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WO1998043957A1 - Cycloalcanes cyano substitues - Google Patents

Cycloalcanes cyano substitues Download PDF

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Publication number
WO1998043957A1
WO1998043957A1 PCT/GB1998/000718 GB9800718W WO9843957A1 WO 1998043957 A1 WO1998043957 A1 WO 1998043957A1 GB 9800718 W GB9800718 W GB 9800718W WO 9843957 A1 WO9843957 A1 WO 9843957A1
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Prior art keywords
formula
compound
optionally substituted
alkyl
halogen
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PCT/GB1998/000718
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English (en)
Inventor
David Philip John Pearson
Christopher John Urch
Roger Salmon
John Finney
Mark Adrian Huggett
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Zeneca Limited
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Publication date
Application filed by Zeneca Limited filed Critical Zeneca Limited
Priority to EP98910859A priority Critical patent/EP0971893A1/fr
Priority to AU65085/98A priority patent/AU6508598A/en
Priority to KR1019997008885A priority patent/KR20010005811A/ko
Priority to JP54126998A priority patent/JP2002504092A/ja
Publication of WO1998043957A1 publication Critical patent/WO1998043957A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/45—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C255/46—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of non-condensed 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
    • A01N43/54—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
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—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
    • A01N43/74—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 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N43/74—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 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
    • 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
    • C07D213/61—Halogen atoms or nitro radicals
    • 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
    • C07D239/26—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having 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
    • C07D241/16—Halogen atoms; Nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
    • C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated

Definitions

  • This invention relates to novel cyano-substituted cycloalkanes, to processes for their preparation, to insecticidal compositions comprising them and to their use in combating insect and like pests.
  • Tetracyanocyclopentadiene salts are disclosed as rocket propellants and dyes
  • the present invention provides a compound of formula (I)
  • R 1 is Ar-(CH 2 ) n - where n is zero or one and Ar is an optionally substituted phenyl or an optionally substituted 5- or 6-membered heterocyclic ring system containing from 1 to 3 heteroatoms independently selected from nitrogen, oxygen and sulfur atoms, and at least one unsaturation (double bond) between adjacent atoms in the ring, wherein the substituents, if present, are selected from halogen atoms, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkenyl, haloalkoxy, alkylthio and alkyl amino groups, said groups having up to six carbon atoms; wherein R 2 and R 3 are independently hydrogen or a group selected from alkyl, aryl, heteroaryl, aralkyl, formyl, alkylcarbonyl, arylcarbonyl, heteroarylalkyl, alkenyl, aralkenyl,
  • the compounds of formula (I) have chiral centres at ring positions 1 and 3 and are therefore capable of existing in four isomeric forms (comprising two pairs of diastereoisomers) which can be designated as (1R,3R), (1R,3S), (1S,3S) and (1S,3R).
  • the present invention embraces all isomeric forms individually and mixtures (including racemic mixtures) thereof in all proportions.
  • Examples of 5- and 6-membered heterocyclic ring systems represented by Ar include those based on pyridine, pyrazine, pyridazine, pyrimidine, pyrrole, pyrazole, imidazole, 1,2,3- and 1,2,4-triazoles, furan, thiophene, oxazole, isoxazole, thiazole.
  • Ar represents a halo-substituted phenyl, pyridyl, or diazinyl group.
  • Halogen includes fluorine, chlorine, bromine and iodine.
  • Alkyl moieties of R 2 and R 3 and substituents of Ar preferably contain from 1 to 6, more preferably from 1 to 4, carbon atoms. They can be in the form of straight or branched chains (for example methyl, ethyl, n- or i-propyl, or n-, s-, i- or t-butyl).
  • Haloalkyl is preferably C, skill 6 haloalkyl, especially fluoroalkyl (for example trifluoromethyl, 2,2,2-trifluoroethyl or 2,2-difluoroethyl).
  • Alkenyl and alkynyl moieties of R 2 and R 3 and substituents of Ar preferably contain from 2 to 6, more preferably from 2 to 4, carbon atoms. They can be in the form of straight or branched chains, and, where appropriate, the alkenyl moieties can be of either (E)- or (Z)-conf ⁇ guration. Examples are vinyl, allyl and propargyl. Aryl includes naphthyl but is preferably phenyl.
  • Heteroaryl includes 5- and 6-membered aromatic rings containing one, two, three or four heteroatoms selected from the list comprising oxygen, sulphur and nitrogen and can be fused to benzenoid ring systems.
  • heteroaryl are pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl (1,2,3-, 1,2,4- and 1,3,5-), furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (1,2,3- and 1,2,4-), tetrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, indolinyl, isoindolinyl
  • the heterocyclyl part of heterocyclylalkyl is a ring containing one or two heteroatoms selected from the list comprising oxygen, sulphur and nitrogen. Examples are piperidine, piperazine, pyrrolidine, tetrahydro furan, morpholine, thietane, pyridine or thiazole.
  • the alkylenedioxy group is a substituent for a ring and is especially C M alkylenedioxy.
  • Alkylenedioxy groups are optionally substituted with halogen (especially fluorine) and are, for example, methylenedioxy (OCH 2 0) or difluoromethylenedioxy (OCF 2 0).
  • Suitable acid addition salts include salts of a compound of formula (I) with an inorganic acid such as hydrochloric, hydrobromic, sulfuric, nitric or phosphoric acid, or an organic carboxylic acid such as oxalic, tartaric, lactic, butyric, toluic, hexanoic or phthalic acid, or a sulphonic acid such as methane, benzene or toluene sulphonic acid.
  • organic carboxylic acids include haloacids such as trifluoroacetic acid.
  • the invention provides a compound of formula (I) wherein R' is Ar-(CH 2 ) n - where n is zero or one and Ar is an optionally substituted phenyl or an optionally substituted 5- or 6-membered heterocyclic ring system containing from 1 to 3 heteroatoms independently selected from nitrogen, oxygen and sulfur atoms, and at least one unsaturation (double bond) between adjacent atoms in the ring, wherein the substituents, if present, are selected from halogen atoms (especially fluorine, chlorine or bromine), alkyl (especially C M alkyl), alkenyl (especially C 2 .
  • R' is Ar-(CH 2 ) n - where n is zero or one and Ar is an optionally substituted phenyl or an optionally substituted 5- or 6-membered heterocyclic ring system containing from 1 to 3 heteroatoms independently selected from nitrogen, oxygen and sulfur atoms, and at least one unsaturation (double bond) between adjacent atoms in the ring, where
  • alkenyl alkynyl (especially C ⁇ alkynyl), alkoxy (especially C M alkoxy), haloalkyl (especially C M haloalkyl), haloalkenyl (especially C 2 . 4 haloalkenyl), haloalkoxy (especially C haloalkoxy), alkylthio (especially C,_ 4 alkylthio), and alkylamino (especially mono- or di-(C,.
  • alkyl)amino such as mono- or di- (C,_ 3 alkyl)amino) groups
  • R 2 and R 3 are independently hydrogen or a group selected from alkyl (especially C alkyl), aryl (especially phenyl), heteroaryl (especially pyridinyl or pyrimidinyl), aralkyl (especially aryl(C )alkyl, such as phenyl(C M )alkyl), heteroarylalkyl (especially heteroaryl(C M )alkyl, such as pyridinyl(C M )alkyl or pyrimidinyl(C, .4 )alkyl), alkenyl (especially C 3 .
  • alkenyl especially aryl(C 3 ⁇ ,)alkenyl, such as phenyl(C 3.4 ) alkenyl), alkynyl (especially C 3 . 4 alkynyl), formyl, alkylcarbonyl, arylcarbonyl (especially phenylcarbonyl), alkoxycarbonyl (especially C alkoxycarbonyl), alkanesulfonyl (especially C, proposition 4 alkylsulfonyl), phenylsulfonyl, alkenyloxycarbonyl (especially C 3 . alkenyloxycarbonyl), aralkyloxycarbonyl (especially phenyl(C,.
  • alkyl moieties of R 2 and R 3 comprise from 1 to 15 carbon atoms (especially 1 to 8 carbon atoms) and are optionally substituted with one or more substituents selected from halogen (especially fluorine or chlorine), cyano, carboxyl(HOC(0)), carboxylic acyl (especially C M alkylcarbonyloxy), formyl, carbamyl (H 2 NC(0)), alkoxycarbonyl (especially C alkoxycarbonyl), alkoxy (especially C,_ 4 alkoxy), alkylenedioxy (especially C alkylenedioxy), hydroxy, nitro, amino, acylamino (especially C M alkyl
  • the invention provides compounds of formula (I) wherein R' represents a group Ar-(CH 2 ) n - where n is zero or one and Ar represents an optionally substituted phenyl or 5- or 6-membered heterocyclic ring system containing from 1 to 3 heteroatoms individually selected from nitrogen, oxygen and sulfur atoms, and at least one unsaturation (double bond) between adjacent atoms in the ring, wherein the substituents, if present, are selected from halogen atoms, alkyl, alkenyl, alkynyl, alkoxy, haloalkyl, haloalkenyl, alkylthio and alkyl amino groups, any of which groups contain up to six carbon atoms, wherein R 2 and R 3 each individually represents hydrogen or cyano or a group selected from alkyl, aryl, heteroaryl, aralkyl, heteroarylalkyl, alkenyl, aralkenyl, alkynyl, alkoxycarbonyl
  • R 2 and R 3 together with the adjacent nitrogen atom represent a nitrogen containing heterocyclic group which may contain a further heteroatom selected from oxygen, sulfur and nitrogen: and acid addition salts and quaternary ammonium salts and N-oxides derived therefrom.
  • Preferred compounds of formula (I) are those wherein n is zero and Ar is a pyridyl or diazinyl group which is optionally substituted with halogen (such as chlorine or bromine).
  • the invention provides a compound of formula (I) wherein R 1 is Ar-(CH 2 ) n - where n is zero or one and Ar is a 5- or 6-membered aromatic heterocyclic ring system containing from 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur, and optionally fused to a benzene ring, the system being optionally substituted by halogen (especially fluorine, chlorine or bromine), haloalkoxy (especially trifluoromethoxy) or haloalkyl (especially trifluoromethyl).
  • halogen especially fluorine, chlorine or bromine
  • haloalkoxy especially trifluoromethoxy
  • haloalkyl especially trifluoromethyl
  • the invention provides a compound of formula (I) wherein R 2 and R 3 are independently hydrogen; alkyl comprising from 1 to 15 carbon atoms (especially 1 to 8 carbon atoms, more especially 1 to 4 carbon atoms) optionally substituted with halogen (especially fluorine) or alkoxy (especially methoxy); phenylalkyl (especially benzyl) optionally substituted with halogen (especially fluorine or bromine) or alkoxy (especially ethoxy); alkenyl (especially allyl); formyl; alkoxycarbonyl (especially t-butyloxycarbonyl); or alkenyloxycarbonyl (especially vinyloxycarbonyl).
  • R 2 and R 3 are independently hydrogen; alkyl comprising from 1 to 15 carbon atoms (especially 1 to 8 carbon atoms, more especially 1 to 4 carbon atoms) optionally substituted with halogen (especially fluorine) or alkoxy (especially methoxy); phenylalkyl (especially benzyl) optional
  • the invention provides a compound of formula (I) wherein R 1 is a group Ar-(CH 2 ) n - where n is zero or one and Ar is a 5- or 6-membered aromatic heterocyclic ring system containing from 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulphur, and optionally fused to a benzene ring, the system being optionally substituted by halogen (especially fluorine, chlorine or bromine), haloalkoxy (especially trifluoromethoxy) or haloalkyl (especially trifluoromethyl); wherein R 2 and R 3 are independently hydrogen; alkyl comprising from 1 to 15 carbon atoms (especially 1 to 8 carbon atoms, more especially 1 to 4 carbon atoms) optionally substituted with halogen (especially fluorine) or alkoxy (especially methoxy); phenylalkyl (especially benzyl) optionally substituted with halogen (especially fluorine or bromine) or alk
  • the invention provides a compound of formula (I) wherein R 1 is Ar-(CH 2 ) n - where n is zero or one and Ar is a 6-membered aromatic heterocyclic ring system containing from 1 to 3 nitrogen atoms, optionally substituted by halogen atoms (especially chlorine or bromine).
  • the invention provides a compound of formula (I) wherein R 2 and R 3 are independently hydrogen; alkyl (especially C alkyl) optionally substituted with halogen (especially fluorine) or alkoxy (especially methoxy) groups; phenylalkyl (especially benzyl) optionally substituted with halogen (especially fluorine or bromine) or alkoxy (especially ethoxy); formyl; alkoxycarbonyl (especially t-butyloxycarbonyl); or alkenyloxycarbonyl (especially vinyloxycarbonyl).
  • the invention provides a compound of formula (I) wherein R 1 is Ar-(CH 2 ) n - where n is zero or one and Ar is a 6-membered aromatic heterocyclic ring system containing from 1 to 3 nitrogen atoms, optionally substituted by halogen atoms (especially chlorine or bromine); wherein R 2 and R 3 are independently hydrogen; alkyl (especially C M alkyl) optionally substituted with halogen (especially fluorine) or alkoxy (especially methoxy); phenylalkyl (especially benzyl) optionally substituted with halogen (especially fluorine or bromine) or alkoxy (especially ethoxy); formyl; alkoxycarbonyl (especially t-butyloxycarbonyl); or alkenyloxycarbonyl (especially vinyloxycarbonyl).
  • R 1 is Ar-(CH 2 ) n - where n is zero or one and Ar is a 6-membered aromatic heterocyclic ring system containing from 1 to 3 nitrogen
  • R 1 , R 2 and R 3 are as defined above;
  • R 4 is hydrogen, optionally substituted alkyl or optionally substituted aryl;
  • X and X 1 are, independently, leaving groups (such as halogen or alkyl sulphonate); and
  • R is optionally substituted alkyl (for example t-butyl), optionally substituted alkenyl or optionally substituted aralkyl (for example benzyl).
  • Substitution on the carbon bearing the nitrile group to give a compound of formula (6) may be effected using a suitable base such as lithium diisopropylamide, lithium hexamethyldisilazide or sodamide in a suitable solvent such as diethyl ether, tetrahydrofuran (THF) or dimethoxy ethane at a variety of temperatures usually between -100 °C and 30 °C and adding an aryl, heteroaryl, benzyl or similar substrate suitably substituted with a leaving group, for example halide.
  • a suitable base such as lithium diisopropylamide, lithium hexamethyldisilazide or sodamide
  • a suitable solvent such as diethyl ether, tetrahydrofuran (THF) or dimethoxy ethane
  • THF tetrahydrofuran
  • dimethoxy ethane dimethoxy ethane
  • Removal of the carbamate residue in a compound of formula (6) may be effected by a variety of methods well known to those skilled in the art and the amine compound of formula (7) can then be converted to a compound of formula (I) either by direct reaction with an alkylating agent, such as an alkyl halide, or by reductive coupling with a carbonyl compound using methods analogous to those described for the preparation of (4).
  • an alkylating agent such as an alkyl halide
  • the order of the stages of the above route may be altered, for instance reductive amination of a compound of formula (3) with a secondary amine can yield a compound of formula (8) directly which may then be substituted adjacent to the nitrile group as described above (for example using lithium diisopropylamide, lithium hexamethyldisilazide or sodamide as a base) to produce a compound of formula (I).
  • a suitably 3-substituted cyclopentenone compound of formula (9), containing a group such as halogen, alkylsulphonate or a trisubstituted tin residue may be reacted with a substrate containing a trisubstituted tin residue, a trifluoromethanesulphonate (OTf) or bromide residue, provided that only one component of the reaction contains tin, in a Stille-type coupling using a metal catalyst (for example Palladium) to give a cyclopentenone compound of formula (10).
  • a metal catalyst for example Palladium
  • a ketone compound of formula (11) may be reacted with a suitable hydro xylamine to give an oxime compound of formula (12) which may be reduced to give a primary amine compound of formula (13) for further elaboration, by methods well known to those skilled in the art, into a compound of formula (I).
  • the preparation of specific compounds of formula (I) according to the invention is exemplified by the preparative details set out in the Examples below. Other compounds of the invention may be prepared by similar procedures to those illustrated using the appropriate reactants.
  • the compounds of formula (I) as defined hereinabove are prepared by reacting the corresponding 3-cyanocyclopentylamine of formula (I) where R 1 is replaced by hydrogen with a compound of formula R'-X in the presence of a base, where R 1 is as defined hereinabove and X is a leaving group, for example a halogen.
  • the present invention provides processes for preparing the compounds of formula (I).
  • the invention provides a method of combating and controlling insect, acarine or nematode pests at a locus which comprises treating the pests or the locus of the pests with an insecticidally, acaricidally or nematocidally effective amount of a composition comprising a compound of formula (I) or an acid addition salt thereof.
  • the compounds of formula (I) and acid addition salts thereof can be used to combat and control infestations of insect pests such as Lepidoptera, Diptera, Homoptera and Coleoptera (including Diabrotica i.e. corn rootworms) and also other invertebrate pests, for example, acarine pests.
  • insect pests such as Lepidoptera, Diptera, Homoptera and Coleoptera (including Diabrotica i.e. corn rootworms) and also other invertebrate pests, for example, acarine pests.
  • the 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.
  • insect and acarine pest species which may be controlled by the compounds of formula (I) include: Myzus persicae (aphid), Aphis gossvpii (aphid), Aphis fabae (aphid), Aedes aegvpti (mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes), Dysdercus fasciatus (capsid), Musca domestica (housefly), Pieris brassicae (white butterfly), Plutella xylostella (diamond back moth), Phaedon cochleariae (mustard beetle), Aonidiella spp.
  • the compound In order to apply the compounds of formula (I) to the locus of the nematode, insect or acarid pest, or to a plant susceptible to attack by the nematode, insect or acarid pest, the compound is usually formulated into a composition which includes in addition to a compound of formula (I) a suitable inert diluent or carrier material, and, optionally, a surface active agent.
  • a suitable inert diluent or carrier material and, optionally, a surface active agent.
  • the amount of composition generally applied for the control of nematode pests gives a rate of active ingredient from 0.01 to 10 kg per hectare, preferably from 0.1 to 6 kg per hectare.
  • the present invention provides an insecticidal, acaricidal or nematicidal composition
  • an insecticidal, acaricidal or nematicidal composition comprising an insecticidally, acaricidally or nematicidally effective amount of a compound of formula (I) and a suitable carrier or diluent therefor.
  • the compositions can be applied to the soil, plant or seed, to the locus of the pests, or to the habitat of the pests, in the form of dusting powders, wettable powders, granules (slow or fast release), emulsifiable concentrates, suspension concentrates, liquid solutions, emulsions, seed dressings, fogging/smoke formulations or controlled release compositions, such as microencapsulated granules or suspensions.
  • Dusting powders are formulated by mixing the active ingredient with one or more finely divided solid carriers and/or diluents, for example natural clays, kaolin, pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulphur, lime, flours, talc and other organic and inorganic solid carriers.
  • Granules are formed either by absorbing the active ingredient in a porous granular material for example pumice, attapulgite clays, fuller's earth, kieselguhr.
  • diatomaceous earths, ground corn cobs, and the like or by adsorbing the active ingredient on to hard core materials such as sands, silicates, mineral carbonates, sulphates, phosphates, or the like.
  • Agents which are commonly used to aid absorption or adsorption include aliphatic and aromatic petroleum solvents, alcohols, polyvinyl acetates, polyvinyl alcohols, ethers, ketones, esters, dextrins, sugars and vegetable oils.
  • Other additives may also be included in granules, such as emulsifying agents, wetting agents or dispersing agents.
  • Microencapsulated formulations may also be used, particularly for slow release over a period of time and for seed treatment.
  • the compositions may be in the form of liquid preparations to be used as dips, irrigation additives 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).
  • the compositions which are to be used in the form of aqueous dispersions or emulsions are generally supplied in the form of an emulsifiable concentrate (EC) or a suspension concentrate (SC) containing a high proportion of the active ingredient or ingredients.
  • EC emulsifiable concentrate
  • SC suspension concentrate
  • An EC is a homogeneous liquid composition, usually containing the active ingredient dissolved in a substantially non-volatile organic solvent.
  • An SC is a fine particle size dispersion of solid active ingredient in water. In use, the concentrates are diluted in water and applied by means of a spray to the area to be treated.
  • Suitable liquid solvents for ECs include methyl ketones, methyl isobutyl ketone, cyclohexanone, xylenes, toluene, chlorobenzene, paraffins, kerosene, white oil, alcohols, (for example, butanol), methylnaphthalene, trimethylbenzene, trichloroethylene, N-methyl-2-pyrrolidone and tetrahydrofurfuryl alcohol (THF A).
  • 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 cetyltrimethyl ammonium bromide.
  • 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 tri i sopropy lnaphthalene 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.
  • Other 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.
  • concentrates are often required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogeneous for a sufficient time to enable them to be applied by conventional spray equipment.
  • the concentrates may contain 10-85% by weight of the active ingredient or ingredients.
  • 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.
  • the compounds of formula (I) may also be formulated as powders (dry seed treatment DS or water dispersible powder WS) or liquids (flowable concentrate FS, liquid seed treatment LS, or microcapsule suspension CS) for use in seed treatments.
  • compositions are applied to the insect pests, to the locus of the pests, to the habitat of the pests, or to growing plants liable to infestation by the pests, by any of the known means of applying pesticidal compositions, for example, by dusting, spraying or incorporation of granules.
  • the compound of formula (I) may be the sole active ingredient of the composition or it may be admixed with one or more additional active ingredients such as insecticides, synergists, herbicides, fungicides or plant growth regulators where appropriate.
  • additional active ingredients for inclusion in admixture with a compound of formula (I) may be compounds which will broaden the spectrum of activity of the compositions of the invention or increase their persistence in the location of the pest.
  • suitable insecticides include the following: a) Pyrethroids such as permethrin, esfenvalerate, deltamethrin, cyhalothrin in particular lambda-cyhalothrin, biphenthrin, fenpropathrin, cyfluthrin, tefluthrin, fish safe pyrethroids for example ethofenprox, natural pyrethrin, tetramethrin, s-bioallethrin, fenfluthrin, prallethrin and 5-benzyl-3-furylmethyl-(E)-(lR,3S)-2,2-dimethyl-3-(2-oxothiolan- 3-ylidenemethyl) cyclopropane carboxy late; b) Organophosphates such as profenofos, sulprofos, methyl parathion, azinphos-methyl, demeton-s-methyl, hepten
  • 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 chlofentezine, flubenzimine, hexythiazox and tetradifon, motilicides such as dicofol or propargite, acaricides such as bromopropylate, chlorobenzilate, or growth regulators such as hydramethylron, cyromazine, methoprene, chlorofluazuron and diflubenzuron may also be included in the compositions.
  • ovo-larvicides such as chlofentezine, flubenzimine, hexythiazox and tetradifon
  • motilicides such as dicofol or propargite
  • acaricides such as bromopropylate, chlorobenzilate
  • growth regulators such as hydramethylron, cyromazine, methoprene, chlorofluazuron and diflubenz
  • synergists for use in the compositions include piperonyl butoxide, sesamax, safroxan 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.
  • 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 formula (I) to the other active ingredient in the composition will depend upon a number of factors including type of target, effect required from the mixture etc. However in general, the additional active ingredient of the composition will be applied at about the rate at which it is usually employed, or at a slightly lower rate if synergism occurs.
  • the invention is illustrated by the following Examples.
  • the following ingredients are referred to by their Registered Trade Marks and have the composition as shown below.
  • This Example illustrates the preparation of N-benzyl-3-cyano-cyclopentylamine.
  • Benzylamine (1.57g, 14.68mmol) was stirred in methanol (20ml) at room temperature and a solution of 3-cyanocyclopentanone (0.80g, 7.34mmol) in methanol (10ml) added dropwise. The solution was stirred for 80min and a solution of sodium cyanoborohydride (0.37g, 5.87mmol) in methanol (10ml) was added dropwise. Stirring was continued and after 18 hours the mixture was acidified to ⁇ pH2 by addition of concentrated hydrochloric acid before being concentrated under reduced pressure.
  • This Example illustrates the preparation of N-benzyl-N-t-butyloxycarbonyl-3- cyanocyclopentylamine.
  • N-Benzyl-3-cyanocyclopentylamine (1.6g, 8mmol) was stirred in dichloromethane (15ml) at room temperature and di-t-butyl dicarbonate (1.92g, 8.8mmol) in dichloromethane (10ml) added dropwise. After 3.5 hours the solvent was removed under reduced pressure leaving a brown oil (3.05g). The product was purified by filtration chromatography on silica using 5% then 10% ethyl acetate in hexane giving the product as a mixture of diastereoisomers (1.335g).
  • Lithium bis(trimethylsilyl)amide (4.58ml of a 1M solution in THF, 4.58mmol) was stirred under nitrogen and cooled to 5°C and N-benzyl-N-t-butyloxycarbonyl-3- cyanocyclopentylamine (550mg, 1.83mmol) in THF (5ml) added dropwise.
  • the reaction mixture was allowed to warm to 15°C and 3,5-dibromopyridine (477mg, 2.01mmol) in THF (5ml) added dropwise and the reaction mixture allowed to warm to room temperature.
  • the reaction mixture was stirred for 5 hours and allowed to stand overnight.
  • the mixture was carefully poured into water (20ml) and extracted with ethyl acetate (4x20ml).
  • N-Benzyl-N-t-butyloxycarbonyl-3-(5-bromopyrid-3-yl)-3-cyanocyclopentylamine 120mgs, 0.263mmol was stirred in dichloromethane (2ml) and trifluoroacetic acid (1ml) added dropwise. The solution was stirred at room temperature for 5h and the solvents removed under reduced pressure. The residue was treated with toluene (92ml) which was evaporated leaving a pale brown solid (134mg). The material was partitioned between dichloromethane (20ml) and saturated sodium bicarbonate (20ml). The organic layer was separated and the aqueous phase extracted with further dichloromethane (2x20ml).
  • N-Benzyl-3-(5-bromopyrid-3-yl)-3-cyanocyclopentylamine (24mg, 0.067mmol) was stirred in acetonitrile (2ml) at room temperature, 37% aqueous formaldehyde (0.06ml, 0.674mmol) added followed by sodium cyanoborohydride (8.5mg, 0.135mmol).
  • N,N-Dimethyl-3-cyanocyclopentylamine (0.52g, 3.77mmol) and 3,5- dibromopyridine (0.983g, 4.15mmol) were stirred together in dry THF (1 Oml) under nitrogen and cooled to 0°C.
  • Lithium bis(trimethylsilyl)amide (5.65ml of a 1M solution in THF, 5.65mmol) was added dropwise at a rate of 2.7ml per hour using a syringe pump. The reaction mixture was stirred for 30 minutes then further lithium bis(trimethylsilyl)amide (2.83ml, 2.83mmol) was added similarly.
  • Residual 3,5-dibromopyridine and N,N-dimethyl-3-cyanocyclopentylamine were partially removed at 100°C and 0.6mm of mercury (80Nm "2 ) and the product (brown oil, 0.96g) was further purified by filtration chromatography on silica using a gradient in dichloromethane of 1% to 3% of a 10% solution of aqueous ammonia in methanol giving a yellow gum (21 Omg).
  • Residual N,N-dimethyl-3-cyanocyclopentylamine was removed at 100°C and 0.3mm of mercury (40Nm "2 ) to give the product as a mixture of diastereoisomers (160mg).
  • the combined extracts were dried using potassium carbonate/magnesium sulphate and evaporated under reduced pressure leaving a brown semi-solid (81 Omg).
  • the product was purified by filtration chromatography on silica using a gradient elution of 5% to 15% ethyl acetate in hexane giving the desired product as a mixture of diastereoisomers (205mg).
  • N-Methyl-N-t-butyloxycarbonyl-3-(5-bromopyrid-3-yl)-3-cyanocyclopentylamine (185mg, 0.49mmol) was stirred in dichloromethane (3ml) and trifluoroacetic acid (1.9ml) was added dropwise. The solution was stirred at room temperature for 2 hours and then allowed to stand overnight. The solvents were removed under reduced pressure and the residue was partitioned between saturated sodium bicarbonate (15ml) and dichloromethane (15ml). The organic layer was separated and the aqueous phase extracted with further dichloromethane (2x15ml).
  • EXAMPLE 13 This Example illustrates the preparation of N-methyl-N-(2,2-difluoroethyl)-3-(5- bromopyrid-3-yl)-3-cyanocyclopentylamine (Compound No.18).
  • N-Methyl-3-(5-bromopyrid-3-yl)-3-cyanocyclopentylamine (lOOmg, 0.36mmol) and 2-bromo- 1 , 1 -difluoroethane (79mg, 0.54mmol) were stirred together in dimethylformamide (DMF) (3ml) at room temperature.
  • DMF dimethylformamide
  • Potassium carbonate 75mg, 0.54mmol
  • potassium iodide 15mg, 0.09mmol
  • reaction mixture was heated to 50°C, held at temperature overnight and then more 2-bromo- 1 ,1 -difluoroethane (522mg, 3.60mmol) in DMF (3ml) was added followed by potassium carbonate (75mg, 0.54mmol). After a further 3 days, the reaction mixture was allowed to cool and was then filtered to remove inorganics, washed through with DMF and concentrated under reduced pressure to give a yellow oil (31 Omg). The oil was purified by preparative thin layer chromatography on silica using a 10% solution in dichloromethane of a 10% solution of aqueous ammonia in methanol giving the desired product as a mixture of diastereoisomers (65mg).
  • EXAMPLE 14 This Example illustrates the preparation of N-mefhyl-N-(4-efhoxybenzyl)-3-(5- bromopyrid-3-yl)-3 -cyanocyclopentylamine (Compound No.24).
  • N-Methyl-3-(5-bromopyrid-3-yl)-3-cyanocyclopentylamine 160mg, 0.57mmol was stirred in methanol (2ml) at room temperature and 4-ethoxybenzaldehyde (171mg, 1.14mmol) in methanol (2ml) was added dropwise. After 90 minutes sodium cyanoborohydride (36mg, 0.57mmol) was added in one portion.
  • the organic extracts were combined, dried using potassium carbonate/magnesium sulphate and evaporated under reduced pressure leaving the product as a colourless oil (140mg).
  • the oil was purified by preparative thin layer chromatography on silica using a 10% solution in dichloromethane of a 10% solution of aqueous ammonia in methanol giving the desired product as a mixture of diastereoisomers (120mg).
  • NMR data is also provided for the intermediate N-allyl-N-t-butyloxycarbonyl-3- cyanocyclopentylamine, 'H NMR (CDC1 3 ): ⁇ 5.80(m,lH), 5.12(m,2H), 3J8(d,2H), 1.80- 4.50(m,8H), 1.47(s,9H)ppm.
  • This Example illustrates an emulsifiable concentrate composition which is readily convertible by dilution with water into a liquid preparation suitable for spraying purposes.
  • the concentrate has the following composition:
  • This Example illustrates a wettable powder composition which is readily convertible by dilution with water into a liquid preparation suitable for spraying purposes.
  • the wettable powder has the following composition:
  • This Example illustrates a dusting powder which may be applied directly to plants or • other surfaces and comprises 1% by weight of Compound No. 1 and 99% by weight of talc.
  • EXAMPLE 18 This Example illustrates a concentrated liquid formulation suitable for application by ultra low volume techniques after mixing with paraffinic diluents.
  • This Example illustrates a capsule suspension concentrate which is readily convertible by dilution with water to form a preparation suitable for application as an aqueous spray.
  • Alkylbenzene solvent for example AROMASOL H
  • Polysaccharide for example KELTROL
  • Nonylphenol ethoxylate for example Synperonic NP8
  • Nonylphenolethoxylate for example Synperonic NP8 1.5
  • Polysaccharide for example KELTROL
  • Bactericide for example Proxel; 0.1 Proxel is a registered Trade Mark
  • EXAMPLE 22 This Example illustrates a water dispersible granule formulation.
  • EXAMPLE 23 This Example illustrates the insecticidal properties of compounds of formula (I).
  • the activities of individual compounds of formula (I) were determined using a variety of pests.
  • the pests were treated with a liquid composition containing 500 parts per million (ppm) by weight of a compound unless otherwise stated.
  • Each composition was made by dissolving the compound in acetone and ethanol (50:50) mixture and diluting the solution with water containing 0.05% by weight of a wetting agent sold under the trade name "SYNPERONIC” NP8 until the liquid composition contained the required concentration of the compound.
  • SYNPERONIC is a Registered Trade Mark.
  • 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 a composition.
  • the mortality of the pests was then assessed at periods usually varying from two to five days after the treatment.
  • results of the tests against peach aphid are presented below.
  • the results indicate a grading of mortality (score) designated as A, B or C wherein C indicates less than 40% mortality, B indicates 40-79% mortality and A indicates 80-100% mortality.
  • Score grading of mortality
  • Chinese cabbage leaves were infested with aphids, the infested leaves were sprayed with the test composition, and the mortality assessed after 3 days.
  • Nos.9 and 88 each gave a mortality score of B.

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Abstract

L'invention concerne un composé de la formule (I) dans laquelle R1 est Ar-(CH¿2?)n-, n étant égal à 0 ou 1 et Ar étant un phényle éventuellement substitué ou un système hétérocyclique à 5 ou 6 chaînons éventuellement substitué contenant entre 1 et 3 hétéroatomes sélectionnés indépendamment dans le groupe constitué par des atomes d'azote, d'oxygène et de soufre, et au moins une insaturation (double liaison) entre des atomes adjacents dans le noyau. Dans ladite formule, les substituants, lorsqu'ils sont présents, sont sélectionnés dans les groupes constitués par des atomes d'halogène, alkyle, alcényle, alkynyle, alcoxy, haloalkyle, haloalcényle, haloalcoxy, alkylthio et alkylamino, lesdits groupes possédant jusqu'à six atomes de carbone; R?2 et R3¿ sont indépendamment hydrogène ou un groupe sélectionné dans les groupes constitués par alkyle, aryle, hétéroaryle, aralkyle, formyle, alkylcarbonyle, arylcarbonyle, hétéroarylalkyle, alcényle, aralcényle, alkynyle, alcoxycarbonyle, alcanesulfonyle, phénylsulfonyle, alcényloxycarbonyle, aralkyloxycarbonyle, aryloxycarbonyle, hétérocyclylalkyle, carbamyle ou dithiocarboxyle; les fractions alkyles de R2 et R3 comprennent entre 1 et 15 atomes de carbone et sont éventuellement substituées par un ou plusieurs substituants sélectionnés dans les groupes constitués par halogène, cyano, carboxyle, acyle carboxylique, formyle, carbamyle, alcoxycarbonyle, alcoxy, alkylènedioxy, hydroxy, nitro, amino, acylamino, imidate et phosphonato; les fractions aryle, hétéroaryle, aralkyle, hétéroarylalkyle, alcényle, aralcényle, alkynyle, alcoxycarbonyle, alcanesulfonyle, phénylsulfonyle, alcényloxycarbonyle, aralkyloxycarbonyle, aryloxycarbonyle, hétérocyclylalkyle, carbamyle et dithiocarboxyle de R2 et R3 sont éventuellement substituées par un ou plusieurs substituants sélectionnés dans les groupes constitués par halogène, cyano, carboxyl, acyle carboxylique, formyle, carbamyle, alcoxycarbonyle, alcoxy, alkylènedioxy, hydroxy, nitro, haloalkyle, alkyle, amino, acylamino, imidate et phosphonato; ou un sel d'addition acide, un sel d'ammonium quaternaire ou un N-oxyde dérivé dudit sel. L'invention concerne en outre des compositions contenant un composé de la formule (I) et une charge ou diluant solide, ainsi qu'un procédé permettant de lutter contre les insectes, acariens ou nématodes parasites au moyen d'un composé ou d'une composition tels que définis ci-dessus.
PCT/GB1998/000718 1997-04-01 1998-03-05 Cycloalcanes cyano substitues WO1998043957A1 (fr)

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EP98910859A EP0971893A1 (fr) 1997-04-01 1998-03-05 Cycloalcanes cyano substitues
AU65085/98A AU6508598A (en) 1997-04-01 1998-03-05 Cyano substituted cycloalkanes
KR1019997008885A KR20010005811A (ko) 1997-04-01 1998-03-05 시아노 치환된 싸이클로알칸
JP54126998A JP2002504092A (ja) 1997-04-01 1998-03-05 シアノ置換シクロアルカン類

Applications Claiming Priority (2)

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GB9706574.2 1997-04-01
GBGB9706574.2A GB9706574D0 (en) 1997-04-01 1997-04-01 Cyano substituted cycloalkanes

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GB (1) GB9706574D0 (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8273902B2 (en) 2005-03-28 2012-09-25 Toyama Chemical Co., Ltd. Process for production of 1-(3-(2-(1-benzothiophen-5-yl)-ethoxy)propyl)azetidin-3-ol or salts thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3759974A (en) * 1968-09-10 1973-09-18 Knoll Ag Substituted 4-cyano-4-phenyl-aminocyclohexanes
EP0035972A2 (fr) * 1980-03-10 1981-09-16 Ciba-Geigy Ag Cyanoalkyl-phényl urées possédant des propriétés herbicides sélectives, leur préparation et leurs compositions
WO1996037494A1 (fr) * 1995-05-24 1996-11-28 Zeneca Limited Amines biclycliques utilisees comme insecticide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3759974A (en) * 1968-09-10 1973-09-18 Knoll Ag Substituted 4-cyano-4-phenyl-aminocyclohexanes
EP0035972A2 (fr) * 1980-03-10 1981-09-16 Ciba-Geigy Ag Cyanoalkyl-phényl urées possédant des propriétés herbicides sélectives, leur préparation et leurs compositions
WO1996037494A1 (fr) * 1995-05-24 1996-11-28 Zeneca Limited Amines biclycliques utilisees comme insecticide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8273902B2 (en) 2005-03-28 2012-09-25 Toyama Chemical Co., Ltd. Process for production of 1-(3-(2-(1-benzothiophen-5-yl)-ethoxy)propyl)azetidin-3-ol or salts thereof

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EP0971893A1 (fr) 2000-01-19
AR012114A1 (es) 2000-09-27
AU6508598A (en) 1998-10-22
JP2002504092A (ja) 2002-02-05
GB9706574D0 (en) 1997-05-21
ZA982408B (en) 1998-10-01

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