CA1230547A - Halogenated esters - Google Patents

Halogenated esters

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Publication number
CA1230547A
CA1230547A CA000509683A CA509683A CA1230547A CA 1230547 A CA1230547 A CA 1230547A CA 000509683 A CA000509683 A CA 000509683A CA 509683 A CA509683 A CA 509683A CA 1230547 A CA1230547 A CA 1230547A
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Prior art keywords
compound
compounds
chloro
formula
cyano
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CA000509683A
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French (fr)
Inventor
Nazim Punja
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

ABSTRACT

A method of combatting insect pests at locations where fish are or are likely to be present in which a composition containing a compound of formula:

Description

1'~30S47 - 1 - PP.32247A
HALOGRNATED ESTERS

This application is a division of Serial No. 425,180, filed April 5, 1983.
This invention relates to a method of combatting insect and similar invertebrate pests and to novel cyclopropane derivatives useful as insecticides, to processes for t'neir preparation, and to compositions comprising them.
Certain naturally occurring esters of cyclopropane carboxylic acids have long been known to possess insecticidal properties, but these compounds have been too easily degraded by ultra violet light to be of much use in agriculture. Several groups of synthetic compounds based on cyclopropane carboxylic acids (for example those disclosed in British patent specifications nos. 1,243,858 and 1,413,491) have been evaluated in an attempt to discover compounds of sufficient light stability for use as general agricultural insecticides.
A particularly useful group of such compounds is that disclosed in 8ritish patent specification no. 2,000,764 an-1 Belgian patent no.~63,151. These compounds combine good light stability with excellent contact and resi~ual insecticidal properties, but, in common with the compounds
2~ described in British patent specifications 1,243,853 and 1,~13,491, they possess an unsatisfactory toxicity to fish which precludes their use as insecticides in certain situations, e.g. in rice where pisciculture is carried on in the rice paddies.
The present invention relates to certain novel halo-substituted phenoxybenzyl esters of 3-(2-halo(or tri-fluoromethyl)-3,3,3-trifluoropropenyl)-2,2-dimethyl-cyclopropane carboxylic acids with an extremely high level of insecticidal and acaricidal activity which are much less toxic to fish.
Accordingly this invention provides a method of combatting insect pests at a locus where fish are present or liXely to be present which comprises applying to the locus a composition comprising a compound of formula~

~23~i47 Rl- Ce CH CH - C~l - C - O - C~

/\
CH3 Ca3 (I) wherein one of Rl and R2 is halomethyl and the other is halomethyl or halo, X is hydrogen or cyano and Y is halo, in an amount which is insecticidally effective but which is substantially non-toxic to the fish.
Particular loci where the method may be practised include for example rice paddies, areas of forest w~ere pesticide run off passes into streams and laXes, and recreational or amenity areas where fish are kept eg, for angling.
Preferably one of Rl and R2 is trifluoromethyl and the other is chloro, X is hydrogen or cyano and Y is fluoro, chloro or bromo. Especially preferred are the compounds 3-(4-chlorophenoxy)benzyl and ~-cyano 3-(4-chlorophenoxy)benzyl 3-(2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane carboxylate.
It will be appreciated by those skilled in the art that the compounds represented by formula I are capable of existing in various geometrical and stereoisomeric forms.
Thus there may be cls and trans isomers arising from the substitution pattern of the cyclopropane ring, and E- and ~-isomers arising from the substituted vinyl group when is not identical with R2. In addition two of the three carbon atoms of the cyclopropane are capable of existing in either R- or S-configurations since they are asymmetrically substituted.
Specific compounds suitable for use in the method of the invention are set out in Table I wherein the meanings 12305~7 for Rl, R2, X and Y and the isomeric composition of each compound is given in the form Z or E (geometry of double bond)- (+), (+) or (-)-cls or trans (stereochemistry of cyclopropane acid moiety)-(2/S), (S) or (2) (absoluble S configuration of carbon bearing group X). -_ ~..230547 TABLE I

COMPOUND Rl R2 X Y ISOMERIC
NUMBER COMPOSITION

1 CF3 Cl CN Cl Z-(+)-c lS- ( R/S) 2 CF3 F CN Cl Z-(+)-cls-(R/S)
3 CF3 Br CN Cl Z-(+)-cls/trans-(R/S)
4 CF3 CF3 CN Cl (+)-cls/trans-(R/S) CF3 Cl H Cl Z-(+)-cis 6 CF3 Cl CN Br Z-(+)-cls-(R/S) 7 CF3 Cl CN F Z-(+)-cls-(R/S) 8 CF3 Cl CN Cl Z-(+)-trans-(R/S) 9 CF3 Cl CN Cl Z-(t)-trans-(R/S) CF3 Cl CN Cl Z-(+)-cis-(S) 11 CF3 Cl CN Cl Z-(~)-trans-(S) .

lZ~05~7 _. 5 In a further aspect the invention provides compounds of formula I wherein Rl, R2 and Y are as defined hereinabove and X is cyano.
The compounds according to ~ormula I are esters and may be prepared by conventional esterification processes, of which the following are examples.

ta) An acid of formula:-Rl--C = CH CH--CH--C--Q
12 \ /
R C (II) /\

where Q represents the hydroxy group and Rl and R2 haveany of the meanings given hereinabove, may be reacted directly with an alcohol of formula:-HO - C'H ~

X 0 ~ Y (III) where X and Y have any of the meanings given hereinabove, the reaction preferably taking place in the presence of an acid catalyst, for example, dry hydrogen chloride.

(b) An acid halide of formula II w~ere Q represents a halogen atom, preferably a chlorine atom, and Rl and R2 have any of the meanings given hereinabove, may be reacted (i) with an alcohol of formula III, the reaction preferably taXing place in the presence or a base, for example, pyridine, alkali metal hydroxide or carbonate, or alkali metal alkoxide, or (ii) when X is cyano, with an aldehyde of formula:

1231)~

O = CE~ ~
O~Y

in the presence of an alkali metal cyanide.

(c) An acid of formula II or, preferably, an alkali metal salt thereof, may be reacted with halide of formula:-Ql _ CH ~

~ Y (IV) where Ql represents a halogen atom, preferably the chlorine atom, X, R3,R4 and R5 have any of the meaningsgiven hereinabove, or with the quaternary ammonium salts derived from such halides with tertiary amines, for example pyridine, or trialkyl amines such as triethylamine.

(d) A lower alkyl ester of formula II where Q represents a lower alkoxy group containing up to six carbon atoms, preferably the methoxy or ethoxy group, and Rl and R2 have any of the meanings given hereinabove, is heated with an alcohol of formula III to effect a transesterification reaction. Preferably the process is performed 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.

123054~7 ~ 11 of these conventional processes for the preparation of esters may be carried out using solvents and diluents for the various reactants where appropriate, and may be accelerated or lead to higher yields of product when performed at elevated temperatures or in the presence of appropriate catalysts, for example phase-transfer catalysts.
The preparation of individual isomers may be carried out in the same mannsr but commencing from the corresponding individual isomers of compounds of formula II. These may be obtained by conventional isomer separation techniques from mixtures of isomers. Thus cis and trans isomers may be separated by fractional crystallisation of the carboxylic acids or salts thereof, whilst the various optically active species may be obtained by fractional crystallisation of salts of the acids with optically active amines, followed by regeneration of the optically pure acid.
The optically pure isomeric form of the acid (or its equivalent acid chloride or ester) may then be reacted with the appropriate alcohol to produce a compound of formula I
in the form of an individually pure isomer thereof.
The preparation of the compounds of Formula II w~erein Q is hydroxy, alkoxy or halo, and Rl and R2 are as defined hereinabove, useful as intermediates in the preparation of the compounds of Formula I, is fully described in British Patent Specification 2,000,764 and in Belgian patent no. 863151.
When the processes for preparing the compounds of Formula I are performed using intermediates which are themselves mixtures of isomers the products obtained will also be mixtures of isomers. Thus, the product would be a mixture of (+)~cis and (+)-trans isomers ~perhaps with one form predominating) if the intermediate acid or acid derivative was used in the form of a mixture of (+)-cls and (+)-trans isomers. If a single isomer, of the acid, ~230547 e.g. the (+)-cis isomer with Z-configuration in the 2-chloro-3,3,3-trifluoropropenyl group, was used, the product would also be the single isomer of t'nat stereochemical configuration, or a pair of isomers if there is an asymmetric carbon atom in the alcohol moiety.
The compounds of formula I may be used to combat and control infestations of insect pests and also other invertebrate pests, for example, acarine pests. The insect and acarine pests which may be combatted and controlled by the use of the invention compounds include those pests associated with agriculture (which term includes the growing of crops for food and fibre products, horticulture and animal husbandry), forestry, the storage of products of vegetable origin, such as fruit, ~rain and timber, and also those pests associated with the transmission of diseases of man and animals.
In order to apply the compounds to the locus of the pests they are usually formulated into compositions which include in addition to the insecticidally active ingredie~t or ingredients of formula I suitable inert diluent or carrier materials, and/or surface active agents. The compositions may also comprise another pesticidal material, for example another insecticide or acaricide, or a fungicids, or may also comprise a insecticide synergist, such as for example dodecyl imidazole, safroxan, or piperonyl butoxide.
The compositions may be in the form of dusting powders wherein the active ingredient is mixed with a solid diluent or carrier, for example kaolin, bentonite, kieselguhr, or talc, or they may be in the form of granules, wherein the active ingredient is absorbed in a porous granular material for example pumice.
Alternatively the compositions may be in the form of liquid preparations to be used as dips or sprays, which are generally aqueous dispersions or emulsions of the active 12305~1L7 _ 9 _ ingredient in the presence of one or more known wetting agents, dispersing agents or emulsifying agents (surface ac~ive agents).
~etting agents, dis~ersing agents and emulsifying agents may be of the cationic, anionic or non-ionic t~pe.
Suitable agents of the cationic type include, for example, quaternary ammonium compounds, for example cetyltrimethyl ammonium bromide. Suitable agents of the anionic type include, for example soaps, salts of aliphatic monoesters or sulphuric acid, for example sodium lauryl sulphate, salts of sulphonated aromatic compounds, for example sodium dodecyLbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of the sodium salts of diisopropyl- and tri-isopropylnaphthalene sulphonates. Suitable agents of thenon-ionic type include, for example, the condensation products of e~hylene oxide with fatty alcohols such as oleyl alcohol or cetyl alcohol, or with alkyl phenols such as octyl phenol, nonyl phenol and octyl cresol. Other non-ionic agents are the partial esters derived from long chainfatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins.
The compositions may be prepared by dissolving the active ingredient in a suitable solvent, for e~ample, a ketonic solvent such as diacetone alcohol, or an aromatic solvent such as trimethylbenzene and adding the mi~ture so obtained to water which may contain one or more '~nown wetting, dispersing or emulsifying agents. Other suitable organic solvents are dimethyl formamide, ethylene dichloride, isopropyl alcohol, propylene glycol and other glycols, diacetone alcohol, toluene, kerosene, white oil, methylnaphthalene, xylenes and trichloroethylene, ~-methyl-2-pyrrolidone and tetrahydro furfuryl alcohol (THFA).

12305'~7 The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant such as fluorotrichloromethane or dichlorodifluoro~ethane.
~he compositions which are to be used in the form of aqueous dispersions or emulsions are generally supp`lied in the form of a concentrate containing a high proportion of the active ingredient or ingredients, the said concentrate to be diluted with water before use. These concentr~tes are often required to withstand storage for prolonged periods and after such storage, to be capable of dilution with water to form aqueous preparations which remain homogenous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may contain 10-85% by weight of the active ingredient or ingredients. ~'nen diluted to form aqueous preparations such preparations may contain varying amounts of the active ingredient depending upon the purpose for which they are to be used. ~or agricultural or horticultural purposes, an aqueous preparation containing between O.OQ01~ and 0.1% by weight of the active ingredient is particularly useful.
In use the compositions are applied to the pests, to the locus of the pests, to the habitat of the pests, or to growing plants liable to infestation by the pests, by any of the known means of applying pesticidal compositions, for example, by dusting or spraying.
The compositions of the invention are very toxic to wide varieties of insect and other invertebrate pests, including, for example, the following:-Aphis fabae (aphids) Megoura viceae (aphids) Aedes aegypti (mosquitoes) Dysdercus fasciatus (capsids) Musca domestica (houseflies) Pieris brassicae (white butterfly, larvae) 1230S~7 Plutella maculipennis (diamond bacX month, larvae) Phaedon cochleariae (mustard beetle) Telarius cinnabarinus (carmine spider mite) Aonidiella spp. (scale insects) Trialeuroides spp. (white flies) Blattella germanica (cockroaches) Spodoptera littoralis (cotton leaf worm) Chortiocetes terminifera (locusts) Diabrotica spp. (rootworms) Nilaparvata lugens (plant hoppers)Nephotettix virescens (leaf hoppers) Chilo suppressalis (stem borers) Tryporyza _ncurtulos (stem borers) The compounds of formula I and compositions comprising them have shown themselves to be particularly useful in controlling pests of rice, for example Nephotettix spp. and Nilaparvata spp. They are also very useful in combatting insect and acarine pests which infest domestic animals, such as Lucilia sericata, and ixodid tic~s such as Boophilus spp., Ixodes spp., Amblyomma spp., Rhipicephalus spp., and - Dermaceutor spp. They are effective in combatting both susceptible and resistant strains of these pests in their adult, larval and intermediate stages of growth, and may be applied to the infested host animal by topical, oral or parenteral administration.
The following Examples illustrate the various aspects of the invention.

12305~7 This Example illustrates the insecticidal properties of Compound no.l of Table I.
The activity of the compound was determined using a variety of insect pests. The compound was used in the form of liquid ~reparations containing 100, 50, 25, 10 or 12 p.p.m. by weight of the compound. The preparations were made by dissolving the compound in a mixture of solvents consisting of 4 parts by volume of acetone and 1 part by volume of diacetone alcohol. The solutions were t'nen diluted with water containing 0.01% by weiqht of a wetting agent sold under the trade name "LISSAPOL" NX until the liquid preparations contained the required concentration of the compound. "Lissapol" is a Trade ~lark.
The test procedure adopted with regard to each pest was basically the same and comprised supporting a number of the pests on a medium which was usually a host plant or a foodstuff on which the pests feed, and treatin~ either or both the pests and the medium with the ~reparations. The mortality of the pests was then assessed at periods usually varying from one to three days after the treatment. Details are given in Table IIA.
The results of the tests are given in Table IIB for each of the products A to ~d at the rate in parts per million given in the second column as a grading of mortality on a scale of 0-9 wherein 0 represents less than 10% mortality 1 " from 10 to 19%
2 " " 20 to 29% "
3 " " 30 to 39% "
4 " " 40 to 49~ "
" " 50 to 59~ "
6 " " 60 to 69~ "

1i:3~)5~7 7 " " 70 to 79% "
8 " " 80 to 8~ "
9 " " 90 to 100% "

In Table IIB the pest organism used is designated by a letter code and the pest species, the support medium or food, and the type and duration of test is given in Table IIA. - -~23C~5~

O^
H ~,q E~ :~ ,i ~ ~t ~ ~ .
~ JJ

a . ~ C
~1 o ~ U C~ U
E~ ~ ~ u~
U~
C ~q ~q ,. ~ h ~, C o ~ a) o o ~ U U ~ ~ U U ,~
S~
I,q (q 3 o o ~ ~ ~ iq s~
E~ O~ s~
~ ~ O ~ ~ ,~
O ~ O ~ ~ ~5 C~ ~3 :~ ~ Q, ~ a~
G ~ ~q C~ ~3 E ~
'- H ~ S ~5 0 ~ ~ X .~ P
¢ ~~ _I p ~ 0-~
H U F U U ~ ~4 cq ~q O~ 3 ~ tq I 1~ n5 S!~ E~
_l la ~1 S
e ~ ~ ~ ~ o C~~5 0 h ~ O
UHU 1~ ~ 3 ~ ~ ~ h~ ~) a) !~ .,1 I .,1 O X ~ ~1 ~ ~_ D~ ~ ~1 ~ ~ U
u~ ~q ~, ~ a) ~ o x ,9 0 E~ F .,~ ~ ~1 ,Q U E ~, u~ O ~ a~ ~1:1 ~ lo ~,~ h Q) S
~ ~a ~ ~ c_ ~ c^ q~ ~q~ O

c~ Q) ~. O o _1 O o ~J 0 3 ~J Iq O ~ ~ o E~ ~ ~q .,, h ~) C.` ~q U ~ ~ ~ ~ ~ ~ ~ ,1 S~ O ., t,q O O O h ::5 ,~ h S Q~ ~a O
~ ,C ~ U n~ --I ~Q, ~ h C
-- u~ ~ _,~ ~ ~a _ .,, u I ,~
ul a~ `' ~ :â ,_, E-l H
E~ H a ~ u ~
a) ~ a ~ ~ .
_ ~ .~ tq C ~ O ~ al o~ ~ ~ V
U_ : - ~

~2305~7 __ PEST SPECIES
COMPOUND RATE
NUMBER( ppm ) 11 DSL PX Al? DB

1 50 9 9 .9 9 9 .
1 25 g O 1 7 9 0 100 9 9ll 9 9 5 ~ 100 9 9 7 9 5 ~3~5~7 This Example illustrates the improved safety to fish of the compounds for use in the method of the invention compared with known compounds of similar chemical type.
Table III sets out the LC50 values for young trout and carp in parts per million for the compounds for use in the method of this invention and parts per billion for the known (reference) compounds.

TABLE III

(Table I) Trout Carp 1 20 ppm 10 ppm 6 _ 10 pp~
7 1 ppm Cyhalothrin* 0.73 ppb 1.34 ppb Cypermethrin** ca 2 ppb (+)~-cyano-3-phenoxybenzyl (+)-cis-3-(2-2-chloro-3,3,3-trifluoroprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate.

** (+)-~-cyano-3-phenoxybenzyl (+)-cis/trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropane carboxylate.

~2~0547 ~ 17 -EXA~IPLE 3 This Example illustrates the preparation of (t)~~~
cyano-3-(4-chlorophenoxy)benzyl alcohol.
Glacial acetic acid (2.0 ml) was added to a well stirred mixture of ~-chlorophenoxybenzaldehyde (4.65 g), sodium cyanide (1.18 g) and water (10 ml), a temperature being maintained in the range 10 15C during the addition.
After completing the addition the mixture was stirred for a further one hour at this tem~erature, extracted with methylene chloride and the extracts dried over anhydrous magnesium sulphate. The residual oil (5.0 g) remaining after evaporation of the solvsnt, which was shown by infra-red spectroscopy to consist principally of the desired ~roduct together with a small amount of unreacted aldehyde, was used without further purification in the followinq ~xample.

Infra red (liquid film): 3400 (broad), 1585, 1485, 1260 cm~l (A small peak at 1700 cm 1 was also present indicating some unreacted aldehyde).

This Example illustrates the preparation of (+)-~-cyano-3-(4-chlorophenoxy)benzyl (+)-cis-3-(Z-2-chloro-3,3,3-trifluoroprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate (compound no.l, Table I).
A mixture of (+)-cis-3-(Z-~-chloro-3,3~3-trifluoro-prop-1-en-1-yl)-2,2-dimethylcyclopropane carboxylic acid (1.0 g) was refluxed with excess thionyl chloride to convert it to its acid chloride. The excess thionyl chloride was removed by evaporation under reduced pressure and the residue freed from the final traces by azeotropic distillation with dry toluene.

12~)54~

The acid chloride was dissolved in dry toluene (10 ml) and mixed with the (+)~ cyano-3-(4-chlorophenoxy)-benzyl alcohol (1.16 g) obtained in the previous Example. To the stirred mixture at the ambient temperature was added a S solution of dry pyridine (0.5 g) in dry toluene (2.0 ml), resulting in the formation of a white precipitate. After stirring for one hour the mixture was diluted with more toluene and then washed with water, and with saturated aqueous sodium bicarbonate solution, and dried over anhydrous magnesium sulphate. After filtering to remove the solid matter the filtrate was concentrated by removal of the solvent by evaporation under reduced pressure and colourless residual oil (2.2 g) was purified by wet column chromatography (silica gel column, chloroform eluent) to yield pure (+)~-cyano-3-(4-chlorophenoxy)benzyl (+)-c1s-3-(Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane carboxylate (1.2 9) as a colourless oil.

N.m.r. (CDC13) ppm : 1.15-1.40 (m,6H); 1.92-2.37 (m,2H);
6.27 (d,l~); 6.67-7.46 (m,9H).
Infra red (liquid film): 3075, 2950, 1740, 1650, 1585, 1485, 1300, 1270, 1250, 1160, 1130, 1075, 1000, 950, 760 cm~

Other compounds useful in the method of the invention may '~e prepared by the procedures of ~xamples 3 and 4 from the appropriate reactants as follows:

(a) (+)-~-cyano-3-(4-chlorophenoxy)benzyl (+)-trans-3-(Z-2-chloro-3,3,3-trifluoroprop-1-en-yl)-2,2-dimethylcyclopropane carboxylate (compound no 8, Table I).

123~5~

E~ n.m.r.(CDC13)ppm: 1.24-1.42(m,6H); 1.82-2.64(m,2H); 6.?2(d,lH);
6.48(d,1ii); 6.98-7.62(m,3H).
Infra red (liquid film): 3060, 2960, 1740, 1650, lS85, 1485, 1280, 1150cm~l (b) (+)~ cyano-3-(4-fluorophenoxy)benzyl (+)-cis-3-(Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimet'nylcyclopropane carboxylate (compound no 7, Table I).
lH n.m.r.(CDC13)ppm: 1.20-1.44(m,6H); 2.00-2.44(m,2~)' 6.46(~,1H); 6.90-7.52(m,9H) Infra red (liquid film): 3070, 2960, 1740, 1650, 1580, 1500, 1200, 1150cm~l (c) (+)-~-cyano-3-(4-bromophenoxy)benzyl (+)-cis-3-(Z-2-chloro-3,3,3-trifluoroprop-1-en-1-yl)-2,2-dimethylcyclopropane carboxylate (compound no 6, Table I).
lH n.m.r.(CDC13)ppm: 1.20-1.44(m,6H); 2.00-2.44(m,2H); 6.48(d,1~);
6.86-7.68(m,9H).
Infra red (liquid film): 3080, 2690, 1740, 1650, 1550, 1460, 1270, 1150cm~l (d) (+)-3-(4-chlorophenoxy)benzyl (+)-cls-3-(Z-2-chloro-3,3,3-trifluoroprop-1-2n-yl)-2,2-dimethylcyclopropane carboxylate (compound no 5, Table I).
H n.m.r.(CDC13)ppm: 1.30(s,6H); 2.00-2.36(m,2H);
5.12(s,2H); 6.90-7.50(m,9H);
Infra red (liquid film): 3070, 2960, 1725, 1650, 1580, 1480, 1140cm~l

Claims (4)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A method of combatting insect pests at a locus where fish are present or likely to be present which comprises applying to the locus a composition comprising a compound of formula:

wherein one of R1 and R 2 is halomethyl and the other is halomethyl or halo, X is hydrogen and Y is halogen, in an amount which is insecticidally effective but which is sub-stantially non-toxic to fish.
2. A method according to Claim 1 where the locus is a rice paddy, a forest area where pesticide run off passes into streams, rivers or lakes, or a recreational or amenity area.
3. A method according to Claim 1 wherein the compound is one wherein one of Rl and R2 is trifluoromethyl and the other is chloro, X is hydrogen and Y is fluoro, chloro or bromo.
4. A method according to Claim 3 wherein the compound is 3-(4-chlorophenoxy)benzyl 3-(2-chloro-3,3,3-trifluoroprop-l-en-l-yl)-2,2-dimethylcyclopropane carboxylate.
CA000509683A 1982-04-05 1986-05-21 Halogenated esters Expired CA1230547A (en)

Priority Applications (1)

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Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB8,210,006 1982-04-05
GB8210006 1982-04-05
CA000425180A CA1224483A (en) 1982-04-05 1983-04-05 Halogenated esters
CA000509683A CA1230547A (en) 1982-04-05 1986-05-21 Halogenated esters

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