DK154642B - AMINOCARBOXYL ACID ESTERS FOR USE IN INSECTICIDES AND ACARICIDES, PREPARES FOR THE FIGHT AGAINST INSECTS AND ACARICIDES AND PROCEDURES FOR THE FIGHT AGAINST INSECTS AND / OR ACARIDES - Google Patents

Description

in

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The invention relates to novel aminocarboxylic acid esters for use in insecticides and acaricides, a composition for controlling insects and acarides and a method for controlling insects and / or acarides.

5

From the specification of DK Patent Application No. 3453/76, α-aryloxycarboxylic acid esters of the general formula are known: R '10 R' '- ^ CH-COO-CH-R' ""

I I

R, · “R.,.

Wherein R7 and R "each represent hydrogen, alkyl of 1-3 carbon atoms, lower alkoxy, lower alkyl thio, halogen, cyano or nitro, or R 'and R77 together form a methylenedioxy group, R777 represents hydrogen, cyano, lower alkenyl, lower alkynyl or lower alkyl, R7 7 7 7 represents lower alkyl, and R77777 represents: wherein X represents an oxygen atom, a sulfur atom or a methylene group, and Q represents hydrogen or fluorine. have insecticide effect.

30

However, it has been found that the compounds of the present invention have a far greater insecticide and also acaricidal effect. The compounds of the invention are characterized in that they have the general formula (A) of the characterizing part of claim 17, wherein R, R, R, R, Y, Z and t have the meanings given in claim 1.

The compounds of the invention represented by the generic formula (A) are useful agents for controlling pests such as insects and acarides (mites). Although the mode of action of

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While the compounds of formula (A) are not fully understood when these compounds are used to control insects and acarides, the compounds of formula (A) appear to be effective in controlling insects and acarides for reasons whose nature is similar to mechanisms. to the insecticides known as pyrethrins and synthetic pyrethroids.

The compounds of formula (A) can be prepared by the reaction of a primary or secondary amine of formula (I) with a haloester of formula (II) (X is bromine, chlorine or iodine).

Y 2 .Jo-4 - * 15 R3 o X - C - C - OR5 (II) if

The substituents have the meanings given above.

20

The reaction between the amine (I) and the haloester (II) is generally carried out at room temperature or above in a mixed form or in an organic solvent such as hexamethylphosphoric triamide, tetrahydrofuran, dimethyl formamide or dimethyl sulfoxide. Reaction 25 generally proceeds rather slowly. It can be supported by a catalyst such as a small amount of potassium iodide. A good account of the synthesis of amino acids and esters of amino acids is given in "Methodicum Chimicum", Academic Press, New York, vol. 6, pages 599-623, (1975).

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Halo esters of formula II can be prepared from acid halides and their ends 5 (II, where OR is replaced by bromine or chlorine) by reaction with an alcohol (R -OH). α-Halogen-substituted acid halides andenides and α-halogen-substituted acids can be prepared by halogenation -35 using molecular halogen-of (1) a monocarboxylic acid or (2) a malonic acid ester followed by saponification, e.g. using the Hell-Volhard-Zelinsky reaction and methods described in Org. Vision. Coll. Vol. 2, 93 (1943); ibid., Vol. 3, 495, 523, 623 and 848 (1955); ibid., Vols. 4, 358 and 608 (1963); Org.

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vision. 50, 31 (1970) and JACS 91, 7090 (1969). Other suitable methods include the reaction of N-bromosuccinimide or N-chlorosuccinimide 5 with an acid halide (II, where OR is replaced by bromine or chlorine) based on the procedures of Harpp et al., J. Org. Chem. 40, 3420 (1975) and the references cited therein. A suitable process in which olefinic unsaturation occurs is alkylation of acetoacetates followed by halogenation of the anion, e.g. sodium enolate, and deacetylation. Rathke et al., Tetrahedron Letters, No.

43, 3995 (1971) and Siotter et al., Ibid., No. 40, 4067 (1972).

10

The compounds of formula (A) may also be synthesized by reacting an acid of formula (III), the acid chloride or bromide thereof with an alcohol R -OH or the salt of the acid, such as sodium or potassium, with the bromide or chloride R5-X , where X represents bromine or chlorine.

, _, E2 R3 O

yy ^ .i-s-oH (1II) 20 Z '' '* = /

The substituents have the meanings given above.

Acids of formula (III) can be prepared from halo acids or lower alkyl esters of formula (IV), (R represents hydrogen or lower alkyl) using the conditions described above during the reaction with the amine of formula (I):

R3 O

X - C - C - OR (IV) i *

Following the reaction of a halogen ester of formula (IV) in which R is lower alkyl, with an amine of formula (I), the resulting amino ester of formula (V) is saponified (4)

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Ytx / -, R2 R3 O

In conventional methods for forming the amino acid of formula (III) or a reactive derivative thereof, such as the acid chloride, acid bromide or an inorganic salt thereof, such as the sodium or potassium salt.

Wherever the following terms are used in the present specification and the appended claims, these terms have the meaning defined below, unless otherwise stated below.

The term "lower alkyl" denotes an all alkyl group that is straight or branched and has a chain length of 1-8 carbon atoms. Examples of haloal cooling groups are chloromethyl, fluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 6-chlorohexyl and 2-fluoroethyl.

The compounds of formula (A) of the present invention 20 have one or more asymmetric carbon atoms. The present invention encompasses any of the optical isomers and racemic mixtures thereof. In the following examples, the compound prepared - unless otherwise stated - is a racemic mixture.

Included in the present invention are salts of the compounds of formula A. The salts are formed from strong inorganic or organic acids such as hydrogen chloride, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, p-benzenesulfonic acid, methanesulfonic acid and Lewis acid. Many of the compounds of formula A are oils which are advantageously converted to salts to be conveniently handled and formulated and have greater stability. The salts are useful for the control of pests in the same way as the compounds of formula A.

The compounds of formula A of the present invention are useful pesticides in controlling insects and acarides. In the use of the compounds of formula A for the control of insects and acarides to protect agricultural crops, e.g. soybeans, cotton and alfalfa, the compound is applied to a compound of formula A or a mixture thereof with a 5

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carries in a pest-effective effective amount. The carrier may be liquid or solid and may include adjuvants such as wetting agents, dispersing agents and other surfactants. The compounds of formula A can be used in compositions such as 5 wettable powders, solutions, powders, small grains and emulsifiable concentrates. Suitable solid carriers include natural and synthetic screens in caterers and clays, small charcoal or charcoal particles, natural and synthetic resins and waxes. Suitable liquid carriers include water, aromatic hydrocarbons, alcohols, vegetable and mineral oils and ketones. The amount of a compound of formula A in the composition can vary widely, generally in the range of about 0.01 to approx. 90.0% by weight.

The compositions of the invention are characterized by the characterizing part of claim 13.

As shown below, the compounds of the present invention are effective against many different insects and acarides. The compounds are effective pesticides for insects 20 such as mosquitoes, flies, aphids, snout beetles and acarides such as spider mites and blood mites. Depending on the particular combination of the substituents of formula A, the compounds have a broad or relatively narrow spectrum of unusually large pest control effect on insects and acarides. Among the pests against which the compounds of the present invention are pesticide-effective are insects of the order Lepidoptera, Orthophera, Heteroptera, Homoptera, Diptera, Coleoptera and Hymenoptera, and acarids of the order Acarina, including mites of the Tetranychidae and Tarsonemidae family, blood mites, such as Ornithodoros.

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The method according to the invention for controlling insects and / or acarides is characterized by the characterizing part of claim 14.

The following examples are provided to illustrate the practice of the present invention. The temperature is given in degrees Celsius.

RT means room temperature.

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Example 1 A. To α-bromoisovaleric acid (10 g, 0.055 mol) in 60 ml ether and cooled to 10 ° dimethyl formamide (DMF) (2.8 ml, 0.0332 mol) is added followed by slow addition of thionyl chloride (5 , 9 ml, 0. 0828 mol). After approx. one hour at 24 °, the intermediate acid chloride is isolated by removing the upper ether layer from the oily residue and removing the ether in vacuo. To the acid chloride (0.055 mol) in 100 ml of ether and cooled to 10 ° is added 10 m-phenoxybenzylal alcohol (11.49 g, 0.0495 mol) followed by addition of pyridine (9 ml, 0.011 mol) ca. 15 min. The resulting white slurry is stirred at 24 ° for approx. For 16 hours, then a little water is added to decompose excess acid chloride. The ester is isolated by pouring the reaction slurry into ice water 15 (100 ml), acidifying with 2N sulfuric acid (60 ml) and extracting with ether (3 x 100 ml). The combined ether extracts are washed with 10% sodium bicarbonate (10 mL), then with water (2 x 100 mL) and brine (25 mL), and dried over calcium sulfate to provide m-phenoxybenzyl-α-bromine in a quantitative manner. yield.

20 nmr (CCl4) δ 1.03 [m, 6, (CH3) 2CH], 2.18 [m, 6, (CH3) 2CH), 3.94 (d, 1, J = 8 Hz, BR-CH -C-), and 5.11 ppm (s, 2, ArOLO-).

IR (film) 1744 cm -1 (C = 0).

B. To m-phenoxybenzyl-α-bromo equivalents (3 g, 0.0083 mol) in 6 ml of hexamethylphosphoric triamide (HMPT), 24 ", aniline (0.0248 mol) is added followed by a catalytic amount of potassium aluminum. (28 mg).

3Q The reaction mixture is heated to 65 ° for approx. 90 hours and then poured into ice water (35 ml) and extracted with ether (3 x 50 ml). The combined ether extracts are washed with 2N sulfuric acid, with water (2 x 50 ml) until neutrality and with brine followed by drying over calcium sulfate. The product is concentrated in vacuo and isolated by preparative thin layer chromatography (TLC). m-Phenoxybenzyl ester of

OD

N-phenylvaline.

nmr (CDCl 3) δ 1.00 [m, 6, CH 3) 2 CH], 2.07 [m, 1, (CH 3) 2-CH], 3.95 [m, 1,> -CH-CO 2 -], 4.00 (m, 1, NH), and 5.13 ppm (s, 2, ArCH 2 O). IR (film) 3400 cm -1 (s) (NH) and 1738 cm -1 (C = 0).

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Example 2

To the m-phenoxybenzyl ester of N-phenylvaline (0.25 g) in HMPT (1 ml) and tetrahydrofuran (1 ml) at 24 ° is added methyl in odide (0.12 ml) followed by potassium carbonate (0.092 g). The reaction mixture is heated to 60 ° for 4 days. The reaction product is worked up by pouring into ice water (5 ml) and extraction with ether (3 x 10 ml). The combined ether extracts are washed with water (2 x 10 ml) and brine (1 x 5 ml) and dried over calcium sulfate. The product is isolated and purified by 10 preparative TLC to provide the m-phenoxybenzyl ester of N-phenyl-N-methylval in n.

nmr (CDCl 3) δ 0.92 [m, 6, (CH 2 CH], 2.3 [m, 1, (CH 32 -CH], 2.88 (s, 3, CH 3 N), 3.96 (d, 1,> CH-CO 2), and 5.08 ppm (s, 2, ArCH 2 O) IR 15 (film) 1740 (C = O).

Example 3

To m-phenoxybenzyl-α-bromoisovalerate (5 g, 0.0138 mol) in 9 ml HMPT 20 at 24 ° is added p-chloroaniline (5.27 g, 0.0413 mol) and a catalytic amount of potassium iodide (60 mg). The reaction mixture is stirred at 70 ° for 4 days. The reaction mixture is then poured into ice water (30 ml) and 10 ml of 2N sulfuric acid extracted with ether (3 x 30 ml). The combined ether extracts are washed with water (2 x 30 ml) and brine (10 ml), dried over calcium sulfate, filtered and evaporated. The crude product is purified by preparative TLC to provide the m-phenoxy-benzyl ester of N- (p-chlorophenyl) valine.

nmr (CDCl 3) δ 0.99 [m, 6, (CH 3) 2 CH], 2.03 [m, 1, (CH 3) 2 CH], 3.93 (m, 2, NH and JY-CH-CO 2), and 5.10 ppm (s, 2, ArCH 2 O -). IR (film) 3410 cm -1 (s) (NH), and 1740 cm -1 (C = O).

Example 4 To m-phenoxybenzyl-α-bromo iso valeriate (2 g, 0.0055 mol) in 4 ml of HMPT at 24 ° is added toluidine (1.77 g, 0.0165 mol) and potassium iodide (25 mg). The reaction mixture is stirred at 60 ° for 5 days, cooled and poured into ice water (20 ml) plus 10 ml of 2N sulfuric acid. The reaction mixture is worked up as in Example 3 to provide m-8

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the phenoxybenzyl ester of N- (p-methylphenyl) valine.

nmr (CDCl 3) δ 0.99 [m, 6, (CH 3) 2 CH], 2.20 (s, 3, C ^-Ar), 3.90 (m, 2, NH and> -CH-CO 2), and 5.11 ppm (s, 2, ArCH 2 O). IR (film) 3400 cm "1 (s) (NH), and 1740 cm" 1 (C = 0).

The above procedure is repeated using anisidine instead of toluidine to provide the n-phenoxybenzyl ester of N- (p-methoxyphenyl) valine.

10 nmr (CDCl 3) δ 0.98 [m, 6, (CH 2 CH], 2.03 [m, 1, (CH 3 CH], 3.73 (s, 3, OCH 3), 3.77 (m , 2, NH and> -CH-CO 2), and 5.10 ppm (s, 2, ArCHgO-).

IR (film) 3400 cm -1 (s) (NH), and 1740 cm -1 (C = 0).

Example 5 A. To α-bromoisovalieric acid (5.18 g, 0.0286 mol) in 30 ml of ether and cooled to 10 ° is added 1.3 ml of DMF followed by the slow addition of 3 ml of thionyl chloride (0.0429 mol). After one hour at 24 ° 20, the acid chloride is isolated in quantitative yield by stripping away the top ether layer and removing the solvent and excess thionyl chloride in vacuo.

To the acid chloride (5.7 g, 0.0286 mol) in 30 ml of ether at 10 ° is added 5.38 g of m-phenoxybenzaldehyde cyanohydrin (0.0257 mol) followed by the slow addition of 4.6 ml of pyridine over a 10 minute period. . The reaction mixture is stirred at 24 ° for 17 hours and then a little water is added to destroy excess acid chloride. The reaction product is worked up by pouring into ice water (50 ml) plus 2N 30 sulfuric acid (30 ml) and extraction with ether (3 x 30 ml). The combined ether extracts are washed with 10% sodium bicarbonate (10 ml), water (2 x 50 ml) and brine (10 ml), dried over calcium sulfate and evaporated to provide m-phenoxy-α-cyanobenzyl-α-bromo isovalerate.

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nmr (CDCl 3) δ 1.05 [m, 6, (CH 3) 2 CH], 2.23 [m, 1, (CH 3) 2 CH], 4.06 (d, 1, 0 = 8 Hz, Br-CH C-), and 6.41 ppm [s, 1, ArCH (CN) O]. IR (film) 1762 cm -1 (C = 0). To m-phenoxy-α-cyanobenzyl-α-bromo iso valeriate (2.0 g, 0.0052 mol) in 4 ml HMPT at 24 ° aniline (1.5 g, 0.016 mol) and potassium iodide (21 mg). The reaction mixture is stirred at 65 ° for 90 hours 10 and then cooled and poured into ice water (20 ml) plus 2N sulfuric acid (10 ml). The reaction product is worked up as in Example 3 and purified by preparative TLC to provide the m-phenoxy-α-cyanobenzyl ester of N-phenylvaline.

15 nmr (CDCl 3) δ 1.02 [m, 6, (CH 3) 2 CH], 2.10 [m, 1, (CH 3) 2 CH], 4.0 (m, 2, -NH and C0), and 6.33 ppm [s, 1, ArCH (CN) 0]. IR (film) 3400 cm -1 (NH), 2260 cm -1 (w) (C = N), 1758 cm -1 (C = 0).

Example 6 20

Following the procedure of Example 4, each of the compounds listed in column I is reacted with m-phenoxybenzyl-α-bromo-isovalerate to provide the respective esters listed in column II.

4-phenethidine 2-anisidine 4-ethylaniline 4-fluoroaniline 4-bromaniline 2-chloro-4-methylaniline 35

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The 10 π m-Phenoxybenzyl ester of: 5 N- (4-ethoxyphenyl) valine, MS m / e 419.1 (M +) N- (2-methoxyphenyl) 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 +) N- (2-chloro-4-methylphenyl) valine, MS m / e 423 (M +)

Example 7

Following the procedure of Example 4, each of the amino compounds listed in column 15 3 is reacted with m-phenoxybenzyl-α-bromo iso valerate to form the respective N-substituted esters listed in column IV.

III

2-Tri-fluoromethylaniline 2,3-dichloroaniline 2-fluoroaniline 4-cyclopropylaniline 4-isopropylaniline 4-methylthi-aniline 2,6-difluoraniline 3.4-dichloroaniline

IV

m-Phenoxybenzyl 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 +) N- (4-methylthiophenyl) valine, MS m / e 421 (M +) N- (2,6-difluorophenyl) valine, MS m / e 411.1 (M +) 11

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N- (3,4-dichlorophenyl) valine, MS m / e 443 (M +)

Example 8 2,4-Dichloroaniline is reacted with m-phenoxybenzyl-2-bromo iso valerate using the procedure of Example 3 to give the m-phenoxybenzyl ester of N- (2,4-dichlorophenyl) valine, MS m / e 443 (M +) .

Example 9 A. Two grams of α-bromoisovaleric acid (0.011 mol) dissolved in 10 ml of methanol are titrated at 0 ° to the phenolphthalein end point with 2N sodium hydroxide / methanol. Then the alcohol is removed and 10 ml of dimethyl formamide and p-trifluoromethylaniline (3.54 g, 0.022 mol) are added. The reaction mixture is heated to 100 ° for 2 hours and left to stand at room temperature for approx. 18 hours. The reaction mixture is poured into 50 ml of 0.1N sodium hydroxide, washed with ether, and the aqueous phase is adjusted to pH 4 with concentrated HCl and then extracted with chloroform (3x). The extracts are combined and washed with brine, dried, concentrated in a rotary evaporator and the solvent removed under vacuum at ca. 50 ° to provide N- (p-1r in fluoromethylphenyl) val i n.

B. A mixture of the acid from Section A (1.84 g, 0.0071 mole) and potassium carbonate (1.95 g) in 10 ml of dry dimethyl formamide is stirred at RT under nitrogen for 0.5 hours and then added -phenoxybenzyl bromide (1.85 g, 0.0071 mol) at 0 °. The reaction mixture is allowed to warm to RT and then stirred for approx. 18 hours. The reaction mixture 30 is then worked up by pouring into ice water and extracting with ether (3 times). The ether extracts are combined and washed with water and brine, dried over calcium sulfate and evaporated in vacuo to give the m-phenoxybenzyl ester of N- (p-trifluoromethylphenyl) valine, MS m / e 443 (M +, 5.9).

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Example 10

Following the procedure of Example 9, N- (2-fluoro-4-chlorophenyl) valine (0.79 g) is reacted with α-12

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ethynyl-m-phenoxybenzyl bromide (0 * 39 g) to give the α-ethynyl-m-phenoxybenzyl ester of N- (2-fluoro-4-chlorophenyl) valine, MS m / e 451 (M +).

Example 11

Following the procedure of Example 9, 3-fluoro-4-methyl-aniline is reacted with α-bromoisovaleric acid to produce N- (3-fluoro-4-methylphenyl) valine which is reacted with α-ethynyl-10 m phenoxy-benzyl bromide to form the α-ethynyl-m-phenoxybenzyl ester of N- (3-fluoro-4-methylphenyl) valine, MS m / e 431 (M +).

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

Example 12 20

To the m-phenoxybenzyl ester of N- (p-trifluoromethylphenyl) val in (1.57 g) for approx. 15 ml of benzene is added under nitrogen and with stirring N-chlorosuccinimide (0.53 g). The reaction mixture is heated under reflux for approx. 2 hours. The reaction mixture is cooled and separated between ether and water. The aqueous phase is back extracted with ether.

The combined ether phases are washed with water and brine, dried over sodium sulfate, filtered and evaporated. The reaction product is placed on preparative TLC plates and eluted using 10% ether / hexane to provide the m-phenoxybenzyl ester of N- (2-30 chloro-4-trifluoromethylphenyl) valine, MS m / e 477.1 (M +).

Following the above procedure, the m-phenoxy-α-cyanobenzyl ester of N- (2-chloro-4-trifluoromethylphenyl) valine, MS m / e 486.3 (M +), is prepared from the m-phenoxy-α-cyanobenzyl ester of N- (p-trifluoromethylphenyl) falls.

Example 13 In a mixture of 1.0 g of the m-phenoxybenzyl ester of 13

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N- (p-methylphenyl) valine and 10 ml of ether are bubbled with stirring and cooling in an ice bath of hydrogen chloride gas for approx. 15 minutes. The reaction product is filtered, washed with ether and recrystallized from hot ethanol to give the hydrochloride salt of the 5 m-phenoxybenzyl ester of N- (p-methylphenyl) val in, m.p. 151-153 °.

Following the procedure of Example 5, 2-fluoro-4-trifluoromethylaniline is reacted with α-cyano-m-phenoxybenzyl-α-bromo isovalerate to form the α-cyano-m-phenoxybenzyl ester of 10 N- (2-fluoro -4-trifluoromethylphenyl) valine, MS m / e 502.1 (M +).

Example 14 N- (4-chlorophenyl) valine is reacted with m-phenoxy-α-methylphenyl bromide in THF / HMPT 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 prepared from m-phenoxybenzaldehyde by reaction with methyl lithium to form the secondary alcohol which is brominated using phosphorous tri bromide.

20

Example 15

A mixture of N-chlorosuccinimide (1.17 mmol), m-phenoxybenzyl ester of N- (p-methoxyphenyl) valine (1.23 mmol) and benzene (20 ml) is refluxed under nitrogen for approx. 60 hours. The reaction mixture is worked up in water / ether. The ether layer is washed with water and brine and dried over sodium sulfate. The crude product is purified by preparative TLC eluting with 15% ether to give the m-phenoxybenzyl ester of N- (2-chloro-4-methoxyphenyl) valine, MS m / e 439 (M +, 7.4), 212 (100).

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Example 16

A solution of α-bromoisovaleric acid (8.17 mmol) in methanol is titrated to the phenolphthalein end point using sodium methoxide. The solvent is removed by rotary evaporation and then potassium carbonate (1.69 g), 2-fluoro-4-methylaniline (16.38 mmol) and 3 ml of HMPT are added. The reaction mixture is heated to 60 ° for approx. 5 hours and then worked up with 5% sodium hydroxide / ether and washed with water (3x). The basic layer is acidified and extracted with 14

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ether, washed with water and brine, dried over sodium sulfate and rotary evaporated to give α- (2-fluoro-4-methyl-phenylamino) isovaleric acid. (2-Fluoro-4-methylaniline is prepared from 3-fluoro-4-nitrotoluene in a Parr flask using platinum oxide and hydrogen in ethanol).

To a mixture of 5.15 mmol of α- (2-fluoro-4-methylphenyl amino) isovaleric acid, potassium carbonate (6.44 mmol), 4 ml of HMPT and 3 ml of THF is added with stirring 5.13 mmol of m-phenoxybenzyl bromide. The reaction mixture is stirred overnight at RT. The reaction mixture is poured into 5% sodium hydroxide / ether, extracted with water (2x) and then washed with water (2x), dried over sodium sulfate and rotary evaporated under vacuum. The crude product is subjected to preparative TLC by eluting with 10% ether / hexane to provide m-phenoxy-benzyl ester of N- (2-fluoro-4-methylphenyl) valine.

nmr (CDCl 3) δ 0.98 [d, 3, J = 7 Hz, CH (CH 3) 2], 1.02 [d, 3, J = 7 Hz, CH (CH 3) 2], 2.22 (s ), 5.13 ppm (s, 2, ArCH 2 O).

IR (unmixed) 1734 cm -1 (C = 0).

Following the above procedure, N- (4-tert-butylphenyl) val is reacted with m-phenoxybenzyl bromide to form the m-phenoxybenzyl ester of N- (4-tert-butylphenyl) valine.

25 nmr (CDCl 3) δ centered at 0.99 [d, 6, J = 7 Hz, (CH 3) 2 CH], 1.28 [s, 9, (CH 3) 3 C-Ar], 3.93 (m, 2 , NH and HN-CH-C-), and 5.11 ppm (s, 2,

ArCO). IR (film) 1743 cm "1 (C = 0)

The procedure of this example is used to prepare the N- (3-chloro-4-fluorophenyl) valine and N- (3-fluoro-4-methylphenyl) valine, each reacted with the m-phenoxybenzyl bromide to form the m-phenoxybenzyl ester of N - (3-chloro-4-fluorophenyl) valine, [MS m / e 427 (M +, 3.2), 200 (100)] and the m-phenoxybenzyl ester of N- (3-fluoro-4-methylphenyl) valine.

nmr (CDCl3) δ centered at 0.97 [d, 6, J = 7 Hz, CH (CH 3) 2], 2.11 (d, 3, J = 2 Hz, x? s ^ CH 3), and 5, 10 ppm (s, 2, ArCl 3).

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IR (unmixed) 1732 cm "1 (C = 0).

Example 17 A mixture of 5 g of p-trifluoromethylaniline, 2.25 g of α-bromoisovaleric acid and 2.0 g of potassium carbonate is heated to 100 ° for 1 hour.

After 1.5 hours, 5 ml of HMPT is added and the mixture is heated to 100 ° for 15 hours. The mixture is then poured into water and potassium carbonate is added to pH ca. 11. The mixture is washed with ether and methylene chloride and the aqueous phase acidified to pH ca. 3, washed with ether and concentrated. The residue is recrystallized in hexane / ether to provide N- (4-trifluoromethylphenyl) valine, which is reacted with m-phenoxybenzyl bromide to form the m-phenoxybenzyl ester of N- (4-trifluoromethylphenyl) valine. MS m / e 443 (M +, 5.9).

15

The acid N- (4-trifluoromethylphenyl) val is introduced at RT in DMF / THF and potassium carbonate to react with m-phenoxy-α-ethynylbenzyl bromide to give the m-phenoxy-α-ethynylbenzyl ester of N- (4-trifluoro-methylphenyl) ) valine. MS m / e 467 (M +, 1.3), 216 (100).

20

The acid N- (4-fluorophenyl) valine is prepared as above from 4-fluoroaniline and α-bromoisovaleric acid and then reacted with the m-phenoxybenzyl bromide as above to form the m-phenoxybenzyl ester of N- (4-fluorophenyl) valine.

25 nmr (CDCl 3) C Centered at 0.90 [m, 6, (CH 2 CH], 2.0 [m, 1, (CH 3) 2 CH], 3.80 (m, 2, NH and V ), and 5.15 ppm (s, 2, ArCH 2 O).

IR (film) 3400 cm -1 (NH). 0 30 N- (3-Fluorophenyl) valine (prepared by reaction of α-bromoiso-valeric acid with 3-fluoroaniline at 140 ° under nitrogen for 3.5 hours) is reacted with m-phenoxybenzyl bromide in HMPT / THF and potassium carbonate at RT to form the m-phenoxybenzyl ester of N- (3-fluoro-phenyl) valine. MS m / e 393 (M +, 2), 166 (100).

35 N- (2-Chloro-4-methylphenyl) val in is prepared as above from α-bromoisovalerianic acid and 2-chloro-4-methylaniline and then reacted with the m-phenoxybenzyl bromide as above to form the m-phenoxybenzyl ester of N- ( 2-chloro-4-methylphenyl) valine. MS m / e 423 (M +, 4), 16

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196 (100).

Example 18 To 1.21 mmol of triethyloxonium tetrafluoroborate in ca. 5 ml of methylene chloride under nitrogen are added 1.05 mmol of m-phenoxybenzyl ester of N- (4-chlorophenyl) valine. The reaction mixture is stirred at RT overnight and then poured into ether / water. The organic phase is washed with water and brine, dried over calcium sulfate and the solvent 10 removed. The crude product is subjected to preparative TLC eluting with 20% ether / hexane to provide the m-phenoxybenzyl ester of N-ethyl, N- (4-chlorophenyl) valine, MS m / e 437 (M +, 3), 210 (100).

Example 19 N- (4-fluoro-2-methylphenyl) valine prepared from 4-fluoro-2-methylaniline and α-bromoisovaleric acid is reacted with m-phenoxybenzyl bromide as in Example 16 to produce m-phe -noxybenzyl ester of N- (4-fluoro-2-methylphenyl) valine, MS m / e 407.2 (M +, 4.5), 180 (100).

Example 20

To a mixture of 0.47 g of N- (4-methylphenyl) valine, 5 ml of HMPT and 0.36 g of potassium carbonate is added with stirring 0.82 g of m- (4-chlorophenoxy) benzyl bromide. The reaction mixture is stirred overnight at RT and then worked up by separation between water / ether. The aqueous phase is extracted with ether (2x) and the combined ether phases are then washed with water and brine, dried over sodium sulfate, filtered and evaporated. The concentrate is subjected to preparative TLC by elution with 10% ether / hexane to provide the m- (4-chlorophenoxy) benzyl ester of N- (4-methylphenyl) valine, MS m / e 443 (M +).

N- (4-Methylphenyl) val in is reacted with m-phenoxy-α-ethynylbenzyl bromide 35 in DMF / THF and potassium carbonate at RT as above to produce the m-phenoxy-α-ethynylbenzyl ester of N- (4-methylphenyl) valine , MS m / e 413.1 (M +, 3.8), 162.1 (100).

Example 21 17

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To the m-phenoxybenzyl ester of N- (4-chlorophenyl) valine (1.19 mmol) in ether (4.5 ml) and under nitrogen is added dimethylaminopyridine (4.25 mmol), then cooled in an ice bath and then slowly added trichloroacetyl chloride (3.58 mmol) in ether. The reaction mixture is heated to 40 * for 3 days. The reaction mixture is worked up with ether / water. The aqueous phase is extracted with ether and then the combined ether phases are washed with water and brine and dried over sodium sulfate. The residue is subjected to preparative TLC by eluting with 10% ether / hexane to provide the m-phenoxybenzyl ester of N-trichloroacetyl, N- (4-chlorophenyl) valine, MS m / e (M +, 1.8), 183 (100).

Example 22

Following the procedure of Example 21, the m-phenoxybenzyl ester of N-acetylformyl, N- (4-chlorophenyl) valine [MS m / e 479 (M +, 0.5), 183 (100)] is prepared by reacting the acid chloride of pyruvic acid 20 with the m-phenoxybenzyl ester of N- (4-chlorophenyl) valine.

Example 23

Following the procedure of Example 20, N- (4-chlorophenyl) valine is reacted with m- (4-chlorophenoxy) benzyl bromide to form the m- (4-chlorophenoxy) benzyl ester of N- (4- chlorophenyl) -valine, MS m / e 443 (M +).

Example 24 30

To the m-phenoxybenzyl ester of N- (4-methoxyphenyl) valine (0.89 mmol) in ether and under nitrogen is added trifluoroacetic anhydride (4.46 mmol). The reaction mixture is stirred for 2.5 hours and then worked up with ether / water. The combined ether layers are washed with saturated sodium carbonate and brine, dried over sodium sulfate and evaporated to provide the m-phenoxybenzyl ester of N-tri fluoroacetyl, N- (4-methoxyphenyl) valine, MS m / e 501 (M +, 22.5 ), 183 (100).

Example 25 18

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A mixture of the m-phenoxybenzyl ester of N- (4-chlorophenyl) valine (1.22 mmol), acetic acid formic anhydride in acetic acid (23.8 mmol, 2.15 g) and formic acid (1.5 ml) is stirred overnight at RT. under nitrogen. The reaction product is concentrated and then subjected to preparative TLC by eluting with 20% ethyl acetate / hexane to give the m-phenoxybenzyl ester of N-formyl, N- (4-chlorophenyl) valine, MS m / e 437 (M +, 8.1), 182 ( 100).

10

Example 26

Following the procedure of Example 24, trifluoroacetic anhydride is reacted with the m-phenoxybenzyl ester of N- (4-chlorophenyl) valine to give the m-phenoxybenzyl ester of N-trifluoroacetyl, N- (4-chlorophenyl) valine, MS m / e 505 (M +, 14.9), 278 (100).

By following the procedure of e.g. Example 20, α-Ethyl-nyl-m-phenoxybenzyl bromide is reacted with N- (4-chlorophenyl) valine to give the α-ethynyl-m-phenoxybenzyl ester of N- (4-chlorophenyl) valine, MS m. e 433 (M +, 2.2), 182 (100).

Example 27 N- (2-Chloro-4-cyanophenyl) valine is reacted with m-phenoxybenzyl bromide in THF / HMPT with potassium carbonate using the procedure of Example 20 to prepare the m-phenoxybenzyl ester of N- (2-chloro or-4- cyanophenyl), MS m / e 434 (M +, 3.7), 207 (100). N- (2-chloro-4-cyanophenyl) valine is prepared by reacting 2-chloro-4-30 cyanoaniline with α-bromoisovalerianic acid using the method of e.g. Example 13.

Likewise, N- (2,4-difluorophenyl) valine is prepared from 2,4-difluoroaniline and α-bromoisovaleric acid. N- (2,4-difluorophenyl) valine is esterified using m-phenoxybenzyl bromide to produce the m-phenoxybenzyl ester of N- (2,4-difluorophenyl) valine, MS m / e 411 (M +, 3.5), 184 (100).

Example 28

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19 N- (2-fluoro-4-chlorophenyl) val in is reacted with m-phenoxybenzyl bromide using the procedure of Example 20 to give the 5 m-phenoxybenzyl ester of N- (2-fluoro-4-chlorophenyl) valine, MS m / a 427.1 (M +, 4.1) 200 (100). N- (2-fluoro-4-chlorophenyl) valine is prepared by heating the potassium salt of α-bromoisovalerianic acid and 2-fluoro-4-chloroaniline without dilution to 130 ° for approx. 2 hours.

The α-cyano-m-phenoxybenzyl ester of N- (2-methylphenyl) val in, MS m / e 414.1 (M +, 5.8), is prepared from α-cyano-m-phenoxybenzyl bromide and N- (2-methylphenyl) collapses.

The m-phenoxybenzyl ester of N- (2-methyl-4-chloro-phenyl) valine is prepared, MS m / e 423.1 (M +, 16.9) from m-phenoxybenzyl bromide and N- (2-methyl-4 -chlorophenyl) val i n.

The m-Phenoxybenzyl ester of N- (4-chlorophenyl) val in and of N- (4-methylphenyl) val in is methylated using the procedure of Example 2 to produce the m-phenoxybenzyl ester of N-methyl, N- (4-chlorophenyl) val in, MS m / e 423 (M +), and the m-phenoxybenzyl ester of N-methyl, N- (4-methylphenyl) valine, MS m / e 403.2 (M +).

Following the procedure of Example 5, α-cyano-m-phenoxy-benzyl-α-bromo isovalerate is reacted with 4-chloroaniline, 4-methoxyaniline and 4-methylaniline respectively to produce α-cyano-m the phenoxybenzyl ester of: N- (4-chlorophenyl) valine, MS m / e 434.1 (M +) 30 N- (4-methoxyphenyl) valine, MS m / e 430.1 (M +), and N- (4-methylphenyl) ) selected, MS m / e 414.2 (M +).

The α-cyano-m-phenoxybenzyl ester of N- (4-chlorophenyl) valine is reacted with methyl iodide using the procedure of Example 2 to produce the α-cyano-m-phenoxybenzyl ester of N-methyl, N- (4- chlorophenyl) valine, MS m / e 448.1 (M +).

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20

Example 29

Following the procedure of Example 13, m-phenoxybenzyl bromide is reacted with N- (2-chlorophenyl) valine to give the 5 m-phenoxybenzyl ester of N- (2-chlorophenyl) valine, MS m / e 409 (M +) .

N- (4-t-butylphenyl) val is reacted with benzyl bromide using the procedure of Example 13 to give the benzyl ester of N- (4-t-butylphenyl) valine, MS m / e 431 (M +).

10

Following the procedure of Example 5, 4-trifluoromethyl-aniline is reacted with α-cyano-m-phenoxybenzyl-α-bromo iso valerate to form the α-cyano-m-phenoxybenzyl ester of N- (4-trifluoromethylphenyl) val in, MS m / e 468.2 (M +).

15

Example 30 In a 100 ml, 3-neck coupler equipped with addition funnel and reflux condenser to which a water-air lock is attached is placed 10.08 g (65 mmol) of 2-fluoro, 4-nitrotoluene. Fill the addition funnel with 7.0 ml (22.3 g, 138 mmol) of bromine and heat the flask. When the temperature (oil bath) is approx. 100 °, the bromine is introduced slowly while the flask is illuminated with a 150 watt light bulb. The bromination starts quickly when the temperature is increased to approx. 160-170 °, and there is a slow evolution of HBr. After 4 hours, the heating is switched off. The cooled mixture is worked up by pouring into saturated sodium bisulfite with ice and extracted with ether (3x). The combined organic layers are washed once more with saturated NaHSO ^, brine (1x), and dried over sodium sulfate. Filtration and evaporation of the solvent gives 17.0 g of a mixture of benzal bromide and benzyl bromide (1.7: 1 according to nmr analysis). The crude material is suspended in a hypobromite solution prepared by combining 60 g of sodium hydroxide and 20 ml of bromine in 600 ml of water. This mixture is stirred for 6 days at RT and then filtered to provide 2-fluoro, 4-nitro-α, α, α-tribromotoluene which can be recrystallized in methanol.

A mixture of 8.5 g of 2-fluoro, 4-nitro-α, α, α-tribromotoluene (22 mmol) and 4.7 g (26 mmol) of antimony trifluoride is placed in a small flask equipped with a condensation equipment for distillation. Flask 21

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is heated slowly and the mixture is distilled both at atmospheric pressure and then at reduced pressure until no further material is distilled. The distillate is separated between 6N hydrochloric acid and ether.

The organic layer is then washed with 6N sodium hydroxide (1x) and 5 brine (1x) and dried over sodium sulfate. Filtration and evaporation of the solvent give 2-fluoro, 4-nitrobenzotrifluoride.

To a solution of 20 ml of concentrated hydrochloric acid and 15 ml of 95% ethanol was added 5.0 g (24 mmol) of 2-fluoro, 4-nitrobenzotrifluoride. The mixture 10 is stirred and 20 g (88 mmol) of stannous chloride dihydrate is added portionwise over a 30 minute period. The reaction is exothermic and during addition the temperature is maintained at 60 °. When the addition is complete, the mixture is stirred at 50 ° for an additional 20 minutes. The reaction mixture is cooled and precipitated on a mixture of ice and 36% sodium hydroxide extracted with ether (3x). The combined ether layers are washed once with brine and dried over sodium sulfate. Filtration and evaporation of the solvent give 4-amino, 2-fluorobenzotrifluoride (3-fluoro-4-trifluoromethylaniline).

Following the procedure of Example 16, 3-fluoro-4-trifluoromethylaniline is reacted with the sodium salt of α-bromo-isovaleric acid to form N- (3-fluoro-4-trifluoromethylphenyl) val esterified to form of the m-phenoxybenzyl ester of N- (3-fluoro-4-trifluoromethylphenyl) is obtained.

25

This procedure is repeated using 3-fluoro-4-nitrotoluene instead of 2-fluoro-4-nitrotoluene to give 2-fluoro-4-trifluoromethylaniline which is converted to N- (2-fluoro-4-trifluoromethylphenyl) valine. and then esterified to give the 30 m-phenoxybenzyl ester of N- (2-fluoro-4-trifluoromethylphenyl) valine, MS m / e 461.1 (M +).

Example 31 To a solution of o-fluoroaniline (3.9 g) in methylene chloride (50 ml) cooled to -20 ° under nitrogen, a solution of 2,4,4,6-tetrabromocyclohexadienone (35 mmol) is added. in methylene chloride. After several hours, the reaction mixture is poured into 15% NaOH solution.

The layers are separated and the organic fraction is shaken with 15% NaOH-22

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resolution. The methylene chloride fraction is washed with saturated NaCl solution, dried over calcium sulfate and evaporated to give 4-bromo-2-fluoroaniline.

To the potassium salt of α-bromoisovaleric acid (1.42 g) is added 4-bromo-2-fluoroaniline (1.9 g). The mixture is heated under nitrogen to 125 ° for 3.5 hours and then cooled to RT. The reaction product is poured into 2M NaOH and ether / chloroform. The basic phase is separated, acidified with concentrated HCl and then extracted with ether, washed with 10 saturated NaCl solution, dried over calcium sulfate and evaporated to give N- (4-bromo-2-fluorophenyl) valine.

A mixture of N- (4-bromo-2-fluorophenyl) valine (0.45 g), potassium carbonate (0.25 g) THF (4 ml), DMF (4 ml) and m-phenoxy-α-cyanobene -15 zyl mesylate (0.43 g) is stirred for approx. 60 hours and then poured into water and hexane / ether (9: 1). The organic phase is washed with water and saturated sodium chloride solution, dried over calcium sulfate and evaporated.

The residue is applied to preparative TLC and eluted with 25% methylene chloride / hexane once and then with 30% methyl enchloride / d / hexane, and the largest band is collected to provide the m-phenoxy-α-cyanobenzyl ester of N (4-bromo-2-fluorophenyl) valine, MS m / e 496 (M +).

Example 32 To 4.9 g of N- (4-chlorophenyl) valine (0.0215 mmol) in 50 ml of 1,4-dioxane are slowly fed a stream of phosgene gas while the solution is stirred.

Cooling is used to keep the solution at RT. When the solution is saturated with phosgene, the phosgene stream is shut off and the mixture is left to stir under nitrogen at RT. After 45 30 hours, approx. 2/3 of the dioxane by distillation with aspirator pressure. The residue is diluted with hexane and then left to crystallize overnight at RT. The solid is collected by filtration and washed with hexane while care is taken to minimize exposure to air. The solid is dried in vacuo to give 3- (4-chlorophenyl) -4-isopropyloxazolidine-2,5-dione, m.p. 137-138 °.

To a mixture of m-phenoxybenzaldehyde (1.7 mmol), 3- (4-chlorophenyl) -4-isopropyloxazolidine-2,5-dione (0.5 g) and potassium cyanide (0.23 g) 23

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in benzene (about 10 ml) is added benzyl triethyl ammonium chloride with stirring (about 0.1 g). The reaction mixture is stirred for approx. 50 hours. The reaction mixture is then worked up by absorption in ether, washing with water and brine, drying over sodium sulfate and evaporation. The concentrate is placed on preparative TLC plates and eluted with 20% ether / hexane to provide the m-phenoxy-α-cyanobenzyl ester of N- (4-chlorophenyl) valine.

Example 33 10

Following the procedure of Example 5, 2-fluoro-4-chloro-aniline is reacted with m-phenoxy-α-cyanobenzyl-α-bromo isovalerate to form the m-phenoxy-α-cyanobenzyl ester of the N- (2-fluoro 4-chlorophenyl) valine, MS m / e 452 (M +). Alternatively, 2-fluoro-4-chloroaniline is reacted with the sodium salt of α-bromoisovaleric acid to form N- (2-fluoro-4-chlorophenyl) valine, which is then esterified using m-phenoxy-α-cyanobenzyl bromide. or mesylate.

N- (4-Chlorophenyl) valine is reacted with m-phenylcarbonyl benzyl bromide or mesylate according to the procedure of Example 13 to give the m-phenylcarbonyl benzyl ester of N- (4-chlorophenyl) valine, MS m / e 421 (M +) .

Example 34 N- (2-Chloro-4-fluorophenyl) -value, N- (4-chloro-3-fluorophenyl) -value, N- (4-cyano-2-fluorophenyl) -value, N- (4- bromo-2-fluorophenyl) val in and N- (4-trifluoromethoxyphenyl) valine are all reacted with 30 m-phenoxybenzyl bromide using the procedure of Example 13 to produce the m-phenoxybenzyl ester of: 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-cyano-2-fluorophenyl) ) valine, MS m / e 418 (M +), N- (4-bromo-2-fluorophenyl) valine, MS m / e 471 (M +), and N- (4-trifluoromethoxyphenyl) valine, MS m / e 459 ( M +).

Following the procedure of Example 31, m-phenoxy-α-24 is prepared

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the cyanobenzyl ester of N- (4-chloro-3-fluorophenyl) valine, MS m / e 452 (M +), and the m-phenoxy-α-cyanobenzyl ester of N- (2-fluoro-4-methyl-phenyl) valine, MS m / e 432 (M +) from N- (4-chloro-3-fluorophenyl) valine and N- (2-fluoro-4-methylphenyl) valine and m-pheoxy-α-cyanobenzyl mesylate or bromide, respectively. The starting materials are prepared by reaction between 4-chloro-3-fluoroaniline and 2-fluoro-4-methylaniline, respectively, and the potassium salt of α-bromoisovaleric acid.

Testing of compounds of the invention 10

Young lima bean leaves (in water) infected with ca. 50 adult Tetranvchus urticae. is sprayed to drain with the compound (m-phenoxy-α-cyanobenzyl ester of N-phenylvaline) diluted to three different concentrations in aqueous vehicles containing 0.025% Tween 20 and 0.1% wetting agent. The treated leaves are stored at 24 ° and a photoperiod of 16 hours for 2 days. Then the number of live adult mites is subtracted from the original total number to obtain the affected number, which is expressed as a percentage of the total. Using Abbott's formula, 20 is corrected for any control mortality. The compound had an LC5Q of less than 0.1%.

Single fava bean leaves are dipped into the compound (m-phenoxybenzyl ester of N-phenyl-N-methylvaline) diluted to three different concentrations in acetone by 0.025%

Tween 20 and 0.1% wetting agent. The leaves are allowed to dry for 2 hours and then infected with 10 adult Aphis fabae. which are confined to the upper surface of the leaves. The treated leaves are stored for 48 hours at 24 ° and a photoperiod of 16 hours. The effect is calculated as 30 deaths calculated as a percent of the total number of leaf lice. This is corrected for control mortality - if any - using Abbott's formula. The compound had an LC5Q of less than 0.05%.

35 Fifteen 72-hour-old adult females of Musca domestica L. are anesthetized with ether vapor. They are then treated with 1 μΐ of the compound [m-phenoxybenzyl ester of N- (p-methylphenyl) valine] diluted to three different concentrations in acetone applied to the dorsal surface of the prothorax (breast). They are kept in an experimental container of 25

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cotton saturated with milk at 25 ° and a photoperiod of 16 hours for 24 hours. The effect is calculated as the number of deaths calculated as a percentage of the total number and corrected for any control mortality using Abbott's formula. The compound gave an LCgg 5 of less than 0.01%.

In a mixture of 45 mg wettable powder [Attaclay (60%), Marosperse N-22 (26.7%) and Igepon T-77 (13.3%)] and 0.5 ml of water containing the compound [ m-phenoxybenzyl ester of N- (p-chlorophenyl) valine] at three different concentrations, dipping 15 fed blood mite nymphs (Ornithodoro's nymph I). The treated nymphs are kept on filter paper for 7 days at 28e, 64% humidity, 16 hours photoperiod and then observed. Correction for any mortality of the control group is corrected using Abbott's formula. The compound LC5Q was less than 0.01%.

15

Two groups of 10 to 24 hour III stage Heliothis virescens larvae were treated with 1 µl of the compound [m-phenoxybenzyl ester of N- (p-methoxyphenyl) valine] in acetone at three different concentrations by application to the thoracic dorsum. Two groups, each of 10 20, were treated as control in identical fashion with 1 µl acetone. The larvae are kept individually in 30 ml plastic cups fitted with artificial medium for 72 hours at 25 ° and 16 hours of photoperiod. After 72 hours, the number of deaths is calculated as a percentage of the total number initially treated and then corrected for any 25 mortality in the control groups using Abbott's formula. The LCg of the compound was less than 0.5%.

Each of the compounds listed below was used to treat aphids (adult Aphis fabael using the method described above. Each of the compounds gave an LC 2 g of less than 15 parts per million (ppm).

m-phenoxy-cc-cyanobenzyl ester of N- (2-chloro-4-trifluoro-methylphenyl) valine, 35 m-phenoxy-α-cyanobenzyl ester of N- (2-fluoro-4-tri-fluoro-methylphenyl) val in, m-phenoxybenzyl ester of N- (2-fluoro-4-trifluoromethyl-phenyl) valine, 26

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m-phenoxybenzyl ester of N- (4-trifluoromethylphenyl) enters.

A 4E emulsion concentrate was prepared using the m-phenoxybenzyl ester of N- (4-trifluoromethylphenyl) val in (51.3%), 5 Atlox 3404F (3%), Atlox 3403F (3%) and Tenneco 500-100 (42, 7%), diluted with water and applied to Tetranvchus urticae as described above. The LCgg value was less than 10 ppm.

The compounds listed below were used to treat 10 blood mite nymphs for nymphodoros nymph I) using the method described above and exhibited an LC5Q of less than 15 ppm.

m-phenoxy-tt-cyanobenzyl ester of N- (2-chloro-4-trifluoro-methylphenyl) -valine, m-phenoxy-oc-cyanobenzyl ester of N- (2-fluoro-4-tri-fluoro-methylphenyl) -valine , 20 m-phenoxy-oc-methylbenzyl ester of N- (4-chlorophenyl) valine, m-phenoxy-oc-ethynylbenzyl ester of N- (4-chloro-2-fluoro-phenyl) valine, m-phenoxy-α- ethynylbenzyl ester of N- (3-fluoro-4-methyl-phenyl) val in, 25 m-phenoxy - «- ethynylbenzyl ester of N- (2-fluoro-4-methyl-phenyl) val in, m-phenoxy-oc- cyanobenzyl ester of N- (2-fluoro-4-methyl-phenyl) val in, 30 m-phenoxy-oc-cyanobenzyl ester of N- (4-chloro-2-fluoro-phenyl) valine.

Each of the compounds listed below was applied to Heliothis virescens larvae using the method described above and gave an LCgQ value of less than 0.1%.

m-phenoxybenzyl ester of N- (4-chloro-2-fluoro-phenyl) valine, m-phenoxy-oc-cyanobenzyl ester of N- (4-chloro-2-fluoro-phenyl) valine, 27

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m-phenoxybenzyl ester of N- (2-fluoro-4-trifluoromethyl-phenyl) valine, m-phenoxy-oc-cyanobenzyl ester of N- (4-bromo-2-fluoro-phenyl) valine, 5 m-phenoxybenzyl ester of N- (2-chloro-4-trifluoromethyl-phenyl) val in, m-phenoxy-α-cyanobenzyl ester of N- (2-fluoro-4-trifluoro-methylphenyl) -val in, 10 m-phenoxy-α-cyanobenzyl ester of N- (2-Chloro-4-trifluoro-methylphenyl) valine, m-phenoxybenzyl ester of N- (2-fluoro-4-methylphenyl) valine.

15 Comparative Testing

The effect of the compounds of the invention was compared to the action of compounds known from DK Patent Application No. 3453/76 and is set forth in subsequent Tables A and B.

20

The numerical values given in Table A indicate the so-called LDg0 values, i.e. the amount of substance required to kill 50% of a given population of that pest.

Table B shows corresponding LDgg values for compounds according to the application. By comparison of Tables A and B, it is evidently desirable that the compounds of this application are far more effective than the compounds known from the Danish patent application, the LDgg values of Table B being from 10 to 100 30 times less than the corresponding values. in Table A, that is, from 10 to 100 times less amount of substance of the compounds of the present application is required to provide the same insecticidal or acaricidal effect.

35

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Claims (14)

1. Aminocarboxylic acid esters for use in insecticides and acari cides, characterized in that they have the general formula 5 (A): 1-a * A compound according to claim 1, characterized in that R is 4 isopropyl, R is hydrogen and t is zero. 35 Compound according to claim 2, characterized in that Z is in para position. A compound according to claim 1, characterized in that both DK and R are hydrogen, t is zero, R is isopropyl and R is m-phenoxy. A compound according to claim 4, characterized in that Z is g at the para position and R is hydrogen or cyano. 5 A compound according to claim 1, characterized in that t is 1. A compound according to claim 1, characterized in that both 2 4 3 10. and R are hydrogen, t is 1 and R is isopropyl. A compound according to claim 7, characterized in that Y is in ortho position and Z is in para position. A compound according to claim 8, characterized in that Y is fluorine. A compound according to claim 7, characterized in that Y is fluorine and Z is bromine, chlorine, fluorine or trifluoromethyl. 20 g Z is W 14 R 2 where R represents hydrogen, alkyl of 1-4 carbon atoms, 15 haloalkyl carbonyl of 1-4 carbon atoms and 1-3 halogen atoms in the 3 haloalkyl or formyl; R represents alkyl of 2-5 carbon atoms, alkenyl of 2-5 carbon atoms, haloalkyl of 1-4 carbon atoms and 1-3 halogen atoms, haloalkenyl of 2-4 carbon atoms and 1-3 halogen atoms 4 or cycloalkyl of 3-4 carbon atoms; R represents hydrogen or fluorine; Y represents chlorine, fluorine or methyl; t is zero or one; Z represents hydrogen, bromine, chlorine, fluorine, trifluoromethyl, trifluoromethoxy, alkyl of 1-4 carbon atoms, alkoxy of 1-3 carbon atoms, alkylthio of 1-3 carbon atoms or cyano; R 5 is -cbk'-Ø '* 9 6 9 wherein R represents hydrogen, methyl, ethynyl or cyano, and R represents phenoxy, chlorophenoxy, fluorophenoxy, methylphenoxy or trifluoromethoxy; and salts thereof with strong inorganic or organic acids. 3 A compound according to claim 10, characterized in that R g is hydrogen or cyano and R is m-phenoxy. A compound according to claim 7, characterized in that Y is g 25. meta-position and Z is in para-position while R is in meta-position. Composition for controlling insects and acarides, characterized in that it comprises a compound of formula (A) 30 according to claim 1 and a suitable inert carrier substance. Method for controlling insects and / or acarides, characterized in that the insects and / or acarides are treated with a compound of formula (A) according to claim 1. 35