WO2005047233A1 - Novel herbicides - Google Patents

Novel herbicides Download PDF

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WO2005047233A1
WO2005047233A1 PCT/EP2004/011477 EP2004011477W WO2005047233A1 WO 2005047233 A1 WO2005047233 A1 WO 2005047233A1 EP 2004011477 W EP2004011477 W EP 2004011477W WO 2005047233 A1 WO2005047233 A1 WO 2005047233A1
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alkyl
substituents selected
phenyl
qalkyl
substituted
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PCT/EP2004/011477
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French (fr)
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Jürgen Schaetzer
Kurt Nebel
André Stoller
Jean Wenger
Fredrik Cederbaum
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Syngenta Participations Ag
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Publication of WO2005047233A1 publication Critical patent/WO2005047233A1/en

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    • 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
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • 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
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • 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
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • 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
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • 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
    • A01N43/707—1,2,3- or 1,2,4-triazines; Hydrogenated 1,2,3- or 1,2,4-triazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/02—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C217/48—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being unsaturated and containing rings
    • C—CHEMISTRY; METALLURGY
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    • C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
    • C07C217/76—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings and etherified hydroxy groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/48—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a six-membered aromatic ring
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/37—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by etherified hydroxy groups
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    • C07—ORGANIC CHEMISTRY
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    • C07C255/00—Carboxylic acid nitriles
    • C07C255/49—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C255/54—Carboxylic acid nitriles having cyano groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
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    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/215—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring having unsaturation outside the six-membered aromatic rings
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
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    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/455—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation with carboxylic acids or their derivatives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
    • C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
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    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/255—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing ether groups, groups, groups, or groups
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    • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
    • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6

Definitions

  • the present invention relates to novel, herbicidally active phenyl-alkynes, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting plant growth. .
  • Phenyl-alkynes having herbicidal action are described, for example, in JP-A-11 147 866, WO 01/55066 and WO 02/28182.
  • the present invention accordingly relates to compounds of formula I
  • n O, 1, 2, 3 or 4;
  • R is hydrogen, COR ⁇ 2 , -S(O) q C r C g alkyl, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl or C 3 -C 6 cycloalkyl; or Ci-Csalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl each substituted from one to five times by halogen and/or once, twice or three times by substituents selected from C ⁇ -C 4 alkoxy, -CN, -S(O) q C ⁇ -C 8 alkyl and phenyl, wherein the phenyl ring may in turn be substituted from one to five times by substituents selected from halogen and Cj- alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, C C 4 alkoxy, -CN, -
  • R is C 3 -C 6 cycloalkyl substituted from one to five times by substituents selected from halogen and C ⁇ -C alkyl and/or once, twice or three times by substituents selected from d-C 4 alkoxy, -CN and phenyl, wherein the phenyl ring may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C alkoxy, -CN, -N0 2 and -S(0) q d-C 8 alkyl, or R is phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and methyl and/or once, twice or three times by substituents selected from -CF 3 , -OCH 3 , -CN, -NO and -S(0) q Ci-C 4 alkyl; or, when n is 0, 1, 2
  • R 6 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, wherem phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, C ⁇ -C alkoxy, -CN, -N0 2 , C ⁇ -C alkylthio, C ⁇ -C 4 alkylsulfmyl and C ⁇ -C 4 alkylsulfonyl, or
  • R 6 is C ⁇ -C 8 alkylcarbonyl, wherein the C ⁇ -C 8 alkyl chain may in turn be substituted by substituents selected from halogen, -CN, C ⁇ -C 6 alkylamino, di(C ⁇ -C 6 alkyl)amino and C ⁇ -C 4 alkoxy; or R 5 and R ⁇ together are a C 2 -C alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 7 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or d-Csalkynyl each substituted from one to five times by halogen and/or once, twice or three times by substituents selected from C ⁇ -C 4 alkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from
  • Ci -C 4 haloalkyl C C 4 alkoxy, -CN, -NO , C ⁇ -C 4 alkylthio, C ⁇ -C 4 alkylsulfmyl and
  • R 8 and R 9 are each independently of the other hydrogen or C]-C 8 alkyl, or C -C 8 alkyl substituted once, twice or three times by substituents selected from -COOH, C ⁇ -C 8 alkoxycarbonyl and -CN, or
  • R 8 and R 9 are each independently of the other C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from d-C halo alkyl, C ⁇ -C alkoxy, -CN, -NO 2 , C ⁇ -C alkylthio, C ⁇ -C alkylsulfmyl and C ⁇ -C 4 alkylsulfonyl; or R 8 and R together are C -C 5 alkylene;
  • Rio is hydrogen, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl or C 3 -C 6 cycloalkyl
  • Rii is hydrogen, d-Cgalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C ⁇ -C 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R 12 is hydrogen, d-C alkyl, C ⁇ -C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • R ⁇ 3 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl; or
  • Ri 3 is phenyl or phenyl-C ⁇ -C 6 alkyl, wherein the phenyl ring may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkoxy, -CN, -NO 2 , Ci-Cgalkylthio, C ⁇ -C 8 alkylsulfinyl and d-C 8 alkylsulfonyl; or R ⁇ 3 is C ⁇ -C 8 alkyl substituted from one to five times by halogen and/or once
  • R] 3 is C ⁇ -C 8 alkylcarbonyl, wherein the C ⁇ -C 8 alkyl chain may in turn be substituted by substituents selected from halogen, -CN, C ⁇ -C 6 alkylamino, di(C ⁇ -C 6 alkyl)amino and
  • R ]4 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or C ⁇ -C 8 alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and C ⁇ -C 4 alkoxy;
  • R 15 , Ri 6 and R ⁇ 7 are each independently of the others C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or d-Qalkynyl, or C ⁇ -C 8 alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and C ⁇ -C 4 alkoxy; Rig is hydrogen or C ⁇ -C 8 alkyl;
  • R ⁇ 9 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, C ⁇ -C alkoxy, -CN, -NO 2 , d-C alkylthio, C ⁇ C 4 alkylsulfinyl and C]-C 4 alkylsulfonyl; or
  • Ris and R ⁇ 9 together are a C -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 20 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkoxy, -CN, -NO 2 , C ⁇ -C alkylthio, C ⁇ -C 4 alkylsulfinyl and C]-C alkylsulfonyl;
  • R 2 ⁇ is hydrogen or C ⁇ -C 8 alkyl;
  • R 22 is hydrogen or C ⁇ -C 8 alkyl, or C ⁇ -C 8 alkyl substituted once, twice or three times by substituents selected from -COOH, C ⁇ -C 8 alkoxycarbonyl and -CN, or R 22 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkoxy, -CN, -NO 2 , d-C 4 alkylthio, C C 4 alkylsulfinyl and C ⁇ -C alkylsulfonyl; or R 21 and R 22 together are C 2 -C 5 alkylene; R 23 is hydrogen, C ⁇ -C 4 alkyl, C ⁇ -
  • R 34 is hydrogen, C ⁇ -C 8 alkyl, CrQalkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkoxy, -CN, -NO 2 , C ⁇ -C 4 alkylthio, C ⁇ -C 4 alkylsulfinyl and C ⁇ -C 4 alkylsulfonyl, or
  • R 34 is Ci-dalkylcarbonyl unsubstituted or substituted by substituents selected from halogen, -CN, C ⁇ -C 6 alkylamino, di(C ⁇ -C 6 alkyl)amino and C ⁇ -C 4 alkoxy; or R 33 and R 3 together are a d-dalkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 35 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl each substituted from one to five times by halogen and/or once, twice or • three times by substituents selected from C ⁇ -C 4 alkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C,-C 4 haloalkyl, C ⁇ -C 4 alkoxy, -CN, -NO 2 , C ⁇ -C 4 alkylthio, d-C 4 alkylsulfmyl and C ⁇ -C 4 alkylsulfonyl; R 36 is hydrogen or C ⁇ -C 8 alkyl;
  • R 37 is hydrogen or C ⁇ -C 8 alkyl, or C ⁇ -C 8 alkyl substituted once, twice or three times by substituents selected from -COOH, Ci-Csalkoxycarbonyl and -CN, or
  • R 37 is C 3 -C 8 alkenyl, C 3 -Csalkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and
  • R 36 and R 37 together are Crdalkylene;
  • R 38 is hydrogen, C ⁇ -C 4 alkyl, C]-C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 39 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C ⁇ -C haloalkyl or
  • R 40 is hydrogen, C ⁇ -C 4 alkyl, C C 4 haloalkyl, C ⁇ -C 8 alkylthio, -C(O)-C(0)OC ⁇ -C 4 alkyl or
  • R 4 ⁇ is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C ⁇ -C 6 alkoxy-C ⁇ -C 6 alkyl,
  • C ⁇ -C 6 alkyl C ⁇ -C 6 alkylsulfinyl-C ⁇ -C 6 alkyl or C ⁇ -C 6 alkylsulfonyl-C ⁇ -C 6 alkyl; or
  • R 41 is phenyl or phenyl-C ⁇ -C 6 alkyl, wherein the phenyl ring may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C]-C 4 haloalkyl, C ⁇ -C 4 alkoxy, -CN,
  • R 41 is C ⁇ -C 8 alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -COOH, C ⁇ -C 8 alkoxycarbonyl, C ⁇ -C 6 alkylamino, di(C ⁇ -C 6 alkyl)amino and -CN;
  • R 2 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or C ⁇ -C 8 alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and C ⁇ -C 4 alkoxy;
  • R 4 and R 44 are each independently of the other C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or C ⁇ -C 8 alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and C ⁇ -C 4 alkoxy;
  • R 45 is C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or C ⁇ -C 8 alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and d-C alkoxy, or
  • R 45 is phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, C ⁇ -C alkoxy, -CN, NO 2 , d-Qalkylthio, d-C 8 alkylsulfinyl and C ⁇ -C 8 alkylsulfonyl;
  • R 46 is hydrogen, Ci-Csalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl or C ⁇ -C 4 haloalkyl;
  • R 7 is hydrogen, C ⁇ -C 8 alkyl, C ⁇ -C 4 alkoxy, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or C ⁇ -C 8 alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, C ⁇ -C 4 alkoxy, C ⁇ -C 8 alkoxycarbonyl, -NH 2 ,
  • R 47 is phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, C]-C 4 alkoxy, -CN, -NO 2 ,
  • R 48 , R 49 , R 5 o, R51, R 5 2 and R 53 are each independently of the others hydrogen, C ⁇ -C 8 alkyl, phenyl, benzyl or naphthyl, wherein the three last-mentioned aromatic radicals may in turn be substituted from one to five times by substituents selected from halogen and
  • Ci-Csalkyl and/or once, twice or three times by substituents selected from
  • R 54 and R 55 are each independently of the other hydrogen, C ⁇ -C 8 alkyl or phenyl which may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from
  • R 56 is hydrogen, C ⁇ -C 8 alkyl, C ⁇ -C 4 haloalkyl, C ⁇ -C alkoxy, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl or benzyl, wherein benzyl may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkoxy, -CN, -NO 2 , C ⁇ -C 8 alkylthio,
  • R 57 is C ⁇ -C 8 alkyl, C ⁇ -C haloalkyl, phenyl, benzyl or naphthyl, wherein the latter three aromatic rings may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, C ⁇ -C alkoxy, d-C 4 alkylamino, di(d-C alkyl)amino, -NH 2 , -CN, -N0 2 , C ⁇ -C 4 alkylthio, C ⁇ -C 4 alkylsulfinyl and d-C 4 alkylsulfonyl;
  • R 58 and R 59 are each independently of the other C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl, benzyl or naphthyl, wherein the latter three aromatic rings may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkoxy, C ⁇ -C 4 alkylamino, di(C ⁇ -C alkyl)amino, -NH 2 , -CN, -N0 2 , C ⁇ -C 4 alkylthio, C ⁇ -C 4 alkylsulfinyl and C ⁇ -C 4 alkylsulfonyl;
  • R 60 and R 6 ⁇ are each independently of the other hydrogen or C ⁇ -C 6 alkyl;
  • R 62 , R ⁇ 53 and 54 are each independently of the others hydrogen or C ⁇ -C 8 alkyl, or R 63 and R 64 together form a C 2 -C 5 alkylene bridge;
  • R 65 , R ⁇ 6 , R 67 , Res, R 69 and R 70 are each independently of the others hydrogen or C ⁇ -C 8 alkyl, or
  • R 72 is hydrogen, C ⁇ -C 8 alkyl, d-Qalkenylj d-dalkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and C]-C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, C ⁇ -C alkoxy, -CN, -NO 2 , C ⁇ -C 4 alkylthio, C ⁇ -C 4 alkylsulfinyl and C ⁇ -C 4 alkylsulfonyl; or
  • R 7 ⁇ and R 72 together are a C 2 -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 73 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or d-Qalkynyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from C ⁇ -C 4 alkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and C]-C 4 alkyl and/or once, twice or three times by substituents selected from Ci-dhaloalkyl, C ⁇ -C 4 alkoxy, -CN, -N0 2 , d-C 4 alkylthio, C ⁇ -C 4 alkylsulfmyl and Ci -C 4 alky
  • R 74 is hydrogen or d-C 8 alkyl
  • R 75 is hydrogen, C ⁇ -C 8 alkyl or d-dcycloalkyl, or C ⁇ -C 8 alkyl substituted once, twice or three times by substituents selected from -COOH, C ⁇ -C 8 alkoxycarbonyl, C ⁇ -C 6 alkoxy and -CN; or
  • R 75 is d-dalkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and
  • C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkoxy, -CN, -N0 2 , d-C 4 alkylthio, C ⁇ -C alkylsulfmyl and
  • R 74 and R 75 together are a d-dalkylene chain which may be interrupted by an oxygen or sulfur atom;
  • R 76 is hydrogen, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl or C 3 -C 6 cycloalkyl
  • R 77 is hydrogen, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl or C 3 -C 6 cycloalkyl
  • R 78 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C ⁇ -C 4 haloalkyl or
  • R 79 is hydrogen or d-C 8 alkyl
  • R 80 is hydrogen or C ⁇ -C 8 alkyl, or C ⁇ -C 8 alkyl substituted once, twice or three times by substituents selected from -COOH, C ⁇ -C 8 alkoxycarbonyl and -CN; or
  • R 8 o is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and
  • C ⁇ -C 4 haloalkyl d-C 4 alkoxy, -CN, -NO 2 , C ⁇ -C 4 alkylthio, C ⁇ -C 4 alkylsulfmyl and C ⁇ -C 4 alkylsulfonyl; or
  • R 9 and R 80 together are C 2 -C 5 alkylene
  • R 8 ⁇ is hydrogen or C ⁇ -C 8 alkyl
  • R 82 is -Si(C ⁇ -C 6 alkyl) 3 , C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl, or C ⁇ -C 8 alkyl which is substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, -NH 2 , C ⁇ -C 6 alkylamino, di(C ⁇ -C 6 alkyl)amino and C]-C 4 alkoxy
  • R 83 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, or Ci-Csalkyl which is substituted from one to five times by halogen and or once, twice or three times by substituents selected from -CN, -NH 2 , C ⁇ -C 6 alkylamino, di(C ⁇ -C 6
  • R 92 and R 93 are each independently of the other C ⁇ -C 6 alkyl
  • R 94 is hydrogen, or C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl each of which may be substituted from one to five times by halogen and/or once, twice or three times by substituents selected from C ⁇ -C 4 alkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkoxy, -CN, -NO 2 , C ⁇ -C 4 alkylthio, C ⁇ -C 4 alkylsulfmyl and C ⁇ -C 4 alkylsulfonyl;
  • R 95 is hydrogen or C ⁇ -C 8 alkyl;
  • R 96 is hydrogen or C ⁇ -C 8 alkyl, or C ⁇ -C 8 alkyl substituted once, twice or three times
  • R 96 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, C ⁇ -C 4 alkoxy, -CN, -NO 2 , C ⁇ -C 4 alkylthio, C ⁇ -C 4 alkylsulfinyl and C ⁇ -C 4 alkylsulfonyl; or
  • R 95 and R 96 together are d-dalkylene
  • R 97 and R 98 are each independently of the other hydrogen, C ⁇ -C 4 alkyl, d-C 4 haloalkyl or
  • R 99 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C C 4 haloalkyl or C 3 -C 6 haloalkenyl; Rioo is hydrogen or C ⁇ -C 8 alkyl; Rioi is hydrogen or d-C 8 alkyl, or C ⁇ -C 8 alkyl substituted once, twice or three times by substituents selected from -COOH, C ⁇ -C 8 alkoxycarbonyl and -CN; or Rioi is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from d-C 4 haloalkyl, C ⁇ -C al
  • R 102 is hydrogen or d-C 8 alkyl
  • R1 0 3 is hydrogen, C C 8 alkyl, -Si(d-C 6 alkyl) 3 , C 3 -C 8 alkenyl or C 3 -C 8 alkynyl;
  • R ⁇ o 4 is C ⁇ -C 6 alkyl
  • R1 0 5 is hydrogen, or Ci-Qalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl each of which may be substituted from one to five times by halogen and/or once, twice or three times by substituents selected from C ⁇ -C 4 alkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and d-C 4 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, d-C 4 alkoxy, -CN, -NO 2 , C r C 4 alkylthio, C ⁇ -C 4 alkylsulfinyl and Ci-Qalkylsulfonyl;
  • R 106 is hydrogen or d-C 8 alkyl;
  • Ri 07 is hydrogen or C ⁇ -C 8 alkyl, or C ⁇ -C 8 alkyl substituted once, twice or three times by substituents selected from -COOH, C ⁇ -C 8 alkoxycarbonyl and -CN, or R 107 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C 4 alkyl and/or once, twice or three times by substituents selected from Ci-dhaloalkyl, C ⁇ -C 4 alkoxy, -CN, -NO 2 , C ⁇ -C 4 alkylthio, C C 4 alkylsulfmyl and C ⁇ -C 4 alkylsulfonyl; or Ri 06 and R 10 7 together are d-dalkylene; R ⁇ o 8 is hydrogen, C ⁇ -C 4 alkyl, C ⁇ -C
  • R ⁇ 4 is hydrogen, C ⁇ -C 8 alkyl, -Si(C ⁇ -C 6 alkyl) 3 , C 3 -C 8 alkenyl or C 3 -C 8 alkynyl;
  • R ⁇ i 5 is C ⁇ -C 6 alkyl;
  • R ⁇ i 6 is hydrogen, or d-dalkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl each of which may be substituted from one to five times by halogen and/or once, twice or three times by substituents selected from C ⁇ -C 4 alkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and C ⁇ -C alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 4 haloalkyl, d-Qalkoxy, -CN, -NO 2 , C ⁇ -C 4 alkylthio, C ⁇ -C 4 alkylsulfmyl and C C 4 alkylsulfonyl;
  • R ⁇ i 7 is hydrogen or C ⁇ -C 8 alkyl;
  • Riis is hydrogen or Ci-Csalkyl, or C ⁇ -C 8 alkyl substituted once, twice or three times by substituents
  • Rn 9 is hydrogen, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl or C3 ⁇ C 6 cycloalkyl;
  • R ⁇ o is hydrogen, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl or C 3 -C 6 cycloalkyl;
  • R 121 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl, d-Qalkynyl, C ⁇ -C 4 haloalkyl or C 3 -C 6 haloalkenyl;
  • R 122 is hydrogen or C ⁇ -C 8 alkyl;
  • Ri 23 is hydrogen or C ⁇ -C 8 alkyl, or C ⁇ -C 8 alkyl substituted once, twice or three times by substituents selected from -COOH, C ⁇ -C 8 alkoxycarbonyl and -CN; or R ⁇ 23 is C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, phenyl
  • R 122 and Ri 23 together are C 2 -C alkylene
  • R ⁇ is hydrogen or d-C 8 alkyl;
  • A is a bridging member Ai, A 2 , A 3 , At or A5
  • bridging members Ai to A 5 are linked to the group Q at the end carrying the oxygen atom;
  • R131, R132, Ri33 > Ri34, R135, Ri36, i37, i38, R139 and R ]4 o are each independently of the others hydrogen, halogen, -CN, -NO 2 , -N(R 20 o)R 2 o ⁇ , C C 6 alkyl, C ⁇ -C 6 haloalkyl, -OH, C ⁇ -C 6 alkoxy, Ci-C ⁇ haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 3 -C 6 alkenyloxy, C 3 -C 6 haloalkenyloxy, C 3 -C 6 alkynyloxy, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, -C(O)OR 202 , -C(O)NR 203 R 2 o 4 , -C(S)NR
  • Ri3L R132, R133, R134, R135, Ri36, R137, i38, R139 and R ! 0 may be each independently of the others phenyl or phenyl substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 6 haloalkyl, -OH, d-C 6 alkoxy, C ⁇ -C 6 haloalkoxy, -CN, -COR 227 , -COOR 228 , -N0 2 , -N(R 2 2 9 )R230, -SH, -S(O) q C C 6 alkyl and -S(0) q Ci-C 6 haloalkyl;
  • R 20 o and R 20 ⁇ are each independently of the other hydrogen, Ci-dalkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 hydroxyalkyl, C ⁇ -C 6 alkoxy- C ⁇ -C 6 alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 6 haloalkyl, -OH, C ⁇ -C 6 alkoxy, C ⁇ -C 6 haloalkoxy and -COR227;
  • R 202 is hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C 3 -C 6 alkenyl, C -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 2 -C 6 hydroxyalkyl, C ⁇ -C 6 alkoxy-C ⁇ -C 6 alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 6 haloalkyl, -OH, C ⁇ -C 6 alkoxy and C ⁇ -C 6 haloalkoxy;
  • R 203 and R 20 are each independently of the other hydrogen, C ⁇ -C 6 alkyl, d-C 6 haloalkyl, C 2 -C 6 alkenyl, d-dhaloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 hydroxyalkyl, C ⁇ -C 6 alkoxy- C]-C 6 alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 6 haloalkyl, -OH, C ⁇ -C 6 alkoxy, C]-C 6 haloalkoxy and -COR 227 ;
  • R 205 and R 2 o ⁇ are each independently of the other hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 halo alkyl, C 2 -C 6 alken
  • R 207 and R 208 are each independently of the other hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C ⁇ -C 6 hydroxyalkyl, C ⁇ -C 6 alkoxy- C ⁇ -C 6 alkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by substituents selected from Ci-Qhaloalkyl, -OH, Cj-C 6 alkoxy, C ⁇ -C 6 haloalkoxy, -CN, -COR 227 , -COOR 228 , -NO 2 , -N(R 229 )R 23 o, -SH, -S(O) q C ⁇ -C 6 alkyl and
  • R 211 is hydrogen, Ci-C ⁇ alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C ⁇ -C 6 hydroxyalkyl, C ⁇ -C 6 alkoxy-C ⁇ -C 6 alkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 6 haloalkyl, -OH, C C 6 alkoxy and d-C 6 haloalkoxy;
  • R 211 is hydrogen, Ci-C ⁇ alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C ⁇ -C
  • R 2 ⁇ 2 is hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 2 -C 6 hydroxyalkyl, Ci-dalkoxy-Ci-C ⁇ alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 6 haloalkyl, -OH, C ⁇ -C 6 alkoxy and C]-C 6 haloalkoxy;
  • R 2 i 3 is hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6
  • R 22 o is hydrogen, d-C 6 alkyl, d-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C ⁇ -C 6 hydroxyalkyl, C ⁇ -C 6 alkoxy-C ⁇ -C 6 alkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 6 haloalkyl, -OH, d-C 6 alkoxy and C ⁇ -C 6 haloalkoxy;
  • R 22 o is hydrogen, d-C 6 alkyl, d-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl,
  • R 222 is hydrogen, d-C 6 alkyl, d-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl,
  • R 223 is hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C ⁇ -C 6 hydroxyalkyl, C ⁇ -C alkoxy-C ⁇ -C 6 alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by substituents selected from Ci-Qhaloalkyl, -OH, d-C 6 alkoxy and C ⁇ -C 6 haloalkoxy;
  • R 24 is hydrogen, C ⁇ -C 6 alkyl, d-C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 2 -C 6 hydroxyalkyl, Ci-dalkoxy-Ci-C ⁇ alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times ' by substituents selected from Ci-Qhaloalkyl, -OH, Ci-Qalkoxy and C ⁇ -C 6 haloalkoxy;
  • R 225 is hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 2 -C 6 hydroxyalkyl, C ⁇ -C 6 alkoxy-C ⁇ -C 6 alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by substituents selected from C]-C 6 haloalkyl, -OH, C ⁇ -C 6 alkoxy and d-C 6 haloalkoxy;
  • R 226 is hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 hydroxyalkyl, C ⁇ -C 6 alkoxy-C ⁇ -C 6 alkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and Cj-C 6 alkyl and/or once, twice or three times by substituents selected from d-C 6 haloalkyl, -OH, C ⁇ -C 6 alkoxy, d-C 6 haloalkoxy, -CN, -COR 227 , -COOR 228 , -N0 2 , -N(R 229 )R 230 , -SH, -S(O) q C ⁇ -C 6 alkyl and -S(O
  • R 227 is hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C ⁇ -C 6 alkoxy-C ⁇ -C 6 alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and
  • R 228 is hydrogen, C C 6 alkyl, C ⁇ -C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl,
  • R 229 and R 230 are each independently of the other hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl,
  • R 23 ⁇ is hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C 3 -C 6 alkenyl, C -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 2 -C 6 hydroxyalkyl, C ⁇ -C 6 alkoxy-C ⁇ -C 6 alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and C C 6 alkyl and or once, twice or three times by substituents selected from C ⁇ -C 6 haloalkyl, -OH, C ⁇ -C 6 alkoxy and C ⁇ -C 6 haloalkoxy;
  • R 2 2 and R 233 are each independently of the other hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl 5 C 2 -C 6 alkynyl, C 2 -C 6 hydroxyalkyl, C ⁇ -C 6 alkoxy-
  • Ri 4 i, i 4 , Ri 43 , i44, j45, i46, i47 and R ]48 are each independently of the others hydrogen, halogen, -CN, -N0 2 , -N(R 20 o)R 2 o ⁇ , C C 6 alkyl, C C 6 haloalkyl, -OH, C ⁇ -C 6 alkoxy, C ⁇ -C 6 haloalkoxy, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 3 -C 6 alkenyloxy, d-Cghaloalkenyloxy, C 3 -C 6 alkynyloxy, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, -C(O)OR 20 2, -C(O)NR 203 R 204 , -C(S)NR 205 R 206 ,
  • R 141 and R i43 together, Rj 43 and R ⁇ 45 together, and/or R ⁇ 45 and R i47 together, each independently of any other(s), may form a C ⁇ -C 6 alkylene or d-Qalkenylene bridge each of which may be substituted from one to five times by substituents selected from halogen and d-C 6 alkyl and/or once, twice or three times by d-dhaloalkyl; and/or R ⁇ 4 ⁇ and R ⁇ 45 together, R ⁇ 4 and R ⁇ 4 7 together, and/or R ] ⁇ and R ] 7 together, each independently of any other(s), may form a C ⁇ -C 6 alkylene or C 2 -C 6 alkenylene bridge each of which may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by d-dhaloalkyl, and also to the compounds of formula I containing N-oxides of the groups Q 2
  • substituents that are formed as a result of R 5 and R 6 together, or R ⁇ 8 and R 19 together, or R 33 and R 3 together, or R 7 1 and R 72 together, or R 74 and R 75 together being a C 2 -C 5 alkylene chain which may be interrupted by an oxygen or sulfur atom are piperidine, morpholine, thiomorpholine and pyrrolidine.
  • Examples of 5- to 7-membered heterocyclic ring systems which maybe aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur in the definition of R 2 are:
  • the alkyl groups appearing in the substituent definitions may be straight-chained or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, ' isobutyl, tert-butyl and the pentyl, hexyl, heptyl and octyl isomers. Preference is given to methyl, ethyl, n-propyl, isopropyl and n-butyl.
  • Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
  • Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, ⁇ dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, l,l-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluor ⁇ ethyl or 2,2,2- trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl or dichlorofluoromethyl.
  • halogen is fluorine it is intended that, in addition to the specific definition "alkyl substituted from one to five times by halogen", perfluorinated alkyl groups are also included; for example, in the definitions of Ri and R 2 "C ⁇ -C 8 alkyl substituted from one to five times by halogen" it is intended in addition that the perfluorinated alkyl groups are also included.
  • halogen substituents on alkyl radicals is not specified, for example in the definitions of R 6 , R ⁇ 3 and R 34 "C ⁇ -C 8 alkylcarbonyl substituted by halogen" and in the definition of R 41 "C ⁇ -C 8 haloalkylcarbonyl", when halogen is chlorine, bromine and/or iodine C ⁇ -C 8 alkylcarbonyl is substituted from one to five times but, when halogen is fluorine, it may be additionally substituted until perfluorinated.
  • the other substituents which are not halogen such as, for example, -CN, C ⁇ -C 6 alkylamino or C ⁇ -C 4 alkoxy, may occur on alkyl radicals once, twice or three times.
  • haloalkenyl alkenyl groups substituted one or more times by halogen are suitable, halogen being in particular bromine, iodine or, especially, fluorine or chlorine, for example 2- and 3-fluoropropenyl, 2- and 3-chloropropenyl, 2- and 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl, 4,4,4-trifluorobut-2-en-l-yl and 4,4,4- trichlorobut-2-en-l-yl.
  • alkenyl radicals substituted once, twice or three times by halogen preference is given to those which have a chain length of ' 3 or 4 carbon atoms.
  • the alkenyl groups may be halo-substituted at saturated or unsaturated carbon atoms.
  • Alkoxy groups have a chain length of preferably from 1 to 6, especially from 1 to 4, carbon atoms.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, or the pentyloxy and hexyloxy isomers; preferably methoxy or ethoxy.
  • Alkoxy, alkenyl, alkynyl, alkoxyalkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, alkylthio- alkyl, alkylsulfmyl-alkyl, alkylsulfonyl-alkyl, alkylaminoalkoxy, alkoxycarbonyl, alkoxy-alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy, alkenylthio, alkenylsulfonyl, alkenylsulfinyl, alkynylsulfonyl, alkynylthio and alkynylsulfinyl groups are derived from the mentioned alkyl radicals.
  • alkenyl and alkynyl groups may be straight-chained or branched and mono- or poly-unsaturated.
  • Alkenyl is, for example, vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-l-yl, pentenyl or 2-hexenyl, preferably an alkenyl radical having a chain length of from 2 to 5 carbon atoms.
  • Alkynyl is, for example, ethynyl, propargyl, 1-methylpropargyl, 3-butynyl, but-2-yn-l-yl, 2-methylbutyn-2-yl or but-3-yn-2-yl, preferably an alkynyl radical having a chain length of 3 or 4 carbon atoms.
  • Alkylthio groups preferably have a chain length of from 1 to 4 carbon atoms.
  • Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio.
  • Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfmyl, sec-butylsulfinyl or tert-butylsulfinyl; preferably methylsulfinyl or ethylsulfinyl.
  • Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
  • Hydroxyalkyl is, for example, 2-hydroxyethyl, 3 -hydroxypropyl or 2,3-dihydroxypropyl.
  • Haloalkoxy is, for example, fluorometh ⁇ xy, difluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy or 2,2,2- trichloroethoxy.
  • Alkoxyalkyl groups preferably have from 1 to 6 carbon atoms.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
  • Cycloalkyl radicals that are suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • the cycloalkyl groups may be unsubstituted or substituted a number of times by halogen, especially from once to four times by fluorine, chlorine and/or bromine, for example, diffuorocyclopropyl, dichlorocyclopropyl, dibromocyclopropyl, 2,2,3,3- tetrafluorocyclobutyl and 2,2-difluoro-3,3-dichlorocyclobutyl.
  • Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the butylamino isomers.
  • Dialkylamino is, for example, dimethylamino, diethylamino or the dipropyl- or dibutyl- amino isomers.
  • Ci-dalkylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and/or which may be substituted from one to five times by halogen and/or by C ⁇ -C 6 alkyl and/or once, twice or three times by C ⁇ -C 6 alkoxy, the total number of ring atoms being at least 5 and at most 9, or where two adjacent R substituents together form a C 2 -dalkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and/or which may be substituted from one to five times by halogen and/or by C ⁇ -C 6 alkyl and/or once, twice or three times by C ⁇ -C 6 alkoxy, the total number of ring atoms being at least 5 and at most 9, have, for example, the following structures:
  • the invention relates also to the salts which the compounds of formula I are able to form preferably with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
  • Suitable salt formers are described, for example, in WO 98/41089.
  • alkali metal and alkaline earth metal hydroxides as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially the hydroxides of sodium and potassium.
  • amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary C ⁇ -C ⁇ 8 alkylamines, C ⁇ -C 4 hydroxyalkylamines and C 2 -C 4 alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl- hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octadecyl
  • Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(R a R b RcRd)]OH wherein R a , R b , Re and Ra are each independently of the others C ⁇ -C 4 alkyl.
  • Other suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.
  • salts of the compounds of formula I having basic groups are also possible, especially having basic pyridyl, pyrimidyl, pyrazinyl and pyridazinyl rings (Q 2 to Q 8 ) or having amino or hydrazino groups as in, for example, the definition of Rj and R 2 , and R 133 to R ⁇ 40 and R 141 to R !48
  • Such salts are, for example, salts with inorganic and organic acids such as, for example, hydrohalic acids, e.g.
  • hydrofluoric acid hydrochloric acid, hydrobromic acid or hydriodic acid, and sulfuric acid, phosphoric acid and nitric acid, and organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, citric acid, benzoic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid.
  • organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, citric acid, benzoic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid.
  • the compounds of formula I are understood to include both the pure optical antipodes and the racemates and diastereoisomers.
  • a i s the bridging member A 2 and B is a direct bond between the sp-hybridised carbon atom of the triple bond and the phenyl ring.
  • Important compounds of formula I are also those wherein Q is a group Q , Q 2 , Q 3 or Q 4
  • A is the bridging member Ai and B is the bridging member
  • A is the bridging member A 2 R 1 1 3 3 1 1 R 132 and B is a direct bond between the sp-hybridised carbon atom of the triple bond and the phenyl ring.
  • Important compounds of formula I are those wherein Q is a group Qi or Q 2
  • each R 2 independently of any other(s), is halogen, -CN, -SCN, -OCN, -N 3 , -NO 2 , -NR 33 R 34 , -CO 2 R 35 ,
  • Q, A, B, R 2 and m are as defined hereinbefore, may be prepared by various known processes.
  • the groups Qi to Q 8 , the phenyl ring, and their substituents Ri (on groups Qi to Q 8 ) and R2 (on the phenyl ring), and also the substituents of the bridging members A (R 131 to R ⁇ 40 ) and B (Rj 4 ⁇ to R ⁇ 48 ) do not restrict those processes; on the contrary, they can be taken into account in synthesis planning so that particular procedures can be used preferentially and carried out selectively and with a high yield.
  • R 2 and m are as defined for formula I and W is halogen or a sulfonate, for example trifluoromethanesulfonate, in accordance with K. Sonogashira, or in the Mitsunobu reaction of the compound of formula VII Q-OH (VII), wherein Q is as defined for formula I, with the alkynyl-alcohol of formula VIII
  • A, B, R 2 and m are as defined for formula I, in the presence of azodicarboxylic acid diethyl ester (DEAD) or N,N,N',N'-tetramethylazodicarboxamide (TMAD) and triphenylphosphine.
  • DEAD azodicarboxylic acid diethyl ester
  • TMAD N,N,N',N'-tetramethylazodicarboxamide
  • triphenylphosphine triphenylphosphine
  • the substituents Ri and/or R 2 for example in compounds of formulae Ila, lib, III, IVbi to TVb 4 , Vb 2 to Vb 4 , Vlai to Via* VII, VIIi, VIII, IXai to IXa 5 , Xai to Xa 5 , XIa 3 to XIa 5 , XV, XlXajbo to XIXa 5 b 0 , XXIa 3 b to XXIa 5 b, XXIIIabi to XXIIIab 4 or XXVa 2 b to XXVa 5 b can already be present at the outset or, however, they may be successively introduced only later in the reaction sequence, for example by means of nucleophihc or electrophilic aromatic substitution.
  • A, Q, R 2 and m are as defined for formula I, may be prepared analogously to known processes described, for example, in K. Sonogashira, Comprehensive Organic Synthesis 1991, Vol. 3, page 521 ff; WO 01/55066; WO 02/28182 and WO 03/013247, by, for example, coupling a compound of formula Ila wherein A and Q are as defined, with a compound of formula III
  • W is a leaving group such as, for example, halogen, e.g. iodine, or sulfonate, e.g. trifluoromethanesulfonate, in the presence of a palladium catalyst under Sonogashira reaction conditions (Reaction Scheme 1).
  • Suitable catalyst mixtures are, for example, tetrakis(triphenylphosphine)palladium or bis(triphenylphosphine)palladiurn dichloride together with copper iodide.
  • amines e.g. triethylamine, diethylamine or diisopropylethylamine, are preferably used.
  • the aryls of formula III preferably carry a leaving group W wherein W is, for example, halogen (N. Krause et ai, J. Org. Chem. 1998, 63, page 8551; and H. Nakamura et al., Tetrahedron Lett. 2000, 41, page 2185) or trifluoromethanesulfonate (K. Ritter, Synthesis 1993, page 735).
  • solvents there are usually used ethers, e.g. tetrahydrofuran or dioxane, chlorinated hydrocarbons, e.g. chloroform, or dipolar aprotic solvents, e.g. dimethylformamide or dimethyl sulfoxide, or also amines, e.g. triethylamine or piperidine.
  • R 1 ⁇ is as defined for formula I and Rj 49 is hydrogen, d-dalkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 hydroxyalkyl, C ⁇ -C 6 alkoxy-C]-C 6 alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 6 haloalkyl, -OH, C ⁇ -C 6 alk
  • a and Q are as defined, with a compound of formula IVbi, IVb 2 , IVb 3 or IVb 4
  • R 2 , m and R ⁇ 43 to R ⁇ 48 are as defined and E is an electrophilic functional group
  • R 1 1 and R 14 are as defined and Xi is a leaving group, for example halogen, e.g. fluorine, chlorine, bromine or iodine, or sulfonate, e.g. para-toluenesulfonate (-OTs, tosylate), methanesulfonate (-OMs, mesylate) or trifluoromethanesulfonate (-OTf, triflate), CH 3 (CH 3 O)N-, imidazolyl, triazolyl, -OR4, -SR 4 or -N(R 4 ) 2 , wherein R 4 is d-C 6 alkyl, C ⁇ -C 6 haloalkyl or phenyl, in the presence either a) of a strong base or b) of zinc salts and a base in an inert, organic solvent at temperatures from -100° to 50°C.
  • halogen e.g. fluorine, chlorine, bromine or
  • Suitable inert organic solvents are, for example, ethers, e.g. diethyl ether, tetrahydrofuran, or hexane-ether mixtures, or chlorinated hydrocarbons, e.g. dichloromethane.
  • the acetylene function in the compound of formula Ila is activated by means of zinc salts, e.g. zinc trifluoromethanesulfonate (CF 3 SO 3 ) 2 Zn, in the presence of a base, e.g. triethylamine or H ⁇ nig's base, in analogous manner to that described in Tetrahedron Lett. 43(15), 2691-94 (2002); and J. Am. Chem. Soc. 121(48), 11245-246 (1999). '
  • zinc salts e.g. zinc trifluoromethanesulfonate (CF 3 SO 3 ) 2 Zn
  • a base e.g. triethylamine or H ⁇ nig's base
  • R 1 1 , R ⁇ 42 and R ⁇ 43 are as defined for formula I, may be prepared analogously to known processes described, for example, in Organic Letters 4(25), 4427-29 (2002); Heterocycles 42(2), 745-74 (1996); and Tetrahedron Lett. 33(37), 5365-68 (1992) and also processes mentioned hereinbefore, by, for example, causing a compound of formula Ila
  • R 2 , m, Rj 4 ⁇ to R ⁇ 43 , and R ⁇ 5 to R ]48 are as defined, in the presence a) of a strong base or b) of zinc salts and a base in an inert, organic solvent at temperatures from -100° to 50°C.
  • Suitable inert organic solvents are, for example, ethers, e.g. tetrahydrofuran, or chlorinated hydrocarbons, e.g. dichloromethane.
  • the epoxy functionality in the compound of formula Vb 2 to Vb 4 is a substitute for the electrophilic functional group E in the compound of formula IVbi to rVb 4 , which reacts with the acetylide or the zinc-activated compound of formula lib
  • A, Q, B, R 2 and m are as defined under formula I, may be prepared using the Mitsunobu reaction in the presence of azodicarboxylic acid diethyl ester (DEAD) and triphenylphosphine in a suitable solvent such as, for example, an ether, e.g. tetrahydrofuran (THF), in a manner analogous to that described, for example, in Synthetic Communic. 1989(19), 1255-59; or Synthesis 1981(1); or, using TMAD reagent as a substitute for DEAD in the two previous references, in a manner analogous to that described, for example, in Chem. Letters 1994, 539 (Reaction Scheme 1). That synthesis route uses, as intermediates, the compound of formula VII Q-OH (VII) and the alkynyl-alcohol of formula VIII
  • the Mitsunobu reaction is especially advantageous for those compounds of formula VII in which Q is a group Qj or a group Q 2 , Q or Q 5 , the hydroxyl function in the latter three groups advantageously being in a position other than a position ortho to a ring nitrogen atom.
  • A, Q, B, R 2 and m are as defined for formula I, is the base-catalysed alkylation or etherification of a compound of formula VII Q-OH (VII) with a compound of formula IXai, IXa 2 , IXa 3 , IXa 4 or IXa 5
  • radicals Q, B and R 2 and the suffix m in the compounds of formulae VII and IXai to IXa 5 being as defined
  • R 131 to R 140 being as defined for formula I and L being a leaving group such as, for example, halogen, e.g. chlorine, bromine or iodine, acetate, or sulfonate, e.g. mesylate, tosylate or triflate.
  • Suitable bases are, for example, hydrides such as, for example, alkali metal and alkaline earth metal hydrides, e.g. sodium or potassium hydride, hydroxides such as, for example, alkali metal hydroxides, e.g. sodium or potassium hydroxide, alcoholates, e.g. sodium methanolate, sodium ethanolate or potassium tert-butanolate, carbonates, e.g. potassium or calcium carbonate, amines, e.g. triethylamine, or also sodium bis(trimethylsilyl)amide
  • Suitable solvents are amides, e.g. N,N-dimethylformamide, or nitriles, e.g. acetonitrile.
  • amides e.g. N,N-dimethylformamide
  • nitriles e.g. acetonitrile.
  • Such etherification procedures are standard processes and may be carried out, for example, in analogy to J. Chem. Soc, Perkin Trans I, 1979, 2756-61; Synth. Communic. 18, 1111-18 (1988); Chem. Communic. 1990, 297-300; J. Org. Chem. 61, 4258-61 (1996); Tetrahedron 1997(53), 12621-628; and Synth. Communic. 24, 1367-79 (1994).
  • the activation of the alcohol of formula VIII to form the compound of formula IXai to IXa 5 is carried out, for example, by sulfonylation or halogenation.
  • Sulfonylation of the alcohol of formula VIII is a standard reaction and may be carried out, for example, using a sulfonic acid chloride, e.g. mesyl chloride or para- toluenesulfonic acid chloride (p-TosCl), in the presence of a tertiary amine, e.g.. triethylamine, or of an aromatic amine, e.g. pyridine, in a solvent such as, for example, a chlorinated hydrocarbon, e.g.
  • Halogenation of the alcohol of formula VIII may be carried out in analogy to standard processes. For example, bromination may be carried out using carbon tetrabromide in the presence of triphenylphosphine (Synthesis 1998, 1015-1018) in methylene chloride. Chlorination may be carried out using mineral acids, e.g. concentrated hydrochloric acid (J. Org. Chem. 1955 (20), 95), or using para-toluenesulfonic acid chloride in the presence of an amine, e.g. triethylamine, in a solvent, e.g. methylene chloride (Tetrahedron Lett. 1984 (25), 2295).
  • mineral acids e.g. concentrated hydrochloric acid (J. Org. Chem. 1955 (20), 95)
  • para-toluenesulfonic acid chloride in the presence of an amine, e.g. triethylamine, in a solvent, e.g. methylene chloride (
  • A, Q, B, R 2 and m are as defined for formula I, comprises, by means of a nucleophilic aromatic substitution reaction, causing the compound of formula VIIi to react with an alcoholate of formula Xai, Xa , Xa 3 , Xa 4 or Xa 5
  • nucleophilic aromatic substitution reaction is facilitated if they are activated compounds. That is the case when Ri is, for example, a substituent having electron-withdrawing properties (-M and/or -I effect), for example -CN, -NO 2 , -C0 2 R7 or CORj 2 , or when the leaving group L ⁇ in the groups Q 2 to Q 8 is in a position ortho to a ring nitrogen atom.
  • Ri is, for example, a substituent having electron-withdrawing properties (-M and/or -I effect), for example -CN, -NO 2 , -C0 2 R7 or CORj 2 , or when the leaving group L ⁇ in the groups Q 2 to Q 8 is in a position ortho to a ring nitrogen atom.
  • substitution reactions with activated compounds of formula VIIi wherein Q is a group Qi to Q 8 and Rj is a substituent having an -M and/or -I effect within the framework of the definition of Ri given for formula I are standard methods and may be carried out, for example, in analogy to Synlett 2000, 874-876; ibid 1998, 794-796; or J. Org. Chem. 1998(63), 9594- 96.
  • a suitable alternative synthesis method is the above-mentioned base-catalysed alkylation or etherification of a compound of formula VII with a compound of formula IXai to IXa 5 .
  • Rj 33 , R ⁇ 35 , R ⁇ 37 and R ⁇ 39 are as defined for formula I and R ⁇ 4 is hydrogen, C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C -C 6 hydroxyalkyl, d-C 6 alkoxy-C ⁇ -C 6 alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 6 haloalkyl, -OH, C ⁇ -C 6 alkoxy, C ⁇ -C 6 haloalkoxy and -COR 227 , wherein R 227 is as defined for formula I, may be
  • R ⁇ 33 , R ⁇ 3 , R ⁇ 7 , Rj 39 and R ⁇ 49 are as defined and Xi is a leaving group such as, for example, halogen, e.g. fluorine, chlorine, bromine or iodine, or sulfonate, e.g.
  • R 133 and R 135 to R ]40 being as defined for formula I, can also be prepared analogously to the above-described process.
  • the epoxy functionality is a substitute for the electrophilic functional group E in the compounds of formulae Vlai to VIa in the previous example, which reacts with the acetylide or the zinc-activated compound of formula lib.
  • the intermediate of formula Ila wherein A and Q are as defined for formula I may be prepared by means of the Mitsunobu reaction already described in detail hereinbefore (Reaction Scheme 1) from the compound of formula VII Q-OH (VII) and the compound of formula XII the radicals A and Q in the compounds of formulae VII and XII being as defined.
  • a further method for the preparation of the intermediate of formula Ila wherein A and Q are as defined for formula I uses the compound of formula VII Q-OH (VII), which is caused to react with a compound of formula Xlllai, XIIIa 2 , XIIIa , Xffl ⁇ or XIIIa 5
  • radicals Q and R 131 to R ⁇ 40 in the compounds of formulae VII and XHIaj to Xlllas being as defined for formula I and L being a leaving group such as, for example, halogen, e.g. chlorine, bromine or iodine, acetate or sulfonate, e.g. mesylate or tosylate.
  • halogen e.g. chlorine, bromine or iodine
  • acetate or sulfonate e.g. mesylate or tosylate.
  • the radicals Q and Ri 3 i to R ⁇ 40 in the compounds of formulae VIIi and XlVai to XTVas being as defined for formula I,
  • R ⁇ 4 ⁇ is as defined for formula I
  • R ]49 is hydrogen, C 1 -C 4 alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C -C 6 alkynyl, C 2 -C 6 hydroxyalkyl, Cj-C 6 alkoxy- C]-C 6 alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 6 haloalkyl, -OH, C ⁇ -C 6 alkoxy,
  • R 227 is as defined for formula I, and Xi is a leaving group such as, for example, halogen, e.g. fluorine, chlorine, bromine or iodine, or a sulfonate, e.g.
  • -OTosyl -OTs
  • -OMesyl -OMs
  • -OTriflate -OTf
  • CH 3 CH 3 O)N-
  • imidazolyl triazolyl
  • -OR 4 -SR
  • -N(R 4 ) 2 wherein R is C ⁇ -C 6 alkyl, d-C 6 haloalkyl or phenyl, may be obtained by means of the Mitsunobu reaction (Reaction Scheme 1) from a compound of formula VII Q-OH (VII) and a compound of formula XVI the radicals A, Q and E in the compounds of formulae VII and XVI being as defined.
  • R 141 is as defined for formula I
  • R 149 is hydrogen, C ⁇ -C 4 alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 hydroxyalkyl, C ⁇ -C 6 alkoxy- C ⁇ -C 6 alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and d-C 6 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 6 haloalkyl, -OH, Cpdalkoxy,
  • R 227 is as defined for formula I, and Xi is a leaving group such as, for example, halogen, e.g. fluorine, chlorine, bromine or iodine, or a sulfonate, e.g.
  • -OTosyl (-OTs), -OMesyl (-OMs) or -OTriflate (-OTf), CH 3 (CH 3 O)N-, imidazolyl, triazolyl, -OR*, -SR 4 or -N(R 4 ) 2 , wherein R 4 is C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl or phenyl, may also be prepared by means of base-catalysed alkylation or etherification of a compound of formula VII Q-OH (VII) with a compound of formula XVIIai, XVIIa 2 , XVIIa , XVI ⁇ or XVIIa 5
  • R 131 to R ⁇ 40 being as defined for formula I and L being a leaving group such as, for example, halogen, e.g. chlorine, bromine or iodine, acetate or sulfonate, e.g. mesylate (-OMs) or tosylate (-OTs).
  • halogen e.g. chlorine, bromine or iodine
  • acetate or sulfonate e.g. mesylate (-OMs) or tosylate (-OTs).
  • a further possible method of preparing the desired intermediates of formula XV wherein A and Q are as defined for formula I and E is an electrophilic functional group as already defined hereinbefore, is provided by the reaction of the compound of formula VIIi with a compound of formula XVIIIai, XVIIIa 2 , XVIIIa 3 , XVIIIa 4 or XVIIIa 5
  • R ⁇ 4] is as defined for formula I
  • R] 49 is hydrogen, d-C 4 alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 hydroxyalkyl, C ⁇ -C 6 alkoxy- C ⁇ -C 6 alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by substituents selected from C C 6 haloalkyl, -OH, C ⁇ -C 6 alkoxy, C ⁇ -C 6 haloalkoxy and -COR 227 , wherein R 227 is as defined for formula I, Li is a leaving group such as, for example, halogen, e.g.
  • chlorine bromine or iodine
  • a sulfonate e.g. -OTs or -OMs
  • M + is an alkali metal ion, e.g. Na + .
  • R 2 , m and R 13 ⁇ to R ⁇ 40 are as defined for formula I and R 3 is hydrogen or a protecting group for the alcohol function such as, for example, methoxymethyl (MOM), benzyl, benzoyl, acetyl, allyl, tetrahydropyranyl, tert-butyloxycarbonyl (BOC), benzyloxycarbonyl, trialkylsilyl, phenyl-dialkylsilyl or di-phenyl-alkylsilyl (T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Chemistry, Wiley 1999), may be prepared, for example, by coupling a compound of formula XXai, XXa , XXa 3 , XXa 4 or XXa 5
  • R 2 and m are as defined and W is a leaving group such as, for example, halogen or trifluoromethanesulfonate (-OTf), in the presence of a palladium catalyst under Sonogashira reaction conditions (Reaction Scheme 1).
  • the Sonogashira reaction has already been described in detail hereinbefore.
  • a protecting group for alcohols such as, for example, MOM, benzyl, benzoyl, acetyl, allyl, tetrahydropyranyl, tert- butyloxycarbonyl (BOC), benzyloxycarbonyl, trialkylsilyl, phenyl-dialkylsilyl or di- pheny
  • R 141 is as defined for formula I and R ⁇ 4 is hydrogen, C ⁇ -C 4 alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C -C 6 haloalkenyl, C 2 -C 6 alkynyl, C -C 6 hydroxyalkyl, C ⁇ -C 6 alkoxy-C ⁇ -C 6 alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 6 haloalkyl, -OH, C ⁇ -C 6 alkoxy, C ⁇ -C 6 haloalkoxy and -COR 227 , wherein R 227 is as defined for formula I, may be prepared by causing a compound of formula XII
  • R 2 , m and R ⁇ 43 to Rj 48 are as defined and E is an electrophilic functional group
  • Rj 4 ⁇ and R ⁇ 49 are as defined and Xi is a leaving group such as, for example, halogen, e.g. fluorine, chlorine, bromine or iodine, or a sulfonate, e.g.
  • -OTosyl -OTs
  • -OMesyl -OMs
  • triflate CH 3 (CH 3 0)N-, imidazolyl, triazolyl, -OR ⁇ -SR 4 or -N(R 4 ) 2 , wherein R 4 is C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl or phenyl, in the presence a) of a strong base or b) of zinc salts and a base in an inert, organic solvent at temperatures from -100° to 50°C, it being possible for the alcohol-protecting group to be removed and for the exposed hydroxyl function to be used for further reactions, e.g. nucleophilic aromatic substitution.
  • R 2 , B, R ⁇ 3 ⁇ to R ⁇ 38 and m are as defined for formula I
  • R 3 is hydrogen or a protecting group for the alcohol function, e.g. MOM, benzyl, benz ⁇ yl, acetyl, allyl, tetrahydropyranyl, BOC or benzyloxycarbonyl
  • E 3 is a bridging member
  • R ⁇ 33 , R ⁇ 35 , R ⁇ 37 and R ]39 are as defined for formula I and R ⁇ 49 is hydrogen, C ⁇ -C alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 hydroxyalkyl, C ⁇ -C6alkoxy-C ⁇ -C 6 alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and C ⁇ -C 6 alkyl and/or once, twice or three times by substituents selected from C ⁇ -C 6 haloalkyl, -OH, d-C 6 alkoxy, C ⁇ -C 6 haloalkoxy and -COR 227 , wherein R 227 is as defined for formula I, may be prepared by causing a compound of formula lib
  • R 2 , B and m are as defined, to react with a compound of formula XXIVa , XXIVa 3 , XXIVa 4 or XXIVa 5 (XXIVa 3 ),
  • R ⁇ 33 , Rj 5 , R ⁇ 37 , R ⁇ 39 and R ⁇ 9 are as defined and ' Xj is a leaving group such as, for example, halogen, e.g. fluorine, chlorine, bromine or iodine, or sulfonate, e.g.
  • -OTs para- toluenesulfonate
  • -OMs methanesulfonate
  • -OTf trifluoromethanesulfonate
  • CH 3 CH 3 0)N-, imidazolyl, triazolyl, -OR 4 , -SR t or -N(R 4 ) 2 , wherein R 4 is C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl or phenyl, in the presence a) of a strong base or b) of zinc salts and a base in an inert, organic solvent at temperatures from -100° to 50°C.
  • XXIHab 4 wherein A, R 2 , R ⁇ 45 to Rj 8 and m are as defined for formula I, it being possible for the alcohol function in group A to be protected by a protecting group for alcohols such as, for example, MOM, benzyl, benzoyl, acetyl, allyl, tetrahydropyranyl, tert- butyloxycarbonyl (BOC), benzyloxycarbonyl, trialkylsilyl, phenyl-dialkylsilyl or di- R 141/ R 142 phenyl-alkylsilyl, and E 2 is a bridging member __V , wherein R 141 , Rj 42 and ⁇ _
  • R ⁇ 43 are as defined for formula I, may be prepared by causing a compound of formula XII HA — C ⁇ CH (XII), wherein A is as defined, to react with a compound of formula Vb 2 , Vb 3 or Vb 4 wherein R , m, Rj 4 ⁇ to R ⁇ 3 , and R ⁇ 45 to R] 8 are as defined, in the presence a) of a strong base or b) of zinc salts and a base in an inert, organic solvent at temperatures from -100° to 50°C, it being possible for the alcohol-protecting group to be removed by means of suitable treatment and for the exposed hydroxyl function to be used for further reactions.
  • R 3 is hydrogen or a protecting group for the alcohol function such as, for example, MOM, benzyl, benzoyl, acetyl, allyl, tetrahydropyranyl, tert-butyloxycarbonyl (BOC), benzyloxycarbonyl, trialkylsilyl, phenyl-dialkylsilyl or di-phenyl-alkylsilyl, and E 4 is a bridging member O.H R 133 OH R 135 OH /R ⁇ / ⁇ or A / ⁇ 135 R 136 R 137 R 138 R 139 140 wherein R ⁇ 33 and R ⁇ 35 to R ⁇ 0 are as defined for formula I, may be prepared by causing a compound of formula lib
  • R 131 to R ⁇ 40 and R 3 are as defined, in the presence a) of a strong base or b) of zinc salts and a base in an inert, organic solvent at temperatures from -100° to 50°C.
  • aprotic, inert solvents are hydrocarbons, e.g. benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, e.g. dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, e.g. diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, e.g.
  • hydrocarbons e.g. benzene, toluene, xylene or cyclohexane
  • chlorinated hydrocarbons e.g. dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene
  • ethers e.g. diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl
  • reaction temperatures are preferably from -20°C to +120°C.
  • the reactions are generally slightly exothermic and may usually be carried out at room temperature. In order to shorten the reaction time or else to initiate the reaction, brief heating up to the boiling point of the reaction mixture may be carried out, where appropriate.
  • the reaction times may also be reduced by adding a few drops of base as reaction catalyst.
  • bases are tertiary amines, e.g.
  • inorganic bases such as hydrides, e.g. sodium or calcium hydride, hydroxides, e.g. sodium or potassium hydroxide, carbonates, e.g. sodium or potassium carbonate, or hydrogen carbonates, e.g. potassium or sodium hydrogen carbonate, to be used as bases.
  • hydrides e.g. sodium or calcium hydride
  • hydroxides e.g. sodium or potassium hydroxide
  • carbonates e.g. sodium or potassium carbonate
  • hydrogen carbonates e.g. potassium or sodium hydrogen carbonate
  • the compounds of formula I, Iab 0 , Iabi to Iab 4 or Ia 2 b to Ia 5 b may be isolated in conventional manner by concentration and/or evaporation of the solvent and purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.
  • the starting compounds of formulae VII and XII are likewise known and in some
  • the compounds of formula I may be used as herbicides in their unmodified form, that is to say as obtained in the synthesis, but they are preferably fo ⁇ nulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • Such formulations are described, for example, on pages 9 to 13 of WO 97/34485.
  • the methods of application such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula I, or at least one compound of formula I, and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient(s) with the formulation adjuvants, for example solvents or solid carriers.
  • formulation adjuvants for example solvents or solid carriers.
  • Surface-active compounds surfactants
  • solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
  • suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
  • suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485.
  • surfactants conventionally employed in formulation technology which are described, ter alia, in "McCutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Kunststoff/Vienna, 1981, and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I- III, Chemical Publishing Co., New York, 1980-81, are also suitable for the preparation of the herbicidal compositions according to the invention.
  • the herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of herbicide, from 1 to 99.9 % by weight, especially from 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant.
  • a surfactant especially from 0.1 to 25 % by weight
  • compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • stabilisers for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • the compounds of formula I are generally applied to the plant or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha.
  • concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.
  • the compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non- selective weed control.
  • crops of useful plants especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non- selective weed control.
  • crops is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic engineering techniques.
  • the weeds to be controlled may be either monocotyledonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Panicum, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Euphorbia, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • Stellaria Nasturtium, Agrostis, Digitaria, Avena, Setaria, Panicum, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Euphorbia, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense
  • Example PI Preparation of 4-(4-fluoro-2-methoxy-phenoxyVl-(3-chlorophenyl)-l- hydroxy-but-2-y ⁇ e
  • Example P2 Preparation of 4-( , 4-fluoro-2-methoxy-phenoxy)-l-(3-chlorophenyl -l- fluoro-but-2-yne
  • the yellow-brown oil obtained is purified by silica gel chromatography (eluant: ethyl acetate/hexane 1/4).
  • the desired target compound is obtained in the form of a yellow powder in a yield of 230 mg (35.7 % of theory) with a melting point of 69-71°C.
  • reaction mixture For working up of the reaction mixture, 20 ml of trifluoroacetic acid are added to the mixture, which is stirred for 1.5 hours at 25 °C.
  • the reaction mixture is poured into 150 ml of ammonium chloride solution, stirred well and extracted three times with diethyl ether.
  • the combined organic phases are washed with 2 portions each of ammonium chloride solution, water and brine and concentrated by evaporation under reduced pressure.
  • the target compound is obtained in the form of a brown oil in a crude yield of 1.67 g.
  • aqueous phase is extracted three times with ethyl acetate and the combined organic phases are dried over magnesium sulfate, filtered and concentrated by evaporation in vacuo.
  • a brown oil is obtained in a crude yield of 14.01 g, which is purified by means of column chromatography (eluant: ethyl acetate/hexane 1/4 to 1/1 as gradient mobile phase).
  • the desired title compound is obtained in the form of a brown oil in a yield of 5.95 g.
  • Example P8 Preparation of 4-(4-fluoro-2-methoxy-phenoxy -l-(3- cyanomethylphenyl)but-2-yn- 1 -one (compound no. 3.075)

Abstract

Compounds of formula (I), wherein Q is a group Q1, Q2, Q3, Q4, Q5, Q6, Q7 or Q8; A is a bridging member A1, A2, A3, A4 or A5 wherein the bridging members A1 to A5 are linked to the group Q at the end carrying the oxygen atom; B either is a direct bond between the sp-hybridised carbon atom of the triple bond and the phenyl ring or is a bridging menber B1, B2, B3 or B4; R, R1, R2, R131, R132, R133, R134, R135, R136, R137, R138, R139 and R140, R141, R142, R143, R144, R145, R146, R147 and R148 and the suffixes n and m are as defined in claim 1, and also the N-oxides of the groups Q2, Q3, Q4, Q5, Q6, Q7 and Q8, the agrochemically acceptable salts and all stereoisomers and tautomers of the compounds of formula (I), with the proviso that, when B is a direct bond between the sp-hybridised carbon atom of the triple bond and the phenyl ring, the bridging member A is other than A1, are suitable for use as herbicides.

Description

NOVEL HERBICIDES
The present invention relates to novel, herbicidally active phenyl-alkynes, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting plant growth. .
Phenyl-alkynes having herbicidal action are described, for example, in JP-A-11 147 866, WO 01/55066 and WO 02/28182.
Novel phenyl-alkynes that have herbicidal and growth-inhibiting properties have now been found.
The present invention accordingly relates to compounds of formula I
Figure imgf000003_0001
wherein Q is a group
Figure imgf000003_0002
(Rl (Q β ).
Figure imgf000003_0003
Figure imgf000003_0004
n is O, 1, 2, 3 or 4; R is hydrogen, CORι2, -S(O)qCrCgalkyl, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl or C3-C6cycloalkyl; or Ci-Csalkyl, C3-C8alkenyl or C3-C8alkynyl each substituted from one to five times by halogen and/or once, twice or three times by substituents selected from Cι-C4alkoxy, -CN, -S(O)qCι-C8alkyl and phenyl, wherein the phenyl ring may in turn be substituted from one to five times by substituents selected from halogen and Cj- alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, C C4alkoxy, -CN, -NO2 and -SCO^d- alkyl, or
R is C3-C6cycloalkyl substituted from one to five times by substituents selected from halogen and Cι-C alkyl and/or once, twice or three times by substituents selected from d-C4alkoxy, -CN and phenyl, wherein the phenyl ring may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C alkoxy, -CN, -N02 and -S(0)qd-C8alkyl, or R is phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and methyl and/or once, twice or three times by substituents selected from -CF3, -OCH3, -CN, -NO and -S(0)qCi-C4alkyl; or, when n is 0, 1, 2 or 3,
R forms a Cι-C6alkylene or C2-C6alkenylene bridge attached to the phenyl ring in the 3- position, which bridge may be interrupted by an oxygen atom and/or may be substituted by Ci -C6alkyl, an oxygen-oxygen bond being excluded and the total number of ring atoms being at least 5 and at most 9; each Ri independently of any other(s) may be halogen, -CN, -SCN, -SF5, -N02, -NRsRό, -C02R7, -CONR8R9, -C( ιo)=NORιι, -COR12, -OR,3, -SRι4, -SOR15, -S02Rι6, -OSO2Rι7, Cι-C8alkyl, C2-C8alkenyl, C2-C8alkynyl or C3-C6cycloalkyl; or is Cι-C8alkyl, C2-C8alkenyl or C2-C8alkynyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, -NO2, -NR18R19, -CO2R20, -CONR2ιR22, -COR23, -C(R2 )=NOR25, -C(S)NR26R27, -C(C1-C4alkylthio)=NR28, -OR29, -SR30, -SOR31, -SO2R32 and C3-C6cycloalkyl; and/or each Ri independently of any other(s) may be C3-C6cycloalkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, -NO2, -NR,8Ri9, -CO2R20, -CONR2,R22, -COR23, -C(R24)=NOR25, -C(S)NR26R27, -C(CrC4alkylthio)=NR28, -OR29, -SR30, -SOR31, -SO2R32 and C3-C6cycloalkyl; and/or each Ri independently of any other(s) may be phenyl which may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, d-C4alkoxy, -CN, -N02, Cι-C4alkylthio, C C4alkylsulfmyl and d-C4alkylsulfonyl; or, when Q is a group Qi, Q2, Q3, Q4, Q5 or Q7, two adjacent Rj radicals may together form a Cι-C alkylene or C2-C7alkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and/or may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by Cι-C6alkoxy, the total number of ring atoms being at least 5 and at most 9; R5 is hydrogen or Cι-C8alkyl;
R6 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherem phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C alkoxy, -CN, -N02, Cι-C alkylthio, Cι-C4alkylsulfmyl and Cι-C4alkylsulfonyl, or
R6 is Cι-C8alkylcarbonyl, wherein the Cι-C8alkyl chain may in turn be substituted by substituents selected from halogen, -CN, Cι-C6alkylamino, di(Cι-C6alkyl)amino and Cι-C4alkoxy; or R5 and Rό together are a C2-C alkylene chain which may be interrupted by an oxygen or sulfur atom;
R7 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl, C3-C8alkenyl or d-Csalkynyl each substituted from one to five times by halogen and/or once, twice or three times by substituents selected from Cι-C4alkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from
Ci -C4haloalkyl, C C4alkoxy, -CN, -NO , Cι-C4alkylthio, Cι-C4alkylsulfmyl and
C 1 -C4alkylsulfonyl;
R8 and R9 are each independently of the other hydrogen or C]-C8alkyl, or C -C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl and -CN, or
R8 and R9 are each independently of the other C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from d-C halo alkyl, Cι-C alkoxy, -CN, -NO2, Cι-C alkylthio, Cι-C alkylsulfmyl and Cι-C4alkylsulfonyl; or R8 and R together are C -C5alkylene;
Rio is hydrogen, Cι-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl; Rii is hydrogen, d-Cgalkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C4haloalkyl or C3-C6haloalkenyl;
R12 is hydrogen, d-C alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl; Rι3 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl; or Ri3 is phenyl or phenyl-Cι-C6alkyl, wherein the phenyl ring may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Ci-Cgalkylthio, Cι-C8alkylsulfinyl and d-C8 alkylsulfonyl; or Rι3 is Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, Cι-C6alkylamino, di(d-C6alkyl)amino and Cι-C alkoxy, or
R]3 is Cι-C8alkylcarbonyl, wherein the Cι-C8alkyl chain may in turn be substituted by substituents selected from halogen, -CN, Cι-C6alkylamino, di(Cι-C6alkyl)amino and
Cι-C alkoxy;
R]4 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and Cι-C4alkoxy;
R15, Ri6 and Rι7 are each independently of the others Cι-C8alkyl, C3-C8alkenyl or d-Qalkynyl, or Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and Cι-C4alkoxy; Rig is hydrogen or Cι-C8alkyl;
Rι9 is hydrogen, d-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C alkoxy, -CN, -NO2, d-C alkylthio, Cι~C4alkylsulfinyl and C]-C4alkylsulfonyl; or
Ris and Rι9 together are a C -C5alkylene chain which may be interrupted by an oxygen or sulfur atom; R20 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C alkylthio, Cι-C4alkylsulfinyl and C]-C alkylsulfonyl; R2ι is hydrogen or Cι-C8alkyl;
R22 is hydrogen or Cι-C8alkyl, or Cι-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl and -CN, or R22 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, d-C4alkylthio, C C4alkylsulfinyl and Cι-C alkylsulfonyl; or R21 and R22 together are C2-C5alkylene; R23 is hydrogen, Cι-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl; R24 is hydrogen, Cι-C4alkyl, d-C4haloalkyl or C3-C6cycloalkyl; R25 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C4haloalkyl or C3-C6haloalkenyl; R26 is hydrogen or Cι-C8alkyl; R27 is hydrogen or d-C8alkyl, or Cj-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl and -CN, or R27 is C3-C8alkenyl, C -C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, Cι-C alkylsulfinyl and d-C4alkylsulfonyl; or R26 and R27 together are C2-C5alkylene; R28 is hydrogen or d-Csalkyl; R29 and R30 are each independently of the other hydrogen, d-C8alkyl, C -C8alkenyl or C3-Csalkynyl, or C]-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and Cι-C4alkoxy; R3ι and R32 are each independently of the other d-Csalkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and Cι-C alkoxy; m is 0, 1, 2, 3, 4 or 5; each R2 independently of any other(s) may be halogen, -CN, -SCN, -OCN, -N3, -SF5, -NO2, -NR33R34, -C02R35, -CONR36R 7, -C(R38)=NOR39, -COR40, -OR41, -SR42, -SOR^, -SO2R44, -OSO2R 5, -N([CO]pR46)COR47, -N(OR54)COR55, -N(R56)SO2R57, -N(SO2R58)SO2R59, -N=C(OR60)R6ι, -CR62(OR63)OR64, -OC(O)NR65R66, -SC(O)NR67R68, -OC(S)NR69R70 or -N-phthalimide; and/or R2 may be a 5- to 7-membered heterocyclic ring system which may be aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, which heterocyclic ring system may in turn be substituted from one to five times by substituents selected from halogen and Cι-C alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, hydroxy-Cι-C4alkyl, d-C4alkoxy, Cι-C4alkoxy-C1-C4alkyl, -CN, -NO2, Cι-C6alkylthio, d-C6alkylsulfmyl and Cι-C6alkylsulfonyl; R33 is hydrogen or Cι-C8alkyl; and
R34 is hydrogen, Cι-C8alkyl, CrQalkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, Cι-C4alkylsulfinyl and Cι-C4alkylsulfonyl, or
R34 is Ci-dalkylcarbonyl unsubstituted or substituted by substituents selected from halogen, -CN, Cι-C6alkylamino, di(Cι-C6alkyl)amino and Cι-C4alkoxy; or R33 and R3 together are a d-dalkylene chain which may be interrupted by an oxygen or sulfur atom;
R35 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl each substituted from one to five times by halogen and/or once, twice or • three times by substituents selected from Cι-C4alkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from C,-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, d-C4alkylsulfmyl and Cι-C4alkylsulfonyl; R36 is hydrogen or Cι-C8alkyl;
R37 is hydrogen or Cι-C8alkyl, or Cι-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Ci-Csalkoxycarbonyl and -CN, or
R37 is C3-C8alkenyl, C3-Csalkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and
Cι-C alkyl and/or once, twice or three times by substituents selected from
Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, Cι-C4alkylsulfmyl and
Cι-C4alkylsulfonyl; or
R36 and R37 together are Crdalkylene; R38 is hydrogen, Cι-C4alkyl, C]-C4haloalkyl or C3-C6cycloalkyl;
R39 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C haloalkyl or
C3-C6haloalkenyl;
R40 is hydrogen, Cι-C4alkyl, C C4haloalkyl, Cι-C8alkylthio, -C(O)-C(0)OCι-C4alkyl or
C3-C6cycloalkyl; R4ι is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C6alkoxy-Cι-C6alkyl,
Cι-C8alkylcarbonyl, Cι-C8haloalkylcarbonyl, Cι-C8alkoxycarbonyl,
C3-C8alkenyloxycarbonyl, Cι-C6alkoxy-Cι-C6alkoxycarbonyl, Cι-C6alkylthio-
Cι-C6alkyl, Cι-C6alkylsulfinyl-Cι-C6alkyl or Cι-C6alkylsulfonyl-Cι-C6alkyl; or
R41 is phenyl or phenyl-Cι-C6alkyl, wherein the phenyl ring may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from C]-C4haloalkyl, Cι-C4alkoxy, -CN,
-NO2 and -S(0)2Ci-C8alkyl, or
R41 is Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl, Cι-C6alkylamino, di(Cι-C6alkyl)amino and -CN;
R 2 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and Cι-C4alkoxy;
R4 and R44 are each independently of the other Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and Cι-C4alkoxy; R45 is Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and d-C alkoxy, or
R45 is phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C alkoxy, -CN, NO2, d-Qalkylthio, d-C8alkylsulfinyl and Cι-C8alkylsulfonyl;
R46 is hydrogen, Ci-Csalkyl, C3-C8alkenyl, C3-C8alkynyl or Cι-C4haloalkyl;
R 7 is hydrogen, Cι-C8alkyl, Cι-C4alkoxy, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, Cι-C4alkoxy, Cι-C8alkoxycarbonyl, -NH2,
Cι-C4alkylamino, di(CrC4alkyl)amino, -NR48COR49, -NR5oSO2R5ι and -NR52CO2R53, or
R47 is phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, C]-C4alkoxy, -CN, -NO2,
Cι-C4alkylthio, Cι-C4alkylsulfinyl and Cι-C4alkylsulfonyl; p is 0 or 1 ;
R48, R49, R5o, R51, R52 and R53 are each independently of the others hydrogen, Cι-C8alkyl, phenyl, benzyl or naphthyl, wherein the three last-mentioned aromatic radicals may in turn be substituted from one to five times by substituents selected from halogen and
Ci-Csalkyl and/or once, twice or three times by substituents selected from
Cι-C4haloalkyl, Cι-C4alkoxy, Cι-C alkylamino, di(Cι-C alkyl)amino, -NH2, -CN, -N02,
Cι-C4alkylthio, Cι-C4alkylsulfmyl and Cι-C4alkylsulfonyl;
R54 and R55 are each independently of the other hydrogen, Cι-C8alkyl or phenyl which may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from
Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C8alkylthio, C C8alkylsulfmyl and
C 1 -C8 alkylsulfonyl ;
R56 is hydrogen, Cι-C8alkyl, Cι-C4haloalkyl, Cι-C alkoxy, C3-C8alkenyl, C3-C8alkynyl or benzyl, wherein benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C8alkylthio,
Ci-Csalkylsulfmyl and Cι-C8alkylsulfonyl; R57 is Cι-C8alkyl, Cι-C haloalkyl, phenyl, benzyl or naphthyl, wherein the latter three aromatic rings may be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C alkoxy, d-C4alkylamino, di(d-C alkyl)amino, -NH2, -CN, -N02, Cι-C4alkylthio, Cι-C4alkylsulfinyl and d-C4alkylsulfonyl;
R58 and R59 are each independently of the other Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl, benzyl or naphthyl, wherein the latter three aromatic rings may be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, Cι-C4alkylamino, di(Cι-C alkyl)amino, -NH2, -CN, -N02, Cι-C4alkylthio, Cι-C4alkylsulfinyl and Cι-C4alkylsulfonyl;
R60 and R6ι are each independently of the other hydrogen or Cι-C6alkyl; R62, R<53 and 54 are each independently of the others hydrogen or Cι-C8alkyl, or R63 and R64 together form a C2-C5alkylene bridge; R65, Rό6, R67, Res, R69 and R70 are each independently of the others hydrogen or Cι-C8alkyl, or
R s and R 6, or R67 and R^s, or Rδ9 and R70 together in each case form a C2-C5alkylene bridge; and/or each R2 independently of any other(s) may be Cι-C8alkyl, or Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, -N3, -SCN, -NO2, -NR7ιR72, -CO2R73, -CONR74R75, -COR76, -C(R77)=NOR78, -C(S)NR79R80, -C(Cι-C4alkylthio)=NR8ι, -OR82, -SR83, -SOR84, -SO2R85, -O(S02)R86, -N(R87)CO2R88, -N(R89)COR90, -S+(R9ι)2, -N+(R92)3, -Si(R93)3 and C3-C6cycloalkyl; and/or each R2 independently of any other(s) may be Cι-C8alkyl substituted by a 5- to 7- membered heterocyclic ring system which may be aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, wherein that heterocyclic ring system may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, hydroxy-Cι-C4alkyl, Cι-C4alkoxy, Cι-C4alkoxy-Cι-C4alkyl, -CN, -NO2, Cι-C6alkylthio, Cι-C6alkylsulfmyl and Cι-C6alkylsulfonyl; and/or each R2 independently of any other(s) may be C2-C8alkenyl, or C2-C8alkenyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, -N02, -C02R94, -CONR95R96, -COR97, -C(R98)=NOR99, -C(S) RιooRιoι,
Figure imgf000012_0001
-OR103, -Si(Rι04)3 and C3-C6cycloalkyl; and/or each R2 independently of any other(s) may be C2-C8alkynyl, or C2-C8alkynyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, -CO2Rι05, -CONR,06Rιo7, -CORι08, -C(Rιo9)=NORn0, -C(S)NRnιRn2, -C(d-C4alkylthio)=NRπ3, -ORn4, -Si(Rπ5)3 and C3-C6cycloalkyl; and/or each R2 independently of any other(s) may be d-dcycloalkyl, or C3-C6cycloalkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, -CO2Rn6, -CONRn7Rn8, -CORn9, -C(Rι20)=NORι2ι, -C(S)NRi2 Ri23 and -C(d-C4alkylthio)==NRι2 ; and/or two adjacent R2 radicals together may form a Cι-C7alkylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and/or may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by Cι-C6alkoxy, the total number of ring atoms being at least 5 and at most 9; and/or two adjacent R2 radicals together may form a C2-C7alkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and/or may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and or once, twice or three times by Cι-C6alkoxy, the total number of ring atoms being at least 5 and at most 9; R71 is hydrogen or Cι-C8alkyl;
R72 is hydrogen, Cι-C8alkyl, d-Qalkenylj d-dalkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and C]-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C alkoxy, -CN, -NO2, Cι-C4alkylthio, Cι-C4alkylsulfinyl and Cι-C4alkylsulfonyl; or
R7ι and R72 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom; R73 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl, C3-C8alkenyl or d-Qalkynyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from Cι-C4alkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and C]-C4alkyl and/or once, twice or three times by substituents selected from Ci-dhaloalkyl, Cι-C4alkoxy, -CN, -N02, d-C4alkylthio, Cι-C4alkylsulfmyl and Ci -C4alkylsulfonyl;
R74 is hydrogen or d-C8alkyl;
R75 is hydrogen, Cι-C8alkyl or d-dcycloalkyl, or Cι-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl, Cι-C6alkoxy and -CN; or
R75 is d-dalkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and
Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -N02, d-C4alkylthio, Cι-C alkylsulfmyl and
Cι-C alkylsulfonyl; or
R74 and R75 together are a d-dalkylene chain which may be interrupted by an oxygen or sulfur atom;
R76 is hydrogen, Cι-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl; R77 is hydrogen, Cι-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl;
R78 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C4haloalkyl or
C3-C6haloalkenyl; and
R79 is hydrogen or d-C8alkyl;
R80 is hydrogen or Cι-C8alkyl, or Cι-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl and -CN; or
R8o is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and
Cι-C4alkyl and/or once, twice or three times by substituents selected from
Cι-C4haloalkyl, d-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, Cι-C4alkylsulfmyl and Cι-C4alkylsulfonyl; or
R 9 and R80 together are C2-C5alkylene;
R8ι is hydrogen or Cι-C8alkyl; R82 is -Si(Cι-C6alkyl)3, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl which is substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, -NH2, Cι-C6alkylamino, di(Cι-C6alkyl)amino and C]-C4alkoxy; R83 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, or Ci-Csalkyl which is substituted from one to five times by halogen and or once, twice or three times by substituents selected from -CN, -NH2, Cι-C6alkylamino, di(Cι-C6alkyl)aminό and d-C4alkoxy; Rs , R85 and R86 are each independently of the others Cι-C8alkyl, C3-Csalkenyl or C -C8alkynyl, or Cι-C8alkyl which is substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and Cι-C4alkoxy; R87 and R89 are each independently of the other hydrogen, Cι-C8alkyl or Cι-C8alkoxy; R88 is C,-C8alkyl; R90 is hydrogen or Cι-C8alkyl; R9ι is Cι-C4alkyl;
R92 and R93 are each independently of the other Cι-C6alkyl;
R94 is hydrogen, or Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl each of which may be substituted from one to five times by halogen and/or once, twice or three times by substituents selected from Cι-C4alkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, Cι-C4alkylsulfmyl and Cι-C4alkylsulfonyl; R95 is hydrogen or Cι-C8alkyl; R96 is hydrogen or Cι-C8alkyl, or Cι-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl and -CN; or
R96 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, Cι-C4alkylsulfinyl and Cι-C4alkylsulfonyl; or
R95 and R96 together are d-dalkylene;
R97 and R98 are each independently of the other hydrogen, Cι-C4alkyl, d-C4haloalkyl or
C3-C6cycloalkyl; R99 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, C C4haloalkyl or C3-C6haloalkenyl; Rioo is hydrogen or Cι-C8alkyl; Rioi is hydrogen or d-C8alkyl, or Cι-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl and -CN; or Rioi is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from d-C4haloalkyl, Cι-C alkoxy, -CN, -NO2, Cι-C4alkylthio, Cι-C4alkylsulfmyl and Ci-Qalkylsulfonyl; or Rioo and R10ι together are d-dalkylene;
R102 is hydrogen or d-C8alkyl;
R103 is hydrogen, C C8alkyl, -Si(d-C6alkyl)3, C3-C8alkenyl or C3-C8alkynyl;
Rιo4 is Cι-C6alkyl; R105 is hydrogen, or Ci-Qalkyl, C3-C8alkenyl or C3-C8alkynyl each of which may be substituted from one to five times by halogen and/or once, twice or three times by substituents selected from Cι-C4alkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and d-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, d-C4alkoxy, -CN, -NO2, CrC4alkylthio, Cι-C4alkylsulfinyl and Ci-Qalkylsulfonyl; R106 is hydrogen or d-C8alkyl;
Ri07 is hydrogen or Cι-C8alkyl, or Cι-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl and -CN, or R107 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Ci-dhaloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, C C4alkylsulfmyl and Cι-C4alkylsulfonyl; or Ri06 and R107 together are d-dalkylene; Rιo8 is hydrogen, Cι-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl; R109 is hydrogen, Cι-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl; Riio is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, d-C4haloalkyl or C3-C6haloalkenyl; Rin is hydrogen or d-C8alkyl; Rn2 is hydrogen or Cι-C8alkyl, or Cι-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl and -CN; or Rn2 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, C C4alkoxy, -CN, -NO2, Cι-C4alkylthio, Cι-C4alkylsulfmyl and Cι-C alkylsulfonyl; or Rin and Rπ2 together are d-dalkylene; Rn3 is hydrogen or Cι-C8alkyl;
Rπ4 is hydrogen, Cι-C8alkyl, -Si(Cι-C6alkyl)3, C3-C8alkenyl or C3-C8alkynyl; Rιi5 is Cι-C6alkyl;
Rιi6 is hydrogen, or d-dalkyl, C3-C8alkenyl or C3-C8alkynyl each of which may be substituted from one to five times by halogen and/or once, twice or three times by substituents selected from Cι-C4alkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, d-Qalkoxy, -CN, -NO2, Cι-C4alkylthio, Cι-C4alkylsulfmyl and C C4alkylsulfonyl; Rιi7 is hydrogen or Cι-C8alkyl; Riis is hydrogen or Ci-Csalkyl, or Cι-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl and -CN; or Rns is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C4alkylthio, Cι-C4alkylsulfmyl and Cι-C4alkylsulfonyl; or Rιi7 and Rπ8 together are C2-C5alkylene;
Rn9 is hydrogen, Cι-C4alkyl, Cι-C4haloalkyl or C3~C6cycloalkyl; Rπo is hydrogen, Cι-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl; R121 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, d-Qalkynyl, Cι-C4haloalkyl or C3-C6haloalkenyl; R122 is hydrogen or Cι-C8alkyl; Ri23 is hydrogen or Cι-C8alkyl, or Cι-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl and -CN; or Rι23 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from
Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, d-C4alkylthio, d-C4alkylsulfmyl and
C]-C4alkylsulfonyl; or
R122 and Ri23 together are C2-C alkylene; and
Rι is hydrogen or d-C8alkyl; A is a bridging member Ai, A2, A3, At or A5
Figure imgf000017_0001
wherein the bridging members Ai to A5 are linked to the group Q at the end carrying the oxygen atom;
R131, R132, Ri33> Ri34, R135, Ri36, i37, i38, R139 and R]4o are each independently of the others hydrogen, halogen, -CN, -NO2, -N(R20o)R2oι, C C6alkyl, Cι-C6haloalkyl, -OH, Cι-C6alkoxy, Ci-Cβhaloalkoxy, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C3-C6alkenyloxy, C3-C6haloalkenyloxy, C3-C6alkynyloxy, C3-C8cycloalkyl, C3-C8halocycloalkyl, -C(O)OR202, -C(O)NR203R2o4, -C(S)NR205R2o6, -COR207, -CSR208, -C(R209)=NOR2ιo, -OC(O)R2π, -OC(0)OR2ι2, -SC(O)R2ι3, -SC(O)OR2ι4j -OC(S)SR2ι5, -SC(S)SR2ι6, -OSO2Cι-C6alkyl, -OS02Cι-C6haloalkyl, -SH, -S(O)qC C6alkyl or -S(O)qCι-C6haloalkyl, and/or Ri3i, Ri32, R133, Ri34, i35, Ri36, i37, Ri38, Ri39 and R]40 may be each independently of the others Cι-C6alkyl or Cι-C6alkoxy each of which is substituted once, twice or three times by substituents selected from -CN, C(O)OR2ι7, -CHO, -COR2ι8, -C(O)NR2i9R22o, -C(S)NR22ιR222, -C(R223)=NOR224, -N(R225)R226, -OH, Cι-C6alkoxy, C,-C6haloalkoxy, -SH, -S(0)qCι-C6alkyl, -S(O)qCι-C6haloalkyl, -Si(CrC6alkyl)3, -Si(Cι-C6alkyl)r(phenyl)s and phenyl, wherein each phenyl ring may in turn be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cι-C6alkoxy, Cι-C6haloalkoxy, -CN, -COR227, -COOR228, -N02, -N(R229)R23o, -SH, -S(O)qCι-C6alkyl and -S(O)qCι-C6haloalkyl; and/or
Ri3L R132, R133, R134, R135, Ri36, R137, i38, R139 and R! 0 may be each independently of the others phenyl or phenyl substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, d-C6alkoxy, Cι-C6haloalkoxy, -CN, -COR227, -COOR228, -N02, -N(R229)R230, -SH, -S(O)qC C6alkyl and -S(0)qCi-C6haloalkyl;
R20o and R20ι are each independently of the other hydrogen, Ci-dalkyl, Cι-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy- Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cι-C6alkoxy, Cι-C6haloalkoxy and -COR227;
R202 is hydrogen, Cι-C6alkyl, Cι-C6haloalkyl, C3-C6alkenyl, C -C6haloalkenyl, C3-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy-Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cι-C6alkoxy and Cι-C6haloalkoxy;
R203 and R20 are each independently of the other hydrogen, Cι-C6alkyl, d-C6haloalkyl, C2-C6alkenyl, d-dhaloalkenyl, C2-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy- C]-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cι-C6alkoxy, C]-C6haloalkoxy and -COR227; R205 and R2oδ are each independently of the other hydrogen, Cι-C6alkyl, Cι-C6halo alkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy- Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cι-C6alkoxy, Cι-C6haloalkoxy and -COR227;
R207 and R208 are each independently of the other hydrogen, Cι-C6alkyl, Cι-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Cι-C6hydroxyalkyl, Cι-C6alkoxy- Cι-C6alkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Ci-Qhaloalkyl, -OH, Cj-C6alkoxy, Cι-C6haloalkoxy, -CN, -COR227, -COOR228, -NO2, -N(R229)R23o, -SH, -S(O)qCι-C6alkyl and -S(0)qd-C6haloalkyl; R209 is hydrogen, Cι-C6alkyl, Cι-C6haloalkyl, C -C6alkenyl, C -C6haloalkenyl, C2-C6alkynyl, Cι-C6hydroxyalkyl, Cι-C6alkoxy-Cι-C6alkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from d-C6haloalkyl, -OH, Cι-C6alkoxy, C C6haloalkoxy, -CN, -COR227, -COOR228, -NO2, -N(R229)R23o, -SH, -S(O)qCι-C6alkyl and -S(O)qCι-C6haloalkyl; R2ιo is hydrogen, Cι-C6alkyl, CrC6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl,
C3-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy-Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, C C6alkoxy and d-C6haloalkoxy; R211 is hydrogen, Ci-Cόalkyl, Cι-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Cι-C6hydroxyalkyl, Cι-C6alkoxy-Cι-C6alkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Ci-Cδhaloalkyl, -OH, C C6alkoxy, C C6haloalkoxy, -CN, -COR227> -COOR228, -N02, -N(R229)R230, -SH, -S(O)qCι-C6alkyl and -S(0)qCi-C6haloalkyl;
R2ι2 is hydrogen, Cι-C6alkyl, Cι-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C2-C6hydroxyalkyl, Ci-dalkoxy-Ci-Cόalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cι-C6alkoxy and C]-C6haloalkoxy; R2i3 is hydrogen, Cι-C6alkyl, Cι-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Cι-C6hydroxyalkyl, C!-C6alkoxy-Cι-C6alkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cι-C6alkoxy, Cι-C6haloalkoxy, -CN, -COR227, -COOR228, -NO2, -N(R229)R230, -SH, -S(0)qCι-C6alkyl and -S(O)qCι-C6haloalkyl; R214, R215 and R2i6 are each independently of the others hydrogen, Cι-C6alkyl, d-C6halo- alkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy- Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings maybe substituted from one to five times by substituents selected from halogen and Ci-Cδalkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cι-C6alkoxy and Cι-C6haloalkoxy; R2i7 is hydrogen, Cι-C6alkyL Cι-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl,
C3-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy-Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and C C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, d-C6alkoxy and Cι-C6haloalkoxy; R2i8 is hydrogen, Cι-C6alkyl, Cι-C6haloalkyl, d-Qalkenyl, C3-C6haloalkenyl,
C3-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy-Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-Cehaloalkyl, -OH, d-C6alkoxy and Cι-C6haloalkoxy; R2i9 is hydrogen, C]-C6alkyl, Ci-dhaloalkyl, C3-C6alkenyl, C3-C6haloalkenyl,
C3-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy-Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, d-C6alkoxy and Cι-C6haloalkoxy; R22o is hydrogen, d-C6alkyl, d-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Cι-C6hydroxyalkyl, Cι-C6alkoxy-Cι-C6alkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and d-C6alkyl and/or once, twice or three times by substituents selected from d-C6haloalkyl, -OH, C C6alkoxy, C,-C6haloalkoxy, -CN, -COR227, -COOR228, -NO2, -N(R229)R230, -SH, -S(O)qCι-C6alkyl and -S(0)qCi-C6haloalkyl; R22ι is hydrogen, Cι-C6alkyl, Cι-C6haloalkyl, C -C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C2-C6hydroxyalkyl, C]-C6alkoxy-Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cι-C6alkoxy and Cι-C6haloalkoxy;
R222 is hydrogen, d-C6alkyl, d-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl,
C2-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy-Cι-C6alkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from
Cι-C6haloalkyl, -OH, Cι-C6alkoxy, Cι-C6haloalkoxy, -CN, -COR227, -COOR228, -NO2,
-N(R229)R23o, -SH, -S(O)qCι-C6alkyl and -S(O)qCι-C6haloalkyl;
R223 is hydrogen, Cι-C6alkyl, Cι-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, Cι-C6hydroxyalkyl, Cι-C alkoxy-Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Ci-Qhaloalkyl, -OH, d-C6alkoxy and Cι-C6haloalkoxy;
R 24 is hydrogen, Cι-C6alkyl, d-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C2-C6hydroxyalkyl, Ci-dalkoxy-Ci-Cόalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times'by substituents selected from Ci-Qhaloalkyl, -OH, Ci-Qalkoxy and Cι-C6haloalkoxy;
R225 is hydrogen, Cι-C6alkyl, Cι-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy-Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from C]-C6haloalkyl, -OH, Cι-C6alkoxy and d-C6haloalkoxy;
R226 is hydrogen, Cι-C6alkyl, Cι-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy-Cι-C6alkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and Cj-C6alkyl and/or once, twice or three times by substituents selected from d-C6haloalkyl, -OH, Cι-C6alkoxy, d-C6haloalkoxy, -CN, -COR227, -COOR228, -N02, -N(R229)R230, -SH, -S(O)qCι-C6alkyl and -S(O)qC C6haloalkyl;
R227 is hydrogen, Cι-C6alkyl, Cι-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Cι-C6alkoxy-Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and
Cι-C6alkyl and/or once, twice or three times by substituents selected from d-C6haloalkyl, -OH, Cι-C6alkoxy and Cι-C6haloalkoxy;
R228 is hydrogen, C C6alkyl, Cι-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl,
C3-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy-Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cι-C6alkoxy and Cι-C6haloalkoxy;
R229 and R230 are each independently of the other hydrogen, Cι-C6alkyl, Cι-C6haloalkyl,
C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy- Cj-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Ci-Cδalkyl and/or once, twice or three times by substituents selected from CpCehaloalkyl, -OH, Cι-C6alkoxy, d-C6haloalkoxy and -COR227; q is 0, 1 or 2; r and s are 0, 1, 2 or 3, the sum of [r + s] being 3; or any one or more of those pairs of substituents Rι33 to Rι40 which are bonded to the same carbon atom together may form, each independently of any other(s), the function =O, =S, =NOR23ι or
=NN(R232)R233;
R23ι is hydrogen, Cι-C6alkyl, Cι-C6haloalkyl, C3-C6alkenyl, C -C6haloalkenyl, C3-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy-Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and C C6alkyl and or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cι-C6alkoxy and Cι-C6haloalkoxy;
R2 2 and R233 are each independently of the other hydrogen, Cι-C6alkyl, Cι-C haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl5 C2-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy-
Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and d-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cι-C6alkoxy, Cι-C6haloalkoxy and -COR2 7; or - Ri3i and'Rι32 together, R133 and R]34 together, Rι35 and Rι36 together, R137 and Rι38 together and/or R09 and Rι40 together, each independently of any other(s), may form a C -C6alkylene or C2-C6alkenylene bridge each of which may be substituted from one to five times by substituents selected from halogen and d-C6alkyl and/or once, twice or three times by Cι-C6haloalkyl; and/or Rι3ι and Rι33 together, Rι33 and Rι35 together, R]35 and Rj37 together, and/or Rι37 and Rι39 together, each independently of any other(s), may form a Cι-C6alkylene or C -C6alkenylene bridge each of which may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by Cι-C6haloalkyl; and/or R1 1 and R!35 together, Rι33 and Rι37 together, and/or R135 and Rι3g together, each independently of any other(s), may form a Cι-C6alkylene or C2-C6alkenylene bridge each of which may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by Cι-C6haloalkyl; and/or R13ι and Rι37 together, Rι33 and R139 together, and/or Rι3] and Rι39 together, each independently of any other(s), may form a Cι-C6alkylene or C2-C6alkenylene bridge each of which may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by Cι-C6haloalkyl, with the proviso that for Rι3ι and Rj32 the meanings -OH, -SH and -N(R2oo)R oι wherein R20o and R20ι are hydrogen are excluded; B either is a direct bond between the sp-hybridised carbon atom of the triple bond and the phenyl ring or is a bridging member Bi, B2, B3 or B
Figure imgf000023_0001
Ri4i, i4 , Ri43, i44, j45, i46, i47 and R]48 are each independently of the others hydrogen, halogen, -CN, -N02, -N(R20o)R2oι, C C6alkyl, C C6haloalkyl, -OH, Cι-C6alkoxy, Cι-C6haloalkoxy, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C3-C6alkenyloxy, d-Cghaloalkenyloxy, C3-C6alkynyloxy, C3-C8cycloalkyl, C3-C8halocycloalkyl, -C(O)OR202, -C(O)NR203R204, -C(S)NR205R206, -COR207, -CSR208,
Figure imgf000024_0001
-OC(O)R2n, -OC(0)OR2ι2, -SC(0)R2ι3, -SC(O)OR2ι4, -OC(S)SR215, -SC(S)SR216, -OSO2Cj-C6alkyl, -OSO2C,-C6haloalkyl5 -SH, -S(O)qCι-C6alkyl or -S(0)qCi-C6haloalkyl, and/or Ri4i, R142, Ri43, Ri44, i45, Ri46, i47 and R]48 may be each independently of the others Cι-C6alkyl or Cι-C6alkoxy each of which is substituted once, twice or three times by substituents selected from -CN, C(O)OR2ι7, -CHO, -COR2ι8, -C(O)NR2i9R22o, -C(S)NR22ιR222, -C(R223)=NOR22 , -N(R225)R226, -OH, C C6alkoxy, d-C6haloalkoxy, -SH, -S(O)qd-C6alkyl, -S(O)qCι-C6haloalkyl, -Si(d-C6alkyl)3, -Si(Cι-C6alkyl)r(phenyl)s and phenyl, wherein each phenyl ring may in turn be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from C]-C6haloalkyl, -OH, Cι-C6alkoxy, Cι-C haloalkoxy, -CN, -COR227, -COOR228, -NO2, -N(R229)R230, -SH, -S(0)qCi-C6alkyl and -S(0)qCi-C6haloalkyl, wherein R200 to R230, q, r and s are as defined hereinbefore; and/or RHI, RI4 , Rι43, R]44J RJ45, Ri46, R147 and Rι48 maybe each independently of the others phenyl or phenyl substituted from one to five times by substituents selected from halogen and Ci-Cβalkyl and/or once, twice or three times by substituents selected from Ci-Qhaloalkyl, -OH, Cι-C6alkoxy, Cι-C6haloalkoxy, -CN, -COR227, -COOR228, -N02, -N(R229)R23o, -SH, -S(0)qCi-C6alkyl and -S(0)qCi-C6haloalkyl; or any one or more of those pairs of substituents R141 to R148 which are bonded to the same carbon atom together may form, each independently of any other(s), the function =O, =S, =NOR23] or =NN(R23 )R23 , wherein R23i to R23 are as defined hereinbefore; and/or R14ι and Rj42 together, Rι43 and Rι44 together, Ri 5 and Rι46 together, and/or Rι4 and Ri48 together, each independently of any other(s), may form a C2-C6alkylene or C2-C6alkenylene bridge each of which may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and or once, twice or three times by d-dhaloalkyl; and/or
R141 and Ri43 together, Rj43 and Rι45 together, and/or Rι45 and Ri47 together, each independently of any other(s), may form a Cι-C6alkylene or d-Qalkenylene bridge each of which may be substituted from one to five times by substituents selected from halogen and d-C6alkyl and/or once, twice or three times by d-dhaloalkyl; and/or Rι4ι and Rι45 together, Rι4 and Rι47 together, and/or R] ι and R] 7 together, each independently of any other(s), may form a Cι-C6alkylene or C2-C6alkenylene bridge each of which may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by d-dhaloalkyl, and also to the compounds of formula I containing N-oxides of the groups Q2, Q3, Q4, Q5, Q6, Q7 and Q8, the agrochemically acceptable salts and all stereoisomers and tautomers of the compounds of formula I, with the proviso that, when B is a direct bond between the sp-hybridised carbon atom of the triple bond and the phenyl ring, the bridging member A is other than
Figure imgf000025_0001
When n is 0, all free valencies on the aromatic and hetero aromatic groups Q to Q8 of the compounds of formula I are occupied by hydrogen. When m is 0, all free valencies on the phenyl ring of the compounds of formula I are occupied by hydrogen.
Examples of substituents that are formed as a result of R5 and R6 together, or Rι8 and R19 together, or R33 and R3 together, or R71 and R72 together, or R74 and R75 together being a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom are piperidine, morpholine, thiomorpholine and pyrrolidine.
Examples of 5- to 7-membered heterocyclic ring systems which maybe aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur in the definition of R2 are:
Figure imgf000026_0001
The alkyl groups appearing in the substituent definitions may be straight-chained or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, ' isobutyl, tert-butyl and the pentyl, hexyl, heptyl and octyl isomers. Preference is given to methyl, ethyl, n-propyl, isopropyl and n-butyl.
Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, ■ dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, l,l-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluorόethyl or 2,2,2- trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl or dichlorofluoromethyl. In general, in cases where halogen is fluorine it is intended that, in addition to the specific definition "alkyl substituted from one to five times by halogen", perfluorinated alkyl groups are also included; for example, in the definitions of Ri and R2 "Cι-C8alkyl substituted from one to five times by halogen" it is intended in addition that the perfluorinated alkyl groups are also included.
Where the number of halogen substituents on alkyl radicals is not specified, for example in the definitions of R6, Rι3 and R34 "Cι-C8alkylcarbonyl substituted by halogen" and in the definition of R41 "Cι-C8haloalkylcarbonyl", when halogen is chlorine, bromine and/or iodine Cι-C8alkylcarbonyl is substituted from one to five times but, when halogen is fluorine, it may be additionally substituted until perfluorinated. The other substituents which are not halogen, such as, for example, -CN, Cι-C6alkylamino or Cι-C4alkoxy, may occur on alkyl radicals once, twice or three times.
As haloalkenyl, alkenyl groups substituted one or more times by halogen are suitable, halogen being in particular bromine, iodine or, especially, fluorine or chlorine, for example 2- and 3-fluoropropenyl, 2- and 3-chloropropenyl, 2- and 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl, 4,4,4-trifluorobut-2-en-l-yl and 4,4,4- trichlorobut-2-en-l-yl. Among the alkenyl radicals substituted once, twice or three times by halogen, preference is given to those which have a chain length of '3 or 4 carbon atoms. The alkenyl groups may be halo-substituted at saturated or unsaturated carbon atoms.
Alkoxy groups have a chain length of preferably from 1 to 6, especially from 1 to 4, carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy, or the pentyloxy and hexyloxy isomers; preferably methoxy or ethoxy.
Alkoxy, alkenyl, alkynyl, alkoxyalkyl, alkylthio, alkylsulfonyl, alkylsulfinyl, alkylthio- alkyl, alkylsulfmyl-alkyl, alkylsulfonyl-alkyl, alkylaminoalkoxy, alkoxycarbonyl, alkoxy-alkoxycarbonyl, alkenyloxycarbonyl, alkylcarbonyloxy, alkenylthio, alkenylsulfonyl, alkenylsulfinyl, alkynylsulfonyl, alkynylthio and alkynylsulfinyl groups are derived from the mentioned alkyl radicals. The alkenyl and alkynyl groups may be straight-chained or branched and mono- or poly-unsaturated. Alkenyl is, for example, vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-l-yl, pentenyl or 2-hexenyl, preferably an alkenyl radical having a chain length of from 2 to 5 carbon atoms. Alkynyl is, for example, ethynyl, propargyl, 1-methylpropargyl, 3-butynyl, but-2-yn-l-yl, 2-methylbutyn-2-yl or but-3-yn-2-yl, preferably an alkynyl radical having a chain length of 3 or 4 carbon atoms.
Alkylthio groups preferably have a chain length of from 1 to 4 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfmyl, sec-butylsulfinyl or tert-butylsulfinyl; preferably methylsulfinyl or ethylsulfinyl. Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
Hydroxyalkyl is, for example, 2-hydroxyethyl, 3 -hydroxypropyl or 2,3-dihydroxypropyl.
Haloalkoxy is, for example, fluoromethόxy, difluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy or 2,2,2- trichloroethoxy.
Alkoxyalkyl groups preferably have from 1 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
Cycloalkyl radicals that are suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The cycloalkyl groups may be unsubstituted or substituted a number of times by halogen, especially from once to four times by fluorine, chlorine and/or bromine, for example, diffuorocyclopropyl, dichlorocyclopropyl, dibromocyclopropyl, 2,2,3,3- tetrafluorocyclobutyl and 2,2-difluoro-3,3-dichlorocyclobutyl.
Alkylamino is, for example, methylamino, ethylamino, n-propylamino, isopropylamino or the butylamino isomers. Dialkylamino is, for example, dimethylamino, diethylamino or the dipropyl- or dibutyl- amino isomers.
Substituents where two adjacent Ri substituents (on the group Oj, Q2, Q3, Q4, Q5 or Q7) together form a Ci-dalkylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and/or which may be substituted from one to five times by halogen and/or by Cι-C6alkyl and/or once, twice or three times by Cι-C6alkoxy, the total number of ring atoms being at least 5 and at most 9, or where two adjacent R substituents together form a C2-dalkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and/or which may be substituted from one to five times by halogen and/or by Cι-C6alkyl and/or once, twice or three times by Cι-C6alkoxy, the total number of ring atoms being at least 5 and at most 9, have, for example, the following structures:
Figure imgf000029_0001
Substituents where two adjacent R substituents together form a Cj-dalkylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen . and sulfur and/or which may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by Cι-C6alkoxy, the total number of ring atoms being at least 5 and at most 9, or where two adjacent R2 substituents together form a d-dalkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and which may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and or once, twice or three times by Cι-C6alkoxy, the total number of ring atoms being at least 5 and at most 9, have, for example, the following structures:
Figure imgf000030_0001
Figure imgf000030_0002
Figure imgf000030_0003
Meanings corresponding to those indicated above may also be given to the substituents in combined definitions, for example alkoxycarbonyl, alkoxy-alkoxycarbonyl, alkylsulfonyl-alkyl, -N(R56)SO2R57, -OC^NR^o, -C(R38)=NOR39, -NR50SO2R5ι and -NR52CO2R53. In the definitions for alkylcarbonyl, alkoxycarbonyl and alkenyloxycarbonyl, the carbon atom of the carbonyl is not included in the lower and upper limits given for the number of carbons in each particular case.
The invention relates also to the salts which the compounds of formula I are able to form preferably with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Suitable salt formers are described, for example, in WO 98/41089.
Among the alkali metal and alkaline earth metal hydroxides as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially the hydroxides of sodium and potassium.
Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary Cι-Cι8alkylamines, Cι-C4hydroxyalkylamines and C2-C4alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl- hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl- octylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n- butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolarmne, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl- 2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p- chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine. Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(RaRbRcRd)]OH wherein Ra, Rb, Re and Ra are each independently of the others Cι-C4alkyl. Other suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.
In addition to the formation of salts of compounds of formula I having acid hydrogen, especially of the derivatives having carboxylic acid groups (e.g. carboxyl-substituted alkyl, cycloalkyl, alkenyl and alkynyl groups for Ri, or aromatic or heteroaromatic rings substituted by Ri (-CO2R7) or aromatic rings substituted by R (-CO2R35), wherein R7 and R35 are hydrogen), or HON=CH- or mercapto-substituted phenyl rings (R2 is
-C(R38)=NOR39 or -SR42, wherein R 9 and R42 are hydrogen), salts of the compounds of formula I having basic groups are also possible, especially having basic pyridyl, pyrimidyl, pyrazinyl and pyridazinyl rings (Q2 to Q8) or having amino or hydrazino groups as in, for example, the definition of Rj and R2, and R133 to Rι40 and R141 to R!48
Figure imgf000032_0001
Such salts are, for example, salts with inorganic and organic acids such as, for example, hydrohalic acids, e.g. hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, and sulfuric acid, phosphoric acid and nitric acid, and organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, citric acid, benzoic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid.
The presence of an asymmetric carbon atom or of a sulfmyl group in the compounds of formula I, for example when the substituent Ri or R2 is a branched alkyl, alkenyl or haloalkyl group or alkylsulfmyl, means that the compounds may occur either in the form of optically active single isomers or in the form of racemic mixtures. In the present invention, the compounds of formula I are understood to include both the pure optical antipodes and the racemates and diastereoisomers.
When an aliphatic C=C double bond or a HON=CH group is present, e.g. -C(R2 )=NOR25 wherein R24 and R25 are hydrogen, geometric isomerism may occur. Such isomers are also included in the present invention. Preference is given to compounds of formula I wherein Q is a group Qi, Q2, Q3 or Q
Figure imgf000033_0001
Figure imgf000033_0002
Amongst those compounds, special preference is given to those wherein Q is a group Q or Q2
(R (Q2).
Figure imgf000033_0003
especially wherein Q is a group Qi
Figure imgf000033_0004
Special preference is likewise given to compounds of formula I wherein Q is a group Q2a or Q4a
Figure imgf000033_0005
Preference is given to those compounds of formula I wherein A is a bridging member Ai or A2
Figure imgf000033_0006
Preference is also given to those compounds of formula I wherein B is a direct bond between the sp-hybridised carbon atom of the triple bond and the phenyl ring or is the R141 ,R1142 / ( J. bridging member B}
Preference is furthermore given to those compounds of formula I wherein A is a bridging R-I33 R \ / 134 member A2 and B is a direct bond between the sp- (A2) R131 R 32 hybridised carbon atom of the triple bond and the phenyl ring.
Of importance are those compounds of formula I wherein A is the bridging member Ai
Figure imgf000034_0001
Likewise of importance are those compounds of formula I wherein Q is a group Q , Q2, Q3 or Q4
Figure imgf000034_0002
A i
Figure imgf000034_0003
s the bridging member A2 and B is a direct bond between the sp-hybridised carbon atom of the triple bond and the phenyl ring. Important compounds of formula I are also those wherein Q is a group Q , Q2, Q3 or Q4
Figure imgf000035_0001
A
Figure imgf000035_0002
is the bridging member Ai and B is the bridging member
Figure imgf000035_0003
Also of importance are compounds of formula I wherein Q is a group Qi or Q2
Figure imgf000035_0004
R,33 R
/ \ (A2),
A is the bridging member A2 R113311 R132 and B is a direct bond between the sp-hybridised carbon atom of the triple bond and the phenyl ring.
Important compounds of formula I are those wherein Q is a group Qi or Q2
Figure imgf000035_0005
is the bridging member Aj
Figure imgf000036_0001
(B,). and B is the bridging member Bi
Likewise of importance are those compounds of formula I wherein each R1 } independently of any other(s), is halogen, -CN, -N02, -C(R1o)=NORπ, -OR13, -SO2Rι6, -OSO2R17, Cι-C8alkyl or C2-C8alkenyl, or Cι-C8alkyl substituted once, twice or three times by halogen and/or by -CN; Rio is hydrogen or C1-C4alkyl; Rn is Cι-C8alkyl, and n is O, 1, 2 or 3.
Especially important compounds of formula I are those wherein each R2, independently of any other(s), is halogen, -CN, -SCN, -OCN, -N3, -NO2, -NR33R34, -CO2R35,
-CONR36R37, -C(R38)=NOR39, -COR40, -OR41, -SO2R44, -OSO2R45, -N([CO]pR46)COR47, -N(R56)S02R57, -N(SO2R58)SO2R59, -N=C(OR60)R6i or Cι-C8alkyl, or Cι-C8alkyl substituted once, twice or three times by halogen, -CN, -N , -SCN, -CO2R73, -CONR74R7;;, -COR76, -C(R77)=NOR78, -C(S)NR79R80, -OR82, -SOR84, -SO2R85 and/or by -N(R89)COR90, and m is 0, 1 , 2, 3 or 4.
The compounds of formula I
Figure imgf000036_0002
wherein Q, A, B, R2 and m are as defined hereinbefore, may be prepared by various known processes. The groups Qi to Q8, the phenyl ring, and their substituents Ri (on groups Qi to Q8) and R2 (on the phenyl ring), and also the substituents of the bridging members A (R131 to Rι40) and B (Rj4ι to Rι48) do not restrict those processes; on the contrary, they can be taken into account in synthesis planning so that particular procedures can be used preferentially and carried out selectively and with a high yield. This will be the case, for example, when the substituents Ri and/or R2 have an activating and/or directing influence, by way of electron-withdrawing or -releasing effects or steric effects, such as, for example, in the nucleophilic aromatic substitution reaction of compounds of formula VIIi
Figure imgf000036_0003
with an alcoholate of formula Xai, Xa , Xa3, Xa4 or Xa5
Figure imgf000037_0001
or in the nucleophilic ring opening of the epoxide of formula Vb2
Figure imgf000037_0002
by the acetylide of the compound of formula Ila (Ila).
Figure imgf000037_0003
In general, the substituents Ri and/or R2, and also the substituents of the bridging members A and B (Rι3ι to R1 o, and R141 to R!48) have little influence, for example, on the palladium-catalysed cross-coupling of propargyl derivatives of formula Ila
Figure imgf000038_0001
wherein Q and A are as defined for formula I, with substituted phenyl derivatives of formula III
Figure imgf000038_0002
wherein R2 and m are as defined for formula I and W is halogen or a sulfonate, for example trifluoromethanesulfonate, in accordance with K. Sonogashira, or in the Mitsunobu reaction of the compound of formula VII Q-OH (VII), wherein Q is as defined for formula I, with the alkynyl-alcohol of formula VIII
Figure imgf000038_0003
wherein A, B, R2 and m are as defined for formula I, in the presence of azodicarboxylic acid diethyl ester (DEAD) or N,N,N',N'-tetramethylazodicarboxamide (TMAD) and triphenylphosphine.
Those two important coupling reactions are illustrated in Reaction Scheme 1.
Reaction Scheme 1 : Sonogashira and Mitsunobu coupling reactions
A Q
Ila
Figure imgf000039_0001
Figure imgf000039_0002
VII VIII
The substituents Ri and/or R2, for example in compounds of formulae Ila, lib, III, IVbi to TVb4, Vb2 to Vb4, Vlai to Via* VII, VIIi, VIII, IXai to IXa5, Xai to Xa5, XIa3 to XIa5, XV, XlXajbo to XIXa5b0, XXIa3b to XXIa5b, XXIIIabi to XXIIIab4 or XXVa2b to XXVa5b can already be present at the outset or, however, they may be successively introduced only later in the reaction sequence, for example by means of nucleophihc or electrophilic aromatic substitution.
For preparation of the compound of formula I and the corresponding intermediates, for example of formulae Ila and XV
Figure imgf000039_0003
wherein A and Q are as defined for formula I and E is an electrophilic functional group, the following bonds shown in Scheme 2, for example, are suitable retrosynthetically as attachment sites: Scheme 2: Retrosynthesis of compounds of formula I and their intermediates
Figure imgf000040_0001
The attachment sites shown retrosynthetically in Scheme 2 in general terms for the synthesis of the compounds of formula I and the intermediates of formulae Ila, XV, XLXaibo to XIXa5b0, XXIa3b to XXIa5b, XXIIIab2 to XXIIIab4 and XXVa2b to XXVa5b are described in detail below.
In accordance with Reaction Scheme 1, the compounds of formula Iab0
Figure imgf000040_0002
wherein A, Q, R2 and m are as defined for formula I, may be prepared analogously to known processes described, for example, in K. Sonogashira, Comprehensive Organic Synthesis 1991, Vol. 3, page 521 ff; WO 01/55066; WO 02/28182 and WO 03/013247, by, for example, coupling a compound of formula Ila
Figure imgf000041_0001
wherein A and Q are as defined, with a compound of formula III
Figure imgf000041_0002
wherein 2 and m are as defined and W is a leaving group such as, for example, halogen, e.g. iodine, or sulfonate, e.g. trifluoromethanesulfonate, in the presence of a palladium catalyst under Sonogashira reaction conditions (Reaction Scheme 1). Suitable catalyst mixtures are, for example, tetrakis(triphenylphosphine)palladium or bis(triphenylphosphine)palladiurn dichloride together with copper iodide. As bases for reductive elimination, amines, e.g. triethylamine, diethylamine or diisopropylethylamine, are preferably used. The aryls of formula III preferably carry a leaving group W wherein W is, for example, halogen (N. Krause et ai, J. Org. Chem. 1998, 63, page 8551; and H. Nakamura et al., Tetrahedron Lett. 2000, 41, page 2185) or trifluoromethanesulfonate (K. Ritter, Synthesis 1993, page 735). As solvents there are usually used ethers, e.g. tetrahydrofuran or dioxane, chlorinated hydrocarbons, e.g. chloroform, or dipolar aprotic solvents, e.g. dimethylformamide or dimethyl sulfoxide, or also amines, e.g. triethylamine or piperidine.
The compounds of formula Iabi, Iab2, Iab3 or Iab4
Figure imgf000041_0003
Figure imgf000042_0001
wherein A, Q, R , m and Rj43 to Rι48 are as defined for formula I and Ej is a bridging member \ \ \ R141 \ ^R141 .C=0 or /C"OH / NHR wherein R1 ι is as defined for formula I and Rj49 is hydrogen, d-dalkyl, Cι-C6haloalkyl, C2-C6alkenyl, C -C6haloalkenyl, C2-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy-C]-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cι-C6alkoxy, Ci-Qhaloalkoxy and -COR227, wherein R227 is as defined for formula I, may be prepared analogously to known processes described, for example, in J. Org. Chem. 68(2), 348-354 (2003); Synth. Communic. 32(13), 1937-45 (2002); Tetrahedron: Asymmetry 12(1), 53-57 (2001); Organic Letters 3(6), 819-21 (2001); Tetrahedron Lett. 43(15), 2691-94 (2002); Acta Chemica Scandinavica 49(7), 543-45 (1995); Synlett (1), 66-68 (1989); and Helv. Chim. Acta 72(3), 447-56 (1989), by, for example, reacting a compound of formula Ila
Figure imgf000042_0002
wherein A and Q are as defined, with a compound of formula IVbi, IVb2, IVb3 or IVb4
Figure imgf000043_0001
Figure imgf000043_0002
wherein R2, m and Rι43 to Rι48 are as defined and E is an electrophilic functional group
Figure imgf000043_0003
wherein R1 1 and R14 are as defined and Xi is a leaving group, for example halogen, e.g. fluorine, chlorine, bromine or iodine, or sulfonate, e.g. para-toluenesulfonate (-OTs, tosylate), methanesulfonate (-OMs, mesylate) or trifluoromethanesulfonate (-OTf, triflate), CH3(CH3O)N-, imidazolyl, triazolyl, -OR4, -SR4 or -N(R4)2, wherein R4 is d-C6alkyl, Cι-C6haloalkyl or phenyl, in the presence either a) of a strong base or b) of zinc salts and a base in an inert, organic solvent at temperatures from -100° to 50°C. As a strong base for variant a) for the formation of the corresponding acetylide there are suitable, for example, organolithium compounds, e.g. n-butyllithium (n-BuLi), lithium diisopropylamide (LDA) or lithium bis(trimethylsilyl)amide ([(CH3)3Si]2NLi), or a Grignard reagent, e.g. ethyl magnesium bromide. Suitable inert organic solvents are, for example, ethers, e.g. diethyl ether, tetrahydrofuran, or hexane-ether mixtures, or chlorinated hydrocarbons, e.g. dichloromethane. In accordance with variant b), the acetylene function in the compound of formula Ila is activated by means of zinc salts, e.g. zinc trifluoromethanesulfonate (CF3SO3)2Zn, in the presence of a base, e.g. triethylamine or Hϋnig's base, in analogous manner to that described in Tetrahedron Lett. 43(15), 2691-94 (2002); and J. Am. Chem. Soc. 121(48), 11245-246 (1999).'
The compounds of formula Iab2, Iab3 or Iab4
Figure imgf000044_0001
wherein A, Q, R2, m and R145 to R148 are as defined for formula I and E2 is a bridging
member , wherein R1 1, Rι42 and Rι43 are as defined for formula I,
Figure imgf000044_0002
may be prepared analogously to known processes described, for example, in Organic Letters 4(25), 4427-29 (2002); Heterocycles 42(2), 745-74 (1996); and Tetrahedron Lett. 33(37), 5365-68 (1992) and also processes mentioned hereinbefore, by, for example, causing a compound of formula Ila
Figure imgf000044_0003
wherein A and Q are as defined, to react with a compound of formula Vb2, Vb3 or Vb
Figure imgf000045_0001
wherein R2, m, Rj4ι to Rι43, and Rι 5 to R]48 are as defined, in the presence a) of a strong base or b) of zinc salts and a base in an inert, organic solvent at temperatures from -100° to 50°C.
As a strong base for variant a) for the formation of the corresponding acetylide there are suitable, for example, organolithium compounds, e.g. n-butyllithium (n-BuLi). Suitable inert organic solvents are, for example, ethers, e.g. tetrahydrofuran, or chlorinated hydrocarbons, e.g. dichloromethane.
In the process, the epoxy functionality in the compound of formula Vb2 to Vb4 is a substitute for the electrophilic functional group E in the compound of formula IVbi to rVb4, which reacts with the acetylide or the zinc-activated compound of formula lib
Figure imgf000045_0002
The addition of the acetylides of compounds of formula Ila to the epoxides of formula Vb2 to Vb4, especially to the epoxide of formula Vb2, may, depending on the substituents Rι41 to Rι43 and R2 and on the reaction conditions, for example in the presence of Lewis acids, result in isomeric mixtures. Those isomeric mixtures can be resolved by customary methods, e.g. by means of column chromatography. Compounds of formula I
Figure imgf000046_0001
wherein A, Q, B, R2 and m are as defined under formula I, may be prepared using the Mitsunobu reaction in the presence of azodicarboxylic acid diethyl ester (DEAD) and triphenylphosphine in a suitable solvent such as, for example, an ether, e.g. tetrahydrofuran (THF), in a manner analogous to that described, for example, in Synthetic Communic. 1989(19), 1255-59; or Synthesis 1981(1); or, using TMAD reagent as a substitute for DEAD in the two previous references, in a manner analogous to that described, for example, in Chem. Letters 1994, 539 (Reaction Scheme 1). That synthesis route uses, as intermediates, the compound of formula VII Q-OH (VII) and the alkynyl-alcohol of formula VIII
Figure imgf000046_0002
which are caused to react with one another under typical Mitsunobu reaction conditions, the radicals A, Q, B and R2 and the suffix m in the compounds of formulae VII and VIII being as defined.
The Mitsunobu reaction is especially advantageous for those compounds of formula VII in which Q is a group Qj or a group Q2, Q or Q5, the hydroxyl function in the latter three groups advantageously being in a position other than a position ortho to a ring nitrogen atom.
A further possibility for the preparation of compounds of formula I
Figure imgf000046_0003
wherein A, Q, B, R2 and m are as defined for formula I, is the base-catalysed alkylation or etherification of a compound of formula VII Q-OH (VII) with a compound of formula IXai, IXa2, IXa3, IXa4 or IXa5
under reaction
Figure imgf000047_0001
conditions typical therefor, the radicals Q, B and R2 and the suffix m in the compounds of formulae VII and IXai to IXa5 being as defined, R131 to R140 being as defined for formula I and L being a leaving group such as, for example, halogen, e.g. chlorine, bromine or iodine, acetate, or sulfonate, e.g. mesylate, tosylate or triflate.
Suitable bases are, for example, hydrides such as, for example, alkali metal and alkaline earth metal hydrides, e.g. sodium or potassium hydride, hydroxides such as, for example, alkali metal hydroxides, e.g. sodium or potassium hydroxide, alcoholates, e.g. sodium methanolate, sodium ethanolate or potassium tert-butanolate, carbonates, e.g. potassium or calcium carbonate, amines, e.g. triethylamine, or also sodium bis(trimethylsilyl)amide
(NaN[(CH3)3Si]2), silver© oxide (Ag2O) or Ag(OH)2.
Suitable solvents are amides, e.g. N,N-dimethylformamide, or nitriles, e.g. acetonitrile. Such etherification procedures are standard processes and may be carried out, for example, in analogy to J. Chem. Soc, Perkin Trans I, 1979, 2756-61; Synth. Communic. 18, 1111-18 (1988); Chem. Communic. 1990, 297-300; J. Org. Chem. 61, 4258-61 (1996); Tetrahedron 1997(53), 12621-628; and Synth. Communic. 24, 1367-79 (1994). Selective O-alkylation procedures in the presence of a ring nitrogen atom maybe carried out in a manner analogous to that described, for example, in Synth. Communic. 1994(24), 1367 and Heterocycles 1990(31), 819, and also in halogenated or aromatic hydrocarbons as solvent, e.g. chloroform or toluene, in the presence of silver carbonate as base.
The activation of the alcohol of formula VIII to form the compound of formula IXai to IXa5 is carried out, for example, by sulfonylation or halogenation. Sulfonylation of the alcohol of formula VIII is a standard reaction and may be carried out, for example, using a sulfonic acid chloride, e.g. mesyl chloride or para- toluenesulfonic acid chloride (p-TosCl), in the presence of a tertiary amine, e.g.. triethylamine, or of an aromatic amine, e.g. pyridine, in a solvent such as, for example, a chlorinated hydrocarbon, e.g. carbon tetrachloride or methylene chloride, or an amine, e.g. pyridine. Such reactions are generally known and described, for example, in J. Org. Chem. 1997 (62), 8987; J. Het. Chem. 1995 (32), 875-882; and also Tetrahedron Lett. 1997 (38), 8671-8674.
Halogenation of the alcohol of formula VIII may be carried out in analogy to standard processes. For example, bromination may be carried out using carbon tetrabromide in the presence of triphenylphosphine (Synthesis 1998, 1015-1018) in methylene chloride. Chlorination may be carried out using mineral acids, e.g. concentrated hydrochloric acid (J. Org. Chem. 1955 (20), 95), or using para-toluenesulfonic acid chloride in the presence of an amine, e.g. triethylamine, in a solvent, e.g. methylene chloride (Tetrahedron Lett. 1984 (25), 2295).
A further general method for the preparation of compounds of formula I
Figure imgf000048_0001
wherein A, Q, B, R2 and m are as defined for formula I, comprises, by means of a nucleophilic aromatic substitution reaction, causing the compound of formula VIIi
Figure imgf000049_0001
to react with an alcoholate of formula Xai, Xa , Xa3, Xa4 or Xa5
Figure imgf000049_0002
under typical substitution reaction conditions, the radicals Q, B and R2 and the suffix m in the compounds of formulae VIIi and Xai to Xa5 being as defined, R13ι to Rι40 being as defined for formula I, Li being a leaving group such as, for example, halogen, e.g. fluorine (for Q = Q2 to Q8), chlorine, bromine or iodine, or a sulfonate, e.g. -OTosyϊ (-OTs) or -OMesyl (-OMs), an alkylsulfonyl (for Q = Q2 to Q8), e.g. CH3SO2-, imidazolyl, triazolyl, -SCH3 or phenoxy, and M+ being an alkali metal ion, e.g. Na+. For compounds of formula VII] wherein Q is a group Qi, the nucleophilic aromatic substitution reaction is facilitated if they are activated compounds. That is the case when Ri is, for example, a substituent having electron-withdrawing properties (-M and/or -I effect), for example -CN, -NO2, -C02R7 or CORj2, or when the leaving group L\ in the groups Q2 to Q8 is in a position ortho to a ring nitrogen atom. Such substitution reactions with activated compounds of formula VIIi wherein Q is a group Qi to Q8 and Rj is a substituent having an -M and/or -I effect within the framework of the definition of Ri given for formula I, are standard methods and may be carried out, for example, in analogy to Synlett 2000, 874-876; ibid 1998, 794-796; or J. Org. Chem. 1998(63), 9594- 96.
For non-activated compounds of formula VII], wherein Q is, for example, a group Qi, and Ri is, for example, a substituent without electron- withdrawing properties (+M and/or +1 effect) such as, for example, -NR Rό or -ORι3, a suitable alternative synthesis method is the above-mentioned base-catalysed alkylation or etherification of a compound of formula VII with a compound of formula IXai to IXa5.
The compounds of formula Ia2b, Ia3b, Ia4b or Ia5b
Figure imgf000050_0001
wherein Q, B, R2, m and Rι3] to Rι38 are as defined for formula I and E3 is a bridging member
Figure imgf000051_0001
\ ,R139 oH ' °r
Figure imgf000051_0002
wherein Rj33, Rι35, Rι37 and Rι39 are as defined for formula I and Rι4 is hydrogen, Cι-C6alkyl, Cι-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C -C6hydroxyalkyl, d-C6alkoxy-Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cι-C6alkoxy, Cι-C6haloalkoxy and -COR227, wherein R227 is as defined for formula I, may be prepared analogously to routes that are known and described hereinbefore for compounds of formula Iabi, Iab2, Iab or Iab4, by causing a compound of formula Vlai , VIa2, VIa3 or VIa4
R 131 R11S32 Q- O E (Via,),
Figure imgf000051_0003
Figure imgf000051_0004
to react with a compound of formula lib
Figure imgf000051_0005
in the presence a) of a strong base or b) of zinc salts and a base in an inert organic solvent at temperatures from -100° to 50°C, the radicals Q, B, R2 and Ri3i to Rι38 and the suffix m in the compounds of formulae Vlai to VI^ and lib being as defined and E being an electrophilic functional group
Figure imgf000052_0001
wherein Rι33, Rι3 , Rι 7, Rj39 and Rι49 are as defined and Xi is a leaving group such as, for example, halogen, e.g. fluorine, chlorine, bromine or iodine, or sulfonate, e.g. para- toluenesulfonate (-OTs, tosylate), methanesulfonate (-OMs, mesylate) or trifluoromethanesulfonate (-OTf, triflate), or CH3(CH3O)N-, imidazolyl, triazolyl, -OR4, -SR4 or -N(R )2, wherein R4 is Cι-C6alkyl, Cι-C6haloalkyl or phenyl.
The compound of formula Ia3b, Ia b or Ia5b
Figure imgf000052_0002
wherein Q, B, R2, m and R131 to Rι36 are as defined for formula I and E4 is a bridging member ,
Figure imgf000053_0001
R133 and R135 to R]40 being as defined for formula I, can also be prepared analogously to the above-described process. In accordance therewith, an epoxide derivative of formula XIa3, X^ or XIa5
Figure imgf000053_0002
is caused to react with a compound of formula lib
Figure imgf000053_0003
in the presence a) of a strong base or b) of zinc salts and a base in an inert organic solvent at temperatures from -100° to 50°C, the radicals Q, B, R2 and R131 to Rι40 and the suffix m in the compounds of formulae XIa3 to XIa5 and lib being as defined.
In the process, the epoxy functionality is a substitute for the electrophilic functional group E in the compounds of formulae Vlai to VIa in the previous example, which reacts with the acetylide or the zinc-activated compound of formula lib.
The intermediate of formula Ila
Figure imgf000054_0001
wherein A and Q are as defined for formula I, may be prepared by means of the Mitsunobu reaction already described in detail hereinbefore (Reaction Scheme 1) from the compound of formula VII Q-OH (VII) and the compound of formula XII
Figure imgf000054_0002
the radicals A and Q in the compounds of formulae VII and XII being as defined.
A further method for the preparation of the intermediate of formula Ila
Figure imgf000054_0003
wherein A and Q are as defined for formula I, uses the compound of formula VII Q-OH (VII), which is caused to react with a compound of formula Xlllai, XIIIa2, XIIIa , Xffl^ or XIIIa5
(Xllla
Figure imgf000055_0001
or
Figure imgf000055_0002
(Xllla5)
Figure imgf000055_0003
under typical base-catalysed reaction conditions of alkylation or etherification, as described in detail hereinbefore for the preparation of the compound of formula I, the radicals Q and R131 to Rι40 in the compounds of formulae VII and XHIaj to Xlllas being as defined for formula I and L being a leaving group such as, for example, halogen, e.g. chlorine, bromine or iodine, acetate or sulfonate, e.g. mesylate or tosylate.
The process of the nucleophilic aromatic substitution reaction described in detail hereinbefore for the preparation of compounds of formula I is also suitable for the preparation of the intermediates of formula Ila
Figure imgf000055_0004
wherein A and Q are as defined for formula I, by causing a compound of formula VIIi
Figure imgf000055_0005
to react with a compound of formula XlVaj , XIVa2, XIVa3, XIV a or XIV a
Figure imgf000056_0001
Figure imgf000056_0002
Figure imgf000056_0003
under typical reaction conditions of nucleophilic aromatic substitution, the radicals Q and Ri3i to Rι40 in the compounds of formulae VIIi and XlVai to XTVas being as defined for formula I, Li being a leaving group such as, for example, halogen, e.g. fluorine (for Q = Q2 to Q8), chlorine, bromine or iodine, or a sulfonate, e.g. -OTosyl (-OTs) or -OMesyl (-OMs), an alkylsulfonyl (for Q = Q2 to Q8), e.g. CH3SO2-, imidazolyl, triazolyl, -SCH3 or phenoxy, and M+ being an alkali metal ion, e.g. Na+.
The intermediate of formula XV
Figure imgf000056_0004
wherein A and Q are as defined for formula I and E is an electrophilic functional group
Figure imgf000056_0005
whereinRι4ι is as defined for formula I, R]49 is hydrogen, C1-C4alkyl, Cι-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C -C6alkynyl, C2-C6hydroxyalkyl, Cj-C6alkoxy- C]-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cι-C6alkoxy,
Cι-C6haloalkoxy and -COR227, wherein R227 is as defined for formula I, and Xi is a leaving group such as, for example, halogen, e.g. fluorine, chlorine, bromine or iodine, or a sulfonate, e.g. -OTosyl (-OTs), -OMesyl (-OMs) or -OTriflate (-OTf), CH3(CH3O)N-, imidazolyl, triazolyl, -OR4, -SR) or -N(R4)2, wherein R is Cι-C6alkyl, d-C6haloalkyl or phenyl, may be obtained by means of the Mitsunobu reaction (Reaction Scheme 1) from a compound of formula VII Q-OH (VII) and a compound of formula XVI
Figure imgf000057_0001
the radicals A, Q and E in the compounds of formulae VII and XVI being as defined.
The intermediate of formula XV
Figure imgf000057_0002
wherein A and Q are as defined for formula I and E is an electrophilic functional group
Figure imgf000057_0003
wherein R141 is as defined for formula I, R149 is hydrogen, Cι-C4alkyl, Cι-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy- Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and d-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cpdalkoxy,
Cι-C6haloalkoxy and -COR227, wherein R227 is as defined for formula I, and Xi is a leaving group such as, for example, halogen, e.g. fluorine, chlorine, bromine or iodine, or a sulfonate, e.g. -OTosyl (-OTs), -OMesyl (-OMs) or -OTriflate (-OTf), CH3(CH3O)N-, imidazolyl, triazolyl, -OR*, -SR4 or -N(R4)2, wherein R4 is Cι-C6alkyl, Cι-C6haloalkyl or phenyl, may also be prepared by means of base-catalysed alkylation or etherification of a compound of formula VII Q-OH (VII) with a compound of formula XVIIai, XVIIa2, XVIIa , XVI^ or XVIIa5
Figure imgf000058_0001
Figure imgf000058_0002
Figure imgf000058_0003
the radicals Q and E in the compounds of formulae VII and XVIIaj to XVIIa5 being as defined, R131 to Rι40 being as defined for formula I and L being a leaving group such as, for example, halogen, e.g. chlorine, bromine or iodine, acetate or sulfonate, e.g. mesylate (-OMs) or tosylate (-OTs).
A further possible method of preparing the desired intermediates of formula XV
Figure imgf000058_0004
wherein A and Q are as defined for formula I and E is an electrophilic functional group as already defined hereinbefore, is provided by the reaction of the compound of formula VIIi
Figure imgf000059_0001
with a compound of formula XVIIIai, XVIIIa2, XVIIIa3, XVIIIa4 or XVIIIa5
Figure imgf000059_0002
Figure imgf000059_0003
Ia5)
Figure imgf000059_0004
under the above-described reaction conditions of the nucleophilic aromatic substitution reaction, the radicals Q and Rj31 to Rι40 in the compounds of formulae VIIi and XVIIIai to XVIIIa5 being as defined for formula I and E being an electrophilic functional group
Figure imgf000059_0005
wherein Rι4] is as defined for formula I, R]49 is hydrogen, d-C4alkyl, Cι-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy- Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from C C6haloalkyl, -OH, Cι-C6alkoxy, Cι-C6haloalkoxy and -COR227, wherein R227 is as defined for formula I, Li is a leaving group such as, for example, halogen, e.g. fluorine (for Q = Q2 to Q8), chlorine, bromine or iodine, or a sulfonate, e.g. -OTs or -OMs, an alkylsulfonyl (for Q = Q2 to Q8), e.g. CH3SO2-, imidazolyl, triazolyl, -SCH3 or phenoxy, and M+ is an alkali metal ion, e.g. Na+.
The intermediates of formula XlXaibo, XIXa2bo, XLXa3bo, XIXa b0 or XIXa5bo
Figure imgf000060_0001
(XIXa2b0),
Figure imgf000060_0002
(XIXa4b0) or
Figure imgf000060_0003
wherein R2, m and R13ι to Rι40 are as defined for formula I and R3 is hydrogen or a protecting group for the alcohol function such as, for example, methoxymethyl (MOM), benzyl, benzoyl, acetyl, allyl, tetrahydropyranyl, tert-butyloxycarbonyl (BOC), benzyloxycarbonyl, trialkylsilyl, phenyl-dialkylsilyl or di-phenyl-alkylsilyl (T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Chemistry, Wiley 1999), may be prepared, for example, by coupling a compound of formula XXai, XXa , XXa3, XXa4 or XXa5
Figure imgf000061_0001
Figure imgf000061_0002
Figure imgf000061_0003
wherein R3 and Rι3ι to R1 0 are as defined, with a compound of formula III
Figure imgf000061_0004
wherein R2 and m are as defined and W is a leaving group such as, for example, halogen or trifluoromethanesulfonate (-OTf), in the presence of a palladium catalyst under Sonogashira reaction conditions (Reaction Scheme 1). The Sonogashira reaction has already been described in detail hereinbefore.
The intermediates of formula XXIa3b, XXIa b or XXIa5b
Figure imgf000062_0001
wherein B, R2, m and R131 to Rι36 are as defined for formula I, R3 is hydrogen or a protecting group for the alcohol function as defined hereinbefore and E4 is a bridging
member
Figure imgf000062_0002
wherein Rι33 and Rι35 to R]40 are as defined for formula I, maybe prepared, for example, by causing a compound of formula XXIIa3, XXIIa4 or XXIIa5
(XXI la4) or
Figure imgf000062_0003
(XXIIa5),
Figure imgf000062_0004
wherein R131 to Rι40 and R3 are as defined, to react with a compound of formula lib
Figure imgf000063_0001
wherein B, R and m are as defined, in the presence a) of a strong base or b) of zinc salts and a base in an inert organic solvent at temperatures from -100° to 50°C. That reaction has also been described in detail hereinbefore.
The intermediates of formula XXOIabi, XXIIIab2, XXIIIab3 or XXIIIab4
Figure imgf000063_0002
XIIIab ),
(XXIIIab3) or
Figure imgf000063_0003
(XXIIIabΛ
Figure imgf000063_0004
wherein A, R2, m and Rι43 to Rι 8 are as defined for formula I, it being possible for the alcohol function in group A to be protected by a protecting group for alcohols such as, for example, MOM, benzyl, benzoyl, acetyl, allyl, tetrahydropyranyl, tert- butyloxycarbonyl (BOC), benzyloxycarbonyl, trialkylsilyl, phenyl-dialkylsilyl or di- phenyl-alkylsilyl, and E] is a bridging member
Figure imgf000063_0005
wherein R141 is as defined for formula I and Rι4 is hydrogen, Cι-C4alkyl, Cι-C6haloalkyl, C2-C6alkenyl, C -C6haloalkenyl, C2-C6alkynyl, C -C6hydroxyalkyl, Cι-C6alkoxy-Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, Cι-C6alkoxy, Cι-C6haloalkoxy and -COR227, wherein R227 is as defined for formula I, may be prepared by causing a compound of formula XII
HA — C=CH (XII), wherein A is as defined, to react with a compound of formula IVbi, IVb2, IVb3 or IVb4
Figure imgf000064_0001
Figure imgf000064_0002
wherein R2, m and Rι43 to Rj48 are as defined and E is an electrophilic functional group
Figure imgf000064_0003
wherein Rj4ι and Rι49 are as defined and Xi is a leaving group such as, for example, halogen, e.g. fluorine, chlorine, bromine or iodine, or a sulfonate, e.g. -OTosyl (-OTs), -OMesyl (-OMs) or triflate (-OTf), CH3(CH30)N-, imidazolyl, triazolyl, -OR^ -SR4 or -N(R4)2, wherein R4 is Cι-C6alkyl, Cι-C6haloalkyl or phenyl, in the presence a) of a strong base or b) of zinc salts and a base in an inert, organic solvent at temperatures from -100° to 50°C, it being possible for the alcohol-protecting group to be removed and for the exposed hydroxyl function to be used for further reactions, e.g. nucleophilic aromatic substitution.
The intermediates of formula XXVa2b, XXVa3b, XXVjub or XXVa5b
Figure imgf000065_0001
wherein R2, B, Rι3ι to Rι38 and m are as defined for formula I, R3 is hydrogen or a protecting group for the alcohol function, e.g. MOM, benzyl, benzόyl, acetyl, allyl, tetrahydropyranyl, BOC or benzyloxycarbonyl, and E3 is a bridging member
Figure imgf000065_0002
,149 wherein Rι33, Rι35, Rι37 and R]39 are as defined for formula I and Rι49 is hydrogen, Cι-C alkyl, Cι-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6hydroxyalkyl, Cι-C6alkoxy-Cι-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by substituents selected from Cι-C6haloalkyl, -OH, d-C6alkoxy, Cι-C6haloalkoxy and -COR227, wherein R227 is as defined for formula I, may be prepared by causing a compound of formula lib
Figure imgf000066_0001
wherein R2, B and m are as defined, to react with a compound of formula XXIVa , XXIVa3, XXIVa4 or XXIVa5 (XXIVa3),
Figure imgf000066_0002
R, (XXIVa5),
Figure imgf000066_0003
wherein R3 and R131 to Rι38 are as defined and E is an electrophilic functional group
Figure imgf000066_0004
wherein Rι33, Rj 5, Rι37, Rι39 and Rι 9 are as defined and'Xj is a leaving group such as, for example, halogen, e.g. fluorine, chlorine, bromine or iodine, or sulfonate, e.g. para- toluenesulfonate (-OTs, tosylate), methanesulfonate (-OMs, mesylate) or trifluoromethanesulfonate (-OTf, triflate), or CH3(CH30)N-, imidazolyl, triazolyl, -OR4, -SRt or -N(R4)2, wherein R4 is Cι-C6alkyl, Cι-C6haloalkyl or phenyl, in the presence a) of a strong base or b) of zinc salts and a base in an inert, organic solvent at temperatures from -100° to 50°C.
The intermediates of formula XXIIIab2, XXIIIab3 or XXIIIab4
Figure imgf000067_0001
(XXIIIab3) or
Figure imgf000067_0002
(XXIHab4),
Figure imgf000067_0003
wherein A, R2, Rι45 to Rj 8 and m are as defined for formula I, it being possible for the alcohol function in group A to be protected by a protecting group for alcohols such as, for example, MOM, benzyl, benzoyl, acetyl, allyl, tetrahydropyranyl, tert- butyloxycarbonyl (BOC), benzyloxycarbonyl, trialkylsilyl, phenyl-dialkylsilyl or di- R 141/ R142 phenyl-alkylsilyl, and E2 is a bridging member __V , wherein R141, Rj42 and \ _
R143 OH
Rι43 are as defined for formula I, may be prepared by causing a compound of formula XII HA — C≡CH (XII), wherein A is as defined, to react with a compound of formula Vb2, Vb3 or Vb4
Figure imgf000068_0001
wherein R , m, Rj4ι to Rι 3, and Rι45 to R] 8 are as defined, in the presence a) of a strong base or b) of zinc salts and a base in an inert, organic solvent at temperatures from -100° to 50°C, it being possible for the alcohol-protecting group to be removed by means of suitable treatment and for the exposed hydroxyl function to be used for further reactions.
The intermediates of formula XXVa3b, XXVa4b or XXVa5b
Figure imgf000068_0002
wherein R2, B, Rι31 to Rι36 and m are as defined for formula I, R3 is hydrogen or a protecting group for the alcohol function such as, for example, MOM, benzyl, benzoyl, acetyl, allyl, tetrahydropyranyl, tert-butyloxycarbonyl (BOC), benzyloxycarbonyl, trialkylsilyl, phenyl-dialkylsilyl or di-phenyl-alkylsilyl, and E4 is a bridging member O.H R 133 OH R135 OH /R \ / \ or A / \ 135 R136 R137 R 138 R139 140 wherein Rι33 and Rι35 to Rι 0 are as defined for formula I, may be prepared by causing a compound of formula lib
Figure imgf000069_0001
wherein R2, B and m are as defined, to react with a compound of formula XXIIa3, XXIL^ or XXIIa5
(XXIIa4) or
Figure imgf000069_0002
wherein R131 to Rι40 and R3 are as defined, in the presence a) of a strong base or b) of zinc salts and a base in an inert, organic solvent at temperatures from -100° to 50°C.
The following applies to the individual reaction steps:
The reactions resulting in the compounds of formula I, Iabo, Iabi to Iab4 or Ia2b to Ia5b are advantageously carried out in aprotic, inert solvents. Such solvents are hydrocarbons, e.g. benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, e.g. dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, e.g. diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, e.g. acetonitrile or propionitrile, and amides, e.g. N,N-dimethylformamide, diethylformamide or N-methylpyrrolidinone. The reaction temperatures are preferably from -20°C to +120°C. The reactions are generally slightly exothermic and may usually be carried out at room temperature. In order to shorten the reaction time or else to initiate the reaction, brief heating up to the boiling point of the reaction mixture may be carried out, where appropriate. The reaction times may also be reduced by adding a few drops of base as reaction catalyst. Especially suitable bases are tertiary amines, e.g. trimethylamine, triethylamine, quinuclidine, 1,4- diazabicyclo[2.2.2]octane, l,5-diazabicyclo[4.3.0]non-5-ene or l,5-diazabicyclo[5.4.0]- Undec-7-ene. It is, however, also possible for inorganic bases such as hydrides, e.g. sodium or calcium hydride, hydroxides, e.g. sodium or potassium hydroxide, carbonates, e.g. sodium or potassium carbonate, or hydrogen carbonates, e.g. potassium or sodium hydrogen carbonate, to be used as bases.
The compounds of formula I, Iab0, Iabi to Iab4 or Ia2b to Ia5b may be isolated in conventional manner by concentration and/or evaporation of the solvent and purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.
The starting compounds of formulae lib, III, IVbi to TVb , Vb2 to Vb4, Vlai to VIa4, VIIi, VIII, IXaj to IXa5, Xai to Xa5, XIa3 to XIa5, Xlllai to XIIIa5, XlVai to XrVa5, XVI, XVIIaj to XVIIa5, XVIIIai to XVIIIa5, XXaj to XXa5, XXIIa3 to XXIIa5 and XXIVa2 to XXrVa5 used for preparation of the compounds of formula I, Iab0, Iabi to Iab or Ia b to Ia5b are for the most part known or they may be prepared in analogy to known methods. The starting compounds of formulae VII and XII are likewise known and in some cases are commercially available, or they can be prepared in analogy to known methods.
For the use according to the invention of the compounds of formula I, or of compositions comprising them, there come into consideration all methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques such as, for example, the controlled release of active ingredient. For that purpose a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If required, it is also possible to apply a coating (coated granules), which allows the active ingredient to be released in metered amounts over a specific period of time. The compounds of formula I may be used as herbicides in their unmodified form, that is to say as obtained in the synthesis, but they are preferably foπnulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The formulations, that is to say the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I, or at least one compound of formula I, and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredient(s) with the formulation adjuvants, for example solvents or solid carriers. Surface-active compounds (surfactants) may also be used in addition in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
Depending upon the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485. In addition, the surfactants conventionally employed in formulation technology, which are described, ter alia, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981, and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I- III, Chemical Publishing Co., New York, 1980-81, are also suitable for the preparation of the herbicidal compositions according to the invention.
The herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of herbicide, from 1 to 99.9 % by weight, especially from 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant. Whereas commercial products will preferably be in the form of concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
The compounds of formula I are generally applied to the plant or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.
The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non- selective weed control. The term "crops" is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic engineering techniques. The weeds to be controlled may be either monocotyledonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Panicum, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Euphorbia, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
The following Examples further illustrate the invention.
Preparation Examples: Example PI : Preparation of 4-(4-fluoro-2-methoxy-phenoxyVl-(3-chlorophenyl)-l- hydroxy-but-2-yήe
Figure imgf000073_0001
7.11 g (39.46 mmol) of 4-fluoro-2-methoxy-0-propargyl-phenol ether are dissolved in 70 ml of THF. 43.4 ml of lithium bis(trimethylsilyl)amide (1.1 equivalents) in hexane (IM solution) are then added dropwise at -65° to -70°C over the course of 10 minutes and stirring is carried out for a further 30 minutes at -70°C. With the aid of a syringe, 6.29 ml of 3-chlorobenzaldehyde (1.1 equivalents) are slowly added at -63°C and further stirring is carried out while the coolant becomes warmer. After 4 hours, aqueous ammonium chloride solution is added to the reaction mixture at -45 °C and the resulting mixture is partitioned between diethyl ether and ice-water. The organic phase that is separated off is washed with dilute brine solution and dried over sodium sulfate. After filtering, concentration under reduced pressure is carried out and the resulting residue is subjected to flash chromatography on a silica gel column (eluant: ethyl acetate/hexane 1/3). The desired title compound is obtained in a yield of 7.88 g (62.3 % of theory) in the form of brown-yellow crystals.
Example P2: Preparation of 4-(,4-fluoro-2-methoxy-phenoxy)-l-(3-chlorophenyl -l- fluoro-but-2-yne
Figure imgf000073_0002
0.59 g (1.839 mmol) of 4-(4-fluoro-2-methoxy-phenoxy)-l-(3-chlorophenyl)-l-hydroxy- but-2-yne (Example PI) is dissolved in 15 ml of dichloromethane and, at -65° to -70°C, 0.30 ml of diethylaminosulfur trifluoride ((C2H5)2NSF3, DAST, 95 %) is added. The reaction mixture is stirred for a further 45 minutes at -70°C, then ice-water is added and extraction with diethyl ether is carried out. The organic phase that is separated off is washed with dilute brine solution and dried over sodium sulfate; the desiccant is filtered off and the solvent is evaporated off under reduced pressure. The residue obtained is subjected to flash chromatography (eluant: ethyl acetate/hexane 1/8). The desired title compound is obtained in a yield of 0.12 g (20.3 % of theory) in the form of a yellow oil.
Example P3: Preparation of 4-(4-fluoro-2-methoxy-phenoxy -l-(3-phenyl-acetonitrile)- but-1-yne
Figure imgf000074_0001
Compound no. 1.013 509.2 mg (2.1 mmol) of 3-iodo-l-phenylacetonitrile are introduced into piperidine under an argon atmosphere and stirred for 30 minutes. Then 117.95 mg (0.102 mmol) of tetrakis(triphenylphosphine)palladium (Pd[(C6H5)3P] ) are added and stirred for 1 hour until a clear solution is formed. Then 400 mg (2.083 mmol) of 4-fluoro-2-methoxy-0-4- (but-l-ynyl)-phenol ether (Example P4) are dissolved in piperidine and, immediately afterwards, 34.10 mg (0.179 mmol) of copper(I) iodide are added in one portion. Stirring is carried out for a further 2.5 hours at 25°C. The reaction mixture is poured into 150 ml of ammonium chloride solution, stirred well and extracted three times with diethyl ether. The combined organic phases are washed with 2 portions each of ammonium chloride solution, water and brine and concentrated by evaporation under reduced pressure. The yellow-brown oil obtained is purified by silica gel chromatography (eluant: ethyl acetate/hexane 1/4). The desired target compound is obtained in the form of a yellow powder in a yield of 230 mg (35.7 % of theory) with a melting point of 69-71°C.
Example P4: Preparation of 4-fluoro-2-methoxy-0-4-(but-l-vnyl)-phenol ether
Figure imgf000074_0002
1.5 g (10.56 mmol) of 4-fluoro-2-methoxyphenol are introduced into 120 ml of dichloromethane and there are then added, with stirring, 4.5 g and 9.0 g (37.56 mmol) of polymer-bound triphenylphosphine (polymer-C6H P(C6H5)2, on copolymer of 98 % styrene and 2 % divinylbenzene) in 2 portions and then 1.4718 g (21 mmol) of 3-butyn- l-ol dissolved in a small amount of dichloromethane. Then 7.267 g (31.56 mmol) of azodicarboxylic acid diethyl ester (DEAD) are added in portions and the brown reaction mixture is stirred overnight at 25 °C. GC analysis shows a conversion of more than 66 %. For working up, 60 ml of trifluoroacetic acid are added to the reaction mixture and the mixture is stirred at 25°C for 1.5 hours. The reaction mixture is poured into 300 ml of ammonium chloride solution, stirred well and extracted three times with diethyl ether. The combined organic phases are washed with 2 portions each of ammonium chloride solution, water and brine and concentrated by evaporation under reduced pressure. The desired title compound is obtained in the form of a viscous oil in a crude yield of 810 mg (40 % of theory).
Example P5: Preparation of 5-("4-fluoro-2-methoxy-phenoxy -l-(3-phenylacetonitrile)- pent-1-vne
Figure imgf000075_0001
500 mg (3.52 mmol) of 4-fluoro-2-methoxyphenol are introduced into 40 ml of dichloromethane under a nitrogen atmosphere at 25°C and 300 mg (9.0 mmol) of polymer-bound triphenylphosphine are added. Then 1393 mg (7.0 mmol) of 5-(3-phenylacetonitrile)- pent-4-yn-l-ol (Example P6) dissolved in a small amount of dichloromethane are slowly added dropwise; then 1612 mg (7.0 mmol) of DEAD are added in portions and that reaction mixture is stirred overnight at 25°C. For working up of the reaction mixture, 20 ml of trifluoroacetic acid are added to the mixture, which is stirred for 1.5 hours at 25 °C. The reaction mixture is poured into 150 ml of ammonium chloride solution, stirred well and extracted three times with diethyl ether. The combined organic phases are washed with 2 portions each of ammonium chloride solution, water and brine and concentrated by evaporation under reduced pressure. The target compound is obtained in the form of a brown oil in a crude yield of 1.67 g. Purification by means of HPLC column chromatography (eluant: ethyl acetate/hexane 1/3 and ethyl acetate as gradient mobile phase over 14 minutes) yields 370 mg of the desired target compound in the form of a yellow oil. Example P6: Preparation of 5-(3-phenylacetonitrile)-pent-4-yn-l-ol
Figure imgf000076_0001
To a solvent mixture of 75 ml of toluene and 150 ml of n-butylamine under a nitrogen atmosphere there are added first 9.80 g (0.05 mol) of 3-bromo-phenylacetonitrile and then 701.9 mg (0.001 mol) of bis(triphenylphosphine)palladium dichloride
(PdCl2(PPh3)2) and 190.44 mg (0.001 mol) of copper(I) iodide at 20°C. Then, at 20°C, 8.42 g (0.10 mol) of 4-pentyn-l-ol, dissolved in a toluene/n-butylamine mixture, are slowly added dropwise, whereupon a yellow-brown clear solution is formed, which is heated at 100°C for 5 hours, with stirring. The reaction mixture is then concentrated completely under reduced pressure, the residue obtained is stirred in a mixture of 100 ml each of ethyl acetate and of water and the two phase-separated solvents are separated off from one another. The aqueous phase is extracted three times with ethyl acetate and the combined organic phases are dried over magnesium sulfate, filtered and concentrated by evaporation in vacuo. A brown oil is obtained in a crude yield of 14.01 g, which is purified by means of column chromatography (eluant: ethyl acetate/hexane 1/4 to 1/1 as gradient mobile phase). The desired title compound is obtained in the form of a brown oil in a yield of 5.95 g.
Example P7: Preparation of l-chloro-4-(4-chlorophenyl -but-3-yn-2-one (Helv. Chim. Acta 85, 3052-3077 (2002) + CI-C-CH2CI -*"
Figure imgf000076_0003
Figure imgf000076_0002
To 1.26 g (1.3 equivalents) of aluminium trichloride (A1C13), for the most part dissolved in 20 ml of dichloromethane there are added dropwise, at -10°C, with cooling in an ice/ethanol mixture, a solution of 1.50 g (1 equivalent, 7.185 mmol) of l-(4- chlorophenyl)-2-(trimethylsilyl)acetylene, 0.58 ml (1 equivalent) of chloroacetyl chloride and 10 ml of dichloromethane over 20 minutes, the reaction mixture becoming a violet- brown colour. Further stirring is then carried out while the coolant mixture slowly warms up to -2°C (internal temperature), that is to say until TLC monitoring indicates that conversion is complete (about 45 minutes). Then the reaction mixture, having warmed up to — 2°C, is cautiously quenched by adding small pieces of ice, and partitioning between diethyl ether and aqueous solution is carried out. The separated organic phase is washed with brine and dried over sodium sulfate. After evaporating off the solvent under reduced pressure, 2.97 g of a solid brown residue are obtained. Purification of that residue is carried out by means of silica gel chromatography (eluant: ethyl acetate/hexane 1:10). The desired title compound is obtained in a yield of 1.1 g (71.9 % of theory) in the form of a yellow-brown solid having a purity of > 95 %.
Example P8: Preparation of 4-(4-fluoro-2-methoxy-phenoxy -l-(3- cyanomethylphenyl)but-2-yn- 1 -one (compound no. 3.075)
Figure imgf000077_0001
To a solution of 0.32 g (0.915 mmol) of 4-(4-fluoro-2-methoxy-phenoxy)-l-(3-_ cyanomethylphenyl)-l-hydroxy-but-2-yne (compound no. 3.089) in 15 ml of ethyl acetate there is added 0.77 g (3 equivalents) of o-iodoxybenzoic acid (IBX; see Organic Letters 4(17), 3001-3003 (2002)) and stirring is carried out for 3.5 hours at 90°C. TLC monitoring shows conversion is complete. The reaction mixture is cooled in an ice bath and the precipitated solid is filtered off. The filtrate is washed with dilute sodium hydrogen carbonate solution and then with brine, dried over sodium sulfate and concentrated under reduced pressure. 0.31 g of a brown- yellow resin is obtained as the crude product, which is purified by means of silica gel chromatography (eluant: ethyl acetate/hexane 1/4). 0.20 g (67.6 % of theory) of the desired title compound is obtained in the form of a yellow oil. MS (ESI): m/z = 322 [M-H]'.
It is also possible for the preferred compounds listed in the following Tables to be obtained in a manner analogous to that described in Examples PI to P8 or by the methods described in the references indicated. In the Table A the compounds prepared from Table 1-3 are compiled with physico-chemical data and technical aspects, respectively. Table 1: Compounds of formula Ia2b0Qι:
Figure imgf000078_0001
Cmp. R Ri R2 Rl31 R132 R133 R134 no.
1.001 CH3 H (n=0) H (m=0) H H H H
1.002 CH3 4-F H (m=0) H H H H
1.003 CH3 4-Cl H (m=0) H H H H
1.004 CH3 4-Br H (m=0) H H H H
1.005 CH3 4-1 H (m=0) H H H H
1.006 CH3 4-CF3 H (m=0) H H H H
1.007 CH3 4-CN H (m=0) H H H H
1.008 CH3 4-CHO H (m=0) H H H H
1.009 CH3 4-CH=NOCH3 H (m-0) H H H H
1.010 CH3 4-CH3 H (m=0) H H H H
1.011 CH3 4-CH=CCl2 H (m=0) H H H H
1.012 CH3 H (n=0) 3-CH2CN H H H H
1.013 CH3 4-F 3-CH2CN H H H H
1.014 CH3 4-Cl 3-CH2CN H H H H
1.015 CH3 4-Br 3-CH2CN H H H H
1.016 CH3 4-1 3-CH2CN H H H H
1.017 CH3 4-CF3 3-CH2CN H H H H
1.018 CH3 4-CN 3-CH2CN H H H H
1.019 CH3 4-CHO 3-CH2CN H H H H Cmp. R Ri R2 Rl31 Rl32 Rl33 R134 no.
1.020 CH3 4-CH=NOCH3 3-CH2CN H H H H
1.021 CH3 4-CH3 3-CH2CN H H H H
1.022 CH3 4-CH=CCl2 3-CH2CN H H H H
1.023 CH3 H (n=0) 3-CH2CN, 4-F H H H H
1.024 CH3 4-F 3-CH2CN, 4-F H H H H
1.025 CH3 4-Br 3-CH2CN, 4-F H H H H
1.026 CH3 4-CN 3-CH2CN, 4-F H H H H
1.027 CH3 4-CF3 3-CH2CN, 4-F H H H H
1.028 CH3 4-CH=NOCH3 3-CH2CN, 4-F H H H H
1.029 CH3 H (n=0) ' 3-'CH2CN, 6-F H H H H
1.030 CH3 4-F 3-CH2CN, 6-F H H H H
1.031 CH3 4-Br 3-CH2CN, 6-F H H H H
1.032 CH3 4-CN 3-CH2CN, 6-F H H . H H
1.033 CH3 4-CF3 3-CH2CN, 6-F H H H H
1.034 CH3 4-CH=NOCH3 ' 3-CH2CN, 6-F H H H H
1.035 CH3 H (n=0) 3-CH2CN, 4-F, 6-F H H H H
1.036 CH3 4-F 3-CH2CN, 4-F, 6-F H H H H
1.037 CH3 4-Br .3-CH2CN, 4-F, 6-F H H H H
1.038 CH3 4-CN 3-CH2CN, 4-F, 6-F H H H H
1.039 CH3 4-CF3 3-CH2CN, 4-F, 6-F H H H H
1.040 CH3 4-CH=NOCH3 3-CH2CN, 4-F, 6-F H H H H
1.041 CH3 4-F 3-CH2CN, 4-Cl, 6-F H H H H
1.042 CH3 4-1 3-CH2CN, 4-Cl, 6-F H H H H
1.043 CH3 4-CN 3-CH2CN, 4-Cl, 6-F H H H H
1.044 CH3 4-CF3 3-CH2CN, 4-Cl, 6-F H H H H
1.045 CH3 4-CH=NOCH3 3-CH2CN, 4-Cl, 6-F H H H H
1.046 CH3 H (n=0) 3-CH(CH3)CN H H H H
1.047 CH3 4-F 3-CH(CH3)CN H H H H
1.048 CH3 4-Cl 3-CH(CH3)CN H H H H
1.049 CH3 4-Br 3-CH(CH3)CN H H H H Cmp. R Ri R2 R131 Rl32 R133 R134 no.
1.050 CH3 4-1 3-CH(CH3)CN H H H H
1.051 CH3 4-CF3 3-CH(CH3)CN H H H H
1.052 CH3 4-CN 3-CH(CH3)CN H H H H
1.053 CH3 4-CHO 3-CH(CH3)CN H H H H
1.054 CH3 4-CH=NOCH3 3-CH(CH3)CN H H H H
1.055 CH3 4-CH3 3-CH(CH3)CN H H H H
1.056 CH3 4-CH=CCl2 3-CH(CH3)CN H H H H
1.057 CH3 H (n=0) 3-CHF2 H H H H
1.058 CH3 4-F 3-CHF2 H H H H
1.059 CH3 4-Cl 3-CHF2 H H H H
1.060 CH3 4-Br 3-CHF2 H H H H
1.061 CH3 4-1 3-CHF2 H H H H
1.062 CH3 4-CF3 3-CHF2 H H H H
1.063 CH3 4-CN 3-CHF2 H H H H
1.064 CH3 4-CHO 3-CHF2 H H H H
1.065 CH3 4-CH=NOCH3 3-CHF2 H H H H
1.066 CH3 4-CH3 3-CHF2 H H H H
1.067 CH3 4-CH=CCl2 3-CHF2 H H H H
1.068 CH3 H (n=0) 3-CHF2, 4-F . H H H H
1.069 CH3 4-F 3-CHF2, 4-F H H H H
1.070 CH3 4-Br 3-CHF2, 4-F H H H H
1.071 CH3 4-CN 3-CHF2, 4-F H H H H •
1.072 CH3 4-CF3 3-CHF2, 4-F H H H H
1.073 CH3 4-CH=NOCH3 3-CHF2, 4-F H H H H
1.074 CH3 H (n=0) 3-CH2CN H H =0
1.075 CH3 4-F 3-CH2CN H H -0
1.076 CH3 4-Br 3-CH2CN H H =0
1.077 CH3 4-CH3 3-CH2CN H H =0
1.078 CH3 4-CN 3-CH2CN H H =0
1.079 CH3 4-CF3 3-CH2CN H H =0
Figure imgf000081_0001
Cmp. R Ri R2 Rl31 Rl32 R133 134 no.
1.110 CH3 H (n=0) 3-CH2CN H H OCH3 H
1.111 CH3 4-F 3-CH2CN H H OCH3 H
1.112 CH3 4-Br 3-CH2CN H H OCH3 H
1.113 CH3 4-CH3 3-CH2CN H H OCH3 H
1.114 CH3 4-CN 3-CH2CN H H OCH3 H
1.115 CH3 4-CF3 3-CH2CN H H OCH3 H
1.116 CH3 4-CH=NOCH3 3-CH2CN H H OCH3 H
1.117 CH3 H (n=0) 3-CH2CN H H CH3 H
1.118 CH3 4-F 3-CH2CN H H CH3 H
1.119 CH3 4-Br 3-CH2CN H H CH3 H
1.120 CH3 4-CH3 3-CH2CN H H CH3 H
1.121 CH3 4-CN 3-CH2CN H H CH3 H
1.122 CH3 4-CF3 3-CH2CN H H CH3 H
1.123 CH3 4-CH=NOCH3 3-CH2CN H H CH3 H
1.124 CH3 H (n=0) 3-CH2CN H H CH3 CH3
1.125 CH3 4-F 3-CH2CN H H CH3 CH3
1.126 CH3 4-Br 3-CH2CN H H CH3 CH3
1.127 CH3 4-CH3 3-CH2CN H H CH3 CH3
1.128 CH3 4-CN 3-CH2CN H H CH3 CH3
1.129 CH3 4-CF3 3-CH2CN H H CH3 CH3
1.130 CH3 4-CH=NOCH3 3-CH2CN H H CH3 CH3
1.131 CH3 H (n=0) 3-CH2CN H H C2alkylene
1.132 CH3 4-F 3-CH2CN H H C2alkylene
1.133 CH3 4-Br 3-CH2CN H H C2alkylene
1.134 CH3 4-CH3 3-CH2CN H H C2alkylene
1.135 CH3 4-CN 3-CH2CN H H C2alkylene
1.136 CH3 4-CF3 3-CH2CN H H C2alkylene
1.137 CH3 4-CH=NOCH3 3-CH2CN H H C2alkylene
1.138 CH3 H (n=0) 3-CHF2 H H OH H
1.139 CH3 4-F 3-CHF2 H H OH H Cmp. R Ri R2 Rl31 Rl32 Rl33 R134 no. 1.140 CH3 4-CN 3-CHF2 H H OH H
1.141 CH3 H (n=0) 3-CH(CH3)CN H H OH H-
1.142 CH3 4-F 3-CH(CH3)CN H H OH H
1.143 CH3 4-CN 3-CH(CH3)CN H H OH H
1.144 CH3 H (n=0) 3-CH2CN, 4-F H H OH H
1.145 CH3 4-F 3-CH2CN, 4-F H H OH H
1.146 CH3 4-CN 3-CH2CN, 4-F H H OH H
1.147 CH3 H (n=0) 3-CHF2 H H F H
1.148 CH3 4-F 3-CHF2 H H F H
1.149 CH3 4-CN 3-CHF2 H H F H
1.150 CH3 H (n=0) 3-CH(CH3)CN H H F H
1.151 CH3 4-F 3-CH(CH3)CN H H F H
1.152 CH3 4-CN 3-CH(CH3)CN H H F H
1.153 CH3 H (n=0) 3-CH2CN, 4-F H H F H
1.154 CH3 4-F 3-CH2CN, 4-F H H F H
1.155 CH3 4-CN 3-CH2CN, 4-F H H F H
1.156 CH3 H (n=0) 3-CHF2 H H F F
1.157 CH3 4-F 3-CHF2 H H F F
1.158 CH3 4-CN ' 3-CHF2 H H F F
1.159 CH3 H (n=0) 3-CH(CH3)CN H H F F
1.160 CH3 4-F 3-CH(CH3)CN H H F F
1.161 CH3 4-CN 3-CH(CH3)CN H H F F
1.162 CH3 4-CH=NOCH3 3-CH(CH3)CN H H F F
1.163 CH3 H (n=0) 3-CH2CN, 4-F H H F F
1.164 CH3 4-F 3-CH2CN, 4-F H H F F
1.165 CH3 4-CN 3-CH2CN; 4-F H H F F
1.166 CH3 H (n=0) 3-CHF2 H H CH3 F
1.167 CH3 4-F 3-CHF2 H H CH3 F
1.168 CH3 4-CN 3-CHF2 H H CH3 F CH3 H (n=0) 3-CH(CH3)CN H H CH3 F
1 169 Cmp. R Ri R2 Rl31 Rl32 R133 Rl34 no.
1.170 CH3 4-F 3-CH(CH3)CN H H CH3 F
1.171 CH3 4-CN 3-CH(CH3)CN H H CH3 F
1.172 CH3 4-CH=NOCH3 3-CH(CH3)CN H H CH3 F
1.173 CH3 H (n=0) 3-CH2CN, 4-F H H CH3 F
1.174 CH3 4-F 3-CH2CN, 4-F H H CH3 F
1.175 CH3 4-CN 3-CH2CN, 4-F H H CH3 F
1.176 CH3 H (n=0) 3-CHF2 H H CH3 CH3
1.177 CH3 4-F 3-CHF2 H H CH3 CH3
1.178 CH3 4-CN 3-CHF2 H H CH3 CH3
1.179 CH3 H (n=0) 3-CH(CH3)CN H H CH3 CH3
1.180 CH3 4-F 3-CH(CH3)CN H H CH3 CH3
1.181 CH3 4-CN 3-CH(CH3)CN H H CH3 CH3
1.182 CH3 H (n=0) 3-CH2CN, 4-F H H CH3 CH3
1.183 CH3 4-F 3-CH2CN, 4-F H H CH3 CH3
1.184 CH3 4-CN 3-CH2CN, 4-F H H CH3 CH3
1.185 CH3 H (n=0) 3-CHF2 H H OCH3 H
1.186 CH3 4-F 3-CHF2 H H OCH3 H
1.187 CH3 4-CN 3-CHF2 H H OCH3 H
1.188 CH3 H (n=0) 3-CH(CH3)CN H H OCH3 H
1.189 CH3 4-F 3-CH(CH3)CN H H OCH3 H
1.190 CH3 4-CN 3-CH(CH3)CN H H OCH3 H
1.191 CH3 H (n=0) 3-CH2CN, 4-F H H OCH3 H
1.192 CH3 4-F 3-CH2CN, 4-F H H OCH3 H
1.193 CH3 4-CN 3-CH2CN, 4-F H H OCH3 H
1.194 CH3 H (n=0) 3-CH2CN H CH3 H H
1.195 CH3 4-F 3-CH2CN H CH3 H H
1.196 CH3 4-Br 3-CH2CN H CH3 H H
1.197 CH3 4-CH3 3-CH2CN H CH3 H H
1.198 CH3 4-CN 3-CH2CN H CH3 H H
1.199 CH3 4-CF3 3-CH2CN H CH3 H H Cmp. R Ri R2 R131 Rl32 Rl33 Rl34 no.
1.200 CH3 4-CH=NOCH3 3-CH2CN H CH3 H H
1.201 CH3 H (n=0) 3-CH2CN H CH3 CH3 H
1.202 CH3 4-F 3-CHaCN H CH3 CH3 H
1.203 CH3 4-Br 3-CH2CN H CH3 CH3 H
1.204 CH3 4-CH3 3-CH2CN H CH3 CH3 H
1.205 CK3 4-CN 3-CΗ2CΗ H CH3 CH3 H
1.206 CH3 4-CF3 3-CH2CN H CH3 CH3 H
1.207 CH3 4-CH=NOCH3 3-CH2CN H CH3 CH3 H
1.208 CH3 H (n=0) 3-CH2CN H CH3 CH3 CH3
1.209 CH3 4-F 3-CH2CN H CH3 CH3 CH3
1.210 CH3 4-Br 3-CH2CN H CH3 CH3 CH3
1.211 CH3 4-CH3 3-CH2CN H CH3 CH3 CH3
1.212 CH3 4-CN 3-CH2CN H CH3 CH3 CH3
1.213 CH3 4-CF3 3-CH2CN H CH3 CH3 CH3
1.214 CH3 4-CH=NOCH3 3-CH2CN H CH3 CH3 CH3
1.215 CH3 H (n=0) 3-CH2CN H CH3 F F
1.216 CH3 4-F 3-CH2CN H CH3 F F
1.217 CH3 4-Br 3-CH2CN H CH3 F F
1.218 CH3 4-CH3 3-CH2CN H CH3 F F
1.219 CH3 4-CN 3-CH2CN H CH3 F F
1.220 CH3 4-CF3 3-CH2CN H CH3 F F
1.221 CH3 4-CH=NOCH3 3-CH2CN H CH3 F F
1.222 CH3 H (n=0) 3-Cl H H H H
1.223 CH3 4-F 3-Cl H H H H
1.224 CH3 4-1 3-Cl H H H H
1.225 CH3 4-CF3 3-Cl H H H H
1.226 CH3 4-CN 3-Cl H H H H
1.227 CH3 4-CH3 3-Cl H H H H
1.228 CH3 H (n=0) 4-Cl H H H H
1.229 CH3 4-F 4-Cl H H H H
Figure imgf000086_0001
Cmp. R Ri ' R2 Rl31 Rl32 R133 R134 no. 1.260 H 4-CN 3-CH2CN H H CH3 H 1.261 CH3 4-F 4-Cl H H -0 1.262 CH3 4-F 3-CH2OC(0)C(CH3)3 H H -0 1.263 CH3 4-F 3-CH2CN H H OCH3 CH3 1.264 CH3 4-F 3-CH2CN H H H OC(0 )C(CH 3)3
Table 2: Compounds of formula Ia2bnQ2 : 4 3
Figure imgf000087_0001
(Ia2b0Q2)
Cmp. Ri R2 Rl31 Rl32 R133 R134 no.
2.001 H (n=0) ' H (m=0) H H H H
2.002 3-F H (m=0) H H H H
2.003 3-Cl H (m=0) H H ■ H H
2.004 3-F, 5-F H (m=0) H H H H
2.005 3-F, 5-C1 H (m=0) H H H H
2.006 3-CF3 H (m=0) H H H H
2.007 3-F, 5-CF3 H (m=0) H H H H
2.008 3-Cl, 5-CF3 H (m=0) H H H H
2.009 5-CN H (m=0) H H H H Cmp. R, R2 Rl31 Rl32 R133 •R134 no.
2.010 3-F, 5-CN H (m=0) H H H H
2.011 3-OCH3 H (m=0) H H H H
2.012 3-OCH3, 5-F H (m=0) . H H H H
2.013 3-OCH3, 5-C1 H (m=0) H H H H
2.014 3-OCH3, 5-CF3 H (m=0) H H H H
2.015 3-OCH3, 5-CN H (m=0) H H H H
2.016 5-N02 . H (m=0) H H H H
2.017 3-Cl, 5-N02 H (m=0) H H H H
2.018 H (n-0) 3-CH2CN H H H H
2.019 3-F 3-CH2CN H H H H
2.020 3-Cl 3-CH2CN H H H H
2.021 3-F, 5-F 3-CH2CN H H H H
2.022 3-F, 5-C1 3-CH2CN H H H H
2.023 5-CF3 3-CH2CN H H H H
2.024 3-F, 5-CF3 3-CH2CN H H H H
2.025 3-Cl, 5-CF3 3-CH2CN H H H H
2.026 5-CN 3-CH2CN H H H H
2.027 3-F, 5-CN 3-CH2CN H H H H
2.028 3-OCH3 3-CH2CN H H H H
2.029 3-OCH3, 5-F 3-CH2CN H H H H
2.030 3-OCH3, 5-C1 3-CH2CN H H H H
2.031 3-OCH3, 5-CF3 3-CH2CN H H H H
2.032 3-OCH3, 5-CN 3-CH2CN H H H H
2.033 5-NO2 3-CH2CN H H H H
2.034 3-Cl, 5-NO2 3-CH2CN H H H H
2.035 3-Cl, 5-NH2 3-CH2CN H H H H
2.036 H (n=0) 3-CH2CN, 4-F H H H H
2.037 3-F 3-CH2CN, 4-F H H H H
2.038 3-Cl 3-CH2CN, 4-F H H H H
2.039 3-F, 5-F 3-CH2CN, 4-F H H H H Cmp. Ri R2 Rl31 Rl32 R133 R134 no.
2.040 3-F, 5-C1 3-CH2CN, 4-F H H H H
2.041 5-CF3 3-CH2CN, 4-F H H H H
2.042 3-F, 5-CF3 3-CH2CN, 4-F H H H H
2.043 3-Cl, 5-CF3 3-CH2CN, 4-F H H H H
2.044 5-CN 3-CH2CN, 4-F H H H H
2.045 3-F, 5-CN 3-CH2CN, 4-F H H H H
2.046 3-OCH3 3-CH2CN, 4-F H H H H
2.047 3-OCH3, 5-F 3-CH2CN, 4-F H H H H
2.048 3-OCH3, 5-C1 3-CH2CN, 4-F H H H H
2.049 3-OCH3, 5-CF3 3-CH2CN, 4-F H H H H
2.050 3-OCH3, 5-CN 3-CH2CN, 4-F H H H H
2.051 5-NO2 3-CH2CN, 4-F H H H H
2.052 3-Cl, 5-NO2 3-CH2CN, 4-F H H H H
2.053 3-F 3-CH2CN, 6-F H H H H
2.054 3-F, 5-F 3-CH2CN, 6-F H H H H
2.055 3-F, 5-C1 3-CH2CN, 6-F H H H H
2.056 5-CF3 3-CH2CN, 6-F H H H H
2.057 3-F, 5-CF3 3-CH2CN, 6-F H H H H
2.058 5-CN 3-CH2CN, 6-F H H H H
2.059 3-OCH3 3-CH2CN, 6-F H H H H
2.060 3-OCH3, 5-F 3-CH2CN, 6-F H H H H
2.061 3-OCH3, 5-C1 3-CH2CN, 6-F H H H H
2.062 3-OCH3, 5-CF3 3-CH2CN, 6-F H H H H
2.063 3-OCH3, 5-CN 3-CH2CN, 6-F H H H H
2.064 3-F 3-CH2CN, 4-F, 6-F H H H H
2.065 3-F, 5-F 3-CH2CN, 4-F, 6-F H H H - H
2.066 3-F, 5-C1 3-CH2CN, 4-F, 6-F H H H H
2.067 5-CF3 3-CH2CN, 4-F, 6-F H H H H
2.068 3-F, 5-CF3 3-CH2CN, 4-F, 6-F H H H H
2.069 5-CN 3-CH2CN, 4-F, 6-F H H H H _ .
Cmp. Ri R2 Rl31 Rl32 R133 R134 no.
2.070 3-OCH3 3-CH2CN, 4-F, 6-F H H H H
2.071 3-OCH3, 5-F 3-CH2CN, 4-F, 6-F H H H H
2.072 3-OCH3, 5-C1 3-CH2CN, 4-F, 6-F H H H H
2.073 3-OCTΪ3, 5-CF3 3-CH2CN, 4-F, 6-F H H H H
2.074 3-OCH3, 5-CN 3-CH2CN, 4-F, 6-F H H H H
2.075 3-F 3-CH2CN, 4-Cl, 6-F H H H H
2.076 3-F, 5-F . 3-CH2CN, 4-Cl, 6-F H H H H
2.077 3-F, 5-C1 3-CH2CN, 4-Cl, 6-F H H H H
2.078 5-CF3 3-CH2CN, 4-Cl, 6-F H H H H
2.079 3-F, 5-CF3 3-CH2CN, 4-Cl, 6-F H H H H
2.080 5-CN 3-CH2CN, 4-Cl, 6-F H H H H
2.081 3-OCH3 3-CH2CN, 4-Cl, 6-F H H H , H
2.082 3-OCH3, 5-F 3-CH2CN, 4-Cl, 6-F H Ή H H
2.083 3-OCH3, 5-C1 3-CH2CN, 4-Cl, 6-F H H H H
2.084 3-OCH3, 5-CF3 3-CH2CN, 4-Cl, 6-F H H H H
2.085 3-OCH3, 5-CN 3-CH2CN, 4-Cl, 6-F H H H H
2.086 3-F 3-CH(CH3)CN H H H H
2.087 3-F, 5-F 3-CH(CH3)CN H H H H
2.088 3-F, 5-C1 3-CH(CH3)CN H H H H
2.089 5-CF3 3-CH(CH3)CN H H H H
2.090 3-F, 5-CF3 3-CH(CH3)CN H H H H
2.091 5-CN 3-CH(CH3)CN H H H H
2.092 3-OCH3 3-CH(CH3)CN H H H H
2.093 3-OCH3, 5-F 3-CH(CH3)CN H H • H H
2.094 3-OCH3, 5-C1 3-CH(CH3)CN H H H H
2.095 3-OCH3, 5-CF3 3-CH(CH3)CN H H H H
2.096 3-OCH3, 5-CN 3-CH(CH3)CN H H H H
2.097 3-F 3-CHF2 H H H H
2.098 3-F, 5-F 3-CHF2 H H H H
2.099 3-F, 5-C1 3-CHF2 H H H H Cmp. Ri R2 R131 Rl32 R133 R134 no.
2.100 5-CF3 3-CHF2 H H H H
2.101 3-F, 5-CF3 3-CHF2 H H H H
2.102 5-CN 3-CHF2 H H H H
2.103 3-OCH3 3-CHF2 H H H H
2.104 3-OCH3, 5-F 3-CHF2 H H H H
2.105 3-OCH3, 5-C1 3-CHF2 H H H H
2.106 3-OCH3, 5-CF3 3-CHF2 H H H H
2.107 3-OCH3, 5-CN 3-CHF2 H H H H
2.108 3-F, 5-F 3-CHF2, 4-F H H H H
2.109 5-CF3 3-CHF2, 4-F H H H H
2.110 3-F, 5-CF3 3-CHF2, 4-F H H H H
2.111 3-OCH3 3-CHF2, 4-F H H H H
2.112 3-OCH3, 5-C1 3-CHF2, 4-F H H H H
2.113 3-OCH3, 5-CF3 3-CHF2, 4-F H H H H
2.114 3-F 3-CH2CN H H =0
2.115 3-F, 5-F 3-CH2CN H H =0
2.116 3-F, 5-C1 3-CH2CN H H =0
2.117 5-CF3 3-CH2CN H H =0
2.118 3-F, 5-CF3 3-CH2CN H H =0
2.119 5-CN 3-CH2CN H H =0
2.120 3-OCH3 3-CH2CN H H =0
2.121 3-OCH3, 5-F 3-CH2CN H H =0
2.122 3-OCH3, 5-C1 3-CH2CN H H =0
2.123 3-OCH3, 5-CF3 3-CH2CN H H =0
2.124 3-OCH3, 5-CN 3-CH2CN H H =0
2.125 3-F 3-CHF2 H H =0
2.126 3-F, 5-F 3-CHF2 H H =O
2.127 3-F, 5-C1 3-CHF2 H H =O
2.128 5-CF3 3-CHF2 H H =O
2.129 3-F, 5-CF3 3-CHF2 H H =O Cmp. Ri R2 Rl31 Rl32 R133 R134 no.
2.130 5-CN 3-CHF2 H H =0
2.131 3-OCH3 3-CHF2 H H =0
2.132 3-OCH3, 5-F 3-CHF2 H H =0
'2.133 3-OCH3, 5-C1 3-CHF2 H H =0
2.134 3-OCH3, 5-CF3 3-CHF2 H H =0
2.135 3-OCH3, 5-CN 3-CHF2 H H =0
2.136 3-F 3-CH2CN H H OH H
2.137 3-F, 5-F 3-CH2CN H H OH H
2.138 3-F, 5-C1 3-CH2CN H H OH H
2.139 5-CF3 3-CH2CN H H OH H
2.140 3-F, 5-CF3 3-CH2CN H H OH H
2.141 5-CN 3-CH2CN H H OH H
2.142 3-OCH3 3-CH2CN H H OH H
2.143 3-OCH3, 5-F 3-CH2CN H H OH H
2.144 3-OCH3, 5-C1 3-CH2CN H H OH H
2.145 3-OCH3, 5-CF3 3-CH2CN H H OH H
2.146 3-OCH3, 5-CN 3-CH2CN H H OH H
2.147 3-F 3-CH2CN H H F H
2.148 3-F, 5-F 3-CH2CN H H F H
2.149 3-F, 5-C1 3-CH2CN H H F H
2.150 5-CF3 3-CH2CN H H F H
2.151 3-F, 5-CF3 3-CH2CN H H F H
2.152 5-CN 3-CH2CN H H F H
2.153 3-OCH3 3-CH2CN H H F H
2.154 3-OCH3, 5-F 3-CH2CN H H F H
2.155 3-OCH3, 5-C1 . 3-CH2CN H H F H
2.156 3-OCH3, 5-CF3 3-CH2CN H H F H
2.157 3-OCH3, 5-CN 3-CH2CN H H F H
2.158 3-F 3-CH2CN H H F F
2.159 3-F, 5-F 3-CH2CN H H F F Cmp. Ri R2 Rl31 Rl32 R133 Rl34 no. 2.160 3-F, 5-C1 3-CH2CN H H F F
2.161 5-CF3 3-CH2CN H H F F
2.162 3-F, 5-CF3 3-CH2CN H H F F
2.163 5-CN 3-CH2CN H H F F
2.164 3-OCH3 3-CH2CN H H F F
2.165 3-OCH3, 5-F 3-CH2CN H H F F
■2.166 3-OCH3, 5-C1 3-CH2CN H H . F F
2.167 3-OCH3, 5-CF3 3-CH2CN. H H F F
2.168 3-OCH3, 5-CN 3-CH2CN H H F F
2.169 3-F, 5-F 3-CH2CN H H OCH3 H
2.170 5-CF3 3-CH2CN H H OCH3 H
2.171 3-F, 5-CF3 3-CH2CN H H OCH3 H
2.172 3-OCH3 3-CH2CN H H OCH3 H
2.173 3-OCH3, 5-C1 3-CH2CN • H H OCH3 H
2.174 3-OCH3, 5-CF3 3-CH2CN H H OCH3 H
2.175 3-F 3-CH2CN H H CH3 H
2.176 3-F, 5-F . 3-CH2CN H H CH3 H
2.177 3-F, 5-C1 3-CH2CN H H CH3 H
2.178 5-CF3 3-CH2CN H H CH3 H
2.179 3-F, 5-CF3 3-CH2CN H H CH3 H
2.180 5-CN 3-CH2CN H H CH3 H
2.181 3-OCH3 3-CH2CN H H CH3 H
2.182 3-OCH3, 5-F 3-CH2CN H H CH3 H
2.183 3-OCH3, 5-C1 3-CH2CN • H H CH3 H
2.184 3-OCH3, 5-CF3 3-CH2CN H H CH3 H
2.185 3-OCH3, 5-CN 3-CH2CN H H . CH3 H
2.186 3-F 3-CH2CN H H CH3 CH3
2.187 3-F, 5-F 3-CH2CN H H CH3 CH3
2.188 3-F, 5-C1 3-CH2CN H H CH3 CH3
2.189 5-CF3 3-CH2CN H H CH3 CH3 Cmp. Ri R2 Rl31 Rl32 R133 R134 no.
2.190 3-F, 5-CF3 3-CH2CN H H CH3 CH3
2.191 5-CN 3-CH2CN H H CH3 CH3
2.192 3-OCH3 3-CH2CN H H CH3 CH3
2.193 3-OCH3, 5-F 3-CH2CN H H CH3 CH3
2.194 3-OCH3, 5-C1 3-CH2CN H H CH3 CH3
2.195 3-OCH3, 5-CF3 3-CH2CN H H CH3 CH3
2.196 3-OCH3, 5-CN 3-CH2CN H H CH3 CH3
2.197 3-F 3-CH2CN H H C2alkylene
2.198 3-F, 5-F 3-CH2CN H H C2alkylene
2.199 3-F, 5-C1 3-CH2CN H H C2alkylene
2.200 5-CF3 3-CH2CN H H C2alkylene
2.201 3-F, 5-CF3 3-CH2CN H H C2alkylene
2.202 5-CN 3-CH2CN H H C alkylene
2.203 3-OCH3 3-CH2CN H H C2alkylene
2.204 3-OCH3, 5-F 3-CH2CN H H C alkylene
2.205 3-OCH3, 5-C1 3-CH2CN H H C2alkylene
2.206 3-OCH3, 5-CF3 3-CH2CN H H C2alkylene
2.207 3-OCH3, 5-CN 3-CH2CN H H C2alkylene
2.208 3-F, 5-F 3-CHF2 H H OH H
2.209 5-CF3 3-CHF2 H H OH H
2.210 3-F, 5-CF3 3-CHF2 H H OH H
2.211 3-OCH3 3-CHF2 H H OH H
2.212 3-OCH3, 5-C1 3-CHF2 H H OH H
2.213 3-OCH3, 5-CF3 3-CHF2 H H OH H
2.214 3-F, 5-F 3-CH(CH3)CN H H OH H
2.215 5-CF3 3-CH(CH3)CN H H OH H
2.216 3-F, 5-CF3 3-CH(CH3)CN H H OH H
2.217 3-OCH3 3-CH(CH3)CN H H OH H
2.218 3-OCH3, 5-C1 3-CH(CH3)CN H H OH H
2.219 3-OCH3, 5-CF3 3-CH(CH3)CN H H OH H
Figure imgf000095_0001
Cmp. Ri R2 Rl31 Rl32 R133 Rl34 no. 2.250 3-OCH3 3-CH(CH3)CN H H F F
2.251 3-OCH3, 5-C1 3-CH(CH3)CN H H F F
2.252 3-OCH3, 5-CF3 3-CH(CH3)CN H H F F
2.253 5-CN 3-CH(CH3)CN H H F F
2.254 3-F, 5-F 3-CH2CN, 4-F H H F F
2.255 5-CF3 3-CH2CN, 4-F H H F F
2.256 3-F, 5-CF3 3-CH2CN, 4-F H H F F '
2.257 3-OCH3, 5-C1 3-CH2CN, 4-F H H F F
2.258 3-OCH3, 5-CF3 3-CH2CN, 4-F H H F F
2.259 3-F, 5-F 3-CHF2 H H CH3 F
2.260 5-CF3 3-CHF2 H H CH3 F
2.261 3-F, 5-CF3 3-CHF2 H H CH3 F
2.262 3-OCH3, 5-C1 3-CHF2 H H CH3 F
2.263 3-OCH3, 5-CF3 3-CHF2 H H CH3 F
2.264 3-F, 5-F 3-CH(CH3)CN H H CH3 F
2.265 5-CF3 3-CH(CH3)CN H H CH3 F
2.266 3-F, 5-CF3 3-CH(CH3)CN H H CH3 F
2.267 3-OCH3, 5-C1 3-CH(CH3)CN H H CH3 F
2.268 3-OCH3, 5-CF3 3-CH(CH3)CN H H CH3 F
2.269 3-F, 5-F 3-CH2CN, 4-F H H CH3 F
2.270 5-CF3 3-CH2CN, 4-F H H CH3 F
2.271 3-F, 5-CF3 3-CH2CN, 4-F H H CH3 F
2.272 3-OCH3, 5-C1 3-CH2CN, 4-F H ' H CH3 F
2.273 3-OCH3, 5-CF3 3-CH2CN, 4-F H H CH3 F
2.274 3-F, 5-F 3-CHF2 H H * CH3 CH3
2.275 5-CF3 3-CHF2 H H CH3 CH3
2.276 3-F, 5-CF3 3-CHF2 H H CH3 CH3
2.277 3-OCH3, 5-C1 3-CHF2 H H CH3 CH3
2.278 3-OCH3, 5-CF3 3-CHF2 H H CH3 CH3
2.279 3-F, 5-F 3-CH(CH3)CN H H CH3 CH3 Cmp. Ri R2 Rl31 Rl32 R133 R134 no.
2.280 5-CF3 3-CH(CH3)CN H H CH3 CH3
2.281 3-F, 5-CF3 3-CH(CH3)CN H H CH3 CH3
2.282 3-OCH3, 5-C1 3-CH(CH3)CN H H CH3 CH3
2.283 3-OCH3, 5-CF3 3-CH(CH3)CN H H CH3 CH3
2.284 3-F, 5-F 3-CH2CN, 4-F H H CH3 CH3
2.285 5-CF3 3-CH2CN, 4-F H H CH3 CH3
2.286 3-F, 5-CF3 3-CH2CN, 4-F H H CH3 CH3
2.287 3-OCH3, 5-C1 3-CH2CN, 4-F H H CH3 CH3
2.288 3-OCH3, 5-CF3 3-CH2CN, 4-F H H CH3 CH3
2.289 3-F, 5-F 3-CHF2 H H OCH3 H
2.290 5-CF3 3-CHF2 H H OCH3 H
2.291 3-F, 5-CF3 3-CHF2 H H OCH3 H
2.292 3-OCH3, 5-C1 3-CHF2 H H • OCH3 H
2.293 3-OCH3, 5-CF3 3-CHF2 H H OCH3 H
2.294 3-F, 5-F 3-CH(CH3)CN H H OCH3 H
2.295 5-CF3 3-CH(CH3)CN H H OCH3 H
2.296 3-F, 5-CF3 3-CH(CH3)CN H H OCH3 H
2.297 3-OCH3, 5-C1 3-CH(CH3)CN H H OCH3 H
2.298 3-OCH3, 5-CF3 3-CH(CH3)CN H H OCH3 H
2.299 3-F, 5-F 3-CH2CN, 4-F H H OCH3 H
2.300 5-CF3 3-CH2CN, 4-F H H OCH3 H
2.301 3-F, 5-CF3 3-CH2CN, 4-F H H OCH3 H
2.302 3-OCH3, 5-C1 3-CH2CN, 4-F H H OCH3 H
2.303 3-OCH3, 5-CF3 3-CH2CN, 4-F H H OCH3 H
2.304 3-F 3-CH2CN H CH3 H H
2.305 3-F, 5-F 3-CH2CN H CH3 H H
2.306 3-F, 5-C1 3-CH2CN H CH3 H H
2.307 5-CF3 3-CH2CN H CH3 H H
2.308 3-F, 5-CF3 3-CH2CN H CH3 H H
2.309 5-CN 3-CH2CN . H CH3 H H Cmp. Ri R2 Rl31 Rl32 R133 R134 no. 2.310 3-OCH3 3-CH2CN H CH3 H H
2.311 3-OCH3, 5-F 3-CH2CN H CH3 H H
2.312 3-OCH3, 5-C1 3-CH2CN H CH3 H H
2.313 3-OCH3, 5-CF3 3-CH2CN H CH3 H H
2.314 3-OCH3, 5-CN 3-CH2CN H CH3 H H
2.315 3-F 3-CH2CN H CH3 CH3 H
2.316 3-F, 5-F 3-CH2CN H CH3 CH3 H
2.317 3-F, 5-C1 3-CH2CN H CH3 CH3 H
2.318 5-CF3 3-CH2CN H CH3 CH3 H
2.319 3-F, 5-CF3 3-CH2CN H CH3 CH3 H
2.320 5-CN 3-CH2CN H CH3 CH3 H
2.321 3-OCH3 3-CH2CN H CH3 CH3 H
2.322 3-OCH3, 5-F 3-CH2CN H CH3 CH3 H
2.323 3-OCH3, 5-C1 3-CH2CN H CH3 CH3 H
2.324 3-OCH3, 5-CF3 3-CH2CN H CH3 CH3 H
2.325 3-OCH3, 5-CN 3-CH2CN H CH3. CH3 H
2.326 3-F 3-CH2CN H CH3 CH3 CH3
2.327 3-F, 5-F 3-CH2CN H CH3 CH3 CH3
2.328 3-F, 5-C1 3-CH2CN H CH3 CH3 CH3
2.329 5-CF3 3-CH2CN H CH3 CH3 CH3
2.330 3-F, 5-CF3 3-CH2CN H CH3 CH3 CH3
2.331 5-CN 3-CH2CN H CH3 CH3 CH3
2.332 3-OCH3 3-CH2CN H CH3 CH3 CH3
2.333 3-OCH3, 5-F 3-CH2CN H CH3 CH3 CH3
2.334 3-OCH3, 5-C1 3-CH2CN H CH3 CH3 CH3
2.335 3-OCH3, 5-CF3 3-CH2CN H CH3 CH3 CH3
2.336 3-OCH3, 5-CN 3-CH2CN H CH3 CH3 CH3
2.337 3-F 3-CH2CN H CH3 F F
2.338 3-F, 5-F 3-CH2CN H CH3 F F
2.339 3-F, 5-C1 3-CH2CN H CH3 F F
Figure imgf000099_0001
Cmp. Ri R2 Rl31 Rl32 R133 R134 . no.
2.370 3-OCH3, 5-CN 4-Cl H H F H
2.371 3-F, 5-F 3-NH2 H H H H
2.372 5-CF3 3-NH2 H H H H
2.373 3-F, 5-CF3 3-NH2 H H H H
2.374 3-OCH3, 5-C1 3-NH2 H H H H
2.375 3-OCH3, 5-CF3 3-NH2 H H H H
2.376 3-F, 5-F 3-NH-COCH3 H H H H
2.377 5-CF3 3-NH-COCH3 H H H H
2.378 3-F, 5-CF3 3-NH-COCH3 H H H H
2.379 3-OCH3, 5-C1 3-NH-COCH3 H H H H
2.380 3-OCH3, 5-CF3 3-NH-COCH3 H H H H
2.381 3-Cl, 5-C1 3-CH2CN H H H H
Table 3: Compounds of formula IaιbjQτ_:_
Figure imgf000100_0001
(IaibiQ
Cmp. R Ri R2 Rl31 Rl32 Rl41 Rl42 no.
3.001 CH3 H (n=0) H (m=0) H H H H
3.002 CH3 4-F H (m=0) H H H H
3.003 CH3 4-Cl H (m=0) H H H H
3.004 CH3 4-Br H (m=0) H H H H
3.005 CH3 4-1 H (m=0) H H H H Cmp. R Ri R2 Rl31 Rl32 Rl41 Rl42 no.
3.006 CH3 4-CF3 H (m=0) H H H H
3.007 CH3 4-CN H (m=0) H H H H
3.008 CH3 4-CHO H (m=0) H H H H
3.009 CH3 4-CH=NOCH3 H (m=0) H H H H
3.010 CH3 4-CH3 H (m=0) H H H H
3.011 CH3 . 4-CH=CCl2 H (m=0) H H H H
3.012 CH3 H (n=0) 3-CH2CN H H H H
3.013 CH3 4-F 3-CH2CN H H H H
3.014 CH3 4-Cl 3-CH2CN H H H H
3.015 CH3 4-Br 3-CH2CN H H H H
3.016 CH3 4-1 3-CH2CN H H H H
3.017 CH3 4-CF3 3-CH2CN H H H H
3.018 CH3 4-CN 3-CH2CN H H H H
3.019 CH3 4-CHO 3-CH2CN H H H H
3.020 CH3 4-CH=NOCH3 3-CH2CN H H H H
3.021 CH3 4-CH3 3-CH2CN H H H H
3.022 CH3 4-CH=CCl2 3-CH2CN H H H H
3.023 CH3 H (n=0) 3-CH2CN, 4-F H H H H
3.024 CH3 4-F 3-CH2CN, 4-F H H H H
3.025 CH3 4-Br 3-CH2CN, 4-F H H H H
3.026 CH3 4-CN 3-CH2CN, 4-F H H H H
3.027 CH3 4-CF3 3-CH2CN, 4-F H H H H
3.028 CH3 4-CH=NOCH3 3-CH2CN, 4-F H H H H
3.029 CH3 H (n=0) 3-CH2CN, 6-F H H H H
3.030 CH3 4-F 3-CH2CN, 6-F H H H H
3.031 CH3 4-Br 3-CH2CN, 6-F H H H H
3.032 CH3 4-CN 3-CH2CN, 6-F H H H H
3.033 CH3 4-CF3 3-CH2CN, 6-F H H H H
3.034 CH3 4-CH=NOCH3 3-CH2CN, 6-F H H H H
3.035 CH3 H (n=0) 3-CH2CN, 4-F, 6-F H H H H Cmp. R Ri R2 Rl31 Rl32 Rl41 Rl42 no. 3.036 CH3 4-F 3-CH2CN, 4-F, 6-F H H H H 3.037 CH3 4-Br 3-CH2CN, 4-F, 6-F H H H H 3.038 CH3 4-CN 3-CH2CN, 4-F, 6-F H H H H
3.039 CH3 4-CF3 3-CH2CN, 4-F, 6-F H H H H
3.040 CH3 4-CH=NOCH3 3-CH2CN, 4-F, 6-F H H H H
3.041 CH3 4-F 3-CH2CN, 4-Cl, 6-F H H H H
3.042 CH3 4-1 3-CH2CN, 4-Cl, 6-F H H H H
3.043 CH3 4-CN 3-CH2CN, 4-Cl, 6-F H H H H
3.044 CH3 4-CF3 3-CH2CN, 4-Cl, 6-F H H H H
3.045 CH3 4-CH=NOCH3 3-CH2CN, 4-Cl, 6-F H H H H
3.046 CH3 H (n=0) 3-CH(CH3)CN H H H H
3.047 CH3 4-F 3-CH(CH3)CN H H H H
3.048 CH3 4-Cl 3-CH(CH3)CN H H H H
3.049 CH3 4-Br 3-CH(CH3)CN H H H H
3.050 CH3 4-1 3-CH(CH3)CN H H H H
3.051 CH3 4-CF3 3-CH(CH3)CN H H H H
3.052 CH3 4-CN 3-CH(CH3)CN H H H H
3.053 CH3 4-CHO 3-CH(CH3)CN H H H H
3.054 CH3 4-CH=NOCH3 3-CH(CH3)CN H H H H
3.055 CH3 4-CH3 • 3-CH(CH3)CN H H H H
3.056 CH3 4-CH=CCl2 3-CH(CH3)CN H H H H
3.057 CH3 H (n=0) 3-CHF2 H H H H
3.058 CH3 4-F 3-CHF2 H H H H
3.059 CH3 4-Cl 3-CHF2 H H H H
3.060 CH3 4-Br 3-CHF2 H H H H
3.061 CH3 4-1 3-CHF2 H H H H
3.062 CH3 4-CF3 3-CHF2 H H H H
3.063 CH3 4-CN 3-CHF2 H H H H
3.064 CH3 4-CHO 3-CHF2 H H H H
3.065 CH3. 4-CH=NOCH3 3-CHF2 H H H H
Figure imgf000103_0001
Cmp. R Ri R2 R131 Rl32 Rl41 Rl42 no.
3.096 CH3 4-F 3-CH2CN H H F H
3.097 CH3 4-Br 3-CH2CN H H F H
3.098 CH3 4-CH3 3-CH2CN H H F H
3.099 CH3 4-CN 3-CH2CN H H F H
3.100 CH3 4-CF3 3-CH2CN H H F H
3.101 CH3 4-CH=NOCH3 3-CH2CN H H F H
3.102 CH3 4-CN 3-CH2CN H H F H
3.103 CH3 H (n=0) 3-CH2CN H H Cl H
3.104 CH3 4-F 3-CH2CN H H Cl H
3.105 CH3 4-Br 3-CH2CN H H Cl H
3.106 CH3 4-CH3 3-CH2CN H H Cl H
3.107 CH3 4-CN 3-CH2CN H H Cl H
3.108 CH3 4-CF3 3-CH2CN H H Cl H
3.109 CH3 4-CH=NOCH3 3-CH2CN H H Cl H
3.110 CH3 H (n=0) 3-CH2CN , H H OCH3 H
3.111 CH3 4-F 3-CH2CN H H OCH3 H
3.112 CH3 4-Br 3-CH2CN H H OCH3 H
3.113 CH3 4-CH3 3-CH2CN H H OCH3 H
3.114 CH3 4-CN 3-CH2CN H H OCH3 H
3.115 CH3 4-CF3 3-CH2CN H H OCH3 H
3.116 CH3 4-CH=NOCH3 3-CH2CN H H OCH3 H
3.117 CH3 H (n=0) 3-CH2CN H H CH3 H
3.118 CH3 4-F 3-CH2CN H H CH3 H
3.119 CH3 4-Br 3-CH2CN H H CH3 H
3.120 CH3 4-CH3 3-CH2CN H H CH3 H
3.121 CH3 4-CN 3-CH2CN H H CH3 H
3.122 CH3 4-CF3 3-CH2CN H H CH3 H
3.123 CH3 4-CH=NOCH3 3-CH2CN H H CH3 H
3.124 CH3 H (n=0) 3-CH2CN H H CH3 CH3
3.125 CH3 4-F 3-CH2CN H H CH3 CH3 Cmp. R Ri R2 R131 Rl32 Rl41 Rl42 no.
3.126 CH3 4-Br 3-CH2CN H H CH3 CH3
3.127 CH3 4-CH3 3-CH2CN H H CH3 CH3
3.128 CH3 4-CN 3-CH2CN H H CH3 CH3
3.129 CH3 4-CF3 3-CH2CN H H CH3 CH3
3.130 CH3 4-CH=NOCH3 3-CH2CN H H CH3 CH3
3.131 CH3 H (n=0) 3-CH2CN H H C2alkylene
3.132 CH3 4-F 3-CH2CN H H C2alkylene
3.133 CH3 4-Br 3-CH2CN H H C2alkylene
3.134 CH3 4-CH3 3-CH2CN H H C2alkylene
3.135 CH3 4-CN 3-CH2CN H H C2alkylene
3.136 CH3 4-CF3 3-CH2CN H H C2alkylene
3.137 CH3 4-CH=NOCH3 3-CH2CN H H C alkylene
3.138 CH3 H (n=0) 3-CHF2 H H OH H
3.139 CH3 4-F 3-CHF2 H H OH H
3.140 CH3 4-CN 3-CHF2 H H OH H
3.141 CH3 H (n=0) 3-CH(CH3)CN H H OH H
3.142 CH3 4-F 3-CH(CH3)CN H H OH H
3.143 CH3 4-CN 3-CH(CH3)CN H H OH H
3.144 CH3 H (n=0) 3-CH2CN, 4-F H H OH H
3.145 CH3 4-F 3-CH2CN, 4-F H H OH H
3.146 CH3 4-CN 3-CH2CN, 4-F H H OH H
3.147 CH3 H (n=0) 3-CHF2 H H F H
3.148 CH3 4-F 3-CHF2 H H F H
3.149 CH3 4-CN 3-CHF2 H H F H
3.150 CH3 H (n=0) 3-CH(CH3)CN H H F H
3.151 CH3 4-F 3-CH(CH3)CN H H F Η
3.152 CH3 4-CN 3-CH(CH3)CN H H F H
3.153 CH3 H (n=0) 3-CH2CN, 4-F H H F H
3.154 CH3 4-F 3-CH2CN, 4-F H H F H
3.155 CH3 4-CN 3-CH2CN, 4-F H H F H Cmp. R Ri R2 Rl31 R132 Rl41 Rl42 no.
3.156 CH3 H (n=0) 3-CHF2 H H Cl H
3.157 CH3 4-F 3-CHF2 H H Cl H
3.158 CH3 4-CN 3-CHF2 H H Cl H
3.159 CH3 H (n=0) 3-CH(CH3)CN H H Cl H
3.160 CH3 4-F 3-CH(CH3)CN H H Cl H
3.161 CH3 4-CN 3-CH(CH3)CN H H Cl H
3.162 CH3 4-CH=NOCH3 3-CH(CH3)CN H H Cl H
3.163 CH3 H (n=0) 3-CH2CN, 4-F H H Cl H
3.164 CH3 4-F 3-CH2CN, 4-F H H Cl H
3.165 CH3 4-CN 3-CH2CN, 4-F H H Cl H
3.166 CH3 H (n=0) 3-CHF2 H H CH3 OH
3.167 CH3 4-F 3-CHF2 H H CH3 OH
3.168 CH3 4-CN 3-CHF2 H H CH3 OH
3.169 CH3 H (n=0) 3-CH(CH3)CN H H CH3 OH
3.170 CH3 4-F 3-CH(CH3)CN H H CH3 OH
3.171 CH3 4-CN 3-CH(CH3)CN H H CH3 OH
3.172 CH3 4-CH=NOCH3 3-CH(CH3)CN H H CH3 OH
3.173 CH3 H (n=0) 3-CH2CN, 4-F H H CH3 OH
3.174 CH3 4-F 3-CH2CN, 4-F H H CH3 OH
3.175 CH3 . 4-CN 3-CH2CN, 4-F H H CH3 OH
3.176 CH3 H (n=0) 3-CHF2 H H CH3 CH3
3.177 CH3 4-F 3-CHF2 H H CH3 CH3
3.178 CH3 4-CN 3-CHF2 H H CH3 CH3
3.179 CH3 H (n=0) 3-CH(CH3)CN H H CH3 CH3
3.180 CH3 4-F 3-CH(CH3)CN H H CH3 CH3
3.181 CH3 4-CN 3-CH(CH3)CN H H CH3 CH3
3.182 CH3 H (n=0) 3-CH2CN, 4-F H H CH3 CH3
3.183 CH3 4-F 3-CH2CN, 4-F H H CH3 CH3
3.184 CH3 4-CN 3-CH2CN, 4-F H H CH3 CH3
3.185 CH3 H (n=0) 3-CHF2 H H OCH3 H Cmp. R Ri R2 Rl31 Rl32 Rl41 Rl42 no.
3.186 CH3 4-F 3-CHF2 H H ■ OCH3 H
3.187 CH3 4-CN 3-CHF2 H H OCH3 H
3.188 CH3 H (n=0) 3-CH(CH3)CN H H OCH3 H
3.189 CH3 4-F 3-CH(CH3)CN H H OCH3 H
3.190 CH3 4-CN 3-CH(CH3)CN H H OCH3 H
3.191 CH3 H (n=0) 3-CH2CN, 4-F H H OCH3 H
3.192 CH3 4-F 3-CH2CN, 4-F H H OCH3 H
3.193 CH3 4-CN 3-CH2CN, 4-F H H OCH3 H
3.194 CH3 H (n=0) 3-CH2CN H CH3 H H
3.195 CH3 4-F 3-CH2CN H CH3 H H
3.196 CH3 4-Br 3-CH2CN H CH3 H H
3.197 CH3 4-CH3 3-CH2CN H CH3 H H
3.198 CH3 4-CN 3-CH2CN H CH3 H H
3.199 CH3 4-CF3 3-CH2CN H CH3 H H
3.200 CH3 4-CH=NOCH3 3-CH2CN H CH3 H H
3.201 CH3 H (n=0) 3-CH2CN H CH3 CH3 H
3.202 CH3 4-F 3-CH2CN H CH3 CH3 H
3.203 CH3 4-Br 3-CH2CN H CH3 CH3 H
3.204 CH3 4-CH3 3-CH2CN H CH3 CH3 H
3.205 CH3 4-CN 3-CH2CN H CH3 CH3 H
3.206 CH3 4-CF3 3-CH2CN H CH3 CH3 H
3.207 CH3 4-CH=NOCH3 3-CH2CN H CH3 CH3 H
3.208 CH3 H (n=0) 3-CH CN H CH3 CH3 CH3
3.209 CH3 4-F 3-CH2CN H CH3 CH3 CH3
3.210 CH3 4-Br 3-CH2CN H CH3 CH3 CH3
3.211 CH3 4-CH3 3-CH2CN H CH3 CH3 CH3
3.212 CH3 4-CN 3-CH2CN H CH3 CH3 CH3
3.213 CH3 4-CF3 3-CH2CN H CH3 CH3 CH3
3.214 CH3 4-CH=NOCH3 3-CH2CN H CH3 CH3 CH3
3.215 CH3 H (n=0) 3-CH2CN H CH3 F H
Figure imgf000108_0001
Figure imgf000109_0001
Table A: Compounds prepared, from Tables 1-3 above
Figure imgf000110_0001
Biological Examples '
Example Bl: Herbicidal action prior to emergence of the plants (pre-emergence action Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. Immediately after sowing, the test compounds, in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example FI, c) according to WO 97/34485), are applied by spraying, in an optimum concentration (500 litres of water per ha). The test plants are then grown in a greenhouse under optimum conditions. After a test duration of 4 weeks, the test is evaluated in accordance with a scale of eleven ratings (10 = total damage, 0 = no action). Ratings of from 7 to 10 (especially from 8 to 10) indicate good to very good herbicidal action.
In this test, the compounds of formula I exhibit strong herbicidal action. The same results are obtained when the compounds of formula I are formulated analogously to the other Examples of WO 97/34485.
Example B2: Post-emergence herbicidal action
Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. When the test plants are at the 2- to 3 -leaf stage, the test compounds, in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example FI, c) according to WO 97/34485), are applied by spraying, in an optimum concentration (500 litres of water per ha). The test plants are then grown on in a greenhouse under optimum conditions.
After a test duration of 2 to 3 weeks, the test is evaluated in accordance with a scale of eleven ratings (10 = total damage, 0 = no action). Ratings of from 7 to 10 (especially from 8 to 10) indicate good to very good herbicidal action.
Test plants: Sida, Abutilon, Amaranthus, Chenopodium, Stellaria, Panicum, Euphorbia, Galium, Veronica, Kochia. Table B2: Concentration: 1000 g of active substance per ha
Figure imgf000112_0001
Table B2a: Concentration: 1000 g of active substance per ha
Figure imgf000112_0002
Table B2b: Concentration: 1000 g of active substance per ha
Figure imgf000112_0003
The same results are obtained when the compounds of formula I are formulated analogously to the other Examples of WO 97/34485. The compounds of formula I according to the invention may also be used in admixture with known herbicides as co-herbicides for controlling weeds, for example as ready- for- use formulations or in the form of a 'tank-mix'. As mixing partners for the compounds of formula I, there are suitable, for example, the following co-herbicides: compound of formula I + triasulfuron; compound of formula I + prosulfuron; compound of formula I + clodinafop; compound of formula I + terbutryn; compound of formula I + dicamba; compound of formula I + cloquintocet-mexyl; compound of formula I + fenoxaprop-P- ethyl; compound of formula I + diclo fop-methyl; compound of formula I + tralkoxydim; compound of formula I + amidosulfuron; compound of formula I + chlorsulfuron; compound of formula I + ethoxysulfuron; compound of formula I + flupyrsulfuron; compound of formula I + flupyrsulfuron-methyl-sodium; compound of formula I + metsulfuron-methyl; compound of formula I + sulfosulfuron; compound of formula I + thifensulfuron-methyl; compound of formula I + tribenuron-methyl; compound of formula I + imazamethabenz-methyl; compound of formula I + flucarbazone; compound of formula I + iodosulfuron; compound of formula I + florasulam; compound of formula I + flumetsulam; compound of formula I + metosulam; compound of formula I + chlorotoluron; compound of formula I + isoproturon; compound of formula I + methabenzthiazuron; compound of formula I + bromoxynil; compound of formula I + ioxynil; compound of formula I + pyridate; compound of formula I + bifenox; compound of formula I + fluoroglycofen-ethyl; compound of formula I + carfentrazone; compound of formula I + JV485 (MON48500); compound of formula I + diflufenican; compound of formula I + flurtamone; compound of formula I + glyphosate; compound of formula I + sulfosate; compound of formula I + glufosinate; compound of formula I + S-glufosinate; compound of formula I + bialaphos; compound of formula I + ethalfluralin; compound of formula I + pendimethalin; compound of formula I + trifluralin; compound of formula I + fluthiamid; compound of formula I + isoxaben; compound of formula I + prosulfocarb; compound of formula I + triallate; compound of formula I + 2,4-D; compound of formula I + 2,4-DB; compound of formula I + dichlorprop (2,4-DP); compound of formula I + MCPA; compound of formula I + MCPB; compound of formula I-+ mecoprop (MCPP); compound of formula I + mecoprop-P; compound of formula I + clopyralid; compound of formula I + fluroxypyr; compound of formula I + quinmerac; compound of formula I + benazolin-ethyl; compound of formula I + difenzoquat; compound of formula I + cyhalofop-butyl; compound of formula I + cinosulfuron; compound of formula I + fenclorim; compound of formula I + butafenacil; compound of formula I + clodinafop- propargyl; compound of formula I + metolachlor; compound of formula I + S-metolachlor; compound of formula I + bensulfuron; compound of formula I + imazosulfuron; compound of formula I + pyrazosulfuron; compound of formula I + metsulfuron; compound of formula I + azimsulfuron; compound of formula I + ACO 14; compound of formula I + esprocarb; compound of formula I + mefenacet; compound of formula I + molinate; compound of formula I + propanil; compound of formula I + pyrazolate; compound of formula I + fenoxaprop-ethyl; compound of formula I + bispyribac; compound of formula I + bispyribac-sodium; compound of formula I + pyriminobac-methyl; compound of formula I + cafenstrole; compound of formula I + MY-100; compound of formula I + dymron; compound of formula I + NB061; compound of formula I + MK243; compound of formula I + HW-52; compound of formula I + oxadiargyl; compound of formula I + halosulfuron-methyl; compound of formula I + clomazone; compound of formula I + oxadiazon; compound of formula I + SAN 1315; compound of formula I + mefenpyr; compound of formula I + chlormequat chloride; compound of formula I + clofencet; compound of formula I + cyclanilide; compound of formula I + ethephon; compound of formula I + flurprimidol; compound of formula I + gibberellic acid; compound of formula I + inabenfide; compound of formula I + maleic, acid hydrazide; compound of formula I + mefluidide; compound of formula I + mepiquat chloride; compound of formula I + paclobutrazol; compound of formula I + prohexadione calcium; compound of formula I + uniconazole; compound of formula I + thidiazuron; compound of formula I + azimsulfuron; compound of formula I + cyclosulfamuron; compound of formula I + fentrazamide; compound of formula I + flazasulfuron; compound of formula I + fluazolate; compound of formula I + flufenacet; compound of formula I + indanofan; compound of formula I + benfuresate; compound of formula I + bentazone; compound of formula I + bromobutide; compound of formula I + dichlorprop-P; compound of formula I + dithiopyr; compound of formula I + ethametsulfuron; compound of formula I + flamprop-M; compound of formula I + methyldymron; compound of formula I + quinclorac; compound of formula I + thiazopyr; compound of formula I + paraquat, and also esters and salts of those mixing partners of the compound of formula I, which are mentioned, for example, in 'The Pesticide Manual', Eleventh Edition, 1997, BCPC.

Claims

What is claimed is:
Figure imgf000115_0001
wherein Q is a group
Figure imgf000115_0002
(Q4), ■ (Qβ).
Figure imgf000115_0004
Figure imgf000115_0003
Figure imgf000115_0005
n is O, 1, 2, 3 or 4; R is hydrogen, COR]2, -S(0)qCι-C8alkyl, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl or C3-C6cycloalkyl; or Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl each substituted from one to five times by halogen and/or once, twice or three times by substituents selected from C]-C alkoxy, -CN, -S(0)qCi-C8alkyl and phenyl, wherem the phenyl ring may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from C C4haloalkyl, C C4alkoxy, -CN, -N02 and -S(0)qC C8alkyl, or R is C3-C6cycloalkyl substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4alkoxy, -CN and phenyl, wherein the phenyl ring may in turn be substituted from one to five times by substituents selected from halogen and Cι-C alkyl and/or once, twice or three times by substituents selected from Cj-C4alkoxy, -CN, -NO2 and -S(0)qCi-C8alkyl, or
R is phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and methyl and/or once, twice or three times by substituents selected from -CF3, -OCH3, -CN, -N02 and -S(0)qCrC4alkyl; or, when n is 0, 1, 2 or 3,
R forms a Cι-C6alkylene or C2-C6alkenylene bridge attached to the phenyl ring in the 3-position, which bridge maybe interrupted by an oxygen atom and/or may be substituted by Cι-C6alkyl, an oxygen-oxygen bond being excluded and the total number of ring atoms being at least 5 and at most 9; each Ri independently of any other(s) may be halogen, -CN, -SCN, -SF5, -N02, -NR5R6, -C02R7, -C0NR8R9, -C(Rι0)=NORπ, -COR12, -OR]3, -SRι4, -SORι5, -SO2R16, -OSO2R17, Cι-C8alkyl, C2-C8alkenyl, C2-C8alkynyl or C3-C6cycloalkyl; or is Cι-C8alkyl, C -C8alkenyl or C2-C8alkynyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, -N02,
-NR,8Rι9, -CO2R20, -C0NR2lR22, -C0R23, -C(R24)=NOR25, -C(S)NR26R27, -C(Cι-C4alkylthio)=NR28, -OR 9, -SR30, -SOR3ι, -S02R32 and C3-C6cycloalkyl; and/or each Ri independently of any other(s) may be C3-C6cycloalkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, -NO2, -NRι8Rι9, -CO2R20, -CONR21R22, -C0R23, -C(R24)=NOR25,
-C(S)NR26R27, -C(Cι-C4alkylthio)=NR28, -OR29, -SR30, -SOR31, -S02R32 and C3-C6cycloalkyl; and/or each Ri independently of any other(s) may be phenyl which may in turn be substituted from one to five times by substituents selected from halogen and Cι-C alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy,
-CN, -N02, Cj-C4alkylthio, Cr alkylsulfinyl and Cι-C alkylsulfonyl; or, when Q is a group Qi, Q2, Q3, Q4, Q5 or Q7, two adjacent Ri radicals may together form a Cι-C7alkylene or C2-C7alkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and/or may be substituted from one to five times by substituents selected from halogen and CrCgalkyl and/or once, twice or three times by Cι-C6alkoxy, the total number of ring atoms being at least 5 and at most 9; R5 is hydrogen or Cι-C8alkyl; R6 is hydrogen, C]-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cj-C4alkoxy, -CN, -NO2, Cι-C alkylthio, Cι-C4alkylsulfinyl and Cι-C4alkylsulfonyl, or
R6 is Cι-C8alkylcarbonyl, wherein the Cι-C8alkyl chain may in turn be substituted by substituents selected from halogen, -CN, Cι-C6alkylamino, di(CrC6alkyl)amino and Cι-C4alkoxy; or R5 and R together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom;
R7 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl each substituted from one to five times by halogen and/or once, twice or three times by substituents selected from Cι-C4alkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, C C4alkoxy, -CN, -NO2, Cι-C4alkylthio, Cr alkylsulfinyl and Cι-C4alkylsulfonyl;
R8 and R are each independently of the other hydrogen or Cι-C8alkyl, or C]-C8alkyl substituted once, twice or three times by substituents selected from -COOH, C]-C8alkoxycarbonyl and -CN, or
R8 and R9 are each independently of the other C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cι-C alkylthio, Cι-C4alkylsulfinyl and Cι-C4alkylsulfonyl; or
R8 and R9 together are C2-C5alkylene;
Rio is hydrogen, Cι-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl; R11 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C haloalkyl or C3-C6haloalkenyl; R1 is hydrogen, Cι-C4alkyl, Cι-C haloalkyl or C3-C6cycloalkyl;
Ri3 is hydrogen, C]-C8alkyl, C3-C8alkenyl or C3-C8alkynyl; or
R13 is phenyl or phenyl-Cι-C6alkyl, wherein the phenyl ring may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from C C haloalkyl, Cι-C4alkoxy, -CN, -NO2, Cr alkylthio, Cι-C8alkylsulfmyl and Ci-Cgalkylsulfonyl; or Ri3 is C!-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, Cι-C6alkylamino, di(Cι-C6-alkyl)amino and Cι-C4 alkoxy, or
Rι3 is d-C8alkylcarbonyl, wherein the Cj-C8alkyl chain may in turn be substituted by substituents selected from halogen, -CN, Ci- alkylamino,
Figure imgf000118_0001
and
Cι-C alkoxy;
R14 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C -C8alkynyl, or Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and Cι-C4alkoxy; '
R15, R16 and Ri are each independently of the others Cι-C8alkyl, C3-C8alkenyl or C3-Csalkynyl, or Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and Cι-C4alkoxy; Ris is hydrogen or Cι-C8alkyl;
Rι is hydrogen, - alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherem phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and or once, twice or three times by substituents selected from Cι-C halo alkyl, Cι-C4alkbxy, -CN, -N02, Cι-C4alkylthio, Cι-C alkylsulfmyl and Cι-C4alkylsulfonyl; or
Ris and Rι together are a C2-Csalkylene chain which may be interrupted by an oxygen or sulfur atom;
R o is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and C -C4alkyl and or once, twice or three times by substituents selected from Cι-C4haloalkyl, C1-C4alkoxy, -CN, -N02, Cι-C alkylthio, C]-C4alkylsulfinyl and Cι-C4alkylsulfonyl; R21 is hydrogen or CpC8alkyl; R22 is hydrogen or Cι-C8alkyl, or Cι-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl and -CN, or
R22 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherem phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and C]-C4alkyl and/or once, twice or three times by substituents selected from CrC4haloalkyl, CrC4alkoxy, -CN, -N02, C C4alkylthio, Cι-C4alkylsulfmyl and Cι-C4alkylsulfonyl; or R21 and R22 together are C2-C5alkylene; R23 is hydrogen, CpC4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl; R24 is hydrogen, Cι-C4alkyl, Ci- haloalkyl or C3-C6cycloalkyl;
R25 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C haloalkyl or
C3-C6haloalkenyl;
R26 is hydrogen or Cι-C8alkyl;
R27 is hydrogen or Cι-C8alkyl, or C]-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl and -CN, or
R27 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Ci-Qhaloalkyl, Cι-C4alkoxy, -CN, -N02, C,-C4alkylthio, Cι-C4alkylsulfmyl and Cι-C4alkylsulfonyl; or
R26 and R27 together are C2-C5alkylene;
R28 is hydrogen or Cι-C8alkyl;
R2 and R30 are each independently of the. other hydrogen, Cι-C8alkyl, C3-C8alkenyl or
C3-C8alkynyl, or Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and C]-C4alkoxy;
R3ι and R32 are each independently of the other Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and - alkoxy; m is 0, 1, 2, 3, 4 or 5; each R2 independently of any other(s) may be halogen, -CN, -SCN, -OCN, -N3, -SF5,
-N02, -NR33R34, -C02R35, -CONR36R37, -C(R38)=NOR39, -CORto, -OR41, -S 42, -SOR43, -S02R44, -OS02R45, -N([CO]pR46)COR47, -N(OR54)COR55, -N(R56)S02R57, -N(S02R58)S02R59, -N=C(OR60)R6ι, -CR62(OR63)OR64, -OC(0)NR65R66, -SC(0)NR67Rδ8, -OC(S)NR69R70 or -N-phthalimide; and/or ' R2 may be a 5- to 7-membered heterocyclic ring system which may be aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, which heterocyclic ring system may in turn be substituted from one to five times by substituents selected from halogen and Cj-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, hydroxy- Q- alkyl, CrC4alkoxy, CrC alkoxy-Cι-C4alkyl, -CN, -N02, C,-C6alkylthio, Cι-C6alkylsulfmyl and Ci-Cόalkylsulfonyl; R33 is hydrogen or d-Csalkyl; and R34 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Ci- alkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, Cι-C4alkoxy, -CN, -N02, C]-C alkylthio, Cι-C4alkylsulfinyl and Q-Qalkylsulfonyl, or R3 is Cι-C8alkylcarbonyl unsubstituted or substituted by substituents selected from halogen, -CN, Cι~C6alkylamino, di(Cι-C6alkyl)amino and Cι-C4alkoxy; or R 3 and R3 together are a C2-C5alkylene chain which may be interrupted by an oxygen or sulfur atom; R35 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl, C -C8alkenyl or C3-C8alkynyl each substituted from one to five times by halogen and/or once, twice or three times by substituents selected from C!-C4alkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from d- haloalkyl, Cι-C alkoxy, -CN, -N02, Cι-C alkylthio, Ci- alkylsulf yl and Cι-C4alkylsulfonyl;
R36 is hydrogen or Cι-C8alkyl;
R37 is hydrogen or Cι-C8alkyl, or Cι-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl and -CN, or R37 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and C -C4alkyl and/or once, twice or three times by substituents selected from d-C4haloalkyl, Cι-C4alkoxy, -CN, -N02, Cι-C4alkylthio, Cι-C4alkylsulfmyl and
CrC4alkylsulfonyl; or
R36 and R37 together are C3-C5alkylene; R38 is hydrogen, Ci-Qalkyl, Cι-C4haloalkyl or C3-C6cycloalkyl;
R39 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C4haloalkyl or C3-C6haloalkenyl; Rto is hydrogen, C C4alkyl, Cι-C4haloalkyl, CrC8alkylthio, -C(0)-C(0)OCι-C4alkyl or C3-C6cycloalkyl;
R41 is hydrogen, Ci-Csalkyl, C -C8alkenyl, C3-C8alkynyl, Cι-C6alkoxy-Cι-C6alkyl, Cι-C8alkylcarbonyl, Cι-C8haloalkylcarbonyl, Cι-C8alkoxycarbonyl, C3-C8alkenyloxycarbonyl, Cι-C6alkoxy-Cι-C6alkoxycarbonyl, Cι-C6alkylthio-
Cι-C6alkyl, Ci-Cδalkylsulfinyl-d-Cealkyl or Cι-C6alkylsulfonyl-Cι-C6alkyl; or Rti is phenyl or phenyl-Cι-C6alkyl, wherein the phenyl ring may in turn be substituted from one to five times by substituents selected from halogen and CpC4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -N02 and -S(0) C C8alkyl, or
R41 is Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl, C]-C6alkylamino, di(Cι-C6alkyl)amino and -CN; ι2 is hydrogen, CrQalkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and Cι-C4alkoxy; (3 and R44 are each independently of the other Cι-C8alkyl, C3-C8alkenyl or C3-Cgalkynyl, or Q-Csalkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and Cι-C4alkoxy; R45 is Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Q-Qalkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and Cι-C alkoxy, or
Rt5 is phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, -CN, N02, Cι-C8alkylthio,
Cι-C8alkylsulfmyl and Cι-C8alkylsulfonyl; (6 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl or C C4haloalkyl; v7 is hydrogen, Cι-C8alkyl, Cι-C4alkoxy, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, Cι-C4alkoxy, Cι-C8alkoxycarbonyl, -NH2,
CrC4alkylamino, di(Cι-C4alkyl)amino, -N tsCORrø, -NR5oS02R5i and -NR52C02Rs3, or Rt7 is phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and C]-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -N02, Cι-C alkylthio, d-C4alkylsulfinyl and Cι-C4alkylsulfonyl; p is 0 or 1 ; Ris, tg, R50, R5ι, R52 and R53 are each independently of the others hydrogen, C]-C8alkyl, phenyl, benzyl or naphthyl, wherein the three last-mentioned aromatic radicals may in turn be substituted from one to five times by substituents selected from halogen and Cι-C8alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, Cι-C4alkylamino, di(Cι-C4alkyl)amino, -NH2,
-CN, -N02, Cι-C4alkylthio, C C4alkylsulfmyl and CrC4alkylsulfoιiyl; R54 and R55 are each independently of the other hydrogen, Cι-C8alkyl or phenyl which may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Ci-Qhaloalkyl, Ci- alkoxy, -CN, -N02, C C8alkylthio, Cι-C8alkylsulfmyl and
Ci -C8alkylsulfonyl;
R 6 is hydrogen, Cι-C8alkyl, Cι-C4haloalkyl, Cι-C alkoxy, C3-C8alkenyl, C3-C8alkynyl or benzyl, wherein benzyl may in turn be substituted from one to five times by substituents selected from halogen and Q-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -NO2,
CpCgalkylthio, Cι-C8alkylsulfϊnyl and Cι-C8alkylsulfonyl;
R57 is Cι-C8alkyl, Cι-C4haloalkyl, phenyl, benzyl or naphthyl, wherein the latter three aromatic rings may be substituted from one to five times by substituents selected from halogen and C]-C4alkyl and/or once, twice or three times by substituents selected from Ci-Qhaloalkyl, Cι-C4alkoxy, Cι-C alkylamino, di(Cι-C alkyl)amino, -NH2, -CN,
-N02, Cι-C4alkylthio, Cι-C alkylsulfinyl and Cj-Qalkylsulfonyl; R58 and R59 are each independently of the other Cι-C8alkyl, C3-Csalkenyl, C3-C8alkynyl, phenyl, benzyl or naphthyl, wherein the latter three aromatic rings may be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from
Cι-C4haloalkyl, Cι-C4alkoxy, Cι-C4alkylamino, di(Cι-C4alkyl)amino, -NH2, -CN,
-N02, C]-C4alkylthio, C]-C4alkylsulfinyl and C]-C4alkylsulfonyl;
R6o and R6ι are each independently of the other hydrogen or Cι-C6alkyl; R<52, Rό3 and Rό4 are each independently of the others hydrogen or Cι-C8alkyl, or Rδ3 and R^4 together form a C2-C5alkylene bridge; Rδ5, Rβό, Rδ7, Rδ8, R69 and R70 are each independently of the others hydrogen or Cι-C8alkyl, or R65 and R66, or R67 and Res, or Rό9 and R70 together in each case form a d-dalkylene bridge; and/or each R2 independently of any other(s) may be Cι-C8alkyl, or Ci-Csalkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, -N3, -SCN, -N02, -NR7ιR72, -C02R73, -CONR74R75, -COR76, -C(R77)=NOR7s, -C(S)NR79R80, -C(C,-C4alkylthio)=NRsι, -OR82, -SR83, -SOR84,
-S02R85, -0(S02)R86, -N(R87)C02R88, -N(R89)COR90, -S+(R9ι)2, -N+(R92)3, -Si(R93)3 and C3-C6cycloalkyl; and/or each R independently of any other(s) may be d-Qalkyl substituted by a 5- to 7- membered heterocyclic ring system which may be aromatic or partially or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, wherein that heterocyclic ring system may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, hydroxy-Cι-C4alkyl, C,-C4alkoxy, CrC4alkoxy-Cι-C4alkyl, -CN, -N02, d-C6alkylthio, Cι-C6alkylsulfmyl and Cι-C6alkylsulfonyl; and/or each R2 independently of any other(s) may be C2-C8alkenyl, or C2-C8alkenyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, -N02, -C02R94, -CONR95R96, -COR97, -C(R98)=NOR99, -C(S)NRιooRιoι, -C(C,-C4alkylthio)=NRι02, -ORι03, -Si(Rι04)3 and C3-C6cycloalkyl; and/or each R2 independently of any other(s) may be C2-C8alkynyl, or C2-C8alkynyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, -CO2R105, -CONRι06Rιo7, -CORι08, -C(Rι09)=NOR110, -C(S)NRniR , -C(C C4alkylthio)=NRπ3, -ORn4, -Si(Rn5)3 and C3-C6cycloalkyl; and/or each R2 independently of any other(s) may be C3-C6cycloalkyl, or C3-C6cycloalkyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, -C02Rn6, -CONRiπRns, -CORπ9,
Figure imgf000124_0001
-C(S)NR122Ri23 and -C(C1-C4alkylthio)=NRι24; and/or two adjacent R2 radicals together may form a Cι-C alkylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur and/or may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and or once, twice or three times by Cι-C6alkoxy, the total number of ring atoms being at least 5 and at most 9; and/or two adjacent R2 radicals together may form a C2-C7alkenylene bridge which may be interrupted by from 1 to 3 hetero atoms selected from oxygen, nitrogen and sulfur , and/or may be substituted from one to five times by substituents selected from halogen and Cι-C6alkyl and/or once, twice or three times by Cι-C6alkoxy, the total number of ring atoms being at least 5 and at most 9;
R7ι is hydrogen or Cι-C8alkyl;
R72 is hydrogen, Ci-Csalkyl, C -C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and d-C4alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C alkoxy, -CN, -N02, Cι-C alkylthio,
Cι-C4alkylsulfinyl and Cι-C4alkylsulfonyl; or
R7ι and R7 together are a d-dalkylene chain which may be interrupted by an oxygen or sulfur atom;
R73 is hydrogen, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl,
C3-C8alkenyl or C3-C8alkynyl substituted from one to five times by halogen and/or once, twice or three times by substituents selected from Cι-C4alkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from C C haloalkyl, C]-C4alkoxy, -CN, -N02, Cι-C alkylthio,
Cι-C4alkylsulfϊnyl and Cι-C4alkylsulfonyl;
R 4 is hydrogen or Cι-C8alkyl;
R75 is hydrogen, Cι-C8alkyl or C3-C7cycloalkyl, or d-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl,
Cι-C6alkoxy and -CN; or
R75 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, CrC4alkoxy, -CN, -N02, CrC4alkylthio, Cι-C4alkylsulfihyl and Cι-C4alkylsulfonyl; or R74 and R 5 together are a Crdalkylene chain which may be interrupted by an oxygen or sulfur atom; R 6 is hydrogen, Cι-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl;
R77 is hydrogen, Cι-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl;
R78 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C4haloalkyl or d-Cghaloalkenyl; and R79 is hydrogen or Cι-C8alkyl;
Rgo is hydrogen or Cι-C8alkyl, or Cι-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl and -CN; or
R8o is C -C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from
C C4haloalkyl, Ci-Qalkoxy, -CN, -N02, C C4alkylthio, Cι-C4alkylsulfmyl and d-C4alkylsulfonyl; or
R 9 and R80 together are C2-C5alkylene;
R8ι is hydrogen or Cι-C8alkyl; R82 is -Si(Cι -C6alkyl)3, Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl, or Cι-C8alkyl which is substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, -NH2, d-C6alkylamino, di(Cι-C6alkyl)amino and Cι-C4alkoxy;
R83 is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, or Cι-C8alkyl which is substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN, -NH2, Cι-C6alkylamino, di(Cι-C6alkyl)amino and
Cι-C4alkoxy;
R84, R85 and R86 are each independently of the others Cι-C8alkyl, C3-C8alkenyl or
C3-C8alkynyl, or Cι-C8alkyl which is substituted from one to five times by halogen and/or once, twice or three times by substituents selected from -CN and Cι-C4alkoxy;
R87 and R89 are each independently of the other hydrogen, Cι-C8alkyl or Cι-C8alkoxy;
Rss is Cι-C8alkyl;
R9o is hydrogen or Cι-C8alkyl; R9ι is Cι-C4alkyl; R92 and R93 are each independently of the other Cι-C6alkyl; R 4 is hydrogen, or d-C8alkyl, C3-C8alkenyl or C3-Cgalkynyl each of which may be substituted from one to five times by halogen and/or once, twice or three times by substituents selected from Cι-C alkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and Ci-Qalkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, Cι-C4alkoxy, -CN, -N02, Cι-C4alkylthio, C C4alkylsulfmyl and Ci -C4alkylsulfonyl; R95 is hydrogen or C \ -C8alkyl;
R96 is hydrogen or Cι-C8alkyl, or Cι-C8alkyl substituted once, twice or three times by substituents selected from -COOH, Cι-C8alkoxycarbonyl and -CN; or R 6 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and d-C4alkyl and/or once, twice or three times by substituents selected from d-C4haloalkyl, C C4alkoxy, -CN, -N02, Cι-C4alkylthio, Cι-C4alkylsulfmyl and
Cι-C4alkylsulfonyl; or
R95 and R9 together are C2-Csalkylene;
R97 and R98 are each independently of the other hydrogen, Cι-C4alkyl, Cι-C4haloalkyl or C3-C6cycloalkyl;
R is hydrogen, Cι-C8alkyl, C -C8alkenyl, C3-C8alkynyl, Cι-C4haloalkyl or
C3-C6haloalkenyl;
Rioo is hydrogen or Cι-C8alkyl;
Rioi is hydrogen or Cι-C8alkyl, or Cι-C8alkyl substituted once, twice or three times by substituents selected from -COOH, C]-C8alkoxycarbonyl and -CN; or
Rioi is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C alkyl and/or once, twice or three times by substituents selected from Ci-Qhaloalkyl, Cι-C alkoxy, -CN, -N0 , C C4alkylthio, C C4alkylsulfmyl and Cι-C4alkylsulfonyl; or
Rioo and Rioi together are C2-C5alkylene;
Rιo2 is hydrogen or Cι-C8alkyl;
Rιo3 is hydrogen, Cι-C8alkyl, -Si(Cι-C6alkyl)3, C3-C8alkenyl or C3-C8alkynyl; Rιo4 is Cι-C6alkyl; Rios is hydrogen, or Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl each of which may be substituted from one to five times by halogen and/or once, twice or three times by substituents selected from Cι-C alkoχy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C alkyl and/or once, twice or three times by substituents selected from Cι-C4haloalkyl, d-C4alkoxy, -CN, -N02, Cι-C4alkylthio, Cι-C4alkylsulfinyl and d -Qalkylsulfonyl; RIOO is hydrogen or Cι-C8alkyl; Rιo7 is hydrogen or Cι-C8alkyl, or Cj-Cgalkyl substituted once, twice or three times by substituents selected from -COOH, Ci-Cgalkoxycarbonyl and -CN, or R o7 is C3-C8alkenyl, C3-C8alkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C4alkyl and/or once, twice or three times by substituents selected from d~C4haloalkyl, Cι-C4alkoxy, -CN, -N02, Cι-C4alkylthio, Cι-C alkylsulfmyl and
Ci -Qalkylsulfonyl; or R106 and R107 together are C2-C5alkylene; Rios is hydrogen, Cι-C4alkyl, Cι-C4haloalkyl or C -C6cycloalkyl; Rιo9 is hydrogen, Cι-C4alkyl, Cι-C4haloalkyl or C -C6cycloalkyl; Rπo is hydrogen, Cι-C8alkyl, C3-C8alkenyl, C3-C8alkynyl, Cι-C haloalkyl or
C3-C6haloalkenyl; Rm is hydrogen or Cι-C8alkyl;
R1 12 is hydrogen or Ci-Cgalkyl, or Ci-Cgalkyl substituted once, twice or three times by substituents selected from -COOH, Cj-Cgalkoxycarbonyl and -CN; or Ri 12 is C3-C8alkenyl, CrCsalkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Cι-C alkyl and/or once, twice or three times by substituents selected from Cι-C haloalkyl, Cι-C4alkoxy, -CN, -N02, Cι-C4alkylthio, Cι-C4alkylsulfinyl and Ci -Qalkylsulfonyl; or Rm and Rn2 together are C2-C5alkylene;
R113 is hydrogen or Cι-C8alkyl;
R114 is hydrogen, Ci-Qalkyl, -Si(Cι-C6alkyl)3, C3-C8alkenyl or C3-C8alkynyl; Rn5 is Cι-C6alkyl; - -
Rιi6 is hydrogen, or Cι-C8alkyl, C3-C8alkenyl or C3-C8alkynyl each of which may be substituted from one to five times by halogen and/or once, twice or three times by substituents selected from Ci-Qalkoxy and phenyl, wherein phenyl may in turn be substituted from one to five times by substituents selected from halogen and Ci-Qalkyl and/or once, twice or three times by substituents selected from
Ci-Qhaloalkyl, Ci-Qalkoxy, -CN, -N02, Q-Qalkylthio, Ci-Qalkylsulfmyl and
Ci -Qalkylsulfonyl;
Riπ is hydrogen or d-Qalkyl;
Rπs is hydrogen or d-Qalkyl, or Ci-Qalkyl substituted once, twice or three times by substituents selected from -COOH, Ci-Qalkoxycarbonyl and -CN; or
Rπs is Q-Qalkenyl, Q-Qalkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and Ci-Qalkyl and/or once, twice or three times by substituents selected from Ci-Qhaloalkyl, Ci-Qalkoxy, -CN, -N02, CrC4alkylthio, Ci-Qalkylsulfmyl and Ci -Qalkylsulfonyl; or
Rn? and Rπs together are Q-Qalkylene;
Rπ9 is hydrogen, Q-Qalkyl, Ci-Qhaloalkyl or Q-Qcycloalkyl;
R120 is hydrogen, Ci-Qalkyl, Ci-Qhaloalkyl or Q-Qcycloalkyl;
R121 is hydrogen, Ci-Qalkyl, Q-Qalkenyl, Q-Qalkynyl, Q-Qhaloalkyl or Q-Qhaloalkenyl;
R122 is hydrogen or Q-Qalkyl;
Rι23 is hydrogen or Q-Qalkyl, or Ci-Qalkyl substituted once, twice or three times by substituents selected from -COOH, Q-Qalkoxycarbonyl and -CN; or
R123 is Q-Qalkenyl, Q-Qalkynyl, phenyl or benzyl, wherein phenyl and benzyl may in turn be substituted from one to five times by substituents selected from halogen and
Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, Q-Qalkoxy, -CN, -N02, Q-Qalkylthio, Q-Qalkylsulfmyl and Ci-Qalkylsulfonyl; or Rι22 and Rι23 together are Q-Qalkylene; and Rj24 is hydrogen or Q-Qalkyl;
A is a bridging member Al5 A2, A3, t or A5
Figure imgf000129_0001
wherein the bridging members Ai to A5 are linked to the group Q at the end carrying the oxygen atom; Ri3i, R132, Ri33, Ri34, R135, i36, Ri37> Ri38, R 39 and R140 are each independently of the others hydrogen, halogen, -CN, -N02, -N(R20o)R2o Q-Qalkyl, Cι-C6haloalkyl, -OH, Q-C6alkoxy, Q-Qhaloalkoxy, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C3-C6alkenyloxy, Q-Qhaloalkenyloxy, C3-C6alkynyloxy, C3-C8cycloalkyl, C3-C8halocycloalkyl, -C(O)OR202, -C(O)NR203R204, -C(S)NR205R2o6, -COR207, -CSR20S,
Figure imgf000129_0002
-OC(0)R2n, -OC(0)OR212, -SC(0)R213, -SC(0)OR2ι4, -OC(S)SR2i5, -SC(S)SR2i6, -OS02Cι-C6alkyl, -OS02Cι-C6haloalkyl, -SH, -S(0)qQ-Qalkyl or -S(0)qQ-C6haloalkyl, and or Ri3i, R132, R133, R134, R135, i36, R137, Ri38, R139 and R140 may be each independently of the others Ci-Qalkyl or Cι-C6alkoxy each of which is substituted once, twice or three times by substituents selected from -CN, C(0)OR2]7, -CHO, -C0R2ι8, -C(O)NR2ι9R220, -C(S)NR221R222, -C(R223)=NOR224, -N(R225)R226, -OH, Q-Qalkoxy, Cι-C6haloalkoxy, -SH, -S(0)qCι-Qalkyl, -S(0)qQ-C6haloalkyl, -Si(Cι-C6alkyl)3, * -Si(Ci-Qalkyl)r(phenyl)s and phenyl, wherein each phenyl ring may in turn be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Ci-Qalkoxy, Q-Qhaloalkoxy, -CN, -COR227, -C00R228, -N02, -N(R229)R23o, -SH, -S(0)qQ-Qalkyl and -S(0)qQ-Qhaloalkyl; and/or Ri3i, i32, R133, R134, i35, i36, Ri37, i3s, )39 and Rι40 may be each independently of the others phenyl or phenyl substituted from one to five times by substituents selected from halogen and Ci-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Ci-Qhaloalkoxy, -CN, -COR227, -COOR228, -N02, -N(R229)R230, -SH, -S(0)qCi-Qalkyl and -S(0)qd-Qhaloalkyl;
R200 and R201 are each independently of the other hydrogen, Q-Qalkyl, Ci-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-C6alkoxy-Q-C6alkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from
Q-Qhaloalkyl, -OH, Q-Qalkoxy, d-Qhaloalkoxy and -C0R227; R202 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy and Q-Qhaloalkoxy; R2o3 and R2o4 are each independently of the other hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and
Q-Qalkyl and or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy and -COR227; R205 and R2o6 are each independently of the other hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy and -COR227; R207 and 208 are each independently of the other hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl,
Q-Qalkoxy-Q-Qalkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and Ci-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-C6haloalkoxy, -CN, -C0R227, -COOR228, -N02, -N(R229)R 30, -SH, -S(0)qQ-C6alkyl and -S(0)qQ-C6haloalkyl;
R2o9 is hydrogen, Q-C6alkyl, Cι-C6haloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Ci-Qalkoxy-Q-Qalkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy, -CN, -COR227, -COOR228, -N02, -N(R229)R230, -SH, -S(0)qCι-Qalkyl and -S(0)qQ-Qhaloalkyl; R210 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy and Q-Qhaloalkoxy; R211 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy, -CN, -COR227, -COOR228, -N02, -N(R229)R230, -SH, -S(0)qQ-Qalkyl and -S(0)qQ-Qhaloalkyl; R2i2 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl,
Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy and Q-Qhaloalkoxy; R i3 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl,
Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy, -CN, -COR227, -COOR228, -N02, -N(R2 9)R230, -SH, -S(0)qQ-Qalkyl and -S(0)qQ-Qhaloalkyl;
R214, R2i5 and R2i6 are each independently of the others hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Ci-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy and Q-Qhaloalkoxy; R217 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Ci-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Ci-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy and Ci-Qhaloalkoxy; R2is is hydrogen, Ci-Qalkyl, Ci-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Ci-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy and Q-Qhaloalkoxy; R2ι is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhalo alkyl, -OH, Q-Qalkoxy and Q-Qhaloalkoxy; R220 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Ci-Qhaloalkoxy, -CN, -COR227, -COOR228, -N02, -N(R229)R23o, -SH, -S(0)qQ-Qalkyl and -S(0)qd-C6haloalkyl; R22i is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl,
Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy and Q-Qhaloalkoxy; R222 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl,
Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q -Qhaloalkoxy, -CN, -COR227, -COOR228, -N02, -N(R229)R23o, -SH, -S(0)qQ-C6alkyl and -S(0)qQ-C6haloalkyl; R223 is hydrogen, Q-C6alkyl, Q-C6haloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy and Q-Qhaloalkoxy; R 24 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Ci-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy and Q-Qhaloalkoxy; R2 5 s hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy and Ci -Qhaloalkoxy; R226 is hydrogen, Ci-Qalkyl, Ci-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Ci-Qalkoxy-Q-Qalkyl or phenyl, wherein the phenyl ring may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy, -CN, -COR227, -COOR228, -N02, -N(R229)R23o, -SH, -S(O)qQ-Qalkyl and -S(0)qQ-Qhaloalkyl; R227 is hydrogen, Q-Qalkyl, Ci-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy and Q-Qhaloalkoxy; R228 is hydrogen, Q-Qalkyl, Q-C6haloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy and Q-Qhaloalkoxy; R 2 and R230 are each independently of the other hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and, Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy and -COR227; q is 0, 1 or 2; r and s are 0, 1, 2 or 3, the sum of [r + s] being 3; or any one or more of those pairs of substituents Rι33 to Rι o which are bonded to the same carbon atom together may form, each independently of any other(s), the function =0, =S, =NOR23ι or =NN(R232)R233;
R231 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy and Q-Qhaloalkoxy; R2 2 and R233 are each independently of the other hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and
Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy and -COR227; or Ri3! and R!32 together, Rι33 and RJ 4 together, Rι35 and Rι36 together, Rj37 and R138 together and/or Rι39 and Rι 0 together, each independently of any other(s), may form a Q-Qalkylene or Q-Qalkenyl ene bridge each of which may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by Q-Qhaloalkyl; and/or
Ri3i and R133 together, R!33 and Rι35 together, Rι35 and R]37 together, and/or R]37 and Rι39 together, each independently of any other(s), may form a Q-Qalkylene or Q-Qalkenyl ene bridge each of which may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by Q-Qhaloalkyl; and/or Ri3i and R]35 together, Rι33 and Rι37 together, and/or RI35 and Rι39 together, each independently of any other(s), may form a Q-Qalkylene or Q-Qalkenylene bridge each of which may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by Q-Qhaloalkyl; and/or Ri3i and Rι37 together, Rι 3 and Rι39 together, and/or Rι3! and Rι39 together, each independently of any other(s), may form a Q-Qalkylene or Q-Qalkenylene bridge each of which may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by Q-Qhaloalkyl, with the proviso that for Rj3ι and Rι32 the meanings -OH, -SH and -N(R2oo)R2oι wherein R2oo and R20ι are hydrogen are excluded;
B either is a direct bond between the sp-hybridised carbon atom of the triple bond and the phenyl ring or is a bridging member Bi, B2, B3 or B4
Figure imgf000135_0001
Ri4i, R142, R143, Ri44, i45, Ri46> i47 and RJ 8 are each independently of the others hydrogen, halogen, -CN, -N02, -N(R200)R2oi, Q-Qalkyl, Q-Qhaloalkyl, -OH,
Q-Qalkoxy, Q-Qhaloalkoxy, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qalkenyloxy, Q-Qhaloalkenyloxy, Q-Qalkynyloxy, C3-C8cycloalkyl, C3-C8halocycloalkyl, -C(O)OR202, -C(0)NR2o3R2θ4, -C(S)NR2o5R206, -COR207, -CSR208, -C(R209)=NOR2ι0j -OC(0)R2U, -OC(0)OR212, -SC(0)R2ι3, -SC(0)OR2ι4, -OC(S)SR2ι5, -SC(S)SR2ι<5, -OS02Q-C6alkyl, -OS02Cι-C6haloalkyl, -SH,
-S(0)qCι-C6alkyl or -S(0)qQ-Qhaloalkyl, and/or
R141, Ri42, R143, Ri44, Ri45, i46> i47 and Rι48 may be each independently of the others Q-Qalkyl or Q-Qalkoxy each of which is substituted once, twice or three times by substituents selected from -CN, C(0)0R2ι7, -CHO, -COR2ιs, -C(O)NR2ι9R220, -C(S)NR22iR222, -C(R223)=NOR224, -N(R225)R226, -OH, Q-C6alkoxy, Q-Qhaloalkoxy,
-SH, -S(0)qd-Qalkyl, -S(0)qQ-C6haloalkyl, -Si(Q-C6alkyl)3, -Si(Cι-Qalkyl)r(phenyl )s and phenyl, wherein each phenyl ring may in turn be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy, -CN, -COR227, -COOR228, -N02, -N(R229)R23o, -SH, -S(0)qQ~Qalkyl and -S(0)qQ-Qhaloalkyl, wherein R200 to
R230, q, r and s are as defined hereinbefore; and/or
Ri4i, Rj42, Rj43, Rj44, Rι 5, Rι46, Rι47 and Rι 8 may be each independently of the others phenyl or phenyl substituted from one to five times by substituents selected from halogen and Ci-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy, -CN, -COR227, -COOR2 8,
-N02, -N(R229)R230, -SH, -S(0)qQ-Qalkyl and -S(0)qQ-Qhaloalkyl; or any one or more of those pairs of substituents Rι41 to Rι48 which are bonded to the same carbon atom together may form, each independently of any other(s), the function =0, =S,
Figure imgf000136_0001
wherein R23ι to R233 are as defined hereinbefore; and/or R]4i and Rj42 together, Rι43 and Rι4 together, Rι 5 and R]46 together, and/or Rι47 and
Rι 8 together, each independently of any other(s), may form a Q-Qalkylene or Q-Qalkenylene bridge each of which may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by Q-Qhaloalkyl; and/or Rι4ι and Rι43 together, Rj43 and R145 together, and/or Rϊ45 and Rι47 together, each independently of any other(s), may form a Q-Qalkylene or Q-Qalkenylene bridge each of which may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by Q-Qhaloalkyl; and/or R1 ι and Rι45 together, Rι43 and Rι47 together, and/or Rι ι and Rι47 together, each independently of any other(s), may form a Q-Qalkylene or Q-Qalkenylene bridge each of which may be substituted from one to five times by substituents selected from halogen and Ci-Qalkyl and/or once, twice or three times by Q-Qhaloalkyl, or compounds of the formula I containing anN-oxide of the groups Q2, Q3, Q4, Q5, Q6, Q7 or Q8, or an agrochemically acceptable salt or any stereoisomer or tautomer of a compound of formula I with the proviso that, when B is a direct bond between the sp-hybridised carbon atom of the triple bond and the phenyl ring, the bridging member A is other than
Figure imgf000137_0001
2. A compound according to claim 1, wherein Q is a group Qi, Q2, Q3 or Q4
Figure imgf000137_0002
Figure imgf000137_0003
3. A compound according to claim 2, wherein Q is a group Qj or Q2
Figure imgf000137_0004
4. A compound according to claim 3, wherein Q is a group Qj
Figure imgf000137_0005
5. A compound according to claim 2, wherein Q is a group Q2a or Q4a
Figure imgf000137_0006
- 13o -
6. A compound according to claim 1, wherein A is a bridging member Ai or A2
Figure imgf000138_0001
7. A compound according to claim 1, wherein B is a direct bond between the sp- ' hybridised carbon atom of the triple bond and the phenyl ring or is the bridging member \
Figure imgf000138_0002
8. A compound according to claim 1, wherein A is a bridging member A
Figure imgf000138_0003
and B is a direct bond between the sp-hybridised carbon atom of the triple bond and the phenyl ring.
9. A compound according to claim 1, wherein A is the bridging member Ai
Figure imgf000138_0004
and B is the bridging member Bi
Figure imgf000138_0005
10. A compound according to claim 1, wherein Q is a group Qls Q2, Q3 or Q4
Figure imgf000139_0001
Figure imgf000139_0002
A is the bridging member A2
Figure imgf000139_0003
and B is a direct bond between the sp-hybridised carbon atom of the triple bond and the phenyl ring.
11. A compound according to claim 1, wherein Q is a group O , Q2, Q3 or Q4
Figure imgf000139_0004
Figure imgf000139_0005
A is the bridging member Aj C (A,). R131 132 and B is the bridging member Bi
Figure imgf000139_0006
12. A compound according to claim 1, wherein Q is a group Q or Q2
Figure imgf000140_0001
A is the bridging member A2
Figure imgf000140_0002
and B is a direct bond between the sp-hybridised carbon atom of the triple bond and the phenyl ring.
13. A compound according to claim 1, wherein Q is a group Qi or Q2
Figure imgf000140_0003
A is the bridging member Ai .O. >< fa), R131 R132 and B is the bridging member Bi
Figure imgf000140_0004
(BJ.
14. A compound according to claim 1, wherein each Ri, independently of any other(s), is halogen, -CN, -N02, -C(Rιo)=NORn, -0Rι3, -S02Rι6, -0S02R,7, Q-C8alkyl or Q-Qalkenyl, or Q-Qalkyl substituted once, twice or three times by halogen and/or by -CN; Rio is hydrogen or Q-Qalkyl; Rπ is Q-Qalkyl, and n is 0, 1, 2 or 3.
15. A compound according to claim 2, wherein each R2, independently of any other(s), is halogen, -CN, -SCN, -OCN, -N3, -N02, -NR33R34, -C02R35, -CONR36R37, -C(R38)=NOR39, -COR40, -ORn, -S02R44, -OS02R45, -N([CO]pR46)COR47, -N(R56)S02R57, -N(S02R58)S02R59, -N-C(OR60)R6i or C,-C8alkyl, or d-Qalkyl substituted once, twice or three times by halogen, -CN, -N3, -SCN, -C02R73, -CONR74R75, -COR76, -C(R77)=NOR78, -C(S)NR79R80, -OR82, -SOR84, -S02R85 and/or by -N(R8 )COR9o, and m is 0, 1, 2, 3 or 4.
16. A process for the preparation of a compound of formula Iabo
Figure imgf000141_0001
wherein A, Q, R2 and m are as defined in claim 1 , which comprises coupling a compound of formula Ila
Figure imgf000141_0002
wherein A and Q are as defined, with a compound of formula III
Figure imgf000141_0003
wherein R2 and m are as defined and W is a leaving group, in the presence of a palladium catalyst under Sonogashira reaction conditions.
17. A process for the preparation of a compound of formula Iabi , Iab2, Iab3 or Iab4
Figure imgf000141_0004
Figure imgf000142_0001
wherein A, Q, R2, m and R143 to Rι48 are as defined in claim 1 and Ei is a bridging member
Figure imgf000142_0002
wherein Rj4ι is as defined in claim 1 and R!49 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy and -COR227, wherein R227 is as defined in claim 1, which comprises causing a compound of formula Ila
Figure imgf000142_0003
wherein A and Q are as defined, to react with a compound of formula IVbi, IVb , IVb3 or IVb4
Figure imgf000142_0004
Figure imgf000142_0005
wherein R2, m and Rι43 to Rι48 are as defined and E is an electrophilic functional group
Figure imgf000143_0001
wherein R141 and R1 9 are as defined and Xi is a leaving group, in the presence a) of a strong base or b) of zinc salts and a base in an inert, organic solvent at temperatures from -100° to 50°C.
18. A process for the preparation of a compound of formula Iab2, Iab3 or Iab4
Figure imgf000143_0002
wherein A, Q, R2, m and Rι 5 to R1 8 are as defined in claim 1 and E2 is a bridging member
Figure imgf000143_0003
wherein R141, Rι42 and Rι 3 are as defined in claim 1, which comprises causing a compound of formula Ila
Figure imgf000144_0001
wherein A and Q are as defined, to react with a compound of formula Vb2, Vb3 or Vb4
Figure imgf000144_0002
wherein R2, m, R1 ι to Rι43, and Rι45 to Rι48 are as defined, in the presence a) of a strong base or b) of zinc salts and abase in an inert, organic solvent at temperatures from -100° to 50°C.
19. A process for the preparation of a compound of formula I
Figure imgf000144_0003
wherein A, Q, B, R2 and m are as defined in claim 1, which comprises causing a compound of formula VII Q-OH (VII) to react with a compound of formula VIII
Figure imgf000144_0004
under typical Mitsunobu reaction conditions, the radicals A, Q, B and R2 and the suffix m in the compounds of formulae VII and VIII being as defined.
0. A process for the preparation of a compound of formula I
Figure imgf000145_0001
wherein A, Q, B, R2 and m are as defined in claim 1 , which comprises causing a compound of formula VII Q-OH (VII) and a compound of formula IXai, L a2, IXa3, IXa4 or IXas
Figure imgf000145_0002
to react with one another under typical base-catalysed reaction conditions of alkylation, the radicals Q, B and R2 and the suffix m in the compounds of formulae VII and IXai to IXa5 being as defined, Rm to Rι40 being as defined in claim 1 and L being a leaving group.
21. A process for the preparation of a compound of formula I
Figure imgf000146_0001
wherein A, Q, B, R2 and m are as defined in claim 1, which comprises causing a compound of formula VIIi
Figure imgf000146_0002
to react with a compound of formula Xai, Xa2, Xa3, Xa4 or Xa5
Figure imgf000146_0003
under typical nucleophilic aromatic substitution reaction conditions, the radicals Q, B and R2 and the suffix m in the compounds of formulae VIIi and Xai to Xa5 being as defined, R131 to RHO being as defined in claim 1, Lj being a leaving group and M+ being an alkali metal ion.
22. A process for the preparation of a compound of formula Ia2b, Ia3b, Ia^ or Ia5b
Figure imgf000147_0001
wherein Q, B, R2, m and Rι3ι to Rι38 are as defined in claim 1 and E3 is a bridging member 0r
Figure imgf000147_0002
XC/Rl3? or XC/Rl39
Figure imgf000147_0003
14499 . / ' "N , Λ"H "R.14.9- "NHR. 149 wherein Rj3 , R135, R137 and Rj3 are as defined in claim 1 and Rj49 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy and -COR227, wherein R227 is as defined in claim 1, which comprises causing a compound of formula Vlai, VIa2, VIa3 or VIa4
Figure imgf000148_0001
to react with a compound of formula lib
Figure imgf000148_0002
< in the presence a) of a strong base or b) of zinc salts and a base in an inert organic solvent at temperatures from -100° to 50°C, the radicals Q, B, R2 and Ri3i to R)38 and the suffix m in the compounds of formulae Vlai to Vla4 and lib being as defined and E being an electrophilic functional group β d O P — C or — CH.*, , or — C — C — Q or 1 R133 R135 ' R137
Figure imgf000148_0003
wherein R133, Rπs, Ri37> R139 and Rι49 are as defined and X! is a leaving group.
3. A process for the preparation of a compound of formula Ia3b, Ia^ or Ia5b
Figure imgf000149_0001
(la5b),
Figure imgf000149_0002
wherein Q, B, R2, m and Rι3ι to Rι36 are as defined in claim 1 and E4 is a bridging member
Figure imgf000149_0003
wherein Rι33 and Rι35 to Rι40 are as defined in claim 1, which comprises causing a compound of formula XIa3, X^ or XIa5
Figure imgf000149_0004
to react with a compound of formula lib
Figure imgf000149_0005
in the presence a) of a strong base or b) of zinc salts and a base in an inert organic solvent at temperatures from -100° to 50°C, the radicals Q, B, R2 and R131 to R] 0 and the suffix m in the compounds of formulae XIa3 to XIa5 and Ub being as defined.
24. A process for the preparation of a compound of formula Ila
Figure imgf000150_0001
wherein A and Q are as defined in claim 1, which comprises coupling a compound of formula VII Q-OH (VII) with a compound of formula XII H A — CΞΞΞCH (χι,)> wherein the radicals A and Q in the compounds of formulae VII and XII are as defined, under typical Mitsunobu reaction conditions.
25. A process for the preparation of a compound of formula Ila
Figure imgf000150_0002
wherein A and Q are as defined in claim 1, which comprises causing a compound of formula VII Q-OH (VII) to react with a compound of formula Xlllai, XIIIa2, XIIIa3, XIIIa4 or XIIIa5 (Xllla22)/'
Figure imgf000151_0001
or
Figure imgf000151_0002
(Xllla5)
Figure imgf000151_0003
under typical base-catalysed reaction conditions of alkylation, the radicals Q and Ri3i to Rι4o in the compounds of formulae VII and Xlllai to XIIIa5 being as defined in claim 1 and L being a leaving group.
26. A process for the preparation of a compound of formula Ila
Figure imgf000151_0004
wherein A and Q are as defined in claim 1, which comprises causing a compound of formula VIIi
Figure imgf000151_0005
to react with a compound of formula XIV a! , XIV a2, XIV 3, XIVa4 or XIV a5
Figure imgf000152_0001
Figure imgf000152_0002
(XIVa4) or
Figure imgf000152_0003
under typical nucleophilic aromatic substitution reaction conditions, the radicals Q and Ri3i to Rι 0 in the compounds of formulae VIIi and XlVaj to XrVa5 being as defined in claim 1, Lj being a leaving group and M+ being an alkali metal ion.
27. A process for the preparation of a compound of formula XV
Figure imgf000152_0004
wherein A and Q are as defined in claim 1 and E is an electrophilic functional group
Figure imgf000152_0005
wherein Rm is as defined in claim 1, Rι 9 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy- Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy and -COR227, wherein R227 is as defined in claim 1, and Xi is a leaving group, which comprises coupling a compound of formula VII Q-OH (VII). with a compound of formula XVI
Figure imgf000153_0001
under typical Mitsunobu reaction conditions, the radicals A, Q and E in the compounds of formulae VII and XVI being as defined.
28. A process for the preparation of a compound of formula XV
Figure imgf000153_0002
wherein A and Q are as defined iii claim 1 and E is an electrophilic functional group
Figure imgf000153_0003
wherein RJ4ι is as defined in claim 1, Rι 9 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy- Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhalo alkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy and -COR227, wherein R227 is as defined in claim 1, and Xi is a leaving group, which comprises causing a compound of formula VII Q-OH (VII) and a compound of formula XVIIai, XVIIa2, XVIIa3, XVI^ or XVIIa5 R R 132 R 132 131 R1 31 \ (XVI la,), (XVIIa2),
R133 R1 34
Figure imgf000154_0001
(XVI la4) or
Figure imgf000154_0002
to react with one another under typical base-catalysed reaction conditions of alkylation, the radicals Q and E in the compounds of formulae VII and XVIIai to XVIIa5 being as defined, Rι3ι to Rι 0 being as defined in claim 1 and L being a leaving group.
29. A process for the preparation of a compound of formula XV
Figure imgf000154_0003
wherein A and Q are as defined in claim 1 and E is an electrophilic functional group
Figure imgf000154_0004
wherein R141 is as defined in claim 1, Rι49 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy- • Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy and -COR227, wherein R227 is as defined in claim 1, and Xi is a leaving group, which comprises causing a compound of formula VIIi
Figure imgf000155_0001
to react with a compound of formula XVIIIai, XVIIIa2, XVIIIa3, XVIIIa4 or XVIIIa5
Figure imgf000155_0002
Figure imgf000155_0003
M+ IIa5)
Figure imgf000155_0004
under typical nucleophilic aromatic substitution reaction conditions, the radicals E, Q and R131 to Rι 0 in the compounds of formulae VIIi and XVIIIai to XVIIIas being as defined in claim 1, Li being a leaving group and M+ being an alkali metal ion.
30. A process for the preparation of a compound of formula XlXaibo, XIXa2b0, XIXa3b0, XIXa4b0 or XIXa5b0
(XlXaibo),
Figure imgf000155_0005
Figure imgf000156_0001
wherein R2, m and R to Rι40 are as defined in claim 1 and R3 is hydrogen or a protecting group, which comprises coupling a compound of formula XXai, XXa2,
Figure imgf000156_0002
Figure imgf000157_0001
Figure imgf000157_0002
(XXa4) or
Figure imgf000157_0003
wherein R3 and Rι3ι to R]4o are as defined, with a compound of formula III
Figure imgf000157_0004
wherein R2 and m are as defined and W is a leaving group, in the presence of a palladium catalyst under Sonogashira reaction conditions.
1. A process for the preparation of a compound of formula XXIa3b, XXIa4b or XXIa5b
Figure imgf000158_0001
wherein B, R2, m and R131 to R136 are as defined in claim 1, R3 is hydrogen or a protecting group and E4 is a bridging member
Figure imgf000158_0002
wherein R133 and Rι35 to Rj40 are as defined in claim 1, which comprises causing a compound of formula XXIIa3, XXIIa4 or XXIIa5
(XXIIa4) or
Figure imgf000158_0003
Figure imgf000158_0004
wherein R131 to RHO and R3 are as defined, to react with a compound of formula lib
Figure imgf000159_0001
wherein B, R2 and m are as defined, in the presence a) of a strong base or b) of zinc salts and a base in an inert organic solvent at temperatures from -100° to 50°C.
32. A process for the preparation of a compound of formula XXIIIabi, XXIIIab2, XXIIIab3 or XXIIIab4
(XXIIlab,), (XXIIIa
Figure imgf000159_0003
Figure imgf000159_0002
(XXIIIab3) or
Figure imgf000159_0004
(XXIIIabΛ
Figure imgf000159_0005
wherein A, R2, m and R143 to Rι48 are as defined in claim 1, it being possible for the alcohol function in group A to be protected by a protecting group for alcohols, and Ei is a bridging member
Figure imgf000159_0006
wherein Rι41 is as defined in claim 1 and R149 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy and -COR227, wherein R227 is as defined in claim 1, which comprises causing a compound of formula XII HA — C≡CH (XII), wherein A is as defined, to react with a compound of formula IVbi, IVb2, IVb3 or
IVb4
Figure imgf000160_0001
Figure imgf000160_0002
wherein R2, m and Rj43 to Rι48 are as defined and E is an electrophilic functional group
Figure imgf000160_0003
wherein Rι j and Rι49 are as defined and Xi is a leaving group, in the presence a) of a strong base or b) of zinc salts and a base in an inert, organic solvent at temperatures from -100° to 50°C, it being possible for the alcohol-protecting group to be removed and for the exposed hydroxyl function to be used for further reactions.
3. A process for the preparation of a compound of formula XXVa2b, XXVa3b, XXVa4b or XXVa5b
Figure imgf000161_0001
(XXVa4b) or
Figure imgf000161_0002
Figure imgf000161_0003
wherein R2, B, Rι31 to RB8 and m are as defined in claim 1, R3 is hydrogen or a protecting group for the alcohol function and E3 is a bridging member
Figure imgf000161_0004
wherein R133, R135, R137 and Ri39 are as defined in claim 1 and Rj4 is hydrogen, Q-Qalkyl, Q-Qhaloalkyl, Q-Qalkenyl, Q-Qhaloalkenyl, Q-Qalkynyl, Q-Qhydroxyalkyl, Q-Qalkoxy-Q-Qalkyl, phenyl or benzyl, wherein the two phenyl rings may be substituted from one to five times by substituents selected from halogen and Q-Qalkyl and/or once, twice or three times by substituents selected from Q-Qhaloalkyl, -OH, Q-Qalkoxy, Q-Qhaloalkoxy and -COR227, wherein R227 is as defined in claim 1, which comprises causing a compound of formula lib
Figure imgf000162_0001
wherein R2, B and m are as defined, to react with a compound of formula XXIVa2, XXrVa3, XXIV34 or XXIVa5
(XXIVa3),
Figure imgf000162_0002
(XXIVa4) or (XX|Va5),
Figure imgf000162_0003
Figure imgf000162_0004
wherein R3 and Rm to Rι38 are as defined and E is an electrophilic functional group P P O p — C \ or — CH , , or — C \ , — C \ ι — C \ or X1 R133 R135 R137
Figure imgf000162_0005
// NR149 R139 wherein R133, R13s, Ri37, Ri3 and Rι4 are as defined and Xi is a leaving group, in the presence a) of a strong base or b) of zinc salts and a base in an inert, organic solvent at temperatures from -100° to 50°C
4. A process for the preparation of a compound of formula XXIIIab2, XXIIIab3 or XXIIIab4 (XXIIIab 'V2)'
Figure imgf000163_0002
Figure imgf000163_0001
(XXIIIabg) or
(XXIIIab4),
Figure imgf000163_0003
wherein A, R , Rι45 to Rι48 and m are as defined in claim 1, it being possible for the alcohol function in group A to be protected by a protecting group for alcohols, and E2 is a bridging member
Figure imgf000163_0004
wherein Rj4ι, Rι 2 and Rι43 are as defined in claim 1, which comprises causing a compound of formula XII HA — C≡CH (XII), wherein A is as defined, to react with a compound of formula Vb2, Vb3 or Vb
Figure imgf000163_0005
wherein R2, m, RHI to Rι43, and Rι45 to Rι 8 are as defined, in the presence a) of a strong base or b) of zinc salts and a base • in an inert, organic solvent at temperatures from -100° to 50°C, it being possible for the alcohol-protecting group to be removed and for the exposed hydroxyl function to be used for further reactions.
35. A process for the preparation of a compound of formula XXV a3b, XXV a4b or XXVa5b
Figure imgf000164_0001
wherein R2, B, Rj3ι to Rι36 and m are as defined in claim 1, R3 is hydrogen or a protecting group for the alcohol function and E4 is a bridging member
Figure imgf000164_0002
wherein Rι3 and R135 to RHO are as defined in claim 1, which comprises causing a i compound of formula lib
Figure imgf000164_0003
wherein R2, B and m are as defined, to react with a compound of formula XXIIa3, XXIL^ or XXIIas OαhJ or
Figure imgf000165_0001
wherein R131 to Rι4o and R are as defined, in the presence a) of a strong base or b) of zinc salts and a base in an inert, organic solvent at temperatures from -100° to 50°C.
36. A herbicidal and plant- growth-inhibiting composition which comprises, on an inert carrier, a herbicidally effective amount of a compound of formula I.
37. A herbicidal and plant-growth-inhibiting composition according to claim 36, which comprises, as additional component, at least one further co-herbicide.
38. A method of controlling undesired plant growth, which comprises applying a herbicidally effective amount of a compound of formula I or of a composition comprising such a compound to the plants or to the locus thereof.
39. A method of inhibiting plant growth, which comprises applying a herbicidally effective amount of a compound of formula I or of a composition comprising such a compound to the plants or to the locus thereof.
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