NL193021C - Alpha-Substituted (Alpha-substituted) Isovaleric Acid 3'-Phenoxybenzyl Esters with Pesticidal Activity and Preparations Containing Such Compound. - Google Patents

Description

1 193021 α-Substituted · (α'-substituted) isovaleric acid-3'-phenoxybenzyl esters with pesticidal activity and preparations containing such a compound

The present invention relates to a'-substituted- (a'-substituted) isovaleric acid-3'-5 phenoxibenzyl esters with pesticidal activity and preparations thereof.

Such compounds are known from Dutch patent application 7608767, which relates to the preparation of benzyl and furylmethyl esters of α-aryloxy C3-C8-alkanoic acids and to pesticides containing these compounds. The esters of this reference may be substituted in the α 'position with a cyano, alkyl, alkenyl or alkenyl group. The furyl group is substituted with a benzyl group and the phenyl moiety of the benzyl group is substituted with a (fluoro) phenyloxy, -thio or -methyl group. The aryloxy group is optionally substituted with alkyl, alkoxy, alkylthio, halogen, cyano, nitro or methylenedioxy. The compounds are said to be particularly suitable for controlling certain insects and representatives of the order Arachnida such as Acarina.

New isovaleric acid esters with pesticidal activity have now been found which are substituted in the α position with a phenylamino group defined below.

The present invention provides isovaleric acid esters as defined in the preamble characterized by formula 1 on the formula sheet wherein R 1 represents hydrogen, methyl or ethyl, R 2 represents hydrogen, cyano or ethynyl, Y represents hydrogen, fluorine, chlorine or methyl, Z represents hydrogen, fluorine, chlorine, bromine, trifluoromethyl, C 1-4 alkyl, C 1 alkoxy or C 1 alkylthio as well as the salts thereof with strong inorganic and organic acids.

The compounds of the invention and their salts are useful for controlling harmful pests such as insects and mites.

Reference is also made to Dutch patent application 7309483 which relates to the preparation of pesticide preparations containing esters of araliphatic carboxylic acids, including isovaleric acid-3'-25-phenoxibenzyl esters, which are substituted in the α-position with a heteroaromatic or aromatic group, such as, for example, a with a halogen atom, cyano group, nitro group, an optionally halogen-substituted alkyl, alkenyl or alkynyl or unsubstituted phenyl group. The aryl group here is directly bound to the alpha carbon of the isovaleric acid.

The new compounds of the formula I of the invention can be prepared by reacting a primary or secondary amine of the formula 2 with an α-halogen ester of the formula 3, wherein X represents a bromine, chlorine or iodine atom. This reaction is generally conducted in the presence or presence of an organic solvent, such as hexamethylphosphoric acid triamide, tetrahydrofuran, dimethylformamide or dimethyl sulfoxide, at room temperature or higher temperature. In general, this reaction is rather slow. The reaction rate can be increased by using a catalyst, such as a small amount of potassium iodide. A good overview of amino acid syntheses and amino acid esters can be found in "Methodicum Chimicum," George Thieme Verlag Stuttgart / Academic Press, New York, Vol. 6, pp. 611-635 (1974).

The halogen esters of formula 3 can be obtained from the corresponding α-halogen isovaleric acid chloride or bromide, by reaction with a compound of formula 5. The α-halogen substituted acid chloride and α-halogen substituted acid can be obtained again by halogenation, with molecular halogen, from 1) a monocarboxylic acid, or 2) a malone ester followed by saponification, for example, using the Hell-Volhard-Zelinsky reaction and methods described in Org. Syn. Coll., Vol. 2, 93 (1943); ibid., Vol. 3, 495, 523, 623, and 848-45 (1955); ibid., vol. 4, 608 (1963); Org. Syn. 50, 31 (1970) and J. Amer. Chem. Soc. 91, 7090 (1969). Examples of other suitable methods are the reaction of N-bromosuccinimide and N-chlorosuccinimide with an isovaleric acid chloride or bromide by the methods of Harpp et al., J. Org. Chem. 40, 3420-3427 (1975) and the references cited therein. A suitable method when olefinic unsaturation is present is the alkylation of acetoacetates followed by halogenation of the anion, for example the sodium enolate and deacetylation. Rathke and med., Tetrahedron Letters, no. 43, 3995-3998 (1971) and Stotter and med., Ibid., No. 40, 4067-4070 (1972).

The compounds of formula 1 can also be prepared by reacting an acid of formula 4, or the acid chloride or bromide thereof, with an alcohol of formula 5 or the salt of the acid, such as the sodium or potassium salt, with a compound of formula 5 in which OH is replaced by chlorine or bromine.

An acid of formula 4 can be again obtained from α-halo-isovaleric acid or an alkyl (with 1 -8 carbon atoms) ester thereof, under the conditions described above, by reaction with the amine of formula 2.

1193021 2

After the reaction of an α-haloisovaleric acid alkyl ester of 1-8 carbon atoms in the alkyl group with an amine of the formula 2, the resulting ester of the compound of the formula 4 is saponified by the usual method to the amino acid of the formula 4 or a reactive derivative thereof, such as the acid chloride, acid bromide or an inorganic salt thereof, such as the sodium or potassium salt.

The compounds of the formula I according to the invention have one or more asymmetric carbon atoms. The invention includes each of the optical isomers and racemic mixtures thereof. In the following examples, the compound is obtained in the form of a racemic mixture, unless otherwise indicated.

The invention also includes salts of the compounds of formula 1. These salts are formed using acids such as hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, p-benzenesulfonic acid and methanesulfonic acid. Many compounds of formula 1 are oils which are converted to salts for ease of use and excellent stability. These salts are similarly useful as the compounds of formula 1 for controlling harmful pests.

The compounds of the formula I according to the invention are useful for controlling harmful pests, in particular insects and mites. When using one or more compounds of the formula 1 and / or their salts to control insects and mites to protect agricultural crops, for example soybeans, cotton and afalfa, one or more compounds of the formula 1 and / or the salts are to be used thereof, optionally together with a carrier, in an effective amount at the appropriate location. As the carrier, it is possible to use a liquid or solid carrier, which may contain additives such as wetting agents, dispersing agents and other surfactants.

The compounds of formula 1 can be used in preparations such as wettable powders, solutions, pollinators, granules, emulsifiable concentrates, etc. Examples of suitable solid carriers are natural and synthetic silicates and clays, carbon and charcoal granules, natural and synthetic resins, waxes, etc. Examples of suitable liquid carriers are water, aromatic hydrocarbons, alcohols, vegetable and mineral oils and ketones.

The amount of the compound (s) of the invention of the formula 1 in the composition may vary widely, but will generally be between 0.01 wt% and 90.0 wt%.

As will be shown below, the compounds of the invention are effective against many different insects and mites. The compounds of the invention effectively control insects such as mosquitoes, flies, lice, calenders and mites such as the spider mite and ticks. Depending on the special combination of the substituents in formula 1, the compounds of the invention have a broad or relatively narrow spectrum with an extremely potent action against insects and mites. Among the harmful pests against which the compounds according to the invention are effective, one can mention insects of the class Lepidoptera, Orthoptera, Heteroptera, Homoptera, Diptera, Coleoptera and Hymenoptera and mites of the Acarina class, including mites of the family Tetranychidae and Tarsonemidae and ticks like Omithodoros.

Example I

40 A. To 10 g (0.055 mol) of α-bromoisovaleric acid in 60 ml of diethyl ether, cooled to 10 ° C, first add 2.8 ml (0.0332 mol) of dimethylformamide and then slowly 5.9 ml (0.0828 mol) ) thionyl chloride. After the reaction mixture is held at 24 ° C for about an hour, the acid chloride intermediate is separated by decanting the top diethyl ether layer from the oily residue and removing the diethyl ether under reduced pressure. Thereafter, 0.055 mol of the acid chloride 45 in 100 ml of diethyl ether, cooled to 10 ° C, is first added, 11.49 g (0.0495 mol) of m-phenoxybenzyl alcohol and then, for about 15 minutes, 9 ml (0.11 mol) ) pyridine. The resulting white slurry is then stirred at 24 ° C for about 16 hours, after which a trace of water is added to decompose the excess acid chloride. The ester is separated by pouring the thick reaction mixture onto 100 ml of ice water, acidifying with 60 ml of 2N sulfuric acid and extracting three times with 100 ml portions of diethyl ether. Washing 50 of the combined ether extracts with 10 ml of 10% sodium bicarbonate followed by washing twice with 100 ml portions of water and 25 ml of a saturated sodium chloride solution and drying over calcium sulfate gives m-phenoxibenzyl α-bromoisovalerate in quantitative yield. | nmr (CCI4) δ 1.03 [m, 6, (CH2), CH1. 2.18 [m, 6, (CH, LCH)] 3.94 (d, 1, J = 8 Hz, Br-CH-C-) and 5.11 µm (s, 2, ArCH 2 O-). IR (film) 1744 cm -1 (C = 0). 11 55 B. To 3 g (0.0083 mol) of m-phenoxibenzyl α-bromoisovalerate in 6 ml of hexamethylphosphoric acid triamide at 24 ° C are first added 0.0248 mol of aniline and then a catalytic amount (28 mg) of potassium iodide.

13 I 9tfV «> I

The mixture is then heated to 65 ° C for about 90 hours, poured onto 35 ml of ice water and extracted three times with 50 ml portions of diethyl ether. The combined ether extracts are then washed first with 2N sulfuric acid, then twice with 50 ml portions of water until neutral reaction and finally with a saturated sodium chloride solution and dried over calcium sulfate. The product is concentrated under reduced pressure and separated by preparative thin layer chromatography. The m-phenoxybenzyl ester of N-phenylvaline is thus obtained.

nmr (CDCI3) δ 1.00 [m. 6, CH3) 2CHJ, 2.07 [m, 1, (CH3) 2-CH], 3.95 [m, 1, N-1H-CO2-], 4.00 (m, 1, NH) and 5 .13 ppm (s, 2, ArCHgO). IR (film) 3400 cm'1 (s) (NH) and 1738 cm'1 (C = 0)

Example II

To 0.25 g of the m-phenoxybenzyl ester of N-phenylvaline in 1 ml of hexamethylphosphoric acid triamide and 1 ml of tetrahydrofuran at 24 ° C are first added 0.12 ml of methyl iodide and then 0.092 g of potassium carbonate. The reaction mixture is then heated to 60 ° C for 4 days. The reaction mixture is then worked up by pouring it onto 5 ml of ice water and extracting three times with 10 ml portions of diethyl ether. The combined ether extracts are washed twice with 10 ml portions of water and once with a 5 ml portion of a saturated sodium chloride solution and dried over calcium sulfate. Separation of the product and purification by preparative thin layer chromatography yield the m-phenoxy benzyl ester and N-phenyl-N-methylvaline. \ | nmr (CDCl3) 6 0.92 [m, 6, (CH3) 2CH], 2.3 [m, 1, (CH3) 2-CH], 2.88 (s, 3, CH3N), 3.96 ( d, 1, N-CH-CO2), and 5.08 ppm (s, 2, ArCHoO). IR (film) 1740 (C = 0). /

Example ///

5.27 g (0.0413 mol) of p-chloroaniline and a catalytic amount (60 mg) of potassium iodide are added to 5 g (0.0138 mol) of m-phenoxibenzyl α-bromoisovalerate in 9 ml of hexamethylphosphoric triamide at 24 ° C. The reaction mixture is then stirred at 70 ° C for 4 days. The reaction mixture is then poured onto 30 ml of ice water and 10 ml of 2N sulfuric acid and extracted three times with 30 ml of diethyl ether. The combined ether extracts are then washed twice with 30 ml of water and 10 ml of a saturated sodium chloride solution, dried over calcium sulfate, filtered and evaporated. Purification of the crude product obtained by preparative thin layer chromatography gives the m-phenoxibenzyl ester of N- (p-30 chlorophenyl) valine. \ | nmr (CDCl3) δ 0.99 [m, 6, (CH3) 2CH], 2.03 [m, 1, (CH3) 2CH], 3.93 (m, 2, NH and N-CH-CO2), and 5.10 ppm (s, 2, ArCHgO-). IR (film) 3410 cm -1 (s) (NH) and 1740 cm -1 (C = 0). 1

Example IV

To 1.75 g (0.0165 mol) of toluidine and 25 mg of potassium iodide are added to 2 g (0.0055 mol) of m-phenoxibenzyl α-bromoisovalerate in 4 ml of hexamethylphosphoric acid triamide at a temperature of 24 ° C. The reaction mixture is then stirred at 60 ° C for 5 days, cooled and poured onto 20 ml of ice water and 10 ml of 2N sulfuric acid.

The m-phenoxybenzyl ester of N- (p-methylphenyl) valine is obtained by working up the reaction mixture as described in example III. \ | 40 mr (CDCl3) δ 0.99 [m, 6, (CH3) 2CH), 2.20 [s, 3, (CH3Ar), 3.90 (m, 2, NH and N-CIH-CO2), and 5.11 ppm (s, 2, ArCH 2 O). IR (film) 3400 cm -1 (s) (NH) and 1740 cm -1 (C = 0). f

By repeating the above-described method using p-anisidine instead of toluidine, the m-phenoxibenzyl ester of N- (p-methoxiphenyl) valine is obtained.

\ nmr (CDCl3) δ 0.98 [m, 6, (CH ^ CH], 2.03 [m, 1, (CH3) 2CH], 3.73 (s, 3.0CH), 3.77 ( m, 2, NH and 45 N-CH-CO 2), and 5.10 ppm (s, 2, ArCHgO-). IR (film) 3400 cm -1 (s) (NH) and 1740 cm -1 (C = 0).

Example V

A. To 5.18 g (0.0286 mol) of α-bromoisovaleric acid in 30 ml of diethyl ether, cooled to 10 ° C, is first added 1.3 ml of dimethylformamide and then slowly 3 ml (0.0429 mol) of thionyl chloride. After the reaction mixture was held at 24 ° C for 1 hour, the acid chloride was separated in quantitative yield by decanting the upper part of the ether layer and removing the solvent and excess thionyl chloride under reduced pressure.

5.7 g (0.0286 mol) of the acid chloride in 30 ml of diethyl ether at a temperature of 10 ° C are first added 5.38 g (0.0257 mol) of m-phenoxibenzaldehyde cyanohydrin and then slowly for 55 minutes 4.6 ml of pyridine. The mixture is then stirred at 24 ° C for 17 hours and then a trace of water is added to decompose the excess acid chloride. The reaction product is worked up by pouring it into 50 ml of ice water and 30 ml of 2N sulfuric acid and extracting three times with 30 ml of diethyl ether.

193021 4

By washing the combined ether extracts with 10 ml of a 10% sodium bicarbonate solution, twice with 50 ml of water and 10 ml of a saturated sodium chloride solution, drying over calcium sulfate and evaporating, m-phenoxy-a-cyanobenzyl a-bromoisovalerate is obtained .

5 nmr (CDCl3) δ 1.05 [m, 6, (CH3) 2CH], 2.23 [m, 1, (CH3) 2CH] 1 4.06 (d, 1, J = 8 Hz, Br-CH -C-) and 6.41 ppm [s, 1, ArCH (CN) Oj. IR (film) 1762 cm -1 (C = 0). II

O

B. 2.0 g (0.0052 mol) of m-phenoxy-α-cyanobenzyl α-bromoisovalerate in 4 ml of hexamethylphosphoric acid triamide at a temperature of 24 ° C are added 1.5 g (0.016 mol) of aniline and 21 mg potassium iodide. The reaction mixture is then stirred at 65 ° C for 90 hours, cooled and poured into 20 ml of ice water and 10 ml of 2N sulfuric acid. The m-phenoxy-α-cyanobenzyl ester of N-phenylvaline is obtained by working up the reaction mixture as described in Example III and purifying by preparative thin layer chromatography. . . , nmr (CDCl3) δ 1.02 [m, 6, (CH3) 2CH], 2.10 [m, 1, (CH3) 2CH], 4.0 (m, 2, -NH and N-CH-CO2) ), and 6.33 ppm 15 [s, 1, ArCH (CN) OJ. IR (film) 3400 cm-1 (s) (NH) and 2260 cm-1 (w) C 4 N), 1758 / cm-1 (C = 0).

Example VI

Following the method of Example IV, each of the compounds listed under column I below were reacted with m-phenoxibenzyl alpha-bromoisovalerate to yield the respective esters listed under column II.

4-phenetidine 2-anisidine 4-ethylaniline 25 4-fluoroaniline 4-bromoaniline 2-chloro-4-methylaniline

II

the m-phenoxybenzyl ester of 30 N- (4-ethoxiphenyl) valine, MS m / e 419.1 (M +) N- (2-methoxiphenyl) valine, MS m / e 405.2 (M +) N- (4-ethylphenyl ) valine, MS m / e 403.2 (M +) N- (4-fluorophenyl) valine, MS m / e 393 (M +) N- (4-bromophenyl) valine, MS m / e 454 (M +) 35 N- (2-chloro-4-methylphenyl) valine, MS m / e 423 (M +)

Example VII

Following the method of Example IV, each of the amino compounds listed in column III below was reacted with m-phenoxibenzyl alpha bromoisovalerate to form the respective 40 N-substituted esters under column IV below.

III

2-trifluoromethylaniline 2,3-dichloroaniline 2-fluoroaniline 45 4-isopropylaniline 4-methylthioaniline 2,6-difluoroaniline 3,4-dichloroaniline

IV

50 m-phenoxibenzyl ester of N- (2-trifluoromethylphenyl) valine, MS m / e 443 (M +) N- (2,3-dichlorophenyl) valine, MS m / e 443 (M +) N- (2-fluorophenyl) valine , MS m / e 493.2 (M +) N- (4-isopropylphenyl) valine, MS m / e 417.2 (M +) 55 N- (4-methylthiophenyl) valine, MS m / e 421 (M +) N- (2,6-difluorophenyl) valine, MS m / e 411.1 (M +) N- (3,4-dichlorophenyl) valine, MS m / e 443 (M +) b 193021

Example VIII

2,4-Dichloroaniline is reacted with m-phenoxybenzyl 2-bromoisovalerate according to the method of Example III to the m-phenoxybenzyl ester of N- (2,4-dichlorophenyl) valine, MS m / e 443 (M +).

Example IX

A. 2 g (0.011 mol) of a-bromoisovaleric acid dissolved in 10 ml of methanol with a 2N solution of sodium hydroxide in methanol at 0 ° C are titrated to the phenolphthalein endpoint. The alcohol is then removed and 10 ml of dimethylformamide and 3.54 g (0.022 mol) of p-trifluoromethylaniline are added. The reaction mixture is then heated at 100 ° C for 2 hours and then left at room temperature for 18 hours. The reaction mixture is then poured onto 50 ml of 0.1 N sodium hydroxide, washed with diethyl ether, the pH of the aqueous phase is adjusted to 4 with concentrated hydrochloric acid and extracted three times with chloroform. By combining the extracts, washing with a saturated sodium chloride solution, drying, concentrating in a rotary evaporator and removing the solvent at 50 ° C under reduced pressure, N- (p-trifluoromethylphenyl) valine is obtained.

B. A mixture of 1.84 g (0.0071 mol) of the acid of part A and 1.95 g of potassium carbonate in 10 ml of dry dimethylformamide is stirred for 30 minutes at room temperature in a nitrogen atmosphere and then added at 0 ° C 1.85 g (0.0071 mol) m-phenoxy benzyl bromide. The temperature of the reaction mixture is then allowed to rise to room temperature and then stirred for 18 hours. The reaction mixture is then worked up by pouring it into ice water and extracting three times with diethyl ether. The ether extracts are combined, washed with water and a saturated sodium chloride solution, dried over calcium sulfate and evaporated under reduced pressure to give the m-phenoxibenzyl ester of N- (p-trifluoromethylphenyl) valine, MS m / e 443 (M + , 5.9).

Example X.

According to the method of Example IX, 0.79 g of N- (2-fluoro-4-chlorophenyl) valine was reacted with 0.39 g of a-ethynyl-m-phenoxybenzyl bromide to form the a-ethynyl-m-phenoxybenzyl ester of N - (2-fluoro-4-chlorophenyl) valine, MS m / e 451 (M'f). N- (2-fluoro-4-chlorophenyl) valine is obtained according to the method of Example IX from 2-fluoro-4-chloroaniline and α-bromoisovaleric acid.

Example XI

Following the method of Example IX, 3-fluoro-4-methylaniline was reacted with α-bromoisovaleric acid to form N- (3-fluoro-4-methylphenyl) valine, which was reacted again with α-ethynyl-m-phenoxibenzyl bromide to the α-ethynyl-m-phenoxybenzyl ester of N- (3-fluoro-4-methylphenyl) valine, MS m / e 431 (M +).

N- (2-Fluoro-4-methylphenyl) valine was prepared from α-bromoisovaleric acid and 2-fluoro-4-methylaniline and reacted with α-ethynyl-m-phenoxibenzyl bromide to form the α-ethynyl-m-phenoxibenzyl ester of N- (2-fluoro-4-methylphenyl) valine, MS m / e 431 (M +, 180).

Example XII

0.53 g of N-chlorosuccinimide are added to 1.57 g of the m-phenoxybenzyl ester of N- (p-40-trifluoromethylphenyl) valine in 15 ml of benzene under stirring and in a nitrogen atmosphere. The reaction mixture is then refluxed for 2 hours. The reaction mixture is then cooled and partitioned between diethyl ether and water. The water phase is back-extracted with diethyl ether. The combined ether phases are then washed with water and a saturated solution of sodium chloride, dried over sodium sulfate, filtered and evaporated. The resulting reaction product is then applied to preparative 45 thin layer chromatography plates and the m-phenoxibenzyl ester of N- (2-chloro-4-trifluoromethylphenyl) valine, MS m / e 477.1 (M +) is obtained by eluting with a mixture of 10% diethyl ether and hexane. ).

According to the method described above, the m-phenoxy-α-cyanobenzyl ester of N- (p-trifluoromethylphenyl) valine is obtained from the m-phenoxy-α-cyanobenzyl ester of N- (2-chloro-4-trifluoromethylphenyl) valine, MS m / e 486.3 (M +) obtained.

50

Example XIII

It is bubbled through a mixture of 1.0 g of the m-phenoxybenzyl ester of N- (p-methylphenyl) valine and 10 ml of diethyl ether, with stirring and cooling in an ice bath, for 15 minutes of hydrogen halide gas. The reaction product is then filtered off, washed with diethyl ether and recrystallized from hot ethanol, giving the hydrochloride salt of the m-phenoxybenzyl ester of N- (p-methylphenyl) valine, mp: 151-153 ° C.

According to the method of Example V, by reaction of 2-fluoro-4-trifluoromethylaniline with 1193021 6 α-cyano-m-phenoxibenzyl α-bromoisovalerate, the α-cyano-m-phenoxybenzyl ester of N- (2-fluoro-4-trifluoromethylphenyl) is obtained valine, MS m / e 502.1 (M +).

Example XIV

N- (4-chlorophenyl) valine is reacted with m-phenoxy-α-methylbenzyl bromide in a mixture of tetrahydrofuran and hexamethylphosphoric acid triamide and potassium carbonate to form the m-phenoxy-α-methylbenzyl ester of N- (4-chlorophenyl) valine, MS m / e 423 (M +). The m-phenoxy-α-methylbenzyl bromide is obtained from m-phenoxy benzenaldehyde by reaction with methyl lithium to the secondary alcohol, which is brominated with phosphorus tribromide.

Example XV

A mixture of 1.17 moles of N-chlorosuccinimide, 1.23 moles of the m-phenoxybenzyl ester of N- (p-methoxiphenyl) vain and 20 ml of benzene is refluxed for 60 hours in a nitrogen atmosphere. The reaction mixture is then worked up in a mixture of water and diethyl ether. The ether layer is washed with water and a saturated solution of sodium chloride and dried over sodium sulfate. The crude product obtained is then purified by preparative thin layer chromatography and eluting with a mixture of 15% diethyl ether and hexane to give the m-phenoxybenzyl ester of N- (2-chloro-4-methoxiphenyl) -valine, MS m / e 439 ( M +, 7.4), 212 (100).

Example XVI

A solution of 8.17 mole mol α-bromoisovaleric acid in methanol with sodium methoxide is titrated to the phenol thalein endpoint. The solvent is then removed in a rotary evaporator and 1.69 g of potassium carbonate, 16.38 moles of 2-fluoro-4-methylaniline and 3 ml of hexamethylphosphoric acid triamide are added thereto. The reaction mixture is then heated at 60 ° C for 5 hours and worked up with a mixture of 5% sodium hydroxide and diethyl ether and washed three times with water. The basic layer is acidified and extracted with diethyl ether, washed with water and a saturated sodium chloride solution, dried over sodium sulfate and evaporated in a rotary evaporator to give α- (2-fluoro-4-methylphenylamino) isovaleric acid.

(2-Fluoro-4-methylaniline is obtained from 3-Fluoro-4-nitrotoluene in a Parr flask using platinum oxide and hydrogen in ethanol).

To a stirred mixture of 5.15 moles mole a- (2-fluoro-4-methylphenylamino) isovaleric acid, 6.44 moles mole potassium carbonate, 4 ml hexamethylphosphoric acid triamide and 3 ml tetrahydrofuran 5.13 moles m-phenoxibenzyl bromide to. The reaction mixture is then stirred at room temperature overnight. The reaction mixture is then poured onto a mixture of 5% sodium hydroxide and diethyl ether, extracted twice with water, washed twice with water, dried over sodium sulfate and evaporated under reduced pressure in a rotary evaporator. The crude product is then subjected to preparative thin layer chromatography using a mixture of 10% diethyl ether and hexane as the eluent to give the m-phenoxybenzyl ester of N- (2-fluoro-4-methylphenyl) valine.

nmr (CDCl3) δ 0.98 [d, 3, J - 7 Hz, CH (C 1 H 3) 2], 1.02 [d, 3, J = 7 Hz, CHiCHg).,], 2.22 (s, ) 40

and 5.13 ppm (s, 2, ArCh 2 O). IR (unmixed) 1734 cm -1 (C = OJ. IN

According to the method described above, the m-phenoxy benzyl ester of N- (4-tert-butylphenyl) valine is obtained by reaction of N- (4-tert-butylphenyl) valine with m-phenoxy benzyl bromide.

45 nmr (CDCl3) δ centered at 0.99 [d, 6, J = 7 Hz, (CH ^ CH], 1.28b [s, 9, (CH ^ C-Ar], 3.93 [m, 2 , NIH

and HN-CH-C-), and 5.11 ppm (s, 2, ArCHO). IR (film) 1743 cm @ -1 (C = 0).

The method of this example was used to prepare N- (3-chloro-4-fluorophenyl) valine 50 and N- (3-fluoro-4-methylphenyl) valine which was reacted again with m-phenoxibenzyl bromide to the m-phenoxy benzyl ester of N- (3-chloro-4-fluorophenyl) valine [MS m / e 427 (M +, 3,2), 200 (100)] and the m-phenoxy benzyl ester of N- (3-fluoro-4 methylphenyl) valine.

nmr (CDCI3) δ centered at 0.97 [d, 6, J = 7 Hz, CH (CH3) 2], 2.11 [d, 3, J = 2 Hz,) and 5.10 ppm (s, 2 , ArCJHgO). IR (unmixed) 1732 cm -1 (C = 0).

7 I9ουέI

Example XVII

A mixture of 5 g of p-trifluoromethylaniline, 2.25 g of α-bromoisovaleric acid and 2.0 g of potassium carbonate is heated at 100 ° C for 1 hour. After 1.5 hours, 5 ml of hexamethylphosphoric acid triamide is added and the mixture is heated at 100 ° C for 15 hours. The mixture is then poured onto water and potassium carbonate is added to a pH of 11. The mixture is then washed with diethyl ether and methylene chloride, the aqueous phase is acidified to a pH of 3, washed with diethyl ether and concentrated. The resulting residue is recrystallized from a mixture of hexane and diethyl ether to yield N- (4-trifluoromethylphenyl) valine, which is reacted again with m-phenoxybenzyl bromide to give the m-phenoxybenzyl ester of N- (4-trifluoromethylphenyl) valine. MS m / e 443 (M +, 5.9).

The acid, N- (4-trifluoromethylphenyl) valine, is reacted at room temperature in a mixture of dimethylformamide and tetrahydrofuran and potassium carbonate with m-phenoxy-a-ethynyl-benzyl bromide to form the m-phenoxy-a-ethynylbenzyl ester of N- (4-trifluoromethylphenyl) valine. MS m / e 467 (M +, 1.3), 216 (100).

The acid, N- (4-fluorophenyl) valine, is obtained in the manner described above from 4-fluoroaniline and α-bromoisovaleric acid and then, in the manner described above, reaction with m-phenoxibenzyl bromide to give the m-phenoxybenzyl ester of N - (4-fluorophenyl) valine is obtained. \ | nmr (CDCi3) δ centered at 0.90 [m, 6, (CH3) 2CHj, 2.0 [m, 1, (CH3) 2CH], 3.80 (m, 2, NH, and N-CH-C- ), 5.15 ppm (s, 2, ArCHgO). IR (film) 3400 cm -1 (NH). 1 11

N- (3-Fluorophenyl) valine (prepared by reacting α-bromoisovaleric acid, in a nitrogen atmosphere and for 3.5 hours, with 3-fluoroaniline at 140 ° C) with m-phenoxibenzyl bromide in a mixture of hexamethylphosphoric triamide and tetrahydrofuran and potassium carbonate react at room temperature to the m-phenoxybenzyl ester of N- (3-fluorophenyl) valine. MS m / e 393 (M +, 2) 166 (100).

N- (2-chloro-4-methylphenyl) valine is prepared in the manner described above from α-bromoisovaleric acid and 2-chloro-4-methylaniline and then, in the manner described above, reaction with m-phenoxibenzyl bromide, whereby the m-phenoxybenzyl ester of N- (2-chloro-4-methylphenyl) valine is obtained. MS m / e 423 (M +, 4), 196 (100).

Example XVIII

To 1.01 moles of triethyloxonium tetrafluoroborate in about 5 ml of methylene chloride in a nitrogen atmosphere is added 1.05 moles of the m-phenoxybenzyl ester of N- (4-chlorophenyl) valine. The reaction mixture is then stirred overnight at room temperature and poured into a mixture of diethyl ether and water. The organic phase is then washed with water and a saturated sodium chloride solution, dried over calcium sulfate and the solvent is removed. By preparative thin layer chromatography and eluting with a mixture of 20% diethyl ether and hexane, the m-phenoxy benzyl ester of N-ethyl, N- (4-chlorophenyl) valine, MS m / e 437 (M +, 3), 210 ( 100).

35

Example XIX

N- (4-Fluoro-2-methylphenyl) valine prepared from 4-fluoro-2-methylaniline and α-bromoisovaleric acid is reacted with m-phenoxibenzyl bromide as described in Example XVI to give the m-phenoxybenzyl ester of N- (4-fluoro-2-methylphenyl) valine, MS m / e 407.2 (M +, 4.5), 180 (100).

40

Example XX

To a mixture of N- (4-methylphenyl) valine in a mixture of dimethylformamide and potassium carbonate at room temperature is added m-phenoxy-α-ethynylbenzyl bromide with stirring. The reaction mixture is then stirred overnight at room temperature and worked up by partition between water and diethyl ether. The aqueous phase is then extracted twice with diethyl ether and the combined ether phases are washed with water and a saturated solution of sodium chloride, dried over sodium sulfate, filtered and evaporated. The resulting concentrate is subjected to preparative thin layer chromatography and eluting with a mixture of 10% diethyl ether and hexane to give the m-phenoxy-α-ethynyl benzyl ester of N- (4-methylphenyl) valine, MS m / e 413.1 (M +, 3.8), 162.1 (100).

50

Example XXI

For example, according to the method of Example XX, a-ethynyl-m-phenoxibenzyl bromide and N- (4-chlorophenyl) valine are reacted to form the α-ethynyl-m-phenoxy benzyl ester of N- (4-chlorophenyl) valine, MS m / e 433 (M +, 2.2), 182 (100).

1193021 8

Example XXII

N- (2,4-difluorophenyl) valine is prepared from 2,4 difluoroaniline and α-bromoisovaleric acid according to the method of example IX. Following the method of Example XX, the N- (2,4-difluorophenyl) valine and m-phenoxibenzyl bromide in a mixture of tetrahydrofuran and hexamethyl phosphoric acid triamide are reacted with potassium carbonate to form the m-phenoxy benzyl ester of N- (2,4-difluortenyl) valine. MS mIe 411 (M +, 3.5), 184 (100).

Example XXIII

N- (2-Fluoro-4-chlorophenyl) valine and m-phenoxibenzyl bromide are reacted according to the method of Example XX 10 to the m-phenoxy benzyl ester of N- (2-fluoro-4-chlorophenyl) valine, MS m / e 427 , 1 (M +, 4.1), 200 (100). N- (2-fluoro-4-chlorophenyl) valine is obtained by heating the potassium salt of α-bromoisovaleric acid and 2-fluoro-4-chloroaniline without diluent at 130 ° C for 2 hours.

The α-cyano-m-phenoxybenzyl ester of N- (2-methylphenyl) valine, MS m / e 414.1 (M +, 5.8) was also prepared from α-cyano-m-phenoxybenzyl bromide and N- (2- methylphenyl) valine.

The m-phenoxy benzyl ester of N- (2-methyl-4-chlorophenyl) valine, MS m / e 423.1 (M +, 16.9) was obtained from m-phenoxy benzyl bromide and N- (2-methyl-4-chlorophenyl ) valine.

Each of the m-phenoxybenzyl esters of N- (4-chlorophenyl) valine and N- (4-methylphenyl) valine is methylated according to the method of Example II to the m-phenoxybenzyl ester of N-methyl, N- (4-chlorophenyl) valine , MS m / e 423 (M +) and the m-phenoxybenzyl ester of N-methyl, N- (4-methylphenyl) valine, MS m / e 403.2 (M +).

According to the method of Example V, a-cyano-m-phenoxibenzyl α-bromoisovalerate with 4-methoxianiline and 4-methylaniline was reacted to form the α-cyano-m-phenoxibenzyl ester of N- (4-methoxiphenyl) valine, MS m / e 430.1 (M +) and N- (4-methylphenyl) valine, MS m / e 414.2 (M +).

By reaction of the α-cyano-m-phenoxybenzyl ester of N- (4-chlorophenyl) valine with methyl iodide, according to the method of Example II, the α-cyano-m-phenoxybenzyl ester of N-methyl, N- (4 chlorophenyl) valine, MS m / e 448.1 (M +).

Example XXIV

According to the method of Example XIII, the m-phenoxy benzyl ester of N- (2-chlorophenyl) valine, MS m / e 409 (M +) is obtained by reacting m-phenoxybenzyl bromide with 30 N- (2-chlorophenyl) valine.

Following the method of Example V, 4-trifluoromethylaniline was reacted with α-cyano-m-phenoxibenzyl α-bromo isovalerate to form the α-cyano-m-phenoxibenzyl ester of N- (4-trifluoromethylphenyl) valine, MS m / e 468.2 (M +).

35 Example XXV

10.08 g (65 mole) of 2-fluoro-4-nitrotoluene are placed in a 100 ml three-necked flask equipped with an addition funnel and reflux condenser, to which a water-gas trap is attached. The addition funnel is filled with 7.0 ml (22.3 g, 138 mole) bromine and the flask is heated. Once the temperature (of the oil bath) has reached 100 ° C, bromine is slowly added while the flask is irradiated with a 150 Watt lamp. The bromination starts quickly as soon as the temperature has risen to 160-170 ° C, easily developing hydrobromic acid. Heating is stopped after 4 hours. The cooled mixture is worked up by pouring it on ice and saturated sodium bisulfite and extracting three times with diethyl ether. The combined organic layers are washed with a saturated solution of NaHSO 3 and once with a saturated solution of sodium chloride and dried over sodium sulfate. Filtering and distilling off the solvent yield 17.0 g of a mixture of benzal bromide and benzyl bromide (1.7: 1 by nmr analyzes). The crude material is then suspended in a hypobromite solution obtained by mixing 60 g of sodium hydroxide and 20 ml of bromine in 600 ml of water. The mixture is then stirred at room temperature for 6 days and filtered to give 2-fluoro-4-nitro-α, α, α-tribromotoluene, which can be recrystallized from methanol.

50 A mixture of 8.5 g (22 mole) of 2-fluoro-4-nitro-a, a, α-tribromotoluene and 4.7 g (26 mole) of antimony trifluoride is placed in a small flask equipped with a cooler for distillation purposes. The flask is then heated slowly and the mixture is distilled first at atmospheric pressure and then under reduced pressure until no more material distills over. The distillate obtained is partitioned between 6N hydrochloric acid and diethyl ether. The organic layer was then washed once with a 6N solution of sodium hydroxide 55 and once with a saturated solution of sodium chloride and dried over sodium sulfate. Filtration and distillation of the solvent gives 2-fluoro, 4-nitrobenzotrifluoride.

A solution of 20 ml of concentrated hydrochloric acid and 15 ml of 95% ethanol (5.0 g) is added.

9 I90U £ I

24 moles) 2-fluoro-4-nitrobenzotrifluoride. The mixture is then stirred and 20 g (88 moles) of stannous chloride dihydrate added in portions over 30 minutes. The reaction is exothermic and the temperature is kept at 60 ° C during the addition. Once the addition is complete, the mixture is stirred at 60 ° C for an additional 30 minutes. The reaction mixture is then cooled and poured onto a mixture of ice and 36% sodium hydroxide and extracted three times with diethyl ether. The combined ether layers are washed once more with a saturated sodium chloride solution and dried over sodium sulfate. Filtration and distillation of the solvent gives 4-amino-2-fluorobenzotrifluoride (3-fluoro-4-trifluoromethylaniline).

Following the method of Example XVI, 3-fluoro-4-trifluoromethylaniline is reacted with the sodium salt of 10α-bromoisovaleric acid to N- (3-fluoro-4-trifluoromethylphenyl) valine, from which the m-phenoxibenzyl ester of N- ( 3-fluoro-4-trifluoromethylphenyl) valine.

This procedure is repeated using 3 * fluoro-4-nitrotoluene instead of 2-fluoro-4-nitrotoluene to prepare 2-fluoro * 4-trifluoromethylaniline, which is converted into N- (2-fluoro-4-trifluoromethyl-) phenyl) valine and then esterifies to the m-phenoxybenzyl ester of N- (2-fluoro-4-trifluoromethylphenyl) valine, MS 15 m / e 461.1 (M *).

Example XXVI

To a solution of 3.9 g of o-fluoroaniline in 50 ml of methylene chloride in a nitrogen atmosphere cooled to -20 ° C, a solution of 35 mole mol of 2,4,4,6-tetrabromocyclohexadienone in methylene chloride is added. After a few hours, the reaction mixture is poured into a 15% solution of sodium hydroxide.

The layers are then separated and the organic fraction is shaken with a 15% solution of sodium hydroxide. The methylene chloride fraction is then washed with a saturated sodium chloride solution, dried over calcium sulfate and evaporated to yield 4-bromo-2-fluoroaniline.

1.9 g of 4-bromo-2-fluoroaniline are added to 1.42 g of the potassium salt of α-bromoisovaleric acid. The mixture is then heated in a nitrogen atmosphere at 125 ° C for 3.5 hours and then cooled to room temperature. The reaction product is then poured into 2M sodium hydroxide and a mixture of diethyl ether and chloroform. The basic phase is then separated, acidified with concentrated hydrochloric acid, extracted with diethyl ether, washed with a saturated sodium chloride solution, dried over calcium sulfate and evaporated to yield N- (4-bromo-2-fluorophenyl) valine.

A mixture of 0.45 g of N- (4-bromo-2-fluorophenyl) valine, 0.25 g of potassium carbonate, 4 ml of tetrahydrofuran, 4 ml of dimethylformamide and 0.43 g of m-phenoxy-α-cyano-benzyl mesylate is stirred for 60 hours. and then pour it into water and a mixture of hexane and diethyl ether (9: 1). The organic phase is then washed with water and a saturated solution of sodium chloride, dried over calcium sulfate and evaporated. Finally, the resulting residue is applied to a preparative thin layer chromatography column and is obtained by eluting once with a mixture of 25% methylene chloride and hexane and then with a mixture of 30% methylene chloride and hexane and collecting the main band the m-phenoxy-a- cyanobenzyl ester of N- (4-bromo-2-fluorophenyl) valine, MS m / e 496 (M +).

Example XXVII

40 A flow of phosgene gas is slowly passed through 4.9 g (0.0215 mol) of N- (4-chlorophenyl) valine in 50 ml of 1,4-dioxane while the solution is stirred. The solution is cooled to maintain the temperature of the room temperature. Once the solution is saturated with phosgene, no more phosgene is introduced and the mixture is stirred in a nitrogen atmosphere at room temperature. After 45 hours, 2/3 of the dioxane is removed by distillation at the reduced pressure of a suction device. The 45 residue is then diluted with hexane and the reaction mixture is allowed to crystallize overnight at room temperature. The resulting solid product is then filtered off and washed with hexane, taking care to minimize exposure to air. Drying the solid product under reduced pressure gives 3- (4-chlorophenyl) -4-isopropyloxazolidine-2,5-dione, mp: 137-138 ° C.

A mixture of 1.7 moles m-phenoxibenzaldehyde, 0.5 g 3- (4-chlorophenyl) -4-50 isopropyloxazolidene-2,5-dione and 0.23 g potassium cyanide in about 10 ml benzene is added to a mixture. while stirring 0.1 g of benzyltriethylammonium chloride. The reaction mixture is then stirred for 50 hours. Finally one works

The reaction product is taken up by taking it up in diethyl ether, washing with water and saturated sodium chloride solution, drying over sodium sulfate and evaporating. The concentrated product is applied to plates and the m-phenoxy-α-cyanobenzyl ester of N- (4-chlorophenyl) valine is obtained by preparative thin layer chromatography and eluting with a 55 mixture of 20% diethyl ether and hexane.

Example XXVIII

According to the method of Example V, 2-fluoro-4-chloroaniline with m-phenoxy-α-cyanobenzyl α-bromoisovalerate is reacted to form the m-phenoxy-α-cyanobenzyl ester of N- (2-fluoro-4-chlorophenyl) valine, MS m / e 452 (M +). Likewise, 2-fluoro-4-chloroaniline was reacted with the sodium salt of α-bromoisovaleric acid 5 to form N- (2-fluoro-4-chlorophenyl) valine, which was then esterified with m-phenoxy-α-cyanobenzyl bromide or mesylate.

N- (4-chlorophenyl) valine with m-phenylcarbonylbenzyl bromide or the mesylate is reacted to the m-phenylcarbonylbenzyl ester of N- (4-chlorophenyl) valine, MS m / e 421 (M +) according to the method of Example XII.

10

Example XXIX

N- (2-chloro-4-fluorophenyl) valine, N- (4-chloro-3-fluorophenyl) valine and N- (4-bromo-2-fluorophenyl) valine are left according to the procedure of Example XIV with m-phenoxibenzyl bromide reacting to the m-phenoxybenzyl ester of 15 N- (2-chloro-4-fluorophenyl) valine, MS m / e 427 (M +); N- (4-chloro-3-fluorophenyl) valine, MS m / e 427 (M +, 200); N- (4-bromo-2-fluorophenyl) valine, MS m / e 471 (M +).

According to the method of Example XXVII, the m-phenoxy-α-cyano-benzyl ester of N- (4-chloro-3-fluorophenyl) valine, MS m / e 452 (M +) and the n-phenoxy-α-cyano-benzyl ester of N- ( 2-fluoro-4-methylphenyl) valine, 20 MS m / e 432 (M +) prepared from N- (4-chloro-3-fluorophenyl) valine and N- (2-fluoro-4-methylphenyl) valine and m-phenoxy -a-cyano-benzyl mesylate or bromide. The starting materials are obtained by reacting 1-4-chloro-3-fluoroaniline and 2-fluoro-4-methylaniline with the potassium salt of α-bromoisovaleric acid, respectively.

Young lima bean leaves (in water) infected with 50 adult Tetranychus urticae are dripped with the (m-phenoxy-α-cyanobenzyl ester of N-phenylvaline contained in an aqueous vehicle containing 0.025% Tween 20 (polyoxiethylene (20)). ) sorbitan monolaurate) and 0.1% of a wetting agent, diluted to three different concentrations, then the treated leaves are kept at a temperature of 24 ° C and exposed for 16 hours for 2 days, then the adult live mites are counted and, to obtain the number of infested mites, subtracted from the original total number, which is expressed as a percentage of the total.A correction is made for any mortality in the control group according to Abbott's formula. LC50 value less than 0.1%.

Individual fava bean leaves are treated with the m-phenoxybenzyl ester of N-phenyl-N-methylvaline diluted in acetone with 0.025% Tween 20 and 0.1% of a wetting agent to three different concentrations. The leaves are then allowed to dry for 2 hours and then infected with 10 adult Aphis 35 Fabae which are kept sealed on the top surface of the leaves. The treated leaves are then kept at 24 ° C for 48 hours and exposed for 16 hours. The effect is expressed as the number of dead lice calculated as a percentage of the total number. This may be corrected for control lice mortality, according to Abbott's formula. The compound has an LC50 value of less than 0.05%.

40 Fifteen 72-hour-old, adult female Museums Domestica L. are anesthetized with diethyl ether vapor. They are then treated with 1 μΙ of the m-phenoxibenzyl ester of N- (p-methylphenyl) valine diluted in acetone to three different concentrations by application to the back surface of the prothorax. They are kept for 16 hours at 25 ° C in a container filled with milk-saturated cotton and exposed for 24 hours. The effect is expressed as the number of dead animals 45 calculated as a percentage of the total number, possibly corrected for mortality among the control animals according to Abbott's formula. The compound has an LC 2 value less than 0.01%.

It is immersed in a mixture of 45 mg of a wettable powder [Attaclay (attapulgite; 60%), Marasperse N-22 (amionic dispersant; 26.7%) and Igepon T-77 (sodium N-methyl-N-oleyl taurate; 13.3%)] and 0.5 ml of water containing three different concentrations of the m-phenoxibenzyl ester of N- (p-50 chlorophenyl) valine, fifteen fed pupae of ticks (Ornithodoros nymph I). The treated dolls are kept on filter paper at a temperature of 28 ° C, a relative humidity of 64% and an irradiation of 16 hours for 7 days and then viewed. If necessary, an adjustment for mortality in the control group, using the Abbott formula, is made. The LCS0 value of the compound was less than 0.01%. 55 Two groups of 10 0-24 hour old Heliothis virescens larvae in the third development phase are treated with 1 μΙ of the m-phenoxibenzyl ester of N- (p-methylphenyl) valine in acetone, at three different concentrations, by applying this compound to the back of the chest. Two groups of

Claims (2)

11 I93U £ I also 10 larvae are treated in a corresponding manner with 1 μΙ acetone as a control. The larvae are kept separately in 25 ml plastic beakers with a synthetic medium at 25 ° C for 72 hours and exposed for 16 hours. After 72 hours, the number of dead larvae is calculated as a percentage of the total number originally treated and, if necessary, corrects for the mortality in the control groups with the Abbott formula. The l_C50 value of the compound is less than 0.5%. Each of the compounds listed below has been used to treat lice (adult Aphis fabae), using the method described above. Each of these compounds has an LC50 value of less than 15 parts per million (ppm). the m-phenoxy-α-cyanobenzyl ester of N- (2-chloro-4-trifluoromethylphenyl) valine 10 the m-phenoxy-α-cyanobenzyl ester of N- (2-fluoro-4-trifluoromethylphenyl) valine the m-phenoxybenzyl ester of N- {2-fluoro-4-trifluoromethylphenyl) valine and the m-phenoxybenzyl ester of N- (4-trifluoromethylphenyl) valine. A dilute emulsion in water is prepared using the m-phenoxibenzyl ester of N- (4-trifluoromethylphenyl) valine (51.3%) and conventional emulsifiers Atlox 3404F (an alkyl aryl sulfate; 3%), Atlox 3402F (an alkyl aryl sulfate; 3 %) and Tenneco 500-100 (a copolymer of chloroethene and ethylene ester of acetic acid; 42.7%), and apply this dilution to Tetranychus urticae as described above. The LCS0 value was less than 10 ppm. The compounds listed below have been used to treat, according to the method described above, tick pupae (Ornithodoros nymph I), wherein LC 2 values are less than 20 ppm. were obtained. the m-phenoxy-α-cyanobenzyl ester of N- (2-chloro-4-trifluoromethylphenyl) valine the m-phenoxy-α-cyanobenzyl ester of N- (2-fluoro-4-trifluoromethylphenyl) valine the m-phenoxy-α-methylbenzyl ester of N- (4-chlorophenyl) valine the m-phenoxy-a-ethynylbenzyl ester of N- (4-chloro-2-fluorophenyl) valine the m-phenoxy-a-ethynylbenzyl ester of N- (3-fluoro-4-methylphenyl ) valine the m-phenoxy-α-ethynylbenzyl ester of N- (2-fluoro-4-methylphenyl) valine the m-phenoxy-α-cyanobenzyl ester of N- (2-fluoro-4-methylphenyl) valine and the m-phenoxy α-cyanobenzyl ester of N- (4-chloro-2-fluorophenyl) valine. Each of the compounds listed below was applied to Heliothis virescens larvae using the above-described 30 method, yielding LC 2 values less than 0.1%. the m-phenoxy benzyl ester of N- (4-chloro-2-fluorophenyl) valine the m-phenoxy-α-cyanobenzyl ester of N- (4-chloro-2-fluorophenyl) valine, the m-phenoxy benzyl ester of N- (2-fluorine -4-trifluoromethylphenyl) valine, the m-phenoxy-α-cyanobenzyl ester of N- (4-bromo-2-fluorophenyl) valine, the m-phenoxybenzyl ester of N- (2-chloro-4-trifluoromethylphenyl) valine, the m -phenoxy-α-cyanobenzyl ester of N- (2-fluoro-4-trifluoromethylphenyl) valine, the m-phenoxy-α-cyanobenzyl ester of N- (2-chloro-4-trifluoromethylphenyl) valine and the m-phenoxybenzyl ester of N- ( 2-fluoro-4-methylphenyl) valine. 1. a-Substituted- (a'-substituted) -isovaleric acid-3'-phenoxybenzyl esters with pesticidal activity, characterized by formula 1 wherein hydrogen represents methyl, or ethyl, Ra represents hydrogen, cyano or ethynyl, Y represents hydrogen, fluorine, chlorine or methyl represents Z represents hydrogen, fluorine, chlorine, bromine, trifluoromethyl, CV 4 alkyl, C 1 alkoxy or C 1 alkylthio and the salts thereof with highly inorganic and organic acids. Preparation with pesticidal action, characterized in that it contains a compound according to claim 1 and 50 conventional carriers and / or auxiliaries. Hereby 1 sheet drawing