CS199712B2 - Insecticide and acaricide and process for preparing effective compound - Google Patents

Description

The invention relates to insecticidal and acaricidal compositions containing, as active ingredient, the m-phenoxybenzyl esters of substituted phenylalkanoic acids as described below, a process for the preparation of these active ingredients and intermediates suitable for their preparation. From the state of the art, South Africa Patent Application No. 73/4462 (Sumitomo Chemical Company Limited) is the closest object of the invention. This application generically describes literally tens of thousands of phenylacetic acid esters, inclusive

3‘-phenoxybenzyl-α-isopropyl-4-methoxyphenylacetate,

3‘-phenoxybenzyl-1'-isopropyl-3-methoxyphenylacetate,

3‘-phenoxybenzyl-α-isopropyl-4-chlorophenylacetate,

3‘-phenoxybenzyl-α-isopropyl-4-methylphenylacetate,

3‘-Phenoxybensyl-α-isopropyl-3-chlorophenylacetate a

3‘-Phenoxybenzyl-α-isopropyl-4-fluorophenylacetate.

It is stated that many of these compounds are effective pesticidal agents and are useful for controlling various insects and mites. However, the m-phenoxybenzyl esters of 2-haloalkyl (oxy-, thio-, sulfinyl-, or sulfonyl) -phenylalkanoic acids, which are the active ingredients of the compositions of the invention, are not disclosed, nor is there any synthesis useful for the preparation of these compounds.

It has surprisingly been found that the compounds of the invention are not only potent insecticidal agents, but also highly potent ixodicidal agents. In addition, the compounds of the invention are insecticidal and ixodicidal agents which can be used systemically in animals. The compounds of the invention can be used effectively to protect domestic, laboratory and farm animals from insect and tick infestation. The compounds of the invention also exhibit improved residual ixodicidal and insecticidal activity compared to known pyrethroids such as permethrin, phenothrin, allerthrin and the like are extremely effective in suppressing Heliothis virescens and Anopheles quadrimaculatus (mosquitoes).

The subject of the invention is an insecticidal and acaricidal composition, characterized in that it contains at least one m199712 as active ingredient.

2-haloalkyl (oxy-, thio-, sulfinyl-, or sulfonyl) -phenylalkanoic acid of the general formula I

O

(t) wherein the RGF2X- group is in the m- or p-position relative to the carbon atom to which the alkanoic ester group is attached and wherein

X is oxy, thio, sulfinyl or sulfonyl,

R is hydrogen, fluoro, chloro, difluoromethyl or trifluoromethyl,

R 2 is ethyl, η-propyl, isopropyl, isopropenyl or tert-butyl, and

R3 is hydrogen or cyano, wherein when X is oxy, R is not fluorine, chlorine, difluoromethyl or trifluoromethyl, or an optical isomer thereof.

The compositions of the present invention can be used to control insects and acarids by contacting insects, acarids, sites where they occur, sites where they hatch, and / or their food with an insecticidally or acaricidally effective amount of 2-haloalkyl m-phenoxybenzyl ester. (oxy-, thio-, sulfinyl-, or sulfonyl) -phenylalkanoic acids of the formula I. With the compositions according to the invention, agricultural crops can be protected either at the growth stage or after harvest and warm-blooded animals from insect and / or mite attack by crops and / or the animals administer an insecticidally or acaricidally effective amount of a compound of formula I as defined above.

Preferably, the m-phenoxybenzyl esters of 2-haloalkyl (oxy-, thio-, sulfinyl-, or sulfonyl) -phenylalanic acids of the formula I can be prepared by reacting a «-substituted 2-haloalkyl (oxy-, thio-, sulfinyl- or sulfonyl) -phenylacetyl halide of the general formula ⁷ of the formula. II, preferably the chloride with m-phenoxybenzyl alcohol of the formula III. the reaction is generally carried out in the presence of a solvent such as diethyl ether, benzene or toluene at a temperature in the range 10 to 30 ^D C, in the presence of an acid acceptor. the acid acceptors can be used for example, tertiary organic amines, trimethylamine, triethylamine, and pyridine.

wherein the RCF2X- group is in the m- or β-position relative to the carbon atom to which the alkanoic ester group is attached and wherein

X is oxy, thio, sulfinyl or sulfonyl,

R is hydrogen, fluoro, chloro, difluoromethyl or trifluoromethyl,

R 2 is ethyl, η-propyl, isopropyl, isopropenyl or tert-butyl, and

R 3 represents hydrogen or a cyano group, and

A is halogen, preferably chlorine.

Preferred compounds of formula I above are

1) those wherein RCF 2 X - is in the β-position to the carbon to which the alkanoic ester group is attached and wherein R, R 2 and R 3 are as defined above,

2) those wherein RCF 2 X - is in the m-position to the carbon to which the alkanoic ester group is attached and wherein R, R 2 and R 3 are as defined above.

It has further been found that more preferred compounds in each of these groups are those wherein X is oxygen or sulfur and R is hydrogen or fluoro, R 3 is hydrogen or cyano, and R 2 is ethyl, n-propyl or isopropyl.

It is clear that various optical isomers of the compounds of formula (I) are formed according to the procedures described above.

For example, in the synthesis of esters of Formula I wherein R 3 is hydrogen, a chirality center is present on the R 2 moiety to form d and 1 isomeric pairs. Also, α-cyanosubstitution at R 3 introduces an additional center of chirality whereby an additional d, 1 pair can be formed.

For example, it has been found that when α-isopropyl-4-trifluoromethoxyphenylacetic acid is mixed with about 0.5 to 1.0 molar equivalent of (-) - 1-ethylamine in a suitable solvent such as ethanol or aqueous ethanol, the salt precipitates. (+) -acids. Upon acidification, the acid is liberated from the salt, typically containing more than 85% of the (+) - isomer. A higher degree of cleavage can be achieved by recrystallization of (-? -? - phenethylamine salt or by repeating the cleavage process with fresh (-) -? - phenethylamine. M-Phenoxybenzyl or α-cyano-m-phenoxybenzyl esters of fully (+) -α-isopropyl-4 Trifluoromethoxyphenylacetic acids are about twice as insecticidally more potent than the corresponding esters made from racemic acid.In the case of α-cyano-m-phenoxybenzyl ester, an additional increase in potency is achieved when the corresponding optically active N -cyan-m-phenoxybenzyl alcohol is used in the ester-forming step.

Substituted 2-haloalkyl (oxy-, thio-, sulfinyl-, or sulfonyl) -phenylacetyl halides of formula II wherein R2 is ethyl, n-propyl, or isopropyl may be prepared using the appropriate toluene of formula IV as the starting material. the preparation comprises 5 steps, the first step being the halogenation of toluene of formula IV with bromine,

IIVI (NBS with chlorine, N-bromosuccinimide (NBS) or the like) This reaction is preferably carried out in the presence of an inert organic solvent such as carbon tetrachloride and a free-radical initiator such as light, benzoyl peroxide or azo-bis-isobutyronitrile. the compound is then converted to the corresponding phenyl acetonitrile of formula VI by reaction with sodium or potassium cyanide in the presence of dimethylsulfoxide (DMSO), ethanol, or the like at elevated temperature, which (substituted phenyl) acetonitrile of formula VI is then easily alkylated when reacted with The alkali metal halide in the presence of a base and an inert organic solvent has been found to be useful as catalysts in the reaction of crown ethers. Hydrolysis of the .alpha.-alkylsubstituted phenyl) acetonitrile of formula VIII using alkali metal hydroxide in the presence of alkylene glycol and water yields .alpha.-alkyl (substituted phenyl) acet onic acid of formula VIII. Reaction of this acid with thionyl chloride,. with thionyl bromide or the like, preferably in the presence of an aromatic solvent such as benzene or toluene, is then obtained an α-alkyl- (substituted phenyl) acetyl halide of formula II which is reacted with m-phenoxybenzyl alcohol of formula III or α-cyano-m-phenoxybenzyl alcohol to form the desired 2-haloalkyl- (oxy-, thio-, sulfinyl-, or sulfonyl) -phenylalkanoic acid m-phenoxybenzyl ester or α-cyano-m-phenoxybenzyl ester of formula I,

The reactions are illustrated graphically in the following Summary Scheme I:

Scheme I

Preparation of 2-haloalkyljoxy-, thio-, sulfinyl-, or sulfonyl) phenylalkanoic acids m-phenoxybenzyl esters

RCf = X = ⁷ (V) +

X 7-CH.Bni-NACN

RCC ^£ *

DMSO

RCF ^ X

CH ^ CN (VI) (V) (VI) £ J-CHCNi-KOU ^R C ^ X ^ = ⁷ k (VID banxan

NaOH (но) - R x —----- 7-CHCN

RCF / X ^ = ⁷ (VID, _H , _{Cl p} . _R X ^ ^ CI ^ COOH HOC ^ C ^ OH 1 _R

....... (VUD v; * '199712

СНСООН t 8СС1 ^ - ^{лп: 1 & п}

^игцап / ~~ \ снсоа * носч RC ^ X + pyk-Cditn -

Instead of the benzyl bromide of formula V used in Scheme I, where the products must be limited to p-substituted compounds, suitable haloalkyl (oxy- or thio-J benzenes of formula IX) can be chloromethylated using a mixture of paraformaldehyde or trioxane with zinc chloride and dry hydrogen chloride. a benzyl chloride of the formula X, which can be used to complete the synthesis of compounds of formula I to the compound of formula V. This modification can be illustrated by the following equation ^RCF RZZ> ^{+ c} ^ κι (IX) ^RCF ^ ^Y ^ ~ Qz ~ CH £ T (X)

Y = O or S

The preparation of m-phenoxybenzyl and α-cyano-m-phenoxybenzyl esters of α-alkyl-3 (or 4] -trifluoromethoxyphenylacetic acid can also be carried out by sequential reactions starting with alkylation of m- or p-methoxyphenylacetonitrile using an alkyl halide in the presence of crown ether and base. Of course, it is common that when used in this reaction of m-methoxyphenylacetonitrile, α-alkyl-3-methoxyphenylacetonitrile is obtained, and when the β-isomer is used, α-alkyl-4-methoxyphenylacetonitrile is obtained. the location of the methoxy group on this phenylacetonitrile starting material determines the position of the trifluoromethoxy substituent in the final product.

The above α-alkyl-3- (or 4) -methoxyphenylacetonitrile is converted to α-alkyl-3- (or 4) -hydroxyphenylacetonitrile by reaction with boron tribromide, preferably in the presence of a solvent such as methylene chloride. Reaction of the phenol so formed with thiophosgene and a base in the presence of a solvent such as chloroform then yields the O- [m or p- (1-cyano-2-methylpropyl) phenyl] formic acid chlorothioester. This ester is readily converted to α-alkyl-3- (or 4) -trifluoromethoxyphenylacetonitrile with molybdenum fluoride and this compound is then hydrolyzed to the corresponding α-alkyl-3- (or 4'-trifluoromethylphenylacetic acid) by reaction with ethylene glycol in the presence of alkaline hydroxide metal and water.

Reaction of α-alkyl-3- (or 4) -trifluoromethoxyphenylacetic acid with thionyl chloride in the presence of an aromatic solvent such as benzene or toluene affords the corresponding acid chloride which is reacted with m-phenoxybenzyl alcohol or α-cyano-m-phenoxybenzyl alcohol to form the desired m-phenoxybenzyl or arcyano-m-phenoxybenzyl-α-alkyl-3- (or 4) trifluoromethoxyphenyl acetate.

These reactions are illustrated in Scheme II below:

Summary scheme II

In the reactions shown in Scheme II, R 2 is ethyl, n-propyl or isopropyl and R 3 is hydrogen or cyano.

While the procedure outlined in Scheme I is generally applicable to the preparation of many of the compounds of the invention, it has been found that cleavage of the HCF2 group may occur by alkaline hydrolysis in those cases where the RCF2X- group is HCF2O- or the HCFsS group. However, this group can be reintroduced by reacting the appropriate phenol or thiophenol with chlorodifluoromethane in a mixture of aqueous alkali and dioxane.

The actual synthesis of those substances that contain the HCF2O group is best shown in Summary Scheme III. According to the process illustrated, the appropriate α-alkyl-3 (or 4) -methoxyphenylacetonitrile (shown in Scheme II) is converted to α-alkyl-3 (or 4 ' 4 ' 4-hydroxyphenylacetic acid using hydrobromic acid) by treatment with chlorodifluoromethane in aqueous alkali metal hydroxide. Dioxane yielded α-alkyl-3- (or 4] difluoromethoxyphenylacetic acid), which was converted to the desired m-phenoxybenzyl or α-cyano-m-phenoxybenzyl ester as described in Scheme II.

Summary scheme III

diox & .n defective Na-OH

CM-CO 4 H * HCCIF 4

D

HCFX)

Н-сн-сар

Although the procedure outlined in Scheme I is suitable for the preparation of most compounds in which X is a group

but it is often more convenient to prepare these compounds by preparing the final acids of formula (VIII) or esters of formula (I) in which X is -S- and then the sulfur atom is oxidized to the desired

O

II —s— or

O

II —s—

II o

an analog with a suitable oxidizing agent such as m-chloroperbenzoic acid, sodium periodate or hydrogen peroxide.

The following reaction sequence, starting from the corresponding m- or p-substituted aldehyde, is used to prepare those compounds of formula I wherein R 2 is t-butyl.

1) reaction with t-butylmagnesium chloride,

2) conversion of neopentyl alcohol to chloride using thionyl chloride;

3) preparing Grignard reagent from chloride using magnesium in tetrahydrofuran; and

4) carboxylation with carbon dioxide.

This approach is illustrated in greater detail in the synthesis of α-t-butyl-3 (or 4) -trifluoromethoxyphenylacetic acid shown in Scheme IV. The acids can be converted to the corresponding esters as shown in Scheme I.

Summary scheme IV

For those compounds of formula (I) wherein R 2 is isopropenyl, the α-isopropenyl group can be run by the following sequence of reactions using the appropriate m- or p-substituted phenylacetic acid:

(1) reaction with two equivalents of isopropylmagnesium chloride and acetone;

2) conversion of hydroxy acid to ester; and

3) dehydration of the hydroxyester with phosphorus pentoxide.

This procedure is illustrated in more detail in the preparation of m-phenoxybenzyl-.alpha.-isopropenyl-4- (or 3) -trifluoromethoxyphenyl acetate, see Summary Scheme V.

Summary scheme

Z-X 1. t-frMgCt in--ch-cooh ---------- 1 * ² CH ₃ COCH.

CH-COOH and C-OH

X \%

Regarding the preparation of α-cyano-m-phenoxybenzyl ester products according to the procedures shown in either Scheme I or II, there is no need to isolate N -cyan-m-phenoxybenzyl alcohol as a precursor. It is the same or even more desirable to react a mixture of m-phenoxybenzaldehyde, an alkali metal cyanide such as sodium cyanide, and a suitable N-substituted 2-haloalkyl (oxy-, thio-, sulfinyl- or sulfonyl) phenylacetyl halide in one step to form the final N -cyanester.

The compounds of the invention are highly effective as contact and gastric poisons for ticks and various insects, in particular double-winged, flake-like (butterflies), beetles and even-winged insects. They are unusual among pyrethhoids. in it, . They exhibit a very broad residual insecticidal activity on plant tissue, are effective in soil and unexpectedly effective for controlling ticks and for protecting animals from insect and tick infestation when administered orally or parenterally or as a topical insecticidal or acaricidal agent. In order to achieve stable insecticidal and acaricidal compositions, it is not necessary to add a stabilizer; however, they can be used in admixture with other biological chemicals, for example pyrehtroid synergetics such as piperonyl butoxide, sesamex or isosafrol n-octylsulfoxide. They can also be used in combination with conventional insecticides such as phosphates, carbaminates, formamidines, chlorinated hydrocarbons or halobenzoylureas. The insecticidal compounds of the invention can be applied to plant foliage, insect habitats and / or insect feed to control insects, including soil insects that attack plants during growth and / or harvested crops, including stored grain. In general, the active compound is administered in the form of a dilution of 199712

1S liquid spray; however, it can also be applied as an aerosol, dust, granulate or wettable powder.

Particularly useful liquid sprays are oil sprays and emulsifiable concentrates which can be further diluted for application. In order to facilitate handling and transport, liquid concentrates are usually employed as the compositions and are usually dispersed in water at the point of use and then applied as a dilute spray onto the foliage of the plant, the soil or the area to be treated.

A typical emulsifiable concentrate useful for protecting various crops such as cereals, cabbages, cucumbers, corn, cotton, tobacco, soybeans, ornamental plants, shrubs and the like may contain about 20% by weight of the active ingredient; 4% by weight of an emulsifying agent commonly used in the preparation of pyrethroid formulations; 4% by weight of a surfactant; 25% by weight of an organic solvent such as cyclohexanone; and about 47% by weight of an oil solvent containing at least 83% by volume of flavorings.

For use as systemic insecticide and acarlide agents for animals, the compounds of the invention may be administered to an animal host either orally or parenterally. When administered orally, they may be in any convenient form suitable for this purpose, such as in the form of a powder, capsule, tablet or beverage. The active ingredient may also be incorporated into the animal feed and administered as a nutrient-balanced diet containing 0.0001 to 0.1% and preferably 0.001 to 0.05% by weight. % of active compound (based on diet).

Optionally, the systemic insecticidal and acaricidal composition can be introduced into the animal body by subcutaneous, intramuscular or intraipeiritoneal injection, so that it can be dispersed in the body by the circulatory system. In practice, the systemic composition may be dissolved or dispersed in a pharmaceutically acceptable carrier such as water, propylene glycol, vegetable oil, glycerin formal or the like prior to administration.

As systemic agents, the compounds of the invention have a wide range of safe applicability, a good margin of protection, and are effective in protecting various animals, particularly cattle and domestic animals such as cattle, sheep, horses, dogs and cats, etc. from attacking fleas, mosquitoes, flies, ticks. etc.

Among the compounds of the invention useful as insecticidal and acaricidal agents, for example, m-phenoxybenzyl-α-isopropyl-4-trifluoromethoxyphenylacetate, α-cyano-m -phenoxybenzyl-α-isopropyl-4-trifluoromethoxyphenylacetate, α-cyan-m-phenoxybenzyl -α-isopropyl-3-trifluoromethoxyphenylacetate, α-cyano-m-phenoxybenzyl-α-isopropyl-4-chlorodifluoromethoxyphenylacetate, m-enoxybenzyl-α-isopropyl-4- (1,1,2,2, -tetrafluoroethoxy) phenylacetate, and- cyan-m-phenoxybenzyl-α-isopropyl-4-pentafluoroethoxyphenylacetate, m-phenoxybenzyl-α-ethyl-3-trifluoromethoxyphenylacetate, α-cyan-m-phenoxybenzyl-propyl-4-chlorodifluoromethoxyphenylacetate, α-cyano-m-phenoxybenzyl. -at-butyl-4-trifluoromethoxyphenylacetate, α-cyano-m-phenoxybenzyl-α-isopropyl-4-difluoromethoxyphenylacetate, α-cyano-m-phenoxybenzyl-α-1-propyl-4-trifluoromethylthiophenylacetate, m-phenoxybenzyl-α-ethyl-4 -trifluoromethylsulfinylphenylacetate, α-cyano-m-phenoxybenzyl-α-isopropyl-3-difluoromethylsulfonylphenylacetate, α-cyano-m-phenoxybenzyl-α-ethyl-4 -trifluoromethoxyphenylacetate; and α-cyano-m-phenoxybenzyl-α-isopropenyl-4-trifluoromethoxyphenylacetate.

The following examples illustrate the invention.

Example 1

Preparation of p- (1,1,2,2-tetrafluoroethoxy) toluene

Tetrafluoroethylene and nitrogen were bubbled through a magnetically stirred mixture of 10.0 g (0.100 mol) of p-cresol, 1.67 g (1.43 grams actually, 0.0255 mol) of potassium hydroxide pellets and 70 ml of dry dimethyl formamide (1 hour). DMF) maintained at 68 ° C. After dilution with 250 ml of water, the reaction mixture is extracted with 100 ml of ether. The ether solution was washed with 200 mL of 5% sodium hydroxide and 2X400 mL of water. The ether solution was dried, filtered and then rotary evaporated to give 18.14 g (87%) of p- (1,1,2,2-tetrafluoroethoxy) toluene.

For C 9 H 8 F 4 O calculated:

% C, 51.93;% H, 3.87;% F, 36.51;

% C, 52.06;% H, 3.76;% F, 41.52.

Example 2

Preparation of p- (1,1,2,2-tetrafluoroethoxy) benzyl bromide

Mechanically stirred mixture of 118.45 g (0.569 mol) of β- (1,1,2,2-tetrafluoroethoxy) toluene, 123.00 g (0.691 mol, 121 mol%) of N-bromosuccinimide (NBS), 1.00 g (4.13 mol, 0.73 mol%) of benzoyl peroxide and 350 ml of carbon tetrachloride were refluxed for 2.25 hours. After cooling, the reaction mixture is diluted with 350 ml of carbon tetrachloride, filtered to remove solids, dried over sodium sulfate, filtered and then evaporated using a rotary evaporator. 160.99 g (99%) of a clear red oil is obtained. This product was used as such in the following reactions. The infrared and NMR spectra confirm the structure of p- (1,1,2,2-tetrafluoroethoxy) benzyl bromide.

Example 3

Preparation of p- (1,1,2,2-tetrafluoroethoxy) phenylacetonitrile

A hot solution of potassium cyanide (75.1 g, 1.15 mol) in water (140 ml) was added over 40 minutes to a 75 ° C, mechanically stirred solution, 160.99 g (0.561 mol) of p- (1,1,2), Of 2-tetrafluoroethoxy) benzyl bromide and 500 mL of anhydrous 2B alcohol. The resulting mixture was heated at reflux for 1.75 hours. Allow to stand overnight, then pour the reaction into 500 ml of cold water and 400 ml of ether. The combined ether solution was washed with 2X500 mL of water, dried over sodium sulfate, filtered and then evaporated on a rotary evaporator to give 114.95 g of an oil. Vacuum distillation of this oil gave 37.10 g (28%) of nitrile as a single distillation fraction, bp 85-100 ° C at 38.7 Pa.

Example 4

Preparation of α-isopropyl-β- (1,1,2,2-tetrafluoroethoxy) phenyl acetonitrile

A mixture of 39.85 g (0.171 mol) of p- (1,1,2,2-tetrafluoroethoxy) -phenylacetonitrile, 3.71 g (9.96 mmol, 5.8 mol%) of dicyclohexyl-18-crown-6-ether, 22 0 ml (28.8 g, 0.234 mol) of 2-bromopropane, 55 ml of benzene and 55 ml of 50% sodium hydroxide are stirred for 45 minutes, during which time the temperature is raised from 25 ° C to 43 ° C. The reaction mixture was extracted with 200 ml of ether, washed with 400 ml of 12% hydrochloric acid, 200 ml of 5% hydrochloric acid and 300 ml of water, and then the ether solution was dried. sodium sulfate, filtered, and then evaporated to give 47.13 g of an oil, which was distilled in vacuo to give 34.83 g (74 percent) of the product, bp 84-85 ° C at 7.3-12.0 Pa. .

For C 13 H 13 F 4 NO calculated:

C 56.73, H 4.76, N 5.09,

27.61% F, found:

% C, 56.12;% H, 4.85;% N, 4.99;

Example 5

Preparation of 3-methyl-2- [p- (1,1,2,2-tetrafluoroethoxy) phenyl] butyric acid

Stirred mixture 48.0 g (24.0 g actual, 0.60 mol) 50% sodium hydroxide, 21.78 g (0.0791 mol) α-isopropyl-β- (1,1,2,2-tetrafluoroethoxy) of phenylacetonitrile and 240 ml of ethylene glycol was heated at 135 ° C for 12 hours. After diluting with 600 ml of water, the reaction mixture is washed with 2X100 ml of ether. The aqueous layer was acidified with concentrated hydrochloric acid and then extracted with 2X300 mL ether. The ether solution was washed with 2X 500 mL water, dried over sodium sulfate, filtered and then evaporated to give 20.74 g (89%) of a brown solid, mp 92-97 ° C (hexane).

For C 13 H 14 F 4 O 3 calculated:

% C, 53.06;% H, 4.80;% F, 25.83.

% C, 53.04;% H, 4.79 _; 93% F.

Example 6

Preparation of 3-methyl-2- [p- (1,1,2,2-tetrafluoroethoxy) phenyl] butyryl chloride

Stirred mixture 20.00 g (0.0680 mol) of 3-methyl-2- [p- (1,1,2,2-tetrafluoroethoxy) phenyl] butyric acid, 20 00 ml (33.2 g, 0.280 mol) of thionyl chloride (Baker) and 75 ml of dry benzene were refluxed for 4 hours. The reaction mixture was then evaporated and the residue was diluted with 50 ml of benzene and evaporated again to give 22.46 g (106%) of a clear dark brown liquid. This product was used as such in the following reactions. The above product was confirmed by infrared spectroscopy.

Example 7

Preparation of m-phenoxybenzyl-α-isopropyl-4- (1,1,2,2-tetrafluoroethoxy) phenyl acetate

To a stirred mixture of 6.81 g (0.0340 mol) of m-phenoxybenzyl alcohol, 3.0 ml (2.95 g, 0.0372 mol) of dry pyridine and 20 ml of methylene chloride are added over 20 minutes 20 ml of methylene chloride solution 10.6 g (0.034 mole) of 3-methyl-2- [p- (1,1,2,2-tetrafluoro-199,712 ethoxy) phenyl] butyryl chloride. The reaction mixture was stirred at room temperature for 66 hours and then diluted with 200 mL of ether. The ether solution was washed with 200 mL of 20% hydrochloric acid and 200 mL of water, dried over sodium sulfate, filtered, and then evaporated to give 16.24 g of product (100%) which was purified using a dry silica gel column (116 cm X 5) The sample was collected between 85 cm and 63 cm (solvent front equals 113 cm) to give 12.60 g (78%) of a clear pale yellow oil.

For C26H24F4O4 calculated:

65.54% C, 5.08% H, 15.95% F, found about:

% C, 64.99;% H, 4.96;% F, 19.10.

Example 8

Preparation of α-cyano-m-phenoxybenzyl-α-isopropyl-4- (1,1,2,2-tetrafluoroethoxy) phenylacetate

To a stirred mixture of 8.81 g (7.49 g of actual, 0.0333 mol) of α-cyano-m-phenoxybenzyl alcohol, 3.0 ml (2.95 g, 0.0372 mol) of dry pyridine and 20 ml of methylene chloride solution 10.6 g (0.034 mole) of 3-nitro-4- (1,12,2-aetrafluoroethoxy) phenyl] butyryl chloride. The reaction mixture was stirred at room temperature for 66 hours and then diluted with 200 mL of ether, washed with 200 mL of 20% hydrochloric acid and 200 mL of water, dried over sodium sulfate, filtered and then evaporated to give a dark red oil. In order to remove m-phenoxybenzaldehyde, such as. impurity, the oil is treated with 0.5 g of sodium borohydride at an ice bath temperature, and the resulting oil is purified on a dry silica gel column (121 cm X 5 cm, eluent = 1: 1 hexane-methylene chloride). A sample is collected between 77 cm and 57 cm (solvent front = 113 cm). 11.17 g (66%) of a clear orange oil are obtained.

For C27H23F4NO4 calculated:

% C, 64.67;% H, 4.62;% N, 2.79.

15.16% F, found:

H, 4.81; N, 2.82.

17.94% F.

Example 9

Preparation of α-isopropyl-4-methoxyphenylacetonitrile

A solution of sodium hydroxide (50%, 300 mL) was added to a solution of p-methoxyphenylacetonitrile (147 g, 1 mol), dicyclohexyl-18-trifluoromethyl ether (18.63 g, 5 mol%), 2-bromopropane (320 g, 2.6 mol) and benzene (300 mL). The reaction mixture was heated to 45 ° C for 4 days. The organic phase was separated, washed well with water (3X200 mL), dilute hydrochloric acid (1X X200 mL), water (2X200 mL) and evaporated to an oil. Vacuum distillation yielded the product (175.6 g, 81% of theory), boiling point 96-100 degrees Celsius (20 Pa), NMR spectrum (CDCl3) showed that the distilled material contained 12.5 mol%. starting nitrile.

Example 10

Preparation of α-isopropyl-4-hydroxyphenyl acttonitrile

Boron tribromide (51.0 g, 0.2 mole) in methylene chloride (20 mL) was added to a solution of α-isopropyl-4-methoxyphenylacetonitrile (37.8 grams, 0.2 mole) in methylene chloride (35 mL) maintained at -40 ° C. The red solution was allowed to warm to room temperature and stirred for 3 days.

The reaction solution was added to ice, then extracted with ether (3X100 mL), washed with water (2X100 mL) and evaporated to an oil. Vacuum distillation yielded the product α-isopropyl β-hydroxylenylacetonitrile (28.9 g, 81%), bp 142-143 ° C (33.3 Pa).

Example 11

Preparation of chlorothio-O- [p- (1-cyano-2-methylpropyl) phenyl] formic acid ester

Thiophosgene (16.43 g, 0.143 mol) in chloroform (50 ml) was added over 30 minutes to a solution of α-isopropyl-4-hydroxyphenylacetonitrile (25.0 g, 0.143 mol) in sodium hydroxide (5%, 5, 72 g, 0.143 mol) occasionally using an ice bath to maintain the temperature below 30 ° C. The mixture was stirred for 15 minutes and the chloroform layer was separated, washed with water and evaporated to a yellow oil (38.2 g). The product was used as such in Example 12.

Example 12

Preparation of α-isopropyl-4-trifluoromethoxyphenethyl acetonitrile

Thiocarbonate (38.2 g) from Example 11. se. was reacted with molybdenum fluoride (15.8 g) at -25 ° C. The dense reaction mass was then allowed to warm to room temperature and then slowly warmed to 160 ° C using an oil bath. The mixture was cooled to room temperature and then poured into water and extracted with 4X50 mL of ether, washed once with 50 mL of water and evaporated to an oil. Vacuum distillation yielded α-isopropyl-4-trifluoromethoxyphenylacetonitrile. The boiling point is 78 to 80 ° C (20 Pa).

Example 13

An alternative procedure for the preparation of α-isopropyl-4-trifluoromethoxy-phenylacetonitrile

A. Preparation of 4-trifluoromethoxybenzyl chloride.

A mixture of trioxane (355 mg), zinc chloride (340 mg) and trifluoromethoxybenzene (600 mg) was heated to 73 ° C while bubbling hydrogen chloride gas through the reaction mixture. The reaction mixture was cooled to room temperature and diluted with ether. The organic phase was washed with saturated sodium carbonate solution and water. Removal of the solvents gave the product as a colorless liquid (1.42 g).

B. Preparation of 4-Trifluoromethoxyphenylacetonitrile

The above chlorinated compound was converted to the corresponding nitrile by the procedure of Example 3. A yield of 93% was obtained.

C. Preparation of α-isopropyl-4-trifluoromethoxyphenylacetonitrile

Alkylation of 4-trifluoromethoxyphenylacetonitrile was performed as illustrated in Example 4. 90% yield was obtained.

Example 14

Preparation of α-isopropyl-4-trifluoromethoxyphenylacetic acid

A mixture of α-isopropyl-4-trifluoromethoxyphenylacetonitrile (2.0 g), potassium hydroxide (3.0 g) in 35 ml of ethylene glycol and 3 ml of water was heated at 140 ° C for 8 hours. The aqueous layer was acidified with dilute hydrochloric acid and extracted with 3x11 ml ether, the extract washed with 25 ml of water, dried over sodium sulfate and evaporated to an oil (1.23 g), infrared spectrum (in Sustanci) 1700 cm ^_1.

Example 15

Preparation of .alpha.-isopropyl-44-trifluoromethoxyphenylacetyl chloride

A solution of α-isopropyl-4-trifluoromethoxyphenylacetic acid (1.2 g) and thionyl chloride (0.6 mL) in 5 mL of benzene was refluxed for 4 hours to evaporate the solvent and excess thionyl chloride to give the acid chloride as such. for esterification in Examples 16 and 17.

Example 16

Preparation atkyan-m-fenQxybenzyl and - c ^ i ^ i ^{^,} (j ^ l ^^^ · 44г if luormetboxylenylacetátu

A solution of α-isopropyl-4-trifluoromethoxyphenylacetyl chloride (4.58 mmol) in 5 mL of ether was added to an ether solution (20 mL) of α-cyano-m-phenoxybenzyl alcohol (4.58 mmol) and pyridine (0.5 mL). The mixture was stirred overnight and filtered. The filtrate and wash liquid were evaporated and the residual oil was purified on 5X2 mm silica gel plates using 1: 1 methylene chloride-hexane as eluent. The band with Rf = 0.55 was extracted with ether and evaporated to give the desired ester (0.85 g).

Infrared spectrum (in substance) 1755 cm ^-1 ,

NMR Spectrum (CDCl3)

6.8 to 7.6 (m, 13H, ArH);

6.31 and 6.28 (s, 1H, —CH — Ar), *.

CN

3.27 (d, J = 7 Hz, 1H, CH - CH (CH 3) 2),

2.0 to 2.6 (m, 1H, CH (CH 3) 2);

0.6 to 1.2 (four doublets, J = 7Hz, 6H, isopropyl CH3),

19F chemical shift of 58.8? Relative to CFCI3.

Example 17

Preparation of m-phenoxybenzyl-α-isopropyl-4-trifluoromethoxyphenylacetate

To a solution of m-phenoxybenzyl alcohol (1.89 grams) and pyridine (1 mL) in methylene chloride (6 mL) was added a methylene chloride [7 mL] solution of α-isopropyl-4-trifluoromethyl-phenylacetyl chloride prepared from the corresponding acid (2.46 g) by the method The reaction mixture was stirred overnight, washed with water, dilute hydrochloric acid solution, dilute potassium hydroxide solution, water and evaporated to an orange oil. Purification by silica gel chromatography gave the desired ester (2.76 g). ).

IR (in substance)

1738 cm ⁴ ,

NMR Spectrum (CDCl3) .delta

6.73 to 7.45 (m, 13H),

5.03 (s, 2H);

3.20 (d, J = 1.5 Hz, 1H),

2.26 (m, 1 H),

0.66 and 0.94 (two d, J = 6.6 Hz, 6H).

Example 18

Preparation of N-ethyl- and N-propyl-4-trifluoromethoxyphenylacetic acids and their esters

The procedure is as described in Example 9 except that ethyl bromide and 1-bromopropane are used instead of 2-bromopropane, and then the steps illustrated in Examples 10, 11, 12 and 14 are carried out. ethyl-4-trifluoromethoxyphenylacetic acid and propyl-4-trifluoromethoxyphenylacetic acid. These acids are then converted to the following. esters as described in Examples 15, 16 and 17. The esters of formula (I) are obtained

R'2

Ri

C2H5

C2H5

II

CN

P-С3Н7 H

П-С3N7 CN

Example 1 9

Preparation of α-bromo-4-trifluoromethylthiotoluene

Bromine (20.5 g, 0.13 mol) in 20 ml of carbon tetrachloride is slowly added to the solution

4-Trifluoromethylthiotoluene (29 g, 0.15 mol) in 90 ml of carbon tetrachloride while heating to gentle reflux with a 275 W infrared lamp. After the addition was complete, the solution was refluxed for 1 hour. Most of the solvent was removed at atmospheric pressure and the residue was then distilled under vacuum. A distillation slice weighing 15.5 g, boiling at 64 DEG-77 DEG C. under a pressure of 80-107 Pa, is 92% monobromo according to gas chromatography.

Example 20

Preparation of 4-Trifluoromethylthiophenylacetonitrile

Sodium cyanide (3.9 g, 0.08 mol) was added to 40 mL of dimethyl sulfoxide at °5 ° C under a nitrogen atmosphere. Heat is removed by α-bromo-4-trifluoromethylthiotoluene (14.3 g true NMR analysis δ

0.83 (t, J = 7.5 Hz, 3H, 2H),

1.90 (m, 2H, —CH'2—),

3.49 (t, J = 7.5Hz, —CH — CH2CH3),

5.04 (s, 2H, -OCH 2 -),

7.10 [(1I, 13H, ArH)) δ

0.84 (two triplets, J = 7.6Hz, 3H, CH3),

1.94 (m, 2H, —CH 2 -).

3.55 (t, J J = 7.4 Hz, 1H, —СНСНгСНз))

6.33 (s, 1H, -CHCN),

7.18 (m, 13H, ArH), .....................

δ

0.6 to 2.4 (m, 7H, —CH 2 CH 2 CH 3),

3.63 (tt, J = 7.2Hz, 1H, —CH — C5H7),

7.12 (m, 13H, ArH);

0.65 to 2.4 (m, 7H, - CH2CH2CH3),

3.71 (t, J = 7.3 Hz, 1H, --CH - C 3 H 7),

7.20 (m, 13H, ArH). ......

(0.053 mol) was added dropwise at such a rate that the temperature did not rise above 75 ° C due to exotherm. The red reaction mixture was heated to 90-95 ° C for about 45 minutes, then cooled to room temperature and 50-100 mL of ice water was added. The aqueous suspension was extracted with several portions of ether, and the extracts were extracted with ethyl acetate. Combine, wash with water and dry over sodium sulfate. Evaporation. 9.7 g of a dark red oil are obtained in vacuo which has a purity of 95% according to gas chromatography.

Example 21

Preparation of α-isopropyl-4-t-fluoromethylthiotenylacetonitrile

50% sodium hydroxide (13.5 mL) was added dropwise over 30 minutes to a suspension of 4-trifluoromethylthiotenylacetonitrile (9.7 g, 0.045 mol), 2-iodopropane (9.5 g, 0.056 mol) and 18crow-6-ether (0.61 g, 0.0023 mol) in 13.5 mL of benzene and the reaction temperature rises to 43 ° C due to exotherm. The mixture was stirred at ambient temperature for 2.5 hours and analysis of the aliquot by gas chromatography showed that the reaction mixture was no longer starting nitrile. . The reaction mixture was worked up by adding water and extracting with ether. The extract was washed with 10% hydrochloric acid, water and dried over sodium sulfate. Evaporation in vacuo gave 10.2 g (86.8.8%) of a red-brown oil.

Comparable results are obtained when ethyl bromide or n-propyl iodide is used instead of 2-iodopropane. Thus, α-ethyl-4-trifluoromethylthiophenyl acetonitrile and α-n-propyl-4-trifluoromethylphenylacetonitrile are synthesized.

Example 22

Preparation of .alpha.-isopropyl-4-trifluormethylthiofenyloctové .alpha.-isopropyl-4-t ^ ^i, ifluormethylthiofenylacetonitril (6.9 g actual weight, 0.0265 mole) and 50% sodium hydroxide (25 g, 0.312 mol) were combined in 53 ml of ethylene glycol and the mixture was heated under gentle reflux for 18 hours. The reaction mixture was poured into ice water and extracted with ether. The aqueous phase was acidified with concentrated hydrochloric acid and extracted again with ether. The extract was washed with water and dried over sodium sulfate. Evaporation by vacuum gave 2.05 g of an oily product.

Similar results are obtained when used as starting materials. α-ethyl-4-trifluoromethylthiophenylacetonitrile or 4-n-propyl-4-trifluoromethylthiophenylacetonitrile. This synthesis yields α-ethyl-4-trifluoromethylthiophenylacetic acid and α-n-propyl-4-trifluoromethylthiophenylacetic acid.

Example 23

Preparation of α-cyano-m-phenoxybenzyl-α-isopropyl-4-trifluoromethylthiophenylacetate

The title compound was prepared from α-isopropyl-4-trifluoromethylthiophenylacetic acid according to the procedures described in Examples 15 and 16. The product was an oil.

For C26H22F3NO3S calculated:

32% C, 4.57% H, 11.74% F,

2.89% N, 6.60% S, found:

64.27% C, 4.62% H, 11.66% F,

N, 2.68; S, 6.43%.

Similar results are obtained using α-ethyl-4-trifluoromethylthiophenylacetic acid or α-n-propyl-4-trifluoromethylthiophenylacetic acid. Α-cyano-m-phenoxybenzybethyl-4-trifluoromethylthiophenylacetate and α-cyano-m-phenoxybenzyl-α-n-propyl-4-difluoromethylthiophenylacetate are obtained.

Example 24

Preparation of m-phenoxybenzyl-α-isopropyl-4-difluoromethylthiophenylacetate

Α-Isopropyl-4-trifluoromethylthiophenylacetic acid was used as starting material and the procedure of Examples 15 and 17 was followed. The product was obtained as an oil.

Example 25

Preparation of α-isopropyl-4-mercaptophenylacetic acid

A solution of α-isopropyl-4-difluoromethylthiophenylacetonitrile (15.7 g, 0.065 mol) in sodium hydroxide (50%, 42 g) and ethylene glycol (80 mL) was refluxed for 18 hours. The reaction mixture was poured into ice water and extracted with ether. The alkaline layer was acidified at 15-20 ° C with concentrated hydrochloric acid and the mixture was extracted with ether. The ether extract was washed with water, saturated sodium chloride solution and evaporated to an oil (11.4 g, 83%). product.

Example 26

Preparation of .alpha.-isopropyl-4-difluoromethylthiophenylacetic acid

Sodium hydroxide (18.4 g, 0.46 mole) in 50 milliliters of water and a-isopropyl-4-Mercaptophenylacetic acid (11 g, 0.05 mole) in 40 ml of dioxane were combined and heated to 50 C. Chlorodifluoromethane ^L0 ( Freon-22) is slowly passed under the surface of the liquid and bubbled through the reaction mixture, immediately resulting in exotherm to the mixture to 75 ° C. The addition was continued until the exotherm slowly subsided (about half an hour). The reaction mixture was cooled to room temperature and 100 mL of ice water was added. The aqueous layer was extracted with 3X200 mL of ether and then acidified at 15-20 ° C with concentrated hydrochloric acid. The resulting oil was separated by extraction with ether. The ether solution was washed with water and saturated sodium chloride solution, dried over sodium sulfate and evaporated in vacuo. 10.2 g of a dark brown resin are obtained. This resin was used in the final esterification step without further purification.

Example 27

Preparation of α-cyano-m-phenoxybenzyl-α-isopropyl-4-difluoromethylthiophenylacetate

Α-Isopropyl-4-difluoromethylthiophenylacetic acid was used as starting material and the procedure of Examples 15 and 16 was followed. The product was obtained as an oil.

198712

For C26H23F2NO3S calculated:

% C, 66.79;% H, 4.96;% F, 8.13;% S, 3.00%;

% C, 66.58;% H, 5.13;

2.87% N, 6.95% S.

Example 28

Preparation of α-isopropyl-4-hydroxyphenylacetic acid

A mixture of α-isopropyl-4-methoxyphenylacetonitrile (40.0 g) and hydrobromic acid (48 percent, 200 mL) was refluxed at 126-128 ° C using an oil bath for 14 hours. The reaction mixture was diluted with ice and water, extracted several times with ether, washed with water and evaporated to a solid residue. The solid was boiled with chloroform (200 mL), cooled, filtered and dried.

Yield: 23.8 g, m.p. 172-174 ° C.

IR (nujol)

3250 to 2900 (wide band, OH)

1690 cm ^-1 (C = O).

Similar results are obtained when α-ethyl-4-methoxyphenylacetonitrile or α-n-propyl-4-methoxyphenylacetonitrile is used as starting material. This afforded α-ethyl-4-hydroxyphenylacetic acid and α-n-propyl-4-hydroxyphenylacetic acid.

Example 29

Preparation of α-isopropyl-4-difluoromethoxyphenylacetic acid

Magnetically stirred mixture at 80 degrees Celsius consisting of 10.00 g (0.0515 mol) of α-isopropyl-4-hydroxyphenylacetic acid, 65 ml of dioxane, 19.08 g (18.56 g of act, weight, 0.464 mol) of hydroxide Sodium chloride and 30 ml of water are bubbled through 46 g (0.532 mol) of chlorodifluoromethane for 4 hours. The reaction mixture was poured into 250 ml of ice-water and the resulting mixture was washed with ether, acidified to pH 3 with concentrated hydrochloric acid and then extracted with 200 ml of ether. The ether solution was washed once with 100 ml of water, dried over sodium sulfate, filtered and evaporated to a white paste. A mixture of hexane and methylene chloride was added and the resulting mixture was filtered to remove the starting material. The filtrate was evaporated to give

5.41 g of a clear brown oil. NMR is estimated to have a purity of at least 85 percent.

NMR (CDCl 3 - d 6 pyridine), δ

7.43 (d, J = 8.2 Hz, 2H), 7.08 (d, J = 8.2 Hz, 2H), 6.57 (t, J = 74.3 Hz, 1H),

3.63 (s, impurity),

3.25 (d, J = 10 Hz, 1H);

2.37 (m, IH);

1.19 (d, J = 6.5 Hz, 3H)

0.78 [d, J = 6.5 Hz, 3H], 13.82 (s, 1H).

Similar results are obtained using α-ethyl-4-hydroxyphenylacetic acid or α-n-propyl-4-hydroxyphenylacetic acid. This afforded α-ethyl-4-difluoromethoxyphenylacetic acid and α-n-propyl-4-difluoromethoxyphenylacetic acid.

Example 30

Preparation of m-phenoxybenzyl-α-isopropyl-4-difluoromethoxyphenylacetate

Α-Isopropyl-4-difluoromethoxyphenyl acetic acid was used as starting material and the procedure of Examples 15 and 17 was followed. The product was obtained as a pale yellow oil.

For C 25 H 24 F 2 O 4 calculated:

70.41% C, 5.67% H, 8.91% F, _{η & 1θ} Ζ 6Π0 '

% C, 73.36;% H, 5.96;% 10.56.

Similar results are obtained using α-ethyl-4-difluoromethoxyphenylacetic acid or α-n-propyl-4-difluoromethoxyphenylacetic acid. There was thus obtained m-phenoxybenzyl-α-ethyl-4-difluoromethoxyphenylacetate or α-n-propyl-4-difluoromethoxyphenylacetate.

Example 31

Preparation of α-cyano-m-phenoxybenzyl-α-isopropyl-4-difluoromethoxyphenylacetate

Using α-isopropyl-4-difluoromethoxyphenylacetic acid and following the procedures of Examples 15 and 16, the title product was obtained as an oil.

NMR (CDCl 3) δ

0.88 (four doublets, J = 6Hz, 6H, СНз),

2.30 [m, 1H, -CH-N (S) 2],

3.24 [d, J = 10.1 Hz, 1H, C H-C H]

6.33 (two singlets, 1H, —CHCN),

6.45 (t, J = 74 Hz, 1H, CHF2O--),

7.16 m, (13H, ArH).

For C 26 H 23 F 2 NO 4 calculated:

69.17% C, 5.13% H, 8.42% F,

3.10% N, found:

% C, 69.41;% H, 5.20;

3.70% N.

Similar results are obtained using α-ethyl-4-difluoromethoxyphenylacetic acid or α-n-propyl-4-difluoromethoxyphenylacetic acid. This afforded α-cyano-m-phenoxybenzyl-α-ethyl-4-difluoromethoxyphenylacetate or α-cyano-m-phenoxybenzyl-α-n-propyl-4-difluoromethoxyphenylacetate.

Example 32

Preparation of m-phenoxybenzyl-α-isopropyl-4-trifluoromethylsulfinylphenylacetate

A mixture of 10.0 g of m-phenoxybenzyl-α-isopropyl-4-trifluoromethylthiophenylacetate of Example 24 and 4.1 g of m-chloroperbenzoic acid (85%) was heated to 100 mL in methylene chloride for several hours. The mixture was filtered and the concentrated residue was purified on a dry silica gel column using 2: 1 methylene chloride-hexane. Obtained as a light yellow oil.

Similar results are obtained using m-phenoxybenzyl-1-α-ethyl-4'-trifluoromethylthiophenylacetate or m-phenoxybenzyl-α-n-propyl-4-trifluoromethylthiophenylacetate. There was thus obtained m-phenoxybenzyl-t-ethyl-44-trifluoromethylsulfinylphenylacetate or m-phenoxybenzyl-ca-n-propyl fluoromethylsulfinylphenylacetate.

Example 3 3

Preparation of α-cyano-m-thenoxybenzyl-α-ethyl-3-difluoromethylsulfonylphenylacetate

A mixture of 10.0 g α-cyan-m-phenoxybenzyl-ethyl-3-difluoromethylthiophenylacetate and 9.0 g m-chloroperbenzoic acid (85%) was refluxed overnight in 100 ml ethylene dichloride. After filtration and concentration, the mixture was purified by dry silica gel column chromatography using 2: 1 methylene chloride-hexane. Obtained as a yellow oil.

Similar results are obtained using atkyan-m-phenoxybenzyl α-isopropyl-4-trifluormethylthiofenylacetátu or .alpha.-cyano-m-phenoxybenzyl · -anp гору 1 -A-U ¹ ifluormethylthlofenylacetátu. There was thus obtained cyanogen-m-phenoxybenzyl-α-sopropyl-4-tritluoromethylsulfonylphenylacetate or α-cyano-m-phenoxybenzyl-n-propyl-44-difluoromethylsulfonylphenylacetate.

Example 34

Preparation of 44-Fluoromethoxy-1 _? b-Climethylatropic acid

To a solution of p-trifluoromethoxyphenylacetic acid (22 g, 0.1 mol, obtained by alkaline hydrolysis of the nitrile prepared according to Example 12) in ether [50 mL] was added a commercially available solution of isopropylmagnesium chloride (0.2 mol) in ether at ice bath temperature. The reaction mixture was stirred at room temperature for 2 hours, dry acetone (5.8 g, 0.1 mol) was added to the reaction mixture, and the mixture was refluxed for 5 hours. The reaction mixture was cooled, carefully acidified with aqueous sulfuric acid and extracted with ether. The combined organic layers were extracted with 10% sodium carbonate solution. The alkaline layer was acidified with hydrochloric acid and extracted with ether. The combined organic layers were extracted with 10% sodium hydroxide solution. The alkaline layer was acidified with hydrochloric acid and extracted with ether. The ether extract was dried over sodium sulfate and evaporated. 4-Trifluoromethoxy- (3H (dimethylatropic acid) was obtained as a residue.

Example 3 5

Preparation of m-phenoxybenzyl-4-trifluoromethoxy-4-sopropenyl-phenylacetate

To a solution of _{4-trifluoromethyl-I} / ^ dimethyIt atropic acid (13.9 g, 0.05 mole) and triethylamine (6.1 g, 0.06 mol) in acetone (100 ml) was added m-phenoxybenzyl ( 13.2 g (0.05 mol) at an ice bath temperature and the mixture was refluxed for 4 hours. The mixture was poured into cold dilute hydrochloric acid and extracted with ether. The ether layer was washed with 10% hydrochloric acid, water, dried over sodium sulfate and evaporated. A hydroxyester is obtained which is dehydrated by treatment with phosphorus pentoxide in benzene at 80 ° C for 18 hours. The crude ester is obtained by filtering the reaction mixture and removing the solvent. Purification was by silica gel dry column chromatography using methylene chloride-hexane as eluent. The product is obtained as a yellow gum.

Example 36

Preparation of 4-Trifluoromethoxy-α'-tert-butylbenzyl alcohol

To a solution of commercially available tert-butyl magnesium chloride in THF (1.0 mol) was added a solution (50 mL) at 38-40 ° C under a nitrogen atmosphere. The reaction solution was stirred at room temperature overnight and carefully acidified with dilute sulfuric acid at 15-20 ° C. Ether is added, the organic phase is washed with water, dried over sodium sulfate and evaporated to a resinous solid. The crude material was purified by silica gel chromatography to give the alcohol used in Example 37.

Example 37

Preparation of β- (1-chloro-2,2-dimethylpropyl) - α 4 α-trifluoroisole

To fresh distilled thionyl chloride (14.87 g, 0.125 mol) cooled in an ice bath containing salt was added portionwise the neopentyl alcohol of Example 36 (12.4 g, 0.05 mol) over 30 minutes. After evaporation of the excess thionyl chloride a solid is obtained.

Example 37

Preparation of α-tert-butyl-4-trifluoromethoxyphenylacetic acid

The neopentyl chloride prepared in Example 37 is converted to the Grignard reagent and then treated with carbon dioxide as described by Weinstein and Morse [Journal of the American Chemical Society 74, 1133 (19512)]. The desired acid was obtained as a white solid.

Example 39

Preparation of α-cyano-m-phenoxybenzyl-α-tert-butyl-4-trifluoromethoxyphenylacetate

Α-tert-butyl-4-trifluoromethoxyphenylacetic acid was used as starting material and the procedure of Examples 15 and 16 was followed. The product was obtained as an oil.

Example 40

Insecticidal activity

The insecticidal activity of the compounds of the invention is demonstrated in the following tests using Heliothis virescens (Fabricius), Empoasca abrupta DeLong and Aphis fabae (Scopoli) as an aphid test species. The procedure used is as follows:

Heliothis virescens (Fabricius)

První instar

Cotton with two developed right-hand leaves is soaked for 3 seconds in a test solution (35% water / 65% acetone) containing 300, 100 or 10 ppm of the test compound. Each leaf is placed in a wick cup and a piece of so-called cheese-infested cloth infested with 50 to 100 freshly hatched larvae is added before the lid of the cup is closed. After three days at 26.7 ° C and 50% relative humidity, the wells are examined and the mortality of newly hatched larvae recorded. The data are reported as percent mortality in Table I.

Aphis fabae (Scopoli) - Poppy Aphid

Five-inch fiber pots, each containing a cress plant about 50 mm high and infested with 100-150 aphids two days in advance, are placed on a turntable (4 rpm) and sprayed with 35% water / 65% solution over two turns. acetone containing 100, 10, 1.0 and 0.1 ppm of the test compound using a DeVilbiss atomizer at a pressure of 137 kPa. The spray nozzle is held at a distance of about 15 centimeters from the plants and sprayed to provide complete coverage of the aphids and plants. The sprayed plants are placed on white enamel trays. Mortality is determined after one day at 21 ° C and 50% relative humidity.

Data are reported as percent mortality determined at a certain dose (Table I).

Empoasca abrupta DeLong

A Sieve bean plant with a primary leaf unfolded to 7.60-10.20 centimeter is soaked in a 35% water / 65% acetone solution containing 100, 10, or 1 ppm of the test compound. The soaked plant is placed in a fume cupboard to dry and then a 2.5 cm long leaf tip is cut and placed in a 10 cm petri dish with wet filter paper at the bottom. 3-10 nymphs at the second instar stage are placed in the dish and the dish is then placed. he covers. The plates are kept at 26.7 degrees Celsius and 50% relative humidity for two days and mortality is determined. Data obtained. are given in Table I. In these tests, permenthrin is used as the standard or comparator.

Table I

Insecticidal evaluation

Compound Mortality% Empoasca

Heliothis virescens abrupta - Aphis fabae

Larvae 1. instar ppm ppm

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Compound Mortality% Empoasca

Heliothis virescens abrupta - Aphis fabae

Larvae 1. instar ppm ppm

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Example 41

Insecticidal activity

The insecticidal activity of the compounds of the invention is further demonstrated in the following tests.

The procedures used to evaluate the effect of the Anaceles quadrimaculatus (Say), Epilachna varivestis (Mulsant) and Spodoptera eridania are as follows:

Anopheles quadrimaculatus (Say) milliliters of a 35% water / 65% acetone solution containing 300 ppm of the test compound is pipetted into a 400 ml beaker containing 250 ml deionized water. The solution was mixed by pipette to reach a concentration of 1.2 ppm. Aliquots of this solution are taken and further diluted to 0.4, 0.04 and 0.004 ppm. The wax paper ring 0.6 cm wide that fits in the beaker is allowed to float on the surface of the test solution so that the eggs do not flood into the meniscus of the liquid and dry on the beaker wall. With a spoon made from a sieve, pick up and transfer about 100 0 to 24 old eggs into a test beaker. After two days at 26.7 ° C and 50% relative humidity, it is examined whether larvae have hatched. Table II shows the percent mortality.

Epilachna varivestis Mulsant

Bean bean plants (2 per pot) with primary leaves 7.5 to 10 cm long are soaked in a test solution with an active substance concentration of 300, 100, 10 or 1 ppm and allowed to dry in a fume cupboard. One leaf was removed from the plant and placed in a 10 cm Petri dish containing bottom filter paper and 10 last instar larvae (13 days after hatching). The day after treatment, another leaf is removed from the plant and left to the larvae as food after removal of the remaining leaf. Two days after treatment, the larvae are given a third leaf, which is usually the last. If the larvae continue to eat, they are given the fourth leaf on the third day after the test. Treatment is now discontinued and waiting until the adult insect hatches, usually hatching begins about nine days after treatment. After hatching is completed, the mortality of larvae, pupae, or adult insects is determined in each dish; deformed pupae or adult insects; transient individuals before puping and hatching; or any other deviation from normal development, transformation and hatching of pupae or adult insects.

The data obtained are shown in Table II.

Spodoptera eridania Cramer

Bean plants (bean) with two unfolded primary leaves of 7.5 to 10 cm are soaked in the test solutions for 3 seconds with stirring and then allowed to dry in a fume cupboard. After drying, the leaves are separated and each leaf is placed on a 10 cm Petri dish containing a piece of wet filter paper and 10 third instar larvae approximately 1 cm long. Cover the petri dishes and place in a temperature and humidity controlled room at 26.7 ° C and 50% relative humidity for 2 days.

After two days, mortality was determined. The results obtained are shown in Table II.

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Insecticidal evaluation

Compound Mortality (%) by σ)

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Compound Mortality (%)

Anopheles Spodoptera larvae Epilachna quadrimaculatus eridania varivestis ppm ppm ppm

1.2 0.4 0.04 0.004 1000 100 10,300 100 IC

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Anopheles Spodoptera larvae Epilachna quadrimaculatus eridania varivestis ppm ppm ppm

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Example 4 2

Insecticidal activity

Tetranychus urticae (Koch) - Weaving Spider

Bean plants (monthly bean) with 3 primary leaves 7.5 to 10 cm long are infested with about 100 adult phosphate-resistant mites, calculated per leaf, 4 hours prior to use in this test to allow them to lay eggs prior to treatment. The contaminated plants are immersed for 3 seconds with stirring in a solution having an active ingredient concentration of 1000, 300, 100 or 10 ppm and the plants are allowed to dry in a fume cupboard. After 2 days at 26.7 ° C, the mortality of adult mites on a single sheet under a stereoscopic microscope at 10X magnification is determined. The next leaf is left on the plant for an additional 5 days and then examined at 10X magnification to determine the mortality of eggs and newly hatched nymphs, thereby determining the ovicidal and residual effect. The results are shown in Table IIL

Heliothis virescens - Fabricus

Third instar

The three cotton plants with the uterus just unfolded are immersed in a 1000 or 100 ppm active ingredient solution and allowed to dry in a fume cupboard. After drying, each uterus is cut in half and 10 leaf portions are placed in 28 g medical cups of plastic containing

A 1.25 cm long dental wick saturated with water and 1 third instar larvae is added. The cup is covered and held at 26.7 ° C and 50% relative humidity for 3 days, and then mortality is determined. The test results are shown in Table III.

Trichoplusia ni Hubner

Third instar

The true leaf on the cotton plant is immersed with stirring for 3 seconds in a test solution containing 1000, 100 or 10 ppm of the test compound and removed and allowed to dry in a fume cupboard. After drying, the leaf is placed in a 9.0 cm petri dish with wet filter paper at the bottom. Ten third instar larvae are added and the dish is covered. Mortality was determined after 3 days at 26.7 ° C and 50 ± 10% relative humidity.

The results are shown in the table

III.

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Insecticidal activity

Compound 0 / o Mortality

Heliothis virescens Trichoplusia ni mites resistant to third instar phosphate in third instar ppm ppm ppm

1000 300 100 10 1000 100 1000 100 К

Compound% Mortality

Heliothis virescens Trichoplusia ni mites resistant to third instar phosphate in third instar ppm ppm ppm

i 0-0

Example 43

Soil insecticidal activity

Diabrotica undecimpunctata howardi, Barber mg of compound is diluted to 10 ml with acetone, and a stock solution (A) is formed. 2 ml of this solution is then diluted to 10 ml with acetone and solution B is formed. Approximately 0.7 g of Rigga ABB talc is then placed in a 28 g wide-necked flask and 1.25 ml of the selected solution is added to the talc to prepare the following concentrations :

1,25 ml of solution A - 56 kg / ha a

1.25 ml of a solution of 11.2 kg / ha.

The selected test solution is mixed with talc so that it is pre-wetted before being dried for 10 to 15 minutes in an oven where it is air-dried. 25 ml of wet sterilized potted soil and about 0.6 g of millet seed (larvae feed) are then added to containers containing the test compound. The containers are sealed and the contents are mixed on a withdrawal mixer. Ten larvae, which are 6-8 days old, are then added to each flask. The containers are then loosely capped and placed in a constant-illumination room at 26.7 ° C and 50% relative humidity. Mortality was determined after 6 days.

In this test, 100% suppression at a concentration of 56 kg / ha and 70% suppression at a concentration with Diabrotica undecimpunctata howardi were obtained with n-cyanophenoxybenzyl- and isopropyl-4-trifluoromethoxy phenylacetate.

11.2 kg / ha.

Example 44

Residual insecticidal activity obtained in the treatment of cotton plant leaves

Young cotton plants with at least 2 developed true leaves growing in 10 cm plastic pots are immersed, usually one leaf, in a solution of the test compound in a mixture of 65% acetone and 35% water with stirring for 3 seconds. The concentration of each compound in the solution is 30 ppm, 100 ppm, 300 ppm or 900 ppm active ingredient.

After drying, the leaves are removed from two plants of 2 leaves each and placed in petri dishes (90 mm x 10 mm) on moist filter paper (9 cm Whatman # 1). Five third instar larvae are placed on each leaf and the Petri dish is covered. The infested dishes are then placed in a constant-light area at 26.7 ° C and 50% relative humidity. After 72 hours, the larvae were counted.

The remaining plants are placed in a greenhouse with high-intensity illumination adjusted to provide 14 hours of light per day. After 3, 7, 10 and 14 days in the greenhouse, leaf samples were tested for third instar larvae infestation.

1BB712

Table IV

Residual insecticidal activity of test compounds on cotton plants using third instar larvae of Heliothis vírescens Compound Residual effect days

Batch 0 3 7 10 14 ppm 14- 24 ^ 4- 14- 24 — H 14- 24-4- 14- 24-4- 1-H 2 + 4oo o

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24-4- = average drought damage (%)

Example 1 5

Ixodicidal activity

Effective control of tick larvae is demonstrated in the following assays using Boophllus microplus larvae, a tick that can remain on a single host during its three developmental stages, ie, larvae, pupae, and adult. In these tests, the 10% acetone-90% water mixture contains 0.025, 0.1, 0.5, 2.5 or 12.5 ppm of the test compound. The 20 larvae are sealed into a pipette sealed at one end with gauze, and the solution containing the test compound is then pipetted through a vacuum hose to mimic the spray system. The ticks are then kept at room temperature for 48 hours and mortality is determined. The results obtained are shown below.

Table V

Percent mortality of Boophilus microplus tick larvae

Compound ppm 12.5 2.5 0.5 0.1 0.025

Table Via

Percent mortality of larvae of Boophilus microplus Compound

F ^ CHO

CN

CH-CO-O-CH i

O

0.1 ppm

0.01 ppm

0.001 ppm

0.0001 ppm

0.00001 ppm

100 ALIGN!

100 ALIGN!

100 ALIGN!

The above procedure was repeated except that the concentration of the test compound was 100 ppm.

Table VIb

Percent mortality of larvae of Boophilus microplus

Compound

100 ppm

CN I CH-CO-O-CH I CH (CH 2>

CH-CO-O-CH

CH 2 CH 2 F 2 CO 4 γ-CH-CO-CH (CH 3

CN

AND

CH-CO-O-CH

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

100 ALIGN!

Example 46

The potency of the compounds of the invention for controlling adult ticks of Boophilus microplus is illustrated by the following tests in which the test compound is dissolved as described in Example 22, except that solutions containing 125, 52.6, 31.2, 15 are prepared. 6 or 7.3 ppm of the test compound.

Adult saturated female ticks are immersed in the test solutions for 3 seconds, placed in separate containers and maintained for 48 hours. hours in an area of 26.7 ° C and 50% relative humidity. Towards the end of this time, the ticks are examined and the eggs are counted. Females that do not load eggs are considered dead. The data obtained are shown in Table VII.

Ixodicidal activity against adult ticks of Boophilus microplus

Compound Percentage mortality of adult ticks at active substance concentration (ppm)

Example 47

The efficacy of the compounds of the invention for controlling Cochliomyia hominivorax, a highly malignant pest of cattle, is demonstrated in the following assay. Cochliomyia hominivorax larvae in the first · instar stage receive food consisting of a mixture of ground beef (8.0 g), blood (7.0 ml), water (2.1 ml) and 0.9 ml of a preparation containing 1, 5 or 25 ppm test compound.

The test involves two experiments - each with 20 larvae at a certain dose. The larvae are fed 24 hours as desired with the mixture. After this time, the number of dead larvae was determined for each dose and each experiment and the percent mortality was calculated. The data obtained are shown in Table VIII.

Table VIII

Efficacy of compounds for controlling Cochliomyia hominivorax larvae

Compound Mortality Percentage (ppm)

Example 48 .......

LC 50 determination for test compounds against Heliothis vlrescens on cotton plants.

Young cotton plants with at least 2 developed true leaves growing in 10 cm plastic pots are immersed, usually one sheet at a time, into a solution of the test compound in a mixture of 65% acetone and 35. . %. of water while stirring for 3 seconds. The concentration of each compound of the solution is 1.1 ppm, 2.8 ppm, 7.5 ppm, 20 ppm, 60 ppm or 150 ppm of the active ingredient.

After the leaves have dried, 2 leaves from two plants are cut off and placed on a petri dish (90 mm x 10 mm) on moist filter paper (9 cm Whatman # 1). Five third instar larvae are placed on each leaf and the petri dish is closed with a lid. The infested dishes are then placed in a constant illumination area at a temperature of 26.7 ° C and 50% relative humidity. Larvae are counted after 72 hours. Each test is repeated four times. IX, which shows that the compound of the invention is about 2 to 5 kilograms more effective in suppressing Heliothis virescens than known compounds evaluated in the same assay.

Table IX

LC50 determination of test compounds against Heliothis virescens at the third instar stage

Compound Dose Number of individuals Number of insect dead LC 50 (ppm) in insect specimen test φ

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Example 49

LC 50 determination of test compounds against adult mosquitoes Anopheles quadrimaculatus Say

Test compounds are dissolved in acetone to the desired concentration in ppm. To prepare the aerosol application, the insecticidal solution (0.15 ml) is pipetted into the top of the nozzle and then sprayed through the nozzle. The atomized droplets are carried by an air flow (6436 m / h) onto the mosquitoes in the cages and allowed to act for 4 to 5. seconds (25 adult females / cage). The mosquitoes are then anesthetized for 3 to 4 seconds with carbon dioxide and transferred to storage cages. These are placed in space. with a temperature of 26.7 + 1 ° C and a relative humidity of 46 + 2%. After 24 hours, mortality was determined.

The data obtained are shown in Table X, which shows that the compound of the invention is approximately 4X more potent than the known compound for controlling adult mosquitoes Anopheles quadrimaculatus.

Table X

LC 50 determination of test compounds against adult female Anopheles quadrimaculatus

Compound

Concentration (ppm)

Mortality Approximate (%) value

LC50 (ppm)

0.5 10 5 - 1,0 10 2,0 5 3.0 5 5.0 52 15.0 95 5.0 (1) io (2) '6 10.0 14 26 20.0 66 60 40.0 62 78 80.0 92 90

(1) 21 (2) 18,8 and -ζζ-c w-co-o-cw-f ^ jr CH (CHJ, + Data obtained in 2 different tests + - + Published in South Africa Patent Application 73/4462 (1) = test 1 (2) = test 2

Example 1 a d 5 0

Residual insecticidal activity determined by application of small volumes of test compounds

Test compounds are dispersed in a 65% acetone-35% water mixture in sufficient quantity to provide 0.08 kg / ha of the compound in 19.30 liters of water. The cotton plants are then placed in a spray cabinet. and sprayed from above with a fixed sprayer.

After drying the leaves are always removed from the .. 2 ......

of 2 leaves each and the leaves are placed in Petri dishes (90 mm x 10 mm). on wet filter paper (9 cm Whatman No. 1). Five third instar larvae of Heliothis virescens are placed on each leaf and the petri dishes are covered with a lid. The contaminated dishes are then placed in a constant illumination area at a temperature of 26.7 ° C and a relative humidity of 50%. After 72 hours, the larvae were counted.

The remaining plants are placed in a greenhouse with high light intensity. Leaf samples · are infested after 3, 7,. 10 and 14 days with Heliothis virescens' larvae at the third instar stage.

The results obtained are shown in Table X1.

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Table XI

Resulting insecticidal activity against Heliothis virescens determined for low-volume spraying of cotton plants

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47 48 Example 51 Strengthen the ixodicidal activity of the compounds of the invention at a concentration of 12.5, 2.5, 0.5, 0.1, Ixodicidal activity 0.02 or 0.004 ppm. The results obtained are summarized in Table XII.

The procedure of Example 45 was used for daemon199712 o cT

in cm

Percent mortality of Boophilus microplus tick larvae

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49 ⁵⁰ Example 52 containing 100, 10 or 1 ppm of the test compound ΤΊ V The activity of the compounds of the invention for the regulation of adult ticks, living during their 3 developmental stages on multiple hosts Rhipicephalus sanguineus (R-S.) And Dermacentor variabilis (D.V.), in dogs is determined in the following tests. The test compound is formulated as described in Example 22. The amount of compound used is such that solutions of the test compound are obtained. ny. . Adult saturated female ticks are then immersed in test solutions for 3 seconds and placed in individual containers and kept in a 26.7 ° C / 50% RH area for 48 hours. At the end of this time, the ticks are examined and the eggs are counted. Saturated females that do not load eggs are considered dead. The results obtained are shown in Table XIII.

Table XIII

Ixodicidal activity against adult ticks Rhipicephalus sanguineus (R.S.) and Der-

macentor variabilis (D.V.) Compound Percent mortality in adult ticks R.S. D.V. in ppm / - \ ^N C CfOfy> C4-COOC ^ ++ - + O d 'l - V 100 100 100 10 100 90 1,100 60 Example 53 acetone / water solution containing 100, 50, 10 or 1 ppm of test compound. Then In vitro activity test against adult fleas Ctenocephalides felis the fleas were kept at room temperature and 80% relative humidity for 48 hours. After 24 and 48 hours, the fleas are examined and determined In this test, 10 adult fleas of Ctenocephalides felis are sprayed for 30 seconds mortality. The results obtained are shown in Table XIV.

Siphonaptericidal activity of test compounds

The above test is repeated except that the concentration of the test compound is 80, 40, 20, 10, 5 or 2.5 ppm. Tabulated data is the average of two experiments performed at each concentration unless otherwise indicated.

Table XlVa

Siphonaptericidní

Hours after treatment 80, the potency of the test compound

Compound

VHO -Q- СУ-С0-0 -pj-0 -Q

Mortality (%) at concentration (ppm)

20 10 5 2.5 0

100+ 70

40

0 + one attempt

Example 54

The experiment of Example 52 was repeated except that adult male and female ticks developing in multiple hosts Rhipicephalus sanguineus (R.S.) and Der macentor variabilis' (D.V.) were used. Such amounts of test compounds are used to provide solutions containing 1.0%, 0.1%, or 0.001% of the test compound. Mortality is determined 24 and 48 hours after treatment.

The data obtained are shown in Table XV below.

Table XV

Ixodicidal effect against adult ticks Rhipicephalus sanguineus (R. S.) and Dermacentor variabilis (D.V.) - values given are mean values from three experiments unless otherwise stated

Compound Concentration Adult tick mortality in%

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Example 1 5

The activity of the compounds of the invention in controlling fly flies. autumnalis is demonstrated by the following tests. The larvae of the 1-day-old Museum of Autumnalis are administered as a diet of cow dung containing 0.13, 0.25 or 0.50 ppm of the test compound.

Ten larvae are used for each dose and control, and each experiment is repeated twice.

The fly food is prepared by adding an acetone solution of an appropriate amount of the test compound to 1 kg of fresh manure and mixing the mixture in an electric mixer for 1 minute. Manure for control trials is processed. the same way, . but. for adding only. acetone. . Manure samples. splits into. of four paper cups. Any concentration effective. The substance or control experiment is carried out with two cups which are contaminated. one . day old. larvae. . Wineglasses. se. keep 7 days at. temperature. 26.7 ° C and 50% relative humidity. Then the pupae are counted in the cups, weighed and placed in plastic bottles, where the flies hatch and die. After death, flies are counted and% suppression is calculated. The data obtained are shown in Table XVI.

Table XVI

Evaluation of the effect of the compounds of the invention as potential dietary supplements in the control of in vitro manure flies of Musea autumnalis (Data presented are mean values from two experiments)

Compound

Concentration Suppression Suppression in manure zakuklení hatching (PPm) (%) of flies from pupae (%)

Control attempt

CN

0.13

0.25

0.50

0.0. 0.0 86.8 90.6 78.9 84.4 97.3 91.9

Claims (9)

Insecticidal and acaricidal composition, characterized in that it contains at least one m-phenoxybenzyl ester of 2-ynAlez as an active ingredient. -haloalkyl (oxy-, thio-, sulfinyl-, or sulfonyl) -phenylalkanoic acid of the general formula I wherein the RCF2X- group is in the m- or p-position to the carbon atom to which the alkanoic ester group is attached and wherein X is oxy, thio, sulfinyl or sulfonyl, R is hydrogen, fluoro, chloro, difluoromethyl or trifluoromethyl, R 2 is ethyl, η-propyl, isopropyl, isopropenyl or tert-butyl, and R3 is hydrogen or cyano, wherein when X is oxy, R is not fluorine, chlorine, difluoromethyl or trifluoromethyl, or an optical isomer thereof. 2. A composition according to claim 1, wherein the compound of formula (I) is a compound wherein X is oxygen and the other symbols are as defined above. 3. A composition according to claim 2, wherein the compound of formula (I) is a compound wherein the RCF2O-sku, pin is in the p-position to carbon, ke. to which an alkanoic ester group is attached and R1, R2 and R3 are as defined in 1. 4. A composition according to claim 2, wherein the compound of formula I comprises a compound wherein the RCF2O-group is in the m-position to the carbon to which the alkanoic ester group is attached and R, R'2 and R3 are as defined above. referred to in point 1. 5. A composition according to claim 1 wherein R is hydrogen or fluoro, X is oxygen or sulfur, R2 is ethyl, isopropyl or n-propyl, and R3 is hydrogen or cyano. 6. A composition according to claim 4, wherein the compound of formula (I) is a compound wherein R is fluorine, R3 is cyano and R2 is ethyl, η-proipyl, isopropyl, t-butyl or isopropenyl. 7. A composition according to claim 3, wherein the compound of formula I comprises .alpha.-cyano-m-phenoxybenzyl-.alpha.-isopropyl-4-difluoromethoxyphenylacetate, .alpha.-cyano-m-phenoxybenzyl-.alpha.-ethyl-4-trifluoromethoxyphenylacetate, and -cyan-m-phenoxybenzyl-N-isopropyl-4-trifluoromethoxyphenylacetate, m-phenoxybenzyl-α-isopropyl-4-trifluoromethoxyphenylacetate, m-phenoxybenzyl-crisopropyl-4-difluoromethoxyphenylacetate, n -cyan-m-phenoxybenzyl-α-ethyl-4 -difluoromethoxyphenylacetate, m-phenoxybenzyl-N-ethyl-4-trifluoromethoxyphenylacetate or α-cyano-m-phenoxybenzyl-N-propyl-4-trifluoromethoxyphenylacetate. 8. A composition according to claim 1, wherein the compound of formula (I) is a-cyano-m-phenoxybenzyl-.alpha.-isopropyl-4-trifluoromethylthiophenylacetate. 9. A process for the preparation of compounds of formula (I) according to claim 1, which comprises reacting a compound of formula (II) wherein A is halogen and R 2 and R 2 are as defined above with the m-phenoxyalcohol of formula III wherein R 3 is as defined above, in the presence of a tertiary organic amine as an acid acceptor and an inert organic solvent at a temperature in the range of 10 to 30 ° C.