EP0579810A1 - Nouveaux esters pyrethrinoides derives d'alcool isoxazolique ou isothiazolique, leur procede de preparation et leur application comme pesticides - Google Patents

Nouveaux esters pyrethrinoides derives d'alcool isoxazolique ou isothiazolique, leur procede de preparation et leur application comme pesticides

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Publication number
EP0579810A1
EP0579810A1 EP93904158A EP93904158A EP0579810A1 EP 0579810 A1 EP0579810 A1 EP 0579810A1 EP 93904158 A EP93904158 A EP 93904158A EP 93904158 A EP93904158 A EP 93904158A EP 0579810 A1 EP0579810 A1 EP 0579810A1
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EP
European Patent Office
Prior art keywords
radical
formula
compounds
alcohol
methyl
Prior art date
Legal status (The legal status 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 status listed.)
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Application number
EP93904158A
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German (de)
English (en)
French (fr)
Inventor
Didier Babin
Marc Benoit
Jean-Pierre Demoute
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Sanofi Aventis France
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Roussel Uclaf SA
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Publication of EP0579810A1 publication Critical patent/EP0579810A1/fr
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two 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

Definitions

  • the present invention relates to new pyrethroid esters derived from isoxazolic or isothiazolic alcohol, their preparation process and their application as
  • - X represents a hydrogen atom, a cyano radical or a saturated or unsaturated, linear or branched alkyl radical containing up to 4 carbon atoms,
  • - Y in position 4 or 5 represents a hydrogen atom, an NO 2 , NH 2 , C ⁇ N radical, a linear or branched saturated or unsaturated alkyl radical containing up to 8 carbon atoms optionally substituted by one or more halogen atoms, a radical - (CH 2 ) n OH in which the OH radical may possibly be etherified or esterified, n representing the number 0,
  • Z 1 and Z 2 each represent a methyl radical
  • Z 3 represents a hydrogen or halogen atom and T 1 and T 2 , which are identical or different, represent a hydrogen atom, a halogen atom, a saturated or unsaturated alkyloxy or alkyl radical containing from 1 to 8 carbon atoms optionally substituted by halogens, a mono-, di- or trifluoromethyl or cyano radical or a phenyl nucleus optionally substituted by a halogen, or T 1 and T 2 together form a cycloalkyl radical containing 3 to 6 carbon atoms or a radical:
  • B represents an oxygen or sulfur atom - or Z 2 represents a radical
  • D represents a hydrogen or halogen atom, an alkyloxy radical containing from 1 to 8 carbon atoms
  • G represents an oxygen or sulfur atom
  • J represents either a linear, branched or cyclic alkyl radical, saturated or unsaturated, containing from 1 to 8 carbon atoms, optionally substituted by one or more functional groups, identical or different, or else an aryl group containing from 6 to 14 carbon atoms, optionally substituted by one or more idectic functional groups or different, or else a heterocyclic radical optionally substituted by one or more functional groups, identical or different
  • U in any position on the benzene ring, represents a halogen atom, an alkyl radical containing from 1 to 8 carbon atoms or an alkoxy radical containing from 1 to 8 carbon atoms, m representing the number 0, 1 or 2 and when m is 2, the substituents U can be the same or different.
  • X represents an alkyl radical, it is preferably a methyl, ethyl or ethynyl radical.
  • Y represents an alkyl radical, it is preferably a methyl, ethyl, isopropyl, n-butyl, isobutyl, terbutyl, vinyl, allyl, ethynyl or propynyl radical.
  • Y is substituted by a halogen atom,
  • halogen and preferably fluorine or chlorine it can be for example the radical CF 3 , CHF 2 , CHCl 2 , CH 2 F or
  • alkyl preferably has one of the values indicated above.
  • Y represents a free - etherified or esterified - (CH 2 ) n OH radical, it is preferably the radical - CH 2 OH, -CH 2 OCH 3 or -CH 2 OCOCH 3 .
  • T 1; T 2 or Z 3 represent a halogen atom, it is preferably a fluorine, chlorine or bromine atom.
  • T 1 or T 2 represents an alkyl or alkyloxy radical, it is preferably a methyl, ethyl, propyl, methoxy, ethoxy or propoxy radical.
  • a, b, c and d preferably represent a chlorine or bromine atom.
  • D represents a halogen atom, it is preferably a fluorine, chlorine or bromine atom.
  • alkyl is preferably understood to mean a radical containing from 1 to 8 carbon atoms such as, for example, the methyl, ethyl, propyl, isopropyl, butyl, isobutyl or tert radical.
  • -butyle and by functional group one of those cited in the European application published under the number 50534.
  • J can also represent an alkyl radical substituted by an aryl radical, in particular an optionally substituted phenyl radical.
  • n 1 is an integer from 1 to 8
  • Hal a halogen atom for example the radical -CH 2 -CCl 3 , -CH 2 -CF 3 , -CH 2 -CH 2 -CCl 3 or CH 2 -CH 2 -CF 3 ;
  • n 1 and Hal are defined as
  • n 1 is defined as above e
  • R a represents a hydrogen atom or a linear or branched alkyl radical containing from 1 to 8 carbon atoms, for example the radical -CH 2 -OCH 3 , -CH 2 -CH 2 -O-CH 3 ,
  • n 1 and R a are defined as above and the two radicals R a can be different from each other, for example the radical:
  • n 1 is defined as above, for example the radical:
  • n 1 is defined as above for example the radical
  • n 1 is defined as above and THP represents the 2-tetrahydropyrannyl radical, for example the radical: -CH 2 -O-THP or -CH 2 -CH 2 -O-THP;
  • n 1 is defined as above, for example the benzyl or phenethyl radical
  • n 1 is defined as above, for example the radical:
  • J represents an optionally substituted aryl radical, it is preferably the optionally substituted phenyl radical.
  • J represents a heterocyclic radical, it is preferably pyridyl, furyl, thienyl, oxazolyl or thiazolyl radicals.
  • a more particular subject of the invention is the compounds of formula (I) in which Z represents an oxygen atom.
  • Y represents an alkyl radical containing up to 4 carbon atoms optionally substituted by one or more halogen atoms for example a radical CHF 2 , CF 3 , CH 3 , CH 2 F or -CHF-C ⁇ CH;
  • alk 1 represents an alkyl radical containing up to 4 carbon atoms optionally substituted by one or more fluorine atoms;
  • alk 2 represents an alkyl radical containing up to 4 carbon atoms optionally substituted by one or more fluorine atoms.
  • the subject of the invention is also a process for preparing the compounds of formula (I) characterized in that an acid of formula (II) is subjected:
  • the functional acid derivative used is preferably an acid chloride.
  • the operation is preferably carried out in the presence of dicyclohexylcarbodiimide.
  • the acids of formula (II) used are known products used in the synthesis of pyrethroid compounds.
  • the alcohols of formula (III) can be prepared by analogy with the following process:
  • the subject of the invention is also a variant of the preceding process, characterized in that a compound of formula (IV) is subjected: in which alk represents an alkyl radical containing up to 4 carbon atoms Hal 1 represents a halogen atom, to the action of a compound of formula (V):
  • the radical Y can be introduced by first transforming the CH 2 Hal radical into the CHO radical, using an oxidizing agent such as, for example, 4-methyl morpholine N-oxide, then by making react the appropriate reagent on this aldehyde, for example diethylaminosulfide trifluoride (DAST) when it is desired to obtain a compound in which Y represents a radical CHF 2 .
  • an oxidizing agent such as, for example, 4-methyl morpholine N-oxide
  • DAST diethylaminosulfide trifluoride
  • the products of formula (VI) are new products and are in themselves an object of the present invention.
  • a more particular subject of the invention is the compound of formula (VI), the preparation of which is given in the experimental part.
  • the compounds of formula (I) have interesting properties which allow their use in the fight against parasites. This can for example be the fight against plant parasites, parasites from premises and parasites from warm-blooded animals.
  • a subject of the invention is in particular the application of the compounds of formula (I) to the fight against plant parasites, local parasites and parasites of warm-blooded animals.
  • the products of formula (I) can also be used to fight against insects and other soil parasites, for example beetles, such as Diabrotica, wireworms and white worms, myriapods such as scutigeria and blaniules, and dipterans as midge moths and lepidoptera such as ground moths.
  • beetles such as Diabrotica, wireworms and white worms
  • myriapods such as scutigeria and blaniules
  • dipterans as midge moths and lepidoptera such as ground moths.
  • the products of formula (I) can also be used to fight against insects in premises, to fight in particular against flies, mosquitoes and cockroaches.
  • the products of formula (I) are more photostable and are not very toxic for mammals.
  • the products of formula (I) can also be used to fight against mites and parasitic nematodes of plants.
  • the compounds of formula (I) can also be used to fight against parasitic mites of animals, to fight for example against ticks and in particular ticks of the species of Boophilus, those of the species Hyalomnia, those of the species Amblyomnia and those of the species Rhipicephalus or for fight against all kinds of scabies, especially sarcoptic scab, psoroptic scab and chorioptic scab.
  • the invention therefore also relates to compositions intended for the fight against parasites of warm-blooded animals, parasites of premises and plants, characterized in that they contain at least one of the products of formula (I) defined above and in particular the products of formula (I) of Examples 2, 6, 7, 32, 33 and 34.
  • the invention particularly relates to insecticide compositions containing as active principle at least one of the products defined above.
  • compositions are prepared according to the usual methods of the agrochemical industry or of the veterinary industry or of the industry for products intended for animal nutrition.
  • compositions intended for agricultural use and for use in premises can optionally be added with one or more other pesticidal agents.
  • These compositions can be in the form of powders, granules, suspensions, emulsions, solutions, solutions for aerosols, combustible strips, baits or other preparations conventionally used for the use of this type of compound.
  • compositions generally contain a vehicle and / or a non-ionic surfactant, ensuring, moreover, a uniform dispersion of the constituent substances of the mixture.
  • vehicle used can be a liquid, such as water, alcohol, hydrocarbons or other organic solvents, a mineral, animal or vegetable oil, a powder such as talc, clays, silicates, kieselguhr or a solid fuel.
  • the insecticidal compositions according to the invention preferably contain from 0.005% to 10% by weight of active material.
  • compositions according to the invention are used in the form of fumigant compositions.
  • compositions according to the invention can then be advantageously constituted, for the non-active part, of a combustible insecticide coil (or coil), or also of an incombustible fibrous substrate.
  • a heating device such as an electric emitter.
  • the inert support can be, for example, composed of pyrethrum marc, Tabu powder (or Machilus Thumbergii leaf powder), pyrethrum stem powder, cedar leaf powder , wood powder (such as sawdust) starch and coconut shell powder.
  • the dose of active ingredient can then be, for example, from 0.03 to 1% by weight.
  • the dose of active material can then be, for example, from 0.03 to 95% by weight.
  • compositions according to the invention for use in premises can also be obtained by preparing a sprayable oil based on active principle, this oil soaking the wick of a lamp and then being subjected to combustion.
  • the concentration of the active ingredient incorporated in the oil is preferably from 0.03 to 95% by weight.
  • the subject of the invention is also the acaricide and nematicide compositions containing as active principle at least one of the products of formula (I) defined above.
  • the insecticide compositions according to the invention can optionally be added with one or more other pesticidal agents.
  • the acaricide and nematicide compositions can be in particular in the form of powder,
  • wettable powders are preferably used for foliar spraying containing from 1 to 80% by weight of active principle or liquids for foliar spraying containing from 1 to 500 g / l of active principle. It is also possible to use powders for leaf dusting containing from 0.05 to 3% of active material.
  • liquids are preferably used for treating soils containing 300 to 500 g / l of active ingredient.
  • the acaricide and nematicide compounds according to the invention are preferably used in doses of between 1 and 100 g of active material per hectare.
  • the compounds of formula (I) have an excellent general tolerance, and the invention therefore also relates to the products of formula (I), in particular for combating the diseases created by ticks and scabies in humans and animal.
  • the products of the invention are especially used to fight against lice as a preventive or curative and to fight against scabies.
  • the products of the invention can be administered externally, by spraying, by shampooing, by bathing or brushing.
  • the products of the invention for veterinary use can also be administered by brushing the backbone according to the method known as the "pour-on" method.
  • products of the invention can be used as biocides or as growth regulators.
  • a subject of the invention is also associations with insecticidal, acaricidal or nematicidal activity, characterized in that they contain as active material, on the one hand at least one of the compounds of general formula (I), and on the other on the other hand, at least one of the pyrethroid esters chosen from the group consisting of the esters of allethrolone, 3,4,5,6-tetrahydrophthalimido methyl alcohol, 5-benzyl 3-furyl methyl alcohol, 3- alcohol benzyl phenoxy and alpha-cyano alcohol 3-phenoxy
  • benzyl chrysanthemic acids by 5-benzyl 3-furyl methyl esters of 2,2-dimethyl 3- (2-oxo 3-tetrahydrothiophenylidene methyl) cyclopropanecarboxylic acids, by 3-phenoxy benzyl alcohol esters and d alpha-cyano 3-phenoxy benzyl alcohol of 2,2-dimethyl 3- (2,2-dichlorovinyl) cyclopropanecarboxylic acids, by alpha-cyano 3-phenoxy benzyl alcohol esters of 2,2-dimethyl 3- acids (2,2-dibromovinyl) cyclopropanecarboxylic, by 3-phenoxy benzyl alcohol esters of 2-parachlorophenyl 2-isopropyl acetic acids, by allethrolone esters, 3,4,5,6-tetrahydrophthalimidomethyl alcohol, d 5-benzyl 3-furyl methyl alcohol, 3-phenoxy benzyl alcohol and alpha-cyano 3-phen
  • Example 1 [1R- [1alpha, 3alpha (Z)]] - 3- (2-chloro-3,3,3-trifluoro-1-propenyl) -2,2-dimethylcyclopropanecarboxylate from (5-methyl-3-isoxazolyl ) methyl.
  • a solution containing 1.10 g of dicyclohexylcarbodiimide (DCC) and 5 cm 3 of methylene chloride is added at 0 ° C. in a solution containing 0.6 g of 5-methyl-3-isoxazol methanol, 13 cm 3 of chloride of chloride methylene 1.3 g of 1R acid [1alpha, 3alpha (Z)] 2,2-dimethyl 3- (3,3,3-trifluoro2-chloropropenyl) cyclopropane carboxylic acid and 0.032 g of dimethylaminopyridine (DMAP). The temperature of the reaction medium is allowed to return to 20 ° C, maintained under stirring at 20 ° C for 17 hours.
  • DCC dicyclohexylcarbodiimide
  • DMAP dimethylaminopyridine
  • Example 2 [1R- [1alpha, 3alpha (Z)]] - 3- (3-ethoxy-2-fluoro-3-oxo-1-propenyl) -2,2-dimethylcyclopropanecarboxylate from (5-methyl-3-isoxazolyl ) methyl.
  • Example 4 [1R- [1alpha, 3alpha (Z)]] - 3- (3-ethoxy-2-fluoro-3-oxo-1-propenyl) -2,2-dimethylcyclopropanecarboxylate (3-trifluoromethyl-5-isoxazolyl ) methyl.
  • Example 5 [1R- [1alpha, 3alpha (Z)]] - 2,2-dimethyl-3- [3-oxo 3- [2,2,2-trifluoro-1- (trifluoromethyl) ethoxy] -1-propenyl ] (3-trifluoromethyl-5-isoxazolyl) methyl cyclopropanecarboxylate.
  • Stage A trifluoroacetaldehyde oxime.
  • Stage B 2,2,2-trifluoro N-hydroxy ethanimidoyl bromide.
  • Stage C (3-trifluoromethyl 5-isoxazol) methanol.
  • a solution containing 22.7 cm 3 of triethylamine and 70 cm 3 of toluene is introduced at approximately 25 ° C. in 1 h 30 minutes into a solution containing 30 g of product prepared in stage B and 14.2 ml of propargyl alcohol in 80 cm 3 of toluene.
  • the reaction mixture is kept under stirring for 20 hours at 20 ° C.
  • Example 6 1R [1apha, 3alpha (Z)] 2,2-dimethyl-3- (3,3,3-trifluoro-2-chloropropenyl) cyclopropane carboxylate 1- [5- (difluoromethyl) -3-isoxazolyl] 2 -propynyl.
  • Stage B (bromomethyl) 3-isoxazol 5-carboxaldehyde.
  • Stage C 5- (bromomethyl) alpha-ethynyl 3-isoxazol methanol 75 cm 3 of ethynyl magnesium bromide are added at 0 ° C. in a solution containing 9.52 g of product prepared in stage B and 100 cm 3 of tetrahydrofuran.
  • the reaction mixture is stirred at 20 ° C for 2 h 30 min. It is poured into a mixture of water, ice and ammonium chloride. Extracted with isopropyl ether, saturated with sodium chloride. It is dried, filtered, rinsed and brought to dryness under reduced pressure. 13.01 g of product are obtained which is chromatographed on silica eluting with a hexane-ethyl acetate mixture 7-3. 8.71 g of sought product is obtained.
  • Stage D 3- (1-hydroxy-2-propynyl) isoxazol-5-carboxaldehyd 9.8 g of 4-methyl morpholine oxide, 68 cm 3 of dimethyl sulfoxide and 34 cm 3 of chloride chloride are added at 0 ° C. methylene in a solution containing 4 g of product prepared in stage C and 30 cm 3 of methylene chloride. The mixture is left to return to 20 ° C. and stirred for 5 hours. It is poured into an aqueous solution of potassium acid phosphate. Extracted with ethyl acetate, dried, filtered and brought to dry. We obtain
  • Stage E 1R [1alpha, 3alpha (Z)] 2,2-dimethyl 3- (3,3,3-trifluoro-2-chloropropenyl) cyclopropane carboxylate of 1- [5 -formyl-3-isoxazol] 2-propynyl.
  • Stage F 1R [1alpha, 3alpha (Z)] 2,2-dimethyl 3- (3,3,3-trifluoro-2-chloropropenyl) cyclopropane carboxylate of 1- [5- (difluoromethyl) -3-isoxazolyl] 2- propynyl.
  • DAST diethylaminosulfide trifluoride
  • 1R [1alpha, 3alpha (Z)] 2,2-dimethyl-3- (3,3,3- 1- [5-formyl-3-isoxazolyl] 2-propynyl trifluoro-2-chloropropenyl) cyclopropane carboxylate obtained in stage E.
  • the reaction mixture is kept under stirring for 4 hours at 20 ° C, and poured onto a solution of sodium hydrogen carbonate. It is extracted with methylene chloride, dried, filtered, rinsed and brought to dryness under reduced pressure. 1.81 g of a product are obtained which is chromatographed on silica eluting with a hexane-ethyl acetate mixture 85-15. 1.39 g of sought product is obtained.
  • Example 7 [1R- [1alpha, 3alpha (Z)]] - 3- (3-ethoxy-2-fluoro-3-oxo-1-propenyl) -2,2-dimethylcyclopropane carboxyl from 1- (5-difluoromethyl- 3-isoxazolyl) -2-propynyl.
  • Example 8 [1R- [1alpha, 3alpha (Z)]] - 2,2-dimethyl 3- (2-chloro-3,3,3-trifluoro 1-propenyl) cyclopropane carboxylate of [3- (difluoromethyl) isoXazol- 5-yl) methyl.
  • Rf 0.2 (hexane-CH 2 Cl 2 6-4).
  • Example 9 [1R- [1alpha, 3alpha (E)]] - 2,2-dimethyl 3- (2-fluoro-3-methoxy 3-oxo 1-propenyl) cyclopropane carboxylate of [3- (difluoromethyl) isoxazol-5 -yl) methyl.
  • Rf 0.2 (hexane-isopropyl ether 7-3).
  • Example 10 [1R- [1alpha, 3alpha (E)]] - 2,2-dimethyl 3- (2-fluoro-3-methoxy 3-oxo 1-propenyl) cyclopropane carboxylate 1-ethynyl [3- (difluoromethyl) isoxazol-5-yl) methyl.
  • Rf 0.17 (hexane-acetone-CH 2 Cl 2 8-10-10).
  • Example 11 [1R- [1alpha, 3alpha (Z)]] - 2,2-dimethyl 3- (2-chloro-3,3,3-trifluoro 1-propenyl) cyclopropane carboxylate 1-ethynyl [3- (difluoromethyl ) isoxazol-5-yl) methyl.
  • Example 12 [1R- [1alpha, 3alpha (Z)]] - 2,2-dimethyl 3- (2-chloro-3,3,3-trifluoro 1-propenyl) cyclopropane carboxylate of [3- (fluoromethyl) isoxazol- 5-yl) methyl.
  • Rf 0.3 (hexane-acetone-CH 2 Cl 2 8-10-10).
  • Example 13 [1R- [1alpha, 3alpha (E)]] - 2,2-dimethyl 3- (2-fluoro-3-methoxy 3-oxo 1-propenyl) cyclopropane carboxylate of [3- (fluoromethyl) isoxazol-5 -yl) methyl.
  • Rf 0.2 (hexane-isopropyl ether 6-4).
  • Example 14 [1R- [1alpha, 3alpha (E)]] - 2,2-dimethyl 3- (2-fluoro-3-methoxy 3-oxo 1-propenyl) 1-ethynyl [3- (fluoromethyl) cyclopropane carboxylate isoxazol-5-yl) methyl.
  • Example 15 [1R- [1alpha, 3alpha (Z)]] - 2,2-dimethyl 3- (2-chloro-3,3,3-trifluoro 1-propenyl) 1-ethynyl [5- (formyl) cyclopropane carboxylate ) isoxazol-3-yl) methyl.
  • Rf 0.2 (hexane-ethyl acetate 75-25).
  • Example 17 [1R- [1alpha, 3alpha (Z)]] - 2,2-dimethyl 3- (2-chloro-3,3,3-trifluoro 1-propenyl) cyclopropane carboxylate of [5- (difluoromethyl) isoxazol- 3-yl) methyl.
  • Example 18 [1R- [1alpha, 3alpha (E)]] - 2,2-dimethyl 3- (2-fluoro-3-methoxy 3-oxo 1-propenyl) cyclopropane carboxylate of [5- (difluoromethyl) isoxazol-3 -yl) methyl.
  • Rf 0.2 (hexane-ethyl acetate 8-2).
  • Example 19 [1R- [1alpha, 3alpha (E)]] -2,2-dimethyl 3- (2- fluoro-3-methoxy 3-oxo 1-propenyl) cyclopropane carboxylate of [5- (methoxymethyl) isoxazol-3 -yl) methyl.
  • Rf 0.2 (hexane-isopropyl ether 7-3).
  • Example 20 [1R- [1alpha, 3alpha (Z)]] - 2,2-dimethyl 3- (2-chloro-3,3,3-trifluoro 1-propenyl) cyclopropane carboxylate of [5- (methoxymethyl) isoxazol- 3-yl) methyl.
  • Rf 0.2 (hexane-ethyl acetate 8-2).
  • Example 22 [1R- [1alpha, 3alpha (E)]] - 2,2-dimethyl 3- (2-fluoro-3-ethox ⁇ 3-oxo 1-propenyl) 1-ethynyl [5- (methoxymethyl) cyclopropane carboxylate isoxazol-3-yl) methyl.
  • Rf 0.2 (hexane-isopropyl ether 5-5).
  • Example 23 [1R- [1alpha, 3alpha (Z)]] - 2,2-dimethyl 3- (2-chloro-3,3,3-trifluoro 1-propenyl) cyclopropane carboxylate of [S- (methylthiomethyl) isoxazol- 3-yl) methyl.
  • Example 24 [1R- [1alpha, 3beta (Z)]] - 2,2-dimethyl 3- (2-fluoro-3-methoxy 3-oxo 1-propenyl) 1-ethynyl [5- (methylthiomethyl) cyclopropane carboxylate isoxazol-3-yl) methyl.
  • Example 25 [1R- [1alpha, 3beta (Z)]] - 2,2-dimethyl 3- (2-fluoro- [5- (methylthiomethyl) isoxazol-3-yl) methyl 3-methoxy 3-oxo 1-propenyl) cyclopropane carboxylate.
  • Example 27 [1R- [1alpha, 3beta (Z)]] - 2,2-dimethyl 3- (2-fluoro-3-methoxy 3-oxo 1-propenyl) cyclopropane carboxylate of [5- (dichloroethenyl) isoxazol-3 -yl) methyl.
  • Example 28 [1R- [1alpha, 3alpha (Z)]] - 2,2-dimethyl 3- (2-chloro-3,3,3-trifluoro 1-propenyl) cyclopropane carboxylate of [5- (dichloroethenyl) isoxazol- 3-yl) methyl.
  • Example 29 [1R- [1alpha, 3beta (Z)]] - 2,2-dimethyl 3- (2-fluoro-3-methoxy 3-oxo 1-propenyl) 1-ethynyl [5- (dichloroethenyl) cyclopropane carboxylate isoxazol-3-yl) methyl.
  • Example 30 [1R- [1alpha, 3alpha (Z)]] - 2,2-dimethyl 3- (2-chloro-3,3,3-trifluoro 1-propenyl) cyclopropane carboxylate 1-ethynyl [5- (dichloroethenyl ) isoxazol-3-yl) methyl. Rf ⁇ 0.2 (hexane-ethyl acetate 9-1).
  • Example 31 [1R- [1alpha, 3alpha (Z)]] - 2,2-dimethyl 3- (2-chloro-3,3,3-trifluoro 1-propenyl) cyclopropane carboxylate of [3- (l-fluoro- 1-prop-2-yn) isoxazol-5-yl] methyl.
  • Rf 0.2 (hexane-CH 2 Cl 2 5-5).
  • Example 32 [1R- [1alpha, 3alpha (E)]] - 2,2-dimethyl 3- (2-fluoro-3-ethoxy 3-oxo 1-propenyl) cyclopropane carboxylate of [3- (1-fluoro-1 -prop-2-yn) isoxazol-5-yl] methyl.
  • Rf 0.2 (hexane-isopropyl ether 8-2).
  • Example 33 [1R- [1alpha, 3alpha (Z)]] - 2,2-dimethyl 3- (2-chloro-3,3,3-trifluoro 1-propenyl) 1-ethynyl [3- (fluoromethyl) cyclopropane carboxylate ) isoxazol-5-yl] methyl.
  • Example 34 [1R- [1alpha, 3alpha (Z)]] - 2,2-dimethyl 3- (3,3,3-trifluoro 2-chloropropenyl) cyclopropane carboxylate from 1 - ([5- (trifluoromethyl) isoxazol-3 -yl] 2-propynyl.
  • Example 35 [1R- [1alpha, 3alpha (Z)]] 3- (2-chloro 3,3,3-trifluoro 1-propenyl) 2,2-dimethyl cyclopropane carboxylate of 1- [3- (trifluoromethyl) isoxazol- 5-yl] 2-propynyl.
  • Example 36 [1R- [1alpha, 3alpha (E)]] 3- (2-fluoro 3-methoxy 3-oxo 1-propenyl) 2,2-dimethyl cyclopropane carboxylate of 1- [5- (trifluoromethyl) isoxazol-3 -yl] 2-propynyl.
  • Example 37 [1R- [1alpha, 3alpha (Z)]] 3- (2-chloro 3,3,3- trifluoro 1-propenyl) 2,2-dimethyl cyclopropane carboxylate of 1- [5- (trifluoromethyl) isoxazol- 4-yl] 2-propynyl.
  • Example 38 [1R- [1alpha, 3alpha (Z)]] 3- (2-chloro 3,3,3-trifluoro 1-propenyl) 2,2-dimethyl cyclopropane carboxylate of [5- (1-fluoro 2-propynyl ) isoxazol-3-yl] methyl.
  • Example 39 [1R- [1alpha, 3alpha (E)]] 3- (3-ethoxy 2-fluoro 3-oxo 1-propenyl) 2,2-dimethyl cyclopropane carboxylate of 5- (1-fluoro-2-propynyl) isoxazol-3-yl] methyl.
  • test insects are last instar larvae of Diabrotica.
  • test insects are 4-day-old female house flies.
  • the operation is carried out by spraying in a Kearns and March chamber using a mixture of acetone (5%) and Isopar L (petroleum solvent) as solvent (quantity of solvent used 2 ml in one second). 50 insects are used per treatment.
  • the controls are carried out every minute up to 10 minutes, then at 15 minutes and the KT 50 is determined by the usual methods.
  • the products of the invention exhibit good activity.

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  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
EP93904158A 1992-02-07 1993-02-05 Nouveaux esters pyrethrinoides derives d'alcool isoxazolique ou isothiazolique, leur procede de preparation et leur application comme pesticides Withdrawn EP0579810A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9201392 1992-02-07
FR9201392A FR2687148A1 (fr) 1992-02-07 1992-02-07 Nouveaux esters pyrethrinouides derives d'alcool isoxazolique ou isothiazolique, leur procede de preparation et leur application comme pesticides.

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EP0579810A1 true EP0579810A1 (fr) 1994-01-26

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Country Status (5)

Country Link
US (1) US5434175A (enrdf_load_stackoverflow)
EP (1) EP0579810A1 (enrdf_load_stackoverflow)
JP (1) JPH06507421A (enrdf_load_stackoverflow)
FR (1) FR2687148A1 (enrdf_load_stackoverflow)
WO (1) WO1993016054A1 (enrdf_load_stackoverflow)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6111139A (en) * 1999-11-04 2000-08-29 Van Der Puy; Michael Process for the preparation of trifluoropropanal
US7214825B2 (en) 2003-10-17 2007-05-08 Honeywell International Inc. O-(3-chloropropenyl) hydroxylamine free base
AR083875A1 (es) 2010-11-15 2013-03-27 Bayer Cropscience Ag N-aril pirazol(tio)carboxamidas

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1398103A (en) * 1972-08-31 1975-06-18 Shell Int Research Cyclopropane derivatives and their use as pesticides
FR2539411B2 (fr) * 1983-01-17 1986-04-25 Roussel Uclaf Nouveaux derives de l'acide cyclopropane carboxylique, leur procede de preparation, leur application a la lutte contre les parasites

Non-Patent Citations (1)

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Title
See references of WO9316054A1 *

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WO1993016054A1 (fr) 1993-08-19
FR2687148A1 (fr) 1993-08-13
US5434175A (en) 1995-07-18
FR2687148B1 (enrdf_load_stackoverflow) 1995-06-02
JPH06507421A (ja) 1994-08-25

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