CS264263B2 - Insecticide and acaricide and method of efficient substances production - Google Patents

Abstract

Insecticidal and acaricidal agent characterized as being an active ingredient it contains a pyrimidin-5-ylcyclopropanecarboxylic ester acids of formula I, wherein R2 is branched C3-1, -alkyl on the .alpha.-carbon and R is a radical of formula A wherein X is oxygen, sulfur, vinylene or residue —CR5 = Y, -, where Y is nitrogen or CR5, R4 is hydrogen, methyl, cyano, or ethynyl, R5 is always independent of each other hydrogen, halogen or optionally halogen substituted C 1-4 -alkyl and R 6 is hydrogen, halogen, C 1-6 -alkyl, C 1-6 -alkenyl or optionally halogen- or C 1-4 -alkyl substituted phenyl, phenoxyl or benzyl, in combination with a diluent or a carrier. The method of manufacture is further described These active ingredients are reacting the acid of formula II with an alcohol of the formula R v, in the presence of an acid catalyst or dehydrating agent.

Description

264263 1

The present invention relates to novel cyclopropanoic acids and their derivatives useful as intermediates, insecticidally active esters of these acids, as well as compositions containing them as active ingredients. In a further aspect, the present invention provides a process for the production of thtonic acids and derivatives thereof, and novel compounds used in such processes.

Accordingly, the invention provides novel cyclopropane derivatives of formula (I)

r Q

RC- CH-CH- / 7V CH 3 XCH 3 (I) wherein R 2 represents an alkyl group having 3 to 6 carbon atoms, branched at the α-position and

R is a radical of formula (A)

wherein X is oxygen, sulfur, vinylene or a radical of formula -CR 5 = Y - wherein Y is N or CR 5, R 4 is hydrogen, methyl, cyano, or ethynyl,

The individual R 5 substituents are selected from the group consisting of hydrogen, halogen atoms, and alkyl groups containing up to 4 carbon atoms, optionally substituted with halo, and R 6 is hydrogen, halogen, alkyl having up to 4 carbon atoms, alkenyl containing up to 6 atoms carbon, phenyl, phenoxy or benzyl, or phenyl, phenoxy or benzyl substituted by halogen or alkyl of 1 to 4 carbon atoms.

It is an object of the present invention to provide an insecticidal and acaricidal composition comprising, as active ingredient, a pyrimidin-5-ylcyclopropanecarboxylic acid ester of formula (IV) as defined above, in combination with a diluent or carrier for the active ingredient.

It will be appreciated that the compounds of formula (I) may exist in different isomeric forms and as mixtures of isomers. Thus, the possibility of the 2 'existence of cis and trans isomers is due to the character of the substitution on the cyclopropane ring and the optical isomerism is based on the presence of two chiral centers in the cyclopropane group leading to the possibility of exisence (-j -) - cis-, - The other isomerism may occur with the insecticidally active esters of the present invention when the alcohol moiety contains an alkenyl group or one or more of the isomers. more chiral centers, all of these individual isomeric forms, as well as mixtures thereof, including racemates, are within the scope of the invention.

Particular insecticidally useful compounds of the invention include esters derived from the following alcohols: 4-methyl-2,3,5, e-tetrafluorobenzyl alcohol, pentafluorobenzyl alcohol, 4-allyl-2,3,5,6-tetrafluorobenzyl alcohol, 4-methoxymethyl-2,3, 5,6-tetrafluorobenzyl alcohol, 3-phenoxybenzyl alcohol, α-cyano-3-femoxybenzyl alcohol, 6-phenoxypyrid-2-ylmethanol, 1-cyano-1- (6-phenoxypyrid-2-yl) methano, 3- ( 4-chlorophenoxybenzyl alcohol, α-ethynyl-3-phenoxybenzyl alcohol, 1- (6-phenoxypyrid-2-yl) ethanol, 4-fluoro-3-phenoxybenzyl alcohol, α-cyano-4-fluoro-3-phenoxybenzyl alcohol, 5 - benzyl 3-furylmethanol, 2-allyl-3-methyl-4-hydiroxycyclopent-2-enone, 2-methyl-3-phenylbenzyl alcohol, including, where applicable, their individual isomers and racemates, and of the corresponding acids of formula (I) in a formic acid mixture of trans-isomers or individual isomers in which R 2 is: 2-propyl, 2-butyl, 2-pentyl, 3-pe ntyl, 2-methylprop-2-yl, 2-methylbut-2-yl, cyclohexyl.

Particularly preferred compounds include: 4-methyl-2,3,5,6-tetrafluorobenzyl - (+) - trans - 2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyridine] -imidin-5-yl] cyclopropanecarboxylate ("Compound 1"), 4-allyl-2,3,5,6-tetrafluorobenzyl- (+ J -trans - 2,2-dimethyl-3- [2- ( 2-methylprop-2-yl) pyrimidin-5-ylcyclopropanecarboxylate (hereinafter "compound 2"), 3-phenoxybenzyl- (+ J-tr-2,2-dimethyl-3- - [2 - (2 -methylprop-2-ylpyrimidin-5-yl] cyclopropanecarboxylate (hereinafter "compound 3"), 264263 3 (+) - α-cyano-3-phenoxybenzyl- (+) - trans-2,2-dimethyl -3- [2- (2-methyliprop-2-yl) pyrimid-in-5-yl] cyclopropanecarboxylate (hereinafter "4", 6-phenoxy-pyrid-2-ylmethyl- (+) - trans) -2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] cyclopropanecarboxylate (hereinafter "compound 5"), (+) -1-cyan-1 - (6-Phenoxypyrid-2-ylmethyl- (+ 1-trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] cyclopropane) xylate (hereinafter "compound 6"), 2-methyl-3-phenylbenzyl- (+ 1 -trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidine-5] 4-fluoro-3-phenoxyfoenzyl- (+) - trans-2,2-dimethyl-3- [2- (2-methylprop-2) -yl] cyclopropanecarboxylate (hereinafter "compound 7") -yl) pyrimidin-5-yl] cyclopropanecarboxylate (hereinafter "compound 8"), (+ 1 -1-cyano-1- (6-phenoxypyrid-2-yl) methyl- (+) - trans- ') 2,2-diethyl-3- (2-prop-2-ylpyrimimidin-5-yl) cyclopropanecarboxylate (hereinafter "compound 9"), (+) -1-cyano-1- (6-phenoxypyride-2) -ethyl] - (+) - trans-2,2-dimethyl-3- (2-cyclohexylpyrimidin-5-yl) cyclopropanecarboxylate (hereinafter "compound 10"), (+) -1-cyano-1- (6 -phenoxypyrid-2-yl) methyl- (+) - trans-2,2-dimethyl-3- (2-cyclopropylpyrimidin-5-yl) cyclopropanecarboxylate ("Compound 11"), (+) -1 (6-phenoxypyrid-2-yl) ethyl (+) - trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl] pyrimidin-5-yl] cyclopropanecarboxylate (hereinafter " compound 1'2 "), pentafluorobenzyl (+) -trans-2,2-dime ethyl 3- (2- (2-methylpyrrolidin-2-yl) pyrimidin-5-yl) cyclopropanecarboxylate (hereinafter "compound 13"), (+) - α-ethynyl-3-phenoxybenzyl - (+) - tri - 2,2-dimethyl-3- [2- (2-methylprop-2-ylpyrimidin-5-yl) cyclopropanecarboxylate (hereinafter "compound 14"), 4-methoxymethyl-2 3,5,6-tetrafluorobenzyl- (+) - trans-2, 2-dimethyl-3- [2- (2-methylprop-2-yl} pyrimidin-5-yl] cyclopropanecarboxylate (hereinafter, "compound 15") "), 2-methyl-3-phenylbenzyl- (+) - trans-2,2-dimethyl-3- (2-proip-2-ylipyrimidin-5-yl) cyclopropanecarboxylate (hereinafter" compound 16 ") .

The esters of the general formula I according to the invention are prepared according to the invention by the action of the insecticidal and acaricidally active esters in such a way that the acid of the general formula II,. 0 // c-cH-C-OH in which

R 2 is as defined above, reacted with an alcohol of the general formula VI R-H (VI) wherein R is as defined above, in the presence of an acid catalyst or a non-hydrating agent.

This method of esterification is also an object of the invention. Other esterification methods are described in our related Czech-Slovak Patent Nos. 264,271,264,272.

A suitable acid catalyst is, for example, dry hydrogen chloride, with a suitable dehydrating agent, for example dicyclohexylcarfoodiimide. The esterification according to the invention can be carried out in the presence of a solvent or diluent.

The individual isomers can be prepared by the same procedures but using the corresponding individual isomers of the compounds of formula II as starting materials. These individual isomers can be obtained by conventional separation techniques from the respective isomer mixtures. Thus, the cis- and trans-isomers separated by fractional crystallization of the corresponding carboxylic acids or salts thereof, while the various optically active substances can be obtained by fractional crystallization of the acid salts with optically active amines, followed by regeneration of the optically pure acid. The optically pure isomeric form of the acid can then be reacted with the appropriate alcohol to form the compound of Formula I in the form of an individual pure isomer.

Intermediates of formula I in which R is an alkoxy group having up to 6 carbon atoms which can serve to produce the corresponding free acids can be prepared from the appropriately substituted 5-bromopyrimidine by the following sequence of reactions: a) 2 -alkyl-5-bromopyridine, wherein the alkyl group is branched in the se-position, converted to the corresponding 5-formyl derivative by conversion to the Grignard compound and subsequent reaction with dimethylformamide. This procedure can be described by the following reaction scheme: 264263

b) 5-formylpyrimidine is reacted with 0,0-dialkyl-alkoxycarbonylmethylphosphonate in the presence of a base such as sodium hydride to give 3- (pyrimidin-5-yl) propenoate, in accordance with the following reaction scheme:

CHO

&Lt; tb &gt; ______________________________________ &lt; tb > ______________________________________ &lt; tb &gt; ______________________________________ < tb &gt; ______________________________________ c) This pyrimidinylpropenoate is not reacted with isopropyl triphenylphosphonium salt in the presence of an organometallic reagent. cyclopropanic acid ester. This reaction proceeds according to the following reaction scheme: R ·CH-CH-CO,

n-BuLL A /.// CH ~ CH-C03 /?

According to an alternative process for the production of 3-pyrimidin-5-ylpropenoates, 5-bromo-pyridio can be directly reacted with alkyl-propenoate (in particular 1,1-dimethylethyl propenoate) in the presence of the divalent salt.

Some of the 5-bromopyridines used in this process are novel. These compounds can be prepared by reacting the mucobromic acid derivative with the appropriate amidine, followed by palladium (e.g., palladium acetate), tetramethylethylenediamine, and preferably a phosphine derivative (e.g., triphenylphosphine), i.e., CH 2 = CH-CO2R9 / Pd (OCOCH3) 2 tetramethylethylenediamine / triphenylphosphine decarboxylation of the resulting pyrimidinecarboxylic acid, according to the following reaction: IV- \ t

CHO 0 ιι

HC r

C03H / i.

R — C — CH — CH — C = CH — G /

Br

R-ONH "C- -------- CH 3 CH 3> 2

CO 2 H

(IV) G = OR 7 (V) G = N (CH 3) 2 c) However, the compound of formula IV or the compound of formula V is not reacted with an amidine of the formula

An alternative process for preparing compounds of formula I wherein R is an alkoxy group having up to 6 carbon atoms and R2 is as defined above is as follows. a) Ylid obtained by the reaction of a phosphonium salt of the general formula [R 7 O — CH 2 —P (R 8) 3] + Y — wherein Y 1 represents any suitable anion, for example a chloride or bromide ion, and R 7 and R 8 represent alkyl or aryl groups preferably R7 is an alkyl group containing up to 6 carbon atoms, such as methyl or ethyl, and R8 is a phenyl group, by a cross-linked base in an aprotic solvent, preferably a sodium dimethylsulfoxide derivative in dimethyl sulfoxide (prepared by the reaction of sodium hydride) with dimethylsulfoxide), is reacted with a compound of the general formula

OO

R-C-CH-CH-C-H

CH3 CH3

NH

Preferably, R 3 is C 3 -NH 2 preferably in the presence of a base such as sodium methoxide in methanol to give a compound of formula I wherein R is a defined alkoxy group.

The compounds of formulas III, IV and V have not been described previously.

Preferred compounds of formula III include (+) - cis- and (-H) -trans-isomers of these compounds, wherein R is methoxy or ethoxy and R7 is alkyl containing up to 6 carbon atoms, including: methyl- (+ j-trans-3 - [(E, Z) -2-methoxy vinyl] -2,2-dimethylcyclopropanecarboxylate, methyl (+) - cis-3 - [(E, Z) -2-methoxy vinyl] - 2,2-dimethylcyclopropanecarboxylate, ethyl (+) - trans-3 - [(E, Z) -2-methoxyvinyl] -2,2-dimethylcyclopropanecarboxylate, ethyl (+) - cis-3- [(E, Z) 2-methoxyvinyl) -2,2-dimethylcyclopipanecarboxylate.

The corresponding compounds of general formula (IV) and general formula (V) which are also preferred include the following: methyl (+) - trans-3 - [(E, Z) -1-methyl-2-methoxyvinyl] -2,2 -dimethylcyclopropanecarboxylate, methyl (+) - cis-3 - [(E, Z) -1-formyl-2-methoxyvinyl] -2,2-dimethylcyclopropanecarboxylate, methyl- (+) - trans- 3 - [(E, Z) -2-dimethylamino-1-formylvinyll-2,2-dimethylcyclopropanecarboxylate and methyl- (4, 1 - [(E, Z) -2-dimethylamino-1-formylvinyl]] -2,2-dimethylcyclopropane carboxylate, as well as the corresponding ethyl esters.

More details of all these procedures are

to give a compound of formula III

OR-C-CH-CH-CH-CH-OR7

Z c / CH 3 CH 3 (III) b) The compound of formula III is treated with phosphoryl chloride and dimethylformamide under the conditions of the Vilsmeier-Haaek reaction to give the compound of formula

IV and / or compounds of formula V 264263 10 are set forth below in the Examples. Those compounds of formula I wherein R is hydroxy may be obtained by hydrolysis of alkyl esters, preferably by alkaline hydrolysis using, for example, aqueous alcoholic sodium hydroxide, and may be used directly to synthesize insectically useful esters by the method of the invention.

The compounds of the above general formula (I) may be used to combat harmful insects and other invertebrate pests such as pests. Insect and mite pests that can be controlled by the compounds of the present invention include the abovementioned agricultural-related pests (which include the cultivation of food and fiber crops, horticulture and livestock production), forestry, storing products of plant origin, such as fruits, grains and wood, as well as pests translating diseases of humans and animals, For the application to sites of pests, the compounds according to the invention are usually treated with compositions which contain, in addition to the insecticidally active substance or compounds of formula I, suitable inert diluents or carriers, and / or surfactants These compositions may also contain other pesticidally active agents, for example other insecticides or acaricides or fungicides, or may also contain synergists of insecticides such as dodecylimidazole, saxane or piperonyl butoxide.

The compositions according to the invention may be dusted in a form wherein the active ingredient is mixed with a solid diluent or carrier, for example, scaffold, bentonite, kieselguhr or grease, or may be in the form of granules in which the active ingredient is adsorbed by a porous granular material, e.g. .

Alternatively, the compositions may take the form of liquid preparations used in a flask or spray. These preparations are usually aqueous dispersions or emulsion active ingredients containing one or more known wetting agents, dispersing or emulsifying agents (surfactants).

The wetting, dispersing and emulsifying agents may be of the cationic, anionic or non-ionic type. Suitable cationic reagents include, for example, quaternary ammonium compounds, such as methyltrimethylammonium bromide. Suitable anionic type agents are, for example, soaps, salts of aliphatic mono-esters of acid, such as sodium lauryl sulfate, salts of sulfonated aromatic compounds, for example sodium dodecylbenzenesulfonate, sodium, calcium or ammonium ligninsulfonate, butylnaphthalenesulfonate and diisopropyl sodium salts and triisopropylnaphthalenesulphonic acids.

Suitable nonionic type agents include, for example, the condensation products of ethylene oxide with matte alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octylphenol, nonylphenol and octylcresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexi-toluic anhydrides, the condensation products of said parenteral esters with ethylene oxide and lecithins.

These compositions may be prepared by dissolving the active ingredient in a suitable solvent, for example, a ketone solvent such as diacetone alcohol, or in an aromatic solvent such as trimethylbenzene, and introducing the mixture thus obtained into water which may contain one or more known wetting agents, dispersing or emulsifying agents.

Other suitable organic solvents include dimethylformamide, ethylene dichloride, isopropyl alcohol, propylene glycol, additional glycols, diacetone alcohol, toluene, ketosene, paraffin oil, methyl naphthalene, xylenes, trichlorethylene, N-methyl-2-pyrrolidone and tetrahydrofurfuryl alcohol.

Compositions intended for application as aqueous dispersions or emulsions are generally provided as concentrates containing a high proportion of active ingredient (s). These concentrates are then diluted with water prior to use. Often, these concentrates are required to withstand long-term storage and can be diluted with water for aqueous storage, which will remain homogeneous for a long time to be applied by conventional spraying. The concentrates may contain 10 to 85% by weight of the active ingredient (s). If such concentrates are to be applied to aqueous preparations, these preparations may contain varying amounts of the active ingredient depending on the intended use. For agricultural and horticultural purposes, aqueous preparations containing between 0.0001 and 0.1% by weight are particularly suitable. active substance. In their own use, the compositions of the present invention are applied to the pests, their habitats, in an environment where the pests live, or to the cultivated plants subjected to pest infestation by any known pesticide application method, for example, by dusting or spraying.

The compositions of the invention are toxic to a wide variety of insects and other invertebrate pests, including, for example, the following:

Myzus persicae (Peach Aphid)

Aphis fabae (Poppy Aphid)

Megoura viceae '\ t

Aedes aegypti; (mosquito)

Dysdercus fasciatus

Musea domestica (House Fly)

Pieris brassicae 264263 11 (Large White, Larvae)

Plutella maculipennis (larvae)

Pbaeclan cochleariae

Tetran ychus c innabarhnusTetranychus urticae

Aonidiella spp.

Trialeuredes app. (whitefly)

Bl.atella germanica

Spodoptera littorallsHeliothis virescens \ t

Chortiocetes terminiferaDiabrotica spp.

Agrotis spp. (donkey)

Chilo partellus.

The compounds of formula (I) and compositions containing them have proven particularly useful in the control of flowable pests such as spider mites, among others. as well as for controlling Lepidoptera cotton pests such as Spo-doptera spp. and Heliothis spp.

The compounds of the invention can also be used to control soil pests, for example, Diabrotica spp. The disclosed compounds and compositions are also useful in the control of insect and mite pests that attack domestic animals, such as the buzzer (Lichii, and sericata) and ticks, for example, Boophilus spp. (tick), Ixodes spp. (tick), Amblyomma spp. (blotter), Rhipicephalus spp. (blotter) and Dermaceutor spp. (blotter).

The disclosed compounds and compositions are effective in combating both sensitive and resistant strains of these pests in the adult, larval, or intermediate development stages, and can be administered topically, orally, or parenterally to the infected host animal. Various aspects of the invention are illustrated by the following non-limiting examples. In preparative examples, products were commonly identified and characterized by nuclear magnetic resonance spectroscopy and infrared spectroscopy. In each of the cases where the product is specifically named, it corresponds to its spectral characteristics given to the structure. Example 1

This example illustrates the preparation of pivalaminidine hydrochloride. To a mixture of 43 g (0.51 motu) of trimethylacetoitrile and 24 g (0.51 mole) of dry ethanol under stirring and cooling in a mixture of ice and sodium chloride, dry gaseous hydrogen chloride was charged until 21 g of 12HCl was consumed. The reaction mixture was allowed to react for 2 days at room temperature and then diluted with 500 ml of dry diethyl ether to precipitate ethyl trimethylacetimidate hydrochloride. This material, after filtering off 34.5 g, was subjected to a further reaction by adding a portion of a solution of 6 g of dry-gas ammonia in 50 ml of dry ethanol under vigorous stirring. During the addition, the solids were gradually dissolved, and the resulting solution was allowed to react at room temperature for 20 hours, after which time the solvent was evaporated under reduced pressure. The solid residue was washed with diethyl ether (23 g) of beer amine hydrochloride. Example 2

This example illustrates the preparation of 5-bromo-2- (2-methylprop-2-yl) pyrimidine-4-carboxylic acid. To a mixture of 5.13 g of pivatamidine hydrochloride and 5 ml of dry ethanol, the ethanolic sodium ethoxide solution (14.5 ml of the solution obtained by dissolving 1.38 g of sodium in 24 ml of dry ethanol) was carefully added with stirring at 40 ° C. The resulting mixture was stirred for a further 10 minutes, then a solution of mucobromic acid (5.4 mL of a solution obtained by dissolving 5.16 g of muco, bromo acid in 8.0 mL of dry ethanol) was added, causing an exothermic reaction during low temperature. will be at 65 CC. After the temperature has dropped to 50 ° C, the remaining portion of the sodium ethoxide solution and the remainder of the coccobromic acid are added.

The reaction temperature is maintained at 50 DEG C. for 1 hour by external heating, the insoluble matter is filtered off at this temperature, washed with ethanol, the filtrate is combined with the wash liquors, and the solvent is evaporated off under reduced pressure. . The solid residue was washed with 10 mL of 2M hydrochloric acid and water, and dried. 3.8 g of 5-bromo-2- (2-methylprop-2-yl) pyrimidine-4-carboxylic acid melting point 142 DEG-144 DEG C. is obtained. NMR and IC spectra correspond to the indicated product structure. 1 H-NMR (CDCl 3, δ): 1.45 (singlet, 9H), 9.05 (singlet, 1H), 9.44 (broad singlet, 1H, IR ( paraffinic suspension): 2,940, 2,860, 2,500 (wide strip), 1,710, 1,570, 1,370, 1,305, 1,290, 1,220, 1,190, 1,175, 750, 680 cm -1.

This example illustrates the preparation of 5-bromo-2- (2-methylprop-2-yl) (pyrimidine. 264263 13 14 1.0 g of 5-bromo-2- (2-methylprop-2-yl) pyrimidine. The 4-carboxylic acid is heated by stirring to 145 ° C, whereupon the decarboxylated product is distilled under a water-jet vacuum, and the distillate, which solidifies upon cooling, is formed by 0.6 g of 5-torom-2- (2-methylprop-2). m.p. 50-51 DEG C. The NMR and IC spectra correspond to the indicated structure. @ 1 H-NMR (CDCl3, .delta.): 1.39 (singlet, 9H, 8.71 (singlet, 2H). paraffinic suspension): 2,940, 2,860, 1530, 1,480, 1,420, 1,170, 1,010, 810, 640 cm -1.

This example illustrates the preparation of 2- (2-methylprop-2-yl) pyrimidine-5-carboxaldehyde. 7.6 g (0.035 mol) of 5-bromo-2- (2-methylprop-2-yl) are added in small amounts to 0.95 g of magnesium shavings for the preparation of Grignard reagents in the presence of several iodine crystals. pyrimidine dissolved in 50 ml of dry tetrahydrofuran. The rate of addition depends on the intensity of the exothermic reaction. After the addition is complete, the mixture is warmed to complete the reaction, then cooled to 5 ° C and a solution of 2.58 g of dlmethylformamide in 15 ml of tetrahydrofuran is added dropwise. The mixture was allowed to warm to room temperature with stirring for 2 hours and then allowed to stand for 16 hours without stirring. After addition of 5 ml of water, the tetrahydrofuran is evaporated off under reduced pressure and the residue is partitioned between 100 ml of dilute aqueous ammonium chloride solution and 150 ml of diethyl ether.

The aqueous phase is extracted with 150 ml of ether, the extract is combined with the ether phase, washed with water and dried over anhydrous magnesium sulfate. After evaporation of the ether under reduced pressure, a greasy residue (5.8 g) was obtained, which was purified by chromatography on a silica gel column (dry column). Elution of the column with 100 parts by volume of methylene chloride and 2 parts by volume of ethyl acetate gave 3.4 g of 2- (2-methylprop-2-yl) pyrimidine-5-carboxaldehyde of 82-83 ° C. 1C (paraffin suspension): 2,940, 2,860, 1,700, 1,590, 1,430, 1,230, 1,150, 860, 650 cm -1. Example 5

This example illustrates the preparation of ethyl 3- [2- (1,1-dimethylethyl) pyrimidin-5-yl] -propopenoate. To a suspension of sodium hydride (0.54 g of a 50% oil dispersion) in 30 ml of dry diethyl ether, a solution of 3.93 g of 0,0-diethyl-ethoxycarbonylmethylphosphonate in 20 ml is added dropwise with stirring at -5 ° C. of dry diethyl ether, the mixture is stirred for 90 minutes, then 2.88 g of 2- (2-methylprop-2-yl) pyrimidine-5-carboxaldehyde in 40 ml are added dropwise with stirring at 0 ° C. dry diethyl ether, the resulting mixture was allowed to warm to room temperature with stirring for 2 hours and was allowed to react for another 16 hours at this temperature.

The reaction mixture is partitioned between 150 ml of water and 250 ml of diethyl ether, the aqueous phase is extracted with 250 ml of ether and the extracts are combined with an ether phase. After washing with 200 ml of water and drying with anhydrous magnesium sulfate, the solvent is evaporated off under reduced pressure, and the oily residue is subjected to chromium chromatography on a column of silica gel prepared by drying with dichloromethane with 5% (v / v) ethyl acetate as eluent. -nidla. 3.6 g of ethyl 3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] propenoate are obtained, which solidifies and melts at 43-45 ° C. NMR spectra data indicate that the product is the corresponding trans-isomer. 1 H-NMR (CDCl 3, δ): 1.35 (triplet, 3H), 1.42 (singlet, 9H), 4.24 (quartet, 2H), 6.50 (doublet, 1H), 7.60 (doublet, 1H), 8.82 (singlet, 2H). IR (paraffinic suspension): 2960, 1730, 1645, 1590, 1585, 1440, 1320, 1185, 1155 cm -1. Example 6

This example illustrates the preparation of ethyl trifluoro-2,2-dimethyl-3- [2- (2-methylprop-2-yl) -pyrimidin-5-yl] cyclopropanecarboxylate. To a solution of 7.1 g of 2-propyl triphenylphosphonium iodide in 20 ml of dry tetrahydrofuran was slowly added a solution of n-butyllithium (10.6 ml of 1.55M hexane solution) with stirring at room temperature. . The resulting mixture was stirred for an additional 15 minutes, then a solution of 3.2 g of ethyl trans-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl) propenoate was added dropwise at -5 ° C. in 25 ml of dry tetrahydrofuran. The reaction mixture was allowed to warm to room temperature with stirring for 30 minutes and was then left to stand for 16 hours, then partitioned between 300 ml of water and 200 ml of diethyl ether. The aqueous phase is extracted twice with 200 ml of ether each time and the ether extracts are combined with the ether phase. After washing twice with 100 ml of water each time and drying with anhydrous magnesium sulfate, the ether is evaporated off under reduced pressure, and the oily residue is chromatographed on a dry column of silica gel, which is first washed with dichloromethane (to remove triphenylphosphine) and then eluting with a mixture of 100 volumes of dichloromethane and 5 volumes of ethyl acetate. 2.8 g of ethyl trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl] pyrimidin-5-yl] cyclopropanecarboxylate are obtained), which has been confirmed by IC and NMR spectroscopy. -NMR (CDCl3): 0.99 (singlet, 3H, 1.31 (triplet, 3H, J, 1.40 (singlet, 12H), 1.96 (doublet, 1H), 2.54 (doublet, 1H), 4.2 (quartet, 2H), 8.5 [singlet, 2Ή] IR (liquid film), 2,960, 1,730, 1,485, 1,450, 1,420, 1,260, 1,180, 1,165 cm '1.

Mass Spectroscopy: M + = 276. Example 7

This example illustrates the preparation of trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] cyclopropanecarboxylic acid.

A solution of 2.6 g of ethyl trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] cyclopropanecarboxylate in 50 ml of ethanol is mixed with the solution. 1.0 g of sodium hydroxide in 50 ml of water and the mixture was stirred at room temperature for 5 hours. After removing most of the ethanol by evaporation under reduced pressure, the resulting mixture was acidified to pH 3 with dilute hydrochloric acid and extracted twice with 200 ml of diethyl ether each time. The combined extracts were washed with water and dried over anhydrous magnesium sulfate. After evaporation of the ether under reduced pressure, 2.1 g of trans-2,2-dimethyl-3- [2- (2-methyl-prop-2-yl) -pyrimidin-5-yl] -cyclopropanecarboxylic acid is obtained. . 1 H-NMR (CDCl 3): 1.03 (singlet, 3H),), 41 (singlet, 9H, 1.48 (singlet, 3H), 2.02 (doublet, 1H), 2.6 (doublet, 1H) ), 8.57 (singlet, 2H, IR (paraffinic suspension): 2,940, 1,700, 1,485, 1,430, 1335, 1250, 1230, 1110 cm -1.

Mass Spectroscopy: M @ + = 248. Example 8

This example illustrates the preparation of 4-allyl-2,3,5,6-tetrafluorobenzyl-trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] - cyclopropanecarboxylate. To a mixture of 504 mg of trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl] pyrimidin-5-yl] cyclopropamarboxylic acid, 462 mg of 4-allyl - 2,3,5, 6-tetrafluorobenzyl alcohol (containing a small amount of isomeric 2-allyl-3,4,5-tetrafluorobenzyl alcohol), 5 mg 4-diethylaminopyridine and 10 ml dry dichloromethane are added in portions at room temperature with stirring 420 mg of dicyclohexylcarbodiimide were added and the mixture was allowed to stir for 105 minutes at room temperature for 16 hours, the precipitate formed was filtered off, washed with ether, and the washings were combined with the filtrate, and the oily residue was removed by evaporation under reduced pressure. subjected to high resolution liquid chromatography (Gilson) using a silica gel column and a mixture of 100 parts by volume of dichloromethane and 2 parts by volume of ethyl acetate as eluent to give 650 mg of a product consisting of 94% by weight of 4-allyl-2,3, Trans-2,2-dimethyl-3- [2- (2-methylprop-2-ylpyrrolidine) 5,6-tetrafluorobenzyl ester and 6% 2-allyl-3,4,5,6-tetrafluorobenzyl ester; midin-5-yl] cyclopropanecarboxylic acids. The product is an oil which solidifies and melts at 64-66 ° C. The identity of the product is confirmed by NMR, IC and mass spectroscopy.

HkNMR (CDCl3, δ): 0.99 (singlet, 3H), 1.39 (singlet, 12H), 1.96 (doublet, 1H), 2.56 (doublet, 1H), 3.5 (multiplet, 2H) , 4.9 to 5.3 (multiplet, 4H), 5.6 to 6.1 (multiplet, 1H), 8.48 (singlet, 2H). IR (paraffinic suspension): 2960, 2930, 2860, 1735, 1490, 1400, 1440, 1420, 1330, 1150 cm -1.

Mass spectroscopy: M + = 450. Example 9

Following the same procedure as in Example 8, the following esters are obtained: a) 6-phenoxypyrid-2-ylmethyl-trans-2,2-di-methyl-1- [2- (2-methylprop-2-yl) pyrimidine-17- 5-yl] cyclopropanecarboxylate from the corresponding carboxylic acid and 6-phenoxy, pyrid-2-ylmethanol. 1 H-NMR (CDCl 3, d): 1.01 (singlet, 3H), 1.41 (singlet, 12H), 2.08 (doublet, 1H), 2.58 (doublet, 1H), 5.18 (singlet; 2H), 6.7-7.8 (multiplet, 8H), 8.50 (siletlet, 2H), IC (liquid film); 2,960, 1,730, 1,600, 1,580, 1,490, 1,540, 1250, 1160 cm -1.

Mass spectroscopy: M + = 431. bj 2-methyl-3-phenylbenzyl-trans-2,2-di, methyl-3- [2- (2-methylprop-2-yl] pyrimidin-5-yl] cyclopropanecarboxylate from the corresponding carboxylic acid and 2-methyl-3-phenyl-benzyl alcohol: 1 H-NMR (CDCl 3, d): 0.99 (singlet, 3H), 1.40 (singlet, 12H), 2.06 (doublet, 1H) , 2.25 (singlet, 3H), 2.60 (doublet, 1H), 5.27 (singlet, 2, H), 7.1-7.5 (multiplet, 8H), 8.50 (singlet, 2H) IC (liquid film): 2960, 1730, 1585, 1420, 1160, 760, 705cm -1.

Mass spectroscopy: M + = 428.c) α-cyano-3-phenoxybenzyl-trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] cyclopropanecarboxylate from the corresponding carboxylic acid and n-alkyne-3-phenoxybenzyl alcohol. 1 H-NMR (CDCl 3, d): 0.99 (singlet), 1.04 (singlet), 1.35 (singlet), 1.39 (singlet), 1.45 (singlet), 2.05 (multiplet), 2.6 (multiplet), 6.42 (siinglet), 6.44 (singlet), 7.26 (multiplet), 8.46 (singlet), 8.50 (singlet). (According to signal integration, these are mixtures of diastereoisomers in a ratio of 2: 1.) 18 IC (liquid film): 2,960, 1,740, 1,590, 1,485, 1,250, 1,140, 695cm -1.

Mass spectroscopy: M + = 455. d) 1-cyano-1- (6-phenoxypyrid-2-ylmethyl-trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidine] -5-yl] cyclopr opancarboxylate of the corresponding carboxylic acid and 1-cyano-1- (6-fluoro-pyrid-2-ylmethanol. 1 H-NMR (CDCl 3, d): 1.00 (singlet), 1.02 ( singlet), 1.35 (singlet), 1.40 (singlet), 2.1 (multiplet), 2.6 (multiplet), 6.4 (three singlets), 6.9 (doublet), 7.2 (multiplet), 7 , 8 (double doublet), 8.50 (two singlets). (According to signal integration, this is a 1: 1 mixture of diastereoisomers.) IR (liquid film: 2,960, 1,745, 1,595, 1,490, 1,450, 1,260) , 1140, 695 cm -1.

Mass spectroscopy: M + = 456. e) 4-Methoxymethyl-2,3,5,6-tetrafluorobenzyl- (+) - trans-2,2-dimethyl-3- [2- (2-methyl-propyl-2 -yl) pyrimidin-5-yl] -2,2-dimethylcyclopropanecarboxylate from the corresponding carboxylic acid and 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol. 1 H-NMR (CDCl 3, d): 0.99 (singlet, 3H), 1.40 (two singlets, 12H), 1.95 (doublet, 1H), 2.55 (doublet, 1H), 3.40 (singlet, 3H ), 4.50 (multiplet, 2H), 5.30 (multiplet, 2H), 8.50 (singlet, 2H). IC (paraffin suspension): 1735, 1595, 1490, 1295, 1150, 910, 880, 770 cm @ -1.

Mass spectroscopy: M + = 454. f) (+) -1- (6-phenoxy-pyrid-2-yl) -ethyl- (+) - trans-2,2-dimethyl-3- [2- (2-methyl-prop- 2-yl-pyrimidin-5-ylcyclopropanecarboxylate of the corresponding carboxylic acid and (+) - 1- (6-emoxypyrid-2-yl) ethanol 264263 19 1 H-NMR (CDCl 3, δ): 1.0 (single!), 1.33 (singlet), 1.40 (singlet), 1.5 (singlet), 1.8 (singlet), 2.05 (two doublets), 2.50 (two doublets), 5 , 85 (quartet), 6.7 (doublet), 7.2 (multiplet), 7.65 (double doublet), 8.50 (two singlets). IR (liquid film): 2980, 1730, 1600, 1580, 1445, 1260, 1170, 990, 700 cm -1.

Mass spectroscopy: (NH +) = 446. g) 4-Fluoro-3-phenoxybenzyl- (+) - trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidine din-5-yl-cyclopropanecarboxylate from the corresponding carboxylic acid and 4-fluoro-3-phenoxybenzyl alcohol. (h) Pentafluorobenzyl (+) - trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] cyclopropanecarboxylate from the corresponding carboxylic acid and pentafluorobenzyl alcohol. g) (+) - α-Ethynyl-3-phenoxybenzyl- (+) - trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] cyclopropaincarboxylate the corresponding carboxylic acid and (+) - N-ethynyl-3-phenoxybenzyl alcohol. Example 10

This example illustrates the preparation of (+) - O - cyano-3-phenoxybenzyl- (+) - trans-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] - 2,2-dimethyl-cyclopropanecarboxylate (compound 4) and separation of the enantiomeric pairs that form the compound. To a mixture of 3.2 g (4 + trans-3- [2- (2-methyl-iprop-2-yl) -pyrimidin-5-yl] -2,2-dimethyl-cyclopropanecarboxylic acid, 3.8 g of 3-phenoxy 2.8 g of di-cyclohexylcarbodiimide are added portionwise at room temperature (about 24 DEG C.) with benzyldehyde cyanohydrin [contaminated with about 20% of 3-phenoxybemaldehyde], 100 .mu.g of 4-dimethylaminopyridine and 100 ml of dichloromethane. After stirring for 2 hours, the reaction mixture was allowed to stand at room temperature for 16 hours, filtered and the solid washed with dichloromethane. The filtrate was combined with washings and the solvent was evaporated under reduced pressure. The oily residue was purified by high-resolution liquid chromatography (Gilson ) using a silica gel column eluted with a mixture of 100 volumes of dichloromethane and 5 volumes of ethyl acetate. From the starting fractions, a mixture of the desired product with 3-phenoxybenzaldehyde was obtained, with the latter eluted fractions with 5.3 g of pure (+) - α-cyano-3-phenoxybenzyl- (+) - trans-3- [2- 2-methylpnp-2-yl) pyrimidin-5-yl] -2,2-dimethylcyclopropanecarboxylate as a resinous material consisting of a mixture of two racemic pairs of enantiomers in a ratio of 2: 1. Initial fractions were rechromatographed using a 2-column silica gel column 5 ml of the same eluent at a rate of 30 ml / min to give 120 mg of the faster progressing (less polar) steam enantiomer.

The more polar (slower-moving) pair of 21 mg enantiomers is obtained by a similar rechromatography later by eluted fractions [containing a 2: 1 (A)] isomer pair pair. The product is a 95: 5 mixture of a more polar and less polar isomer. Mixing the dehumidified fractions and evaporating them gives a 7: 1 (B) mixture of less polar and more polar isomers. In biological tests against spider mite (Tetranychus urticae) on bean, the more polar pair of enantiomers appears to be about tenfold more effective (LC 50 = 4.5 ppm) than the less polar pair (LC 50 = 49 ppm).

A 7: 1 mixture of less polar and more polar steam enantiomers (10 mg) was dissolved in 0.1 mL of isopropanol containing 5% by weight of triethylamine and stirred at room temperature. After 22.5 hours, this ratio is due to the base-induced epimerization, to the α-carbon alcohol residue about 1: 1. 1 H-NMR (CDCl 3, δ): A. 0.95 (singlet) , 1.0 (singlet), 1.35 (singlet), 1.4 (singlet), 1.45 (singlet), 2.0 [two doublets], 2.6 (two doublets), 6.4 (two singlets), 7.2 (multiplet), 8.45 (two singlets). (According to signal integration, the mixture is a diastereoisomer 2: 1 mixture.) B. 1.0 (singlet, 3H), 1.40 (singlet, 9H), 1.45 (singlet, 3H), 2.05 (doublet, 1H) , 264263 21 22 2.55 (doublet, 1H), 6.40 (singlet, 1H), 7.2 (multiplet, 9H), 8.40 (singlet, 2H). IR (liquid film): A. 2960, 1740, 1590, 1490, 1445, 1250, 1140, 695 cm -1; B. 2960, 1740, 1585, 1480, 1445, 1245.1 140, 695 cm -1. Example 11 Preparation of methyl (+) - trans-2,2-dimethyl-3-formylcyclopropanecarboxylate

A mixture of 40.0 g of methyl 2,2-dimethyl-3- (dimethoxymethylcyclopropanecarboxylate (95% (+) 'trans-isomer), 120 ml of glacial acetic acid, 160 ml of acetone and 280 ml of water was stirred at room temperature for 5 hours, the aqueous residue is washed twice with 500 ml of ether each time, the wash liquors are combined with the extract and the mixture is washed with saturated sodium bicarbonate solution until acidity is lost. The solution was dried over anhydrous magnesium sulfate and the solvent was evaporated to an oil which was purified by distillation as a fraction of 28.5 g of methyl (+) - trans-2 as a fraction boiling at 46-48 ° C / 6.7 Pa. Example 12 Preparation of (+) - trans-Methyl-3 - [(E, Z) -2-methoxyvinyl] -2-dimethylcyclopropanecarboxylate

Sodium hydride obtained by washing 9.6 g of a 50% oil dispersion with n-hexane to remove oil was suspended in 150 ml of dry dimethyl sulfoxide freshly distilled over calcium hydride, the suspension was stirred at 38 ° C for 5 hours in a dry nitrogen atmosphere. to about 40 ° C, a solution of 68.8 gmethoxymethyl triphenylphosphonium chloride in 200 ml of dry dimethyl sulfoxide is then added over 15 minutes while maintaining the reaction temperature by external cooling to about 20 ° C. The resulting ylide solution was added dropwise to a solution of 28.5 g of freshly distilled methyl (+) - trans-2,2-dimethyl-3-formylcyclopropanecarboxylate in 50 ml of dimethyl sulfoxide while maintaining the reaction temperature for about 2 hours. to 20 ° C. The mixture was stirred for a further 30 minutes and then allowed to stand at room temperature for 72 hours. After addition of 1500 ml of water, the mixture was extracted with 1000 ml of diethyl ether and twice with 500 ml of diethyl ether, the extracts were combined, washed three times with 300 ml of water and dried. with anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure and the residue was triturated with petroleum ether (150 ml of a 60-80 ° C fraction). The insoluble matter was filtered off and the filtrate was evaporated to a yellow oil residue (29.0 g) which was distilled under reduced pressure. 21.4 g of methyl (+) - trans-3 - [(E, Z) -2-, methoxy vinyl] -2,2-dimethylcyclopropanecarboxylate of boiling point 64 DEG C./6 mm Hg are obtained. 1 H-NMR (CDCl 3, δ): 1.13 (singlet), 1.24 (singlet), 1.26 (singlet), 1.4 (multiplet), 1.9 (multiplet), 2.3 (multiplet), 3.5 ( singlet), 3.6 (singlet), 3.66 (singlet), 4.1 (two doublets), 4.56 (two doublets), 6.0 (double doublet), 6.4 (doublet).

[According to signal integration, this is a 2: 1 mixture of (E) and (Z) isomers) IR (liquid film): 2,960, 1,730, 1,650, 1,440, 1,270, 1,135, 1,170, 920 cm -1. Example 13

This example illustrates the preparation of a mixture of methyl (+) - trans-3 - [(E, Z) -2-dimethylamino-1H-vinylvinyl] -2,2-dimethylCyclopropanecarboxylate and methyl (+) - trans. -3 - [(E, -Z) -1-formyl-2-methoxyviinyl] -2,2-dimethyl-cyclopropanecarboxylate A solution of 12 is added dropwise to the mixture of 29.5 ml of dimethylformamide and 100 ml of 1,2-dichloroethane, while stirring. Ml of phosphoryl chloride in 10.0 ml of 1,2-dichloroethane. After the addition is complete, the mixture is stirred for 15 minutes, then cooled to 15 ° C and a solution of 10.0 g of methyl (+ 1-trans-3 - [(E, Z) -2-methoxy vinyl] is added in part. -2,2-dimethylcyclopropanecarboxylate in 80 ml of 1,2-dichloroethane The resulting mixture was allowed to stand at room temperature for 16 hours, then 150 g of anhydrous potassium carbonate and ice were added, and the mixture was extracted twice each time after the exothermic reaction had subsided. 300 ml of methylene chloride, the extracts were combined, washed with 300 ml of water and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure and the residual oil was heated to 55 ° C / 6.7 Pa to remove volatile components. 10.3 g of a mixture containing a small amount of methyl (+) - trans-3- (2B4263) 23 - [(E, Z) -1-formyl-2-methoxyvinyl] -2,2-dimethylethyl} are obtained. cycloproparboxylate and the prevailing amount of methyl (+) - trans-3 - [(E, Z) -1-dimethylamino-1-formylvinyl] -2,2-dimethylcyclopentanecarboxylate 1 H-NMR (CDCl 3, δ): (A) 1.0 (singlet), 1.05 (singlet), 1.27 (singlet), 1.30 (singlet), 2.0 (multiplet), 3.18 (singlet), 3.37 (singlet), 3.68 (singlet), 3.70 (singlet), 6.75 (broad singlet), 8.35 (broad singlet), 8, 8 (singlet).

[According to signal integration, it is a mixture of (E) and (Z) isomers in a ratio of 2: 1], IR (paraffin suspension): 2,960, 2,720, 1,730, 1,600, 1,450, 1410, 1,280, 1,230 , 1175 cm -1. Example 14

This example illustrates the preparation of methyl (+) - trans-3- (2-cyclohexylpyrimidin-5-yl) -cyclopropanecarboxylate To a mixture of 1.0 g of methyl (+) - trans-3- [(E, Z) - 2-dimethylamino-1-formylimidyl-2,2-dimethylcyclopropanecarboxylate (in the form of the product of Example 13, containing a small amount of methyl- (+ H +) - [3 - [(E, Z) -1-formyl] Of 2-methoxyvinyl) -2,2-dimethylcyclopropanecarboxylate), 1.08 g of cyclohexanoylamidine and 8 ml of methanol were added dropwise while stirring at room temperature to 3.2 ml of a 2M solution of sodium methoxide in methanol. The resulting mixture was refluxed for 3.5 hours, cooled to room temperature, poured into 200 ml of water and extracted twice with 200 ml of diethyl ether each time. The combined extracts were washed with 50 ml of water, dried. The solvent was evaporated under reduced pressure and the oily residue was purified by silica gel column chromatography using 3 parts by volume of methylene chloride and 1 part by volume of diethyl ether as eluent. 790 mg of methyl (+) - trans-3- [E, -Z) -2-dimethylamino-1-formylvinyl) -2,2-dimethylcyclopto-pancarboxylate are obtained. 1 H-NMR (CDCl 3): 1.0 (singlet, 3H), 1.4 (singlet, 3H), 1.2-1.8 (broad signal, 10H), 24 1.95 (doublet, 1H) ), 2.5 (doublet, 1H), 2.8 (broad signal, 1H), 3.7 (singlet, 3H), 8.5 (singlet, 2H). Ic (liquid film): 2,940, 2,860, 1,730, 1,600, 1,500, 1,440, 1,290, 1,175 cn1. Example 15

In an analogous manner to Example 7, except that methanol was used instead of ethanol, 790 mg of the product of Example 14 was converted to 750 mg of (+) - trans-3- (2-cyclohexylpyridine-5- of (1,2-dimethylcyclopopanecarboxylic acid), m.p. 128-130 ° C. IR (paraffinic suspension): 3500-2200 (broad band), 1710, 1550, 1340, 1290, 1260, 1190, 1120 cm -1.

Mass Spectroscopy: M + = 274. Example 16

This example illustrates the preparation of (RS) -1-cyano-1- (6-phenoxypyrid-2-yl) methyl- (1R, trans) -3- (2-cyclohexylpyrimidin-5-yl) -2,2-dimethylcyclopropanecarboxylate . To a stirred mixture of 150 mg of (+) - trans-3- (2-cyclohexylpyrimidin-5-yl) -2,2-dimethyl-cyclopropanecarboxylic acid, 130 mg of 1-cyano-1- (6-phenoxypyrid-2-yl) ) methanol, 5 mg of 4-dimethylaminopyridine and 5 ml of dichloromethane were added 118 mg of dicyclohexylcarbodiimide, the resulting mixture was stirred at room temperature for 7 hours and allowed to stand for 16 hours without stirring. The product is isolated by filtering the reaction mixture through a pad of silica gel, eluting with dichloromethane and then with a mixture of 20 volumes of dichloromethane and 1 volume of ethyl acetate. 248 mg of (RS) -1-cyano-1- (6-phenoxypyrid-2-yl) methyl- (1RS, trans) -3- (2-cyclohexylpyrimidin-5-yl) -2- 2-dimethylcyclopropanecarboxylate Identified by NMR spectroscopy as a mixture of equal parts of two amino-diastereomeric pairs: 1 H-NMR (CDCl 3, δ): 1.0 (two singlets), 1.35 (Singlet), 1.43 ( singlet), 1.2 to 2.0 (broad multiplet), 2.05 (multiplet), 2.6 (multiplet), 2.85 (multiplet), 26 26 426 3

2S 6.35 (broad singlet), 6.9 (doublet), 7.25 (multiplet), 7.8 (double doublet), 8.45 (two singlets). (According to signal integration, this is a mixture of equal parts of diastereomers). IR (liquid film): 2940, 2860, 1745, 1600, 1450, 1150, 810, 700 cm -1. Example 17

Using analogous procedures to Example 14, the following amides are also prepared: (i)

Methyl (+) - tri-3- (2-prop-2-ylpyrimidin-5-yl) -2,2-dimethylcyclopropanecarboxylate 1 H-NMR (CDCl 3, δ): 0.98 (singlet, 3H) , 1.30 (singlet, 3H), 1.38 (singlet, 3H), 1.40 (3H), 1.95 (doublet, 1H), 2.25 (doublet, 1H), 3.2 (multiplet) (1H), 3.75 (singlet, 1H), 8.48 (singlet, 2H); IR (liquid film): 2 980, 1 735, 1 595, 1 550, 1 440, 1 340, 1 260, 1 175, 830 cm · 1. (ii)

Methyl (+) - trans-3- (2-cyclopropylpyrimidin-3-yl) -2H-dimethylcyclopropanecarboxylate 1 H-NMR (CDCl 3, δ): 0.96 (singlet, 3H), 1.05 (multiplet, 4H), 1.40 &apos; (singlet, 3H), 1.95 (doublet, 1H), 2.2 (multiplet, 1H), 2.5 (doublet, 2 &apos;), 3.75 (singlet; 3H), 8.4 (singlet, 2H); IR (liquid film): 3070, 2960, 1730, 1600, 1550, 1470, 1445, 1175, 915 cm -1. Example 18

By the same procedure as in Examples 15 and 16, the following insecticidal and acaricidally active compounds are obtained: (i) 2-methyl-3-phenylbenzyl- (+) - trans-2,2-di-methyl-3- (2-prop- 2-ylpyrimidin-5-yl) cyclopropanecarboxylate. 1 H-NMR (CDCl 3, δ): 0.99 (singlet, 3H), 1.30 (singlet, 3H), 1.38 (singlet, 3H), 1.42 (singlet, 3H), 2.1 (doublet, 1H) , 2.25 (singlet, 3H), 2.65 (doublet, 1H), 3.2 (multiplet, 1H), 5.27 (singlet, 2H), 7.3 (multiplet, 8H), 8.49 (singlet, 2H) . IR (liquid film): 2980, 1730, 1595, 1550, 1425, 1240, 1165, 740, 710 cm -1. (ii) (+) -1-cyano-1- (6-phenoxypyrid-2-yl) methyl - (+) - tri-2,2-dimethyl-3- (2-prop-2-ylpyrimidine-5) 1 H-NMR (CDCl 3, δ): 1.00 (singlet), 1.03 (singlet), 1.31 (singlet), 1.36 (singlet), 1.38 (singlet), 1, 42 (singlet), 2.05 (multiplet), 2.60 (multiplet), 3.2 (multiplet), 6.35 (broad singlet), 6.9 (doublet), 7.3 (multiplet), 7.8 (double doublet) 8.5 (two singlets). (Integration is a mixture of equal parts of isomers) IR (liquid film) 2,980 1,745 1,595 1,580 1,450 1,250 1,145 (Iii) (i) -1-cyano-1- (6-phenoxy-pyrid-2-yl) -methyl- (+) - trans-2,2-dimethyl-3- (2-cyclopropyl-pyrimidine) 5-yl) cyclopropanecarboxylate. 1 H-NMR (CDCl 3, δ): 1.0 (singlet), 27 26 42 8 3 28 1.03 (multiplet), 1.06 (singlet), 1.34 (singlet), 1, 42 (singlet), 2.0 (two doublets), 2 "2.2 (multiplet), 2.8 (multiplet), 6.4 (singlet), 6.9 (doublet), 7.3 (multiplet), 7.8 (double doublet), 8.35 (two singlets) signals is a mixture of equal parts of diastereoisomers). IR (liquid film): 3070, 2940, 1750, 1600, 1450, 1260, 1150, 910, 800, 700 cm -1. Example 19 The following table shows the insecticidal and acaricidal activity values This activity is reported using steps A, B and C having the following meanings: A 80 to 100% mortality was observedB 50 to 79% mortality was observedC 0 to 49% mortality was observed.

The tests are carried out by applying the test species to a suitable environment (for example, suitable crop plants or filter paper) and spraying the pests and test medium (contact test - CT symbol in the table), or spraying the environment before placing the pest (residual test). effect - in the sym-RT RT table). Mortality evaluation is performed 72 hours after spraying, with the exception of Musa domestica, which is evaluated 24 hours later. The active ingredients are tested in the form of aqueous compositions containing 500 ppm of active ingredient. These compositions are prepared by dissolving the active ingredient in a solvent mixture consisting of 4 volumes of acetone and 1 volume of diacetone alcohol, and diluting the resulting solution with water containing 0.01% w / w wetting agent ("Lissapol" NX).

The experimental insects, environment and results are shown in the following table. The active ingredients are referred to in this table by numbers corresponding to the numbers given for specific compounds on pages 7 to 10 of the description, 00 co.

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Claims (2)

Table 4 shows that the compounds of the invention exhibit useful insecticidal and acaricidal activity against a number of experimental 30 pests representing a wide range of insect and acarid pests of economic importance. pSedsem VYNALEZU What is claimed is: 1. An insecticidal and acaricidal composition comprising, as active ingredient, a pyrimidin-5-ylcyclopropanecarboxylic acid ester of the formula (I) wherein R @ 2 represents an alkyl group carbonyl and R is a radical of formula A and R6 is hydrogen, halogen, alkyl having up to 4 carbon atoms; alkenyl having up to 6 carbon atoms, phenyl, phenoxy or benzyl, or phenyl, phenoxy or benzyl substituted with halogen or C1-4 alkyl, in combination with a diluent or carrier for the active ingredient. 2. Process for the preparation of the active compounds according to item 1, characterized in that the acid of general formula (II) CH-CH-C-OHXC CH. In which X represents oxygen, sulfur, vinylene group or a radical of formula —CR5 = Y—, where Y represents a nitrogen atom or CR5, R4 represents a hydrogen atom, a methyl group the individual substituents R 5 are selected from the group consisting of hydrogen, the atoms h and R 2 are as defined above, reacted with an alcohol of the formula VI R Η (VI) in which R has as defined above, in the presence of an acid catalyst or a dehydrating agent.