AU608372B2 - Cyclopropane carboxylic acid esters and alcohol intermediates therefor - Google Patents

Description

I Z7 7 4r 9~s 6L~ S F Ref: 72685 FORM COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952 COMPLETE SPECIFICATION This document contains the amendments made under Section 49 and is correct for printing.

(ORIGINAL)

FOR OFFICE USE: Class Int Class Complete Specification Lodged: Accepted: o0o Published: 'Priority: S Related Art: S"Name and Address of Applicant: Adrrre, S 0 0 Address for Service: o Oo Ciba-Geigy AG Klybeckstrasse 141 4002 Basle

SWITZERLAND

Spruson Ferguson, Patent Attorneys Level 33 St Martins Tower, 31 Market Street Sydney, New South Wales, 2000, Australia Complete Specification for the invention entitled: ICyclopropane Carboxylic Acid Esters and Alcohol Intermediates Therefor".

The following statement is a full description of this invention, including the best method of performing it known to me/us 5845/3 gAI i

L

1- 'Y

I-

5-16721 /1+2 ,,Cyclopropane Carboxylic Acid Esters and Alcohol Intermediates Therefor".

Abstract Novel cyclopropanecarboxylic acid esters of formula '066., COOrH\ 0- 0 00. R 2 00:wherein 0 0 each of R, and R 2 is F, Cl or Br and, if R, is Cl, R 2 may also be CF 3 Process for the preparation of these compounds, and compositions containing them and their use in pest control.

0 0 0 0 00S

'A-

5-16721/1+2 Cyclopropane Carboxylic Acid Esters and Alcohol Intermediate Therefor The present invention relates to novel insecticidally active cyclopropanecarboxylic acid esters, a process for their preparation ind their use in pest control.

The cyclopropanecarboxylic acid esters according to the invention have the formula I 00 00 o 0 o 0 0 6000 0 00 0 0 0.1 0 0 0 R/ R2\ C 3

"CH

3

"F

0 000000 03 0 wherein each of R 1 and R2 is Cl, F or Br and, if R 1 is Cl, R 2 may also be CF 3 Preferred as an insecticide is the mixture of isomers 2,2-dimethyl-3cis-(2' ,2'-dichlorovinyl)-cyclopropane-1R-carboxylic acid 3-phenoxy-4fluoro-c(RS)-(2'-phenyl-ethynyl)-benzyl ester.

Especially preferred are the two diastereoisomers of that mixture: 2,2dimethyl-3-cis-(2' ,2'-dichlorovinyl)-cyclopropane-1R-carboxylic acid 3-phenoxy- 4 -fluoro-ct(+)-(2'-phenylethynyl)-benzyl ester and 2,2-dimethyl-3-cis-(2' ,2'-dichlorovinyl)-cyclopropane-1R-carboxvlic acid 3phenoxy-4-fluoro--c(-)-(2'-phenylethynyl)-benzyl ester.

~A~LI~44, 0 i;aaru*~Li. r -2- It is known from EP-A 190096 that the ester of formula Clg C=CH-CH-CH-COO H 0 Cl* C 3\CH 3 I I is suitable for protecting keratin-containing material against attack by keratin pests.

It is also known from EP-A 57384 that 4-fluoro-3-halophenoxy-benzyl esters of formula 0. o S° wherein o o:R is a radical that can be used in the acid component of pyrethroids, RI is hydrogen, cyano or an unsubstituted or halo-substituted radical selected from the series alkyl, alkenyl and alkynyl (each having up to 3 carbon atoms) and 0 is chlorine or bromine, are insecticidally active.

o o 0000 has now been found that the compounds of formula I, in addition to being insecticidally active, are better tolerated by fish than the com- 0 4 1 "o t pounds of the prior art.

The compounds of formula I can be prepared by reacting a 3-cis-1R-cyclopropanecarboxylic acid halide of formula II

R\

RC=CH-Cq--CH-COY

(II),

R2

H

3 C CH 3 wherein RI and R 2 are as defined for formula I and Y is halogen, with 3-phenoxy-4-fluoro-a-phenylethynyl-benzyl alcohol of formula III rr~i~- ri~r~ 3-

HO\H-<

HO- (III) H- F in the presence of a base.

The intermediate of formula III is novel and the present application relates to this intermediate also. It is prepared, for example, by reacting phenylacetylene with alkylmagnesium bromide and with 3-phenoxy-4fluorobenzaldehyde. The starting materials for this reaction stage are generally known.

o *The cyclopropanecarboxylic acid halides of formula II are also known from as the literature.

O0 0 0 0 o o 0 The compounds of formula I are suitable for controlling various types of pests in and on animals and plants. They can be used for controlling 0 oo insects, for example of the orders Lepidoptera, Coleoptera, Homoptera, O0 O e Heteroptera, Diptera, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera, and mites o.o and ticks of the order Acarina.

0 t o a 'The compounds of formula I are suitable especially for controlling plant-destructive insects, especially plant-destructive feeding insects, S in ornamentals and useful plants, especially in cotton and rice crops (for example against Nephotettix cincticeps, Spodoptera littoralis, Heliothis virescens, Chilo suppressalis and Laodelphax) and also vegetable and fruit crops (for example against Leptinotarsa decemlineata, Myzus persicae, Laspeyresia pomonella and Adoxophyes reticulana) and soil insects (for example Aulacophora femoralis, Chortophila brassicae, Diabrotica balteata, Pachnoda savigni and Scotia ypsilon).

-4- Compounds of formula I also exhibit a very favourable activity against flies, for example Musca domestica, and mosquito larvae.

The good pesticidal activity of the compounds according to the invention corresponds to a mortality of at least from 50 to 60 of the mentioned pests.

The acaricidal and insecticidal activity can be substantially broadened and adapted to prevailing circumstances by adding other insecticides and/or acaricides. Suitable additives are, for example, organophosphorus compounds; nitrophenols and derivatives thereof; formamidines'; ureas; other pyrethrin-like compounds and also carbamates and chlorinated hydroocarbons.

ao ,,.Compounds of formula I are also especially advantageously used in combio0 nation with compounds that exert a synergistic or reinforcing effect on pyrethroids. Examples of such compounds are, inter alia, piperonyl 00 0 o °obutoxide, propionyl ethers, propynyl oximes, propynyl carbamates and propynyl phosphonates, 2-(3,4-methylenedioxyphenoxy)-3,6,9-trioxaundecane 0 0o (sesamex or sosoxane), S,S,S-tributyl phosphorotrithionates and 1,2o *O methylenedioxy-4-(2-(octylsulfinyl)-propyl)-benzene.

00 0 The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in thT art of formulation, and are therefore formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

The formulations, i.e. the compositions, preparations or mixtures containing the compound (active ingredient) of formula I and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surfaceactive compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or .""'epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; 'or water.

The solid carriers used e.g. for dusts and dispersible powders are o a $o a "normally natural mineral fillers, such as calcite, talcum, kaolin, ro Omontmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly S dispersed absorbent polymers. Suitable granulated adsorptive carriers are S o porous types, for example pumice, broken brick, sepiolite or bentonite; Q;,,'and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or t44 organic nature can be used, e.g. especially dolomite or pulverised plant residues.

I: i Depending on the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties.

The term "surfactants" will also be understood as comprising mixtures of surfactants.

Both so-called water-soluble soaps and also water-soluble synthetic surface-active compounds are suitable anionic surfactants.

I

6 Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (Clo-C22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tall oil. Other suitable surfactants that may be mentioned are fatty acid methyltaurin salts.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

V C1 C CoO o ;Oq Ci~ C~r~ C V O O O 04d C ('C o 04

C

C CC o 'C 04 I O 40 Ci The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and generally contain a Cs-Ca 2 alkyl radical which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecylsulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde.

Also suitable are corresponding phosphates, e.g. salts of the phosphoric S acid ester of an adduct of p-nonylphenol with 4 to 14 moles of ethylene oxide, and phospholipids.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.

'snlC i i r 7 Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers,.polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

0 9 0 Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

ea~B 9. =o Cationic surfactants are preferably quaternary ammonium salts which 0 0 0 ocontain, as N-substituent, at least one Cs-C22alkyl radical and, as 0 0 0 S"further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of o ohalides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium o chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

surfactants customarily employed in the art of formulation are described, inter alia, in the following publications: a 4 0 4' "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood, New Jersey, 1979; Dr. Helmut Stache "Tensid Taschenbuch", Carl Hanser Verlag, Munich/Vienna 1981.

The pesticidal compositions usually contain 0.1 to 99 preferably 0.1 to 95 of a compound of formula I, 1 to 99.9 of a solid or liquid adjuvant, and 0 to 25 preferably 0.1 to 25 of a surfactant.

Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

grm~ C nrr~ I 8- The compositions may also contain further additives such as stabilisers, antifoams, viscosity regulators, binders and tackifiers as well as fertilisers or other active ingredients for -btaining special effects.

Examples: Preparation of the compounds of formulae I and III P.1 Preparation of 3-phenoxy-4-fluoro-a-phenylethynyl-benzyl alcohol II I II I HOH- -F (III), An ethylmagnesium bromide solution (prepared from 14.6 g of magnesium 'chips; 50.6 ml of ethyl bromide in 250 ml of tetrahydrofuran) is added "o °dropwise over a period of three hours at 0-5°C to a solution of 66 ml of 0 B phenylacetylene (0.61 mole) in 250 ml of tetrahydrofuran, and the solution is stirred for one hour. 108.1 g of 3-phenoxy-4-fluoro-benzaldehyde 0 04

S

0 oare then added dropwise to the solution over a period of 2 hours at 0-50° o 0* oand the reaction mixture is stirred for 14 hours at room temperature.

After the addition of ice, 100 ml of concentrated HC1 are added to the etee s...'reaction mixture at 5-7°C. The aqueous phase is separated off, extracted with ether and the combined organic phase is washed with brine and dried with sodium sulfate. After evaporation of the solvent, the residue is ,'purified by chromatography using silica gel and ethyl acetate/ hexane 1/3 to give the title compound in the form of an oil; refractive index n2 3 1.5971.

D

P.2 Preparation of 2,2-dimethyl-3-cis-(2' ,2'-dichlorovinyl)-cyclopropane-IR-carboxylic acid 3-phenoxy-4-fluoro-oU(RS)-(2 '-phenyl.ethynyl)-benzyl ester I t_ Ci \7 \F 2.8 ml of triethylamine (0.02 mole) are added at 0-5*C with stirring to 2.3 g of 2,2-dimethyl--3-cis-(2' ,2'-dichlorovinyl)-cyclopropane-lRcarboxylic acid chloride (0.01 mole), 4.8 g of 3-phenoxy-4-fluoro-a- %b.phenylethynyl-benzyl alcohol (0.015 mole) in 30 ml of toluene and 50 mg Sof 4-dimethylaminopyridine and the reaction mixture is maintained at 460-70%C for 7 hours. After evaporation of the solvent, the residue is dissolved in methylene chloride, the solution is washed with 2N hydrochloric acid, then with water and finally with brine, and then dried over ~sodium sulfate and concentrated by evaporation. Chromatographic purification of the reaction mixture in a toluene solution on silica gel gives the title compound (compound no. 1.1, Table 1) in the form of a yellow oil; refractive index n 26 1.5813.

D

The following compounds nf formula I are prepared analogously to *"Example P2.

10 Table 1 Rl\ COO 0- H o-F Ji3 \F R2 C3\C Soo 0000 Ot o o a .0 O 0 00 00 0 0 00 0D 01 d 0 No. RI R 2 stereochemistry physic. data 25 1.1 Cl Cl 1-R-cis, a-RS oil, n 25 1.5826

D

1.2 C1 C124,5 1.2 Cl Cl cis, a-RS oil, n 1.5849

D

25 1.3 Cl Cl trans, a-RS oil, n 1.5805 1.4 CF 3 C1 cis, a-RS oil, n 4 1.5558 25 1.5 Br Br mixture cis/trans oil, n 1.5859 25 1.6 F F mixture cis/trans oil, n2 1.5611 1.7 Cl Cl mixture cis/trans oil, n24,5 1.5894 85/15 D Separation of the diastereoisomers from P.2, compound 1.1, Table 1 S P.

otta p.3 It is possible to cribed under P.2, sc I isolate the two isomers from the reaction product deswhich is a mixture of isomers, in the following manner: After being left to stand for several days, the oil obtained according to Example P.2 crystallises out. The crystallisate is recrystallised from an ether/pentane mixture. M.p. 134-136 0 C (compound 2.1).

-36.7° 0.2.

D

The isomeric product (compound 2.2) is isolated from the mother liquor.

M.p. 71-73 0 C. [a]2 0 +19.10 0.2.

11 Formulation Examples F.1 Emulsifiable concentrates compound or combination calcium dodecylbenzenesulfonate castor oil polyethylene glycol ether (36 moles of ethylene oxide) tributylphenol polyethylene glycol ether (30 moles of ethylene oxide) cyclohexanone xylene mixture c) 50 6% 12 15 5 25 4 20 20 Emulsions of any desired concentration Ss trates by dilution with water.

9 C can be produced from such concen- Solutions :compound or combination ethylene glycol monomethyl atLer ,",polyethylene glycol 0 00 .o ((mol. wt. 400) N-methyl-2-pyrrolidone "",epoxidised coconut oil petroleum fraction (boiling range 160-190 0

C)

a) 80 20 b) 10 c) 5% d) 95 70 20 94 These solutions are suitable for application in the form of micro-drops.

F.3 Granulates compound or combination kaolin highly dispersed silicic acid attapulgite a) 5% 94 1 b) 10 -90 12 The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.

F.4 Dusts a) b) compound or combination 2 5 highly dispersed silicic acid 1 5 talcum 97 kaolin 90 Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient.

i Biological Examples 0 i o a a B.1: Stomach toxicant action against Laodelphax striatellus and a Nilaparvata lugens (nymphs) °The test is carried out with growing plants. For this purpose 4 rice plants (thickness of the stem 8 mm) about 20 cm in height are planted o ""into each of a number of pots (8 rm in diameter).

o *o 0 00 0 0 The plants are sprayed on a rotary table with 100 ml of an acetonic 9 *o,solution containing 400 ppm of the respective test compound. When the ,spray coating has dried, each plant is populated with 20 nymphs of the test-organisms in the third stage. To prevent the cicadas from escaping, So",a glass cylinder open at both ends is slipped over each of the populated plants and covered with a gauze top. The nymphs are kept for 10 days on the treated plant until they have reached the next stage of development.

A mortality count is made 2, 4 and 8 days after treatment.

Compounds nos. 1.1, 1.2, 1.3 and 1.4 according to Table 1 and nos. 2.1 and 2.2 according to Example P.3 exhibit good activity in this test.

5845/3 i I r L. i i 13 B.2 Action against Nephotettix cincticeps (nymphs) The test is carried out with growing plants. For this purpose approximately 20-day-old rice plants about 15 cm in height are planted into pots (diameter 5.5 cm).

The plants are each sprayed on a rotary table with 100 ml of an acetonic solution containing 400 ppm of the test compound. When the spray coating has dried, each plant is populated with 20 nymphs of the test organisms in the second or third stage. To prevent the cicadas from escaping, a plexiglass cylinder is slipped over each of the populated plants and covered with a gauze top. The nymphs are kept for 5 days on the treated plants, which have to be watered again at least once. The test is carried out at a temperature of about 23 0 C at 55 relative humidity and with an 4900 illumination period of 16 hours per day.

o 0 Compounds nos. 1.1, 1.2, 1.3 and 1.4 according to Table 1 and nos. 2.1 0 0 040 cand 2.2 according to Example P.3 exhibit good activity in this test.

B.3 Action against ticks: killing action in various development stages o o About 50 larvae, about 25 nymphs or about 10 imagines of the tick species oo 00Boophilus microplus are used as test organisms. The test organisms are immersed for a short time in aqueous emulsions or solutions containing .O'o the salts of the test compounds in a specific concentration. The 04o4 $emulsions or solutions, which are contained in test tubes, are then absorbed by cotton wool, and the wetted test organisms are left in the s2 ttest tubes which have thus been contaminated. Evaluation is made 3 days later in the case of the larvae and 14 days later in the case of the nymphs and imagines. The minimum concentration of test compound required to bring about 100 mortality (LDioo), expressed in ppm of test compound based on the total amount of emulsion or solution, is ascertained.

Compounds nos. 1.1, 1.2, 1.6 and 1.7 according to Table 1 and nos. 2.1 and 2.2 according to Example P.3 exhibit good activity.

14 B.4 Action against Dermanyssus gallinae 2 to 3 ml of a solution containing 100 ppm of the test compound and about 200 mites in various development stages are placed in a glass container open at the top. The container is then closed with a cotton wool plug, shaken for 10 minutes until the mites are completely wet and then briefly inverted in order that the remaining test solution can be absorbed by the cotton wool. After 3 days the percentage mortality of the mites is determined by counting the dead insects.

Compounds nos. 1.1 and 1.7 according to Table 1 and 2.1 and 2.2 according to Example P.3 exhibit 80-100 activity (mortality).

*o01 B.5 Action against Lucilia sericata o*6+ 1 ml of an aqueous formulation containing 0.5 of test compound is added at 50 0 C to 9 ml of culture medium. Then about 30 freshly hatched Lucilia sericata larvae are added to the culture medium, and the insecticidal 0 o 4o action is determined after 48 and 96 hours by evaluating the mortality rate.

So, 0 Compounds nos. 1.1 according to Table 1 and 2.1 and 2.2 according to 0 *o Example P.3 exhibit good activity against Lucilia sericata in this test.

0 0 B.6 Action against Musca domestica SA sugar cube is so moistened with a solution .of the test compound that 0 (4tt the concentration of active ingredient in the cube after drying is 500 ppm. The treated cube is placed on a dish together with a wet cotton 66 wool plug and covered with a beaker. 10 adult one-week-old, OP-resistant flies are placed under the beaker and kept at 25 0 C and 50 humidity. The insecticidal action is determined after 24 hours by evaluating the mortality rate.

Compounds nos. 1.1, 1.3, 1.4 and 1.6 according to Table 1 and 2.1 and 2.2 according to Example P.3 exhibit good activity in this test.

15 B.7 Action against Blattella germanica An amount of a 0.1 acetonic solution of the test compound equivalent to a rate of application of 2 g/m 2 is introduced into a Petri dish 10 cm in diameter. When the solvent has evaporated, 20 Blattella germanica nymphs (final nymph stage) are placed in the prepared dish and exposed to the action of the test compound for 2 hours. The nymphs are then narcotised with C02, placed in a fresh Petri dish and kept in the dark at 25°C and to 70 humidity. After 48 hours the insecticidal action is evaluated by determining the mortality rate.

Compound no. 1.3 according to Table 1 exhibits good activity -in this test.

0 oa 0 0 0 C, 0 0 0.

bo l3 0 0 0 0 00 0 0 0.

0 00 0 4 0000 0 &1 00 0 890 t

Claims (10)

1. Cyclopropanecarboxylic acid esters of formula I Ri' /l (I) C 3 "CH, v/ F wherein each of R 1 and R 2 is Cl, F or Br and, if R 1 is Cl, R 2 may also be CF 3 00*)

2. The mixture of isomers 2,2-dimethyl-3-cis-(2' ,2'-dichlorovinyl)-cyclo- 0 propane-IR-carboxylic acid 3-phenoxy-4-fluoro-a(RS)-(2'-phenylethynyl)- benzyl ester according to claim 1.

3. 2,2-dimethyl-3-cis-(2',2'-dichlorovinyl)-cyclopropane-IR-carboxylic -acid 3-phenoxy-4-fluoro-(+)-(2'-phenylethynyl)-benzy1 ester according to claim 2. '044. 2,2-dimethyl-3-cis-(2',2'-dichlorovinyl)-cyclopropane-1R-carboxylic o -acid 3-phenoxy-4-fluoro-c(-)-(2'-phenylethynyl)-benzyl ester according to 00 claim 2. 0044 A process for the preparation of the compounds of formula I, claim 1, which comprises reacting a 3-cis-iR-cyclopropanecarboxylic acid halide of formula II R\ C=CH-CCH-COY (II) H 3 C/ \CH 3 wherein R 1 and R 2 are as defined in claim 1 and Y is halogen, with 3-phenoxy-4-fluoro--penylethynyl-benzy1 alcohol of formula III ^L 17 II I II I HO-H- -F (III), in the presence of a base. s 6. The 3-phenoxy-4-fluoro-a-phenylethynyl-benzyl alcohol of formula III 0 0 as defined in claim Q 0o00

7. A pesticidal composition that contains as active component a compound o090 according to any one of claims 1 to 4 together with suitable carriers °o o and/or other adjuvants. 0 0 o o 0

8. Use of a compound according to any one of claims 1 to 4 for controll- ing insects and representatives of the order Acarina in and on animals and plants. 0 ooo 9. Use according to claim 8 for controlling plant-destructive insects. oo a

10. Use according to claim 9 for controlling plant-destructive insects in 0 4 rice crops.

11. A method of controlling insects and representatives of the order 0 1 Acarina, wherein the pests or their various development stages and/or their locus is brought into contact with or treated with a pesticidally effective amount of a compound of formula I according to any one of claims 1 to 4 or with a composition containing a pesticidally effective amount of that compound together with adjuvants and carriers. 18

12. Cyclopropanecarboxylic acid esters substantially as hereinbefore described with reference to Example P.2 or P.3 or any one of compounds 1.1 to 1.7, 2.1 or 2.2.

13. A process for preparing cyclopropanecarboxylic acid esters substantially as hereinbefore described with reference to Example P.2 or P.3.

14. A pesticidal composition for controlling insects and representations of the order Acarina, comprising a compound according to claim 12 together with a pesticidally acceptable adjuvant, carrier and/or diluent. A method of controlling insects and representations of the order Acarina, wherein the pests or their various development stages and/or their locus is brought into contact with or treated with a pesticidally effective ,q amount of a compound according to claim 12 or a composition according to o000 o.S claim 14. o 16. A cyclopropane carboxylic acid ester whenever produced by the 0 process of claim 5 or claim 13. DATED this SECOND day of JANUARY 1991 Ciba-Geigy AG o o i 0 0 0 Patent Attorneys for the Applicant SPRUSON FERGUSON