CA1092145A - Pesticidal metaphenoxybenzylcyclopropane carboxylate derivatives - Google Patents
Pesticidal metaphenoxybenzylcyclopropane carboxylate derivativesInfo
- Publication number
- CA1092145A CA1092145A CA249,592A CA249592A CA1092145A CA 1092145 A CA1092145 A CA 1092145A CA 249592 A CA249592 A CA 249592A CA 1092145 A CA1092145 A CA 1092145A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
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- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Cyclopropanecarboxylic acid esters of the formula
Cyclopropanecarboxylic acid esters of the formula
Description
~O~ZiL~L5 The present invention relates to cyclopropanecarboxylic acid esters, to processes for their produc~ion, and to their use in pest control.
The said cyclopropanecarboxylic acid esters have the formula x2/ CH y ~ ~ (I) C~13 wherein Xl and X2 each represent fluorine, chlorine or bromine, and Y represents hydrogen, cyano or ethynyl.
Compounds of the formula I that are of particular importance by virtue of their action are those wherein Xl is identical to X2 and represents fluorine or chlorine, and Y represents hydrogen, cyano or ethynyl.
The compounds of the formula I are produced by methods -known per se, for example as follows:
X ~ O Y acid-binding C=CH-CH - CH-C~Hal + HO-CH~-O~ agent - ~ I
CH3 ~III) (II) `~
~Z~4S
Xl. o Y acid-binding
The said cyclopropanecarboxylic acid esters have the formula x2/ CH y ~ ~ (I) C~13 wherein Xl and X2 each represent fluorine, chlorine or bromine, and Y represents hydrogen, cyano or ethynyl.
Compounds of the formula I that are of particular importance by virtue of their action are those wherein Xl is identical to X2 and represents fluorine or chlorine, and Y represents hydrogen, cyano or ethynyl.
The compounds of the formula I are produced by methods -known per se, for example as follows:
X ~ O Y acid-binding C=CH-CH - CH-C~Hal + HO-CH~-O~ agent - ~ I
CH3 ~III) (II) `~
~Z~4S
Xl. o Y acid-binding
2) ~ C=CH-C\ /CH-C-OH + Hal-CH ~ -O ~ agent ~ I
. CH3 ~V) ~IV) X~' O
. CH3 ~V) ~IV) X~' O
3) ~ C=CH-C ~ -/CH-C-OH ~ HO-CH ~ -O ~ water-bindin~
CH3 (III) (IV) In the ~ormulae II to V, the symbols Xl, X2 and Y
have the meanings given for the formula I, and Hal stands for a halogen atom, especially for chlorine or bromine.
Suitable acid-binding agents for the processes 1 and 2 are, in particular, tertiary amines such as trialkylamines a~d pyridine, also hydroxides, oxides, carbonates and bicarbonates of alkali metals and alkaline-earth metals, as well as alkali metal alcoholates such as potassium-t.
butylate and sodium methylate.~The water-binding agent used for the process 3 can be, for example, dicyclohexylcarbo-diimide. The processes 1 to 4 are performed at a reaction temperature of between -10 and ~100C~ usually between 20 and 80C, at normal or elevated pressure, and preferably z~s in an inert solvent or diluent.
Suitable solvents or diluents are, e.g., ethers and ethereal compounds such as diethyl ether, dipropyl ether, dioxane, dimethoxyethane and tetrahydrofuran; amides such as N,N-dialkylated carboxylic acid amides; aliphatic, aromatic as well as halogenated hydrocarbons, especially benzene, toluene, xylene, chloroform and chlorobenzene;
nitriles such as acetonitrile; dimethylsulphoxide and ketones such as acetone and methyl ethyl ketone. The process 2 can be performed also in an aqueous solution.
The starting materials of the formulae II to IV are known or can be produced by methods analogous to known methods.
The compounds of the formula I are obtained as mixtures of various optically active compounds and cis/trans isomers, unless the starting materials used to produce the said compounds are homogeneous optically active compounds or - cis/trans isomers. The ~ferent stable isomeric mixtures can be separated by ~nown methods into the homogeneous isomers.
It is understood that compounds of the formula I embrace both the individual isomers and the mixtures thereof.
The compo-mds of the formula I are suitable for the control of various animal and plant pests. They are suitable ~09Z~4~
in particular for controlling insects and members of ~he order Acarina. They can be used, for example, against insects of the families: Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Pyrrhocoridae, Cimicîdae, Delphacidaeg Aphididae, Diaspididae, Pseudo-coccidae, Scarabaeidae, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymantriidae 3 Pyralidae, Culicidae, Tripulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae; as well as against acarids of the families: Tetranychidae and Dermanyssidae.
The compounds of the formula I are especially suitable for combatting insects that damage plants, particularly insects tnat damage plants by eating, in crops of ornamental plants and useful plants, especialLy in cotton crops (e.g.
against Spodoptera littora]is and Heliothis virescens) and in crops of vegetables (e.g. against Leptinotarsa decemlineata and ~Iyzus persicae). The active substances of the formula I
have a very good action also against flies, such as Musca domestica and mos~uito larvae.
The acaricidal or insecticidal action can be substantially broadened and adapted to suit given circumstances by the addition of other insecticides and/or acaricides. Suitable z~
additives are for example:
organic phosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas, o-ther pyrethrin-like compounds, as well as carbamates and chlorinated hydrocarbons.
Compounds of the formula I are combined particularly advantageously with substances that have a synergistic or intensifying effect on pyrethroids. Examples of such compo~mds are, inter alia, piperonylbutoxide, propynyl ether and propynyl phosphonates, 2-(3,4-methylenedioxyphenoxy)-3,6,9-trioxaundecane (Sesamex or Seso~ane), S,S,S-tributyl-phosphorotrithioates and 1,2-methylenedioxy-4-(2 (octyl-1~ sulphinyl)-propyl)-benzene.
The compounds of the formula I can be used on their own or together with suitable carriers and/or additives.
Suitable additives can be solid or liquid and they correspond to the substcmces common in formulation practice, such as natural or regenerated substances, solvents, dispersing agents, wetting agents, adhesives, thickeners~
binders and/or fertilisers.
~z~s The compositions according to the invention are produced in a manner known per se by the intimate mixing and/or grinding of active substances of the formula I
with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances. The active substances can be obtained and used in the following forms:
solid preparations: dust, scattering agents, granulates (coated granulates, impregnated granulates and homogeneous granulates);
liquid preparations:
a) water-dispersible active-substance concentrates:
wettable powders, pastes or emulsions;
b) solutions.
The content of active substance in the described compositions is between 0.1 and 95%; in this connection it is to be mentioned that in the case of application from an aeroplane, or by means of other sui~able devices, con-centrations of up to 99.5% may be used, or even the pure 2Q active substance.
The active substances of the formula I can be formulated, for example, as follows ['parts' denote parts by weight].
Dusts:
The following substances are used in the preparation of a) a 5% dust, and b) a 2% dust:
a) 5 parts of active substance, 95 parts of talcum;
~) 2 parts of active substance, 1 part of highly dispersed silicic acid, 97 parts of talcum.
The active substances are mixed and ground with the carriers.
Granulate:
The following substances are used to produce a 5%
granulate:
5 parts of active substance, 0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin ~particle size 0.3 - 0.8 mm).
The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ethcr are then added. The . ~
1~31Z~
solution thus obtained is sprayed onto kaolin, and the acetone is subsequently evaporated off in vacuo.
Wettable powder:
The following constituents are used to prepare a) a 40%, b) and c) a 25%, and d) a 10% wettable powder:
a~ ~0 parts of active substance, parts of sodium lignin sulphonate, 1 part of sod~um dibutyl-naphthalene sulphonate, 54 parts of silicic acid;
10b) 25 parts of active substance,
CH3 (III) (IV) In the ~ormulae II to V, the symbols Xl, X2 and Y
have the meanings given for the formula I, and Hal stands for a halogen atom, especially for chlorine or bromine.
Suitable acid-binding agents for the processes 1 and 2 are, in particular, tertiary amines such as trialkylamines a~d pyridine, also hydroxides, oxides, carbonates and bicarbonates of alkali metals and alkaline-earth metals, as well as alkali metal alcoholates such as potassium-t.
butylate and sodium methylate.~The water-binding agent used for the process 3 can be, for example, dicyclohexylcarbo-diimide. The processes 1 to 4 are performed at a reaction temperature of between -10 and ~100C~ usually between 20 and 80C, at normal or elevated pressure, and preferably z~s in an inert solvent or diluent.
Suitable solvents or diluents are, e.g., ethers and ethereal compounds such as diethyl ether, dipropyl ether, dioxane, dimethoxyethane and tetrahydrofuran; amides such as N,N-dialkylated carboxylic acid amides; aliphatic, aromatic as well as halogenated hydrocarbons, especially benzene, toluene, xylene, chloroform and chlorobenzene;
nitriles such as acetonitrile; dimethylsulphoxide and ketones such as acetone and methyl ethyl ketone. The process 2 can be performed also in an aqueous solution.
The starting materials of the formulae II to IV are known or can be produced by methods analogous to known methods.
The compounds of the formula I are obtained as mixtures of various optically active compounds and cis/trans isomers, unless the starting materials used to produce the said compounds are homogeneous optically active compounds or - cis/trans isomers. The ~ferent stable isomeric mixtures can be separated by ~nown methods into the homogeneous isomers.
It is understood that compounds of the formula I embrace both the individual isomers and the mixtures thereof.
The compo-mds of the formula I are suitable for the control of various animal and plant pests. They are suitable ~09Z~4~
in particular for controlling insects and members of ~he order Acarina. They can be used, for example, against insects of the families: Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Pyrrhocoridae, Cimicîdae, Delphacidaeg Aphididae, Diaspididae, Pseudo-coccidae, Scarabaeidae, Dermestidae, Coccinellidae, Tenebrionidae, Chrysomelidae, Bruchidae, Tineidae, Noctuidae, Lymantriidae 3 Pyralidae, Culicidae, Tripulidae, Stomoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae; as well as against acarids of the families: Tetranychidae and Dermanyssidae.
The compounds of the formula I are especially suitable for combatting insects that damage plants, particularly insects tnat damage plants by eating, in crops of ornamental plants and useful plants, especialLy in cotton crops (e.g.
against Spodoptera littora]is and Heliothis virescens) and in crops of vegetables (e.g. against Leptinotarsa decemlineata and ~Iyzus persicae). The active substances of the formula I
have a very good action also against flies, such as Musca domestica and mos~uito larvae.
The acaricidal or insecticidal action can be substantially broadened and adapted to suit given circumstances by the addition of other insecticides and/or acaricides. Suitable z~
additives are for example:
organic phosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas, o-ther pyrethrin-like compounds, as well as carbamates and chlorinated hydrocarbons.
Compounds of the formula I are combined particularly advantageously with substances that have a synergistic or intensifying effect on pyrethroids. Examples of such compo~mds are, inter alia, piperonylbutoxide, propynyl ether and propynyl phosphonates, 2-(3,4-methylenedioxyphenoxy)-3,6,9-trioxaundecane (Sesamex or Seso~ane), S,S,S-tributyl-phosphorotrithioates and 1,2-methylenedioxy-4-(2 (octyl-1~ sulphinyl)-propyl)-benzene.
The compounds of the formula I can be used on their own or together with suitable carriers and/or additives.
Suitable additives can be solid or liquid and they correspond to the substcmces common in formulation practice, such as natural or regenerated substances, solvents, dispersing agents, wetting agents, adhesives, thickeners~
binders and/or fertilisers.
~z~s The compositions according to the invention are produced in a manner known per se by the intimate mixing and/or grinding of active substances of the formula I
with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances. The active substances can be obtained and used in the following forms:
solid preparations: dust, scattering agents, granulates (coated granulates, impregnated granulates and homogeneous granulates);
liquid preparations:
a) water-dispersible active-substance concentrates:
wettable powders, pastes or emulsions;
b) solutions.
The content of active substance in the described compositions is between 0.1 and 95%; in this connection it is to be mentioned that in the case of application from an aeroplane, or by means of other sui~able devices, con-centrations of up to 99.5% may be used, or even the pure 2Q active substance.
The active substances of the formula I can be formulated, for example, as follows ['parts' denote parts by weight].
Dusts:
The following substances are used in the preparation of a) a 5% dust, and b) a 2% dust:
a) 5 parts of active substance, 95 parts of talcum;
~) 2 parts of active substance, 1 part of highly dispersed silicic acid, 97 parts of talcum.
The active substances are mixed and ground with the carriers.
Granulate:
The following substances are used to produce a 5%
granulate:
5 parts of active substance, 0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether, 3.50 parts of polyethylene glycol, 91 parts of kaolin ~particle size 0.3 - 0.8 mm).
The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ethcr are then added. The . ~
1~31Z~
solution thus obtained is sprayed onto kaolin, and the acetone is subsequently evaporated off in vacuo.
Wettable powder:
The following constituents are used to prepare a) a 40%, b) and c) a 25%, and d) a 10% wettable powder:
a~ ~0 parts of active substance, parts of sodium lignin sulphonate, 1 part of sod~um dibutyl-naphthalene sulphonate, 54 parts of silicic acid;
10b) 25 parts of active substance,
4.5 parts of calcium lignin sulphonate, 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutyl naphthalene sulphonate, 19.5 parts of silicic acid, 19.5 parts of Champagne chalk, 28.1 parts of kaolin;
c~ 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxyethylene-2Q ethanol, 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture ~1:1), _ g _ 3L~9~5 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, 46 parts of kaolin;
d) 10 parts of active substance, 3 parts of a mix~ure of the sodium salts of saturated fatty alcohol sulphates, parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin~
The active substances are intimately mixed in suitable mixers with the additives, and the mixture is then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.
Emulsifiable concentrates:
-The following substances aTe used to produce a) a 10%, b~ a 25%, and c) a 50% emulsifiable concentrate:
a) 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, 3.4 parts o a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium salt, 40 parts of dimethylformamide, ~z~s 43.2 parts of xylene;
b) 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, parts of alkylarylsulphonate/fatty alcohol polyglycol ether mixture, parts of dimethylformamide, 57.5 parts of xylene;
c) 50 parts of active substance, 4.2 parts of tributylphenol-polyglycol ether,
c~ 25 parts of active substance, 2.5 parts of isooctylphenoxy-polyoxyethylene-2Q ethanol, 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture ~1:1), _ g _ 3L~9~5 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, 46 parts of kaolin;
d) 10 parts of active substance, 3 parts of a mix~ure of the sodium salts of saturated fatty alcohol sulphates, parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin~
The active substances are intimately mixed in suitable mixers with the additives, and the mixture is then ground in the appropriate mills and rollers. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.
Emulsifiable concentrates:
-The following substances aTe used to produce a) a 10%, b~ a 25%, and c) a 50% emulsifiable concentrate:
a) 10 parts of active substance, 3.4 parts of epoxidised vegetable oil, 3.4 parts o a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium salt, 40 parts of dimethylformamide, ~z~s 43.2 parts of xylene;
b) 25 parts of active substance, 2.5 parts of epoxidised vegetable oil, parts of alkylarylsulphonate/fatty alcohol polyglycol ether mixture, parts of dimethylformamide, 57.5 parts of xylene;
c) 50 parts of active substance, 4.2 parts of tributylphenol-polyglycol ether,
5.8 parts of calcium-dodecylbenzenesulphonate, parts of cyclohexanone, parts of xylene.
It is possible to prepare from these concentrates, by dilution with water, emulsions of any desired concentration.
Spray:
The following constituents are used to prepare a) a 5% spray, and b) a 95% spray:
a) 5 parts of active substance, 1 part of epichlorohydrin, 2~ 94 parts of ligroin ~boiling limits 160 - 190C);
b) 95 parts of active substance, . par~s of epichlorohydrin.
The invention is further illustrated by the following Examples.
~Z~9LS
_ ample 1 Production of 2-methyl-3~ dichlorovinyl)-cyclopr carboxylic acid-(3-phenoxy-benzyl)-ester _.
To a solution of 3.5 g of 2-methyl-3-(~,~-dichloro-vinyl)-cyclopropanecarboxylic acid (b.p.: 102-104C/0.07 Torr) in 15 ml of ~ethyl ethyl ketone there are added dropwise at 15-20C, with stirring, firstly 2.92 g of triethylamine and then 5.25 g of 3-phenoxybenzyl bromide. The reaction mixture is stirred for 5 hours at 70-80QC, and subsequently poured into 100 ml of ice water. The crude product is extracted with ether, the resulting ether solution is washed with sodium bicarbonate solution and with water and dried over sodium sulphate.
After removal of the ether by distillation, there is obtained the compound of the formula ~C=CH-CH - CH COOCH2 ~ ~
in the form of colourless oil having a refractive index of nD= 1~5739.
The following compounds are produced in an analogous manner: / CH=CH-CH -/ H - C00-CH ~ -o ~0~3~ S
Xl X2 _ Physical data .. .. ~
- Cl Cl CN nD = 1,5702 - F F CN nD = 1,5403 F F H nD = 1,5424 F F ~C_CH nD = 1,5402 Cl Cl -C-=CH nD = 1,5748 A) Insecticidal stomach poison action Tobacco and potato plants were sprayed with a 0.05%
aqueous active-substance emulsion ~obtained from a 10%
emulsifiable concen~rate).
After drying of the coating, caterpillars of Spodoptera littoralis in the L3-stage and of Heliothis virescens in the L3-stage were placed onto the tobacco and potato plants, The test was carried out at 24C with 60%
relative humidity.
Compounds according to Example 1 exhibited in the ahove test a good insecticidal stomach poison action against Spodoptera littoralis and Heliothis virescens caterpillars.
B) Insecticidal contact action .
One day before application of the active-substance emulsion, broad beans (Vicia faba) grown in pots were infested with about 200 bean aphids (Aphis fabae) per plant. The spray emulsion at a concentration of 1000 ppm (prepared from a 25% wettable powder) was applied, by means of a compressed~air sprayer, to the leaves infested with bean aphids. An evaluation was made 24 hours after application.
Compounds according to Example 1 exhibited in the above test a good contact action against Aphis fabae.
~ 9 ~ ~ 5 Example 3 Action against Acarina Phaseolus vulgaris (bush beans) were infested, 12 hours before the ~est for acaricidal action, with an infested piece of leaf from a mass culture of Tetranychus urticae.
The transferred mobile stages were sprayed with the emulsified test preparations from a chromatography-sprayer in a manner ensuring no overflowing of the spray liquor.
An assessment was made after 2 to 7 days, by examination under a binocular, of living larvae and dead larvae, adults and eggs, and the results were expressed in percentages.
The treated plants were kept during the "holding time"
in greenhouse compartments at 25C.
Compounds according to Example 1 were effective in the above test against eggs, larvae and adults o~
Tetranychus urticae.
It is possible to prepare from these concentrates, by dilution with water, emulsions of any desired concentration.
Spray:
The following constituents are used to prepare a) a 5% spray, and b) a 95% spray:
a) 5 parts of active substance, 1 part of epichlorohydrin, 2~ 94 parts of ligroin ~boiling limits 160 - 190C);
b) 95 parts of active substance, . par~s of epichlorohydrin.
The invention is further illustrated by the following Examples.
~Z~9LS
_ ample 1 Production of 2-methyl-3~ dichlorovinyl)-cyclopr carboxylic acid-(3-phenoxy-benzyl)-ester _.
To a solution of 3.5 g of 2-methyl-3-(~,~-dichloro-vinyl)-cyclopropanecarboxylic acid (b.p.: 102-104C/0.07 Torr) in 15 ml of ~ethyl ethyl ketone there are added dropwise at 15-20C, with stirring, firstly 2.92 g of triethylamine and then 5.25 g of 3-phenoxybenzyl bromide. The reaction mixture is stirred for 5 hours at 70-80QC, and subsequently poured into 100 ml of ice water. The crude product is extracted with ether, the resulting ether solution is washed with sodium bicarbonate solution and with water and dried over sodium sulphate.
After removal of the ether by distillation, there is obtained the compound of the formula ~C=CH-CH - CH COOCH2 ~ ~
in the form of colourless oil having a refractive index of nD= 1~5739.
The following compounds are produced in an analogous manner: / CH=CH-CH -/ H - C00-CH ~ -o ~0~3~ S
Xl X2 _ Physical data .. .. ~
- Cl Cl CN nD = 1,5702 - F F CN nD = 1,5403 F F H nD = 1,5424 F F ~C_CH nD = 1,5402 Cl Cl -C-=CH nD = 1,5748 A) Insecticidal stomach poison action Tobacco and potato plants were sprayed with a 0.05%
aqueous active-substance emulsion ~obtained from a 10%
emulsifiable concen~rate).
After drying of the coating, caterpillars of Spodoptera littoralis in the L3-stage and of Heliothis virescens in the L3-stage were placed onto the tobacco and potato plants, The test was carried out at 24C with 60%
relative humidity.
Compounds according to Example 1 exhibited in the ahove test a good insecticidal stomach poison action against Spodoptera littoralis and Heliothis virescens caterpillars.
B) Insecticidal contact action .
One day before application of the active-substance emulsion, broad beans (Vicia faba) grown in pots were infested with about 200 bean aphids (Aphis fabae) per plant. The spray emulsion at a concentration of 1000 ppm (prepared from a 25% wettable powder) was applied, by means of a compressed~air sprayer, to the leaves infested with bean aphids. An evaluation was made 24 hours after application.
Compounds according to Example 1 exhibited in the above test a good contact action against Aphis fabae.
~ 9 ~ ~ 5 Example 3 Action against Acarina Phaseolus vulgaris (bush beans) were infested, 12 hours before the ~est for acaricidal action, with an infested piece of leaf from a mass culture of Tetranychus urticae.
The transferred mobile stages were sprayed with the emulsified test preparations from a chromatography-sprayer in a manner ensuring no overflowing of the spray liquor.
An assessment was made after 2 to 7 days, by examination under a binocular, of living larvae and dead larvae, adults and eggs, and the results were expressed in percentages.
The treated plants were kept during the "holding time"
in greenhouse compartments at 25C.
Compounds according to Example 1 were effective in the above test against eggs, larvae and adults o~
Tetranychus urticae.
Claims (11)
1. A cyclopropanecarboxylic acid ester of the formula wherein X1 and X2 each represent fluorine, chlorine or bromine, and Y represents hydrogen, cyano or ethynyl.
2. A compound according to Claim 1, wherein X1 is identical to X2 and each represents fluorine or chlorine, and Y represents hydrogen, cyano or ethynyl.
3. The compound according to Claim 2 of the formula
4. The compound according to Claim 2 of the formula
5. The compound according to Claim 2 of the formula
6. The compound according to Claim 2 of the formula
7. The compound according to Claim 2 of the formula
8. The compound according to Claim 2 of the formula
9. Process for the production of compounds according to Claim 1, which process comprises reacting a compound of the formula in the presence of an acid-binding agent, with a compound of the formula wherein X1, X2 and Y have the meanings given in claim 1, and Hals stands for a halogen atom.
10. A method of combatting various animal and plant pests at a locus which method comprises applying to the locus a compound as claimed in claim 1.
11. A method as claimed in claim 10 for combatting pests of the class Insecta or of the order Acarina.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH4366/75 | 1975-04-07 | ||
| CH436675A CH602006A5 (en) | 1975-04-07 | 1975-04-07 | Cyclopropane carboxylic esters |
| CH2319/76 | 1976-02-25 | ||
| CH231976 | 1976-02-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1092145A true CA1092145A (en) | 1980-12-23 |
Family
ID=25690133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA249,592A Expired CA1092145A (en) | 1975-04-07 | 1976-04-05 | Pesticidal metaphenoxybenzylcyclopropane carboxylate derivatives |
Country Status (14)
| Country | Link |
|---|---|
| JP (1) | JPS51127051A (en) |
| AT (1) | AT342921B (en) |
| AU (1) | AU497093B2 (en) |
| BR (1) | BR7602093A (en) |
| CA (1) | CA1092145A (en) |
| DE (1) | DE2614648A1 (en) |
| EG (1) | EG12221A (en) |
| FR (1) | FR2306971A1 (en) |
| GB (1) | GB1537873A (en) |
| HU (1) | HU176210B (en) |
| IL (1) | IL49357A0 (en) |
| MX (1) | MX3200E (en) |
| NL (1) | NL7603488A (en) |
| TR (1) | TR18934A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1594462A (en) * | 1977-02-09 | 1981-07-30 | Shell Int Research | Pesticidal composition |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IN142702B (en) * | 1974-09-10 | 1977-08-20 | Sagami Chem Res |
-
1976
- 1976-03-25 MX MX000116U patent/MX3200E/en unknown
- 1976-04-02 NL NL7603488A patent/NL7603488A/en not_active Application Discontinuation
- 1976-04-05 FR FR7609801A patent/FR2306971A1/en active Granted
- 1976-04-05 CA CA249,592A patent/CA1092145A/en not_active Expired
- 1976-04-05 DE DE19762614648 patent/DE2614648A1/en not_active Withdrawn
- 1976-04-06 GB GB13964/76A patent/GB1537873A/en not_active Expired
- 1976-04-06 TR TR18934A patent/TR18934A/en unknown
- 1976-04-06 EG EG76202A patent/EG12221A/en active
- 1976-04-06 IL IL7649357A patent/IL49357A0/en unknown
- 1976-04-06 HU HU76CI1651A patent/HU176210B/en unknown
- 1976-04-06 BR BR7602093A patent/BR7602093A/en unknown
- 1976-04-06 AU AU12705/76A patent/AU497093B2/en not_active Expired
- 1976-04-06 AT AT247376A patent/AT342921B/en not_active IP Right Cessation
- 1976-04-07 JP JP51039152A patent/JPS51127051A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS51127051A (en) | 1976-11-05 |
| GB1537873A (en) | 1979-01-04 |
| FR2306971A1 (en) | 1976-11-05 |
| DE2614648A1 (en) | 1976-10-21 |
| TR18934A (en) | 1977-12-20 |
| AU1270576A (en) | 1977-10-13 |
| BR7602093A (en) | 1976-10-05 |
| ATA247376A (en) | 1977-08-15 |
| MX3200E (en) | 1980-07-03 |
| NL7603488A (en) | 1976-10-11 |
| AU497093B2 (en) | 1978-11-30 |
| EG12221A (en) | 1978-12-31 |
| HU176210B (en) | 1981-01-28 |
| FR2306971B1 (en) | 1978-11-17 |
| AT342921B (en) | 1978-04-25 |
| IL49357A0 (en) | 1976-06-30 |
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| MKEX | Expiry |