KR830001067B1 - Method for preparing halogenated ester of cyclopropanoic acid - Google Patents

Abstract

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Description

Method for preparing halogenated ester of cyclopropanoic acid

The present invention relates to a process for the preparation of halogenated esters of novel cyclopropanoic acids of the following general formula (1) which are useful as insecticides.

Food,

The invention also relates to a composition containing formula (1) and a method of combating insects and similar invertebrate pests using the same.

It has been known for a long time that esters of naturally occurring cyclopropane carboxylic acids have pesticidal properties, but these compounds are so readily decomposed by ultraviolet light, which is often used for farming. Several groups of synthetic compounds based on cyclopropanecarboxylic acids (such as those described in British Patent Nos. 1,243,858 and 1,413,491) attempt to find compounds with sufficient light stability for use as general agricultural pesticides. Obtained from

Particularly useful groups of such compounds are described in British Patent No. 2,000,764 and Belgian Patent 863,151. These compounds have good light stability, good contact and residual pesticides at the same time, but have little fumigant like the compounds described in British Patent Nos. 1,243,858 and 1,413,491. Another group of compounds, namely the halobenzyl esters of 3- (2,2-dihalovinyl) 2,2-dimethylcyclopropane carboxylic acid, are insecticidal but do not have fumigating activity, according to Belgian Patent No. 862,109. Described.

The present invention is a novel 3- (2-halo (or trifluoro methyl) -3,3,3-trifluoro with extremely high levels of insecticidal and detoxifying that can be used as a contact or residual pesticide as well as a fumigant. Perfluorophenyl) -2,2-dimethylcyclopropane carboxylic acid.

Among the compounds of the present invention, preferably R is a tetrahalo phenyl or pentahalo phenyl group having at least four fluoro atoms, for example 2,3,4,5-tetrafluoro phenyl, 2,3,4,6 Tetrafluorophenyl, 4-chlorine-2,3,5-trifluoro phenyl, 4-chlorine-2,3,5,6-tetrafluorophenyl, 4-bromo-2,3,5,6 -Tetrafluoro phenyl or pentafluoro phenyl group.

TABLE 1

However, compounds in which R is a halophenyl group containing 1-3 fluoro atoms also have useful pesticidal properties.

Specific compounds according to the invention as defined by formula (1) above are given R ¹ , R ² and R as shown in Table 1.

It is apparent to those skilled in the art that the compound represented by formula (1) may exist in various geometric and stereoisomeric forms. Thus, they may be cis and trans isomers resulting from the substituted shape of the cyclo propane ring and the E- and Z-isomers resulting from substituted vinyl groups when R ¹ is not trifluoro methyl. In addition, two of the three carbon atoms of cyclo propane may be present in the R- or S-configuration sequence because they are asymmetrically substituted.

Particularly useful single isomers of the compounds according to the invention are (+)-cis-3- (Z-2-chlorine-3,3,3-trifluoroprop-1-en-yl) -2,2-dimethylcyclo It is a pentafluorobenzyl ester of propane carboxylic acid, which is thought to have a (1R, 3R) configuration in the cyclopropane ring.

The compound of the present invention according to general formula (1) is an ester, and can be prepared by the following conventional esterification.

(A) The acid of the following general formula (a) may be directly reacted with the alcohol of the following general formula (b).

Wherein R ¹ , R ² , and R are as described above.

The reaction is preferably carried out under an acid catalyst such as anhydrous hydrogen chloride.

(B) The acid halide of the following general formula (c) may be reacted with an alcohol of the following general formula (b).

Food,

The reaction is preferably brought about in the presence of a base such as pyridine, alkali metal hydroxide or carbonate or alkali metal alkoxide.

(C) the acid of formula (a) or preferably its metal salt is derived from a halide of formula (d) or a trialkyl amine such as this halide and trimethyl amine or a tertiary amine such as pyridine Grade Ammonium Salts

Can react.

Food,

(D) The lower alkyl ester of the following general formula (e) is heated with the alcohol of the following general formula (b) to cause a transesterification reaction.

Food,

The reaction is preferably carried out in the presence of a suitable catalyst such as an alkali metal alkoxide such as sodium methoxide, or an alkylated titanium derivative such as tetra methyl titanate.

All conventional methods for preparing esters can be carried out using solvents or diluents for a variety of suitable reactants and proceed faster when run in the presence of a high temperature or in the presence of a suitable catalyst, such as a phase transfer catalyst, It can be obtained in high yield.

Individual isomer preparation can be carried out in the same manner but starts from the corresponding respective isomer of the compound of formula (c). This can be obtained by conventional isomeric separation operations from mixtures of isomers. Thus, cis or trans isomers can be separated by fractional crystallization of carboxylic acids and their salts, while various optically active species are obtained by fractional determination of salts of acids with optically active amines, followed by optically pure acid regeneration. .

Acids in optically pure isomeric form (or their equivalent acid chlorides or esters) may be reacted with a suitable alcohol to prepare the compounds of formula (1) in the form of pure isomers.

Methods of preparing the following general formula (c) compounds useful as intermediates in the preparation of the compounds of the invention are described fully in British Patent Specification No. 2,000,764 and Belgian Patent No. 863,151.

Food,

Q is hydroxy, alkoxy or halogen,

R ¹ and R ² are as described above.

Compounds (b) and (d) are known in nature (see eg Belgian Patent No. 862,109 and FG Drakesmith J. Chem SOC. Perkin Trans. I, 1972 (2), 184-9) or unknown If not, it can be prepared by a method similar to that used to prepare known compounds.

When the compound of formula (1) is prepared using an intermediate material which is an isomer mixture, the product obtained may also be a mixture of isomers. Thus, when intermediate acids or acid derivatives are used in the form of (+)-cis and (+)-trans isomers, the product may be predominantly in the form of (+)-cis and (+)-trans isomers. When a single isomer of an acid, such as a (+)-cis isomer with a Z-configuration in a 2-chloro-3,3,3- lorifluoropropylene group, is used, the product is also a single isomer of such stereochemical configuration. Or when there is an asymmetric carbon atom in the alcohol reaction, it becomes a pair of isomers. In order to avoid confusion, the product prepared by the method described in the following example is called an A-Z product, and each product is defined in terms of an isomeric composition with reference to the compound of Table 1 below.

A product pentafluorobenzyl 3- (2-trifluoromethyl-3,3,3-tri consisting of the (+)-cis isomer of 30% W / W and the (±) -trans isomer of 70% W / W Fluoroprop-1-en-1-yl) -2,2-dimethyl cyclopropane carboxylate (Compound No. 1, Table 1)

B product pentafluorobenzyl3- (2,3,3,3-tetrafluoroprop- consisting of (±) -cis isomer of 50% W / W and (±) -trans isomer of 50% W / W 1-en-1-yl) -2,2-dimethyl cyclopropane carboxylate (Compound No. 2, Table 1)

C product pentafluoro benzyl 3- (2-bromo-3,3,3-trifluoro consisting of (±) -cis isomer of 30% W / W and (±) -trans isomer of 70% W / W Prop-1-en-1-yl) -2,2-dimethyl cyclopropane carboxylate (Compound No. 3, Table 1)

D product pentafluorobenzyl-3 (2-chlorine-3,3,3-trifluoropropene) consisting of (±) -cis isomer of 40% W / W and (±) -trans isomer of 60% W / W Ph-1-en-1-yl) -2,2-dimethyl cyclopropane carboxylate (Compound No. 4, Table 1)

E product Pentafluorobenzyl3- (2-chlorine-3,3,3-trifluoropro) consisting of the (±) -cis isomer of 50% W / W and the (±) -trans isomer of 50% W / W Ph-1-en-1-yl) -2,2-dimethyl cyclopropane carboxylate (Compound No. 4, Table 1)

F product pentafluoro benzyl (±) -cis-3- (Z-2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclopropane carboxyl Rate

G product pentafluorobenzyl (±) -cis-3- (Z-2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclopropanecarb Carboxylate

H product pentafluorobenzyl (-)-cis-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclo propane carboxylate

I product pentafluorobenzyl (±) -trans-3- (Z-2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclopropanecarb Carboxylate

J product pentafluorobenzyl (-)-trans-3- (Z-2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarb Carboxylate

K product pentafluorobenzyl (-)-trans-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclo propane carboxylate

(±) -1- (1-pentafluorophenyl) ethyl3-2-chlorine consisting of the (±) -cis isomer of L product 50% W / W and the (±) -trans isomer of 50% W / W 3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclopropane (Compound No. 5, Table 1)

M compound (±) -α-cyano-pentafluoro benzyl (±) -cis-3- (Z-2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclopropane carboxylate (Compound No. 6, Table 1)

N compound 4-chlorine tetrafluoro benzyl 3- (2-chlorine-3,3,3-tree consisting of the (±) -cis isomer of 50% W / W and the (±) -trans isomer of 50% W / W Fluoroprop-1-en-1-yl) -2,2-dimethyl cyclo propane carboxylate (Compound No. 7, Table 1)

O product 4-chloro tetrafluoro benzyl (+)-cis-3- (2-chlorine-3,3,3-trifluoro prop-1-en-1-yl-2,2-dimethyl cyclopropanecarb Carboxylate

P product 4-bromo tetrafluoro benzyl 3- (2-chlorine-3,3,3- consisting of the (±) -cis isomer of 50% W / W and the (±) -trans isomer of 50% W / W Trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclo propane carboxylate (Compound No. 8, Table 1)

Q product 2,3,4,5-tetrafluorobenzyl (±) -cis-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2, 2-dimethyl cyclopropane carboxylate (Compound No. 9, Table 1)

R product 2,3,4,6-tetrafluorobenzyl (±) -cis-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2, 2-dimethyl cyclopropane carboxylate (Compound No. 10, Table 1)

S product 4-chlorine-2,3,5-trifluorobenzyl 3- (2-chlorine-) consisting of the (±) -cis isomer of 50% W / W and the (±) -trans isomer of 50% W / W 3,3,3-trifluoro prop-1-en-1-yl) -2,2-dimethyl cyclo propane carboxylate (Compound No. 11 Table 1)

T product 2,3-difluoro benzyl (±) -cis-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclo Propane Carboxylate (Compound No. 12, Table 1)

U product 2,4-difluoro benzyl (±) -cis-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclo Propane Carboxylate (Compound No. 13, Table 1)

V product 2,5-difluoro benzyl (±) -cis-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclo Propane Carboxylate (Compound No. 14, Table 1)

W product 2,6-difluoro benzyl (±) -cis-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclo Propane Carboxylate (Compound No. 15, Table 1)

X product 2-fluorobenzyl (±) -cis-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclo propane carboxyl Rate (Compound No. 16, Table 1)

Y product 3-fluorobenzyl (±) -cis-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclopropane carboxyl Rate (Compound No. 17, Table 1)

Z product 4-fluoro benzyl (±) -cis-3- (2-chlorine-3,3,3-trifluoro prop-1-en-1-yl) -2,2-dimethyl cyclo propane carboxyl Rate (Compound No. 18, Table 1)

The compounds of formula (1) can be used to prevent and combat the damage of pests and also other invertebrate pests such as acarin pests. Insects and acarinic pests that can be combated and prevented using the compounds of the present invention include pests associated with agriculture (including crop cultivation for food and textile products, horticulture and animal breeding), forestry, vegetable products, ie fruits, grains and timber, And also pests associated with disease transmission in humans and animals.

In order to apply the compound to the pest area, the compound is usually formulated into a composition comprising a suitable inert diluent or mediator, and / or a surfactant, in addition to the pesticidal active ingredient of formula (1). The composition may contain pesticides such as other pesticides or acaricides or fungicides or may contain pesticidal co-agents such as dodecyl imidazole, saffoxane, piperonyl, butoxide.

The composition may be in the form of a powder that can be powdered, in which the active ingredient is mixed with a solid diluent or media such as, for example, kaolin, bentonite, gigelgur, or talc, or the composition may be in granular form As such, the active ingredient is absorbed into porous granular material such as, for example, fumeis.

Alternatively, the composition may be in the form of a liquid formulation used for soaking or spraying, which is an aqueous acid solution or emulsion of the active ingredient under one or more wetting, spraying or emulsifying agent (surfactant) dependence.

Wetting agents, dispersants and emulsifiers may be in cation, anionic or non-ionic form. Suitable reagents of the cation include, for example, tetravalent ammonium compounds such as cetyl trimethyl ammonium bromide. Suitable reagents in anionic form include salts of soap, sulfuric acid or aliphatic monoesters such as sodium lauryl sulfate, salts of sulfonated aromatic compounds such as sodium dodecyl benzene sulfonate, sodium, calcium or ammonium lignosulfonate, butyl naphthalene Sulfonate and a mixture of sodium salts of diisopropyl and triisopropyl naphthalene sulfonates. Suitable reagents in non-ionic form include condensation products of ethylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol or alkyl phenols such as octylphenol, nonylphenol and octyl cresol. Other nonionic agents are condensation products of the partial esters derived from long chain fatty acids and hexitol anhydrides, of the partial esters mentioned, of ethylene oxide and lecithin.

The composition may be prepared by dissolving the active ingredient in a suitable solvent such as a ketone solvent such as diacetone alcohol or an aromatic solvent such as trimethyl benzene and adding the mixture thus obtained to water containing one or more known wetting agents, dispersing agents or emulsifiers. Can be. Other suitable organic solvents are dimethyl formamide, ethylene dichloride, isopropyl alcohol, propylene glycol and other glycols, diacetone alcohol, toluene, kerosene, white oil, methyl naphthalene, xylene and trichloroethylene, N -Methyl-2-pyrrolidone and tetra hydrofurfuryl alcohol (THFA).

The composition used as a nebulizer may also be in the form of an aerosol, which is inhibited in the vessel under pressure in the presence of a propellant such as fluoro trichloro methane or dichloro difluoro methane.

Compositions used in the form of aqueous dispersions or emulsions are generally in the form of concentrates containing a high proportion of active ingredient, which concentrates are diluted with water before use. This concentrate sometimes needs to withstand storage for a long period of time, and after standing, it is diluted with water to make an aqueous formulation that remains homogeneous for a sufficient time that can be used by conventional spraying equipment. The concentrate may comprise 10-85% by weight of the active ingredient or ingredients.

When diluting such preparations into aqueous preparations they may be included by varying the amount of active ingredient depending on the purpose for which they are used. Especially useful for agriculture or horticulture are aqueous preparations comprising 0.0001 -0.1% by weight of active ingredient.

When the composition is used, it is added by any known method for adding the pesticidal composition to pests, pest sites, pest habitats, or growing plants susceptible to invasion of the pest, for example by misting or spraying.

The compositions of the present invention are highly toxic against a wide variety of insects and for example other invertebrate pests, including the following.

Apis fabae (aphids)

Megoura viceae (aphids)

Addes aegypti (Mosquito)

Dysdercus fasciatus capsids

Musca domestica (housefly)

Pieris brassicae (white butterfly, larva)

Flutella maculipennis cabbage moth, larva

Pedon cochleariae (mustard leaf beetle)

Telarius cinnabarinus (Carmine spider mite)

Aonidiella spp.

Triareuroides spp. (Trialeuroides spp, white fly)

Blattella germanica (Aphid)

Spodoptera littoralis (Cotton Leaf Moth)

Cortiocetes terminifera (grasshopper)

Diabrotica (Diabrotica spp.root moth)

The compound of the formula (1) and a composition containing the same may be prepared by itself as a pest of cotton, such as sporopterra spp. And Heliothis spp. Are shown to be particularly useful. Because of the fumigation of the compounds, they can be used to combat soil-dwelling pests such as Diabrotica spp. Compounds are also good knock down agents and can be used in combination with other pesticides to combat public health pests such as flies. They are also insect pests and mite pests that harm animals such as Lucilia sericata, Boophilus spp., Ixodes spp., Amblyomma spp., And Lipisoparus ( Very useful for combating ixodid ticks such as Rhipicephalus spp.) And Dermaceutor spp. The compounds are effective in combating adult, larval and mid-growth susceptible and resistant pests and can be applied topically, orally or parenterally to infected host animals.

Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1

In this example, the pesticidal properties of the A-Z product were described.

The activity of the product was measured using various pests. The product was used in the form of a liquid formulation containing 100, 50, 25 and 12.5 ppm by weight of the product. The formulation was prepared by dissolving the product in a mixture of a solvent consisting of 4 parts by volume of acetone and 1 part by diacetone alcohol. The solution was diluted with water containing 0.01% by weight of a humectant sold under the trade name "LISSAPOL" NX until the liquid formulation contained the desired concentration of product. "Lisapol" is a trademark.

The test procedure adopted for each pest is the same in principle and usually consists of injecting a large number of pests into the subject or foodstuff medium and treating one or both pests and the medium with the product. Pest eradication was measured at varying periods of 1-3 days after treatment and is shown in the following table (2A).

The test results for each of the products A-Z in the ratio of parts per million described in the second column are listed in Table (2A) with a rating of 0-9.

0 is less than 10% eradication.

1 is 10-19% eradication rate. 2 is 20-29% eradication rate,

3 is 30-39% eradication. 4 is 40-49% eradication rate,

5 is 50-59% eradication rate. 6 is 60-69% eradication rate,

7 is 70-79% eradication rate. 8 is 80-89% eradication rate,

9 is 90-100% eradication rate.

Pest structures used in Table (2B) are shown in abbreviated letters, and pest types, support medium or food, and test form and duration are described in Table (2A).

^* "Contact" test indicates that pests and media are treated together and "residue" test indicates that the media has been treated before being infected with the pest.

TABLE 2A

TABLE 2B

Example 2

This example shows pentafluorobenzyl (±) -cis-3- (Z-2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclo The preparation of propane carboxylate (F product) is described.

A solution of pentafluorobenzyl alcohol (0.75 g) in toluene (4.0 ml) was dissolved at room temperature in (±) -cis-1-chlorinyl-3- (Z-2-chlorine-3,3) in toluene (10.0 ml). Pyridine (0.325 g) in toluene (4.0 ml) after addition to a stirred solution of, 3-trifluoro prop-1-en-1-yl) -2,2-dimethyl cyclo propane carboxylate (1.1 g) Was added to this mixture. After maintaining at room temperature for 18 hours, the mixture was diluted with water and extracted with chloroform. The extract was washed with dilute hydrochloric acid, washed with water, dried over anhydrous magnesium sulfate, and the solvent was concentrated by evaporation. The residual oil was purified under column chromatography using chloroform and silica gel as eluent. The purified oil was purified by nmr pentafluoro-benzyl (±) -cis-3- (Z-2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2, It was identified as 2-dimethyl cyclopropane carboxylate.

_{^{Nmr (1 H) (CCl 4}} ): 1.20-1.44 (m, 6H): 1.80-2.28

(m, 2H): 5.16 (s, 2H): 6.75-6.92 (m, 1H)

Example 3

This example shows pentafluorobenzyl (+)-cis / trans-3- (2-trifluoro methyl-3,3,3 containing 30% W / W of the (±) -cis isomer (A product) -Trifluoro prop-1-en-1-yl) -2,2-dimethyl cyclopropane carboxylate is described.

(±) -cis / trans-3- (2-trifluoro methyl-3,3,3-trifluoro prop-1-en-1-yl) -2,2-dimethyl cyclo propane carboxylate ( The mixture of 30% W / W (±) -cis isomer, 250 mg) and thionyl chloride (2.0 ml) was heated at reflux for 2 hours followed by azeotropic distillation with benzene to remove excess thionyl chloride. (±) -cis / trans-1-chloro carbonyl-3- (2-trifluoro methyl-3,3,3-trifluoro prop-1-en-1-yl)-by infrared spectroscopy The residual oil identified as 2,2-dimethyl cyclopropane was diluted with benzene (5.0 ml), pentafluoro benzyl alcohol (180 mg) and dry pyridine (75 mg) were added to the solution and the mixture was stirred at room temperature for 2 hours. . The mixture was poured into a mixture of ice and dilute hydrochloric acid (100 ml) and extracted with diethyl ether (4 × 25 ml). The extract was washed successively with cold water, dilute sodium bicarbonate solution, and water and dried over anhydrous magnesium sulfate. After evaporation under reduced pressure to remove the volatile portion, the oil was purified by column chromatography using silica gel and chloroform as eluent. After evaporation under reduced pressure to remove chloroform, the eluted material (30 mg) was pentafluoro containing 30% W / W of (±) -cis isomer and 70% W / W of (±) -trans isomer (Product A). Rhobenzyl (±) -cis / trans-3-(-2-trifluoro-methyl-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclopropane The carboxylate was confirmed by nuclear magnetic resonance spectroscopy.

_{^{Nmr (1 H) (CCl 4}} ): 1.22-1.46 (m, 6H); 1.80-2.64

(m, 2H); 5.28 (s, 2 H); 6.32-7.40 (m, ¹ H)

Example 4

I product (pentafluoro benzyl (±) -trans-3- (Z-2-chloro-3,3,3-trifluoro prop-1-ene-1- using the process described in Example 2) (I) -2,2-dimethyl cyclo propane carboxylate) was prepared from the corresponding acid and acid chlorides of pentafluorobenzyl alcohol.

_{^{Nmr (1 H) (CCl 4}} ): 1.20-1.64 (m, 6H); 1.72-1.82

Example 5

The process described in Example 3 was also used to prepare B-E, G, H and J-Z products from the corresponding carboxylic acids and alcohols as follows.

B product: pentafluorobenzyl alcohol and (±) -cis / trans-3- (2,3,3,3-tetrafluoroprop-1-en-1-yl, -2,2-dimethyl cyclopropane Prepared from carboxylic acid (containing (±) cis isomer of 50% W / W).

C product: pentafluorobenzyl alcohol and (±) -cis / trans-3-2-bromo-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl Prepared from cyclo propane carboxylic acid (containing (±) cis isomer of 30% W / W).

D product: pentafluorobenzyl alcohol and (±) -cis / trans-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl Prepared from cyclo propane carboxylic acid (containing (+)-cis isomer of 40% W / W).

E product: pentafluorobenzyl alcohol and (+)-cis / trans-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl Prepared from cyclo propane carboxylic acid (containing (±) -cis isomer of 50% W / W).

G product: pentafluorobenzyl alcohol and (+)-cis-3- (Z-2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl Manufactured from cyclopropane carboxylic acid.

H product: pentafluorobenzyl alcohol and (-)-cis-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclopropane Manufactured from carboxylic acids.

J product: pentafluorobenzyl alcohol and (+)-trans-3- (Z-2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl Manufactured from cyclopropane carboxylic acid.

K product: pentafluorobenzyl alcohol and (-)-trans-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclopropane Manufactured from carboxylic acids.

L product: (±) -1- (pentafluorophenyl) ethanol and (±) -cis / trans-3- (2-chlorine-3,3,3-trifluoro prop-1-ene-1- Prepared from mono-2,2-dimethyl cyclopropane carboxylic acid (containing (±) -cis isomer of 50% W / W).

M product: (+)-α-cyano-3pentafluorobenzyl (±) -cis-3- (Z-2-chlorine-3,3,3-trifluoroprop-1-ene-1- Prepared from yl) -2,2-dimethyl cyclopropane carboxylic acid.

N product: 4-chloro tetrafluoro benzyl alcohol and (±) -cis / trans-3- (2-chlorine-3,3,3-trifluoro prop-1-en-1-yl) -2, Prepared from 2-dimethyl cyclopropane carboxylic acid (containing (±) -cis isomer of 50% W / W).

O product: 4-chloro tetrafluoro benzyl alcohol and (±) -cis-3- (2-chlorine-3,3,3-trifluoro prop-1-en-1-yl) -2,2- Prepared from dimethyl cyclopropane carboxylic acid.

P product: 4-bromotetrafluorobenzyl alcohol and (±) -cis / trans-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2 Prepared from 2-dimethyl cyclopropane carboxylic acid (containing (±) -cis isomer of 50% W / W).

Q product: 2,3,4,5-tetrafluorobenzyl alcohol and (±) -cis-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) Prepared from -2,2-dimethyl cyclopropane carboxylic acid.

R product: 2,3,4,6-tetrafluorobenzyl alcohol and (±) -cis-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) Prepared from -2,2-dimethyl cyclopropane carboxylic acid.

S product: 4-chlorine-2,3,5-trifluoro benzyl alcohol and (±) -cis / trans-3- (2-chlorine-3,3,3-trifluoro prop-1-ene- Prepared from 1-yl) -2,2-dimethyl cyclopropane carboxylic acid (containing (±) -cis isomer of 50% W / W).

T product: 2,3-difluoro benzyl alcohol and (±) -cis-3- (2-chlorine-3,3,3-trifluoro prop-1-en-1-yl) -2,2 Prepared from dimethyl cyclopropane carboxylic acid.

U product: 2,4-difluoro benzyl alcohol and (±) -cis-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2 Prepared from dimethyl cyclopropane carboxylic acid.

V product: 2,5-difluoro benzyl alcohol and (±) -cis-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2 Prepared from dimethyl cyclopropane carboxylic acid.

W product: 2,6-difluoro benzyl alcohol and (±) -cis-3- (2-chlorine-3,3,3-trifluoroprop-1-en-1-yl) -2,2 Prepared from -dimethyl cycloprop-1-en-1-yl) -2,2-dimethyl cyclo propane carboxylic acid.

X product: 2-fluoro benzyl alcohol and (±) -cis-3- (2-chlorine-3,3,3-trifluoro prop-1-en-1-yl-2,2-dimethyl cyclopropane Manufactured from carboxylic acids.

Y product: 3-fluoro benzyl alcohol and (±) -cis-3- (2-chlor-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclo Manufactured from propane carboxylic acid.

Z product: 4-fluoro benzyl alcohol and (±) -cis-3- (2-chlor-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl cyclo Manufactured from propane carboxylic acid.

The product was N.m.r. It was confirmed by spectroscopic analysis and / or elemental trace analysis.

Claims (1)

As described above in the text, a process for preparing a novel compound of formula (1) consisting of reacting a compound of formula (c) with a compound of formula (b):

Food, R ¹ is chlorine, bromo, fluoro or trifluoro methyl, R ² is hydrogen, methyl or cyano, R is a halophenyl group containing at least one fluorine atom, Q is a halogen atom, preferably a chlorine atom.