CH641638A5 - PHENYL ALKANIC ACID-M-PHENOXYBENZYL ESTER. - Google Patents

Description

The invention relates to m-phenoxybenzyl esters of substituted phenylalkanoic acids of the formula:

rcf2x

^ -CH-CO-O-CKY1 ^

(X-f \ 4.0 kr-

(I)

wherein RCF2X, Y and Z are all in the m or p-position to the carbon atom to which the alkanoic acid ester group is attached, and

X stands for O, S, SO or S02,

Y and Z, which are the same or different, stand for H, Cl, F, Br, N02, CH3 or OCH3,

R stands for H, F, Cl, CHF2 or CF3,

R2 denotes ethyl, n-propyl, isopropyl, isopropenyl or tert-butyl,

rcf2x

R3 stands for H, CN or -C s CH and R4 stands for H, F, Cl, CH3 or OCH3,

where at least one of the symbols Z, Y and R4 has a meaning other than hydrogen when R3 is H or i5 CN; these compounds can exist as optically active isomers.

The compounds of the formula I are prepared according to the invention by using a compound of the formula:

(II)

in the presence of pyridine with a compound of the formula:

HIGH-r ^^ - O-

I.

R3

implements.

The following reaction schemes explain the manufacture of the phenylalkanoic acids in their acid chlorides of the formula II lung of corresponding phenylalkanoic acids and of m- and the process according to the invention for the preparation of the

Phenoxybenzyl alcohols of the formula III, the transfer compounds of the formula I.

(in)

Reaction schemes

HO- ^ ~ ^ -CH-COOH + Br2 ° d0rCl2 CHC1 ^ HO- ^ T ^ R2

(Z and'Y stand for H, Br or Cl)

2nd

(Z and Y stand for H, Br or Cl)

Reaction schemes (continued)

HO

F ^ '* 2

-1- NaOH + CHF2C1 -> F

2C "0-Ç> -

■ CHCOOH * 2

HO-v V-CHCÜOH + HN03 «2

HO-

NO,

CHCOOH + NaOH + CHF "C1 • I z

«2

-> F2ClIO- ^ ~ y-CHCOOH

R2

ho2

V CH20-

WcH2GH + PBr3 Ether> (/ \ yCH2Q-Çy CH2Br

OCH.

OCH.

NaCN DMS0> (/ \\ - CH20y-CH2CN

OCH.

\ -CH2CN + R2Br + NaOH i ^ H_2Et3NC1 [

\ ■. / V *

^ y ~ CH20- ^ \ y_CHCN

OCH.

R,

OCH.

-COOH + CHF2Ci + KOH »F ^ HO-K '^ VCHCOOH

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Reaction Schemes' (continued)

(f OH + NaOCH- + pyridine + / \ + X 7-CHO + CuCl,

r,

3rd ^ 2

Br

CHO

R.

R,

CHO + HCN>

OH I

-CHCN

.CHO

R,

+ C H2 + C2 «5MgBr

R,

,, -ClIOH <-

H i «cu

'/ V,

HX

CHCN + CSC1.

■ * 2

z y

CHCI3

C1CX

s // \ —CHCN + MoF (

-CHCN

Z y

> £ X)

cf3x ^ / A2

Z Y

^ y — chcn hoch2ch2oh koh

CF3X [\ .R2 Z Y

H20 ^ (C. \ chcooh

CF3X 'v "^ R2 Z Y

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Reaction schemes' (continued)

RCF-X / -

l '' M-CHCOOH + SOCI.

benzene

CHCOCl + HO-CH -4_y! I.

R2 R3

RCF_X-. A

CH-CO-O-CH i

R-,

> RCF „X-V ^ V-CHCOCl

benzene

Preparation 1 Preparation of alpha-isopropyl-4-trifluoro-methoxyphenylacetyl chloride A solution of 1.2 g of alpha-isopropyl-4-trifluorometh-oxyphenylacetic acid and 0.6 ml of thionyl chloride in 5 ml of benzene is heated to boiling under reflux for 4 hours. Evaporation of the solvent and excess thionyl chloride gives the acid chloride which is used as such for the esterification described in Examples 1 and 2.

example 1

Preparation of [alpha-cyano-m-phenoxybenzyl] alpha-isopropyl-4-trifluoromethoxyphenylacetate A solution of 4.58 mmol of alpha-isopropyl-4-trifluoro-methoxyphenylacetyl chloride in 5 ml of ether is converted into a solution of 4.58 mmol of alpha Cyano-m-phenoxybenzyl alcohol and 0.5 ml pyridine in 20 ml ether. The mixture is stirred overnight and filtered. The filtrate and washings are evaporated and the remaining oil is purified on silica gel plates using 1: 1 methylene chloride / hexane as eluent. The band of Rf = 0.55 is extracted with ether and, after evaporation, provides 0.85 g of the desired ester.

IR (without addition) 1755 cm "" 1, nmr (CDC13) delta 6.8-7.6 (m, 13H, ArH), 6.31 and 6.28 (S, 1H, -CH-Ar), 3 , 27 [d, J =

CN

7Hz, 1H, CH-CH (CH3) 2], 2.0-2.6 [m, 1H, CH (CH3) 2], 0.6-1.2 (4 doublets, J = 7 Hz, 6H, Isopropyl-CH3), 19F chemical shift 58.8 delta with respect to CFC13.

Preparation 2 Preparation of alpha-isopropyl-4-hydroxy-phenylacetic acid A mixture of 40.0 g of alpha-isopropyl-4-methoxy-phenylacetonitrile and 200 ml of 48 percent hydrobromic acid is boiled at 126 to 128 ° C. for 14 hours using an oil bath Reflux heated. The reaction mixture is diluted with ice and water, extracted several times with ether, washed with water and evaporated to a solid residue. The residue is heated to boiling with 200 ml of chloroform, cooled, filtered and dried. Yield 23.8 g, m.p. 172-30 30 ° C, ir (Nujol) 3250-2900 (broad, OH), 1690 cm-1 (C = 0).

Comparable results are obtained using alpha-ethyl-4-methoxyphenylacetonitrile or alpha-n-propyl-4-methoxyphenylacetonitrile for the production of alpha-35 ethyl-4-hydroxyphenylacetic acid or alpha-n-propyl-4-hy-hydroxyphenylacetic acid achieved.

Preparation 3 Preparation of alpha-isopropyl-4-difiuormethoxy-40 phenylacetic acid

In a mixture of 10.00 g (0.0515 mol) of alpha-iso-propyl-4-hydroxyphenylacetic acid, 65 ml of dioxane, 19.08 g of NaOH content, 18.56 g, (0.464 mol) of sodium hydroxide and 30 ml of water of 80 ° C. 46 g (0.532 mol) of chlorodifluoromethane are introduced with stirring using a 45 magnetic stirrer within 4 hours. The reaction mixture is poured into 250 ml of ice water, and the mixture obtained is washed with ether, acidified to pH 3 with concentrated hydrochloric acid and then extracted with 200 ml of ether. The ether solution is washed once with 100 ml of water, dried with sodium sulfate, filtered and evaporated to give a white paste. After adding a mixture of hexane and methylene chloride, the mixture is filtered, whereby the solid, which is the starting material, is removed. The filtrate is evaporated to give 5.41 g of a clear brown oil. Due to the NMR spectrum, the product can be regarded as at least 85% pure. NMR (CDCl3-d5 pyridine), delta 7.43 (d, J = 8.2Hz, 2H) delta 7.08 (d, J = 60 8.2Hz, 2H), delta 6.57 (t, J = 74 , 3Hz, IH), delta 3.63 (s, unr.), Delta 3.25 (d, J = 10 Hz, IH), delta 2.37 (m, IH), delta 1.19 (d, J = 6.5Hz, 3H), delta 0.78 (d, J = 6.5Hz, 3H) delta 13.82 (s, 1H).

Comparable results are obtained using 65 alpha-ethyl-4-hydroxyphenyl- or alpha-n-propyl-4-hydroxy-phenylacetic acid for the production of alpha-ethyl-4-difluoromethoxyphenyl- or alpha-n-propyl-4-difluorometh -oxyphenylacetic acid obtained.

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Production 4 Production of alpha-isopropyl-3-bromo-4-hydroxy-

phenylacetic acid A mixture of 20 g (0.103 mol) of alpha-isopropyl-4-hydroxyphenylacetic acid and 250 ml of chloroform is cooled to 0 ° C. and 16.5 g (0.103 mol) of bromine in 15 ml of chloroform are added in 30 minutes. The reaction mixture is stirred at 0 ° C for 30 minutes and then allowed to warm to room temperature. The solvent is evaporated and the residue is recrystallized from hexane / benzene to give 22.1 g of the monobromo derivative of mp = 113 to 116 ° C.

Production 5 Production of alpha-isopropyl-3-bromo-4-difluoro

methoxyphenylacetic acid Following the procedure described in Preparation 3, 18.0 g of alpha-isopropyl-3-bromo-4-hydroxyphenyl-acetic acid are converted into the corresponding difluoromethoxy compound. The desired acid is obtained as a waxy solid in an amount of 4.7 g by separating the unreacted starting material by chromatography on silica gel using chloroform containing 2.5% of methanol as eluent. This crude acid is used as such in Examples 2 and 3.

Example 2

Preparation of m-phenoxybenzyl-alpha-isopropyl-3-

bromo-4-difluoromethoxyphenylacetate A solution of alpha-isopropyl-3-bromo-4-di-fluoromethoxyphenylacetyl chloride in methylene chloride is added to a solution of m-phenoxybenzyl alcohol and pyridine in methylene chloride from the corresponding acid according to the procedure described in Preparation 1. After stirring overnight, the reaction mixture is washed with water, dilute hydrochloric acid, dilute potassium hydroxide solution and water and evaporated to an orange oil. After purification by chromatography on silica gel, the desired ester is obtained as a pale yellow smear.

NMR (CDC13), delta 6.8-7.7 (m, 12H, ArH), 6.45 (t, J = 74Hz, 1H, OCHF2), 5.10 (broad, 1H, CH2), 3.18 (d, J = 9Hz, 1H, CH-CH (CH3) 2), 1.0 and 0.71 (2d, J = 6Hz, 6H, isopropyl-CH3).

Example 3

Preparation of [alpha-cyano-m-phenoxybenzyl] -alpha-isopropyl-3-bromo-4-difluoromethoxyphenyl acetate According to the procedures described in preparation 1 and example 1, using alpha-iso-propyl-3-bromo-4- difluoromethoxyphenylacetic acid received the product as a yellow smear.

NMR (CDC13) delta 6.9-7.7 (m, 12H, ArH), 6.50 (t, J = 74Hz, 1H, OCHF2), 6.33 and 6.36 (2S, IH, CH-CN ), 3.25 (d, 1H, CH-CH (CH3), 0.6-1.1 (4d, 6H, isopropyl-CH3).

Production 6 Production of alpha-isopropyl-3-chloro-4-hydroxy-

phenylacetic acid A mixture of 30 g (0.154 mol) of alpha-isopropyl-4-hydroxyphenylacetic acid and 600 ml of chloroform is cooled to 0 to 5 ° C., and then 12.0 g (0.169 mol) of chlorine gas are slowly introduced. The solvent is removed and the product is recrystallized from benzene / hexane. F. = 125 to 128 ° C.

Example 4

Preparation of [alpha-cyano-m-phenoxybenzyl] -alpha-iso-propyl-3-chloro-4-difluoromethoxyphenylacetate According to the procedures described in Preparations 1 and 3 and Example 1, using al-pha-isopropyl-3- chlor-4-hydroxyphenylacetic acid received the product as grease.

NMR (CDC13) delta 6.8-7.5 (m, 12H, ArH), 6.50 (t, J = 74Hz, 1H, OCHF2), 6.33 and 6.30 (2S, 1H, -CH- CN), 3.25 (d, J = 10Hz, 1H, CH-CH (CH3) 2).

Analysis, C26H22C1F2N04:

calculated: C 64.26 H 4.56 N2.88 C17.3Q F 7.82 found: C 64.27 H 4.70 N2.94 Cl 7.20 F 7.78.

Example 5

Preparation of m-phenoxybenzyl-alpha-isopropyl

3-chloro-4-difluoromethoxyphenylacetate According to the procedures described in Preparations 1 and 3 and Example 2, the product is obtained as a yellow oil using al-pha-isopropyl-3-chloro-4-hydroxyphenylacetic acid. '

NMR (CDC12) delta 6.8-7.6 (m, 12H, ArH), 6.47 (t, J = 74Hz, OCHF2), 5.07 (bs, 2H, CH2).

Analysis, C25H23C1F204:

calculated: C 65.15 H 5.03 Cl 7.69 F 8.24 found: C 65.46 H 5.05 Cl 7.73 F 8.08

Preparation 7 Preparation of alpha-rsopropyl-3,5-dichloro-4-hydroxyphenylacetic acid A mixture of 30 g (0.155 mol) of alpha-isopropyl-4-hydroxyphenylacetic acid and 500 ml of chloroform is cooled in an ice-salt bath and at 5 ° C 30 to 35 g of chlorine gas are introduced for 90 minutes. The solution is stirred for an additional hour at 0 to 5 ° C and then allowed to warm to room temperature. The solvent is evaporated and the product is recrystallized from hexanes to give 29.8 g of a white solid, mp = 152-154 ° C.

Manufacturing 8

Preparation of alpha-isopropyl-3,5-dichloro-4-trifluoro

methoxyphenylacetic acid According to the procedure described in Example 5, the acid mentioned in the heading is obtained as an oil using alpha-isopropyl-3,5-dichloro-4-hydroxyphenylacetic acid. The NMR spectrum of the product shows

that it contains about 15 mol% of the starting material. It is used as such in Example 15.

Example 6

Preparation of [alpha-cyano-m-phenoxybenzyl] alpha-isopropyl-3-bromo-4-difluoromethoxyphenylacetate According to the procedure described in preparation 1 and example 1, alpha-isopropyl-3,5-dichloro-4-difluoromethoxyphenylacetic acid is used received the product as a yellow smear. NMR (CDC13) delta 6.9-7.7 (m, 11GH, ArH), 6.67 (t, J = 74Hz, 1H, OCHF2), 6.33 and 6.40 (2S, 1H, CH-CN ), 3.23 (d, J = 10Hz, 1H, CH-CH (CH3) 2, 0.6-1.1 (4d, 6H, isopropyl-CH3).

Analysis, C22H2C12F2N04:

calculated: C 60.01 H 4.07 N 2.69 found: C 59.78 H 4.30 N 2.31

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641638

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Example 7

Preparation of m-phenoxybenzyl-alpha-isopropyl

3,5-dichloro-4-difluoromethoxyphenylacetate According to the procedures described in Preparation 1 and Example 2, the product is obtained as grease using alpha-isopropyl-3,5-dichloro-4-difluoromethoxyphenylacetic acid.

Analysis, C25H22C12F204:

calculated: C 60.61 H 4.48 Cl 14.32 F 7.67 found: C 60.50 H 4.60 Cl 14.13 F 7.52

Production 9 Production of alpha-isopropyl-3-methyl-4-difluoro

methoxyphenylacetic acid 3-methyl-4-methoxyphenylacetonitrile is converted into the compound mentioned in the heading according to the procedures described in Preparations 2 and 3. The product, as its NMR spectrum shows, is contaminated with some alpha-isopropyl-3-methyl-4-hydroxyphenylacetic acid. However, it is used as such for the esterification according to Example 9, where the ester obtained is then purified by chromatography.

Example 8

Preparation of [alpha-cyano-m-phenoxybenzyl] -alpha-iso-propyl-3-methyl-4-difluoromethoxyphenylacetate According to the procedures described in Preparation 1 and Example 1, the ester obtained as Preparation 9 is obtained as a viscous oil . NMR (CDC13) delta 6.8-7.6 (m, 12H, ArH), 6.45 (t, J = 74Hz, 1H, OCHF2), 6.48 and 6.53 (2S, 1H, CH-CN ), 2.25 (S, 3H, CH3).

Analysis, C27H25F2N04:

calculated: C 69.66 H 5.41 N 3.01

found: C 70.05 H 5.86 N 2.83

Preparation 10 Preparation of 3-fluoro-4-methoxyphenylacetonitrile A mixture of 45.8 g (0.21 mol) of 4- (bromomethyl) -2-fluoroanisole, 1.4 g of trihexylamine and 20.5 g (0.42 mol) Sodium cyanide in 50 ml of water is heated to 60 to 65 ° C for 18 hours. The mixture is cooled and extracted with ether. The ether extract is washed with water and saturated sodium chloride solution and dried over Na2S04. Evaporation of the solvent gives 33.2 g of a solid of mp = 42 to 46 ° C.

Production 11 Production of alpha-isopropyl-3-fluoro-4-methoxy

phenylacetonitrile A mixture of 30 g (0.18 mol) of 3-fluoro-4-methoxy-phenylacetonitrile, 27.7 g (0.225 mol) of 2-bromopropane, 2.3 g (0.01 mol) of benzyltriethylammonium chloride and 66 ml of a 50 -percent sodium hydroxide solution is heated to 55 ° C. for 1 hour and cooled. The mixture is diluted with water and extracted with ether, and the extract is washed with water, in HCl and water and dried over Na2S04. Evaporation gives the product as a brown oil in an amount of 30.7 g. The NMR spectrum shows the benzyl proton as a doublet at 3.6 delta.

Production 12 Production of alpha-isopropyl-3-fluoro-4-difluoro-methoxyphenylacetic acid Starting from aIpha-isopropyl-3-fluoro-4-methoxy-phenylacetonitrile, is carried out according to the in the preparations 2 and

3 described ways of working get the product as a brown oil. The NMR spectrum shows that it is contaminated by starting material. Therefore, the crude reaction mixture is subjected to the Freon 22 reaction described in Preparation 3 two more times, whereby the product is obtained as a brown oil. The NMR spectrum shows that the product makes up about 96 percent by weight.

Example 9

Production of [alpha-cyano-m-phenoxybenzyl] -alpha-iso-propyl-3-fluoro-4-difluoromethoxyphenylacetate Starting from alpha-isopropyl-3-fluoro-4-difluorometh-oxyphenylacetic acid, is according to the in preparation 1 and example 1 described operations of the esters obtained as a yellow oil. NMR (CDC13) delta 6.8-7.5 (m, 12H, ArH), 6.63 (t, J = 74Hz, 1H, OCHF2), 6.33 and 6.37 (2S, 1H CH-CN) .

Analysis, C26H22F3N04:

calculated: C 66.52 H 4.72 N 2.98

found: C 66.27 H 4.87 N 2.99

Production 13 Production of alpha-isopropyl-3-nitro-4-hydroxy-

phenylacetic acid A mixture of 18.2 g (0.094 mol) of alpha-isopropyl-4-hydroxyphenylacetic acid and 130 ml of acetic acid is heated to 40 ° C. and mixed with 9.56 g (0.095 mol) of 70 percent nitric acid at a rate at which the reaction temperature remains at 38 to 40 ° C and never exceeds 45 ° C. The reaction mixture is stirred at 40 to 42 ° C. overnight and poured into ice water. The yellow solid is filtered off, washed and dried. 19.1 g of substance with a melting point of 103 to 105 ° C. are obtained.

Preparation 14 Preparation of alpha-isopropyl-3-nitro-4-difluoro-methoxyphenylacetic acid Using alpha-isopropyl-3-nitro-4-hy-hydroxyphenylacetic acid, the acid mentioned in the heading is used as the unreacted starting material according to the procedure described in Preparation 3 get contaminated crude product. By repeating the Freon 22 reaction described in Preparation 3 three times, using the product obtained each time, the product is finally obtained from hexanes as a fine beige solid of F. = 88 to 90 ° C.

Example 10

Preparation of [alpha-cyano-m-phenoxybenzyl] -alpha-iso-propyl-3-nitro-4-difluoromethoxyphenylacetate Using alpha-isopropyl-3-nitro-4-di-fluoromethoxyphenylacetic acid, the procedure described in Preparation 1 and Example 1 is followed the product described as a yellow oil.

Analysis, C26H22F2N206:

calculated: C 62.90 H 4.47 N 5.64

found: C 62.51 H 4.77 N 5.58

Example 11

Preparation of [alpha-cyano-m-phenoxybenzyl] alpha-iso-propyl-3-methoxy-4-difluoromethoxyphenylacetate Using alpha-isopropyl-3-methoxy-4-difluoromethoxyphenylacetic acid is carried out according to the procedures described in Preparation 1 and Example 1 received the product as a goo.

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Preparation 15 Preparation of m- (m-fluorophenoxy) benzaldehyde The sodium salt of 3-fluorophenol is prepared by mixing 15.13 g (0.135 mol) of 3-fluorophenol with 7.29 g (0.135 mol) of sodium methoxide in 115 ml of pyridine . The reaction mixture is heated to 110 ° C., 34 ml of pyridine / methanol being distilled off. After cooling to 80 ° C., 25.0 g (0.135 mol) of m-bromobenzaldehyde and 4.05 g (0.049 mol) of copper (I) chloride are added. The reaction mixture is heated to boiling under reflux overnight. The following day, most of the pyridine is distilled off and the cooled reaction mixture is diluted with 80 ml of toluene. The solids are filtered off and the filtrate is washed with 20 percent HCl, water, 5 percent NaOH and water and evaporated to a dark brown oil. By vacuum styleRCF_0

hQ-çh-

9 641 638

lation, the product is obtained as a clear liquid in an amount of 6.6 g. Kp = 82-88 ° C (0.5 mm).

Analysis, C13H9F02:

s calculated: C 72.22 H 4.20 F 8.79 found: C 72.03 H 4.30 F 8.60

Example 12

Preparation of substituted [alpha-cyano-m-phenoxy

10 benzyl] esters of fluoroalkoxyphenylacetic acids starting from alpha-isopropyl-4-difluoromethoxy

phenylacetic acid or alpha-isopropyl-4-trifluoromethoxy-phenylacetic acid and the cyanohydrin of an appropriately substituted aldehyde, the following esters are obtained according to the procedures described in Preparation 11 and Example 1:

COO-CH-

CN

CH (CH3) 2

R "

R R4 NMR

H p-Cl

H p-OCH3

H p-CH3

H p-F

F p-F

Court

H m-F

F p-Cl

F p-CH3

F p-OCH3

Production 16 Production of alpha-ethynyl-m-phenoxybenzyl alcohol Acetylene is dried in succession by dropping with dry ice acetone, concentrated sulfuric acid and calcium chloride and 10 minutes under pressure

Analysis, calc. Analysis, found

of about 0.35 kg / cm 2 in 100 ml of dry tetrahydrofuran 65. 0.14 mol of technical grade ethyl magnesium bromide is added dropwise over a period of 2 hours at a rate at which slow and uniform evolution of ethane takes place. Then acetylene is added for 6.8 minutes to 6.8-7.5 (m, 12H, ArH), C 64.27 C 64.54

6.45 (t, J = 74Hz, IH, OCHF2), H 4.56 H 4.92

6.30, 6.33 (2S, IH, CH-CN), N 2.88 N 2.82 3.25 (d, J = 10Hz, 1H, CH-CH (CH3) 2,

0.6-1.2 (d, 6H, isopropyl CH3)

6.8-7.4 (m, 12H, ArH) C 67.35 C 67.30

6.47 (t, J = 74Hz, IH, OCHF2), H 5.23 H 5.46

6.28, 6.33 (2S, IH, CN-CN), N 2.91 N 2.92 3.80 (S, 3H, OCH3)

6.8-7.5 (m, 12H, ArH), C 69.67 C 69.37

6.50 (t, J = 74Hz, 1H, OCHF2), H 5.41 H 5.72

6.33.6.37 (2S, 1H, CH-CN), N 3.01 N 2.82 2.40 (S, 3H, CH3)

6.8-7.5 (m, 12H, ArH), C 66.51 C 66.48

6.47 (t, J = 74Hz, 1H, OCHF2), H 4.73 H 4.95

6.30.6.36 (2S, IH, -CH-CN), N 2.98 N 2.64

6.8-7.5 (m, 12H, ArH), C 64.06 C 63.85

6.32, 6.37 (2S, 1H, -CH-CN), H 4.35 H 4.31

3.30 (d, J = 10 Hz, IH, CH-CH (CH3) 2) N 2.87 N 2.63

6.8-7.4 (m, 12H, ArH), C 66.52 C 66.68

6.43 (t, J = 74Hz, IH, OCHF2), H 4.72 H 4.80

6.30 and 6.34 (2S, IH, -CH-CN), N 2.98 N 3.04

3.27 (d, J = 10Hz, IH, CH-CH (CH3) 2) F 12.14 F 12.05 6.5-7.5 (m, 12H, ArH), C 66.52 C 66.80 6 , 33 and 6.39 (2S, IH, -CH-CN), H 4.72 H 4.77 6.47 (t, J = 74Hz, 1H, 0CHF2), N 2.98 N 2.89

3.28 d, J = 10Hz, 1H, CH-CH (CH3) 2) F 12.14 F 11.93 6.8-7.5 (m, 12H, ArH), C 61.97 C 62.05 6, 37 and 6.41 (2S, 1H, -CH-CN, H 4.20 H 4.25 3.33 (d, J = 10Hz, CH-CH (CH3) 2), N 2.78 N 2.52 0.6-1.2 (4d, bH, isopropyl CH3)

6.8-7.4 (m, 12H, ArH), C 67.07 C 65.28 6.37 and 6.41 (2S, 1H, -CH-CN) H 5.00 H 5.18 2.40 ( S, 3H, CH3) N 2.90 N 2.26

6.9-7.5 (m, 12H, ArH), C 64.92 C 64.04 6.25 and 6.30 (2S, 1H, CH-CN), H 4.84 H 4.87 3.63 ( S, 3H, OCH3) N 2.80 N 2.65

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headed. At 15 to 20 ° C, 27.7 g (0.14 mol) of m-phenoxybenzaldehyde in 25 ml of THF is added to the reaction mixture. The mixture is then stirred at room temperature overnight. Saturated ammonium chloride solution is added to the complex. The product is extracted with ether and the ether extract is washed with water and dried over Na2S04. Evaporation of the solvent and subsequent vacuum distillation using Kugelrohn give 21.5 g of the alcohol.

Example 13

Preparation of [alpha-ethynyl-m-phenoxybenzyl] alpha

iso-

propyl-4-trifluoromethoxyphenylacetate Using the alcohol obtained after preparation 16 and alpha-isopropyl-4-trifluoromethoxyphenylacetic acid, the product is obtained as yellow smear * according to the procedures described in preparation 1 and example 2. The NMR spectrum shows the characteristic alkynyl proton as a multiplet at 2.52 delta and benzyl protons at 6.35 delta.

Analysis, C27H23F3O4 .:

calculated: C 69.22 H 4.95 found: C 68.17 H 4.11

The same procedure is followed using the alcohol of preparation 16 and alpha-isopropyl-4-difluoromethoxyphenylacetic acid to give the [alpha- "ethynyl-m-phenoxybenzyl] alpha-isopropyl-4-difluoromethoxyoxyphenylacetate.

Analysis, C27H24F 2O4:

calculated. Found C 71.99 H 5.37: C 71.59 H 5.53

The compounds according to the invention are highly effective as contact and gastric poisons for ixodide ticks and a large variety of different insects, in particular Diptera, Lepidoptera, Coleoptera and Homoptera insects. In a manner unusual for pyrethroids, they exhibit a large-scale insecticidal residue action on plant tissue, are effective in the soil and are surprisingly effective in controlling Ixodidae and protecting animals against insects and Ixodidae when administered orally or parenterally to the animals or as topical insecticides or Acaricidal preparation to be used on the animals. For insecticidal and acaricidal preparations with stabilized effects, mixing with a stabilizing agent is required. However, the active ingredients can also be used together with other biologically active chemicals, e.g. with pyrethroid synergists, such as piperonyl butoxide, sesamex or n-octyl sulfoxide from Isosa-frol. The compounds according to the invention can also be used together with conventional insecticides, e.g. Phosphates, carbamates, formamidines, chlorinated hydrocarbons or halobenzoylureas can be used. In order to control insects, including soil insects which attack growing plants and / or harvested material, including stored grain, the insecticidal compounds according to the invention can be applied to the foliage of plants, the place where the insects occur and / or their food. In general, the active ingredient is used in the form of a dilute liquid spray, but it can also be used as an aerosol, dust, granulate or wettable powder.

Liquid spray agents that are particularly well suited are oil spray agents and emulsifiable concentrates that can be further diluted for use. While they are produced as liquid concentrates, these preparations are usually first dispersed in water at the point of use because of the easier handling and easier transport and then applied as diluted liquid spray to the foliage of the plants, the soil or the surface of the area to be treated.

An emulsifiable concentrate that can be used to protect a variety of crops such as cereals, cabbage, pumpkin, corn, cotton, tobacco, soybeans, ornamental plants, shrubs, and the like can be about 20 percent by weight of active ingredient, 4 percent by weight of an emulsifier, as is customary is used to prepare pyrethroid formulations containing 4 percent by weight of a surfactant, 25 percent by weight of an organic solvent such as cyclohexa-non, and about 47 percent by weight of a petroleum solvent with an aromatic content of about 83 percent by volume.

Example 14 Insecticidal activity The insecticidal activity of the compounds according to the invention is demonstrated on the basis of the following tests, in which the tobacco caterpillar Heliothis virescens (Fabricius), the potato leaf hopper, Western Potato leaf-hopper, Empoasca abrupta (DeLong) and the bean aphid, Aphis fabae (Scopoli) , are used as insect species. The procedures used are as follows:

Tobacco caterpillar, Heliothis virescens (Fabricius) in the first stage of development

A cotton plant with two real folded leaves is immersed for 3 seconds with stirring in the solution to be examined (35% water / 65% acetone), which contains 300, 100 or 10 ppm of the compound to be examined. Then you put each leaf in a cup with a wick and add a gauze cloth filled with 50 to 100 newly hatched larvae before closing the cup with a lid. After 3 days at a temperature of 27 ° C (80 ° F) and a relative humidity of 50%, the cups are examined and the kill of the newly hatched larvae is assessed. The numerical values obtained are listed as a percentage of the kill in Table I.

Bean aphid, Aphis fabae (Scopoli)

Five pots of fiber, each containing a 5 cm (2 inch) nasturtium planted with 100 to 150 aphids two days earlier, are placed on a turntable operating at 4 rpm and spray the plants with a solution containing 35% water and 65% acetone containing 100, 10, 1, 0 and 0.1 ppm of the compound to be examined, the solution being sprayed for two turns using a spray device ( De-Vilbis Atomizer), which is operated with air at a pressure of 1.41 kg / cm2 (20 psi). The spray nozzle is placed about 15 cm from the plant and the spray is directed so that the aphids and plants are completely covered. The sprayed plants are then placed in white enamel bowls. Mortality is determined after one day at 21 ° C (70 ° F) and a relative humidity of 50%. The numerical values obtained are listed as a percentage of mortality in Table I below.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

Table I

Assessment of insecticidal effects

% Mortality T abakraupenlarvq

Compound 1st stage of aphid aphid development

300 100 10 100 10 1 100 10 1 0.1

ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm cn f2cho ~ ^ y- ch-co-o-ch-i ch (ch3) 2

Cl f ^ cho - ^ "^ ch-c0-0- &

\ /

ch (ch,),

100 100 100 100 100 0 100 100 100 0

100 100 0 100 90 0 100 100 75

f? cho- <f ~ ^ ch-co-o-ch-

ch (cl3) 2

100 100 0 90 50 0 100 100 70

2CH0- ^ r ~ ^ CH-C0-0-ÒH-Y ^

ch (ch3) 2

\ f

100 100 100 100 0

100 100 90 0

2cho- ^ ~ ^) - ch-co-o-óh ^ = - 'ch (ch3) 2

100 100 50 100 100 50 100 100 50 0

> 2cho- <Q> -

cn

I.

ch-c0-0-ch-

ch (ch3),

100 100 0 50

100 100 0

F3C ° ^ 0V

cn I

ch-co-o-ch ch (ch3) 2

cn f co -ù y— ch-co-o-ch - ch (ch3) 2

cn f3co- <;

// v \ I

t \\ - CH-C0-0-C.il

CH (CH3) 2

cn

.f, c0 çh-co-o-ch

\ = zJ ch (ch3) 2

ch-

f2ch0

Jt \

cn ch-co-o-ch ch (ch3) 2

f2cho ch-co-o-ck2

ch {ch,) _

O £

Table I (continued)

% Mortality T tobacco caterpillar larva

1. Developmental aphid aphid

300 100 10 100 10 1 100 10 1

ppm ppm ppm ppm ppm ppm ppm ppm ppm

100 100 100 100 100 80 100 100 90

100 100 0 100 100 50 100 100 100

90 80 0 100 100 0 100 100 100

100 100 100 100 60 - 100 100 100

100 100 100 100 100 100 100 100 90

100 80 0 100 50 - 100 100 100

F2CH0

Ù v

Br

CN I

CH-CO-O-CH I

CH (CH.,) 2

-un ■ Jf \ v ■ rH-rn-n-fH

F 2 CHO

"X CN

// \\ i

F-CHO -V x> - CH-CO-O-CH-r ^

£. \ / I

F CHO-v M-w

2 A_ / 7 2

CH (CH3> 2

0-

100

100

100

100

100

100 100 100 75 - 100 100 75

0 90 50 - 100 100 100 0

100 100 100 100 100 100 100 100 100

80 0 100 0 - 100 100 50

100 100 100 100 0 100 100 100 o

£

On w

00

641 638

Potato leafhopper, Empoasca abrupta (DeLong)

A bean plant (Sieva lima) with the first leaf folded out to 7.5 to 10 cm (3 to 4 inches) is immersed in a solution of 35% water and 65% acetone containing 100.10 and 1 ppm of the compound to be examined . Then place the immersed plant in a hood to dry and cut a 2.5 cm piece of the tip of a leaf and place it in a 10 cm (4 inch) diameter petri dish containing a damp filter paper on the bottom . Then you transfer three to ten nymphs of the second stage of development into the petri dish, which is then covered. The mortality is then counted after storing the Petri dishes for two days at 27 ° C (80 ° F) and a relative humidity of 50%. The numerical values obtained are listed in Table I. Permethrin is used as the reference standard in these studies.

Example 15 Insecticidal Activity The insecticidal activity of the compounds according to the invention is further determined with the aid of the following test methods, in which the action against mosquito larvae, Mexican ladybugs and cotton worms is investigated.

Malaria mosquito, Anopheles quadrimaculatus (Say)

Pipette 1 ml of a solution of 35% water and 65% acetone, which contains 300 ppm of the compound to be investigated, into a 400 ml beaker containing 250 ml of deionized water, stir with the pipette and reach a concentration of 1. 2 ppm. Then aliquots of this solution are removed and further diluted to 0.4, 0.04 and 0.004 ppm. In order to prevent the eggs from floating on the side wall of the beaker and drying out there, a wax paper ring with a width of 0.6 cm that fits into the beaker is floated on the surface of the solution to be examined. A sieve spoon is used to hold and transfer approximately 100 eggs (0 to 24 hours old) into the beaker. Hatching is observed after 2 days at 27 ° C (80 ° F) and 50% relative humidity. The percentage mortality is shown in Table II below.

Mexican ladybird, Epilachna varivestis (Mulsant)

Bean plants (Sieva lima) (two per pot) with 7.5 to 10 cm long first leaves are immersed in the solution containing 300, 100, 10 or 1 ppm of the compound to be investigated and allowed to dry in the hood. Then you take a leaf from the plant and place it in a 10 cm petri dish, which contains a moist filter paper and 10 larvae in the last stage of development (13 days before hatching) on the bottom. The day after the treatment, another leaf is removed from the plant and fed to the larvae after the remains of the first leaf have been removed. Two days later, a third leaf is fed to the larvae, which is generally the last leaf required. The fourth leaf is given on the third day after the start of treatment when the larvae have not stopped feeding. The petri dishes are then set aside and stored until the adult animals hatch, which is the case about 9 days after the start of treatment. Upon complete leakage of the animals, each petri dish becomes the normal one for slaughtered larvae, pupa or adult animals, deformed pupa or adult animals, intermediate stages between the larval stage and the pupa stage and the pupa stage and the adult stage, or for any other effects on the normal moult Development and normal appearance of dolls or adult animals were examined.

The numerical values obtained are listed in Table II below.

Cotton worm, (Southern Armyworm), Spodoptera erida-lo nia (Cramer)

Bean plants (Sieva lima) with two folded 7.5 to 10 cm long first leaves are immersed in the treatment solutions for 3 seconds with stirring and then left to dry in a hood. After the leaves are dry, they are cut out, and each cut sheet is placed in a 10 cm petri dish containing a piece of damp filter paper and 10 cotton caterpillar larvae in the third stage of development, about 1 cm long. The Petri dishes are covered and stored for 20 days at a temperature of 27 ° C (80 ° F) and a relative humidity of 50%. Mortality is counted after 2 days. The results obtained are summarized in Table II below.

25 Example 16

Insecticidal effect Spotted spider mite, Tetranychus urticae (Koch)

Bean plants (Sieva lima), the first leaves of which are 7.5 to 10 cm long, are populated with about 100 adult, 30 phosphate-resistant mites per leaf, 4 hours before the examination is carried out, in order to lay eggs before the To allow treatment. The infected plants are then immersed for 3 seconds with stirring in the solution containing 1000, 300, 100 or 10 ppm of active ingredient 35, whereupon the plants are placed in the fume cupboard to dry. After 2 days at 27 ° C (80 ° F), the mortality of the adult mites on a leaf is estimated under a stereoscopic microscope at 10X magnification. The other 40 leaves are left on the plant for a further 5 days and then examined at 10-fold intensification in order to estimate the killing of the eggs of the newly hatched nymphs, as a result of which the ovicidal action or the remaining action can be determined. The results are summarized in Table III below.

Tobacco caterpillar, Heliothis virescens (Fabricius) in the third stage of development

Three cotton plants with just cotyledon leaves folded are dipped into the solution containing 1000 or 100 ppm of the active ingredient and then transferred to a hood for drying. After drying, each cotyledon is halved and 10 leaf sections are placed in a 28 g plastic medication beaker containing a 1.25 cm thick dental tampon saturated with water, followed by a third stage of tobacco caterpillar development Brings in the mug. The cup is closed and stored for 3 days at 27 ° C (80 ° F) and a relative humidity of 50%, whereupon the mortality is counted. The results obtained are summarized in Table III below.

Cabbage looper Trichoplusia ni (Hübner) in the third stage of development.

«S A real leaf of a cotton plant is dipped into the solution to be examined, which contains 1000, 100 or 10 ppm of the compound to be examined, is stirred for 3 seconds, the plant is removed and left in the hood.

Table II Evaluation of insecticidal activity

connection

% Mosquito larvae mortality 1.2 0.4 ppm ppm

Cotton worm 0.04 0.004 1000 100 10 ppm ppm ppm ppm ppm

Mexican ladybug 300 100 10 1 ppm ppm ppm ppm

'Court\-

f2ch0 - </ y-ch-c0-0-ch ch (ch3) 2

FjCHO

ch-c0-0-ch ch (ch3) 2

f9ch0

f2ch0

> -Q-

ch-c0-0-ch ~

ch (ch3) 2

- // \ v ch-c0-0-ch - |

ch (ch3) 2

100 100 100 80 100 90 0 100 40 0 0

80 100 100 80 100 100 0 90 90 0

100 100 100 80 100 0 0 100 80 0

100 100 100 100 100 100 90 100 50 0

f2ch0

cn I

ch-co-o-ch 1 '

ch (ch3) 2 •

-0

CS

cn

_ // \\ I

f2ch0 ~ \ __ y-ch-co-o-ch -

ch (ch3) 2

f

100 100 100 50 100 100 40 100 100 100 0

100 100 100 0 100 100 0 100 100 100 0

F ^ CO

cn!

/ \ v ch-co-o-ch ch (ch3) 2

Cl

100 100 100 100 100 100 60 100 100 100 0

Connection cn I

• ch-

F3C0H ^ CH-CO-O-

ch (ch3)?

-o-r> "

ch.

f co-y y-ch-co-o-3 ch (ch 3) 2

cn ch-co-o-ch

F3- ° - \ _ / Ì

\ _— / r

CH

f2cho-

ch (ch3) 2

cn I

CH-CO-O-CH

/ l ch (ch3) 2

och

f f2cho ch-co-o-ch ch (ch3) 2

Table II (continued)

% Mortality

Mosquito larvae Cotton caterpillar Mexican ladybug

1.2 0.4 0.04 0.004 1000 100 10 300 100 10

ppm ppm ppm ppm ppm ppm ppm ppm ppm ppm

100 100 80 - 100 50 0 100 100 50

100 100 100 0 100 100 0 100 100 50

100 100 100 100 100 100 100 100 80 40

100 100 100 100 100 100 20 100 100 90

100 100 100 0 100

100 100 100 0 100

100 100 80 50 100 0 0 0

f2ch0

Cl

• CH-CO-O-CH CH (CK3) 2

Cl

F2CH0 - ([ÇH-C0-0-CH2

Cl Cl

F "CHO

CH (CH3) 2

^ ° o

CN I

. ^ <TV CH-CO-O-CH CiW • ÌH {CH3) 2

rO

80 100 100 0 100 100 70 100

100

100

100 90 0 100

100 100 0 100

Table III Insecticidal activity

connection

% Mortality resistant to mites

1000 300 100

ppm ppm ppm

Tobacco caterpillar i. Cabbage caterpillar i.

3rd stage of development 3rd stage of development 10 1000 100 1000 100 10

ppm ppm ppm ppm ppm ppm

CN

100

100

100 40

100

50

100 60

100 100

F2CK0

// V

CN!

CH-C0-0-CH CH (CH3) 2

■ ° T H

CH ,,

100

100 20 100 100

30th

connection

/ ck f2ch0 -v y- ch-co-o-ch \ r = y cH (CH3) 2

f3c0

cn

/ m-ch-co-o-ch -r ^ y-0 ch (ch3) 2

f co -v y-ch-co-o-ch ch (ch3) 2

ÇN

f.cho-v Vch-co-o-ch -v = / ch (CH3) 2

F2CJH0 CH-C0-0-CH2

y ^ l / n-u fru i f

Br ch (ch3; 2

F2CH0 ~ ^^ y-ÇH-C0-0 "CHi ^ rN-C

ch (ch3) 2

Cl

F, CHO

cn

I.

ch-co-o-ch- ^

ch (ch3) 2

Table III (continued)

% Mortality

Phosphate-resistant mites tobacco caterpillar i. Cabbage caterpillar i.

3, stage of development 3rd stage of development 1000 300 100 10 1000 100 1000 100 10

ppm ppm ppm ppm ppm ppm ppm ppm ppm

100 100 0 - 100 100 100 100 100

100 100 0 - 100 80 100 100 90

100 100 80 - 100 100 100 100 100

100 0 0 - 100 80 100 100 50

100 0 - - 90 30 90 50

100 - 0 100 100 100 0 0

100 100 0 - 100 90 100 100 100

19th

641 638

nen. After drying, the sheet is transferred to a 9.0 cm petri dish, which contains a moist filter paper on the bottom. Then add 10 third-stage larvae and cover the dish with the lid. Mortality is counted after 3 days at 27 ° C (80 ° F) and a relative humidity of 50 + 10%. The numerical values obtained are summarized in Table III.

Example 17

Ixodicidal effect

The following studies investigate the effective control of mite larvae, larvae of Boophilus microplus, a host tick, which i5 during their three stages of development, i.e. the larval stage, the nymph stage and the adult stage, which can be present on a single host. In this test, a mixture of 10% acetone and 90% water is used, which contains 700,100,1,0,1, 20 0.01, 0.001.0.004 and 0.00001 ppm of the compound to be tested. 20 larvae are introduced into a pipette which is closed at one end with a gauze material, and the solution containing the compound to be examined is drawn through the 25 pipette with the aid of a vacuum hose, thereby simulating a spraying system. The ticks are then kept at room temperature for 48 hours, after which the mortality is determined. The results obtained are summarized in Table IV below.

30th

Example 18

The effectiveness of the compounds according to the invention in combating adult ticks (Boophilus microplus) is determined using the following 35 test methods, in which the compound to be tested is dissolved according to the procedure of Example 17, with the difference that the active ingredient is dissolved in such amounts are used that solutions are obtained which contain 500.125, 62, 37.9.32, 31.15, 16, 8.2 and 0.25 ppm of the 40 compound to be investigated.

Then, mature, rich, female ticks are immersed in the solutions to be examined for 3 seconds, transferred to individual containers and kept for 48 hours at 27 ° C (80 ° F) and a relative humidity of 50% on. After the storage period has elapsed, the ticks are examined and the egg deposits are counted. Rich female ticks that have not separated eggs are rated as dead. The results obtained are summarized in Table V below.

641638

20th

r

Y

Z

Ra r4

% Mortality bel ppm

H

H

H

CN

p-Cl

100 at 100

H

H

H

CN

P-OCH3

75 at 100

H

H

H

CN

p-CH3

100 at 100

H

H

H

CN

p-F

100 at 0.1; 30 at 0.01

H

H

H

CN

m-F

100 at 100

H

H

H

CN

o-F

100 at 100

F

H

H

CN

p-Cl

80 at 100

F

H

H

CN

p-CH3

100 at 0.1; 10 at 0.01

F

H

H

CN

p-och3

90 at 100

F

H

H

CN

p-F

75 at 0.01; 20 at 0.001

F

h h

H

III O S

H

100 at 100

H

ch3

H

CN

H

0 at 100

H

Br

H

H

H

0 at 100

H

Br

H

CN

H

100 at 700

H

Cl h

H

H

100 at 100

H

Cl

H

CN

H

75 at 100

H

Cl

Cl

H

H

40 at 100

F

H

H

H

H

100 at 0.004

r

Y

Z

R3

R *

percentage reduction in viable eggs at ppm

H

H

H

CN

p-Cl

94 at 125; 80 at 31

H

H

H

CN

p-CH3

85 at 125; 52 at 31

H

H

H

CN

p-F

94.9 at 125; 37.9 at 32

H

H

H

CN

m-F

94 at 125; 52 at 31

H

H

H

CN

o-F

99 at 500; 65 at 125

F

H

H

CN

p-ch3

89 at 16; 73 at 8

F

H

H

CN

p-F

96 at 8; 49.6 at 2

F

H

H

H

H

67 at 0.25

s

Claims (13)

641 638 PATENT CLAIMS 1. Phenylalkanoic acid m-phenoxybenzyl ester of the formula: rcf2x .. ch-co-o-ch 1 I (i) wherein RCF2X, Y and Z are all in the m or p position to the carbon atom to which the alkanoic acid ester group is attached, X stands for O, S, SO or SOz, Y and Z, which are the same or different, stand for H, Cl, F, Br, N02, CH3 or OCH3, R stands for H, F, Cl, CHF2 or CF3, R2 denotes ethyl, n-propyl, isopropyl, isopropenyl or tert-butyl, R3 stands for H, CN or -C s CH and R4 stands for H, F, Cl, CH3 or OCH3, where at least one of the symbols Z, Y and R4 has a meaning other than hydrogen if R3 is H or CN 1S. 2. Compounds according to claim 1, characterized in that they have the formula: rcf2x correspond to ch-co-o-ch, where RCF2X is in the m or p position to the carbon atom to which the alkanoic acid ester group is attached, and R represents H or F, X represents O or S, R2 means ethyl, n-propyl or isopropyl and R4 represents F, Cl, CH3 or OCH3. 3. Compounds according to claim 2, characterized in that R2 is isopropyl, R3 is CN, X is O and R4 is F. 4. [a-Cyano-m- (p-fluorophenoxy) benzyl] a-isopropyl-4-difluoromethoxyphenylacetate and [cc-cyano-m- (p-fluorophenoxy-oxy) -benzyl-a-isopropyl-4-trifluoromethoxyphenylacetate according to claim 2. 5. Compounds according to one of claims 1 to 4 in their optically active form 6. A process for the preparation of the compounds according to claim 1, characterized in that a compound of the formula: rcf2x. X> \ 'chc0c1 1 FU (II) in the presence of pyridine with a compound of the formula: (III) implements. 7. The method according to claim 6 for the preparation of the compounds according to any one of claims 2 to 5. 8. A method for controlling insects and mites, characterized in that the insects and mites, 30th 40 brings their location, their breeding grounds or their feed into contact with an insecticidally or acaricidally effective amount of a compound according to claim 1. 9. The method according to claim 8, characterized in that one uses a compound according to any one of claims 2 to 5. 10. The method according to claim 9, characterized in that one uses a compound according to claim 2. 11. Insecticidal agent, characterized in that it contains a compound according to claim 1, an emulsifier, a surface-active agent and a solvent. 12. Composition according to claim 11, characterized in that it contains a compound according to one of claims 2 to 5. 13. Composition according to claim 11 or 12, characterized in that X represents S or O. ZA patent application No. 73/4462 describes tens of 50 sends of phenylacetic acid esters, among others. 3'-phenoxybenzyl-a-isopropyl-4-methoxyphenylacetate, -a-isopropyl-3-methoxy-phenylacetate, -a-isopropyl-4-chlorophenylacetate, -a-isopropyl-4-methylphenyl acetate, -a-isopropyl-3 -chlorophenylacetate and -a-isopropyl-4-fluorophenylacetate. 55 It is stated that many of these compounds are effective pesticides and are suitable for controlling a wide variety of insects and mites. However, neither the esters according to the invention nor processes for the synthesis thereof are described. It has now surprisingly been found that the esters according to the invention are not only effective insecticidal agents, but also highly effective iododicidal (tick-killing) agents. In addition, the esters according to the invention are systemic insecticidal and iodicidal agents for animals. They can be used effectively to protect pets, laboratory animals and farm animals against infestation by insects and (actual) ticks. The esters according to the invention also show a better residual 3rd 641 638 ixodicidal and insecticidal activity as known pyrethroids, such as permethrin, phenotrin, allethrin and the like, and are outstandingly suitable for combating tobacco Budworm »[Heliothis virescens (Fabricus)].