OA11434A - Derivatives of 2,2-dimethyl 3-(2-fluoro vinyl) cyclopropane carboxylic acid, their preparation process and their use as pesticides. - Google Patents

Abstract

Compounds of formula (I) in which R represents the remainder of an alcohol used in the pyrethroid series, in all their possible stereoisomer forms as well as their mixtures, and compositions comprising them. The compounds of formula (I) are useful as pesticides.

Description

011434 1 Dérivatives of 2,2-dimethyl 3-(2-fluoro vinyl) cyclopropane carboxylic acid, theirpréparation process and their use as pesticides

Pyrethroids are lipophilie synthethic compounds orginally derived from the activeprinciple of pyrethrum. They show insecticidal properties, based on on a stronginfluence on the sodium channels in the nerve membranes of the insects.

Several commercial ly used pyrethroids are of the general structure

wherein R1, R2 can be halogen, CF3 or CH3 (see, e.g., EP-A 0 638 543, EP-A 0 498 724, EP-A 0 779 269 or EP-A 0 638 542).

In US-A 4,176,189 hydanthoin methylols are disclosed as alcohol component of suchpyrethroids. 011434 2

The mentioned compounds show good activities as insecticides. There are howevergrowing demands on pesticides with respect to, e.g., efficacy, dosage, range ofcontrolled pests, toxicity, economy of production and résistance management.Therefore, it is an ongoing task to provide new pyrethroids which show at least partialimprovement with respect to one or more of the mentioned items.

It has now surprisingly been found that pyrethroids of the formula (l) below areespecially useful in combatting harmful pests.

Therefore, in one aspect of the invention there are provided compounds of formula (I):

in all their possible stereoisomer forms as well as their mixtures in which R representsthe remainder of an alcohol used in the pyrethroid sériés.

Preferably, R represents: an alkyl radical containing 1 and 18 atoms of carbon; a benzyl radical optionally substituted by one or more radicals selected from the groupconsisting of alkyl radicals containing 1 to 4 carbon atoms, alkenyl radicals containing 2to 6 carbon atoms, alkenyloxy radicals containing 2 to 6 carbon atoms, alkadienyl 0.11434 radicals containing 4 to 8 carbon atoms, the methylene dioxy radical and halogenatoms; either a group:

in which the substituent R! represents a hydrogen atom or a methyl radical and thesubstituent R2 représente a monocyclic aryl or a -CH2-OCH group;or a group:

in which a represents a hydrogen atom or a methyl radical and R3 represents the-CH2-CH=CH2, -CH2-C=CH,-CH2-CH=CH-CH3i-CH2-CH=CH-CH=CH2 or -CH2-CH=CH-CH2-CH3 radical;or a group:

in which a represents a hydrogen atom or a methyl radical, R3 retains the samemeaning as previously, R\ and R'2 identical or different, represent a hydrogen atom, ahalogen atom, an alkyl radical containing 1 to 6 carbon atoms, an aryl radical 011434 containing 6 to 10 carbon atoms, an alkyloxycarbonyl group containing 2 to 5 carbonatoms, or a cyano group;or a group:

in which B represents an oxygen or sulphur atom , -C(O)- or -CK2-, R4 represents a hydrogen atom, a -ON radical, a methyl radical, a CONH2 radical, aCSNH2radical or a -OCH radical, R5represents a halogen atom or a methyl radicaland π represents a number equal to 0,1 or 2; or a group:

o 011 434 in which the substituents R6i R7, R8and Rgrepresent a hydrogen atom, a chlorine atom,or a methyl radical and in which S/l symbolizes an aromatic cycle or an analogousdihydro or tetrahydro cycle; or a group: -ch2

or a group:

in which R10 represents a hydrogen atom or a CH radical, preferably CH3, R12représente a -CH2- radical or an oxygen atom, R-ii represents a thiazyl radical or a thiadiazyl whose bond with: -ch- can be located at any one of the available positions, R12being linked to Rn by thecarbon atom between the sulphur atom and a nitrogen atom;or a group: 011434

or a group: M3

CH

,b — c d in which R13 represents a hydrogen atom or a C^CH or CN radical, a, b, c, d, erepresent a hydrogen atom, a halogen atom, an alkyl, O-alkyl or S-alkyl radicalcontaining up to 8 carbon atoms, saturated or insaturated, optionally substituted by oneor more halogen atoms, a CN, NO2, NH2 or OH radical, or R represents a radical:

in which e and f represent a methyl, CH2F, CHF2or CF3 radical; or R represents an aryl group containing 6 to 14 carbon atoms, optionally substituted 011434 7 by one or more OH, O-alkyl or alkyl groupe containing 1 to 8 carbon atoms or by a CF3,OCF3or SCF3group; or R represents a pyridinyl, furanyl, thiophenyl oxazolyl or thiazolyl radical.

Especially preferred are the compounds in which R represents a radical:

wherein Y represents a hydrogen or halogen atom, a hydroxyl, NO2, CN or NH2, CH2OHor CH2OCH3 radical, an alkyl, O-alkyl or S-alkyl radical containing up to 8 carbonatoms, optionally substituted by one or more halogen atoms, and/or optionally 011434 interrupted by one or more, preferably one or two, heteroatoms, preferably from thegroup consisting of O, S and N.

Among these preferred compounds, there can be particularly mentioned thecompounds in which R represents the radical:

A more particular subject of the invention is the compounds the préparation of which isgiven below in the experimental part and in particular the products of Examples 14,27and 43.

The subject of the invention is also a préparation process characterized in that an acidof formula (II):

CO2H (II) h3c or a functional dérivative of this acid in ail possible stereoisomer forms as well as theirmixtures is subjected to the action of an alcohol of formula (III): ROH (III) wherein R is preferably the remainder of an alcohol used in the pyrethroid sériés, or a 011434 functional dérivative of this alcohol, and in this way, the sought compound of formula (l)is obtained.

The functional dérivative of the acid is preferably an acid chloride. When an acid offormula (II) is reacted with the alcohol of formula (III), the operation is preferably carriedout in the presence of diclohexylcarbodiimide. - 4

The acids of formula (II) used as starting products of the process of the invention arenew products and are themselves a subject of the présent invention, their préparationis given below in the experimental part.

They are prepared from the products of formula (A): (A) in which R, and R2 represent a hydrogen atom or an alkyl radical containing up to 8carbon atoms. The products of formula (A) are known products described inEP-A 0 050 354.

While being tolerated well by plants and having favorable toxicity toward warm-bloodedanimais, the compounds of formula (I) are suitable for controlling animal pests,especially insects, arachnids, helminths and molluscs, and very particularly preferablyfor controlling insects and arachnids, which are encountered in the hygiene sector, in U I 1^04 10 animal breeding, in forestry, in the protection of stored products and materials, and inagriculture. They are active against normally sensitive and résistant species andagainst ail or certain stages of development. The abovementioned pests include:

From the order of the Acarina, for example, Acarus siro, Argas spp., Ornithodoros spp.,Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boôphilus spp.,Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,Chorioptes spp,, Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychusspp., Tetranychus spp., Eotetranychus spp., Oligonychus spp. and Eutetranychus spp..From the order of the Isopoda, for example, Oniscus asselus, Armadium vulgar andPorcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigeraspp·· ‘

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis, Periplaneta americana,Leucophaea madeirae, Blattella germanica, Acheta domesticus, Gryllotalpa spp.,Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria.From the order of the Isoptera, for example, Reticulitermes spp..

From the order of the Anoplura, for example, Phylloera vastatrix, Pemphigus spp.,Pediculus humanus corporis, Haematopinus spp. and Linognathus spp..

From the order of the Mallophaga, for example, Trichodectes spp. and Damalinea spp. 011434 11

From the order of the Thysanoptera, for example, Hercinothrips femoralis, Thrips tabaciand Frankliniella spp..

From the order of the Heteroptera, for example, Eurygaster spp., Dysdercusintermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp..From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci,Trialeurodes vaporariorum, Aphis spp., Brevicoryne brassicae, Cryptomyzifs ribis, 4Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphumavenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelusbilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcusspp. and Psylla spp..

From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupaluspiniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella,Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp.,Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp.,Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolisflammea, Prodenia litura, Spodoptera spp., Trichoplysia ni, Carpocapsa pomonella,Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella,Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima, Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum, Rhizoperthadominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, 011434 12

Ageiastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp.,Psylloides chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilussurinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolitessordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma,Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptushololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes Spp.,Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytrazealandica and Lissorhoptus spp..

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp.,Lasius spp., Monomorium pharaonis and Vespa spp..

From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp.,Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Luciliaspp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hypobosca spp., Stomoxysspp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus,Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae andTipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopsis andCeratophyllus spp..

From the order of the Arachnida, for example, Scorpio maurus and Latrodectusmactans.

From the class of the helminths, for example, Haemonchus, Trichostrongulus,Ostertagia, Cooperia, Chabertia, Strongyloides, Oesophagostomum, Hyostronguius,Ancylostoma, Ascaris and Heterakis and also Fasciola. 01 1434 13

From the class of the Gastropoda, for example, Deroceras spp., Arion spp., Lymnaeaspp., Galba spp., Succinea spp., Biomphalaria spp., Bulinus spp. and Oncomelaniaspp..

From the class of the Bivalva, for example, preissena spp..

The plant-parasitic nematodes which can be controlled in accordance with theinvention include, for example, the root-parasitic soil nematodes such as those of thegénéra Meloidogyne (root knot eelworms, such as Meloidogyne incognita, Meloidogynehapla and Meloidogyne javanica), Heterodera and Globodera (cyst-forming nematodes,such as Globodera rostochiensis, Globodera pallida, Heterodera trifolii) and of thegénéra Radopholus (such as Radopholus similis), Pratylenchus (such as Pratylenchusneglectus, Pratylenchus penetrans and Pratylenchus curvitatus), Tylenchulus (such asTylenchulus semipenetrans), Tylenchorhynchus (such as Tylenchorhynchus dubiusand Tylenchorhynchus claytoni), Rotylenchus (such as Rotylenchus robustus),Helicotylenchus (such as Helicotylenchus multicinctus), Belonoaimus (such asBelonoaimus longicaudatus), Longidorus (such as Longidorus elongatus), Trichodorus(such as Trichodorus primitivus), and Xiphinema (such as Xiphinema index).

The compounds according to the invention can also be used to control the nematodegénéra Ditylenchus (stem parasites, such as Ditylenchus dipsaci and Ditylenchusdestructor), Aphelenchoides (leaf nematodes, such as Aphelenchoides ritzemabosi)and Anguina (leaf-gall nematodes, such as Anguina tritici). 011434 14

The invention also relates to compositions, especially insecticidal and acaricidalcompositions, which comprise the compounds of the formula (I) in addition to suitableformulation auxiliaries.

The compositions according to the invention comprise the active compounds of theformula (I) in general in a proportion of from 0.001 % to 95% by weight.

They can be formulated in various ways depending on the biological and/orchemicophysical parameters which prevail. Preferred possible formulations aretherefore: wettable powders (WP), emulsifiable concentrâtes (EC), émulsions, sprayableémulsions, sprayable solutions, oil- or water-based dispersions (SC), suspoemulsions(SE), dusting agents (DP), seed-dressing products, granules in the form ofmicrogranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), ULV formulations, microcapsules, waxes or baits.

These individual types of formulation are known in principle and are described, forexample, in:

Winnacker-Küchler, ‘Chemische Technologie” [Chemical Technology), Volume 7, C.Hauser Verlag Munich, 4th ed. 1986; van Falkenberg, “Pesticides Formulations",Marcel Dekker N.Y., 2nd ed. 1972-73; K. Martens, “Spray Drying Handbook”, 3rd ed. 1979, G. Goodwin Ltd. London. 011434 15

The formulation auxiliaries required, such as inert materials, surfactants, solvents andother additives, are likewise known and are described, for example, in:

Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2nd ed., DarlandBooks, Caldwell N.J.; H.v. Olphen, “Introduction to Clay Colloid Chemistry”, 2nd ed., J.Wiley & Sons, N.Y.; Marsden, “Solvents Guide”, 2nd ed., Interscience, N.Y. 1950;McCutcheon's, "Détergents and Emulsifiers Annual”, MC Publ. Corp., Ridgewood N.J.;,Sisley and Wood, “Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y.1964; Schônfeldt, “Grenzflàchenaktive Âthylenoxidaddukte” [Surface-Active EthyleneOxide Adducts], Wiss. Verlagsgesell., Stuttgart 1967; Winnacker-Küchler, “ChemischeTechnologie”, Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.

Based on these formulations, it is also possible to produce combinations with other .pesticidally active compounds, fertilizers and/or growth regulators, for example in theform of a readymix or a tank mix. Wettable powders are préparations, uniformlydispersible in water, which contain, beside the active compound and in addition to adiluent or inert material, wetting agents, for example polyethoxylated alkylphenols,.polyethoxylated fatty alcohols, alkyl- or alkylphenolsulfonates, and dispersing agents,for example sodium ligninsulfonate or sodium 2,2'-dinaphthylmethane-6,6'-disuifonate.

Emulsifiable concentrâtes are prepared by dissolving the active compound in anorgariic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene orhigher-boiling aromatics or hydrocarbons, with addition of one or more emulsifiers. Asemulsifiers, the following can be used, for example: calcium salts of alkylarylsulfonates, υι 1434 16 such as Ca dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acidpolyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propyleneoxide/ethylene oxide condensation products, alkyl polyethers, sorbitan fatty acid esters,polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitoi esters.

Dusting agents are obtained by grinding the active compound with finely divided solidsubstances, for example talc, natural clays such as kaolin, bentonite, pyrophillite ordiatomaceous earth. Granules can be prepared either by atomizing the activecompound onto adsorptive, granulated inert material or by applying active compoundconcentrâtes onto the surface of carriers such as sand or kaolinites, or of granulatedinert material, by means of adhesives, for example polyvinyl alcohol or sodiumpolyacrylate, or alternatively minerai oils. Suitable active compounds can also begranulated in the fashion conventional for the préparation of fertilizer granules, ifdesired as a mixture with fertilizers.

In wettable powders, the concentration of active compound is generally fromapproximately 10 to 90% by weight, the remainder to 100% by weight being composedof customary formulation components. In the case of emulsifiable concentrâtes, theconcentration of active compound may generally be from approximately 5 to 80% byweight. Formulations in dust form generally comprise from 5 to 20% by weight of activecompound, sprayable solutions from about 2 to 20% by weight. In the case of granules,the content of active compound dépends partly on whether the active compound is inliquid or solid form and on which granulation auxiliaries, fillers, etc. are being used. 011434 17

In addition, the above mentioned formulations of active compound comprise, ifappropriate, the adhesives, wetting agents, dispersants, emulsifiers, pénétrants,solvents, fillers or carriers which are customary in each case.

The concentrâtes, which are in the commercial ly customary form, are if appropriatediluted in the customary manner for their use, for example using water in the case of 4wettable powders, emulsifiable concentrâtes, dispersions and some microgranules.Dust and granule préparations, and also sprayable solutions, are normally not dilutedany further with other inert substances before being used.

The application rate required varies with the extemal conditions, such as températureand humidity among others. It can fluctuate within wide limits, for example between0.0005 and 10.0 kg/ha or more of active compound, but is preferably between 0.001and 5 kg/ha.

The active compounds according to the invention may be présent in their commerçiallycustomary formulations, and in the application forms prepared from these formulations,as mixtures with other active compounds, such as insecticides, attractants, sterilants,acaricides, nematicides, fungicides, growth regulators or herbicides.

The pesticides include, for example, phosphoric esters, carbamates, carboxylates,formamidines, tin compounds, compounds prepared by microorganisms, inter alia.Preferred co-components for mixtures are U1 1434 18 1. from the group of the phosphorus compounds acephate, azamethiphos, azinphosethyl, azinphosmethyl, bromophos, bromophos-ethyl, cadusafos (F-67825), chlorethoxyphos, chlorfenvinphos, chlormephos,chlorpyrifos, chlorpyrifos-methyl, demeton, demeton-S-methyl, demeton-S-methylsulphone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, EPN, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitriothion, fensulfothion,fenthion, fonofos, formothion, fosthiazate (ASC-66824), heptenophos, isozophos,isothioate, isoxathion, malathion, methacrifos, methamidophos, methidathion, sallthion,mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion,parathion-methyl, phenthoate, phorate, phosalone, phosfolan, phosphocarb (BAS-301),phosmet, phosphamidon, phoxim, pirimiphos, primiphos-ethyl, pirimiphos-methyl,profenofos, propaphos, proetamphos, prothiofos, pyraclofos, pyridapenthion,quinalphos, sulprofos, temephos, terbufos, tebupirimfos, tetrachlorvinphos, thiometon,triazophos, trichtorphon, vamidothion; 2. from the group of the carbamates alanylcarb (OK-135), aldicarb, 2-sec-butylphenyl methylcarbamate (BPMC), carbaryl,carbofuran, carbosulfan, cloethocarb, benfuracarb, ethiofencarb, furathiocarb, HCN-801, isoprocarb, methomyl, 5-methyl-m-cumenylbutyryl (methyl)carbamate, oxamyl,pirimicarb, propoxur, thiodicarb, thiofanox, l-methylthio(ethylideneamino) N-methyl-N-(morpholinothio)carbamate (UC 51717), triazamate; 011434 19 3. from the group of the carboxylates acrinathrin, allethrin, alphametrin, beta-cypermethrin, 5-benzyl-3-furylmethyl (E)-(1 R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, beta-cyfluthrin, beta-cypermethrin, bioallethrin, bioallethrin((S)-cyciopentyl isomer),bioresmethrin, biphenate, (RS)-1 -cyano-1 -(6-phenoxy-2-pyridyl)methyl (1 RS)-trans-3-(4-tert-butylphenyI)-2,2-dimethylcyclopropanecarboxylate (NCI 85193), cycloprothrin, „cyfluthrin, cyhalothrin, cythithrin, cypermethrin, cyphenothrin, deltamethrin, empenthrin,esfenvaierate, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin,fiuvalinate (D-isomer), imiprothrin (S-41311 ), lambda-cyhalothrin, permethrin, pheothrin((R)-isomer), prallethrin, pyrethrine (natural products), resmethrin, tefluthrin,tetramethrin, theta-cypermethrin (TD-2344), tralomethrin, transfluthrin, zeta-cypermethrin (F-56701); 4. from the group of the amidines amitraz, chlordimeform; 5. from the group of the tin compounds cyhexatin, fenbutatin oxide; 6. others abamectin, ABG-9008, acetamipirid, Anagrapha falcitera, AKD-1022, AKD3059, ANS-118, Bacillus thuringiensis, Beauveria bassianea, bensultap, bifenazate (D-2341),binapacryl, BJL-932, bromopropylate, BTG-504, BTG-505, buprofezin, camphechlor, 20 cartap, chlorobenzilatei chlorfenapyr, chlorfluazuron, 2-(4-chlorophenyl)-4,5-diphenylthiophene (UBI-T 930), chlorfentezine, chromafenozide, (ANS-118), CG-216,CG-217, CG-234, A-184699, (2-naphthylmethyl) cyclopropanecarboxylate (Ro12-0470), cyromazin, diacloden (thiamethoxam), diafenthiuron, ethyl N-(3,5-dichloro- 4-(1,1,2,3,3,3-hexafluoro-1 -propyloxy)phenyl)carbamoyl)-2-chloro-benzocarboximidate,DDT, dicofol, difluobenzuron, N-(2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene)-2,4-ylidene)-2,4-xylidene, dinobuton, dinocap, diofenolan, DPX-062, emamcetin-benzoate(MK-244), endosulfan, ethiprole, (sulfethiprole), ethofenprox, etoxazole (YI-5301),fenazaquin, fenoxycarb, fipronil, flumite, (flufenzine, SZI-121), 2-fluoro-5-(4-(4-ethoxyphenyl)-4-methyl-1-pentyl)diphenyl ether (MTI 800), granulosis and nuclearpolyhedrosis viruses, fenpyroximate, fenthiocarb, flubenzimine, flucycloxuron,flufenoxuron, flufenprox (lCI-A-5683), fluproxyfen, gamma-HCH, halofenozide (RH-0345), halofenprox (MTI-732), hexaflumuron (DE-473), hexythiazox, HOI-9004,hydramethylnon (AC 217300), lufenuron, imidacloprid, indoxacarb (DPX-MP062),kanemite (AKD-2023), M-020, MIT-446, ivermectin, M-020, methoxyfenozide (Intrepid,RH-2485), milbemectin, NC-196, neemgard, nitenpyram (TI-304), 2-nitromethyl- .4,5-dihydro-6H-thiazine (DS 52618), 2-nitromethyi-3,4-dihydrothiazole (SD 35651), 2-nitromethylene-1,2-thiazinan-3-ylcarbamaldehyde (WL108477), pyriproxyfen (S-71639), NC-196, NC-111, NN1-9768, novaluron (MCW-275), OK-9701, OK-9601, OK-9602, propargite, pymethrozine, pyridaben, pyrimidifen (SU-8801), RH-0345, RH-2485,RYI-210, S-1283, S-1833, SB7242, Sl-8601, silafluofen, silamadine (CG-177),spinosad, SU-9118, tebufenozide, tebufenpyrad (MK-239), teflubenzuron,tefuranitozine (MIT-446), tetradifon, tetrasul, thiacloprid, thiocyclam, TI-435, tolfenpyrad 011 434 21 (OMI-88), triazamate (RH-7988), trifumuron, verbutin, vertalec (Mykotal), YI-5301.

The above mentioned components for combinations are known active compounds ofwhich many are described in The Pesticide Manual (Editor Clive Tomlin), 11th édition(1997), Crop Protection Publications/ISBN 1-90-901396-11-8 795. The content ofactive compound in the use forms prepared from the commercial formulations can vary,within wide limits, and the concentration of active compound in the use forms can befrom 0.0001 up to 95 % by weight of active compound, preferably between 1 and 50 %by weight. Application is effected in a conventional fashion, matched to the use forms.

The content of the active compound in the use forms prepared from the commercialformulations may be from 0.00000001 to 95% by weight of active compound, preferablybetween 0.00001 and 1% by weight.

The compounds of formula (I) hâve useful properties which allow their use preferred forcombating parasites. ,t can, for example, be used for combating parasites ofvégétation, parasites of premises and parasites in humans and animais.

Thus it is that the products of the invention can be used to combat parasitic insects,nematodes and acariên parasites of végétation and animais. A particular subject of the invention is the use of the compounds of formula (I) tocombat parasites of végétation, parasites of premises and parasites of warm-bloodedanimais. ulI434 22

The active compounds according to the invention of the formula (I) are thus suitable forcontrolling endo- and ectoparasites in the veterinary sector or in the sector of animalhusbandry.

The active compounds according to the invention are in this case applied in a knownfashion, such as by oral application in the form of, for example, tablets, capsules,potions or granules, by dermat application in the form of, for example, dipping,spraying, pouring-on and spotting-on and powdering, and also by parentéral appli-cation in the form of, for example, injection.

The novel compounds, according to the invention, of the formula (I) can accordinglyalso be employed particularly advantageously in livestock husbandry (for examplecattle, sheep, pigs and poultry such as chickens, geese etc.). In a preferredembodiment of the invention, the novel compounds, if appropriate in suitableformulations (cf. above) and if appropriate with the drinking water or feed, areadministered orally to the animais. Since excrétion in the droppings occurs in aneffective fashion, the development of insects in the animal droppings can be preventedvery simply in this fashion. The dosages and formulations suitable in each case areparticularly dépendent on the type and stage of development of the productive animaisand also on the degree of infestation, and can easily be determined and fixed byconventional methods. In the case of cattle, the novel compounds can be employed, forexample, in dosages of 0.01 to 1 mg/kg of body weight. 011434 23

In addition, the compounds according to the invention are also suitable for use intechnical fields, for example as wood preservatives, as preservatives in paints, incooling lubricants for metalworking, or as preservatives in drilling and cutting oils.

The products of formula (I) can also be used preferably to combat insects and otherparasites of the soil, for example, coleoptera such as Diabrotica, click beetles, andcockchafer grubs, myriapoda such as ‘greenhouse’ centipedes and millipedes, anddiptera such as gall midges and lepidoptera such as owlet moths.

They are preferably used in doses of between 10 g and 300 g of active ingrédient perhectare.

The products of the invention présent an excellent shock effect.

The products of formula (I) can also be preferably used to combat insects in premises,in particulàr to combat flies, mosquitoes and cockroaches, particularly Blatellagermanica and Periplanta americana.

The products of formula (I) are also photostable and are less toxic for mammals.

The combination of these properties means that the products of formula (1) correspondperfectly to modem demands: they allow for combating parasites whilst preserving theenvironment.

The products of formula (1) can also be used to combat vegetable acarien andnematode parasites.

The compounds of formula (I) can also be used to combat acarien parasites of animais, 011434 24 to combat, for example, ticks and notably ticks of the Boophilus species, those of theHyalomnia species, those of the Amblyomnia species and those of the Rhipicephalusspecies or to combat ail sorts of mange and notably sarcoptic mange, psoroptic mangeand chorioptic mange.

Therefore a subject of the invention is also a composition for combatting parasites ofwarm-blooded animais, parasites of premises and végétation, comprising one or more,preferably 1 to 3, of the products of formula (I) defined below and in particular theProducts of formula (I) of Examples 14, 27 and 43.

The subject of the invention is particularly an insecticide composition comprising one ormore of the products defined below as active ingrédient.

These compositions are prepared according to the usual processes of theagrochemical industry or the veterinary industry or the industry for products intendedfor animal fodder.

In those compositions intended for agricultural use and for use in premises, the activeingrédient or ingrédients can optionally hâve added to them one or more otherpesticide agents preferably from the group listed above. These compositions can bepresented in the form of powders, granules, suspensions, émulsions, solutions, aérosolsolutions, combustible strips, baits or other préparations usually employed for the useof this type of compound. In addition to the active ingrédient, these compositionscomprise, in general, a vehicle and/or a non-ionic surfactant, ensuring, moreover, auniform dispersion of the constitutive substances of the mixture. The vehicle used canbe a liquid, such as water, alcohol, hydrocarbons or other organic solvents, a minerai, 011434 25 animal or vegetable oil, a powder such as talc, clays, silicates, kieselguhr or acombustible solid.

The insecticide compositions according to invention comprise preferably 0.001 % to10% by weight of active ingrédient.

According to an advantageous operating method, for use in premises, the composition^according to the invention are used in the form of fumigant compositions and in theform of a solvent-based or water-based aérosol.

The compositions according to the invention can then advantageously comprise, for thenon-active part, a combustible insecticide coil, or also an incombustible fibroussubstrate. In the latter case, the fumigant obtained after incorporation of the activeingrédient is placed on a heating apparatus such as an electric heater.

In the case where an insecticide coil is used, the inert support can be, for example,composed of Pyrethrum marc, Tabu powder (or Machiius Thumbergii leaf powder),Pyrethrum stem powder, cedar leaf powder, sawdust (such as pine sawdust), starchand coconut shell powder.

The dose of active ingrédient can then be, for example, 0.03 to 1% by weightIn the case where an incombustible fibrous support is used, the dose of activeingrédient can then be, for example, 0.03 to 95% by weight

The compositions according to the invention for use in premises can also be obtainedby preparing a sprayable oil based on the active ingrédient, this oil soaking a lamp wickand then being set alight. 011434 26

The concentration of active ingrédient incorporated in the oil is, preferably, 0.03 to 95%by weight.

Another subject of the invention coves acaricidal and nematicidal compositionscomprising at ieast one of the products of formula (I) defined below as activeingrédient.

The insecticide compositions according to the invention, as acaricide and nematicidecompositions, can optionally hâve one or more other pesticide agents added to them.The acaricide and nematicide compositions can be presented in particular in the formof powder, granules, suspensions, émulsions, solutions.

For acaricide use, wettable powders are preferably used, for foliar spraying, comprising1 to 80% of active ingrédient by weight, or liquids for foliar spraying comprising 1 to500 g/l of active ingrédient are preferably used. Powders for foliar dusting containingC .05% to 3% of active ingrédient can also be used.

For nematicide use, liquids for soil treatment comprising 300 to 500 g/l of activeingrédient are preferably used.

The acaricide and nematicide compounds according to the invention are used,preferably, at doses comprised between 1 and 100 g of active ingrédient per hectare.To increase the biological activity of the products of the invention, they can be added tostandard synergists used in such cases, such as 1-(2,5,8-trioxadodecyl) 2-propyl 4,5-methylenedioxy benzene (piperonyl butoxide) or N-(2-ethyl heptyl) bicyclo[2,2-1]5-heptene-2,3-dicarboximide, or piperonyl-bis-2-(2'-n-butoxyethoxy) ethylacetal (tropital). 01 1 434 27

The compounds of formula (I) hâve an excellent general tolérance, and therefore asubject of the invention is also the products of formula (I), in particular to combatillnesses caused by ticks and mange in humans and animais.

The products of the invention are in particular used to combat lice as a preventative orcurative and to combat mange.

The products of the invention can be administered by external route, by spraying, byshampooing, by bathing or painting on.

The product of the invention for veterinary use can also be administered by painting thespine according to the "pour-on" method.

It can also be pointed out that the products of the invention can also be used asbiocides or as growth regulators.

Also a subject of the invention is the combinations endowed with insecticide, acaricideor nematicide activity, characterized in that they comprise as active ingrédient, on theone hand at least one of the compounds of the general formula (I) and on the otherhand, at least one of the pyrethrinoid esters chosen from the group constituted by theesters of allethrone, of 3,4,5,6-tetrahydrophthal-imidomethyl alcohol, of 5-benzyl-3-furylmethyl alcohol, of 3-phenoxybenzyl alcohols and of alpha-cyano-3-phenoxybenzylalcohol with chrysanthemic acids, by the esters of 5-benzyl-3-furyl methyl alcohol with 2,2-dimethyl-3-(2-oxo-3-tetrahydrothiophenyl-idene-methyl)-cyclopropane-carboxylicacid, by the esters of 3-phenoxybenzyl alcohol and of alpha-cyano-3-phenoxybenzylalcohols with 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropanecarboxylic acids, by theesters of alpha-cyano 3-phenoxybenzyl alcohol with 2,2-dimethyl 3-(2,2-dibromovinyl) 011 434 28 cyclopropane carboxylic acids, by the esters of 3-phenoxybenzyl alcohol with 2-parachlorophenyl-2 isopropyl acetic acids, by the esters of allethrolone, of 3,4,5,6-tetrahydrophthalimidomethyl alcohol, of 5-benzyl-3-furyl methyl alcohol, of 3-phenoxybenzyl alcohol and of alpha-cyano-3-phenoxybenzyl alcohol with 2,2-dimethyl- 3-(1,2,2,2-tetrahaloethyl) cyclopropanecarboxylic acids, in which "halo" représente afluorine, chlorine or bromine atom, it being understood that the compounds(l) can existin ail their possible stereoisomer forms as well as the acid and alcohol copulas of theabove pyrethrinoid esters.

The compounds of the formula (I) can also be employed for controlling pests in crops ofknown or still to be developed plants which are modified by genetic engineering. Thetransgenic plants generally hâve particularly advantageous properties, for example byrésistance toward certain crop protection agents, résistance toward plant diseases orcausative organisms of plant diseases, such as certain insects or microorganisms, suchas fungi, bacteria or viruses. Other particular properties concem, for example, theharvest with respect to amount, quality, storage stability, composition and spécifie,ingrédients. Thus, transgenic plants having increased starch content or a modifiedquality of the starch, or those having a different fatty acid composition of the harvestedgoods are known.

Preference is given to the use in transgenic crops of economically important usefulplants and omamental plants, for example in cereals, such as wheat, barley, rye, oats,millet, rice, maniok and maize or else in crops of sugar beet, cotton, soya, rapeseed, 011434 29 potato, tomato, pea and other vegetable species.

When used in transgenic crops, in particular with résistance against insects, effects arefrequently observed, in addition to the effects which can be observed in other cropstoward posts, which are spécifie for the application in the respective transgenic culture,for example a modified or specifically broadened spectrum of pests which can becontrolled, or modified application rates which can be used for the application.

The invention therefore also provides the use of compounds of the formula (I) forcontrolling harmful organisme in transgenic crop plants.

Throughout this spécification, unless the context requires otherwise, the word“comprise”, or variations such as “comprises” or “comprising”, will be understood toimply the inclusion of a stated item or group of items, but not he exclusion of any otheritem or group of items, including method steps.

The disclosures in French patent application No. 97 16 24 30 00, from which thisapplication claims priority, and in the abstract accompanying this application areincorporated herein by référencé. 30

Examples of formulations. PREPARATION 1: (1R-cis(Z)] 2'2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropanecarboxylic acid chloride

Stage A: [IR-cis(Z)] 2,2-dimethyl-3-(2-fluoro-3-methoxy-3 -oxo-l-propeny|) cyciopropanecarboxylic acid

Two drops of bromine were added at 20*C to a solution containing 250 cm3of a solutionof carbon tetrachloride and 15 g of (IR-cis(E)J 2J2-dimethyl-3-(2-fluoro-3-methoxy-3-oxo-1-propenyl) cyclopropane carboxylic acid. Irradiation was carried out using a 250watt lamp. The reaction mixture was concentrated under reduced pressure at 40“C and15 g of the sought product (acid ester Z) was obtained.

Stage B: [IR-cis(Z)] 2,2-dimethyl-3-(2-fluoro-3-methoxy-3-oxo-1-propenyl) cyclopropanecarboxylate of (1,1-dimethyl) ethyl 2 drops of DMF and then 11 cm3of (C0CI)2 were added at O°C to a solution containing15 g of the product of the preceding stage and 160 cm3 of methylene chloride. The.mixture was agitated for 15 minutes at 0eC, then for 3 hours at 20eC. It wasconcentrated under reduced pressure at 40°C, then taken up in 100 cm3of toluene andconcentrated under reduced pressure at 40°C. A product was obtained that wasdissolved in 160 cm3 of toluene, followed by cooling down under nitrogen to 0’C. 21cm3of terbutanol and then 9 cm3of pyridine were added. The température was allowedto rise to ambient température and agitation was carried out for 18 hours at 20’C. Thereaction medium was diluted with ethyl acetate and washed with water, with an 011434 31 aqueous solution of sodium acid carbonate, with a 0.5 N solution of hydrochloric acidand with water. After drying, filtering and coneentrating 21.61 g of sought product wasobtained. STAGE C: (1R-cis(Z)] 2,2-dimethyl-3-(2-fluoro-3-hydroxy-3-oxo-1-propenyl)cyclopropane carboxylate of (1,1-dimethyl) ethyl 90 cm3 of a normal soda solution was added at 20°C to a solution containing 21.61 g ofthe product of the preceding stage and 200 cm3of methanol. The reaction medium wasagitated for 30 minutes. The methanol was eliminated under reduced pressure,followed by taking up in water, washing with isopropyi ether, acidifying with a 2Nsolution of hydrochloric acid and extracting with ethyl acetate. After drying, filtering andconeentrating 18.75 g of sought product was obtained. STAGE D: [IR-cis(Z)] 2,2-dimethyl-3-(2-fluoro-3-hydroxy-1-propenyl) cyclopropanecarboxyiateof (1,1-dimethyl) ethyl 11 cm3 of triethylamine then 7.6 cm3 of ethyl chloroformate were added at 0°C to a.solution containing 18.75 g of the product of the preceding stage and 170 cm3of THF.The reaction medium was agitated for 2 hours at 0°C, filtered, the precipitate wasrinsed with 20 cm3of THF. The filtrate obtained was introduced at -70°C into a solutioncontaining 140 cm3of THF and 35 cm3of methanol, and 6.8 g of sodium borohydride.The reaction medium was agitated for one hour at -70°C and the température wasallowed to rise to -30eC until the end of gas évolution. The température was retumed to-60°C followed by pouring into a 2N solution of hydrochloric acid. 600 cm3 of ethyl 32 acetate was added followed by saturation with sodium chioride. The reaction mediumwas decanted and extracted with ethyl acetate, followed by washing, drying, filteringand concentrating at 40°C under reduced pressure. The residue was chromatographiedon silica eluting with a heptane - ethyl acetate mixture, followed by washing with water,with a saturated solution of sodium acid carbonate and with sait water. The productobtained was dried, filtered, concentrated, chromatographied on silica eluting with aheptane - ethyl acetate mixture (7-3). In this way 12.38 g of sought product wasobtained. STAGE E: [1R-cis(Z)] 2,2-dimethyl-3-(3-bromo-2-fluoro-l-propenyl) cyclopropanecarboxyiate of (1,1-dimethyl). ethyl 12.33 g of the product obtained in the preceding stage was dissolved at 0°C undernitrogen in 150 cm3of methylene chioride. 23.55 g of carbon tetrabromide and then asolution of 16 g of triphenylphosphine and 20 cm3 of methylene chioride were added.The reaction medium was agitated for 1 hour at 0eC, filtered, rinsed in methylene .chioride and concentrated. After taking up in isopropyl ether, 40 cm3of ethyl acetateand then 20 cm3of methylene chioride were added. The reaction medium wastriturated, filtered, concentrated and chromatographed on silica eluting with a hexaneethyl acetate mixture (9-1). 15.55 g of product was obtained. STAGE F: [1R-cis(Z)] 2,2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropane carboxyiate of(1,1-dimethyl) ethyl 01 1 434 33 1.7 g of sodium borohydride was added at about 20°C to a solution containing 15.55 gof the product of the preceding stage and 150 cm3of DMSO. The reaction mixture wasagitated for 1 hour 30 minutes, poured into a mixture of water, ice and hydrochloricacid. Extraction was carried out three times with isopropyl ether followed by washing,drying, filtering and concentration. The product obtained was chromatographed elutingwith a heptane-isopropyl ether mixture (95-5). 4.85 g of sought product was obtained. STAGE G: [IR-cis(Z)] 2,2-dimethyl-3-(2-fIuoro-1-propenyl) cyclopropane carboxylic acid0.5 g of p-toluene sulfonic acid (PTSA) was added to a solution containing 5.78 g of theproduct of the preceding stage and 50 cm3 of toluene. The reaction medium was takento 120°C until the end of gas évolution. The reaction medium was retumed to 20°C,diluted with isopropyl ether, washed with water, dried, filtered and concentrated. 4.40 g .of sought product was obtained. STAGE H: [IR-cis(Z)] 2,2-dimethyl-3-(2 fluoro-1-propenyl) cyclopropane carboxylic acidchloride 1 drop of DMF and 4.5 cm3 of (COCl)2 were added at 0°C to a solution containing 4.4 gof the product of the preceding stage and 50 cm3of methylene chloride. The reactionmedium was concentrated, taken up in toluene and concentrated to dryness. Aftertaking up in 35 cm3 of toluene a solution was obtained which was used as it was in thefollowing examples.

General operating method starting from a solution of acid chloride in toluene: 011434 34 5 cm3of acid chloride (3.6 mmoles) is added at 20°C to toluene in a solution containing4 mmoles of alcohol to be esterified and 8 cm3 of toluene. The réaction medium iscooled down to O’C, 0.35 cm3 of pyridine is added and the whole is left to retum to20’C. Filtration is carried out and the filtrate is chromatographed eluting with aheptane-ethyi acetate mixture. In this way the sought product is obtained.

By operating as above starting from the corresponding alcohols, the following productswere obtained: TLC eluent: heptane-ethyi acetate EXAMPLE 1:

rf = 0.27TLC (80-20) EXAMPLE 2:

rf=0.18TLC (80-20) EXAMPLE 3: rf=0.3TLC ( 06-40)

H,C

011434

rf = 0.38TLC ( 90-10) rf = 0.45TLC (90-10)

rf=0.35TLC ( 90-10) EXAMPLE 7:

rf = 0.42TLC (80-20) uI1404 36 PREPARATION 2: [1 R-trans(Z)] 2,2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropanecarboxylic acid chloride STAGE A: [IR-trans(Z)] 2,2-dimethyl-3-(2-fluoro-3-methoxy-3- oxo-1 -propenyl) cyclopropane carboxylate of (1,1 -dimethyl) ethyl 15 g of [1R- trans(Z)] 2,2-dimethyl-3-(2-fluoro-3-methoxy-3-oxo-l-propenyl)'cyclopropane carboxylic acid was dissolved in 150 cm3of methylene chloride at 5°C. 1drop of DMF and 10 cm3of oxalyl chloride were added. The température was allowed toreturn to 20°C. The reaction medium was agitated for 3 hours under a nitrogen stream.Another drop of DMF and 2 cm3 of oxalyl chloride were added. The reaction mediumwas concentrated at 45eC under reduced pressure, taken up in methylene chloride andbrought to dryness. The residue obtained was taken up in 150 cm3of methylenechloride and cooled down to 0°C. 20 cm3of terbutanol was added. 12 cm’oftriethylamine was added. The température was allowed to rise to 20°C and agitationwas carried out under nitrogen pressure. 7 cm3 of pyridine was added, followed byagitation overnight at 20eC. The reaction medium was poured into a normal solution ofhydrochloric acid to which ice was added. Extraction was carried out with methylenechloride followed by drying over magnésium sulphate. After filtering and concentrating 19.33 g of sought product was obtained. STAGE B: [IR-trans(Z)] 2,2-dimethyl-3-(2-fluoro-3-hydroxy-3-oxo-1-propenyl)cyclopropane carboxylate of (1,1-dimethyl) ethyl 25 cm3of a normal solution of soda was added to a solution containing 5.62 g of the 01 1434 37 product obtained in the preceding stage in 100 cm3of methanol. The methanol wasevaporated off under reduced pressure at 40°C followed by dilution with 150cm3ofsolution containing water and 10 cm3of a normal soda solution. Extraction was carriedout with isopropyl ether. The aqueous phase was acidified with 20 cm3 of a 2N solutionof hydrochloric acid. Extraction was carried out with methylene chloride followed bydrying, filtering and concentrating. 5.25 g of product was obtained. STAGE C: (IR-trans(Z)J 2,2-dimethyl-3-(2-fluoro-3-hydroxy-1-propenyl) cyclopropanecarboxylate of (1,1-dimethyl) ethyl 54 g of the product of the preceding stage was dissolved in 1 I of THF at 0°C. 32 cm3 ofTEA (triethyl amine) and then 22 cm3 of ethyl chloroformate were added. The reactionmedium was agitated for 2 hours at 0°C, filtered, rinsed with THF and maintainedovernight at 0°C. After cooling down to 70°C, 19.8 g of sodium borohydride and 100cm3 of methanol were added. The température rose to -35’C. The reaction medium wasagitated for 2 hours at -70°C. 100 cm3of a 2N solution of hydrochloric acid was slowlypoured in between -70°C and -40°C. The reaction medium was poured into 2Nhydrochloric acid. Sodium chloride was added until saturation, and extraction wascarried out with ethyl acetate followed by drying, filtering and concentrating.Chromatography on silica was carried out, eluting with a heptane-ethyl acetate mixture(7-3) and in this way 27.58 g of sought product was obtained. 011434 38 STAGE D: [1 R-trans(Z)] 2,2-dimethyl-3-(3-bromo-2-fluoro-1-propenyl) cyclopropanecarboxylate of (1,1 -dimethyl) ethyl 26.5 g of the product of the preceding stage was added at 2.5°C to a solutioncontaining 50 g of carbon tetrabromide and 250 cm3of methylene chloride. 34 g oftriphenyl phosphine in solution in 100 cm3of methylene chloride was added over onehour. The reaction medium was concentrated at 40°C under reduced pressure, takenup in 250 cm3of isopropyl ether and maintained under agitation ovemight at 20eC. Afterfiltering, rinsing and concentrating 65.85 g of sought product was obtained. STAGE E: [1R-trans (Z)] 2,2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropane carboxylateof (1,1-dimethyl) ethyl 3.8 g of sodium borohydride was added at 20°C to a solution containing 28 g of theproduct prepared previously and 300 cm3 of DMSO. The reaction medium was agitatedfor 1 hour 30 minutes, poured into a mixture of hydrochloric acid, water and ice. .Extraction was carried out with isopropyl ether, followed by washing, drying, filteringand concentrating. 19.38 g of a product was obtained which was chromatographed onsilica, eluting with a heptane-isopropyl ether mixture (95-5). 13.86 g of sought productwas obtained. 011434 39 STAGE F: [1R-trans(Z)] 2,2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropane carboxylicacid 1.2 g of APTS was added to a solution containing 13.86 g of the product of thepreceding stage and 140 cm3of toluene.

The reaction medium was taken to l20eC, maintained under agitation for 30 minutesand the température retumed to 20eC. Dilution was carried out with 250 cm3 ofisopropyl ether followed by washing with water, drying, filtering and concentrating. 11gof sought product was obtained. STAGE G: [IR-trans(Z)] 2,2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropane carboxylicacid chloride 3 drops of DMF and 10 cm3of (COCI)2 were added at 0°C to a solution containing 10 gof the product of the preceding stage in solution in 100 cm3of methylene chloride. Thereaction medium was agitated for 45 minutes at 0°C then for 2 hours 15 minutes at20°C. Concentration was carried out at 40“C followed by taking up in toluene andbringing to dryness. A product was obtained which was dissolved in 55 cm3 of toluene.In this way a 1M solution of acid chloride in toluene was obtained.

Operating method 1 : 50 mg of DMAP and 454 mg of DCC are added at 0eC to a solution containing 379 mgof acid and 588 mg of the alcohol to be esterified and 20 cm3of methylene chloride. 011434 40

The température is allowed to rise to 20°C and agitation is carried out for 1 hour 30minutes followed by filtering, diluting and washing with a 0.5N solution of hydrochloricacid. Decanting is carried out followed by drying, filtering, concentrating and taking upin toluene at 20°C. 0.5 g of tosyl alcohol is added followed by taking the reactionmedium to 12O0C and retuming it to 20°C when the gas évolution is finished. Dilution iscarried out with ethyl acetate followed by washing with sodium acid carbonate, drying,filtering and concencentrating. A product is obtained which is chromatographed onsiiica, eluting with a heptane-ethyl acetate mixture (80-20).

This operating method was particular to the alcohol

The operating method for the other esters was the same as for préparation A.Operating method 2:

The operation was carried out in the same way as Operating Method 1 used forPréparation 1.

In this way the following products were prepared: TLC eluent - heptane-ethyl acetate (80-20) 011434 41 EXAMPLE 8:

rf=0.25 rf = 0.30

II

O rf = 0.20

EXAMPLE 12:

EXAMPLE 13: 0

rf = 0.60 011434 43 EXAMPLE 14:

EXAMPLE 15:

rf = 0.52 rf = 0.45 44 EXAMPLE 17:

rf = 0.23 EXAMPLE 18:

rf = 0.40 EXAMPLE 19:

PREPARATION 3: [1 R-cis(E)l 2,2-dimethyl-3-{2-fluoro-1-propenyl) cyclopropanecarboxylic acid chloride STAGE A: [1R cis(E)] 2,2-dimethyl-3-(2-fluoro-3-hydroxy-3-oxo-l-propenyl)cyclopropane carboxylate of (1,1 -dimethyl) ethyl 011434 45 A mixture of 56.87 g of [1R-cis(E)] 2,2-dimethyl-3-(2-fIuoro-3-methoxy-3-oxo-1-propenyl) cyclopropane carboxylate of (1,1-dimethyl) ethyl, 260 cm3of a normalsolution of soda and 600 cm3 of methanol was maintained under agitation for 1 hour at20°C. The reaction medium was acidifed, extracted with methylene chloride and withethyl acetate. In this way 54.32 g of sought product was obtained. STAGE B: [1R-cis(E)J 2,2-dimethyl-3-(2-fluoro-3-hydroxy-1-propenyl) cyclopropane of λ(1,1-dimethyl) ethyl 54.32 g of the product of Stage A were solubilized at 0°C in 500 cm3of tetrahydrofuran.32 cm3 of triethylamine and 22 cm3 of ethyl chloroformate were added. The reactionmedium was agitated for 2 hours at 0°C followed by filtering, rinsing with THF, thenmaintained at 20eC for 15 hours. A solution of 400 cm3of THF and 100 cm3of methanolwas prepared which was cooled down to -70°C. This solution was added to the reactionmixture prepared previously and 19.8 g of sodium borohydride was also added over 30minutes. The reaction mixture was agitated for 1 hour at -70°C. The température wasallowed to rise to -30°C, producing a gas évolution. When this évolution slowed down,the température was returned to -70°C, followed by pouring into a 2N solution ofhydrochloric acid. Ethyl acetate was added and the reaction medium was saturated withsodium chloride. Extraction was carried out with ethyl acetate followed by washing,drying, filtering and concentrating to dryness. After taking up in ethyl acetate, dryingand filtering, concentration was carried out and 52 g of product was obtained whichwas chromatographed on silica eluting with a heptane-ethyl acetate mixture (7-3). Inthis way 38.26 g of sought product was obtained. 011 434 46 STAGE C: [1R-cis(E)] 2,2-dimethyl-3-(3-bromo-2-fluoro-1-propenyl) cyclopropanecarboxylate of (1,1-dimethyl) ethyl 38.26 g of the product obtained in the previous stage was solubilized in 400 cm3 ofmethylene chlorîde. 72.7 g of carbon tetrabromide and then a solution of 49.3 g oftriphenyl phosphine in 150 cm3of methylene chloride were added followed byconcentration at 40’C at reduced pressure. 143 g of an oil was obtained to which360 cm3of isopropyl ether was added followed by bringing to dryness and taking up inethyl acetate. After decanting and bringing to dryness 61.65 g of product was obtainedwhich was chromatographed eluting with a heptane-ethyl acetate mixture (9-1). 49.58 gof product was obtained. STAGE D: [1 R-cis(E)] 2,2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropane carboxylate of(1,1-dimethyl) ethyl 28 g of the product prepared in the preceding stage was dissolved in 300 cm3of DMSOat 20°C. 3.8 g of sodium hydroboride was added, while maintaining the températurebetween 16’C and 20eC. The reaction mixture was maintained under agitation for 1hour followed by pouring into a mixture of water, ice and hydrochloric acid, washingwith water, drying, filtering and concentrating. 18.94 g of product was obtained whichwas chromatographed on silica eluting with a heptane-isopropyl ether mixture (95-5), inthis way the sought product was obtained (9.91 g). The impure product resulting fromthe first chromatography was chromatographed again eluting with a heptane-isopropylmixture (95-5) and in this way 2.09 g of sought product was obtained. Thus a total of 011 434 47 12 g of sought product was obtained. STAGE E: [1 R-cis(E)] 2,2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropane carboxylicacid 12 g of the product prepared in the preceding stage was dissolved at 20°C in 120 cm3of toluene. 1.3 g of PTSA was added. The reaction medium was taken to 120°C until 4the end of gas évolution followed by diluting with 250 cm3 of isopropyl ether, washingwith water, drying, fiitering and concentrating at reduced pressure. 8.82 g of soughtproduct was obtained. STAGE F: [1R-cis(E)] 2,2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropane carboxylicacid chioride 8.88 g of the product obtained in the preceding stage was dissolved at 0°C in 100 cm3of methylene chioride. 2 drops of DMF then 9 cm3of (C0Cl)2were added over1 minute. The reaction medium was agitated for 30 minutes at 0°C, the températurewas allowed to rise to 20eC and agitation was carried out ovemight. Concentration wascarried out followed by taking up in toluene and retuming the température to 40°C.After diluting with 52 cm3of toluene a 1 M/l solution of acid chioride was obtained whichwas used as it was for préparation of the corresponding esters.

By using the product of the préparation above the following products were prepared:TLC eluent - heptane-ethyl acetate (80-20) 48 EXAMPLE 20:

EXAMPLE 21:

O 011434 49 EXAMPLE 24:

rf = 0.30 EXAMPLE 25:

rf = 0.50 EXAMPLE 26:

rf = 0.50 011434 50 EXAMPLE 27:

rf=0.05 EXAMPLE 28:

O 011434 51 EXAMPLE 30:

rf=0.30TLC (90-10) EXAMPLE 31:

rf = 0.25TLC (90-10) EXAMPLE 32:

F rf=0.90TLC (90-10) rf=0.30TLC (90-10) 52 PRÉPARATION 4 :[1R-trans(E)] 2,2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropanecarboxylic acid chloride STAGE A: [1 R-trans(E)] 2,2-dtmethyl-3-(2-fluoro-3-hydroxy-1-propeny!) çyclopropanecarboxylate of(1,1 -dimethyl) ethyl 37.51 g of [1 R-trans(E)] 2,2-dimethyl-3(2-fluoro-3-hydroxy-3-oxo-1-propenyl)cyclopropane carboxylate of (1,1-dimethyl) ethyl was dissolved at 0°C in 300 cm3ofTHF. 22 cm3of triethylamine, then 15 cm3of ethyl chloroformate were added. Thereaction medium was agitated for 1 hour 30 minutes at 0eC, filtered, rinsed with THFand separated. The solution obtained was added to a solution which was prepared asfollows: a mixture of 250 cm3of THF and 70 cm3of methanol was cooled down to -70°Cand 12 g of sodium borohydride was added. Agitation was carried out for 1 hour at-70°C. The température was allowed to rise to -35’C, then retumed to -50”C and thereaction medium was poured into a 2N solution of HCl. Agitation was carried out for 10minutes followed by saturation with sodium chloride, extraction with ethyl acetate, .washing with sodium acid carbonate, drying, filtering and concentrating. The productobtained was chromatographed eluting with a heptane-ethyi acetate mixture (7-3). Inthis way 26.37 g of sought product was obtained. 011 434 53 STAGE B: [1 R-trans (E)J 2,2-dimethyl-3-(3-bromo-2-fluoro-1 -propenyl) cyclopropanecarboxylate of (1,1-dimethyl) ethyl 26.37 g of the product obtained in the preceding stage was dissolved at 0°C under anitrogen atmosphère in 300 cm3of methylene chloride. 40 g of carbon tetrabromidethen 27 g of triphenyl phosphine dissolved in 40 cm3 of methylene chloride were added.The reaction medium was concentrated and isopropyl ether is added. The températurewas taken to 20°C and filtration was carried out. The filtrate was concentrated andchromatographed on silica eluting with a heptane-ethyl acetate mixture (9-1 ). In thisway 35.12 g of sought product was obtained. STAGE C: [1 R-trans(E)] 2,2-dimethy1-3-(2-fluoro-1-propenyl) cyclopropane carboxylateof (1,1-dimethyl) ethyl 33 g of the product of Stage B was dissolved at 1.8eC in 330 cm3 of DMSO. 3 g ofsodium borohydride was added. The réaction medium was agitated for 1 hour 15minutes then poured into a mixture of water and ice. Extraction was carried out withisopropyl ether followed by washing, drying, filtering and concentrating. The productobtained was chromatographed eluting with a heptane-isopropyl ether mixture (95-5).11.21 g of sought product was obtained. STAGE D: [1 R-trans(E)] 2,2-dimethyl-3-(2-fluoro-l-propenyl) cyclopropane carboxylateof (1,1-dimethyl) ethyl 1 g of PTSA was added at 20eC to a solution containing 11.21 g of the product of thepreceding stage and 100 cm3 of toluene. The reaction medium was taken to 120°C for 011434 54 15 minutes, retumed to 20eC, diluted with isopropyl ether, washed with water, dried,filtered and concentrated. 8.52 g of sought product was obtained. STAGE E: [1 R-trans(E)] 2,2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropane carboxylicacid chloride 1 drop of DMF and 9 cm3 of (COCI)2 were added to a solution containing 8.52 g of theproduct of the preceding stage and 100 cm3of methylene chloride. The reactionmedium was agitated for 1 hour at 0°C then for 16 hours at 20°C. The solvent wasevaporated off followed by taking up in toluene and bringing to dryness. After taking upin 60 cm3 of toluene 60cm3 of a toluenic solution of acid chloride was obtained at0.8 mole per litre which was used as it was for the préparation of corresponding esters.The following esters were prepared: TLC êluent - heptane-ethyl acetate (80-20) EXAMPLE 34:

O

55 011434 EXAMPLE 35:

rf = 0.35TLC (90-10) EXAMPLE 36:

rf = 0.48 rf = 0.35TLC (90-10) 011434 56 EXAMPLE 38:

EXAMPLE 39:

rf = 0.35 EXAMPLE 40:

rf=0.50TLC (90-10) 57 011434 EXAMPLE 41:

rf=0.50TLC (90-10) EXAMPLE 42:

rf=0.20TLC = (80-20)

rf=0.25TLC = (60-40)

rf = 0.33 011434

Biological activity: 1 - Activity on Musca domestica a) A fixed quantity of aérosol was sprayed in the centre of a room where the insectshad previously been released. b) The number of flies knocked down was determined at regular intervals. The KT^, thetime required for knocking down 50% of the insects originally présent in the' room, wascalculated. c) Ail of the flies, knocked down or alive, were collected and observed in a réceptacleprovided with food and water. The mortality was measured 24 hours after the treatmentand expressed as a percentage of the initial population. 2 - Action on Culex pipiens

The protocol used was the same as the protocol of the activity test for Muscadomestica.

In the activity tests 1 and 2, the products showed a good action: a knock-down effectand a léthal effect. 3 - Activity on cockroaches

The action of the products was studied on Blatella germanica and Periplanetaamericana using the standard so-called blowing tunnel test.

The products showed a good activity: knock-down activity and léthal effect. 59 011434

Example of pesticide compositions Aérosols were prepared which had the following formulations. The quantifies indicatedwere quantifies by weight. EXAMPLE A: solvent base

Product of Example 14 0.030

Vegetableoil 1.000

Deodorized petroleum 33.970

Butane CAP 40 65.000 100.000 EXAMPLE B: solvent base

Product of Example 43 0.025

Solvent BVAXK3® 1.000

Deodorized petroleum 33.975

Butane CAP 40 65.000 100.000 EXAMPLE C: aqueous baseProduct of Example 27 0.030

Xylene 4.000

Span 80® 0.500

Shell sol T® 5.470 011454 60

Deionised water 52.000

Butane 38.000 100.000

Comparative Example

The knockdown-effect at 30 seconds and 2 minutes of the compounds of Examples 14,27, 43 and Imiprothrin, a commercially used pyrethroid, against Blattela was assessed.

The tests were carried out in a windtunnel. The active ingrédient was diluted to0.003 % w/v in an 80 % OPD / 20 acetone mixture. Controls (i.e., sprayed with thecarrier liquid alone) were inserted at the beginning of the test, and twice at the end.

Rate: 0.003 %

Compound 30 sec.: 2 min: Ex. 14 30 % 70% Ex. 27 70% 90% Imiprothrin 0% 10%

Surprisingly, the compounds according to the invention are significantly more effectiveagainst Blattela than Imiprothrin. *

Claims (16)

1. 61 01 1 434 CLAIMS:

   1. Compounds of formula (I):

   in ail their possible stereoisomer forms as well as their mixtures in which R représentethe remainder of an alcohol used in the pyrethroid sériés.
2. 2. The compounds of formula (!) as defined in claim 1, wherein R represents:an alkyl radical containing 1 and 18 atoms of carbon; a benzyl radical optionally substituted by one or more radicals selected from the groupconsisting of alkyl radicals containing 1 to 4 carbon atoms, alkenyl radicals containing 2to 6 carbon atoms, alkenyloxy radicals containing 2 to 6 carbon atoms, alkadienylradicals containing 4 to 8 carbon atoms, the methylene dioxy radical and halogenatoms; either a group: CH2 R, CHjRj in which the substituent R1 represents a hydrogen atom or a methyl radical and thesubstituent R2 represents a monocyclic aryl or a -CH2-OCH group; 011 434

   62 or a group: in which a represents a hydrogen atom or a methyl radical and R3 représente the-CH2-CH=CH2, -CH2-CsCH,-CH2-CH=CH-CH3, -CH2-CH=CH-CH=CH2 or -CH2-CH=CH-CH2-CH3 radical;or a group:

   in which a represents a hydrogen atom or a methyl radical, R3 retains the samemeaning as previously, R\ and R'2 identical or different, represent a hydrogen atom, ahalogen atom, an alkyl radical containing 1 to 6 carbon atoms, an aryl radicalcontaining 6 to 10 carbon atoms, an alkyloxycarbonyl group containing 2 to 5 carbonatoms, or a cyano group; or a group: (Rs)n

   in which B represents an oxygen or sulphur atom , -C(O)- or -CH2-, 011434 63 R4 represents a hydrogen atom, a -C=N radical, a methyl radical, a CONH2 radical, a -CSNH2 radical or a -C=CH radical, Rs represents a halogen atom or a methyl radicaland n represents a number equal to 0,1 or 2; or a group:

   in which the substituants R6, R7, R8and R9represent a hydrogen atom, a chlorine atom,or a methyl radical and in which S/l symbolizes an aromatic cycle or an analogousdihydro or tetrahydro cycle; or a group:

   o 011434 or a group: Rio -CH- R11

   in which R10 représente a hydrogen atom or a CH radical, R12 représente a -CH2- radicalor an oxygen atom, Rn represents a thiazyl radical or a thiadiazyl whose bond with: Rio -CH- is located at any one of the available positions, R,2 being linked to Rn by the carbonatom between the sulphur atom and a nitrogen atom;or a group: O

   or a group:

   e d 011434 65 in which R13représente a hydrogen atom or a OCH or CN radical, a, b, c, d, erepresent a hydrogen atom, a halogen atom, an alkyl, O-alkyl or S-alkyl radicalcontaining up to 8 carbon atoms, saturated or insaturated, optionally substituted by oneor more halogen atoms, a CN, NO2, NH2 or OH radical, or R represents a radical:

   in which e and f represent a methyl, CH2F, CHF2or CF3 radical; or R represents an aryl group containing 6 to 14 carbon atoms, optionally substitutedby one or more OH, O-alkyl or alkyl groups containing 1 to 8 carbon atoms or by a CF3,OCF3or SCF3 group; or R represents a pyridinyl, furanyl, thiophenyl oxazolyl orthiazolyl radical.
3. 3. The compounds of formula (I) defined in claim 1 or 2, in which R represents aradical:

   011434 66

   wherein Y représente a hydrogen or halogen atom, a hydroxyl, NO2, CN or NH2, CH2OHor CH2OCH3 radical, an alkyl, O-alkyl or S-alkyl radical containing up to 8 carbonatoms’ optionally substituted by one or more halogen atoms, and/or optionallyinterrupted by one or more heteroatoms.
4. 4. The compounds of formula (I) defined in one or more of daims 1 to 3, in which Rreprésente the radical:

   O . 011434 67
5. 5. The compounds of formula (I) defined in one or more of claims 1 to 4, the names ofwhich follow: - [IR-trans(Z)] 2,2-dimethyl-3-(2-fluoro-l-propenyl) cyclopropane carboxylate of [2,5-dioxo-3-(2-propynyl)-1 -imidazolidinyl] methyl - [IR-cis(E)] 2,2-dimethyl-3-(2-fluoro-l-propenyl) cyclopropane carboxylate of [2,5-dioxo-3-(2-propynyl)-1-imidazolidinyl] methyl - [IR-trans(E)] 2,2-dimethyl-3-(2-fluoro-l-propenyI) cyclopropane carboxylate of [2,5-dioxo-3-(2-propynyl)-1 -imidazolidinyl] methyl.
6. 6. A préparation process for the compounds of formula (I) defined in daim 1,characterized in that an acid of formula (II):

   co2h (») h3c or a functional dérivative of this acid in ail possible stereoisomer forms as well as theirmixtures is subjected to the action of an alcohol of the formula (III): ROH (lll) wherein R is the reminder of an alcohol used in the pyrethroid sériés, or a functional dérivative of this alcohol, and in this way, the sought compound of formula (I) is obtained.
7. 7. Compounds of formula (II) defined in claim 5. 011434 68
8. 8. Pesticide compositions comprising at least one compound defined in any one ofciaims 1 to 5 as an active ingrédient.
9. 9. The pesticide composition as claimed in claim 8, wherein the active ingrédient is acompound as defined in claim 5.
10. 10. A insecticidal, acaricidal or nematicidal composition as claimed in claim 8,comprising auxiliaries and additives which are customary for these applications.
11. 11. A crop protection agent, comprising at least one compound of the formula (I) andat least one further active compound selected from the group of the fungicides,insecticides, acaricides, nematicides, herbicides, plant-growth regulators, sterilants andattrapants together with the auxiliaries and additives which are customary for theseapplications.
12. 12. A composition for protecting wood or as a preservative in sealing compounds, inpaints, in cooling lubricants for metalworking or in drilling and cutting oils, whichcomprises an effective amount of at least one of the formula I as claimed in any ofciaims 1 to 5 together with auxiliaries and additives which are customary for thisapplication.
13. 13. Use of a compound of formula (I) as claimed in any of ciaims 1 to 5 in animalhealth for controlling endo- and ectoparasites. 69 01 1 434
14. 14. A process for preparing a composition as ciaimed in claim 8, which comprisesmixing one or more active compounds and other auxiliaries and additives andconverting them into a suitable use form,
15. 15. A method of controliing harmful insects, acarids and nematodes, whichcomprises applying an effective amount of a compound of the formula (!) as ciaimed inany of daims 1 to 5 or of a composition as ciaimed in claim 8 to these harmful insects,acarids and nematodes, or to the plants, areas or substrates infected with them.
16. 16. Seed, treated or coated with an effective amount of a compound of the formula(!) as ciaimed in any of claims 1 to 5 or of a composition as ciaimed in claim 8.