CS205108B2 - Insecticide means and method of making the active elements - Google Patents

Description

The present invention relates to novel cyclopropane derivatives useful as insecticides, to processes for their preparation, to compositions containing them as active ingredients, and to methods for controlling insects and like invertebrate pests using the above-mentioned substances and compositions.

Certain naturally occurring cyclopropanecarboxylic acid esters have long been known to exhibit insecticidal properties, but these compounds are too easily subject to ultraviolet degradation to be used in agriculture. Several groups of synthetic cyclopropanecarboxylic acid compounds (such as those disclosed in British Patent Specification Nos. 1,243,858 and 1,413,491) have been evaluated to find compounds with sufficient light fastness for general use as insecticides in agriculture.

It has now been found that compounds of formula II

O li II

R R C = CH-CH-CH-C-R 1 /

CH, CH.

³ * ttn in which

R @ 1 and R @ ² are each both haloalkyl having 1 or 2 carbon atoms, or one of R @ ¹ and R @ ² is as defined above, haloalkyl and the other of which is halogen or methyl, and

R represents a phenoxybenzyloxy group, optionally substituted in the «-position by a cyano or ethynyl group, has very good insecticidal properties associated with good resistance to light degradation and that analogous compounds in which R represents a hydroxyl group or an alkoxy group containing up to 6 carbon atoms, or a halogen atom, are useful as intermediates in the preparation of insecticides.

When R is phenoxybenzyloxy or n-substituted phenoxybenzyloxy, it is preferably 3-phenoxybenzyloxy or α-substituted 3-phenoxybenzyloxy.

Thus, the active compounds according to the invention correspond to the general formula I (I) / R ' ^ηλ

O

C = CH-CH-CH-C-O-CH (R ³ );

ch.

wherein one of R ¹ and R ² represents a group of the formula

W (CF ₂ ) _m -, where

W represents a hydrogen, fluorine or chlorine atom, and m is 1 or 2, the other of which represents a fluorine, chlorine or bromine atom or a group of the formula

Y

X — C—,. From where

X, Y and Z are each independently hydrogen, fluorine or chlorine, and

R ³ represents a hydrogen atom, a cyano group or an ethynyl group.

A preferred group of compounds of the invention are those compounds of formula (I) above wherein one of R ¹ and R ² is a radical of formula

WCFz— where

W is hydrogen, fluorine or chlorine, and the other of R ¹ and R ² is a radical of formula

Y

I x — c—, z

where

X, Y and Z are as defined above, and

R ³ represents hydrogen or cyano.

Of this group of compounds are particularly preferred above-mentioned compounds in which both R ¹ and R ² are trifluoromethyl.

Another preferred group of compounds of the present invention are those compounds of formula (I) wherein one of R ¹ and R ² is a radical of formula

WCFz— where

W is hydrogen, fluorine or chlorine, and the other of R ¹ and R ² is fluorine, chlorine or bromine, R ³ is hydrogen or cyano. Particularly preferred compounds of this group are those wherein one of R ¹ and R ² is trifluoromethyl, and the other is ⁴ chloro or bromo.

It will be appreciated that the compounds of formula I may exist in various geometric and stereoisomeric forms. Thus, substitution of the cyclopropane ring * indicates the possible existence of cis and trans isomers as a result of substitution of the vinyl group in the case where R ¹ has the same meaning as R ² may be the E- and Z-isomers. In addition, two or three carbon atoms of the cyclopropane derivative may have the R- or S-configuration because they are asymmetrically substituted, and if R ^{3 is} not hydrogen, the carbon atom to which this residue is attached may also be present in R- or S-configuration.

Thus, for a compound of formula I in which R ¹ and R ² are the same and R ³ represents a hydrogen atom, there is the possibility of four isomeric forms resulting from the substitution of the cyclopropane ring. These isomers, due to their absolute configuration, can be designated as (1R, 3R), (1R, 3S), (1S, 3SJ and (1S, 3R). If R ^{3 is} not hydrogen, there may be eight isomers because each of the four Possible configurations of the cyclopropane ring must exist in two forms - one corresponding S-configuration and * one corresponding R-configuration of the carbon atom bearing the radical R ^3. Alternatively, when R ³ represents a hydrogen atom and R ¹ does not have the same meaning, like R ² , there can again be eight isomeric forms, since each of the four possible cyclopropane ring configurations must exist in two forms - one corresponding to the Z-configuration and one corresponding to the E-configuration of the vinyl group.

Finally, when R ¹ is not the same as R ² and R ^{3 is} not hydrogen, each such compound may exist in sixteen isomeric forms.

Table I provides an overview of the compounds of the invention. Each of these compounds represents a racemic mixture of the (+) - and (-) - isomers, although a distinction is made between the cis- and trans-substitution on the cyclopropane ring and the E- and Z-substitution of the optionally present vinyl group.

All compounds in Table I correspond to the general formula

R '\ c = R ^{and /} H 0 / λ ... ¹¹ OC / He><7<h Cha ^Ch i Compound Rl TABLE I R ² R ³ Substrate Configuration number cyclopropa-

new circle

1 CF3 CF3 CN cis 2 CF3 CF3 CN trance 3 CF3 CF3 H cis 4 CF3 CF3 H trance 5 CHFz chf ₂ H cis 6 CHFz CHF2 H trance 7 CHFz CHFz CN cis 8 CHFz CHFz CN trance 9 CF2CI CFzCl H cis 10 CF2CI CFzCl H trance 11 CFzCl CF2CI CN cis 12 CFzCl CFzCl CN trance 13 CF3 iCF3 C = CH cis 14 CF3 1CF3 C ^ CH trance 15 Dec CHFz cf ₃ CN cis 16 CF3 CHFz CN cis 17 CHFz CF3 CN trance 18 CF3 CHFz CN trance 19 Dec CH3 CRs CN cis 20 May CF3 CH3 CN cis 21 ch ₃ CF3 ČN trance 22nd CF3 CH3 CN trance 23 CHs CF3 H cis 24 CF3 CHs H cis 25 ch ₃ CF3 H trance 26 CF3 CH3 H trance 27 Mar: CHFz CFzCl CN cis 28 CFzCl CHFz CN cis 29 CHFz CF2CI CN trance 30 CFzCl CHFz CN trance 31 CF3 Cl CN cis 32 Cl CF3 CN cis 33 CF3 Cl CN trance 34 Cl CF3 CN trance 35 CF3 Cl H cis 36 Cl CFs H cis 37 CF3 Cl H trance 38 Cl CF3 H trance 39 CFzCl Cl H cis 40 Cl CFzCl H cis 41 CFzCl Cl H trance 42 Cl CF2C1 H trance 43 CF2C1 Cl CN cis 44 Cl CFzCl CN cis 45 CFzCl Cl CN trance 46 Cl CF2C1 CN trance 47 CF2C1 F CN cis 48 CF2C1 F CN trance 49 CFzCl F H cis

Compound R ¹ no

R ²

R ³ Configuration of cyclopropane ring substituents

50 CF2CI F H trance 51 CICF2GF2 Cl CN cis 52 CICF2CF2 ‘Cl CN trance 53 CF3CF2 Cl CN trance 54 1CF3 Br ' CN cis 55 Br CF3 CN cis 56 CF3 Br CN trance 57 Br CF3 CN trance 58 CF3 Cl C = CH cis 59 Cl 1CF3 C = CH cis 60 CF3 Cl C = CH trance 61 Cl CF3 C = CH trance

Particularly useful compounds of formula I according to the invention include:

(±) -? - cyano-3-phenoxybenzyl- [±] - cis / trans -3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate (±) -cyano-3-phenoxybenzyl (+ 1-cis / trans-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate, ( ± cyano-3-phenoxybenzyl (±) - cis / trans-3- (3-chloro-2,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate, (±) -. alpha.-cyano-3-phenoxybenzyl (. + -. cis -cis / trans-3- (3-bromo-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate);

3-Phenoxybenzyl (±) - cis / trans -3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate; and

3-Phenoxybenzyl-1H-cis-trans-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate.

The compounds of the formula I according to the invention are esters and can be prepared by conventional esterification procedures.

Accordingly, in accordance with the invention, the compounds of formula (I) above are prepared by producing a compound of formula (V)

O

R * R ^ OCH-CH-CH-C-Q;

C i ' ^C itV>

in which

R ¹ and R ² are as defined above, and Q represents a hydroxyl group, a chlorine atom, a bromine atom or an alkoxy group having 1 to 6 carbon atoms, esterified by reaction with an alcohol of formula IV

HO-CH

wherein R ³ is as defined above.

This known esterification can be accomplished by a number of methods, including:

(a) The acid of formula III

O r'R * O CH-CH- CH-C-OH \ /

CH 2 CH 2 (where R ¹ and R ² are as defined above), they can be directly reacted with an alcohol of formula IV

WO-CH 2? ³ ), OC _b H _s (IV) wherein R ³ represents a hydrogen atom, a cyano group or an ethynyl group. This reaction is preferably carried out in the presence of an acid catalyst, for example dry hydrogen chloride.

(b) An acid halide of the formula

RWoCH-CH-CH-Č- Hal \ / cw ₃ cw ₃

0510 8 wherein Hal represents halogen, preferably chlorine, and R ¹ and R ² are as hereinbefore defined may be reacted with an alcohol of the formula IV

HOCH (R ³ ) 4 OC ₆ Hr (IV) wherein R ³ represents a hydrogen atom, a cyano group or an ethynyl group. This reaction is preferably carried out in the presence of a base, for example pyridine, alkali metal hydroxide or carbonate or alkali metal alkoxide. In the case that R ³ represent a cyano group may be, instead of a-cyano-3-phenoxybenzyl use a mixture of alkali metal cyanide and 3-phenoxybenzaldehyde.

(c) The acid of formula III

O (R ') (c = CH-CH- CH-C-OH X)

CH.

wherein R ¹ and R ² are as defined above, or preferably an alkali metal salt thereof, may be reacted with a halide of formula VI

wherein Q ¹ represents a halogen atom, preferably chlorine, and R ³ represents a hydrogen atom, a cyano group or an ethynyl group, or with a quaternary ammonium salt derived therefrom and a tertiary amine such as pyridine or a trialkylamine such as triethylamine.

(d) The lower alkyl ester of formula (VII)

R ^ O-CH-CH-CH-C-OR * \ / / ^C CH ₃ CH ₃ (VID wherein R ⁴ represents a lower alkyl group containing up to 6 carbon atoms, preferably methyl or ethyl, and R ¹ and R ² as defined above, may be heated with an alcohol of formula IV

WO-CHIR ³ )

wherein R ³ is as defined above to carry out the transesterification reaction. This reaction is preferably carried out in the presence of a suitable catalyst, for example an alkali metal alkoxide such as sodium methoxide or an alkylated titanium derivative such as tetramethyl titanate.

All of these conventional processes for the production of esters can be carried out using solvents and diluents for the various reactants, as appropriate in each case, and can be accelerated or controlled to achieve higher product yields at elevated temperatures or in the presence of suitable catalysts. , for example, phase transfer catalysts.

The preparation of the individual isomers may be carried out in the same manner, but using the corresponding individual isomers of the compounds of formula V. These individual isomers may be obtained from mixtures of isomers by conventional isomer separation techniques. Thus, cis- and trans-isomers can be separated by fractional crystallization of carboxylic acids or salts thereof, while various optically active isomers can be obtained by fractional crystallization of acid salts with optically active amines, followed by regeneration of optically pure acid.

The optically pure isomeric form of the acid (or its equivalent acid chloride or acid ester) can then be reacted with 3-phenoxybenzyl alcohol to give the compounds of formula I as individual pure isomers. isomers, since it is not possible to carry out the reaction of optically pure α-cyano-3-phenoxybenzyl alcohol with an acid or equivalent without racemization of the alcohol.

(±] -? - cyano-3-phenoxybenzyl (1R, 3R) -3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate and (+) - N -cyano-3-phenoxybenzyl (1R, 3S) -3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate.

These compounds are expected to be particularly useful as insecticides.

The preparation of the individual isomers of these compounds can be accomplished by first preparing optically pure acid chloride, which is reacted with (±) -3-phenoxymandelic acid amide to give the corresponding (+) -carboxamidoester. The two isomeric esters can be separated by fractional crystallization and individually dehydrated to the corresponding α-cyano-3-phenoxybenzyl ester. In this way, the following individual isomers can be obtained:

(S) -N-Cyano-3-phenoxybenzyl- (1R, 3R) -3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2- dimethylcyclopropanecarboxylate and (S) -α-cyano-3-phenoxybenzyl- (1R, 3S) -3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2 -dimethylcyclopropanecarboxylate, which is believed to be the most insecticidally effective isomers of the corresponding compounds.

The various cyclopropane derivatives described above as useful intermediates for the preparation of the compounds of formula (I) by the process of the invention are themselves novel substances.

Accordingly, the invention further encompasses compounds of Formula V

O

CH - CH - CH - C - GL · ^CH and ^CH * (V) wherein one of R ¹ and R ² represents a group of the formula

W (CF ₂ ) _m -, where

W represents a hydrogen, fluorine or chlorine atom and m is 1 or 2, the other of which represents a fluorine, chlorine or bromine atom or a group of the formula

Y

X — C—,

From where

X, Y and Z are each independently hydrogen, fluorine or chlorine, and

Q represents a hydroxyl group, an alkoxy group containing up to 6 carbon atoms, a chlorine atom or a bromine atom.

One of the preferred groups of intermediates within the scope of the invention are those compounds of formula (V) above wherein one of R ¹ and R ² is a group of formula

WCFz— where

W represents a hydrogen, fluorine or chlorine atom, and the other represents a group of the formula

Y

X — C—,

Wherein X, Y and Z are as defined above, and

Q represents a hydroxy group, a lower alkoxy group having 1 to 3 carbon atoms, a chlorine atom or a bromine atom.

Of this preferred group of compounds, those in which R @ ¹ and R @ ² are both trifluoromethyl are particularly preferred.

Another preferred group of intermediates within the scope of the invention are those compounds of formula (V) above wherein one of R ¹ and R ² is a group of the formula

WCFz— where

W represents a hydrogen, fluorine or chlorine atom, and the other of R ¹ and R ² represents a fluorine, chlorine or bromine atom, and

Q represents a hydroxyl group, a lower alkoxy group having 1 to 3 carbon atoms, a chlorine atom or a bromine atom.

Particularly preferred compounds within this group are those wherein one of R ¹ and R ² is trifluoromethyl and the other of them is chlorine or bromine.

Compounds of formula V may also exist in various geometric and stereoisomeric forms, as well as compounds of formula I. Thus, they may exist in the form of cis- and trans-isomers resulting from cyclopropane ring substitution, and in the form of E- and Z- isomers arising from the substitution of vinyl group in the case where R ¹ has the same meaning as R ^2nd In addition, two of the three carbon atoms of the cyclopropane ring may exist in either the R- or S-configuration because they are asymmetrically substituted.

Examples of specific intermediates of the invention include compounds of the following formula

wherein R ¹ and R ² have the specific meanings listed in Table I above for the corresponding compounds of formula (I), and Q 1 represents a chlorine atom, a hydroxyl group or an ethoxy group.

Compounds of formula V wherein

Q is a hydroxyl group, may be obtained by hydrolysis of compounds of formula V wherein Q is lower alkoxy and may be converted by reaction with, for example, thionyl chloride or thionyl bromide to compounds of formula V wherein Q is chloro or chloro, respectively. bromine. All of these compounds of formula (V) may be used either directly or indirectly to prepare the insecticidally active esters of formula (I) as described above.

Various processes for the preparation of compounds of formula (V) are described in our related Czechoslovak patents (48,720 / Nn and 48,721 / Nn).

In the various preparations of the compounds of the formula (V), they usually result as mixtures of different geometric isomers. Thus, these methods yield mixtures of the cis and trans isomers in which one often form predominates, and where R ¹ has the same meaning as R ^2, to give the Z isomer Ea both the cis- and trans- forms, where again one of the forms prevails.

If these forms do not separate any of the physical methods, such as fractional »crystallization of carboxylic acids are the final products of formula I also comprise mixtures of various isomers containing more than one of the compounds mentioned above the _# in Table I. Typical examples of insecticidal obtained products, most of which are mixtures of several compounds, include the following products:

Product 1:

a mixture of 1 part of Compound No. 1 with 4 parts of Compound No. 2, Product No. 2:

a mixture of 1 part of Compound No. 1 with 1 part of Compound No. 2, Product No. 3: Compound No. 2, Product No. 4 alone:

_x Compound No. 1, Product No. 5 alone:

a mixture of 19 parts of Compound No. 31 with 1 part of Compound No. 32, Product No. 6:

a mixture of 19 parts of Compound No. 31, 1 part of Compound No. 32, 19 parts of Compound No. 33 and 1 part of Compound No. 34, Product No. 7:

a mixture of 11 parts of Compound No. 3 with 14 parts of Compound No. 4, Product No. 8:

Mixture of compounds Nos 15, 16, 17 and 18 of undefined composition, Product No 9:

mixture of 1 part of compound No. 39 with 1 part of compound No. 41, product No. 10:

a mixture of 19 parts of Compound No. 43, 1 part of Compound No. 44, 19 parts of Compound No. 45 and 1 part of Compound No. 46, Product No. 11:

a mixture of 19 parts of Compound No. 43 with 1 part of Compound No. 44, Product No. 12:

a mixture of 19 parts of Compound No. 39 with 1 part of Compound No. 40, Product No. 13:

a mixture of 1 part of compound No. 19, 9 parts of compound No. 20, 1 part of compound No. 21 and 9 parts of compound No. 22, product No. 14:

a mixture of 1 part of compound 23, 9 parts of compound 24, 1 part of compound 25 and 9 parts of compound 26, product 15:

a mixture of 1 part of compound No. 47 with 1 part of compound No. 48, product No. 16: compound No. 47, product No. 17:

a mixture of 1 part of compound No. 49 with 1 part of compound No. 50, product No. 18:

a mixture of 1 part of Compound No. 1 with 2 parts of Compound No. 2, Product No. 19:

a mixture of 3 parts of Compound No. 5 with 2 parts of Compound No. 6, Product No. 20:

a mixture of 3 parts of compound 7 with 2 parts of compound 8, product 21:

a mixture of 9 parts of Compound No. 35, 1 part of Compound No. 36, 6 parts of Compound No. 37 and 4 parts of Compound No. 38, Product No. 22:

a mixture of 9 parts of Compound No. 51 with 1 part of Compound No. 52, Product No. 23: Compound No. 53 alone, Product No. 24:

a mixture of 7 parts of Compound No. 9 with 13 parts of Compound No. 10, Product No. 25:

a mixture of 7 parts of compound 11 with 13 parts of compound 12, product 26:

an unspecified mixture containing compounds No 27, 28, 29 and 30, product No 27:

a mixture of 10 parts of compound No. 54, 1 part of compound 205108

14 valuables 6. 55, 10 parts of Compound No. 56 and part of Compound No. 57, Product No. 28:

a mixture of 10 parts of Compound No. 58, 1 part of Compound No. 59, 10 parts of Compound No. 60 and 1 part of Compound No. 61, Product No. 29:

a mixture of 2 parts of Compound No. 13 with 3 parts of Compound No. 14.

The compounds of formula (I) above may be used to control harmful insects and other invertebrate pests, such as mites, and to prevent infestation thereof. Insect and acarid pests which can be controlled using the compounds of the invention are the above mentioned pests occurring in agriculture (which includes growing crops for the production of food products and industrial products such as fibers, horticulture and livestock production), forestry, storage products of plant origin, such as fruit, grain and wood, as well as pests transmitting diseases of humans and animals.

For application to pests, the compounds of the invention are generally formulated to contain compositions which, in addition to the insecticidally active compound or compounds of formula I, contain suitable inert diluents or carriers and / or surfactants. These compositions may also contain other pesticidal active ingredients, such as other insecticides or acaricides, or fungicides, or may also contain insecticide synergists, such as dodecylimidazole, safroxan or piperonyl butoxide.

The compositions of the invention may be in the form of dusts, where the active ingredient is mixed with a solid diluent or carrier, for example kaolin, bentonite, diatomaceous earth or talc, or they may be in the form of granules, where the active ingredient is adsorbed on a porous granular material, e.g. .

Alternatively, these compositions may take the form of liquid preparations used for dressing or spraying. These preparations are usually aqueous dispersions or emulsions of the active ingredient containing one or more known wetting, dispersing or emulsifying agents (surfactants).

The wetting, dispersing and emulsifying agents may be of the cationic, anionic or non-ionic type. Suitable cationic agents include, for example, quaternary ammonium compounds such as cetyltrimethylammonium bromide. Suitable anionic agents include, for example, soaps, salts of aliphatic monoesters of sulfuric acid, such as sodium lauryl sulfate, salts of sulfonated aromatic compounds such as sodium dodecylbenzenesulfonate, sodium, calcium or ammonium ligninsulfonate, butylnaphthalenesulfonate, and mixtures of diisopropyl- and triisopropyl sodium salts.

Suitable nonionic agents include, for example, ethylene oxide condensation products with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octylphenol, nonylphenol and octylcresol. Other nonionic agents include partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of said partial esters with ethylene oxide and lecithins.

These compositions may be prepared by dissolving the active ingredient in a suitable solvent, for example a ketone solvent such as diacetone alcohol, or an aromatic solvent such as trimethylbenzene, and introducing the mixture thus obtained into water which may contain one or more wetting, dispersing or emulsifying agents, which are known per se. Other suitable organic solvents include dimethylformamide, ethylene dichloride, isopropyl alcohol, propylene glycol and other glycols, diacetone alcohol, toluene, kerosene, paraffin oil, methylnaphthalene, xylenes and trichlorethylene, N-methyl-2-pyrrolidone, and tetrhydrofurfuryl alcohol.

Spray formulations may also be in the form of aerosols in which the formulation is stored in a container under pressure in the presence of a propellant, such as fluorotrichloromethane or dichlorodifluoromethane.

Compositions intended for application in the form of aqueous dispersions or emulsions are generally supplied as concentrates containing a high proportion of the active ingredient or substances. The concentrates are then diluted with water before use. These concentrates are often required to withstand long-term storage and, after such storage, to be diluted with water to form aqueous preparations which remain homogeneous as long as they can be applied by conventional spray equipment. The concentrates may contain 10 to 85% by weight of the active substance or substances. When such concentrates are diluted to apply aqueous preparations, these preparations may contain varying amounts of active ingredient, depending on the intended use.

Aqueous preparations containing between 0.0001 and 0.1% by weight of active ingredient are particularly suitable for agricultural and horticultural purposes.

In use, the compositions of the invention are applied to the pest, to the locus of the pest, to the environment where the pest lives, or to cultivated plants exposed to the pest by any known method of pesticide application, for example by dusting or spraying.

The compositions of the invention are very toxic to a wide variety of insects and other invertebrate pests such as:

Aphis fabae (Poppy Aphid)

Megoura viceae

Aedes aegypti (mosquito)

Dysdercus fasciatus

Musea domestica (house fly)

Pieris brassicae (Large White) - larvae Plutella maculipennis (larvae)

Phaedon cochleariae

Telarius cinnabarinus

Aonidlella spp.

Trialeuroides spp. (whitefly)

Blatella germanica

Spodoptera littoralis

Chortiocetes terminifera

The compounds of formula (I) and compositions containing them have been shown to be particularly useful for controlling cotton pests of the order Lepidoptera, such as Spodoptera spp. and Heliothis spp. Said substances and compositions are also very useful in combating insect and acarid pests attacking domestic animals such as buzzard (Lucilia sericata) and ticks such as Boophilus spp. (tick), Ixodes spp. (tick), Amblyomma spp. (drinker), Rhipicephalus spp. (drinker) and Dermaceutor spp. (blotter). The disclosed compounds and compositions are effective in controlling both susceptible and resistant strains of these pests at the adult, larval, or intermediate stages of development, and can be administered topically, orally or parenterally to the infected host animal.

The invention is illustrated by the following non-limiting examples.

For NMR spectra, the abbreviations have the following meanings:

s = singlet d = doublet t = triplet q = quartet m = multiplet

Example 1

This example illustrates the preparation of (±) - cis - trans -3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid.

A mixture of 0.52 g of ethyl (±) - cis / trans-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropcarboxylate, 2.52 ml glacial acetic acid, 3.36 ml of 48% (w / v) hydrobromic acid and 1.12 ml of water are refluxed for 10 hours. After cooling, the reaction mixture is diluted with 50 ml of water and extracted several times with diethyl ether. The extracts were combined, washed with water and, after drying over anhydrous sodium sulfate, concentrated by evaporation of the ether under reduced pressure.

According to spectroscopic analysis, the oily residue consists predominantly of (± 1-cis / trans-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid).

Example 2

This example illustrates the conversion of (±) - cis - trans - 3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid to the corresponding acid chloride.

A mixture of 0.4 g of (±) - cis / trans-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid and 5.0 ml of thionyl chloride is added. After refluxing for 2 hours, excess thionyl chloride was distilled off under reduced pressure. (±) - cis - trans - 1-Chlorocarbonyl-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropane was obtained as a residue.

Example 3

This example illustrates the preparation of (±) - N -cyano-3-phenoxybenzyl- (±) - cis / trans-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2J _. 2-dimethylcyclopropanecarboxylate, referred to herein as Product No. 1.

To the residue containing (±) - cis / trans-1-chlorocarbonyl-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropane (obtained in Example 15) A mixture of 33 g of (. + -.) - cyano-3-phenoxybenzyl alcohol and 0.12 g of pyridine was added and the reaction mixture was stirred at room temperature for 16 hours. After addition of 20 ml of water, the resulting mixture is extracted three times with 10 ml of diethyl ether each time. The combined extracts were washed with water, saturated sodium bicarbonate solution and again with water, and dried over anhydrous sodium sulfate. After the ether was evaporated under reduced pressure, the oily residue was subjected to preparative thin layer chromatography. Glass plates with a 2 mm thick silica gel layer and chloroform as solvent system are used. There was obtained (±) -? - cyano-3-phenoxybenzyl- (±) - cis / trans-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2, 2-Dimethylcyclopropanecarboxylate of Rf = 0.53 containing about 20% cis isomer and about 80% trans isomer.

IR: 1755, 1680, 1600, 1490, 1300, 1160 cm -1; NMR: 0.9-2.5 τ, 6.0-6.15 τ, 6.35-7.2; Mass Spectrum: M + 483 (275, 259, 231);

209, 208, 181).

Example 4

This example illustrates the preparation of (±) - cis - trans -3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid.

A mixture of 0.52 g of ethyl (±) - cis / trans-3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2205108

dimethyl cyclopropanecarboxylate, 2.52 ml of glacial acetic acid, 3.36 ml of 48% (w / v) hydrobromic acid and 1.12 ml of water are heated at reflux for 10 hours. After cooling, the mixture was diluted with water (50 mL) and extracted several times with diethyl ether. The extracts were combined, washed with water, dried over anhydrous sodium sulfate and concentrated by evaporation of the ether under reduced pressure. According to spectroscopic analysis, the oily residue is predominantly (±) - cis / trans-3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid.

Example 5

This example illustrates the conversion of (±) - cis - trans - 3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid to the corresponding acid chloride.

A mixture of 0.4 g of (±) - cis / trans-3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid and 5.0 ml of thionyl chloride was heated at reflux for 2 hours, after which excess thionyl chloride was distilled off under reduced pressure. (±) - cis / trans-1-chlorocarbonyl-3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropane was obtained as a residue.

Example 6

This example illustrates the preparation of (±) -? - cyano-3-phenoxybenzyl- (±) - cis / trans -3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2, 2-dimethylcyclopropanecarboxylate referred to herein as Product No. 6.

To the residue containing (±) - cis / trans-1-chlorocarbonyl-3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropane (obtained in Example 5) A mixture of 0.12 g of pyridine and 0.33 g of [±] -? - cyano-3-phenoxybenzyl alcohol was added and the resulting mixture was stirred at room temperature for 16 hours. After addition of 20 ml of water, the reaction mixture is extracted three times with 10 ml of ether each time, the combined extracts are washed with water, saturated sodium bicarbonate solution and again with water, and dried over anhydrous sodium sulfate. After removal of the ether by evaporation under reduced pressure, the oily residue is subjected to preparative thin layer chromatography on glass plates having a 2 mm thick silica gel layer, using chloroform as the solvent system, to give (±) -α-cyano-3-phenoxybenzyl- ( ±) cis-3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate of Rt = 0.52 and the corresponding trans-isomer of Rt = 0, Each of these products contains about 90 to 95% of the Z-isomer.

IR (chloroform): 1740, 1660, 1590, 1480,

1460 cm ^-1 ;

NMR (carbon tetrachloride): 6.90 - 7.50 τ,

1,60 - 2,70 τ, 1,50 - 1,00 τ and specific signals at 6,3 τ (benzylic hydrogen), 6,85,

6.50, 6.11 and 5.84 τ (vinyl hydrogen), experimentally attributed to Z-cis-, Ε-cis-, Z-trans-, respectively. E-trans-isomers.

Example 7

The following carboxylic acids were prepared from the corresponding ethyl esters in analogy to Examples 14 and 17:

(i) (±) - cis / trans -3- (3,3-difluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid;

IR (liquid film): 3500 - 2400, 1700, 1665 cm ^-1 .

(ii) (±) - cis / trans -3- (3,3-difluoro-2-difluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid;

NMR (carbon tetrachloride, ppm): 1.30-1.50 (m, 6H), 1.70-2.60 (complex signal, 2H),

5.70 - 7.13 (complex signal, 3H).

(iii) (±) - cis / trans-3- (E / Z-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid;

NMR (carbon tetrachloride, ppm): 1.22-1.44 (m, 6H), 1.6-2.3 (m, 5H), 5.36-6.6 (m, 1H), 11.9 ( s, 1H).

(iv) (±) - cis, trans -3- (3-chloro-3,3-difluoro-2-chlorodifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid;

NMR (carbon tetrachloride, ppm): 1.24-1.42 (m, 6H), 1.80-2.68 (m, 2H), 6.16 and 7.12 (double d, 1H), 11.6 (s, 1 H).

(v) (±) - cis / trans-3- (E / Z-3,3-difluoro-2-chlorodifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid;

IR (chloroform): 3450 - 2500, 1705, 1675 cm ^-1 .

(vi) (±) - cis / trans -3- (2-bromo-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid;

IR (chloroform): 3400-2450, 1700, 1650,

1275, 1140 cm ¹ .

(vii) (±) - cis / trans -3- (3-chloro-2,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid;

IR (oil film): 3400 - 2200, 1700, 1450, 1140, 1070 cm ^-1 .

(vili) (±) - cis / trans -3- (2,3-dichloro-3,3-difluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid;

IR (chloroform): 3400-2200, 1700 cm ^-1 , (ix)

Pure (±) -cis-3- (2,3-dichloro-3,3-difluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid is precipitated by cooling from a concentrated solution of a mixture of cis and trans-acids in hexane;

NMR (CDCl 3, ppm): 1.25 (s, 6H), 1.80-2.25 (m, 2H), 6.73 (d, 1H).

(±) - cis / trans-3- (2-chloro-3,3,4,4,4-pentafluorobut-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid;

NMR (CDCl3, ppm): 1.10-1.50 (m, 6H), 1.68-2.58 (m, 2H), 6.14 and 6.85 (double d, 1H).

(xi) (±) - cis / trans -3- (2,4-dichloro-3,3,4,4-tetrafluorobut-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylic acid.

Example 8

The various carboxylic acids of Example 7 are converted to the insecticidally active ester derivatives corresponding to the general formula I by reaction of the corresponding acid chlorides with 3-phenoxybenzyl alcohol, (±) -α-cyano-3-phenoxybenzyl alcohol or (±) -α-ethynyl-3-phenoxybenzyl alcohol. The products of these reactions (referred to as products Nos. 2 to 5 and 7 to 29) are mostly mixtures of more than one of the compounds listed in Table I, as follows: Product # 2:

(±) -? - cyano-3-phenoxybenzyl- (±? - cis / trans-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2- dimethylcyclopropanecarboxylate - a mixture of 1 part of Compound No. 1 with 1 part of Compound No. 2;

NMR (carbon tetrachloride, ppm): 1.20-1.40 (m, 6H), 1.80-2.30 (m, 2H), 6.17-6.37 and 6.85-7.42 (mm) 11H).

Product 3:

(±) -? - cyano-3-phenoxybenzyl (±) -trans-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate - Compound 2 alone.

Product 4:

(±) -? - cyano-3-phenoxybenzyl- (±) -cis-320

- (3,3,3-Trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate - Compound No. 1 alone.

Product 5:

(±) - N -cyano-3-phenoxybenzyl- (±) -cis-3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate mixture 19 parts of Compound No. 31 with 1 part of Compound No. 32.

Product 7:

3-Phenoxybenzyl (±) - cis / trans-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate - a mixture of 11 parts of Compound No. 3 is 14 parts of Compound No. 4;

NMR (carbon tetrachloride, ppm): 1.18-1.40 (m, 6H), 1.75-2.55 (m, 2H), 5.15 (s, 2H), 6.30 and 6.70- 7.40 (double m, 10H).

Product 8:

(±) -? - cyano-3-phenoxybenzyl- (±) - cis / trans-3- (3,3-difluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate - mixture compounds No. 15, 16, 17, and 18 of an undefined composition;

IR (liquid film): 1745, 1665, 1595 cm ^-1 .

Product 9:

3-Phenoxybenzyl (±) - cis / trans-3- (Z-2,3, -dichloro-3,3-difluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate - 1 part mixture of Compound No. 3 39 with 1 part of Compound No. 41; NMR (CDCl3, ppm): 1.20-1.37 (m, 6H), 1.73-2.50 (m, 2H), 5.10 (d, 2H), 6.12 and 6.88- 7.48 (double m, 10H).

Product 10:

(±) - N -cyano-3-phenoxybenzyl- (±) - cis / trans-3- (Z / E-2,3-dichloro-3,3-difluoroprop-1-en-1-yl) -2, 2-dimethylcyclopropanecarboxylate - a mixture of 19 parts of Compound No. 43, 1 part of Compound No. 44, 19 parts of Compound No. 45 and 1 part of Compound No. 46;

NMR (carbon tetrachloride, ppm): 1.18-1.45 (m, 6H), 1.73-2.50 (m, 2H), 6.32 (m, 1H), 6.08 and 6.81 (double d) (1H), 6.90-7.44 (m, 9H).

Product 11:

(±) -? - cyano-3-phenoxybenzyl- (±) -cis-3- (Z / E-2,3-dichloro-3,3-difluoroprop-1-en-1-yl) -2,2- dimethylcyclopropanecarboxylate - a mixture of 19 parts of Compound No. 43 with 1 part of Compound No. 44;

NMR (carbon tetrachloride, ppm): 1.18-1.40 (m, 6H), 1.92-2.32 (m, 2H), 6.31 (d, 1H), 6.81 (d, 1H) 6.90-7.45 (m, 9H).

Product 12:

3-Phenoxybenzyl- (±) -cis-3- (Z / E-2,3-dichloro-3,3-difluoroprop-1-en-1-yl) -2,2-dimethyl205108 Cyclopropanecarboxylate - A mixture of 19 parts of the compound # 39 with 1 part of Compound # 40;

NMR (carbon tetrachloride, ppm): 1.05-1.48 (m, 6H), 1.84-2.38 (m, 2H), 5.02 (s, 2H), 6.72-7.45 ( m, 10H).

Product 13:

(±] -? - cyano-3-phenoxybenzyl (±) - cis / trans-3- (Z / E-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate - mixture 1 part of compound No. 19, 9 parts of compound No. 20, 1 part of compound No. 21a, 9 parts of compound No. 22;

NMR (carbon tetrachloride, ppm): 1.22-1.40 (m, 6H), 1.60-2.30 (m, 5H), 5.2-6.45 (m, 1H).

Product 14:

3-Phenoxybenzyl (±) - trans / 3- (Z / E-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate - mixture of 1 part of Compound No. 23, 9 parts of Compound No. 3 24, 1 part of Compound No. 25 and 9 parts of Compound No. 26;

NMR (carbon tetrachloride, ppm): 1.22-1.40 (m, 6H), 1.58-2.2 (m, 5H), 5.02 (s, 2H),

5.2 - 6.45 (m, 1H); 6.85 - 7.42 (m, 9H).

Product 15:

(±) -? - cyano-3-phenoxybenzyl- (±) - cis / trans-3- (Z-3-Chloro-2,3,3-trifluoroprop-1-en-1-yl) -2,2 -dimethylcyclopropanecarboxylate - a mixture of 1 part of compound No. 47 with 1 part of compound No. 48;

NMR (carbon tetrachloride, ppm): 1.15-1.40 (m, 6H), 1.65-2.40 (m, 2H), 5.08, 5.39, 5.80 and 6.12 (4d) , 1H), 6.35 (m, 1H), 6.92-7.50 (m, 9H).

Product 16:

(±) -α-cyano, n-3-phenoxybenzyl- (±) -cis-3- (Z-3-chloro-2,3,3-trifluoroprop-1-en-1-yl) -2,2 -dimethylcyclopropanecarboxylate - Compound No. 47;

NMR (carbon tetrachloride, ppm): 1.18-1.40 (m, 6H), 1.85-2.33 (m, 2H), 5.80 and 6.11 (double d, 1H), 6.35 (d, 1H) and 6.95-7.60 (m, 9H).

Product 17:

3-Phenoxybenzyl- (±) - cis / trans-3- (Z-3-chloro-2,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethyl-cyclopropanecarboxylate - 1 part mixture of compound no. 49 with 1 part of Compound No. 50;

NMR (carbon tetrachloride, ppm): 1.15-1.30 (m, 6H), 1.65-2.40 (m, 2H), 5.10, 5.40, 5.92 and 6.23 (m , 3d, 3H), 6.90-7.45 (m, 9H).

Product 18:

(±) -? - cyano-3-phenoxybenzyl (+) - cis / trans -3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate - a mixture of 1 part of Compound No. 1 with 2 parts of Compound No. 2.

Product 19:

3-Phenoxybenzyl (± β-cis / trans-3- (3,3-difluoro-2-difluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate - a mixture of 3 parts of Compound No. 5 with 2 parts of Compound No. 6;

NMR (carbon tetrachloride, ppm): 1.18-1.37 (m, 6H), 1.60-2.45 (m, 2H), 5.03-5.1 (m, 2H), 5.13-7 47 (complex, 12Hi).

Product 20:

(±) -? - cyano-3-phenoxybenzyl- (±? - cis / trans-3- (3,3-difluoro-2-difluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate A mixture of 3 parts of Compound No. 7 with 2 parts of Compound No. 8;

NMR (carbon tetrachloride, ppm): 1.20-1.40 (m, 6H), 1.80-2.47 (m, 2H), 6.17-6.37 and 6.85-7.43 (mm) , 13H).

Product 21:

3-Phenoxybenzyl- (±) - cis / trans-3- (Z / E-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate - mixture of 9 parts Compound No. 35, 1 part of compound No. 36, 6 parts of compound No. 37 and 4 parts of compound No. 38.

Product 22:

(±) -?, Cyano-3-phenoxybenzyl- (±? - cis / trans-3- (Z-2,4-dichloro-3,3,4,4-tetrafluorobut-1-en-1-yl) ) -2,2-dimethylcyclopropanecarboxylate - a mixture of 9 parts of Compound No. 51 with 1 part of Compound No. 52.

Product # 23:

(±) -? - cyano-3-phenoxybenzyl- (±) -trans-3- (Z-2-chloro-3,3,4,4,4-pentafluorobut-1-en-1-yl) -2, 2-dimethylcyclopropanecarboxylate Compound No. 53;

NMR (carbon tetrachloride, ppm): 1.16-1.42 (m, 6H), 1.74-2.60 (m, 2H), 5.98-6.40 and 6.77-7.55 (mm) 11H).

Product 24:

3-Phenoxybenzyl- (±) - cis / trans-3- (3-chloro-3,3-difluoro-2-chlorodifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate - a mixture of 7 parts of compound no. 9 with 13 parts of Compound No. 10;

NMR (carbon tetrachloride, ppm): 1.24-1.42 (m, 6H), 1.76-2.60 (m, 2H), 5.02 (s, 2H), 6.16 and 7.12 ( double d, 1H), 6.76-7.40 (m, 9H).

Product 25:

(±) -? - cyano-3-phenoxybenzyl- (±) - cis / trans -3- (3-chloro-3,3-difluoro-2-chlorodifluoromethylprop-1-en-1-yl) -2 2-dimethylcyclopro205108 pancarboxylate - a mixture of 7 parts of Compound No. 11 with 13 parts of Compound No. 12;

NMR (carbon tetrachloride, ppm): 1.24-1.42 (m, 6H), 1.84-2.70 (m, 2H), 6.16 and 7.12 (double d, 1H), 6.36 (ss, 1H), 6.90-7.50 (m, 9H).

Product 26:

(±) -? - cyano-3-phenoxybenzyl- (±) - cis / trans-3- (Z / E-3,3-difluoro-2-chloro difluoromethylprop-1-en-1-yl) -2 2-dimethylcyclopropanecarboxylate - a mixture of unspecified composition containing compounds No. 27, 28, 29 and 30;

NMR (carbon tetrachloride, ppm): 1.24-1.52 (m, 6H), 1.76-2.70 (m, 2H), 5.6-7.6 (m, 12H).

Product 27:

(±) -? - cyano-3-phenoxybenzyl- (±? - cis / trans-3- (Z / E-2-bromo-3,3,3-trifluoroprop-1-en-1-yl) -2, 2-dimethylcyclopropyl opanecarboxylate - a mixture of 10 parts of Compound No. 54, 1 part of Compound No. 55, 10 parts of Compound No. 56 and 1 part of Compound No. 57;

NMR (carbon tetrachloride, ppm): 1.24-1.50 (m, 6H), 1.75-2.55 (m, 2H), 5.96-7.26 (m, 1H), 6.36- 6.56 (m, 1H); 7.0-7.6 (m, 9H).

Product 28:

(±) -? - ethynyl-3-phenoxybenzyl- (±) - cis / trans-3- (Z / E-2-chloro-3,3,3-trifluoroprop-1-en-1-yl) - 2,2-dimethylcyclopropanecarboxylate - a mixture of 10 parts of Compound No. 58, 1 part of Compound No. 59, 10 parts of Compound No. 60 and 1 part of Compound No. 61;

NMR (carbon tetrachloride, ppm): 1.16-1.44 (m, 6H), 1.64-2.56 (m, 3H), 5.7-7.0 (m, 1H), 6, 28-6.40 (m, 1H) 6.70-7.40 (m, 9H).

Product 29:

(±) -? - ethynyl-3-phenoxybenzyl- (±) - cis / trans-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate A mixture of 2 parts of Compound No. 13 with 3 parts of Compound No. 14;

NMR (carbon tetrachloride, ppm): 1.16-1.44 (m, 6H), 1.76-2.56 (m, 3H), 6.12-7.04 (m, 1H), 6.24- 6.40 (m, 1H), 6.76-7.36 m, 9H).

Example 9

This example illustrates the insecticidal properties of (±) -? - cyano-3-phenoxybenzyl- (±) - cis / trans -3- (2-chloro-3,3,3-trifluoro-2-trifluoro-24-methylprop-1-ene) 1-yl) -2,2-dimethylcyclopropanecarboxylate containing 60% cis-isomer (Product No. 6) and (±) -. &lt; - &gt; - cyano-3-phenoxybenzyl- (±) - cis / trans-3- (3, 3,3-Trifluoro-2-trifluoromethylprop-1-enyl 1) -2,2-dimethylcyclopropanecarboxylate containing 20% cis isomer (Product No. 1) as representative examples of esters of the invention.

The efficacy of the products is tested against a number of insect and other invertebrate pests. Each of the products tested is used in the form of a liquid preparation containing, for product No. 1000, 500, 125 and 62.5 ppm (by weight) and for product No. 6, 50, 25, 12.5 and 6.25. ppm by weight of the active substance. These preparations are prepared by dissolving the active ingredient in a mixture of 4 parts by volume of acetone and 1 part by volume of diacetone alcohol and diluting the solution with water containing 0.01% w / w wetting agent "LISSÁPOL" NX until the desired concentration of the test compound in liquid preparation.

The performance of the test is essentially the same for all pest species, in that several specimens of the relevant pest are transferred to an appropriate environment, which is usually the host plant or food (feed) on which the pest feeds, and then the pest or environment, eventually on the pest and the environment, apply the tested preparation.

Mortality is then determined at time intervals which usually range from 1 to 3 days after treatment.

The test results are shown in Tables II and III below. The first column of these tables lists the name of the pest and the following columns the host plant or environment, the number of days between treatment and mortality, and the results obtained with the individual concentrations of test compounds.

The evaluation is carried out on a scale of 0 - 3, in which the symbols have the following meaning:

= less than 30% of pests killed = 30 - 49% of pests killed = 50 - 90% of pests killed = over 90% of pests killed

The term 'contact test' means that both the pest and the environment have been treated, the term 'residual effect' means that the environment has been treated before the pest has been contaminated. The (-) sign indicates that the test was not performed in this case.

Table II shows the results obtained with Product No. 1, and Table III shows the results obtained with Product No. 6.

TABLE II

Type of pest Environment Number Effect at concentration (ppm) days 1000 500 125 62.5

Tetranychus telarius bean 3 3 3 3 3 (Spider Mite - adults) general Aphis fabae bean 2 3 3 3 3 (Poppy Aphid) general Megoura viceae bean 2 3 3 3 3 (Whorled Aphid) general Aedes aegypti (Adult Mosquito) plywood 1 3 3 3 3 Musea domestica (fly milk/ 2 3 3 3 3 home - contact test) Plutella maculipennis (field lizard larvae - contact test) /sugar 3 3 3 3 3 Phaedon cochleariae corn 3 3 3 3 3 (Crimson Colorado beetle - residual effect) Musea domestica (fly plywood 3 3 3 3 3 home - residual effect) corn 3 3 3 3 _

black - residual effect)

TABLE III

Type of pest Environment Number days Effect at concentration (ppm) 50 25 12.5 6.25 Tetranychus telarius bean (Red spider mite — adolescents) general 3 2 2 2 1 Aphis fabae bean (Poppy Aphid) general 2 3 3 3 3 Megoura viceae bean (Whorled Aphid) general 2 3 3 3 3 Aedes aegypti (mosquito - adults) plywood 1 3 3 2 2 Musea domestica (fly milk/ home - contact test) /sugar 2 3 3 3 3 Plutella maculipennis (larvae field embroidery — contact test) mustard 3 3 3 3 3 Phaedon cochleariae (Colorado beetle (residual effect) corn 3 3 3 3 3 Musea domestica (fly domestic - residual effect) plywood 3 3 2 2 0

Example 10

This example illustrates the insecticidal properties of the products of Example 8. The tests are carried out under the same conditions as those of Example 9. The results obtained are shown in Table IV in percent of pest mortality at the respective application rate of the test composition.

The individual symbols in Table IV have the following meanings:

Pč. = Product No. (as defined in Example 8) Dose = Concentration in ppm of active ingredient in the test formulation * = In addition to the stated mortality, the remaining live specimens of the test insect are severely damaged and can be expected to die if the test is prolonged.

Individual pests are indicated in the table by letters A - M with the following meanings:

A = Tetranychus telarius (Admiral Spider - adults)

B = Tetranychus telarius (Common Spider Moth)

C = Aphis fabae (Poppy Aphid)

D = Megoura viceae

E = Aedes aegypti (mosquito)

F = Musea domestica (house fly - - contact effect)

G = Musea domestica (house fly - - residual effect)

H = Plutella xylostella - residual effect (3 days)

I = Plutella xylostella - residual effect (10 days)

J = Phaedon cochleariae

K = Calandra granaria (Black Weevil)

L = Tribolium. castaneum

M = Spodoptora littoralis

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Example 11

This example illustrates the efficacy of product # 2 and product # 6 against Boophilus microplus (tick).

Suspensions of the above products are prepared by grinding 10 parts of the respective product with 985 parts of water and 5 parts of a non-ionic "Teric" N9 surfactant (1: 9 molar ratio of nonylphenol with ethylene oxide) in a ball mill to give preparations containing 1, 0% active substance. By diluting a portion of each of the suspensions prepared above with water, formulations containing 0.1 and 0.01% by weight of the active ingredient are then prepared.

The efficacy of each of the above products on drunk adult female Boophilus microplus (Yeerongpilly strain) was tested by applying to each specimen of about 20 experimental ticks a microdroplet of the appropriate active compound concentration. After 14 days, the mortality of adult ticks is counted by counting their eggs and the percentage of eggs from which the larvae hatched. The results obtained are shown in Table V.

The efficacy of the above products against tick larvae (Yeerongpilly strain) was tested as follows:

A suspension of the appropriate concentration is soaked into the filter paper sheet and the paper is allowed to dry. A wrapper is made from the treated paper and about 100 tick larvae are sealed. 48 hours after sealing, the mortality of the larvae of the tick is determined by means of a scale of 0 to 5, where each value has the following meanings:

= killed 0 - 20% larvae = killed 20 - 50% larvae = killed 50 - 80% larvae = killed 80 - 95% larvae = killed 95 - 99% larvae = 100% larvae killed.

The results are summarized in Table V.

In another test, an emulsion was prepared from each of the above products by mixing 25 parts of the respective compound with 75 parts of cyclohexanone and 25 parts of the "Teric" N9 surfactant and diluting the mixture with water to volume. 10 000 parts.

Each of the emulsions thus obtained is sprayed until dripping, calves heavily infested with a tick of Boophilus microplus (Blarraj strain at different developmental stages) .The efficacy of the individual products is evaluated as follows:

(ij) All adult female ticks, fully drunk at the time of spraying, are removed from the calves shortly after spraying and placed in a petri dish in an incubator to detect egg-laying mortality and, in the case of egg-loading, viable egg larvae hatching. Additional drinking adults, if any, will also be taken at 24 hours and 48 hours after spraying and mortality is determined in the same way.The results of this evaluation are listed in Table VI in the column "Mortality of drinking adults".

(iij At daily intervals, pre-determined test sites on individual calves are examined for the effects of test substances on juvenile adolescents and nymphs. The evaluation is performed using the 0 to 5 scale defined above and the results are shown in Table VI in the columns "juvenile adult mortality" and "nymph mortality."

The sign used 'indicates that no drinking adults were present in the present case.

Permethrin was used as a standard comparator in these tests

3-Phenoxybenzyl (± J-cis / trans-3- (2,2-dichlorvinyl) -2,2-dimethylcyclopropane carboxylate).

TABLE V

In vitro activity against Boophilus microplus adults and larvae

Product Adult mortality in% at active substance concentration Larval mortality at active substance concentration of 1% 0.1% 0.01 ^L 1% 0.1% 2 100 ALIGN! 90 5 5 1 6 100 ALIGN! 100 ALIGN! 5 5 5

TABLE VI

In vivo efficacy against tense adults, juveniles and larvae of Boophilus microplus

Product Concentration Mortality of the active substance in% Drinking in adults (%) Juvenile Nymphs (24 hours / 24 hours / 48 hours) adults

2 0.05 - / - / - 5 5 2 0,025 5 5 2 0.02 - / - / - 5 4 2 0.01 - / - / - 5 5 2 0.005 - / - / - 5 14 2 0,0025 - / - / - 4 3 6 0.02 5 5 6 0.01 0.005 5 5 6 - / - / - 5 '5/4 6 0,0025 - / - / - 5 '5/4 permethrin 0.1 5 5 permethrin 0.05 5 5 permethrin 0.01 20/59 / - 3 1

Subject

Claims (16)

An insecticidal composition, characterized in that it contains, as active ingredient, an esterified cyclopropanecarboxylic acid derivative of the formula I O R = C-CH-CH-CH-C-O-CH 2 *! \ /, C, H $ C CH 2 (I) wherein one of R ¹ and R ² represents a group of the formula W (CFz) _m - where W represents a hydrogen, fluorine or chlorine atom and m is 1 or 2 and the other of the two represents a fluorine, chlorine or bromine atom or a group of the formula X — C—, From where X, Y and Z are each independently hydrogen, fluorine or chlorine and R ³ represents a hydrogen atom, a cyano group or an ethynyl group, in combination with an inert diluent or carrier. 2. A composition according to claim 1, characterized in that as active substances they comprise compounds of the formula I wherein one of R ¹ and R ² represents a group of formula WCFz— where W represents a hydrogen, fluorine or chlorine atom, and the other of these represents a group of the formula Y X — C—, From where X, Y and Z are each independently hydrogen, fluorine or chlorine and R ³ represents hydrogen or cyano. 3. The composition of claim 2 wherein said active ingredient is a compound of the formula I wherein each R ¹ and R ² each represents a trifluoromethyl group and R ³ is defined as in point 2. 4. A composition according to claim 1, wherein the active ingredient is a compound of formula (I), wherein one of R &lt; ¹ &gt; and R &lt; ² &^gt; WCFz— where W represents a hydrogen, fluorine or chlorine atom and the other of these represents a fluorine, chlorine or bromine atom; R ³ represents hydrogen or cyano. 5. A composition according to claim 4, characterized in that as active substances they comprise compounds of the formula I wherein one of R ¹ and R ² is a trifluoromethyl group and the other of the symbols represents a chlorine or bromine atom and R ³ is as defined in 4. 6. A composition according to claim 1, wherein the active ingredient is (. + -.) -. Alpha.-cyano-3-phenoxybenzyl- (. + -.) - cis / trans-3- (2-chloro-3,3,3-trifluoropropane). 1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate. 7. A composition according to claim 1, wherein the active ingredient is (. + -. -Cyano-3-phenoxybenzyl- (. + -.) - cis / trans-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-). en-1-yl] -2,2-dimethylcyclopropanecarboxylate. 8. A composition according to claim 1, wherein the active ingredient is (. + -.) -. Alpha.-cyano-3-phenoxybenzyl- (. + -.) - cis / trans-3- (3-chloro-2,3,3-trifluoropropane). 1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate. 9. A composition according to claim 1, wherein the active ingredient is (.alpha.-cyano-3-phenoxybenzyl- [. + -.) Cis / trans-3- (2-bromo-3,3,3-trifluoroprop-1). -en-1-yl] -2,2-dimethylcyclopropanecarboxylate. 10. A composition according to claim 1, wherein the active ingredient is 3-phenoxybenzyl- (±) - cis / trans-3- (2-chloro-3,3,3-trifluoroprop-1-en-1-yl). -2,2-dimethylcyclopropanecarboxylate. 11. A composition according to claim 1, wherein the active ingredient is 3-phenoxybenzyl- (±) - cis / trans-3- (3,3,3-trifluoro-2-trifluoromethylprop-1-en-1). -yl j -2,2-diimethylcyclopropanecarboxylate. 12. A composition according to claim 1, wherein the active ingredient is (. + -.) -. Alpha.-cyano-3-phenoxybenzyl- (1R, 3R) -3- (3,3,3-trifluoro-2-trifluoromethylprop- 1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate. 13. A composition according to claim 1, wherein the active ingredient is (. + -.) -. Alpha.-cyano-3-phenoxybenzyl- [1R, 3S] -3- (2-chloro-3,3,3-trifluoroprop-1). -en-1-yl) -2,2-dimethylcyclopropanecarboxylate. 14. A composition according to claim 1, wherein the active ingredient is (S1-.alpha.-cyano-3-phenoxybenzyl- (1R, 3R) -3- (3,3,3-trifluoro-2-trifluoromethylprop-). 1-en-1-yl) -2,2-dimethylcyclopropanecarboxylate. 15. A composition according to claim 1, wherein the active ingredient is (S1-.alpha.-cyano-3-phenoxybenzyl- (1R, 3S) -3- (2-chloro-3,3,3-trifluoroprop-1-). en-1-yl) -2,2-dimethylcyclopropanecarboxylate. 16. A method according to claim 1, characterized in that the compound of the formula (V) (CW-CW-CW-CW-C-GL): C ^H 3 ^{C CH} $ (V) in which R ¹ and R ² are as defined in 1 and Q is a hydroxyl group, a chlorine atom, a bromine atom or an alkoxy group having 1 to 6 carbon atoms, esterified by reaction with an alcohol of formula IV (IV) wherein R ³ is as in 1. Severography, n. P „závod 7, Most