CS200226B2 - Insecticide and acaricide and process for preparing effective compound - Google Patents

Description

The invention relates to insecticidal and acaricidal compositions containing, as active ingredient, the m-phenoxybenzyl esters of substituted phenylalkanoic acids as described below, a process for the preparation of these active ingredients and intermediates suitable for their preparation. From the state of the art, South Africa Patent Application No. 73/4462 (Sutnitorno Chemical Company Limited) is the closest to the subject of the invention. This application genetically describes tens of thousands of phenylacetic acid esters, including 3'-phenoxybenzyl-alpha-isopropyl-4-methoxyphenylacetate, 3'-phenoxybenzyl-alpha-isopropyl-3-methoxyphenylacetate, 3'-phenoxybenzyl-alpha-isopropyl-4- chlorophenylacetate, 3'-phenoxybenzyl-alpha-isopropyl-4-methylphenylacetate, 3'-phenoxybenzyl-alpha-isopropyl-4-fluorophenylacetate. It is reported that many of these compounds are effective pesticidal agents and are useful for controlling various insects and mites. However, the m-phenoxybenzyl esters of 2- (haloalkoxyphenyl) alkanoic acids, which are the active ingredients of the compositions of the present invention, are not disclosed, nor is there any synthesis useful for the preparation of these compounds.

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

The invention relates to an insecticidal and acaricidal composition characterized in that it contains at least one 2- (haloalkoxyphenyl) alkanoic (I) m-phenoxybenzyl ester of the formula I as active ingredient.

CH-CO-CH ₂ -C ₂ O

O

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

R is fluoro, chloro, difluoromethyl or trifluoromethyl,

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

R 3 is hydrogen or cyano, or an optical isomer thereof.

The compositions of the present invention can be used to control insects and mites by contacting insects, mites, habitats, hatching areas and / or food thereof with an insectioid or acaricidally effective amount of 2- (haloalkoxyphenyl) m-phenoxybenzyl ester. The alkanic acids of the general formula I can be protected by means of the compositions according to the invention either in the growth or post-harvest stage and warm-blooded animals against insect and / or acarid attack by applying an insectioid or acaricidally effective amount of crops as defined above. compounds of formula I.

Preferably, the m-phenoxybenzyl esters of 2- (haloalkoxyphenyl) alkanoic acids of formula I may be prepared by reacting an alpha-substituted (haloalkoxyphenyl) acetyl halide of formula II, preferably chloride with m-phenoxybenzyl alcohol of formula III. The reaction is generally carried out in the presence of a solvent such as diethyl ether, benzene or toluene, at a temperature in the range of 10 to 30 ° C in the presence of an acid acceptor. As acid acceptors, for example, tertiary organic amines such as trimethylamine, triethylamine and pyridine can be used. The reaction can be illustrated as follows:

(II) (III) an acid acceptor

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

R is fluoro, chloro, difluoromethyl or trifluoromethyl,

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

R 3 is hydrogen or cyano; and

X is halogen, preferably chlorine.

Preferred compounds of formula I above are 1, those wherein RCFgO- is in the p-position to the carbon to which the alkanoic ester group is attached and wherein R, Rg and R3 are as defined above, or 2. those wherein RCFgO it is in the m-position to the carbon atom to which the alkanoic ester group is attached and wherein R, R2 and R3 are as defined above.

It has also been found that more preferred compounds in each of these groups are those wherein R is fluoro, R 3 is cyano and R 2 is ethyl, η-propyl, isopropyl, t-butyl or isopropenyl.

It is clear that the various optical isomers of the compounds of formula I are formed in the above-described procedures.

For example, in the synthesis of esters of formula I wherein R 3 is hydrogen, a chirality center is present on the remainder of R ₂ and the d isomeric pairs are formed. Also, alpha-cyansubstitution at R3 introduces another center of chirality, whereby an additional d, 1 pair can be formed.

The alpha-substituted (haloalkoxyphenyl) ethyl halide of formula II can be prepared using the appropriate haloalkoxytoluene of formula XV as a starting material. The process comprises 5 steps, the first step being halogenation of the haloalkoxytoluene of formula IV with bromine, chlorine, N-bromosuccinimide (NBS) or the like. This reaction is preferably carried out in the presence of an inert organic solvent such as carbon tetrachloride and a free-radical initiator such as light, benzoyl peroxide or azo-bis-isobutyronitrile to give the haloalkoxybenzyl halide of formula V. This compound is then converted to the corresponding haloalkoxyphenylacetonitrile of VI by reaction with sodium cyanide. or potassium in the presence of dimethylsulfoxide (DMSO), ethanol or the like at elevated temperature. This (haloalkoxyphenyl) acetonitrile of formula VI is then easily alkylated by reaction with an alkyl halide in the presence of a base and an inert organic solvent. In this reaction, crown ethers can be used as catalysts. Hydrolysis of the formed alpha-alkyl (haloalkoxyphenyl) acetonitrile of formula VII using an alkali metal hydroxide in the presence of alkylene glycol and water affords alpha-alkyl (haloalkoxyphenyl) acetic acid of formula VIII. Reaction of this acid with thionyl chloride, thionyl bromide or the like, preferably in the presence of an aromatic solvent such as benzene or toluene, yields the alpha-substituted (haloalkoxyphenyl) acetyl halide of formula II which is reacted with m-phenoxybenzyl alcohol of formula III or alpha-cyano. -phenoxybenzyl alcohol to give the desired 2- (haloalkoxyphenyl) alkanoic acid m-phenoxybenzyl ester or alpha-cyano-m-phenoxybenzyl ester of formula I.

These reactions are shown in Scheme I below.

S c hé m a 1

Preparation of 2- (haloalkoxyphenyl) alkanoic acid m-phenoxybenzyl esters (IV)

or

RCF10 (NBS) rcf ₂ o (v) rcf ₂ o rcf ₂ o

(VI) (VI)

ΓV ch, cn ₊ R, x rcf ₂ o / <= / Crown ether (VI). fy r ™

F ₂ ° ^R 2 (VII) o?

h ₂ o

-CHCN + KOH

I HOCH ₂ CH ₂ OH (vil) by CHCOOH RCF 10 Rj (vin) by

CHCOOH + SOCl ₂ benzene

RCF, 0 (Vlil)

CHCOCI

I (11)

+ pyridine benzene

The preparation of m-phenoxybenzyl and alpha-cyano-m-phenoxybenzyl esters of alpha-alkyl-3 (or 4) -trifluoromethoxyphenylacetic acid can also be carried out by a sequence starting the alkylation of m- or p-methoxyphenylacatonitrile using an alkyl halide in the presence of crown ether and base. Of course, it is common that when using m-methoxyphenylacetonitrile in this reaction, alpha-alkyl-3-methoxyphenylacetonitrile is obtained, and when the β-isomer is used, alpha-alkyl-4-methoxyphenylacetonitrile is obtained. It will be apparent from the following discussion that the positioning of the methoxy group on this phenylaetonitrile starting material determines the position of the trifluoromethoxy substituent in the final product.

The above alpha-alkyl-3 (or 4) -methoxyphenylacetonitrile is converted to alpha-alkyl-3 (or 4) -hydroxyphenylacetonitrile by reaction with boron tribromide, preferably in the presence of a solvent such as methylene chloride. Treatment of the thus formed alcohol with thiophosgene and a base in the presence of a solvent such as chloroform then yields the chlorothioester O-fm or p- (1-cyano-2-methylpropyl) phenyl formic acid. This ester is readily converted to alpha-alkyl-3 (or 4) -trifluoromethoxyphenylacetonitrile with molybdenum fluoride and this compound is then hydrolyzed to the corresponding alpha-alkyl-1-3 (or 4) -trifluoromethoxyphenylacetic acid by reaction with ethylene glycol in the presence of alkali metal hydroxide and water .

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

These reactions are illustrated in Scheme II below:

Scheme II

Crown ether

50% NaOH

CH-CN ₃ or ₂

CHoO

V-CH-CN + BBr, I ^{3 R} 2 ch ₂ or ₂

CHCN

HIM

I WANT,

CH-CN + CSCI ^From NaOH

HIM

WITH

II

Cl-CO

CH-CN < - > -CH-CN &lt; + &gt;

WITH

II

CI-C-O cf ₃ or ₂

CH-CN + HOCH ₂ CH ₂ OH

KOH

CH-COOH ca ₃ o

CH-COOH + SOCl ₂ cf ₃ o R ₂

ZA-ch-what

CF, OR,

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

Regarding the preparation of alpha-cyano-m-phenoxybenzyl ester products according to the procedures shown in either Scheme I or II, there is no need to prepare alpha-cyano-m-phenoxybenzyl alcohol as a precursor. It is the same or even more convenient to react a mixture of m-phenoxybenzaldehyde, an alkali metal cyanide such as sodium cyanide and a suitable alpha-substituted (haloalkoxyphenyl) acetyl halide in one step to form the final alpha-cyaneeter.

The compounds according to the invention are highly effective as contact and gastric poisons for clichés and for various insects, in particular double-winged, butterflies, beetles and even-winged insects. They are unusual among pyrethroids in that they exhibit a very broad residual insecticidal activity on plant tissue, are effective in soil and unexpectedly effective for controlling germs and for protecting animals from insect and tick infestations, when administered orally or parenterally to animals, or when administered as a local insecticidal or acaricidal agents. Stabilizers are not required to produce stable insecticidal and acaricidal compositions. The active compounds according to the invention can be used in admixture with other biological chemicals, for example pyrethroid synergists such as piperonyl butoxide, sesamex or isosafrol n-octylsulfoxide. They can also be used in combination with conventional insecticides such as phosphates, carbamates, formamidines, chlorinated hydrocarbons or halobenzoylureas. Insecticidal compounds of the invention may be applied to plant foliage, insect habitats and / or insect feed to control insects, including non-plant soil insects in growth and / or harvested crops, including stored grain. In general, the active compound is administered in the form of a diluted liquid spray; however, it can also be applied as an aerosol, dust, granulate or wettable powder.

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

A typical emulsifiable concentrate useful for protecting various crops such as cereals, cabbages, cucumbers, corn, cotton, tobacco, soybeans, ornamental plants, shrubs and the like may contain about 20 wt. active substance; 4 wt. an emulsifying agent commonly used in the preparation of pyrethroid preparations; 4 wt. surfactants; 25 wt. an organic solvent such as cyclohexanone; % and about 47 wt. petroleum solvents containing a minimum of 83% arom.

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

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

As systemic agents, the compounds of the invention have a wide range of safe applicability and are effective to protect a variety of animals, particularly cattle and domestic animals such as cattle, sheep, horses, dogs, cats and the like, prior to attack by fleas, mosquitoes, flies, ticks and the like. The compounds of the invention which are useful as insecticidal and acaricidal agents include, for example:

m-phenoxybenzyl-alpha-isopropyl-4-trifluoromethoxyphenylacetate, alpha-cyano-m-phenoxybenzyl-alpha-isopropyl-4-trifluoromethoxyphenylacetate, alpha-cyano-m-phenoxybenzyl-alpha-isopropyl-3-trifluoromethoxybenzyl acetate, alpha-cyano-m- phenoxybenzyl-alpha-isopropyl-4-chloridifluoromethoxyphenylacetate, m-phenoxybenzyl-alpha-isopropyl-4- (1,1,2,2-tetrafluoroethoxy) phenylacetate, alpha-cyano-m -phenoxybenzyl-alpha-isopropyl-4-pentafluoroethoxyphenylacetate, m -phenoxybenzyl-alpha-ethyl-3-trifluoromethoxyphenylacetate;

alpha-cyano-m-phenoxybenzyl-alpha-n-propyl-4-chlorodifluoromethoxyphenylacetate, alpha-cyano-m-phenoxybenzyl-alpha-t-butyl-4-trifluoromethoxyphenylacetate.

The invention will be illustrated in the following examples.

Example 1

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

Tetrafluoroethylene and nitrogen were bubbled through a magnetically stirred mixture of 10.0 g (0.100 mol) of p-cresol, 1.67 g (1.43 g indeed, 0.0255 mol) of potassium hydroxide pellets and 70 ml of dry dimethylformamide (DMF) for 1 hour. maintained at 68 ° C. After diluting with 250 ml of water, the reaction mixture is extracted with 100 ml of ether. The ether solution was washed with 200 mL of 556 sodium hydroxide and 2 x 400 mL of water. The ether solution was dried, filtered and then rotary evaporated to give 18.14 g of (87%) p- (1,1,2,2-tetrafluoroethoxy) toluene.

Analysis for C 8 H 9 F 6:

calculated: 51.93% C, 3.87 56 H, 36.51 56 F;

found: 52.06 56 C, 3.76 56 H, 41.52 56 F.

Example 2,

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

Mechanically stirred mixture of 118.45 g (0.569 mol) p- (1,1,2,2-tetrafluoroethoxy) toluene, 123.00 g (0.691 mol, 121 mol. 56) N-bromosuccinimide (NBS), 1.00 g (4.13 mol, 0.73 mol 56) of benzoyl peroxide and 350 ml of carbon tetrachloride were refluxed for 2.25 hours.

After cooling, the reaction mixture is diluted with 350 ml of carbon tetrachloride, filtered to remove solids, dried over sodium sulfate, filtered and then evaporated using a rotary evaporator. 160.99 g (99.56) of a clear red oil are obtained. This product was used as such in the following reactions. The infrared and NMR spectra confirm the structure of p- (1,1,2,2-tetrafluoroethoxy) benzyl bromide.

Example 3

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

A hot solution of potassium cyanide (75.1 g, 1.15 mol) in water (40 ml) was added over 40 minutes to a 75 ° C, mechanically stirred solution, 160.99 g (0.561 mol) of p- (1,1,2 mol). , 2-tetrafluoroethoxy) benzyl bromide and 500 mL of anhydrous 2-butanol. The resulting mixture was heated to reflux for 1.75 hours. After standing overnight, the reaction mixture was poured into 500 ml of cold water and 400 ml of ether. The combined ethereal solution was washed with water (2.times.500 ml), dried over sodium sulfate, filtered and then evaporated on a rotary evaporator to give 114.95 g of an oil. Vacuum distillation of this oil yielded, as a single distillation fraction, 37.10 g (28 56) of nitrile, bp 85-100 ° C at 38.7 Pa.

1 ø 1 to 1 and d 4

Preparation of alpha-isopropyl-β- (1,1,2,2-tetrafluoroethoxy) phenylacetonitrile

A mixture of 39.85 g (0.171 mol) of p- (1,1,2,2-tetrafluoroethoxy) phenylacetonitrile, 3.71 g (9.96 mmol, 4.8 mol%) of dicyclohexyl-18-crown-6-ether 22.0 ml (28.8 g, 0.234 mol) of 2-bromopropane, 55 ml of benzene and 55 ml of 50% sodium hydroxide are stirred for 45 minutes, during which time the temperature is raised from 25 ° C to 43 ° C. The reaction mixture was then heated at 45 ° C for 16.5 hours. After dilution with 200 ml of water, the reaction mixture is extracted with 200 ml of ether. The ethereal solution is washed with 400 ml of 12% hydrochloric acid, 200 ml of 5% hydrochloric acid and 300 ml of water. The ether solution was dried over sodium sulfate, filtered and then evaporated to give 47.13 g of an oil. This oil was distilled in vacuo to give 34.83 g (74%) of the product, bp 83-85 ° C at 7.3-12.0 Pa.

H, 4.76; N, 5.09; F, 27.61.

Found: C, 56.12, H, 4.85, N, 4.99, F, 34.07.

Example 5 '

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

Stirred mixture 48.0 g (24.0 g actual, 0.60 mol) 50% sodium hydroxide, 21.78 g (0.0791 mol) alpha-isopropyl-β- (1,1,2,2-tetrafluoroethoxyphenylacetonitrile) and 240 ml of ethylene glycol was heated for 12 hours at 135 DEG C. After diluting with 600 ml of water, the reaction mixture was washed with ether (2.times.100 ml), the aqueous layer acidified with concentrated hydrochloric acid and then extracted with ether (2.times.300 ml). The mixture was dried over sodium sulfate, filtered and then evaporated to give 20.74 g (89%) of a brown solid, mp 92-97 ° C (hexane).

Analysis for C 13 H 14 F 4 O 3;

calculated: 53.06% C, 4.80% H, 25.83% F;

Found:% C, 53.04;% H, 4.79;% F, 25.93.

Example 6

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

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

200226 10

Example 7

Preparation of m-phenoxybenzyl-alpha-isopropyl-4- (1 ', 2,2-tetrafluoroethoxy) phenylacetate

X of a stirred mixture of 6.81 g (0.0340 mol) of m-phenoxybenzyl alcohol, 5.0 ml (2.95 g, 0.0372 mol) of dry pyridine and 20 ml of methylene chloride are added over 20 minutes 20 ml of methylene chloride solution 10.6 g (0.034 mol) of 3-methyl-2-C- (1,1,2,2-tetrafluoroethoxy) phenyl] butyryl chloride. The reaction mixture was stirred at room temperature for 66 hours and then diluted with 200 mL of ether. The ether solution was washed with 200 mL of 20% hydrochloric acid and 200 mL of water, dried over sodium sulfate, filtered and then evaporated to give 16.24 g of product (100%). The product was purified on a dry silica gel column (116 cm x 5 cm, eluent 1: 1 hexane-methylene chloride). A sample is collected between 85 cm and 63 cm (solvent front equals 113 centimeters). Yield: 12.60 g (78%) of a clear, pale yellow oil.

Analysis for C26H24F4O4:

calculated: 65.54% C, 5.08% H, 15.95% F (found: 64.99% C, 4.96% H, 19.10% F).

Example

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

X stirred mixture 8.81 g (7.49 g real, 0.0333 mol) alpha-cyano-m-phenoxybenzyl alcohol, 3.0 ml (2.95 g, 0.0372 mol) dry pyridine and 20 ml methylene chloride were added. 20.6 ml of a methylene chloride solution of 10.6 g (0.034 mol) of 3-methyl-2- [p- (1,1,2,2-tetrafluoroethoxy) phenyl] butyryl chloride are added over 20 minutes. The reaction mixture was stirred at room temperature for 66 hours and then diluted with 200 mL of ether, washed with 200 mL of 20% hydrochloric acid and 200 mL of water, dried over sodium sulfate, filtered and then evaporated to give a dark red oil. To remove m-phenoxybenzaldehyde as an impurity, the oil is treated with 0.5 g of sodium borohydride at an ice bath temperature and the resulting oil is purified on a dry silica gel column (121 cm x 5 cm, 1: 1 hexane-methylene chloride). A sample is collected between 77 cm and 57 cm (solvent front = 113 cm). 11.17 g (66%) of a clear orange oil are obtained.

Analysis for C27H23F4NO4.

calculated: 64.67% C, 4.62% H, 2.79% N, 15.16% F;

Found: C 65.26, H 4.81, N 2.82, F. 17.94.

Example 9

Preparation of alpha-isopropyl-4-methoxyphenylacetonitrile

Sodium hydroxide solution (50%, 300 mL) was added to a solution of p-methoxyphenylacetonitrile (147 g, 1 mol), dicyclohexyl-18-erown-6-ether (18.63 g, 5 mol%), 2-bromopropane ( 320 g, 2.6 mol) and benzene (300 mL). The reaction mixture is heated to 45 ° C and kept at this temperature for 4 days. The organic phase was separated, washed well with water (3 x 200 ml), dilute hydrochloric acid (1 x 200 ml), water (2 x 200 ml) and evaporated to an oil. Vacuum distillation gave the product (175.6 g, 81% of theory), boiling point 96-100 [deg.] C (20 Pa), NMR (CDCl3) showed that the distilled material contained 12.5 mol%. starting nitrile.

ti

He did

Preparation of alpha-isopropyl-4-hydroxyphenylaeetonitrile

Boron tribromide (51.0 g, 0.2 mol) in methylene chloride (20 mL) was added to a solution of alpha-isopropyl-4-methoxyphenylacetonitrile (37.8 g, 0.2 mol) in methylene chloride (35 mL) maintained at -30 ° C. Deň: 32 ° C. The red solution was allowed to warm to room temperature and stirred for 3 days. The reaction solution was poured onto ice, then extracted with ether (3 x 100 mL), washed with water (2 x 100 mL) and evaporated to an oil. Vacuum distillation yielded alpha-isopropyl-4-hydroxyphenyiacetonitrile (28.9 g, 81%), bp 142-143 ° C (33.3 Pa).

They did

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

Thiophosgene (16.43 g, 0.143 mol) in chloroform (50 mL) was added over 30 minutes to a solution of alpha-isopropyl-4-hydroxyphenylacetonitrile (25.0 g, 0.143 mol) in sodium hydroxide (5%, 5.72 g) (0.143 mol) with occasional use of an ice bath to maintain the temperature below 30 ° C. The mixture was stirred for 15 minutes and the chloroform layer was separated, washed with water and evaporated to a yellow oil (38.2 g). The product was used as such in Example 12.

Example 12

Preparation of alpha-isopropyl-4-trifluoromethoxyphenylaoetonitrile

The thiocarbonate (38.2 g) of Example 11 was treated with molybdenum fluoride (15.8 grams) at -25 ° C. The dense reaction mass was then allowed to warm to room temperature and then slowly warmed to 160 ° C using an oil bath. The mixture was cooled to room temperature and then poured into water and extracted four times with 50 ml of ether, washed once with 50 ml of water and evaporated to an oil. Vacuum distillation yielded alpha-isopropyl-4-trifluoromethoxyphenylacetonitrile, bp 78-80 ° C (20 Pa).

Example 13

Preparation of alpha-isopropyl-4-trifluoromethoxyphenylacetic acid

A mixture of alpha-isopropyl-4-trifluoromethoxyphenylacetonitrile (2.0 g), potassium hydroxide (3.0 g) in 35 ml of ethylene glycol and 3 ml of water was heated at 140 ° C for 8 hours. The aqueous layer was acidified with dilute hydrochloric acid and extracted 3 times with 11 ml of ether, the extract was washed with 25 ml of water, dried over sodium sulfate and evaporated to an oil (1.23 g); IR (neat) 1700 M ^- '.

Example 14

Preparation of alpha-isopropyl-4-trifluoromethoxyphenylacetyl chloride

A solution of alpha-isopropyl-4-trifluoromethoxyphenylacetic acid (1.2 g) and thionyl chloride (0.6 ml) in 5 ml of benzene was refluxed for 4 hours. Evaporation of the solvent and excess thionyl chloride afforded the acid chloride which was used as such for the ester of the examples 15 and 16.

200226 12

Example 15

Preparation of alpha-cyano-m-phenoxybenzyl-alpha-isopropyl-4-trifluoromethoxyphenylacetate

A solution of alpha-isopropyl-4-trifluoromethoxyphenylacetyl chloride (4.58 mmol) in 5 mL of ether was added to an ether solution (20 mL) of alpha-cyano-m-phenoxybenzyl alcohol (4.58 mmol) and pyridine (0.5 mL). The mixture was stirred overnight and filtered. The filtrate and washings were evaporated and the residual oil was purified on 5 x 2 mm silica gel plates using 1: 1 methylene chloride-hexane as eluent. The band with Rf = 0.55 was extracted with ether and evaporated to give the desired ester (0.85 g). ’

IR (neat) 1755 cm ^- ', NMR (CDCl @), delta 6.8 to 7.6 (m, 13H, Ar-H), 6.31 and 6.28 (s, 1H, -CH Ar), 3.27 (d, J = 7Hz, 1H, CH-CH _{(CH3) 2),} 2.0 to 2.6 CN (m, 1H, CH _{(CH3) 2),} 0.6 1.2 (four doublets, J = 7Hz, 6H, isopropyl CH ^{_3), 9} F chemical shifts of 58.8, relative to delta CFCly

Example 16

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

The above ester was prepared from m-phenoxybenzyl alcohol and alpha-isopropyl-4-trifluoromethoxyphenylacetyl chloride using the same procedure as described in Example 14.

IR (neat), 1738 cm ^- ', NMR (CDC1 ₃₎ w from 6.73 to 7.45 (m, 13H), 5.03 (s, 2H), 3.20 (d, J = 10 5Hz, 1H), 2.26 (m, 1H) 0.66 and 0.94 (2 d, J = 6.6Hz, 6H).

Example 17

Insecticidal activity

The insecticidal activity of the compounds of the invention is demonstrated in the following tests, using Heliothi9 virescens (Fabricius), Empoasca abrupta DeLong and Aphis fabae (Scopoli) as a test insect species. The procedure used is as follows:

Heliothis virescens (Fabricius)

První instar

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

Aphis fabae (Scopoli) i

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

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

Empoasca abrupta DeLong

A Sieve bean plant with a primary leaf unfolded to 7.60-10.20 cm is soaked in a 35% water / 65% acetone solution containing 100, 10 or 1 ppm of the test compound. The soaked plant is placed in a fume hood to dry, and then a 2.5 cm long leaf tip is cut and placed in a 10 cm petri dish, with the wet filter paper at the bottom.

Place 3 to 10 second instar nymphs in the dish and cover the dish. The plates are kept at 26.7 ° C for 50 days at 50 ° C for two days, and mortality is determined. The data obtained are given in Table I. In these tests, permethrin is used as the standard or reference substance.

Table 1

Compound

PP®

Heliothis virescens Larvae 1. instar 300 100 10

Mortality%

Emphasca Aphis fabae abrupta

100 10 11 100 10 1 0.1

CN

100 100 100 100 100 70 100 100 90 50

CHF ₂ CF ₂ CO -O-CH ₂ - <^> - o

CH _{(CH3) 2}

90 0 50 0 - 100.00 0

CN

CH 2 CO-O-CH-O

CH _{(CH3) 2}

I I 100, 00 o 100 o-100 100 50

- = not tested \ = / I

Example 18

Insecticidal activity

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

The procedures used to evaluate the effect against the mosquito Anopheles quadrimaculatus (Say), Epilachna varivestis (Mulsant) and Spodoptora eridania are as follows:

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

Epilachna verivestis Mulsant

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

The data obtained are shown in Table II.

Spodoptera eridania Cramer

Bean plants (monthly bean) with two unfolded primary leaves of 7.5 to 10 cm are soaked in mixed test solutions for 3 seconds and then allowed to dry in a fume cupboard. After drying, the leaves were detached and placed on a 10 cm petri dish containing a piece of wet filter paper and 10 third instar larvae, approximately 1 cm long. Cover the petri dishes and place in room 8 for 2 days at controlled temperature and humidity at 26.7 ° C and 50% relative humidity.

After two days, mortality is established. The results obtained are shown in Table II.

Table II

Insecticidal evaluation

Compound

Mortality%

Larvae of Anopheles Spodoptera quadrimaculatus eridania ppm ppm

1.2 0.4 0.04 0.004 1,000 100 10

Epilachna variyestis ppm

300 100 10 1

CN ^CF 3 ° - / V-CH-CO-O-CH -ΑΑ \ = / I CH _{(CH3) 2}

100 100 100 90 100 100 100 100 100 100 100

CHF ₂ CF ₂ OA 2 'CH ~ CO-O-CH ₂ -AA- oA \

CH _{(CH3) 2}

100 100 90 100 100 100 100

CN

CHF ₂ CF ₂ O - CH-CO-OCH = ^{CH, CH} 3 ^, 2

100 100 80 0 100 100 0 100 - = not tested

Example 19

Insecticidal activity

Tetranychus urticae (Koch) - Weaving Spider

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

Heliothis virescens (Fabricus) Third instar

The three cotton plants with the uterus just unfolded are immersed in a solution with an active ingredient concentration of 1000 or 100 ppm and allowed to dry in a fume cupboard. After drying, each uterus is cut in half, and 10 leaf portions are placed in 28g plastic medical cups containing a 1.25 cm long dental wick saturated with water and 1 third instar larvae is added. The cup is covered and held at 26.7 ° C and 50% relative humidity for 3 days, and then mortality is determined. The test results are shown in Table III.

Trichoplusia ni

Third instar

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

The results obtained are shown in Table III.

T and b u 1 k and III

Mortality%

Mite-resistant Heliothis virescens Tricho- Compound phosphate in the third plusium ni ppm instar ppm in the third instaru 1,000 300 100 10 ppm 1,000 100 1,000 100 10

CN

CF, O

100 100 80 100 100 100 100 100

CHF ₂ CF ₂ o 4 -> - CH - CO - O - CH _{2 -} f -> - O - CH (CH ₃ ) ₂

100 50 0 50 1,100 0

CN

CHF, CF, O-CH-CO-O- _2- i, _2- u-y-uti-u-u-CH-j-O-ch (ch ₃ ) ₂

61 0 80 0 100 30 0

- Not tested

Example 20

Soil insecticidal activity

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

1.25 ml of solution A - 56 kg / ha 1.25 ml of solution B - 11.2 kg / ha.

The selected test solution is mixed with talc to be pre-wetted before being dried for 10 to 15 minutes in an oven where it is air-dried. 25 ml of wet sterilized potted soil and about 0.6 g of millet seed (larvae feed) are then added to containers containing the test compound. The containers are sealed and the contents are mixed on a vibrating mixer.

Ten larvae, which are 6-8 days old, are then added to each flask. The containers are then loosely capped and placed in a constant illumination area with a temperature of 26.7 ° C and 50% relative humidity. Mortality was determined after 6 days.

In this test, 100% suppression at a concentration of 56 kg / ha and 70% suppression at a concentration of 11.2 kg / ha were obtained with alpha-cyano-m-phenoxybenzyl-alpha-isopropyl-4-trifluoromethoxyphenylacetate in Diabrotica undecimpunctata howardi.

Example 21

Residual insecticidal activity obtained in the treatment of cotton plant leaves

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

After drying the leaves are removed from 2 plants of 2 leaves each and the leaves are placed in petri dishes (90 mm x 10 mm) on moist filter paper (9 cm Whatman No. 1). Five third instar larvae are placed on each leaf and the Petri dish is covered. The infested dishes are then placed in a constant-light area at 26.7 ° C and 50% relative humidity.

After 72 hours, the larvae were counted.

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

í8

M

P

0 <0

P

OJ

Ol

P

O ►

w a

H> «

O a

> 3 a

>

CU

X »

X0 a

• rl

Φ X4 3 O — — 1

%

O

N

P

0) o

K>

* 3

-š ro o

o o o

O lf \ o kO O \ o o o

o o o o

O lA O O kO, Os O o o o o o o O O lTs O

0- O O tA trs irs o o o o o o o o o o o o

O tfs ia o S0 Axis T r ia

O o o o o o o o o o o o

o o o o 00 t o o o o o o o o o o ro i οι

ΙΛ Q ΙΛ Q!

Os OS O »O trs o

oooo ¹ o pers

IA O o O! t - O O O lA

WITH

0)

O

Φ >>

Ω +

OJ ®

T o g> a xd a P o o o o o o o o o o o o o o o o o o o

- ΡΊ θ 'ro ro o o o o o o o o o o

Γ0

O O O O

ΙΛ lfs O O Sat 00 O O - ro

O O O O S OS tA IA O O S O O O O

PO o

* o o o o o

IA O LA O SO O OS O O §

O * φ g

XD

. G

and it +

+

Oí>

H a

rH (0

EH

P

0) co

XO 3 3 3 τ), etc. • hp and what you> _Those ¢ 3 · Η

Example 22

Ixodicidal activity

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

Table V

Percent mortality of Boophilus microplus tick larvae

Compound ppm 12.5 2.5

0,5 0,1

0,025

CN

CF 3 O- / VcH-CO-O-CH-r 1

100 ALIGN!

100 100

100 100 CH _{(CH3) 2}

The above procedure is repeated except that the concentration of the test compound is 0.1, 0.025, 0.005 or 0.001. ppm.

T a b u 1 k and VI

Percent mortality of Boophilus Microplus larvae

Compound ppm 0.1 0.025 0.005 0.001 cf ₃ o

-CH ₂ (CH ₃ ) ₂

CN

CO-O-CH

100, 00

Example 23

The efficacy of the compounds of the invention for the control of adult ticks of Boophilus microplus is illustrated by the following tests in which the test compound is dissolved as described in Example 22, except that solutions containing 125, 52.6, 31.2 are prepared. 15.6 or 7.3 ppm of the test compound.

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

Table VII

Ixodicidal activity against adult ticks Boophilus microplus

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

125 62.5 31.2 15.6 7.3 cf ₃ o

CN

AND

COOCH CH CH _{(CH3) 2}

100 100

99.4 98.8 87.2

Example 24

The efficacy of the compounds of the invention for controlling Cochliomyia hominivorax, a highly malignant pest of cattle, is demonstrated in the following test. Cochliomyia hominivorax larvae in the first instar stage receive a diet consisting of a mixture of ground beef (8.0 g), blood (7.0 ml), water (2.1 ml) and 0.9 ml of a preparation containing 1.5 or 25 ppm test compounds.

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

Table VIII

Efficacy of compounds for controlling Cochliomyia hominivorax larvae

Compound

Percentage mortality at concentration (ppm)

CF ₃ O

CN

AND

CH-CO-O-CH ₂ (CH ₃ ) ₂

2.4

69.2

100 ALIGN!

Example 1 d 25

LCjq determination for test compounds against Heliothis virescens on cotton plants

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

After drying the leaves, 2 leaves from two plants were cut and placed on a petri dish (90 mm x 10 mm) on a damp filter paper (9 cm Whatman # 1). Five third instar larvae are placed on each leaf and the petri dish is capped. The infested dishes are then placed in a constant illumination area at. temperature of 26.7 ° C and 50% relative humidity. Larvae are counted after 72 hours. Repeat each test 4 times. The data obtained are shown in Table IX, which shows that the compound of the invention is about 2 to 5 times more potent for suppressing Heliothis virescens than the known compounds evaluated in the same assay.

Table IX

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

Compound

CN

CF ₃ O

Dose (ppm) Number of insect individuals tested Number of dead insects LC50 1.10 20 May 3 2.94 2.80 20 May 9 7.50 20 May 18 20,00 20 May 19- 60,00 20 May 20 May 7.50 20 May 2 14.4 20,00 20 May 16 60,00 20 May 19 Dec 150.00 20 May 20 May ** 2,80 ^{20 May} 3 6.4 7.50 '20 13 20,00 20 May 17 60,00 20 May 20 May 150.00 20 May 20 May

x = permethrin, xx = published South Patent Application No. 73/4,462

Example 26

Determination of LC50 of test compounds against adult mosquitoes Anopheles quadrimaculatus Say

Test compounds are dissolved in o-acetone to the desired concentration in ppm. To prepare the aerosol formulation, the insecticidal solution (0.15 ml) is pipetted into the top of the nozzle and then sprayed through the nozzle. The atomized droplets are carried by a stream of air (6,436 meters / hr) onto mosquitoes in cages and allowed to act for 4 to 5 seconds (25 adult females / kleys). These were placed in an area of 26.7 ° C to 1 ° C and a relative humidity of 46 ° C. Mortality was determined after 24 hours.

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

Table X

LC50 determination of test compounds against adult female Anopheles quadrimaculatus

Compound

CF ₃ O

CN

AND

CH-CO-O-CH ₂ (CH ₃ ) ₂

Concentration Mortality Approximate value (ppm) (%) * LC50 (ppm)

0,5 10 5

1,0 10

2,0 5

3,0 5

5,0 52

15.0 95 c-0

CN

CH-CO-O-CH

I ch (ch ₃ ) ₂

5.0 10 (2) 6 (1) 21 10.0 14 26 20.0 66 60 (2) 18.8 40.0 62 78 80.0 92 90

x = data obtained in 2 different tests xx = published in South Africa Patent Application 73/4462 (1) - test 1, (2) = test 2

Example 27

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

The test compounds are dispersed in a mixture of 65% acetone and 35% water in sufficient quantity to ensure a concentration of 0.08 kg / ha of the compound. Use 19.30 L of water. The cotton plants are then placed in a spray box and sprayed with a fixed sprayer from above.

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

The remaining plants are placed in a greenhouse with high light intensity. Leaf samples are infested after 3, 7, 10a, 4 days with third instar larvae of Heliothis virescens. The results obtained are shown in Table XI.

T-a b u 1 k and XI

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

Compound Dose Days of residual effect kg / ha 0 3 7 10 1 2 1 2,2 1 2

CN

0.08 95 0.03 100 o 90 0.03 90 0 80 0.03 ^Cl ~ dy * ^_CH_co

CN

AND

0.08 95 0.1 90 3.0 80 2.5 80 0.78 50 1.6

Control

92.5 0 88.5 0 87.5 30 41.3 0 67.5 = average% mortality 20 HV / test (mortality after 72 hours) = average% drought damage (4 trials)

Example 28,

Ixodicidal activity

The procedure of Example 22 was used to demonstrate the ixodicidal activity of the compounds of the invention at a concentration of 12.5, 2.5, 0.5, 0.1, 0.02 or 0.004 ppm. The results are summarized in Table XIX.

200226 24

Table XIX

Percent mortality of Boophilus microplus tick larvae

Compound

Days to Percent Mortality at Treatment Concentration (ppm)

12.5 2.5 0.5 0.1 0.02 0.004 f ₂ chcf ₂ o

CN

AND

CH-COO-CH

AND

CH _{(CH3) 2}

, 00

100 ALIGN!

100 100 100 100 100 100 00 45

CL 2.7 408 f ₂ chcf ₂ -o

CH-COO-CH ₂ (CH ₃ ) ₂

100, 00

100, 00 o

100, 20, 5, 5

CL 217 407

Example 29

The efficacy of the compounds of the invention for the control of adult germs living during their 3 stages of development of no more hosts, Rhipieephalus sanguineus (R. S.) and Dermacentos Variabilis (D.V.), in dogs is determined in the following tests. The test compound is formulated as described in Example 22. Amounts of compound are used to obtain solutions containing 100, 10, or 1 ppm of the test compound.

Adult saturated female germinates are then immersed in test solutions for 3 seconds and placed in individual containers and kept in a room temperature of 26.7 ° C and 50% relative humidity for 48 hours. At the end of this time, the spears are examined and the eggs are counted. Saturated females that do not load eggs are considered dead. The results obtained are shown in Table XIII.

Table XIII

Ixodicidal activity against adult glanders Rhipieephalus sanguineus (R. S.) and Dermacentor variabilis (D.V.)

Compound

Concentration in ppm

Percentage mortality of adult germs R. S. D. V.

CF ₃ O

CN CH CH COOCH (CH _{3) 2}

100, 0

100 100 00 90

100 60

Example 30

In vitro activity test against adult fleas Ctenocephalides felis

In this test, 10 adult Ctenocephalides felis fleas were sprayed for 30 seconds with an acetone / water solution containing 100, 50, 10 or 1 ppm of the test compound. The fleas are then kept at room temperature and 80% relative humidity for 48 hours. After 24 and 48 hours, the fleas are examined for mortality. The results obtained are shown in Table XIV.

Table XIV

Siphonapterioid activity of test compounds

Compound

Hours after treatment

100 ALIGN!

Mortality (%) at concentration (ppm)

10 1

CN f ₂ chcf ₂ -? -? - ch-cooch ch (ch ₃ ) ₂

100 70

100 90 θ

0

CL 217 408

F, CHCF, O - + - CH-COOCH, -., ² W and 11 ch (ch ₃ ) ₂

50

50

Claims (9)

Insecticidal and acacicidal composition, characterized in that it contains at least one 2- (haloalkoxyphenyl) alkanoic acid m-phenoxybenzyl ester of the general formula I (I) r-cf ₂ o as active ingredient. CH-C-O-CH wherein the ϊΚΠίί Ο- group is in the m- or β-position relative to the carbon atom to which the alkanoic ester group is attached and wherein R is fluoro, chloro, difluoromethyl or trifluoromethyl, R 6 is ethyl, η-propyl, isopropyl, isopropenyl or tert-butyl and R 1 is hydrogen or cyano, or an optical isomer thereof. Second insecticidal and acaricidal composition according to claim 1, characterized in that a compound of formula I comprises a compound wherein RCK2O- ^{SKU Pi e} d in m-position to the carbon to which is attached an alkanoic acid ester group and R 82 ^{and R3} is as defined in point 1. 3. The insecticidal and acaricidal composition of claim 1, wherein the compound of formula (X) comprises a compound wherein the RCFgO group is m-polose to carbon to which the alkanoic acid ester group is attached and R, R1 and Ej are as defined above. referred to in point 1. Fourth insecticidal and acaricidal composition according to claims 2 and 3, characterized in that a compound of formula I comprises a compound wherein R is fluoro, R is cyano and R ₂ is ethyl, n-propyl, isopropyl, t-butyl or isopropyl. 5. An insecticidal and acaricidal composition according to claim 2, wherein the compound of formula I is m-phenoxybenzyl-alpha-isopropyl-4- (1,1,2,2-tetrafluoroethoxy) phenylacetate. 6. The insecticidal and acaricidal composition of claim 2, wherein the compound of formula (I) is alpha-cyano-m-phenoxybenzyl-alpha-isopropyl-4- (1,1,2,2-tetrafluoroethoxy) phenylacetate. 7. The insecticidal and acaricidal composition of claim 2, wherein the compound of formula (I) is alpha-cyano-m-phenoxybenzyl-alpha-isopropyl-4- (trifluoromethoxy) phenylacetate. 8. The insecticidal and acaricidal composition of claim 2, wherein the compound of formula (I) is m-phenoxybenzyl-alpha-1-isopropyl-4- (trifluoromethoxy) phenylacetate. 9. A process for preparing compounds of formula I according to claim 1 vyznačený.tlm, reacting a compound of formula II the RCF ₂ CH-COX AND R, (II) wherein X is halogen and R 1 and R 2 are as defined above, with m-phenoxybenzyl alcohol of formula III (III) wherein R 1 is as defined above, in the presence of a tertiary organic amine as an acid acceptor and an inert organic solvent at a temperature in the range of 10 to 30 ° C.