MXPA06005261A - Substituted nicotinoylcarbamates as pesticides - Google Patents

Abstract

Novel nicotinoylcarbamates represented by the general formula (I) wherein W, R1, R2, W and m are as defined in the specification, their use as pesticides, and processes for their preparation are described.

Description

NICOTINOILCARBAMATES SUBSTITUTED AS PESTICIDES FIELD OF THE INVENTION The invention relates to new nicotinoylcarbamates, to their use as pesticides, preferably as insecticides and processes for their preparation. BACKGROUND OF THE INVENTION JP 321903/1994 and JP 101648/1998 disclose amide-type compounds or their salts and their use as agents for the control of harmful organisms. DETAILED DESCRIPTION OF THE INVENTION Thus, the invention provides new nicotinoylcarbamates of the general formula (I) wherein m means 0 or 1, W means O or S, R 2 signifies hydrogen, alkyl, alkenyl, aralkyl, cyanomethyl, alkoxycarbonylalkyl, aralkyloxycarbonyl, acyl, alkoxyalkyl or phenyl, and R1 means where Ref.:172579 R3 means hydrogen or alkyl, R4 means hydrogen, alkyl, haloalkyl, phenyl or alkoxycarbonyl, Rs means hydrogen or alkyl, p means 0 or 1, q means 0 or 1, and Q means aryl, which may be substituted, if applicable; a heterocyclic group with 5 or 6 members, containing at least one heteroatom selected from the group consisting of N, O and S and may be substituted, if appropriate; cycloalkyl substituted by phenyl; a bicyclic, condensed hydrocarbon group; trimethylsilyl; alkenyl or alkynyl. The compounds of the formula (I), according to the present invention, have a potent insecticidal activity and show good compatibility with various crops. Surprisingly, the compounds of the formula (I), according to the present invention, show a very excellent insecticidal action in comparison with that of the compounds similar to the compounds of the formula (I), described in the prior art (see, for example, publications JP 321903/1994 and JP 101648/1998). In the present description, the following definitions will apply, insofar as no other specific definitions are given: "Halogen" means fluorine, chlorine, bromine or iodine, and, preferably, means fluorine, chlorine or bromine. "Alkyl" means alkyl with 1 to 12 carbon atoms straight-chain or branched chain, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec. - or tere. -butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, etc. and, preferably, means alkyl having 1 to 6 carbon atoms. Each "haloalkyl", "alkoxycarbonyl", "alkoxycarbonylalkyl" and "alkoxyalkyl" alkyl portion can be considered the same as the one described above for "alkyl". "Alkenyl" means alkenyl with 2 to 6 carbon atoms, straight chain or branched chain, for example vinyl, allyl, 1-propenyl, isopropenyl, 2-butenyl, 2-pentenyl, 2-hexenyl, etc. and, preferably, means alkenyl with 2 to 4 carbon atoms. "Alkynyl" means alkynyl with 2 to 6 carbon atoms, straight chain or branched chain, for example, ethenyl, propargyl, 1-propynyl, isopropenyl, 1- (2- or 3-butynyl, 1- (2- or 3-) pentenyl, 1- (2- or 3-) hexenyl, etc. and, preferably, means alkynyl with 2 to 4 carbon atoms. "Aryl" means a cyclic, aromatic hydrocarbon group with 6 to 10 carbon atoms, for example, phenyl, naphthyl, etc. and, preferably, phenyl.

"Aralkyl" means, for example, benzyl, α-methylbenzyl, 2-phenylethyl, α, α-dimethylbenzyl, etc. and, preferably, benzyl. "Heterocyclic group" means a heterocyclic group with 5 to 6 members, saturated or unsaturated, containing, at least preferably, 1 to 3 heteroatoms selected from the group consisting of N, 0 and S and means, for example, furyl, thienyl , pyrrolyl, pyrrolidinyl, tetrahydrofuryl, tetrahydrothienyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, pyridyl, pyrimidinyl, piperidinyl, pyrazinyl, pyranyl, tetrahydropyranyl, tetrahydrothiopyranyl, thiopyranyl, etc.

"Bicyclic, condensed hydrocarbon group" means a hydrocarbon group with 9 to 10 carbon atoms, bicyclic, condensed, for example, indenyl, indanyl, tetrahydronaphthyl, etc. and, preferably, means indanyl or tetrahydronaphthyl. "Aralkyl" means, as part of "aralkyloxycarbonyl", the same group that has been described in the definition, indicated above for "aralkyl". "Cycloalkyl" means cycloalkyl with 3 to 8 carbon atoms, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, preferably means cycloalkyl with 5 to 7 carbon atoms, and, particularly preferably, cyclohexyl.

The preferred substituents or preferred ranges of the radicals present in the formula (I) and the corresponding intermediate compounds have been defined below. Preferably, W means 0 or S. Preferably, R 3 is hydrogen or alkyl having 1 to 4 carbon atoms. Preferably, R 4 is hydrogen, alkyl having 1 to 4 carbon atoms, halogen-alkyl having 1 to 4 carbon atoms, phenyl or alkoxycarbonyl having 2 to 4 carbon atoms. Preferably, R5 means hydrogen or alkyl having 1 to 4 carbon atoms. Preferably, p means 0 or 1. Preferably, q means 0 or 1. Preferably, Q means aryl which may be substituted, if appropriate, by at least one group selected from the group consisting of alkoxy with 1 to 4 carbon atoms. , alkylthio with 1 to 4 carbon atoms, halogen, cyano, alkyl with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms, nitro, halogenoalkyl with 1 to 4 carbon atoms; phenoxy; phenyl which may be substituted, if appropriate; a heterocyclic group with 5 to 6 members, containing N, O or S, a heterocyclic group with 5 to 6 members, containing at least one heteroatom selected from the group consisting of N, 0 and S and which may be substituted, if appropriate, by halogen-alkyl having 1 to 2 carbon atoms, by alkoxycarbonyl having 1 to 4 carbon atoms or by oxo; 4- phenylcyclohexyl; a hydrocarbon group with 9 to 10 bicyclic carbon atoms, condensed; trimethylsilyl; alkenyl with 2 to 6 carbon atoms; alkynyl with 2 to 6 carbon atoms. Preferably, R 2 is hydrogen, alkyl having 1 to 6 carbon atoms, alkenyl having 2 to 6 carbon atoms, benzyl, cyanomethyl, alkoxycarbonyl having 1 to 4 carbon atoms, alkyl having 1 to 4 carbon atoms, benzyloxycarbonyl, alkylcarbonyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms - alkyl with 1 to 2 carbon atoms or phenyl. Preferably, m means 0 or 1. Particularly preferably, W means O or S. Particularly preferably, R3 means hydrogen or methyl. Particularly preferably R 4 is hydrogen, methyl, trichloromethyl, trifluoromethyl, phenyl or methoxycarbonyl. Particularly preferably R5 means hydrogen or methyl. Particularly preferably, p means 0 or 1. Particularly preferably q means 0 or 1. Particularly preferably Q denotes phenyl, which is optionally substituted by one or more groups selected from the group consisting of methoxy, methylthio, fluorine, chlorine, bromine, iodine, cyano, methyl, vinyl, nitro, trifluoromethyl, phenoxy, phenyl, phenyl substituted by chlorine, tolyl and thienyl, furyl, thienyl, trifluoromethylpyrazolyl, pyridyl, trifluoromethylpyridyl, tetrahydropyranyl, tetrahydrothiopyranyl, piperidinyl , l- (tert-butoxycarbonyl) -4-piperidinyl, pyrrolidinyltetrahydrofuryl, 1,1-dioxo-tetrahydrothiopyranyl, 4-phenylcyclohexyl, indanyl, tetrahydronaphthyl, trimethylsilyl, alkenyl with 2 to 4 carbon atoms, alkynyl with 2 to 4 carbon atoms .

Particularly preferably, R 2 represents hydrogen, alkyl having 1 to 4 carbon atoms, alkenyl having 2 to 4 carbon atoms, benzyl, cyanomethyl, alkoxy with 1 to 2 carbon atoms - carbonylmethyl, benzyloxycarbonyl, acetyl, alkoxy ethyl with 1 to 2 carbon atoms or phenyl. Particularly preferably, m means 0. Very particularly preferably, W means O. Very particularly preferably, R 2 is hydrogen. Very particularly preferably R3 means hydrogen. Very particularly preferably R4 means hydrogen. The definitions of the radicals, mentioned above, generally or preferentially, are applicable both to the final products of the formula (I) and also, correspondingly, to the starting products or to the intermediate products, necessary, in each case, to obtain. These definitions of the radicals can be combined, arbitrarily, with each other, for example even in combinations between the above-mentioned ranges.

According to the invention, the compounds of the formula (I), which contain a combination of the meanings indicated above as preferred, will be preferred. In accordance with the invention, the compounds of the formula (I), which contain a combination of the abovementioned and particularly preferred meanings, are particularly preferred. According to the invention, the compounds of the formula (I), which contain a combination of the above-mentioned meanings as being very particularly preferred, are very particularly preferred. The compounds of the formula (I) can be obtained by one of the following obtaining processes a), b), c), d) or e). Particularly, the compounds of the formula (I), wherein R 2 signifies hydrogen and m means 0, can be synthesized by the processes of obtaining a), b) or c), and the compounds of the formula (I), wherein R 2 means another group different from hydrogen and m means 0, they can be synthesized by the obtaining process d), and, in addition, the compounds of the formula (I), wherein m means 1, can be synthesized by the obtaining process e). Obtaining procedure (a): in the case where R2 = hydrogen, m = 0: The compounds of the formula wherein W has the same meaning as indicated above, they are reacted with compounds of the formula R 1 -OH (III) in which R 1 has the same meaning as indicated above, in the presence of inert solvents. Obtaining procedure (b): in the case where W = 0, R2 = hydrogen, m = 0: The 4-trifluoromethyl-nicotinamide is reacted with compounds of the formula OR II 1 Cl-C-OR1 (IV) wherein R1 has the same meaning as indicated above, in the presence of inert solvents and, if appropriate, in the presence of a base. Obtaining procedure (c): in the case where W = 0, R2 = hydrogen, m = 0: The 4-trifluoromethylnicotinoyl chloride is reacted with compounds of the formula wherein R1 has the same meaning as indicated above, in the presence of inert solvents and, if appropriate, in the presence of a base. Obtaining procedure (d): in the case where R2 = as defined above, except hydrogen, m = 0: The compounds of the formula wherein W and R1 have the same meaning as indicated above, are reacted with compounds of the formula R2 '- Hal (VI) in which R2' has the meaning indicated above, except hydrogen and Hal means halogen, in the presence of inert solvents and, if convenient, in the presence of a base. Obtaining procedure (e): in the case where m = 1: The compounds of the formula wherein W, R1 and R2 have the same meaning as indicated above, are oxidized in the presence of inert solvents. The process for obtaining a), for the preparation of the compounds of the formula (I), can be illustrated by the following reaction scheme, if, for example, the isocyanate of 4-trifluoromethylnicotinoyl and the benzyl alcohol are used as products. of departure.

The process for obtaining b), for obtaining compounds of the formula (I), can be illustrated by the following reaction scheme, if, for example, 4-trifluoromethyl-nicotinamide and benzyl chloroformate are used as starting materials.

The process for obtaining c), for the preparation of compounds of the formula (I), can be illustrated by the following reaction scheme, if, for example, 4-trifluoromethylnicotinoyl chloride and benzyl carbamate are used as products of departure.

The process for obtaining d), for the preparation of compounds of the formula (I), can be illustrated by the following reaction scheme, if, for example, N- (4-trifluoromethyl-3-pyridylcarbonyl) carbamate is used. benzyl and methyl chloride as starting products.

The process for obtaining e), for the preparation of compounds of the formula (I), can be illustrated by the following reaction scheme, if, for example, N- (4-trifluoromethyl-3-pyridylcarbonyl) carbamate is used. benzyl as starting material and m-chloroperbenzoic acid as an oxidizing agent.

The compounds of the formula (II), in the preparation process a), can be obtained easily according to the method described, for example, in the publication J. Med. Chem., P. 1630 (1991), J. Chem. Soc, p. 153 (1958). The alcohols of the formula (III) are well known in the field of organic chemistry; as representative examples thereof, the following compounds may be mentioned: benzyl alcohol, α-methylbenzyl alcohol, phenol, 2-phenyl-isopropanol, trimethylsilylmethanol, 2- (trimethylsilyl) ethanol, 3-furylmethanol, 2-furylmethanol, 2-thienylmethanol, alcohol 2-methoxybenzyl, 3-methoxybenzyl alcohol, 4-methoxybenzyl alcohol, 4-vinylbenzyl alcohol, 4-methylthiobenzyl alcohol, 2-chlorobenzyl alcohol, 3-chlorobenzyl alcohol, 4-chlorobenzyl alcohol, 2-pyridylmethyl alcohol, 3-pyridyl ethyl alcohol, 4-pyridylmethyl alcohol, 3-cyanobenzyl alcohol, trimethylsilylmethanol, 4-methylbenzyl alcohol, 2,4-dichlorobenzyl alcohol, 2,6-dichlorobenzyl alcohol, 2-bromobenzyl alcohol, 3-bromobenzyl alcohol, 4-bromobenzyl alcohol, 2-nitrobenzyl alcohol , 3-nitrobenzyl alcohol, l-phenyl-2, 2, 2-trifluoroethanol, dif enylmethanol, 2-trifluoromethylbenzyl alcohol, 3-trifluoromethylbenzyl alcohol, 4-trifluoromethylbenzyl alcohol lico, 2-fluorobenzyl alcohol, 3-fluorobenzyl alcohol, 4-fluorobenzyl alcohol, 4-nitrobenzyl alcohol, alcohol-methoxycarbonylbenzyl alcohol, 3-iodobenzyl alcohol, 5-trifluoromethyl-2-pyridylmethanol, 3-phenoxybenzyl alcohol, 4-phenoxybenzyl alcohol, alcohol 2-methylbenzyl, 3-methylbenzyl alcohol, 2,4-dimethylbenzyl alcohol, 4-biphenylylmethanol, 1-naphthylmethanol, 2-naphthylmethanol, 2,2-dimethyl-3-phenylpropanol, l-phenyl-2, 2,2-trichloroethanol, 2-phenethyl alcohol, 2-phenylpropanol, 1-indanyl alcohol, 2-indanyl alcohol, 1- (1, 2, 3, 4-tetrahydronaphthyl) alcohol, 2 - (1, 2, 3, 4-tetrahydronaphthyl) alcohol , 4-tetrahydropyranyl alcohol, 4-tetrahydrothiopyranyl alcohol, 4-piperidinyl alcohol, 2-pyrrolidinyl alcohol, 3-pyrrolidinyl alcohol, 2-tetrahydrofurfuryl alcohol, 4-phenyl-cyclohexyl alcohol, 4- (2-thienyl) benzyl alcohol, 4-alcohol - (4-chlorophenyl) benzyl, etc. Among the aforementioned alcohols, there can be easily obtained, for example, 4-tetrahydrothiopyranyl alcohol, 2- (1,2,3,4-tetrahydronaphthyl) alcohol, 4-phenoxybenzyl alcohol, for example, by reduction of its known ketones corresponding, using sodium borohydride. The 4-trifluoromicotinamide is a known compound (see JP 321903/1994). The esters of chloroformic acid, of the formula (IV), are well known in the field of organic chemistry and can be easily obtained, in general, by the reaction of phosgene with the corresponding alcohols, in the presence of a tertiary amine. The 4-trifluoromethylnicotinoyl chloride can be obtained easily, for example, by reaction of the known 4-trifluoromethylnicotinic acid and thionyl chloride. Carbamic acid esters of the formula (V) are well known in the field of organic chemistry and can be obtained by known processes. The compounds of the formula (la), in the preparation process d) are the compounds of the formula (I) of the present invention, in the case where R2 denotes hydrogen, obtained by the methods of obtaining a), b) (in the case where W = 0) or c) (in the case where W = 0). The halides, of the formula (VI), are well known in the field of organic chemistry, and may be mentioned, as its representative examples, the following: chloromethyl ethyl ether, acetyl chloride, benzyl chloroformate, ethyl bromoacetate, benzyl bromide, allyl bromide, ethyl iodide, etc. The compounds of the formula (le), in the preparation process e), are the compounds of the formula (I) of the present invention, in the case where m = 0. As representative example of the oxidizing agent, used for the oxidation, m-chloroperbenzoic acid may be mentioned. The process of obtaining a), mentioned above, can be carried out, for example, in accordance with the procedure described in the publication J. Chem. Soc, p.1091 (1957) and ibid. p. 4458 (1956). The reaction of the obtaining process a) can be carried out by using a suitable diluent alone or in a mixture. As examples of diluents used in this case, mention may be made of the aliphatic, alicyclic and aromatic hydrocarbons (which may be chlorinated, if appropriate), for example pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, etc.; the ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM), etc .; nitriles, for example, acetonitrile, propionitrile, acrylonitrile, etc .; the amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphorotriamide (HMPA), etc. The reaction of the preparation process a) can be carried out over a wide range of temperatures. However, it can be carried out, generally, in a range between about 0 and about 100 ° C, preferably between about 0 and about 50 ° C. While it is desirable to carry out said reaction under normal pressure, this may be carried out, optionally, also under elevated pressure or under reduced pressure. In carrying out the preparation process a), the desired compounds can be obtained, for example, by reacting an amount of 1 mole, up to a slightly excess amount of the compounds of the formula (III), with 1 mole of the compounds of the formula (II) in a diluent, for example, 1,2-dichloroethane. The above-mentioned processes for obtaining, b), c), d) and e) can be carried out under similar reaction conditions, by means of the use of a diluent already mentioned, in the above-mentioned obtaining process a), with the exception of of dimethylformamide. The process for obtaining b) can be carried out, for example, in accordance with the procedure described in the publication J. Med. Chem., P. 2504 (1991). The process for obtaining c) can be carried out, for example, in accordance with the method described in the publication J. Chem. Soc., P. 451 (1964). The process for obtaining d) can be carried out, for example, in accordance with the method described in the Heterocycles publication, p. 373 (1987). The process for obtaining e) can be carried out, for example, in accordance with the publication J. Med. Chem., P. 2925 (1995). The obtaining procedures b), c) and d) can also be carried out in the presence of a base. Suitable bases can be mentioned: alkali metal carbonates, for example, potassium carbonate; tertiary amines, N, N-dialkylanilines and pyridines, for example, triethylamine, 1, 1,4,4-tetramethylethylenediamine (TMEDA), N, N-dimethylaniline, N, N-diethylaniline, pyridine , 4-dimethylaminopyridine (DMAP), 1,4-diazabicyclo [2, 2, 2] octane (DABCO), 1,8-diazabicyclo [5,, 0] undec-7-ene (DBU), etc. The compounds of the formula (I) show a potent insecticidal action. Therefore, the compounds of the present invention can be used as insecticidal agents. And the active compounds of the present invention have an exact control effect against the harmful insects, without phytotoxicity for the crop plants. The compounds of the present invention can be used for the control of a wide variety of pests, for example, harmful sucking insects, biting insects and other parasitic pests of plants, stored grain pests, hygiene pests, etc. and they can be applied for their destruction. As examples of such pests, the following pests may be mentioned: As insects, mention may be made of Coleoptera pests, for example, Callosobruchus Chinensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomalous rufocuprea, Leptinotarsa decemlineata, Diabrotica spp. , Manochamus alternatus, Lissorhoptrus oryzophilus, Lictus bruneus; pests of Lepidoptera, for example, limantria dispar, Malacosoma neustria, Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo suppressalis, Pirusta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotis fucosa, Galleria mellonella, Plutella maculipennis, Heliothis virescens, Phyllocnistis citrella; pests of Hemiptera, for example, Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nazara spp., Cimex lectularius, Trialeurodes vaporariorum, Psylla spp.Bemisia argentífolii; Orthoptera pests, for example, Germanic Blatella, Periplaneta americana, Gryllotalpa africana, Locusta migratoria migratoriodes; Homoptera pests, for example, Reticulitermes speratus, Coptotermes formosanus; Diptera pests, for example, Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens, Anopheles slnensis, Culex tritaeniorhynchus, etc. Thysanoptera pests, for example, Thrips palmi Karny, Frankliniella occidentalis. In addition, the compounds of the present invention can be used effectively in the field of veterinary medicine against various parasitic pests harmful to animals (endoparasites and ectoparasites), for example, insects and helminths. As examples of such pests pests of animals may be mentioned the following pests: As insects can be mentioned, for example: Gastrophilus spp. , Stomoxys spp., Trichodectes spp. , Rhodnius spp., Ctenocephalides canis, etc. In the present invention, insecticides are referred to, in some cases, to substances that have an insecticidal action against pests, including all of them. The active compounds of the formula (I) can be obtained in customary formulation forms, when used as insecticides. As formulation forms, there may be mentioned, for example, solutions, emulsifiable concentrates, wettable powders, water-dispersible granules, suspensions, powders, foaming agents, pastes, tablets, granules, aerosols, natural and synthetic substances impregnated with the compound, microcapsules, agents for the coating of seeds, formulations used with fumigation equipment (as combustion equipment, for example, cartridges, cans, streamers etc, for the fumigation and production of smoke, cans, rolls, etc.), LTLV [cold fog , hot fog], etc. These formulations can be prepared according to processes known per se, for example by mixing the active compounds with extenders, specifically with liquid diluents; liquefied gaseous diluents; solid diluents or excipient materials and, optionally, by the use of surfactants, specifically emulsifiers and / or dispersants and / or foam-generating agents. When water is used as an extender, organic solvents may also be used as auxiliary solvents, for example. As liquid diluents or excipient materials there can be mentioned, for example, aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalenes, etc.), chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons [eg, cyclohexane, etc. or paraffins (for example, fractions of mineral oil, etc.)], alcohols (for example, butanol, glycols and their ethers, their esters, etc.), ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strongly polar solvents (for example, dimethylformamide, dimethyl sulfoxide, etc.), and water. The diluents or gaseous, liquefied excipient materials are substances that are gaseous at normal temperature and pressure and may be mentioned, for example, propellants for aerosols such as butane, propane, nitrogen gas, carbon dioxide, halogenated hydrocarbons. As solid diluents there may be mentioned, for example, ground natural minerals (eg, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, etc.), ground synthetic minerals (eg, highly dispersed silicic acid, alumina, silicates, etc.). As solid excipient materials there may be mentioned, for example, broken and fractionated minerals (for example, calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic granules of inorganic and organic flours, particles of organic materials (for example, sawdust). , coconut husks, corn cobs, tobacco stems, etc.), etc. As emulsifiers and / or foaming agents, there may be mentioned, for example, nonionic and anionic emulsifiers [for example, polyoxyethylenated esters of fatty acids, polyoxyethylenated ethers of fatty alcohols (for example, alkylaryl polyglycol ethers), sulfonates of alkyl, alkyl sulphates, aryl sulfonates, etc.], products of albumin hydrolysis, etc.

Dispersants include, for example, sulphite lignin bleach, methylcellulose, etc. In the formulations, adhesives (powders, granules, emulsifiable concentrates) can also be used. As such adhesives, there may be mentioned, for example, carboxymethylcellulose, natural and synthetic polymers (for example, gum arabic, polyvinyl alcohol, polyvinyl acetate, etc.), etc. In the same way, dyes can be used. Examples of such dyes are, for example, inorganic pigments (for example, iron oxide, titanium oxide, Prussian blue, etc.), organic dyes such as alizarin dyes, azo dyes or phthalocyanine dyes, metals, as well as trace nutrients such as iron, manganese, boron, copper, cobalt, molybdenum and zinc salts. Such formulations can contain the active components, indicated above, in an amount generally comprised in the range from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight. The active compounds of the formula (I) of the present invention can also be presented as agents in admixture with other active compounds, for example, insecticides, poisonous baits, bactericides, miticides, nematicides, fungicides, growth regulators, herbicides, etc. ., in the form of its customary formulations in commerce and in the forms of application prepared from such formulations. In this case, for example, the organophosphorus agents, the carbamate agents, the carboxylate-type chemicals, the chlorinated hydrocarbon-type chemicals, the insecticidal substances produced by microbes, etc. may be mentioned as the insecticides mentioned above. In addition, the active compounds of the formula (I) can also be present as agents in admixture with a synergist and, as such, the commercially available formulations and application forms can be mentioned. Said synergists do not have to be active by themselves, but rather it is a compound that improves the action of the active compound. The content of active compounds of the formula (I) in an application form, commercially available, can vary within wide limits. The concentration of the active compounds of the formula (I) at the time of application can be, for example, in a range from 0.0000001 to 100% by weight, preferably in the range from 0, 00001 up to 1% by weight. The compounds of the formula (I) can be used by customary methods, suitable for the application forms.

When applied against the pests of hygiene and against stored grain pests, the active compounds of the present invention have a good stability against alkalis on calcified substances and, in addition, show a very excellent residual effectiveness in the wood and in the wood. floor. The present invention will be described in more detail by means of examples. However, the present invention is not limited by them in any way. Synthesis example 1 After addition of oxalyl chloride (0.14 ml) to a suspension of 4-trifluoromethyl-nicotinamide (0.2 g) in 1,2-dichloroethane (10 ml), at room temperature, the mixture was subjected to low distillation. for 2 hours. The solvent was removed by distillation under reduced pressure and the residue was dissolved in methylene chloride. Benzyl alcohol (0.11 g) was added to the solution and the mixture was stirred at room temperature during 2 hours . The solvent was distilled off under reduced pressure and the residue was separated and purified by column chromatography on silica gel (hexane: ethyl acetate = 3: 1) to obtain the N- (4-trifluoromethyl-3-carbamate. -pyridylcarbonyl) benzyl carbamate (0.24 g).

XH-NMR: 8.85 (1H, d), 8.72 (1H, s), 7.94 (1H, broad), 7.56 (1H, d), 7.4-7.2 (5H, m), 5.11 (2H, s) Synthesis Example 2 Oxalyl chloride (0.5 ml) was added to a methylene chloride solution of 4-trifluoromethyl-nicotinic acid (1 g) and a catalytic amount of N, N-dimethylformamide, and the mixture was stirred at room temperature for 1 hour. The solvent was removed by distillation under reduced pressure and the residue was dissolved in toluene. Potassium carbonate (0.5 g) and tetrabutylammonium thiocyanate (1.89 g) were added to the solution and the mixture was stirred for 30 minutes. Then trimethylsilylmethanol (0.66 g) was added and the mixture was stirred at room temperature for 1 hour. After dilution of the reaction mixture with ethyl acetate, it was washed with water, with 1N hydrochloric acid and with saturated aqueous sodium chloride solution and the organic phase was dried with magnesium sulfate. The solvent was distilled off under reduced pressure and the residue was separated and purified by column chromatography on silica gel (hexane: ethyl acetate = 5: 1) to obtain N- (4-trifluoromethyl-3-pyridylcarbonyl) ) trimethylsilanylmethyl thiocarbamate (0.77 g). mp: 105-107 ° C.

Synthesis example 3 Sodium hydride 60% (36 mg) was suspended in N, N-dimethylformamide and a solution of N- (4-trifluoromethyl-3-pyridylcarbonyl) benzyl carbamate was added slowly in N, N-dimethylformamide. (0.4 g). After stirring the mixture at room temperature for 30 minutes, methyl iodide (0.35 g) was added and the mixture was stirred at room temperature for 1 hour. The reaction mixture was diluted with ethyl acetate, washed with a saturated aqueous solution of sodium chloride and the organic phase was dried with magnesium sulfate. The solvent was distilled off under reduced pressure and the residue was separated and purified by column chromatography on silica gel (hexane: ethyl acetate = 6: 1) to obtain N-methyl-N- (4-trif). benzyl l-butyl-3-pyridylcarbonyl) carbamate (0.33 g). nD20: 1, 5185. Synthesis example 4 M-chloroperbenzoic acid (0.27 g) was added slowly to a methylene chloride solution of benzyl N- (4-trifluoromethyl-3-pyridylcarbonyl) carbamate (0.3 g). After stirring at room temperature for 12 hours, the reaction solution was washed with a saturated aqueous solution of sodium bicarbonate and with a saturated aqueous solution of sodium chloride, and the organic phase was dried with magnesium sulfate. The solvent was distilled off under reduced pressure and the obtained crystals were recrystallized from toluene to obtain benzyl (1-oxy-4-trifluoromethyl-3-pyridylcarbonyl) carbamate (0.18 g). mp: 204-205 ° C. Table 1 shows the compounds of the formula (I) of the present invention, obtained by means of procedures similar to those of the synthesis examples, mentioned above, together with the compounds shown in the synthesis examples mentioned above. In the table, Ph means phenyl, Me means methyl, Et means ethyl, tere. -Bu means tere. -butyl, Fu means furyl, Th means thienyl, Py means pyridyl, Nap means naphthyl, Pyz means pyrazolyl, Pip means piperidinyl, Pyrr means pyrrolidinyl and c-Hex means cyclohexyl.

Table 1 Fu = furanyl, Th = thienyl, PH = phenyl, Py = pyridyl, Pyrr = pyrrolyl The values 1H-NMR mentioned as a-t in table 1, indicated above, are as follows (chemical shift d in ppm): Biological test example 1: Test against Myzus persicae * resistant to organophosphorus agents and to carbamates Preparation of test solution: solvent: 7 parts by weight of dimethylformamide; emulsifier: 3 parts by weight of polyoxyethylene alkyl phenyl ether. In order to prepare an appropriate formulation of an active compound, 1 part by weight of the active compound was dissolved in the aforesaid amount of solvent containing the aforementioned amount of emulsifier and the solution was diluted with water to an established concentration. Test procedure: approximately 30 aphids of Myzus persicae * resistant to organophosphorus agents and carbamates were inoculated, respectively, in 1 seedling plant of eggplant, planted in vinyl sherds of 6 cm in diameter. After one day, from the inoculation, a sufficient quantity of a dilute aqueous solution of a given concentration of an active compound, prepared as mentioned above, was sprayed by the use of a spray gun. After spraying, it was placed in a greenhouse at 28 ° C and the proportion of deaths was calculated after 7 days from spraying. In the test, it was repeated twice. Results: compounds No. 1, 3, 5, 6, 8, 9, 14, 18, 23, 29, 33, 35, 38, 40, 44, 54, 55, 59, 62, 70, 73, 84 employees in the trial, as specific examples, they showed a 100% death rate at the 100 ppm concentration of active product. Formulation Example 1 (granulate) 25 parts of water were added to a mixture formed by parts of the compounds of the present invention (No. 1), 30 parts of bentonite (montmorillonite), 58 parts of talc and 2 parts of lignin sulphonate salt, were kneaded well, to form granules of 10 to 40 mesh by a granulator by extrusion and drying at 40 to 50 ° C, to obtain granulates.

Formulation Example 2 (granulates) 95 parts of mineral clay particles having a diameter distribution of the particles in the range from 0.2 to 2 mm are placed in a rotary mixer. During rotation, 5 parts of the compound of the present invention (No. 1) are sprayed together with a liquid diluent, uniformly moistened and dried at 40 to 50 ° C to obtain granulates. Formulation Example 3 (emulsifiable concentrate) 30 parts of the compound of the present invention (No. 1), 55 parts of xylene, 8 parts of polyoxyethylene alkyl phenyl ether and 7 parts of calcium alkylbenzene sulfonate are mixed and stirred to obtain a concentrate. emulsifiable Formulation Example 4 (wettable powder) 15 parts of the compounds of the present invention (No. 1), 80 parts of a mixture of white carbon (fine powder of hydrous amorphous silicone oxide) and clay powder (1: 5) are comminuted. ), 2 parts of sodium alkylbenzene sulfonate and 3 parts of sodium alkylbenzenesulfonate formalin condensate and mixed to obtain a wettable powder. Formulation Example 5 (water-dispersible granulate) 20 parts of the compounds of the present invention (No. 1), 30 parts of sodium lignin sulfonate, 15 parts of bentonite and 35 parts of calcined diatomaceous earth powder are mixed well. they are added water, extruded with a 0.3 mm sieve and dried to obtain dispersible granules in water. It is noted that, in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (8)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. Compounds of formula (I) characterized in that m means 0 or 1, W means O or S, R 2 signifies hydrogen, alkyl, alkenyl, aralkyl, cyanomethyl, alkoxycarbonylalkyl, aralkyloxycarbonyl, acyl, alkoxyalkyl or phenyl, and
2. R1 means where R3 signifies hydrogen or alkyl, R4 signifies hydrogen, alkyl, haloalkyl, phenyl or alkoxycarbonyl, R5 signifies hydrogen or alkyl, p signifies 0 or 1, q signifies 0 or 1, and Q signifies aryl, which may be substituted, if appropriate; a heterocyclic group with 5 or 6 members containing at least one heteroatom selected from the group consisting of N, 0 and S and which may be substituted, if appropriate; cycloalkyl substituted by phenyl; a bicyclic, condensed hydrocarbon group; trimethylsilyl; alkenyl or alkynyl. 2. Compounds of formula (I) according to claim 1, characterized in that W means 0 or S, R3 is hydrogen or alkyl having 1 to 4 carbon atoms, R4 is hydrogen, alkyl having 1 to 4 carbon atoms, halogen-C 1 -C 4 -alkyl, phenyl or alkoxycarbonyl with 2 to 4 carbon atoms, R 5 denotes hydrogen or alkyl with 1 to 4 carbon atoms, p means 0 or 1, q means 0 or 1, Q means aryl , which may be substituted, if appropriate, by one or more groups selected from the group consisting of alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogen, cyano, alkyl having 1 to 4 carbon atoms, carbon, alkenyl with 2 to 4 carbon atoms, nitro, halogenoalkyl with 1 to 4 carbon atoms; phenoxy; phenyl which may be substituted, if appropriate; a heterocyclic group with 5 to 6 members, containing N, O or S, a heterocyclic group with 5 to 6 members, containing at least one heteroatom selected from the group consisting of N, O and S and which may be substituted, if appropriate, by halogen-alkyl having 1 to 2 carbon atoms; C 1 -C 4 alkoxycarbonyl or oxo; 4- phenylcyclohexyl; a hydrocarbon group with 9 to 10 bicyclic carbon atoms, condensed; trimethylsilyl; alkenyl with 2 to 6 carbon atoms; alkynyl with 2 to 6 carbon atoms, R 2 signifies hydrogen, alkyl having 1 to 6 carbon atoms, alkenyl having 2 to 6 carbon atoms, benzyl, cyanomethyl, alkoxycarbonyl having 1 to 4 carbon atoms-alkyl having 1 to 4 atoms carbon, benzyloxycarbonyl, alkylcarbonyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms-alkyl with 1 to 2 carbon atoms or phenyl, m means 0 or 1.
3. 3. Compounds according to claim 1 or 2 characterized in that W is 0 or S, R3 is hydrogen or methyl, R4 is hydrogen, methyl, trichloromethyl, trifluoromethyl, phenyl or methoxycarbonyl, R5 is hydrogen or methyl, p is 0 or 1, q is 0 or 1, Q is phenyl, which is substituted, if appropriate, by one or more groups selected from the group consisting of methoxy, methylthio, fluorine, chlorine, bromine, iodine, cyano, methyl, vinyl, nitro, trifluoromethyl, phenoxy, phenyl, phenyl substituted by chlorine, tolyl or thienyl, furyl or, thienyl, trifluoromethylpyrazolyl, pyridyl, trifluoromethylpyridyl, tetrahydropyranyl, tetrahydrothiopyranyl, piperidinyl, 1- (tert-butoxycarbonyl) -4-piperidinyl, pyrrolidinyltetrahydrofuryl, 1,1-dioxo-tetrahydrothiopyranyl, 4-phenylcyclohexyl, indanyl, tetrahydronaphthyl, trimethylsilyl, alkenyl with 2 to 4 carbon atoms, alkynyl with 2 to 4 carbon atoms, R2 means hydrogen, alkyl with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms, benzyl, cyanomethyl, alkoxy with 1 to 2 carbon atoms. carbon-carbonylmethyl, benzyloxycarbonyl, acetyl, alkoxymethyl with 1 to 2 carbon atoms or phenyl, m means 0.
4. 4. Process for obtaining the compounds of the formula (I), according to claim 1, characterized in that a) in the case where R2 means hydrogen and m means 0: the compounds of the formula are reacted wherein W has the same meaning as indicated above, with compounds of the formula R 1 -OH (III) in which R 1 has the same meaning as indicated above, in the presence of one or more inert solvents, or, b) in the case of if W means oxygen 0 and R2 means hydrogen and m means 0 (zero), 4-trifluoromethyl-nicotinamide is reacted with compounds of formula O II! Cl-C-OR (IV) wherein R1 has the same meaning as indicated above, in the presence of inert solvents and, if necessary, in the presence of a base, or, c) in the case where W means oxygen 0 and R2 means hydrogen and m means 0 (zero ): 4-trifluoromethylnicotinoyl chloride is reacted with compounds of the formula wherein R1 has the same meaning as indicated above, in the presence of inert solvents and, if necessary, in the presence of a base, or, d) in the case where R2 has the meaning indicated above, except hydrogen, and m means 0 (zero): the compounds of the formula are made wherein W and R1 have the same meaning as indicated above, with compounds of the formula R2 '- Hal (VI) in which R2' means a group as defined above in R2, other than hydrogen, and Hal means halogen, in the presence of inert solvents and, if convenient, in the presence of a base, or, e) in the case where m means 1: the compounds of the formula are oxidized wherein W, R1 and R2 have the same meaning as indicated above, in the presence of inert solvents.
5. 5. Insecticidal compositions characterized in that they contain at least one compound of the formula (I), according to any one of claims 1, 2 or 3.
6. 6. - A method for controlling pests, characterized in that the compounds of the formula (I), according to any one of claims 1, 2 or 3, act on the pests and / or on their environment. - Use of the compounds of the formula (I), according to any one of claims 1, 2 or 3, for the control of pests. 8 - A process for the preparation of pesticidal compositions, characterized in that the compounds of the formula (I) are mixed with extenders and / or surfactants.