CA1100991A - Esters - Google Patents
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- CA1100991A CA1100991A CA271,762A CA271762A CA1100991A CA 1100991 A CA1100991 A CA 1100991A CA 271762 A CA271762 A CA 271762A CA 1100991 A CA1100991 A CA 1100991A
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/743—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a three-membered ring and with unsaturation outside the ring
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Abstract of the Disclosure Cyclopropanecarboxylic acid esters of the formula
Description
The present invention relates to cyclopropanecarboxylic acid es~ers, to processes ~or producing them and to their use in combating pests.
The cyclopropanecarboxylic acid ~sters have the forrnula X o Rl, ~
` & = CH -- CH -- CH -- C -- O -- CH -~ (I) wherein X and Y each represent chlorine, fluorine or bromine, Kl represents Cl-CS-alkyl, and R2 represents hydrogen or methyl. The alkyl,groups represented by Rl can be straight-chain or branched-chain. ~xamples of such groups are methyl, ethyl, propyl, isopropyl, n~ , sec.-, tert.-butyl, n pentyl and isomers thereof. Compounds of the formula I preferred on account of their action are those wherein X and Y are identical and represent fluorine, chlorine or bromine, and Rl and R2 each represent methyl.
The compounds of the formula I are produced by methods known per se, for example as follows:
.
1 ~ acid-' 1~ C=C~CH-C~C-Hal ~ HO~CH ~ ~ - b ~ ~ ~ ~ binding agent r Cll tII~ 2 (III) . ;: , :, :
. . ~ , ;
o ~
X~ O Rl ~ acid-binding
The cyclopropanecarboxylic acid ~sters have the forrnula X o Rl, ~
` & = CH -- CH -- CH -- C -- O -- CH -~ (I) wherein X and Y each represent chlorine, fluorine or bromine, Kl represents Cl-CS-alkyl, and R2 represents hydrogen or methyl. The alkyl,groups represented by Rl can be straight-chain or branched-chain. ~xamples of such groups are methyl, ethyl, propyl, isopropyl, n~ , sec.-, tert.-butyl, n pentyl and isomers thereof. Compounds of the formula I preferred on account of their action are those wherein X and Y are identical and represent fluorine, chlorine or bromine, and Rl and R2 each represent methyl.
The compounds of the formula I are produced by methods known per se, for example as follows:
.
1 ~ acid-' 1~ C=C~CH-C~C-Hal ~ HO~CH ~ ~ - b ~ ~ ~ ~ binding agent r Cll tII~ 2 (III) . ;: , :, :
. . ~ , ;
o ~
X~ O Rl ~ acid-binding
2~ C-CII-CH-C~I-C-OH ~ ~al-CH ~
Y /C agent C~3 R2 ~IV) ' lV) J \C C ll C H - C H -C -O H ~ I10- C II ~ ~
Y C water-binding agent (IV) ~III) In the formulae II, III, IV and V, the symbols Rl, R2, X
and Y have the meanings given under the formula I, and "Hal"
represents a halogen atom, particularly chlorine.
Suitable acid-binding agents for the processes 1 and 2 are, in particular, tertiary amines such as trialkylamines and pyridine, also hydroxides, oxides and carbonates and bicarbonates of alkali metals and alkaline-earth metals, and alkali metal alcoholates such as potassium-t.-butylate and sodium methylate.' The water-binding agent used for the process 3 can be, for example, dicyclohexylcarbodiimide. The processes 1, 2 and 3 are performed at a reaction temperature of between -10 and 100C, usually between 20 and 80C, at normal or elevated pressure and preferably in an inert solvent or diluent.
~"
., . - ~
Suitable solvents or dil~tents 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 and 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 ormulae II to V are known or can be produced by methods analogous to known methods.
The compounds of the formula I are obtained as mixtures of various optica]ly active compounds and cis/trans isomers, unless the starting materials used to produce the sai.d compounds are homogeneous optically active compounds or cis/trans isomers.
The di~ferent isomeric mixtures can be separated by known methods into the homogeneous isomers. It is understood that ~`
the term compounds of the ormula I embraces both the individual isomers and the mixtures thereof. The compo~mds of the ormula I
are suitable or combating various animal and plant pests.
They can thus be used for combating mites and ticks, for example of the genera Tetranychus and Panonychus, and the families Dermanyssidae and Ixodidae. They are however in particular suitable for combating insects, e.g. of the families:
", , - . . . . . . .
Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Pyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae, Dermestidae, Coccinel]idae, Tenebrionidae, Chrysomelidae, Bruchidae~ Tineidae, Noctuidae, Lymantriidae, Pyralidae, Culicidae, Tipulidae, S~omoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae. The compounds of the formula I are especially suitable for combating insects that damage plants, particularly insects that damage plants by eating, in crops of ornam~ntal plants and useful plants, especially in cotton crops (e.g. against Spodoptera littoralis and Heliothis virescens) and in crops of vegetables (e.g. against Leptinotarsa decemlinea-ta and Myzus persicae). Active substances of the formula I also have a very good action against flies, such as Musca domes~ica, and against mosqui~o larvae.
The acaricidal and insPcticidal action can be substantially broadened and adapted to suit given circumstances by the addition of other insec~icides and/or acaricides. Suitable additives are, e.g., organic phosphorus compounds; nitrophenols and derivatives thereof; formamidines; ureas; other pyrethrin-like compounds; as well as carbamates and chlorinated hydro-carbons.
Compo-tnds of the formula I are combined particularly _ 5 _ .. . ...
, ~
.
, ~ .
. . .
: ' .- . . : , ,~ . '. . ~ : : .
,, advantageously also with substances which have a synergistic or intensifying effect on pyrethroids. Examples of such compounds are, inter alia, piperonylbutoxide, propynyl ~thers, propynyl oximes, propynyl carbamates and propynyl phosphonates, 2-(3,4-methylenedioxyphenoxy) 3,6,9-trioxaundecane (Sesamex or Sesoxane~, S,S,S~ributylphosphorotrithioates and 1,2-methylenedioxy-4-(2-(octylsulphonyl)-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 substances common in formulation practice, such as natural or regenerated substances, solvents, dispersing agents, wettlng agents, adhesives, thickeners, binders and/or fertilisers.
: .
. . :: ., - ., . .. :
. ~ . -, . ~ . . . .
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 ~o the active substances. The active substances can be obtained and used in the following forms:
ol_d preparations: dusts, scattering agents, granulates (coated granulates, impregnated granulates and homogeneous granulates);
liquid preparatio_s: --) water-dispersible concentrates of active substance:
wettable powders, pastes or emulsions;
b) solutions.
The content of active substance in the described compositions is between 0.1 and 95%; in this respect it is to be mentioned that in the case of application from an aeroplane~ or by means of other suitable devices, concentrations of up to 99.5% or even the pure active substance can be used.
The active substances of the formula I can be formulated for example as ~ollows (parts are by weight):
Dusts:
-The following substances are used to produce a) a 5% dustand b) a 2% dust:
a) S parts of active substance, parts of talcum;
. - ~
; ~:
b) 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:
parts of active substance, 0.25 part of epichlorohydrin, 0.25 part of cetyl polyglycol ether,
Y /C agent C~3 R2 ~IV) ' lV) J \C C ll C H - C H -C -O H ~ I10- C II ~ ~
Y C water-binding agent (IV) ~III) In the formulae II, III, IV and V, the symbols Rl, R2, X
and Y have the meanings given under the formula I, and "Hal"
represents a halogen atom, particularly chlorine.
Suitable acid-binding agents for the processes 1 and 2 are, in particular, tertiary amines such as trialkylamines and pyridine, also hydroxides, oxides and carbonates and bicarbonates of alkali metals and alkaline-earth metals, and alkali metal alcoholates such as potassium-t.-butylate and sodium methylate.' The water-binding agent used for the process 3 can be, for example, dicyclohexylcarbodiimide. The processes 1, 2 and 3 are performed at a reaction temperature of between -10 and 100C, usually between 20 and 80C, at normal or elevated pressure and preferably in an inert solvent or diluent.
~"
., . - ~
Suitable solvents or dil~tents 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 and 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 ormulae II to V are known or can be produced by methods analogous to known methods.
The compounds of the formula I are obtained as mixtures of various optica]ly active compounds and cis/trans isomers, unless the starting materials used to produce the sai.d compounds are homogeneous optically active compounds or cis/trans isomers.
The di~ferent isomeric mixtures can be separated by known methods into the homogeneous isomers. It is understood that ~`
the term compounds of the ormula I embraces both the individual isomers and the mixtures thereof. The compo~mds of the ormula I
are suitable or combating various animal and plant pests.
They can thus be used for combating mites and ticks, for example of the genera Tetranychus and Panonychus, and the families Dermanyssidae and Ixodidae. They are however in particular suitable for combating insects, e.g. of the families:
", , - . . . . . . .
Tettigoniidae, Gryllidae, Gryllotalpidae, Blattidae, Reduviidae, Pyrrhocoridae, Cimicidae, Delphacidae, Aphididae, Diaspididae, Pseudococcidae, Scarabaeidae, Dermestidae, Coccinel]idae, Tenebrionidae, Chrysomelidae, Bruchidae~ Tineidae, Noctuidae, Lymantriidae, Pyralidae, Culicidae, Tipulidae, S~omoxydae, Trypetidae, Muscidae, Calliphoridae and Pulicidae. The compounds of the formula I are especially suitable for combating insects that damage plants, particularly insects that damage plants by eating, in crops of ornam~ntal plants and useful plants, especially in cotton crops (e.g. against Spodoptera littoralis and Heliothis virescens) and in crops of vegetables (e.g. against Leptinotarsa decemlinea-ta and Myzus persicae). Active substances of the formula I also have a very good action against flies, such as Musca domes~ica, and against mosqui~o larvae.
The acaricidal and insPcticidal action can be substantially broadened and adapted to suit given circumstances by the addition of other insec~icides and/or acaricides. Suitable additives are, e.g., organic phosphorus compounds; nitrophenols and derivatives thereof; formamidines; ureas; other pyrethrin-like compounds; as well as carbamates and chlorinated hydro-carbons.
Compo-tnds of the formula I are combined particularly _ 5 _ .. . ...
, ~
.
, ~ .
. . .
: ' .- . . : , ,~ . '. . ~ : : .
,, advantageously also with substances which have a synergistic or intensifying effect on pyrethroids. Examples of such compounds are, inter alia, piperonylbutoxide, propynyl ~thers, propynyl oximes, propynyl carbamates and propynyl phosphonates, 2-(3,4-methylenedioxyphenoxy) 3,6,9-trioxaundecane (Sesamex or Sesoxane~, S,S,S~ributylphosphorotrithioates and 1,2-methylenedioxy-4-(2-(octylsulphonyl)-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 substances common in formulation practice, such as natural or regenerated substances, solvents, dispersing agents, wettlng agents, adhesives, thickeners, binders and/or fertilisers.
: .
. . :: ., - ., . .. :
. ~ . -, . ~ . . . .
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 ~o the active substances. The active substances can be obtained and used in the following forms:
ol_d preparations: dusts, scattering agents, granulates (coated granulates, impregnated granulates and homogeneous granulates);
liquid preparatio_s: --) water-dispersible concentrates of active substance:
wettable powders, pastes or emulsions;
b) solutions.
The content of active substance in the described compositions is between 0.1 and 95%; in this respect it is to be mentioned that in the case of application from an aeroplane~ or by means of other suitable devices, concentrations of up to 99.5% or even the pure active substance can be used.
The active substances of the formula I can be formulated for example as ~ollows (parts are by weight):
Dusts:
-The following substances are used to produce a) a 5% dustand b) a 2% dust:
a) S parts of active substance, parts of talcum;
. - ~
; ~:
b) 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:
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 ether are then added. The solution obtained is sprayed onto kaolin, and the acetone is then evaporated off in vacuo.
Wettable powder:
The following constituents are used to produce a) a 40~/0, b) and c) a 25%, and d) a 10% wettable powder:
a) 40 parts of ac~ive substance, parts of sodi~ lignin sulphonate, 1 part of sodium dibutyl-naphthalene sulphonate, 54 parts of silicic acid;
- 8 ~
. .
:
~ 9 b) 25 parts of active substance,
The active substance is mixed with epichlorohydrin and dissolved with 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The solution obtained is sprayed onto kaolin, and the acetone is then evaporated off in vacuo.
Wettable powder:
The following constituents are used to produce a) a 40~/0, b) and c) a 25%, and d) a 10% wettable powder:
a) 40 parts of ac~ive substance, parts of sodi~ lignin sulphonate, 1 part of sodium dibutyl-naphthalene sulphonate, 54 parts of silicic acid;
- 8 ~
. .
:
~ 9 b) 25 parts of active substance,
4 5 parts of calcium ligni~ 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, ~ 8.1 parts of kaolin;
c) 25 parts of active substance 5 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1~7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 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 mixture of the sodium salts of saturated fatty alcohol sulphates, parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.
The active substance is 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 swspensions of the desired concentration.
_ 9 _ , .,: . ,.: , . .
. . .. ~
Emulsifiabl.e concentrates:
.
The following substances are used to produce a) a 10%, b) a 25V/o~ and c) a 50% emulsifiable concentrate:
a) 10 parts of active substance, 3.4 parts of epoxidised vegetable oil~
3.4 parts of a combination emulsifi.er consisting ~, of fatty alcohol polyglycol ether and alkylaryl.-sulphonate calcium salt, parts of dimethylformamide, 43.2 parts of xylene, -.
b) 25 par~s 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 5 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol, 1~7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 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 mixture of the sodium salts of saturated fatty alcohol sulphates, parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.
The active substance is 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 swspensions of the desired concentration.
_ 9 _ , .,: . ,.: , . .
. . .. ~
Emulsifiabl.e concentrates:
.
The following substances are used to produce a) a 10%, b) a 25V/o~ and c) a 50% emulsifiable concentrate:
a) 10 parts of active substance, 3.4 parts of epoxidised vegetable oil~
3.4 parts of a combination emulsifi.er consisting ~, of fatty alcohol polyglycol ether and alkylaryl.-sulphonate calcium salt, parts of dimethylformamide, 43.2 parts of xylene, -.
b) 25 par~s 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-dodecylbenzeneswlphonate, parts of cyclohexanone, parts of xylene.
Emulsions of the desired concentration can be prepared from these concentrates by dilution with water.
.
Spray:
The following consti~uents are used to produce a) a 5%
spray and b) a 95% spray:
a) S parts of active substance, 1 part of epichlorohydrin, 94 parts of ligroin (boiling limits 160-190C);
b) 95 parts of active substance, S parts of epichlorohydrin.
., The invention is further illustrated by the following Examples.
..
. ~, . , .. , ~ -.- ~ .. :: . ::. : , : . . , ., ~ ;.. ,. , .. . ~ ,:
- . .: .:, . ~ ,. , - , , . : . -.: .
Example l Production of the compound of the formula Cl 0 CH3 C 1 ~ C
~H3 CH3 1.72 g of pyridine is added dropwise at room temperature to a solution of 4.5 g of 2,2-dimethyl-3~ dichlorovinyl)-cyclopropanecarbGxylic acid chloride and 4.25 g of 3-phenoxy-..
a hydroxyethylbenzene in 100 ml of toluene. The temperature meanwhile rises to 30C. The reaction mixture is subsequently stirred for 15 hours at 20-25C; it is then extracted by shaking with H20, dried over sodium sulphate and completely concentrated by evaporation.
By chromatographing the resulting crude product with toluene through silica gel is obtained the compou-nd of the formula Cl 0 C~3 /
~ C}13 CH3 in the form of colourless oil having a refractive index of n20 - 1 563 . .
.. 'Y
.
The ollowing compounds are produced analogously:
X\c~cE~-cll~c~-c-Rl; . .. ~2 Refractive Inde~
Cl Cl iso-C3~7 C~3 n20 1, 5518 Cl Cl C5 11 ( ) CH3 n20 1 5465 . -:
Br Br CH3 CH3 n20 l, 574 Br Br iso-C3H7 CH3 n l ~ 5613 Cl Cl n~C3~l7 ( l~3 n2~0 1, 5228 F F C~33 C~13 21 Cl Cl CH3 D O l, 561 F F C2HS . 21 Br Br C5Hll (n) CH3 n~ 556 Cl Cl C2H5 CH3 ~ n22 1, S55 F F C3H7 (iso3 ~ C~3 nD l,5245 Br Br C2H5 C~3 n2l 1, 568 Cl Cl C4Hg (n) CH3 nD l~545 Cl Cl C~H9 ~lso) C~3 nDl 1,546 ., , ' ' ' , :
,: : :. : . , -- : , : . .
Example 2 A) Insecticidal stomach~ ion Tobacco and potato plants were sprayed with a 0.05%
aqueous active-substance emulsion (obtained from a 10%
emulsifiable concentrate).
After drying of the coating~ caterpillars of Spodoptera littoralis in the L3 stage and of Heliothis virescens in the L3-stage were placed on the tobacco and potato plants.
The test was carried out at 24C with 60% relative humidity.
Compounds according to Example 1 exhibited in the above 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 emùlsion at a concentration of lO00 ppm (prepared from a 25% wettable powder) was applied by means of a compressed-air sprayer to the leaves infested with aphids.
An evaluation was made 24 hours after application. Compounds according to Example 1 exhibited in the above ~est a good contact action against Aphis fabae.
-Example 3 Acaricidal action -Phaseolus vulgaris (bush beans) were infested, 12 hours before the test 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 overflow of the spray liquor. An assessment was made after 2 to 7 days, by examination under a binocular microscope, of the living and of the dead larvae, adults and eggs, and the results were expressed as percentages.
The treated plants were kept during the "holding time" in greenhouse compartments at 25C.
Compounds according to Example 1 exhibited a good action in the above test against adults, larvae and eggs of Tetranychus urticae.
Emulsions of the desired concentration can be prepared from these concentrates by dilution with water.
.
Spray:
The following consti~uents are used to produce a) a 5%
spray and b) a 95% spray:
a) S parts of active substance, 1 part of epichlorohydrin, 94 parts of ligroin (boiling limits 160-190C);
b) 95 parts of active substance, S parts of epichlorohydrin.
., The invention is further illustrated by the following Examples.
..
. ~, . , .. , ~ -.- ~ .. :: . ::. : , : . . , ., ~ ;.. ,. , .. . ~ ,:
- . .: .:, . ~ ,. , - , , . : . -.: .
Example l Production of the compound of the formula Cl 0 CH3 C 1 ~ C
~H3 CH3 1.72 g of pyridine is added dropwise at room temperature to a solution of 4.5 g of 2,2-dimethyl-3~ dichlorovinyl)-cyclopropanecarbGxylic acid chloride and 4.25 g of 3-phenoxy-..
a hydroxyethylbenzene in 100 ml of toluene. The temperature meanwhile rises to 30C. The reaction mixture is subsequently stirred for 15 hours at 20-25C; it is then extracted by shaking with H20, dried over sodium sulphate and completely concentrated by evaporation.
By chromatographing the resulting crude product with toluene through silica gel is obtained the compou-nd of the formula Cl 0 C~3 /
~ C}13 CH3 in the form of colourless oil having a refractive index of n20 - 1 563 . .
.. 'Y
.
The ollowing compounds are produced analogously:
X\c~cE~-cll~c~-c-Rl; . .. ~2 Refractive Inde~
Cl Cl iso-C3~7 C~3 n20 1, 5518 Cl Cl C5 11 ( ) CH3 n20 1 5465 . -:
Br Br CH3 CH3 n20 l, 574 Br Br iso-C3H7 CH3 n l ~ 5613 Cl Cl n~C3~l7 ( l~3 n2~0 1, 5228 F F C~33 C~13 21 Cl Cl CH3 D O l, 561 F F C2HS . 21 Br Br C5Hll (n) CH3 n~ 556 Cl Cl C2H5 CH3 ~ n22 1, S55 F F C3H7 (iso3 ~ C~3 nD l,5245 Br Br C2H5 C~3 n2l 1, 568 Cl Cl C4Hg (n) CH3 nD l~545 Cl Cl C~H9 ~lso) C~3 nDl 1,546 ., , ' ' ' , :
,: : :. : . , -- : , : . .
Example 2 A) Insecticidal stomach~ ion Tobacco and potato plants were sprayed with a 0.05%
aqueous active-substance emulsion (obtained from a 10%
emulsifiable concentrate).
After drying of the coating~ caterpillars of Spodoptera littoralis in the L3 stage and of Heliothis virescens in the L3-stage were placed on the tobacco and potato plants.
The test was carried out at 24C with 60% relative humidity.
Compounds according to Example 1 exhibited in the above 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 emùlsion at a concentration of lO00 ppm (prepared from a 25% wettable powder) was applied by means of a compressed-air sprayer to the leaves infested with aphids.
An evaluation was made 24 hours after application. Compounds according to Example 1 exhibited in the above ~est a good contact action against Aphis fabae.
-Example 3 Acaricidal action -Phaseolus vulgaris (bush beans) were infested, 12 hours before the test 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 overflow of the spray liquor. An assessment was made after 2 to 7 days, by examination under a binocular microscope, of the living and of the dead larvae, adults and eggs, and the results were expressed as percentages.
The treated plants were kept during the "holding time" in greenhouse compartments at 25C.
Compounds according to Example 1 exhibited a good action in the above test against adults, larvae and eggs of Tetranychus urticae.
Claims (20)
1. A cyclopropanecarboxylic acid ester of the formula wherein X and Y each represent fluorine, chlorine or bromine, R1 represents C1-C5-alkyl, and R2 represents hydrogen or methyl.
2. A compound according to Claim 1, wherein X and Y are identical and represent fluorine, chlorine or bromine, and R1 and R2 each represent methyl.
3. The compound according to Claim 2 of the formula .
4. The compound according to Claim 1 of the formula .
5. The compound according to Claim 1 of the formula .
6. The compound according to Claim 2 of the formula .
7. The compound according to Claim 1 of the formula .
8. The compound according to Claim 2 of the formula .
9. The compound according to Claim 1 of the formula .
10. The compound according to Claim 1 of the formula .
11. The compound according to Claim 1 of the formula .
12. The compound according to Claim 1 of the formula .
13. The compound according to Claim 1 of the formula .
14. The compound according to Claim 1 of the formula .
15. The compound according to Claim 1 of the formula .
16. The compound according to Claim 1 of the formula .
17. The compound according to claim 1 of the formula
18. Process for producing compounds according to claim 1, which process comprises reacting, in the presence of an acid-binding agent, a compound of the formula with a compound of the formula Wherein R1, R2, X and Y have the meanings given in claim 1, and "Hal"
represents a halogen atom.
represents a halogen atom.
19. A method of combating animal and plant pests at a locus, which method comprises applying to the locus a compound as claimed in claim 1.
20. A method according to claim 19 wherein the pest are of the class Insecta or of the order Acarina.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH187176A CH600772A5 (en) | 1976-02-16 | 1976-02-16 | (3)-Phenoxy-benzyl dihalo-vinyl-cyclopropane-carboxylates |
| CH1871/76 | 1976-02-16 | ||
| CH7111/76 | 1976-06-04 | ||
| CH711176 | 1976-06-04 | ||
| CH1113376 | 1976-09-02 | ||
| CH11133/76 | 1976-09-02 | ||
| CH5877 | 1977-01-04 | ||
| CH58/77 | 1977-01-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1100991A true CA1100991A (en) | 1981-05-12 |
Family
ID=27427750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA271,762A Expired CA1100991A (en) | 1976-02-16 | 1977-02-14 | Esters |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS52100450A (en) |
| BE (1) | BE851423A (en) |
| CA (1) | CA1100991A (en) |
| DE (1) | DE2706222A1 (en) |
| FR (1) | FR2340925A1 (en) |
| GB (1) | GB1567692A (en) |
| IL (1) | IL51454A0 (en) |
| NL (1) | NL7701641A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1595081A (en) * | 1977-02-08 | 1981-08-05 | Shell Int Research | Pesticidal composition |
| GB1594462A (en) * | 1977-02-09 | 1981-07-30 | Shell Int Research | Pesticidal composition |
| DE2805193A1 (en) * | 1977-02-11 | 1978-08-17 | Ciba Geigy Ag | CYCLOPROPANIC CARBON ACID ESTERS, THE PROCESS FOR THEIR MANUFACTURING AND THEIR USE IN PEST CONTROL |
| JPS609715B2 (en) * | 1977-06-20 | 1985-03-12 | 住友化学工業株式会社 | Carboxylic acid esters, their production methods, and insecticides and acaricides containing them as active ingredients |
| EP0000962B1 (en) * | 1977-08-10 | 1981-11-18 | Shell Internationale Researchmaatschappij B.V. | Pesticidal composition and method of combating pests |
| DE2860310D1 (en) | 1977-11-09 | 1981-02-19 | Ciba Geigy Ag | 3-phenoxy-alpha-vinylbenzylesters of vinylcyclopropanecarboxylic acids, process for their preparation and their use as pesticides |
| FR2482955A1 (en) * | 1980-05-23 | 1981-11-27 | Roussel Uclaf | NOVEL DERIVATIVES OF CYCLOPROPANE CARBOXYLIC ACID, PROCESS FOR PREPARING THEM AND THEIR APPLICATION TO THE FIGHT AGAINST PARASITES |
| FR2488603A1 (en) * | 1980-08-12 | 1982-02-19 | Roussel Uclaf | NOVEL ACID DERIVATIVES (1R, CIS) 2,2-DIMETHYL 3 (2,2-DI-FLUORO ETHENYL) CYCLOPROPANE CARBOXYLIC, PROCESS FOR THE PREPARATION THEREOF AND THEIR USE FOR THE CONTROL OF PARASITE MITES OF PLANTS AND VEGETABLES |
-
1977
- 1977-02-14 DE DE19772706222 patent/DE2706222A1/en not_active Withdrawn
- 1977-02-14 FR FR7704088A patent/FR2340925A1/en active Granted
- 1977-02-14 CA CA271,762A patent/CA1100991A/en not_active Expired
- 1977-02-15 GB GB6265/77A patent/GB1567692A/en not_active Expired
- 1977-02-15 BE BE174927A patent/BE851423A/en unknown
- 1977-02-15 IL IL51454A patent/IL51454A0/en unknown
- 1977-02-16 JP JP1601877A patent/JPS52100450A/en active Pending
- 1977-02-16 NL NL7701641A patent/NL7701641A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| FR2340925B1 (en) | 1980-02-08 |
| DE2706222A1 (en) | 1977-08-18 |
| FR2340925A1 (en) | 1977-09-09 |
| GB1567692A (en) | 1980-05-21 |
| NL7701641A (en) | 1977-08-18 |
| IL51454A0 (en) | 1977-04-29 |
| JPS52100450A (en) | 1977-08-23 |
| BE851423A (en) | 1977-08-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |