GB2108123A

GB2108123A - Pesticidal aromatic and heteroaromatic alcohol esters

Info

Publication number: GB2108123A
Application number: GB08230153A
Authority: GB
Inventors: Jean Tessier; Jean-Pierre Demoute
Original assignee: Roussel Uclaf SA
Current assignee: Sanofi Aventis France
Priority date: 1981-10-23
Filing date: 1982-10-22
Publication date: 1983-05-11
Also published as: CH655302A5; FR2515176A1; IT1158023B; NL8204049A; JPS5879955A; IT8249340A0; FR2515176B1; DE3239200A1

Abstract

Compounds of general formula I <IMAGE> in which Ar represents an optionally substituted aromatic or heteroaromatic radical, X1, X2 and X3 identical or different, each represent a hydrogen atom or a halogen atom, one at least of the radicals X1, X2 and X3 representing a halogen atom, and B represents an alkyl radical or a substituted cyclopropyl or benzyl radical, are of use in combating pests. Alcohols used in the preparation of these compounds are also claimed.

Description

SPECIFICATION Aromatic and heteroaromatic alcohol esters This invention relates to new esters of aromatic and heteroaromatic alcohols, to processes for their preparation and to compositions containing them as well as to new intermediates.

According to one feature of the invention there are provided compounds of general formula I:

in which Ar represents an optionally substituted aromatic or heteroaromatic radical; X1,X2a and X3, which may be the same or different, each represents a hydrogen atom or a halogen atom, with the proviso that one at least of the radicals Xr, X2 and X3 represents a halogen atom; and B represents: a) an alkyl radical containing from 1 to 1 8 carbon atoms; b) a radical of formula:

in which: either Zr and Z2 each represents a methyl radical or Z, represents a hydrogen atom and either2 represents a radical of formula::

(in which R3 represents a hydrogen or a halogen atom and either R, and R2 which may be the same or different, each represents a halogen atom or an alkyl radical containing from 1 to 8 carbon atoms1 or R, and R2, together with the carbon atom to which they are attached, represent a cyclo-alkyl radical containing from 3 to 6 carbon atoms or a radical of formula:

in which the ketone is in position cr with respect to the double bond and in which X represents an oxygen or a sulphur atom or an -NH- radical) orZ2 represents a radical of formula:

(in which R4, R5, R6 and R7, which may be the same or different each represents a halogen atom), orZ2 represents a radical of formula::

of E or Z geometry [in which R8 represents a hydrogen, chlorine, fluorine or bromine atom and R represents a linear, branched or cyclic hydrocarbyl radical, which may be saturated or unsaturated and which contains from 1 to 1 8 carbon atoms (optionally substituted by one or more functional groups, which may be the same or different); an aryl group containing from 6 to 14 carbon atoms (optionally substituted by one or more functional groups, which may be the same or different) or a heterocyclic radical (optionally substituted by one or more functional groups, which may be the same or different)j; c) a radical of formula::

(in which Y and Y', which may be in any position on the benzene nucleus and which may be the same or different, each represents a hydrogen or halogen atom, an alkyl radical containing from 1 to 8 carbon atoms or an alkoxy radical containing from 1 to 8 carbon atoms); in all their possible isomeric forms as well as the mixtures of the isomers; with the exception of compounds of general formula I in which X1, X2 and X3 each represents a fluorine atom and with the exception of 2-chloro-1 -(3-phenoxyphenyl)-ethyl 3-(2-methyl-1 -propenyl)- 2,2-dimethyl-cyclopropane- 1 -carboxylate.

When Ar represents a substituted aromatic or heteroaromatic radical, it is preferred to be an aromatic or heteroaromatic radical substituted by one or more substituents selected from alkyl radicals containing from 1 to 4 carbon atoms; alkoxy radicals containing from 1 to 4 carbon atoms; aryloxy, arylcarbonyl, arylmethyl, arylthio, arylsulphenyl or arylsulphonyl groups; halogen atoms; and trifluoromethyl radicals. The aromatic or heteroaromatic radical may also be substituted by another aromatic or heteroaromatic radical which can itself be substituted by one or more of the substituents indicated above.

A preferred aromatic radical is the phenyl radical. Preferred substituted aromatic radicals are those of formula:

in which Y1,Y11, Y2 and Y2,, which may be in any position on their respective benzene nuclei, each represents a hydrogen atom, a halogen atom or a methyl radical and A represents an oxygen atom, a methylene group, a carbonyl group, a sulphur atom, a sulphoxide group or a sulphone group.

Especially preferred substituted aromatic radicals are the following:

Preferred heteroaromatic radicals are those derived from pyridine, from thiophene, from furan or from pyrimidine. Particular heteroaromatic radicals which may be cited are the substituted heteroaromatic radicals, for example, those of formula:

When X1, X2 and/or X3 represents a halogen atom, it is preferred to be a fluorine, chlorine or bromine atom.

When B represents an alkyl radical containing from 1 to 1 8 carbon atoms, this may be a linear, branched or cyclic alkyl radical, such as for example methyl, ethyl, n-propyl, isopropyl, cyclopropyl, butyl, tert-butyl, cyclobutyl or n-pentyl.

When Fl1, R2 and/or R3 represents a halogen atom, it is preferably a fluorine, chlorine or bromine atom. When R, and/or R2 represents an alkyl radical, it is preferred to be a methyl radical. When R, and R2, together with the carbon atom to which they are attached, represent a cycloalkyl radical it is preferred to be a cyclopropyl radical.

R4, R,, RB and R7 preferably represent atoms of fluorine, chlorine or bromine.

R is preferred to represent a methyl, ethyl, n-propyl isopropyl, tert-butyl, phenyl, benzyl, thienyl or furyl radical.

One of Y and Y' preferably represents a halogen atom, for example a chlorine atom, in the para position on the benzene nucleus and the other preferably represents a hydrogen atom.

Preferred compounds of formula I are those in which B represents a radical of formula:

[in which Z1 represents a hydrogen atom and Z2 represents a radical of formula:

(in which Ra, R2 and R3 are as defined above and in particular those in which R, and R2 are the same and each represents a halogen atom and R3 represents a hydrogen atom)].

Also preferred are compounds of formula I in which Ar represents a radical of formula:

(in which Ya, Y1,, Y2 and Y2,, which may be in any position on their respective benzene nuclei, each represents a hydrogen atom, a halogen atom or a methyl radical and A represents an oxygen atom, a methylene group, a carbonyl group, sulphur atom, a sulphoxide group or a sulphone group, and in particular those in which A represents an oxygen atom as well as those in which Y1, Y1,, Y2 and Y: each represents a hydrogen atom).

Especially preferred compounds of the invention are those in which X, and X2 each represents a hydrogen atom and X3 represents a halogen atom and particularly those in which X3 represents a chlorine atom.

According to a further feature of the invention the compounds of general formula I may, for example, be prepared by reacting an acid of formula II, BCO2H (II) (in which B is as defined above), or a functional derivative of this acid, with an alcohol of formula Ill,

(in which Ar, X" X2 and X3 are as defined above) or a functional derivative of this alcohol.

As a functional derivative of the acid is preferably used an acid halide, for example the acid chloride.

In a preferred method for carrying out the process of the invention, the acid and the alcohol are reacted in the presence of dicyclohexylcarbodiimide or of diisopropylcarbodiimide.

It will be appreciated that the esterification reaction can be carried out according to conventional esterification methods.

The invention has more especially as its subject the process wherein an acid of formula II or a functional derivative of this acid is reacted with an alcohol of formula IIIAE

(in which Yr, Y1,, Y2, Y2,, A, Xr, X2 and X3 are as defined above), or a functional derivative of this alcohol, so as to obtain a compound of formula lA,

The alcohols of formula Ill (in which Ar, X1, X2 and X3 are as defined above, it being understood that X1, X2 and X3 cannot simultaneously represent a fluorine atom) and functional derivatives thereof are new products which constitute, together with processes for their preparation, still further features of the invention.

In particular there may be mentioned the alcohols of formula IIIA as defined above as well as their functional derivatives, especially those wherein A represents an oxygen atom and more especially those wherein A represents an oxygen atom and Ya, Y;, Y2 and Y2 each represents a hydrogen atom.

The compounds of general formula Ill may, for example, be prepared by reacting a compound of formula IV, Ar < HO (IV) (wherein Ar is as defined above) with a compound of formula:

(wherein X1, X2 and X3 are as defined above).

In a preferred method of carrying out this process the reaction is effected at a low temperature, i.e. at from -300C to -1 000 C, and in the presence of an alkaline alcoholate such as e.g. potassium tert. butylate or of another strong base able to form an anion from the compound of formula::

Alternatively, when it is desired to prepare compounds of formula Ill in which Xr, X2 and X3 represent atoms of chlorine or bromine, a compound of formula V, ArCOCH3 (V) (where A, is as defined above), may be reacted with a halogen, so as to obtain the corresponding compound of formula VI,

(where n is 1, 2 or 3) which is then submitted to the action of a reducing agent, so as to obtain the corresponding compound of formula IIIB,

As reducing agent, there can be used a hydroboride of an alkali metal such for example as NaBH4.

The compounds of formula VI are also new and constitute a yet further feature of the present invention.

If it is desired to obtain compounds of formula IIIB in which there are two different halogen atoms, first one and then the other of the two halogens may be introduced successively on the compound of formula V.

According to the conditions employed, compounds are obtained in which 1, 2 or 3 halogen atoms are present.

Compounds of formula IIIB thus obtained, can also be submitted to the action of a reducing agent, so as to replace the weakest halogen atom by a hydrogen atom. As reducing agents, can be used, for example (Bu)3 SnH or any other tin di- or trialkyl hydride.

The compounds of general formula I possess interesting properties which enable them to be of use in combating pests, for example, pests of vegetation, of warm-blooded animals and of buildings.

Thus the compounds of general formula I can be used to combat insects, nematodes and acarida of vegetation and of warm-blooded animals. The product of Example 2 has given quite remarkable results as is illustrated hereinafter.

According to a further feature of the invention there are provided compositions for use in combating pests of warm-blooded animals, vegetation and of buildings, comprising as active principle, at least one compound of formula I.

The compounds of formula I can be used in particular to combat insects in the agricultural domain, for example flies, but also aphids and the larvae of lepidoptera and coleoptera. They are generally used at dosages of from 10 g to 300 g of active material per hectare.

The compounds of formula I can also be used to combat insects in buildings, in particular to combat flies, mosquitoes and cockroaches.

Therefore the invention particularly relates to insecticidal compositions comprising, as active principle at least one compound of formula I in association with carrier.

The compounds of formula I can also be used to combat acarida and nematodes in vegetation.

In addition, the compounds of formula I can be used to combat acarida in animals, to combat in particular ticks and especially ticks of the Boophilus species, those of the Hyalomnia species, those of the Amblyomnia species, and those of the Rhipicephalus species, or to combat all sorts of mites and in particular the sarcoptic mite, the psoroptic mite and the chorioptic mite.

A further feature of the invention is thus compositions intended for combating nematodes of vegetation and acarida of warm-blooded animals, buildings and vegetation, comprising at least one compound of formula I.

The invention has particularly as its subject acaricidal compositions containing as active principle at least one compound of formula When it is a question of combating acarida in animals, the compounds of formula I are very often incorporated in feedstuff compositions in association with a nutrient material adapted for animals. The nutrient material may vary depending on the animal species; it can contain, for example, cereals, sugars, grains, soya, peanut and sunflower cakes, flours of animal origin for example fish flour, synthetic amino acids, mineral salts, vitamins and anti-oxidants.

The compositions according to the invention may be prepared according to conventional processes in the agro-chemical industry, the veterinary industry and the animal feedstuff industry.

In the compositions intended for agricultural use and for use in buildings the active material or materials may have added to them if desired one or more other pesticidal agents. These compositions can be presented in the form of powders, granules, suspensions, emulsions, solutions, solutions for aerosols, combustible strips, baits or other preparations normally employed for this class of compound.

In addition to the active principle, these compositions in general contain a vehicle and/or a nonionic surface active agent, ensuring in addition a uniform dispersion of the substances which form the mixture. The vehicle may be a liquid, such as e.g. water, an alcohol, a hydrocarbon or some other organic solvent, a mineral, animal or vegetable oil, a powder such as e.g. talc, clay, a silicate, kieselguhr or a combustible solid such as e.g. tabu powder or pyrethrum marc.

Insecticidal compositions according to the invention preferably contain from 0.005% to 10% by weight of active material.

The acaricidal and nematocidal compositions can more particularly be presented in the form of a powder, granules, suspensions, emulsions and solutions.

For acaricidal use, it is preferred to use wettabie powders for foliar atomisation, containing from 1 to 80% by weight of active material or liquids for foliar atomisation containing from 1 to 500 g/l of active material. There can equally be used powders for foliar powdering containing from 0.05 to 3% by weight of active material.

For nematocidal use, it is preferred to use liquids for soil treatment containing from 300 to 500 g/l of active material.

For acaricidal and nematocidal use, the compounds of formula I are used for preference at doses of from 1 to 100 g of active material per hectare.

To increase the biological activity of the compounds of formula I they can have added to them a standard synergist such as e.g. 1 -(2,5,8-trioxadodecyl)-2-propyl-4,5-methylenedioxy-benzene (piperonyl butoxide), N-(2-ethyl-heptyl)-bicyclo[2,2- 1 j 5-heptene-2,3-dicarboximide, or piperonyl-bis-2 (2'-n-butoxy-ethoxy)-ethylacetal (tropital).

The compounds of formula I present an excellent general tolerance, and the invention therefore also includes the use of the compounds of formula I as medicaments, in particular to combat disorders created by ticks and mites.

The medicaments of the invention can be used both in human medicine and in veterinary medicine.

The medicaments according to the invention are in particular used in human medicine to combat lice both preventively and curatively and to combat scabies.

The medicaments according to the invention can be administered by external route, by vaporisation, by bathing, or by painting on.

The medicaments according to the invention for veterinary use can also be applied by painting on the dorsal spine according to the so-called "pour on" method, they can also be administered by digestive or parenteral route.

Therefore the invention has as a further subject pharmaceutical compositions comprising, as active principle at least one compound of formula I, in association with a pharmaceutical carrier or excipient.

The compounds of formula I can also be used as biocides or as growth regulators.

A further subject of the invention is compositions endowed with insecticidal, acaricidal, fungicidal or nematocidal activity, comprising at, least one compound of formula I and at least one pyrethrinoide ester selected from esters of allethrolones, 3,4,5,6-tetrahydrophthalimidomethyl alcohol, 5-benzyl-3furyl-methyl alcohol, 3-phenoxybenzyl alcohol and cr-cyano-3-phenoxybenzyl alcohols with chrysanthemic acids, esters of 5-benzyl-3-furyl-methyl alcohol with 2,2-dimethyl-3-(2-oxo-3-tetrahydrothiophenylidenemethyl)-cyclopropane-1 -carboxylic acids, esters of 3-phenoxybenzyl alcohol and (e-cyano-3-phenoxybenzyl alcohols with 2,2-dimethyl-3-(2,2-dichlorovinyl)-cyclopropane- 1 -carboxylic acids, esters of cr-cyano-3-phenoxybenzylic alcohols with 2,2-dimethyl-3-(2,2-dibromovinyl) cyclopropane-1-carboxylic acids, esters of 3-phenoxybenzyl alcohol with 2-parachlorophenyl-2- isopropyl-acetic acids, and esters of allethrolones, 3,4,5,6-tetrahydrophthalimidomethyl alcohol, 5benzyl-3-furyl-methyl alcohol, 3-phenoxybenzyl alcohol and cr-cyano-3-phenoxybenzyl alcohol with 2,2-dimethyi-3-(1,2,2,2-tetrahaloethyl)-cyclopropane-1-carboxylic acids (in which "halo" represents a fluorine, chlorine or bromine atom), it being understood that the compounds of formula I can exist in any of the possible stereoisomeric forms, as can also the acid and alcohol moieties of the above pyrethrinoid esters.

According to a still further feature of the invention there is provided a method of combating insect, acarida, fungus or nematode pests which comprises applying to a site infested with or susceptible to infestation by the said pests an effective amount of a compound of formula I.

The following examples illustrate the invention without limiting it.

Examples Example 1:1 R cis 3(2,2-difluorovinyl)-2.2-dimethyl cyclopropane carboxylate of RS[2-chloro 1 (3-phenoxyphenyl)]ethyl A solution containing 1.6 g of 1 R cis 3(2,2-difluorovinyl)-2,2-dimethyl cyclopropane carboxylic acid in 20 cm3 of methylene chloride is cooled to OOC. Then 1.6 g of dicyclohexylcarbodiimide and 15 mg of N,N-dimethylamino pyridine are added all at once. After agitating for 20 minutes 1.5 g of 1 RS 2chloro 1 -(3-phenoxyphenyl)ethan-1 -ol and 20 cm3 of ethylene chloride are added. The solution obtained is agitated for 5 hours while allowing the temperature to rise slowly to ambient.After filtering, washing the filtrate with water, drying and evaporating to dryness, 3.1 g of product is obtained which is chromatographed on silica, eluting with a mixture of hexane-ethyl acetate 95-5. 1.8 g of the product sought is obtained.

NMR CHCI3 p.p.m.

1.18 to 1.22 H's of the CH3 1.83 H's of the cyclopropyl in position 1 and 3 3.67-3.77 H's of CH2CI 4.3-4.7 H of

5.8-5.9-6 H of

6.9-7.6 H aromatics Example 2:1 R cis 3(2,2-difluorovinyl) 2,2-dimethyl cyclopropane carboxylate of RS[2-fluoro-1(3 phenoxyphenyl)jethyl By operating as in Example 1 starting with 1.8 9 of 1 R cis 3(2,2-difluorovinyl) 2,2-dimethyl cyclopropane carboxylic acid and with 1.5 g of 1 RS 2-fluoro 1 (3-phenoxyphenyl) ethan-1 -ol, 2.2 g of the product sought is obtained.

NMR CDCI3 p.p.m.

1.12 and 1.23 H of the methyls in position 2 1.8-2.08 H in positions 1 and 3 of the cyclopropyl

4.15-4.25 4.95-5 H of the CH2F 4.175 Hofthe

5.8-5.9-6 6--6.11-6.2 H of the

6.9-7.6 H aromatics Example 3:1 R cis 3-(2,2-difluorovinyl) 2,2-dimethyl cyclopropane carboxylate of RS[2-bromo1 (3-phenoxyphenyl)jethyl By operating as in Example 1 starting with 0.88 g of 1 R cis 3(2,2-difluorovinyl) 2,2-dimethyl cyclopropane carboxylic acid and with 1 g of 1 RS 2-bromo 1 -(3-phenoxyphenyl) ethan-1 -ol, 1.33 g of the product sought is obtained.

NMR CDCI3 p.p.m.

1.1-1.22-1.25 H of the methyls in position 2 1.75-1.92 H of the cyclopropyl 3.5-3.6 H of the CH2Br 4.25 to 5 Hofthe

5.8-5.9-6 H of the

7-7.6 H aromatics.

Example 4:1 R trans 3(2,2-difluorovinyl) 2,2-dimethyl cyclopropane carboxylate of RS[2-fluoro- 1 (3-phenoxyphenyl)]ethyl By operating as in Example 1 starting with 1.8 g of 1 R trans 3(2,2-difluorovinyl) 2,2-dimethyl cyclopropane carboxylic acid and 1.5 g of 1 RS 2-fluoro 1 (3-phenoxyphenyl) ethan-1 -ol, 1.6 g of the product sought is obtained.

NMR CDCI3 p.p.m.

1.13-1.25 H's of the methyls in position 2 of the cyclopropane 1.52-1.6 H in position a of the CO2

3.75--3.88 4.2 4.3 H of the

4.12 4-.2 4.9-5 H of the CH2F 5.7-6.25 H of the

6.8-7.5 H aromatics Example 5:1 R trans-3(2,2-difluorovinyl) 2,2-dimethyl cyclopropane carboxylate of RS[2-bromo 1 (3-phenoxyphenyl)]ethyl By operating as in Example 1, starting with 0.88 g of 1 R trans 3(2,2-difluorovinyl) 2,2-dimethyl cyclopropane carboxylic acid and with 1 RS 2-bromo 1 (3-phenoxyphenyl) ethan-1 -ol, 1.38 g of the product sought is obtained NMR CDCI3 p.p.m.

1.15-1.2-1.27 H of the methyls in position 2 1.5-1.6 H in position a of the CO2 1.88-2.2 the other H of the cyclopropyl 3.55-3.65 H of the CH2Br

3.8-3.9 4.2-4.3 H of the

5.8-5.9-6 H of the

Example 6:1 R trans 3-(2,2-difluorovinyl) 2,2-dimethyl cyclopropane carboxylate of RS[2-chloro 1(3-phenoxyphenyl)] ethyl By operating as in Example 1, starting with 1.6 g of 1 R trans 3(2,2-difluorovinyl) 2,2-dimethyl cyclopropane carboxylic acid and with 1.5 g of 1 RS 2-chloro 1 (3-phenoxyphenyl) ethan-1 -ol, 1.7 g of the product sought is obtained.

NMR CDCI3 p.p.m.

1.15-1.18-1.21 H'softheCH3 1.53-1.62 H in position 1 of the cyclopropyl 1.88-2.13 H in position 3 of the cyclopropyl 3.72-3.8 H of the CH2CI 3.42--4.36 H of the

5.9-6-6.1 H of the CO2-CH 6.9-7.6 H of the aromatics.

Example 7:1 R trans 3(2,2-difluorovinyl) 2,2-dimethyl cyclopropane carboxylate of RS[2,2dichloro 2-fluoro 1 (3-phenoxyphenyl)]ethyl By operating as in Example 1 starting with 2.2 9 of 1 R trans 3(2,2-difluorovinyl) 2,2-dimethyl cyclopropane carboxylic acid and 3.8 g of 1 RS 2,2-dichloro 2-fluoro 1 (3-phenoxyphenyl) ethan-1 -ol 4 g of the product sought is obtained.

NMR CDCI3 p.p.m.

1.15-1.18-1.21 H's of the methyls in position 2

1.92--2.13 1.55--1.64 H of the cyclopropane

3.8--3.9 1 4.2 4.3 H of the

6.18--6.33 6.38 J H of the

6.9-7.6 H aromatics Example 8: (1R cis) 3(2,2-difluorovinyl) 2,2-dimethyl cyclopropane carboxylate of RS[2-fluoro-2- chloro 1(3-phenoxyphenyl 1 (3-phenoxyphenyl)]ethyl By operating as in Example 1, starting with 0.86 g of (1 Fl cis) 3(2,2-difluorovinyl) 2,2-dimethyl cyclopropane carboxylic acid and with 1 g of 2-fluoro 2-chloro 1 (3-phenoxyphenyl) ethan-1 -ol, 1.4 g of the product sought is obtained.

NMR CDCI3 p.p.m.

1.15--1.25--1.26 H's of the methyls in position 2 1.75--2 H of the cyclopropane 4.1 7-4.9 H of the

5.75-6.2 6.6-6.7 H of the

H of the

6.9-7.5 H aromatics Example W: 1 Fl cis 3(2,2-dibromovinyl) 2,2-dimethyl cyclopropane carboxylate of RS[2,2-dichloro 2-fluoro 1 (3-phenoxyphenyl)] ethyl A solution containing 1.2 g of 1 RS 2,2-dichloro 2-fluoro 1-(3-phenoxyphenyl) ethan-1 -ol, 40 cm3 of benzene, and 1.8 g of 1 R cis 3(2,2-dibromovinyl) 2,2-dimethyl cyclopropane carboxylic acid chloride is cooled to 00C/50C. 0.7 cm3 of pyridine is added, and the temperature is allowed to rise to ambient with agitation for 17 hours.After pouring on to an iced solution 0.1 N of hydrochloric acid, and decanting, the benzene phase is washed with water, dried and evaporated to dryness under reduced pressure. 2.9 g of product is obtained which is chromatographed on silica, eluting with a mixture of hexane-ethyl acetate 8-2. In this way 1.9 g of the product sought is obtained.

NMR CDCI3 p.p.m.

1.18-1.26-1.34 H of the methyls in position 2 2-2.05 H of the cyclopropane

6--6.2 6.3 H of the CO2 CH 6.6-6.8 ethylene H 6.9 to 7.5 H aromatics Example 10:1 R cis 3(2,2-dibromovinyl) 2,2-dimethyl cyclopropane carboxylate of RS[2-fluoro 1 (3-phenoxyphenyl)] ethyl By operating as in Example 9, starting with 1.2 g of RS 2-fluoro 1 (3-phenoxyphenyl) ethan-1-ol and with 2.5 g of 1 R cis 3(2,2-dibromovinyl) 2,2-dimethyl cyclopropane carboxylic acid chloride, 1.7 g of the product sought is obtained.

NMR CDCI3 p.p.m.

1.1 5 and 1.27 H of the methyls in position 2 1.83-2.08 H of the cyclopropyl

4.13--4.22 4.95 J 5.7-6.25 H of the CH2F H of the CO2CH 6.6-6.9 H of the

6.8-7.5 H aromatics Example 11::1 R cis 3-[dihydro 2-oxo 3-(2H-thienylidene)-methyl] 2,2-dimethyl cyclopropane carboxylate of RS[2-chloro 1 -(3-phenoxyphenyl)]ethyl Preparation of the chloride of the acid A mixture of 5 g of 1 R cis 3-[dihydro 2-oxo 3-(2H-thienylidene) methyl]cyclopropane 1-carboxylic acid, 50 cm3 of petroleum ether and 10 cm3 of thionyl chloride is taken to reflux for 4 hours, then concentrated to dryness, taken up with benzene and again concentrated to dryness.

Esterification 50 cm3 of benzene is added to the above chloride of the acid, cooled to +50C and 6.5 g of 1 RS 2 chloro 1-(3-phenoxyphenyl) ethan-1-ol in 60 cm3 of benzene is added. After agitation there is introduced over 30 minutes at +50C, 7.3 cm3 of pyridine in 20 cm3 of benzene. The whole is agitated for 16 hours at 200 C, poured into water, then decanted. The organic phase is washed with 0.1 N hydrochloric acid and then with water, dried and concentrated to dryness. The residue is chromatographed on silica eluting with a mixture of cyclohexane and ethyl acetate (75-25) and 9.3 g of the expected product is obtained.

nD20=1.583 αD=+25.5 +1 (c=1% CHCl3) Example 12:1H cis 3-(2,2-dibromoethenyl) 2,2-dimethyl cyclo-propane carboxylate of RS and of S[2-chloro 1-(3-phenoxyphenyl)] ethyl By operating in a manner similar to that described in Example 1 starting with 5.05 g of 1 R cis 3-(2,2-dibromoethenyl) 2,2-dimethyl cyclopropane carboxylic acid and with 4.2 g of 1 RS 2-chloro 1 (3-phenoxyphenyl) ethan-1-ol; after chromatographing on silica, eluting with a mixture of petroleum ether diisopropyl ether (9-1), 6.1 g of product is obtained which is then recrystallised from petroleum ether. 1.9 g of S isomer is isoiated, M.Pt.=760C ctD=+67 +1 .5 (c=1% CHCl3) The mother liquors, evaporated to dryness, provide 3.6 g of (RS) isomer.

αD= -260 1.5 (c=1% CHCI3) Example 13: (1 R cis AZ), 2,2-dimethyl 3-(2-methoxycarbonylethenyl) cyclopropane carboxylate of RS [2-chloro 1-(3-phenoxyphenyl)] ethyl By operating in a manner similar to that described for Example 1, starting with 1.8 g of (1 R cis AZ) 2,2-dimethyl 3-(2-methoxy carbonylethenyl) cyclopropane carboxylic acid and with 1.5 g of alcohol, 1.8 g of the expected ester is obtained.

Analysis: C24 H25 Cl 05 (428.912) Calculated: C% 67.2 H% 5.9 Cl% 8.3 Found: C% 67.0 H% 5.9 Cl% 8.8 Example 14(1 R cis AZ) 2,2-dimethyl 3-(2-methoxycarbonylethenyl) cyclopropane carboxylate of RS[2-fluoro 1 -(3-phenoxyphenyl)]ethyl By operating in a manner similar to that described for Example 2, starting with 1.98 g of (1R cis, AZ) 2,2-dimethyl 3-(2-methoxycarbonylethenyl) cyclopropane carboxylic acid and with 1.5 g of alcohol, 2.5 g of expected ester is obtained.

Analysis: C24H25F 05(412.457) Calculated: C% 70.0 H% 6.1 F% 4.6 Found: C% 69.7 H% 6.1 F% 4.8 Example 15(1 R cis) 3-(2,2-dibromoethenyl) 2,2-dimethyl cyclopropane carboxylate of Rand S [2,bromo 1 -(3-phenoxyphenyl)] ethyl By operating in a manner similar to that described in Example 3, utilising at the start 6.3 g of (1 Fl cis) 3-(2,2-dibromoethenyl) 2,2-dimethyl cyclopropane carboxylic acid chloride and 5.86 g of alcohol, and by operating in the presence of pyridine in benzene, after crystallisation from petroleum ether, 1.9 g of the S isomer of the expected alcohol is obtained. M.Pt.=760C D=+66.5 + 1.5 (c=1% CHCl3) 5.25 g of the expected R isomer is obtained =l 80110 (c=1.5% CHCl3) n21=1.593 (evaporation to dryness of the mother liquors) Example 16:: (1R cis) 3-[dihydro 2-oxo 3-(2H)-thienylidene methyl] 2,2-dimethyl cyclopropane carboxylate of (RS) [2-bromo 1 -(3-phenoxyphenyl)]ethyl By operating in a manner similar to that described in Example 11, using at the start 5 g of acid and 7.6 g of 1 RS 2-bromo 1 -(3-phenoxyphenyl) ethan-1 -ol, 10.3 g of the expected product is obtained which is purified by chromatography on silica eluting with a mixture of benzene and ethyl acetate (82).

αD=+24.5 -1.5 (c=0.8% CHCl3) Example 17: 1 R trans 3-(2,2-dimethylethenyl) 2,2-dimethyl cyclopropane carboxylate of (RS) [2bromo 1-(3-phenoxyphenyl)]ethyl By operating in a manner similar to that described in Example 3, utilising at the start 5.6 g of 1 R trans 3-(2,2-dimethylethenyl) 2,2-dimethyl cyclopropane carboxylic acid chloride and 8.8 g of alcohol, operating in benzene in the presence of pyridine, 6.15 g of the expected product is obtained.

nD23=1.554 Analysis: C24H27Br 03 (443.38) Calculated: C% 65.0 H% 6.13 Br% 18.02 Found: C% 64.9 H% 6.2 Br% 17.8 Example 18: (1 R cis AZ) 2,2-dimethyl 3-(2-methoxycarbonylethenyl) cyclopropane carboxylate of (RS) [2-bromo 1 -(3-phenoxyphenyl)]ethyl By operating in a manner similar to that described in Example 3 utilising at the start 0.99 g of (1 R cis AZ) 2,2-dimethyl 3-(2-methoxycarbonylethenyl) cyclopropane carboxylic acid and 1 g of alcohol, 1.33 g of the expected ester is obtained.

Analysis: C24H25Br 05 (473.368) Calculated: C% 61.15 H% 5.3 Br 16.95 Found: C% 60.8 H% 5.4 Br 17.00 Example 19:1 R trans 2,2-dimethyl 3-(2,2-difluoroethenyl) cyclopropane carboxylate of (RS) [2fluoro 2-chloro 1 -(3-phenoxyphenyl)]ethyl By operating in a manner similar to that described in Example 8 utilising at the start 0.86 g of 1 R trans 2,2-dimethyi 3-(2,2-difluoroethenyl) cyclopropane carboxylic acid and 1 g of alcohol, 1.5 g of the expected ester is obtained.

Analysis: C22H20CI F3 O3 (424.846) Calculated: C% 62.2 H% 4.75 Cl% 8.3 F% 13.4 Found: C% 62.5 H% 4.8 Cl% 8.3 F% 13.6 Example 20:1 R cis 2,2-dimethyl 3-(2,2-dibromoethenyl) cyclopropane carboxylate of (RS) [2,2,2-trichloro 1-(3-phenoxyphenyl)]ethyl By operating in a manner similar to that described in Example 15, utilising at the start 10 g of acid which is transformed into the chloride of the acid and 3.8 g of 1 RS[2,2,2-trichloro 1-(3phenoxyphenyl)] ethan-1-ol, 5.97 g of the expected ester is obtained.

Analysis: C22 H19 Br2 Cl3 03 (597,571) Calculated: C% 44.2 H% 3.2 Br% 26.7 Cl% 17.8 Found: C% 44.4 H% 3.3 Br% 26.3 CI% 17.4 Example 21:1 R trans 2,2-dimethyl 3-cyclopentylidene methyl cyclopropane carboxylate of (RS) [2,2,2-trichloro 1-(3-phenoxy phenyl)]ethyl 21.6 g of 1 R trans 2,2-dimethyl 3-cyclopentylidene methyl cyclopropane carboxylate of sodium is put into suspension in 75 cm3 of benzene and 60.5 cm3 of pyridine. 32.5 cm3 of oxalyl chloride is added slowly at a temperature of 1 20C maximum, maintained for 15 minutes at +5, +1 00C, then 30 cm3 of benzene is added the whole is maintained for 3 hours at 200 C. After filtering, the filtrate is concentrated to dryness, 30 cm3 of benzene is added to the residue which is then concentrated again.

Esterification The operation is carried out as indicated in Example 20, utilising at the start 3.96 g of alcohol.

After chromatography on silica, eluting with a mixture of cyclohexane and ethyl acetate (9-1), then with petroleum ether and diethyl ether (95-5), 2.57 g of the expected ester is obtained.

Analysis: C26 H27 Cl3 03 (493.862) Calculated: C% 63.2 H% 5.5 CI% 21.5 Found: C% 63.5 H% 5.5 CI% 21.6 Example 22: 1 R trans 2,2-dimethyl 3-cyclopentylidene methyl cyclopropane carboxylate of (RS) [2,2,2-tribromo 1-(3-phenoxyphenyl) ethyl By operating in a manner similar to that described in Example 21, utilising at the start 9.115 g of 1 RS 2,2,2-tribromo 1 -(3-phenoxyphenyl) ethan-1 -ol, 3.76 of the expected ester is obtained.

Analysis: C26 H27 Br3 03 (627.23) Calculated: C% 49.8 H% 4.3 Br% 38.2 Found: C% 50.2 H% 4.6 Br% 38.4 Example 23: 1 R cis 2,2-dimethyl 3-(2,2-dibromoethenyl) cyclopropane carboxylate of (RS) [2,2,2-tribromo 1 -(3-phenoxyphenyl)] ethyl By operating in a manner similar to that described in Example 15, utilising at the start 10 g of acid which is converted into the chloride of the acid and 4.51 g of 1 RS 2,2,2-tribromo 1 -(3-phenoxyphenyl) ethan-1 -ol, 4.71 g of the expected ester is obtained.

NMR Spectrum CDCI3 p.p.m.

1.21-1.28-1.31 H's of the methyls in position 2 2.06 H of the cyclopropane 6.4 and 6.43 H in position a of the -COO- 6.72-6.88 H of

7-7.67 H aromatics.

Example 24(1 R cis AZ) 2,2-dimethyl 3-(2-methoxycarbonyl ethenyl) cyclopropane carboxylate of (RS) [2,2-dichloro 1 -(3-phenoxyphenyl)]ethyl By operating in a manner similar to that described in Example 13, utilising at the start 1 g of the acid and 0.89 g of 1 RS 2,2-dichloro 1-(3-phenoxyphenyl) ethan-1 -ol, 1 g of the expected ester is obtained.

NMR Spectrum: CDCI3 p.p.m.

1.22-1.28-1.32 H of the CH3 in position 2 2-2.14 H in position a to the --COO--.

3.13 to 3.43 H of the cyclopropane 2.7-2.27 H of the -COOCH3 5.73 to 6.08 ethylene H in position a to the -COO-CH3 and H of the -CHCl2 6.33 to 6.72 H in position p to the OOCH3 6.92 to 7.5 Aromatic H Example 25: 1 R cis 3-[dihydro 2-oxo 3-(2H-thienylidene) methyl] 2,2-dimethyl cyclopropane carboxylate of (RS) [2,2-dichloro 1 -(3-phenoxyphenyl)] ethyl By operating in a manner similar to that described in Example 11, utilising at the start 5 g of the acid and 7.3 g of 1 RS 2,2-dichloro 1-(3-phenoxyphenyl) ethan-1-ol, 10 g of the expected ester is obtained.

αD=+27.5 +1.5 (c=1% CHCl3) Analysis: C25 H24 Cl2 04 S (491.422) Calculated: C% 61.09 H% 4.92 Cl% 14.42 S% 6.52 Found: C% 61.2 H% 5.0 Cl% 14.4 S% 6.4 Example 26: 1 R cis 2,2-dimethyl 3-(2,2-dibromoethenyl) cyclopropane carboxylate of (RS) [2,2dichloro 1 -(3-phenoxyphenyl)]ethyl By operating in a manner similar to that described in Example 9, utilising at the start 6.3 g of a chloride of the acid and 6.52 g of 1 RS 2,2-dichloro 1-(3-phenoxyphenyl) ethan-1-ol 9 g of the expected product is obtained.

nDss ss =1.5915. aD=1 1.5 ~1 (c=0.5% CHCl3) Analysis: C22 H20 Br2 Cl2 03 (563.13) Calculated: C% 46.92 H% 3.57 Br% 28.38 Cl% 12.59 Found: C% 47.0 H% 3.6 Br% 28.2 Cl% 13.0 Example 27: 1 R trans 2,2-dimethyl 3-(2-methyl 1-propenyl) cyclopropane carboxylate of (RS) [2,2-dichloro 1-(3-phenoxyphenyl)]ethyl By operating in a manner similar to that described in Example 26, utilising at the start 4.04 g of the chloride of 1 R trans 2,2-dimethyl 3-(2-methyl 1 -propenyl) cyclopropane carboxylic acid and 6.52 g of alcohol, 6.25 g of the expected ester is obtained.

nD8 6 = 1.556 α,=+1 +1 (c=0.9% CHCl3) Analysis: C24 H26 Cl2 03 (433.36) Calculated: C% 66.51 H% 6.04 CI% 16.36 Found: C% 66.2 H% 6.1 Cl% 16.5 Preparation 1:1 RS 2-chloro 1 -(3-phenoxyphenyl) ethan-1 -ol Stage A: 3-phenoxy chloro acetophenone A solution containing 3.6 g of chlorine in 50 cm3 of acetic acid is introduced at 21 C over 30 minutes into a solution containing 10.5 g of 3-phenoxyacetophenone in 50 cm3 of acetic acid. The mixture is left for 30 minutes at ambient temperature, then taken to dryness under reduced pressure.It is taken up with ether and washed with a saturated solution of sodium bicarbonate, the organic phase is dried and taken to dryness, 11.5 g of product is obtained which is chromatographed on silica, eluting with a mixture of benzene and petroleum ether (B.Pt. 600 800C) so obtaining 8.1 g of the product sought.

Stage B: 1 RS 2-chloro 1 (3-phenoxyphenyl) ethan-1 -ol 3.7 g of sodium hydroboride is added over 30 minutes at 1 00C to a solution containing 1 1.8 g of the product prepared in Stage A in 70 cm3 of methanol. This is maintained under agitation for 30 minutes at 100C and then 4.5 cm3 of acetic acid is added.After taking to dryness, taking up the dry extract with methylene chloride, washing with water, extracting again with ethylene chloride, drying and taking to dryness under reduced pressure, 8.3 g of the product sought is obtained nD23=1.5855 Preparation 2:1 RS 2-bromo 1 (3-phenoxyphenyl) ethan-1 -ol Stage A: 3-phenoxy bromo acetophenone 16 g of bromine is added drop by drop to a solution containing 21.2 g of 3 phenoxyacetophenone, 120 cm3 of dioxan and 60 cm3 of diethyl ether After maintaining for 40 minutes under agitation, taking to dryness, taking up with 200 cm3 of ethyl acetate, washing with water, drying, and taking to dryness under reduced pressure at 500C, 29 g of a product is obtained which is chromatographed on silica eluting with a mixture of benzene and petroleum ether (B.Pt.

600N700C) (9-1). 21.5 g of the product sought is obtained. n2' 3=1.613 Stage B: 1 RS 2-bromo 1 (3-phenoxyphenyl) ethan-1 -ol 14.6 g of the product prepared in stage A is introduced under agitation at 200C over 30 minutes into 80 cm3 of methanol. Then 3.8 g of sodium borohydride is added and after keeping for 30 minutes at 200C acetic acid is added to bring it to pH2, and the whole is then poured into 400 cm3 of water.

After extracting with diethyl ether, the organic phase is dried, taken to dryness at 500C under reduced pressure and 11 g of the product sought is obtained. n25=1.605 Preparation 3:1 RS 2,2-dichloro 2-fluoro 1 (3-phenoxyphenyl) ethan-1 -ol A: Condensation 30 cm3 of 2,2-dichloro 2-fluoro methane, condensed to -400C under nitrogen, 40 g of 3phenoxybenzyl aldehyde and 250 cm3 of anhydrous diethyl ether are cooled to --600C. Then 43 g of potassium tert-butylate dissolved in 200 cm3 of tetrahydrofuran and 1 50 cm3 of tert-butyl alcohol are introduced. After agitating for 17 hours at -400C and pouring on monosodium phosphate, extracting with methylene chloride, washing with water, drying and evaporating to dryness 59 g of the crude product sought is obtained.

B: Blocking with dehydropyran 34 g of the product prepared in stage A above, 300 cm3 of benzene, 18 cm3 of dihydropyran and 100 mg of paratoluene sulphonic acid are agitated at ambient temperature for 45 minutes. After evaporating to dryness under reduced pressure, 50 g of a product is obtained which is chromatographed on silica, eluting with a mixture of benzene and ethyl acetate (95-5), and in this way 1 6.4 g of the expected blocked product is obtained.

C: Unblocking i 6 g of the product prepared at Stage B is introduced into 200 cm3 of methanol and 100 mg of paratoluene sulphonic acid. The mixture is agitated at ambient temperature, then heated to 400C for 2 hours. After diluting with water, extracting with methylene chloride, washing the organic phase with water, drying and evaporating to dryness under reduced pressure, and chromatographing on silica with a mixture of hexane and ethyl acetate (8-2), 11 A g of 1 RS 2,2-dichloro 2-fluoro 1-(3-phenoxyphenyl) ethan-1-ol is recovered.

NMR CDCI3 p.p.m.

2.95-3 H of the mobile OH 5-5.13 Hof

6.9 to 7.6 Aromatic H Preparation 4:1 RS 2RS 2-fluoro 2-chloro-1 (3-phenoxyphenyl) ethan-1-ol A mixture of 4.2 g of 1 RS-2,2-dichloro 2-fluoro 1 (3-phenoxyphenyl) ethan-1 -ol as obtained in Preparation 3, 10.2 g of tributyl tin hydride and 50 cm3 of benzene are heated to reflux for 10 hours.

After allowing this to cool, 100 cm3 of diethyl ether is added and agitated strongly with an aqueous solution at 1 00 g per litre of potassium fluoride. After filtering, decanting the aqueous phase and washing the organic phase several times with water, drying and evaporating to dryness under reduced pressure, chromatographing on silica, eluting with a mixture of hexane and ethyl acetate, (8-2), 2.4 g of the product sought is obtained.

NMR CDCI3 p.p.m.

5.75.75 6.5-6.6 H of the

4.7to5 Hofthe

2.65-2.7-2.8-2.9H of the OH 6.8 to 7.5 Aromatic H Preparation 5:1 RS 2-fluoro 1 (3-phenoxyphenyl) ethan-1 -ol 10.5 g of 1 RS 2,2-dichloro 2-fluoro 1 (3-phenoxyphenyl) ethan-1 -ol as obtained in Preparation 3, 200 cm3 of xylene and 51 g of tributyl tin hydride are heated to reflux for 54 hours, then the xylene is evaporated.After taking up with diethyl ether and agitating with an aqueous solution of potassium fluoride at 100 g/l, filtering, washing the filtrate with water, drying and evaporating to dryness under reduced pressure, the product obtained is chromatographed on silica, eluting with a mixture of hexane and ethyl acetate (8-2), and 7.4 g of the product sought is obtained.

NMR CDCI3 p.p.m.

2.52.55 HoftheOH 3.9 to 4.2 H of the CH OH 4.7 to 5.25 H of the CH2F 6.8 to 7.5 Aromatic H Preparation 6:1 RS 2,2,2-trichloro 1 -(3-phenoxyphenyl) ethan-1 -ol 4.95 g of m-phenoxybenzyl aldehyde is dissolved in 40 cm3 of dimethoxyethane, 4 cm3 of chloroform is added, the whole is cooled to -350C and over 1 5 minutes a solution of 3.36 g of potassium tert-butylate in 1 5 cm3 of tert-butanol and 1 5 cm3 of dimethoxyethane are added.Agitation is maintained for 55 minutes, then after pouring into iced water containing 35 m-moles of hydrochloric acid, agitating, extracting with ether, washing the ether phase with water, drying and evaporating the solvent, the residue is chromatographed on silica, eluting with a mixture of cyclohexane and ethyl acetate (8-2) and 7.5 g of the product sought is obtained.

Analysis: C14 H,1 Cl3 02(317.602) Calculated: C% 52.9 H% 3.5 CI% 33.5 Found: C% 52.9 H% 3.6 Cl% 33.5 Preparation 7:1 RS 2,2,2-tribromo 1 -(3-phenoxyphenyl)ethan-1 -ol By operating in a manner similar to that described for Preparation 6, utilising 9.9 g of mphenoxybenzyl aldehyde and 8.7 cm3 of bromoform, after purification by chromatographing on silica, eluting with a mixture of cyclohexane and ethyl acetate (85-1 5), 24.25 g of the expected product is obtained which is re-crystallised from a mixture of petroleum ether and diisopropyl ether. 1 9.4 g of the expected product is obtained.M.Pt.=700C Analysis: C14 H1, Br3 O2 (450.96) Calculated: C% 37.3 H% 2.4 3r% 53.1 Found: C% 37.2 H% 2.7 Br% 52.8 Preparation 8:1 RS 2,2-dichloro 1-(3-phenoxyphenyl) ethan-1-ol Stage A: 2,2-dichloro 1-(3-phenoxyphenyl) ethan-1-ol 21.2 g of methylene chloride, 200 cm3 of tetrahydrofuran and 100 cm3 of diethyl ether are mixed together, then at --1000C over 30 minutes and under agitation, 123 cm3 of a solution of 1 5 g/1 00 g of butyllithium in hexane is introduced. The mixture is agitated for 30 minutes, then 24.2 g of ethyl 3phenoxybenzoate in 100 cm3 of anhydrous ether is added.After leaving under agitation for 3 hours at -1 000C, 1 50 cm3 of 2N hydrochloric acid is introduced at 600 C. The temperature is allowed to rise to OOC, then by decanting extracting with diethyl ether, drying and evaporating the solvent, and rectifying the residue 18 g of the expected product is obtained. (B.Pt0.1=1 42-1 440C) no4=1.610 Stage B: 1 RS 2,2-dichloro 1-(3-phenoxyphenyl) ethan-1 -ol 1 8 g of 3-phenoxy o,w-dichloroacetophenone and 75 cm3 of ethanol are mixed together, then at 200C, 7 g of sodium borohydride is added and the whole is maintained under agitation for 1 hour at 200 C. 1 cm3 of acetic acid is then added, and after pouring int6 water, extracting with ether, washing the organic phase with water, drying it, evaporating the solvent, taking up again with ether, treating with activated charcoal, filtering, evaporating the solvent and drying, 13 g of the expected product is obtained. nod4=1.5950 Analysis: C,4 H,2 Cl2 02(283.15) Calculated:C% 59.38 H% 4.27 Cl% 25.04 Found: C% 59.4 H% 4.3 Cl% 24.9 Example 28: Preparation of a soluble concentrate A homogenous mixture is made of: Product of Example 1 0.25 g piperonyl butoxide 1 g Tween 80 0.25 g Topanol A 0.1 g Water 98.4 g Example 29: Preparation of an emulsifiable concentrate There are mixed intimately: Product of Example 1 0.015 g piperonyl butoxide 0.5 g TopanolA 0.1 g Xylene 99.385 g Example 30: Preparation of an emulsifiable concentrate A homogenous mixture is made of: Product of Example 1 1.5 g Tween 80 20 g Topanol A 0.1 g Xylene 78.4g Example 31:Preparation of a fumigating composition The following are mixed together homogenously: Product of Example 1 0.25 g Tabu powder 25 g cedar leaf powder 40 g pine wood powder 33.75 g brilliant green 0.5 g p-nitrophenol 0.5 g Study of the activity of the compounds according to the invention on parasites Study of the activity of the compound of Example 2 by topical application on house-flies (Musca domestica) The insects tested are female house-flies aged from 4 to 5 days on which one /ti of acetone solution of the compound is applied topically on the dorsal thorax of the insect by means of an Arnold micromanipulator and at the rate of 50 individuals per dose tested.

Checks on mortality are carried out 24 hours after treatment. The experimental results expressed in LD50 give a dose of 68.46 nanogrammes per individual as necessary to kill 50% of the population.

Conclusion The compound of Example 2 is endowed with a useful insecticidal activity on house-flies.

Study of the lethal activity of the compound of example 2 by tarsal contact on german cockroaches (blattella germanica) The male german cockroach insects stay for one hour on the glass bottom of a petri dish previously treated with an acetone solution of the compound under test. Checks of mortality are carried out 1 hour, 24 hours and 3 days after the beginning of the experiment, the insects being transferred after their contact with the poison into the normal growing conditions. The experimental results expressed in LC50 give a concentration of 2.09 mg/m2 as necessary to kill by tarsal contact 50% of the population.

Conclusion The compound of Example 2 is endowed with a useful insecticidal activity against german cockroaches Study of the knock down activity of the compound of example 2 by atomisation on house-flies The insects utilised are females aged 4 days. The test is carried out by atomising directly into a Kears and March chamber a solution of the compound under test in a mixture of equal volumes of acetone and of petroleum solvent (Isopar L).

50 insects per dose are utilised and checks on the knock down are made every minute up to 1 5 minutes then the KT50 or the time necessary to knock 50% of the insects down is determined by the usual methods.

The knock down tests give for the compound of Example 2 a KT50 of 9.86 mn.

Conclusion The compound of Example 2 is endowed with a good shock activity on house-flies.

Study of the acaricidal activity of the compound of example 2 on the acaridae tetranychus urticae Bean plants comprising two cotyledon leaves were treated at different doses. After drying the atomisation, the leaves were infested at the rate of 50 female acaridae per dose. The number of deaths was counted after 24 hours and the results obtained enabled the LC50 to be calculated. With the compound of Example 2 the LC50 is 1,732.7 mg/hl.

Conclusion The compound of Example 2 is endowed with a good acaricidal activity against Tetranychus urticae.

Claims

1. Compounds of general formula I:

in which Ar represents an optionally substituted aromatic or heteroaromatic radical; X1, X2 and X3, which may be the same or different, each represents a hydrogen atom or a halogen atom, with the proviso that one at least of the radicals X1, X2 and X3 represents a halogen atom; and B represents: a) an alkyl radical containing from 1 to 1 8 carbon atoms; b) a radical of formula:

in which either Za and Z2 each represents a methyl radical or ZX represents a hydrogen atom and either2 represents a radical of formula::

(in which R3 represents a hydrogen or a halogen atom and either R, and R2, which may be the same or different, each represents a halogen atom or an alkyl radical containing from 1 to 8 carbon atoms, or R, and R2, together with the carbon atom to which they are attached, represent a cycloalkyl radical containing from 3 to 6 carbon atoms or a radical of formula:

in which the ketone is in position a with respect to the double bond and in which X represents an oxygen or a sulphur atom or an -NH- radical) orZ2 represents a radical of formula::

(in which R4, R5, Rs and R7, which may be the same or different, each represents a halogen atom), orZ2 represents a radical of formula:

of E or Z geometry [in which R8 represents a hydrogen, chlorine, fluorine or bromine atom and R represents a linear, branched or cyclic hydrocarbyl radical, which may be saturated or unsaturated and which contains from 1 to 1 8 carbon atoms (optionally substituted by one or more functional groups, which may be the same or different); an aryl group containing from 6 to 14 carbon atoms (optionally substituted by one or more functional groups, which may be the same or different) or a heterocyclic radical (optionally substituted by one or more functional groups, which may be the same or different)]; c) a radical of formula:

(in which Y and Y', which may be in any position on the benzene nucleus and which may be the same or different, each represents a hydrogen or halogen atom, an alkyl radical containing from 1 to 8 carbon atoms or an alkoxy radical containing from 1 to 8 carbon atoms); in all their possible isomeric forms as well as the mixtures of the isomers;; with the exception of compounds of general formula I in which Xr, X2 and X3 each represents a fluorine atom and with the exception of 2-chloro-1 -(3-phenoxyphenyl)-ethyl 3-(2-methyl-1 -propenyl)- 2,2-dimethyl-cyclopropane- 1 -carboxylate.

2. Compounds as claimed in claim 1 in which B represents a radical of formula:

[in which Z represents a hydrogen atom and Z2 represents a radical of formula:

(in which Fl1, R2 and R3 are defined as in claim 1)].

3. Compounds as claimed in claim 2, in which R, and R2 are the same and each represents a halogen atom and R3 represents a hydrogen atom.

4. Compounds as claimed in any preceding claim in which A, represents a radical of formula:

(in which Y1, Y" Y2 and Y2 which may be in any position on their respective nuclei each represents a hydrogen atom, a halogen atom or a methyl radical and A represents an oxygen atom, a methylene group, a carbonyl group, a sulphur atom, a sulphoxide group or a sulphone group).

5. Compounds as claimed in any preceding claim in which X, and X2 each represents a hydrogen atom and X3 represents a halogen atom.

6. Compounds as claimed in claim 1 as herein specificaliy disclosed in any one of Examples 1 to 27.

7. A process for the preparation of compounds as claimed in claim 1 which comprises reacting an acid of formula II, BCO2H (II) (in which B is defined as in claim 1 ) or a functional derivative of this acid, with an alcohol of formula Ill,

(in which Ar, X1, X2 and X3 are as defined in claim 1), or a functional derivative of this alcohol.

8. A process for the preparation of compounds as claimed in claim 4, which comprises reacting an acid of formula II as defined in claim 7 or a functional derivative of this acid, with an alcohol of formula 111A'

(in which Y,, Y,, Y2,Y2, and A are as defined in claim 4 and X1, X2 and X3 are as defined in claim 1), or a functional derivative of this alcohol.

9. A process for the preparation of compounds as claimed in claim 1 substantially as herein described.

1 0. A process for the preparation of compounds as claimed in claim 1 substantially as herein described in any one of Examples 1 to 27.

11. Compounds as claimed in claim 1 whenever prepared by a process as claimed in any one of claims 7 to 10.

12. Compounds as claimed in any one of claims 1 to 6 for use in combating pests of warmblooded animals, vegetation and buildings.

1 3. Compositions for use in combating pests of warm-blooded animals, vegetation and buildings comprising as active principle at least one compound as defined in any one of claims 1 to 6.

14. Insecticidal compositions comprising, as active principle, at least one compound as defined in any one of claims 1 to 6 in association with a carrier.

1 5. Acaricidal compositions comprising, as active principle, at least one compound as defined in any one of claims 1 to 6 in association with a carrier.

1 6. Feedstuff compositions comprising, as active principle, at least one compound as defined in any one of claims 1 to 6, in association with a nutrient material.

1 7. Pharmaceutical compositions comprising as active principle, at least one compound as claimed in any one of claims 1 to 6 in association with a pharmaceutical carrier or excipient.

1 8. Compositions endowed with insecticidal, acaricidal, fungicidal or nematocidal activity, comprising at least one compound of formula I as claimed in claim 1, and at least one pyrethrinoid ester selected from esters of allethrolones, 3, 4, 5, 6-tetrahydrophthalimido-methyl alcohol, 5-benzyl 3-furyl-methyl alcohol, 3-phenoxybenzyl alcohol and sx-cyano-3-phenoxybenzyl alcohol with chrysanthemic acids, esters of 5-benzyl-3-furyl-methyl alcohol with 2,2-dimethyl-3-(2-oxo-3-tetra- hydrothiophenylidenemethyl)-cyclopropane-1 -carboxylic acids, esters of 3-phenoxybenzyl alcohol and cr-cyano-3-phenoxybenzyl alcohol with 2,2-dimethyl-3-(2,2,-dichlorovinyl)-cyclopropane- 1 -carboxylic acids, esters of -cyano-3-phenoxybenzylic alcohols with 2,2-dimethyl-3-(2,2-dibromovinyl) cyclopropane-1-carboxylic acids, esters of 3-phenoxybenzyl alcohol with 2-parachlorophenyl-2isopropyl-acetic acids, and esters of allethrolones, 3, 4, 5, 6-tetrahydrophthalimidomethyl alcohol, 5benzyl-3-furyl-methyl alcohol, 3-phenoxybenzyl alcohol and c-cyano-3-phenoxybenzyl alcohol with 2,2-dimethyl-3-(1,2,2,2-tetrahaloethyl)-cyclopropane-1-carboxylic acids (in which "halo" represents a fluorine, chlorine or bromine atom), it being understood that the compound of formula I can exist in any of the possible stereoisomeric forms, as can also the acid and alcohol moieties of the above pyrethrinoid esters.

1 9. Compositions as claimed in any one of claims 13 to 1 8 substantially as herein described.

20. Compositions substantially as herein described in any one of Examples 28 to 31.

21. A method of combating insect, acarida, fungus or nematode pests which comprise applying to a site infested with or susceptible to infestation by the said pests an effective amount of a compound as claimed in claim 1.

22. Compounds of general formula III

(wherein Ar, X" X2 and X3 are as defined in claim 1, it being understood that X1, X2 and X3 cannot each simultaneously represent a fluorine atom) and functional derivatives thereof.

23. Compounds of general formula IIIA

(wherein X1, X2, X3 are as defined in claim 1, it being understood that X1, X2 and X3 cannot each simultaneously represent a fluorine atom and Y1, Y1,, Y2, Y2 and A are as defined in claim 4) and functional derivatives thereof.

24. A process for the preparation of compounds as claimed in claim 21 or claim 22 substantially as herein described.

25. Each and every novel method, process, compound and composition herein disclosed.