DD143601A5 - PROCESS FOR THE PREPARATION OF PHENYL ALKANSAEURE M-PHENOXYBENZYL ESTERS - Google Patents

Description

Field of application of the invention :

The invention relates to a process for the preparation of m-phenoxybenzyl esters of substituted phenylalkanoic acids of general formula I.

CH-CO-O-CH

wherein RCF ₂ X-, Y and Z are all in meta or para position to the carbon atom to which the alkanoic acid ester group is bonded, and wherein

X is 0, S, SO or SO ₃ ,

Y and ZH, Cl, F, Br, NO ₂ , CH ₃ or OCH ₃ ,

H, F, Cl, CHF ₂ or CF ₃ ,

an ethyl, n-propyl, isopropyl, isopropenyl or t-butyl group,

R _{3 is} H, CH or -C ^ CH and R _{4 is} H, F, Cl, CH ₃ or OCH ₃

with the proviso that at least one of Z, Y and R is other than hydrogen when R is H or CN

 Characteristic of the known technical solutions:

DD-PS 136 689 discloses phenylalkanoic acid-m-phenoxybenzyl esters, which are valuable agents for controlling insects and mites and are already known with the compounds obtainable in the present case. Although these known compounds are well-suited for the stated purpose, their effectiveness is still good in need of improvement. Corresponding phenylacetic acid esters with pesticideric, insecticidal and acaricidal efficacy are also evident from ZA-PS 73/44 62, but the efficacy of these compounds leaves much to be desired.

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All known. Means against insects and mites thus have more or less pronounced disadvantages, for example, too low an efficacy, too narrow a spectrum of action, no sufficient residual effect or too low a safety margin

Object of the invention :

As a result of the above-mentioned disadvantages of the known agents for controlling insects and mites, the invention has now set itself the task of remedy this situation and to provide a new method by which can produce new compounds with superior insecticidal and acaricider effectiveness.

Explanation of the essence of the invention :

The above object is achieved in the method of the type mentioned in the present invention by reacting compounds of general formula II

(ID

in the presence of pyridine with compounds of general formula III

0-f

(III)

implements.

The preparation of the substituted phenylalkanoic acid m-phenoxybenzyl esters of the general formula I and the intermediates required for this purpose is illustrated by the following reaction examples and examples.

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schemes

// ч \ or СНГІ

ff W-CH-cooH + Br, ei rrr ± 3_> но

I г. δ

^R 2

CHCOOH R ₂

(Z and У stand for H, Br or Cl)

CHCOOH I

CiICOOH + NaOH + CHF ₀ Cl- ^ F ₀ CHO-i 2

2 ^ Ί? * 2

(Z and У stand for H, Br or CI)

CH 2 O- / V-CHCN + HBr- /

R

Н0 CHCOOH

CH.

CII

KO-v v- ^{CHCÜ (JH +}

I R,

NaOH + CHF Cl W-C

CHCOOH I

^R 2

CH. CH

^CH 3 °

ff W-CH ₂ Br - NaCN

N +

CH ₃ O

+ MaOH

^ y-CHCN + HBr F ^R 2

KO

COOH

CHCN I

^R 2

ΗΟ-γ V-CHCOOH + NaOH -5- CHF_C1> F ₀ CHO - // \ S_CH

R, F ^;

COOH

W-CHCOOH I U,

Ent.

CHCOOH I

KO.

¹ M 14 9 3

Reaction Schemes (continued)

- // \ - CHCOOH + NaOH + CIIF-Cl>

R

HO.

CHCOOH I

^R 2

f / ⁴ VV-CH ₂ O- / ^{7 4} V-CH ₂ OH + PBr ₃

осн.

CH ₂ Br + NaCN

2- \ - ~ - ₂ ~ " 2

OCH

(fW -CH ₂ O- ^ V) -CH ₃ Br

OCH.

OCiI.

f / \ Ѵгн п .// \\ _ CHC2i ОСП

<QU vV-CKCN +

HCl> H

- / I

- (^ nS-chcooh

; - '

OCH

CH-COOH + CHF-Cl + COCK

I 2

-> г сно

осн.

осн

W-CHCOOH I

^R 2

OH + NaOCH ₃ + pyridine + / j ± + V ⁴ V-CHO + CuCl

br

CHO

CHO + HCN >

ОН I

CHClM

211693

CHO Reaction Schemes (continued ) + CH-. + С «

R

СНОП <-

HCN + CSCI

CHCl ₃

Z У

s / TV

ClCX

CHCN +

KOH

cHCN + HIGH ₂ CH ₂ OH

COOH

Z Y

Z Y

benzene

CHCOOH + SOCl. I

RCF

CHCOCl

HO-CH ^R 3

if + pyriclin

CH-CO-O-CHI »R.R.

В э η ζ о L

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example 1

Preparation of alpha-isopropyl-4-trifluoromethoxyphenylacetyl chloride

A solution of 1.2 g of alpha-isopropyl-4-trifluoromethoxyphenylacetic acid and 0.6 ml of thionyl chloride in 5 ml of benzene is refluxed for 4 hours. By evaporation of the solvent and excess thionyl chloride, the acid chloride is obtained, as such for those in Examples. 2 and 3 described esterification is used.

Example 2

Preparation of alpha-cyano-m-phenoxybenzyl-alpha-isopropyl

4-trifluormethoxyphenylacetat

A solution of 4.58 mmol of alpha-isopropyl-4-trifluoro-araoxyphenylacetyl chloride in 5 ml of ether is added to a solution of 4.58 mmol of alpha-cyano-m-phenoxybenzyl alcohol and 0.5 ml of pyridine in 20 ml of ether. The mixture is stirred overnight and filtered. The filtrate and washings are evaporated and the residual 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, yields 0.85 g of the desired ester.

IR (no added) 1755 cm, nmr (CDCl) delta 6.8-7.6 (κι, 13H ₇ ArH), 6.31 and 6.28 (S, 1H, -CH-Ar), 3.27 / d,

CN J = 7Hz, 1H, CH-CH (CH-J-, / 2.0-2.6 / m, 1H, CH (CH-J ₀ /,

0.6-1.2 (4 doublets, J = 7Hz, 6H, isopropyl CH ^, ¹⁹ F chemical shift 58.8 delta with respect to CFCl ,.

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В * Ч η

eispxel 3

Preparation of m-phenoxybenzyl-alpha-isopropyl-4-trifluoromethoxyphenylate tat

To a solution of 1.89 g of m-phenoxybenzyl alcohol and 1 ml of pyridine in .mu.l of methylene chloride is added a solution of prepared from 2.46 g of the corresponding acid according to the procedure described in Example 1, alpha-isopropyl-4-trifluoromethoxyphenylacetylchlorid in 7 ml of methylene chloride 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, 2.76 g of the desired ester are obtained.

IR (no added) 1738 cm ^-1 , -nmr (CDCl ₃ ) delta 6.73-7.45 (π, 13H), 5.03 (S, 2H), 3.2 O (d, J = 10.5 Hz , 1H), 2.26 (m, 1H), 0.66 and 0.94 (two d, J = 6.6Hz, 6H).

Example 4

Preparation of alpha-1 - orthopyl-4-hydroxyphenylacetic acid

A mixture of 40 O g of alpha-isopropyl-4-methoxyphenylacetonitrile and 200 ml of 48 percent hydrobromic acid is heated using an oil bath for 14 hours at 126 to 128 ⁰ C to reflux. 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, mp - 172 to 174 ⁰ C, IR (Nujol) 325О - 2900 (broad, OH), IGSO cm "" ¹ (CO).

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Comparable results are achieved using alpha-ethyl-4-methoxyphenylacetonitrile or alpha-n-propyl-4-methoxyphenylacetonitrile to produce alpha-ethyl-4-hydroxyphenyl acetic acid and alpha-n-propyl-4-hydroxyphenyl acetic acid, respectively ,

Example 5

Preparation of alpha-isopropyl-4-difluoromethoxyphenylacetic acid

acid

To a mixture of 10.00 g (0.0515 KoI) of alpha-xsopropyl-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. are introduced with stirring with a magnetic stirrer within 4 hours 46 g (O, 532 mol) of chlorodifluoromethane. The reaction mixture is poured into 250 ml of ice-water and the resulting mixture 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, it is filtered to remove the solid which is the starting material. The filtrate is evaporated to yield 5.41 g of a clear brown oil. Due to the NMR spectrum, the product can be considered at least 85% pure. NMR (CDCl ₃ -d ₅ pyridine), delta 7.43 (α, J = 8.2Hz, 2H) delta 7, Ο 8 (d, J = 8.2Hz, 2H), delta 6.57 (t, J = 74.3Hz, 1H), delta 3.63 (s, un.), Delta 3.25 (d, J = 10Hz, 1H), delta 2.37 (m, 1H), delta 1.19 (d, J - 6.5Hz, 3H), delta 0.78 (d, J = 6.5Hz, 3H) delta 13.82 (s, 1H).

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Comparable results are obtained using alpha-ethyl-4-hydroxyphenyl or alpha-n-propyl-4-hydroxyphenylacetic acid to produce alpha-ethyl-4-difluoromethoxyphenyl and alpha-n-propyl-4-difluoromethoxyphenylacetic acid, respectively.

Example 6

Preparation of alpha-isopropyl-3-bromo-4-hydroxyphenylacetic acid

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 for 30 minutes at 0 ⁰ C 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.

Example 7

Preparation of alpha-isopropyl-3-bromo-4-difluoromethoxyphenyl acetic acid

According to the procedure described in Example 5, 18.0 g of alpha-isopropyl-3-bromo-4-hydroxyphenylacetic acid are converted into the corresponding difluoromethoxy compound. The desired acid is obtained by separation of the unreacted starting material by chromatography on silica gel using 2.5% Methanoi containing chloroform as an eluent as a waxy solid in an amount of 4.7 g. This crude acid is used as such in Examples 8 and 9.

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Example 8

Preparation of m-phenoxybenzyl-alpha-isopropyl-3-bromo-4-di-

^ fluor:? ethoxypheny lace did

Using alpha-isopropyl-3-bromo-4-difluoroethoxyphenylacetic acid, the product is obtained as a pale yellow greasy according to the procedures described in Examples 1 and 3. "NMR (CDCl ₃ ), delta 6.8-7.7 (m, 12H, ArH), 6.45 (t, J = 7 ₄ Hz, 1H, OCHF ₂ ), 5.1 O (broad, 1H, CH _2), 3.18 (d, J = 9Hz, 1H, CH-CH (CH-J _0), 1.0 and 0.71 (2d, J = 6Hz, 6H, isopropyl CH _3).

Example 9

Preparation of alpha-cyano-m-phenoxybenzyl-alpha-isopropyl-S- bromo-4-dif-luormethoxypheny lace tat

Using the procedures described in Examples 1 and 2, using alpha-isopropyl-3-bromo-4-difluoromethoxyphenylacetic acid, the product is obtained as a yellow greasy NMR (CDCl ₃ ) delta 6.9-7.7 (m, 12H, ArH), 6.50 (t, J = 7 ₄ Hz, 1H, OCHF ₂ ), 6.33 and 6.36 (2S, 1H, CH-CN), 3.25 (d, 1H, CH-). CH (CH ₀ ), 0.6-1.1 (4d, 6H, isopropyl CH-.).

Example 10

Preparation of alpha-isopropyl-3-chloro-4-hydroxyphenylacetic acid

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 recrystallised from benzene / hexane. F. = -125 to 128

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Example 11

Preparation of alpha-cyan-m-phenoxybenzyl-alpha-isopropyl

3-chloro-4 - di fluorine thoxypheny lace did

Following the procedures described in Examples 1, 2 and 5, the product is obtained as a lubricant using alpha-isopropyl-3-chloro-4-hydroxyphenylacetic acid. NMR (CDCl ₃ ) delta 6.8-7.5 (m, 12H, ArH) ₇ 6.50 (t, J = 7 ₄ Hz, IH, OCHF ₂ ), 6.33 and 6.30 (2S, 1H , -CH-CN), 3.25 (d, J = IOHz, IH, CH-CH (CH,... ₀ ) .

Analysis, C ₃₆ H ₂₂ ClF ₂ NO ₄ :

Calculated: C, 64.26; H 4.56; N, 2.88; Cl, 7.30; F, 7.82; Found: C, 64.27; H 4.70; N 2,94; Cl 7,20; F 7,78.

Example 12

Preparation of m-Phenoxybenzyl-alpha-isopropyl-S-chloro - ^ -

dif luorr ^ ethoxvohenvlacetat

Following the procedures described in Examples 1, 3 and 5, the product is obtained as a yellow oil using alpha-isopropyl-S-chloro-hydroxyphenylacetic acid. NMR (CDCl ₂₎ delta 6.8 to 7.6 (ia, 12H, ArH), 6.47 (t, J ^ ₄ Hz, OCHF _2), 5.07 (bs, 2H, CH _2).

Analysis, C ₂₅ H ₂₃ ClF ₃ O ₄ :

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.

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Example 13

Preparation of alpha-isopropyl-3, S-dichloro-hydroxyphenyl acetic acid

A mixture of 30 g (0.155 mol) of alpha-isopropyl-4-hydroxyphenyl acetic 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 another hour at 0 to 5 ⁰ 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.

Example 14

Preparation of alpha-isopropyl-3,5-dichloro-4-trifluoromethoxy-phenylacetic acid

Following the procedure described in Example 5, is obtained as an oil using alpha-isopropyl-3 ₇ 5-dichloro-4-hydroxyphenyiessigsäure the the title 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 15

Preparation of alpha-cyan-m-phenoxybenzyl-alpha-isopropyl

3-bron \ -4-dif luormethoxyphepy lace did

Using the procedure described in Examples 1 and 2, the product is obtained as yellow greasy using alpha-isopropyl-3,5-dichloro-4-difluoromathoxyphenylacetic acid. NMR _(CDCl3) delta 6.9-7.7 (m, 11GH, AxH), 6.67 (t, J = 7 ₄ Hz, 1 H, OCHF _2), 6.33 and 6.40 (2S, 1H , CH-CN), 3.23 (d, J = IOHz, 1H, CH-CH (CH ₃ ) ₂ , 0.6-1.1 (4d, 6H,

Analysis, C ₂₂ H ₂₂₃₄

calculated: C 60.01; II 4.07; N, 2.69; Found: C 59.78; H 4.30; N 2.31.

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Example 16

Preparation of m-phenoxybenzyl-alpha-isopropyl-3,5-dichloro- 4-difluoromethoxyphenylacetate

Using the procedures described in Examples 1 and 3, the product is obtained as a lubricant using alpha-isopropyl-3,5-dichloro-4-difluoro-methoxyphenyl acetic acid.

Analysis, C ₂₅ H ₂₂ Cl ₂ F ₂ O ₄ :

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.

Example 17

Preparation of alpha-isoprorone-3-methyl-4-difluoromethoxyphenyl-1- acetic acid

3-Methyl-4-methoxyphenylacetonitrile is converted to the title compound by the procedures described in Examples 4 and 5. The product, as shown by its NMR spectrum, is contaminated with some alpha-isopropyl-3-methyl-4-hydroxyphenylacetic acid. However, it is used as such for the esterification of Example 18, where then the resulting ester is purified by chromatography.

Example 18

Preparation of alpha-cyano-m-phenoxybenzyl-alpha-isopropyl-S- me- thyl 1-4-di- fluoride- thoxy-phenoxide

Following the procedures described in Examples 1 and 2, the ester is obtained as a viscous oil using the acid obtained in Example 17. NMR (CDCl-) delta 6.8-7.6

(ir _f 12H, ArH), 6.45 (t, J = 7 ₄ Hz, 1H, OCHF ₂ ), 6.48 and 6.53

(2S, 1H, CH-CN), 2.25 (S, 3H, CH _3).

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Analysis, C ₂₇ H ₃₅ F ₂₄

Calculated: C 69.66; H 5.41; N, 3.01; Found: C, 70.05; H 5.86; N 2,83.

Example 19

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) of sodium cyanide in 50 ml of water is heated to 60 to 18 hours Heated to 65 ⁰ C. The mixture is cooled and extracted with ether. The ether extract is washed with water and saturated sodium chloride solution and dried over Na ₃ SO ₄ . By evaporation of the solvent, 33.2 g of a solid of F. = 42 to 46 ⁰ C are obtained.

Example 20

Preparation of alpha-isopropyl-3-fluoro-4-methoxyphenylaceto-

nitrile

A mixture of 30 g '(0.18 mol) of 3-fluoro-4-methoxyphenylacetonitrile, 27.7 g (0.255 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 for 1 hour at 55 ⁰ C and cooled. The mixture is diluted with water and extracted with ether, and the extract is washed with water, 1N KCl and water, and Na ₉ SO 4. dried. By evaporation, the product is obtained 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.

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Example 21

Preparation of alpha-isopropyl-3-fluoro-4-difluoromethoxyphenyl

acetic acid

Starting from alpha-isopropyl-3-fluoro-4-methoxyphenylacetonitrile, the product is obtained as a brown oil according to the procedures described in Examples 4 and 5. The NMR spectrum shows that it is contaminated by starting material. Therefore, the crude reaction mixture is subjected two more times to the Freon 22 reaction described in Example 5 to give the product as a brown oil. The NMR spectrum shows that the product is about 96% by weight.

Example 22

Preparation of alpha-cyano-m-phenoxybenzyl-alpha-isopropyl- 3-fluoro-4-difluoromethoxyphenylacetate

Starting from alpha-isopropyl-3-fluoro-4-difluoromethoxyphenylacetic acid, the ester is obtained as a yellow oil according to the procedures described in Examples 1 and 2. NMR (CDCl ₃ ) delta 6.8-7.5 (m, 12H, ArH), 6.63 (t, J = 7 ₄ Hz, 1H, OCHF ₂ ), 6.33 and 6.37 (2S, 1H , CH-CN).

Analysis, ^C 2g ^H 22 ^F 3 ^NO 4 ^:

calculated: C 66.52; H 4.72; N 2,98; found: C 66.27; H 4.87: N 2.99.

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Example 23

Preparation of alpha-isopropyl-3-nitro-4-hydroxyphenylacetic acid

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 ⁰ C and added to 9.55 g (0.095 mol) of 70 percent nitric acid at a rate at which the Reaction temperature at 38 to 40 ⁰ C and at no time exceeds 45 ⁰ C. The reaction mixture is stirred overnight at 40 to 42 ⁰ C and poured into ice water. The yellow solid is filtered off, washed and dried. This gives 19.1 g of substance of mp = 103 to 1O5 ⁰ C.

Example 24

Preparation of alpha-isopropyl-3-nitro-4-difluoromethoxyphenyl acetic acid

Using alpha-isopropyl-S-nitro-hydroxyphenylacetic acid, the title acid is obtained as the raw product contaminated with unreacted starting material by the procedure described in Example 5. Through three repetitions of Freon 22 conversion described in Example 5, the product each time wobai obtained is used, the product is finally obtained from hexanes as a fine beiqefarbener solid, mp = 88 to 90 ⁰ C.

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Example 25

Preparation of alpha-cyan-m-phenoxybenzyl-alpha-isoprubyl

3-nitro-4-dif luarmethoxyphenylacetaf

Using alpha-isopropyl-3-nitro-4-difluoro-methoxyphenylacetic acid, the product is obtained as a yellow oil according to the procedures described in Examples 1 and 2.

Analysis, ^C 26 ^H 22 ^F 2 ^N 2 ° 6 ^:

calculated: C 62.90; H 4,47; N 5.64 ;. found: C 62.51, - H 4.77; N 5.58.

Example 26

Preparation of alpha-cyano-m-phenoxybenzyl-alpha-isopropyl- 3-raethoxy-4-difluoromethoxyphenylacetate

Using alpha-isopropyl-3-methoxy-4-difluoromethoxyphenyl acetic acid, the product is obtained as a Schiniere according to the procedures described in Examples 1 and 2.

Example 27

Preparation of та- (rtv-fluorophenoxy) benzaldehyde

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 bismuth salt of 3-fluorophenol is prepared ^C C heated 110 with 34 ml distilled off pyridine / methanol. After cooling to 80 ⁰ C 25.0 g (0.135 mol) xn-bromobenzaldehyde and 4.05 g (0.049 mole) of copper are added (I) chloride. The reaction mixture is refluxed overnight to boil

21 16 9 3

During the 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% HCl, water, 5% NaOH and water and evaporated to a dark brown oil. By vacuum distillation, the product is obtained as a clear liquid in an amount of 6.6 g. Kp = 82-88 ⁰ C (0.5 mm).

Analysis, C., HqFO ₂ :

calculated: C 72.22; H 4,20; F, 8.79; Found: C, 72.03; H 4.30; F 8,60.

Example 28

Preparation of substituted alpha-cyano-m-phenoxybenzyl esters of fluoroalkoxyphenylacetic acids

Starting from alpha-isopropyl-4-difluoromethoxyphenylacetic acid or alpha-isopropyl-4-trifluoromethoxyphenylacetic acid and the cyanohydrin of a correspondingly substituted aldehyde, the following esters are obtained according to the procedures described in Examples 1 and 2:

JiI 169 3

* Ч-і кг гм 03 CN ^^ о VD CM ГО го Γ 1 -P ГМ ^ - ^ о іЛ г \ Г U m кг <J \ оГ ΙΟ СО ГО kf кг " O <** г- ΙΛ см " α VO со о CM VO ~ α ѵх) о α α CJ о и к VO VO и U р-; 1 О к "Z > pi α, S3 ti сз O о го ro β сэ (Л tr " ι-! VO .. CN LO сі H ГО ел У) о co о  he" кг " г " ІЛ CN VO η VO "Z. Tr) ѵо о CJ • τ · о CD U VO О к со · "· W -I -о " CN Anal • ~ *  » O Ό ^ .- ^  <- CM CN 2 ' Si CM "о fc. _ ^ Си О см Ьч 2; 4 . · --ч 2 £ 1 ~~ ^ о о CJ О и I U о I О и ¹ о <с m CJ CJ - CM VO К IT ro " о CM ^ r CN CN - \ .-H ·. - і-Ч а. N N cn N  *. - ГМ ·· ГС СП кг cn · "· - е CM - Γ ГМ • - * г> - • - ^ - ^ Ι) - - И ГО и > -э 7 ^ ₁ ГО г " VO г- 4J VO ѵо I о ¹ UO ro г-> со ro сэ кг VD сэ KP ГМ ro VO ѵо "~ ѵо ѵо VO vo Ό , -I ГО O о · - P-J о ΰ χ Li

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a СО in Il VO 4b in гЧ 4ъ VO co co O in O r- · - cn I ГО О tn СП CN rc co ro · τ- СЧ VO ro O co rc co cn ѵхГ ^ r гЧ r * T "4 * гЧ VO CN VD гЧ CN ill VO -P 2 VO 2 VO 2 гЧ vo rc гЧ ш CJ τ * ^ " CJ rc α Ьч O - Сч гЧ CO co co с  · ч co C-J CM r- CN co CN CN 5ц гЧ ГО VO cn ~ - ' vo in - co r- cn "Ч * CN r * · - co О 1Л г- · CN O ГО oT ІЛ CN rh in cn гЧ ѵо CU VO "с VO CN vo CTi CN ΓΝ 4ъG vo ГО VO , ro vo rc гЧ VO rc ГО гЧ U) _-1 и ГС VO CJ rc VO CJ U 2 Сч Ana! CN VO O CN ^ TO CN CN ro ro • Τ- ⁴ 2 ГО 2 -a го • 4 VO vo α υ rc a rc ·. Сч I a 1 ro V CJ ^^ Tr; CN rc • - ro .-. - CN O 2 U. CJ t | υ rc U VO CN [І, 1 CJ 1 · ". rc 1 O 4 * I о - * "- rc " I α \ rc 1 ГС и α rc rc CJ rc O rc! rc CJ о I S-I U rc O V-I O CJ <^ I 4 * •H rc • 4th ·. • k. 4 ' rc ·. rc ГС rc rc LO ,H гЧ fH CN CN 4V CN CN CN - ( г- ( N N "- H. гЧ ·>. N • -. rc N N ». rc ». O - ^ * "Τ · - rc В • у  ε ε - ro O O ci  - Il * - * ! I · - ^ j - · r ~ 2 · t-3 1-3 VO It -! I Il 2 ІП 1Л H} in Ό J  d с - [J 4 »• a І 1 O 1 ro a "^ 1 ro • a · ГО   co со co ΓΟ co VO VO CN in ^ r CN VO vo Сч I ro VO VO ro di OI Сч X egg к

ί " T i F ^R 4 6.8 - 7 NMR , ArH), (4d, bH , sopropyl CH) analysis , over. Analysis, gof. 62.05 г 6.37 and. UI, -CH-CN), (m, 12I , ArH), C 61 j 9 7 C 4.25 £ -Cl 3.33 (D, J = IOHz, CH-CH (CH.),), 41 (2S, IH, -CH-CN) H 4.20 H 2.52 F- 0.6 - 1 (η, 12Η ΐ2 <CH ₃ ) N 2.78 N 6.8 .- 7 41 (2S, ι * (m, 12H , ArH), 65.28 C, 37 and" 30 (2S, IH, CH-CN), C 67 ₇ 07 C 5.18 E " ^CI b 2.40 (S, зн / OCH ₃ ) и 5.00 H 2.26 6.9 - 7 N 2.90 N 64.04 6.25 and ⁶ y C 64.92 C 4 j 87 P _- OCH ₃ 3.63 (Ξ, ЗН H 4.84 H 2.65 N 2.80 N

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Example 29

Preparation of alpha-ethynyl-m-phenoxybenzyl alcohol l

Acetylene is successively dried by falling with dry ice-acetone, concentrated sulfuric acid and calcium chloride and introduced into 100 ml of dry tetrahydrofuran at a pressure of about 0.35 kg / cm ^{2 for} 10 minutes. 0.14 moles of technical grade ethylmagnesium bromide are added dropwise at a rate for 2 hours added, in which a slow and uniform Ethanentwicklung takes place. Thereafter, acetylene is introduced for 15 minutes. At 15 to 20 ⁰ C, the reaction mixture with 27.7 g (0.14 mol) of m-phenoxybenzaldehyde in 25 ml of THF. Then it is stirred overnight at room temperature. The complex is treated with saturated ammonium chloride solution. The product is extracted with ether and the ether extract is washed with water and dried over Na 2 SO 4. dried. Evaporation of the solvent followed by vacuum distillation using Kugelrohn gives 21.5 g of the alcohol.

Example 30

Preparation of alpha-ethynyl-m-phenoxybenzyl-alpha-isopropyl- 4-trifluoroethoxy phenyl ac eta t

Using the alcohol obtained from Example 29 and from alpha-isopropyl-4-trifluoromethoxyphenylacetic acid, the product is obtained as a yellow greasy according to the procedures described in Examples 1 and 3. The NMR spectrum shows the characteristic alkyne proton as a multiplet at 2.52 delta and benzyl protons at 6.35 delta.

2 \ 16 9 3

Analysis, C ₃₇ H ₂₃ F ₃ O ₄ :

calculated: С 69,22; H 4.95; found: С 68,17; H 4,11.

Following the same procedure, using the alcohol of Example 29 and alpha-isopropyl-4-difluoro-methoxyphenylacetic acid, the alpha-ethynyl-m-phenoxybenzyl-alpha-isopropyl-4-difluoromethoxyphenylacetate is obtained.

Analysis, C ₂₇ K ₂₄ F ₃ O ₄ :

calculated: C 71.99; H 5.37; found: C 71.59; H 5.53.

The compounds of the invention are highly effective as contact and stomach poisons for iodide ticks and a wide variety of different insects, in particular Diptera, Lepidoptera, Coleoptera and Homoptera insects. Unusually, in pyrethroids, they exhibit a highly extended insecticidal activity on plant tissue, are effective in soil and surprisingly effective in controlling Ixodidae and protecting animals against insects and Ixodidae when administered orally or parenterally to animals, or as topical insecticides or acaricidal preparation applied to the animals. For insecticidal and acaricidal preparations with stabilized effects, mixing with a stabilizing agent is required. However, the active ingredients may also be used together with other biologically active chemicals, e.g. with pyrethroid synergists such as piperonyl butoxide, sesamex or n-octylsulfoxide from isosafrole. The compounds of the invention may also be used together with conventional insecticides, e.g. Phosphates, carbamatane, formamidines, chlorinated hydrocarbons or halobenzoylureas

become. In order to control insects, including soil insects which attack plants and / or harvested crops, including stored grain, the insecticidal compounds of the invention may be applied to the foliage of plants, the location of the insects 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, granules or wettable powder.

Liquid sprayers which are particularly well suited are oil spray and emulsifiable concentrates, which can be further diluted for use. While prepared as liquid concentrates, these preparations are usually dispersed in water first at the point of use for ease of handling and transportation and then applied to the foliage of the plants, the soil or the surface of the area to be treated as dilute liquid sprays.

An ingestible concentrate which may be used to protect a variety of crops such as cereals, cabbage, squash, corn, cotton, tobacco, soybeans, ornamentals, shrubs and the like may contain about 20% by weight of active ingredient, 4% by weight of emulsifier, as is conventional for the preparation of pyrethroid formulations, 4 weight percent of a surfactant, 25 weight percent of an organic solvent such as cyclohexanone, and about 47 weight percent of a petroleum solvent having an aromatic content of about 83 volume percent.

When used as a systemic insecticide and acaricidal agent for the treatment of animals, the inventive

21 U93

Compounds may be administered orally or parenterally. For oral administration, the active compounds may be formulated in any suitable manner for this route of administration, for example, in the form of a bolus, capsule, tablet or soak. The active ingredient can be incorporated also be incorporated into the animal feed, for example in nutrient moderately balanced food in amounts from 0.0001 to 0.1 and preferably from O ₇ OOI to 0.05 weight percent, based on the weight of the feed.

If desired, the systemically anti-insect and acaricidal agents may be introduced into the carcass by subcutaneous, intramuscular or intraperitoneal injection so as to spread throughout the animal body via the circulatory system of the animals. In practice, the systemically active agent may be dissolved or dispersed in a pharmaceutically acceptable carrier such as water, propylene glycol, vegetable oil, glycerol formal or the like.

Advantageously, the systemic agents have a good safety range and protect a variety of animals, especially livestock and pets, such as cattle, sheep, horses, dogs, cats and the like, against infestation by fleas, mosquitoes, flies, ticks and the like.

Example 31

Insecticidal activity

The insecticidal activity of the compounds according to the invention is demonstrated by the following investigations in which the tobacco caterpillar Heliothis virescens (Fabricius),

1 16 9 3

potato leafhopper, western potato leafhopper, empoasca abrupta (DeLong) and 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 true unfolded leaves is immersed for 3 seconds with stirring in the solution to be tested (35% water / 65% acetone) containing 300, 100 or 10 ppm of the compound to be tested. Then put each leaf in a beaker with a wick and add a 50 to 100 freshly hatched larvae gauze cloth before closing the cup with a lid. After 3 days at a temperature of 27 ⁰ C (80 ⁰ F) and a relative humidity of 50% to be examined of the cup and rated the kill of newly hatched larvae. The numerical values obtained are listed as percent kill in Table I.

Bean aphid, Aphis fabae (Scopoli)

Place five fiber pots, each containing a 5 cm (2 inch) nasturtium plant, which has been occupied 100 to 150 aphids two days previously, on a turntable operated at a speed of 4 minutes. and spray the plants with a solution containing 35% water and 65% acetone containing 100, 10, 1.0 and 0.1 ppm, respectively, of the compound to be tested, allowing the solution to invert for two turns using a spray device (DeVilbis Atomizer ), which is operated with air at a pressure of 1.41 kg / cm ² (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 spattered plants are then deposited in white enamel shells. The mortality is determined after one day at 21 ⁰ C.

2116

(70 ⁰ F) and a relative humidity of 50%. The numerical values obtained are listed as a percentage of the mortality in the following Table I.

Potato leafhopper, Empoasca abrupta (DeLong)

Dip a bean plant (Sieva lirna) with a first leaf folded down to between 3 and 4 inches into a solution of 35% water and 65% acetone containing 100, 10 and 1 ppm, respectively, of the compound to be tested , The dipped plant is then placed in a fume hood to dry and cut off a 2.5 cm piece of the tip of a leaf and placed in a 10 cm (4 inch) diameter Petri dish containing wet filter paper on the bottom , Then 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 storage of the Petri dishes for two days at 27 ⁰ C (80 ⁰ F) and a relative humidity of 50%. The numerical values obtained are listed in Table I below. In these studies, permethrin is used as reference standard.

Table I Evaluation of insecticidal activity

connection

Mortality

TahaltraupcnlarvG; t \ /ickiunas.4tadium

300 ppm

100

10 ppm

Blatthüpfor

100 ppm

10 ppm

1 ppm

BlattIi us

100 ppm

10 ppm

ppm ppm

F ₂ CHO

/ - \

-V V ~ CH-CO-O-

100

100

100

100

100

100

100

100

F-CHO - // \\ - CH-CO-O-CH

~~ CH

100

100

100

90

100

100

75

F ₂ CHO -M \ V CH-CO-O- ^ = ^ CH (CH ₃ ) ₂

CN CH

100

100

90

50

100

100

70

CH-CO-O-CH CH (CH ₃ ) ₂

100

100

100

100

100

100

90

\ CN

⁴ V-CH-CO-O-OH

CH (CH ₃ J ₂

100

100

50

100

100

50

100

100

50

T a b e 1 1 e- · I (continued)

connection

% Mortality

Tabakraup.qnlarve .developers stadium

ppm

100 ppm

10 ppm

.Blatthüpfer

100110 ppm I ppm ppm

aphid

IOOIIO

ppm ppm

ppm

0, Г

ppm

F ₂ CHO - // V

CN ι

CH-CO-O-CH

100

100

50

100

100

F ₃ CO

CN

CH-CO-O-CH CII (CH ₃ ) ₂

0 ~

100

100

100

100

100

80

100

100

90

CN I CII-CO-O-CH-.

CH (CH ₃ ) ₂

100

100

100

100

50

100

100

100

CN

CH (CH)

O-,

90

80

100

100

100

100

100

T a b e I (continued)

connection Tabdkraupenlarve 1 .Entwicklup ^ si fcz? 100 ppm el ium- % Mortality 10 ppm 1 ppm aphid 10 ppm 1 ppm 0.1 ppm CN F-CG - (/ V- CH -CO-O-CH-r ^ VO 3 / ^{W w} см (CH ₃ ) ₂ k ^ J 3UO ppm 100 10 ppm leafhopper 60 - 100 ppm 100 100 0 CH _{3 CN} F .CIiO -V y- CH-CO-O-CII ~ Y \ ~ ^ = ^ CH (CH ₃ ) ₂ Ц ^> 100 100 100 100 ppm 100 100 100 100 90 0 100 100 100 100 100

Table I (continued )

Connection..

mortality

Tabalraupenlarvc! _ J " ¹ 1 \ fc.WL. C l <luncr ^ qtnd j_um_

300 ppm

100 ppm

10 ppm

100 ppm

10

ppm

ppm

aphid

100 ppm

10

ppm

ppm

ppm

F ₂ CHO-

br

CH-CO-O-CH, I *

CH (CH)

100

80

50

100

100

100

CN

CH-CO-O-CH CH)

br

100

100

100

75

100

10Q

75

CHO

CH-CO-O-CH-H

CH (CH ₃ )

100

50

100

100

100

F ₂ CHO

CN CH-CO-O-CH

Cl

100

100

100

100

100

100

100

100

100

T abe .1 le I (continued)

connection % Mortality Tabakraupenlarvo L. developmental precipitate 10u ppm 10 ppm leafhopper 10 ppm 1 ppm aphid 10 ppm i ppm 0.1 ppm Cl ^ F ₂ CKO - // NVcH-CO-O-CH η ^^^ Ο-γ ^ ⁴ ^ У ^ CH (CH,), U ₄ U U. JJ Cl ^{3 2} ^^^^ 3o0 ppm 80 0 "TÖÖ ppm 0 - 100 ppm 100 50 - Cl у CN F ₂ CHO-f Vсn-со-о-сн Y ^ jT ⁰ "] ^ ⁴ ?! C ₁ ^ - ⁷ сн (CII ₃ ) ₂ ЧУ ЧУ 100 100 100 100 100 0 100 100 100 0 100 100 100

21 1 6 93

Example 32

Insecticidal action

The insecticidal activity of the compounds of the invention is further determined using the following Untersuchungsnethoden in which the action against mosquito larvae, Mexican ladybugs and caterpillars cotton is investigated.

Malaria mosquito, Anopheles quadrimaculatus (Say)

Pipette 1 ml of a solution of 35% water and 65 % acetone containing 3OO ppm of the compound to be tested into a 4OO ml beaker containing 250 ml of deionized water, stir with the pipette and reach a concentration of 1.2 ppm. Aliquots of this solution are then removed and diluted further to 0.4, 0.04 and 0.004 ppm, respectively. In order to prevent the eggs from floating up and drying out on the side wall of the beaker, a wax paper ring, 0.6 cm wide, is placed on the surface of the solution to be examined, and is then fitted into the beaker. Use a sifting spoon to pick up and transfer about 100 eggs (aged 0 to 24 hours) to the beaker. After 2 days at 27 ^° C. (80 ^° F.) and a relative humidity of 50%, hatching is observed. The percentage mortality is listed in the following Table II.

Mexican ladybugs , Epilachna varivestis (Mulsant)

One dips bean plants (Sieva lima) (two per pot) with 7.5 to 10 cm long first leaves in the 300, 100, 10 or 1 ppm of the compound to be examined containing solution and allowed to dry in a fume hood. Then you take a sheet of

21 16 9 3

Remove the plant and place it in a 10 cm petri dish containing a wet filter paper on the bottom and 10 larvae in the last stage of development (13 days before hatching). On the day after the treatment, take another leaf from the plant and feed it to the larvae after removing the remains of the first leaf. 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, if the larvae have not stopped eating. Then the Petri dishes are set aside and kept until the adult animals have hatched, which is about 9 days after the start of treatment. After complete leaching of the animals, each Petri dish becomes normal with respect to killed larvae, pupae or adult animals, deformed pupae or adult animals, intermediate stages between larval stage and pupal stage and pupal stage and adult stage, or any other effects in normal moulting Development and normal occurrence of pupae or adult animals studied.

The numerical values obtained are listed in the following Table II.

Cotton caterpillar, (Southern Armyworm), Spodoptera eridania

(Cramer)

Pour bean plants (Sieva Lima) into the treatment solutions for 3 seconds with two folded 7.5 to 10 cm long first leaves with stirring and then allow to dry in a fume hood. After the leaves are dry, they are cut out and each cut leaf is placed in an 10 cm Petri dish containing a piece of wet filter paper and 10 cotton caterpillars in the third developmental state about 1 cm in length. The Petri dishes are covered and kept for 2 days at a temperature of

21 16 93

stored temperature of 27 ⁰ C (80 ⁰ F) and a relative humidity of 50%. Mortality is counted after 2 days. The results obtained are summarized in the following Table II.

T abe 1 1 о 11 _- Assessment of insecticidal activity

connection

Moskitolarvcn

τ;

ppm

0, ppm

ü _; ü4 ppm

0.004 ppm

cotton caterpillar

IQOU

ppm

IOC) ppm

10

ppm

Mexican

  M'rii onkfifor

JOO ppm

100 ppm

10

ppm

F ₂ CHO

CN I CH-CO-O-CH

CH (CH-) ₀

100

100

100

so

100

90

100

40

CN

F ₂ CHO

-v NV-ch-co-o-ch

CH (CH ₃ J ₂

80

100

100

80

100

100

90

90

ч ^CN

-V V-CH-CO-O-CH-ι

CH

100

100

100

80

100

100

80

F ₂ CHO

си (CH ₃ ) ₂

100

100

100

100

100

100

90

100

50

Table II (continued)

connection

mortality

Moskitolarvon

1.2

ppm

0.4

ppm

U j0 ppm

ppm

cotton caterpillar

тішшго "

ppm! ppm

"To"

ppm

Mexican ladybug

300

ppm

10 ppm

Dead

ppm

F ₂ CHO '

CN

CH-CO-O-CH

I CH (CH ₃ J ₂

-0

100

100

100

50

40

100

100

CN

⁴⁴ X-CH-CO-O-CH

CH (CH ₃ ) ₂

100

100

100

100

100

100

100

100

F ₃ CO

CN

CH-CO-O-CH CH (CH ₃ J ₂

10.0

100

100

100

100

100

60

100

100

100

F ₃ CO

CN I CH-CO-O-CH

CiI (CH ₃ J ₂

100

100

80

100

50

100

100

50

Table II (continued) connection

1 mortality

mosquito larvae

0.4 ppm

0.04 ppm

O7O4 ppm

Bumwo11raup Q

TÖÜO

ppm

IOD ppm

10

ppm

Mexican Marion beetle

300 100 ppm ppm

10

ppm

I ppm

F CO

CN I CH-CO-O-CH

CH (CH ₃ ) ₂

100

100

100

100

100

100

50

F ₃ CO-

CN I CH-CO-O-CH

CH (CH ₃ ) ₂

100

100

100

100

100

100

100

40

Tabel le II (continued)

connection tockitolarven ppm Ü, 04 рргг ppm I mortality ppm e Mexican 100 ppm 1 0 CH, 3 ν CN F ₂ CHO- C Ч-CH-CO-O-CH η ^ ⁴ ^ S CH (CH ₃ ) ₂ Ц ^. ppm 100 100 100 3aum, o, 100 ppm 300 ρ pn 100 90 mm F сно-ѵ \\ - сн-со-о-сн-ητ ^ ⁴⁴ 2 ^{U υ} \ _ ~ / I ² LI 'CH (CH,), 4 ^ - Br ^{J ι} 100 - - - lüTÖ "ppm 100 20 100 - - - CN F-CHO - // ^ У-СН-СО-О-СН-т ^^ \ - / ^! j ^ CH (CfU) ₀ VS. , Br ^J ^ 100 - - - 100 100 0 100 - - 100 100 80 50 100 0 0 100 100 100 0 0 100 F-CHO -У VV-сн-со-о-сн ^ пг ^^ гО-т ^^ Гі) CH (CI!,) - Х> ^ ¹ ^ У Cl 3 2 ^ - \ ^

T a belle II (continuation)

connection mosquito larvae 0.4 ppm υ, 04 ppm OjOM ppm mortality 100 ppm 10 ppm Mexican ladybug 100 ppm 10 ppm 1 ppm F ₂ CHO -v ^ Vch-co-o-ch ^^^ iY-o- ^ ⁴ ^ Г ^ CH (CH,), ^> ^ ^ / ei - ³ 1.2 ppm 100 100 0 100 70 300 ppm - F ₂ CHO - (^ ^"4 V CH-CO-O-CH _2" "[^ jT ^0" T ^ T ^4] _c] W сн (CH _{3) 2} Ч ^ 4JJ 80 - - cotton caterpillar 90 0 100 - - - Cl ^ ₇ CN г -LHU \ / "[Il ^ l ι! Cl 3 2 ^ i>" ^ ^ n / ^ 100 - - 1000 ppm 100 0 100 - - - 100 100 100 100 100

Bexspiel 33

Insecticidal action Two-sided angular pirawtil, Tetranychus urticae (cook)

One occupied bean plants (Sieva lima), the first sheets 7 _r are 5 to 10 cm long, allow about 1o0 adult, phosphate-resistant mites per leaf, and swar 4 hours before carrying out the investigation to zn the deposition of eggs before treatment The infected plants are then immersed for 3 seconds with stirring in the solution containing 1000, 30%, 10% or 10 ppm of the active ingredient, after which the plants are put into the fume hood to dry. After 2 days bai 27 * C? 8O ⁰ F), the corticality of full-grown mites is estimated on a leaf under a stereoscopic microscope with 10-fold magnification. The other leaf is left on the plant for another 5 days and then examined at 10-fold amplification to kill the eicx the: newly hatched ütfyraphen abxuschäteen, whereby the оѵігіае effect bsw »the residual effect can be determined» Oif results are in the following table e III

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

Immerse three cotton patches with just cotyledons in the solution containing 100 ppm of the active substance and then transfer them to dry in a drawer. Kach drying each cotyledon is halved, and there are 10 leaf sections into a 28 g Kunststoffarzneixnitteloecher containing a 1.25 cm thick Sahnarssttampon, Фес with; Saturated with water, followed by a third stage tobacco caterpillar

21 U93

bring in the cup. Close the cup and store it for 3 days at 27 ⁰ C (80 ⁰ F) and a relative humidity of 50%, on which counts the mortality. The results obtained are summarized in the following Table III.

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

Immerse a true leaf of a cotton plant in the test solution containing 100O ₇ 100 or 10 ppm of the compound to be examined, stir for 3 seconds, remove the plant and leave to dry in a fume hood. After drying, the sheet is transferred to a 9.0 cm Petri dish containing moist filter paper at the bottom. Then add 10 larvae in the third stage of development and cover the bowl with the lid. The mortality is counted after 3 days at 2 7 ⁰ C (8O ⁰ F) and a relative humidity of 50 + 10%. The numerical values obtained are summarized in the following Table III.

Table III Insecticidal activity

f "* *" - "'' '' '' - - '' - '· - - ч \ Cl -0- ^сн з Phosphatres mites 300 ppm istente 10 ppm % Mortality · i "3.Ent stadium Kohlraupe i.ü.Ent- • icklungsstadium 100 ppm ppm connection ^^ ^ ч ^ ⁴ OCH ₃ Λ ρ 100 ppm 0 ~ TSUP - Tobacco Fruit Development ^ iOppm 1000 ppm 100 60 F ₂ CHO- / у- CH-CC-O-CH -η ^^ ΥρΟη ^^^ ^^ CH (CH ₃ I ₂ I ₄ ^ JJ ^ ,, L 100 0 - - 1000 ppm 40 100 100 0 F ₂ CHO - // y-CH-CO-O-CH- ^ jV-O- ^ == - / CH (CH ₃ J ₂ Ч ^ CN F ₂ CHO - // y ~ CH-CO-O-CH- ^^ ClI (CII ₃ J ₂ 100 0 - - 100 - 100 100 30 F ₂ CHO - // у-СН-СО-О-СН- ^ 'CH (CH ₃ J ₂ 100 100 - - 50 20 100 100 100 100 0 100 100 100 100

Table III (continued)

connection

mortality

Phosphate Rosi stents

Mi Ibon

1OÜÜ

ppm

30μppm

100 ppm

10 ppm

Tobacco caterpillar · ¹ І.З. Enty Kohlraupe i.3.Ent-

development stage

1000 ppm

100 ppm

winding stage

1000 ppm

100 ppm

10

ppm

CN CH-CO-O-CH

CH (CH ₃ )

100

100

100

80

100

100

90

CN CH-CO-O-CH

си (CH ₃ ) ₂

100

100

80

100

100

100

100

100

a belle III (continued)

connection

mortality

Phosphatrosistento

'mites

To ~ 0o

300 years

ppm [ppm

10 ppm

Tobacco caterpillar 1.3.Ent winding stage

1000 ppm

IDU ppm

r Kohlraupe 'i.Ti'development stage

1000 ppm

100

ppm

CN (CH-CO-O-CH

CH (CH ₃ ) ₂

100

80

100

100

F ₂ CHO

br

CH-CO-O-CH. CH (CH ₃ ) ₂

90

30

90

50

F ₂ CHO

Cl

CH-CO-O-CH-,

CH (CH ₃ J ₂

100

100

100

T abe 1 1 e III (continued)

connection

mortality

Phosphatresifetente

mites

1000 ppm

30μppm

100 ppm

10 ppm

TabakraupG iOnt- • / icklun gs stadium

1000 ppm

100 ppm

Kohlraupe i.3.Entvicklungsgt adium

10Ü0 ppm

100 ppm

F ₂ CHO

Cl

CN I CH-CO-O-CH

CH (CH ₃ )

100

100

90

100

100

Cl

F ₂ CHO

Cl

CH-CO-O-CH

CH (CH ₃ )

50

90

10

100

80

egg

F ₂ CHO Cl

CN I

CH-CO-O-CH

CH (CH J ₂

90

100

40

100

100:

21 1693

Example 34

Ixodizide effect

The following studies investigate the effective control of mite larvae using larvae of Boophilus microplus, a mongrel tick which, during its three stages of development, i. larval stage, nymphal stage and adult stage, may be present on a single host. In this study, a mixture of 10% acetone and 90% water containing 7OO, 100, 1, 0, 1, 0, 01, 0.001, 0.004 and 0.00001 ppm of the compound to be tested is used. There are 20 larvae into a pipette closed at one end with a gauze material, whereupon the solution containing the compound to be examined is drawn through the pipette by means of a vacuum tube, whereby a spraying system is simulated. The ticks are then stored for 48 hours at room temperature, after which the mortality is determined. The results obtained are summarized in the following Table IV.

21 1 693

Table IV

RCF ₂ O-

CH СО-О-CH

CH (CH ₃ J ₂

Y 2 H ₂ * 3 % Mortality ppm R H II CN P-Cl at - at 100 ppm H H H CN P-OCH ₃ 100 "100 H H H CN · P-CH ₃ 75 ¹¹ 100 H H H CN P-F 100 "° jl; 3 0 at Ο, ΟΙ H H H CN , Eleven 100 "100 H H H CN O-F 100 "100 H H H CN p-Cl 100 "100 P H к CN P-CH ₃ 80 O ₇ I; 10 at Ο, ΟΙ F H H CN P-OCH ₃ 100 "100 F H H CN p-F 90 ° _; 01; 20 at Ο, ΟΟΙ P H H -C = CH H 75 ' ¹ 100 F CH ₃ H CN H 100 " '100 H br H H H 0 " 100 H br H CN H 0 " 700 H Cl H H H 100 ' 100 H Cl H CN H loo " 100 H Cl Cl H H 75 " 100 H Cl Cl H. CN 40 " '100 H H H H H 90 ' Ο, 004 F 100 '

Table IV

(Continuation)

21 1693

% Mortality at ppm

-Ethyl F

lOO bai 100 1OO "1OO

cC-ethyl

CN

10000

CN

85 ", ΟΟΟΟΐ

21 1693

Example 35

The efficacy of the compounds according to the invention in the control of adult ticks (Boophilus microplus) is determined by means of the following test method in which the compound to be tested is solubilized according to the procedure of Example 38, except that the active substance is treated in such , Quantities used to obtain solutions containing 500, 125, 62, 37.9, 32, 31, 15, 16, 8, 2 and O, 25 ppm of the compound to be tested.

Then, full-grown, rich, female ticks are immersed in the solutions to be examined for 3 seconds, transferred to individual containers and stored for 48 hours at 27 ⁰ C (80 ⁰ F) and a relative humidity of 50%. At the end of the storage period, the ticks are examined and excretions are counted. Large female ticks that have not deposited eggs are considered dead. The results obtained are summarized in Table V below.

table

СО-О-Сй

aiuigac · Eggs bai - ppm

H H H CN ρ-Cl H Il Ji CN P-CU ₃ H H и CN P-JP H H и СП TR-F H H к CN O-F F H H CN P-CH ₃ F F и H H H И p-F H F и и H H α-ethyl F я H H 1! α-RthyL. F H H CN H F H H CN H

і 125; ®Qtoai31

^м 125j 52 "31, 9" 125? 3? _? $ Ьэі

^вд 125? 52 ^ 2x31

^м :>€> 0ί 65 ^ч 125

"16; 73 ^и -в

" ¹ Oj25

О «

О «500 О ^w 500

Claims (5)

CLAIMS INVENTION wherein RCF "X-, У and Z in meta or para position to the
Carbon atom to which the alkanoic acid ester group is bonded, and wherein X is O, S, SO or SO-, Y and ZH, Cl, F, Br, NO ₂ , CH ₃ or OCH ₃ , RH, F, Cl, CHF ₂ or CF ₃ , R _{2 is} an ethyl, n-propyl, isopropyl, isopropenyl or t-butyl group, R _{3 is} H, CN or -C ^ CH and R _{4 is} H, F, Cl _{1 is} CH ₃ or OCH ₃ with the proviso that at least one of Z, Y and R has a meaning other than hydrogen, when R 1 is H or CN, characterized in that compounds of general formula II 21 16 .η Presence of pyridine with compounds of the general ormel III (III) implements. 2. The method according to item 1, characterized in that / a compound of the general formula wherein RCF-X- in m- or p-position to the carbon atom to which the alkanoic acid ester group is bonded, and H or F, O or S, an ethyl, n-propyl or isopropyl group, H, CN or -C = CH and F, Cl, CH ₃ or OCH ₃ mean is produced. 3. The method according to item 2, characterized in that a compound in whose formula R is H or F, R "isopropyl, R is CN, X 0 and R is F, is prepared. 21 U93 4. The method according to item 2, characterized in that / made alpha-cyan-m- (p-fluorophenoxy) benzylalphaisopropyl-4-dif luormethoxyphenylacetat
becomes. 5. The method according to item 2, characterized in that alpha-cyano-m- (p-fluorophenoxy) benzyl alpha-isopropyl-4-trifluoromethoxyphenylacetate is prepared.