WO1992013451A1 - Pesticides a base d'imidazole - Google Patents

Pesticides a base d'imidazole Download PDF

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Publication number
WO1992013451A1
WO1992013451A1 PCT/GB1992/000233 GB9200233W WO9213451A1 WO 1992013451 A1 WO1992013451 A1 WO 1992013451A1 GB 9200233 W GB9200233 W GB 9200233W WO 9213451 A1 WO9213451 A1 WO 9213451A1
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WO
WIPO (PCT)
Prior art keywords
compound
dichloro
formula
optionally substituted
trifluoromethylphenyl
Prior art date
Application number
PCT/GB1992/000233
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English (en)
Inventor
Robert John Willis
Mary Josephine O'mahony
Bryan Glyn Roberts
Ian David Marlow
Ian Kenneth Boddy
Original Assignee
Schering Agrochemicals Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB919102838A external-priority patent/GB9102838D0/en
Priority claimed from GB919102835A external-priority patent/GB9102835D0/en
Priority claimed from GB919102847A external-priority patent/GB9102847D0/en
Priority claimed from GB919102848A external-priority patent/GB9102848D0/en
Priority claimed from GB919102834A external-priority patent/GB9102834D0/en
Priority claimed from GB919102857A external-priority patent/GB9102857D0/en
Priority claimed from GB919102841A external-priority patent/GB9102841D0/en
Priority claimed from GB919114712A external-priority patent/GB9114712D0/en
Priority claimed from GB919117822A external-priority patent/GB9117822D0/en
Application filed by Schering Agrochemicals Limited filed Critical Schering Agrochemicals Limited
Publication of WO1992013451A1 publication Critical patent/WO1992013451A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • This invention relates to new imidazoles having pesticidal and especially insecticidal, acaricidal and animal endoparasiticidal activity.
  • the bulk of the compounds have a priority date earlier than the publication date of EP 412 849.
  • the ⁇ prior art disclosed..in that application is incorporated by reference.
  • Y is O, S or N 12.
  • w 4 is C or can also be S when Y is 0;
  • A is S(0) m , 0 or NR 13 ;
  • R 1 and R 2 are hydrogen, optionally substituted alkyl, cyano, halogen or nitro;
  • R 3 is hydrogen, optionally substituted alkyl, acyl, optionally substituted alkoxycarbonyl or sulfamoyl;
  • R 5 is hydrogen, halogen, optionally substituted alkyl, optionally substituted alkoxy, -NR 16 R 17 , cyano, nitro, S0 2 NR 16 R 17 , CYNR 16 R 17 , COOR 18 or R 19 S(0) m ;
  • R 4 and R 10 which may be the same or different, are hydrogen, halogen, hydroxy, mercapto, cyano, nitro, optionally substituted alkyl, optionally substituted alkoxy, -NR 16 R 17 , -S0 2 NR 16 R 17 , CHO, CH 2 OH, COOR 18 or
  • R _6° is substituted alkyl, hydroxy, alkoxy, haloalkoxy, cyano, nitro, R 19 S(0) m or an N-linked 5-membered heteroaryl group containing 1-4 nitrogen atoms; and when R 5 is cyano, -CYNR 16 R 17 , -COOR 18 , optionally substituted alkoxy, nitro, -NR 16 R 17 or _S0 2 NR 16 R 17 , R 6 . can also be hydrogen, halogen, alkyl or -NR 16 R 17 ; R 7 , R 8 and R 11 , which may be the same or different, are hydrogen, halogen, optionally substituted alkyl or optionally substituted alkylthio;
  • R 9 is hydrogen, halogen, optionally substituted alkyl, for yl, optionally substitutjed_alkoxy r aryl., cyano, nitro, hydroxy, trialkylsilyloxy, CYNR 16 R 17 , COOR 18 or R 19 S(0) m ;
  • R 12 is hydrogen, optionally substituted alkyl or acyl
  • R 13 is hydrogen, alkyl or acyl
  • R 16 and R 17 are the same or different and are hydrogen, optionally substituted alkyl, acyl or aryl, or together with the nitrogen to which they are attached, form a 5 to 7 membered ring which can contain other hetero atoms;
  • R 18 is hydrogen or optionally substituted alkyl
  • R 19 is optionally substituted alkyl
  • R 40 is hydrogen, optionally substituted alkyl or acyl
  • R 41 and R 42 which may be the same or different, are hydrogen or optionally substituted alkyl; and when V 1 is CR 9 and V 2 is CR 10 , R 9 and R 4 together with the carbon atoms to which they are attached can form a six membered ring; and when V 1 and V 2 are both N, R 4 can form a sulfur, nitrogen or carbon containing bridge to an ortho carbon atom on Ar; m is 0, 1 or 2; and p is 0 or 1, when Z is Z 1 or Z 2 and is 0 when Z is Z 3 , Z 4 or Z 5 .
  • Ar is preferably a substituted phenyl or pyridyl group. It is generally preferred that it is a 4-trifluoromethyl- phenyl or 5-trifluoromethyl-2-pyridyl, in which the phenyl or pyridyl is optionally further substituted, generally by halogen, especially chloro, nitro diT cyano. Other substituents include trifluoromethoxy, trifluoromethylthio or trifluoromethylsulfonyl.
  • a particularly preferred group of compounds are those where Ar is 2,6-dichloro- 4-trifluoro ethylphenyl, 2-nitro-4-trifluoromethylphenyl, 2-chloro-6-nitro-4-trifluoromethylphenyl or 2-chloro- 6-cyano-4-trifluoromethylphenyl.
  • Alkyl groups are preferably of 1 to 4 carbon atoms and may be substituted by one or more of the same or different groups such as halogen, hydroxy, alkoxy, alkylthio, dihalocyclopropyl, cyano, nitro, optionally substituted amino, optionally substituted imino, acyloxy and aryl.
  • aryl groups are usually phenyl, optionally substituted, e.g. by halogen, alkyl, haloalkyl, alkoxy or nitro.
  • aryl may include heteroaryl groups such as imidazolyl, thienyl, furyl or pyridyl.
  • acyl' includes the residue of sulfonic and phosphorus containing acids as well as carboxylic acids.
  • Acyl groups may be for example alkanoyl, e.g. of 1 to 4 carbon atoms, or alkylsulfonyl or haloalkylsulfonyl.
  • Optionally substituted amino groups are generally of formula NR 16 R 17 .
  • Imino groups may be substituted by groups such as hydroxy or alkoxy.
  • Heterocyclyl groups are generally 4 to 6 membered and can contain various hetero atoms, such as oxygen, nitrogen or sulfur.
  • R 16 and R 17 form a ring this is generally a morpholine or piperidine ring.
  • This ring can be fused to another ring and/or can be substituted, e.g. by one or more optionally substituted alkyl groups.
  • Other rings that R 16 and R 17 can form are optionally substituted 5-membered heteroaryl groups containing 1 to 4 nitrogen atoms, preferably pyrrole.
  • the compounds of the invention have insecticidal and acaricidal activity and are particularly useful in combating a variety of economically important insects, and acarids including animal ectoparasites, e.g. Lepidoptera, including Spodoptera littoralis, Heliothis armi ⁇ era, and Pieris brassicae; Diptera, including Musca domestica, Ceratitis*. ⁇ capitat , Erioischia bra-gsicae, Lucilia- sericata and Aedes aecrvpti; Homoptera, including aphids such as Me ⁇ oura viciae and Nilaparvata lu ⁇ ens; Coleoptera, including Phaedon cochleariae f Anthonomus grandis and corn rootworms fDiabrotica spp., eg.
  • animal ectoparasites e.g. Lepidoptera, including Spodoptera littoralis, Heliothis armi ⁇ era
  • Some compounds also have activity against plant parasitic nematodes, for example root-knot nematodes, such as Meloidocrvne spp. and cyst forming nematodes, such as Heterodera spp..
  • root-knot nematodes such as Meloidocrvne spp.
  • cyst forming nematodes such as Heterodera spp.
  • the compounds of the invention are also active against animal and human endoparasites and especially helminths, ie nematodes, trematodes and cestodes, especially Trichostron ⁇ loidea, e.g. Haemonchus contortus, Trichostroncrylus spp; Dictvocaulus spp; Ascaridoidea. e.g. Toxocara spp; Stron ⁇ ylus spp; and Filarioidea. e.g. Dirofilaria immitis.
  • the invention thus provides a method of combating pests, especially insects, acarids or animal endoparasites, at a locus or host for the pest, infested or liable to be infested therewith, which comprises applying to the locus, host and/or the pest, a"compound of formula I, as defined above.
  • the invention also provides a pesticidal composition which comprises a compound of the invention in admixture with an agriculturally or veterinarily acceptable diluent or carrier.
  • the invention also provides a pharmaceutical composition which comprises a compound of the invention in admixture with a pharmaceutically acceptable diluent or carrier.
  • More than one compound of the invention can, of course, be included in the compositions.
  • compositions can comprise one or more additional pesticides for example compounds known to possess herbicidal, fungicidal, insecticidal, acaricidal or nematicidal properties.
  • additional pesticides for example compounds known to possess herbicidal, fungicidal, insecticidal, acaricidal or nematicidal properties.
  • the compounds of the invention can be used in sequence with the other pesticides.
  • the diluent or carrier in the composition of the invention can be a solid or a liquid optionally in association with a surface-active agent, for example a dispersing agent, emulsifying agent or wetting agent.
  • Suitable surface-active agents include anionic compounds such as a carboxylate, for example a metal carboxylate of a long chain fatty acid; an N-acylsarcosinate; mono- or di-esters of phosphoric acid with fatty alcohol ethoxylates or salts of such esters; fatty alcohol sulfates such as sodium dodecyl sulfate, sodium octadecyl sulfate or sodium cetyl sulfate; ethoxylated fatty alcohol sulfates; ethoxylated alkylphenol sulfates; lignin sulfonates; petroleum sulfonates; alkyl-aryl sulfonates such as alkyl-benzene s
  • butyl-naphthalene sulfonate salts of sulfonated naphthalene-formaldehyde condensates; salts of sulfonated phenol-formaldehyde condensates; or more complex sulfonates such as the amide sulfonates, e.g. the sulfonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulfosuccinates, e.g. the sodium sulfonate of dioctyl succinate.
  • amide sulfonates e.g. the sulfonated condensation product of oleic acid and N-methyl taurine or the dialkyl sulfosuccinates, e.g. the sodium sulfonate of dioctyl succinate.
  • Nonionic agents include condensation products of fatty acid esters, fatty alcohols, fatty acid amides or fatty-alkyl- or alkenyl-substituted phenols with ethylene oxide, fatty esters of polyhydric alcohol ethers, e.g. sorbitan fatty acid esters, condensation products of such esters with ethylene oxide, e.g. polyoxyethylene sorbitan fatty acid esters, block copolymers of ethylene oxide and propylene oxide, acetylenic glycols such as 2,4,7,9-tetramethyl- 5-decyne-4,7-diol, or ethoxylated acetylenic glycols.
  • a cationic surface-active agent examples include, for instance, an aliphatic mono-, di-, or polyamine as an acetate, naphthenate or oleate; an oxygen-containing amine such a amine oxide or polyoxyethylene alkylamine; an amide-linked amine prepared by the condensation of a carboxylic acid with a di- or polyamine; or a quaternary ammonium salt.
  • compositions of the invention can take any form known in the art for the formulation of insecticidal or acaricidal compounds, for example, a solution, a dispersion, an aqueous emulsion, a dusting powder, a seed dressing, a fu igant, a smoke, a dispersible powder, an emulsifiable concentrate, granules or baits; and when being used as an animal or human parasiticide, can be in the form of a preparation, e.g. for oral, parenteral or dermal application, e.g.
  • the composition comprises a compound of the invention dispersed in a liquid medium, preferably water. It is often convenient to supply the consumer with a primary composition which can be diluted with water to form a dispersion having the desired concentration.
  • the primary composition can be provided in any one of the following forms. It can be a dispersible solution which comprises a compound of the invention dissolved in a water-miscible solvent with the addition of a dispersing agent.
  • a further alternative comprises a compound of the invention in the form of a finely ground powder in association with a dispersing agent and intimately mixed with water to give a paste or cream which can if desired be added to an emulsion of oil in water to give a dispersion of active ingredient in an aqueous oil emulsion.
  • An emulsifiable concentrate comprises a compound of the invention dissolved in a water-immiscible solvent together with an emulsifying agent and which is formed into an emulsion on mixing with water.
  • a dusting powder comprises a compound of the invention intimately mixed with a solid pulverulent diluent, for example, kaolin.
  • a granular solid comprises a compound of the invention associated with similar diluents to those which may be employed in dusting powders, but the mixture is granulated by known methods. Alternatively it comprises the active ingredient adsorbed or absorbed on a pre-granular diluent, for example. Fuller's earth, attapulgite or limestone grit.
  • a wettable powder usually comprises the active ingredient in admixture with a suitable surfactant and an inert powder diluent such as china clay.
  • Another suitable concentrate particularly when the product is a solid, is a flowable suspension concentrate which is formed by grinding the compound with water, a wetting agent and a suspending agent.
  • Baits can include an attractant and may comprise a protein hydrolysate e.g. for the control of fruit flies, sugar e.g. for the control of adult Musca spp. or corn cob e.g. for the control of cockroaches.
  • concentration of the active ingredient in the composition of the present invention is preferably within the range of 1 to 30 per cent by weight, especially 5 to 30 per cent by weight.
  • the amount of active ingredient can vary widely and can be, for example, from 5 to 95 per cent by weight of the composition.
  • the compounds of the invention may be prepared by a variety of methods known in the art.
  • Suitable reagents for ring closure include N-chlorosuccinimide and
  • the compound of formula II can be prepared by reacting a compound of formula III
  • Z-R 23 (IV) where R 23 is cyano or an alkoxycarbonyl group can be reduced, e.g. using diisobutylaluminiu hydride in an inert solvent at very low temperature.
  • a compound of formula IV where R 23 is an alkoxycarbonyl group may be reduced by methods known in the art, e.g. using lithium aluminium hydride, diisobutylaluminium hydride or zirconium borohydride (prepared in situ from zirconium tetrachloride and sodium borohydride) in an inert solvent, such as tetrahydrofuran, to give a compound of formula IV, where R 23 is hydroxymethyl.
  • This can be oxidised to give the compound of formula III, e.g. using pyridinium dichromate or manganese dioxide.
  • a compound of formula IV where R 23 is halomethyl may also be reacted with trimethylamine-N-oxide in dimethyl sulfoxide to give a compound of formula III.
  • a compound of formula III can also be prepared by cleavage of the compound of formula IV, where R 23 ia an optionally substituted carbon-carbon double bond, e.g. using ozone.
  • the compound of formula IV where R 23 is hydroxymethyl can also be prepared by reduction of a carboxylic acid of formula IV where R 23 is carboxyl, by known methods.
  • the compound of formula III can also be prepared by formylation, e.g. where Z is Z 2 , by reacting a compound of formula V
  • a compound of formula V may be prepared in known manner by reaction of the diazonium salt of an arylamine, ArNH 2 ⁇ with a compound of formula VI R 5 CH(COMe)-CH 2 COOalkyl (VI)
  • a compound of formula III where Z is Z 2 and R 5 is nitro may be prepared by reaction of an aryl diazonium salt ArN 2 + with diethyl nitrosuccinate in the presence of sodium acetate, followed by cyclisation, for example, with sodium ethoxide. Diethyl nitrosuccinate may be prepared by oxidation of a compound
  • This compound may be prepared by reaction of diethyl succinate with hydroxylamine hydrochloride in the presence of acid or base.
  • a compound of formula IV, where R 23 is alkoxycarbonyl, Z is Z 2 , R 5 is S0 2 C1 and R 6 is amino, may be obtained from the corresponding compound where R 5 is optionally substituted benzylthio, by known methods, e.g. by oxidation with chlorine in acetic acid, with optional protection of the amino group. This compound may then be reacted with a compound HNR 16 R 17 to give a compound where R 5 is S0 2 NR 16 R 17 .
  • R 5 is optionally substituted benzylthio and R 6 is amino
  • R 5 is optionally substituted benzylthio and R 6 is amino
  • R J CN where R 5 is optionally substituted benzylthio and R 24 is optionally substituted alkyl.
  • Ar where R 5 is optionally substituted benzylthio and R 23 is cyano may be similarly prepared by reaction of an arylhydrazine ArNHNH 2 with a compound of formula
  • R 5 where R 5 is optionally substituted benzylthio.
  • a compound of formula VII, in which R 23 is alkoxycarbonyl and R 6 is an N-linked 5-membered heterocycle group containing 1-4 nitrogen atoms may be prepared from a compound of formula VIII by known methods. For example to obtain the compound, where R 6 is pyrrole, the compound of formula VIII can be reacted with 2,5-dimethoxytetrahydro- furan.
  • a compound of formula VII, in which R 6 is halogen, hydrogen, cyano, hydroxy or R 19 S, may be prepared from the compound of formula VIII by known methods, e.g. diazotisation.
  • a compound of formula VII, in which R 6 is hydroxy may subsequently be modified in known manner, e.g. by alkylation with an alkyl halide or dialkyl sulfate.
  • a compound of formula VII, in which R 6 is R 19 S(0) m , where m is 0, may be oxidised in known manner, e.g. using hydrogen peroxide or a per-acid such as m-chloroperbenzoic acid, to give compounds where m is 1 or 2.
  • a compound of formula VIII, in which R 5 is optionally substituted alkoxy may be prepared by reaction of an arylhydrazine, ArNHNH 2 with diethyl cyanomalonate to give a compound of formula VIII, in which R 5 is hydroxy, followed by treatment with an appropriate alkylating agent in the presence of a base.
  • a compound of formula VII, in which R 5 is R 19 S(0) m , where m is 0 and R 19 is optionally substituted alkyl, may be prepared from the corresponding compound where R 5 is SH, e.g. by alkylation with an alkyl halide, ' in the presence of a, base.
  • a compound of formula VII, where R 5 is SH, may be obtained from the corresponding compound where R 5 is optionally substituted benzyl, in known manner.
  • a compound of formula IX may be prepared in known manner from the corresponding compound where R 25 is hydrogen.
  • a compound of formula VII, where R 6 is nitro, may be obtained by nitration of the corresponding compound where R 6 is hydrogen.
  • a compound of formula VII, where R 6 is hydrogen, may be obtained by reaction of a compound of formula IX, where R 25 is halogen, with a compound of formula HCsC-COOR 24 where R 24 is optionally substituted alkyl, in the presence of a base.
  • a compound of formula VIII may be modified by reaction with a suitable alkyl or acyl halide in the presence of a base to give compound of formula VII, where R 6 is NR 16 R 17 .
  • R 3 where R 26 is halogen, preferably chlorine, is reacted a) with a compound of formula XI
  • R 4 -CH CH-R 27 (XI) where R 4 is hydrogen, nitro or optionally substituted alkyl and R 27 is a leaving group, such as alkoxy or substituted amino, e.g. morpholino, to give a compound of formula I, where p is 0, Z is Z 1 , V 1 is CR 9 and V 2 is N, where R 9 is hydrogen and R 4 is hydrogen, nitro or optionally substituted alkyl, or b) with a compound of formula XII
  • R 4 is amino
  • the amino group may be modified in known manner to give other desired values for R 4 .
  • a compound of formula I in which R 3 is H may be further modified in known manner, e.g. by alkylation to give other R 3 groups.
  • the reagent for ring closure and halogenation is preferably the same compound e.g. an N-halosuccinimide.
  • the compound of formula XIII can be obtained by reacting a compound of formula XIV
  • the compound of formula XIV can be obtained by reacting a phenylhydrazine, ArNHNH 2 with glyoxal.
  • a compound of formula IV in which R 23 is cyano, Z is Z 1 , V 1 is CR 9 and V 2 is N, where R 9 is R 19 S(0)m, halogen, nitro, formyl, haloalkyl and R 4 is NH 2 may be prepared from compound of formula XV
  • a compound of formula XV in which R 28 is cyano, R 9 is H and R 4 is NH 2 may be prepared in known manner, e.g. as described in EP 295117.
  • a compound of formula XV where R 28 is alkoxycarbonyl, R 9 is H and R 4 is alkoxy or haloalkoxy may be formed from a compound of formula XV, where R 28 is alkoxycarbonyl, R 9 is H and R 4 is hydroxy, by alkylation in the presence of a base.
  • a compound of formula XV where R 28 is alkoxycarbonyl, R 9 is formyl and R 4 is halogen e.g. chloro may be prepared by reaction of a compound of formula XV where R 28 is alkoxycarbonyl, R 9 is H and R 4 is hydroxy by reaction with dimethylformamide and phosphorous oxychloride.
  • the formyl group may be optionally protected or modified in known manner.
  • a compound of formula XV where R 28 is alkoxycarbonyl, R 9 is hydrogen and R 4 is hydroxy may be prepared in known manner e.g. as described in EP 385 809.
  • R 24 is an ester forming group such as alkyl, e.g. ethyl, using general methods indicated above.
  • the compound of formula XVI can be obtained by ring closing a compound of formula XVII NH,
  • Ar-NH-N C-COOR 24 (XVII) using an appropriate carbony1 compound depending on the desired value of R 4 .
  • R 4 is hydrogen
  • a suitable reagent is an orthoformate ester, e.g. the triethyl ester
  • R 4 is an optionally substituted alkyl or phenyl
  • the corresponding alkanoyl or benzoyl chloride can be used.
  • Compounds of formula XVI, where R 4 is OH can be obtained using phosgene as the ring closing reagent. This group can then be modified in known manner, for example by reaction with phosphorus oxychloride to give a compound where R 4 is chlorine.
  • the compound of formula XVII can be obtained by reacting a compound of formula XVIII with ammonia Br
  • the compound of formula XVI, where R 4 is hydroxy can be obtained by reaction of a compound of formula XVIII with a cyanafe"salt, s c ' as potassium cyariate.
  • the compound of formula XVI, where R 4 is alkylthio can be obtained by reaction of a compound of formula XVI where R 4 is halogen with a compound of formula, R 19 SH in the presence of a base.
  • the alkylthio group can then be oxidised using a suitable oxidising agent, e.g. hydrogen peroxide or m-chloroperbenzoic acid.
  • the compound of formula XVI, where R 4 is nitro can be obtained by nitration of a compound of formula XVI where R 4 is hydrogen.
  • the compound of formula XVI, where R 4 is cyano can be obtained by reaction of a compound of formula XVI where R 4 is trichloromethyl with aqueous ammonia.
  • R 4 is trichloromethyl
  • This group can then in turn be modified in known manner as will be apparent to those skilled in the art.
  • the compound of formula XVIII can be obtained by bro ination of a compound of formula XIX, usually in the presence of an acetate salt
  • Ac Ar-NH-N C-C00R 24 (XIX) where Ac is an alkanoyl group, usually acetyl.
  • the compound of formula XIX can be obtained by diazotisation of a compound
  • the compound of formula XX may be prepared by reaction of a compound of formula XXI (XXI)
  • Ar 1 (which is equivalent to compound XVI) , where Ar 1 and R 29 have the meaning given in formula XXIII can be cyclised in a similar manner and then treated as described for formula XVI.
  • the compound of formula X, where R 26 is amino is novel and forms one aspect of the invention and may be obtained by reacting a compound of formula X, where R 26 is halogen, with ammonia.
  • R 32 is a leaving group, such as halogen, especially fluorine.
  • R 3 may be for example a protecting group, e.g. one of those described in "Protective Groups in Organic Synthesis” by T W Greene, published by John Wiley & Sons.
  • a compound of formula XXV may be prepared by a variety of methods known in the art for synthesis of imidazole rings such as those described in Comprehensive Heterocyclic Chemistry, Volume 5, ed. Katritzky and Rees, Chapter 4.08, pp 457, Pergamon 1984.
  • R 4 or R 10 is NH 2
  • the amino group may be modified in known manner, for example by diazotisation, to give other desired values for R 4 or R 10 , such as halogen, cyano or alkylthio or by reaction with e.g. 2 ,5-dimethoxytetrahydrofuran to give compounds where R 4 or R 10 is pyrrole.
  • a compound of formula III, where Z is Z 1 , V 1 is N and V 2 is CR 10 , in which R 10 is amino, may also be prepared by formylation of a compound of formula XXVI
  • R 4 is hydrogen, optionally substituted alkyl or halogen, e.g. with dimethylformamide and phosphorous oxychloride.
  • a compound_of formula XXVI in which R 4 -is-hydrogen, may be obtained by cyclising a compound of formula XXVII
  • the compound of formula XXVII may be prepared by reacting a compound of formula XXVIII
  • Ar-N CH-OR 35 (XXVIII) in which R 35 is alkyl, with a compound of formula NH 2 CH 2 CN.
  • a compound of formula XXVIII may be prepared by reaction of ArNH 2 With HC(OR 35 ) 3 .
  • a compound of formula XXVI in which R 4 is optionally substituted alkyl or halogen may be prepared from a compound of formula XXVII in which R 34 is cyano and R 33 is optionally substituted alkyl or halogen.
  • a compound of formula XXVII, in which R 34 is cyano and R 33 is optionally substituted alkyl or halogen may be prepared by reacting a compound of formula XXIX
  • a compound of formula XXIX may be- repared-in known manner.
  • Other useful intermediates are compounds of formula XXX
  • a compound of formula III where Z is Z 1 , V 1 is CR 9 and V 2 is CR 10 may also be prepared by formylation of a compound of formula XXXI
  • R 37 is hydrogen, e.g. with dimethylformamide and phosphorous oxychloride.
  • a compound of formula XXXI in which R 37 is hydrogen, cyano, alkoxycarbonyl or an optionally protected formyl group, may be prepared by reaction of a compound of formula XXXII
  • R 37 is hydrogen, cyano, alkoxycarbonyl or a protected formyl group, with a compound of formula Ar-R 32 , where R 32 is a leaving group, such as halogen, especially chlorine or fluorine.
  • a compound of formula XXXII may be prepared by a variety of methods known in the art for synthesis of pyrrole rings such as those described in Comprehensive Heterocyclic Chemistry Volume 4, ed. Katritzky and Rees, Chapter 3.06, pp 313, Pergamon 1984.
  • a compound of formula XXXI in which R 4 and R 10 are optionally substituted alkyl can also be prepared by reaction of a compound of formula XXXIII
  • a compound of formula III in which Z is Z 1 , V 1 is CR 9 and V 2 is CR 10 , where R 9 is cyano, R 4 is hydrogen and R 10 is amino may be prepared by hydrolysing a compound of formula XXXIV NC_ R 38 S j (XXXIV) ⁇
  • R 38 is a bis(alkylthio)methyl or bis(arylthio)- methyl group.
  • a compound of formula XXXIV may be prepared from a compound of formula XXXIV in which R 38 is hydrogen, by reaction with a tris(alkylthio)methane or tris(arylthio)- methane in the presence of a Lewis acid, e.g. dimethyl( ethylthio) sulfonium tetrafluoroborate.
  • a Lewis acid e.g. dimethyl( ethylthio) sulfonium tetrafluoroborate.
  • a ⁇ ompound-of formula XXXIV'in which R 38 is hydrogen, may be prepared by reaction of formylsuccinonitrile or its alkali metal salt with Ar-NH 2 .
  • a compound of formula XXXI in which R 9 is a formyl group, R 4 is an amino group, R 10 is hydrogen and R 37 is a cyano group may be transformed using methods for conversion of formyl groups known to those skilled in the art.
  • the formyl group may be converted to a difluoromethyl group using diethylaminosulfur trifluoride.
  • a compound of formula XXXI in which R 9 is R 19 S, R 4 is amino, R 10 is hydrogen and R 37 is cyano may be prepared by reacting the corresponding compound in which R 9 is hydrogen with a sulfenyl halide of formula R 19 S-Hal (where Hal represents halogen) in the presence of an acid acceptor, e.g. a tertiary amine.
  • a compound of formula XXXI in which R 4 is amino, R 10 is hydrogen and R 37 is cyano may be halogenated to the corresponding compound in which R 10 is halogen or sulfenylated using a sulfenyl halide of formula R 19 S-Hal to the corresponding compound in which R 10 is R 19 S.
  • a compound in which R 9 , R 4 or R 10 represents a group of formula R 19 S0 or R 19 S0 2 may be prepared by oxidising the corresponding compound in which R 9 , R 4 or R 10 represents R 19 S, using, for example a per-acid.
  • Z' is the heterocyclic radical Z, in which the Ar is replaced by H, with a compound Ar-R 32 , where R 32 is a leaving group, such as halogen, e.g. fluorine or chlorine, in the presence of a base.
  • R 3 may be a protecting group such as those described in "Protective Groups in Organic Chemistry” by T W Greene, published by John Wiley and Sons.
  • Other methods for preparing the compound of formula XXXV will be readily apparent those skilled in the art.
  • a compound of formula I where p is 0, Z is Z 5 , Y is NR 12 and R 12 is hydrogen, may be prepared from a compound of formula X, where R 26 is halogen, preferably chlorine, by reaction with a metal thiocyanate, preferably sodium, thiocyanate, in the presence of a base, e.g. triethylamine.
  • R 26 is halogen, preferably chlorine
  • a metal thiocyanate preferably sodium, thiocyanate
  • This compound may be further derivatised, e.g. by alkylation or acylation, to give other values of R 12 .
  • a compound of formula I where p is 0, Z is Z 5 and Y is 0, W 3 is S and W 4 is C, may be prepared by heating a compound of formula XXXVI
  • the compound of formula XXXVI may be prepared by diazotising a compound of formula I where p is 0, Z is Z , Y is NH, W 3 is S and W 4 is C, e.g. by reaction with a nitrite, e.g. sodium nitrite, in acetic acid.
  • a nitrite e.g. sodium nitrite
  • a compound of formula III where Z is Z 5 and ⁇ is O, W 4 is C and W 3 is NR 40 , can be prepared for example by reduction of a compound of formula XXXVII (XXXVII )
  • R 24 is an ester forming group such as alkyl, e.g. ethyl, using general methods indicated above.
  • the compound of formula XXXVII can be obtained by reaction of the compound of XVIII with potassium cyanate, followed by alkylation or by reaction with a substituted isocyanate of formula R ⁇ NCO.
  • R 24 is an ester forming group such as alkyl, e.g. ethyl, R 41 is methyl and R 42 is hydrogen, using general methods indicated above.
  • the compound of formula XXXIX can be obtained by reaction of the compound of formula XIX with triethyl phosphonoacetate and sodium hydride in tetrahydrofuran.
  • a compound of formula III in which p is 0, Z is Z 5 and Y is 0, W 4 is S and W 3 is NH, can be prepared for example by reduction of a compound of formula XXXX (XXXX)
  • R 24 is an ester forming group such as alkyl, e.g. ethyl, using general methods indicated above.
  • the compound of formula XXXX can be obtained by reaction of the compound of XVII with thionyl chloride.
  • the compound of " formula XXXXI may be prepared from a compound of formula IV, where R 23 is cyano by reaction with e.g. gaseous hydrogen chloride in ethanol.
  • the compound of formula IV is known or may be prepared in known manner.
  • a compound of formula I, where R 2 and R 3 are hydrogen, may be obtained by reaction of a compound of formula III, with a compound of formula R l _ C0 -.cHBr 2 and ammonia.
  • R 1 and/or R 2 are hydrogen may be modified by known methods such as e.g. electrophilic substitution reactions to give compounds of formula I where R 1 and/or R 2 are e.g. halogen, nitro etc. These groups may be modified by methods known to those skilled in the art to give other R 1 and R 2 groups. In some cases it may be necessary to have a suitable protecting group at R 3 , which can subsequently be removed, in known manner.
  • R 1 is e.g. trifluoromethyl
  • this may be further reacted with ammonia to give a compound of formula I, where R 1 is cyano.
  • R 1 is e.g. cyano or trifluoromethyl and R 2 is hydrogen
  • the compound may be reacted with a brominating agent, e.g. N-bromosuccinimide, to give a compound of formula I, where R 2 is bromo.
  • a brominating agent e.g. N-bromosuccinimide
  • a compound of formula I in which R 3 is H may be further modified in known manner, e.g. by alkylation to give other R 3 groups.
  • a compound of formula I in which p is 1 may be obtained by reaction of a compound of formula XXXXIII
  • R 39 is a leaving group, such as a halogen, under basic conditions.
  • a compound of formula XXXXIV may be formed from a compound of formula XXXXV
  • the group R 3 is a protecting group, e.g. containing silicon
  • the resulting compound of formula I may be optionally further modified in known manner, e.g. by hydrolysis or reaction with a source of fluoride ion to give compounds of formula I in which R 3 is H.
  • this group can be oxidised using a suitable oxidising agent, e.g. m-chloroperbenzoic acid.
  • a suitable oxidising agent e.g. m-chloroperbenzoic acid.
  • the compounds of formula I in which R 3 is hydrogen may form pesticidally and pharmaceutically acceptable salts with organic or inorganic bases, especially where R 1 and/or R 2 are electron withdrawing groups. These salts also form part of the invention.
  • Pesticidally acceptable salts means salts, the cations of which are known and accepted in the art as being suitable for the formation of salts of pesticidally active acids for use in agriculture or horticulture.
  • pharmaceutically acceptable salts means salts, the cations of which are known and accepted in the art as being suitable for the formation of salts of biologically active acids for use in veterinary or human medicine.
  • the salt is an alkali metal, alkaline earth metal, quaternary ammonium or an amine salt.
  • Amine salts include salts derived from primary, secondary and tertiary amines, including amino sugars, such as N-methylglucamine. Salts may be prepared by reacting the compound of the invention, in known manner, with a suitable base.
  • substituents on the various Z groups in a compound of formula I or its precursors may be modified in known manner to give other desired substituents.
  • compounds containing an alkoxycarbonyl group may be reduced, e.g. with diisobutylaluminium hydride at low temperature to give to give the corresponding carboxaldehyde.
  • they may be reduced by methods known in the art, e.g.
  • Example 1 A solution of 3-[(2-amino-l,2-dicyanoethenylimino)methyl]- 1-(2 ,6-dichloro-4-trifluoromethylphenyl)-2 ,5-dimethyl- pyrrole, (0.53 g) and 2,3-dichloro-5,6-dicyano- 1,4-benzoquinone (0.28 g) in dioxane was heated under reflux for 6 hours. The mixture was poured into water and extracted with ethyl acetate.
  • 2,5-Dimethylpyrrole (2.29 ml) was stirred with sodium hydride (0.54 g of 60% dispersion in oil) for half an hour.
  • l,3-Dichloro-2-fluoro-5-trifluoromethylbenzene (5 g) was added and the mixture heated under reflux for 2 hours.
  • the mixture was poured into water and extracted with ethyl acetate.
  • the extract was washed with water, dried and evaporated and the oil purified by silica gel chromatography to give 1-(2,6-dichloro-4-trifluoro ⁇ methylphenyl)-2 ,5-dimethylpyrrole, as an oil.
  • This compound (5.72 g) was added to a preformed mixture of phosphorus oxychloride (71.6 ml) and dimethylformamide (1.35 ml) . The resulting mixture was then heated under reflux overnight and excess phosphorus oxychloride removed under reduced pressure. Ice was added to the residue and the mixture extracted with dichloro- methane. The extract was worked up to give an oil which was passed through a silica gel column using ether as eluent and the fraction having an R f value of 0.83 was collected, which was shown by nmr to be 5-chloro- 1-(2,6-dichloro-4-trifluoromethylphenyl)-3-ethoxy- carbonyl-4-formyl-lH-pyrazole.
  • Ethyl 1-(2,6-dichloro-4-trifluoromethylphenyl)-4-hydroxy- lH-pyrazole-3-carboxylate was brominated with N-bromosuccinimide in chloroform to give ethyl 5-bromo- 1-(2,6-dichloro-4-trifluoromethylphenyl)-4-hydroxy- lH-pyrazole-3-carboxylate, m.p. 139-140°.
  • Lithium borohydride (4.3 g) was added to a solution of this product (35 g) in dry tetrahydrofuran (700 ml) . The mixture was stirred for % hour at room temperature, and then heated under reflux for 2 hours. It was poured into ice/hydrochloric acid and extracted with ethyl acetate. The extract was dried and evaporated and the residue worked up to give 1-(2,6-dichloro-4-trifluoromethyl ⁇ phenyl)-4,5-dihydro-3-hydroxymethyl-5-oxo- lH-l,2,4-triazole, m.p. 231-2°.
  • Ethyl 1-(2,6-dichloro-4-trifluoromethylphenyl)-4-hydroxy- lH-pyrazole-3-carboxylate was methylated using methyl iodide/sodium hydride in tetrahydrofuran to give ethyl 1-(2,6-dichloro-4-trifluoromethylphenyl)-4-methoxy- lH-pyrazole-3-carboxylate, m.p. 148-151°.
  • Chlorodifluoromethane was bubbled through a mixture of ethyl 1-(2,6-dichloro-4-trifluoromethylphenyl)-4-hydroxy- lH-pyrazole-3-carboxylate (10 g) and aqueous sodium hydroxide (100 ml of 2M) and dioxane (100 ml) . Solvent was evaporated, the residue acidified and the solid collected and dried to give l-(2,6-dichloro-4-trifluoromethyl- phenyl)-4-difluoromethoxy-lH-pyrazole-3-carboxylic acid, m.p. 177-8°.
  • Example 2 l,l-Dibromo-3,3,3-trifluoroacetone (7 g) was added to a solution of sodium acetate trihydrate (7 g) in water (25 ml) and the resulting solution heated on a steam bath for 30 mins. The mixture was cooled to room temperature and added slowly to a solution of l-(2,6-dichloro- 4-trifluoromethylphenyl)-1H-1,2,4-triazole- 3-carboxaldehyde (6.8 g) and aqueous ammonia (30 ml) in methanol (60 ml) . The suspension was stirred for 3 hours, reduced in volume and water added.
  • Example 8 A mixture of vinyl butyl ether (1.13 ml) and triethylamine (1.21 ml) in toluene (2 ml) was added dropwise to a stirred suspension of 2-[ (chloro) (2,6-dichl ro- ... , 4-trifluoromethylphenylhydrazono)methyl]-4 ,5-dicyano- 1H-imidazole (1.75 g) in toluene (3 ml) at 90°. The mixture was heated at this temperature for 3 hours, cooled and filtered. 2N Hydrochloric acid was added and the mixture extracted with ethyl acetate.
  • Example 11 A mixture of compound 10a (2.01 g) and thionyl chloride (40 ml) was heated under reflux for 2 hours. Excess thionyl chloride was evaporated and the residue dissolved in tetrahydrofuran (20 ml) and added to aqueous ammonia (40 ml) . The mixture was stirred at room temperature for 15 minutes and water (200 ml) was added.
  • Example 15 Compound lg was reduced with lithium borohydride in a manner similar to that described in the preparation of the starting material for compound is, to give 5-chloro- 1-(2,6-dichloro-4-trifluoromethylphenyl)-4-(4,5-dicyano- lH-imidazol-2-yl)-3-hydroxymethyl-lH-pyrazole, m.p. 186-8°. (Compound 15a) .
  • Trifluoroacetic anhydride (0.08 g) was added to a solution of Compound 17a (0.16 g) and pyridine (0.11 g) in dioxane (5 ml) . with ice-cooling. The mixture was stirred at room temperature overnight, and then heated under reflux for 4 hours. It was diluted with 2M hydrochloric acid, extracted with ether and the extract worked up to give 5-chloro- 3-cyano-l-(2,6-dichloro-4-trifluoromethylphenyl)- 4-(4,5-dicyano-lH-imidazol-2-yl)-lH-pyrazole, m.p. 119-123°. (Compound 18a).
  • Triethylamine (1.4 g) was added dropwise to a stirred mixture of 2-[ (chloro) (2,6-dichloro-4-trifluoromethyl- phenylhydrazono)methyl]-4,5-dicyano-lH-imidazole (5.5 g) , fumaronitrile (2.1 g) , chloroform (100 ml) and silver acetate (2.5 g) .
  • the mixture was heated under reflux 5 hours and then subjected to flash column chromatography to give 1-(2,6-dichloro-4-trifluoromethylphenyl)-4-cyano- 3-(4,5-dicyano-lH-imidazol-2-yl)-lH-pyrazole, m.p. 308-9° (Compound 21a) .
  • Example 22 tert-Butyl nitrite (3 ml) was added dropwise to a mixture of compound 7c (3 g) and copper (II) chloride (2 g) in acetonitrile (100 ml) . The mixture was stirred overnight at room temperature, poured into dilute hydrochloric acid and extracted with ethyl acetate. The extract was dried and evaporated and the residue worked up to give 5-chloro- 1-(2,6-dichloro-4-trifluoromethylphenyl)-4-cyano- 3-(4,5-dicyano-lH " -imidazol-2-yl)-lH-pyrazole, m.p. >300° (dec) (Compound 22a).
  • Compounds are assessed for activity against one or more of the following:
  • Lucilia sericata (sheep blow fly) a) contact test (LS) b) systemic test (LSS) Boophilus icroplus (blue tick) a) injection test (BMI) Musca domestica (house fly) a) contact test (MD)
  • Blattella germanica cockroach
  • BG contact test
  • BGB bait test
  • Helminths a) Trichostrongylus colubriformis (TC) b) Heligmosomoides polygyrus (HP)
  • test compound 100 mg are dissolved in 0.2 ml dimethyl sulfoxide and diluted with corn oil to the desired concentration. Approx 0.25 ml doses are fed to male mice, using 5 mice for each dose. 4 hours after treatment the mice are killed with carbon dioxide and the upper parts of hind legs removed and skinned. These are placed individually into sample tubes which are infested with first instar larvae of sheep blow fly (Lucilia sericata) , closed by a cotton wool plug and held at 25° for 24 hours. The activity is then assessed in comparison to controls. Compounds are considered active if the LC 50 is less than 100 mg/kg of mouse.
  • Test compounds are dissolved in a suitable solvent to a desired concentration.
  • a microapplicator 2 microlitres of the solution are injected into the blood filled stomach of a tick (Boophilus microplus.. 5 replicate ticks are treated at each concentration and subsequently each tick is retained separately in partitioned petri dish held at 25°C and >80% R.H. , until mortality of ticks or fecundity and viability of eggs produced by survivors can be assessed.
  • the percentage reduction in total reproductive capacity i.e. the combined effects of adult mortality, reduced fecundity and mortality of eggs is then recorded and compared with controls.
  • Compounds are considered active if they result in at least 50% reduction of reproductive capacity at a concentration of 20 microgram/tick or less.
  • Trichostrongylus colubriformis adults worms of the parasitic nematode Trichostrongylus colubriformis are cultured in multi-well plates containing sterile culture medium and test compound at a concentration of 100 ppm. The cultures are maintained in a sterile carbon dioxide incubator at 37°, at a constant air/carbon dioxide ratio of 95:5 (v/v). After 5 days the mortality is assessed in comparison with controls. Compounds are considered active if the LC 50 is less than 100 ppm.
  • mice Groups of five mice are infected orally with 100 infective stage larvae (L3) of the murine gastrointestinal nematode Heligmosomoides polygyrus. After six days the mice are orally dosed with 50 ⁇ l of the test compound at the desired concentration in a carrier solution containing 1% wetter and 0.05% ethyl cellulose. A control group receives carrier only. After 7 days the mice are killed and the small intestine examined for worm count. Compounds are considered active if they give >50% worm reduction compared with the controls at a rate of 100 mg/kg mouse body weight.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Composés de la formule (I) pouvant être utilisés pour lutter contre des organismes nuisibles, en particulier des insectes, des acariens et des endoparasites d'animaux.
PCT/GB1992/000233 1991-02-11 1992-02-10 Pesticides a base d'imidazole WO1992013451A1 (fr)

Applications Claiming Priority (18)

Application Number Priority Date Filing Date Title
GB9102838.1 1991-02-11
GB919102838A GB9102838D0 (en) 1991-02-11 1991-02-11 Pyrazole pesticides
GB9102847.2 1991-02-11
GB919102835A GB9102835D0 (en) 1991-02-11 1991-02-11 Pyrrole pesticides
GB9102841.5 1991-02-11
GB9102848.0 1991-02-11
GB919102847A GB9102847D0 (en) 1991-02-11 1991-02-11 Imidazole pesticides
GB9102834.0 1991-02-11
GB919102848A GB9102848D0 (en) 1991-02-11 1991-02-11 Pyrazole pesticides
GB919102834A GB9102834D0 (en) 1991-02-11 1991-02-11 1,2,4-triazole pesticides
GB9102835.7 1991-02-11
GB919102857A GB9102857D0 (en) 1991-02-11 1991-02-11 Pyrazole pesticides
GB9102857.1 1991-02-11
GB919102841A GB9102841D0 (en) 1991-02-11 1991-02-11 Imidazole pesticides
GB919114712A GB9114712D0 (en) 1991-07-08 1991-07-08 Imidazole pesticides
GB9114712.4 1991-07-08
GB9117822.8 1991-08-17
GB919117822A GB9117822D0 (en) 1991-08-17 1991-08-17 Imidazole pesticides

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WO1992013451A1 true WO1992013451A1 (fr) 1992-08-20

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AU (1) AU1191292A (fr)
WO (1) WO1992013451A1 (fr)

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EP0585014A2 (fr) * 1992-08-18 1994-03-02 Shionogi & Co., Ltd. Procédé pour la préparation d'imidazoles substitués en positions 2 et 5
WO1995025719A1 (fr) * 1994-03-21 1995-09-28 Bayer Aktiengesellschaft N-aryl- et n-alkylsulfonylaminales utilises comme pesticides
WO1996031123A1 (fr) * 1995-04-05 1996-10-10 Rhone-Poulenc Agriculture Ltd. Nouveau procede de lutte contre les insectes
EP0846686A1 (fr) * 1996-11-30 1998-06-10 Pfizer Limited Dérivés de phenyl-1-pyrazoles et leur utilisation comme parasiticide
WO1998028279A1 (fr) * 1996-12-24 1998-07-02 Rhone-Poulenc Agrochimie Derives pesticides de 1-arylpyrazole et de pyridylpyrazole
WO1998028278A1 (fr) * 1996-12-24 1998-07-02 Rhone-Poulenc Agrochimie 1-arylpyrazoles pesticides
WO1998039302A1 (fr) * 1997-03-03 1998-09-11 Rhone-Poulenc Agro Procedes pour la preparation de produits intermediaires pesticides
EP0911329A1 (fr) * 1997-10-07 1999-04-28 Rhone-Poulenc Agro Dérivés 3-substitués d'arylpyrazole
US5981565A (en) * 1997-10-07 1999-11-09 Rhone-Poulenc Inc. Pyrazole pesticides
EP0957094A1 (fr) * 1998-05-14 1999-11-17 Pfizer Inc. 1-(2-Halogénaryl)azoles comme agents antiparasitaires
US6069157A (en) * 1997-11-25 2000-05-30 Pfizer Inc. Parasiticidal compounds
US6107314A (en) * 1997-10-07 2000-08-22 Rhone-Poulenc Inc. Pesticides
US6159980A (en) * 1996-09-16 2000-12-12 Dupont Pharmaceuticals Company Pyrazinones and triazinones and their derivatives thereof
WO2001007413A1 (fr) * 1999-07-22 2001-02-01 3-Dimensional Pharmaceuticals, Inc. 1-aryle-3-thioalkyle pyrazoles, leur synthese et leur utilisation comme insecticides
US6409988B1 (en) 1999-07-01 2002-06-25 3-Dimensional Pharmaceuticals, Inc. Radiolabeled 1-aryl pyrazoles, the synthesis thereof and the use thereof as pest GABA receptor ligands
US6500850B2 (en) 1996-12-24 2002-12-31 Rhone-Poulenc Inc. Pesticidal 1-arylpyrazoles
US6506784B1 (en) 1999-07-01 2003-01-14 3-Dimensional Pharmaceuticals, Inc. Use of 1,3-substituted pyrazol-5-yl sulfonates as pesticides
US6545033B1 (en) 1999-10-06 2003-04-08 3-Dimensional Pharmaceuticals, Inc. Fused 1-(2,6-dichloro-4-trifluoromethylphenyl)-pyrazoles, the synthesis thereof and the use thereof as pesticides
WO2004035566A1 (fr) * 2002-10-18 2004-04-29 Pfizer Products Inc. Ligands des recepteurs des cannabinoides et applications de ceux-ci
FR2869905A1 (fr) * 2004-05-10 2005-11-11 Sanofi Synthelabo Procede de preparation d'ester de l'acide 1,5-diphenylpyrazole carboxylique.
US20090318455A1 (en) * 2008-06-03 2009-12-24 Intermune, Inc. Compounds and methods for treating inflammatory and fibrotic disorders
US9051309B2 (en) 2013-03-15 2015-06-09 Monsanto Technology Llc 3,5-disubstituted-1,3,4-oxadiazol-2(3H)-ones and compositions and methods for controlling nematode pests
US9156837B2 (en) 2011-07-29 2015-10-13 Takeda Pharmaceutical Company Limited Heterocyclic compound
JPWO2014007228A1 (ja) * 2012-07-03 2016-06-02 小野薬品工業株式会社 ソマトスタチン受容体作動活性を有する化合物およびその医薬用途
US9359379B2 (en) 2012-10-02 2016-06-07 Intermune, Inc. Anti-fibrotic pyridinones
US9527816B2 (en) 2005-05-10 2016-12-27 Intermune, Inc. Method of modulating stress-activated protein kinase system
US10112930B2 (en) 2007-08-13 2018-10-30 Monsanto Technology Llc Compositions and methods for controlling nematodes
US10233195B2 (en) 2014-04-02 2019-03-19 Intermune, Inc. Anti-fibrotic pyridinones

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AT375933B (de) * 1979-04-10 1984-09-25 Ciba Geigy Ag Verfahren zur herstellung neuer 2-substituierter mercaptoimidazolderivate und ihrer salze
EP0284277A1 (fr) * 1987-03-21 1988-09-28 AgrEvo UK Limited Fongicides de cyanoimidazole
GB2214180A (en) * 1988-01-12 1989-08-31 Shell Int Research Pytotoxic pyrrole-3,4-dicarboxylate derivatives
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Cited By (60)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0585014A2 (fr) * 1992-08-18 1994-03-02 Shionogi & Co., Ltd. Procédé pour la préparation d'imidazoles substitués en positions 2 et 5
EP0585014A3 (fr) * 1992-08-18 1994-12-14 Shionogi & Co Procédé pour la préparation d'imidazoles substitués en positions 2 et 5.
WO1995025719A1 (fr) * 1994-03-21 1995-09-28 Bayer Aktiengesellschaft N-aryl- et n-alkylsulfonylaminales utilises comme pesticides
US5994389A (en) * 1994-03-21 1999-11-30 Bayer Aktiengesellschaft N-aryl- and N-alkylsulfonylaminals
WO1996031123A1 (fr) * 1995-04-05 1996-10-10 Rhone-Poulenc Agriculture Ltd. Nouveau procede de lutte contre les insectes
AP849A (en) * 1995-04-05 2000-06-13 Rhone Poulenc Agriculture Use of phenylpyrazole derivatives for surface treatment to control cockroaches or ants.
US6218391B1 (en) 1996-09-16 2001-04-17 Dupont Pharmaceuticals Company Triazinones and derivatives thereof
US6159980A (en) * 1996-09-16 2000-12-12 Dupont Pharmaceuticals Company Pyrazinones and triazinones and their derivatives thereof
EP0846686A1 (fr) * 1996-11-30 1998-06-10 Pfizer Limited Dérivés de phenyl-1-pyrazoles et leur utilisation comme parasiticide
US6156782A (en) * 1996-11-30 2000-12-05 Pfizer Inc Parasiticidal compounds
WO1998028279A1 (fr) * 1996-12-24 1998-07-02 Rhone-Poulenc Agrochimie Derives pesticides de 1-arylpyrazole et de pyridylpyrazole
US6500850B2 (en) 1996-12-24 2002-12-31 Rhone-Poulenc Inc. Pesticidal 1-arylpyrazoles
US6350771B1 (en) 1996-12-24 2002-02-26 Rhone-Poulenc, Inc. Pesticidal 1-arylpyrazoles
US6638956B2 (en) 1996-12-24 2003-10-28 Rhone-Poulenc, Inc. Pesticidal 1-arylpyrazoles
AP1039A (en) * 1996-12-24 2002-01-23 Rhone Poulenc Agrochimie Pesticidal 1-arylpyrazoles.
WO1998028278A1 (fr) * 1996-12-24 1998-07-02 Rhone-Poulenc Agrochimie 1-arylpyrazoles pesticides
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