CA1296360C - Cyclopropanecarboxamides - Google Patents

Abstract

Abstract of the disclosure: Cyclopropanecarboxamides of the general formula I

(I), where R is C1-C12-alkyl, C2-C12-alkenyl, C2-C12-alkynyl, C1-C12-haloalkyl, C2-C12-haloalkenyl, C2-C12-haloalkynyl, C3-C12-alkoxyalkyl, C3-C8-cycloalkyl, C4-C12-cycloalkyl-alkyl, C3-C8-halocycloalkyl, C4-C12-halocycloalkylalkyl, C4-C12-cycloalkylhaloalkyl or C4-C12-halocycloalkylhaloalkyl and X is oxygen or sulfur.
The present invention furthermore relates to the preparation of the compounds I, pesticides which contain the compounds I, and a method for controlling pests.

Description

O.Z. OOS0/39081 Cyclopropanecarboxamides The present invention relates to novel cyclo-propanecarboxamides of the general formula I

D--C--NH~O~X--R I I ), where R is C1-C12-alkyl, C2-C12-alkenyl, C2-C1z-alkynyl, C1-C12-haloa~kyl~ C2-C12-haloalkenyl~ Cz-C1z-haloalkynyl, C3-C12-alkoxyalkyl, C3-C8-cycloalkyl, C4-C1z-cycloalkyl-alkyl, C3-Cg-halocycloalkyl, C4-C1z-halocycloalkylalkyl, C4-C12-cycloalkylhaloalkyl or C4-C12-halocycloalkylhalo-alkyl and X is oxygen or sulfur.
The present invention furthermore relates to the preparation of the compounds I, pest;cides which contain the compounds I and a method for controlling pests.
The cyclopropanecarboxylate I' o ~ 0 ~ 0 ~ ~ (~

is disclosed as a pesticide in DE-A 26 33 069 and the com-pound I

is dis:clos;ed as a pesticide in EP-A-4334. Furthermore, EP:-A-169 169 d;~scloses that~the compound IIII
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is a pe~s~icide, and;DE~-A-26 37 395 discloses that~the ~compound~ :V

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Cl-C4-Alkyl-H~-Y-0-~~0 ~ ~ (IV) is a pesticide and plant growth regulator.
However, the action of the stated compounds is unsatisfactory.
Compounds of the structure IV

15D-Y-N~~O~3~,~ (IV) have been described by R. Zurfluh and S. Dorn in Abetracts, The Sixth International Congress of Pesticide Chemistry (IUPAC)~, 2A-Ol, August l986, Canada. The aromatic phenoxyphenyl unit is essential for the insecticidal activity. ~Such compounds are also disclosed in the Canadian 25Patent Application no. 54~3,716 filed on August 4, 1987 in the name of the Applicant.
; ~ The~ob~ect of th present invention to provide novel cyclopropanecarboxamides of formula (I) having an improved action and/or which are more effective against~
other pests.
n;accordance with the invention, it has been ~found~-~that~th~1s~ ob~jec~t is achieved by the novel ~cyclopropanecarboxamides of formula (I) as defined herein above. It has also been found that the compounds of formula are~very~suitable as pesticides.

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-2a-The compounds of formula (I) are obtainable by reaction of a 2-phenoxye-thylamine of formula lII) with a cyclopropanecarbonyl halide of formula (III), preferably the chloride derivation, o C--Y ~ H2N~--~_~O ~ _ lIII) ~II1 ~-N~ ~ O

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-' - 3 - O.z. 0050/39~81 in the presence of an acid acceptor at from -30 to 1Z0C, preferably from -10 to 80C, particularly preferably from 0 to 50C, and under from 1 to 10 bar Leads to the cyclo-propanecarboxamides I. A suitable acid accept~r is 2-phenoxyethylamine, but the conventional basic agents areusually used, in particular aliphatic, aromatic or hetero-cyclic amines, for example triethylam;ne, dimethylamine, piperidine, dimethylanil;ne, dimethylbenzylamine, pyridine and 4-dimethylaminopyridine. The ratio of acid acceptor to compound III is from 0.5 : 1 to Z0 : 1, preferably from 0.7 : 1 to 5 : 1, particularly preferably from 0.9 : 1 to 1.5 : 1.
The starting materials II and III are usually used in a stoichiometric ratio. An excess of one or other component may be quite advantageous in specific cases.
The reaction usually takes place at a sufficient velocity above -30C. In general, it is not necessary to exceed 100C. Since in some cases it takes place with evolut;on of heat, it may be advantageous to provide a means of cooling.
Some of the 2-phenoxyethylamines II are known;
those which are unknown can be prepared by a conventional method ~EP-A1-4334). Among the cyclopropanecarbonyl halides III, such as the fluoride, chloride or bromide, the chloride is-commercially available.
The reactions are advantageously carried out in a solvent or diluent. Examples of suitable solvents or diluents are aliphatic and aromatic hydrocarbons and chlorohydrocarbons, such as petroleum ether, benzene, toluene, xylene, gasoline, dichloromethane, chloroform, tetrachloromethane, 1,Z-dichloromethane and chlorobenzene, ethers and~esters, such as diethyl and di-n-butyl ether, methyl tert-butyl ether, tetrahydrofuran, dioxane and ethyl acetate, ketones, for example acetone, methyl `35` ethyl ketone and methyl isopropyl ketone, nitriles, such as acetonitrile and propionitrile, and aprotic dipolar soLvents, such ~s dimethylformamide, dimethyl sulfoxide .

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- 4 - O.t. 0050/39081 and pyridine. Mixtures of these substances can also be used as solvents or diluents.
Some of the novel compounds of the formula I are obtained in the form of colorless or pale brownish oils, which can be freed from the final volatile constituents by prolonged heating at moderately elevated temperatures under reduced pressure (incipient d;stillation) and can be-purified in this manner. If the compounds of the formula I are obtained in crystalline form, they can be purified 1û by recrystallization.
The novel compounds of the formula I can also be prepared by virtually any known method of carboxamide synthesis, for example by reacting a 2-phenoxyethylamine with an appropriate carboxylate, carboxylic acid or one of its salts, anhydrides or ketene derivatives (cf. C.
Ferri, Reaktionen der Organischen Synthese, Georg Thieme Verlag, Stuttgart 1978, page 542, and the literature cited therein).
In the compounds I, R is:
- straight-chain or branched C1-C12-alkyl, preferably C1-Cg-alkyl, particularly preferably branched C3-Cg-alkyl, such as isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 1-methylbutyl, isohexyl, 1-methylpentyl, isoheptyl, 1-methylhexyl, 1-methylheptyl, 1,3-dimethylbutyl, 1,2-dimethylbutyl, 3-methylpent-1-yl, 4-methylbut-1-yl, 1-ethylprop-1-yl or 1-ethylbut-1-yl, - straight-chain or branched C2-C12-alkenyl, preferably C2-Cg-alkenyl~particularly preferably C3-C6-alkenyl, such~as allyl, 1-methylallyl, 1,3-dimethylbut-2-enyl, 1-met~h~ylbut-2-enyl or but-3-en-1-yl, - straight-chain or branched C2-C12-alkynyl, preferably C2-Cg~-alkynyl,~ particularly preferab~ly C2-C4-alkynyl, such ethynyl, prop-1-yn-1-yl, prop-2-yn-1-yl, 1-methyl-prop-2-yn~y~l, but-2-yn-1-yl or but-3-yn-1-yl, - straight-c~ha;n or branched C1-C12-haloalkyl, preferably ~C1-C4-haloalkyl, particularly preferably C1-C4-fl~uoro-~or chloroalkyl,~such as trifluoromethyl, : ~ :
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- 5 - O.Z~ 0050/39081 difluoromethyl, fluoromethyl, trichloromethyl, penta-fluoroethyl, 2,2,2-trifluoroeth-1-yl, 2,2,2-trichloro-eth-l-yl, 1-fluoromethyl-2-fluoroethyl or 1-chloromethyl-2-chloroethyl, - straight-chain or branched C2-C1z-haloalkenyl, prefer-ably C2-C4-haloalkenyl, particularly preferably C2-C4-fluoro- or chloroalkenyl, such as 1,2,2-tr;fluoro-ethen-1-yl, 1,2,2-trichloroethen-1-yl, 3,3-di~luoroprop-2-en-1 yl or 3,3-dichloroprop-2-en-1-yl, - straight-chain or branched Cz-C12-haloalkynyl, prefer-ably C2-C4-haloalkynyl, particularly preferably C2-C4-fluoro- or chloroalkynyl, such as fluoroethynyl, chloroethynyl, 3-fluoroprop-2-yn-1-yl or 3-chloroprop--2-yn-l-yl, - straight-chain or branched C3-C12-alkoxyalkyl, prefer-abLy C3-Cg-alkoxyalkyl, particularly preferably C1-C4-alkoxy-substituted C1-Cs-alkoxyalkyl, for example 2-methoxyethyl, 2-methoxyprop-1-yl, 3-methoxyprop-2-yl, 3-methoxybut-1-yl, 4-methoxybut-2-yl, 4-methoxybut-3-yl, 5-methoxypent-3-yl, 2 ethoxyethyl, 2-ethoxyprop-1-yl, 3-ethoxyprop-1-yl, 3-ethoxybut-1-yl, 3-ethoxybut-2-yl, 5-ethoxypent-2-yl, 2-propoxyethyl, 2-propoxyprop-1-yl, 3-propoxybut-1-yl, butoxymethyl or 2-butoxyprop-2-yl, - C2-Cg-cycloalkyl, preferably C3-C6-cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, - C4-C12-cycloalkylalkyl, preferably:C4-Cg-cycloalkyl-alkyl, such as cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl or cy:clohexylethyl, - C3-Cg-halocycloalkyl~ preferably C3-C6-halocyclo-alkyl, particularly preferably C3-C6-fluoro- or chloro-cycloalkyl, such as 2,2-difluoroprop-1-yl or 2,2-di-chlorocycloprop-1-yl, - C4-C12-halo:cycloalkylalkyl, preferably C4-Cg-halocyclo-~: 35 alky~lalkyl, particularly preferably C4-Cg-fluoro- or ch`lorocycloalkyl:alkyl, such as 2,2-difluorocycloprop-1-yl-methy~l or 2,2-dichlorocycloprop-1-yl methyl, : ~ :

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- 6 - O.Z. 0~50/39081 - C4-C1z-cycloalkylhaloalkyl, preferably C4-Cg-cyclo-alkylhaloalkyl, particularly preferably C4-Cg-cyclo-alkylfluoro- or -chloroalkyl, such as 2-cyclopropyl-2-chloroethyl or 2-cyclopropyl-1,1-difluoroethyl, S - C4-C12-halocycloalkylhaloalkyl, preferably C4-Cg-halocycloalkylhaloalkyl, particularly preferably C4-Cg-fluoro- or chlorocycloalkylfluoro- or -chloroalkyL, such as 2,2-dichlorocycloprop-1-yl-2-chloroethyl.
Among the radicals X, oxygen is preferred.
The novel compounds I may contain one or more cen-ters of asymmetry in the substituent R. The present in-vention includes all possible stereoisomers, diastereomers, enantiomers and diastereomer and enantiomer mixtures. The relevant compounds in the Table of the exemplary compounds are the particular racemic mixtures.
In contrast to most of the pesticides known to date, which act as contact or ingested poisons and kill, incapacitate or repel the animals, the compounds of the formula I intervene in the hormonal system of the animal organism. In the case of insects, for example, the trans-formation to the imago, the laying of viable eggs and the development of normal laid eggs are disturbed and hence t~he sequ~ence of generations interrupted. The novel agents are virtually completely non-toxic for vertebrates. The compounds of the formula I are furthermore readily degraded to give substances which occur in nature and are further de~composèd by microorgan~isms. There is therefore no danger of accumulation. Accordingly, they can safely be used for contro~lling pests in animals, crops and stored materials and :in: wate~r.
` The cyclopropanecarboxamides I in which R is a branched~alkyl,;alkenyl, ilkynyl or alkoxyalkyl radical whi`c~h~carries a methyl group in the 1-positio;n^and X is oxygen~have prove~n particularly effective~

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BASF Aktiengesellschaft 7 O,Z. ooso/~soa1 The cyclopropanecarboxamides of the formula I are suitable for effectively combating pests from the class of insects, Arachnida and nematodes, They may be used for protecting crop plants, and in the hygiene, stores protection and veterinary sectors as pesticides, Examples of injurious insects from the Lepidoptera order are Plutella maculipennis, Leucoptera coffeella, Hyponomeuta malinellus, Argyresthia conjugella, Sitotroga cerealella, Phthorimaea operculella, Capua reticulana, Sparganothis pilleriana, Cacoecia murinana, Tortrix viridana, 0 Clysia ambiguella, Evetria buoliana, Polychrosis botrana, Cydia pomonella, Laspeyresia molesta, Laspeyresia funebra, Ostrinia nubilalis, Loxostege sticticalis, Ephestia kuehnielIa, Chilo suppressalis, Galleria mellonella, Malacosoma neustria, Dendrolimus pini, Thaumatopoea pityocampa, Phalera bucephela, Cheimatobia brumata, Hibernia defoliaria, Bupalus pinarius, 15 Hyphantria cunea, A9rotis segetum, Agrotis ypsilon, Barathra brassicae, Cirphis unipuncta, Prodenia litura, Laphygma exigua, Panolis flammea, Earis insulana, Plusia gamma, Alabama argillacea, Lymantria dispar, Lymantria monacha, Pieris brassicae, and Aporia crataegi;

20 examples from the Coleoptera order are:Blitophaga undata, Melanotus communis, Limonius californicus, Agriotes lineatus, Agriotes obscurus, Agrilus sinuatus, Meligethes aeneus-, Atomaria linearis, Epilachna ~ varicestris, Phy:llopertha hbrticola, Popillia japonica, Melolontha : melolontha, Melolonth~a hippocastani, Amphimallus solstitialis, Crioceris25 asparagi, Lema melanopus, Leptinotarsa decemlineata, Phaedon cochleariae, Phyllotreta nemorum, Chaeto~nema tibialis, Phylloides chrysocephala, Diabrotica 12-punctata, Cassida nebulosa, Bruchus lentis, Bruchus rufimanus, Bruchus pisorum, Sitona lineatus, Otiorrhynchus sulcatus, Otiorrhynchus~ova:tus,~Hylobies~abietis, Byctiscus betulae, Anthonomus 30 pomorum, Anthonomus:grandis, Cèuthorrhynchus assimilis, Ceuthorrhynchus napi,~Sitophilus granaria, Anisa'ndrus dispar, Ips typographus, and Blastophagus~pin~perda~
examples-from~the~Diptera order a:re Lycoria pectoralis, Mayetiola 35~destructor,~Dasyneura brassicae~, Contarinia tritici, Haplodiplosis equestris, Tipula:~:paludosa, Tipula oleracea, Dacus cucurbitae, Dacus oleae, Cerà~titis~capitata,~Rhagoletis: cerasi,~Rhagoletis pomonella, Anastrepha~ludens,~ Oscinella frit, Phorbia coarctata, Phorbia antiqua, ` Phorbia brassicae,~Pegomya hyoscyami, Anopheles maculipennis, Culex : ~
40 pipiens,:Aedes~aegypti~,;Aedes:~vexans, Tabanus bovinus, Tipula paludosa, - Musca:domèstica~ Fannia:canicu~laris:,~Muscina stabulans, Glossina morsitans,:~Oestrus ovis,:Chrysomya macellaria, Chrysomya hominivorax, Lucllia~cuprlna~ Lucllla~ serlcats, and Hypoderms llneata.

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BASF Aktiengesellschaft 8 O.Z. 0050/39081 examples from the Hymenoptera order are Athalia rosae, Hoplocampa rninuta, Monomorium pharaonis, Solenopsis geminata, and Atta sexdens;
examples from the Heteroptera order are Nezara viridula, Eurygaster 5 integriceps, 31issus leucopterus, Dysdercus cingulatus, Dysdercus intermedius, Piesma quadrata, and Lygus pratensis;
examples from the Homoptera order are Perkinsiella saccharicida, Nilaparvata lugens, Empoasca fabae, Psylla mali, Psylla piri, Trialeurodes 10 vaporariorum, Aphis fabae, Aphis pomi, Aphis sambuci, Aphidula nasturtii, Cerosipha gossypii, Sappaphis mali, Sappaphis mala, Dysaphis radicola, Brachycaudus cardui, 9revicoryne brassicae, Phorodon humuli, Rhopalomyzus ascalonicus, Myzodes persicae, Myzus cerasi, Dysaulacorthum pseudosolani, Acyrthosiphon onobrychis, Macrosiphon rosae, Megoura viciae, Schizoneura 15 lanuginosa, Pemphigus bursarius, Dreyfusia nordmannianae, Dreyfusia piceae, Adelges laricis, and Viteus vitifolii;
examples from the Isoptera order are Reticulitermes lucifugus, Calotermes flavicollis, Leucotermes flavipes, and Termes natalensis;
examples from the Orthoptera order are Forficula auricularia, Acheta domestica, Gryllotalpa gryllotalpa, Tachycines asynamorus, Locusta migratoria, Stauronotus maroccanus, Schistocerca peregrina, Nomadacris septemfasciata, Melanoplus spretusj Melanoplus femur-rubrum, 81atta 25 orientalis, 91attella germanica, Periplaneta americana, and Blabera gigantea.
, ~xamples of mites and ticks (Acarina~ belonging to the Arachnida class are Tetranychus telarius, Tetranychus pacificus, Paratetranychus pilosus, 30 Bryobia praetiosa, Ixodes ricinus, Ornithodorus moubata, Amblyomma americanum, Dermacentor s~ilvarum,~and Boophilus microplus.
Examples from the Nemathelminthes class are root-knot nematodes, e.g., Meloidogyne incognita, Meloidogyne hapla, and Meloidogyne javanica, 35 cyst-forming nematodes, e.g., Heterodera rostochiensis, Heterodera schachtii, Heterodera avenae, Heterodera glycines, and Heterodera trifolii, and stem and leaf eelworms, e.g., Ditylenchus dipsaci, Ditylenchus destructor,~ Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchu~s goodeyi, Pratylenchus curvitatus and Tylenchorhynchus dubius, 40 Tylenchorhynchus claytoni, Rotylenchus robustus, Heliocotylenchus multicinctus, Radopholus similis, 9elonolaimus longicaudatus, Longidorus elongatus, and Trichodorus primitivus, , ~: :

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BASF Aktiengesellschaft ~ 0,Z 0050/~908l The active ingredients may be applied for instance in the form o-f dirsctly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dis-persions, pastes, dusts, broadcasting agents, or granules by ~praying, 5 atomizing, dusting, broadcasting or watering, The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients accord-ing to the invention as possible.

10 For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, 5 alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide,~dimethyl sulfoxide, N-methyl-pyrrolidone, water, etc. are suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing 25 agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsi~fying or dispersing agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and 30 ammonium salts~ of ligninsulfonic acid, naphthalenesulfonic acids.
phenolsulfonic acids,~alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutyl-naphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of 35 sulfat~ed hexadecanols~,- heptadecanoLs, and octadecanols, salts af sulfated ~fatty alcohol gly~col~ethers, condensation products of sulfonated naphthalene~and naphthalene derivatives with formaldehyde, condensation produc;ts~of:naphthalene or naphthalenesulfonic acids with phenol and formald~e~hyde,~polyoxyethylene octylphenol ethers, ethoxylated isooctyl-40 phenol, ethoxylated~octylphenol and ethoxylated nonylphenol, alkylphenolpo~lyglycol ethers, tributyIphenyl polyglycol~ethers, alkylaryl polyether alcohol~s, isotri~decyl alcohol, fatty aIcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated poly-~ oxypr`o~pylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, ; l~gnln, sulf~lte~waste~llquors and methyl cellulose.

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BASF Aktiengesellschaft 10 0,Z, 0050/39081 Powders, dusts and broadcasting agents may be prepared by mi~ing orgrinding the active ingredients with a solid carrier, Examples of formulations are given below.
I 5 parts by weight of compound no 2 is intimately mixed with g5 parts by weight of particulate kaolin. A dust is obtained containing 5Z by weight of the active ingredient.

10 II. 30 parts by weight of compound no. 2 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
III. 10 parts by weight of compound no. 2 is dissolved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 2 parts by weight of the calcium salt of dodecylbenzene-20 sulfonic acid, and 2 parts by weight of the adduct of 40 moles of ethyleneoxide and 1 mole of castor oil.
, IV. 20 parts by weight of compound no. 2 is dissolved in a mixture consisting of 60 parts`by weight of cyclohexanone, 30 parts by weight of 25 isobutanol, 5 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphènol, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and l mole of castor oil.

~. 20 parts by weight of compound no. 2 is well mixed with 3 parts by 30 weight of the sodium salt of diisobutylnaph~thalene-alpha-sulfonic acid, 10 parts by weight of the sodium:salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and~7 parts~by weight of powdered silica gel, and triturated-in a:hammer mill. .~.

35 Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingr;edients to solid carriers. Examples of solid carriers are mineral earths~s~uch as silicic acid, silica gels, : silicates,~talc,~kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium 4Q sulfate;,~mag~nesium oxide, ground~plastics, fertilizers such as ammonium sulfate,~ammonium:phospha~te, ammonium nitrate, and ureas, and vegetable products such;~as~grain;~flours, bark meal, wood meal, and nutshsll meal, celluloslc powd~ers,~ ete.

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3ASF Aktiengesellscha~t 11 O,Z, 0050/3~0~1 The formulations generally contain from 0,1 to 95, and preferably 0,5 to 90, Z by weight of active ingredient.
The active ingredient concentrations in the ready-to-use formulations may 5 vary within a wide range generally, they are from 0.0001 to ~Ol, and preferably from 0.01 to 1~, The active ingredients may also be success-fully used in the ultra-low-volume (ULV) process, in which it is possible to apply formulations containing more than 95 wtZ of active ingredient, or even the active ingredient without additives.
When agents containing the compounds according to the invention are used in the open, the amount of active ingredient employed is from 0.2 to 10, and preferably from 0 5 to 2, kg/ha.
5 Oils of various types, herbicides, fungicides, other pesticides and bactericides may be added to the active ingredients, if desired immediately before use (tankmix), in a weight ratio of from 1:10 to 10:1.
Examples of active ingredients which may be admixed are as follows:
20 1,2-dibromo-3-chloropropane, 1,3-dichloropropene, 1,3-dichloropropene 1,2-dichloropropane, 1,2-dibromoethane, 2-sec-butylphenyl-N-methyl-carbamate, o-chlorophenyl-N-methylcarbamate, 3-isopropyl-5-methylphenyl-N-methylcarbamate, o-isopropoxyphenyl-N-methylcarbamate, 3,5-dimethyl-4-methylmercaptophenyl-N-methylcarbamate, 4-dimethylamino-3,5-xylyl-N-25 methYlcarbamate. 2-ii,3-dioxolan-2-yl)-phenyl-N-methylcarbamate, 1-naphthyl-N-methylcarbamatej 2,3-dihydro-2,2-dimethylbenzofuran-7-yl-N-methylcarbama~te~, 2,2-dimethyl-~,3-benzodioxol-4-yl-N-methylcarbamate, 2-dimethylamino-5,6-dimethyl~-4-pyrimidinyldimethylcarbamate, 2-methyl-2-~methylthio)-propionaldehyde-O-(methylcarbamoyl)-oxime, S-methyl-N-30 ~methylcarbamoyl)-oxy]-thioacetimidate, methyl-N',N'-dimethyl-N-[(methyl-carbamoyl~-oxy]-1-thiooxamidate, N-(2-methyl-4-chlorophenyl)-N'N'-di-methylformamidi~ne,~tetrachlorothiophene, 1-(2,6-difluorobenzyl)-3-(~-`chlorophenyl)-urea, O,O-dimethyl-O-(p-nitrophenyl)-phosphorothioate.
O,O-diethyl-O-~(p-nitrophenyl)-phosphorothioate, O-ethyl-O-(p-nitro-35 phenyll-phenylphosphonothioate-, OiO-dimethyl-0-(3-methyl-4-nitrophenyl)-ph-osphorothio~ate,~O,O-dlethyl-0-(2,4-dichlorophenyl)-phosphorothioate, O-ethyl-0-(2,4-dichIorophenyl)-phenylphosphonothioate, 0,0 dimethyl-0-(~2:,4,5-trichlorophenyl)-phosphorothioate, 0-ethyl-0-(2,4,5-tri-chlorophenyl)-~ethylphosphonothioate, 0,0-dimethyl-0-~4-bromo-2,5-dichloro-40 phenyl~)-phosphorothioate,~O,O-dimethyl-0-(2,5-dichloro-4-iodophenyl)--:phosph~or~othioate~ O;,O-dimethyl-0-(3-methyl-4-methylthiophenyl)-phosphoro;thioat~e~,~ O-ethyl-0-(3-methyl-4-methylthiophenyl)-~ isopropy~lphosphoramidate,~O,O-diethyl-O-[p-(methylsulfynyl)-phenyl]-s phosphor~othioate, O~-ethyl-S~-phenylethylphosphonodithioate, :
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BASF Aktiengesellschaft 12 O.Z, OOSD/39DBl 0,0-diethyl-B2-chloro-1-(2,4-dichlorophenyl)-vinyl]-phosphate, 0,0-dimethyl-[-2-chloro-1-(2,4,5-trichlorophenyl)]-vinylphosphate, 0,0-dimethyl-S-(l-phenyl)-ethylacetate phosphorodithioate, bis-(dimethylamino)-fluorophosphine oxide, octamethylpyrophosphoramide.
5 0,0,0,0-tetraethyldithiopyrophosphate, S-chloromethyl-0,0-diethyl-phosphorodithioate, 0-ethyl-S,S-dipropyl-phosphorodithioate, 0,0-dimethyl-0-2,2-dichlorovinylphosphate, 0,0-dimethyl-1,2-dibromo-2,2-di-chloroethylphosphate, 0,0-dimethyl-2,2,2-trichloro-1-hydroxyethylphos-phonate, 0,0-dimethyl-S-[1,2-biscarbethoxyethyl-(1)]-phosphorodithioate, 0~0-dimethyl-0-(1-methyl-2-carbomethoxyvinyl)-phosphate~ 0,0-dimethyl-S-(N-methylcarbamoylmethyl)-phosphorodithioate, 0,0-dimethyl-S-(N-methyl-carbamoylmethyl)-phosphorothioate, 0,0-dimethyl-S-(N-methoxyethyl-carbamoylmethyl)-phosphorodithioate, 0,0-dimethyl-S-(N-formyl-N-methyl-carbamoylmethyl)-phosphorodithioate, 0,0-dimethyl-0-[1-methyl-2-lmethyl-5 carbamoyl)-vinyl]-phosphate, 0,0-dimethyl-0-~l1-methyl-2-dimethyl-carbamoyl~-vinyl]-phosphate, 0,0-dimethyl-0-~(1-methyl-2-chloro-2-diethyl-carbamoyl)-vinyl]-phosphate, 0,0-diethyl-S-(ethylthiomethyl)-phosphorodi-thioate, 0,0-diethyl-S-t(p-chlorophenylthio)-methyl]-phosphorodithioate, 0,0-dimethyl-S-(2-ethylthioethyl)-phosphorothioate, 0,0-dimethyl-S-(2-20 ethylthioethyl)-phosphorodithioate, 0,0-dimethyl-S-(2-ethylsulfynyl-ethyl)-phosphorothioate, 0,0-diethyl-S-(2-ethylthioethyl)-phosphorodithio-ate, 0,0-diethyl-S-(2-ethylsulfynylethyl)-phosphorothioate, 0,0-diethyl-thiophosphoryliminophenyl-acetonitrile, 0,0-diethyl-S-(2-chloro-1-phthal-imidoethyl)-phosphorodithioate, 0,0-diethyl-S-[6-chlorobenzoxazolon-(2)-25 yl-(3)]-methyldithiophosphate, 0,0-dimethyl-S-~2-methoxy-1,3,~-thia-diazol-5t4H]-onyl-(~)-methyl]-phosphorodithioate, 0,0-diethyl-0-[3,5,~-trichloropyridyl-(2)]-phosphorothioate, 0,0-diethyl-0-(2-pyrazinyl)-phosphorothioate, 0,0-diethyl-0-[2-isopropyl-4-methylpyrimidinyl-(6)]-phosphorothioate, 0,0-diethyl-0-[2-(diethylamino)-6-methyl-~-30 pyrimidinyl]-thionophosphate, 0,0-dimethyl-S-(4-oxo-1,2,3-benzotriazin-3-~4H]-yl-methyl)-phosphorodithioate, 0,0-dimethyl-S-[(4,6-diamino-1,3,5-triazin-2-yl)-methyl]-phosphorodithioate, 0,0-diethyl-(1-phenyl-1,2,~-triazol-3-yl)-thionophosphate, 0,S-dimethylphosphoro-amidothioate, 0,S-dimethyl-N-acetylphosphoramidothioate, alpha-hexa-35 chlorocyclohexane, 1,1-di-(p-méthoxyphenyl)-2,2,2-trichloroethane, 6,7,8,9,10,10-hexachloro-1,5,5a.6.9,9a-hexahydro-6,9-methano-Z,4,3-benzo-dioxathiepine-3-oxide, pyrethrins, DL-2-allyl-3-methyl-cyclopenten-(2)-on-(1)-yl-(4)-DL-cis,trans-chrysanthemate, 5-benzylfuryl-(3)-methyl-DL-: cis,trans-chrysanthemate, 3-phenoxybenzyl(+)-cis,trans-2,2-dimethyl-~-40 (2,2-dichlorovinyl)-cyclopropanecarboxylate, alpha-cyano-3-phenoxy-benzyl(+)-cis,trans-2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane-carboxylate,~(s)-alpha-cyano-3 -phenoxybenzyl-cis(lR,3R)-2,2~dimethyl-3-(2,2-dibromovinyl)-cyclopropanecarboxylate, 3,4,5,6-tetrahydrophthalimido-ethyl-DL-cis,trans-chrysanthemate, 2-methyl-5-(2 -propynyl)-3-furyl-methyl-chrysanthemate, and alpha-cyano-3-phenoxybenzyl-alpha-isopropyl-~-chlorophenylacetate.

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BASF Aktiengesellschaft 13 O.Z. 0050/39031 Manufacturing example N-{2-[4-(1-methylprop-1-yloxy)-phenoxy]-ethyl}-cyclopropanec~rboxarnide 5 At 5C, 3.4 g of cyclopropanecarbaxylic chloride was dripped into a solution of 6.5 g of 2-~4-(1-methylprop-1-yloxy~-phenoxy]-ethylamine and 3.5 g of triethylamine in 100 ml of absolute methylene chloride. After the mixture had been stirred for a hours it was poured onto 200 g of icelwater and the resultant solution was adjusted to a pH of 2 with 2N aqueous 10 hydrochloric acid. The aqueous phase was then extracted twice, each time with 50 ml of methylene chloride, and the combined organic phases were washed with saturated sodium carbonate solution and water, and dried over sodium sulfate. After removal of the solvent under reduced pressure and recrystallization from cyclohexane, there was ob~ained 6.4 g of N-~2-[4-5 (1-methylprop-1-yloxy)-phenoxy]-ethyl}-cyclopropanecarboxamide (compound no. 2); m.p.: 65-6~C.

The compounds I listed in the tables below without any physical character-istics may be readily prepared from the corresponding starting materials 20 and may be expected to have a similar action.

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36~3 6ASF Aktiengesellschaft 14 O.Z, 0050/3308l Tcable ompound I
\ 11 C-NH ~ 0 ~ (I) ~ X-R
Compound R X m.p. [C] ~ NMR
No. in CDCl-~
H3C\

H3C\

; H3C-CH2 H3C\
3 : CH- 0 6.84 (s) H3c-icH2)2 : : H3C\

4 : CH- 0 52-54 H3C-(CH2)3 : ` ~ H3C
. 5 ~ CH- 0 : 58-61 H3C-(CH2)4 :
: ~ :
~ H3C
\
6 ~ /CH-~ : O
; H3C-(cH2i5~ ~
:
:

;

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63~
BASF Aktiengesellschaft 15 O.Z. 0050/3gO81 Compound R Xm.p. ~C] 1H-NMR
No __ _ _ in CDC11 _ H3C\

H3C\

H3C-(CH2)2 H3C\

H3C-(CH2)3 H3C\

` \ / O6.80 (s) : ~H3C

11 \ / : 0 6.81 (s) CH
/

: ~ H3C ~ ~
12 H3C\ /CH- ~ S

H3C~
H3C\
` 13 CH- O
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: H2C=CH
., :
1~ ~ HzC=CH-CH2- 0 ~ Cl ~
15~ ~ ~ C=CH-CH2- 0 : : : :: Cl :

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BASF Aktiengesellschaft 16 O.Z, 0050/33081 Compound R X m.p. ~C] 1H-NMR
n CDCl~
H3C\
16 H3C\ /CH-C=CH

H3C\

17 ~ / S
/C=CH

18 cyclobutyl 0 19 cyclopentyl 0 cyclohexyl 090- 93 21 cyclopropylmethyl 0 22 cyclohexyImethyl 0 Cl\ /Cl Cl\ /Cl 24 C S 6.72 and / \ 7.~8 (2d) H2C - CH-CH2-;:

26 Cl-C-C-CH2- 0 27 `/CH-~ 0115-117 - HC-C :~
H3C\ :~ ~ :
~ H CH-28 ~ 0 C=CH
~H3C
- : :: : :: : :
~H3C\~
29 ~ CH-CH2- ~ ~ 0 94- 96 : H3C

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BASF Aktiengesellschaft 17 0,Z. 0050/33081 Compound R X m.p. ~C] 1H-NMR
No. __ _ in cn /CH-(CH2~2- 0 110-112 H3C\

H3C-CH2\
32 CH- 0 6.80 (s) F-CH2\

3~ F3C-CH2- 0 H H
\ /
/C\ fH3 0 36 ~Cl-CH=CH-CH2- O
..

37 ::H3C-IC- 0 75- 76 : ` CH3 : ~
:
3 a H 3 C--C H 2--C H 2-- o 39 : H3C-CH2-CH2-CH2- 0 100-10Z
.
40 : H3C- ` 0 106-109 H3C-CH2-~ ~ 102-104 2~ H3cl:cH2~4- : 102-10 f H~3 ~

43~H3C-~f - CH2-cH~2~ 62- 65 ; , ~ C H 8 : ~

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BASF Aktiengesellschaft 18 O.Z, 0050/390a1 Compound R X m.p, [C] lH-NMR
NQ _ __ in CDCl CH3 fH3 ~4 H3C-IC-cH2-cH- 0 57- 61 H3C-CH~
~6 CH- 0 ~.ao ~S) H3C-(CH2)2 ~7 H3C /CH- 0 6.82 (sl H3C\
~8 C=CH-CHz- 0 77~ 79 ~9 H3C-CH-CH- ~ o :

Cl-CH2-CH~ 0 :
: : CH3 51 Cl-CH2-CH2-CH- ~ 0 : : : :
:
52 H3C-0-fH-CH2- ~ ; 69- 73 ~ : : CH3 53~HI~ H3C-0-fH-CH2-CH2-~ 0 95- 97 CH3~
~:5~ H~C-C-;H2-lH- ~ ~ :0 3.40 (s) 55~ H3c-o-cH2-cH2~ 0 108~

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CASF Aktiengesellschaft 19 0 Z. ODgO/39081 Compound R Xm.p. ~C] 1H-NMR
No. _ _ _ __in CDCla fH3 : 56 H3C-0-CH2-CHz-CH 0 3.28 (s) 57 H3C-0-CHz-CHz- S 3.32 (s) 5B H3C-0-CHz-CH- S 3.42 (s) Use examples In the following examples the action on pests of the compounds according to the invention was compared with that of the following prior art compounds:
O
C-0 ~ ~0 ~ ~ from DE-A-26 33 069 : O
0-C~NH ~ 0 ~ ~ from EP~A-4334 and :
O
I
: ~ ~NH ~ 0 ~ ~ from EP-A-169 169.

5 The concentrations~at which the investigated compounds achieved a 100X
kill or:inhibition are the minimum concentrations. At least.one replicate was~ run ~for each concentration.
: : : :
Breeding:experiment with mosquito larvae (Aedes aegypti) ; ~The active ingredient formulations were added to 200 ml of tapwater and 20 : ~ ~ to~30~mosquito larv~ae in the fourth larval stage Were introdused. The vesseIs were~kept at 25C. Pupation and hatching of the imagoes, which took~place a~fter~lO:to 12 days,~were monitored. A powdered tropical ~fl~s~hf~ood was¦;Fed once durlng the observation period.
:`In~this;experlment, compound no. 2, at a rate of 0.03 ppm, achieved 100a kill;,lw~hereas~comparative~compound I achieved a kilI of 50X and compara-tlve~agèn~ ;a~kll1 of 80X~. ~

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o 9ASF Aktiengesellschaft 20 O.Z. 0050/39081 Breeding experiment with cotton stainers (Dysdercus intermedius) Moist quartz sand treated with solutions of the active ingredients was introduced into 1 liter jars and larvae of the fourth larval stage were 5 kept on it at 25C. The experiment was run until the following generation hatched. The imagoes were assessed for morphogenesis disturbances.
In this experiment, compound no. 2, at a rate of 1 ppm in the sand, achieved BOZ kill, whereas comparative compound I' had no effect and com-10 parative compound Ill exhibited a kill rate of 30%. Comparative compoundI~ll had to be used in a tenfold amount to achieve 80X kill.

Development inhibition in Prodenia litura 15 (experiment on treated nutrient medium) 100 g of the standard nutrient medium for Prodenia was filled into 250 ml beakers~, and carefully mixed, while warm, with aqueous formulations of the active ingredients. After the medium had cooled, 10 caterpillars of the 20 fourth larval stage were introduced into each vessel, and the vessels were kept at 23C. The observation period extended up to hatching of the moths.
':
In this experiment, compound no. 2 achieved 100X. kill at a rate of 0.3 ppm,;80'l kill at a rate of 0.1 and 0.03, and 60'l kill at a rate of 25 o.ol ppm. Comparative compound I' had no effect at-all these rates. Com-parative compound Ill achieved 100~ mortality at 0.3, 0.1 and 0.03 ppm, but the kill dropped~to 60~ at a rate of O.01 ppm.

30 Ovicidal action on Ceratitis capitata (Mediterranean fruit fly) 20 to 30 eggs from O to 24 hours old were placed on a 5 x 5 cm filter paper in a~closed~vessel; half a roll of absorbent cotton moistened with water and a~ball of mashed carrots i.5 cm in diameter were introduced. The 35 filter paper was moistened~with 1.5 ml of the candidate solution and kept at 25`to 26C during~thei5 to 6 days the experiment was run. Hatching and development~of the larvae were assessed.
~, ~
In:this experiment~, compound~no. 2, at a rate of 1X, had the same action 40~as c~omparàtive~compound Ill. Compound no. 2 retained its action at 0.3X, wherea~s~ compound ~ wa~s~ineffective. Comparative compound I was ineffect-iye at;all the~rates investigated.

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BASF Aktiengesellschaft 21 O,Z. 0050/3908l In the following examples, the aCtion on pests of compounds 3, lO and 30 is compared with that of the following prior art compound (IV) ~ C-NH ~ O ~ ~ lI 1 The concentration at which the compounds investigated achieve lOOZ. kill or inhi'oition are the minimum concentrations, ht least one replicate was run 5 for each concentration, Breeding experiment with Dysdercus intermedius ~cotton stainer) 0 Moist quartz sand treated with solutions of the active ingredients was introduced into l liter jars and larvae of the third larval stage were kept on it at 25C. The experiment was run until the following generation hatched.
5 In this experiment, compounds nos. 10 and 30 achieved 1 ooa kill at a rate of less than O.S ppm, whereas:comparative compound (IV) only achieved 100X
kill at a rate of 1 ppm. In the case of compound no. 3, 4 ppm was required.

Ovicidal action on Dysdercus intermedius (cotton stainer) Pieces of double-s-ded adhesive tape we~re stuck to the top edge of plastic plant markers. 24 hours before commencement of the experimsnt, eggs of the 25 cotton stainer were attached to the adhesive strips. The eggs were then treated with aqueous formulations`of the active ingredients. The markers were then placed in plastic trays (~adhesive strip at the top).~Half a roll of absorbent cotton was moistened with:water:and placed:in each beaker to prevent drying out;. Assessment took~pIace after the contr'ol bugs hatched 30 ~after about~8 days~. The~batch inhlbition~in l was aSsessed.

In thls experimené, compound~30~and~comparative agent~(IV) were ineffect-ive at lOOO~ppm,~whereas~compounds~ and lO inhibited hat:ching to a degree of 8ûZ at:far`lower concentrati~ons:~(200 ppm and less).:

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.

BASF Aktiengesellschaft 22 0,Z, 0050/39081 Development inhibition in Prodenia litura ~experiment on treated nutrient medium) 100 9 of the standard nutrient rnedium for Prodenia was filled into 250 ml 5 beakers, and carefully mixed, while warm, with aqueous formulations of the active ingredients, After the medium had cooled, 5 caterpillars of the third larval stage were introduced into each vessel, and the vessels were kept at 25 to 26C The observation period extended up to hatching of the moths In this experiment, concentrations of 0,02 ppm of IIV), 0,02 and 0 04 ppm (compounds 3 and 10) and 0.1 ppm (compound 30) achieved 100X kill, 5 Breeding experiment with Tribolium castaneum (red flour beetle) 10 9 of wheat flour was introduced into 250 ml yoghurt bottles and mixed with the appropriate amount of the active ingredients as a dust formul-ation. 20 beetles were introduced and kept in the bottles for 14 days 2D until they had laid eggs, and were then removed. The experiment was run until the next generation hatched. The temperature was kept at 24C.

In this experiment, compounds 3, 10 and 30 according to the invention achieved 100/. kill at a concentration of 10 ppm, whereas the comparative 25 compound only achieved 80X kill at a concentration four times higher Breeding experiment~with Ceratitis capitata (Meditarranean fruitfly) 30 The experiments were carried out in 100 ml plastic beakers containing 40 9 of a nutrient medium consisting of carrot powder and water with added yeast. The active ingredient was stirred as an aqueous formulation into the mash, which was then inoculated with 100 to 200 fresh eggs The beakers were kept closed at from 24 to 26C. After about a week, hatching 35 was assessed.
In this experiment, compound 3 achieved 100Z kill at a rate of 10 ppm, whereas all other compo~unds including (IV) were ineffective at a concen-tration ten times higher.~
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BASF Aktiengesellschaft 23 O.Z, 0050/39081 Breeding experiment on larvae of the flour moth (Ephestia kuehniella) Wheat flour heavily infested with eggs of the flour moth was intimately mixed with the active ingredients. 10 g of the mixture was filled into 5 250-ml bottles, which were then kept at 25C. The development of the larvae was assessed after 6 weeks.
In this experiment, all the compounds according to the invention achieved loOZ kill, whereas comparative agent IIV) only achieved 75/ kill at a 10 concentration four times higher.

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Claims (6)

1. Cyclopropanecarboxamides of the general formula I
(I), where the substituents have the following meanings:

R C1-C12-alkyl, C2-C12-alkenyl, C2-C12-alkynyl, C1-C12-haloalkyl, C2-C12-haloalkenyl, C2-C12-haloalkynyl, C3-C12-alkoxyalkyl, C3-C8-cycloalkyl, C4-C12-cycloalkylalkyl, C3-C8-halocycloalkyl, C4-C12-halocycloalkylalkyl, C4-C12-cycloalkylhaloalkyl or C4-C12-halocycloalkylhaloalkyl and X oxygen or sulfur.

2. A process for the manufacture of cyclopropanecarboxamides of the general formula I
(I), where the substituents have the following meanings:

R C1-C12-alkyl, C2-C12-alkenyl, C2-C12-alkynyl, C1-C12-haloalkyl, C2-C12-haloalkenyl, C2-C12-haloalkynyl, C3-C12-alkoxyalkyl, C3-C8-cycloalkyl, C4-C12-cycloalkylalkyl, C3-C8-halocycloalkyl, C4-C12-halocycloalkylalkyl, C4-C12-cycloalkylhaloalkyl or C4-C12-halocycloalkylhaloalkyl and X oxygen or sulfur;
wherein a 2-phenoxyethylamine of the general formula II
(II), is reacted with a cyclopropanecarboxylic acid halide of the general formula III

(III), where Y is halogen.

3. A cyclopropanecarboxamide of the general formula (I) as set forth in claim 1, where R denotes branched alkyl, alkoxyalkyl, alkenyl or alkynyl with a methyl group in the 1-position, and X is oxygen.

4. A cyclopropanecarboxamide of the general formula (I) as set forth in claim 1, where R denotes 1-methylprop-1-yl and X is oxygen.

5. A pesticide of composition containing an effective amount of a cyclopropanecarboxamide of the formula (I) as set forth in claim 1, 3 or 4, in admixture with at least one carrier.

6. A process for combating pests, wherein an effective amount of a cyclopropanecarboxamide of the formula (I) as set forth in claim 1, 3 or 4, is allowed to act on the pests or their habitat.