HU196696B - Insecticidal and/or acaricidal compositions comprising cyclopropane derivatives as active ingredient and process for producing the active ingredients - Google Patents

Abstract

Substd. cyclopropane cpds. of the formula (I) are new. Cpds. of the formulae (III), (IV) and (VI) are also new. (R2=1 3-6C alpha-branched alkyl gp.). - In (I), R=halo, OH, 1-6C alkoxy or -OR1 in which R1 is the residue of an alcohol R1OH which forms an insecticidal ester with chrysanthemic acid, permethrin acid or cyhalothrin acid. In (III) and(IV), R=1-6C alkoxy. Z=Br, formyl or -CH=CH-CO-OR9. R9=1-6C alkyl. G=OR7 or dimethylamino. R7=1-6C alkyl. (i) 2-Cyano-3-phenoxy benzyl trans-3-(2-(2-methylprop-2-yl) pyrimidin-5-yl)-2,2 -dimethylcyclopropane carboxylate, is specifically claimed. USE - (I) in which R is -OR1 are insecticides, and are esp. useful in controlling acarine pests of plants e.q. red mites and rust mites, and lepidopteran pests of cotton. They may also be used against pests which inhabit the soil e.g.. Diabrotica species, and pests which infest domestic animals. Compsns. contg. (I) are conventional . Other cpds. (I) and cpds. (III), (IV) and VI), are used in the prepn. of

Description

FIELD OF THE INVENTION The present invention relates to formulations containing tendon insecticides and / or acaricides containing cyclopropane derivatives. The invention further relates to a process for the preparation of the active compounds.

A 105 006 st. European Patent Specification discloses insecticidal compositions containing cyclopropanecarboxylic acid esters substituted with alkenyl groups. No. 184,360. U.S. Patent No. 5,123,125 relates to insecticidal and other invertebrate compositions containing halogenated cyclopropanecarboxylic acid esters as active ingredients.

In our experiments, we have found that cyclopropane derivatives of the general formula (I) other than the active compounds disclosed in the cited patents

R ² is C 3 -C 6 alkyl or C 3 -C 7 cycloalkyl branched at the α-position; and

R is an OR 'radical and R ¹ represents in (VI) is a group of formula and the latter formula wherein

X represents a vinylene group or a group of the formula -CR ^S = Y- in which Y represents a nitrogen atom or a group CR ⁵ ,

R ^{5 is} hydrogen, halo or C 1 -C 4 alkyl, n is 1, 2, 3 or 4, and the R ⁵ groups may be the same or different,

R ^{4 is} hydrogen, methyl, cyano or ethynyl; and

R ^{6 is} hydrogen, halogen, C 1 -C 4 alkyl, (1) C 4 alkoxy) -C 1 -C 4 alkyl, C 2 -C 6 alkenyl, phenyl or phenoxy, provided that when R ^{6 is} hydrogen, halogen, R ^{4 is} C 1 -C 6 alkyl or C 2 -C 6 alkenyl, R ⁴ is hydrogen only - they have very strong insecticidal and / or acaricidal activity.

The invention thus relates to compositions having a tendency to act as insecticides and / or acaricides. The compositions of the present invention contain from 0.0004 to 90% by weight of the cyclopropane derivative of formula (I), wherein R and R ² are as defined above, together with solid or liquid carriers of mineral or organic origin and optionally surfactants.

The invention further relates to a process for the preparation of cyclopropane derivatives of formula (I).

The compounds of formula (I) may exist in the form of various isomers and mixtures of isomers. These compounds can be cis and trans, depending on the relative position of the substituents on the cyclopropane ring. The cyclopropane group also contains two centers of asymmetry, and thus the compounds can form the (*) - cis, (-) - cis, (+) - trans and (-) - trans isomers. Compounds of formula (I) wherein the -OR ¹ group in R contains one or more asymmetric centers may form additional isomers. Their protection extends to the preparation of all possible isomers and isomeric mixtures of the compounds of general formula (I) (including racemic compounds) and to compositions containing all possible isomers and isomeric compounds of the compounds of formula (I).

The compounds of formula (I) according to the invention may be prepared as follows:

a) (II) carboxylic acids of general formula: - wherein O is hydroxy and R ² is as defined above - is reacted with alcohols of formula R * OH - wherein R ¹ is as defined above. The reaction is preferably carried out in the presence of an acidic catalyst (e.g., anhydrous hydrogen chloride) or a dehydrating agent (e.g., dicyclohexyl, carbodiimide).

b) The carboxylic acids of formula (II): - wherein O is hydroxy and R ² is as defined above - or (preferably) are alkali metal salts of O, ^{1 -R1} halides of formula - is 0, ¹ is halogen, preferably chlorine atoms in the formula, and R ¹ is as defined above - or a quaternary ammonium salt of a compound of the formula O, ^1- R ¹ with tertiary amines such as pyridine or trialkylanines such as triethylamine.

The reactions listed are optionally suitable olR ² for prop-2-yl, but-2-yl, pent-2-yl, pent-3-yl, 2-methylprop-2-yl, 2- methyl-but-2-yl, cyclopropyl or cyclohexyl. Particularly preferred examples of these compounds are:

(±) -trans-2,2-dimethyl-3- (2-prop-2-yl-pyrimidin-5-yl) -cyclopropanecarboxylic acid ethyl ester, (±) trans-2,2-dimethyl-3 - [2- (2-Methyl-prop-2-yl) -pyrimidin-5-yl] -cyclopropanecarboxylic acid ethyl ester and the corresponding methyl and 2-methyl-prop-2-yl esters.

Compounds of formula I wherein R is C 1-6 alkoxy can be prepared from the corresponding substituted 5-bromopyrimidines by the following reactions:

the starting 2- (α- / branched-alkyl) -5-bromopyrimidine compound is converted to the corresponding 5-formyl derivative by Griguard reagent formation followed by dimethylformamide reaction. This reaction sequence is illustrated in Scheme (A).

The resulting 5-formylpyrimidine compound is reacted with an O-dialkyl ester of alkoxycarbonylmethylphosphonic acid in the presence of a base such as sodium hydride. This reaction is illustrated in Scheme (B).

Finally, the resulting 3- (pyrimidin-5-yl) -propenoic acid ester is reacted with an isopropyl triphenylphosphonium salt in the presence of an organic metal compound such as n-butyllithium. This reaction is illustrated in Scheme (C). The product is obtained from the corresponding cyclopropanecarboxylic acid esters, i.e. compounds of formula I wherein R is alkoxy.

In the formulas (A), (B) and (C), R ² is as defined above and R ^{9 is C} 1-6 alkyl.

The 3- (pyrimidin-5-yl) -propionic carboxylic acid esters used as starting materials in Step (C) can also be prepared by reacting the corresponding 5-bromopyrimidine compounds with palladium (II) salts (e.g. ) -acetate), tetramethyl-ethyl. in the presence of lindiamine and, preferably, a phosphine compound (e.g. triphenylphosphine), the corresponding propylene carboxylic acid alkyl ester (preferably propenecarboxylic acid 1,1-dimethylethyl ester). illustrated, wherein R ² and R ⁹ are as defined above.

Some of the 5-bromopyrimidine compounds used as starting materials in the reactions described above are new materials. These compounds are reacted in Reaction (E)

The reaction may be prepared by reacting bromo-mucic acid with the corresponding amidine compound and then decarboxylating the resulting pyrimidine carboxylic acid derivative.

The compounds of formula I wherein R is C 1 -C 6 alkoxy may also be prepared by the following method:

A phosphonium salt of formula (VII) wherein Y is an anion such as chloride or bromide and R ⁷ and R ^{8 are} alkyl or aryl (preferably R ^{7 is C} 1-6 alkyl such as methyl or ethyl). And ^R8 is phenyl) in an aprotic solvent with a strong base (preferably dimethylsulfoxide sodium salt in dimethylsulfoxide) and the resulting ylide is reacted with a compound of formula (VIII). The compound of formula (Ifi) thus obtained is treated with phosphoryl chloride and dimethylformamide under the conditions of the Vilsmeier-Haack reaction, and the resulting compound of formula (IV) and / or V is then treated with an amidine of formula (IX). reacted. The latter reaction is preferably carried out in the presence of a base (e.g., methanolic sodium methoxide). The product obtained is a compound of formula I wherein R is an alkoxy group.

The compounds of formulas III, IV and V are novel substances.

Preferred compounds of formula (III) are the (±) - cis and (±) - trans isomers of R @ ⁷ is methoxy or ethoxy and R @ ⁷ is (C1 -C6) -alkyl, of which:

(±) -trans-3 - [(E, Z) -2-methoxyvinyl] -2,2-dimethylcyclopropanecarboxylic acid methyl ester, (±) -cis-3 - [(E, Z) -2-methoxyvinyl] -2,2-dimethylcyclopropanecarboxylic acid methyl ester, (±) -trans-3 - [(E) -2-methoxyvinyl] -2,2-dimethyl- ethyl cyclopropanecarboxylic acid, and (±) -cis-3 - [(E) -2-methoxyvinyl] -2,2-dimethylcyclopropanecarboxylic acid ethyl ester.

Preferred compounds of formula (IV) and (V) include: (±) -trans-3 - [(E) -1-formyl-2-methoxyvinyl] -2,2-dimethylcyclopropane methyl carboxylic acid, (±) -cis-3 - [(E, Z) -1-formyl-2-methoxyvinyl] -2,2-dimethylcyclopropanecarboxylic acid methyl ester, (±) Trans-3 - [(E) -2-Dimethylamino-1-formyl-vinyl] -2,2-dimethyl-cyclopropanecarboxylic acid methyl ester, (±) -cis-3 - [( (E) -2-Dimethylamino-1-formyl-vinyl] -2,2-dimethyl-cyclopropanecarboxylic acid methyl ester and the corresponding ethyl esters.

In the insecticidal compounds of formula (I), R ^{2 is} preferably prop-2-yl, 2-methylprop-2-yl, cyclopropyl or cyclohexyl. In these compounds, the acyclopropanecarboxylic acid moiety is preferably (±) - trans- configuration.

Particularly preferred insecticidal compounds of formula I are (±) -trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] cyclopropanecarboxylic acid (4-methyl-2,3,5,6-tetrafluorobenzyl ester (Compound No. 1)), diluent or diluent, if desired, to increase the rate of the reaction or to obtain a higher yield. The reaction rate and / or yield may also be increased, if appropriate, using suitable catalysts (e.g., phase transfer catalysts).

The individual isomers of the compounds of formula (I) may be prepared as described above from the corresponding isomers of the compounds of formula (II). The individual isomers of the compounds of formula (II) may be separated from the mixture of isomers by known methods. The counter- and trans-isomers can be separated, for example, by fractional crystallization of the corresponding carboxylic acids or carboxylic acid salts. During the separation of optically active isomers, the salts of carboxylic acids with optically active amines are separated by fractional crystallization and the optically active carboxylic acids of formula II are liberated from the individual diastereoisomers.

The starting materials of formula (II) may be prepared by hydrolysis of esters corresponding to formula (I) which, however, contain an alkoxy group of 1 to 6 carbon atoms in R. The hydrolysis is preferably carried out in the presence of an alkali, for example, aqueous alcoholic sodium hydroxide solution.

Among the compounds of formula (I) which may be used in the preparation of insecticidal starting materials, wherein R is a (C1-C6) alkoxy group, those compounds in which R is methoxy, ethoxy, propoxy or butoxy, (±) -trans-2,2 -Dimethyl-3- [2- (2-methyl-prop-2-yl) -pyrimidin-5-yl] -cyclopropanecarboxylic acid (4-allyl-2,3,5,6-tetrafluorobenzyl) ester (2 orb), (±) trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] -2-cyclopropanecarboxylic acid (3-phenoxybenzyl). ) ester (Compound 3), (±) -trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] cyclopropanecarboxylic acid ( α-cyano-3-phenoxybenzyl) ester (# 4 or above), (±) -trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidine -5-yl] -cyclopropanecarboxylic acid (6-phenoxypyrid-2-ylmethyl) ester (Compound 5), (±) -trans-2,2-dimethyl-3- [2- (2-Methyl-prop-2-yl) -pyrimidin-5-yl] -cyclopropanecarboxylic acid [(±) -1-cyano-1- (6-phenoxy-pyrid-2-yl) -methyl] -ester (6 s Compound z), (±) Trans-2,2-Dimethyl-3- [2-methylprop-2-yl) -pyrimidin-5-yl] -cyclopropanecarboxylic acid (2-methyl-3-phenyl) benzyl) ester (7. s. compound), (±) -trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl]) - pyrimidin-5-yl] -cyclopropanecarboxylic acid (4-fluoro-3- phenoxybenzyl) ester (Compound 8), (±) -trans-2,2-dimethyl-3- (2-prop-2-yl-pyrimidin-5-yl) -cyclop; (±) -1-Cyano-1- (6-phenoxypyrid-2-yl) methyl] ester (Compound 9), (±) -trans-2,2-dimethyl-3- (2) -cyclohexylpyrimidin-5-yl) -cyclopropanecarboxylic acid [(±) -1-cyano-1- (6-phenoxypyrid-2-f) methyl] ester (Compound 10), (± Trans-2,2-dimethyl-3- (2-cyclopropylpyrimidin-5-yl) -cyclopropanecarboxylic acid [(±) -1-cyano-1- (6-phenoxypyrid-2-i ')] methyl methyl ester (Compound 11), (±) -trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] cyclopropane- Carboxylic acid [(±) -1- (6-phenoxypyrid-2-i ') ethyl] ester (Compound 12), (±) -trans-2,2-dimethyl-3- [2 - (2-Methyl-prop-2-yl) -pyrimidin-5-yl] -cyclopropanecarboxylic acid pentafluorobenzyl ester (Compound 13), (±) -trans-2,2-dimethyl-3- [2- (2-Methyl-prop-2-yl) -pyrimidin-5-yl] -cyclopropanecarboxylic acid ((±) - α-ethynyl-3-phenoxybenzyl ester (Figure 14). s. compound), (±) -trans-2,2-dimethyl-3- [2- (2-methyl-prop-2-yl) -pyrimidin-5-yl] -cyclopropanecarboxylic acid [4- (methoxymethyl) -31

-2,3,5,6-tetrafluoro-benzyl ester (Compound # 15); and (±) -trans-2,2-dimethyl-3- (2-prop-2-yl-pyrimidin-5-one). yl) cyclopropanecarboxylic acid (2-methyl-3-phenylbenzyl) ester (Compound 16).

The formulations containing the compounds of formula I can be used to suppress insect pests and other invertebrate pests (in particular mites). These compositions are mainly used in agriculture (horticulture, horticulture, animal husbandry), forestry, storage of plant products (such as fruits, seeds and tubers), and in controlling pests that infect humans and animals.

The compositions of the invention contain one or more of the active compounds of formula (I) together with suitable inert diluents or carriers and / or surfactants. Optionally, the compositions may contain additional pesticidal agents other than the compounds of formula I, such as other insecticidal or acaricidal agents, tungicidal agents, or insecticidal agents (such as dodecylimidazole, safroxane or piperonyl butoxide).

The compositions may be, for example, dustable powders containing, in addition to the active ingredient, a solid diluent or carrier, such as kaolin, bentonite, silica gel or talc. Solid compositions can also be prepared in the form of granules, in which case the active ingredient is absorbed onto a porous particulate carrier (e.g., pumice stone).

The compositions may also be liquid compositions for application by spraying, flooding or spraying. Liquid formulations are usually aqueous dispersions or emulsions of the active ingredient, and may contain, in addition to the active ingredient and the water, one or more known surfactants (wetting agents, dispersing agents, or emulsifying agents).

Cationic, anionic and nonionic surfactants can be used to prepare the compositions. Suitable cationic surfactants are, for example, quaternary ammonium compounds such as cetyltrimethylammonium bromide. Anionic surfactants include, for example, soaps, aliphatic sulfuric acid monoester salts (such as sodium lauryl sulfate) and salts of sulfonated aromatic compounds (such as sodium flodecylbenzene sulfonate, sodium, calcium or ammonium lignin sulfonate, butyl naphthalene, and triisopropylnaphthalenesulfonate sodium salts, etc.). Examples of nonionic surfactants are the condensation products of ethylene oxide with fatty alcohols (such as oleyl alcohol or cetyl alcohol) or alkyl phenols (such as octylphenol, nonylphenol and octylcresol), partial hexanohydrides of long chain fatty acids. esters, condensation products of the latter partial esters with ethylene oxide, and lexitins.

Liquid compositions may be prepared, for example, by dissolving the active ingredient in a suitable solvent (such as a ketone solvent such as diacetone alcohol or an aromatic solvent such as trimethylbenzene) and adding the resulting solution to water. The water may contain one or more known wetting, dispersing or emulsifying agents. Organic solvents include dimethylformamide, ethylene dichloride, isopropanol, propylene glycol, other glycols, diacetone alcohol, toluene, kerosene, white oil, methylnaphthalene, xylene, trichlorethylene, N-methyl-2-pyrrolidone and tetrahydrofurfur. alcohol can also be used.

Formulations for use in the form of aqueous dispersions or emulsions are usually commercially available in the form of high active compound concentrates, which are diluted with water to the desired active ingredient content before use. The most common requirement for concentrates is that they can be stored unchanged for a long period of time and, after storage, dilute with water to form homogeneous formulations that can be applied by conventional spraying equipment for a sufficient period of time. The concentrates usually contain from 10 to 85% by weight of the active ingredient. Ready-to-use, dilute aqueous formulations may have a relatively broad range of drug content depending on the intended use. Compositions for use in agriculture and horticulture may preferably contain from 0.001 to 0.1% by weight of the active ingredient,

In practical use, the compositions of the invention are applied to pests, pests, areas of pests, pests, or plants at risk of infection, by known means (e. G., By spraying or spraying).

The compositions of the invention are highly toxic to a wide variety of insects and other invertebrate pests. The compositions are particularly useful for controlling the following pests:

Myzus persiace (lice),

Aphis fabae (lice),

Megoura vicae (lice),

Aedes aegypti (mosquitoes),

Dysdcrcus fasciatus (bugs),

Musca domestica (domestic fly),

Pieris brassicae (cabbage butterfly, larvae),

Plutefla maculipennis (cabbage moth, larvae),

Phaedon cochleariae (horseradish beetle),

Tetranychus cinnaberius (carmine weave mite), Tetranychus urticae (red weave mite),

Apnidiella spp. (Scale insects),

Trialeuroides spp. (White flies),

Blattella germanica (cockroach),

Spotodptera littoralis (cotton seed drill), Heliothis virescens (cotton seed drill),

Chortiocetes terminifera (locusts),

Diabrotica spp. (Rootworms)

Agrotis spp. (Cutworm),

Chilo partellus (corn borer).

Compositions containing the compounds of formula I are particularly useful for controlling acarid pests, such as red mite and spider mites, as well as cotton-borne moth pests such as Spodoptera species and Heliothis species. The compositions are also useful for controlling soil pests such as Diabrotica species. The compositions are preferably used to control insect and mite infections in domestic animals, such as Licilia sercata, and ticks such as Boophilus, Ixodes, Amblyomma, Rhipicephalus and Dermaceutor. The compositions are effective against both susceptible and resistant varieties of the pests listed, and the pests are in an advanced state, larval state and transient.

196.696 are also in their advanced stages of development. For the treatment of pets, the compositions may be used in the form of compositions for oral, parenteral or topical administration.

The invention is further illustrated by the following non-limiting Examples.

Example 1 .ί θ

Preparation of Pivalamidine Hydrochloride A mixture of g (0.51 mole) trimethylacetonitrile and 24 g (0.51 mole) in anhydrous ethanol was treated with anhydrous hydrogen chloride gas up to 21 g of hydrochloric acid under ice-cooling (90 minutes). After 2 days at room temperature, the reaction mixture was diluted with 500 µg of anhydrous diethyl ether. The precipitated 34.5 g of ethyl trimethylacetimidate hydrochloride is filtered off and a solution of 6 g of anhydrous ammonia gas in 50 ml of anhydrous ethanol is added under vigorous stirring. As the solution is added, the solid gradually dissolves. The resulting solution was kept at room temperature for 20 hours, then the solvent was evaporated under reduced pressure and the solid residue was washed with diethyl ether. 23 g of pivalamidine hydrochloride are obtained. '

Example 2 25

Preparation of 5-Bromo-2- (2-methylprop-2-yl) pyrimidine-4-carboxylic acid

1.38 g of sodium metal are dissolved in 24 ml of anhydrous ethanol. 14.5 ml of the resulting sodium ethoxide solution was gently stirring pivalamidin __-hydro- chloride and 5.18 g of anhydrous ethanol was added 5 mL of 40 ^lb C under nitrogen. After stirring for a further 10 minutes, 5.4 ml of a solution of bromobutyric acid in ethanol were added (5.16 g of bromobutyric acid was dissolved in 8.0 ml of anhydrous ethanol).

An exothermic reaction begins and the mixture warms to 65 ° C. When the temperature of the mixture drops to 50 ° C, the remainder of the sodium ethoxide solution and the bromobutyric acid solution prepared above are added. After 1 hour at 50 ° C, the insoluble material is filtered off at 50 ° C and washed with ethanol. The filtrate and the washings were combined and the solvent was evaporated under reduced pressure. The solid residue was washed with 10 mL of 2M aqueous hydrochloric acid and then with water and dried. 3.8 g of 5-bromo-2- (2-methylprop-2-yl) -pyridinidine-4-carboxylic acid are obtained, m.p. 142-144 ° C (dec.).

Nuclear Magnetic Resonance Spectrum (CDCl ₃ ) δ 1.45 (s, 9H),

9.05 (s, 1H), 9.44 (broad s, 1H) ppm.

Infrared bands (paraffin): 2940, 2860,

2500 (wide), 1710, 1570-1370; 1305, 1290, 1220,

1190, 1175,750, 680 cm ^-1 .

, -m ⁵ θ

Example 3

Preparation of 5-Bromo-2- (2-methylprop-2-yl) -pinimidine

5-Bromo-2- (2-methylprop-2-yl) -pyrimidine-4-carboxylic acid (1.0 g) was stirred at 145 ° C and the decarboxylated product was evaporated in a water jet under a ball-cooler. The distillate solidifies on standing 55. 0.6 g of 5-bromo-2- (2-methyl-prop-2-yl) -pyrimidine is obtained, m.p. 50-51 ° C.

NMR (CDC1 ₃₎ '5 = 1.39 (s, 9H);

8.71 (s, 2H) ppm.

Infrared Bands (Paraffin): 294.0, 2860,

1530, 1480, 1420, 1170, 1010, 810, 640 ^cm-first 60

Example 4

Preparation of 2- (2-Methyl-prop-2-yl) -pyrimidine-5-carboxaldehyde

To a mixture of 0.95 g of magnesium turnings (Grignard reagent grade) and some iodine crystals were added in small portions 7.6 g (0.035 mol) of 5-bromo-2- (2-methylprop-2-yl) pyrimidine in 50 ml of anhydrous tetrahydrofuran prepared solution. The rate of reagent addition is controlled as a function of the exothermic reaction. After the addition of the reagent, the mixture is heated to complete the reaction. The mixture was then cooled to 5 ° C and a solution of 2.58 g of dimethylformamide in 15 ml of tetrahydrofuran was added dropwise. The mixture was allowed to warm to room temperature with stirring for 2 hours and allowed to stand at room temperature for 16 hours. Water (5 ml) was added, the tetrahydrofuran was evaporated under reduced pressure and the residue was partitioned between dilute aqueous ammonium chloride (100 ml) and diethyl ether (150 ml). The aqueous phase is extracted with 150 ml of ether. The extract and ether layer were combined, washed with water, dried over anhydrous magnesium sulfate and the ether evaporated under reduced pressure. An oily solid residue (5.8 g, weight) is obtained, which is chromatographed on a dry silica gel column. Elution with 100 volumes of methylene chloride and 2 volumes of ethyl acetate gave 3.4 g of 2- (2-methylprop-2-yl) pyrimidine-5-carboxaldehyde, m.p. 82-83 ° C.

Infrared bands (paraffin): 2940.2860, 1700, 1590, 1430, 1230, 1150, 860, 650 cm @ ^-1 .

Example 5

Preparation of 3- (2- (1,1-Dimethylethyl) pyrimidin-5-yl] propenecarboxylic acid ethyl ester

0.54 g of a 50% sodium hydride dispersion in mineral oil is suspended in 30 ml of anhydrous diethyl ether and 3.93 g of 0.0-diethyl-ethoxycarbonylmethyl- is stirred at -5 ° C. solution of the phosphonate in 20 ml of anhydrous diethyl ether is added dropwise. After the addition of the reagent, the mixture was stirred for a further 90 hours and then mixed with 2- (2-methylprop-2-yl) -pyrimidine-5-carboxaldehyde (2.88 g) in anhydrous diethyl ether (2.88 g) at 0 ° C. of the prepared solution. The mixture was allowed to warm to room temperature with stirring for 2 hours and then allowed to stand at room temperature for 16 hours. Water (150 ml) and diethyl ether (250 ml) were then added. The aqueous phase was separated, extracted with ether (250 mL) and the extract was combined with the ether phase. The ethereal solution was washed with water (200 mL), dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The oily residue was chromatographed on a dry silica gel column using 5% ethyl acetate in dichloromethane as the eluent. 3.6 g of ethyl 3- [2- (2-methylprop-2-yl) -pyrimidin-5-yl] -propenecarboxylic acid are obtained. The product solidifies on standing, m.p. 43-45 ° C. The product is a trans isomer according to NMR and IR spectra.

NMR (CDC1 ^_3)! Δ = 1.35 (t, 3H), 1.42 (s, 9H), 4.24 (q, 2H), 6.50 (d, 1H), 7.60 (d, 1H), 8.82 (s, 2H) ppm.

Infrared bands (paraffin): 2960.1730, 1645, 1590, 1485, 1440, 1320, 1185, 1155 cm ^-1 .

196 696

Example 6

Preparation of Trans-2,2-Dimethyl-3- [2- (2-methylprop-2-yl) -pyrimidin-5-yl] -cyclopropanecarboxylic acid ethyl ester

To a solution of 7.1 g of prop-2-yl-phenylphosphonium iodide in 20 ml of anhydrous tetrahydrofuran is added 10.6 ml of a 1.55 molar solution of n-butyllithium in hexane at room temperature with stirring. The solution was added under a nitrogen atmosphere. After the addition of the reagent, the mixture was stirred for 15 minutes and then 3.2 g of trans-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] propane was added at -5 ° C. A solution of ethyl carboxylic acid in 25 ml of dry tetrahydrofuran was added dropwise. After the addition of the reagent, the mixture was allowed to warm to room temperature over 30 minutes with stirring and then allowed to stand at room temperature for 16 hours. Water (300 mL) and diethyl ether (200 mL) were added. The ether layer was separated and the aqueous layer was extracted with ether (2 x 200 mL). The ethereal solutions were combined, washed with water (2 x 100 mL), dried over anhydrous magnesium sulfate and the solvent evaporated under reduced pressure. The oily residue was chromatographed on a silica gel column. The triphenylphosphine was dissolved in dichloromethane and eluted with a mixture of 100 volumes of dichloromethane and 5 volumes of ethyl acetate, 2.8 g of trans-2,2-dimethyl-3- [2- (2-methylprop) -2-yl) -pyrimidin-5-yl] -cyclopropanecarboxylic acid ethyl ester is obtained.

Nuclear Magnetic Resonance Spectrum (CDCl ₃ ) ^: δ = 0.99 (s, 3H), 1.31 (1, 3H), 1.40 (s, 12H), 1.96 (d, 1H), 2.54 (d, 1H), 4.2 (q, 2H), 8.5 (s, 2H) ppm.

Infrared spectral lines (liquid film), 2960, 1730, 1485, 1450, 1420, 1260, 1180, 1165 cm &^lt; -1 &^gt;.

Peak mass spectrum: M ⁺ 276.

Example 7

Preparation of trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] cyclopropanecarboxylic acid

To a solution of 2.6 g of trans-2,2-dimethyl-3- [2- (2-ethyl-prop-2-yl) -pyrimidin-5-yl] -cyclopropanecarboxylic acid ethyl ester in 50 ml of ethanol 1.0 g A solution of sodium hydroxide (g) in water (50 ml) was added and the mixture was stirred at room temperature for 5 hours. The bulk of the ethanol was evaporated under reduced pressure and the concentrate was acidified to pH 3 with dilute hydrochloric acid. The resulting mixture was extracted twice with 200 ml of diethyl ether. The extracts were combined, washed with water, dried over anhydrous magnesium sulfate and the ether evaporated under reduced pressure. 2.1 g of trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] cycloproparecarboxylic acid are obtained, m.p. 168-169 ° C.

NMR (CDC1 ^_3)! δ = 1.03 (s, 3H), 1.41 (s, 9H), 1.48 (s, 3H), 2.02 (d, 1H), 2.6 (d, 1H), 8.57 (s, 2H) ppm.

Infra-red lines (paraffin): 2940, 1700, 1485, 1430, 1335, 1250, 1230, 1210 cm ^-1 .

Mass Spectrum: (M ⁺ ): 248.

Example 8

Preparation of trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] cyclopropanecarboxylic acid (3-phenoxybenzyl) ester

500 mg trans-2,2-dimethyl-3- (2- (2-methylprop-2-yl) pyrimidin-5-ylcyclopropanecarboxylic acid, 552 mg 3-phen55 oxybenzyl bromide, 304 mg After stirring for 2 hours at room temperature, the mixture was allowed to stand at room temperature for 16 hours. The precipitated solid precipitate was filtered off and the filtrate was concentrated under reduced pressure by high performance liquid chromatography (GC). ), purified on silica gel, eluting with a mixture of 100 volumes of dichloromethane and 2 volumes of ethyl acetate to give 800 mg of trans-2,2-dimethyl-3- [2- (2-methyl] prop-2-yl) as an oil. Pyrimidin-5-yl] -cyclopropanecarboxylic acid (3-phenoxybenzyl) ester is obtained.

NMR (CDC1 ^_3): δ = 0.98 (s, 3H), 1.40 (s, 12H), 2.02 (d, 1H), 2> (d, 1H), 5.15 ( s, 2H), 6.8-7.5 (m, 9H) ppm.

IR (liquid film) bands: 2960, 1730, 1590, 1490, 1260, 1220, 1160 cm ^-1 .

Mass Spectrum (M ⁺ ): 430.

Example 9

Trans-2,2-Dimethyl-3- [2- (2-methyl-prop-2-yl) -pyrimidin-5-yl] -cyclopropanecarboxylic acid (4-allyl-2,3,5,6-tetrafluoro) Preparation of benzyl) ester

Trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) -pyrimidin-5-yl] -cyclopropanecarboxylic acid (504 mg), 4-allyl-2,3,5,6 (462 mg) -Tetrafluorobenzyl alcohol (a small amount of isomeric material containing 2-allyl-3,4,5,5-tetrafluorobenzyl alcohol), mixed with 5 mg of 4- (methylmethylamino) pyrimidine and 10 ml of anhydrous dichloromethane 420 mg of dicyclohexylcarbodiimide were added portionwise at room temperature. After the addition of the reagent, the mixture was stirred for 105 minutes and then allowed to stand at room temperature for 16 hours. The solid precipitate is filtered off, washed with ether and the washings are combined with the filtrate. The solvent was evaporated under reduced pressure and the oily residue was purified by high performance liquid chromatography (Gilson). Silica gel was used as adsorbent and 100 volumes of dichloromethane and 2 volumes of ethyl acetate were used as eluent. 650 mg of an oily solid are obtained, m.p. 64-66 ° C. The product is 94% by weight of trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl). pyrimidin-5-yl] -cyclopropanecarboxylic acid (4-ani] -2,3,5 _one 6-tetrafluoro-benzyl) ester and 6 wt% of isomeric 2-allyl-3,4,5,6-tetrafluoroethane Contains benzyl ester.

NMR ^_(CDCl3): δ = 0.99 (s, 3H);

1.39 (s, 12H), 1.96 (d, 1H), 2.56 (d, 1H), 3.5 (m, 2H), 4.95-5.3 (m, 4H), δ , 6-6.1 (m, 1H), 8.48 (s, 2H) ppm.

Infrared bands (paraffin): 2960, 2930, 1860, 1735, 1490, 1460, 1440, 1420, 1330, 1150 cm ^-1 .

Mass Spectrum (M ⁺ ): 450.

Example 10

By reaction of the corresponding carboxylic acid and benzyl bromide compound with the procedure described in Example 8, trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) -pyrimidin-5-yl] -cyclopropane- Carboxylic acid (4-methyl-2,3,5,6-tetrafluorobenzyl) ester is prepared. The product is an oily substance.

IR (liquid film) bands: 2960, 1740, 1495, 1420, 1290, 1155, 1075 cm ^-1 .

NMR (CDC1 _3> δ = 0.99 (s, 3H);

1.39 (s, 12H), 1.96 (d, 1H), 2.30 (m, 3H), 2.56 (d, 1H), 5.28 (s, 2H), 8.48 (s) , 2H) ppm.

196 696

Mass Spectrum (M ⁺ ): 424.

Example 11

The following compounds were prepared according to the procedure described in Example 9:

a) By reaction of the corresponding carboxylic acid with 6-phenoxypyrid-2-ylmethanol, trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] - cyclopropanecarboxylic acid (6-phenoxypyrid-2-ylmethyl) ester is prepared.

NMR (CDC1 ^_3): S = 1.01 (s, 3H);

1.41 (s, 12H), 2.08 (d, 1H), 2.58 (d, 1H), 5.18 (s, 2H), 6.7-7.8 (m, 8H), 8.50 (s, 2H) ppm.

Infrared (liquid film) bands: 29.60, 1730, 1600, 1580, 1490, 1540, ₊ 1250, 1160 cm ^-1 .

Mass Spectrum (M): 431.

b) By reaction of the corresponding carboxylic acid with 2-methyl-3-phenylbenzyl alcohol, trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] - cyclopropanecarboxylic acid (2-methyl-3-phenylbenzyl) ester was prepared.

NMR (CDC1 ^_3): δ = 0.99 (s, 3H);

1.40 (s, 12H), 2.06 (d, 1H), 2.25 ( _s , 3H), 2.60 (d, 1H), 5.27 (s, 2H), 7.1-7 , Δ (m, 2H), 8.50 (s, 2H) ppm. infrared bands (my fluids): 2960,

1730,1485, 1420,1160,760,705 ₊ cm.

Mass Spectrum (M): 428.

c) By reaction of the corresponding carboxylic acid with α-cyano-3-phenoxybenzyl alcohol, trans-2,2-dimethyl] -3- [2- (2-methylprop-2-yl) pyrimidin-5-yl] cyclopropanecarboxylic acid (α-cyano-3-phenoxybenzyl) ester is prepared.

NMR (CDC1 ^_3): δ = 0.99 (s), 1.04 (s), 1.35 (s), 1.39 (s), 1.45 (s), 2.05 ( m), 2.6 (m),

6.42 (s), 6.44 (s), 7.26 (m), 8.46 (s), 8.50 (s) ppm.

According to the spectral data, the product is a 2: 1 mixture of diastereoisomers.

IR (liquid film) bands: 2960, 1740, 1590, 1485, 1250, 1140, 695 cm ^-1 .

Peak mass spectrum (M): 455.

d) Reaction of the appropriate carboxylic acid with 1-cyano-1- (5-phenoxypyrid-2-yl) methanol to give trans-2,2-dimethyl-32- (2-methylprop-2-yl) pyrimidine. 5-yl] -cyclopropanecarboxylic acid [1-cyano-1- (6-phenoxypyrid-2-yl) methyl] ester is prepared.

NMR (CDC1 ₃₎ δ = 1.00 (s), 1.02 (s), 1.35 (s), 1.40 (s), 2.1 (m), 2.6 ( m), 6.4 (3s), 6.9 (d), 7.2 (m), 6.8 (dd), 8.50 (2s) ppm.

According to spectral data, the product is a 1: 1 mixture of diastereoisomers.

IR (liquid film) bands: 2960, 1745, 1595, 1490, 1450, 1260, ₊ 1140, 695 cm ^-1 . Mass spectral peak (M): 456.

e) Reaction of the corresponding carboxylic acid with 4- (methoxymethyl) -2,3,5,6-tetrafluorobenzyl alcohol to give (±) -trans-2,2-dimethyl-3- {2- (2-methylprop) 2-yl) -pyrimidin-5-yl] -cyclopropanecarboxylic acid [4- (methoxymethyl) -2,3,5,6-tetrafluorobenzyl] ester is prepared.

NMR (CDC1 _3> δ = 0.99 (s, 3H);

1.40 (2s, 12H), 1.95 (d, 1H), 2.55 (d, 1H), 3.40 (s, 3H), 4.50 (m, 2H), 5.30 (m , 2H), 8.50 (s, 2H) ppm.

Infra red (paraffin): 1735.1595, 1490,1295,1150,910,880, 770 ^cm-first Mass Spectrum (M ⁺ ): 454.

f) Reaction of the corresponding carboxylic acid with (±) -1- (4-phenoxyl-pyrid-2-yl) -ethanol to give (±) -trans-2,2-dimethyl-3- (2- (2-methylprop) 2 ij) -pyrimidin-5-yl-cyclopropanecarboxylic acid - [(+) - l- (6-phenoxypyrid-2-yl) ethyl ester was prepared NMR (CDC1 _3):. y ≫ 1.0 (s), 1.33 (s), 1.40 (s,), 1.5 (s), 1.8 (s), 2.05 (2d), 2.50 (2d) , 5.85 (q), 6.7 (d), 7.2 (m), 7.65 (dd), 8.50 (2s) ppm.

According to the spectral data, the product is a 3: 2 mixture of diastereoisomers.

IR (liquid film) bands: 2980, 1730, 1600, 1580, 1445, 1260, 1170, 990, 700 cm ^-1 .

Mass Spectrum (MH +): 446.

g) By reaction of the corresponding carboxylic acid with 4-fluoro-3-phenoxybenzyl alcohol, (+) - trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) pyrimidin-5 -yl] -cyclopropanecarboxylic acid [4- (fluoro-3-phenoxybenzyl) ester is prepared.

h) reacting the corresponding carboxylic acid with pentafluorobenzyl alcohol to give (±) -trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl) -pyrimidin-5-yl] -cyclopropane- Carboxylic acid (pentafluorobenzyl) ester is prepared.

i) By reaction of the corresponding carboxylic acid with (±) -α-ethynyl-3-phenoxybenzyl alcohol (± trans-2,2-dimethyl-3- [2- (2-methylprop-2-yl)), pyrimidin-5-yl] -cyclopropanecarboxylic acid [(±) -? - ethynyl-3-phenoxybenzyl] ester is prepared.

Example 12 (±) -Trans-3- [2- (2-methyl-prop-2-yl) -pyrimidin-5-yl] -2,2-dimethyl-cyclopropanecarboxylic acid [(±) - a-cyano Preparation of 3-phenoxybenzyl] ester (Compound 4) and separation of the individual enantiomers

3.2 g of (±) -trans-3- [2- (2-roethyl] -prop-2-yl) -pyrimidin-5-yl] -2,2-dimethyl-cyclopropanecarboxylic acid, 3.8 g of phenoxy-benzaldehyde cyanohydrin (contaminated with about 20% of 3-phenoxybenzaldehyde material) 100 mg4- (dimethylamino) pyridine and 100 mL of dichloromethane at room temperature (about 24 ^J C) with stirring, portionwise 2.8 g of dicyclohexylcarbodiimide are added. The reaction mixture was stirred for 2 hours and then kept at room temperature for 16 hours. The solid is filtered off, washed with dichloromethane, the filtrate and the washings are combined and the solvent is evaporated under reduced pressure. The residue was purified by high performance liquid chromatography (Gilson) using silica gel as the adsorbent, eluting with a mixture of 100 volumes of dichloromethane and 5 volumes of ethyl acetate. The initial eluate fractions contained the desired product together with 3-phenoxybenzaldehyde, the remaining fractions 5.3 g of pure (±) -trans-3- [2- (2-methylprop-2-yl) -pyrimidin-5-yl ] 2,2-dimethyl-cyclopropyl, opropán-karboti5av - [(±) - ^a -cyano-3-phenoxy-Methoxybenzyl ester isolated. The gum-like material contains the two enantiomers (both enantiomeric racemates) in a 2: 1 ratio. The material separated from the initial eluate fractions was rechromatographed on a 2.5 cm column of silica gel using the solvent mixture as described above. The eluent was applied at a rate of 30 ml / min. 120 mg of the product, which is the less polar enantiomeric pair, is obtained with higher mobility. The material isolated from the later eluate fractions was rechromatographed as before. This gives 21 mg of the product which is the more polar enantiomeric pair (hereafter referred to as Substance A, containing 2: 1 isomeric pairs). The final product contains the more polar and less polar isomers in a ratio of 95: 5. Chromatography combined and evaporated the fractions not used for product recovery to give B, a 7: 1 mixture of less polar and more polar isomers.

Biological studies on red weaver mites (Tet-71 ranychus urticae) on green bean leaves show that the more polar enantiomeric pair is about ten times more potent than the less polar enantiomeric pair (LC50 =

4.5 ppm and 49 ppm, respectively).

A mixture of 7 mg of less polar and more polar isomers (7: 1) is dissolved in 0.1 ml of isopropanol containing 5% by weight of triethylamine and the solution is stirred at room temperature.

After stirring for 22.5 hours, the product contains the isomers in a ratio of about 1: 1, which is explained by the base-catalyzed epimerization of the alpha carbon atom of the alcohol moiety.

NMR (CDC1 _3):

A: δ = 0.95 (s), 1.0 (s), 1.35 (s), 1.4 (s), 2.0 (2d),

2.6 (2d), 6.4 (2s), 7.2 (m), 8.45 (2s) ppm.

According to the spectral data, the product contains the diastereoisomers in a ratio of 2: 1.

B: δ = 1.0 (s, 3H), 1.40 (s, 9H), 1.45 (s, 3H), 2.05 (d, 1H), 2.55 (d, 1H), δ , 40 (s, 1H), 7.2 (m, 9H), 8.40 (s, 2H) ppm.

Infrared (liquid film) bands: a: 2960, 1740, 1590, 1490, 1445, 1250, 1140,

695 cm ''.

N: 2960, 1740, 1585, 1480, 1445, 1245, 1140, 695, cm < -1 >.

Example 13 Preparation of (±) -Trans-2,2-dimethyl-3-formylcyclopropanecarboxylic acid methyl ester

A mixture of 40.0 g of methyl 2,2-dimethyl-3- (dimethoxymethyl) cyclopropanecarboxylic acid (containing 95% (±) -transomer), 120 ml of glacial acetic acid, 160 ml of acetone and 280 ml of water Stir at room temperature for 5 hours. The reaction mixture was diluted with water (1500 mL) and extracted with diethyl ether (1000 mL). The aqueous residue was washed twice with 500 mL of ether. The washings and extracts were combined and washed with anhydrous saturated aqueous sodium bicarbonate solution. The ethereal solution was dried over anhydrous magnesium sulfate and the solvent was evaporated. The oily residue was purified by distillation. Yield: 28.5 g (±) -trans-2,2-dimethyl-3-formylcyclopropanecarboxylic acid methyl ester as a boiling point of 46-48 ° C / 0.5 mmHg.

Example 14 Preparation of (±) -Trans-3 - [(E, Z) -2-methoxyvinyl] -2,2-dimethylcyclopropanecarboxylic acid methyl ester

9.6 g of a 50% sodium hydride dispersion in mineral oil are washed with n-hexane and the oil is suspended in 150 ml of anhydrous dimethyl sulfoxide (freshly distilled from calcium hydride) and the suspension is anhydrous under nitrogen for 5 hours. and stirred at 38-40 ° C. A solution of 68.8 g of methoxymethyltriphenylphosphonium chloride in 200 ml of anhydrous dimethylsulfoxide was added over 15 minutes while maintaining the reaction temperature at about 20 ° C with external cooling. A solution of the ylide thus obtained was added dropwise to a solution of 28.5 g of freshly distilled (±) -trans-2,2-dimethyl-3-formylcyclopropanecarboxylic acid methyl ester in 50 ml of dimethyl sulfoxide. The addition takes about 2 hours. During the addition of the reagent, the mixture is stirred and the temperature is maintained at about 20 ° C. After the addition of the reagent, the mixture was stirred for an additional 30 minutes and then allowed to stand at room temperature for 72 hours. The mixture was diluted with 1500 mL of water. The extracts were combined, washed with water (3 x 300 mL), dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was triturated with 150 ml of light petroleum (b.p. 60-80 ° C). The insoluble solid was filtered off and the filtrate was evaporated. The resulting yellow oil (29.0 g) was filtered off with suction and the filtrate was evaporated. The resultant 29.0 g of a yellow oily substance is distilled under reduced pressure on a ball head. 21.4 g of (+) - trans-3 - ((E, Z) -2-methoxyvinyl) -2,2-dimethylcyclopropanecarboxylic acid methyl ester, m.p. 05 mmHg.

NMR (CDCl?) ¹ δ = 1.13 (s), 1.24 (s), 1.26 (s), 1.4 (m), 1.9 (m), 2.3 (m ), 3.5 (s), 3.6 (s), 3.66 (s), 4.1 (2d), 4.56 (2d), 6.0 (dd), 6.4 (d) ppm.

According to the spectral data, the product contains the E and Z isomers in a ratio of 2: 1.

Infra red (liquid film): 2960, 1730, 1650, 1440, 1270, 1235, 1170, 920 ^cm-first

Example 15 (±) -Trans-3 - [(E, Z) -2- (dimethylamino) -1-formylvinyl] -2,2-dimethylcyclopropanecarboxylic acid methyl ester and ( ±) -trans-3- [E, Z) -1-formyl-2-methoxyvinyl] 2,2-dimethylcyclopropanecarboxylic acid methyl ester mixture

A solution of phosphoryl chloride (12.0 ml) in 1,2-dichloroethane (12.0 ml) was added dropwise to a mixture of dimethylformamide (29.5 ml) and 1,2-dichloroethane (100 ml) at room temperature. After the addition of the reagent, the mixture was stirred for an additional 15 minutes and then cooled to 15 ° C. To the mixture was added portionwise 10.0 g of (±) -trans-3 - [(E) -2-methoxyvinyl] -2,2-dimethylcyclopropanecarboxylic acid methyl ester with 80 ml of 1,2-dichloroethane. page. After 16 hours at room temperature, 150 g of anhydrous solid potassium carbonate and ice were added. After completion of the exotherm, the mixture was extracted with methylene chloride (2 x 300 mL). The extracts were combined, washed with water (300 mL), dried over anhydrous magnesium sulfate and the solvent evaporated under reduced pressure. The oily residue is maintained at 55 ° C at 0.05 mmHg in a ball-cap device to remove volatile components. 10.3 g of product are obtained, which is a small amount of (±) -trans-3 - [(E) -1-formyl-2-methoxyvinyl] -2,2-dimethylcyclopropanecarboxylic acid methyl ester (A). component).

NMR (CDC1 ₃₎ (component A); δ =, 0 (s), 1.05 (s), 1.27 (s), 1.30 (s), 2.0 (m), 3.18 (s), 3.37 (s), 3.68 (s), 3.70 (s), 6.75 (broad s), 8.35 (broad s), 8.8 (s) ppm.

According to the spectral data, the product contains the E and Z isomers in a ratio of 2: 1.

Infrared bands (paraffin): 2960, 2720, 1730, 1600, 1450, 1410, 1280, 1230, 1175 cm ^-1 .

Example 16 Preparation of (-) - Trans-2,2-dimethyl-3- (2-cyclohexyl-pyrimidin-5-yl) -cyclopropanecarboxylic acid methyl ester

1.0 g of (±) -trans-3- [E, Z) -2- (dimethylamino) -1-formylvinyl] -2,2-dimethylcyclopropanecarboxylic acid methyl ester (Example 15). containing small amounts of (±) '-trans-3 - [(E) -1-formyl-2-methoxyvinyl] -2,2-dimethylcyclopropanecarboxylic acid methyl ester prepared according to

(196696), 1.08 g of cyclohexanoylamide and 8 ml of methanol were added dropwise at room temperature with 3.2 ml of 2M methanolic sodium methoxide solution. The resulting mixture was refluxed for 3.5 hours, cooled to room temperature and poured into water (200 mL). The aqueous mixture was extracted with diethyl ether (2 x 200 mL). The extracts were combined, washed with water (50 mL), dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The oily residue was chromatographed on a silica gel column using 3 volumes of methylene chloride and 1 volume of diethyl ether as eluent. 790 mg (±) -trans-3 - [(E, Z) -2- (dimethylamino) -1-formylvinyl] -2,2-dimethylcyclopropane carboxylic acid methyl ester we get.

NMR ^(CDCl): <5 = 1.0 (s, 3H);

1.4 (s, 3H), 1.2-1.8 (b, 10H), 1.95 (d, 111), 2.5 (d,

1H), 2.8 (b, 1H), 3.7 (s, 3H), 8.5 (s, 2H) ppm.

Infrared spectral bands (liquid film). 2940,

2860, 1730, 1600, 1500, 1440, 1290, 1175 cm ' ^1. ' 20

Example 17

The procedure of Example 7 was followed, however, starting from 790 mg of the product of Example 16 and using methanol instead of ethanol. 750 mg of (±) -trans-3- (2-cyclohexylpyrimidin-5-yl) -2,2,2-dimethylcyclopropanecarboxylic acid are obtained, m.p. 128-130 ° C.

Infrared bands (paraffin); 3500-2200 (wide), 1710, 1550, 1340, 1290, 1260, 1190, 1120 cm ^-1 .

Peak mass spectrum (M *): 274.

Example 18 (RS, Trans) -3- (2-Cyclohexyl-pyrimidine-5,41) -2,2-dimethyl-cyclopropanecarboxylic acid [(RS) -1-cyano-1- (6-phenoxypyrid) -2-yl) methyl] ester 150 mg of (±) -trans-3- (2-cyclohexylpyrimidin-5-yl) -2,2-dimethylcyclopropanecarboxylic acid, 130 mg of 1-cyano-1 - (6-Phenoxypyrid-2-yl) methanol, 118 mg of dicyclohexylcarbodiimide are added with stirring to a mixture of 5 mg of 4- (dimethylamino) pyridine and 5 ml of dichloromethane. The reaction mixture was stirred at room temperature for 7 hours and then allowed to stand at room temperature for 16 hours. The reaction mixture was loaded onto a silica gel column, eluting with dichloromethane, followed by 20 volumes of dichloromethane and 1 volume of ethyl acetate. 248 mg of (1RS, trans) -3- (2-cyclohexylpyrimidin-5-yl) -2,2-dimethylcyclopropanecarboxylic acid [(RS) -1-cyano-1- {6-phenoxypyridine]. 2- (III) -methyl] ester is obtained.

NMR (CDC1 ^_3): δ = 1.0 (2s), 1.35 (s), 1.43 (s), from 1.20 to 2.0 (m, br), 2.05 (m) , 2.6 (m),

2.85 (m), 6.35 (broad s), 6.9 (d), 7.25 (m), 7.8 (dd),

8.45 (2s) ppm.

According to the spectral data, the product contains the two diastereoisomeric pairs in a ratio of 1: 1.

Infrared Spectrum Bands (Liquid Film), 2940,

2860, 1745, 1600, 1450, 1150, 810, 700 cm ^-1 .

Example 19

Following the procedure described in Example 16, the following compounds were prepared from the corresponding amjdj;

(i) (±) -Trans-3- (2-prop-2-yl-pyrimidin-5-yl) -2,2-dinyl-cyclopropanecarboxylic acid methyl ester.

NMR (CDC1 ₃₎ ·· δ = 0.98 (s, 3H), 60

138 (s, 3H), 1.40 (s, 3H), 1.95 (d, 1H), 2.25 (d, 1H),

3.2 (m, 1H), 3.75 (s, 1H), 8.48 (s, 2H) ppm.

Infrared (liquid film) bands: 2980,

1735, 1595, 1550, 1440, 1340, 1260, 1175,830 cm.

(h) (±) -Trans-3- (2-cyclopropylpyridinidine-541) -2,2-dimethylcyclopropanecarboxylic acid methyl ester.

NMR (CDC1 ^_3): δ = 0.96 (s, 3H), 1.05 (m, 4H), 1.40 (s, 3H), 1.95 (d, 1H), 2.2 (m, 1H), 2.5 (d, 2H), 3.75 (s, 3H), 8.4 (s, 2H) ppm.

IR (liquid film) bands: 3010, 2960, 1730, 1600, 1550, 1470, 1445, 1175, 915 cm *.

Example 20.

The following compounds of formula (I) having insecticidal and acaricidal activity were prepared according to the procedure described in Examples 17 and 18:

(i) (±) - Trans-2,2-Dimethyl-3- (2-prop-241) -pyrimidin-5-yl) -cyclopropanecarboxylic acid (2-methyl-3-phenyl-benzyl) - ester

NMR (CDC1 ^_3): δ - 0.99 (s, 3H), 1.30 (s, 3H), 1.38 (s, 3H), 1.42 (s, 3H), 2.1 (d, 1H), 2.25 (s, 3H), 2.65 (d, 1H), 3.2 (m, 1H), 5.27 (s, 2H),

7.3 (m, 811), 8.49 (s, 2H) ppm.

Infrared (liquid film) bands: 2980,

1730, 1595, 1550, 1425, 1240, 1165, 740, 710 cm ^-1 .

(ii) (±) - Trans-2,2-Dimethyl-3- (2-prop-2-yl-pyrimidin-5-yl) -cyclopropanecarboxylic acid - [(±) -1-cyano-1- (6-) phenoxypyrid-2-yl) methyl] ester.

NMR (CDC1 ^_3): δ = 1.00 (s), 1.03 (s), 1.31 (s), 1.36 (s), 1.38 (s), 1.42 ( s), 2.05 (m), 2.60 (m), 3.2 (m), 6.35 (broad s), 6.9 (d), 7.3 (m), 7.8 ( dd), 8.5 (2s) ppm.

The spectral data of the product in the diastereoisomeric 1: 1 ratio of alpha Infra red (liquid film): 2980, 1745, 1595,1580,1450,1280,1150,745,700 cm ^1st

(iii) (±) - Trans-2,2-Dimethyl-3- (2-cyclopropyl-pyrimidin-5-yl) -cyclopropanecarboxylic acid - ((±) -1-cyano-1- (6-phenoxypyrid) -241) methyl] ester.

NMR (CDC1 ^_3): δ - 1.0 (s), 1.03 40 (m), 1.06 (s), 1.34 (s), 1.42 (s), 2.0 (2d), 2.2 (m), 2.8 (m), 6.4 (s), 6.9 (d), 7.3 (m), 7.8 (dd), 8.35 ( 2s) ppm.

According to the spectral data, the product contains the diastereoisomers in a ratio of 1: 1.

IR (liquid film) bands: 3010, 2940, 1750, 1600, 1450, 1260, 1150, 918, 800, 45,700 cm ^-1 .

Example 21

Investigation of insecticidal activity

1-7. s. The insecticidal activity of the compound was investigated as follows (the serial numbers refer to the same number of compounds listed in the introductory part of the description)

The test compound was dissolved in a mixture of 4 volumes of acetone and 1 volume of diacetone alcohol and diluted with water containing 0.01% w / w Lissapol NX wetting agent to 500 ppm. In the contact effect assay, the insects to be tested were placed on a suitable carrier medium (e.g., plant leaves or filter paper) and the insects and vehicle were sprayed with the above-mentioned spray liquid.

196.696 pins of insects on the carrier medium. The insect mortality rate was evaluated 72 hours after spraying, and in the case of house flies, the mortality was evaluated 24 hours after spraying. The mortality rate is denoted by A, B, and C, where A denotes 80-100% mortality, B denotes 50-79% mortality, and C denotes mortality 0-49%.

The results are shown in Table I below. The horizontal lines (-) in Table I indicate that no experiment was performed.

The data listed in Table I show that the compounds of the formula I have potent insecticidal and acaricidal activity and are effective against a wide variety of insect and acaricides.

Table I

Type and stage of development of the pest

Tetranychus urticae (red mite), adult specimens

Tetranychus urticae (red weaver mite), eggs Myzus persicae (peach aphid), mixed Clülo partellus (corn borer), larvae Heliothis virescens (cotton bug beetle), larvae Diabrotica white bug (rootworm) Blatella germanica (cockroach) adult specimens Tetranychus urticae (red weaver mite), adult specimens

Tetranychus urticae (red mite), eggs Myzus persicae (peach leaf lice), mixed Chilo partellus (corn borer), larvae Heliothis virescens (cotton bug beetle), larvae Diabrotica balteata (root rot) specimens Blatella germanica (cockroach), adult specimens

Medium Medium Type of test First Second Effectiveness 3. 4. 5. 6. 7. 8 bean-down with contact THE THE A A A Á A THE bean-down with contact THE THE C A A A A THE Juüskabab- letter contact THE THE A B A A A THE oilseed rape. -letter the rest THE THE A A A A A A THE cotton leaf the rest THE C V A A A A THE filter paper / corn piece the rest C THE A A A A C THE cotton / sza- dextrose, sucrose contact C THE A V C B C C filter paper the rest THE C C A C A C C green bean leaf contact B THE C A A A A THE bean-down with contact THE C A A C A C C Juliskabab- -letter contact C C C A A A A B oilseed rape leaf the rest THE c A A A A A A THE cotton leaf the rest C c C A A A C THE filter paper / corn piece the rest C THE C C A C C C cotton / sza- dextrose, sucrose contact THE C B ---- C filter paper the rest C C C C A C C C

Example 22

Preparation of Emulsifiable Concentrate By mixing the components, an emulsifiable concentrate is prepared which is easy to dilute with water and can be applied by dilution with water by spraying:

No. 2 compound 25.0% by weight

Lubrol ^R (condensation product of alkylphenol with ethylene oxide) 2.5% by weight

Calcium dodecylbenzene sulfonate 2.5% by weight

Aromasol H ^K (70.0% w / w alkylbenzene solvent)

Example 23

Preparation of Emulsifiable Concentrate By mixing the components, an emulsifiable concentrate is prepared which is easy to dilute with water and has the following composition:

r. s. vagvij.et

Lubrol L ^K

Calcium dodecylbenzene sulphonate Aromasol H ^K

25.0% by weight

4.0 wt% 6.0 wt% 65.0 wt% gQ Example 24

Preparation of Wettable Powder Formulation By mixing the components, a wettable powder formulation of the following composition is prepared:

No. 1 compound 25.0% by weight

Sodium silicate 5.0% by weight

Calcium lignosulfonate 5.0% by weight

Kaolin 65.0% by weight

Example 25

Preparation of Sprayable Liquid By mixing the components, the following composition of sprayable liquid is prepared:

-101

No. 4 compound 25.0% by weight

Xylene 75.0% by weight

Example 26

Production of dusting agent

By mixing the components, a pollen composition having the following composition is prepared:

Compound No. 5 1% by weight

Talc 99% by weight

Example 27

Preparation of an emulsion composition

By mixing the components, an emulsion formulation directly applied by spray application to protect domestic animals against parasitic infection is prepared:

No. 6 compound 25% by weight

XiJol 65% by weight

Triton X 100 ^K (alkylaryl polyether alcohol 10% by weight)

Example 28

Production of dusting agent

By grinding the components, we obtain the following composition, which can be used directly for the treatment of domestic animals against parasites:

No. 7 compound 5% by weight

Talc 95% by weight

Example 29

Preparation of liquid concentrate

By mixing the components, the following concentrate can be used for dilution with water:

No. 8 compound 10% by weight

Lissapol NX ^K (condensation product of ethylene oxide with octylphenol) 10% by weight

Diacetone alcohol 80% by weight

Example 30

Preparation of an emulsifiable concentrate

By mixing the components, an emulsifiable concentrate is prepared having the following composition:

No. 9 compound 20% by weight

Lubrol L ^K 17% by weight

Calcium dodecylbenzene sulfonate 3% by weight

Ethylene dichloride 45% by weight

Aromasol 11 'by 15% by weight

Example 31

Preparation of a dispersible powder composition

By homogenizing the components by grinding, a powder composition which is readily dispersible in liquids is prepared as follows:

No. 10 compound 50% by weight

Dispersol T ^K (disodium salt of methylene bis-naphthalenesulfonic acid) 5% by weight

Kaolin 45% by weight

Example 32

Preparation of a high concentration concentrate

By mixing the components, a liquid concentrate of the following composition, diluted alone or diluted with paraffin-type diluents, is prepared in very small volumes:

No. 11 compound 90% by weight

Mixture of Xylenes 10% by weight

Example 33

Production of granules

Granules having the following composition were prepared: compound 1% by weight

Pumice granulate 99% by weight

The active ingredient is dissolved in methylene chloride and the solution is sprayed onto pumice granules filled in a rotary drum. The solvent is removed from the granules by air drying.

Claims (6)

Claims An insecticidal and / or acaricidal composition, wherein the active ingredient is 0.0004-90% by weight of a cyclopropane derivative of formula (I): R ² is C 3 -C 6 alkyl or C 3 -C 7 cycloalkyl branched at the α-position; and R ¹ is -OR ¹ and R ^{1 is} (VI) and in the latter formula X represents a vinylene group or a group of formula -CR ⁵ = Y-, wherein Y represents a nitrogen atom or a group CR ³ , R ^{5 is} hydrogen, halo or C 1-4 alkyl, n is 1, 2, 3 or 4, and R ⁵ may be the same or different, R ^{4 is} hydrogen, methyl, cyano or ethynyl; and R ^{6 is} hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, C 2 -C 6 alkenyl, phenyl or phenoxy, provided that when R ^{6 is} hydrogen, halogen, R ⁴ is hydrogen, containing a liquid or solid mineral or organic carrier or diluent, preferably liquid hydrocarbon, silicate, talc, clay and / or pumice, and optionally ionic or a condensation product of a nonionic surfactant, preferably calcium dodecylbenzene sulfonate or alkylphenyl ethylene oxide. (Priority: 22nd February 1985) An insecticidal and / or acaricidal composition, wherein the active ingredient is 0.0004-90% by weight of a cyclopropane derivative of the formula R ² is C 3 -C 6 alkyl or C 3 -C 7 cycloalkyl branched at the α-position; and R ¹ is -OR ¹ and R ^{1 is} (VI) and in the latter formula X represents a vinylene group or a group of formula -CR ⁵ = Y-, wherein Y represents a nitrogen atom or CR ^S group, ^R5 is hydrogen, halogen or C1-4 alkilesoportot, n is 1,2,3 or 4 and R ⁵ may be the same or different. -111 R ^{4 is} hydrogen, cyano or ethynyl, and R ⁶ is hydrogen, halogen, l 4szénatoinos alkyl, C2-6 alkenyl, phenyl or phenoxy, with the proviso that if R® is hydrogen, halogen, C1-4 alkyl or C2-6 alkenyl, R ⁴ only hydrogen, containing a liquid or solid mineral or organic carrier or diluent, preferably liquid hydrocarbon, alcohol, chlorinated hydrocarbon, silicate, talc, clay and / or pumice, and optionally ionic or non-ionic surfactant, with a sulfonate or a condensation product of alkylphenol with ethylene oxide. (Priority: 11.11.1985) 3. A process for the preparation of cyclopropane derivatives of the general formula (1) - in the formula R ² is C 3 -C 6 alkyl or C 3 -C 7 cycloalkyl branched at the α-position; and R is -OR 'and R' is (VI) and in the latter formula X represents a vinylene group or a group -CR ⁵ = Y, wherein Y represents a nitrogen atom or a CR ⁴ group, ^R5 is hydrogen, halogen or C1-4 alkyl, n is 1, 2, 3 or 4 and R ^s may be the same or different, R ^{4 is} hydrogen, methyl, cyano or ethynyl, and R @ 3 is hydrogen, halogen, (C1-C4) -alkyl, (C1-C4) -alkoxy (C1-C4) -alkyl, (C2-C6) -alkenyl, phenyl or phenoxy, provided that when R @ 1 is hydrogen, halogen, -C 4 alkyl or C 2 -C 6 alkenyl, R ⁴ can only be hydrogen, characterized in that a) the carboxylic acids of formula (I): - wherein represents 0, hydroxy, and ^R2 are as defined above is reacted with ^R1-OH alcohols of general formula - wherein R * is as defined above -, or b) Compound (II) carboxylic acids of the formula: - wherein R 0 is hydroxy and R ² is as defined above - or their alkali metal salts O, halides of formula ¹ -R ¹ - is and R ^{1 1} is halo wherein O is as defined above - or quaternary ammonium salts thereof with their derivatives. (Priority; III. 22, 1985) A process for the preparation of a cyclopropane derivative of formula (I): wherein: R ² is C 3 -C 6 alkyl or C 3 -C 7 cycloalkyl branched at the α-position, and R ¹ is -OR ¹ and R ^{1 is} (VI) and in the latter formula X represents a vinylene group or -CR ^S = Y, wherein Y represents a nitrogen atom or a group CR ', R ^{5 is} hydrogen, halo or C 1-4 alkyl, n is 1, 2, 3 or 4, and R ⁵ may be the same or different, R ^{4 is} hydrogen, cyano or ethynyl; and R @ 4 is hydrogen, halogen, C1 -C4 alkyl, C2 -C6 alkenyl. is a phenyl or phenoxy group, provided that R @ 4 is hydrogen, halo, (C1-C4) -alkyl or (C2-C6) -alkenyl, R @ ⁴ is hydrogen only - a) reacting a carboxylic acid of formula (11) wherein O is hydroxy and R ² is as defined above with an alcohol of formula R '-OH wherein R ¹ is as above or b> a carboxylic acid of formula (II) - wherein O is hydroxy and R ² is reacted with the above halogenides of the formula - or the alkali metal salts thereof - 10, '- R * - in which O is halogen and R' is - or their quaternary ammonium salts with tertiary amines. (Priority: 2.4.1985) An insecticidal and / or acaricidal composition, characterized in that the active ingredient is 0.0004 to 90% by weight of a cyclopropane derivative of the formula R ^{2 at} the α-position is a branched C 3 -C 6 alkyl group, and R represents a group -OR ¹ and in this case R ¹ (VI) and in the latter formula X represents a vinylene group or -CR ⁵ = Y, wherein Y represents a nitrogen atom or a CR ⁵ group, R ^{5 is} hydrogen, halo or C 1 -C 4 alkyl, n is 1, 2, 3 or 4, and the R ⁵ groups may be the same or different, R ^{4 is} hydrogen, halogen, C 1 -C ⁴ alkyl, C 2 -C 6 alkenyl, phenyl or phenoxy, with the proviso that when R ^{4 is} hydrogen, halo, C 1 -C 4 alkyl or C 2 -C 6 alkenyl, R ⁴ can be hydrogen only - contains, liquid or solid, mineral or organic carrier or diluent, preferably liquid hydrocarbon, alcohol, chlorinated hydrocarbon, silicate, talc, clay and / or pumice, and optionally ionic or non-ionic surfactant, , with a condensation product of benzenesulfonate or alkylphenol ethylene oxide. (Priority: 26 February 1984) A process for the preparation of a cyclopropane derivative of formula (I): wherein: R ^{2 at} the α-position is a branched C 3 -C 6 alkyl group, and R ¹ is -OR ¹ and R ^{1 is} (VI) and in the latter formula X is vinylene or -CR ^S = Y, wherein Y is N -121 196 696 Represents CR ⁵ groups, R ^{5 is} hydrogen, halo or C 1 -C 4 alkyl, n is 1, 2, 3 or 4, and the R ⁵ groups may be the same or different, R ^{4 is} hydrogen, cyano or ethynyl, and R ^{6 is} hydrogen, halogen, C 1 -C 4 alkyl, C 2 -C 6 alkenyl, phenyl or phenoxy, with the proviso that when R 0 is hydrogen, halo, C 1 -C 4 alkyl or C 2 -C 6 alkenyl, R ⁴ can only be hydrogen - characterized in that a) the carboxylic acids of the formula II can be reacted with the alcohols of the formula R ¹ -OH in the formula - O is a hydroxy group and R ^J is as defined above - wherein R 'is as defined above or b) The carboxylic acids of formula (II): - wherein O represents ^one halogen atom, and - wherein O is hydroxy and ^R5 are, "above - or their alkali metal salts of O, '- R ¹ Formula' ^υ off needle halides We reacted or their quaternary ammonium salts formed with tertiary amiíokkal - ^R1 ea above. (Preferred: III, 26, 1984)