion, spray drying or the fluidized bed. This gives granules to be applied undiluted.
  • Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
  • 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.
  • the active ingredient concentrations in the ready-to-use products can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 %.
  • the active ingredients may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active ingredient, or even to apply the active ingredient without additives.
  • compounds I may be applied with other active ingredients, for example with other pesticides, insecticides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides.
  • additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix).
  • the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
  • Organo(thio)phosphates acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methi- dathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimi- phos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazo- phos, trichlorfon;
  • chitin synthesis inhibitors benzoylureas: chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, te- flubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
  • Nicotinic receptor agonists/antagonists compounds clothianidin, dinotefuran, imida- cloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid and AKD-1022, (6) GABA antagonist compounds: acetoprole, endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, the phenylpyrazole compound of formula F 2
  • Macrocyclic lactone insecticides abamectin, emamectin, milbemectin, lepimectin, spinosad;
  • METI I compounds fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
  • METI Il and III compounds acequinocyl, fluacyprim, hydramethylnon;
  • Oxidative phosphorylation inhibitor compounds cyhexatin, diafenthiuron, fenbu- tatin oxide, propargite;
  • Anthranilamides such as chlorantraniliprole and the compound of formula F 5 and their preparation have been described in WO 01/70671 ; WO 02/48137; WO 03/24222, WO 03/15518, WO 04/67528; WO 04/33468; and WO 05/118552.
  • the pests are controlled by contacting the target parasite/pest, its food supply, habitat, breeding ground or its locus with a pesti- cidally effective amount of compounds of formula I or with a salt thereof or with a composition containing a pesticidally effective amount of a compound of formula I or a salt thereof.
  • “Locus” means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is growing or may grow.
  • pesticidally effective amount means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the pesticidally effective amount can vary for the various compounds/compositions used in the invention.
  • a pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
  • the compounds of the invention can also be applied preventively to places at which occurrence of the pests is expected.
  • the compounds of formula I may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of compounds of formula I.
  • "contacting” includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).
  • compositions are particularly useful for protecting crop plants against infestation of said pests or for combating these pests in infested plants.
  • the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.
  • the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m 2 , preferably from 0.001 to 2O g per 100 m 2 .
  • the compounds of formula I are also suitable for the treatment of seeds in order to protect the seed from insect pest, in particular from soil-living insect pests and the resulting plant's roots and shoots against soil pests and foliar insects.
  • the compounds of formula I are particularly useful for the protection of the seed from soil pests and the resulting plant's roots and shoots against soil pests and foliar insects.
  • the protection of the resulting plant's roots and shoots is preferred. More preferred is the protection of resulting plant's shoots from piercing and sucking insects, wherein the protection from aphids is most preferred.
  • the present invention therefore comprises a method for the protection of seeds from insects, in particular from soil insects and of the seedlings' roots and shoots from insects, in particular from soil and foliar insects, said method comprising contacting the seeds before sowing and/or after pregermination with a compound of the general formula I or a salt thereof.
  • a method wherein the plant's roots and shoots are protected, more preferably a method, wherein the plants shoots are protected form piercing and sucking insects, most preferably aa method, wherein the plants shoots are protected from aphids.
  • seed embraces seeds and plant propagules of all kinds including but not Nm- ited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
  • compositions which are useful for seed treatment are e.g.: A Soluble concentrates (SL, LS) D Emulsions (EW, EO, ES) E Suspensions (SC, OD, FS)
  • Preferred FS formulations of compounds of formula I for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/L) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/L) of at least one surfactant, e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g.
  • a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight.
  • a binder sticker /adhesion agent
  • a preservative such as a biocide, antioxidant or the like
  • Suitable pigments or dyes for seed treatment formulations are 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 1 12, 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.
  • Binders which are also referred to as stickers / adhesion agents are added to improve the adhesion of the active materials on the seeds after treatment.
  • Suitable adhesives are block copolymers EO/PO surfactants but also polyvinylalcohols, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines (Lupasol®, Polymin®), polyethers and copolymers derived from these polymers.
  • the application rates of the compounds I are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed.
  • the invention therefore also relates to seed comprising a compound of the formula I or an agriculturally useful salt of I, as defined herein.
  • the amount of the compound I or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed.
  • the compounds of the invention may also be applied against non-crop insect pests, such as ants, termites, wasps, flies, mosquitos, crickets, or cockroaches.
  • non-crop insect pests such as ants, termites, wasps, flies, mosquitos, crickets, or cockroaches.
  • compounds of formula I are preferably used in a bait com- position.
  • the bait can be a liquid, a solid or a semisolid preparation (e.g. a gel).
  • Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks.
  • Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources.
  • Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickyness, moisture retention or aging characteristics.
  • the bait employed in the composition is a product which is sufficiently attractive to in- cite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it.
  • the attractiveness can be manipulated by using feeding stimulants or sex pheromones.
  • Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey.
  • Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant.
  • Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.
  • the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound.
  • Formulations of compounds of formula I as aerosols are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches.
  • Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, etha- nol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocar- bons (e.g.
  • kerosenes having boiling ranges of approximately 50 to 250°C, dimethyl- formamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
  • emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of
  • the oil spray formulations differ from the aerosol recipes in that no propellants are used.
  • the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
  • the compounds of formula I and its respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
  • the mixture was diluted by adding methyl tert-butyl ether and cooled to 0°C. Aqueous NH 4 CI was added, the layers were separated and the aqueous layer was extracted two times with methyl terf-butyl ether. The combined organic layers were washed with brine, dried over a drying agent and filtered off with suction. The filtrate was concentrated in vacuo and purified by flash chromatography (cyclohexane/ethyl acetate 4:1 ) to afford 0.10 g (8 % of theory) of 2- methyl-6-(2-oxo-pyrrolidine-1 -sulfonyl)benzonitrile.
  • Example 20 ⁇ /-(2,2-Dimethylpropionoyl)- ⁇ /-methyl-2-cyano-3-methyl-benzene- sulfonamide 42 mg (1.05 mmol) of NaH (60 % in mineral oil) were suspended in 10 ml of dry THF under an inert atmosphere. 0.21 g (1.0 mmol) of ⁇ /-methyl-2-cyano-3-methyl-benzene- sulfonamide in 10 ml of dry THF were added slowly at room temperature. Stirring was continued for 30 min at room temperature before 0.12 g (1.0 mmol) of pivaloyl chloride were slowly added and stirring was continued overnight at room temperature.
  • Example 22 ⁇ /-Ethyl- ⁇ /-(2-cyano-3-methyl-benzenesulfonyl)- ⁇ /'-phenyl urea
  • Example 29 ⁇ /-(lsopropylamino-ethoxy-methylene)-2-cyano-3-methyl-benzene- sulfonamide 0.50 g (1.7 mmol) of 2-cyano- ⁇ /-diethoxymethylene-3-methyl-benzenesulfonamide and 1.00 g (16.9 mmol) of isopropylamine were mixed and heated at 70°C for 4 h.
  • Example 46 2-Methyl-6-(pyrazole-1-sulfonyl)-benzonitrile To a solution of 0.41 g (1.90 mmol) of 2-cyano-3-methyl-benzenesulfonylchloride in 10 ml of dichloromethane was added 0.19 g (2.81 mmol) of pyrazole and 0.39 g of triethylamine at room temperature. After stirring overnight, TLC showed completion of the reaction. Ammonium chloride solution was added, the layers were separated and the aqueous layer was extracted three times with dichloromethane. The combined organic extracts were dried over a drying agent and filtered off with suction.
  • Table I The products were characterized by coupled High Performance Liquid Chromatography / mass spectrometry (HPLC/MS), by NMR or by their melting points.
  • the active compounds were formulated in a mixture of 50 vol.-% acetone:50 vol.-% water.
  • a nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % v/v.
  • the formulated solutions of the active compounds were diluted to an active ingredient concentration of 300 ppm and the diluted solutions were applied in the below mentioned tests.
  • Cotton plants at the cotyledon stage were infested prior to treatment by placing a heavily infested leaf from the main aphid colony on top of each cotyledon. The aphids were allowed to transfer overnight and the host leaf was removed. The infested cotyledons were then dipped and agitated in the test solution for 3 seconds and allowed to dry in a fume hood. Test plants were maintained under fluorescent lighting in a 24-hr photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated check plants, was determined after 5 days.
  • Bell pepper plants at the first true-leaf stage were infested prior to treatment by placing heavily infested leaves from the main aphid colony on top of the treatment plants.
  • the aphids were allowed to transfer overnight to accomplish an infestation of 30-40 aphids per plant and the host leaves were removed.
  • the infested leaves of the test plants were then dipped and agitated in the test solution for 3 seconds and allowed to dry in a fume hood.
  • Test plants were maintained under fluorescent lighting in a 24-hr photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated check plants, was determined after 5 days.
  • 300 ppm provided at least 86 % mortality of green peach aphidin comparison with untreated controls.
  • Nasturtium plants grown in Metro mix in the 1 st leaf-pair stage were infested with approximately 2-30 laboratory-reared aphids by placing infested cut plants on top of the test plants. The cut plants were removed after 24 hr. Each plant was dipped into the test solution to provide complete cover- age of the foliage, stem, protruding seed surface and surrounding cube surface and allowed to dry in the fume hood. The treated plants were kept at about 25°C with continuous fluorescent light. Aphid mortality is determined after 3 days.
  • each of examples 2, 5, 6, 7, 8, 1 1 , 12, 13, 14, 15, 17, 18, 21 , 23, 25, 26, 27, 30, 31 , 32, 33, 35, 36, 37, 38, 41 , 42, 44 at 300 ppm provided at least 86 % mortality of bean aphid in comparison with untreated controls.

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Abstract

The present invention relates to a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of at least one cyanobenzene compound of the formula (I) and/or at least one agriculturally acceptable salt thereof: where m is 0, 1 or 2; is a radical of the formulae N=CR5R6, N=SR7R8, NR10-C(=X)-R9, where X is O, S A or NR11, or A is a N-bound 5-, 6- or 7-membered heterocycle, which is ethylenically unsaturated or aromatic, and which additionally may contain 1, 2, or 3 further heteroatoms or heteroatom groups, selected from O, S, SO, SO2, N, and NR12, and/or 1, 2 or 3 carbonyl groups as ring members and which may carry 1, 2, 3 or 4 radicals R13, where the radicals R1 to R13 are as defined in the claims or the description. The invention further relates to specific compounds I and to agricultural compositions comprising them.

Description

Cyanobenzene compounds for combating animal pests
The present invention relates to a method of combating animal pests by using cyanobenzene compounds and/or agriculturally acceptable salts thereof. The invention also relates to certain cyanobenzene compounds and/or their agriculturally acceptable salts and also to compositions comprising them.
Animal pests destroy growing and harvested crops and attack wooden dwelling and commercial structures, causing large economic loss to the food supply and to property. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new agents for combating animal pests. In particular, animal pests such as insects and acaridae are difficult to be effectively controlled.
EP 33984 discloses 2-cyanobenzene sulfonamides having aphicidal activity. Their activity, however, is not satisfactory. Similar compounds are described in WO 2005/035486.
EP-A-0303863 describes benzenesulfonyl-2-imidazolin-5-one compounds which are useful as herbicides. An activity against animal pests is not mentioned.
EP-A-0107624 describes a method for producing sulfonylurea compounds by reacting a sulfonylamidocarbonic diester with an amino-substituted pyrimidine or triazine. The sulfonylurea compounds are said to have a herbicidal activity.
D. -H. Kweon et al. describe in J. Heterocyclic Chem. 39, 2002, 203 the synthesis of certain pyridazinones. The compounds are supposed to be useful agrochemicals. An activity against animal pests is not specifically described.
N. Masuda et al. describe in Bioorganic and Medicinal Chemistry 13, 2005, 949 2- cyano-N-(4,5-dialkylthiazol-2-yl)-benzenesulfonamides. These compounds are used as intermediates for the synthesis of 2-cyano-N-(3-methyl-4,5-dialkylthiazol-2(3H)- ylidene)-benzenesulfonamides which are said to have a potent anti-HIV-1 activity.
The object of the present invention is to provide compounds having a good pesticidal activity, especially against difficult to control insects and acaridae.
It has been shown that this object is achieved by a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of at least one cyanobenzene compound of the formula I and/or at least one agriculturally acceptable salt thereof:
Figure imgf000003_0001
where
m is O, 1 or 2;
A is a radical of the formulae
N=CR5R6, N=SR7R8, NR10-C(=X)-R9, where X is O, S or NR11,
or A is a N-bound 5-, 6- or 7-membered heterocycle, which is ethylenically unsaturated or aromatic, and which additionally may contain 1 , 2, or 3 further het- eroatoms or heteroatom groups, selected from O, S, SO, SO2, N, and NR12, and/or 1 , 2 or 3 carbonyl groups as ring members and which may carry 1 , 2, 3 or 4 radicals R13,
R1 is hydrogen, nitro, cyano, azido, amino, halogen, sulfenylamino, sulfinylamino, sulfonylamino, C(=O)R14, CrC6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8- cycloalkyl, d-C6-alkoxy, (Ci-C6-alkyl)amino, di(Ci-C6-alkyl)amino, CrC6-alkylthio, Ci-Cβ-alkylsulfinyl or Ci-C6-alkylsulfonyl, wherein the ten last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, CrC4-alkoxy, CrC4-alkylthio, CrC4-alkylsulfinyl, CrC4-alkylsulfonyl, CrC4-haloalkoxy, CrC4- haloalkylthio, (CrC4-alkoxy)carbonyl, (C-ι-C4-alkyl)amino, di(C-ι-C4-alkyl)amino, C3-C8-cycloalkyl and phenyl, it being possible for phenyl to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy; R2, R3 and R4 are independently of one another selected from the group consisting of hydrogen, halogen, cyano, azido, nitro, CrC6-alkyl, C3-C8-cycloalkyl, CrC4- haloalkyl, d-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-alkylsulfinyl, CrC4-alkylsulfonyl, Ci-C4-haloalkoxy, Ci-C4-haloalkylthio, C2-C6-alkenyl, C2-C6-alkynyl, amino, (Cr C4-alkyl)amino, di(C-i-C4-alkyl)amino, sulfonylamino, sulfinylamino, sulfenylamino and C(=O)-R15;
R5 is H, OR5a, NR5bR5c, aryl, aryl-CrC4-alkyl, heteroaryl, heteroaryl-CrC4-alkyl, het- erocyclyl, heterocyclyl-Ci-C4-alkyl, Ci-Cio-alkyl, C3-Ci0-cycloalkyl, CrCi0- alkylthio, CrCi0-alkylsulfonyl, CrCiO-alkylsulfinyl, wherein the five last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another each selected from the group consisting of cyano, nitro, amino, CrCi0-alkoxy, CrCi0-alkylthio, CrCiO-alkylsulfinyl, Cr Cio-alkylsulfonyl, CrCi0-haloalkoxy, CrCi0-haloalkylthio, CrCi0-alkoxycarbonyl, (Ci-Cio-alkyl)amino, di-(CrCi0-alkyl)amino, C3-Ci0-cycloalkyl and phenyl, it being possible for phenyl to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC4-alkyl, CrC4-haloalkyl, Ci-C4-alkoxy and CrC4- haloalkoxy;
wherein
R5a is Ci-CiO-alkyl, C3-Ci0-cycloalkyl, C2-Ci0-alkenyl, C2-Ci0-alkynyl, aryl, aryl- CrC4-alkyl, heteroaryl or heteroaryl-CrC4-alkyl, heterocyclyl or heterocy- clyl-CrC4-alkyl;
R5b, R5c, independently from each other, are selected from hydrogen, CrCi0- alkyl, C3-Ci0-cycloalkyl, C2-Ci0-alkenyl, C2-Ci0-alkynyl, aryl, aryl-Ci-C4-alkyl, heteroaryl and heteroaryl-CrC4-alkyl, heterocyclyl or heterocyclyl-CrC4- alkyl;
wherein CrCiO-alkyl, C3-Ci0-cycloalkyl, C2-Ci0-alkenyl and C2-Ci0-alkynyl in R5a, R5b and R5c may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, Cr C4-alkoxy, CrC4-alkylthio, CrC4-alkylsulfinyl, CrC4-alkylsulfonyl, CrC4- haloalkoxy, CrC4-haloalkylthio, (CrC4-alkoxy)carbonyl, (CrC4-alkyl)amino, di(CrC4-alkyl)amino and C3-C8-cycloalkyl;
wherein the heteroaryl moiety in heteroaryl and heteroaryl-CrC4-alkyl of R5, R5a, R5b and R5c is 5- or 6 membered and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO2, N or NRa, as ring members, Ra being hydrogen or Ci-Cβ-alkyl;
wherein the heterocyclyl moiety in heterocyclyl and
Figure imgf000005_0001
of R5, R5a, R5b and R5c is 3- to 7 membered, is saturated or partly unsaturated and con- tains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO,
SO2, N or NRb, as ring members, Rb being hydrogen or d-C6-alkyl, and additionally may contain 1 , 2 or 3 CO groups as ring members;
and wherein the carbon atoms of aryl, hetaryl, and heterocyclyl moieties in R5, R5a, R5b and R5c may be unsubstituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of halogen, CrC4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and CrC4-haloalkoxy;
R6 independently has one of the meanings given for R5;
R7, R8, independently from each other, are selected from aryl, aryl-Ci-C4-alkyl, het- eroaryl, heteroaryl-Ci-C4-alkyl, heterocyclyl, heterocyclyl-CrC4-alkyl, Ci-CiO-alkyl, C3-Ci0-cycloalkyl, C2-Ci0-alkenyl and C2-Ci0-alkynyl, wherein the four last- mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another each selected from the group consisting of cyano, nitro, amino, CrCio-alkoxy, CrCio-alkylthio, CrCi0- alkylsulfinyl, CrCiθ-alkylsulfonyl, CrCiθ-haloalkoxy, CrCiθ-haloalkylthio, CrCi0- alkoxycarbonyl, (CrCiθ-alkyl)amino, di-(CrCiθ-alkyl)amino, C3-Ciθ-cycloalkyl and phenyl, it being possible for phenyl to be unsubstituted, partially or fully halo- genated and/or to carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC4-alkyl, CrC4-haloalkyl, CrC4-alkoxy and CrC4-haloalkoxy; or
R7 and R8 together with the sulfur atom they are bound to form a saturated or ethyleni- cally unsaturated 5- to 10-membered ring, optionally substituted by 1 , 2, 3 or 4 radicals selected from CrC5-alkyl and halogen, wherein the ring may contain, in addition to the sulfur atom, 1 , 2 or 3 heteroatoms and/or heteroatom-containing groups as ring members selected from the group consisting of nitrogen, oxygen, sulfur, CO, SO, SO2 and N-R17;
wherein the heteroaryl moiety in heteroaryl and heteroaryl-Ci-C4-alkyl of R7 and R8 is 5- or 6 membered and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO2, N or NRC, as ring members, Rc being hydrogen or CrC6-alkyl, wherein the heterocyclyl moiety in heterocyclyl and
Figure imgf000006_0001
of R7 and R8 is 3- to 7-membered, is saturated or partly unsaturated and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO2, N or NRd, as ring members, Rd being hydrogen or Ci-Cβ-alkyl, and additionally may contain 1 , 2 or 3 CO groups as ring members,
and wherein the carbon atoms of aryl, hetaryl, and heterocyclyl in R7 and R8 may be unsubstituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, CrC4-alkoxy and CrC4-haloalkoxy;
is selected from the group consisting of hydrogen, OR9a, NR9bR9c, aryl, aryl-d- C4-alkyl, heteroaryl, heteroaryl-Ci-C4-alkyl, heterocyclyl,
Figure imgf000006_0002
CrCio-alkyl, C2-Ci0-alkenyl, C2-Ci0-alkynyl and C3-Ci0-cycloalkyl, wherein the four last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another each selected from the group consisting of cyano, nitro, amino, Ci-Cio-alkoxy, Ci-Ci0-alkylthio, CrCio-alkylsulfinyl, Ci-Ci0-alkylsulfonyl, Ci-Cio-haloalkoxy, Ci-Ci0-haloalkylthio, CrCio-alkoxycarbonyl, (Ci-Ci0-alkyl)amino, di-(Ci-Ci0-alkyl)amino, C3-Ci0- cycloalkyl and phenyl, it being possible for phenyl to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC4-alkyl, CrC4-haloalkyl, CrC4- alkoxy and CrC4-haloalkoxy,
and wherein
R9a is Ci-Ciθ-alkyl, C3-Ci0-cycloalkyl, C2-Ci0-alkenyl, C2-Ci0-alkynyl, aryl, aryl- CrC4-alkyl, heteroaryl or heteroaryl-CrC4-alkyl, heterocyclyl or heterocy- clyl-CrC4-alkyl,
R9b, R9c, independently from each other, are selected from hydrogen, CrCi0- alkyl, C3-Ci0-cycloalkyl, C2-Ci0-alkenyl, C2-Ci0-alkynyl, aryl, aryl-Ci-C4-alkyl, heteroaryl and heteroaryl-Ci-C4-alkyl, heterocyclyl or heterocyclyl-CrC4- alkyl,
wherein CrCiO-alkyl, C3-Ci0-cycloalkyl, C2-Ci0-alkenyl and C2-Ci0-alkynyl in
R9a, R9b and R9c may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, CrC4-alkoxy, CrC4-alkylthio, CrC4-alkylsulfinyl, CrC4- alkylsulfonyl, CrC4-haloalkoxy, CrC4-haloalkylthio, (CrC4-alkoxy)carbonyl, (CrC4-alkyl)amino, di(CrC4-alkyl)amino and C3-C8-cycloalkyl, wherein the heteroaryl moiety in heteroaryl and heteroaryl-Ci-C4-alkyl of R9, R9a, R9b and R9c is 5- or 6-membered and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO2, N or NRe, as ring members, Re being hydrogen or Ci-Cβ-alkyl,
wherein the heterocyclyl moiety in heterocyclyl and heterocyclyl-d-Q-alkyl of R9, R9a, R9b and R9c is 3- to 7-membered, is saturated or partly unsaturated and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, se- lected from O, S, SO, SO2, N or NRf, as ring members, Rf being hydrogen or CrC6-alkyl, and additionally may contain 1 , 2 or 3 CO groups as ring members,
and wherein the carbon atoms of aryl, hetaryl and heterocyclyl moieties in R9, R9a, R9b and R9c may be unsubstituted or may carry 1 , 2 or 3 substitu- ents, independently of one another selected from the group consisting of halogen, d-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;
R10 is selected from the group consisting of hydrogen, C(=O)-R16, CrCio-alkyl, C2- Cio-alkenyl, C2-Cio-alkynyl, Ci-Cio-alkoxy and C3-Cio-cycloalkyl, wherein the five last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another each selected from the group consisting of cyano, nitro, amino, CrCio-alkoxy, CrCio-alkylthio, Ci-Cio-alkylsulfinyl, Ci-Cio-alkylsulfonyl, Ci-Cio-haloalkoxy, CrCio-haloalkylthio, CrCio-alkoxycarbonyl, (Ci-Ci0-alkyl)amino, di-(Ci-Ci0-alkyl)amino, C3-Ci0- cycloalkyl and phenyl, it being possible for phenyl to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC4-alkyl, Ci-C4-haloalkyl, CrC4- alkoxy and Ci-C4-haloalkoxy; or
R9 and R10 together with the adjacent nitrogen and carbon atoms form a saturated or ethylenically unsaturated 5 to 10-membered ring, optionally substituted by 1 , 2, 3 or 4 radicals selected from CrC5-alkyl and halogen, wherein the ring may contain, in addition to the nitrogen and carbon ring members, 1 , 2 or 3 heteroatoms and/or heteroatom groups as ring members selected from the group consisting of nitrogen, oxygen, sulfur, CO, SO, SO2 and N-R17;
R11 is Ci-Ce-alkyl or CrC6-alkoxy;
or R11 and R9 together with the adjacent nitrogen and carbon atoms form an ethylenically unsaturated aromatic or non-aromatic 5 to 10-membered ring, optionally substituted by 1 , 2 or 3 CrC5-alkyl radicals, wherein the ring may contain, in addition to the nitrogen and carbon ring members, 1 , 2 or 3 heteroatoms and/or heteroatom groups as ring members selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO2 and N-R17;
or
R11 and R10 together with the adjacent nitrogen and carbon atoms form an ethylenically unsaturated aromatic or non-aromatic 5 to 10-membered ring, optionally substituted by 1 , 2 or 3 CrC5-alkyl radicals, wherein the ring may contain, in addition to the nitrogen and carbon ring members, 1 , 2 or 3 heteroatoms and/or heteroatom groups as ring members selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO2 and N-R17;
R12 is hydrogen, d-C6-alkyl, Ci-C4-alkoxy-Ci-C4-alkyl or CrC6-alkoxy;
each R13 independently is selected from halogen, cyano, nitro, sulfenylamino, sulfinyl- amino, sulfonylamino, aryl, aryl-Ci-C4-alkyl, heteroaryl, heteroaryl-Ci-C4-alkyl, heterocyclyl, heterocyclyl-Ci-C4-alkyl, CrC6-alkyl, C3-C8-cycloalkyl, CrC6-alkoxy, CrC6-alkoxycarbonyl, d-Ce-alkylcarbonyl, (C-ι-C6-alkyl)amino, di(CrC6- alkyl)amino, Ci-Cβ-alkylthio, Ci-Cβ-alkylsulfinyl or Ci-C6-alkylsulfonyl, wherein the ten last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, OH, Ci-C4-alkoxy, CrC4-alkylthio, CrC4-alkylsulfinyl, CrC4- alkylsulfonyl, Ci-C4-haloalkoxy, Ci-C4-haloalkylthio, CrC4-alkylcarbonyloxy, (Cr C4-alkoxy)carbonyl, (Ci-C4-alkyl)amino, di(CrC4-alkyl)amino, C3-C8-cycloalkyl and phenyl, it being possible for phenyl to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC4-alkyl, CrC4-haloalkyl, Ci-C4-alkoxy and CrC4-haloalkoxy,
wherein the heteroaryl moiety in heteroaryl and heteroaryl-Ci-C4-alkyl of R13 is 5- or 6 membered and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO2, N or NR9, as ring members, R9 being hydrogen or d-Cβ-alkyl,
wherein the heterocyclyl moiety in heterocyclyl and heterocyclyl-CrC4-alkyl of R 13 is 3- to 7-membered and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO2, N or NRh, as ring members, Rh being hydrogen or CrC6-alkyl, and additionally may contain 1 , 2 or 3 CO groups as ring members,
and wherein the carbon atoms of aryl, hetaryl, and heterocyclyl in R13 may be un- substituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, CrC4- alkoxy and CrC4-haloalkoxy;
R14 and R15 independently of one another are selected from the group consisiting of hydrogen, hydroxy, CrC6-alkoxy, amino, Ci-C4-alkylamino, di(C-i-C4-alkyl)amino, aryl, aryl-Ci-C4-alkyl, Ci-C4-alkyl, where the alkyl moiety in the two last- mentioned radicals and the aryl moiety in aryl and aryl-Ci-C4-alkyl may be par- tially or fully halogenated,
3- to 7-membered heteroaryl or heteroaryl-Ci-C4-alkyl, wherein the heteroaryl ring contains as ring members 1 , 2 or 3 heteroatoms and/or heteroatom groups, selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO2 and N-Rn, wherein Rn is hydrogen or Ci-C4-alkyl,
3- to 7-membered heterocyclyl or heterocyclyl-CrC4-alkyl, wherein the heterocyclic ring is saturated or partly unsaturated and contains 1 , 2 or 3 heteroatoms and/or heteroatom groups, selected from the group consisting of nitrogen, oxy- gen, sulfur, SO, SO2 and N-R0, wherein R0 is hydrogen or d-C4-alkyl,
and wherein the carbon atoms of the heterocyclic rings may by unsubstituted or substituted by 1 or 2 radicals selected from halogen or Ci-C4-alkyl;
R16 is Ci-C6-alkyl, aryl, aryl-Ci-C4-alkyl,
5- to 7-membered heteroaryl or heteroaryl-Ci-C4-alkyl, wherein the heteroaryl ring contains as ring members 1 ,2 or 3 heteroatoms and/or heteroatom groups, selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO2 and N-Rk, wherein Rk is hydrogen or CrC4-alkyl,
3- to 7-membered heterocyclyl or heterocyclyl-CrC4-alkyl, wherein the heterocyclic ring is saturated or partly unsaturated and contains as ring members 1 , 2 or 3 heteroatoms and/or heteroatom groups, selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO2 and N-Rm, wherein Rm is hydrogen or Ci-C4- alkyl, and wherein the carbon atoms of the heterocyclic rings may be unsubstituted or substituted by 1 or 2 radicals selected from halogen or d-C4-alkyl;
or
R16 and R9 together with the adjacent nitrogen and carbon atoms form a saturated or ethylenically unsaturated 5 to 10-membered ring, where the ring may be partially or fully halogenated and/or may be substituted by 1 , 2 or 3 substituents selected from CrC5-alkyl and CrC5-haloalkyl, wherein the ring may contain, in addition to the nitrogen and carbon ring members, 1 , 2 or 3 heteroatoms and/or heteroatom groups as ring members selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO2 and N-R17;
each R17 independently is hydrogen, heteroaryl, heteroaryl-Ci-C4-alkyl or Ci-Cβ-alkyl, where the alkyl moiety in the two last-mentioned radicals may be partially or fully halogenated;
and/or the agriculturally acceptable salts thereof.
The compounds of the formula I and their agriculturally acceptable salts are highly active against animal pest, i.e. harmful arthropodes and nematodes, especially against difficult to control insects and acaridae.
Moreover, the present invention relates to the use of compounds I and/or their salts for combating animal pests.
The invention is also related to seed comprising a compound of the formula I or an ag- riculturally useful salt of I, as defined above, in an amount of from 0.1 g to 10 kg per 100 kg of seed.
The invention further relates to compounds of the formula (I) and agriculturally acceptable salts thereof,
except for compounds of the formula I, wherein R1 is H, NO2 or NH2 if R2 is H, R3 is H, Cl or CO2CH3, R4 is H and A is a radical N=CH-N(CH3)2; except for compounds of the formula I, wherein R1 is H if R2 is H or Cl, R3 is H, R4 is H and A is an optionally substituted pyridazin-6-on-1-yl radical or an optionally substituted imidazolin-5-on-1-yl radical;
except for compounds of the formula I, wherein R1 is H if R2 is H, R3 is H, R4 is H and A is a radical N=C(O-ethyl)2; and
except for compounds of the formula I, wherein A is a radical of the formula
Figure imgf000011_0001
where Rx and Ryare, independently of each other, hydrogen or Ci-C5-alkyl and R10 is H or CrCio-alkyl;
in particular
except for compounds of the formula I, wherein R1 is H, NO2 or NH2 if R2 is H, R3 is H, Cl or CO2CH3, R4 is H and A is a radical N=CH-N(CH3)2;
except for compounds of the formula I, wherein R1 and R2 are both H;
except for compounds of the formula I, wherein R1, R3 and R4 are H and R2 is halogen; and
except for compounds of the formula I, wherein A is a radical of the formula
Figure imgf000011_0002
where Rx and Ryare, independently of each other, hydrogen or d-C5-alkyl and R10 is H or CrCio-alkyl.
Finally, the invention also relates to agricultural compositions comprising at least one cyanobenzene derivative of the formula I and/or at least one agriculturally useful salt of I and at least one inert liquid and/or solid agronomically acceptable carrier and, if de- sired, at least one surfactant. The compound I and/or its salt is of course comprised in such an amount that it has a pesticidal action.
The compounds of the general formula I may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The present invention provides both the pure enantiomes or diastereomers or mixtures thereof. The compounds of the general formula I may also exist in the form of different tautomers, e.g. if one of R5b or R5c is H or if X is NR11 and R10 is H, but also in other cases. The invention comprises the single tautomers, if separable, as well as the tautomer mix- tures. The compounds of formula I may further exist in the form of different stereoisomers, in particular E/Z-isomers, e.g. in case A is N=CR5R6, with R5 and R6 being different substituents, or in case A is N=SR7R8, with R7, R8 being different substituents. The invention comprises single stereoisomers as well as stereoisomer mixtures.
Salts of the compounds of the formula I are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality or by reacting an acidic compound of formula I with a suitable base.
Suitable agriculturally useful salts are especially the salts of those cations or the acid addition salts of those acids the cations and anions of which do not have any adverse effect on the action of the compounds according to the present invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, 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 ammonium (NH4 +) and substituted ammonium in which one to four of the hydrogen atoms are replaced by CrC4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Cr C4-alkyl, hydroxy-Ci-C4-alkoxy-CrC4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammo- nium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl- ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl- triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(CrC4- alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of CrC4-alkanoic acids, preferably formiate, acetate, propionate and bu- tyrate. They can be formed by reacting the compounds of the formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
By the term "veterinarily acceptable salts" is meant salts of those cations or anions which are known and accepted in the art for the formation of salts for veterinary use. Suitable acid addition salts, e.g. formed by compounds of formula I containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hy- drochlorids, sulphates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group.
"Halogen" will be taken to mean fluoro, chloro, bromo and iodo.
The term "partially or fully halogenated" will be taken to mean that 1 or more, e.g. 1 , 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by a halogen atom, in particular by fluorine or chlorine.
The term "Cn-Cm-alkyl" as used herein (and also in Cn-Cm-alkylamino, di-Cn-Cm- alkylamino, Cn-Cm-alkylaminocarbonyl, di-(Cn-Cm-alkylamino)carbonyl, Cn-Cm-alkylthio (synonymous with Cn-Cm-alkylsulfenyl), Cn-Cm-alkylsulfinyl and Cn-Cm-alkylsulfonyl) refers to a branched or unbranched saturated hydrocarbon group having n to m, e.g. 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1 ,1-dimethylethyl, pentyl, 1- methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1 ,1- dimethylpropyl, 1 ,2-dimethylpropyl, 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, 1-ethyl-2-methylpropyl, heptyl, octyl, 2- ethylhexyl, nonyl and decyl and their isomers. CrC4-alkyl means for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1 ,1-dimethylethyl. Ci-C5-alkyl additionally means pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1 ,1- dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl and constitutional isomers thereof, d- C6-alkyl additionally means hexyl and constitutional isomers thereof. CrC2-alkyl means methyl and ethyl. The term "Cn-Cm-haloalkyl" as used herein refers to a straight-chain or branched alkyl group having n to m carbon atoms, e.g. 1 to 10 in particular 1 to 6 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, for example CrC4-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, pentafluoroethyl and the like. The term Ci-Cio-haloalkyl in particular comprises CrC2-fluoroalkyl, which is synonym with methyl or ethyl, wherein 1 , 2, 3, 4 or 5 hydrogen atoms are substituted by fluorine atoms, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl and pentafluoromethyl.
Similarly, "Cn-Cm-alkoxy" and "Cn-Cm-alkylthio" (= Cn-Cm-alkylsulfenyl) (and also Cn-Cm- alkylsulfinyl or Cn-Cm-alkylsulfonyl) refer to straight-chain or branched alkyl groups having n to m carbon atoms, e.g. 1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages (or SO (sulfinyl) or S(O)2 linkages (sulfonyl)), respectively, at any bond in the alkyl group. Examples include Cr C4-alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobu- toxy and tert-butoxy, further d-C4-alkylthio such as methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio further CrC4-alkylsulfinyl such as methylsulfinyl, ethyl- sulfinyl, propylsulfinyl, isopropylsulfinyl, and n-butylsulfinyl, and further CrC4- alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, and n-butylsulfonyl.
Accordingly, the terms "Cn-Cm-haloalkoxy" and "Cn-Cm-haloalkylthio" (= Cn-Cm- haloalkylsulfenyl) (and also Cn-Cm-haloalkylsulfinyl and Cn-Cm-haloalkylsulfonyl) refer to straight-chain or branched alkyl groups having n to m carbon atoms, e.g. 1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages (or SO (sulfinyl) or S(O)2 (sulfonyl) linkages), respectively, at any bond in the alkyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example CrC2-haloalkoxy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoro- methoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluorometh- oxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2- fluoroethoxy, 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 and penta- fluoroethoxy, further CrC2-haloalkylthio, such as chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoro- methylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1- chloroethylthio, 1-bromoethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2- difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2- difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio and pentafluoro- ethylthio and the like, further Ci-C2-haloalkylsulfinyl, such as chloromethylsulfinyl, bromomethylsulfinyl, dichloromethylsulfinyl, trichloromethylsulfinyl, fluoromethylsulfinyl, difluoromethylsulfinyl, trifluoromethylsulfinyl, chlorofluoromethylsulfinyl, dichlorofluoro- methylsulfinyl, chlorodifluoromethylsulfinyl, 1-chloroethylsulfinyl, 1-bromoethylsulfinyl, 1-fluoroethylsulfinyl, 2-fluoroethylsulfinyl, 2,2-difluoroethylsulfinyl, 2,2,2- trifluoroethylsulfinyl, 2-chloro-2-fluoroethylsulfinyl, 2-chloro-2,2-difluoroethylsulfinyl, 2,2- dichloro-2-fluoroethylsulfinyl, 2,2,2-trichloroethylsulfinyl and pentafluoroethylsulfinyl and the like, further Ci-C2-haloalkylsulfonyl, such as chloromethylsulfonyl, bromomethylsul- fonyl, dichloromethylsulfonyl, trichloromethylsulfonyl, fluoromethylsulfonyl, difluoro- methylsulfonyl, trifluoromethylsulfonyl, chlorofluoromethylsulfonyl, dichlorofluoro- methylsulfonyl, chlorodifluoromethylsulfonyl, 1-chloroethylsulfonyl, 1- bromoethylsulfonyl, 1-fluoroethylsulfonyl, 2-fluoroethylsulfonyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2- difluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl and pentafluoroethylsulfonyl and the like. Similarly the terms Ci-C2-fluoroalkoxy and C1-C2- fluoroalkylthio (and also fluoroalkylsulfinyl and fluoroalkylsulfonyl) refer to C1-C2- fluoroalkyl which is bound to the remainder of the molecule via an oxygen atom or a sulfur atom (or a SO (sulfinyl) or a S(O)2 (sulfonyl) linkage), respectively.
The term "C2-Cm-alkenyl" as used herein intends a branched or unbranched unsatu- rated hydrocarbon group having 2 to m, e.g. 2 to 10 or 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 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 and 1-ethyl-2-methyl-2-propenyl.
The term "C2-Cm-alkynyl" as used herein refers to a branched or unbranched unsaturated hydrocarbon group having 2 to m, e.g. 2 to 10 or 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, propynyl, 1-butynyl, 2-butynyl, and the like.
The term Ci-C4-alkoxy-Ci-C4-alkyl as used herein refers to alkyl having 1 to 4 carbon atoms, wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C4-alkoxy group.
The term Ci-C4-alkylthio-Ci-C4-alkyl as used herein refers to alkyl having 1 to 4 carbon atoms, wherein one hydrogen atom of the alkyl radical is replaced by a Ci-C4-alkylthio group.
The term d-C6-alkylcarbonyl as used herein refers to a carbonyl group carrying a Cr C6-alkyl group.
The term Ci-Ci0-alkoxycarbonyl or Ci-C4-alkoxycarbonyl as used herein refers to a carbonyl group carrying a Ci-CiO-alkyl group or a Ci-C4-alkyl group.
The term Ci-C4-alkylcarbonyloxy refers to a carbonyl group which is bound via an oxy- gen atom and which carries a Ci-C4-alkyl group.
The term "C3-Cm-cycloalkyl" as used herein refers to a monocyclic 3- to m-membered saturated cycloaliphatic radical, for example to a monocyclic 3- to 10-membered or 3- to 8-membered saturated cycloaliphatic radical such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
The term aryl as used herein refers to an aromatic hydrocarbon radical such as naphthyl or in particular phenyl.
The term aryl-Ci-C4-alkyl as used herein refers to an aromatic hydrocarbon radical, which is bound to the remainder of the molecule via a CrC4-alkylene group. Examples comprise benzyl, 1-phenylethyl and 2-phenylethyl.
The term "heterocyclyl" as used herein (and also in "heterocyclyl-Ci-C4-alkyl") refers to a saturated or partially unsaturated non-aromatic heterocyclic radical having preferably 3 to 7 ring members ("C3-C7-heterocyclyl" or "3- to 7-membered heterocyclyl") and containing 1 , 2, 3 or 4 heteroatoms selected from O, N and S and/or heteroatom groups, selected from S=O, S(O)2 and N-R, with R being H or alkyl, e.g. CrC6-alkyl,, as ring members, and optionally additionally containing 1 , 2 or 3 CO groups as ring members. Examples for such non-aromatic heterocyclyl rings include azetidinyl, pyrrolidinyl, pyr- rolidinonyl, pyrrolidindionyl, pyrazolinyl, pyrazolinonyl, imidazolinyl, imidazolinonyl, imi- dazolindionyl, pyrrolinyl, pyrrolinonyl, pyrrolindionyl, pyrazolinyl, imidazolinyl, imidazolinonyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3-dioxolanyl, dioxolenyl, thiolanyl, dihy- drothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperidinonyl, piperidindionyl, piperazinyl, pyridinonyl, pyridindionyl, pyridazinonyl, pyridazindionyl, pyrimidinonyl, pyridazindionyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, thiopyranyl, dihy- drothiopyranyl, tetrahydrothiopyranyl, morpholinyl, thiazinyl and the like.
The term "heteroaryl" as used herein (and also in "heteroaryl-Ci-C4-alkyl") refers to an aromatic heterocyclic radical having preferably 5 or 6 ring members ("C5-C6-heteroaryl" or "5- or 6-membered heteroaryl"), wherein 1 , 2, 3 or 4 ring members are heteroatoms selected from O, N and S or heteroatom groups, selected from S=O, S(O)2 or N-R, with R being H or alkyl. Examples for monocyclic 5- or 6-membered heteroaromatic rings include triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyra- zolyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, isothi- azolyl and isoxazolyl.
The terms heterocyclyl-CrC4-alkyl" and "heteroaryl-Ci-C4-alkyl" as used herein refer to a non-aromatic or aromatic heterocyclic radical which is bound to the remainder of the molecule via a CrC4-alkylene group, such as methylene, 1 ,2-ethylene, 1 ,2- or 1 ,3- propylene or 1 ,4-butylene. Typical examples for heteroaryl-Ci-C4-alkyl are benzyl and 2-phenylethyl. Examples for
Figure imgf000017_0001
are cyclopropylmethyl, 2- cyclopropylethyl, cyclopentylmethyl, 2-cyclopentylethyl cyclohexylmethyl and 2- cyclohexylethyl.
The term "ethylenically unsaturated ring" as used herein means that the ring contains at least one double bond which may be a C-C double bond but also a double bond containing at least one heteroatom, e.g. C=N or N=N.
With respect to the use according to the invention of the compounds of formula I, particular preference is given to the following meanings of the substituents and variables (R1, R2, R3, R4, A, m), in each case on their own or in combination: In one preferred embodiment of the invention, at least one of the radicals R1, R2, R3 or R4 is not hydrogen.
In a more preferred embodiment of the invention, R1 is not hydrogen.
Preferably, R1 is selected from halogen, d-C4-alkyl, CrC4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy. More preferably, R1 is selected from CrC2-alkyl, d-haloalkyl, CrC2- alkoxy and d-haloalkoxy. Even more preferably, R1 is selected from methyl, methoxy, trifluoromethyl, trichloromethyl, methoxy, trifluoromethoxy, difluoromethoxy, fluoro- methoxy and chlorodifluoromethoxy and in particular from methyl, methoxy, and difluoromethoxy. In a specific embodiment of the invention, R1 is selected from methyl, methoxy, trifluoromethoxy, difluoromethoxy, fluoromethoxy and chlorodifluoromethoxy and more specifically from methyl, methoxy and difluoromethoxy. In another specific embodiment of the invention R1 is halogen and in particular chlorine. In another specific embodiment of the invention R1 is selected from Ci-C4-alkoxy and Ci-C4-haloalkoxy and more specifically from Ci-C2-alkoxy, such as methoxy and ethoxy, and d- haloalkoxy, such as trifluoromethoxy, difluoromethoxy, fluoromethoxy and chlorodifluoromethoxy and in particular difluoromethoxy.
R2, R3, and R4 are preferably selected, independently from each other, from H, CrC4- alkyl, CrC4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and halogen. More preferably R2, R3 and R4 are selected, independently from each other, from hydrogen, halogen, d- C4-alkyl and CrC4-haloalkyl, especially from hydrogen, halogen, Ci-C2-alkyl, and d- haloalkyl, most preferably, from H, F, Cl, Br, I, CH3 and CF3. In a specific embodiment of the invention, two of the radicals R2, R3 or R4 are hydrogen and the remaining radical is selected from halogen, Ci-C4-alkyl and Ci-C4-haloalkyl and preferably from halogen. More specifically, R2 and R3 are H and R4 is different from H and is preferably halogen. In another specific embodiment of the invention, all three radicals R2, R3 and R4 are hydrogen.
Preferred embodiments of the radical A:
A. In one preferred embodiment, A is a radical N=CR5R6.
Preferably, R5 and R6 are not both hydrogen. More preferably, R5 is not hydrogen.
Preferably, R5 is OR5a, NR5bR5c, aryl-CrC4-alkyl or Ci-Cio-alkyl which may be unsubsti- tuted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from the group consisting of CrCio-alkoxy and phenyl, it being possible for phenyl to be unsubstituted, partially or fully halogenated or carry 1 , 2 or 3 radicals, independently of one another selected from the group consisting of CrC4- alkyl, CrC4-haloalkyl, CrC4-alkoxy and CrC4-haloalkoxy, wherein R5a, R5b and R5c are as defined above.
Preferably, R6 is hydrogen, OR6a, NR6bR6c, aryl-Ci-C4-alkyl or CrCi0-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from the group consisting of Ci-Cio-alkoxy and phenyl, it being possible for phenyl to be unsubstituted, partially or fully halogenated or carry 1 , 2 or 3 radicals, independently of one another selected from the group consist- ing of CrC4-alkyl, CrC4-haloalkyl, CrC4-alkoxy and CrC4-haloalkoxy, wherein R6a, R6b and R6c have one of the meanings given above for R5a, R5b and R5c.
However, following meanings of R5a, R5b, R5c, R6a, R6b and R6c are preferred:
Preferably, R5a is CrCio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from CrC4- alkoxy, or is C2-Ci0-alkenyl or C2-Ci0-alkynyl. More preferably, R5a is CrCio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from CrC4-alkoxy. In particular, R5a is unsubsti- tuted CrCio-alkyl.
Preferably, R5b and R5c are, independently from each other, hydrogen, CrCio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from CrC4-alkoxy, or are C2-CiO- alkenyl or C2-Ci0-alkynyl. More preferably, R5b and R5c are, independently from each other, hydrogen or CrCio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from CrC4-alkoxy. In particular, R5b and R5c are, independently from each other, hydrogen or unsubstituted CrCio-alkyl. Preferably, at least one of R5b and R5c is not hy- drogen.
Preferably, R6a is CrCio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from CrC4- alkoxy, or is C2-Ci0-alkenyl or C2-Ci0-alkynyl. More preferably, R6a is CrCio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from CrC4-alkoxy. In particular, R6a is unsubstituted CrCio-alkyl.
Preferably, R6b and R6c are independently from each other, hydrogen, CrCio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from Ci-C4-alkoxy, or is C2-Cio-alkenyl or C2-Cio-alkynyl. More preferably, R6b and R6c are, independently from each other, hydrogen or Ci-Cio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another selected from CrC4- alkoxy. In particular, R6b and R6c are, independently from each other, hydrogen or unsubstituted CrCio-alkyl. Preferably, at least one of R6b and R6c is not hydrogen.
A.1 In a more preferred embodiment, A is a radical N=CR5R6, wherein
R5 is Ci-Cio-alkyl, preferably CrC6-alkyl, or a radical OR5a, and
R6 is a radical OR6a,
wherein R5a and R6a have, independently of each other, one of the meanings of R5a given above.
Preferably, R5a and R6a are, independently of each other, Ci-Cio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals selected from Ci-C4-alkoxy, or are C2-Cio-alkenyl or C2-Cio-alkynyl.
More preferably, R5a and R6a are, independently of each other, d-C6-alkyl, C2-C6- alkenyl, C2-C6-alkynyl, Ci-C4-alkoxy-Ci-C4-alkyl or CrC4-haloalkyl. Even more preferably, R5a and R6a are, independently of each other, CrC4-alkyl, in particular Ci-C2-alkyl, C2-C6-alkenyl, in particular C2-C4-alkenyl, C2-C6-alkynyl, in particular C2-C4-alkynyl, Cr C4-alkoxy-Ci-C4-alkyl, in particular Ci-C2-alkoxy-Ci-C2-alkyl, or CrC4-haloalkyl, in particular CrC2-haloalkyl. In a specific embodiment R5a and R6a are, independently of each other, CrC4-alkyl, in particular Ci-C2-alkyl.
A.2 Alternatively, in a more preferred embodiment, A is a radical N=CR5R6, wherein
R5 is Ci-C6-alkyl, which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, CrC4-alkoxy, CrC4-alkylthio, CrC4-alkylsulfinyl, CrC4-alkylsulfonyl, d- C4-haloalkoxy, CrC4-haloalkylthio, (CrC4-alkoxy)carbonyl, (Ci-C4-alkyl)amino, di(Ci-C4-alkyl)amino and Cs-Cβ-cycloalkyl, or is phenyl or phenyl-CrC4-alkyl, wherein the phenyl group in the two last-mentioned radicals may be unsubstituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of halogen, CrC4-alkyl, CrC4-haloalkyl, CrC4-alkoxy and CrC4-haloalkoxy; and R6 is hydrogen, Ci-Cβ-alkyl, which may be unsubstituted, partially or fully halo- genated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, CrC4-alkoxy, CrC4-alkylthio, Ci-C4-alkylsulfinyl, CrC4- alkylsulfonyl, Ci-C4-haloalkoxy, Ci-C4-haloalkylthio, (CrC4-alkoxy)carbonyl, (Cr C4-alkyl)amino, di(CrC4-alkyl)amino and Cs-Cβ-cycloalkyl, or is phenyl or phenyl-
CrC4-alkyl, wherein the phenyl group in the two last-mentioned radicals may be unsubstituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of halogen, Ci-C4-alkyl, CrC4-haloalkyl, Cr C4-alkoxy and Ci-C4-haloalkoxy.
Preferably,
R5 is d-Ce-alkyl, Ci-C4-alkoxy-CrC4-alkyl, CrC4-haloalkyl or phenyl-CrC4-alkyl, wherein phenyl may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC4-alkyl, CrC4-haloalkyl, Ci-C4-alkoxy and CrC4-haloalkoxy; and
R6 is hydrogen, CrC6-alkyl, Ci-C4-alkoxy-CrC4-alkyl, CrC4-haloalkyl or phenyl-d-
C4-alkyl, wherein phenyl may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC4-alkyl, CrC4-haloalkyl, Ci-C4-alkoxy and CrC4- haloalkoxy.
Specifically, R5 and R6 are, independently of each other, CrCβ-alky!, in particular Cr C4-alkyl, or phenyl-CrC4-alkyl, in particular benzyl. More specifically, R5 and R6 are, independently of each other, CrC6-alkyl, in particular CrC4-alkyl.
A.3 Alternatively, in a more preferred embodiment, A is a radical N=CR5R6, wherein
R5 is a radical NR5bR5c; and
R6 is hydrogen, CrCβ-alky!, which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, Ci-C4-alkoxy, CrC4-alkylthio, CrC4-alkylsulfinyl, CrC4- alkylsulfonyl, Ci-C4-haloalkoxy, CrC4-haloalkylthio, (CrC4-alkoxy)carbonyl, (Cr
C4-alkyl)amino, di(CrC4-alkyl)amino and Cs-Cβ-cycloalkyl, or is phenyl or phenyl- CrC4-alkyl, wherein the phenyl group in the two last-mentioned radicals may by unsubstituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of halogen, Ci-C4-alkyl, CrC4-haloalkyl, Cr C4-alkoxy and CrC4-haloalkoxy, or is a radical OR6a, wherein R5a and R5b are, independently of each other, as defined above, and R6a has one of the meanings given above for R5a.
Preferably, R5b and R5c are, independently of each other, hydrogen, Ci-Cio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals selected from d-C4-alkoxy, or are C2-Ci0-alkenyl or C2-Ci0-alkynyl.
More preferably, R5b and R5c are, independently of each other, hydrogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C4-alkoxy-Ci-C4-alkyl or Ci-C4-haloalkyl. Even more preferably, R5b and R5c are, independently of each other, hydrogen, Ci-C4-alkyl, C2-C6- alkenyl, in particular C2-C4-alkenyl, C2-C6-alkynyl, in particular C2-C4-alkynyl, CrC4- alkoxy-CrC4-alkyl, in particular Ci-C2-alkoxy-CrC2-alkyl, or Ci-C4-haloalkyl, in particular Ci-C2-haloalkyl. In a specific embodiment R5b and R5c are, independently of each other, hydrogen or CrC6-alkyl and more specifically hydrogen or Ci-C4-alkyl.
It is preferred that at least one of the radicals R5b and R5c is not hydrogen.
Preferably, R6a is CrCio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals selected from Ci-C4-alkoxy, or is C2-Cio-alkenyl or C2-Cio-alkynyl.
More preferably, R 36baa is CrC6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C4-alkoxy-CrC4- alkyl or Ci-C4-haloalkyl. Even more preferably, R6a is CrC4-alkyl, in particular CrC2- alkyl, C2-C6-alkenyl, in particular C2-C4-alkenyl, C2-C6-alkynyl, in particular C2-C4- alkynyl, Ci-C4-alkoxy-CrC4-alkyl, in particular Ci-C2-alkoxy-CrC2-alkyl, or CrC4- haloalkyl, in particular CrC2-haloalkyl. In a specific embodiment R6a is CrC4-alkyl, in particular Ci-C2-alkyl.
Preferably, R6 is hydrogen; CrC6-alkyl, which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from Ci-C4-alkoxy; phenyl- CrC4-alkyl, wherein the phenyl group may by unsubstituted or may carry 1 , 2 or 3 sub- stituents, independently of one another selected from the group consisting of halogen,
CrC4-alkyl, CrC4-haloalkyl, CrC4-alkoxy and CrC4-haloalkoxy; or a radical OR6a.
More preferably, R6 is hydrogen, CrCβ-alkyl or a radical OR6a. Specifically, R6 is hydrogen, Ci-C4-alkyl or a radical OR6a. The preferred embodiments of R6a are as defir above.
B. In another preferred embodiment, A is a radical N=SR7R8. Preferably, R7 and R8 are, independently of each other, aryl, aryl-Ci-C4-alkyl, C2-C6- alkenyl, C2-C6-alkynyl, CrC6-alkyl which may be unsubstituted, partially or fully halo- genated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of Cr C4-alkoxy, or R7 and R8, together with the sulfur atom they are bound to, form a 5-, 6- or 7-membered saturated or ethylenically unsaturated ring which may be unsubstituted or may carry 1 , 2, 3 or 4 substituents selected from halogen and CrC4-alkyl, and which may contain 1 or 2 carbonyl groups and/or heteroatoms selected from N, O and S and/or heteroatom groups selected from SO, SO2 and NR#, R# being H or Ci-C4-alkyl, as ring members.
More preferably, R7 and R8 are, independently of each other, Ci-Cβ-alkyl, C2-C6- alkenyl, C2-C6-alkynyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-haloalkyl, phenyl or phenyl-d- C4-alkyl, wherein phenyl in the last two radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC4-alkyl, Ci-C4-haloalkyl, CrC4-alkoxy and CrC4- haloalkoxy, or R7 and R8 together form a moiety (CH2)k , wherein k is 4, 5 or 6 and wherein 1 , 2, 3 or 4 hydrogen atoms may be replaced by CrC4-alkyl or halogen and wherein 1 or 2 non-adjacent CH2 moieties may be replaced by a carbonyl group, a heteroatom or a heteroatom group, selected from O, S, SO2 and N-R# with R# being H or CrC4-alkyl.
Even more preferably, R7 and R8 are, independently of each other, CrC6-alkyl, in particular CrC4-alkyl, Ci-C4-alkoxy-Ci-C4-alkyl, in particular Ci-C2-alkoxy-CrC2-alkyl, Cr C4-haloalkyl, phenyl, or phenyl-CrC4-alkyl, in particular benzyl, or R7 and R8 together form a moiety (CH2)k , wherein k is 4 or 5. Specifically, R7 and R8 are CrC6-alkyl, in particular CrC4-alkyl, or together form a moiety (CH2)k , wherein k is 4 or 5, in particular 4.
C. In another preferred embodiment, A is a radical of the formula NR10-C(=X)-R9, wherein X, R9 and R10 are as defined above.
C.1 In a more preferred embodiment, A is a radical of the formula NR10-CO-R9, wherein R9 and R10 are as defined above.
Preferably, R9 is selected from the group consisting of hydrogen, OR9a, NR9bR9c, aryl, aryl-Ci-C4-alkyl, CrCio-alkyl, C2-Ci0-alkenyl and C2-Ci0-alkynyl, wherein CrCio-alkyl, C2-Cio-alkenyl and C2-Ci0-alkynyl may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals selected from Ci-Cio-alkoxy, and wherein
R9a is CrCio-alkyl, C3-Ci0-cycloalkyl, C2-Ci0-alkenyl, C2-Ci0-alkynyl, aryl, aryl-CrC4- alkyl, heteroaryl or heteroaryl-Ci-C4-alkyl, heterocyclyl or
Figure imgf000024_0001
R9b, R9c, independently from each other, are selected from hydrogen, d-Cio-alkyl, C3- Cio-cycloalkyl, C2-Ci0-alkenyl, C2-Ci0-alkynyl, aryl and aryl-CrC4-alkyl,
wherein d-Cio-alkyl, C3-Ci0-cycloalkyl, C2-Ci0-alkenyl and C2-Ci0-alkynyl in R9a, R9b aanndd RR99cc mmaayy bbee uunnssuubbssttiittuutteedd,, ppaarrttiiaally or fully halogenated and/or may carry 1 , 2 or 3 radicals selected from d-C4-alkoxy,
and wherein the carbon atoms of aryl, heteroaryl and heterocyclyl moieties in R9, R9a, R9b and R9c may be unsubstituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of halogen, CrC4-alkyl, CrC4- haloalkyl, CrC4-alkoxy and CrC4-haloalkoxy.
Preferably, R10 is selected from the group consisting of hydrogen, C(=O)-R16, CrCi0- alkyl, C2-C6-alkenyl, C2-Ci0-alkynyl and CrCi0-alkoxy, wherein the four last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another each selected from CrCi0-alkoxy.
Alternatively, it is preferred that R9 and R10 together with the adjacent nitrogen and carbon atoms form a saturated or ethylenically unsaturated 5 to 10-membered ring, op- tionally substituted by 1 , 2, 3 or 4 radicals selected from CrC5-alkyl and halogen, wherein the ring may contain, in addition to the nitrogen and carbon ring members, 1 , 2 or 3 heteroatoms or heteroatom-containing groups as ring members selected from the group consisting of nitrogen, oxygen, sulfur, a group CO, SO, SO2 or N-R17.
C.1.1 In an even more preferred embodiment, A is a radical of the formula NR10-C(=O)-R9, wherein
R10 is selected from hydrogen, CrC6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, CrC6- alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, CrC4-haloalkyl and acetyl; and
R9 is selected from CrC6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C4-alkoxy-Ci-C4- alkyl, CrC4-haloalkyl, phenyl and phenyl-CrC4-alkyl, wherein phenyl in the last two radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents, independently of one another selected from the group consist- ing of Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, or
R10 and R9 together form a moiety of the (CH2)P, wherein p is 3, 4 or 5 and wherein 1 ,
2, 3 or 4 hydrogen atoms may be replaced by CrC4-alkyl or halogen and wherein 1 or 2 non-adjacent CH2 moieties may be replaced by a carbonyl group, a het- eroatom or a heteroatom group, selected from O, S, SO2 and N-R# with R# being H or Ci-C4-alkyl.
In a specific embodiment,
R10 is selected from hydrogen, d-C4-alkyl, C2-C6-alkynyl and CrC4-alkoxy and in particular from Ci-C4-alkyl; and
R9 is selected from CrC4-alkyl, C2-C6-alkenyl, CrC4-haloalkyl and phenyl, or
R10 and R9 together form a moiety of the (CH2)P, wherein p is 3 or 4.
In an alternative specific embodiment,
R10 is selected from hydrogen and Ci-Cβ-alkyl; and
R9 is selected from CrC6-alkyl and CrC4-haloalkyl.
C.1.2 In another even more preferred embodiment, A is a radical of the formula NR10-C(=O)-R9, wherein
R10 is selected from hydrogen, CrC6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, CrC6- alkoxy, Ci-C4-alkoxy-CrC4-alkyl and CrC4-haloalkyl; and
R9 is OR9a or a radical NR9bR9c,
wherein R9a, R9b, and R9c are as defined above.
Preferably, R9a is Ci-CiO-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals selected from Ci-C4-alkoxy, or is C2-Cio-alkenyl, C2-
Cio-alkynyl, aryl or aryl-Ci-C4-alkyl. More preferably, R9a is Ci-Cβ-alkyl, C2-C6-alkenyl,
C2-C6-alkynyl, Ci-C4-alkoxy-Ci-C4-alkyl, CrC4-haloalkyl, phenyl or phenyl-CrC4-alkyl.
Specifically, R9a is C2-C6-alkenyl, in particular vinyl or allyl, phenyl or phenyl-CrC4- alkyl, in particular benzyl. Preferably, R9b and R9c are, independently of each other, hydrogen, Ci-Cio-alkyl which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals selected from d-C4-alkoxy, or are C2-Ci0-alkenyl, C2-Ci0-alkynyl, aryl or aryl-CrC4- alkyl. More preferably, R9b and R9c are, independently of each other, hydrogen, C1-C6- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C4-alkoxy-CrC4-alkyl, Ci-C4-haloalkyl, phenyl or phenyl-Ci-C4-alkyl. It is preferred that R9b and R9c are not both hydrogen. Specifically, one of R9b and R9c is hydrogen and the other radical is CrC6-alkyl or phenyl.
In a specific embodiment, R10 is selected from hydrogen and CrC4-alkyl, more specifi- cally from hydrogen and CrC2-alkyl.
D. In another preferred embodiment, A is an N-bound 5-, 6- or 7-membered aromatic or non-aromatic unsaturated heterocycle and which additionally may contain 1 , 2, or 3 further heteroatoms or heteroatom groups, selected from O, S, SO, SO2, N, and NR12, and/or 1 , 2 or 3 carbonyl groups as ring members and which may carry 1 , 2, 3 or 4 radicals R13, where R13 is as defined above. Preferably, at least one double bond is positioned α to the nitrogen atom through which the radical A is bound. In case the heterocycle contains 1 , 2 or 3 further heteroatoms or heteroatom groups as ring members, it is preferred that these are selected from N and NR12.
In a more preferred embodiment, A is an N-bound 5-membered aromatic heterocycle which additionally may contain 1 , 2, or 3 further nitrogen atoms as ring members and which may carry 1 , 2, 3 or 4 radicals R13, where R13 is as defined above.
Preferably, R13 is independently selected from halogen and Ci-C4-alkyl which may be partially or fully halogenated and/or may be substituted by 1 , 2 or 3 radicals selected from OH, Ci-C4-alkoxy and Ci-C4-alkylcarbonyloxy.
Even more preferably, A is 1-pyrrolyl, 1-pyrazolyl, 1-imidazolyl or [1 ,2,4]-triazol-1-yl, where the heterocycle may be unsubstituted or may carry 1 , 2 or 3 substituents, specifically 1 substituent, selected from halogen and CrC4-alkyl, wherein Ci-C4-alkyl may be unsubstituted or may be substituted by hydroxy or acetyloxy. In particular, A is 1- pyrrolyl which may be unsubstituted or may carry 1 , 2 or 3 substituents, specifically 1 substituent, selected from halogen and CrC4-alkyl, wherein Ci-C4-alkyl may be unsub- stituted or may be substituted by hydroxy or acetyloxy.
In a particularly preferred embodiment, A is a radical of the formula NR10-CO-R9, wherein R10 is selected from hydrogen, Ci-C4-alkyl, C2-C6-alkynyl and CrC4-alkoxy and R9 is selected from Ci-C4-alkyl, C2-C6-alkenyl, Ci-C4-haloalkyl and phenyl; or A is a radical of the formula NR10-CO-R9, wherein R10 and R9 together form a moiety of the (CH2)P, wherein p is 3 or 4; or
A is a radical of the formula NR10-CO-OR9a, wherein R9a is CrC6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C4-alkoxy-CrC4-alkyl, Ci-C4-haloalkyl, phenyl or phenyl-Ci-C4-alkyl and R10 is hydrogen or Ci-C4-alkyl; or
A is a radical of the formula NR10-CO-NR9bR9c, wherein one of R9b and R9c is hydrogen and the other radical is CrC6-alkyl or phenyl and R10 is hydrogen or d-C4-alkyl; or A is a radical of the formula N=CR5R6, wherein R5 is CrC6-alkyl, Ci-C4-alkoxy-Ci-C4- alkyl, Ci-C4-haloalkyl or phenyl-Ci-C4-alkyl and R6 is is hydrogen, Ci-Cβ-alkyl, C1-C4- alkoxy-CrC4-alkyl, CrC4-haloalkyl or phenyl-CrC4-alkyl; or
A is a radical of the formula N=CR5OR63, wherein R5 is CrC6-alkyl and R6a is CrC6- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C4-alkoxy-CrC4-alkyl or Ci-C4-haloalkyl; or A is a radical of the formula N=C(OR5a)2, wherein R5a is CrC6-alkyl, C2-C6-alkenyl, C2- C6-alkynyl, Ci-C4-alkoxy-Ci-C4-alkyl or CrC4-haloalkyl; or A is a radical of the formula N=C(NR5bR5c)(OR6a), wherein R5b and R5c are, independently of each other, hydrogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C4-alkoxy- CrC4-alkyl or CrC4-haloalkyl and R6a is CrC6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cr C4-alkoxy-Ci-C4-alkyl or CrC4-haloalkyl; or A is a radical of the formula N=SR7R8, wherein R7 and R8 are, independently of each other, CrC6-alkyl, Ci-C4-alkoxy-Ci-C4-alkyl, CrC4-haloalkyl, phenyl, phenyl-CrC4-alkyl or R7 and R8 together form a moiety (CH2)k , wherein k is 4, 5 or 6; or A is an N-bound 5-membered aromatic heterocycle which additionally may contain 1 , 2, or 3 further nitrogen atoms as ring members and which may carry 1 , 2, 3 or 4 radicals R13, where R13 is as defined above.
In a specific embodiment of the invention, A is a radical of the formula NR10-CO-R9, wherein R10 is selected from hydrogen, Ci-C4-alkyl and C2-C6-alkynyl; and R9 is selected from CrC4-alkyl, C2-C6-alkenyl, CrC4-haloalkyl and phenyl, or R10 and R9 together form a moiety of the (CH2)P, wherein p is 3 or 4; or A is an N-bound 5-membered aromatic heterocycle which additionally may contain 1 , 2, or 3 further nitrogen atoms as ring members and which may carry 1 , 2, 3 or 4 radicals R13, where R13 is as defined above. Preferred embodiments of R10, R9, R13 and of the N-bound 5-membered aromatic heterocycle are as defined above.
In formula I the variable m is preferably 2. These compounds are also referred to as compounds Ia. Compounds I, where m is 0 are also referred to as compounds Ib, while compounds I, where m is 1 , are also referred to as compounds Ic.
Examples of preferred compounds which are represented by the formulae Ia, Ib and Ic are the individual compounds compiled in the tables 1 to 264 below, where the variable A has the meanings given in one row of table A and the variables R1, R2, R3 and R4 have the meanings given in the respective table.
Table A:
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
εd3(0)0(εH0)N ZZ 1.-V ε(εH3)0(0)0(εH0)N 9/ 1 -V z(εHθ)Hθ(θ)θ(εHθ)N 9/ 1 -V εHOzHOzHθ(θ)θ(εHθ)N 17/1- -V
5Hzθ(θ)θ(εHθ)N εzι.-v εH3(0)0(εH0)N ZLi-M
5H9O(O)O(H)N ILl-V
2HO=HO(O)O(H)N OLl-V εd0(0)0(H)N 691- -V ε(εH0)0(0)0(H)N 891- -V z(εH0)H0(0)0(H)N L91-V εH0zH0zH0(0)0(H)N 991- -V
5H2O(O)O(H)N 991- -V εH0(0)0(H)N 1791- -V
=N-# C9I.-V s=N-# 291 -V z(εdθ)S=N U9U-V
(z(εH0)H0)(εd0)S=N 091- -V z(z(εH0)H0)S=N 691- -V
(εH0zH0zH0)(εd0)S=N 891- -V
(εH0zH0zH0)(z(εH0)H0)S=N /91 -V z(εH0zH0zH0)S=N 991- -V
(5Hz0)(εd0)S=N 991- -V
(5Hz0)(z(εH0)H0)S=N 1791- -V
(5Hz0)(εH0zH0zH0)S=N ZSl-V z(5Hz0)S=N 291- -V
(εH0)(εd0)S=N 191-V
(εH0)(z(εH0)H0)S=N 091- -V
(εH0)(εH0zH0zH0)S=N Qn-v
(εH0)(5Hz0)S=N SPl-V z(εH0)S=N LPl-V
(ε(εH0)0)(z(zH0=H0zH0)N)0=N 9H-V
(ε(εHθ)θ)(z(|Aβjedojd)N)θ=N 9H-V
(ε(εH0)0)(z(z(εH0)H0)N)0=N m-v
V ON
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
propargyl: -CH2C=CH # point of attachment to S(O)m
Table 1 : Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R2 is H, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 2: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R2 is F, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 3: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R2 is Cl, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 4: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R2 is Br, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 5: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R2 is I, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 6: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R2 is CH3,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 7: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R2 is CF3,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 8: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R2 is CCI3,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 9: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R3 is F, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 10: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R3 is Cl, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 11 : Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R3 is Br, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 12: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R3 is I, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 13: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R3 is CH3,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 14: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R3 is CF3,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 15: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R3 is CCI3,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 16: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R4 is F, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 17: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R4 is Cl, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 18: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R4 is Br, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 19: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R4 is I, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 20: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R4 is CH3,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 21 : Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R4 is CF3,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 22: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R4 is CCI3,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 23: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R2 is H, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 24: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R2 is F, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 25: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R2 is Cl, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 26: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R2 is Br, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 27: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R2 is I, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 28: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R2 is CH3,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 29: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R2 is CF3,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 30: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R2 is CCI3,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 31 : Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R3 is F, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 32: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R3 is Cl, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 33: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R3 is Br, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 34: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R3 is I, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 35: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R3 is CH3,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 36: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R3 is CF3,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 37: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R3 is CCI3,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 38: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R4 is F, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 39: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R4 is Cl, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 40: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R4 is Br, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 41 : Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R4 is I, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 42: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R4 is CH3,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 43: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R4 is CF3,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 44: Compounds of the formulae Ia, Ib and Ic in which R1 is C2H5, R4 is CCI3,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 45: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R2 is H, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 46: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R2 is F, R3 and
R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 47: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R2 is Cl, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 48: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R2 is Br, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 49: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R2 is I, R3 and
R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 50: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R2 is CH3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 51 : Compounds of the formulae Ia, Ib and Ic in which R1 is F, R2 is CF3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 52: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R2 is CCI3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 53: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R3 is F, R2 and
R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 54: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R3 is Cl, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 55: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R3 is Br, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 56: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R3 is I, R2 and
R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 57: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R3 is CH3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 58: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R3 is CF3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 59: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R3 is CCI3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 60: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R4 is F, R2 and
R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 61 : Compounds of the formulae Ia, Ib and Ic in which R1 is F, R4 is Cl, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 62: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R4 is Br, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 63: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R4 is I, R2 and
R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 64: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R4 is CH3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 65: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R4 is CF3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 66: Compounds of the formulae Ia, Ib and Ic in which R1 is F, R4 is CCI3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 67: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R2 is H, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 68: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R2 is F, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 69: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R2 is Cl, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 70: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R2 is Br, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 71 : Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R2 is I, R3 and
R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 72: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R2 is CH3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 73: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R2 is CF3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 74: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R2 is CCI3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 75: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R3 is F, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 76: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R3 is Cl, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 77: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R3 is Br, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 78: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R3 is I, R2 and
R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 79: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R3 is CH3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 80: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R3 is CF3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 81 : Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R3 is CCI3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 82: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R4 is F, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 83: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R4 is Cl, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 84: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R4 is Br, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 85: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R4 is I, R2 and
R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 86: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R4 is CH3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 87: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R4 is CF3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 88: Compounds of the formulae Ia, Ib and Ic in which R1 is Cl, R4 is CCI3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 89: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R2 is H, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 90: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R2 is F, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 91 : Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R2 is Cl, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 92: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R2 is Br, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 93: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R2 is I, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 94: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R2 is CH3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 95: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R2 is CF3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 96: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R2 is CCI3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 97: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R3 is F, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 98: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R3 is Cl, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 99: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R3 is Br, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 100: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R3 is I, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 101 : Compounds of the formulae Ia, Ib and Ic in which R1 Br, R3 is CH3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 102: Compounds of the formulae Ia, Ib and Ic in which R1 is CH3, R3 is CF3,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 103: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R3 is CCI3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 104: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R4 is F, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 105: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R4 is Cl, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 106: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R4 is Br, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 107: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R4 is I, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 108: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R4 is CH3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 109: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R4 is CF3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 1 10: Compounds of the formulae Ia, Ib and Ic in which R1 is Br, R4 is CCI3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 1 11 : Compounds of the formulae Ia, Ib and Ic in which R1 is I, R2 is H, R3 and
R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 1 12: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R2 is F, R3 and
R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 1 13: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R2 is Cl, R3 and
R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 1 14: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R2 is Br, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 1 15: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R2 is I, R3 and
R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 1 16: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R2 is CH3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 1 17: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R2 is CF3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 1 18: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R2 is CCI3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 1 19: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R3 is F, R2 and
R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 120: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R3 is Cl, R2 and
R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 121 : Compounds of the formulae Ia, Ib and Ic in which R1 is I, R3 is Br, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 122: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R3 is I, R2 and
R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 123: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R3 is CH3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 124: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R3 is CF3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 125: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R3 is CCI3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 126: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R4 is F, R2 and
R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 127: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R4 is Cl, R2 and
R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 128: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R4 is Br, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 129: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R4 is I, R2 and
R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 130: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R4 is CH3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 131 : Compounds of the formulae Ia, Ib and Ic in which R1 is I, R4 is CF3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 132: Compounds of the formulae Ia, Ib and Ic in which R1 is I, R4 is CCI3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 133: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R2 is H, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 134: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R2 is F, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 135: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R2 is Cl, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 136: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R2 is Br, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 137: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R2 is I, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 138: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R2 is CH3,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 139: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R2 is CF3,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 140: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R2 is CCI3,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 141 : Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R3 is F, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 142: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R3 is Cl, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 143: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R3 is Br, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 144: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R3 is I, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 145: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R3 is CH3,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 146: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R3 is CF3,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 147: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R3 is CCI3,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 148: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R4 is F, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 149: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R4 is Cl, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 150: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R4 is Br, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 151 : Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R4 is I, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 152: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R4 is CH3,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 153: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R4 is CF3,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 154: Compounds of the formulae Ia, Ib and Ic in which R1 is CF3, R4 is CCI3,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 155: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R2 is H,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 156: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R2 is F, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 157: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R2 is Cl,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 158: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R2 is Br,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 159: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R2 is I, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 160: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R2 is CH3,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 161 : Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R2 is CF3,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 162: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R2 is
CCI3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 163: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R3 is F, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 164: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R3 is Cl,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 165: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R3 is Br,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 166: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R3 is I, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 167: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R3 is CH3,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 168: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R3 is CF3,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 169: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R3 is
CCI3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 170: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R4 is F, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 171 : Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R4 is Cl,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 172: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R4 is Br,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 173: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R4 is I, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 174: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R4 is CH3,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 175: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R4 is CF3,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 176: Compounds of the formulae Ia, Ib and Ic in which R1 is OCH3, R4 is
CCI3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 177: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R2 is H,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 178: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R2 is F,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 179: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R2 is Cl,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 180: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R2 is Br,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 181 : Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R2 is I,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 182: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R2 is
CH3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 183: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R2 is
CF3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 184: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R2 is
CCI3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 185: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R3 is F,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 186: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R3 is Cl,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 187: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R3 is Br,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 188: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R3 is I,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 189: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R3 is
CH3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 190: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R3 is
CF3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 191 : Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R3 is
CCI3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 192: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R4 is F,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 193: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R4 is Cl,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 194: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R4 is Br,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 195: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R4 is I,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 196: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R4 is
CH3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 197: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R4 is
CF3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 198: Compounds of the formulae Ia, Ib and Ic in which R1 is OC2H5, R4 is
CCI3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 199: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R2 is H, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 200: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R2 is F, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 201 : Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R2 is Cl,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 202: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R2 is Br,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 203: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R2 is I, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 204: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R2 is CH3,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 205: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R2 is CF3,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 206: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R2 is CCI3,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 207: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R3 is F, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 208: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R3 is Cl,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 209: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R3 is Br,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 210: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R3 is I, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 211 : Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R3 is CH3,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 212: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R3 is CF3,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 213: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R3 is CCI3,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 214: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R4 is F, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 215: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R4 is Cl,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 216: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R4 is Br,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 217: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R4 is I, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 218: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R4 is CH3,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 219: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R4 is CF3,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 220: Compounds of the formulae Ia, Ib and Ic in which R1 is OCF3, R4 is CCI3,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 221 : Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R2 is H,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 222: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R2 is F,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 223: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R2 is Cl,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 224: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R2 is Br,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 225: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R2 is I,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 226: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R2 is
CH3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 227: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R2 is
CF3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 228: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R2 is
CCI3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 229: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R3 is F,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 230: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R3 is Cl,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 231 : Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R3 is Br,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 232: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R3 is I,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 233: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R3 is
CH3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 234: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R3 is
CF3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 235: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R3 is
CCI3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 236: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R4 is F,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 237: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R4 is Cl,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 238: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R4 is Br,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 239: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R4 is I,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 240: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R4 is
CH3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 241 : Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R4 is
CF3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 242: Compounds of the formulae Ia, Ib and Ic in which R1 is OCHF2, R4 is
CCI3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 243: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R2 is H,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 244: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R2 is F,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 245: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R2 is Cl,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 246: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R2 is Br,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 247: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R2 is I,
R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 248: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R2 is
CH3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 249: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R2 is
CF3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 250: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R2 is
CCI3, R3 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 251 : Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R3 is F,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 252: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R3 is Cl,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 253: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R3 is Br,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 254: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R3 is I,
R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A; Table 255: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R3 is
CH3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 256: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R3 is
CF3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 257: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R3 is
CCI3, R2 and R4 are H and A for each individual compound corresponds in each case to one row of table A;
Table 258: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R4 is F,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 259: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R4 is Cl,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 260: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R4 is Br,
R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A;
Table 261 : Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R4 is I, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 262: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R4 is
CH3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 263: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R4 is
CF3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A; Table 264: Compounds of the formulae Ia, Ib and Ic in which R1 is OCCIF2, R4 is
CCI3, R2 and R3 are H and A for each individual compound corresponds in each case to one row of table A.
2-Cyanobenzene compounds Ia, in which A is a radical of the formula NR10C(O)-R9 in which R9 is aryl, aryl-Ci-C4-alkyl, heteroaryl, heteroaryl-Ci-C4-alkyl, heterocyclyl, het- erocyclyl-CrC4-alkyl, Ci-Cio-alkyl or C3-Cio-cycloalkyl and R10 has the meanings given above may be prepared, for example, by reacting a 2-cyanobenzene sulfonamide (II) with an acyl halide (Ilia), especially an acyl chloride, an acid anhydride (MIb) or a mixed acid anhydride in the presence of an appropriate base, see scheme 1. Appropriate bases include organic bases, for example tertiary amines, such as aliphatic amines, for example trimethylamine, triethylamine or diisopropylethylamine, cycloaliphatic tertiary amines, for example N-methylpiperidine, or aromatic amines, for example pyridine, substituted pyridines such as 2,4,6-collidine, 2,4-lutidine or 4-dimethylaminopyridine. The reaction is usually carried out in a solvent, for example an alkyl cyanide, such as acetonitrile or propionitrile. The compounds of the formula Ia can be prepared analogously to a procedure described in Bull. Chem. Soc. Jpn. 1988, 61 , 3999-4004.
The reaction may also be carried out under acidic conditions, e.g. with sulfuric acid as catalyst. Usually the reaction is carried out in a suitable solvent. Suitable solvents are polar and inert under the given reaction conditions. Examples of suitable solvents include alkyl cyanides such as acetonitrile or propionitrile. The reaction is e.g. analogous to a procedure described in Tetrahedron Letters 2003, 44, 5461-5463 to which reference is made
Scheme 1 :
Figure imgf000059_0001
(1Mb)
(H) (Ia)
In scheme 1 , the variables R1, R2, R3, R4 have the meanings mentioned above and in particular the meanings mentioned as being preferred and Hal is halogen, especially chlorine.
2-Cyanobenzene compounds Ia, in which A is a radical of the formula NR10C(O)-R9, wherein R9 is OR9a in which R9a has the meanings mentioned above and R10 has the meanings mentioned above, may be prepared by reacting a 2-cyanobenzene sulfonamide (II) with chloroformates of the formula CIC(O)OR9a in the presence of suitable bases. Suitable bases include those mentioned above, e.g., triethylamine. The reaction is usually carried out in an appropriate solvent such as an alkyl cyanide, for example acetonitrile or propionitrile. The reaction can be carried out analogously to processes known from the prior art, for example in accordance with J. Med. Chem. 2004, 47, 627- 643.
2-Cyanobenzene compounds Ia, in which A is a radical of the formula NR10-C(O)-R9, wherein R9 and R10 together with the adjacent nitrogen and carbon atoms form a saturated or ethylenically unsaturated 5- to 10-membered ring as defined above and which may be substituted as described above, may be obtained by reacting a sulfonylhalide (IV), especially a sulfonylchloride, with a cyclic amide (V) in the presence of a strong base such as an organometallic base, for example an alkyllithium compound or aryllith- ium compound, e.g. n-butyllithium, terf-butyllithium or phenyllithium. The reaction is usually carried out in a polar organic solvent which is inert under the reaction condi- tions such as ether, for example, dialkyl ether or cyclic ethers such as tetrahydrofuran (THF) or dioxane, see scheme 2. In scheme 2, the variables R1, R2, R3, R4 have the meanings mentioned above and in particular the meanings mentioned as being preferred and Hal is halogen, especially chlorine.
Scheme 2:
Figure imgf000060_0001
(IV) (V) (Ia)
2-Cyanobenzene compounds Ia, in which A is a radical NR10-C(O)-R9, wherein R9 is a radical NR9bR9c in which R9b and R9c are as defined above and R10 has the meanings given above may be obtained by reacting a 2-cyanobenzene sulfonamide (II) with an appropriately substituted isocyanate (Vl). The reaction can be performed in analogy to a process described in J. Med. Chem. 1979, 22, 321-325 (see scheme 3). In scheme 3, the variables R1, R2, R3, R4 have the meanings mentioned above and in particular the meanings mentioned as being preferred.
Scheme 3:
Figure imgf000060_0002
Figure imgf000060_0003
H}
Conversion of compounds Ia in which R9c is H to compounds Ia in which R9c is different from H may be obtained by alkylating the compounds Ia (where R9c is H and which are obtainable according to scheme 3) with suitable alkylating agents in the presence of a base. The required reaction conditions are known in the art, for example from J. March, Advanced Organic Synthesis, 3nd edition, Wiley Interscience, New York, 1985, page 377.
2-Cyanobenzene compounds Ia where A is a radical NR10-C(O)-R9 may be converted by known methods to compounds Ia where A is a radical NR10-C(S)-R9 by treatment with sulfurizing agents. Examples of suitable sulfurizing agents are organophosphorus sulfides such as Lawesson reagent, organotin sulfides or phosphorus(V) sulfides, see also J. March, Advanced Organic Synthesis, 3rd edition, Wiley Interscience, 1985, p. 794 and literature cited therein. The reaction can be carried out in a solvent or in sub- stance. The temperature required for the reaction is generally above room temperature and is in particular in the range from 50 to 200°C.
2-Cyanobenzene compounds Ia, in which A is a radical of the formula N=CR5R6 where R5 is a radical OR5a where R5a has the meanings mentioned above and R6 has the meanings mentioned above except for OR6a and NR6bR6c may be obtained by reacting a cyanobenzenesulfonamide (II) (where R10 is H) with an orthoester (VII) in analogy to a procedure described in Chemische Berichte 1965, 623-628, see scheme 4. In scheme 4, the variables R1, R2, R3 and R4 have the meanings mentioned above and in particular the meanings mentioned as being preferred.
Scheme 4:
Figure imgf000061_0001
(II) {R10 = H} (VI I) (Ia)
2-Cyanobenzene compounds Ia, in which A is a radical of the formula N=CR5R6 where R5 is a radical OR5a and R6 is a radical OR6a, where R5a and R6a are as defined above can be obtained by reacting a 2-cyanobenzene sulfonamide (II) (where R10 is H) with a carbonic acid orthoester (VIII) in a process similarly described in Journal of Organic Chemistry 1963, 28, 2902-2903, see scheme 5. In scheme 5 the variables R1, R2, R3 R4, R5a and R6a have the meanings mentioned above and in particular the meanings mentioned as being preferred.
Scheme 5:
Figure imgf000061_0002
(II) {R10 = H} (VIII) (Ia) 2-Cyanobenzene compounds Ia, wherein A is N=CR5R6 in which R5 is OR5a and R6 is
NR ~)6bbDrR~)6bcc where R5a, R ->6bbD and R 36bcc have the meanings mentioned above may be prepared by reacting the cyanobenzene compounds Ia (A is N=CR5R6 where R5 is OR5a and R6 is OR6a and which are obtainable according to scheme 5) with amines IX, in analogy to a procedure described in in J. Med. Chem. 1999, 42, 1235-1249. In scheme 6, the variables R1, R2, R3 and R4 have the meanings mentioned above and in particular the meanings mentioned as being preferred.
Scheme 6:
Figure imgf000062_0001
(IX)
2-Cyanobenzene compounds Ia, wherein A is N=CR5R6 in which R5 is NR5bR5c where R5b and R5c are as defined above and R6 has the meanings mentioned above, except for OR6a and NR6bR6c, may be obtained by reacting a cyanobenzene sulfonamide (II) (R10 is H) with amides (X) in analogy to J. Med. Chem. 2001 , 44, 1085-1098, see scheme 7. It may be advantageous to use the amine (X) in an excess based on the amount of sulfonamide (II), e.g. the molar ratio of sulfonamide Il to amine (X) is 1 :1 ,01 to 1 :3. The reaction is usually carried out in an inert organic solvent, such as alkanes, cycloalkanes or aromatic solvents, e.g. toluene. In scheme 7, the variables R1, R2, R3 and R4 have the meanings mentioned above and in particular the meanings mentioned as being preferred and R is CrC6-alkyl, especially CrC2-alkyl, in particular methyl.
Scheme 7:
Figure imgf000062_0002
(M) (R10 = H} (X) (Ia) 2-Cyanobenzene compounds Ia, in which A is a radical of the formula N=CR5R6 where R5 and R6 have the meanings mentioned above, except for R5 = OR5a or NR5bR5c and R6 = OR6a or NR6bR6c, may be prepared by reacting a sulfonamide (II) with ketones (Xl) and a Lewis acid such as titanium(IV) chloride. The reaction is usually carried out in a polar solvent, for example CrC4-alkanols such as methanol, ethanol, n-propanol or isopropanol, carboxamides such as N,N-dimethyl formamide, N,N-dimethyl acetamide or N-methylpyrrolidinone. The reaction of Il with a ketone Xl may be carried out analogously to the procedure described in Tetrahedron 1986, 42, 5649-5656.
Scheme 8:
Figure imgf000063_0001
(II) (R10 = H) (Xl) (Ia)
In scheme 8, the variables R1, R2, R3 and R4 have the meanings mentioned above and in particular the meanings mentioned as being preferred.
2-Cyanobenzene compounds Ia, wherein A is N=SR7R8 in which R7 and R8 have the meanings mentioned above, can be prepared reacting a sulfonamide (II) with sulfides (XII) and a chlorinating agent such as f-butyl-hypochlorite in the presence of a base, see scheme 9. Suitable bases are for example those bases mentioned above. The reaction is usually carried out in a polar solvent, for example CrC4-alkanols such as methanol, ethanol, n-propanol or isopropanol, carboxamides such as N,N-dimethyl formamide, N,N-dimethyl acetamide or N-methylpyrrolidinone. The reaction of Il with Xl can be carried out analogously to methods known from prior art, for example, in analogy to Tetrahedron 1986, 42, 5649-5656.
Scheme 9:
Figure imgf000064_0001
(II) (R10 = H) (XII) (Ia)
In scheme 9, the variables R1, R2, R3 and R4 have the meanings mentioned above and in particular the meanings mentioned as being preferred.
2-Cyanobenzene compounds Ia, wherein A is an N-bound 5-, 6- or 7-membered aromatic or non-aromatic unsaturated heterocycle as defined above, may be prepared by reacting a sulfonamide (II) with a 2,5-dialkoxytetrahydrofuran (XIII) which may be un- substituted or may carry 1 , 2, 3 or 4 radicals R13 (where R13 has the meanings men- tioned above), see scheme 10. The reaction is carried out in an acidic solvent such as carboxylic acids, for example Ci-C4-carboxylic acids, e.g. acetic acid. The reaction of Il with XIII can be carried out analogously to methods known from the literature, for example, as described in Synthetic Communications 1983, 13, 741-744.
Scheme 10:
Figure imgf000064_0002
In scheme 10, the variables R1, R2, R3 and R4 have the meanings mentioned above and in particular the meanings mentioned as being preferred R is Ci-Cε-alkyl, especially CrC2-alkyl, in particular methyl.
Alternatively, 2-cyanobenzene compounds Ia, wherein A is an N-bound 5-, 6- or 7- membered aromatic or non-aromatic unsaturated heterocycle as defined above, may be prepared by reacting a sulfonylchloride (IV) with an appropriate 5-, 6- or 7- membered aromatic or non-aromatic unsaturated N containing heterocycle (XIV) in the presence of an inorganic base, see scheme 1 1. Suitable bases are, for example, alkali metal or alkaline earth metal hydroxides, bicarbonates or carbonates such as lithium hydroxide, lithium bicarbonate or lithium carbonate, sodium hydroxide, sodium bicarbonate or sodium carbonate, potassium hydroxide, potassium bicarbonate or potassium carbonate, calcium hydroxide, calcium bicarbonate or calcium carbonate, or magnesium hydroxide, magnesium bicarbonate or magnesium carbonate. The reaction is carried out under phase transfer catalysis conditions. Suitable for use as phase- transfer catalysts are quaternary ammonium or phosphonium salts. Suitable compounds which may be mentioned are the following: tetraalkyl-(Ci-Ci8)-ammonium chlorides, bromides or fluorides, N-benzyltrialkyl-(Ci-Ci8)-ammonium chlorides, bromides or fluorides, tetraalkyl-(Ci-Ci8)-phosphonium chlorides or bromides, tetraphenyl- phosponium chloride or bromide, (phenyl)o(Ci-Ci8-alkyl)p-phosponium chlorides or bromides, where o = 1 to 3, p = 3 to 1 and o + p = 4. The reaction of IV with XIV can be carried out analogously to methods known from the literature, for example, as described in Can. J. Chem 1985, 63, 896-902.
Scheme 11 :
Figure imgf000065_0001
(IV) (XIV) (Ia)
In scheme 11 , the variables R1, R2, R3 and R4 have the meanings mentioned above and in particular the meanings mentioned as being preferred.
In a similar way, 2-cyanobenzene compounds Ia, wherein A is an optionally substituted imidazole may be prepared in analogy to a method described in Indian Journal of Heterocyclic Chemistry 2003, 13, 79-80; 2-cyanobenzene compounds Ia, wherein A is an optionally substituted pyrazole, may be prepared in analogy to a method described in Heterocycles 1988, 27, 2443-2457; or 2-cyanobenzene compounds Ia, wherein A is an optionally substituted triazole may be prepared in analogy to a method described in Bioorganic & Medicinal Chemistry 2004, 2317-2333.
The starting material of the formula Il as well as the starting material of the formula IV required for preparing the compounds Ia are known from the literature, for example from WO 2005/035486 cited at the introductory part or they can be prepared in accordance with the literature cited therein. 2-Cyanobenzene compounds Ib, i.e. compounds I in which m = 0, may be prepared by the processes as described in schemes 1 to 11 , but using the corresponding sulfenyl- amide compound XV and sulfenylhalogenide compound XVI, respectively.
The sulfenylamide compounds of the formula XV, may be prepared, for example, by reacting a 2-cyanobenzenesulfenylhalide, (XVI), especially a 2-cyanobenzenesulfenyl- chloride, with ammonia or a primary amine (XVII) by analogy to a process described in Journal of Organic Chemistry 1977, VO. 42, No. 4, pp. 597-600 or in Journal of Medicinal Chemistry 2001 , Vol. 44, No. 13, pp. 2253-2258, see Scheme 12.
Scheme 12:
Figure imgf000066_0001
In scheme 12, the variables R1, R2, R3, R4 and R10 have the meanings mentioned above and in particular the meanings mentioned as being preferred and Hal is halogen, in particular chlorine. The reaction of a sulfenylhalide XVI with an amine XVII is usually carried out at a reaction temperature ranging from 0°C to the boiling point of the solvent, preferably from 0 to 30°C.
In general, the amine XVII is employed in an at least equimolar amount, preferably at least 2-fold molar excess, based on the sulfenylhalide XVI, to bind the hydrogen halide formed. It may be advantageous to employ the primary amine XVII in an up to 6-fold molar excess, based on the sulfenylhalide XVI.
The reaction is usually carried out in the presence of a solvent. Suitable solvents are polar solvents which are inert under the reaction conditions, for example CrC4-alkanols such as methanol, ethanol, n-propanol or isopropanol, dialkyl ethers such as diethyl ether, diisopropyl ether or methyl tert-butyl ether, cyclic ethers such as dioxane or tet- rahydrofuran, acetonitrile, carboxamides such as N,N-dimethyl formamide, N1N- dimethyl acetamide or N-methylpyrrolidinone, water, (provided the sulfenylhalide XVI is sufficiently resistent to hydrolysis under the reaction conditions used) or a mixture thereof. The sulfenylhalide compounds XVI may be prepared, for example by the process as described hereinafter comprising steps a) and b), see scheme 13.
Scheme 13:
Figure imgf000067_0001
\ (XVIII) (XVI)
In scheme 13, the variables R1, R2, R3 and R4 have the meanings mentioned above and in particular the meanings mentioned as being preferred and Hal is halogen, in particular chlorine.
a) Reduction of a sulfonylhalide IV to the corresponding thiol XVIIII using a suitable reducing agent. Suitable reducing agents include (1 ) tris(2- carboxyethyl)phosphine in a mixture of dioxane and water as described in Syn- thetic Communications 2003, Vol. 33, No. 20, pp. 3503-351 1 ; or (2) triphenyl- phosphine with or without the addition of iodine in an aromatic solvent like benzene or toluene as described in Bulletin of the Chemical Society of Japan 1983, Vol. 56, No. 12, pp. 3802-3812; or (3) zinc in combination with dichlorodimethylsi- lane, dimethylacetamide in a chlorinated hydrocarbon like dichloroethane as de- scribed in Tetrahedron Letters 1999, Vol. 40, pp. 3179-3182. b) Direct conversion of the thiol XVIII to the sulfenylhalide XVI by oxidative haloge- nation, for example oxidative chlorination using N-chlorosuccinimide in a chlorinated hydrocarbon such as dichloromethane as described in the Journal of Organic Chemistry 1985, Vol. 50, No. 19 pp. 3592-3595.
2-Cyanobenzene compounds Ic, i.e. compounds I in which m = 1 , may be prepared by following the procedures analogous to those described in schemes 1 to 11 , but using the sulfinylamide compound XIX and sulfinylhalide compound XX, respectively.
The sulfinylamide compounds of the formula XIX can be prepared, for example, by reacting a 2-cyanobenzenesulfinylhalide (XX) with ammonia or a primary amine (XVII) in analogy to a process described in Journal of Organic Chemistry 1983, Vol. 48 pp. 4803-4807, see scheme 14.
Scheme 14:
Figure imgf000068_0001
In scheme 14, the variables R1, R2, R3 and R4 have the meanings mentioned above and in particular the meanings mentioned as being preferred and Hal is halogen, in particular chlorine. In general, the amine XVII is employed in an at least equimolar amount, preferably at least 2-fold molar excess, based on the sulfinylhalide XX, to bind the hydrogen halide formed. It may be advantageous to employ the primary amine XVII in an up to 6-fold molar excess, based on the sulfinylhalide XX. The reaction of XVII with XX is usually carried out at a reaction temperature ranging from 0°C to the boiling point of the solvent, preferably from 0 to 30°C.
The reaction of a sulfinylhalide XX with an amine XVII is usually carried out in the presence of a solvent. Suitable solvents are polar solvents which are inert under the reac- tion conditions, for example CrC4-alkanols such as methanol, ethanol, n-propanol or isopropanol, dialkyl ethers such as diethyl ether, diisopropyl ether or methyl tert-butyl ether, cyclic ethers such as dioxane or tetrahydrofuran, acetonitrile, carboxamides such as N,N-dimethyl formamide, N,N-dimethyl acetamide or N-methylpyrrolidinone, water, (provided the sulfinylhalide XX is sufficiently resistent to hydrolysis under the reaction conditions used) or a mixture thereof.
The sulfinylhalide compounds XX may be prepared for example by the process as described hereinafter, (see scheme 15) comprising steps (a) and (b):
Scheme 15:
Figure imgf000068_0002
In scheme 15, the variables R1, R2, R3 and R4 have the meanings mentioned above and in particular the meanings mentioned as being preferred and Hal is halogen, in particular chlorine.
(a) Reduction of a sulfonylhalide IV to the corresponding thiol XXI using a suitable reducing agent as described in step a) in scheme 13.
(b) Conversion of the thiol XXI into the sulfinylhalide XX by oxidative halogenation, for example oxidative chlorination using sulfuryl chloride in acetic acid as described in Synthesis 1987, No. 1 , pp. 72-73.
If individual compounds cannot be prepared via the above-described routes, they can be prepared by derivatization of other compounds I 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 on silica gel. Some of the intermediates and end products may be obtained in the form of colorless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystallization or digestion.
The compounds of the formula I and their salts are in particular suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes.
In particular, they are suitable for controlling insect pests, such as insects from the order of
Lepidoptera: for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, An- ticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumifer- ana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Gra- pholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, HeIIuIa undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinel- lus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera cof- feella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticti- calis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pecti- nophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudo- plusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera eridania, Spodoptera frugiperda, Spodoptera Ht- toralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis,
Coleoptera (beetles), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufi- manus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cero- toma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12- punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, lps typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hip- pocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhyn- chus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyl- lopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria,
Diptera, for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chry- somya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophi- lus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia ca- prina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phor- bia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea and Tipula paludosa,
Thysanoptera (thrips), e.g. Dichromothrips spp., Frankliniella fusca, Frankliniella occi- dentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
Hymenoptera e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplo- campa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta,
Heteroptera, e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysder- cus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiven- tris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor,
Homoptera (in particular aphids), e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis craccivora, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci,
Acyrthosiphon pisum, Aulacorthum solani, Bemisa tabaci, Bemisa argentifolii, Brachy- caudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus pruni- cola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Em- poasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Mac- rosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Si- tobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii,
lsoptera (termites), e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus und Termes natalensis,
Orthoptera, e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auri- cularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schisto- cerca peregrina, Stauronotus maroccanus and Tachycines asynamorus, and
Collembola (springtails), e.g. Onychiurus ssp..
They are also suitable for controlling Nematodes : plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javani- ca, and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, An- guina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursa- phelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Cricone- ma species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Dity- lenchus species; AwI nematodes, Dolichodorus species; Spiral nematodes, Heliocoty- lenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvi- tatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus and other Rotylenchus species; Scutellonema species; Stubby root nemato- des, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Ty- lenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species.
The compounds of the formula I and their salts are also useful for controlling arachnids (Arachnoidea), such as acarians {Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persi- cus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendi- culatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis.
Compounds of the formula I are particularly useful for controlling insects, preferably sucking or piercing insects such as insects from the genera Thysanoptera, Hymenop- tera, Orthoptera and Homptera, in particular the following species:
Thysanoptera (thrips): Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci, Hymenoptera: Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta,
Orthoptera: Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricu- laria, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus fe- mur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schisto- cerca peregrina, Stauronotus maroccanus and Tachycines asynamorus ;
Homoptera, in particular aphids: Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosi- phum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mail, Psylla piri, Rho- palomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mail, Schizaphis graminum, Schizoneura lanu- ginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii;
Compounds of the formula I are particularly useful for controlling insects of the orders Homoptera and Thysanoptera and more preferably for controlling aphids.
For use in a method according to the present invention, the compounds I can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules and directly sprayable solutions. The use form depends on the particular purpose and application method. Formulations and application methods are chosen to ensure in each case a fine and uniform distribution of the compound of the formula I according to the present invention.
The formulations are prepared in a known manner, e.g. by extending the active ingredient with solvents and/or carriers, if desired using surfactants, i.e. emulsifiers and dis- persants and other formulation auxiliaries. Solvents/carriers, which are suitable, are e.g.:
solvents such as water, aromatic solvents (for example Solvesso products, xy- lene and the like), paraffins (for example mineral fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexa- none, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diace- tate), alkyl lactates, lactones such as g-butyrolactone, glycols, fatty acid di- methylamides, fatty acids and fatty acid esters, triglycerides, oils of vegetable or animal origin and modified oils such as alkylated plant oils. In principle, solvent mixtures may also be used. carriers such as ground natural minerals and ground synthetic minerals, such as silica gels, finely divided silicic acid, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, 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 are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl 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 methylcellulose.
Suitable auxiliaries comprise stabilizers, buffers, antioxidants, biocides, antifoams, thickeners, antifreeze and the like.
Suitable thickeners are compounds which confer a pseudoplastic flow behavior to the formulation, i.e. high viscosity at rest and low viscosity in the agitated stage. Mention may be made, in this connection, for example, of cammercial thickeners based on polysaccharides, such as Xanthan Gum® (Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum® (from RT. Vanderbilt), or organic phyllosilicates, such as Atta- clay® (from Engelhardt). Antifoam agents suitable for the dispersions according to the invention are, for example, silicone emulsions (such as, for example, Silikon® SRE, Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof. Biocides can be added to stabilize the compositions according to the invention against attack by microorganisms. Suitable biocides are, for example, based on isothiazolones such as the compounds marketed under the trademarks Proxel® from Avecia (or Arch) or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas. Suitable antifreeze agents are organic polyols, for example ethylene glycol, propylene glycol or glycerol. These are usually employed in amounts of not more than 10% by weight, based on the total weight of the active compound composition. If appropriate, the active compound compositions according to the invention may comprise 1 to 5% by weight of buffer, based on the total amount of the formulation prepared, to regulate the pH, the amount and type of the buffer used depending on the chemical properties of the active compound or the active compounds. Examples of buffers are alkali metal salts of weak inorganic or organic acids, such as, for example, phosphoric acid, boronic acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.
Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are 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, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, etha- nol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients 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, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, 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. In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
The following are examples of formulations:
1. Products for dilution with water
A Soluble concentrates (SL) 10 parts by weight of a compound according to the invention are dissolved in water or in a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active ingredient dissolves upon dilution with water.
B Dispersible concentrates (DC) 20 parts by weight of a compound according to the invention are dissolved in cyclohexanone with addition of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion.
C Emulsifiable concentrates (EC) 15 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxy- late (in each case 5% strength). Dilution with water gives an emulsion.
D Emulsions (EW, EO) 40 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxy- late (in each case 5% strength). This mixture is introduced into water by means of an emulsifier (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.
E Suspensions (SC, OD)
In an agitated ball mill, 20 parts by weight of a compound according to the invention are milled with addition of dispersant, wetters and water or an organic solvent to give a fine active ingredient suspension. Dilution with water gives a stable suspension of the active ingredient.
F Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of a compound according to the invention are ground finely with addition of dispersants and wetters and made into water-dispersible or wa- ter-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active ingredient.
G Water-dispersible powders and water-soluble powders (WP, SP) 75 parts by weight of a compound according to the invention are ground in a ro- tor-stator mill with addition of dispersant, wetters and silica gel. Dilution with water gives a stable dispersion or solution with the active ingredient.
2. Products to be applied undiluted
H Dustable powders (DP)
5 parts by weight of a compound according to the invention are ground finely and mixed intimately with 95% of finely divided kaolin. This gives a dustable product.
I Granules (GR, FG, GG, MG)
0.5 parts by weight of a compound according to the invention is ground finely and associated with 95.5% carriers. Current methods are extrusion, spray drying or the fluidized bed. This gives granules to be applied undiluted.
J ULV solutions (UL)
10 parts by weight of a compound according to the invention are dissolved in an organic solvent, for example xylene. This gives a product to be applied undiluted.
Aqueous use 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 substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such con- centrates are suitable for dilution with water.
The active ingredient concentrations in the ready-to-use products can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 %.
The active ingredients may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active ingredient, or even to apply the active ingredient without additives. In the method of this invention compounds I may be applied with other active ingredients, for example with other pesticides, insecticides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
The following list of pesticides together with which the compounds according to the invention can be used and with which potential synergistic effects might be produced is intended to illustrate the possible combinations, but not to impose any limitation:
(1 ) Organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methi- dathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimi- phos-methyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazo- phos, trichlorfon;
(2) Carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, pro- poxur, thiodicarb, triazamate;
(3) Pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, teflu- thrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin;
(4) Growth regulators: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, te- flubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
(5) Nicotinic receptor agonists/antagonists compounds: clothianidin, dinotefuran, imida- cloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid and AKD-1022, (6) GABA antagonist compounds: acetoprole, endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, the phenylpyrazole compound of formula F2
Figure imgf000079_0001
(7) Macrocyclic lactone insecticides: abamectin, emamectin, milbemectin, lepimectin, spinosad;
(8) METI I compounds: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim;
(9) METI Il and III compounds: acequinocyl, fluacyprim, hydramethylnon;
(10) Uncoupler compounds: chlorfenapyr;
(1 1 ) Oxidative phosphorylation inhibitor compounds: cyhexatin, diafenthiuron, fenbu- tatin oxide, propargite;
(12) Moulting disruptor compounds: cyromazine;
(13) Mixed Function Oxidase inhibitor compounds: piperonyl butoxide;
(14) Sodium channel blocker compounds: indoxacarb, metaflumizone,
(15) Various: amitraz, benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetro- zine, sulfur, thiocyclam, flubendiamide, cyenopyrafen, flupyrazofos, cyflumetofen, ami- doflumet, pyrifluquinazon, N-R'-2,2-dihalo-1 -R"cyclo-propanecarboxamide-2-(2,6- dichloro- α,α,α-tri-fluoro-p-tolyl)hydrazone or N-R'-2,2-di(R"')propionamide-2-(2,6- dichloro-α,α,α-trifluoro-p-tolyl)-hydrazone, wherein R' is methyl or ethyl, halo is chloro or bromo, R" is hydrogen or methyl and R'" is methyl or ethyl, anthranilamide com- pounds such as chlorantraniliprole or the compound of formula F5
Figure imgf000080_0001
and malononitrile compounds as described in JP 2002 284608, WO 02/89579, WO 02/90320, WO 02/90321 , WO 04/06677, WO 04/20399, JP 2004 99597, WO 05/68423, WO 05/68432, WO 05/63694 or WO 05/63694, especially the malononitrile compounds CF3(CH2)2C(CN)2CH2(CF2)3CF2H, CF3(CH2)2C(CN)2CH2(CF2)5CF2H, CF3(CH2)2C(CN)2(CH2)2C(CF3)2F, CF3(CH2)2C(CN)2(CH2)2(CF2)3CF3, CF2H(CF2)3CH2C(CN)2CH2(CF2)3CF2H, CF3(CH2)2C(CN)2CH2(CF2)3CF3, CF3(CF2)2CH2C(CN)2CH2(CF2)3CF2H, and CF3CF2CH2C(CN)2CH2(CF2)SCF2H.
The commercially available compounds of the group (1 ) to (15) may be found in The P Peessttiicciiddee MMaainual, 13th Edition, British Crop Protection Council (2003) among other publications.
Thioamides of formula r2 and their preparation have been described in WO 98/28279. Lepimectin is known from Agro Project, PJB Publications Ltd, November 2004. Ben- clothiaz and its preparation have been described in EP-A1 454621. Methidathion and Paraoxon and their preparation have been described in Farm Chemicals Handbook, Volume 88, Meister Publishing Company, 2001. Acetoprole and its preparation have been described in WO 98/28277. Metaflumizone and its preparation have been de- scribed in EP-A1 462 456. Flupyrazofos has been described in Pesticide Science 54, 1988, p.237-243 and in US 4822779. Pyrafluprole and its preparation have been described in JP 2002193709 and in WO 01/00614. Pyriprole and its preparation have been described in WO 98/45274 and in US 6335357. Amidoflumet and its preparation have been described in US 6221890 and in JP 21010907. Flufenerim and its prepara- tion have been described in WO 03/007717 and in WO 03/007718. Cyflumetofen and its preparation have been described in WO 04/080180. The aminoquinazolinone compound pyrifluquinazon has been described in EP A 109 7932.
Anthranilamides such as chlorantraniliprole and the compound of formula F5 and their preparation have been described in WO 01/70671 ; WO 02/48137; WO 03/24222, WO 03/15518, WO 04/67528; WO 04/33468; and WO 05/118552. The malononitrile compounds CF3(CH2)2C(CN)2CH2(CF2)3CF2H, CF3(CH2)2C(CN)2CH2(CF2)5CF2H, CF3(CH2)2C(CN)2(CH2)2C(CF3)2F, CF3(CH2)2C(CN)2(CH2)2(CF2)3CF3, CF2H(CF2)SCH2C(CN)2CH2(CF2)SCF2H, CF3(CH2)2C(CN)2CH2(CF2)3CF3, CF3(CF2)2CH2C(CN)2CH2(CF2)3CF2H, and CF3CF2CH2C(CN)2CH2(CF2)3CF2H have been described in WO 05/63694.
In the methods according to the invention the pests are controlled by contacting the target parasite/pest, its food supply, habitat, breeding ground or its locus with a pesti- cidally effective amount of compounds of formula I or with a salt thereof or with a composition containing a pesticidally effective amount of a compound of formula I or a salt thereof.
"Locus" means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is growing or may grow.
In general, "pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
The compounds of the invention can also be applied preventively to places at which occurrence of the pests is expected.
The compounds of formula I may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of compounds of formula I. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).
The aforementioned compositions are particularly useful for protecting crop plants against infestation of said pests or for combating these pests in infested plants.
For use in treating crop plants, the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare. In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 2O g per 100 m2.
The compounds of formula I are also suitable for the treatment of seeds in order to protect the seed from insect pest, in particular from soil-living insect pests and the resulting plant's roots and shoots against soil pests and foliar insects.
The compounds of formula I are particularly useful for the protection of the seed from soil pests and the resulting plant's roots and shoots against soil pests and foliar insects. The protection of the resulting plant's roots and shoots is preferred. More preferred is the protection of resulting plant's shoots from piercing and sucking insects, wherein the protection from aphids is most preferred.
The present invention therefore comprises a method for the protection of seeds from insects, in particular from soil insects and of the seedlings' roots and shoots from insects, in particular from soil and foliar insects, said method comprising contacting the seeds before sowing and/or after pregermination with a compound of the general formula I or a salt thereof. Particularly preferred is a method, wherein the plant's roots and shoots are protected, more preferably a method, wherein the plants shoots are protected form piercing and sucking insects, most preferably aa method, wherein the plants shoots are protected from aphids.
The term seed embraces seeds and plant propagules of all kinds including but not Nm- ited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
Compositions which are useful for seed treatment are e.g.: A Soluble concentrates (SL, LS) D Emulsions (EW, EO, ES) E Suspensions (SC, OD, FS)
F Water-dispersible granules and water-soluble granules (WG, SG) G Water-dispersible powders and water-soluble powders (WP, SP, WS) H Dustable powders (DP, DS)
Preferred FS formulations of compounds of formula I for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/L) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/L) of at least one surfactant, e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g. 1 to 40 % by weight of a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight.
Suitable pigments or dyes for seed treatment formulations are 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 1 12, 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.
Binders, which are also referred to as stickers / adhesion agents are added to improve the adhesion of the active materials on the seeds after treatment. Suitable adhesives are block copolymers EO/PO surfactants but also polyvinylalcohols, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines (Lupasol®, Polymin®), polyethers and copolymers derived from these polymers.
In the treatment of seed, the application rates of the compounds I are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed.
The invention therefore also relates to seed comprising a compound of the formula I or an agriculturally useful salt of I, as defined herein. The amount of the compound I or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed.
The compounds of the invention may also be applied against non-crop insect pests, such as ants, termites, wasps, flies, mosquitos, crickets, or cockroaches. For use against said non-crop pests, compounds of formula I are preferably used in a bait com- position.
The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks. Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickyness, moisture retention or aging characteristics.
The bait employed in the composition is a product which is sufficiently attractive to in- cite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.
For use in bait compositions, the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound.
Formulations of compounds of formula I as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, etha- nol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocar- bons (e.g. kerosenes) having boiling ranges of approximately 50 to 250°C, dimethyl- formamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
The oil spray formulations differ from the aerosol recipes in that no propellants are used.
For use in spray compositions, the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %. The compounds of formula I and its respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
The present invention is now illustrated in further details by the following examples.
Synthesis Examples
Example 2: /V-Acetyl-ZV-ethyl^-cyano-S-methyl-benzene-sulfonamide
1.0 g (4.6 mmol) of Λ/-Ethyl-2-cyano-3-methyl-benzene-sulfonamide was dissolved in 50 ml of acetonitrile and 0.91 g (8.9 mmol) of acetic acid anhydride and 50 mg of (0.45 mmol) of 4-DMAP (4-dimethylaminopyridine) were added. The solution was stirred overnight at room temperature. After concentrating the reaction mixture water and methyl terf-butyl ether were added. The layers were separated and the aqueous layer was extracted three times with methyl tert-butyl ether. The combined organic layers were washed with phosphate buffer, dried over a drying agent and filtered off with suction. The filtrate was concentrated in vacuo to afford 1.07 g (90 % of theory) of N- Acetyl-ZV-Ethyl^-cyano-S-methyl-benzene-sulfonamide.
Example 18: 2-Methyl-6-(2-oxo-pyrrolidine-1 -sulfonyl)benzonitrile
0.79 g (9.3 mmol) of 2-pyrrolidin-2-one were dissolved in 20 ml of dry tetrahydrofuran (THF) and cooled to -78°C under inert atmosphere. 4.4 ml (7.0 mmol) of n-butyllithium were added slowly. Stirring was continued for 15 min at -78°C and for 30 min at 0°C. The solution was slowly added to a solution of 1.00 g (4.6 mmol) of 2-cyano-3-methyl- benzenesulfonylchloride in 20 ml of dry THF and stirring was continued until consumption of the sulfonyl chloride could be observed. The mixture was diluted by adding methyl tert-butyl ether and cooled to 0°C. Aqueous NH4CI was added, the layers were separated and the aqueous layer was extracted two times with methyl terf-butyl ether. The combined organic layers were washed with brine, dried over a drying agent and filtered off with suction. The filtrate was concentrated in vacuo and purified by flash chromatography (cyclohexane/ethyl acetate 4:1 ) to afford 0.10 g (8 % of theory) of 2- methyl-6-(2-oxo-pyrrolidine-1 -sulfonyl)benzonitrile.
Example 20: Λ/-(2,2-Dimethylpropionoyl)-Λ/-methyl-2-cyano-3-methyl-benzene- sulfonamide 42 mg (1.05 mmol) of NaH (60 % in mineral oil) were suspended in 10 ml of dry THF under an inert atmosphere. 0.21 g (1.0 mmol) of Λ/-methyl-2-cyano-3-methyl-benzene- sulfonamide in 10 ml of dry THF were added slowly at room temperature. Stirring was continued for 30 min at room temperature before 0.12 g (1.0 mmol) of pivaloyl chloride were slowly added and stirring was continued overnight at room temperature. The mixture was diluted with dichloromethane and aqueous ammonium chloride. The layers were separated and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were washed water, dried over a drying agent and filtered off with suction. The filtrate was concentrated in vacuo and purified by flash chromatography (cyclohexane/ethyl acetate) to afford 0.27 g ( 92 % of theory) of N- (2,2-dimethylpropionoyl-Λ/-methyl-2-cyano-3-methyl-benzene-sulfonamide.
Example 22: Λ/-Ethyl-Λ/-(2-cyano-3-methyl-benzenesulfonyl)-Λ/'-phenyl urea
1.0 g (4.5 mmol) of Λ/-ethyl-2-cyano-3-methyl-benzene-sulfonamide was dissolved in 25 ml of dichloromethane followed by the addition of 0.8 g of phenylisocyanate and 0.6 g of Λ/-ethyldiisopropylamine. The solution was stirred overnight at room temperature. Aqueous HCI was added, the layers were separated and the aqueous layer was extracted three times with dichloromethane. The combined organic layers were washed with water, dried over a drying agent and filtered off with suction. The filtrate was concentrated in vacuo and purified by flash chromatography (toluene/ethyl acetate) to afford 0.97 g (63 % of theory) of Λ/-Ethyl-Λ/-(2-cyano-3-methyl-benzenesulfonyl)-Λ/'- phenyl urea.
Example 28: Λ/-(Benzyloxycarbonyl)-2-cyano-3-methyl-benzenesulfonamide
1.00 g (5.1 mmol) of 2-cyano-3-methyl-benzenesulfonamide was dissolved in 25 ml of acetone and cooled to 0°C. 0.20 g of NaOH (5.1 mmol) were added, followed by adding 0.87 g (5.1 mmol) of benzylchloroformate. The mixture was stirred at 0-5°C for 1 h. The mixture was concentrated, diluted with water and acidified by the addition of 10% HCI. The solution was extracted three times with dichloromethane. The combined organic extracts were dried over a drying agent and filtered off with suction. The filtrate was concentrated in vacuo and purified by flash chromatography (cyclohexane/ethyl acetate) to afford 1.03 g (61 % of theory) of Λ/-(benzyloxycarbonyl)-2-cyano-3-methyl- benzenesulfonamide.
Example 29: Λ/-(lsopropylamino-ethoxy-methylene)-2-cyano-3-methyl-benzene- sulfonamide 0.50 g (1.7 mmol) of 2-cyano-Λ/-diethoxymethylene-3-methyl-benzenesulfonamide and 1.00 g (16.9 mmol) of isopropylamine were mixed and heated at 70°C for 4 h. The mixture was concentrated and the residue was purified by flash chromatography on silica (cyclohexane/ethyl acetate) to yield 220 mg (42 % of theory) of Λ/-(isopropyllamino- ethoxy-methylene)-2-cyano-3-methyl-benzenesulfonamide having a melting point of 139-142°C.
Example 32: 2-Cyano-Λ/-dimethoxymethylene-3-methyl-benzenesulfonamide
2.00 g (10.2 mmol) of 2-cyano-3-methyl-benzenesulfonamide and 2.08 g of tetrameth- oxymethane (15.3 mmol) were heated to 160°C slowly and under stirring and under removal of methanol from the mixture. The mixture was cooled to room temperature. The residue was washed with methyl f-butyl ether and dried to afford 1.71 g (63 % of theory) of 2-cyano-Λ/-dimethoxymethylene-3-methyl-benzenesulfonamide.
Example 34: 2-Cyano-Λ/-(1 -methoxyethylidene)-3-methyl-benzenesulfonamide
1.00 g (5.1 mmol) of 2-cyano-3-methyl-benzenesulfonamide and 6.12 g of trimeth- oxyethane (51.0 mmol) were heated to reflux for 3 h. The mixture was cooled to room temperature. Excess of trimethoxyethane was removed by distillation. Cyclohexane was added. The precipitate was sucked off and dried to afford 1.12 g (87 % of theory) of 2-cyano-Λ/-(1-methoxyethylidene)-3-methyl-benzenesulfonamide.
Example 35: 2-Cyano-3-methyl-Λ/-dimethylaminomethylene-benzenesulfonamide
2.00 g (10.2 mmol) of 2-cyano-3-methyl-benzenesulfonamide and 1.82 g of dimethyl- formamide dimethyl acetal in 25 ml of toluene were heated to reflux for 2 h. The mixture was cooled to room temperature. The brownish precipitate was sucked off and purified by chromatography to yield 0.66 g (26 % of theory) of 2-cyano-3-methyl-/V- dimethylaminomethylene-benzenesulfonamide having a melting point of 168-174°C.
Example 37: 2-Cyano-3-methyl-Λ/-(1 ,2,2-trimethyl-propylidene)-benzenesulfonamide
0.70 g (3.6 mmol) of 2-cyano-3-methyl-benzenesulfonamide and 0.36 g (3.6 mmol) of 3,3-dimethyl-butan-2-one were mixed in 15 ml of 1 ,1 ,2-trichloroethane and cooled to 0°C. 0.68 g of titaniumtetrachloride, dissolved in 5 ml of dry dichloromethane, was added slowly. The reaction mixture was heated to reflux for 14 h. The reaction mixture was concentrated, the residue was dissolved in dichloromethane and washed 3 times with 5 % K2Cθ3-solution. The organic layer was dried and concentrated. The residue was purified by flash chromatography on silica (cyclohexane/ethyl acetate 4:1 ) to yield 45 mg (5 % of theory) of 2-cyano-3-methyl-Λ/-(1 ,2,2-trimethyl-propylidene)-benzene- sulfonamide.
Examples 38: 2-Cyano-3-methyl-N-(tetrahydro-thiphophen-1 -ylidene)- benzenesulfonamide
To a solution of 0.44 g (5.00 mmol) of tetrahydrothiophene in 10 ml of methanol were added 0.57 g terf-butylhypochlorite at -78°C. After 20 min, 0.7 ml of triethylamine and 0.98 g of 2-cyano-3-methylbenzenesulfonamide dissolved in 5ml of methanol and 3 ml of DMF were added. Stirring was continued at -78 ° for 2h and overnight at room temperature. 5 % NaOH-solution was added, the layers were separated and the aqueous layer was extracted two times with dichloromethane. The combined organic extracts were dried over a drying agent and filtered off with suction. The filtrate was concentrated in vacuo and purified by chromatography on silica (toluene/ethanol 4:1 ) to afford 0.153 g (11 % of theory) of the title compound.
Example 41 : 2-Methyl-6-(pyrrole-1-sulfonyl)-benzonitrile
To a solution of 1.00 g (5.10 mmol) of 2-cyano-3-methyl-benzenesulfonamide in 25 ml of acetic acid was added 1.01 g (7.64 mmol) of 2,5-dimethoxy-tetrahydrofuran at room temperature while stirring. After completion of addition, the solution was heated to reflux for 1 hour. After cooling to room temperature water was added, and the solution was extracted with ethyl acetate. The combined organic extracts were dried over a drying agent and filtered off with suction. The filtrate was concentrated in vacuo and puri- fied by chromatography on silica (cyclohexane/ethyl acetate 4:1 ) to afford 0.64 g (51 % of theory) of 2-methyl-6-(pyrrole-1-sulfonyl)-benzonitrile.
Example 45: 2-Methyl-6-(3-bromo-pyrrole-1 -sulfonyl)-benzonitrile
1.0 g (4.1 mmol) of 2-methyl-6-(pyrrole-1-sulfonyl)-benzonitrile were suspended in 15 ml of glacial acetic acid at room temperature. 0.22 ml (4.3 mmol) of bromine were dissolved in 15 ml of acetic acid and added slowly at room temperature during 30 min. The mixture was heated to reflux for 1.5 h and stirred overnight at room temperature. The mixture was poured on ice. The precipitate was sucked off, dissolved in ethyl ace- tate, dried over a drying agent and concentrated in vacuo. The residue was repetitively purified by chromatography on silica to afford 81 mg (6 % of theory) of 2-methyl-6-(3- bromo-pyrrole-1-sulfonyl)-benzonitrile having a melting point of 98-100°C.
Example 46: 2-Methyl-6-(pyrazole-1-sulfonyl)-benzonitrile To a solution of 0.41 g (1.90 mmol) of 2-cyano-3-methyl-benzenesulfonylchloride in 10 ml of dichloromethane was added 0.19 g (2.81 mmol) of pyrazole and 0.39 g of triethylamine at room temperature. After stirring overnight, TLC showed completion of the reaction. Ammonium chloride solution was added, the layers were separated and the aqueous layer was extracted three times with dichloromethane. The combined organic extracts were dried over a drying agent and filtered off with suction. The filtrate was concentrated in vacuo and purified by chromatography on silica (cyclohexane/ethyl acetate 1 :1 ) to afford 0.184 g (40 % of theory) of 2-methyl-6-(pyrazole-1-sulfonyl)- benzonitrile having a melting point of 99-104°C.
Example 47: 2-Methyl-6-([1.2.4]-triazole-1-sulfonyl)-benzonitrile
To a solution of 0.41 g (1.90 mmol) of 2-cyano-3-methyl-benzenesulfonylchloride in 10 ml of dichloromethane was added 0.19 g (2.79 mmol) of [1.2.4]-triazole and 0.39 g triethylamine at room temperature. After stirring overnight, TLC showed completion of the reaction. Ammonium chloride solution was added, the layers were separated and the aqueous layer was extracted three times with dichloromethane. The combined organic extracts were dried over a drying agent and filtered off with suction. The filtrate was concentrated in vacuo and purified by chromatography on silica (cyclohexane/ethyl acetate 1 :1 ) to afford 0.108 g (23 % of theory) of 2-methyl-6-([1.2.4]-triazole-1-sulfonyl)- benzonitrile having a melting point of 142-144°C.
Example 48: 2-Methyl-6-(imidazole-1-sulfonyl)-benzonitrile
To a solution of 0.41 g (1.90 mmol) of 2-cyano-3-methyl-benzenesulfonylchloride in 10 ml of dichloromethane was added 0.19 g (2.81 mmol) of imidazole and 0.39 g of triethylamine at room temperature. After stirring overnight, TLC showed completion of the reaction. Ammonium chloride solution was added, the layers were separated and the aqueous layer was extracted three times with dichloromethane. The combined or- ganic extracts were dried over a drying agent and filtered off with suction. The filtrate was concentrated in vacuo and purified by chromatography on silica (cyclohexane/ethyl acetate 1 :1 ) to afford 0.126 g (27 % of theory) of 2-methyl-6-(imidazole-1-sulfonyl)- benzonitrile having a melting point of 93-95°C.
The compounds of the formula I with m = 2, R2 = H, R3 = H, R4 = H or F listed in the following table I were prepared in an analogous manner.
Table I:
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
The products were characterized by coupled High Performance Liquid Chromatography / mass spectrometry (HPLC/MS), by NMR or by their melting points.
1) m.p. melting point
2) 1H-NMR: The signals are characterized by chemical shift (ppm) vs. tetramethylsilane, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m = multiplett, q = quartett, t = triplett, d = doublet and s = singulett.
3) RT = tr retention time
Analytical HPLC column: RP-18 column Chromolith Speed ROD (Merck KgaA, Germany). Elution: acetonitrile + 0.1 % trifluoroacetic acid / water + 0.1 % trifluoroacetic acid in a ratio of from 5:95 to 95:5 in 5 min at 40°C.
II. Examples of action against pests
The active compounds were formulated in a mixture of 50 vol.-% acetone:50 vol.-% water. A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % v/v.
In the following tests, the formulated solutions of the active compounds were diluted to an active ingredient concentration of 300 ppm and the diluted solutions were applied in the below mentioned tests.
The action of the compounds of the formula I against pests was demonstrated by the following experiments:
11.1 Cotton aphid {aphis gossypii), mixed life stages
Cotton plants at the cotyledon stage were infested prior to treatment by placing a heavily infested leaf from the main aphid colony on top of each cotyledon. The aphids were allowed to transfer overnight and the host leaf was removed. The infested cotyledons were then dipped and agitated in the test solution for 3 seconds and allowed to dry in a fume hood. Test plants were maintained under fluorescent lighting in a 24-hr photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated check plants, was determined after 5 days. In this test compounds each of examples 1 , 2, 3, 5, 6, 7, 8, 9, 10, 1 1 , 12, 13, 14, 15, 16, 17, 18, 19, 21 , 22, 23, 24, 25, 26, 27, 28, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 44, 45, 48 at 300 ppm provided at least 86 % mortality of cotton aphid {Aphis gossypii, mixed life stages) in comparison with untreated controls.
11.2 Green Peach Aphid (Myzus persicae), mixed life stages
Bell pepper plants at the first true-leaf stage were infested prior to treatment by placing heavily infested leaves from the main aphid colony on top of the treatment plants. The aphids were allowed to transfer overnight to accomplish an infestation of 30-40 aphids per plant and the host leaves were removed. The infested leaves of the test plants were then dipped and agitated in the test solution for 3 seconds and allowed to dry in a fume hood. Test plants were maintained under fluorescent lighting in a 24-hr photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated check plants, was determined after 5 days.
In this test compounds each of examples 1 , 2, 3, 5, 6, 7, 8, 9, 11 , 12, 13, 14, 15, 16, 21 , 22, 23, 27, 28, 31 , 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 44, 45, 48 at
300 ppm provided at least 86 % mortality of green peach aphidin comparison with untreated controls.
11.3 Bean Aphid (Aphis fabae)
Nasturtium plants grown in Metro mix in the 1st leaf-pair stage (variety 'Mixed Jewel') were infested with approximately 2-30 laboratory-reared aphids by placing infested cut plants on top of the test plants. The cut plants were removed after 24 hr. Each plant was dipped into the test solution to provide complete cover- age of the foliage, stem, protruding seed surface and surrounding cube surface and allowed to dry in the fume hood. The treated plants were kept at about 25°C with continuous fluorescent light. Aphid mortality is determined after 3 days.
In this test compounds each of examples 2, 5, 6, 7, 8, 1 1 , 12, 13, 14, 15, 17, 18, 21 , 23, 25, 26, 27, 30, 31 , 32, 33, 35, 36, 37, 38, 41 , 42, 44 at 300 ppm provided at least 86 % mortality of bean aphid in comparison with untreated controls.

Claims

We claim:
A method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of at least one cyanobenzene compound of the formula I and/or at least one agriculturally acceptable salt thereof:
Figure imgf000099_0001
where
m is 0, 1 or 2;
A is a radical of the formulae
N=CR5R6, N=SR7R8, NR10-C(=X)-R9, where X is O, S or NR11,
or A is a N-bound 5-, 6- or 7-membered heterocycle, which is ethylenically unsaturated or aromatic, and which additionally may contain 1 , 2, or 3 further heteroatoms or heteroatom groups, selected from O, S, SO, SO2, N, and NR12, and/or 1 , 2 or 3 carbonyl groups as ring members and which may carry 1 , 2, 3 or 4 radicals R13,
R1 is hydrogen, nitro, cyano, azido, amino, halogen, sulfenylamino, sulfinyl- amino, sulfonylamino, C(=O)R14, CrC6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, d-C6-alkoxy, (Ci-C6-alkyl)amino, di(Ci-C6-alkyl)amino, Ci-Cβ-alkylthio, Ci-Cβ-alkylsulfinyl or Ci-C6-alkylsulfonyl, wherein the ten last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, CrC4-alkoxy, CrC4-alkylthio, CrC4-alkylsulfinyl, CrC4- alkylsulfonyl, CrC4-haloalkoxy, CrC4-haloalkylthio, (CrC4-alkoxy)carbonyl, (Ci-C4-alkyl)amino, di(Ci-C4-alkyl)amino, C3-C8-cycloalkyl and phenyl, it being possible for phenyl to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents, independently of one another se- lected from the group consisting of CrC4-alkyl, Ci-C4-haloalkyl, CrC4- alkoxy and Ci-C4-haloalkoxy;
R2, R3 and R4 are independently of one another selected from the group consist- ing of hydrogen, halogen, cyano, azido, nitro, CrC6-alkyl, C3-C8-cycloalkyl,
CrC4-haloalkyl, CrC4-alkoxy, CrC4-alkylthio, CrC4-alkylsulfinyl, CrC4- alkylsulfonyl, CrC4-haloalkoxy, CrC4-haloalkylthio, C2-C6-alkenyl, C2-C6- alkynyl, amino, (Ci-C4-alkyl)amino, di(Ci-C4-alkyl)amino, sulfonylamino, sulfinylamino, sulfenylamino and C(=O)-R15;
R5 is H, OR5a, NR5bR5c, aryl, aryl-Ci-C4-alkyl, heteroaryl, heteroaryl-CrC4- alkyl, heterocyclyl,
Figure imgf000100_0001
Ci-Cio-alkyl, C3-Cio-cycloalkyl, Ci-Cio-alkylthio, CrCio-alkylsulfonyl, Ci-Cio-alkylsulfinyl, wherein the five last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another each selected from the group consisting of cyano, nitro, amino, CrCio-alkoxy, Cr Cio-alkylthio, CrCio-alkylsulfinyl, CrCio-alkylsulfonyl, Ci-Cio-haloalkoxy, CrCio-haloalkylthio, d-Cio-alkoxycarbonyl, (Ci-Ci0-alkyl)amino, di-(Ci-Ci0- alkyl)amino, C3-Cio-cycloalkyl and phenyl, it being possible for phenyl to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 sub- stituents, independently of one another selected from the group consisting of CrC4-alkyl, CrC4-haloalkyl, CrC4-alkoxy and CrC4-haloalkoxy;
wherein R5a is CrCio-alkyl, C3-Ci0-cycloalkyl, C2-Ci0-alkenyl, C2-Ci0-alkynyl, aryl, aryl-Ci-C4-alkyl, heteroaryl or heteroaryl-CrC4-alkyl, heterocyclyl or
Figure imgf000100_0002
R5b, R5c, independently from each other, are selected from hydrogen, d- Cio-alkyl, C3-Ci0-cycloalkyl, C2-Ci0-alkenyl, C2-Ci0-alkynyl, aryl, aryl-
CrC4-alkyl, heteroaryl and heteroaryl-Ci-C4-alkyl, heterocyclyl or het- erocyclyl-CrC4-alkyl;
wherein d-Cio-alkyl, C3-Ci0-cycloalkyl, C2-Ci0-alkenyl and C2-Ci0-alkynyl in R5a, R5b and R5c may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, CrC4-alkoxy, CrC4-alkylthio, CrC4-alkylsulfinyl, CrC4- alkylsulfonyl, CrC4-haloalkoxy, CrC4-haloalkylthio, (CrC4-alkoxy)carbonyl, (CrC4-alkyl)amino, di(CrC4-alkyl)amino and C3-Ce-CyClOaI kyl;
wherein the heteroaryl moiety in heteroaryl and heteroaryl-CrC4-alkyl of R5, R5a, R5b and R5c is 5- or 6 membered and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO2, N or NRa, as ring members, Ra being hydrogen or d-C6-alkyl;
wherein the heterocyclyl moiety in heterocyclyl and heterocyclyl-CrC4-alkyl of R5, R5a, R5b and R5c is 3- to 7 membered, is saturated or partly unsaturated and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO2, N or NRb, as ring members, Rb being hydrogen or Ci-C6-alkyl, and additionally may contain 1 , 2 or 3 CO groups as ring members;
and wherein the carbon atoms of aryl, hetaryl, and heterocyclyl moieties in R5, R5a, R5b and R5c may be unsubstituted or may carry 1 , 2 or 3 substitu- ents, independently of one another selected from the group consisting of halogen, CrC4-alkyl, CrC4-haloalkyl, CrC4-alkoxy and CrC4-haloalkoxy;
R6 independently has one of the meanings given for R5;
R7, R8, independently from each other, are selected from aryl, aryl-Ci-C4-alkyl, heteroaryl, heteroaryl-Ci-C4-alkyl, heterocyclyl,
Figure imgf000101_0001
Cr
Cio-alkyl, C3-Ci0-cycloalkyl, C2-Ci0-alkenyl and C2-Ci0-alkynyl, wherein the four last-mentioned radicals may be unsubstituted, partially or fully halo- genated and/or may carry 1 , 2 or 3 radicals, independently of one another each selected from the group consisting of cyano, nitro, amino, C1-C10- alkoxy, Ci-Ci0-alkylthio, Ci-CiO-alkylsulfinyl, Ci-Ci0-alkylsulfonyl, C1-C10- haloalkoxy, Ci-Cio-haloalkylthio, Ci-Ci0-alkoxycarbonyl, (C1-C10- alkyl)amino, di-(Ci-Cio-alkyl)amino, C3-Cio-cycloalkyl and phenyl, it being possible for phenyl to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC4-alkyl, CrC4-haloalkyl, CrC4-alkoxy and Cr
C4-haloalkoxy; or
R7 and R8 together with the sulfur atom they are bound to form a saturated or ethylenically unsaturated 5- to 10-membered ring, optionally substituted by 1 , 2, 3 or 4 radicals selected from Ci-C5-alkyl and halogen, wherein the ring may contain, in addition to the sulfur atom, 1 , 2 or 3 heteroatoms and/or heteroatom-containing groups as ring members selected from the group consisting of nitrogen, oxygen, sulfur, CO, SO, SO2 and N-R17;
wherein the heteroaryl moiety in heteroaryl and heteroaryl-Ci-C4-alkyl of R7 and R8 is 5- or 6 membered and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO2, N or NRC, as ring members, Rc being hydrogen or d-C6-alkyl,
wherein the heterocyclyl moiety in heterocyclyl and heterocyclyl-Ci-C4-alkyl of R7 and R8 is 3- to 7-membered, is saturated or partly unsaturated and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO2, N or NRd, as ring members, Rd being hydrogen or CrC6- alkyl, and additionally may contain 1 , 2 or 3 CO groups as ring members,
and wherein the carbon atoms of aryl, hetaryl, and heterocyclyl in R7 and
R8 may be unsubstituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and CrC4-haloalkoxy;
is selected from the group consisting of hydrogen, OR9a, NR9bR9c, aryl, aryl-
Ci-C4-alkyl, heteroaryl, heteroaryl-Ci-C4-alkyl, heterocyclyl, heterocyclyl-Cr C4-alkyl, Ci-CiO-alkyl, C2-Ci0-alkenyl, C2-Ci0-alkynyl and C3-Ci0-cycloalkyl, wherein the four last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another each selected from the group consisting of cyano, nitro, amino, Cr
Cio-alkoxy, CrCio-alkylthio, CrCio-alkylsulfinyl, CrCio-alkylsulfonyl, d- Cio-haloalkoxy, CrCio-haloalkylthio, CrCio-alkoxycarbonyl, (C1-C10- alkyl)amino, di-(CrCio-alkyl)amino, C3-Cio-cycloalkyl and phenyl, it being possible for phenyl to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC4-alkyl, CrC4-haloalkyl, CrC4-alkoxy and Cr C4-haloalkoxy,
and wherein R9a is Ci-Cio-alkyl, C3-Ci0-cycloalkyl, C2-Ci0-alkenyl, C2-Ci0-alkynyl, aryl, aryl-Ci-C4-alkyl, heteroaryl or heteroaryl-CrC4-alkyl, heterocyclyl or
Figure imgf000102_0001
R9b, R9c, independently from each other, are selected from hydrogen, d- Cio-alkyl, C3-Ci0-cycloalkyl, C2-Ci0-alkenyl, C2-Ci0-alkynyl, aryl, aryl-
CrC4-alkyl, heteroaryl and heteroaryl-CrC4-alkyl, heterocyclyl or het- erocyclyl-CrC4-alkyl,
wherein Ci-Cio-alkyl, C3-Cio-cycloalkyl, C2-Cio-alkenyl and C2-Cio-alkynyl in R9a, R9b and R9c may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, CrC4-alkoxy, Ci-C4-alkylthio, CrC4-alkylsulfinyl, C1-C4- alkylsulfonyl, CrC4-haloalkoxy, CrC4-haloalkylthio, (CrC4-alkoxy)carbonyl, (Ci-C4-alkyl)amino, di(Ci-C4-alkyl)amino and C3-C8-cycloalkyl,
wherein the heteroaryl moiety in heteroaryl and heteroaryl-Ci-C4-alkyl of R9,
R9a, R9b and R9c is 5- or 6-membered and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO2, N or NRe, as ring members, Re being hydrogen or Ci-Cβ-alkyl,
wherein the heterocyclyl moiety in heterocyclyl and
Figure imgf000103_0001
of R9, R9a, R9b and R9c is 3- to 7-membered, is saturated or partly unsaturated and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO2, N or NRf, as ring members, Rf being hydrogen or CrC6-alkyl, and additionally may contain 1 , 2 or 3 CO groups as ring members,
and wherein the carbon atoms of aryl, hetaryl and heterocyclyl moieties in R9, R9a, R9b and R9c may be unsubstituted or may carry 1 , 2 or 3 substitu- ents, independently of one another selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and CrC4-haloalkoxy;
R10 is selected from the group consisting of hydrogen, C(=O)-R16, Ci-Cio-alkyl, C2-Ci0-alkenyl, C2-Ci0-alkynyl, Ci-Cio-alkoxy and C3-Ci0-cycloalkyl, wherein the five last-mentioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, independently of one another each selected from the group consisting of cyano, nitro, amino, d- Cio-alkoxy, Ci-Ci0-alkylthio, Ci-CiO-alkylsulfinyl, Ci-Ci0-alkylsulfonyl, d- Cio-haloalkoxy, Ci-Cio-haloalkylthio, Ci-Ci0-alkoxycarbonyl, (C1-C10- alkyl)amino, di-(Ci-Ci0-alkyl)amino, C3-Ci0-cycloalkyl and phenyl, it being possible for phenyl to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Cr C4-haloalkoxy; or
R9 and R10 together with the adjacent nitrogen and carbon atoms form a saturated or ethylenically unsaturated 5 to 10-membered ring, optionally substituted by 1 , 2, 3 or 4 radicals selected from CrC5-alkyl and halogen, wherein the ring may contain, in addition to the nitrogen and carbon ring members, 1 , 2 or 3 heteroatoms and/or heteroatom groups as ring mem- bers selected from the group consisting of nitrogen, oxygen, sulfur, CO,
SO, SO2 and N-R17; R11 is d-Ce-alkyl or CrC6-alkoxy;
or
R11 and R9 together with the adjacent nitrogen and carbon atoms form an ethylenically unsaturated aromatic or non-aromatic 5 to 10-membered ring, optionally substituted by 1 , 2 or 3 CrC5-alkyl radicals, wherein the ring may contain, in addition to the nitrogen and carbon ring members, 1 , 2 or 3 het- eroatoms and/or heteroatom groups as ring members selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO2 and N-R17;
or
R11 and R10 together with the adjacent nitrogen and carbon atoms form an ethylenically unsaturated aromatic or non-aromatic 5 to 10-membered ring, optionally substituted by 1 , 2 or 3 CrC5-alkyl radicals, wherein the ring may contain, in addition to the nitrogen and carbon ring members, 1 , 2 or 3 het- eroatoms and/or heteroatom groups as ring members selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO2 and N-R17;
R12 is hydrogen, CrC6-alkyl, Ci-C4-alkoxy-Ci-C4-alkyl or CrC6-alkoxy;
each R13 independently is selected from halogen, cyano, nitro, sulfenylamino, sulfinylamino, sulfonylamino, aryl, aryl-Ci-C4-alkyl, heteroaryl, heteroaryl-
Ci-C4-alkyl, heterocyclyl, heterocyclyl-Ci-C4-alkyl, CrC6-alkyl, C3-C8- cycloalkyl, CrC6-alkoxy, CrC6-alkoxycarbonyl, CrCβ-alkylcarbonyl, (CrC6- alkyl)amino, di(C-ι-C6-alkyl)amino, Ci-Cβ-alkylthio, Ci-Cβ-alkylsulfinyl or Cr C6-alkylsulfonyl, wherein the ten last-mentioned radicals may be unsubsti- tuted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, OH, Ci-C4-alkoxy, CrC4-alkylthio, CrC4-alkylsulfinyl, Ci-C4-alkylsulfonyl, Ci-C4-haloalkoxy, Ci-C4-haloalkylthio, Ci-C4-alkylcarbonyloxy, (CrC4-alkoxy)carbonyl, (CrC4- alkyl)amino, di(CrC4-alkyl)amino, C3-C8-cycloalkyl and phenyl, it being possible for phenyl to be unsubstituted, partially or fully halogenated and/or to carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC4-alkyl, CrC4-haloalkyl, Ci-C4-alkoxy and Cr C4-haloalkoxy,
wherein the heteroaryl moiety in heteroaryl and heteroaryl-Ci-C4-alkyl of
R13 is 5- or 6 membered and contains 1 , 2, 3 or 4 heteroatoms and/or het- eroatom groups, selected from O, S, SO, SO2, N or NR9, as ring members, R9 being hydrogen or d-C6-alkyl,
wherein the heterocyclyl moiety in heterocyclyl and heterocyclyl-Ci-C4-alkyl of R13 is 3- to 7-membered and contains 1 , 2, 3 or 4 heteroatoms and/or heteroatom groups, selected from O, S, SO, SO2, N or NRh, as ring members, Rh being hydrogen or CrC6-alkyl, and additionally may contain 1 , 2 or 3 CO groups as ring members,
and wherein the carbon atoms of aryl, hetaryl, and heterocyclyl in R13 may be unsubstituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of halogen, Ci-C4-alkyl, C1-C4- haloalkyl, Ci-C4-alkoxy and CrC4-haloalkoxy;
R14 and R15, independently of one another, are selected from the group consisting of hydrogen, hydroxy, CrC6-alkoxy, amino, Ci-C4-alkylamino, di(CrC4- alkyl)amino, aryl, aryl-Ci-C4-alkyl, CrC4-alkyl, where the alkyl moiety in the two last-mentioned radicals and the aryl moiety in aryl or aryl-Ci-C4-alkyl may be partially or fully halogenated,
3- to 7-membered heteroaryl or heteroaryl-Ci-C4-alkyl, wherein the het- eroaryl ring contains as ring members 1 , 2 or 3 heteroatoms and/or heteroatom groups, selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO2 and N-Rn, wherein Rn is hydrogen or CrC4-alkyl,
3- to 7-membered heterocyclyl or
Figure imgf000105_0001
wherein the heterocyclic ring is saturated or partly unsaturated and contains 1 , 2 or 3 heteroatoms and/or heteroatom groups, selected from the group consisting of nitrogen, oxygen, sulfur, group SO, SO2 and N-R0, wherein R0 is hydrogen or Ci-C4-alkyl,
and wherein the carbon atoms of the heterocyclic rings may be unsubstituted or substituted by 1 or 2 radicals selected from halogen or CrC4-alkyl;
R16 is d-Cβ-alkyl, aryl, aryl-CrC4-alkyl,
5- to 7-membered heteroaryl or heteroaryl-Ci-C4-alkyl, wherein the heteroaryl ring contains as ring members 1 ,2 or 3 heteroatoms and/or heteroatom groups, selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO2 and N-Rk, wherein Rk is hydrogen or CrC4-alkyl, 3- to 7-membered heterocyclyl or
Figure imgf000106_0001
wherein the heterocyclic ring is saturated or partly unsaturated and contains as ring members 1 , 2 or 3 heteroatoms and/or heteroatom groups, selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO2 and N-Rm, wherein Rm is hydrogen or Ci-C4-alkyl,
and wherein the carbon atoms of the heterocyclic rings may be unsubsti- tuted or substituted by 1 or 2 radicals selected from halogen or Ci-C4-alkyl;
or
R16 and R9 together with the adjacent nitrogen and carbon atoms form a saturated or ethylenically unsaturated 5 to 10-membered ring, where the ring may be partially or fully halogenated and/or may be substituted by 1 , 2 or 3 substituents selected from Ci-Cs-alkyl and CrC5-haloalkyl, wherein the ring may contain, in addition to the nitrogen and carbon ring members, 1 , 2 or 3 heteroatoms and/or heteroatom groups as ring members selected from the group consisting of nitrogen, oxygen, sulfur, SO, SO2 and N-R17;
each R17 independently is hydrogen, heteroaryl, heteroaryl-Ci-C4-alkyl or C1-C6- alkyl, where the alkyl moiety in the two last-mentioned radicals may be partially or fully halogenated;
and/or the agriculturally acceptable salts thereof.
2. The method as claimed in claim 1 , wherein m in formula I is 2.
3. The method as claimed in any of the preceding claims, wherein R1 in formula I is different from hydrogen.
4. The method as claimed in claim 3, wherein R1 is selected from halogen, C1-C4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
5. The method as claimed in any of the preceding claims, wherein two of the radi- cals R2, R3 and R4 in formula I are hydrogen and the remaining radical of R2, R3 or R4 is selected from halogen, Ci-C4-alkyl, and Ci-C4-haloalkyl.
6. The method as claimed in any of claims 1 to 4, wherein all of the radicals R2, R3 and R4 in formula I are hydrogen.
7. The method as claimed in any of the preceding claims, wherein A is a radical N=CR5R6, wherein R5 and R6 are as defined in claim 1.
8. The method as claimed in claim 7, wherein
R5 is d-Ce-alkyl or a radical OR5a, and
R6 is a radical OR6a
wherein R5a and R6a have, independently of each other, one of the meanings given for R5a in claim 1.
9. The method as claimed in claim 8, wherein R5a and R6a are, independently of each other, selected from CrC6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, CrC4-alkoxy- Ci-C4-alkyl and CrC4-haloalkyl.
10. The method as claimed in claim 7, wherein
R5 is Ci-C6-alkyl, which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, Ci-C4-alkoxy, Ci-C4-alkylthio, Ci-C4-alkylsulfinyl, CrC4- alkylsulfonyl, Ci-C4-haloalkoxy, Ci-C4-haloalkylthio, (CrC4-alkoxy)carbonyl, (Ci-C4-alkyl)amino, di(C-i-C4-alkyl)amino and Cs-Cβ-cycloalkyl, or is phenyl or phenyl-CrC4-alkyl, wherein the phenyl group in the two last-mentioned radicals may be unsubstituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of halogen, d- C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and CrC4-haloalkoxy; and
R6 is hydrogen, CrC6-alkyl, which may be unsubstituted, partially or fully halo- genated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, CrC4-alkoxy, CrC4-alkylthio, CrC4- alkylsulfinyl, CrC4-alkylsulfonyl, Ci-C4-haloalkoxy, CrC4-haloalkylthio, (Cr C4-alkoxy)carbonyl, (Ci-C4-alkyl)amino, di(CrC4-alkyl)amino and C3-C8- cycloalkyl, or is phenyl or phenyl-CrC4-alkyl, wherein the phenyl group in the two last-mentioned radicals may be unsubstituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of halogen, CrC4-alkyl, CrC4-haloalkyl, Ci-C4-alkoxy and CrC4- haloalkoxy.
1 1. The method as claimed in claim 10, wherein R5 is selected from Ci-Cβ-alkyl, Ci-C4-alkoxy-CrC4-alkyl, Ci-C4-haloalkyl and phenyl-Ci-C4-alkyl, wherein phenyl may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC4-alkyl, Ci-C4-haloalkyl, d- C4-alkoxy and CrC4-haloalkoxy; and
R6 is selected from hydrogen, CrC6-alkyl, Ci-C4-alkoxy-Ci-C4-alkyl, CrC4- haloalkyl and phenyl-Ci-C4-alkyl, wherein phenyl may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents, independ- ently of one another selected from the group consisting of CrC4-alkyl, d-
C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy.
12. The method as claimed in claim 7, wherein
R5 is a radical NR5bR5c, and
R6 is hydrogen, CrC6-alkyl, which may be unsubstituted, partially or fully halogenated and/or may carry 1 , 2 or 3 radicals, selected from the group consisting of cyano, nitro, amino, CrC4-alkoxy, CrC4-alkylthio, CrC4- alkylsulfinyl, CrC4-alkylsulfonyl, CrC4-haloalkoxy, CrC4-haloalkylthio, (Cr
C4-alkoxy)carbonyl, (Ci-C4-alkyl)amino, di(CrC4-alkyl)amino and C3-C8- cycloalkyl, or is phenyl or phenyl-CrC4-alkyl, wherein the phenyl group in the two last-mentioned radicals may be unsubstituted or may carry 1 , 2 or 3 substituents, independently of one another selected from the group consist- ing of halogen, CrC4-alkyl, CrC4-haloalkyl, Ci-C4-alkoxy and CrC4- haloalkoxy, or a radical OR6a,
wherein R6a has one of the meanings given for R5a in claim 1 and R5b and R5c are as defined in claim 1.
13. The method as claimed in any of claims 1 to 6, wherein A is a radical N=SR7R8, wherein R7 and R8 are as defined in claim 1.
14. The method as claimed in claim 13, wherein R7 and R8 are, independently of each other, selected from CrC6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C4-alkoxy-
CrC4-alkyl, CrC4-haloalkyl, phenyl and phenyl-CrC4-alkyl, wherein phenyl in the last two radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC4-alkyl, CrC4-haloalkyl, Ci-C4-alkoxy and CrC4-haloalkoxy,
or R7 and R8 together form a moiety (CH2)k , wherein k is 4, 5 or 6 and wherein 1 , 2, 3 or 4 hydrogen atoms may be replaced by CrC4-alkyl or halogen and wherein 1 or 2 non-adjacent CH2 moieties may be replaced by a carbonyl group, a het- eroatom or a heteroatom group, selected from O, S, SO2 and N-R# with R# being H or Ci-C4-alkyl.
15. The method as claimed in any of claims 1 to 6, wherein A is a radical of the formula
NR10-C(=O)-R9 wherein
R10 is selected from hydrogen, CrC6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, CrC6- alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, d-C4-haloalkyl and acetyl; and
R9 is selected from CrC6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C4-alkoxy-Cr C4-alkyl, CrC4-haloalkyl, phenyl and phenyl-CrC4-alkyl, wherein phenyl in the last to radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents, independently of one another selected from the group consisting of CrC4-alkyl, CrC4-haloalkyl, CrC4-alkoxy and CrC4-haloalkoxy, or
R10 and R9 together form a moiety of the (CH2)P, wherein p is 3, 4 or 5 and wherein 1 , 2, 3 or 4 hydrogen atoms may be replaced by CrC4-alkyl or halogen and wherein 1 or 2 non-adjacent CH2 moieties may be replaced by a carbonyl group, a heteroatom or a heteroatom group, selected from O, S, SO2 and N-R# with R# being H or CrC4-alkyl.
16. The method as claimed in claim 15, wherein
R10 is selected from hydrogen, Ci-C4-alkyl, C2-C6-alkynyl and CrC4-alkoxy and in particular from CrC4-alkyl; and
R9 is selected from Ci-C4-alkyl, C2-C6-alkenyl, CrC4-haloalkyl and phenyl, or
R10 and R9 together form a moiety of the (CH2)P, wherein p is 3 or 4.
17. The method as claimed in claim 15, wherein
R9 is Ci-C6-alkyl or CrC4-haloalkyl, and
R10 is hydrogen or CrCβ-alky!.
18. The method as claimed in any of claims 1 to 6, wherein A is a radical of the formula
NR10-C(=O)-R9 wherein
R10 is selected from hydrogen, CrC6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, CrC6- alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl and Ci-C4-haloalkyl; and
R9 is OR9a or a radical NR9bR9c,
wherein R9a, R9b, and R9c are as defined in claim 1.
19. The method as claimed in any of claims 1 to 6, wherein A is a N-bound 5- membered aromatic heterocycle, which additionally may contain 1 , 2, or 3 nitrogen atoms as ring members and which may carry 1 , 2, 3 or 4 radicals R13, which are as defined in claim 1.
20. The method as claimed in claim 19, wherein A is 1-pyrrolyl, 1-pyrazolyl, 1- imidazolyl or [1 ,2,4]-triazol-1-yl, where the heterocycle may be unsubstituted or may carry 1 , 2 or 3 substituents selected from halogen and CrC4-alkyl, wherein Ci-C4-alkyl may be unsubstituted or may be substituted by hydroxy or acetyloxy.
21. A method as claimed in any of the preceding claims , which is a method for protecting crops from attack or infestation by animal pests, which comprises contacting a crop with a pesticidally effective amount of at least one compound of the formula I and/or at least one salt thereof, as defined in claim 1.
22. A method as claimed in any of claims 1 to 20, which is a method for the protection of seeds from soil insects and of the seedlings' roots and shoots from insects comprising contacting the seeds before sowing and/or after pregermination with a compound of the formula I as defined in claim 1 and/or at least one agriculturally acceptable salt thereof, as defined in claim 1 , in pesticidally effective amounts.
23. The method as claimed in claim 22, wherein the compound of formula I is applied in an amount of from 0, 1 g to 10 kg per 100 kg of seeds.
24. The method as claimed in claim 22 or 23, wherein the resulting plant's roots and shoots are protected.
25. The method as claimed in claim 22 or 23, wherein the resulting plant's shoots are protected from aphids.
26. The use of a cyanopyridine compound of the formula I or a salt thereof as defined in any of claims 1 to 20 for combating animal pests.
27. Seed comprising a compound of the formula I or an agriculturally useful salt of I, as defined in any of claims 1 to 20, in an amount of from 0.1 g to 10 kg per 100 kg of seed.
28. Cyanobenzene compounds of the formula (I)
Figure imgf000111_0001
where m, A, R1, R2, R3 and R4 are as defined in any of claims 1 to 20,
and agriculturally acceptable salts thereof,
except for compounds of the formula I, wherein R1 is H, NO2 and NH2 if R2 is H, R3 is H, Cl or CO2CH3, R4 is H, and A is a radical N=CH-N(CH3)2 and also
except for compounds of the formula I, wherein R1 is H, R2 is H or Cl, R3 is H, R4 is H and A is an optionally substituted pyridazin-6-on-1-yl-radical or an optionally substituted imidazolin-5-on-1-yl radical, and also
except for compounds of the formula I, wherein R1 is H, R2 is H, R3 is H, R4 is H and A is a radical N=C(O-ethyl)2. and also
except for compounds of the formula I, wherein A is a radical of the formula
Figure imgf000111_0002
where Rx and Ryare, independently of each other, hydrogen or d-C5-alkyl and
R10 is H or Ci-Cio-alkyl.
29. An agricultural composition comprising at least one compound of the formula I and/or at least one agriculturally useful salt of I, as defined in claim 28, and at least one inert liquid and/or solid agriculturally acceptable carrier.
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