WO2014019609A1 - Methods of pest control in soybean - Google Patents

Methods of pest control in soybean Download PDF

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Publication number
WO2014019609A1
WO2014019609A1 PCT/EP2012/064937 EP2012064937W WO2014019609A1 WO 2014019609 A1 WO2014019609 A1 WO 2014019609A1 EP 2012064937 W EP2012064937 W EP 2012064937W WO 2014019609 A1 WO2014019609 A1 WO 2014019609A1
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Prior art keywords
trifluoromethyl
formula
chloro
compounds
phenyl
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PCT/EP2012/064937
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French (fr)
Inventor
Myriem El Qacemi
Jérôme Yves CASSAYRE
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Syngenta Participations AG
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Syngenta Participations AG
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Priority to US14/418,213 priority Critical patent/US9867375B2/en
Priority to PCT/EP2012/064937 priority patent/WO2014019609A1/en
Priority to BR112015001908A priority patent/BR112015001908A2/en
Publication of WO2014019609A1 publication Critical patent/WO2014019609A1/en
Anticipated expiration legal-status Critical
Priority to US15/838,466 priority patent/US20180098542A1/en
Ceased legal-status Critical Current

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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
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/08—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hydrocarbon radicals, substituted by hetero atoms, attached to ring carbon atoms
    • C07D207/09—Radicals substituted by nitrogen atoms, not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
    • C07D207/20—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06Q—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES; SYSTEMS OR METHODS SPECIALLY ADAPTED FOR ADMINISTRATIVE, COMMERCIAL, FINANCIAL, MANAGERIAL OR SUPERVISORY PURPOSES, NOT OTHERWISE PROVIDED FOR
    • G06Q30/00—Commerce
    • G06Q30/018—Certifying business or products

Definitions

  • the present invention relates to methods of pest control in soybean crops.
  • Stink bugs (Hemiptera Pentatomidae) are true bugs which can be significant pests when present in large numbers. The nymphs and adults have piercing mouthparts which most use to suck sap from 5 plants. According to Stewart et al., Soybean Insects - Stink bugs, University of Tennessee Institute of Agriculture, W200 09-0098, stink bugs are probably the most common pest problem in soybean.
  • stinkbugs in soybean are often vital to prevent significant economic damage.
  • Insecticides commonly used to control stinkbugs include pyrethroids, neonicotinoids and
  • organophosphates although pyrethroid insecticides are usually the method of choice for controlling stink bugs in soybean.
  • insecticide resistance particularly in 20 brown stink bug populations and particularly to pyrethroids.
  • Euschistus hews can also be difficult to manage using organophosphates or endosulfan (Sosa-Gomez et al., 2009). There is therefore a need for effective alternative methods of controlling stinkbugs in soybean.
  • GABA gamma-aminobutyric acid
  • GABA gamma- 35 aminobutyric acid
  • stinkbugs and in some cases can provide greater control than the current market standard. It has also surprisingly been found that these compounds exhibit significantly higher activity against stinkbugs than structurally similar compounds. These compounds therefore represent an important new solution for safeguarding soybean crops from stinkbugs, particularly where stink bugs are resistant to current methods.
  • the invention provides a method comprising applying to a crop of soybean plants, the locus thereof, or propagation material thereof, a compound of formula I
  • X 2 is C-X 6 or nitrogen
  • ⁇ ', ⁇ 3 and X 6 are independently hydrogen, halogen or trihalomethyl, wherein at least one of X 1 , X 3 and
  • X 6 is not hydrogen
  • A is selected from group Al to A4
  • Y 1 is C-R 6 , CH or nitrogen
  • Y 2 and Y 3 are independently CH or nitrogen;
  • R 5 is hydrogen, halogen, cyano, nitro, NH 2 , Ci-C 4 alkyl, Ci-C 4 haloalkyl, C 3 -C 5 cycloalkyl, C 3 - C 5 halocycloalkyl, Ci-C 2 alkoxy, or Ci-C 2 haloalkoxy;
  • R 7 is C C 4 alkyl
  • R 8 is Ci-C 4 alkyl, C r C 4 haloalkyl, Ci-C 4 alkoxy(C r C 4 )alkyl, Ci-C 4 alkylthio(C r C 4 )alkyl, C r
  • each Z is independently halogen, Ci-Ci 2 alkyl or Ci-Ci 2 alkyl substituted by one to five R 12 , nitro, d-
  • k 0, 1,2 or 3.
  • the invention provides a method of controlling and/or preventing infestation of stinkbugs in soybean comprising applying to a crop of soybean plants, the locus thereof, or propagation material thereof, a compound of formula I.
  • the stinkbugs may be those that are resistant to one or more other insecticides.
  • the invention provides a method of controlling and/or preventing infestation of stinkbugs in a crop of useful plants comprising applying to a crop of useful plants, the locus thereof, or propagation material thereof, a compound of formula I.
  • the stinkbugs may be those that are resistant to one or more other insecticides.
  • the invention provides use of a compound of formula I for control of stinkbugs in a crop of useful plants.
  • the use may be for controlling stinkbugs that are resistant to one or more other insecticides.
  • the invention provides a method of controlling and/or preventing infestation of insects from the genus Euschistus in a crop of useful plants comprising applying to a crop of useful plants, the locus thereof, or propagation material thereof, a compound of formula I.
  • the insects from the genus Euschistus may be those that are resistant to one or more other insecticides.
  • the invention provides use of a compound of formula I for control of insects from the genus Euschistus in a crop of useful plants.
  • the use may be for controlling insects from the genus Euschistus that are resistant to one or more other insecticides.
  • the invention provides a method of controlling and/or preventing infestation of insects from the genus Euschistus in a crop of soybean plants comprising applying to a crop of soybean, the locus thereof, or propagation material thereof, a compound of formula I.
  • the insects from the genus Euschistus may be those that are resistant to one or more other insecticides.
  • the invention provides use of a compound of formula I for control of insects from the genus Euschistus in a crop of soybean plants.
  • the use may be for controlling insects from the genus Euschistus that are resistant to one or more other insecticides.
  • the invention provides a method of controlling and/or preventing infestation of Euschistus heros in a crop of useful plants comprising applying to a crop of useful plants, the locus thereof, or propagation material thereof, a compound of formula I.
  • the Euschistus heros may be resistant to one or more other insecticides.
  • the invention provides use of a compound of formula I for control of
  • Euschistus heros in a crop of useful plants The use may be for controlling Euschistus heros that is resistant to one or more other insecticides.
  • the invention provides a method of controlling and/or preventing infestation of Euschistus heros in a crop of soybean plants comprising applying to a crop of soybean, the locus thereof, or propagation material thereof, a compound of formula I.
  • the Euschistus heros may be resistant to one or more other insecticides.
  • the invention provides use of a compound of formula I for control of
  • Euschistus heros in a crop of soybean plants The use may be for controlling insects Euschistus heros that are is resistant to one or more other insecticides.
  • Stinkbugs that are resistant to one or more other insecticides are preferably resistant to pyrethroid, neonicotinoids and/or organophosphates, more preferably pyrethroid insecticides.
  • the invention provides a method for obtaining regulatory approval for the use of one or more of a compound of formula I to control stinkbugs, in particular the genus Euschistus and in particular the species Euschistus heros, and in particular in soybean plants, comprising at least one step of referring to, submitting or relying on biological data showing that said active ingredient reduces insect pressure.
  • the compounds of the invention may exist in different geometric or optical isomers or tautomeric forms. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
  • the compounds of the invention may contain one or more asymmetric carbon atoms, for example, at the C(R 1 )R 2 group, and may exist as enantiomers (or as pairs of diastereoisomers) or as mixtures of such.
  • Alkyl groups can be in the form of a straight or branched chain and are, for example, methyl, ethyl, propyl, prop-2-yl, butyl, but-2-yl, 2 -methyl-prop -1-yl or 2-methyl-prop-2- yl.
  • the alkyl groups are preferably i- e, more preferably C 1 -C4, most preferably C 1 -C3 alkyl groups.
  • the alkyl moiety is preferably substituted by one to four substituents, most preferably by one to three substituents.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Haloalkyl groups are alkyl groups which are substituted by one or more of the same or different halogen atoms and are, for example, difluoromethyl, trifluoromethyl,
  • Cycloalkyl groups or carbocyclic rings can be in mono- or bi-cyclic form and are, for example, cyclopropyl, cyclobutyl, cyclohexyl.
  • the cycloalkyl groups are preferably C 3 -C 6 cycloalkyl groups.
  • R 1 is trifluoromethyl, or chlorodifluoromethyl, most preferably trifluoromethyl.
  • X 1 , X 3 and X 6 are independently hydrogen, halogen or trifluoromethyl, wherein at least two of X 1 , X 3 and X 6 are not hydrogen. More preferably X 1 , X 3 and X 6 are independently hydrogen, chloro, bromo or trifluoromethyl, wherein at least two of X 1 , X 3 and X 6 are not hydrogen. Preferably at least two of X 1 , X 3 and X 6 are chloro, bromo or trifluoromethyl.
  • R 2 is 3,5-dichlorophenyl-, 3-chloro-4-fluorophenyl-, 3-fluoro-4- chlorophenyl-, 3,4-dichlorophenyl-, 3-chloro-4-bromophenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5- trichlorophenyl-, 3,5-dichloro-4-iodophenyl-, 3,4,5-trifluorophenyl-, 3-chloro-5-bromophenyl-, 3-chloro- 5-fluorophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,4-dichloro-5-(trifluoromethyl)phenyl-, 3,5- bis(trifluoromethyl)phenyl-, 4-chloro-3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6- dichloro-4-pyr
  • Y 1 is CH, Y 2 is CH, Y 3 is CH, or Y 1 is N, Y 2 is CH, Y 3 is CH, or Y 1 is N, Y 2 is N, Y 3 is CH, orY 1 is CH, Y 2 is N, Y 3 is CH, or Y 1 is CH, Y 2 is CH, Y 3 is N. Most preferably Y 1 is CH, Y 2 is CH, and Y 3 is CH.
  • R 5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, methoxy, nitro, trifluoromethoxy, cyano, cyclopropyl, more preferably R 5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, nitro, cyano, cyclopropyl, most preferably R 5 is hydrogen, cyano, chloro, bromo, fluoro, methyl, or trifluoromethyl.
  • R 8 is C r C 4 alkyl, C r C 4 haloalkyl, Ci-C 4 alkyl-0-CH 2 -, C r C 4 haloalkyl-0-CH 2 -,C 3 - Cgcycloalkyl, C 3 -C 6 cycloalkyl-CH 2 -, C C 4 alkyl-S(0)-CH 2 -, Ci-C 4 alkyl-S(0 2 )-CH 2 -, more preferably C r C 4 alkyl, C r C 4 alkyl-0-CH 2 -, C r C 4 alkyl-S-CH 2 -, C r C 4 alkyl-SO-CH 2 -, C r C 4 alkyl-S0 2 -CH 2 -, C 3 - C 4 cycloalkyl, or C3-C 4 cycloalkyl-CH 2 -, most preferably R 8 is methyl, ethyl, isopropyl, CH
  • each Z is independently halogen, cyano, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, or Ci-C 4 haloalkoxy, most preferably each Z is independently hydrogen, cyano, halogen, methyl, halomethyl, methoxy or halomethoxy, most preferably cyano or trifluoromethyl.
  • Each R 12 is preferably bromo, chloro, fluoro, methoxy, or methylthio, most preferably chloro, fluoro, or methoxy
  • k is 0 or 1.
  • R D and R 8° are as defined for a compound of formula I
  • R 1 is trifluoromethyl, or chlorodifluoromethyl, most preferably trifluoromethyl.
  • X 1 , X 3 and X 6 are independently hydrogen, halogen or trifluoromethyl, wherein at least two of X 1 , X 3 and X 6 are not hydrogen. More preferably X 1 , X 3 and X 6 are independently hydrogen, chloro, bromo or trifluoromethyl, wherein at least two of X 1 , X 3 and X 6 are not hydrogen. Preferably at least two of X 1 , X 3 and X 6 are chloro, bromo or trifluoromethyl.
  • R 2 is 3,5-dichlorophenyl-, 3-chloro-4-fluorophenyl-, 3-fluoro-4- chlorophenyl-, 3,4-dichlorophenyl-, 3-chloro-4-bromophenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5- trichlorophenyl-, 3,5-dichloro-4-iodophenyl-, 3,4,5-trifluorophenyl-, 3-chloro-5-bromophenyl-, 3-chloro- 5-fluorophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,4-dichloro-5-(trifluoromethyl)phenyl-, 3,5- bis(trifluoromethyl)phenyl-, 4-chloro-3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6- dichloro-4-pyr
  • Y 1 is CH, Y 2 is CH, Y 3 is CH, or Y 1 is N, Y 2 is CH, Y 3 is CH, or Y 1 is N, Y 2 is N, Y 3 is CH, orY 1 is CH, Y 2 is N, Y 3 is CH, or Y 1 is CH, Y 2 is CH, Y 3 is N. Most preferably Y 1 is CH, Y 2 is CH, and Y 3 is CH.
  • R 5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, methoxy, nitro, trifluoromethoxy, cyano, cyclopropyl, more preferably R 5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, nitro, cyano, cyclopropyl, more preferably R 5 is hydrogen, cyano, chloro, bromo, fluoro, methyl, or trifluoromethyl, even more preferably hydrogen, chloro, bromo, methyl or trifluoromethyl, most preferably chloro, bromo, fluoro or methyl.
  • R 8 is C r C 4 alkyl, C r C 4 haloalkyl, Ci-C 4 alkyl-0-CH 2 -, C r C 4 haloalkyl-0-CH 2 -,C 3 - Cgcycloalkyl, C 3 -C 6 cycloalkyl-CH 2 -, C r C 4 alkyl-S(0)-CH 2 -, Ci-C 4 alkyl-S(0 2 )-CH 2 -, more preferably C r Qalkyl, C r C 4 alkyl-0-CH 2 -, C r C 4 alkyl-S-CH 2 -, C r C 4 alkyl-SO-CH 2 -, C r C 4 alkyl-S0 2 -CH 2 -, C 3 - C 4 cycloalkyl, or C3-C 4 cycloalkyl-CH 2 -, most preferably R 8 is methyl, ethyl, isopropyl,
  • Y 3 is CH
  • R 1 is CF 3
  • R 8 is methyl, ethyl, isopropyl, CH 3 -0-CH 2 -, CH 3 -S-CH 2 -, CH 3 -S(0)-CH 2 -, CH 3 - S0 2 -CH 2 -, cyclobutyl, cyclopropyl or cyclopropyl-CH 2 -.
  • R 1 is CF 3
  • R 8 is methyl, ethyl, isopropyl, CH 3 -0-CH 2 -, CH 3 -S-CH 2 -, CH 3 -S(0)-CH 2 -, CH 3 -S0 2 - CH 2 -, cyclobutyl, cyclopropyl or cyclopropyl-CH 2 -.
  • Y 1 is CH
  • Y 2 is CH
  • Y 3 is CH
  • R 1 is CF 3
  • R 5 is chloro, bromo, fluoro or methyl
  • R 8 is methyl, ethyl, isopropyl, CH 3 -0-CH 2 -, CH 3 -S- CH 2 -, CH 3 -S(0)-CH 2 -, CH 3 -S0 2 -CH 2 -, cyclobutyl, cyclopropyl or cyclopropyl-CH 2 -.
  • R 8 methyl, ethyl, isopropyl, CH 3 -0-CH 2 -, CH 3 -S-CH 2 -, CH 3 -S(0)-CH 2 -, CH 3 -S0 2 -CH 2 -, cyclobutyl, cyclopropyl or cyclopropyl-CH 2 -.
  • R 5 is chloro, bromo, fluoro or methyl
  • R 8 methyl, ethyl, isopropyl, CH 3 -0-CH 2 -, CH 3 -S-CH 2 -, CH 3 -S(0)-CH 2 -, CH 3 -S0 2 -CH 2 -, cyclobutyl, cyclopropyl or cyclopropyl-CH 2 -,
  • R 1 is CF 3
  • Y 1 , Y 2 and Y 3 are CH
  • R 5 is chloro or methyl.
  • R 1 is trifluoromethyl, or chlorodifluoromethyl, most preferably trifluoromethyl.
  • X 1 , X 3 and X 6 are independently hydrogen, halogen or trifluoromethyl, wherein at least two of X 1 , X 3 and X 6 are not hydrogen. More preferably X 1 , X 3 and X 6 are independently hydrogen, chloro, bromo or trifluoromethyl, wherein at least two of X 1 , X 3 and X 6 are not hydrogen. Preferably at least two of X 1 , X 3 and X 6 are chloro, bromo or trifluoromethyl.
  • R 2 is 3,5-dichlorophenyl-, 3-chloro-4-fluorophenyl-, 3-fluoro-4- chlorophenyl-, 3,4-dichlorophenyl-, 3-chloro-4-bromophenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5- trichlorophenyl-, 3,5-dichloro-4-iodophenyl-, 3,4,5-trifluorophenyl-, 3-chloro-5-bromophenyl-, 3-chloro- 5-fluorophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,4-dichloro-5-(trifluoromethyl)phenyl-, 3,5- bis(trifluoromethyl)phenyl-, 4-chloro-3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6- dichloro-4-pyr
  • R 2 is 3,5-dichlorophenyl or 3,4,5-trichloro-phenyl, most preferably 3,5-dichloro-phenyl.
  • Y 1 is CH
  • Y 2 is CH
  • Y 3 is CH
  • Y 1 is N
  • Y 2 is CH
  • Y 3 is CH
  • Y 1 is N
  • Y 2 is N
  • Y 3 is CH
  • Y 1 is CH
  • Y 2 is N
  • Y 3 CH
  • Y 1 is CH
  • Y 2 is N
  • Y 3 CH
  • Y 1 is CH
  • Y 2 is N
  • Y 3 is CH
  • Y 1 is CH
  • Y 2 is N
  • Y 3 is CH
  • Y 1 is CH
  • Y 2 is CH
  • Y 3 is N.
  • Y 1 is CH
  • Y 2 is CH
  • Y 3 is CH.
  • R 7 is methyl
  • R 8 is C r C 4 alkyl, C r C 4 haloalkyl, Ci-C 4 alkyl-0-CH 2 -, C r C 4 haloalkyl-0-CH 2 -,C 3 -
  • R 1 is CF 3 and R 7 is methyl.
  • R 1 is CF 3
  • R 8 is methyl, ethyl, isopropyl, CH 3 -0-CH 2 -, CH 3 -S-CH 2 -, CH 3 -S(0)-CH 2 -, CH 3 -S0 2 -
  • R 7 is methyl and R 8 is methyl, ethyl, isopropyl, CH 3 -0-CH 2 -, CH 3 -S-CH 2 -, CH 3 -S(0)-CH 2 -, CH 3 -
  • R 1 is CF 3
  • R 7 is methyl
  • R 8 is methyl, ethyl, isopropyl, CH 3 -0-CH 2 -, CH 3 -S-CH 2 -, CH 3 -S(0)-CH 2 -, CH 3 -S0 2 -CH 2 -, cyclobutyl, cyclopropyl or cyclopropyl-CH 2 - and
  • R 2 is 3-chloro-5-bromophenyl-, 3- chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-, 3,5- bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-, 2,6-bis(trifluoromethyl)-
  • R 7 is methyl
  • R 8 is methyl, ethyl, isopropyl, CH 3 -0-CH 2 -, CH 3 -S-CH 2 -, CH 3 -S(0)-CH 2 -, CH 3 -S0 2 -CH 2 -, cyclobutyl, cyclopropyl or cyclopropyl-CH 2 -
  • R 7 is methyl
  • R 8 is methyl, ethyl, isopropyl, CH 3 - O-CH 2 -, CH 3 -S-CH 2 -, CH 3 -S(0)-CH 2 -, CH 3 -S0 2 -CH 2 -, cyclobutyl, cyclopropyl or cyclopropyl-CH 2 -
  • R 1 is CF 3
  • -C N-CH 2 - or -N-CH 2 -CH 2 -
  • Y 1 , Y 2 and Y 3 are CH.
  • R 1 is trifluoromethyl, or chlorodifluoromethyl, most preferably trifluoromethyl.
  • X 1 , X 3 and X 6 are independently hydrogen, halogen or trifluoromethyl, wherein at least two of X 1 , X 3 and X 6 are not hydrogen. More preferably X 1 , X 3 and X 6 are independently hydrogen, chloro, bromo or trifluoromethyl, wherein at least two of X 1 , X 3 and X 6 are not hydrogen. Preferably at least two of X 1 , X 3 and X 6 are chloro, bromo or trifluoromethyl.
  • R 2 is 3,5-dichlorophenyl-, 3-chloro-4-fluorophenyl-, 3-fluoro-4- chlorophenyl-, 3,4-dichlorophenyl-, 3-chloro-4-bromophenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5- trichlorophenyl-, 3,5-dichloro-4-iodophenyl-, 3,4,5-trifluorophenyl-, 3-chloro-5-bromophenyl-, 3-chloro- 5-fluorophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,4-dichloro-5-(trifluoromethyl)phenyl-, 3,5- bis(trifluoromethyl)phenyl-, 4-chloro-3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6- dichloro-4-pyr
  • Y 1 is CH, Y 2 is CH, Y 3 is CH, or Y 1 is N, Y 2 is CH, Y 3 is CH, or Y 1 is N, Y 2 is N, Y 3 is CH, orY 1 is CH, Y 2 is N, Y 3 is CH, orY 1 is CH, Y 2 is CH, Y 3 is N. Most preferably Y 1 is CH, Y 2 is CH, and Y 3 is CH.
  • R 5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, methoxy, nitro, trifluoromethoxy, cyano, cyclopropyl, more preferably R 5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, nitro, cyano, cyclopropyl, even more preferably R 5 is hydrogen, cyano, chloro, bromo, fluoro, methyl, or trifluoromethyl, most preferably cyano.
  • each Z is independently halogen, cyano, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, or Ci-C 4 haloalkoxy, more preferably each Z is independently hydrogen, cyano, halogen, methyl, halomethyl, methoxy or halomethoxy, most preferably cyano or trifluoromethyl.
  • k is 0 or 1.
  • R 1 is CF 3
  • R 5 is cyano and k is 0 or k is 1
  • Z is cyano or trifluoromethyl.
  • Y 3 is CH and R 1 is CF 3 .
  • R 1 is CF 3
  • R 5 is cyano and k is 0 or k is 1
  • Z is cyano or trifluoromethyl.
  • R 5 is cyano, k is 0 or 1 and Z is cyano or trifluoromethyl.
  • R 5 is cyano
  • R 1 is CF 3
  • R 1 is trifluoromethyl, or chlorodifluoromethyl, most preferably trifluoromethyl.
  • X 1 , X 3 and X 6 are independently hydrogen, halogen or trifluoromethyl, wherein at least two of X 1 , X 3 and X 6 are not hydrogen. More preferably X 1 , X 3 and X 6 are independently hydrogen, chloro, bromo or trifluoromethyl, wherein at least two of X 1 , X 3 and X 6 are not hydrogen. Preferably at least two of X 1 , X 3 and X 6 are chloro, bromo or trifluoromethyl.
  • R 2 is 3,5-dichlorophenyl-, 3-chloro-4-fluorophenyl-, 3-fluoro-4- chlorophenyl-, 3,4-dichlorophenyl-, 3-chloro-4-bromophenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5- trichlorophenyl-, 3,5-dichloro-4-iodophenyl-, 3,4,5-trifluorophenyl-, 3-chloro-5-bromophenyl-, 3-chloro- 5-fluorophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,4-dichloro-5-(trifluoromethyl)phenyl-, 3,5- bis(trifluoromethyl)phenyl-, 4-chloro-3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6- dichloro-4-pyr
  • Y 1 is CH, Y 2 is CH, Y 3 is CH, or Y 1 is N, Y 2 is CH, Y 3 is CH, or Y 1 is N, Y 2 is N, Y 3 is CH, orY 1 is CH, Y 2 is N, Y 3 is CH, orY 1 is CH, Y 2 is CH, Y 3 is N. Most preferably Y 1 is CH, Y 2 is CH, and Y 3 is CH.
  • R 5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, methoxy, nitro, trifluoromethoxy, cyano, cyclopropyl, more preferably R 5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, nitro, cyano, cyclopropyl, even more preferably R 5 is hydrogen, cyano, chloro, bromo, fluoro, methyl, or trifluoromethyl, most preferably cyano.
  • each Z is independently halogen, cyano, Ci-C 4 alkyl, Ci-C 4 haloalkyl, Ci-C 4 alkoxy, or Ci-C 4 haloalkoxy, more preferably each Z is independently hydrogen, cyano, halogen, methyl, halomethyl, methoxy or halomethoxy, most preferably cyano or trifluoromethyl.
  • k is 0 or 1.
  • R 1 is CF 3
  • R 5 is cyano and k is 0 or k is 1
  • Z is cyano or trifluoromethyl.
  • Y 3 is CH, R 1 is CF 3 , and k is 0 or k is 1 and Z is cyano or trifluoromethyl.
  • R 1 is CF 3 and R 5 is cyano.
  • R 5 is cyano, k is 0 or 1 and Z is cyano or trifluoromethyl.
  • Table 11 provides 288 compounds of formula la wherein R5 is hydrogen, B1-B2-B3 is N-CH2-CH2, and R2 and R8 are as defined in Table P.
  • Table 12 provides 288 compounds of formula la wherein R5 is methyl, B1-B2-B3 is N-CH2-CH2, and R2 and R8 are as defined in Table P.
  • Table 13 provides 288 compounds of formula la wherein R5 is trifluoromethyl, B1-B2-B3 is N-CH2- CH2, and R2 and R8 are as defined in Table P.
  • Table 14 provides 288 compounds of formula la wherein R5 is chloro, B1-B2-B3 is N-CH2-CH2, and R2 and R8 are as defined in Table P.
  • Table 15 provides 288 compounds of formula la wherein R5 is bromo, B1 -B2-B3 is N-CH2-CH2, and R2 and R8 are as defined in Table P.
  • Table 23 provides 288 compounds of formula lb wherein B1 -B2-B 3 is N-CH2-CH2, and R2 and R8 are as defined in Table P.
  • Table 27 provides 18 compounds of formula Ic wherein B1-B2-B3 is N-CH2-CH2, and R2 is as defined in Table Q.
  • Table 33 provides 18 compounds of formula Id wherein k is CN, B1-B2-B3 is N-CH2-CH2 and R2 is as defined in Table Q.
  • Table 34 provides 18 compounds of formula Id wherein k is CF3, B1-B2-B3 is N-CH2-CH2 and R2 is as defined in Table Q.
  • Compounds of formula I include at least one chiral centre and may exist as compounds of formula I* or compounds of formula I**.
  • Compounds I* and I** are enantiomers if there is no other chiral center or epimers otherwise. (I * ) (I ** )
  • compounds of formula I** are more biologically active than compounds of formula I*.
  • the invention includes mixtures of compounds I* and I** in any ratio e.g. in a molar ratio of 1 :99 to 99: 1, e.g. 10:1 to 1 :10, e.g. a substantially 50:50 molar ratio.
  • the molar proportion of compound I** compared to the total amount of both enantiomers (or epimers) is for example greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90,
  • the molar proportion of the compound of formula I* compared to the total amount of both enantiomers (or epimers) is for example greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95,
  • Enantiomerically (or epimerically) enriched mixtures of formula I** are preferred.
  • Each compound disclosed in Tables 1 to 36 represents a disclosure of a compound according to the compound of formula I* and a compound according to the compound of formula I**.
  • group A2 may be group A2* or A2**.
  • the invention includes mixtures of compounds of formula I with A2 as A2* and A2** in any ratio e.g. in a molar ratio of 1 :99 to 99: 1, e.g. 10: 1 to 1 : 10, e.g. a substantially 50:50 molar ratio.
  • the molar proportion of formula I with A2 as A2* compared to the total amount of both enantiomers (or epimers) is for example greater than 50%, e.g.
  • the molar proportion of the compound of formula I with A2 as A2**, compared to the total amount of both enantiomers (or epimers) is for example greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or at least 99%.
  • Enantiomerically (or epimerically) enriched mixtures of formula I with A2 as A2** are preferred.
  • Each compound disclosed in Tables 21 to 24 represents a disclosure of I with A2 as A2* and a compound I with A2 as A2**.
  • Each compound disclosed in Tables 21 to 24 represents a disclosure of a compound according to formula I* with A2 as A2*.
  • Each compound disclosed in Tables 21 to 24 represents a disclosure of a compound according to formula I** with A2 as A2*.
  • Each compound disclosed in Tables 21 to 24 represents a disclosure of a compound according to formula I* with A2 as A2**.
  • Each compound disclosed in Tables 21 to 24 represents a disclosure of a compound according to formula I** with A2 as A2**.
  • Enantiomerically (or epimerically) enriched mixtures of formula I** with A2 as A2** are preferred.
  • Reference to compounds of the invention also includes reference to salts and N-oxides.
  • the compounds of formula I may be prepared as described in WO08128711, WO10043315,
  • the methods and uses of the invention are preferably for controlling and/or preventing infestation of the soybean crop by stink bugs, including stink bugs that are resistant to other insecticides, e.g.
  • Stinkbugs that are "resistant" to a particular insecticide refers e.g. to strains of stinkbugs that are less sensitive to that insecticide compared to the expected sensitivity of the same species of stinkbug.
  • the expected sensitivity can be measured using e.g. a strain that has not previously been exposed to the insecticide.
  • Application is of the compounds of the invention is preferably to a crop of soybean plants, the locus thereof or propagation material thereof. Preferably application is to a crop of soybean plants or the locus thereof, more preferably to a crop of soybean plants. Application may be before infestation or when the pest is present.
  • Application of the compounds of the invention can be performed according to any of the usual modes of application, e.g. foliar, drench, soil, in furrow etc. However, control of stinkbugs is usually achieved by foliar application, which is the preferred mode of application according to the invention.
  • the compounds of the invention may be applied in combination with an attractant.
  • An attractant is a chemical that causes the insect to migrate towards the location of application.
  • Stinkbugs are often located near to the ground, and application of an attractant may encourage migration up the plant towards the active ingredient.
  • Suitable attractants include glucose, sacchrose, salt, glutamate (e.g. Aji-no-motoTM), citric acid (e.g. OroborTM), soybean oil, peanut oil and soybean milk. Glutamate and citric acid are of particular interest, with citric acid being preferred.
  • An attractant may be premixed with the compound of the invention prior to application, e.g. as a readymix or tankmix, or by simultaneous application or sequential application to the plant. Suitable rates of attractants are for example 0.02kg/ha-3kg/ha.
  • the compounds of the invention are preferably used for pest control on soybean at 1 :500 g/ha, preferably 10-70g/ha.
  • the compounds of the invention are suitable for use on any soybean plant, including those that have been genetically modified to be resistant to active ingredients such as herbicides, or to produce biologically active compounds that control infestation by plant pests.
  • transgenic plants and plant cultivars obtained by genetic engineering methods are treated.
  • plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention.
  • Plant cultivars are understood as meaning plants having novel properties ("traits") which have been obtained by
  • cultivars can be cultivars, bio- or genotypes.
  • the treatment according to the invention may also result in superadditive "synergistic" effects.
  • the preferred transgenic plants or plant cultivars which are to be treated according to the invention include all plants which, by virtue of the genetic modification, received genetic material which imparts particularly advantageous, useful traits to these plants. Examples of such traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products.
  • Traits that are emphasized in particular are the increased defence of the plants against insects, arachnids, nematodes and slugs and snails by virtue of toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CrylA(a), CrylA(b), CrylA(c), CryllA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF and also combinations thereof) (referred to herein as "Bt plants”).
  • Traits that are also particularly emphasized are the increased defence of the plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins.
  • SAR systemic acquired resistance
  • trasits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (for example the "PAT" gene).
  • herbicidally active compounds for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (for example the "PAT" gene).
  • PAT phosphinotricin
  • Bt plants are soya bean varieties which are sold under the trade names YIELD GARD(®)
  • herbicide -tolerant plants which may be mentioned are soybean varieties which are sold under the trade names Roundup Ready(®) (tolerance to glyphosate), Liberty Link(®) (tolerance to phosphinotricin), IMI(®) (tolerance to imidazolinones) and STS(®) (tolerance to sulphonylureas).
  • Herbicide -resistant plants plants bred in a conventional manner for herbicide tolerance
  • plants bred in a conventional manner for herbicide tolerance include the varieties sold under the name Clearfield(®) (for example maize).
  • soybean plants carrying trains conferring resistance to 2.4D e.g. Enlist®
  • glyphosate e.g. Roundup Ready®, Roundup Ready 2 Yield®
  • sulfonylurea e.g. STS®
  • glufosinate e.g. Liberty Link®, Ignite®
  • Dicamba e.g. isoxaflutole herbicide
  • Double or triple stack in soybean plants of any of the traits described here are also of interest, including glyphosate and sulfonyl-urea tolerance (e.g.
  • the compounds of the invention may be used on soybean to control, for example, Elasmopalpus lignosellus, Diloboderus abderus, Diabrotica speciosa, Sternechus subsignatus, Formicidae, Agrotis ypsilon, Julus ssp. , Anticarsia gemmatalis, Megascelis ssp. , Procornitermes ssp. , Gryllotalpidae, Nezara viridula, Piezodorus spp. , Acrosternum spp. , Neomegalotomus spp.
  • the compounds of the invention are preferably used on soybean to control stinkbugs, e.g. Nezara spp. (e.g. Nezara viridula, Nezara antennata, Nezara hilare), Piezodorus spp. (e.g. Piezodorus guildinii), Acrosternum spp. Euchistus spp. (e.g. Euchistus heros, Euschistus servus), Halyomorpha halys, Plautia crossota, Riptortus clavatus, Rhopalus msculatus, Antestiopsis orbitalus, Dichelops spp. (e.g. Nezara spp. (e.g. Nezara viridula, Nezara antennata, Nezara hilare), Piezodorus spp. (e.g. Piezodorus guildinii), Acrosternum spp. Euchistus spp. (e.g. Euchist
  • Scotinophara lurida, Scotinophara coarctatd Preferred targets include Antestiopsis orbitalus, Dichelops furcatus, Dichelops melacanthus, Euchistus heros, Euschistus servus, Nezara viridula, Nezara hilare, Piezodorus guildinii, Halyomorpha halys.
  • the stinkbug target is Nezara viridula, Piezodorus spp., Acrosternum spp, Euchistus heros.
  • the compounds of the invention are particularly effective against Euschistus and in particular Euchistus heros. Euschistus and in particular Euchistus heros are the preferred targets.
  • compounds of the invention is usually formulated into a composition which includes, in addition to the compound of the invention, a suitable inert diluent or carrier and, optionally, a surface active agent (SFA).
  • SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting).
  • compositions both solid and liquid formulations
  • the composition is generally used for the control of pests such that a compound of the invention is applied at a rate of from O.lg to 10kg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to 1kg per hectare.
  • a compound of the invention When used in a seed dressing, a compound of the invention is used at a rate of 0.000 lg to lOg (for example O.OOlg or 0.05g), preferably 0.005g to lOg, more preferably 0.005g to 4g, per kilogram of seed.
  • Compositions comprising a compound of the invention can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro- emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations.
  • the formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of the invention.
  • Dustable powders may be prepared by mixing a compound of the invention with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
  • solid diluents for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, talc and other organic and inorganic solid carriers
  • Soluble powders may be prepared by mixing a compound of the invention with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulfate
  • water-soluble organic solids such as a polysaccharide
  • compositions may also be granulated to form water soluble granules (SG).
  • WP Wettable powders
  • WG Water dispersible granules
  • Granules may be formed either by granulating a mixture of a compound of the invention and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of the invention (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of the invention (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulfates or phosphates) and drying if necessary.
  • a hard core material such as sands, silicates, mineral carbonates, sulfates or phosphates
  • Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters
  • sticking agents such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils.
  • One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
  • DC Dispersible Concentrates
  • a compound of the invention may be prepared by dissolving a compound of the invention in water or an organic solvent, such as a ketone, alcohol or glycol ether.
  • organic solvent such as a ketone, alcohol or glycol ether.
  • surface active agent for example to improve water dilution or prevent crystallization in a spray tank.
  • Emulsifiable concentrates or oil-in-water emulsions (EW) may be prepared by dissolving a compound of the invention in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents).
  • Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as Cg-Qo fatty acid dimethylamide) and chlorinated hydrocarbons.
  • aromatic hydrocarbons such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark
  • ketones such as cyclo
  • An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment.
  • Preparation of an EW involves obtaining a compound of the invention either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion.
  • Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
  • Microemulsions may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation.
  • a compound of the invention is present initially in either the water or the solvent/SFA blend.
  • Suitable solvents for use in MEs include those hereinbefore described for use in ECs or in EWs.
  • An ME may be either an oil-in- water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation.
  • An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
  • SC Suspension concentrates
  • SCs may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of the invention.
  • SCs may be prepared by ball or bead milling the solid compound of the invention in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound.
  • One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle.
  • a compound of the invention may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
  • Aerosol formulations comprise a compound of the invention and a suitable propellant (for example n-butane).
  • a compound of the invention may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non- pressurized, hand-actuated spray pumps.
  • a compound of the invention may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.
  • Capsule suspensions may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerization stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of the invention and, optionally, a carrier or diluent therefor.
  • the polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure.
  • the compositions may provide for controlled release of the compound of the invention and they may be used for seed treatment.
  • a compound of the invention may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
  • a composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of the invention).
  • additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of the invention).
  • a compound of the invention may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS).
  • DS powder for dry seed treatment
  • SS water soluble powder
  • WS water dispersible powder for slurry treatment
  • CS capsule suspension
  • compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
  • Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.
  • Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
  • Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (for example sodium lauryl sulfate), salts of sulfonated aromatic compounds (for example sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butylnaphthalene sulfonate and mixtures of sodium di-z ' opropyl- and tri-wopropyl-naphthalene sulfonates), ether sulfates, alcohol ether sulfates (for example sodium laureth-3 -sulfate), ether carboxylates (for example sodium laureth-3- carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and
  • Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.
  • Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide);
  • alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof
  • fatty alcohols such as oleyl alcohol or cetyl alcohol
  • alkylphenols such as octylphenol, nonylphenol or octylcresol
  • partial esters derived from long chain fatty acids or hexitol anhydrides condensation products of said partial esters with ethylene oxide
  • alkanolamides alkanolamides
  • simple esters for example fatty acid polyethylene glycol esters
  • amine oxides for example lauryl dimethyl amine oxide
  • lecithins alkanolamides
  • simple esters for example fatty acid polyethylene glycol esters
  • amine oxides for example lauryl dimethyl amine oxide
  • lecithins lecithins
  • Suitable suspending agents include hydrophilic colloids (such as polysaccharides,
  • polyvinylpyrrolidone or sodium carboxymethylcellulose and swelling clays (such as bentonite or attapulgite).
  • a compound of the invention may be applied by any of the known means of applying pesticidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapor or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water- soluble bag) in soil or an aqueous environment.
  • a locus of the pests such as a habitat of the pests, or a growing plant liable to infestation by the pests
  • a compound of the invention may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
  • compositions for use as aqueous preparations are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use.
  • These concentrates which may include DCs, SCs, ECs, EWs, MEs, SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
  • Such aqueous preparations may contain varying amounts of a compound of the invention (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
  • a compound of the invention may be used in mixtures with fertilizers (for example nitrogen-, potassium- or phosphorus-containing fertilizers).
  • Suitable formulation types include granules of fertilizer.
  • the mixtures preferably contain up to 25% by weight of the compound of the invention.
  • the invention therefore also provides a fertilizer composition comprising a fertilizer and a compound of the invention.
  • compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.
  • the compound of the invention may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate.
  • An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergize the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of the invention; or help to overcome or prevent the development of resistance to individual components.
  • suitable pesticides include the following:
  • a) Pyrethroids such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin and gamma cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, S-bioallethrin, fenfluthrin, prallethrin, acrinathirin, etofenprox or
  • Organophosphates such as profenofos, sulprofos, acephate, methyl parathion, azinphos-methyl, demeton-s -methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl, pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon;
  • Benzoyl ureas such as diflubenzuron, triflumuron, hexaflumuron, flufenoxuron, diafenthiuron, lufeneron, novaluron, noviflumuron or chlorfluazuron;
  • Organic tin compounds such as cyhexatin, fenbutatin oxide or azocyclotin;
  • Pyrazoles such as tebufenpyrad, tolfenpyrad, ethiprole, pyriprole, fipronil, and fenpyroximate;
  • Macrolides such as avermectins or milbemycins, for example abamectin, emamectin benzoate, ivermectin, milbemycin, spinosad, azadirachtin, milbemectin, lepimectin or spinetoram;
  • Organochlorine compounds such as endosulfan (in particular alpha-endosulfan), benzene hexachloride, DDT, chlordane or dieldrin;
  • Amidines such as chlordimeform or amitraz
  • Fumigant agents such as chloropicrin, dichloropropane, methyl bromide or metam
  • Neonicotinoid compounds such as imidacloprid, thiacloprid, acetamiprid, nitenpyram, dinotefuran,0 thiamethoxam, clothianidin, or nithiazine;
  • Diacylhydrazines such as tebufenozide, chromafenozide or methoxyfenozide
  • Diphenyl ethers such as diofenolan or pyriproxifen
  • Ketoenols such as Spirotetramat, spirodiclofen or spiromesifen
  • Diamides such as flubendiamide, chlorantraniliprole (Rynaxypyr®) or cyantraniliprole;
  • Essential oils such as Bugoil® - (Plantlmpact); or
  • a comopund selected from buprofezine, flonicamid, acequinocyl, bifenazate, cyenopyrafen, cyflumetofen, etoxazole, flometoquin, fluacrypyrim, fluensulfone, flufenerim, flupyradifuone, harpin, iodomethane, dodecadienol, pyridaben, pyridalyl, pyrimidifen, flupyradifurone, 4-[(6-Chloro-pyridin-3-0 ylmethyl)-(2,2-difluoro-ethyl)-amino]-5H-furan-2-one (DE 102006015467), CAS: 915972-17-7
  • pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the5 composition.
  • selective insecticides for particular crops for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed.
  • insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).
  • acaricidal ovo-larvicides such as clofentezine, flubenzimine, hexythiazox or tetradifon
  • acaricidal motilicides such as dicofol or propargite
  • acaricides such as bromopropylate or chlorobenzilate
  • growth regulators such
  • fungicidal compounds which may be included in the composition of the invention are (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy-iminoacetamide (SSF-129), 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-l -sulfonamide, -[N-(3-chloro-2,6- -xylyl)-2-methoxyacetamido]-y-butyrolactone, 4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-l - sulfonamide (IKF-916, cyamidazosulfamid), 3 -5 -dichloro-N-(3 -chloro- 1 -ethyl- 1 -methyl-2-oxopropyl)-4- methylbenzamide (RH-7281 ,
  • oxpoconazole oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-Al, phosphorus acids, phthalide, picoxystrobin (ZA1963), polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, propionic acid, pyrazophos, pyrifenox,
  • pyrimethanil pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, sipconazole (F-155), sodium pentachlorophenate, spiroxamine, streptomycin, sulfur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamid,
  • pyrazole-4-carboxamide [1072957-71-1]
  • l-methyl-3-difluoromethyl-lH-pyrazole-4-carboxylic acid (2- dichloromethylene-3-ethyl-l-methyl-indan-4-yl)-amide
  • l-methyl-3-difluoromethyl-4H-pyrazole-4- carboxylic acid [2-(2,4-dichloro-phenyl)-2-methoxy-l -methyl-ethyl] -amide.
  • Preferred additional pesticidally active ingredients are those selected from neonicotinoids, pyrethroids, strobilurins, triazoles and carboxamides (SDHI inhibitors).
  • Pyrethroids are of interest of which lambda-cyhalothrin is of particular interest.
  • a method comprising applying to a crop of soybean plants, the locus thereof, or propagation material thereof, a combination of a compound a compound of the invention and lambda cyhalothrin in a synergistically effective amount, wherein the method is for control and/or prevention of stinkbugs, preferably Euschistus, e.g. Euschistus heros.
  • the compounds of the invention may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
  • synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole.
  • Suitable herbicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
  • An example of a rice selective herbicide which may be included is propanil.
  • An example of a plant growth regulator for use in cotton is PIXTM.
  • Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type.
  • other formulation types may be prepared.
  • one active ingredient is a water insoluble solid and the other a water insoluble liquid
  • the resultant composition is a suspoemulsion (SE) formulation.
  • weight ratio of the compound of I with an additional active ingredient may generally be between 1000 : 1 and 1 : 1000.
  • weight ratio of A to B may be between 500 : 1 to 1 : 500, for example between 100 : 1 to 1 : 100, for example between 1 : 50 to 50 : 1, for example 1 : 20 to 20 : 1, for example 1 :10 to 10:1, for example 1 :5 to 5:1, for example 1 :1.
  • compositions of the invention include those prepared by premixing prior to application, e.g. as a readymix or tankmix, or by simultaneous application or sequential application to the plant.
  • Example 1 Preparation of N-r(lS -l -r4-r3-r3,543is(trifluoromethyl phenyl1-3- ftrifluorometh Dpyrrolidin-l-yllphenyllethyllcyclopropanecarboxamide
  • Tris(dibenzylideneacetone)dipalladium(0) (32 mg), 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (61 mg) and sodium tert-butoxide (190 mg) were added to a solution of 3-(3,5-dichlorophenyl)-3- (trifluoromethyl)pyrrolidine (520 mg, prepared as described in WO08128711) and N-[(lS)-l -(4- bromophenyl)ethyl]cyclopropanecarboxamide (prepared as described in WO 2012001107, 520 mg) in Toluene (15mL) under argon atmosphere. The mixture was heated in the microwave at 130C for 30 min.
  • Step 1
  • Step 4 Preparation of 2-fluoro-5-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-dihydropyrrol-5- ljbenzonitrile
  • Step 5 Preparation of 2-(l,2,4-triazol-l-yl)-5-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4- dih dropyrrol-5-yl]benzonitrile
  • Example 5 Preparation of N-r(lS)-l -r4-r5-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-dihvdropyrrol- 3-yllphenyllethyllcyclopropanecarboxamide
  • Ste 1 Preparation of tert-butyl N-[(lS)-l -(4-bromophenyl)ethyl "
  • Step 2 Preparation of 4-[(lS)-l -(tert-butoxycarbonylamino)ethyl]benzoic acid
  • reaction mass was quenched with water 50 ml and compound was extracted with ethyl acetate 30ml x 2 in order to remove debromo compound.
  • Aqueous layer was acidified with ammonium chloride and extracted with ehylacetate 30 ml x 2 times.
  • the combined organic layers were dried with sodium sulfate and evaporated off under vacuum and dried under vacuum. Weight- 0.61 g
  • Step 3 Preparation of tert-butyl N-[(lS)-l -[4-(trimethylsilylmethylcarbamoyl)phenyl]ethyl]carbamate
  • reaction mass was cooled to 0 C and 3-(ethyliminomethyleneamino)-N,N-dimethyl-propan-l-amine hydrochloride (848 mg, 4.4234 mmol) was added and reaction was stirred at 0 °C to RT for overnight. TLC showed reaction was completed.
  • the reaction mass was quenched with water (30mL) and extracted with DCM (35 ml x 2) and combined organic layer was washed with water (20 ml x 2) and dried with sodium sulfate and evaporated of under reduced pressure and compound was purified by combiflash. Weight - 0.93 g
  • Step 5 Preparation of tert-butyl N-[(l S)-l -[4-[5-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4- dih dropyrrol-3-yl]phenyl]ethyl]carbamate
  • reaction mass was diluted with ethyl acetate and washed with water (20 ml x 3 times) and dried with sodium sulphate and evaporated off under vacuum.
  • reaction mass was taken into THF (25ml) and l,2,3-trichloro-5-[l -(trifluoromethyl)vinyl] benzene (1 equiv., 1 mmol) was added into it.
  • reaction mass was diluted with DCM (20 ml) and washed with water (20ml). The organic layer was then dried over anhydrous sodium sulphate, and the solvent was removed under vacuum.
  • Combiflash 35 % EtOAC-hexane
  • Example 6 Preparation of N- ⁇ 2-bromo-4-
  • Step 1 Bromination of 3-bromo-4-methyl benzoic acid.
  • Step 2 Preparation of 3-bromo-4-(dibromomethyl)-N-[(trimethylsilyl)methyl]benzamide.
  • Step 3 Preparation of 3-bromo-4-formyl-N-[(trimethylsilyl)methyl]benzamide.
  • Step 5 Preparation of Acetic acid 2-bromo-4- (trimethylsilanylmethyl-carbamoyl)-benzylester.
  • Step 6 Preparation of 3-bromo-4-(2-oxo-propyl)-N-trimethylsilanylmethyl-thiobenzamide.
  • Step 7 Preparation of Acetic acid 2-bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5-dihydro- 3H-pyrrol-2yl]-benzylester.
  • Step 8 Preparation of 2-bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2yl]- phenyl-methanol.
  • Step 9 Preparation of Methanesulfonic acid-2-bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5- dih dro-3H-pyrrol-2yl]-benzylester.
  • Step 10 Preparation of 2-bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5-dihydro-3H-pyrrol- 2yl] -benzylamine.
  • Step 11 Preparation of N- ⁇ 2-bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5-dihydro-3H- rrol-2yl] -benzyl ⁇ acetamide.
  • Example 7 Preparation of N- ⁇ 4-r3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidinl-yl1- 2-methyl- benzyPacetamide.
  • Step 1 Preparation of l-Benzyl-3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine.
  • Step 2 Preparation of 3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine.
  • Step 3 Preparation of N-(4-bromo-2-methyl-benzyl)acetamide.
  • Step 4 Preparation of N- ⁇ 4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidinl -yl]- 2-methyl- benz l)acetamide.
  • Solvent degasser Solvent degasser, quaternary pump, heated column compartment and diode-array detector.
  • Type of column Waters ACQUITY UPLC BEH CI 8; Column length: 50 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.7 micron; Temperature: 60°C.
  • Example 8

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Abstract

The present invention provides methods comprising applying to a crop of soybean plants, the locus thereof, or propagation material thereof, a compound a compound of formula (I) wherein -B1-B2-B3- is -C=N-O-, -C=N-CH2-, -N-CH2-CH2-, or -C=C-O-; R1 is trifluoromethyl, difluoromethyl or chlorodifluoromethyl; R2 is group (X) wherein X2 is C-X6 or nitrogen; X1, X3 and X6 are independently hydrogen, halogen or trihalomethyl, wherein at least one of X1, X3 and X6 is not hydrogen; A is selected from group (A1) to (A4) and Y1, Y2, Y3, R5 and R8 are as defined in claim 1. The methods are preferably for the control of stinkbugs, in particular Euschistus.

Description

METHODS OF PEST CONTROL IN SOYBEAN
The present invention relates to methods of pest control in soybean crops.
Stink bugs (Hemiptera Pentatomidae) are true bugs which can be significant pests when present in large numbers. The nymphs and adults have piercing mouthparts which most use to suck sap from 5 plants. According to Stewart et al., Soybean Insects - Stink bugs, University of Tennessee Institute of Agriculture, W200 09-0098, stink bugs are probably the most common pest problem in soybean.
Although they may feed on many parts of the plant, they typically target developing seed including the pods, meaning that injury to soybean seed is the primary problem associated with stink bug infestations.
Of the complex of sucking bugs that occur in cultivation, the brown stinkbug Euschistus hews is 10 currently considered to be the most abundant species in northern Parana to Central Brazil (Correa-Ferreira & Panizzi, 1999), and is a significant problem in soybean (Schmidt et al., 2003). The bugs occur in soybeans from the vegetative stage and are harmful from the beginning of pod formation until grain maturity. They cause damage to the seed (Galileo & Heinrichs 1978a, Panizzi & Slansky Jr., 1985) and can also open the way to fungal diseases and cause physiological disorders, such as soybean leaf retention 15 (Galileo & Heinrichs 1978, Todd & Herzog, 1980).
Control of stinkbugs in soybean is often vital to prevent significant economic damage. Insecticides commonly used to control stinkbugs include pyrethroids, neonicotinoids and
organophosphates, although pyrethroid insecticides are usually the method of choice for controlling stink bugs in soybean. However, there are increasing problems with insecticide resistance, particularly in 20 brown stink bug populations and particularly to pyrethroids. Euschistus hews can also be difficult to manage using organophosphates or endosulfan (Sosa-Gomez et al., 2009). There is therefore a need for effective alternative methods of controlling stinkbugs in soybean.
Compounds that are insecticidally, acaricidally, nematicidally and/or moluscicidally active by antagnonism of the gamma-aminobutyric acid (GABA)-gated chloride channel, and which comprise a 25 partially saturated heterocycle that is substituted by a haloalkyl substituent and one or two optionally substituted aromatic or heteroaromatic rings, represent a new class of pesticides that are described for example in Ozoe et al. Biochemical and Biophysical Research Communications, 391 (2010) 744-749. Compounds from this class are broadly described in WO 2005/085216 (EP1731512), WO 2007/123853, WO 2007/075459, WO2009/002809, WO 2008/019760, WO 2008/122375, WO 2008/128711, WO 30 2009/097992, WO 2010/072781, WO 2010/072781, WO 2008/126665, WO 2007/125984, WO
2008/130651, JP 2008110971, JP2008133273, JP2009108046, WO2009/022746, WO 2009/022746, WO 2010/032437, WO2009/080250, WO2010/020521, WO2010/025998, WO2010/020522,
WO2010/084067, WO2010/086225, WO2010/149506 and WO2010/108733.
It has now surprisingly been found that particular insecticides from this new class of gamma- 35 aminobutyric acid (GABA)-gated chloride channel antagonists are highly effective at controlling
stinkbugs, and in some cases can provide greater control than the current market standard. It has also surprisingly been found that these compounds exhibit significantly higher activity against stinkbugs than structurally similar compounds. These compounds therefore represent an important new solution for safeguarding soybean crops from stinkbugs, particularly where stink bugs are resistant to current methods.
In a first aspect the invention provides a method comprising applying to a crop of soybean plants, the locus thereof, or propagation material thereof, a compound of formula I
Figure imgf000004_0001
wherein -β'-Β^Β3- is -C=N-0-, -C=N-CH2- , -N-CH2-CH2-, or -C=C-0-;
1 is trifluoromethyl, difluoromethyl or chlorodifluoromethyl;
Figure imgf000004_0002
X2 is C-X6 or nitrogen;
Χ', Χ3 and X6 are independently hydrogen, halogen or trihalomethyl, wherein at least one of X1, X3 and
X6 is not hydrogen;
A is selected from group Al to A4
Figure imgf000004_0003
Y1 is C-R6, CH or nitrogen;
Y2 and Y3 are independently CH or nitrogen;
wherein no more than two of Y1, Y2 and Y3 are nitrogen and wherein Y2 and Y3 are not both nitrogen; R5 is hydrogen, halogen, cyano, nitro, NH2, Ci-C4alkyl, Ci-C4haloalkyl, C3-C5cycloalkyl, C3- C5halocycloalkyl, Ci-C2alkoxy, or Ci-C2haloalkoxy;
R6 when present together with R5 forms a -CH=CH-CH=CH- bridge;
R7 is C C4alkyl;
R8 is Ci-C4alkyl, CrC4haloalkyl, Ci-C4alkoxy(CrC4)alkyl, Ci-C4alkylthio(CrC4)alkyl, Cr
C4alkylsulfmyl(Ci-C4)alkyl, Ci-C4alkylsulfonyl(CrC4)alkyl, C3-C6cycloalkyl, C3-C6cycloalkyl(Cr C4)alkyl-, or tetrahydrofuranyl;
each Z is independently halogen, Ci-Ci2alkyl or Ci-Ci2alkyl substituted by one to five R12, nitro, d-
Ci2alkoxy or Ci-Ci2alkoxy substituted by one to five R12 ; cyano, Ci-Ci2alkylsulfinyl, Ci-Ci2alkylsulfonyl, Ci-Ci2haloalkylsulfinyl, Ci-Ci2haloalkylsulfonyl, hydroxyl or thiol; each R12 is halogen, cyano, nitro, hydroxy, Q-Cgalkoxy-, Q-Cghaloalkoxy-, mercapto, CpCgalkylthio-, or Ci-Cghaloalkylthio; and
k is 0, 1,2 or 3.
In a further aspect the invention provides a method of controlling and/or preventing infestation of stinkbugs in soybean comprising applying to a crop of soybean plants, the locus thereof, or propagation material thereof, a compound of formula I. The stinkbugs may be those that are resistant to one or more other insecticides.
In a further aspect the invention provides a method of controlling and/or preventing infestation of stinkbugs in a crop of useful plants comprising applying to a crop of useful plants, the locus thereof, or propagation material thereof, a compound of formula I. The stinkbugs may be those that are resistant to one or more other insecticides.
In a further aspect the invention provides use of a compound of formula I for control of stinkbugs in a crop of useful plants. The use may be for controlling stinkbugs that are resistant to one or more other insecticides.
In a further aspect the invention provides a method of controlling and/or preventing infestation of insects from the genus Euschistus in a crop of useful plants comprising applying to a crop of useful plants, the locus thereof, or propagation material thereof, a compound of formula I. The insects from the genus Euschistus may be those that are resistant to one or more other insecticides.
In a further aspect the invention provides use of a compound of formula I for control of insects from the genus Euschistus in a crop of useful plants. The use may be for controlling insects from the genus Euschistus that are resistant to one or more other insecticides.
In a further aspect the invention provides a method of controlling and/or preventing infestation of insects from the genus Euschistus in a crop of soybean plants comprising applying to a crop of soybean, the locus thereof, or propagation material thereof, a compound of formula I. The insects from the genus Euschistus may be those that are resistant to one or more other insecticides.
In a further aspect the invention provides use of a compound of formula I for control of insects from the genus Euschistus in a crop of soybean plants. The use may be for controlling insects from the genus Euschistus that are resistant to one or more other insecticides.
In a further aspect the invention provides a method of controlling and/or preventing infestation of Euschistus heros in a crop of useful plants comprising applying to a crop of useful plants, the locus thereof, or propagation material thereof, a compound of formula I. The Euschistus heros may be resistant to one or more other insecticides.
In a further aspect the invention provides use of a compound of formula I for control of
Euschistus heros in a crop of useful plants. The use may be for controlling Euschistus heros that is resistant to one or more other insecticides.
In a further aspect the invention provides a method of controlling and/or preventing infestation of Euschistus heros in a crop of soybean plants comprising applying to a crop of soybean, the locus thereof, or propagation material thereof, a compound of formula I. The Euschistus heros may be resistant to one or more other insecticides.
In a further aspect the invention provides use of a compound of formula I for control of
Euschistus heros in a crop of soybean plants. The use may be for controlling insects Euschistus heros that are is resistant to one or more other insecticides.
Stinkbugs that are resistant to one or more other insecticides are preferably resistant to pyrethroid, neonicotinoids and/or organophosphates, more preferably pyrethroid insecticides.
In a further aspect the invention provides a method for obtaining regulatory approval for the use of one or more of a compound of formula I to control stinkbugs, in particular the genus Euschistus and in particular the species Euschistus heros, and in particular in soybean plants, comprising at least one step of referring to, submitting or relying on biological data showing that said active ingredient reduces insect pressure.
The compounds of the invention may exist in different geometric or optical isomers or tautomeric forms. This invention covers all such isomers and tautomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds. The compounds of the invention may contain one or more asymmetric carbon atoms, for example, at the C(R1)R2 group, and may exist as enantiomers (or as pairs of diastereoisomers) or as mixtures of such.
Alkyl groups (either alone or as part of a larger group, such as alkoxy-, alkylthio-, alkylsulfinyl-, alkylsulfonyl-, alkylcarbonyl- or alkoxycarbonyl-) can be in the form of a straight or branched chain and are, for example, methyl, ethyl, propyl, prop-2-yl, butyl, but-2-yl, 2 -methyl-prop -1-yl or 2-methyl-prop-2- yl. Unless otherwise stated the alkyl groups are preferably i- e, more preferably C1-C4, most preferably C1-C3 alkyl groups. Where an alkyl moiety is said to be substituted, the alkyl moiety is preferably substituted by one to four substituents, most preferably by one to three substituents.
Halogen is fluorine, chlorine, bromine or iodine.
Haloalkyl groups (either alone or as part of a larger group, such as haloalkoxy-, haloalkylthio-, haloalkylsulfinyl- or haloalkylsulfonyl-) are alkyl groups which are substituted by one or more of the same or different halogen atoms and are, for example, difluoromethyl, trifluoromethyl,
chlorodifluoromethyl or 2,2,2-trifluoro-ethyl.
Cycloalkyl groups or carbocyclic rings can be in mono- or bi-cyclic form and are, for example, cyclopropyl, cyclobutyl, cyclohexyl. The cycloalkyl groups are preferably C3-C6 cycloalkyl groups.
The preferences for B1, B2, B3, R1, R2, Y1, Y2, Y3, R5, R6' R7, R8, R12, X1 X2, X3, Z and k are, in any combination, as described below.
Preferably R1 is trifluoromethyl, or chlorodifluoromethyl, most preferably trifluoromethyl.
Preferably X1, X3 and X6 are independently hydrogen, halogen or trifluoromethyl, wherein at least two of X1, X3 and X6 are not hydrogen. More preferably X1, X3 and X6 are independently hydrogen, chloro, bromo or trifluoromethyl, wherein at least two of X1, X3 and X6 are not hydrogen. Preferably at least two of X1, X3 and X6 are chloro, bromo or trifluoromethyl. In one group of compounds R2 is 3,5-dichlorophenyl-, 3-chloro-4-fluorophenyl-, 3-fluoro-4- chlorophenyl-, 3,4-dichlorophenyl-, 3-chloro-4-bromophenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5- trichlorophenyl-, 3,5-dichloro-4-iodophenyl-, 3,4,5-trifluorophenyl-, 3-chloro-5-bromophenyl-, 3-chloro- 5-fluorophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,4-dichloro-5-(trifluoromethyl)phenyl-, 3,5- bis(trifluoromethyl)phenyl-, 4-chloro-3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6- dichloro-4-pyridyl-, 2,6-bis(trifluoromethyl)-4-pyridyl-, more preferably 3,5-dichlorophenyl-, more preferably 3-chloro-5-bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4- pyridyl-, 2,6-bis(trifluoromethyl)-4-pyridyl-, 3,5-dichloro-4-bromophenyl-, 3-bromo-5- (trifluoromethyl)phenyl-, 3,5-dibromophenyl-, or 3,4-dichlorophenyl-, more preferably R2 is 3,5-dichlorophenyl, 3,5-dichloro-4-fluorophenyl- or 3,4,5-trichloro-phenyl, most preferably 3,5-dichloro-phenyl.
Preferably Y1 is CH, Y2 is CH, Y3 is CH, or Y1 is N, Y2 is CH, Y3 is CH, or Y1 is N, Y2 is N, Y3 is CH, orY1 is CH, Y2 is N, Y3 is CH, or Y1 is CH, Y2 is CH, Y3 is N. Most preferably Y1 is CH, Y2 is CH, and Y3 is CH.
Preferably R5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, methoxy, nitro, trifluoromethoxy, cyano, cyclopropyl, more preferably R5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, nitro, cyano, cyclopropyl, most preferably R5 is hydrogen, cyano, chloro, bromo, fluoro, methyl, or trifluoromethyl.
Preferably R8 is CrC4alkyl, CrC4haloalkyl, Ci-C4alkyl-0-CH2-, CrC4haloalkyl-0-CH2-,C3- Cgcycloalkyl, C3-C6cycloalkyl-CH2-, C C4alkyl-S(0)-CH2-, Ci-C4alkyl-S(02)-CH2-, more preferably Cr C4alkyl, CrC4alkyl-0-CH2-, CrC4alkyl-S-CH2-, CrC4alkyl-SO-CH2-, CrC4alkyl-S02-CH2-, C3- C4cycloalkyl, or C3-C4cycloalkyl-CH2-, most preferably R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3- S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
Preferably each Z is independently halogen, cyano, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, or Ci-C4haloalkoxy, most preferably each Z is independently hydrogen, cyano, halogen, methyl, halomethyl, methoxy or halomethoxy, most preferably cyano or trifluoromethyl.
Each R12 is preferably bromo, chloro, fluoro, methoxy, or methylthio, most preferably chloro, fluoro, or methoxy
Preferably k is 0 or 1.
In one group of compounds -B'-B^B3- is -C=N-0-.
In another group of compounds -B1-B2-B3- is -C=N-CH2-.
In another group of compounds -B1-B2-B3- is -N-CH2-CH2-.
In another group of compounds -B1-B2-B- is -C=C-0-.
In another group of compounds Y1 is C-R6 and R6 together with R5 forms a -CH=CH-CH=CH- bridge.
In one embodiment the compound of formula I is a compound of formula IA
Figure imgf000008_0001
wherein B 1 , 5
Figure imgf000008_0002
RD and R 8° are as defined for a compound of formula I
In compounds of formula IA preferred definitions of B1, B2, B3, R1, R2, Y1, Y2, Y3, R5 and R8 are, in any combination, as set out below:
Preferably R1 is trifluoromethyl, or chlorodifluoromethyl, most preferably trifluoromethyl.
Preferably X1, X3 and X6 are independently hydrogen, halogen or trifluoromethyl, wherein at least two of X1, X3 and X6 are not hydrogen. More preferably X1, X3 and X6 are independently hydrogen, chloro, bromo or trifluoromethyl, wherein at least two of X1, X3 and X6 are not hydrogen. Preferably at least two of X1, X3 and X6 are chloro, bromo or trifluoromethyl.
In one group of compounds R2 is 3,5-dichlorophenyl-, 3-chloro-4-fluorophenyl-, 3-fluoro-4- chlorophenyl-, 3,4-dichlorophenyl-, 3-chloro-4-bromophenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5- trichlorophenyl-, 3,5-dichloro-4-iodophenyl-, 3,4,5-trifluorophenyl-, 3-chloro-5-bromophenyl-, 3-chloro- 5-fluorophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,4-dichloro-5-(trifluoromethyl)phenyl-, 3,5- bis(trifluoromethyl)phenyl-, 4-chloro-3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6- dichloro-4-pyridyl-, 2,6-bis(trifluoromethyl)-4-pyridyl-, more preferably 3,5-dichlorophenyl-, more preferably 3-chloro-5-bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4- pyridyl-, 2,6-bis(trifluoromethyl)-4-pyridyl-, 3,5-dichloro-4-bromophenyl-, 3-bromo-5- (trifluoromethyl)phenyl-, 3,5-dibromophenyl-, or 3,4-dichlorophenyl-, more preferably R2 is 3,5-dichloro- phenyl or 3,4,5-trichloro-phenyl, most preferably 3,5-dichloro-phenyl.
Preferably Y1 is CH, Y2 is CH, Y3 is CH, or Y1 is N, Y2 is CH, Y3 is CH, or Y1 is N, Y2 is N, Y3 is CH, orY1 is CH, Y2 is N, Y3 is CH, or Y1 is CH, Y2 is CH, Y3 is N. Most preferably Y1 is CH, Y2 is CH, and Y3 is CH.
Preferably R5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, methoxy, nitro, trifluoromethoxy, cyano, cyclopropyl, more preferably R5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, nitro, cyano, cyclopropyl, more preferably R5 is hydrogen, cyano, chloro, bromo, fluoro, methyl, or trifluoromethyl, even more preferably hydrogen, chloro, bromo, methyl or trifluoromethyl, most preferably chloro, bromo, fluoro or methyl.
Preferably R8 is CrC4alkyl, CrC4haloalkyl, Ci-C4alkyl-0-CH2-, CrC4haloalkyl-0-CH2-,C3- Cgcycloalkyl, C3-C6cycloalkyl-CH2-, CrC4alkyl-S(0)-CH2-, Ci-C4alkyl-S(02)-CH2-, more preferably Cr Qalkyl, CrC4alkyl-0-CH2-, CrC4alkyl-S-CH2-, CrC4alkyl-SO-CH2-, CrC4alkyl-S02-CH2-, C3- C4cycloalkyl, or C3-C4cycloalkyl-CH2-, most preferably R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3- S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-. In one group of compounds of formula IA -B1-B2-B3- is -C=N-0-.
In another group of compounds of formula IA -B'-B^B3- is -C=N-0- and Y1 is CH, Y2 is CH, Y3 is CH.
In another group of compounds of formula IA -B'-B^B3- is -C=N-0-, Y1 is CH, Y2 is CH, Y3 is CH and R1 is CF3.
In another group of compounds of formula IA -B'-B^B3- is -C=N-0-, Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3 and R5 is chloro, bromo, fluoro or methyl.
In another group of compounds of formula IA -B'-B^B3- is -C=N-0-, Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02- CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of formula IA -B'-B^B3- is -C=N-0-, Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is chloro, bromo, fluoro or methyl and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of formula IA -B'-B^B3- is -C=N-0-, Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is chloro, bromo, fluoro or methyl, R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S- CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2- and R2 is 3-chloro- 5-bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5- trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-, 2,6-bis(trifluoromethyl)-4-pyridyl-, 3,5-dichloro-4-bromophenyl-, 3-bromo-5-(trifluoromethyl)phenyl-, 3,5-dibromophenyl-, or 3,4-dichlorophenyl-.
In one group of compounds of formula IA -B1-B2-B3- is -C=N-CH2-.
In another group of compounds of formula IA -β'-Β^Β3- is -C=N-CH2- and Y1 is CH, Y2 is CH, Y3 is CH.
In another group of compounds of formula IA -β'-Β^Β3- is -C=N-CH2-, Y1 is CH, Y2 is CH, Y3 is CH and R1 is CF3.
In another group of compounds of formula IA -β'-Β^Β3- is -C=N-CH2-, Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3 and R5 is chloro, bromo, fluoro or methyl.
In another group of compounds of formula IA -β'-Β^Β3- is -C=N-CH2-, Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3- S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of formula IA -β'-Β^Β3- is -C=N-CH2-, Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is chloro, bromo, fluoro or methyl and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of formula IA -β'-Β^Β3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is chloro, bromo, fluoro or methyl and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2- and R2 is 3- chloro-5-bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5- trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-, 2,6-bis(trifluoromethyl)-4-pyridyl-, 3,5-dichloro-4-bromophenyl-, 3-bromo-5-(trifluoromethyl)phenyl-,
3.5- dibromophenyl-, or 3,4-dichlorophenyl-
In one group of compounds of formula IA -B1-B2-B3- is -N-CH2-CH2-.
In another group of compounds of formula IA -B'-B^B3- is -N-CH2-CH2-, Y1 is CH, Y2 is CH, Y3 is CH.
In another group of compounds of formula IA -B'-B^B3- is -N-CH2-CH2-, Y1 is CH, Y2 is CH, Y3 is CH and R1 is CF3.
In another group of compounds of formula IA -B'-B^B3- is -N-CH2-CH2-, Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3 and R5 is chloro, bromo, fluoro or methyl .
In another group of compounds of formula IA -β'-Β^Β3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH,
Y3 is CH, R1 is CF3, and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3- S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of formula IA -B'-B^B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is chloro, bromo, fluoro or methyl and R8 is methyl, ethyl, isopropyl, CH3-0-CH2- , CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of formula IA -B'-B^B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is chloro, bromo, fluoro or methyl, R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2- and R2 is 3- chloro-5-bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5- trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-,
2.6- bis(trifluoromethyl)-4-pyridyl-, 3,5-dichloro-4-bromophenyl-, 3-bromo-5-(trifluoromethyl)phenyl-, 3,5-dibromophenyl-, or 3,4-dichlorophenyl-
In one group of compounds of formula IA -B1-B2-B3- is -C=C-0-.
In another group of compounds of formula IA -B1-B2-B3- is -COO- and Y1 is CH, Y2 is CH, Y3 is CH.
In another group of compounds of formula IA -B1-B2-B3- is -COO- , Y1 is CH, Y2 is CH, Y3 is CH and R1 is CF3.
In another group of compounds of formula IA -B1-B2-B3- is -COO- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3 and R5 is chloro, bromo, fluoro or methyl.
In another group of compounds of formula IA -B1-B2-B3- is -COO- , Y1 is CH, Y2 is CH, Y3 is
CH, R1 is CF3, and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02- CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of formula IA -B1-B2-B3- is -COO- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is chloro, bromo, fluoro or methyl, R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S- CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of formula IA -B1-B2-B3- is -COO- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is chloro, bromo, fluoro or methyl and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2- and R2 is 3- chloro-5-bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5- trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-, 2,6-bis(trifluoromethyl)-4-pyridyl-, 3,5-dichloro-4-bromophenyl-, 3-bromo-5-(trifluoromethyl)phenyl-, 3,5-dibromophenyl-, or 3,4-dichlorophenyl- In another group of compounds of formula IA R5 is chloro, bromo, fluoro or methyl and
R8 methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of formula IA R5 is chloro, bromo, fluoro or methyl;
R8 methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-, R1 is CF3, -B'-B^B3 is -C=N-0- or -C=N-CH2-, Y1, Y2 and Y3 are CH, and R5 is chloro or methyl.
In one embodiment the compound of formula I is a compound of formula IB
Figure imgf000011_0001
wherein B 1 , B2,
Figure imgf000011_0002
RV' and R 8° are as defined for a compound of formula I
In compounds of formula IB preferred definitions of B1, B2, B3, R1, R2, Y1, Y2, Y3, R7 and R8 are, in any combination, as set out below
Preferably R1 is trifluoromethyl, or chlorodifluoromethyl, most preferably trifluoromethyl.
Preferably X1, X3 and X6 are independently hydrogen, halogen or trifluoromethyl, wherein at least two of X1, X3 and X6 are not hydrogen. More preferably X1, X3 and X6 are independently hydrogen, chloro, bromo or trifluoromethyl, wherein at least two of X1, X3 and X6 are not hydrogen. Preferably at least two of X1, X3 and X6 are chloro, bromo or trifluoromethyl.
In one group of compounds R2 is 3,5-dichlorophenyl-, 3-chloro-4-fluorophenyl-, 3-fluoro-4- chlorophenyl-, 3,4-dichlorophenyl-, 3-chloro-4-bromophenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5- trichlorophenyl-, 3,5-dichloro-4-iodophenyl-, 3,4,5-trifluorophenyl-, 3-chloro-5-bromophenyl-, 3-chloro- 5-fluorophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,4-dichloro-5-(trifluoromethyl)phenyl-, 3,5- bis(trifluoromethyl)phenyl-, 4-chloro-3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6- dichloro-4-pyridyl-, 2,6-bis(trifluoromethyl)-4-pyridyl-, more preferably 3,5-dichlorophenyl-, more preferably 3-chloro-5-bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4- pyridyl-, 2,6-bis(trifluoromethyl)-4-pyridyl-, 3,5-dichloro-4-bromophenyl-, 3-bromo-5-
(trifluoromethyl)phenyl-, 3,5-dibromophenyl-, or 3,4-dichlorophenyl-, more preferably R2 is 3,5-dichlorophenyl or 3,4,5-trichloro-phenyl, most preferably 3,5-dichloro-phenyl. Preferably Y1 is CH, Y2 is CH, Y3 is CH, or Y1 is N, Y2 is CH, Y3 is CH, or Y1 is N, Y2 is N, Y3 is CH, orY1 is CH, Y2 is N, Y3 is CH, orY1 is CH, Y2 is CH, Y3 is N. Most preferably Y1 is CH, Y2 is CH, and Y3 is CH.
Preferably R7 is methyl.
Preferably R8 is CrC4alkyl, CrC4haloalkyl, Ci-C4alkyl-0-CH2-, CrC4haloalkyl-0-CH2-,C3-
Cgcycloalkyl, C3-C6cycloalkyl-CH2-, C C4alkyl-S(0)-CH2-, Ci-C4alkyl-S(02)-CH2-, more preferably Cr C4alkyl, CrC4alkyl-0-CH2-, CrC4alkyl-S-CH2-, CrC4alkyl-SO-CH2-, CrC4alkyl-S02-CH2-, C3- C4cycloalkyl, or C3-C4cycloalkyl-CH2-, most preferably R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3- S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In one group of compounds of formula IB -B'-B^B3- is -C=N-0-.
In another group of compounds of formula IB -B'-B^B3- is -C=N-0- and Y1 is CH, Y2 is CH, Y3 is CH.
In another group of compounds of formula IB -B'-B^B3- is -C=N-0- , Y1 is CH, Y2 is CH, Y3 is CH and R1 is CF3.
In another group of compounds of formula IB -B'-B^B3- is -C=N-0- , Y1 is CH, Y2 is CH, Y3 is
CH, R1 is CF3 and R7 is methyl.
In another group of compounds of formula IB -B'-B^B3- is -C=N-0- , Y1 is CH, Y2 is CH, Y3 is
CH, R1 is CF3, and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02-
CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of -B'-B^B3- is -C=N-0- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is
CF3, R7 is methyl and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-
S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of formula IB -B'-B^B3- is -C=N-0- , Y1 is CH, Y2 is CH, Y3 is
CH, R1 is CF3, R7 is methyl, R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2- and R2 is 3-chloro-5-bromophenyl-, 3- chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-, 3,5- bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-, 2,6-bis(trifluoromethyl)-
4-pyridyl-, 3,5-dichloro-4-bromophenyl-, 3-bromo-5-(trifluoromethyl)phenyl-, 3,5-dibromophenyl-, or
3,4-dichlorophenyl- In one group of compounds of formula IB -B'-B^B3- is -C=N-CH2-.
In another group of compounds of formula IB -B'-B^B3- is -C=N-CH2- and Y1 is CH, Y2 is CH, Y3 is CH.
In another group of compounds of formula IB -B'-B^B3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH and R1 is CF3.
In another group of compounds of formula IB -B'-B^B3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3 and R7 is methyl. In another group of compounds of formula IB -β'-Β^Β3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3- S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of formula IB -β'-Β^Β3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R7 is methyl and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)- CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of formula IB -β'-Β^Β3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R7 is methyl, R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2- and R2 is 3-chloro-5-bromophenyl-, 3- chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-, 3,5- bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-, 2,6-bis(trifluoromethyl)- 4-pyridyl-, 3,5-dichloro-4-bromophenyl-, 3-bromo-5-(trifluoromethyl)phenyl-, 3,5-dibromophenyl-, or 3,4-dichlorophenyl-
In one group of compounds of formula IB -B'-B^B3- is -N-CH2-CH2-.
In another group of compounds of formula IB -B'-B^B3- is -N-CH2-CH2- and Y1 is CH, Y2 is
CH, Y3 is CH.
In another group of compounds of formula IB -B'-B^B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH, Y3 is CH and R1 is CF3.
In another group of compounds of formula IB -B'-B^B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3 and R7 is methyl.
In another group of compounds of formula IB -B'-B^B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3- S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of formula IB -B'-B^B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R7 is methyl and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3- S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of formula IB -B'-B^B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R7 is methyl, R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)- CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2- and R2 is 3-chloro-5-bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-, 3,5- bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-, 2,6-bis(trifluoromethyl)- 4-pyridyl-, 3,5-dichloro-4-bromophenyl-, 3-bromo-5-(trifluoromethyl)phenyl-, 3,5-dibromophenyl-, or 3,4-dichlorophenyl-
In one group of compounds of formula IB -B'-B^B3- is -C=C-0-.
In another group of compounds of formula IB -B1-B2-B3- is -C=C-0- and Y1 is CH, Y2 is CH, Y3 is CH.
In another group of compounds of formula IB -B1-B2-B3- is -C=C-0- , Y1 is CH, Y2 is CH, Y3 is CH and R1 is CF3. In another group of compounds of formula IB -B'-B^B3- is -COO- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3 and R7 is methyl.
In another group of compounds of formula IB -B'-B^B3- is -COO- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02- CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of formula IB -B1-B2-B3- is -COO- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R7 is methyl and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)- CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-.
In another group of compounds of formula IB -B1-B2-B3- is -COO- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R7 is methyl, R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2- and R2 is 3-chloro-5-bromophenyl-, 3- chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-, 3,5- bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-, 2,6-bis(trifluoromethyl)- 4-pyridyl-, 3,5-dichloro-4-bromophenyl-, 3-bromo-5-(trifluoromethyl)phenyl-, 3,5-dibromophenyl-, or 3,4-dichlorophenyl-
In another group of compounds of formula IB R7 is methyl, and R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-
In another group of compounds of formula IB R7 is methyl, R8 is methyl, ethyl, isopropyl, CH3- O-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-, R1 is CF3, -B1-B2-B3- is -C=N-0-, -C=N-CH2- or -N-CH2-CH2-, and Y1, Y2 and Y3 are CH.
In one embodiment the compound of formula I is a compound of formula IC
Figure imgf000014_0001
wherein B 1 , 5
Figure imgf000014_0002
Z and k are as defined for a compound of formula I
In compounds of formula IC preferred definitions of B1, B2, B3, R1, R2, Y1, Y2, Y3, R5, Z and k are, in any combination, as set out below
Preferably R1 is trifluoromethyl, or chlorodifluoromethyl, most preferably trifluoromethyl.
Preferably X1, X3 and X6 are independently hydrogen, halogen or trifluoromethyl, wherein at least two of X1, X3 and X6 are not hydrogen. More preferably X1, X3 and X6 are independently hydrogen, chloro, bromo or trifluoromethyl, wherein at least two of X1, X3 and X6 are not hydrogen. Preferably at least two of X1, X3 and X6 are chloro, bromo or trifluoromethyl.
In one group of compounds R2 is 3,5-dichlorophenyl-, 3-chloro-4-fluorophenyl-, 3-fluoro-4- chlorophenyl-, 3,4-dichlorophenyl-, 3-chloro-4-bromophenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5- trichlorophenyl-, 3,5-dichloro-4-iodophenyl-, 3,4,5-trifluorophenyl-, 3-chloro-5-bromophenyl-, 3-chloro- 5-fluorophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,4-dichloro-5-(trifluoromethyl)phenyl-, 3,5- bis(trifluoromethyl)phenyl-, 4-chloro-3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6- dichloro-4-pyridyl-, 2,6-bis(trifluoromethyl)-4-pyridyl-, more preferably 3,5-dichlorophenyl-, more preferably 3-chloro-5-bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4- pyridyl-, 2,6-bis(trifluoromethyl)-4-pyridyl-, 3,5-dichloro-4-bromophenyl-, 3-bromo-5- (trifluoromethyl)phenyl-, 3,5-dibromophenyl-, or 3,4-dichlorophenyl-, more preferably R2 is 3,5-dichlorophenyl or 3,4,5-trichloro-phenyl, most preferably 3,5-dichloro-phenyl.
Preferably Y1 is CH, Y2 is CH, Y3 is CH, or Y1 is N, Y2 is CH, Y3 is CH, or Y1 is N, Y2 is N, Y3 is CH, orY1 is CH, Y2 is N, Y3 is CH, orY1 is CH, Y2 is CH, Y3 is N. Most preferably Y1 is CH, Y2 is CH, and Y3 is CH.
Preferably R5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, methoxy, nitro, trifluoromethoxy, cyano, cyclopropyl, more preferably R5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, nitro, cyano, cyclopropyl, even more preferably R5 is hydrogen, cyano, chloro, bromo, fluoro, methyl, or trifluoromethyl, most preferably cyano.
Preferably each Z is independently halogen, cyano, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, or Ci-C4haloalkoxy, more preferably each Z is independently hydrogen, cyano, halogen, methyl, halomethyl, methoxy or halomethoxy, most preferably cyano or trifluoromethyl.
Preferably k is 0 or 1.
In one group of compounds of formula IC -B'-B^B3- is -C=N-0-.
In another group of compounds of formula IC -B1-B2-B3- is -C=N-0-and Y1 is CH, Y2 is CH, Y3 is CH.
In another group of compounds of formula IC -B1-B2-B3- is -C=N-0-, Y1 is CH, Y2 is CH, Y3 is CH and R1 is CF3.
In another group of compounds of formula IC -B1-B2-B3- is -C=N-0-, Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3 and R5 is cyano.
In another group of compounds of formula IC -B1-B2-B3- is -C=N-0-, Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, and k is 0 or k is 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula IC -B1-B2-B3- is -C=N-0-, Y1 is CH, Y2 is CH, Y3 is
CH, R1 is CF3, R5 is cyano and k is 0 or k is 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula IC -B1-B2-B3- is -C=N-0-, Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is cyano and k is 0 or k is 1 and Z is cyano or trifluoromethyl and R2 is 3-chloro-5- bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-, 2,6- bis(trifluoromethyl)-4-pyridyl-, 3 ,5 -dichloro-4-bromophenyl-, 3 -bromo-5 -(trifluoromethyl)phenyl-, 3,5- dibromophenyl-, or 3,4-dichlorophenyl-.
In one group of compounds of formula IC -B'-B^B3- is -C=N-CH2-. In another group of compounds of formula IC -B'-B^B3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH.
In another group of compounds of formula IC -B'-B^B3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH and R1 is CF3.
In another group of compounds of formula IC -B'-B^B3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3 and R5 is cyano.
In another group of compounds of formula IC -B'-B^B3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, and k is 0 or k is 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula IC -B'-B^B3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is cyano and k is 0 or k is 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula IC -B'-B^B3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is cyano and k is 0 or k is 1 and Z is cyano or trifluoromethyl and R2 is 3-chloro-5- bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-,
3.5- bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-, 2,6- bis(trifluoromethyl)-4-pyridyl-, 3,5-dichloro-4-bromophenyl-, 3-bromo-5-(trifluoromethyl)phenyl-, 3,5- dibromophenyl-, or 3,4-dichlorophenyl-.
In one group of compounds of formula IC -B'-B^B3- is -N-CH2-CH2-.
In another group of compounds of formula IC -B1-B2-B3- is -N-CH2-CH2- and Y1 is CH, Y2 is CH, Y3 is CH.
In another group of compounds of formula IC -B1-B2-B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH,
Y3 is CH and R1 is CF3.
In another group of compounds of formula IC -B1-B2-B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3 and R5 is cyano.
In another group of compounds of formula IC -B1-B2-B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, and k is 0 or k is 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula IC -B1-B2-B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is cyano and k is 0 or k is 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula IC -B1-B2-B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is cyano and k is 0 or k is 1 and Z is cyano or trifluoromethyl and R2 is 3-chloro- 5-bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5- trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-,
2.6- bis(trifluoromethyl)-4-pyridyl-, 3,5-dichloro-4-bromophenyl-, 3-bromo-5-(trifluoromethyl)phenyl-, 3,5-dibromophenyl-, or 3,4-dichlorophenyl-.
In one group of compounds of formula IC -B'-B^B3- is -C=C-0-.
In another group of compounds of formula IC -B1-B2-B3- is -C=C-0- and Y1 is CH, Y2 is CH, Y3 is CH.
In another group of compounds of formula IC -B1-B2-B3- is -C=C-0- , Y1 is CH, Y2 is CH, Y3 is CH and R1 is CF3. In another group of compounds of formula IC -B'-B^B3- is -C=C-0- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3 and R5 is cyano.
In another group of compounds of formula IC -B'-B^B3- is -C=C-0- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, and k is 0 or k is 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula IC -B'-B^B3- is -C=C-0- , Y1 is CH, Y2 is CH, Y3 is
CH, R1 is CF3, R5 is cyano and k is 0 or k is 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula IC -B'-B^B3- is -C=C-0- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is cyano and k is 0 or k is 1 and Z is cyano or trifluoromethyl and R2 is 3-chloro-5- bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-, 2,6- bis(trifluoromethyl)-4-pyridyl-, 3 ,5 -dichloro-4-bromophenyl-, 3 -bromo-5 -(trifluoromethyl)phenyl-, 3,5- dibromophenyl-, or 3,4-dichlorophenyl-.
In another group of compounds of formula IC R5 is cyano, k is 0 or 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula IC R5 is cyano, R1 is CF3, -B1-B2-B3- is -C=N-0- or -
C=N-CH2-, Y1, Y2 and Y3 are CH, and k is 0.
In one embodiment the compound of formula I is a compound of formula ID
Figure imgf000017_0001
wherein B 1 , B2, 5
Figure imgf000017_0002
Z and k are as defined for a compound of formula I
In compounds of formula ID preferred definitions of B1, B2, B3, R1, R2, Y1, Y2, Y3, R5 Z and k are, in any combination, as set out below
Preferably R1 is trifluoromethyl, or chlorodifluoromethyl, most preferably trifluoromethyl.
Preferably X1, X3 and X6 are independently hydrogen, halogen or trifluoromethyl, wherein at least two of X1, X3 and X6 are not hydrogen. More preferably X1, X3 and X6 are independently hydrogen, chloro, bromo or trifluoromethyl, wherein at least two of X1, X3 and X6 are not hydrogen. Preferably at least two of X1, X3 and X6 are chloro, bromo or trifluoromethyl.
In one group of compounds R2 is 3,5-dichlorophenyl-, 3-chloro-4-fluorophenyl-, 3-fluoro-4- chlorophenyl-, 3,4-dichlorophenyl-, 3-chloro-4-bromophenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5- trichlorophenyl-, 3,5-dichloro-4-iodophenyl-, 3,4,5-trifluorophenyl-, 3-chloro-5-bromophenyl-, 3-chloro- 5-fluorophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,4-dichloro-5-(trifluoromethyl)phenyl-, 3,5- bis(trifluoromethyl)phenyl-, 4-chloro-3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6- dichloro-4-pyridyl-, 2,6-bis(trifluoromethyl)-4-pyridyl-, more preferably 3,5-dichlorophenyl-, more preferably 3-chloro-5-bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4- pyridyl-, 2,6-bis(trifluoromethyl)-4-pyridyl-, 3,5-dichloro-4-bromophenyl-, 3-bromo-5- (trifluoromethyl)phenyl-, 3,5-dibromophenyl-, or 3,4-dichlorophenyl-, more preferably R2 is 3,5-dichloro- phenyl or 3,4,5-trichloro-phenyl, most preferably 3,5-dichloro-phenyl.
Preferably Y1 is CH, Y2 is CH, Y3 is CH, or Y1 is N, Y2 is CH, Y3 is CH, or Y1 is N, Y2 is N, Y3 is CH, orY1 is CH, Y2 is N, Y3 is CH, orY1 is CH, Y2 is CH, Y3 is N. Most preferably Y1 is CH, Y2 is CH, and Y3 is CH.
Preferably R5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, methoxy, nitro, trifluoromethoxy, cyano, cyclopropyl, more preferably R5 is hydrogen, chloro, bromo, fluoro, trifluoromethyl, methyl, ethyl, nitro, cyano, cyclopropyl, even more preferably R5 is hydrogen, cyano, chloro, bromo, fluoro, methyl, or trifluoromethyl, most preferably cyano.
Preferably each Z is independently halogen, cyano, Ci-C4alkyl, Ci-C4haloalkyl, Ci-C4alkoxy, or Ci-C4haloalkoxy, more preferably each Z is independently hydrogen, cyano, halogen, methyl, halomethyl, methoxy or halomethoxy, most preferably cyano or trifluoromethyl.
Preferably k is 0 or 1.
In one group of compounds of formula ID -B1-B2-B3- is -C=N-0-.
In another group of compounds of formula ID -B'-B^B3- is -C=N-0-and Y1 is CH, Y2 is CH, Y3 is CH.
In another group of compounds of formula ID -B'-B^B3- is -C=N-0-, Y1 is CH, Y2 is CH, Y3 is CH and R1 is CF3.
In another group of compounds of formula ID -B'-B^B3- is -C=N-0-, Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3 and R5 is cyano.
In another group of compounds of formula ID -B'-B^B3- is -C=N-0-, Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, and k is 0 or k is 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula ID -B'-B^B3- is -C=N-0-, Y1 is CH, Y2 is CH, Y3 is
CH, R1 is CF3, R5 is cyano and k is 0 or k is 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula ID -B'-B^B3- is -C=N-0-, Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is cyano and k is 0 or k is 1 and Z is cyano or trifluoromethyl and R2 is 3-chloro-5- bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-, 2,6- bis(trifluoromethyl)-4-pyridyl-, 3 ,5 -dichloro-4-bromophenyl-, 3 -bromo-5 -(trifluoromethyl)phenyl-, 3,5- dibromophenyl-, or 3,4-dichlorophenyl-.
In one group of compounds of formula ID -B1-B2-B3- is -C=N-CH2-.
In another group of compounds of formula ID -B1-B2-B3- is -C=N-CH2- andY1 is CH, Y2 is CH, Y3 is CH.
In another group of compounds of formula ID -B1-B2-B3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH and R1 is CF3. In another group of compounds of formula ID -β'-Β^Β3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3 and R5 is cyano.
In another group of compounds of formula ID -β'-Β^Β3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, and k is 0 or k is 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula ID -β'-Β^Β3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is cyano and k is 0 or k is 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula ID -β'-Β^Β3- is -C=N-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is cyano and k is 0 or k is 1 and Z is cyano or trifluoromethyl and R2 is 3-chloro-5- bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-, 2,6- bis(trifluoromethyl)-4-pyridyl-, 3 ,5 -dichloro-4-bromophenyl-, 3 -bromo-5 -(trifluoromethyl)phenyl-, 3,5- dibromophenyl-, or 3,4-dichlorophenyl-.
In one group of compounds of formula ID -B1-B2-B3- is -N-CH2-CH2-.
In another group of compounds of formula ID -B1-B2-B3- is -N-CH2-CH2- and Y1 is CH, Y2 is CH, Y3 is CH.
In another group of compounds of formula ID -B1-B2-B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH, Y3 is CH and R1 is CF3.
In another group of compounds of formula ID -B1-B2-B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3 and R5 is cyano.
In another group of compounds of formula ID -B1-B2-B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH,
Y3 is CH, R1 is CF3, and k is 0 or k is 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula ID -B1-B2-B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is cyano and k is 0 or k is 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula ID -B1-B2-B3- is -N-CH2-CH2- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is cyano and k is 0 or k is 1 and Z is cyano or trifluoromethyl and R2 is 3-chloro- 5-bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5- trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-, 2,6-bis(trifluoromethyl)-4-pyridyl-, 3,5-dichloro-4-bromophenyl-, 3-bromo-5-(trifluoromethyl)phenyl-, 3,5-dibromophenyl-, or 3,4-dichlorophenyl- In one group of compounds of formula ID -B1-B2-B3- is -C=C-0-.
In another group of compounds of formula ID -B1-B2-B3- is -C=C-0- and Y1 is CH, Y2 is CH, Y3 is CH.
In another group of compounds of formula ID -B1-B2-B3- is -C=C-0- , Y1 is CH, Y2 is CH, Y3 is CH and R1 is CF3.
In another group of compounds of formula ID -B1-B2-B3- is -C=C-0- , Y1 is CH, Y2 is CH, Y3 is
CH, R1 is CF3 and R5 is cyano.
In another group of compounds of formula ID -B1-B2-B3- is -C=C-0- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, and k is 0 or k is 1 and Z is cyano or trifluoromethyl. In another group of compounds of formula ID -B'-B^B3- is -COO- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is cyano and k is 0 or k is 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula ID -B'-B^B3- is -COO- , Y1 is CH, Y2 is CH, Y3 is CH, R1 is CF3, R5 is cyano and k is 0 or k is 1 and Z is cyano or trifluoromethyl and R2 is 3-chloro-5- bromophenyl-, 3-chloro-5-(trifluoromethyl)phenyl-, 3,5-dichloro-4-fluorophenyl-, 3,4,5-trichlorophenyl-, 3,5-bis(trifluoromethyl)phenyl-, 3-(trifluoromethyl)phenyl-, 2,6-dichloro-4-pyridyl-, 2,6- bis(trifluoromethyl)-4-pyridyl-, 3 ,5 -dichloro-4-bromophenyl-, 3 -bromo-5 -(trifluoromethyl)phenyl-, 3,5- dibromophenyl-, or 3,4-dichlorophenyl-.
In another group of compounds of formula D R5 is cyano, k is 0 or 1 and Z is cyano or trifluoromethyl.
In another group of compounds of formula ID R5 is cyano, k is 0 or 1 and Z is cyano or trifluoromethyl, R1 is CF3, -B1-B2-B3- is -C=N-0- or -C=N-CH2-, Y1, Y2 and Y3 are CH.
The following compounds of formula 1-1, 1-2, 1-3 and 1-4 illustrate the compounds of formula I when -B1-B2-B3- is -C=N-0-, -C=N-CH2- , -N-CH2-CH2-, or -COO- respectively.
Figure imgf000020_0001
(1-1 ) (I-2) (I-3) (1-4)
Tables 1 to 36 below illustrate compounds of the invention.
Figure imgf000020_0002
Table 1
Table 1 provides 288 compounds of formula la wherein R5 is hydrogen, B 1 -B2-B3 is C=N-0, and R2 and R8 are as defined in Table P.
Table 2
Table 2 provides 288 compounds of formula la wherein R5 is methyl, B 1 -B2-B3 is C=N-0, and R2 and R8 are as defined in Table P.
Table 3
Table 3 provides 288 compounds of formula la wherein R5 is trifluoromethyl, B1 -B2-B3 is C=N-0, and R2 and R8 are as defined in Table P.
Table 4
Table 4 provides 288 compounds of formula la wherein R5 is chloro, B1 -B2-B3 is C=N-0, and R2 and R8 are as defined in Table P.
Table 5
Table 5 provides 288 compounds of formula la wherein R5 is bromo, B1-B2-B3 is C=N-0, and R2 and R8 are as defined in Table P.
Table 6
Table 6 provides 288 compounds of formula la wherein R5 is hydrogen, B1 -B2-B3 is C=N-CH2, and R2 and R8 are as defined in Table P.
Table 7 Table 7 provides 288 compounds of formula la wherein R5 is methyl, B1-B2-B3 is C=N-CH2, and R2 and R8 are as defined in Table P.
Table 8
Table 8 provides 288 compounds of formula la wherein R5 is trifluoromethyl, B1 -B2-B3 is C=N-CH2, and R2 and R8 are as defined in Table P.
Table 9
Table 9 provides 288 compounds of formula la wherein R5 is chloro, B1-B2-B3 is C=N-CH2, and R2 and R8 are as defined in Table P.
Table 10
Table 10 provides 288 compounds of formula la wherein R5 is bromo, B1 -B2-B3 is C=N-CH2, and R2 and R8 are as defined in Table P.
Table 11
Table 11 provides 288 compounds of formula la wherein R5 is hydrogen, B1-B2-B3 is N-CH2-CH2, and R2 and R8 are as defined in Table P.
Table 12
Table 12 provides 288 compounds of formula la wherein R5 is methyl, B1-B2-B3 is N-CH2-CH2, and R2 and R8 are as defined in Table P.
Table 13
Table 13 provides 288 compounds of formula la wherein R5 is trifluoromethyl, B1-B2-B3 is N-CH2- CH2, and R2 and R8 are as defined in Table P.
Table 14
Table 14 provides 288 compounds of formula la wherein R5 is chloro, B1-B2-B3 is N-CH2-CH2, and R2 and R8 are as defined in Table P.
Table 15
Table 15 provides 288 compounds of formula la wherein R5 is bromo, B1 -B2-B3 is N-CH2-CH2, and R2 and R8 are as defined in Table P.
Table 16
Table 16 provides 288 compounds of formula la wherein R5 is hydrogen, B1-B2-B3 is C=C-0, and R2 and R8 are as defined in Table P.
Table 17
Table 17 provides 288 compounds of formula la wherein R5 is methyl, B1-B2-B3 is C=C-0, and R2 and R8 are as defined in Table P.
Table 18
Table 18 provides 288 compounds of formula la wherein R5 is trifluoromethyl, B1-B2-B3 is C=C-0, and R2 and R8 are as defined in Table P.
Table 19
Table 19 provides 288 compounds of formula la wherein R5 is chloro, B1-B2-B3 is C=C-0, and R2 and R8 are as defined in Table P.
Table 20
Table 20 provides 288 compounds of formula la wherein R5 is bromo, B1 -B2-B3 is C=C-0, and R2 and R8 are as defined in Table P.
Table P
R2 R8
1 3,5-dichlorophenyl methyl
2 3 -chloro-4-fluorophenyl methyl
3 3 -fluoro-4-chlorophenyl methyl
4 3 ,4-dichlorophenyl methyl
5 3 -chloro-4-bromophenyl methyl
6 3,5-dichloro-4-fluorophenyl methyl
7 3,4,5 -trichlorophenyl methyl
8 3,5-dichloro-4-iodophenyl methyl 3,4,5 -trifluorophenyl methyl
3-chloro-5-bromophenyl methyl
3-chloro-5-fluorophenyl methyl
3-chloro-5-(trifluoromethyl)phenyl methyl
3,4-dichloro-5-(trifluoromethyl)phenyl methyl
3,5-bis(trifluoromethyl)phenyl methyl
4-chloro-3,5-bis(trifluoromethyl)phenyl methyl
3 -(trifluoromethyl)phenyl methyl
2,6-dichloro-4-pyridyl methyl
2,6-bis(trifluoromethyl)-4-pyridyl methyl
3,5-dichlorophenyl ethyl
3 -chloro-4-fluorophenyl ethyl
3 -fluoro-4-chlorophenyl ethyl
3 ,4-dichlorophenyl ethyl
3 -chloro-4-bromophenyl ethyl
3,5-dichloro-4-fluorophenyl ethyl
3,4,5 -trichlorophenyl ethyl
3,5-dichloro-4-iodophenyl ethyl
3,4,5 -trifluorophenyl ethyl
3-chloro-5-bromophenyl ethyl
3-chloro-5-fluorophenyl ethyl
3-chloro-5-(trifluoromethyl)phenyl ethyl
3,4-dichloro-5-(trifluoromethyl)phenyl ethyl
3,5-bis(trifluoromethyl)phenyl ethyl
4-chloro-3,5-bis(trifluoromethyl)phenyl ethyl
3 -(trifluoromethyl)phenyl ethyl
2,6-dichloro-4-pyridyl ethyl
2,6-bis(trifluoromethyl)-4-pyridyl ethyl
3,5-dichlorophenyl propyl
3 -chloro-4-fluorophenyl propyl
3 -fluoro-4-chlorophenyl propyl
3 ,4-dichlorophenyl propyl
3 -chloro-4-bromophenyl propyl
3,5-dichloro-4-fluorophenyl propyl
3,4,5 -trichlorophenyl propyl
3,5-dichloro-4-iodophenyl propyl
3,4,5 -trifluorophenyl propyl
3-chloro-5-bromophenyl propyl
3-chloro-5-fluorophenyl propyl
3-chloro-5-(trifluoromethyl)phenyl propyl
3,4-dichloro-5-(trifluoromethyl)phenyl propyl
3,5-bis(trifluoromethyl)phenyl propyl
4-chloro-3,5-bis(trifluoromethyl)phenyl propyl
3 -(trifluoromethyl)phenyl propyl
2,6-dichloro-4-pyridyl propyl
2,6-bis(trifluoromethyl)-4-pyridyl propyl
3,5-dichlorophenyl isopropyl 3 -chloro-4-fluorophenyl isopropyl
3 -fluoro-4-chlorophenyl isopropyl
3 ,4-dichlorophenyl isopropyl
3 -chloro-4-bromophenyl isopropyl
3,5-dichloro-4-fluorophenyl isopropyl
3,4,5 -trichlorophenyl isopropyl
3,5-dichloro-4-iodophenyl isopropyl
3,4,5 -trifluorophenyl isopropyl
3-chloro-5-bromophenyl isopropyl
3-chloro-5-fluorophenyl isopropyl
3-chloro-5-(trifluoromethyl)phenyl isopropyl
3,4-dichloro-5-(trifluoromethyl)phenyl isopropyl
3,5-bis(trifluoromethyl)phenyl isopropyl
4-chloro-3,5-bis(trifluoromethyl)phenyl isopropyl
3 -(trifluoromethyl)phenyl isopropyl
2,6-dichloro-4-pyridyl isopropyl
2,6-bis(trifluoromethyl)-4-pyridyl isopropyl
3,5-dichlorophenyl CH3CH2CH(CH3)-
3 -chloro-4-fluorophenyl CH3CH2CH(CH3)-
3 -fluoro-4-chlorophenyl CH3CH2CH(CH3)-
3 ,4-dichlorophenyl CH3CH2CH(CH3)-
3 -chloro-4-bromophenyl CH3CH2CH(CH3)-
3,5-dichloro-4-fluorophenyl CH3CH2CH(CH3)-
3,4,5 -trichlorophenyl CH3CH2CH(CH3)-
3,5-dichloro-4-iodophenyl CH3CH2CH(CH3)-
3,4,5 -trifluorophenyl CH3CH2CH(CH3)-
3-chloro-5-bromophenyl CH3CH2CH(CH3)-
3-chloro-5-fluorophenyl CH3CH2CH(CH3)-
3-chloro-5-(trifluoromethyl)phenyl CH3CH2CH(CH3)-
3,4-dichloro-5-(trifluoromethyl)phenyl CH3CH2CH(CH3)-
3,5-bis(trifluoromethyl)phenyl CH3CH2CH(CH3)-
4-chloro-3,5-bis(trifluoromethyl)phenyl CH3CH2CH(CH3)-
3 -(trifluoromethyl)phenyl CH3CH2CH(CH3)-
2,6-dichloro-4-pyridyl CH3CH2CH(CH3)-
2,6-bis(trifluoromethyl)-4-pyridyl CH3CH2CH(CH3)-
3,5-dichlorophenyl CH30CH2-
3 -chloro-4-fluorophenyl CH30CH2-
3 -fluoro-4-chlorophenyl CH30CH2-
3 ,4-dichlorophenyl CH30CH2-
3 -chloro-4-bromophenyl CH30CH2-
3,5-dichloro-4-fluorophenyl CH30CH2-
3,4,5 -trichlorophenyl CH30CH2-
3,5-dichloro-4-iodophenyl CH30CH2-
3,4,5 -trifluorophenyl CH30CH2-
3-chloro-5-bromophenyl CH30CH2-
3-chloro-5-fluorophenyl CH30CH2-
3-chloro-5-(trifluoromethyl)phenyl CH30CH2- 103 3,4-dichloro-5-(trifluoromethyl)phenyl CH30CH2-
104 3,5-bis(trifluoromethyl)phenyl CH30CH2-
105 4-chloro-3,5-bis(trifluoromethyl)phenyl CH30CH2-
106 3 -(trifluoromethyl)phenyl CH30CH2-
107 2,6-dichloro-4-pyridyl CH30CH2-
108 2,6-bis(trifluoromethyl)-4-pyridyl CH30CH2-
109 3,5-dichlorophenyl CH30CH2CH2-
110 3 -chloro-4-fluorophenyl CH30CH2CH2-
111 3 -fluoro-4-chlorophenyl CH30CH2CH2-
112 3 ,4-dichlorophenyl CH30CH2CH2-
113 3 -chloro-4-bromophenyl CH30CH2CH2-
114 3,5-dichloro-4-fluorophenyl CH30CH2CH2-
115 3,4,5 -trichlorophenyl CH30CH2CH2-
116 3,5-dichloro-4-iodophenyl CH30CH2CH2-
117 3,4,5 -trifluorophenyl CH30CH2CH2-
118 3-chloro-5-bromophenyl CH30CH2CH2-
119 3-chloro-5-fluorophenyl CH30CH2CH2-
120 3-chloro-5-(trifluoromethyl)phenyl CH30CH2CH2-
121 3,4-dichloro-5-(trifluoromethyl)phenyl CH30CH2CH2-
122 3,5-bis(trifluoromethyl)phenyl CH30CH2CH2-
123 4-chloro-3,5-bis(trifluoromethyl)phenyl CH30CH2CH2-
124 3 -(trifluoromethyl)phenyl CH30CH2CH2-
125 2,6-dichloro-4-pyridyl CH30CH2CH2-
126 2,6-bis(trifluoromethyl)-4-pyridyl CH30CH2CH2-
127 3,5-dichlorophenyl CH30CH(CH3)CH2-
128 3 -chloro-4-fluorophenyl CH30CH(CH3)CH2-
129 3 -fluoro-4-chlorophenyl CH30CH(CH3)CH2-
130 3 ,4-dichlorophenyl CH30CH(CH3)CH2-
131 3 -chloro-4-bromophenyl CH30CH(CH3)CH2-
132 3,5-dichloro-4-fluorophenyl CH30CH(CH3)CH2-
133 3,4,5 -trichlorophenyl CH30CH(CH3)CH2-
134 3,5-dichloro-4-iodophenyl CH30CH(CH3)CH2-
135 3,4,5 -trifluorophenyl CH30CH(CH3)CH2-
136 3-chloro-5-bromophenyl CH30CH(CH3)CH2-
137 3-chloro-5-fluorophenyl CH30CH(CH3)CH2-
138 3-chloro-5-(trifluoromethyl)phenyl CH30CH(CH3)CH2-
139 3,4-dichloro-5-(trifluoromethyl)phenyl CH30CH(CH3)CH2-
140 3,5-bis(trifluoromethyl)phenyl CH30CH(CH3)CH2-
141 4-chloro-3,5-bis(trifluoromethyl)phenyl CH30CH(CH3)CH2-
142 3 -(trifluoromethyl)phenyl CH30CH(CH3)CH2-
143 2,6-dichloro-4-pyridyl CH30CH(CH3)CH2-
144 2,6-bis(trifluoromethyl)-4-pyridyl CH30CH(CH3)CH2-
145 3,5-dichlorophenyl cyclopropyl
146 3 -chloro-4-fluorophenyl cyclopropyl
147 3 -fluoro-4-chlorophenyl cyclopropyl
148 3 ,4-dichlorophenyl cyclopropyl
149 3 -chloro-4-bromophenyl cyclopropyl 150 3,5-dichloro-4-fluorophenyl cyclopropyl
151 3,4,5 -trichlorophenyl cyclopropyl
152 3,5-dichloro-4-iodophenyl cyclopropyl
153 3,4,5 -trifluorophenyl cyclopropyl
154 3-chloro-5-bromophenyl cyclopropyl
155 3-chloro-5-fluorophenyl cyclopropyl
156 3-chloro-5-(trifluoromethyl)phenyl cyclopropyl
157 3,4-dichloro-5-(trifluoromethyl)phenyl cyclopropyl
158 3,5-bis(trifluoromethyl)phenyl cyclopropyl
159 4-chloro-3,5-bis(trifluoromethyl)phenyl cyclopropyl
160 3 -(trifluoromethyl)phenyl cyclopropyl
161 2,6-dichloro-4-pyridyl cyclopropyl
162 2,6-bis(trifluoromethyl)-4-pyridyl cyclopropyl
163 3,5-dichlorophenyl Cyclopropyl-CH2-
164 3 -chloro-4-fluorophenyl Cyclopropyl-CH2-
165 3 -fluoro-4-chlorophenyl Cyclopropyl-CH2-
166 3 ,4-dichlorophenyl Cyclopropyl-CH2-
167 3 -chloro-4-bromophenyl Cyclopropyl-CH2-
168 3,5-dichloro-4-fluorophenyl Cyclopropyl-CH2-
169 3,4,5 -trichlorophenyl Cyclopropyl-CH2-
170 3,5-dichloro-4-iodophenyl Cyclopropyl-CH2-
171 3,4,5 -trifluorophenyl Cyclopropyl-CH2-
172 3-chloro-5-bromophenyl Cyclopropyl-CH2-
173 3-chloro-5-fluorophenyl Cyclopropyl-CH2-
174 3-chloro-5-(trifluoromethyl)phenyl Cyclopropyl-CH2-
175 3,4-dichloro-5-(trifluoromethyl)phenyl Cyclopropyl-CH2-
176 3,5-bis(trifluoromethyl)phenyl Cyclopropyl-CH2-
177 4-chloro-3,5-bis(trifluoromethyl)phenyl Cyclopropyl-CH2-
178 3 -(trifluoromethyl)phenyl Cyclopropyl-CH2-
179 2,6-dichloro-4-pyridyl Cyclopropyl-CH2-
180 2,6-bis(trifluoromethyl)-4-pyridyl Cyclopropyl-CH2-
181 3,5-dichlorophenyl cyclobutyl
182 3 -chloro-4-fluorophenyl cyclobutyl
183 3 -fluoro-4-chlorophenyl cyclobutyl
184 3 ,4-dichlorophenyl cyclobutyl
185 3 -chloro-4-bromophenyl cyclobutyl
186 3,5-dichloro-4-fluorophenyl cyclobutyl
187 3,4,5 -trichlorophenyl cyclobutyl
188 3,5-dichloro-4-iodophenyl cyclobutyl
189 3,4,5 -trifluorophenyl cyclobutyl
190 3-chloro-5-bromophenyl cyclobutyl
191 3-chloro-5-fluorophenyl cyclobutyl
192 3-chloro-5-(trifluoromethyl)phenyl cyclobutyl
193 3,4-dichloro-5-(trifluoromethyl)phenyl cyclobutyl
194 3,5-bis(trifluoromethyl)phenyl cyclobutyl
195 4-chloro-3,5-bis(trifluoromethyl)phenyl cyclobutyl
196 3 -(trifluoromethyl)phenyl cyclobutyl 197 2,6-dichloro-4-pyridyl cyclobutyl
198 2,6-bis(trifluoromethyl)-4-pyridyl cyclobutyl
199 3,5-dichlorophenyl CH3-S-CH2-
200 3 -chloro-4-fluorophenyl CH3-S-CH2-
201 3 -fluoro-4-chlorophenyl CH3-S-CH2-
202 3 ,4-dichlorophenyl CH3-S-CH2-
203 3 -chloro-4-bromophenyl CH3-S-CH2-
204 3,5-dichloro-4-fluorophenyl CH3-S-CH2-
205 3,4,5 -trichlorophenyl CH3-S-CH2-
206 3,5-dichloro-4-iodophenyl CH3-S-CH2-
207 3,4,5 -trifluorophenyl CH3-S-CH2-
208 3-chloro-5-bromophenyl CH3-S-CH2-
209 3-chloro-5-fluorophenyl CH3-S-CH2-
210 3-chloro-5-(trifluoromethyl)phenyl CH3-S-CH2-
211 3,4-dichloro-5-(trifluoromethyl)phenyl CH3-S-CH2-
212 3,5-bis(trifluoromethyl)phenyl CH3-S-CH2-
213 4-chloro-3,5-bis(trifluoromethyl)phenyl CH3-S-CH2-
214 3 -(trifluoromethyl)phenyl CH3-S-CH2-
215 2,6-dichloro-4-pyridyl CH3-S-CH2-
216 2,6-bis(trifluoromethyl)-4-pyridyl CH3-S-CH2-
217 3,5-dichlorophenyl CH3-S(0)-CH2-
218 3 -chloro-4-fluorophenyl CH3-S(0)-CH2-
219 3 -fluoro-4-chlorophenyl CH3-S(0)-CH2-
220 3 ,4-dichlorophenyl CH3-S(0)-CH2-
221 3 -chloro-4-bromophenyl CH3-S(0)-CH2-
222 3,5-dichloro-4-fluorophenyl CH3-S(0)-CH2-
223 3,4,5 -trichlorophenyl CH3-S(0)-CH2-
224 3,5-dichloro-4-iodophenyl CH3-S(0)-CH2-
225 3,4,5 -trifluorophenyl CH3-S(0)-CH2-
226 3-chloro-5-bromophenyl CH3-S(0)-CH2-
227 3-chloro-5-fluorophenyl CH3-S(0)-CH2-
228 3-chloro-5-(trifluoromethyl)phenyl CH3-S(0)-CH2-
229 3,4-dichloro-5-(trifluoromethyl)phenyl CH3-S(0)-CH2-
230 3,5-bis(trifluoromethyl)phenyl CH3-S(0)-CH2-
231 4-chloro-3,5-bis(trifluoromethyl)phenyl CH3-S(0)-CH2-
232 3 -(trifluoromethyl)phenyl CH3-S(0)-CH2-
233 2,6-dichloro-4-pyridyl CH3-S(0)-CH2-
234 2,6-bis(trifluoromethyl)-4-pyridyl CH3-S(0)-CH2-
235 3,5-dichlorophenyl CH3-S(02)-CH2-
236 3 -chloro-4-fluorophenyl CH3-S(02)-CH2-
237 3 -fluoro-4-chlorophenyl CH3-S(02)-CH2-
238 3 ,4-dichlorophenyl CH3-S(02)-CH2-
239 3 -chloro-4-bromophenyl CH3-S(02)-CH2-
240 3,5-dichloro-4-fluorophenyl CH3-S(02)-CH2-
241 3,4,5 -trichlorophenyl CH3-S(02)-CH2-
242 3,5-dichloro-4-iodophenyl CH3-S(02)-CH2-
243 3,4,5 -trifluorophenyl CH3-S(02)-CH2- 244 3-chloro-5-bromophenyl CH3-S(02)-CH2-
245 3-chloro-5-fluorophenyl CH3-S(02)-CH2-
246 3-chloro-5-(trifluoromethyl)phenyl CH3-S(02)-CH2-
247 3,4-dichloro-5-(trifluoromethyl)phenyl CH3-S(02)-CH2-
248 3,5-bis(trifluoromethyl)phenyl CH3-S(02)-CH2-
249 4-chloro-3,5-bis(trifluoromethyl)phenyl CH3-S(02)-CH2-
250 3 -(trifluoromethyl)phenyl CH3-S(02)-CH2-
251 2,6-dichloro-4-pyridyl CH3-S(02)-CH2-
252 2,6-bis(trifluoromethyl)-4-pyridyl CH3-S(02)-CH2-
253 3,5-dichlorophenyl tetrahydrofuran-2-yl
254 3 -chloro-4-fluorophenyl tetrahydrofuran-2-yl
255 3 -fluoro-4-chlorophenyl tetrahydrofuran-2-yl
256 3 ,4-dichlorophenyl tetrahydrofuran-2-yl
257 3 -chloro-4-bromophenyl tetrahydrofuran-2-yl
258 3,5-dichloro-4-fluorophenyl tetrahydrofuran-2-yl
259 3,4,5 -trichlorophenyl tetrahydrofuran-2-yl
260 3,5-dichloro-4-iodophenyl tetrahydrofuran-2-yl
261 3,4,5 -trifluorophenyl tetrahydrofuran-2-yl
262 3-chloro-5-bromophenyl tetrahydrofuran-2-yl
263 3-chloro-5-fluorophenyl tetrahydrofuran-2-yl
264 3-chloro-5-(trifluoromethyl)phenyl tetrahydrofuran-2-yl
265 3,4-dichloro-5-(trifluoromethyl)phenyl tetrahydrofuran-2-yl
266 3,5-bis(trifluoromethyl)phenyl tetrahydrofuran-2-yl
267 4-chloro-3,5-bis(trifluoromethyl)phenyl tetrahydrofuran-2-yl
268 3 -(trifluoromethyl)phenyl tetrahydrofuran-2-yl
269 2,6-dichloro-4-pyridyl tetrahydrofuran-2-yl
270 2,6-bis(trifluoromethyl)-4-pyridyl tetrahydrofuran-2-yl
271 3,5-dichlorophenyl tetrahydrofuran-3 -yl
272 3 -chloro-4-fluorophenyl tetrahydrofuran-3 -yl
273 3 -fluoro-4-chlorophenyl tetrahydrofuran-3 -yl
274 3 ,4-dichlorophenyl tetrahydrofuran-3 -yl
275 3 -chloro-4-bromophenyl tetrahydrofuran-3 -yl
276 3,5-dichloro-4-fluorophenyl tetrahydrofuran-3 -yl
277 3,4,5 -trichlorophenyl tetrahydrofuran-3 -yl
278 3,5-dichloro-4-iodophenyl tetrahydrofuran-3 -yl
279 3,4,5 -trifluorophenyl tetrahydrofuran-3 -yl
280 3-chloro-5-bromophenyl tetrahydrofuran-3 -yl
281 3-chloro-5-fluorophenyl tetrahydrofuran-3 -yl
282 3-chloro-5-(trifluoromethyl)phenyl tetrahydrofuran-3 -yl
283 3,4-dichloro-5-(trifluoromethyl)phenyl tetrahydrofuran-3 -yl
284 3,5-bis(trifluoromethyl)phenyl tetrahydrofuran-3 -yl
285 4-chloro-3,5-bis(trifluoromethyl)phenyl tetrahydrofuran-3 -yl
286 3 -(trifluoromethyl)phenyl tetrahydrofuran-3 -yl
287 2,6-dichloro-4-pyridyl tetrahydrofuran-3 -yl
288 2,6-bis(trifluoromethyl)-4-pyridyl tetrahydrofuran-3 -yl
Figure imgf000028_0001
Table 21
Table 21 provides 288 compounds of formula lb wherein B1 -B2-B 3 is C=N-0, and R2 and R8 are as defined in Table P.
Table 22
Table 22 provides 288 compounds of formula lb wherein B 1-B2-B 3 is C=N-CH2, and R2 and R8 are as defined in Table P.
Table 23
Table 23 provides 288 compounds of formula lb wherein B1 -B2-B 3 is N-CH2-CH2, and R2 and R8 are as defined in Table P.
Table 24
Table 24 provides 288 compounds of formula lb wherein B1-B2-B 3 is C=C-0, and R2 and R8 are as defined in Table P.
Figure imgf000028_0002
Table 25
Table 25 provides 18 compounds of formula Ic wherein B1-B2-B3 is C=N-0, and R2 is as defined in Table Q.
Table 26
Table 26 provides 18 compounds of formula Ic wherein B1-B2-B3 is C=N-CH2, and R2 is as defined in Table Q.
Table 27
Table 27 provides 18 compounds of formula Ic wherein B1-B2-B3 is N-CH2-CH2, and R2 is as defined in Table Q.
Table 28
Table 28 provides 18 compounds of formula Ic wherein B1-B2-B 3 is C=C-0, and R2 is as defined in Table Q.
Figure imgf000029_0001
Table 29
Table 29 provides 18 compounds of formula Id wherein k is CN, B1-B2-B3 is C=N-0 and R2 is as defined in Table Q.
Table 30
Table 30 provides 18 compounds of formula Id wherein k is CF3, B1-B2-B3 is C=N-0 and R2 is as defined in Table Q.
Table 31
Table 31 provides 18 compounds of formula Id wherein k is CN, B1-B2-B3 is C=N-CH2 and R2 is as defined in Table Q.
Table 32
Table 32 provides 18 compounds of formula Id wherein k is CF3, B1-B2-B3 is C=N-CH2 and R2 is as defined in Table Q.
Table 33
Table 33 provides 18 compounds of formula Id wherein k is CN, B1-B2-B3 is N-CH2-CH2 and R2 is as defined in Table Q.
Table 34
Table 34 provides 18 compounds of formula Id wherein k is CF3, B1-B2-B3 is N-CH2-CH2 and R2 is as defined in Table Q.
Table 35
Table 35 provides 18 compounds of formula Id wherein k is CN, B1-B2-B3 is C=C-0 and R2 is as defined in Table Q.
Table 36
Table 36 provides 18 compounds of formula Id wherein k is CF3, B1-B2-B3 is C=C-0 and R2 is as defined in Table Q.
Table O
R2
1 3,5-dichlorophenyl
2 3 -chloro-4-fluorophenyl
3 3 -fluoro-4-chlorophenyl
4 3 ,4-dichlorophenyl
5 3 -chloro-4-bromophenyl
6 3,5-dichloro-4-fluorophenyl
7 3,4,5 -trichlorophenyl
8 3,5-dichloro-4-iodophenyl
9 3,4,5 -trifluorophenyl
10 3-chloro-5-bromophenyl
11 3-chloro-5-fluorophenyl
12 3-chloro-5-(trifluoromethyl)phenyl 13 3,4-dichloro-5-(trifluoromethyl)phenyl
14 3,5-bis(trifluoromethyl)phenyl
15 4-chloro-3,5-bis(trifluoromethyl)phenyl
16 3 -(trifluoromethyl)phenyl
17 2,6-dichloro-4-pyridyl
18 2,6-bis(trifluoromethyl)-4-pyridyl
Of compounds of formula la, compounds in Tables 2, 4, 7 and 9 are particularly preferred. Of compounds of formula lb, compounds in Tables 21, 22 and 23 are particularly preferred. Of compounds of formula Ic, compounds in Tables 25 and 26 are particularly preferred. Of compounds of formula Id, compounds in Tables 29, 30, 31, and 32 are particularly preferred.
Of particular interest are compounds 25.1, 25.7, 26.1 and 26.7.
Compounds of formula I include at least one chiral centre and may exist as compounds of formula I* or compounds of formula I**. Compounds I* and I** are enantiomers if there is no other chiral center or epimers otherwise.
Figure imgf000030_0001
(I*) (I**)
Generally compounds of formula I** are more biologically active than compounds of formula I*. The invention includes mixtures of compounds I* and I** in any ratio e.g. in a molar ratio of 1 :99 to 99: 1, e.g. 10:1 to 1 :10, e.g. a substantially 50:50 molar ratio. In an enantiomerically (or epimerically) enriched mixture of formula I**, the molar proportion of compound I** compared to the total amount of both enantiomers (or epimers) is for example greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90,
95, 96, 97, 98, or at least 99%. Likewise, in enantiomerically (or epimerically) enriched mixtures of formula I*, the molar proportion of the compound of formula I* compared to the total amount of both enantiomers (or epimers) is for example greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95,
96, 97, 98, or at least 99%. Enantiomerically (or epimerically) enriched mixtures of formula I** are preferred. Each compound disclosed in Tables 1 to 36 represents a disclosure of a compound according to the compound of formula I* and a compound according to the compound of formula I**.
Likewise, group A2 may be group A2* or A2**.
Figure imgf000030_0002
(A2*) (A2**) The invention includes mixtures of compounds of formula I with A2 as A2* and A2** in any ratio e.g. in a molar ratio of 1 :99 to 99: 1, e.g. 10: 1 to 1 : 10, e.g. a substantially 50:50 molar ratio. In an enantiomerically (or epimerically) enriched mixture of formula I with A2 as A2*, the molar proportion of formula I with A2 as A2* compared to the total amount of both enantiomers (or epimers) is for example greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or at least 99%. Likewise, in enantiomerically (or epimerically) enriched mixture of formula I with A2 as A2**, the molar proportion of the compound of formula I with A2 as A2**, compared to the total amount of both enantiomers (or epimers) is for example greater than 50%, e.g. at least 55, 60, 65, 70, 75, 80, 85, 90, 95, 96, 97, 98, or at least 99%. Enantiomerically (or epimerically) enriched mixtures of formula I with A2 as A2** are preferred.
Each compound disclosed in Tables 21 to 24 represents a disclosure of I with A2 as A2* and a compound I with A2 as A2**. Each compound disclosed in Tables 21 to 24 represents a disclosure of a compound according to formula I* with A2 as A2*. Each compound disclosed in Tables 21 to 24 represents a disclosure of a compound according to formula I** with A2 as A2*. Each compound disclosed in Tables 21 to 24 represents a disclosure of a compound according to formula I* with A2 as A2**. Each compound disclosed in Tables 21 to 24 represents a disclosure of a compound according to formula I** with A2 as A2**. Enantiomerically (or epimerically) enriched mixtures of formula I** with A2 as A2** are preferred.
Reference to compounds of the invention also includes reference to salts and N-oxides.
The compounds of formula I may be prepared as described in WO08128711, WO10043315,
WOl 1051455, WO07105814, WO08122375, WO09035004, WO09045999, WO09072621,
WO09097992, WO10133336, WO10043315, WOl 1051455, WOl 1080211, JP2010235590,
JP2011037817, JP2011178724, CN102210317, CN102246777, WO0907261, WO09097992,
WO09051956.
The methods and uses of the invention are preferably for controlling and/or preventing infestation of the soybean crop by stink bugs, including stink bugs that are resistant to other insecticides, e.g.
pyrethroid insecticides. Stinkbugs that are "resistant" to a particular insecticide refers e.g. to strains of stinkbugs that are less sensitive to that insecticide compared to the expected sensitivity of the same species of stinkbug. The expected sensitivity can be measured using e.g. a strain that has not previously been exposed to the insecticide.
Application is of the compounds of the invention is preferably to a crop of soybean plants, the locus thereof or propagation material thereof. Preferably application is to a crop of soybean plants or the locus thereof, more preferably to a crop of soybean plants. Application may be before infestation or when the pest is present. Application of the compounds of the invention can be performed according to any of the usual modes of application, e.g. foliar, drench, soil, in furrow etc. However, control of stinkbugs is usually achieved by foliar application, which is the preferred mode of application according to the invention. The compounds of the invention may be applied in combination with an attractant. An attractant is a chemical that causes the insect to migrate towards the location of application. For control of stinkbugs it can be advantageous to apply the compounds of the invention with an attractant, particularly when the application is foliar. Stinkbugs are often located near to the ground, and application of an attractant may encourage migration up the plant towards the active ingredient. Suitable attractants include glucose, sacchrose, salt, glutamate (e.g. Aji-no-moto™), citric acid (e.g. Orobor™), soybean oil, peanut oil and soybean milk. Glutamate and citric acid are of particular interest, with citric acid being preferred.
An attractant may be premixed with the compound of the invention prior to application, e.g. as a readymix or tankmix, or by simultaneous application or sequential application to the plant. Suitable rates of attractants are for example 0.02kg/ha-3kg/ha.
The compounds of the invention are preferably used for pest control on soybean at 1 :500 g/ha, preferably 10-70g/ha.
The compounds of the invention are suitable for use on any soybean plant, including those that have been genetically modified to be resistant to active ingredients such as herbicides, or to produce biologically active compounds that control infestation by plant pests.
In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof, are treated. Particularly preferably, plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention. Plant cultivars are understood as meaning plants having novel properties ("traits") which have been obtained by
conventional breeding, by mutagenesis or by recombinant DNA techniques.
These can be cultivars, bio- or genotypes. Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive "synergistic") effects.
Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected.
The preferred transgenic plants or plant cultivars (obtained by genetic engineering) which are to be treated according to the invention include all plants which, by virtue of the genetic modification, received genetic material which imparts particularly advantageous, useful traits to these plants. Examples of such traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products. Further and particularly emphasized examples of such traits are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds.
Traits that are emphasized in particular are the increased defence of the plants against insects, arachnids, nematodes and slugs and snails by virtue of toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CrylA(a), CrylA(b), CrylA(c), CryllA, CrylllA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CrylF and also combinations thereof) (referred to herein as "Bt plants"). Traits that are also particularly emphasized are the increased defence of the plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins.
Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (for example the "PAT" gene). The genes which impart the desired traits in question can also be present in combination with one another in the transgenic plants.
Examples of "Bt plants" are soya bean varieties which are sold under the trade names YIELD GARD(®)
Examples of herbicide -tolerant plants which may be mentioned are soybean varieties which are sold under the trade names Roundup Ready(®) (tolerance to glyphosate), Liberty Link(®) (tolerance to phosphinotricin), IMI(®) (tolerance to imidazolinones) and STS(®) (tolerance to sulphonylureas).
Herbicide -resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield(®) (for example maize).
Of particular interest are soybean plants carrying trains conferring resistance to 2.4D (e.g. Enlist®), glyphosate (e.g. Roundup Ready®, Roundup Ready 2 Yield®), sulfonylurea (e.g. STS®), glufosinate (e.g. Liberty Link®, Ignite®), Dicamba (Monsanto) HPPD tolerance (e.g. isoxaflutole herbicide) (Bayer CropScience, Syngenta). Double or triple stack in soybean plants of any of the traits described here are also of interest, including glyphosate and sulfonyl-urea tolerance (e.g. Optimum GAT®, plants stacked with STS® and Roundup Ready® or Roundup Ready 2 Yield®), dicamba and glyphosate tolerance (Monsanto). Soybean Cyst Nematode resistance soybean (SCN® - Syngenta) and soybean with Aphid resistant trait (AMT® - Syngneta) are also of interest.
These statements also apply to plant cultivars having these genetic traits or genetic traits still to be developed, which plant cultivars will be developed and/or marketed in the future.
The compounds of the invention may be used on soybean to control, for example, Elasmopalpus lignosellus, Diloboderus abderus, Diabrotica speciosa, Sternechus subsignatus, Formicidae, Agrotis ypsilon, Julus ssp. , Anticarsia gemmatalis, Megascelis ssp. , Procornitermes ssp. , Gryllotalpidae, Nezara viridula, Piezodorus spp. , Acrosternum spp. , Neomegalotomus spp. , Cerotoma trifurcata, Popillia japonica, Edessa spp., Liogenys fuscus, Euchistus hews, stalk borer, Scaptocoris castanea, phyllophaga spp., Pseudoplusia includens, Spodoptera spp., Bemisia tabaci, Agriotes spp., preferably Diloboderus abderus, Diabrotica speciosa, Nezara viridula, Piezodorus spp. , Acrosternum spp. , Cerotoma trifurcata, Popillia japonica, Euchistus heros, phyllophaga spp., Agriotes spp..
The compounds of the invention are preferably used on soybean to control stinkbugs, e.g. Nezara spp. (e.g. Nezara viridula, Nezara antennata, Nezara hilare), Piezodorus spp. (e.g. Piezodorus guildinii), Acrosternum spp. Euchistus spp. (e.g. Euchistus heros, Euschistus servus), Halyomorpha halys, Plautia crossota, Riptortus clavatus, Rhopalus msculatus, Antestiopsis orbitalus, Dichelops spp. (e.g. Dichelops furcatus, Dichelops melacanthus), Eurygaster spp. (e.g. Eurygaster intergriceps, Eurygaster maura), Oebalus spp. (e.g. Oebalus mexicana, Oebalus poecilus, Oebalus pugnase, Scotinophara spp. (e.g.
Scotinophara lurida, Scotinophara coarctatd). Preferred targets include Antestiopsis orbitalus, Dichelops furcatus, Dichelops melacanthus, Euchistus heros, Euschistus servus, Nezara viridula, Nezara hilare, Piezodorus guildinii, Halyomorpha halys. In one embodiment the stinkbug target is Nezara viridula, Piezodorus spp., Acrosternum spp, Euchistus heros. The compounds of the invention are particularly effective against Euschistus and in particular Euchistus heros. Euschistus and in particular Euchistus heros are the preferred targets.
In order to apply a compounds of the invention as an insecticide, acaricide, nematicide or molluscicide to a pest, a locus of pest, or to a plant susceptible to attack by a pest, compounds of the invention is usually formulated into a composition which includes, in addition to the compound of the invention, a suitable inert diluent or carrier and, optionally, a surface active agent (SFA). SFAs are chemicals which are able to modify the properties of an interface (for example, liquid/solid, liquid/air or liquid/liquid interfaces) by lowering the interfacial tension and thereby leading to changes in other properties (for example dispersion, emulsification and wetting). It is preferred that all compositions (both solid and liquid formulations) comprise, by weight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%>, of a compound of the invention. The composition is generally used for the control of pests such that a compound of the invention is applied at a rate of from O.lg to 10kg per hectare, preferably from lg to 6kg per hectare, more preferably from lg to 1kg per hectare.
When used in a seed dressing, a compound of the invention is used at a rate of 0.000 lg to lOg (for example O.OOlg or 0.05g), preferably 0.005g to lOg, more preferably 0.005g to 4g, per kilogram of seed.
Compositions comprising a compound of the invention can be chosen from a number of formulation types, including dustable powders (DP), soluble powders (SP), water soluble granules (SG), water dispersible granules (WG), wettable powders (WP), granules (GR) (slow or fast release), soluble concentrates (SL), oil miscible liquids (OL), ultra low volume liquids (UL), emulsifiable concentrates (EC), dispersible concentrates (DC), emulsions (both oil in water (EW) and water in oil (EO)), micro- emulsions (ME), suspension concentrates (SC), aerosols, fogging/smoke formulations, capsule suspensions (CS) and seed treatment formulations. The formulation type chosen in any instance will depend upon the particular purpose envisaged and the physical, chemical and biological properties of the compound of the invention.
Dustable powders (DP) may be prepared by mixing a compound of the invention with one or more solid diluents (for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, talc and other organic and inorganic solid carriers) and mechanically grinding the mixture to a fine powder.
Soluble powders (SP) may be prepared by mixing a compound of the invention with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (such as a polysaccharide) and, optionally, one or more wetting agents, one or more dispersing agents or a mixture of said agents to improve water
dispersibility/solubility. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water soluble granules (SG).
Wettable powders (WP) may be prepared by mixing a compound of the invention with one or more solid diluents or carriers, one or more wetting agents and, preferably, one or more dispersing agents and, optionally, one or more suspending agents to facilitate the dispersion in liquids. The mixture is then ground to a fine powder. Similar compositions may also be granulated to form water dispersible granules (WG).
Granules (GR) may be formed either by granulating a mixture of a compound of the invention and one or more powdered solid diluents or carriers, or from pre-formed blank granules by absorbing a compound of the invention (or a solution thereof, in a suitable agent) in a porous granular material (such as pumice, attapulgite clays, fuller's earth, kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing a compound of the invention (or a solution thereof, in a suitable agent) on to a hard core material (such as sands, silicates, mineral carbonates, sulfates or phosphates) and drying if necessary. Agents which are commonly used to aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars and vegetable oils). One or more other additives may also be included in granules (for example an emulsifying agent, wetting agent or dispersing agent).
Dispersible Concentrates (DC) may be prepared by dissolving a compound of the invention in water or an organic solvent, such as a ketone, alcohol or glycol ether. These solutions may contain a surface active agent (for example to improve water dilution or prevent crystallization in a spray tank).
Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may be prepared by dissolving a compound of the invention in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or a mixture of said agents). Suitable organic solvents for use in ECs include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100, SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol), N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone), dimethyl amides of fatty acids (such as Cg-Qo fatty acid dimethylamide) and chlorinated hydrocarbons. An EC product may spontaneously emulsify on addition to water, to produce an emulsion with sufficient stability to allow spray application through appropriate equipment. Preparation of an EW involves obtaining a compound of the invention either as a liquid (if it is not a liquid at room temperature, it may be melted at a reasonable temperature, typically below 70°C) or in solution (by dissolving it in an appropriate solvent) and then emulsifiying the resultant liquid or solution into water containing one or more SFAs, under high shear, to produce an emulsion. Suitable solvents for use in EWs include vegetable oils, chlorinated hydrocarbons (such as chlorobenzenes), aromatic solvents (such as alkylbenzenes or alkylnaphthalenes) and other appropriate organic solvents which have a low solubility in water.
Microemulsions (ME) may be prepared by mixing water with a blend of one or more solvents with one or more SFAs, to produce spontaneously a thermodynamically stable isotropic liquid formulation. A compound of the invention is present initially in either the water or the solvent/SFA blend. Suitable solvents for use in MEs include those hereinbefore described for use in ECs or in EWs. An ME may be either an oil-in- water or a water-in-oil system (which system is present may be determined by conductivity measurements) and may be suitable for mixing water-soluble and oil-soluble pesticides in the same formulation. An ME is suitable for dilution into water, either remaining as a microemulsion or forming a conventional oil-in-water emulsion.
Suspension concentrates (SC) may comprise aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of the invention. SCs may be prepared by ball or bead milling the solid compound of the invention in a suitable medium, optionally with one or more dispersing agents, to produce a fine particle suspension of the compound. One or more wetting agents may be included in the composition and a suspending agent may be included to reduce the rate at which the particles settle. Alternatively, a compound of the invention may be dry milled and added to water, containing agents hereinbefore described, to produce the desired end product.
Aerosol formulations comprise a compound of the invention and a suitable propellant (for example n-butane). A compound of the invention may also be dissolved or dispersed in a suitable medium (for example water or a water miscible liquid, such as n-propanol) to provide compositions for use in non- pressurized, hand-actuated spray pumps.
A compound of the invention may be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating, in an enclosed space, a smoke containing the compound.
Capsule suspensions (CS) may be prepared in a manner similar to the preparation of EW formulations but with an additional polymerization stage such that an aqueous dispersion of oil droplets is obtained, in which each oil droplet is encapsulated by a polymeric shell and contains a compound of the invention and, optionally, a carrier or diluent therefor. The polymeric shell may be produced by either an interfacial polycondensation reaction or by a coacervation procedure. The compositions may provide for controlled release of the compound of the invention and they may be used for seed treatment. A compound of the invention may also be formulated in a biodegradable polymeric matrix to provide a slow, controlled release of the compound.
A composition may include one or more additives to improve the biological performance of the composition (for example by improving wetting, retention or distribution on surfaces; resistance to rain on treated surfaces; or uptake or mobility of a compound of the invention). Such additives include surface active agents, spray additives based on oils, for example certain mineral oils or natural plant oils (such as soy bean and rape seed oil), and blends of these with other bio-enhancing adjuvants (ingredients which may aid or modify the action of a compound of the invention).
A compound of the invention may also be formulated for use as a seed treatment, for example as a powder composition, including a powder for dry seed treatment (DS), a water soluble powder (SS) or a water dispersible powder for slurry treatment (WS), or as a liquid composition, including a flowable concentrate (FS), a solution (LS) or a capsule suspension (CS). The preparations of DS, SS, WS, FS and LS compositions are very similar to those of, respectively, DP, SP, WP, SC and DC compositions described above. Compositions for treating seed may include an agent for assisting the adhesion of the composition to the seed (for example a mineral oil or a film-forming barrier).
Wetting agents, dispersing agents and emulsifying agents may be surface SFAs of the cationic, anionic, amphoteric or non-ionic type.
Suitable SFAs of the cationic type include quaternary ammonium compounds (for example cetyltrimethyl ammonium bromide), imidazolines and amine salts.
Suitable anionic SFAs include alkali metals salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (for example sodium lauryl sulfate), salts of sulfonated aromatic compounds (for example sodium dodecylbenzenesulfonate, calcium dodecylbenzenesulfonate, butylnaphthalene sulfonate and mixtures of sodium di-z' opropyl- and tri-wopropyl-naphthalene sulfonates), ether sulfates, alcohol ether sulfates (for example sodium laureth-3 -sulfate), ether carboxylates (for example sodium laureth-3- carboxylate), phosphate esters (products from the reaction between one or more fatty alcohols and phosphoric acid (predominately mono-esters) or phosphorus pentoxide (predominately di-esters), for example the reaction between lauryl alcohol and tetraphosphoric acid; additionally these products may be ethoxylated), sulfosuccinamates, paraffin or olefine sulfonates, taurates and lignosulfonates.
Suitable SFAs of the amphoteric type include betaines, propionates and glycinates.
Suitable SFAs of the non-ionic type include condensation products of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or with alkylphenols (such as octylphenol, nonylphenol or octylcresol); partial esters derived from long chain fatty acids or hexitol anhydrides; condensation products of said partial esters with ethylene oxide; block polymers (comprising ethylene oxide and propylene oxide);
alkanolamides; simple esters (for example fatty acid polyethylene glycol esters); amine oxides (for example lauryl dimethyl amine oxide); and lecithins.
Suitable suspending agents include hydrophilic colloids (such as polysaccharides,
polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
A compound of the invention may be applied by any of the known means of applying pesticidal compounds. For example, it may be applied, formulated or unformulated, to the pests or to a locus of the pests (such as a habitat of the pests, or a growing plant liable to infestation by the pests) or to any part of the plant, including the foliage, stems, branches or roots, to the seed before it is planted or to other media in which plants are growing or are to be planted (such as soil surrounding the roots, the soil generally, paddy water or hydroponic culture systems), directly or it may be sprayed on, dusted on, applied by dipping, applied as a cream or paste formulation, applied as a vapor or applied through distribution or incorporation of a composition (such as a granular composition or a composition packed in a water- soluble bag) in soil or an aqueous environment.
A compound of the invention may also be injected into plants or sprayed onto vegetation using electrodynamic spraying techniques or other low volume methods, or applied by land or aerial irrigation systems.
Compositions for use as aqueous preparations (aqueous solutions or dispersions) are generally supplied in the form of a concentrate containing a high proportion of the active ingredient, the concentrate being added to water before use. These concentrates, which may include DCs, SCs, ECs, EWs, MEs, SGs, SPs, WPs, WGs and CSs, are often required to withstand storage for prolonged periods and, after such storage, to be capable of addition to water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment. Such aqueous preparations may contain varying amounts of a compound of the invention (for example 0.0001 to 10%, by weight) depending upon the purpose for which they are to be used.
A compound of the invention may be used in mixtures with fertilizers (for example nitrogen-, potassium- or phosphorus-containing fertilizers). Suitable formulation types include granules of fertilizer. The mixtures preferably contain up to 25% by weight of the compound of the invention.
The invention therefore also provides a fertilizer composition comprising a fertilizer and a compound of the invention.
The compositions of this invention may contain other compounds having biological activity, for example micronutrients or compounds having fungicidal activity or which possess plant growth regulating, herbicidal, insecticidal, nematicidal or acaricidal activity.
The compound of the invention may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as a pesticide, fungicide, synergist, herbicide or plant growth regulator where appropriate. An additional active ingredient may: provide a composition having a broader spectrum of activity or increased persistence at a locus; synergize the activity or complement the activity (for example by increasing the speed of effect or overcoming repellency) of the compound of the invention; or help to overcome or prevent the development of resistance to individual components. The particular additional active ingredient will depend upon the intended utility of the composition. Examples of suitable pesticides include the following:
a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate, esfenvalerate, deltamethrin, cyhalothrin (in particular lambda-cyhalothrin and gamma cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids (for example ethofenprox), natural pyrethrin, tetramethrin, S-bioallethrin, fenfluthrin, prallethrin, acrinathirin, etofenprox or
5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl- 3-(2-oxothiolan-3-ylidenemethyl)cyclopropane carboxylate; b) Organophosphates, such as profenofos, sulprofos, acephate, methyl parathion, azinphos-methyl, demeton-s -methyl, heptenophos, thiometon, fenamiphos, monocrotophos, profenofos, triazophos, methamidophos, dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos, fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl, pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon; 5 c) Carbamates (including aryl carbamates), such as pirimicarb, triazamate, cloethocarb, carbofuran,
furathiocarb, ethiofencarb, aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur, methomyl or oxamyl;
d) Benzoyl ureas, such as diflubenzuron, triflumuron, hexaflumuron, flufenoxuron, diafenthiuron, lufeneron, novaluron, noviflumuron or chlorfluazuron;
Θ) Organic tin compounds, such as cyhexatin, fenbutatin oxide or azocyclotin;
f) Pyrazoles, such as tebufenpyrad, tolfenpyrad, ethiprole, pyriprole, fipronil, and fenpyroximate;
g) Macrolides, such as avermectins or milbemycins, for example abamectin, emamectin benzoate, ivermectin, milbemycin, spinosad, azadirachtin, milbemectin, lepimectin or spinetoram;
h) Hormones or pheromones;
5 i) Organochlorine compounds, such as endosulfan (in particular alpha-endosulfan), benzene hexachloride, DDT, chlordane or dieldrin;
j) Amidines, such as chlordimeform or amitraz;
k) Fumigant agents, such as chloropicrin, dichloropropane, methyl bromide or metam;
1) Neonicotinoid compounds, such as imidacloprid, thiacloprid, acetamiprid, nitenpyram, dinotefuran,0 thiamethoxam, clothianidin, or nithiazine;
m) Diacylhydrazines, such as tebufenozide, chromafenozide or methoxyfenozide;
n) Diphenyl ethers, such as diofenolan or pyriproxifen;
o) Pyrazolines such as Indoxacarb or metaflumizone;
p) Ketoenols, such as Spirotetramat, spirodiclofen or spiromesifen;
5 q) Diamides, such as flubendiamide, chlorantraniliprole (Rynaxypyr®) or cyantraniliprole;
r) Essential oils such as Bugoil® - (Plantlmpact); or
s) a comopund selected from buprofezine, flonicamid, acequinocyl, bifenazate, cyenopyrafen, cyflumetofen, etoxazole, flometoquin, fluacrypyrim, fluensulfone, flufenerim, flupyradifuone, harpin, iodomethane, dodecadienol, pyridaben, pyridalyl, pyrimidifen, flupyradifurone, 4-[(6-Chloro-pyridin-3-0 ylmethyl)-(2,2-difluoro-ethyl)-amino]-5H-furan-2-one (DE 102006015467), CAS: 915972-17-7
(WO 2006129714; WO2011/147953; WO2011/147952), CAS: 26914-55-8 (WO 2007020986), chlorfenapyr, pymetrozine, sulfoxaflor and pyrifluqinazon.
In addition to the major chemical classes of pesticide listed above, other pesticides having particular targets may be employed in the composition, if appropriate for the intended utility of the5 composition. For instance, selective insecticides for particular crops, for example stemborer specific insecticides (such as cartap) or hopper specific insecticides (such as buprofezin) for use in rice may be employed. Alternatively insecticides or acaricides specific for particular insect species/stages may also be included in the compositions (for example acaricidal ovo-larvicides, such as clofentezine, flubenzimine, hexythiazox or tetradifon; acaricidal motilicides, such as dicofol or propargite; acaricides, such as bromopropylate or chlorobenzilate; or growth regulators, such as hydramethylnon, cyromazine, methoprene, chlorfluazuron or diflubenzuron).
Examples of fungicidal compounds which may be included in the composition of the invention are (E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy-iminoacetamide (SSF-129), 4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-l -sulfonamide, -[N-(3-chloro-2,6- -xylyl)-2-methoxyacetamido]-y-butyrolactone, 4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-l - sulfonamide (IKF-916, cyamidazosulfamid), 3 -5 -dichloro-N-(3 -chloro- 1 -ethyl- 1 -methyl-2-oxopropyl)-4- methylbenzamide (RH-7281 , zoxamide), N-allyl-4,5,-dimethyl-2-trimethylsilylthiophene-3 -carboxamide (MON65500), N-(l -cyano-l,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide (AC382042), N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide, acibenzolar (CGA245704), alanycarb, aldimorph, anilazine, azaconazole, azoxystrobin, benalaxyl, benomyl, biloxazol, bitertanol, blasticidin S, bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazim chlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397, chinomethionate, chlorothalonil, chlorozolinate, clozylacon, copper containing compounds such as copper oxychloride, copper oxyquinolate, copper sulfate, copper tallate and Bordeaux mixture, cymoxanil, cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulfide 1,1 '-dioxide, dichlofluanid, diclomezine, dicloran, diethofencarb, difenoconazole, difenzoquat, diflumetorim, OjO-di-z' o-propyl-S-benzyl thiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol, diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride, dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethirimol, ethyl-(Z)-N-benzyl-N—
([methyl(methyl-thioethylideneaminooxycarbonyl)amino]thio)- -alaninate, etridiazole, famoxadone, fenamidone (RPA407213), fenarimol, fenbuconazole, fenfuram, fenhexamid (KBR2738), fenpiclonil, fen- propidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, fluoroimide, fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl, furametpyr, guazatine, hexaconazole, hydroxyisoxazole, hymexazole, imazalil, imibenconazole, iminoctadine, iminoctadine triacetate, ipconazole, iprobenfos, iprodione, iprovalicarb (SZX0722), isopropanyl butyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054, LY211795, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil, metalaxyl, metconazole, metiram, metiram-zinc, metominostrobin, myclobutanil, neoasozin, nickel dimethyldithiocarbamate, nitrothal-wo- propyl, nuarimol, ofurace, organomercury compounds, oxadixyl, oxasulfuron, oxolinic acid,
oxpoconazole, oxycarboxin, pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-Al, phosphorus acids, phthalide, picoxystrobin (ZA1963), polyoxin D, polyram, probenazole, prochloraz, procymidone, propamocarb, propiconazole, propineb, propionic acid, pyrazophos, pyrifenox,
pyrimethanil, pyroquilon, pyroxyfur, pyrrolnitrin, quaternary ammonium compounds, quinomethionate, quinoxyfen, quintozene, sipconazole (F-155), sodium pentachlorophenate, spiroxamine, streptomycin, sulfur, tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole, thifluzamid,
2-(thiocyanomethylthio)benzothiazole, thiophanate -methyl, thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph, trifloxystrobin (CGA279202), triforine, triflumizole, triticonazole, validamycin A, vapam, vinclozolin, zineb, ziram; N- [9-(dichloromethylene)-l,2,3,4 etrahydro
pyrazole-4-carboxamide [1072957-71-1], l-methyl-3-difluoromethyl-lH-pyrazole-4-carboxylic acid (2- dichloromethylene-3-ethyl-l-methyl-indan-4-yl)-amide, and l-methyl-3-difluoromethyl-4H-pyrazole-4- carboxylic acid [2-(2,4-dichloro-phenyl)-2-methoxy-l -methyl-ethyl] -amide.
Preferred additional pesticidally active ingredients are those selected from neonicotinoids, pyrethroids, strobilurins, triazoles and carboxamides (SDHI inhibitors). Pyrethroids are of interest of which lambda-cyhalothrin is of particular interest. Combinations of compounds of the invention and pyrethroids, in particular lambda-cyhalothrin, exhibit synergistic control of stinkbugs (according to the Colby formula), in particular Euschistus, e.g. Euschistus heros.
In a further aspect of the invention there is provided a method comprising applying to a crop of soybean plants, the locus thereof, or propagation material thereof, a combination of a compound a compound of the invention and lambda cyhalothrin in a synergistically effective amount, wherein the method is for control and/or prevention of stinkbugs, preferably Euschistus, e.g. Euschistus heros.
The compounds of the invention may be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
Examples of suitable synergists for use in the compositions include piperonyl butoxide, sesamex, safroxan and dodecyl imidazole.
Suitable herbicides and plant-growth regulators for inclusion in the compositions will depend upon the intended target and the effect required.
An example of a rice selective herbicide which may be included is propanil. An example of a plant growth regulator for use in cotton is PIX™.
Some mixtures may comprise active ingredients which have significantly different physical, chemical or biological properties such that they do not easily lend themselves to the same conventional formulation type. In these circumstances other formulation types may be prepared. For example, where one active ingredient is a water insoluble solid and the other a water insoluble liquid, it may nevertheless be possible to disperse each active ingredient in the same continuous aqueous phase by dispersing the solid active ingredient as a suspension (using a preparation analogous to that of an SC) but dispersing the liquid active ingredient as an emulsion (using a preparation analogous to that of an EW). The resultant composition is a suspoemulsion (SE) formulation.
Unless otherwise stated the weight ratio of the compound of I with an additional active ingredient may generally be between 1000 : 1 and 1 : 1000. In other embodiments that weight ratio of A to B may be between 500 : 1 to 1 : 500, for example between 100 : 1 to 1 : 100, for example between 1 : 50 to 50 : 1, for example 1 : 20 to 20 : 1, for example 1 :10 to 10:1, for example 1 :5 to 5:1, for example 1 :1.
Compositions of the invention include those prepared by premixing prior to application, e.g. as a readymix or tankmix, or by simultaneous application or sequential application to the plant.
The invention will now be illustrated by the following non-limiting Examples. All citations are incorporated by reference. Example 1 : Preparation of N-r(lS -l -r4-r3-r3,543is(trifluoromethyl phenyl1-3- ftrifluorometh Dpyrrolidin-l-yllphenyllethyllcyclopropanecarboxamide
Figure imgf000042_0001
To a solution of 3-[3,5-bis(trifluoromethyl)phenyl]-3-(trifluoromethyl)pyrrolidine (0.15 g, 0.4271 mmol, prepared as described in WO08128711) and N-[(lS)-l-(44oromophenyl)ethyl]cyclopropanecarboxamide (0.134 g, 0.4997 mmol, prepared as described in WO 12001107) in Toluene (6.03 mL) stirred under argon were added Tris(dibenzylideneacetone)dipalladium(0) (9 mg), 4,5-Bis(diphenylphosphino)-9,9- dimethylxanthene (18 mg) and sodium tert-butoxide (96 mg). The mixture was heated in the microwave at 130C for 15 min. The reaction was then diluted with ethyl acetate and water then brine and then the mixture was extracted with ethyl acetate. The organic layers were combined and dried over magnesium sulphate, filtered then concentrated under reduced pressure to give a yellow oil which was purified by chromatography on column (cyclohexane/EtOAc as solvent) to afford the desired product as a white foam (172 mg).
lH NMR (CDC13, 400MHz): d = 7.92 (s, 1 H), 7.86 (s, 2 H), 7.27 (m, 2 H), 6.63 (d, J=8.4 Hz, 2 H), 5.74 (d, J=7.7 Hz, 1 H), 5.09 (t, J=7.3 Hz, 1 H), 4.16 (d, J=10.3 Hz, 1 H), 3.85 (d, J=10.3 Hz, 1 H), 3.60 (d, J=8.1 Hz, 1 H), 3.51 (d, J=2.9 Hz, 1 H), 2.91 - 3.03 (m, 1 H), 2.61 (d, J=13.6 Hz, 1 H), 1.50 (d, J=7.0 Hz, 3 H), 1.17 - 1.34 (m, 1 H), 0.90 - 1.04 (m, 2 H), 0.63 - 0.80 ppm (m, 2 H)
Example 2: Preparation of N-r(lS)-l -r4-r3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidin-l - llphenyl] ethyl] cyclopropanecarboxamide
Figure imgf000042_0002
Tris(dibenzylideneacetone)dipalladium(0) (32 mg), 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (61 mg) and sodium tert-butoxide (190 mg) were added to a solution of 3-(3,5-dichlorophenyl)-3- (trifluoromethyl)pyrrolidine (520 mg, prepared as described in WO08128711) and N-[(lS)-l -(4- bromophenyl)ethyl]cyclopropanecarboxamide (prepared as described in WO 2012001107, 520 mg) in Toluene (15mL) under argon atmosphere. The mixture was heated in the microwave at 130C for 30 min. The reaction was then diluted with ethyl acetate and water then brine and then the mixture was extracted with ethyl acetate. The organic layers were combined and dried over sodium sulphate, filtered then concentrated under reduced pressure to give a yellow oil which was purified by chromatography on column (Heptane/EtOAc as solvent (10/0 to 0/10) to afford the desired product as a white foam (650 mg). NMR (CDC13, 400MHz): _ = 7.40 (s, 1 H), 7.31 (s, 2 H), 7.26 (m, 2 H), 6.62 (d, 2 H), 5.73 (d, 1 H), 5.09 (t, 1 H), 4.06 (d, 1 H), 3.85 (d, 1 H), 3.57 (m, 1 H), 3.50 (m, 1 H), 2.84 (m, 1 H), 2.56 (m, 1 H), 1.50 (d, 3 H), 1.2 (m, 1 H), 0.99 (m, 2 H), 0.72 ppm (m, 2 H)
Example 3: Preparation ofN-[nS -l -r4-[5-f3.5-dichlorophenyl -5-ftrifluoromethylN)-4H-isoxazol-3- yllphenyl] ethyl] acetamide
Step 1 :
Figure imgf000043_0001
To a suspension of N-[(lS)-l -(4-acetylphenyl)ethyl]acetamide (3 g) and l-(3,5-dichlorophenyl)-2,2,2- trifluoro-ethanone (3.6 g) in 1 ,2-dichloroethane (40 mL) was added triethylamine (0.2 mL) and potassium carbonate (1 g). The solution was stirred at 80C. After 40 minutes, more potassium carbonate (1 g) was added. The solution was heated at 80C for another 20 minutes then more potassium carbonate (1 g) was added and the suspension was refluxed for 16 hours. The mixture was then cooled to room temperature, then water was added. The mixture was extracted with dichloromethane then washed with brine. The organic layers were combined and dried over magnesium sulphate, filtered then concentrated under reduced pressure to give a yellow oil which was purified by chromatography on column (Heptane/EtOAc as solvent (1/0 to 3/7) to afford the desired product as a yellow oil (5 g).
1 H NMR (CDC13, 400MHz): Π = 7.78 - 7.87 (m, 2 H), 7.42 - 7.40 (m, 2 H), 7.33 (m, 1 H), 7.16 (d, 2 H), 5.69 (d, 1 H), 5.02 - 5.26 (m, 1 H), 2.02 (s, 3 H), 1.48 - 1.51 ppm (d, 3 H)
Step 2:
Figure imgf000043_0002
To a solution of N-[(lS)-l-[4-[3-(3,5-dichlorophenyl)-4,4,4-trifluoro-but-2-enoyl]phenyl]ethyl]acetamide (100 mg) in 1 ,2-dichloroethane (4 mL) was added tetrabutylammonium hydrobromide (40 mg), hydroxylamine (0.03 mL, 50% in water) and sodium hydroxide (0.46 mL, 1M) at room temperature. The solution was stirred at room temperature for 6 hours then a solution of saturated ammonium chloride was added. The mixture was extracted with DCM then washed with brine. The organic layers were combined and dried over magnesium sulphate, filtered then concentrated under reduced pressure to give a yellow oil which was purified by chromatography on column (Heptane/EtOAc as solvent (1/0 to 1/1) to afford the desired product as a yellow oil (77 mg). NMR (CDC13, 400MHz): _ = 7.59 - 7.69 (m, 2 H), 7.49 - 7.57 (m, 2 H), 7.43 (t, J=1.8 Hz, 1 H), 7.34 - 7.41 (m, J=8.4 Hz, 2 H), 5.65 (d, J=7.3 Hz, 1 H), 5.15 (t, J=7.2 Hz, 1 H), 4.01 - 4.13 (m, 1 H), 3.68 (d, J=17.2 Hz, 1 H), 2.01 (s, 3 H), 1.50 (d, J=7.0 Hz, 3 H), 1.27 ppm (t, J=7.2 Hz, 1 H). Example 4: Preparation of 2-( l^^-triazol-l-yn-S-rS-fS^^-trichlorophenyD-S-ftrifluoromethyl ^^- dihydropyrrol-5 -yl"|benzonitrile
Step 1 : Preparation of 3-bromo-4-fluoro-N-(trimethylsilylmethyl)benzamide
Figure imgf000044_0001
To a solution of 3-bromo-4-fluoro-benzoic acid (500 mg, 2.2830 mmol) in dichloromethane (15 mL) was added N,N-dimethylpyridin-4-amine (28mg, 0.22830 mmol) , EDCI HC1 (570mg, 2.9679 mmol) . To this was added trimethylsilylmethanamine (260mg, 2.5113 mmol) and reaction was stirred at RT under nitrogen atmosphere for overnight, monitored by TLC. Reaction mass was diluted with water (lOmL), extracted with DCM (3*50mL). Combined organic layer was dried over sodium sulphate, concentrated under vacuum. Purification by chromatography (hexane/ethyl acetate) provided 3-bromo-4-fluoro-N- (trimethylsilylmethyl)benzamide(55 Omg, 80%).
lU NMR (400MHz, CDC13): 7.94(dd,lH); 7.65(m,lH); 7.15(t, 1H); 5.9(brs, 1H); 2.94(d, 2H); 0.12(s, 9H), LCMS (methanol, ESI): RT=2.06, m/z = 302.0(M-H) Ste 2: Preparation of 3-cyano-4-fluoro-N-(trimethylsilylmethyl)benzamide
Figure imgf000044_0002
In a sealed tube was taken a solution of 3-bromo-4-fluoro-N-(trimethylsilylmethyl)benzamide (10 g, 32.870 mmol) in N,N-dimethylformamide (60 mL) was added zinc formonitrile (7.85g, 65.740 mmol) followed by palladium(0)tetrakis(triphenylphosphine) (7.6 lg, 6.5740 mmol) . Reaction was degassed and purged with nitrogen, stirred at 100°C for 4-5 hrs. Reaction was diluted with water (100 ml) extracted with ethyl acetate (3*100ml), washed with sodium bicarbonate (50 ml) .Combined organic layer was dried over sodium sulphate, concentrated under vacuum. Purification by chromatography (hexane/ethyl acetate) provided 3-cyano-4-fluoro-N-(trimethylsilylmethyl)benzamide(6.7g, 81%)
lU NMR (400MHz, CDC13): 7.98-8.02(m, 2H); 7.3(m, 1H); 5.94(brs, 1H); 2.95-2.98(m, 2H); 0.13(s, 9H). LCMS (methanol, APCI): RT=4.11, m/z = 249.09(M-H) Step 3: Preparation of 3-cyano-4-fluoro-N-(trimethylsilylmethyl)benzenecarbothioamide
Figure imgf000045_0001
A solution of 3-cyano-4-fluoro-N-(trimethylsilylmethyl)benzamide (6.5 g, 26 mmol) and 2,4-bis(4- methoxyphenyl)-2,4-dithioxo-l,3,2,4-dithiadiphosphetane (1 lg, 26 mmol) in tetrahydrofuran (75 mL,) was refluxed for 2hrs. Reaction mass was concentrated to remove THF, diluted with water (50ml), extracted with ethyl acetate (3* 100ml). Combined organic layer was dried over sodium sulphate, concentrated under vacuum. Purification by chromatography (hexane/ethyl acetate) provided 3-cyano-4- fluoro-N-(trimethylsilylmethyl) benzenecarbothioamide (4.8g, 69%).
lU NMR (400MHz, CDC13): 8.2(m,lH); 7.93-7.99(m,lH); 7.64(brs, lH);7.22(m,lH); 3.52(d, 2H);
0.18(s, 9H), LCMS (methanol, APCI): RT=4.55, m/z = 265.45(M-H).
Step 4: Preparation of 2-fluoro-5-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-dihydropyrrol-5- ljbenzonitrile
Figure imgf000045_0002
To a solution of 3-cyano-4-fluoro-N-(trimethylsilylmethyl)benzenecarbothioamide (4 g, 15.02 mmol) in N,N-dimethylformamide (40 mL) was added dipotassium carbonic acid (5.26g, 37.54 mmol). To this was added iodomethane (21.31g, 150.2 mmol). Reaction mass was stirred at RT for 3hrs, monitored by TLC. Reaction mass was quenched with water (lOmL), extracted with ethyl acetate (3*50mL). Combined organic layer was dried over sodium sulphate, concentrated under vacuum to give methyl-3-cyano-4- fluoro-N-(trimethylsilylmethyl) benzenecarboximidothioate.To a -5°C cooled solution of methyl-3-cyano- 4-fluoro-N-(trimethylsilylmethyl) benzenecarboximidothioate (4 g, 14.27 mmol) and l,2,3-trichloro-5- [l-(trifluoromethyl)vinyl]benzene (3.97g., 14.41 mmol) in tetrahydrofuran (5 mL) was slowly added tetrabutylammonium hydrofluoride (7.13 ml, 7.133 mmol, 1 mol/L) . Reaction was stirred at -5°C for 30 mins, then allowed to come at RT, and stirred at RT for 2hrs under Nitrogen atmosphere. Reaction was diluted with water (50ml), extracted with ethyl acetate (3*100 ml). Combined organic layer was dried over sodium sulphate, concentrated under vacuum. Purification by chromatography (hexane/ethyl acetate) provided 2-fluoro-5-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-dihydropyrrol-5- yl]benzonitrile(2.5g, 40%). lH NMR(400MHz, CDC13): 8.04-8.13(m, 2H); 7.37(s, 2H); 7.35(m, 1H); 4.82(dd, 1H); 4.36(d, 1H); 3.7(dd, 1H); 3.35(d, 1H) ,LCMS (methanol, APCI): RT=5.05, m/z = 434.88(M+H)
Step 5: Preparation of 2-(l,2,4-triazol-l-yl)-5-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4- dih dropyrrol-5-yl]benzonitrile
Figure imgf000046_0001
A solution of 2-fluoro-5-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-dihydropyrrol-5- yljbenzonitrile (1.0 g, 2.3 mmol) , dipotassium carbonic acid (390mg, 2.8 mmol) and lH-l,2,4-triazole (190mg, 2.8 mmol) were heated at 120°C for 2-3 hrs, monitored by TLC. Reaction was diluted with water (10ml), extracted with ethyl acetate (3*30ml). Combined organic layer was dried over sodium sulphate, concentrated under vacuum. Purification by chromatography (hexane/ethyl acetate) provided 2-( 1,2,4- triazol-l-yl)-5-[3-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-dihydropyrrol-5-yl]benzonitrile as solid (950mg, 85%). Melting point: 162-164°C.
'H NMR (400MHZ, CDCI3): 8.9(s, 1H), 8.29-8.34(m, 2H); 8.21(s, 1H); 7.93(d, 1H); 7.40(s, 2H); 4.94(d, 1H); 4.51(d, 1H); 3.84(d, 1H); 3.54(d, 1H);, LCMS (methanol, APCI): RT=4.96, m/z = 483.94(M+H)
Example 5: Preparation of N-r(lS)-l -r4-r5-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-dihvdropyrrol- 3-yllphenyllethyllcyclopropanecarboxamide Ste 1 : Preparation of tert-butyl N-[(lS)-l -(4-bromophenyl)ethyl"|carbamate
Figure imgf000046_0002
To a stirring solution of compound (l S)-l-(4-bromophenyl)ethanamine (50 mmol) in 50ml RB and tert- butoxycarbonyl tert-butyl carbonate (50 mmol) was added over period of 20 min and stirring was continued vigorously, After 5 min solid was precipitated out from reaction mass and thus obtained solid was filtered and washed with hexane and dried under vacuum. Weight- 13 g (85%)
¾-NMR (400 MHz, CDCI3): 7.45(2H, d), 7.18(2H, d), 4.74(1H, m), 1.40-1.48 (12H, m).
Step 2: Preparation of 4-[(lS)-l -(tert-butoxycarbonylamino)ethyl]benzoic acid
Figure imgf000047_0001
To a stirring solution of compound tert-butyl N-[(lS)-l -(4-bromophenyl)ethyl]carbamate (1 g, 3.331 mmol,) in THF ( 30ml) cooled to -78 °C, methyl lithium (5.33 mmol,1.6 eq) was added drop wise under nitrogen atmosphere and stirring was continued for 15 min followed by addition of butyllithium(5.33 mmol, 1.6 eq) drop wise and stirring was continued for 30 min. Dry carbon dioxide was added and stirring continued for lh at -70 °C to rt. The reaction mass was quenched with water 50 ml and compound was extracted with ethyl acetate 30ml x 2 in order to remove debromo compound. Aqueous layer was acidified with ammonium chloride and extracted with ehylacetate 30 ml x 2 times. The combined organic layers were dried with sodium sulfate and evaporated off under vacuum and dried under vacuum. Weight- 0.61 g
¾-NMR (400 MHz, CDC13): 7.86(2H, d), 7.37(2H, d), 4.64(1H, m), 1.28-1.31 (12H, m). LC-MS (methanol, ESI): m/z =264(M-H), RT 1.95-2.07.
Step 3: Preparation of tert-butyl N-[(lS)-l -[4-(trimethylsilylmethylcarbamoyl)phenyl]ethyl]carbamate
Figure imgf000047_0002
To a stirring solution of 4-[(lS)-l -(tert-butoxycarbonylamino)ethyl]benzoic acid (1 g, 3.769 mmol), 1- hydroxybenzotriazole hydrate (542 mg, 3.5mmol) in DMF (5 ml), in DCM (30 ml),
trimethylsilylmethanamine (0.38 g, 3.7 mmol), trimethylsilylmethanamine (0.38 g, 3.7 mmol) and the o
reaction mass was cooled to 0 C and 3-(ethyliminomethyleneamino)-N,N-dimethyl-propan-l-amine hydrochloride (848 mg, 4.4234 mmol) was added and reaction was stirred at 0 °C to RT for overnight. TLC showed reaction was completed. The reaction mass was quenched with water (30mL) and extracted with DCM (35 ml x 2) and combined organic layer was washed with water (20 ml x 2) and dried with sodium sulfate and evaporated of under reduced pressure and compound was purified by combiflash. Weight - 0.93 g
¾-NMR (400 MHz, CDC13): 7.68 (2H, d), 7.34(2H, d), 5.93(1H, m). 4.81 (2H, d), 2.95(2H, d), 1.40-1.45 (12H, m). LC-MS (methanol, ESI): m/z =349(M-H), RT 1.95-2.07 . Step 4: Preparation of tert-butyl N-[(lS)-l -[4(trimethylsilylmethylcarbamothioyl)phenyl]ethyl]carbamate
Figure imgf000048_0001
To a solution of tert-butyl N-[(lS)-l -[4-(trimethylsilylmethylcarbamoyl)phenyl]ethyl]carbamate (1 g, 2.853 mmol) in THF (25ml) was added 2,4-bis(4-methoxyphenyl)-l,3,2,4-dithiadiphosphetane-2,4- disulfide (1 eq, 2.853 mmol,) and reaction mass was stirred at 65 °C for 4h. TLC showed reaction was completed. The solvent was removed from the reaction mass on rotary evaporator and resultant reaction mass was diluted with ethyl acetate, washed with water (twice). The organic layer was dried over anhydrous sodium sulfate and concentrated under reduced pressure. Crude mass thus obtained was purified by combiflash (silica gel). Weight - 0.8 g
'H-NMR (400 MHz, CDC13): 7.65 (2H, d), 7.51-7.52 (1H, m), 7.30(2H, d), 4.76-4.81 (2H, m), 3.51 (2H, d), 1.40-1.45 (12H, m). LC-MS (methanol, ESI): m/z =365 (M-H), RT 2.51 -2.57.
Step 5: Preparation of tert-butyl N-[(l S)-l -[4-[5-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4- dih dropyrrol-3-yl]phenyl]ethyl]carbamate
Figure imgf000048_0002
To stirring solution of compound tert-butyl N-[(lS)-l-[4-
(trimethylsilylcarbamothioyl)phenyl] ethyl] carbamate (0.5 g, 1 mmol) in DMF (25ml), potassium carbonate (2 eq., 2 mmol,) was added followed by addition of iodomethane (10 equiv., 10 mmol) over period of lhr and stirring was continued for 3h. After completion of reaction (monitored by TLC) reaction mass was diluted with ethyl acetate and washed with water (20 ml x 3 times) and dried with sodium sulphate and evaporated off under vacuum. Thus obtained reaction mass was taken into THF (25ml) and l,2,3-trichloro-5-[l -(trifluoromethyl)vinyl] benzene (1 equiv., 1 mmol) was added into it.
The mixture was cooled to 0 °C, TBAF (1 eq, 1 mmol) was added and stirring was continued for 3h at to rt.
After completion of reaction (monitored by TLC), solvent was evaporated off under vacuum and reaction mass was diluted with ethyl acetate and washed with water (30ml x 2 times) and dried with sodium sulphate and evaporated off under vacuum. Compound was purified by combiflash, (25-30% EtOAC- hexane). Weight - 0.1 lg (20%) ¾-NMR (400 MHz, CDC13): 7.97 (2H, d), 7.33-7.56 (4H, m), 4.85-4.92 (2H, m), 4.50 (1H, dd), 3.91 (1H, dd), 3.58 (1H, dd), 1.40-1.45 (12H, m). LC-MS (methanol, ESI): m/z = 533 (M-H), RT 2.51-2.57. Step 6: Preparation of N-[(lS)-l-[4-[5-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-dihydropyrrol-3- yl]phenyl]ethyl]cyclopropanecarboxamide
Figure imgf000049_0001
To a solution of tert-butyl N-[(lS)-l-[4-[5-(3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-dihydropyrrol- 3 -yl]phenyl] ethyl] carbamate (0.35 g) in DCM (20ml) was added 2,2,2-trifluoroacetic acid (3 equiv) and reaction mass was stirred for 5h at RT. After completion of the reaction, solvent was removed under vaccuo and compound thus obtained was directly taken for the next step. A Solution of (l S)-l-[4-[5- (3,4,5-trichlorophenyl)-3-(trifluoromethyl)-2,4-dihydropyrrol-3-yl]phenyl]ethanamine TFA salt ( 0.3 g, 0.7 mmol), in DCM ( 20ml) was cooled at 0° C. To the cooled mixture was added triethylamine (2.2 eq, 1.54 mmol) followed by dropwise addition of cyclopropane carboxylic acid chloride (1 equiv, 0.7 mmol) over period of 5min and stirring was continued for overnight. After completion of reaction (monitored by TLC), reaction mass was diluted with DCM (20 ml) and washed with water (20ml). The organic layer was then dried over anhydrous sodium sulphate, and the solvent was removed under vacuum. Compound was purified by Combiflash (35 % EtOAC-hexane) Weight - 0.2 g, MPt. 80-82 °C.
¾-NMR (400 MHz, CDCI3): 7.82(2H, d), 7.35-7.41 (4H, m), 6.05 (1H, m), 5.13 (1H, m), 4.86 (1H, dd), 4.42 (1H, dd), 3.78 (1H, dd), 3.45 (1H, dd). 1.46-1.50 (4H, m), 0.93-0.96 (2H, m), 0.72-0.731 (2H, m) LC-MS (methanol, ESI): m/z = 501(M-H), RT 2.23-2.30.
Example 6: Preparation of N- {2-bromo-4- |"4-(3.5-dichlorophenyl )-4-trifluoromethyl-4.5-dihydro-3H- pyrrol-2yl1 -benzyl} acetamide. Step 1 : Bromination of 3-bromo-4-methyl benzoic acid.
Figure imgf000049_0002
3-bromo-4-methyl benzoic acid (lOg, 46.72mmol), NBS (8.7g,49.15mmol)) and benzoylperoxide (0.5g, 2mmol)) were suspended in CC14 and then heated to reflux for 5hrs. After completion of the reaction (TLC monitoring) water was added into the reaction mixture. The organic layer was separated, dried over anhydrous sodium sulphate and concentrated in vaccuo. The crude mixture thus obtained containing 3- bromo-4-bromomethyl benzoic acid and the 3-bromo-4-dibromomethyl benzoic acid was taken directly into the next step.
LC-MS (methanol, ESI): m/z =291 (M-H) and 368 (M-H)
Step 2: Preparation of 3-bromo-4-(dibromomethyl)-N-[(trimethylsilyl)methyl]benzamide.
Figure imgf000050_0001
A mixture of of 3-bromo-4-(bromomethyl)-N-[(trimethylsilyl)methyl]benzamide and 3-bromo-4- (dibromomethyl)-N-[(trimethylsilyl)methyl]benzamide (19 g, 51mmol), 1- (trimethylsilyl)methylamine (5.78g,56mmol), N,N-dimethylaminopyridine (O.lg) and N-(3- dimethylaminopropyl)-N'-ethylcarbodiimide.HCl (12.74g, 66mmol) was dissolved in tetrahydrofuran solvent and stirred for lh at rt. After completion of the reaction (TLC monitoring), Reaction mixture was concentrated on rotary evaporator. Water was added to the reaction mixture, and extracted with ethylacetate. The organic layer was separated and dried using sodium sulphate. The residue was purified by silica gel chromatography to obtain 3-bromo-4-(dibromomethyl)-N-[(trimethylsilyl) methyl] benzamide (16g).
3-bromo-4-(dibromomethyl)-N-[(trimethylsilyl)methyl]benzamide.
LC-MS (methanol, ESI): m/z =456 (M+H).
IH-NMR (400 MHz, CDC13): 8.01 (1H, dd), 7.87(1H, d), 7.04(1H, dd), 6.13(lH,bs) , 3.51 (2H, d), 0.17 (9H,s).
Step 3: Preparation of 3-bromo-4-formyl-N-[(trimethylsilyl)methyl]benzamide.
Figure imgf000050_0002
Compound B (3-bromo-4-(dibromomethyl)-N-[(trimethylsilyl)methyl]benzamide.) (0.25g, 0.69mmol) was taken in acetone (5ml) and water (2.5ml). Silver nitrate (0.3g, 1.7mmol) was added to the reaction mixture. The reaction was stirred at rt for 6hrs. The reaction mass was then concentrated and extracted with ethylacetate. The organic layer was separated and dried using sodium sulphate. The organic layer was concentrated to obtain the product 3-bromo-4-formyl-N-[(trimethylsilyl)methyl]benzamide. (0.15g). LC-MS (methanol, ESI): m/z =314(M+H).
1H-NMR (400 MHz, CDC13): 10.33(lH,s),7.90 (1H, m), 7.60 (1H, dd), 7.56 (1H, m), 5.99(lH,s),2.99 (2H, d), 0.17 (9H,s). Step 4: Preparation of 3-bromo-4-hydroxymethyl-N-[trimethylsilaylmethyl] benzamide.
Figure imgf000051_0001
3-bromo-4-formyl-N-[(trimethylsilyl)methyl]benzamide(0.1g, 0.3mmol) was dissolved in methanol and to this was added NaBH4 (0.014g, 0.38 mmol). Reaction was stirred at rt for lhr. Methanol was removed under vaccuo and water was added to the reaction mass which was then extracted using ethyl acetate. The organic layer was seperated and dried using sodium sulphate followed by concentration to get the product 3-bromo-4-hydroxymethyl-N-[trimethylsilaylmethyl] benzamide (0.05g).
LC-MS (methanol, ESI): m/z =316 (M+H).
1H-NMR (400 MHz, CDC13): 7.90 (1H, m), 7.60 (1H, m), 7.53 (1H, m), 6.02(1H, s),4.75
(2H,s),2.99(2H,s), 0.17 (9H,s).
Step 5: Preparation of Acetic acid 2-bromo-4- (trimethylsilanylmethyl-carbamoyl)-benzylester.
Figure imgf000051_0002
3-bromo-4-hydroxymethyl-N-[trimethylsilaylmethyl] benzamide (0.25g, 0.7mmol) was dissolved in DMF solvent, triethyl amine (0.159g, 1.5mmol) and acetyl chloride (0.061g, 0.8mmol) were added to the reaction mixture at rt.The reaction was stirred at rt for 30min. Water was added and reaction mass was then extracted with ethyl acetate. The organic layer was separated, dried using sodium sulphate and concentrated to get the product Acetic acid 2-bromo-4- (trimethylsilanylmethyl-carbamoyl)-benzylester (0.15g).
LC-MS (methanol): m/z =358 (M+H).
¾-NMR (400 MHz, CDC13): 7.90 (1H, m), 7.60 (1H, m), 7.38 (1H, m), 6.14(1H, bs), 5.11(2H, s), 2.99 (2H, d), 2.15 (3H, s), 0.17 (9H, s).
Step 6: Preparation of 3-bromo-4-(2-oxo-propyl)-N-trimethylsilanylmethyl-thiobenzamide.
Figure imgf000052_0001
Acetic acid 2-bromo-4- (trimethylsilanylmethyl-carbamoyl)-benzylester (2.4g,7.6mmol) and Lawesson reagent (2.7g,6.6mmol) were suspended in THF. The mixture was heated to reflux for 3hrs, concentrated, washed with water and extracted with ethyl acetate. The organic layer was separated and dried using sodium sulphate. The residue was purified by silica gel chromatography to obtain 3-bromo-4-(2-oxo- propyl)-N-trimethylsilanylmethyl-thiobenzamide ( 1.8g).
LC-MS (methanol, ESI): m/z =374(M+H).
'H-NMR (400 MHz, CDC13): 7.90 (1H, m), 7.60 (1H, m), 7.38 (1H, m), 6.01(1H, br s), 5.11 (2H, d), 2.99 (2H, d), 2.15 (3H, s), 0.17 (9H, s)
Step 7: Preparation of Acetic acid 2-bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5-dihydro- 3H-pyrrol-2yl]-benzylester.
Figure imgf000052_0002
A mixed solution of methyliodide (0.69g,4.8mmol), potassium carbonate (0.80g, 5.7mmol) and 3-bromo- 4-(2-oxo-propyl)-N-trimethylsilanylmethyl-thiobenzamide (1.8g, 5.4mmol) in DMF (25ml) was stirred at 0 oC for 4hrs.The reaction mixture was poured into ice-cold water, extracted with ethyl acetate. The organic layer was separated, dried using sodium sulphate and concentrated to get the crude Acetic acid 2- bromo-4 {methylsulfanyl-[(E)- trimethylsilanylmethylimino] -methyl} -benzyl ester.(0.95g) which was dissolved in THFand was cooled to 0 oC under N2 arm. A solution of TBAF (1.0M in THF) (0.56ml) was added gradually into it and reaction mixture was stirred for 8hrs at rt. The reaction mass was then concentrated and extracted with ethylacetate. The organic layer was separated and dried using sodium sulphate. The resulting mixture was then purified by silica gel chromatography to obtain Acetic acid 2- bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2yl]-benzylester (1. lg). LC-MS (methanol, ESI): m/z =508 (M+H).
'H-NMR (400 MHz, CDC13): 8.07 (1H, m), 7.71 (1H, m), 7.47 (1H, m), 7.38 (1H, m), 7.24(2H, m), 5.23(2H, s), 4.90 (1H, m),4.43 (1H, d), 3.75 (1H, m), 3.43 (1H, d), 2.17 (3H, s).
Step 8: Preparation of 2-bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2yl]- phenyl-methanol.
Figure imgf000053_0001
To a solution of Acetic acid 2-bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5-dihydro-3H- pyrrol-2yl]-benzylester (l . lg, 2.1mmol) in methanol (20ml) was added sodium methoxide (O.lg, 1.85 mmol) and the solution was stirred for lh at rt. The reaction mass was then concentrated and extracted with ethylacetate. The organic layer was separated and dried using sodium sulphate. The resulting mixture was then purified by silica gel chromatography to obtain 2-bromo-4- [4-(3,5-dichlorophenyl )-4- trifluoromethyl-4,5-dihydro-3H-pyrrol-2yl]-phenyl-methanol (0.95g).
LC-MS (methanol, ESI): m/z =466 (M+H).
'H-NMR (400 MHz, CDC13): 8.07 (1H, m), 7.78 (1H, m), 7.59 (1H, m), 7.38 (3H, m), 4.90 (3H, d),4.43 (1H, d), 3.75 (1H, m), 3.43 (1H, d).
Step 9: Preparation of Methanesulfonic acid-2-bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5- dih dro-3H-pyrrol-2yl]-benzylester.
Figure imgf000053_0002
To a solution of 2-bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2yl]- phenyl-methanol (0.95g, 2mmol) and triethylamine (0.4g, 4.0mmol) in THF was added methanesulfonyl chloride (0.35g, 3.0mmol) gradually. The mixture was stirred for lhr at rt. The reaction mixture was washed with water. The organic layer was separated and dried using sodium sulphate. The organic layer was evaporated to get the solid compound Methanesulfonic acid-2-bromo-4- [4-(3,5-dichlorophenyl )-4- trifluoromethyl-4,5-dihydro-3H-pyrrol-2yl]-benzylester (0.9 g).
LC-MS (methanol, ESI): m/z =544 (M+H).
'H-NMR (400 MHz, CDC13): 8.13 (1H, m), 7.81 (1H, m), 7.58 (1H, m), 7.38 (1H, m),
7.24(2H,m),5.36(2H, s), 4.90 (1H, m),4.43 (1H, d), 3.75 (1H, m), 3.43 (1H, d), 3.04 (3H,s). Step 10: Preparation of 2-bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5-dihydro-3H-pyrrol- 2yl] -benzylamine.
Figure imgf000054_0001
To a solution of Methanesulfonic acid-2-bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5- dihydro-3H-pyrrol-2yl]-benzylester (1.0g,1.8mmol) in THF (30 niL) and MeOH (30 niL) was added dropwise to a mixed solution of aq. ammonia (30%), 30ml), and the reaction was stirred for 12hrs at rt. The reaction mass was then concentrated and extracted with ethylacetate. The organic layer was separated and dried using sodium sulphate. The organic layer was evaporated to get the gummy compound 2-bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2yl]- benzylamine.
LC-MS (methanol, ESI): m/z = 467(M+H).
'H-NMR (400 MHz, CDC13): 8.07 (IH, m), 7.71 (IH, m), 7.59 (IH, m), 7.38 (IH, m), 7.24(2H,m), 4.90 (IH, d),4.43 (3H, m), 3.75 (IH, m), 3.43 (IH, d).
Step 11 : Preparation of N- {2-bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5-dihydro-3H- rrol-2yl] -benzyl} acetamide.
Figure imgf000054_0002
To a solution of 2-bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2yl]- benzylamine (0.15g, 0.32mmol) in THF was added acetic anhydride (0.04g, 0.39mmol) and the mixture was stirred at rt for lhr. The reaction mass was then concentrated under reduced pressure and extracted with ethylacetate. The organic layer was separated and dried using sodium sulphate. The resulting mixture was then purified by silica gel chromatography to obtain N- {2-bromo-4- [4-(3,5-dichlorophenyl )-4-trifluoromethyl-4,5-dihydro-3H-pyrrol-2yl]-benzyl} acetamide.
LC-MS (methanol,ESI): m/z = 509 (M+H).
'H-NMR (400 MHz, CDC13): 8.07 (IH, m), 7.71 (IH, m), 7.47 (IH, m), 7.38 (IH, m),
7.24(2H,m),5.98(lH, s), 4.90 (IH, d),4.43 (3H, m), 3.75 (IH, m), 3.43 (IH, d), 2.04 (3H,s).
Example 7: Preparation of N- {4-r3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidinl-yl1- 2-methyl- benzyPacetamide.
Step 1 : Preparation of l-Benzyl-3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine.
Figure imgf000055_0001
To a cooled solution of l ,3-dichloro-5(l -trifluoromethyl)vinyl)benzene (0.5g, 2.0mmol) and N-benzyl-1 - methoxy-N-9trimethylsilyl)methyl)methanamine (0.4g, 2.0mmol) in DCM (10 niL) was added dropwise a solution of TFA (0.024g, 0.2mmol) in DCM (1 niL). The reaction mixture was stirred for 3hrs at rt. The organic layer was washed with water ( 2 x 10 mL) and 10% aq sodium carbonate solution(10 mL). The organic layer was separated, dried with sodium sulphate and concentrated under reduced pressure The residue was purified by silica gel chromatography to yield l -Benzyl-3-(3,5-dichlorophenyl)-3- (trifluoromethyl)pyrrolidine (0.5g).
LC-MS (methanol, ESI): m/z = 374 (M+H).
'H-NMR (400 MHz, CDC13): 7.36 (4H, m), 7.30(2H, m), 7.23 (2H, m), 3.67 (2H, s), 3.08 (2H, dd), 2.69 (2H,m), 2.53 (1H, m), 2.27(lH,m).
Step 2: Preparation of 3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine.
Figure imgf000055_0002
To a solution of l -Benzyl-3-( -(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine (0.22 g, 0.59mmol) and 1 -chloroethylchloroformate(0.17g, 1.2mmol) in DCM was heated for reflux for 3hrs. The mixture was cooled to rt and concentrated under reduced pressure. Methanol was added to the residue which was then heated with stirring for 3hrs at 60 OC. The mixture was concentrated and water was added to it. The residue was extracted with ethylacetate (20 ml x 3) washed with brine, dried over sodium sulphate and concentrated under reduced pressure. Purification over silica gel yielded 3-(3,5-dichlorophenyl)-3- (trifluoromethyl)pyrrolidine (4.2g).
LC-MS (methanol, ESI): m/z = 284 (M+H).
'H-NMR (400 MHz, CDC13): 7.35 (1H, t), 7.25 (2H, d), 3.74 (1H, d), 3.19 (2H, m), 2.97(lH,m),2.53 (1H, m), 2.27(lH,m).
Step 3 : Preparation of N-(4-bromo-2-methyl-benzyl)acetamide.
Figure imgf000056_0001
4-bromo-2 -methyl benzonitrile (2.0g, O.Olmol) was taken in methanol along with NiC12 (2.41g,
O.Olmol). In the same pot acetic anhydride was taken (2.0g, 0.020mol). The reaction was cooled to 0 OC. NaBH4 (2.7g, 0.07mol) was added slowly to the reaction while stirring at the same temperature for lhr. The reaction mixture was concentrated under reduced pressure and was extracted with ethylacetate. The organic layer was separated, dried using sodium sulphate and concentrated under reduced pressure. The residue thus obtained was purified by silica gel chromatography to yield N-(4-bromo-2-methyl- benzyl)acetamide.( 1.1 g).
LC-MS (methanol, ESI): m/z = 242 (M+H).
1H-NMR (400 MHz, CDC13): 7.71 (1H, m), 7.47 (1H, m), 7.38 (1H, m), 5.98(1H, s), 3.75 (1H, m), 3.43 (1H, d), 2.31 (3H, s),2.04 (3H, s).
Step 4: Preparation of N- {4-[3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidinl -yl]- 2-methyl- benz l)acetamide.
Figure imgf000056_0002
To the mixture of 3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine (0.25g, 0.88mmol) and the N-(4- bromo-2-methyl-benzyl)acetamide (0.8g, 0.7mmol) in anhydrous toluene under N2 arm was added Tris (dibenzylidineacetone)dipalladium (0.02g, 0.02mmol) and the ligand xanthphos (0.03g, 0.053mmol) followed by the addition of sodium tertiary butoxide (0.127g, 1.3mmol). The reaction mixture was heated at 80 OC for 3hrs. After completion of the reaction (TLC monitoring), reaction mass filtered over celite. The filtrate was concentrated and purified using column chromatography.
LC-MS (methanol, ESI): m/z = 445 (M+H).
1H-NMR (400 MHz, CDC13): 7.37 (1H, d), 7.29 (2H, m), 7.11 (1H, d), 6.41 (2H, m), 5.45(lH,b s), 4.35 (2H, s),4.01 (1H, d), 3.75 (1H, d), 3.43 (2H, m), 2.81 (lH,d),2.51 (lH,d),2.31 (3H,s),1.97 (3H,s).
The following examples have been prepared according to methods described in US2009/0156643 and analysed by the LCMS methods described below:
Method A:
ZQ Mass Spectrometer from Waters (Single quadrupole mass spectrometer) Instrument Parameter:
Ionization method: Electrospray
Polarity: positive and negative ions
Capillary: 3.00 kV
Cone: 30.00 V
Extractor: 2.00 V
Source Temperature: 100°C,
Desolvation Temperature: 250°C
Cone Gas Flow: 50 L/Hr
Desolvation Gas Flow: 400 L/Hr
Mass range: 100 to 900 Da
HP 1100 HPLC from Agilent:
Solvent degasser, quaternary pump, heated column compartment and diode-array detector.
Column: Phenomenex Gemini CI 8, 3 m, 30 x 3 mm,
Temp: 60 °C
DAD Wavelength range (nm): 210 to 500
Solvent Gradient:
A = H20 + 5% MeOH + 0.05 % HCOOH
B= Acetonitril + 0.05 % HCOOH
Time A% B% Flow (ml/min)
0.00 100 0 1.700
2.00 0 100.0 1.700
2.80 0 100.0 1.700
2.90 100 0 1.700
3.00 100 0 1.700
Method B:
ACQUITY SQD Mass Spectrometer from Waters (Single quadrupole mass spectrometer)
Ionisation method: Electrospray
Polarity: positive ions
Capillary (kV) 3.00, Cone (V) 20.00, Extractor (V) 3.00, Source Temperature (°C) 150, Desolvation Temperature (°C) 400, Cone Gas Flow (L/Hr) 60, Desolvation Gas Flow (L/Hr) 700
Mass range: 100 to 800 Da
DAD Wavelength range (nm) : 210 to 400
Method Waters ACQUITY UPLC with the following HPLC gradient conditions (Solvent A: Water/Methanol 9: 1,0.1% formic acid and Solvent B: Acetonitrile,0.1%> formic acid )
Time (minutes) A (%) B (%) Flow rate (ml/min)
0 100 0 0.75
2.5 0 100 0.75
2.8 0 100 0.75
3.0 100 0 0.75
Type of column: Waters ACQUITY UPLC BEH CI 8; Column length: 50 mm; Internal diameter of column: 2.1 mm; Particle Size: 1.7 micron; Temperature: 60°C. Example 8:
Figure imgf000058_0001
Method A RT 2.17 min, MH+ 511
Example 9:
Figure imgf000058_0002
Method A RT 2.19 min, MH+ 493
Exam le 10:
Figure imgf000058_0003
Method B RT 1.98 min, MH+ 479
The following Examples have been prepared according to methods described in WO2008/150393
Example 11 :
Figure imgf000059_0001
Method A RT 2.1 min, MH+ 470
The following example have been prepared according to methods described in WO2009/051956
Exam le 12:
Figure imgf000059_0002
IH NMR in CDC13: 3.73 ppm (d, IH), 4.12 ppm (d, IH), 7.58 ppm (d, 2H), 7.93 (m, IH), 8.07-8.12 (m, 3H), 8.62 (s, IH)
Table A
Compounds of formula la
Figure imgf000059_0003
Figure imgf000059_0004
Table B
Compounds of formula lb
Figure imgf000060_0001
Figure imgf000060_0004
Table C
Compounds of formula Ic
Figure imgf000060_0002
Figure imgf000060_0005
Table D
Compounds of formula Id
Figure imgf000060_0003
B1 -B2-B3 R2 Z
Dl C=N-0 2,4-dichloro-3-fluorophenyl cyano
Biological Examples
Euschistus heros (Neotropical brown stink bug) (contact/feeding activity)
2 week old soybean plants are sprayed in a turn table spray chamber with the diluted spray solutions. After drying, 2 soybean seeds are added and plants are infested with 10 N-2 nymphs of the neotropical brown stink bug Euschistus heros in plastic test boxes. Boxes are incubated in a climate chamber at 25°C and 60 % RH. Evaluation is done 5 days after infestation on mortality and growth effects.
The following gave at least 50% control at 50 ppm: Al, A2, A3, A4, A5, Bl, B2, B3, B4, C2, C3, Dl The following compounds gave more than 80%> control at 50 ppm: Al, A3, Bl, B2, B3, B4, C2, C3, Dl . Compounds C2, C3 and Dl demonstrated excellent control at low application rates.

Claims

Claims:
1. A method comprising applying to a crop of soybean plants, the locus thereof, or propagation material thereof, a compound of formula I
Figure imgf000062_0001
wherein
-B'-B^B3- is -C=N-0-, -C=N-CH2- , -N-CH2-CH2-, or -C=C-0-;
R1 is trifluoromethyl, difluoromethyl or chlorodifluoromethyl;
R2 is group X
Figure imgf000062_0002
X2 is C-X6 or nitrogen;
Χ', Χ3 and X6 are independently hydrogen, halogen or trihalomethyl, wherein at least one of X1, X3 and
X6 is not hydrogen;
A is selected from group Al to A4
Figure imgf000062_0003
Y1 is C-R6, CH or nitrogen;
Y2 and Y3 are independently CH or nitrogen;
wherein no more than two of Y1, Y2 and Y3 are nitrogen and wherein Y2 and Y3 are not both nitrogen; R5 is hydrogen, halogen, cyano, nitro, NH2, Ci-C4alkyl, Ci-C4haloalkyl, C3-C5cycloalkyl, C3- C5halocycloalkyl, Ci-C2alkoxy, or Ci-C2haloalkoxy;
R6 when present together with R5 forms a -CH=CH-CH=CH- bridge;
R7 is C C4alkyl;
R8 is Ci-C4alkyl, CrC4haloalkyl, Ci-C4alkoxy(CrC4)alkyl, Ci-C4alkylthio(CrC4)alkyl, Cr
C4alkylsulfmyl(Ci-C4)alkyl, Ci-C4alkylsulfonyl(CrC4)alkyl, C3-C6cycloalkyl, C3-C6cycloalkyl(Cr C4)alkyl-, or tetrahydrofuranyl;
each Z is independently halogen, Ci-Ci2alkyl or Ci-Ci2alkyl substituted by one to five R12, nitro, d-
Ci2alkoxy or Ci-Ci2alkoxy substituted by one to five R12, cyano, Ci-Ci2alkylsulfinyl, Ci-Ci2alkylsulfonyl, Ci-Ci2haloalkylsulfinyl, Ci-Ci2haloalkylsulfonyl, hydroxyl or thiol; each R12 is halogen, cyano, nitro, hydroxy, Q-Cgalkoxy-, Q-Cghaloalkoxy-, mercapto, CpCgalkylthio-, or Ci-Cghaloalkylthio; and
k is 0, 1,2 or 3.
2. A method according to claim 1, wherein the method is a method of controlling and/or preventing infestation of stinkbugs in soybean comprising applying to a crop of soybean plants, the locus thereof, or propagation material thereof, a compound of formula I.
3. A method of controlling and/or preventing infestation of stinkbugs in a crop of useful plants comprising applying to a crop of useful plants, the locus thereof, or propagation material thereof, a compound of formula I as defined in claim 1.
4. Use of a compound of formula I as defined in claim 1 for control of stinkbugs in a crop of useful plants.
5. A method or use according to any one of claims 1 to 4, wherein the compound of formula I is a compound of formula IA
Figure imgf000063_0001
(IA)
wherein
R5 is chloro, bromo, fluoro or methyl;
R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-; and
R1, R2, B1, B2, B3, Y1, Y2 and Y3 are as defined in claim 1.
6. A method or use according to claim 5, wherein
R1 is CF3;
-B'-B^B3- is -C=N-0- or -C=N-CH2-;
Y1, Y2 and Y3 are CH; and
R5 is chloro or methyl.
7. A method or use according to any one of claims 1 to 4, wherein the compound of formula I is a compound of formula IB
Figure imgf000064_0001
R7 is methyl;
R8 is methyl, ethyl, isopropyl, CH3-0-CH2-, CH3-S-CH2-, CH3-S(0)-CH2-, CH3-S02-CH2-, cyclobutyl, cyclopropyl or cyclopropyl-CH2-; and
R1, R2, B1, B2, B3, Y1, Y2 and Y3 are as defined in claim 1.
8. A method or use according to claim 7, wherein
R1 is CF3;
-B'-B^B3- is -C=N-0-, -C=N-CH2- or -N-CH2-CH2-; and
Y1, Y2 and Y3 are CH.
9. A method or use according to any one of claims 1 to 4, wherein the compound of formula I is a compound of formula IC
Figure imgf000064_0002
wherein
R5 is cyano;
K is O or 1;
Z is cyano or trifluoromethyl; and
R1, R2, B1, B2, B3, Y1, Y2 and Y3 are as defined in claim 1.
10. A method or use according to claim 9, wherein
R1 is CF3;
-B'-B^B3- is -C=N-0- or -C=N-CH2-;
Y1, Y2 and Y3 are CH; and
K is 0.
11. A method or use according to any one of claims 1 to 4, wherein the compound of formula I is a compound of formula ID
Figure imgf000065_0001
wherein
5 R5 is cyano;
k is 0 or 1 ;
Z is cyano or trifluoromethyl; and
R1, R2, B1, B2, B3, Y1, Y2 and Y3 are as defined in claim 1.
10 12. A method or use according to claim 11, wherein
R1 is CF3;
-B'-B^B3- is -C=N-0- or -C=N-CH2-;
Y1, Y2 and Y3 are CH;
k is 1 ; and
15 Z is cyano or trifluoromethyl.
13. A method or use according to any one of claims 1 to 12, wherein R2 is 3,5-dichlorophenyl-, 3,5- dichloro-4-fluorophenyl- or 3,4,5-trichlorophenyl-.
20 14. A method or use according to any one of claims 1 to 13, wherein the stinkbug is selected from Nezara spp. (e.g. Nezara viridula, Nezara antennata, Nezara hilare), Piezodorus spp. (e.g. Piezodorus guildinii), Acrosternum spp. Euchistus spp. (e.g. Euchistus heros, Euschistus servus), Halyomorpha halys, Plautia crossota, Riptortus clavatus, Rhopalus msculatus, Antestiopsis orbitalus, Dichelops spp. (e.g. Dichelops furcatus, Dichelops melacanthus), Eurygaster spp. (e.g. Eurygaster intergriceps,
25 Eurygaster maura), Oebalus spp. (e.g. Oebalus mexicana, Oebalus poecilus, Oebalus pugnase, and
Scotinophara spp. (e.g. Scotinophara lurida, Scotinophara coarctata).
15. A method or use according to any one of claims 1 to 13, wherein the stinkbug is from the genus Euschistus.
30
16. A method or use according to any one of claims 1 to 13, wherein the stinkbug is Euschistus heros.
17. A method for obtaining regulatory approval for the use of one or more of a compound of formula I as defined in any one of claims 1 to 13 to control stinkbugs, in particular the genus Euschistus and in particular the species Euschistus hews, comprising at least one step of referring to, submitting or relying on biological data showing that said active ingredient reduces insect pressure.
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