WO1994021606A1 - Pentafluorosulphanylphenyl and pentafluorosulphanylpyridil substituted heteroaromatic compounds with insecticidal or acaricidal activity - Google Patents

Pentafluorosulphanylphenyl and pentafluorosulphanylpyridil substituted heteroaromatic compounds with insecticidal or acaricidal activity Download PDF

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Publication number
WO1994021606A1
WO1994021606A1 PCT/GB1994/000612 GB9400612W WO9421606A1 WO 1994021606 A1 WO1994021606 A1 WO 1994021606A1 GB 9400612 W GB9400612 W GB 9400612W WO 9421606 A1 WO9421606 A1 WO 9421606A1
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group
optionally substituted
hydrogen
alkyl
halogen
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PCT/GB1994/000612
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English (en)
French (fr)
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Roger Salmon
David Philip John Pearson
David Rees Parry
Anthony Marian Kozakiewicz
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Zeneca Limited
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Priority to AU62872/94A priority Critical patent/AU6287294A/en
Publication of WO1994021606A1 publication Critical patent/WO1994021606A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • 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
    • C07D207/30—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 two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—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 two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/28—Two oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/38—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/84—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/88—Nitrogen atoms, e.g. allantoin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/34—One oxygen atom
    • C07D239/36—One oxygen atom as doubly bound oxygen atom or as unsubstituted hydroxy radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • This invention relates to heteroaromatic compounds, and more
  • n 0, 1 or 2 and R 6' is a haloalkyl group
  • Y 1' and Y 2' are independently selected from hydrogen, nitro, amino or alkyl optionally substituted by halogen, by cycloalkyl, by formyl , by C 2-7 alkanoyl, by C 4-7 cycloalkylcarbonyl, by C 2-7 alkoxycarbonyl, by C 2-7 haloalkoxycarbonyl, by an aryl group or by an aromatic heterocyclic group or
  • Y 1' and Y 2' together with the nitrogen to which they are attached form an aliphatic heterocyclic group containing from 4 to 8 atoms in the ring and optionally substituted by halogen or alkyl or
  • Y 1' is hydrogen and Y 2' is alkoxycarbonyl, alkylcarbonyl, optionally substituted aralkyl or a group -S(O) n ' R 6' where R 6' and n are as
  • R a does not represent 2,6-dihalo.
  • substituted alkoxy optionally substituted alkenyl or optionally
  • R 1' is hydrogen, halogen, or a group NR 4' R 5' wherein R 4' and R 5' are independently selected from hydrogen or alkyl
  • R 2' is a group -S(O) n ' R 6' wherein n is 0, 1 or 2 and R 6' is a haloalkyl group
  • Y 1' and Y 2' are independently selected from hydrogen, nitro, amino or alkyl optionally substituted by halogen, by cycloalkyl, by formyl , by C 2-7 alkanoyl, by C 4-7 cycloalkylcarbonyl, by C 2-7 alkoxycarbonyl, by C 2-7 haloalkoxycarbonyl, by an aryl group or by an
  • Y 1' and Y 2' together with the nitrogen to which they are attached form an aliphatic heterocyclic group containing from 4 to 8 atoms in the ring and optionally substituted by halogen or alkyl or
  • Y 1' is hydrogen and Y 2' is alkoxycarbonyl, alkylcarbonyl, optionally substituted aralkyl or a group -S(O) n ' R 6' where R 6' and n ' are as
  • R 1 and R 2 do not both represent halo.
  • heterocyclic group A may be independently selected for example from one or more of optionally substituted alkyl, optionally substituted cycloalkyl, halogen, cyano, nitro, optionally substituted alkoxy, optionally
  • alkyl as used herein, including when present as a moiety in another group such as for example alkoxy, includes branched or straight chain alkyl, preferably containing from 1 to 6, and especially from 1 to 4 carbon atoms.
  • Optional substituents which may be present when the term "optionally substituted alkyl" is used include for example halogen, C 3 - 7 cycloalkyl, alkoxy, thioalkyl, haloalkoxy, alkoxycarbonyl, hydroxy, cyano, nitro, optionally substituted aryl, optionally substituted amino.
  • the alkyl moiety present in the above groups or other groups may be similarly substituted.
  • optionally substituted amino includes a group -NR 11 R 12 wherein wherein R 11 and R 12 are independently selected from hydrogen, optionally substituted alkyl, alkoxycarbonyl, acyl,
  • alkylthio-thiocarbonyl alkyl aminocarbonyl, aminocarbonyl or R 11 and R 12 , together with the nitrogen atom joining them, form a saturated or
  • alkenyl as used herein includes branched or straight chain alkenyl, preferably containing from 2 to 6, and especially from 2 to 4 carbon atoms.
  • Optional substituents which may be present in optionally substituted alkenyl groups include those mentioned above for alkyl.
  • alkynyl as used herein includes branched or straight chain alkynyl, preferably containing from 2 to 6, and especially from 2 to 4 carbon atoms.
  • Optional substituents which may be present in optionally substituted alkenyl groups include those mentioned above for alkyl.
  • aryl as used herein includes phenyl and naphthyl optionally substituted with up to five substituents which may be independently selected from halogen, optionally substituted alkyl, optionally substituted alkoxy, hydroxy, cyano, nitro, optionally substituted amino, alkoxy carbonyl or a group -S(O) m R 5 as hereinbefore defined.
  • aralkyl indicates an alkyl group substituted by aryl. Optional substitution present in an aralkyl group may be present in either the alkyl or the aryl moiety or both.
  • heterocyclyl as used herein includes aromatic or non-aromatic single or fused rings comprising up to four heteroatoms in the rings selected from oxygen, nitrogen and sulphur and optionally substituted with aryl or with those substituents mentioned above as suitable for aryl.
  • R 3 and R 4 are both hydrogen.
  • R 1 (if present) and R 2 are independently selected from halogen, cyano and the group C(Y)-NR 6 R 7 .
  • R 1 (if present) is halogen, for example chloro
  • R 2 is selected from halogen, for example chloro, cyano and the group -C(Y)-NR 6 R 7 .
  • Y S and R 6 and R are independently selected from hydrogen or C, .alkyl.
  • R 5 is preferably unsubstituted C 1-4 alkyl or
  • Suitable haloalkyl groups include fluoroalkyl or
  • chlorofluoroalkyl groups for example trifluoromethyl, pentafluoroethyl, chlorodifluoromethyl, dichlorofluoromethyl or difluoroethyl such as
  • R 11 and R 12 are independently selected from hydrogen and
  • A is is optionally substituted N-linked imidazole, optionally substituted N-linked pyrrole, optionally substitued N-linked pyrimidinone or optionally substituted N-linked pyridone.
  • A represents optionally substituted N-linked imidazole preferably have the structure (III) wherein X, R 2 , R 3 and R 4 have the meanings given previously;
  • R 8 represents hydrogen, optionally substituted alkyl, halogen, optionally substituted alkoxy, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aralkyl or a -S(O) m R 5 as hereinbefore defined;
  • R 9 represents hydrogen or optionally substituted alkyl, for example haloalkyl, or a group -S(O) m R 5 wherein m and R 5 are as defined previously;
  • R 10 represents hydrogen or a group -S(O) m R 5 as hereinbefore defined or -NR 1 1 R 12 as hereinbefore defined. If R 1 or R 2 is cyano or a group -C(Y)-NR 6 R 7 and R 10 is a group
  • vyclisation may take place between the groups R 1 (or R 2 ) and R 10 . It is preferred therefore that if R 1 or R 2 is cyano or a group -C(Y)-NR 6 R 7 , and R 10 is a group -NR 11 R 12 then both R 11 and R 12 are alkyl.
  • R 8 is hydrogen, alkyl or halogen.
  • R 9 is hydrogen, haloalkyl or a group -S(O) m R 5 wherein m is 0, 1 or 2 and R 5 is haloalkyl.
  • R 9 and R 5 are haloalkyl, they are preferably fluoroalkyl or fluorochloroalkyl, for example
  • R 10 is hydrogen or a group -NR 11 R 12 wherein R 11 and R 12 are independently selected from hydrogen and alkyl.
  • R 8 , R 9 and R 10 is other than hydrogen.
  • R 1 is halogen
  • R 2 is halogen, cyano or the group -C(Y)-NR 6 R 7 wherein Y is
  • R 6 and R 7 are independently selected from hydrogen or C 1-4 alkyl;R 3 and R 4 are hydrogen; R 8 is hydrogen, C 1-4 alkyl optionally substitued by halogen, halogen, or a group -S(O) m R 5 wherein m is 0, 1, or 2 and R 5 is C 1 -4 alkyl optionally substituted by halogen; R 9 is hydrogen or
  • R 10 represents hydrogen or -NR 1 1 R 12 wherein R 11 and R 12 are are independently selected from hydrogen and C 1-4 alkyl.
  • Compounds of the invention wherein A represents optionally substituted N-linked pyrazole preferably have the structure (IV) wherein X, R 2 , R 3 and
  • R 4 have the meanings given previously; and wherein R 13 is cyano or a group
  • R 14 is a group -S(O) m R 5 as hereinbefore defined;
  • R 15 is hydrogen, halogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkeneoxy, optionally substituted alkyneoxy, optionally substituted aryl, a group -S(O) m R 5 as hereinbefore defined, a group -NR 11 R 12 as hereinbefore defined or a group
  • R 16 and R 17 are independently selected from hydrogen, optionally substituted alkyl, optionally substituted alkoxy, a group
  • -S(O) m R 5 as hereinbefore defined, a group -NR 11 R 12 as hereinbefore defined, optionally substituted aryl, optionally substituted aromatic heterocyclyl, or R 16 and R 17 together with the carbon atom joining them form a 5-8 saturated or unsaturated carbocyclic ring or heterocyclic ring, provided that when X is -CR 1 and A represents a group of formula (IC) wherein R 1' is hydrogen, halogen, or a group NR 4' R 5' wherein R 4' and R 5' are independently selected from hydrogen or alkyl; R 2' is a group -S(O) n ' R 6' wherein n ' is 0,
  • R is a haloalkyl group
  • R 3' is -CN or is a group
  • cycloalkylcarbonyl by C 2-7 alkoxycarbonyl, by C 2-7 haloalkoxycarbonyl, by an aryl group or by an aromatic heterocyclic group or
  • Y 1' and Y 2' together with the nitrogen to which they are attached form an aliphatic heterocyclic group containing from 4 to 8 atoms in the ring and optionally substituted by halogen or alkyl or
  • Y 1' is hydrogen and Y is alkoxycarbonyl, alkylcarbonyl, optionally substituted aralkyl or a group -S(O) n ' R 6' where R 6' and n ' are as
  • R 1 and R 2 do not both represent halo.
  • compounds of the invention wherein A represents optionally substituted N-linked pyrazole may have a structure (IV) wherein
  • R 13 and R 14 are as defined above and R 15 is optionally substituted alkyl, optionally
  • R 16 and R 17 are independently selected from hydrogen, optionally substituted alkyl, optionally substituted alkoxy, a group -S(O) m R 5 as hereinbefore defined, a group -NR 11 R 12 as hereinbefore defined, optionally substituted aryl, optionally substituted aromatic heterocyclyl, or R 16 and R 17 together with the carbon atom joining them form a 5-8 saturated or unsaturated carbocyclic ring or heterocyclic ring.
  • R 13 is cyano.
  • R 14 is a group -S(O) m R 5 wherein m is 0, 1 or 2 and R 5 is haloalkyl, and especially fluoroalkyl such as trifluoromethyl or
  • R 6 and R 7 are independently selected from hydrogen or C 1-4 alkyl; R 3 and R 4 are hydrogen; R 13 is cyano or a group -C(Y)-NR 6 R 7 as herein defined; R 14 is a group -S(O) m R 5 wherein m is 0, 1, or 2 and R 5 is C 1-4 alkyl optionally substituted by halogen; and R 15 is C 1-4 alkoxy, or a group -S(O) m R 5 as herein defined.
  • A represents optionally substituted N-linked pyrrole preferably have the structure (V) wherein X, R 2 , R 3 and R 4 have the meanings given previously; and wherein R 19 represents hydrogen, halogen, a group -S(O) m R 5 as hereinbefore defined, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkeneoxy, optionally substituted alkyneoxy, a group -NR 11 R 12 as defined herein or a group
  • R 20 represents hydrogen, a group -S(O) m R 5 as hereinbefore defined, optionally substituted alkyl, optionally substituted alkenyl or optionally substituted alkynyl;
  • R 21 represents cyano or a group
  • R 22 represents hydrogen, halogen, a group -S(O) m R 5 as hereinbefore defined, optionally substituted alkyl optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkeneoxy or optionally
  • R 1 or R 2 is cyano or a group -C(Y)-NR 6 R 7 and R 19 is a group
  • R 1 and R 2 may take place between the groups R 1 (or R 2 ) and R 19 (or R 22 ). It is preferred therefore that if R 1 or R 2 is cyano or a group -C(Y)-NR 6 R 7 , and R 19 or R 22 is a group -NR 11 R 12 then both R 11 and R 12 are alkyl.
  • R 19 represents, hydrogen, halogen, a group -NR 11 R 12 wherein
  • R 11 and R 12 independently represent hydrogen or alkyl and preferably both represent hydrogen, or a group -S(O) m R5 wherein m is 0 and R 5 is alkyl.
  • R20 represents a group -S(O) m R 5 wherein m is 0, 1 or 2 and
  • R 5 is haloalkyl, for example fluoroalkyl or chlorofluoroalkyl. As specific examples of such groups there may be mentioned trifluoromethyl,
  • R 21 represents cyano
  • R 22 represents hydrogen, halogen, for example chloro, or a group -S(O) m R 5 wherein R 5 is haloalkyl, for example trifluoroalkyl or pentafluoroethyl.
  • a represents optionally substituted N-linked pyrimidinone preferably have the structure (VI) wherein X, R 2 , R 3 and R 4 have the meanings given previously; R 23 is oxygen or sulphur; R 24 is hydrogen, halogen, -NR 11 R 12 as hereinbefore defined, -S(O) m R 5 as hereinbefore defined, alkyl or cycloalkyl; R 25 is halogen, nitro,
  • R 26 is hydrogen, optionally substituted alkyl, halogen, cyano, alkoxy, -S(O) m R 5 as hereinbefore defined, , NR 11 R 12 as hereinbefore defined, formyl or nitro.
  • R 23 is oxygen
  • R 24 is hydrogen
  • R 25 is fluoroalkyl, for example trifluoromethyl or
  • R 26 is hydrogen or alkyl.
  • R 26 is hydrogen or C 1-4 alkyl.
  • Compounds of the invention wherein A represents optionally substituted N-linked pyridone preferably have the structure (VII) wherein X, R 2 , R 3 and
  • R 4 have the meanings given previously;
  • R 27 is oxygen or sulphur,
  • R 28 is hydrogen, halogen, a group -NR 11 R 12 as hereinbefore defined, optionally substituted alkyl, for example haloalkyl, optionally substituted alkoxy, for example haloalkoxy and optionally substituted thioalkyl, for example halothioalkyl;
  • R 29 is hydrogen, halogen, a group -NR 11 R 12 as hereinbefore defined, optionally substituted alkyl, for example haloalkyl, optionally substituted alkoxy, for example haloalkoxy and optionally substituted thioalkyl, for example halothioalkyl, cyano, nitro, optionally substituted oximino, optionally substituted alkenyl, optionally substituted aryloxy, or a group -S(O) m R 5 as hereinbefore defined;
  • R30 is hydrogen, optionally substituted alkyl,
  • R 27 is oxygen
  • R 28 is hydrogen
  • R 29 is hydrogen, halogen or haloalkyl, for example
  • fluoroalkyl such as trifluoromethyl or pentafluoroethyl.
  • R 30 is hydrogen or haloalkyl.
  • R 31 is hydrogen, halogen, nitro or cyano.
  • R 1 is halogen
  • R 3 and R 4 are hydrogen
  • R 28 is hydrogen
  • R 29 is hydrogen, halogen or C 1 -4 haloalkyl
  • R30 is hydrogen, or C 1-4 haloalkyl
  • R 31 is hydrogen, halogen, nitro or cyano.
  • R 1 is Cl and R 2 is CN should also be considered as being specifically disclosed as should compounds wherein R 1 is Cl and R 2 is F.
  • compounds of formula (IA), (IB) and (II) may be prepared by the reaction of Scheme I wherein AH is the appropriate heterocyclic compound carrying a hydrogen atom on the heterocyclic nitrogen and Z is a leaving group such as halogen, and especially chlorine or fluorine.
  • AH is the appropriate heterocyclic compound carrying a hydrogen atom on the heterocyclic nitrogen
  • Z is a leaving group such as halogen, and especially chlorine or fluorine.
  • Scheme (1) is as more specifically illustrated is Scheme (2).
  • the reaction suitably takes place in the presence of a base such as an alkali metal hydride, an alkali metal alkoxide or an alkali metal carbonate and in a suitable solvent.
  • An especially suitable base is sodium hydride and the reaction suitably takes place under an inert atmosphere and in the presence of a polar aprotic solvent such as dimethyl formamide or dimethylacetamide or
  • N-methylpyrrolin-2-one N-methylpyrrolin-2-one.
  • suitable solvents include hydrocarbon solvents such as petroleum ether or toluene or an alcohol or an ether such as tetrahydrofuran.
  • the reaction temperature is conveniently in the range 0°C to 120°C , for exampl e 20°C to 65°C.
  • the heterocyclic ring may be prepared by cyclisation.
  • Such a cyclisation process for the imidazole ring is illustrated for example in Scheme 3 using a general method more
  • Scheme 2 illustrates a reaction in which the substituents R 1 , R 2 , R 3 , R 4 , R 8 , R 9 and R 10 are present in the starting materials.
  • substituents R 1 , R 2 , R 3 , R 4 , R 8 , R 9 and R 10 are present in the starting materials.
  • precursors to any of the groups R 1 , R 2 , R 3 , R 4 , R 8 , R 9 and R 10 to be present in the starting materials and for such groups to be converted to the groups R 1 , R 2 , R 3 , R 4 ,
  • Compound (XX) may be prepared as described in the Journal of the Americal Chemical Society 843064 (1962).
  • the compounds of formula (I) may be used to combat and control infestations of insect pests and also other invertebrate pests, for example, acarine pests.
  • insect and acarine pests which may be combated and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products), horticulture and animal husbandry, forestry, the storage of products of vegetable origin, such as fruit, grain and timber, and also those pests associated with the transmission of diseases of man and animals.
  • an insecticidal or acaricidal composition comprising an insecticidally or acaricidally effective amount of a compound according to the invention in association with an insecticidally or acaricidally inert dilutent or carrier.
  • compositions which include in addition to the insecticidally active ingredient or ingredients of formula I suitable inert diluent or carrier materials, and/or surface active agents.
  • compositions may also comprise another pesticidal material, for example another insecticide or acaricide, or a fungicide, or may also comprise an insecticide synergist, such as for example dodecyl imidazole, safroxan, or piperonyl butoxide.
  • another pesticidal material for example another insecticide or acaricide, or a fungicide
  • an insecticide synergist such as for example dodecyl imidazole, safroxan, or piperonyl butoxide.
  • compositions may be in the form of dusting powders wherein the active ingredient is mixed with a solid diluent or carrier, for example kaolin, bentonite, kieselguhr, or talc, or they may be in the form of granules, wherein the active ingredient is absorbed in a porous granular material for example pumice.
  • a solid diluent or carrier for example kaolin, bentonite, kieselguhr, or talc
  • granules wherein the active ingredient is absorbed in a porous granular material for example pumice.
  • compositions may be in the form of baits wherein the active ingredient is mixed with a nutrient carrier for example sucrose, yeast, malt extract, cereal or cereal products and optionally an attractant such as a pheromone or pheromone analogue.
  • a nutrient carrier for example sucrose, yeast, malt extract, cereal or cereal products
  • an attractant such as a pheromone or pheromone analogue.
  • compositions may be in the form of liquid
  • preparations to be used as dips or sprays which are generally aqueous dispersions or emulsions of the active ingredient in the presence of one or more known wetting agents, dispersing agents or emulsifying agents (surface active agents).
  • Wetting agents, dispersing agents and emulsifying agents may be of the cationic, anionic or non-ionic type.
  • Suitable agents of the cationic type include, for example, quaternary ammonium compounds, for example
  • Suitable agents of the anionic type include, for example, soaps, salts of aliphatic monoesters of sulphuric acid, for example sodium lauryl sulphate, salts of sulphonated aromatic compounds, for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, or butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl- and triisopropylnaphthalene sulphonates.
  • Suitable agents of the non-ionic type include, for example, the
  • condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octyl phenol, nonyl phenol and octyl cresol.
  • fatty alcohols such as oleyl alcohol or cetyl alcohol
  • alkyl phenols such as octyl phenol, nonyl phenol and octyl cresol.
  • non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the
  • condensation products of the said partial esters with ethylene oxide, and the lecithins are condensation products of the said partial esters with ethylene oxide, and the lecithins.
  • compositions may be prepared by dissolving the active ingredient in a suitable solvent, for example, a ketonic solvent such as diacetone alcohol, or an aromatic solvent such as trimethylbenzene and adding the mixture so obtained to water which may contain one or more known wetting, dispersing or emulsifying agents.
  • a suitable solvent for example, a ketonic solvent such as diacetone alcohol, or an aromatic solvent such as trimethylbenzene and adding the mixture so obtained to water which may contain one or more known wetting, dispersing or emulsifying agents.
  • Suitable organic solvents are dimethyl formamide, ethylene dichloride, isopropyl alcohol, propylene glycol and other glycols, diacetone alcohol, toluene, kerosene, white oil, methylnaphthalene, xylenes and trichloroethylene, N-methyl-2- pyrrolidone and tetrahydrofurfuryl alcohol (TUFA).
  • dispersions or emulsions are generally supplied in the form of a
  • the said concentrate containing a high proportion of the active ingredient or ingredients, the said concentrate to be diluted with water before use.
  • concentrates may contain 10-85% by weight of the active ingredient or ingredients.
  • aqueous preparations When diluted to form aqueous preparations such preparations may contain varying amounts of the active ingredient depending upon the purpose for which they are to be used.
  • an aqueous preparation containing between 0.0001% and 0.1% by weight of the active ingredient (approximately equivalent to from
  • compositions are applied to the pests, to the locus of the pests, to the habitat of the pests, to growing plants liable to infestation by the pests, or, where there is systemic uptake by plants, to the soil surrounding plants liable to infestation, by any of the known means of applying pesticidal compositions, for example, by dusting or spraying.
  • a method of combating insect and acarine pests at a locus which comprises treating the locus with an insecticidally or acaricidally effective amount of a composition according to the present invention.
  • the compounds of the invention may be the sole active ingredient of the composition or they may be admixed with one or more additional active ingredients such as insecticides, insecticide synergists, herbicides, fungicides or plant growth regulators where appropriate.
  • Suitable additional active ingredients for inclusion in admixture with the compounds of the invention may be compounds which will broaden the spectrum of activity of the compounds of the invention or increase their persistence in the location of the pest. They may synergise the activity of the compound of the invention or complement the activity for example by increasing the speed of effect, improving knockdown or overcoming
  • insecticide such as permethrin, esfenvalerate, deltamethrin,
  • cyhalothrin in particular lambda-cyhalothrin, cypermethrin, alpha cypermethrin, bifenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids for example ethofenprox, natural pyrethrin,
  • Organic tin compounds such as cyhexatin, fenbutatin oxide, or azocyclotin;
  • Macrolides such as avermectins or milbemycins, for example such as abamectin, ivermectin, and milbemyci ⁇ ;
  • Hormones such as pheromones
  • Organochlorine compounds such as benzene hexachloride, DDT, chlordane or dieldrin.
  • Amidines such as chlordimeform or amitraz.
  • insecticides having particular targets may be employed in the mixture if appropriate for the intended utility of the mixture.
  • selective insecticides for particular crops for example stemborer specific insecticides for use in rice such as cartap or buprofezin can be employed.
  • insecticides specific for particular insect species/stages for example ovo-larvicides such as clofentezine, flubenzimine, hexythiazox and tetradifon, acaricides such as dicofol, propargite, bromopropylate, chlorobenzilate, or growth regulators such as hydramethylnon, cyromazine, methoprene, hydroprene, chlorfluazuron and diflubenzuron may also be included in the compositions.
  • ovo-larvicides such as clofentezine, flubenzimine, hexythiazox and tetradifon
  • acaricides such as dicofol, propargite, bromopropylate, chlorobenzilate
  • growth regulators such as hydramethylnon, cyromazine, methoprene, hydroprene, chlorfluazuron and diflubenzuron
  • compositions include piperonyl butoxide, sesamex, and dodecyl imidazole.
  • Suitable herbicides, fungicides 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 can be included is propanil, an example of a plant growth regulator for use in cotton is "Pix", and examples of fungicides for use in rice include blasticides such as blasticidin-S.
  • the ratio of the compound of the invention to the other active ingredient in the composition will depend upon a number of factors
  • composition will be applied at about the rate as it is usually employed, or at a slightly lower rate if synergism occurs.
  • the compounds of the present invention and compositions comprising them have shown themselves active against a variety of insect and other invertebrate pests.
  • Compounds of the present invention are also generally characterised by a relatively broad spectrum of activity which may include Lepidoptera and Coleoptera in addition to public health pests such as flies and cockroaches.
  • cross-resistance may mean that even a novel insecticide is effective only against susceptible strains of the target species and has relatively little effect on resistant strains. This can prove a serious limitation.
  • compounds of the present invention may also be active against organophosphate, pyrethroid or cyclodiene (for example lindane or dieldrin) resistant strains of public and animal health pests. They may be effective in combating both susceptible and resistant strains of the pests in their adult and immature stages of growth, and may be applied to the infested host animal by topical, oral or parenteral administration.
  • organophosphate, pyrethroid or cyclodiene for example lindane or dieldrin
  • N-chlorosuccinimide (26.7g) in portions over 2 hours. The mixture was stirred for 18 hours, heated to reflux for 11 ⁇ 4 hour and evaporated under reduced pressure. The residue was partitioned between hexane (600 cm 3 ) and aqueous sodium bicarbonate. The hexane fraction was washed twice with water and dried (anhydrous magnesium sulphate) and evaporated under reduced pressure to give the required product as a pale brown solid.
  • the proportion of the product (B) obtained in repeat preparations was variable. Unless indicated otherwise, the minor product (B) was usually eliminated during subsequent reaction and isolation or purfication of end-products obtained using the product of Preparation 4 as a starting material.
  • reaction mixture was stored for 48 hours, the solvent evaporated under reduced pressure, the residue washed with hexane and filtered to give the required product as a yellow solid.
  • 1,2-dicyano propionate (0.64g), acetic acid (3cm 3 ) and water (6.25cm 3 ) at
  • stage 1 (0.29g) in dry dichloromethane (8cm 3 ) was stirred and cooled to -14°C. Trifluoromethylsulphenyl chloride was slowly bubbled into the solution and retained at reflux using a carbon
  • the material from Preparation 10 was dissolved in dry methanol (350 cm 3 ) under an atmosphere of nitrogen and treated over 0.5 hour with sodium methoxide (1.08g) in methanol (50 cm 3 ) at 0°, stirred at 0° for 2 hours and at ambient temperature for 1 hour.
  • the solvent was evaporated under reduced pressure and the residue treated with water (100 cm 3 ) and extracted with dichloromethane (2 x 300 cm 3 ).
  • the organic fractions were dried (magnesium sulphate) and evaporated under reduced pressure to yield the required product as an oil, which partially solidified on storing.
  • Stage 2 Preparation of 5-Amino-1(2,6-dichlorobenzene-4- pentaf1uorosulphanyl)-4-trifluoro-methylsulphenylimidazole (Compound No 6 of Table I) The material from Stage 1 (5.5g) was dissolved in dry
  • 1,2-dichloroethane 350 cm 3
  • trifluoromethyl sulphenyl chloride 4.5g
  • the reaction was allowed to warm to ambient temperature and stored for 18 hours.
  • the solvent was evaporated under reduced pressure and the residue partitioned between ethyl acetate and water.
  • the organic fraction was dried (magnesium sulphate), evaporated under reduced pressure and fractionated using chromatography (silica gel; hexane/ethyl acetate; 9:1 and 4:1 by volume) to give the required product as a solid.
  • Example 2 The product from Example 1 (2.5g) in tetrahydrofuran (dry; 50 cm 3 ) containing tertiary butylnitrite (3.3cm 3 ) was stirred under an atmosphere of nitrogen and heated to reflux for 2 hours. The reaction was cooled, evaporated under reduced pressure, and the residue dissolved in ethyl acetate and washed with water. The organic fraction was dried (magnesium sulphate) and re-evaporated to give a brown oil. A portion (1.5g) was fractionated using chromatography (silica gel hexane/ethyl acetate, 4:1 by volume) to give the required product as a pale yellow solid.
  • chromatography sica gel hexane/ethyl acetate, 4:1 by volume
  • Example 2 The material from Example 2 (1.5g) was dissolved in dichloromethane (dry; 20 cm 3 ) and cooled to 0°. Meta chloroperbenzoic acid (1.05g; 80% strength) was added in portions to the above stirred solution, and held for an additional 1 hour at 0°. The reaction was allowed to warm to ambient temperature and was stirred for 60 hours. The mixture was diluted with ethyl acetate (200 cm 3 ), washed with aqueous sodium hydrogen carbonate, and water (twice) and dried (magnesium sulphate). The solvent was evaporated under reduced pressure and the residual gum fractionated using
  • 2-Methyl-4-pentafluoroethylimidazole was reacted with 3,5-dichloro-4- fluorobenzenesulphurpentafluoride (Preparation 4) using the general method of Example 4.
  • the 2-Methyl-4-pentafluoroethylimidazole starting material was prepared by reaction of 2-methylimidazole with pentafluoroethyl iodide using the method described in J. Oro.Chem. (1982)472867.
  • Example 11 [10.0g] in dichloromethane [200cm 3 ], at 4°C. The mixture was allowed to stand at 5°C for 24 hours. The solution was stirred with saturated aqueous sodium hydrogen carbonate [32cm 3 ] and 1M sodium sulphite [16cm 3 ] whereupon an emulsion formed. Sufficient magnesium sulphate to absorb all the water was added, the mixture filtered, the residue washed with dichloromethane and the filtrate plus washings evaporated under reduced pressure to leave the crude product. The product was purified using column chromatography on silica gel, eluting with dichloromethane to give a light brown solid [2.0g].
  • Trifluoromethyl sul phenyl chloride [about 8g] was bubbled into a stirred solution of 2-amino-4-cyano-1-(2,6-dichlorobenzene-4-pentafluoro- sulphinyl)pyrrole [2.06g - Example 9] in dichloromethane [40cm 3 ] for 10 minutes at 5°C. After stirring for another 45 minutes at 5°C, saturated aqueous sodium hydrogen carbonate [100cm 3 ] was added and the mixture was thoroughly stirred.
  • Example 14 2-Amino-4-cyano-1-(2,6-dichlorobenzene-4-pentafluorosulphanyl)- 3,5-bis(trifluoro-methylthio)pyrrole [1.0g, Example 14] was treated with dimethyldisulphide using the general method of Example 13 to give the desired product as a yellow solid. Melting point 130-1°C.
  • Example 14 2-Aminn-4-cyano-1-(2,6-dichlorobenzene-4-pentafluorosulphanyl)- 3-trifluoromethylthiopyrrole [0.11g, Example 14] was treated with thionyl chloride using the general method of Example 11 to give the desired product as a solid mixed with a small amount of the starting material.
  • Imidazole (0.55g) was added at ambient temperature to a stirred suspension of sodium hydride (0.39g; 50% oil dispersion) in N-methyl- pyrrolidin-2-one (dry,; 20cm 3 ) under an atmosphere of nitrogen. The mixture was stirred for 10 minutes and a solution of
  • N-methy1pyrrolid-2-one (10cm 3 ) was added slowly dropwise. On complete addition the reaction was heated to 60-5°C for 2.75 hours, cooled, diluted with water and extracted with ethyl acetate. The organic factions were combined, washed with water, dried and evaporated under reduced pressure. The residual liquid was re-dissolved in diethyl ether (300cm 3 ), washed with water, dried and evaporated under reduced pressure to give a brown solid which was fractioned using chromatography (silica gel hexane/ethyl acetate
  • Example 22 The material from Example 22 (1.26g) in dichloromethane (10cm 3 , dry) was treated dropwise at ambient temperature with
  • dichlorofluoromethylsulphenyl chloride (0.67g) in dichloromethane (dry; 4cm 3 ) with stirring. The mixture was stirred for 60 hours, and further dichlorofluoromethylsulphenyl chloride (0.224g) in dichloromethane (1cm 3 ) added at 24 hour and 48 hour intervals. The mixture was diluted with dichloromethane, washed with diluted hydrochloric acid, water and dried (magnesium sulphate).
  • the title compound was prepared using the general method of Example 5. Melting point 137-138°C. Molecular ion 456.
  • the title compound was prepared using the general method of Example 6. Melting point 168.4-169.0°C. Molecular ion 461.
  • the activity of the compounds of the invention was determined using a variety of pests.
  • the pests were treated with a liquid composition containing 500 parts per million (ppm) by weight of the compound.
  • the compositions were made by dissolving the compound in acetone and ethanol (50:50) mixture and diluting the solutions with water containing 0.1% by weight of a wetting agent sold under the trade name "SYNPERONIC" NP8 until the liquid composition contained the required concentration of the
  • the test procedure adopted with regard to each pest was basically the same and comprised supporting a number of the pests on a medium which was usually a substrate, a host plant or a foodstuff on which the pests feed, and treating either or both the medium and the pests with the compositions.
  • the mortality of the pests was then assessed at periods usually varying from two to five days after the treatment.
  • the results of the tests are presented in Table VI for each of the compounds.
  • the results indicate a grading of mortality, designated as A, B or C wherein A indicates 80-100% mortality, B indicates 40-79% mortality and C indicates 0-39% mortality.
  • a dash (-) indicates that no data is available.
  • the pest species is designated by a letter code.

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