CA1076135A - 4-phenylbut-2-enyl esters of 2,2-dimethyl-3-vinyl-cyclopropane carboxylic acid and their use as pesticides - Google Patents
4-phenylbut-2-enyl esters of 2,2-dimethyl-3-vinyl-cyclopropane carboxylic acid and their use as pesticidesInfo
- Publication number
- CA1076135A CA1076135A CA238,661A CA238661A CA1076135A CA 1076135 A CA1076135 A CA 1076135A CA 238661 A CA238661 A CA 238661A CA 1076135 A CA1076135 A CA 1076135A
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- formula
- dimethyl
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Abstract
Abstract of the Disclosure Cyclopropane carboxylic acid esters of the formula
Description
.
This invention relates to cyclopropane carboxylic acid esters and their use as pesticides.
According to the present invention, there are provided compounds of the formula I
~ C=CH-CH - CH-COOCH~-CII=C-C~2 ~ (1 ÇH3 C~3 : ' wberein Xl represents a chlorine, fluorine or bromine atom and X2 represents a fluorine or bromine atom.
The compounds of formula I can be prepared by .
process analogaus to ~nown methods for example by reacting a compound of the formula II
X
C=CH-CH - CH-COOH
~: X2 cl~3 CH -:~ 3 ;~ wherein Xl and X2 have the sa~e meanings as given for formula I, with a compound of the formula .
~:
X-CH -CH-C-CH ~ ~III) Cl ':
~ . ,,;, '.
'~"D
~."' .
. ... ; .. , .. , . . ,, . ., ., , .... ... ~ " ,. , .. , . .
,., . . ;. .. . . ... .. . .. . .. .. . . .. .
~7 61 3 5 wherein X represents a halogen atom, i~ particular a chlorine or bromine atom, in the presence of a base such as a tertiary amine, for example a trialkylamlne or pyridine, or a hydroxide, oxide, carbonate or b~carbonate of an alkali metal and alkaline earth metal, or an alkali metal alcoholate, for exa~ple potassium ~;
tert.butylate or sodium methylate.
The process is carried out at a reaction temperature generally between -10 and 100C, pre~erably between 20 and 80C, at normal or elevated pressure, ~ ~
and preferably in a solvent or diluent which is inert ~ `
: .:
to the reactants.
~ xamples of suitable solvents or diluents that may be used are: ethers and ethereal compounds, for example diethyl ether, dipropyl e her, dioxan, d~methoxy ethane, tetrahydrofuran; amides, for example N,N-diethylated carboxy amides; aliphatic, aromatic and halogenated hydrocarbons, especially b~nzene, toluene, xylene, chloroform, chlorobenzene; nitriles, for example acetonitrile; dimethyl sulfoxide; and ~etones, for example acetone, methylethyl ketone.
The starting materials of formulae II and III are known and can be prepared by methods analogous to known methods.
The compounds of formula I occur in different optically active and cis/trans-isomeric forms. If therefore individual isomers are not used asstarting materials, then 1~37f~13S
"_ ~
_ 4 _ racemic and/or cis/trans-iso~eric mixtures are r.ecessarily obtained.
The different isomeric mixtures obtained can be separated into the individual isomeric for~s t for example by recrystallis~tion or by means of chromatographic separating met~ods, for example by gas chro~atography or by adsorption o~ a separating material with selective ~adsorption activity, such as silica gel or aluminium oxide, and subsequently eluting the separated iso~ers with a suitable sol~ent.
T~e compounds of formula I co~prise both the lndividual optically active isomers and cis- or trans-isomers 2nd mixtures thereof~
The compounds of the formuIa I are suitable for controlling a variety of animal and plant pests. In partic-ular, the compounds of the formula I are suitable for con-trolling insects, phytopathogenic mites and ticks, for example of the orders: Lepidoptera, Coleoptera, Homoptera, ~; Heteroptera, Diptera, Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera.
In particular, the compounds of the formula I are suitable for controlling insects which are harmful to plants, especially insects which damage plants by eating, in ornam-entals and crops of useful plants, especially in cotton plantations (e.g. Spodoptera littoralis and Heliothis virescens) and in vegetable crops (for example Leptinotarsa decemlineata and Myzus persicae).
'~r ` "'i ? : ~ ~
0'76~ 3 5 , ~ :
The active compounds of the formula I also have a very good action against flies, for example Musca do~estica and mosquito larvae.
The insecticidal and/or acaricidal action can be substan-tially broadened and adapted to prevailing circumstances by addition of other insecticides and/or acaricides. Examples of suitable additives include: organic phosphorus compounds, nitrophenols and derivatives thereof, form~midines, ureas, pyethroids, carbamates, and chlorinated hydrocarbons.
Compounds of the formula I are also combined with parti-cular advantage with substances which exert a synergistic or potentiating effect on pyrethroids. Examples of such com-pounds include: piperonyl butoxide, propynyl ether~propynyl oximes, propynyl carbamates and propynyl phosphonates, 2-(3,4-methylenedioxyphenoxy)-3,6,9~trioxaundecane (Sesamex or Seso~ane), S,S,S-tributylphosphorotrithioate, 1,2-Methy-lenedioxy-4(2-(octylsulphonyl)-propyl)-benzene.
The compounds of the formula I may be used as pure acti-ve substance or together with suitable carriers and/or addi-tives. Suitable carriers and additives can be solid or liquld and correspond to the substances conventionally used in the art of formulation, for example natural or regenerated sub-stances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders and/or fertilisers.
~; The compositions of the pr~sent invention are m~tnufac-tured in known manner by homogeneously mixing and/or grin-ding active substances of the formula I with the suitable carriers, with or without the addition of dispersants or solvents which are inert to the active substances.
The compounds of the for~ula I may be processed to the following formulations:
: ., :
', '. ', '' ., ~ ' ' . ., ',.~,:' ' ' , ,', ;, . ',. .
.. . ..
.. ., , - . .. . .
-- ~076135 . ~ .
Solid formulations:
Dusts, tracking powders and granules (coated granules, impregnated granules and homogeneous granules).
Liquid formulations:
a) active substances which are dispersable in water:
wettable powders, pastes and emulsions;
b ) so lutions.
The content of active substance in the above described co~positions is generally between 0.1% and 95%, though con-centrations of up to 99.5% or even pure active substance aIso be used if the co~positions are applied from an aircraft or other appropriate application devices.
The compounds (active substances) of the formula I can, for example, be formulated as follows (throughout the pre-~ sen~ specification all parts and percentages are by weight):
: , ' ~ I)UBt8 The following substances are used to produce a) a 5% and b) a 2% dust: -a) 5 parts of active substance, parts of talc;
b) 2 parts of active substance, 1 part of highly disperse silicic acid, ~ ;~
97 parts o~ talc.
The active substances are mixed with the carriers and ground.
Granules .,, ,-.~
The following substances are used to produce 5%
granules:
:' ' ;
, . . . " . , ,, . : " . .. .. . . . ............. . .... .
.", ' ' .'" , ,' '- ',, ' ' . ', ' ' ',, ,. , . " , ' ' '' '. ',, ' ,: ' " . .: ,"
1(~7613S ~ ~
.
5 parts of active substance -0.25 parts of epi~hlorohydrin, .
0.25 parts 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 .
the mixture is dissol~ed in 6 parts of acetone; the poly-ethylene glycol and cetyl polyglycol ether are then added.
The resultant solution is sprayed on kaolin, and the ace-tone is subsequently evaporated in vacuo.
Wettable ~owders:
The ollowing constituents are used or the preparation of a~ a 40%, b) and c) a 25%, and d) a 10% wettable powder:
a) 40 parts of active substance, parts of sodium ligninsulphonate, 1 part of sodium dibutylnaphthalenesulphonate, : 54 parts parts of silicic acid.
b) 25 parts of active substance, 4 5 parts of calcium ligninsulphonate, 1,9 parts of Champagne chalk/hydroxyethyl cellulose : mixture (1:1), 1~5 parts of sodium dibutylnaphthalenesulphonate, 19,1 parts of silicic acid, - : 19,5 parts of Champagne chalk, .
28,1 parts of kaolin, :
: c) 25 parts of active substance,
This invention relates to cyclopropane carboxylic acid esters and their use as pesticides.
According to the present invention, there are provided compounds of the formula I
~ C=CH-CH - CH-COOCH~-CII=C-C~2 ~ (1 ÇH3 C~3 : ' wberein Xl represents a chlorine, fluorine or bromine atom and X2 represents a fluorine or bromine atom.
The compounds of formula I can be prepared by .
process analogaus to ~nown methods for example by reacting a compound of the formula II
X
C=CH-CH - CH-COOH
~: X2 cl~3 CH -:~ 3 ;~ wherein Xl and X2 have the sa~e meanings as given for formula I, with a compound of the formula .
~:
X-CH -CH-C-CH ~ ~III) Cl ':
~ . ,,;, '.
'~"D
~."' .
. ... ; .. , .. , . . ,, . ., ., , .... ... ~ " ,. , .. , . .
,., . . ;. .. . . ... .. . .. . .. .. . . .. .
~7 61 3 5 wherein X represents a halogen atom, i~ particular a chlorine or bromine atom, in the presence of a base such as a tertiary amine, for example a trialkylamlne or pyridine, or a hydroxide, oxide, carbonate or b~carbonate of an alkali metal and alkaline earth metal, or an alkali metal alcoholate, for exa~ple potassium ~;
tert.butylate or sodium methylate.
The process is carried out at a reaction temperature generally between -10 and 100C, pre~erably between 20 and 80C, at normal or elevated pressure, ~ ~
and preferably in a solvent or diluent which is inert ~ `
: .:
to the reactants.
~ xamples of suitable solvents or diluents that may be used are: ethers and ethereal compounds, for example diethyl ether, dipropyl e her, dioxan, d~methoxy ethane, tetrahydrofuran; amides, for example N,N-diethylated carboxy amides; aliphatic, aromatic and halogenated hydrocarbons, especially b~nzene, toluene, xylene, chloroform, chlorobenzene; nitriles, for example acetonitrile; dimethyl sulfoxide; and ~etones, for example acetone, methylethyl ketone.
The starting materials of formulae II and III are known and can be prepared by methods analogous to known methods.
The compounds of formula I occur in different optically active and cis/trans-isomeric forms. If therefore individual isomers are not used asstarting materials, then 1~37f~13S
"_ ~
_ 4 _ racemic and/or cis/trans-iso~eric mixtures are r.ecessarily obtained.
The different isomeric mixtures obtained can be separated into the individual isomeric for~s t for example by recrystallis~tion or by means of chromatographic separating met~ods, for example by gas chro~atography or by adsorption o~ a separating material with selective ~adsorption activity, such as silica gel or aluminium oxide, and subsequently eluting the separated iso~ers with a suitable sol~ent.
T~e compounds of formula I co~prise both the lndividual optically active isomers and cis- or trans-isomers 2nd mixtures thereof~
The compounds of the formuIa I are suitable for controlling a variety of animal and plant pests. In partic-ular, the compounds of the formula I are suitable for con-trolling insects, phytopathogenic mites and ticks, for example of the orders: Lepidoptera, Coleoptera, Homoptera, ~; Heteroptera, Diptera, Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonaptera, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenoptera.
In particular, the compounds of the formula I are suitable for controlling insects which are harmful to plants, especially insects which damage plants by eating, in ornam-entals and crops of useful plants, especially in cotton plantations (e.g. Spodoptera littoralis and Heliothis virescens) and in vegetable crops (for example Leptinotarsa decemlineata and Myzus persicae).
'~r ` "'i ? : ~ ~
0'76~ 3 5 , ~ :
The active compounds of the formula I also have a very good action against flies, for example Musca do~estica and mosquito larvae.
The insecticidal and/or acaricidal action can be substan-tially broadened and adapted to prevailing circumstances by addition of other insecticides and/or acaricides. Examples of suitable additives include: organic phosphorus compounds, nitrophenols and derivatives thereof, form~midines, ureas, pyethroids, carbamates, and chlorinated hydrocarbons.
Compounds of the formula I are also combined with parti-cular advantage with substances which exert a synergistic or potentiating effect on pyrethroids. Examples of such com-pounds include: piperonyl butoxide, propynyl ether~propynyl oximes, propynyl carbamates and propynyl phosphonates, 2-(3,4-methylenedioxyphenoxy)-3,6,9~trioxaundecane (Sesamex or Seso~ane), S,S,S-tributylphosphorotrithioate, 1,2-Methy-lenedioxy-4(2-(octylsulphonyl)-propyl)-benzene.
The compounds of the formula I may be used as pure acti-ve substance or together with suitable carriers and/or addi-tives. Suitable carriers and additives can be solid or liquld and correspond to the substances conventionally used in the art of formulation, for example natural or regenerated sub-stances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders and/or fertilisers.
~; The compositions of the pr~sent invention are m~tnufac-tured in known manner by homogeneously mixing and/or grin-ding active substances of the formula I with the suitable carriers, with or without the addition of dispersants or solvents which are inert to the active substances.
The compounds of the for~ula I may be processed to the following formulations:
: ., :
', '. ', '' ., ~ ' ' . ., ',.~,:' ' ' , ,', ;, . ',. .
.. . ..
.. ., , - . .. . .
-- ~076135 . ~ .
Solid formulations:
Dusts, tracking powders and granules (coated granules, impregnated granules and homogeneous granules).
Liquid formulations:
a) active substances which are dispersable in water:
wettable powders, pastes and emulsions;
b ) so lutions.
The content of active substance in the above described co~positions is generally between 0.1% and 95%, though con-centrations of up to 99.5% or even pure active substance aIso be used if the co~positions are applied from an aircraft or other appropriate application devices.
The compounds (active substances) of the formula I can, for example, be formulated as follows (throughout the pre-~ sen~ specification all parts and percentages are by weight):
: , ' ~ I)UBt8 The following substances are used to produce a) a 5% and b) a 2% dust: -a) 5 parts of active substance, parts of talc;
b) 2 parts of active substance, 1 part of highly disperse silicic acid, ~ ;~
97 parts o~ talc.
The active substances are mixed with the carriers and ground.
Granules .,, ,-.~
The following substances are used to produce 5%
granules:
:' ' ;
, . . . " . , ,, . : " . .. .. . . . ............. . .... .
.", ' ' .'" , ,' '- ',, ' ' . ', ' ' ',, ,. , . " , ' ' '' '. ',, ' ,: ' " . .: ,"
1(~7613S ~ ~
.
5 parts of active substance -0.25 parts of epi~hlorohydrin, .
0.25 parts 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 .
the mixture is dissol~ed in 6 parts of acetone; the poly-ethylene glycol and cetyl polyglycol ether are then added.
The resultant solution is sprayed on kaolin, and the ace-tone is subsequently evaporated in vacuo.
Wettable ~owders:
The ollowing constituents are used or the preparation of a~ a 40%, b) and c) a 25%, and d) a 10% wettable powder:
a) 40 parts of active substance, parts of sodium ligninsulphonate, 1 part of sodium dibutylnaphthalenesulphonate, : 54 parts parts of silicic acid.
b) 25 parts of active substance, 4 5 parts of calcium ligninsulphonate, 1,9 parts of Champagne chalk/hydroxyethyl cellulose : mixture (1:1), 1~5 parts of sodium dibutylnaphthalenesulphonate, 19,1 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- ~
ethanol, .
1,7 parts of Champagne chalk/hydroxyethyl cellulose ~ixture (1:1), 8~3 parts of sodium aluminium silicate, ..
.~,, ' 11~ .
, .. , ~ ;. ,. ... . ., .. . ' ' : : ' :
.. . , ~ , , ~ .
.
07~35 16~5 parts of kieselguhr, 46 parts of kaolin;
d) 10 parts of active substance,
ethanol, .
1,7 parts of Champagne chalk/hydroxyethyl cellulose ~ixture (1:1), 8~3 parts of sodium aluminium silicate, ..
.~,, ' 11~ .
, .. , ~ ;. ,. ... . ., .. . ' ' : : ' :
.. . , ~ , , ~ .
.
07~35 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 substances are homogeneously ~ixed with the ~ additives in suitable mixers and the mixture is then ground ;~ in appropriate ~ills and roLlers. Wettable powders are ob-tained which can be diluted with water to give suspensions of the desired concentration.
Emulsifiable concentrates~
: .
The following substances are 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 of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium salt, parts of dimethyl formamide, 43.2 parts of xylene;
b) 25 parts of active substance, 2~5 parts of epoxidised vegetable oil, parts o~ alkylarylsulphonate/fatty alcohol polyglycol ether mixture, 5 parts of dimethyl forma~ide, -57.5 parts of xylene;
.: :
'; ."'' :" ' , ' . ' - ":" ;' '. ; :
,, . ~ . .. .
` 1~7 ~1 3 5 . .
_ 9 _ c) 50 parts of active substance,
The active substances are homogeneously ~ixed with the ~ additives in suitable mixers and the mixture is then ground ;~ in appropriate ~ills and roLlers. Wettable powders are ob-tained which can be diluted with water to give suspensions of the desired concentration.
Emulsifiable concentrates~
: .
The following substances are 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 of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsulphonate calcium salt, parts of dimethyl formamide, 43.2 parts of xylene;
b) 25 parts of active substance, 2~5 parts of epoxidised vegetable oil, parts o~ alkylarylsulphonate/fatty alcohol polyglycol ether mixture, 5 parts of dimethyl forma~ide, -57.5 parts of xylene;
.: :
'; ."'' :" ' , ' . ' - ":" ;' '. ; :
,, . ~ . .. .
` 1~7 ~1 3 5 . .
_ 9 _ c) 50 parts of active substance,
4 2 parts of tributylphenol-polyglycol ether,
5.8 parts of cylcium dodecylbenzenesulphonate, parts of cyclohexanene, parts of xylene.
By diluting these concentrates with water it ispo~ible to obtain emulsions of the required concentration.
Sprays:
The following ingredients are used to prepare a) a 5%
spray, and b) a 95% spray:
a) 5 parts of active substance, 1 part o~ epichlorohydrin~
94 parts of ligroin (boiling range 160 190C), b~ 95 parts of active substance, 5 parts of epichlorohydrin. -~
The invention is further illustrated by the following Exa~pIes.
, : -,':
. ~ .
- , ., ~ :
. : , . .: . . . . . .
' .. , " ' '~
:,:, , ~ , ,; , - ~xam~le 1 Manufacture of 2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropanecarboxylic acid-4-phenyl-3-chloro-2-butene ester of formula - 9.95 ~ of 2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropanecarboxylic acid are added by small amounts to a solution of 3.4 g of potassium tert. butylate in 50 ml of methyl ethyl ketone. Then 9.5 g of 2,4-dichloro-butenyl(2)-benzene is added to the reaction mixture, whichis stirred for 8 hours at 70 - 80C.
After it has cooled, the reaction mixture is poured onto ice water. The product is extracted into ether and the etherealextract is washed with 3 x 100 ml of 3~ Na2C03 solution. The ether solution is dried over sodium sulphate, the ether i~ distilled of~ and the c~ de product ~ractionated in a high ~acuum. The desired product is obtained as a yellowish li~uid with a boiling point of 179 - 180C/0.015 Torr.
The following compounds of formula I are obtained in analogous manner:
~ 6~L35 . .
C = CH - CH - CH - COOCH~-CH = I - CH2 _9 ~3 H3 Boiling point 130 - 1~2C/0.02 Torr.
. ~:
Cl C = CH - CH - CH - COOCH2-CH = C - CH
Br /C\ Cl Boiling point 160 - 1?0C/0.15 Torr.
.
. .
Insecticidal Stomach poison action Tobacco and potato plants were sprayed with a 0.05% aqueous emulsion ~obtained from a 10~ emulsifiable conoentrate). After the coating had dried, the tobacco plants were populated with Spodoptera littoralis larvae.L
and Heliothis virescens larvae L3 and the potatoe plants wlth Colorado potato beetle larvae L3 (Le~tinotarsa decem-lineata). The test was carried out at 24C and 60% relative humidity. In the above test, the compounds of Example 1 -exhibited good stomach poison action against S~odoptera ::
littoralls, Heliothis virescens and Leptinotarsa decem- ` -llneata.
.' ' . "
' ' ' . ', ,' ' ' . ;,.. ;..... ~: ~ , :
" " '' . , ' ' ~ .
.. .. . . .... . ... .
, ~()76~3S
Example 3 ::
Insecticidal action against Musca domestica A given amount of a solution of the active substance in acetone (concentration of active substance =
0.05%) was pipetted onto 50 g of maggot substrate in beakers. After the treated substrate had been thoroughly -mixed, the acetone was allowed to evaporate off over the course of at least 20 hours.
25 one day-old maggots were then put into each ~ -beaker. After 5 days the pupae were flushed out and --deposited in the same beaker. Mortality was determined after 10 days. In this test the compounds of Example 1 acted well against Musca domestica. ~ -~: ' , , " , .. :
, "
' ~,:"' :~ .
: ', :
, .
' '' ' . ,' :
~; ,, :,~ .
,' "'''' . . ' : .. , . -. ' '- '- , ' ,': . :,, , .: .. ' :,, . " : , . . . ...
. :, , , ,, . ,. . . .. ,-, .. ~ ,. ,:, .. .. , , . : .
''': , ,. ' ' ' ,.,"., '", ', ', ' '" .',' ' '~
By diluting these concentrates with water it ispo~ible to obtain emulsions of the required concentration.
Sprays:
The following ingredients are used to prepare a) a 5%
spray, and b) a 95% spray:
a) 5 parts of active substance, 1 part o~ epichlorohydrin~
94 parts of ligroin (boiling range 160 190C), b~ 95 parts of active substance, 5 parts of epichlorohydrin. -~
The invention is further illustrated by the following Exa~pIes.
, : -,':
. ~ .
- , ., ~ :
. : , . .: . . . . . .
' .. , " ' '~
:,:, , ~ , ,; , - ~xam~le 1 Manufacture of 2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropanecarboxylic acid-4-phenyl-3-chloro-2-butene ester of formula - 9.95 ~ of 2,2-dimethyl-3-(2,2-dibromovinyl)-cyclopropanecarboxylic acid are added by small amounts to a solution of 3.4 g of potassium tert. butylate in 50 ml of methyl ethyl ketone. Then 9.5 g of 2,4-dichloro-butenyl(2)-benzene is added to the reaction mixture, whichis stirred for 8 hours at 70 - 80C.
After it has cooled, the reaction mixture is poured onto ice water. The product is extracted into ether and the etherealextract is washed with 3 x 100 ml of 3~ Na2C03 solution. The ether solution is dried over sodium sulphate, the ether i~ distilled of~ and the c~ de product ~ractionated in a high ~acuum. The desired product is obtained as a yellowish li~uid with a boiling point of 179 - 180C/0.015 Torr.
The following compounds of formula I are obtained in analogous manner:
~ 6~L35 . .
C = CH - CH - CH - COOCH~-CH = I - CH2 _9 ~3 H3 Boiling point 130 - 1~2C/0.02 Torr.
. ~:
Cl C = CH - CH - CH - COOCH2-CH = C - CH
Br /C\ Cl Boiling point 160 - 1?0C/0.15 Torr.
.
. .
Insecticidal Stomach poison action Tobacco and potato plants were sprayed with a 0.05% aqueous emulsion ~obtained from a 10~ emulsifiable conoentrate). After the coating had dried, the tobacco plants were populated with Spodoptera littoralis larvae.L
and Heliothis virescens larvae L3 and the potatoe plants wlth Colorado potato beetle larvae L3 (Le~tinotarsa decem-lineata). The test was carried out at 24C and 60% relative humidity. In the above test, the compounds of Example 1 -exhibited good stomach poison action against S~odoptera ::
littoralls, Heliothis virescens and Leptinotarsa decem- ` -llneata.
.' ' . "
' ' ' . ', ,' ' ' . ;,.. ;..... ~: ~ , :
" " '' . , ' ' ~ .
.. .. . . .... . ... .
, ~()76~3S
Example 3 ::
Insecticidal action against Musca domestica A given amount of a solution of the active substance in acetone (concentration of active substance =
0.05%) was pipetted onto 50 g of maggot substrate in beakers. After the treated substrate had been thoroughly -mixed, the acetone was allowed to evaporate off over the course of at least 20 hours.
25 one day-old maggots were then put into each ~ -beaker. After 5 days the pupae were flushed out and --deposited in the same beaker. Mortality was determined after 10 days. In this test the compounds of Example 1 acted well against Musca domestica. ~ -~: ' , , " , .. :
, "
' ~,:"' :~ .
: ', :
, .
' '' ' . ,' :
~; ,, :,~ .
,' "'''' . . ' : .. , . -. ' '- '- , ' ,': . :,, , .: .. ' :,, . " : , . . . ...
. :, , , ,, . ,. . . .. ,-, .. ~ ,. ,:, .. .. , , . : .
''': , ,. ' ' ' ,.,"., '", ', ', ' '" .',' ' '~
Claims (5)
PRIVILEGE OR PROPERTY IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A compound of the formula wherein X1 represents a chlorine, fluorine or bromine atom and X2 represents a fluorine or bromine atom.
2. The compound according to claim 1 of the formula .
3. The compound according to claim 1 of the formula .
4. The compound according to claim 1 of the formula .
5. A method of combatting insect pests at a locus, which method comprises applying to the locus a compound as claimed in claim 2.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1466774A CH602009A5 (en) | 1974-11-01 | 1974-11-01 | Insecticidal cyclopropane carboxylates |
| CH589375 | 1975-05-07 | ||
| CH853975A CH611489A5 (en) | 1975-07-01 | 1975-07-01 | Pesticides |
| CH1301075 | 1975-10-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1076135A true CA1076135A (en) | 1980-04-22 |
Family
ID=27428952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA238,661A Expired CA1076135A (en) | 1974-11-01 | 1975-10-30 | 4-phenylbut-2-enyl esters of 2,2-dimethyl-3-vinyl-cyclopropane carboxylic acid and their use as pesticides |
Country Status (10)
| Country | Link |
|---|---|
| JP (1) | JPS5173123A (en) |
| AT (1) | AT345033B (en) |
| BR (1) | BR7507163A (en) |
| CA (1) | CA1076135A (en) |
| DE (1) | DE2548450A1 (en) |
| FR (1) | FR2289485A1 (en) |
| GB (1) | GB1523736A (en) |
| IL (1) | IL48386A (en) |
| IT (1) | IT1045594B (en) |
| TR (1) | TR19005A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52151149A (en) * | 1976-06-09 | 1977-12-15 | Sumitomo Chem Co Ltd | Cyclopropanecarboxylic acid esters, their preparation, and insecticides and miticides containing same |
| FR2373966A1 (en) * | 1976-12-16 | 1978-07-13 | Grouyellec Andre Le | USE OF DIMETHYLFORMAMIDE AS A SYNERGIZER AND IMPROVEMENT OF NATURAL AND SYNTHETIC PYRETHRINS, PYRETHRINOIDS AND ROTENONES |
| JP5076555B2 (en) * | 2007-03-05 | 2012-11-21 | 東亞合成株式会社 | Pest control agent |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5638563B2 (en) * | 1973-07-28 | 1981-09-08 |
-
1975
- 1975-10-28 FR FR7532903A patent/FR2289485A1/en active Granted
- 1975-10-29 DE DE19752548450 patent/DE2548450A1/en not_active Withdrawn
- 1975-10-30 CA CA238,661A patent/CA1076135A/en not_active Expired
- 1975-10-30 IL IL48386A patent/IL48386A/en unknown
- 1975-10-31 BR BR7507163A patent/BR7507163A/en unknown
- 1975-10-31 TR TR1900575A patent/TR19005A/en unknown
- 1975-10-31 GB GB45411/75A patent/GB1523736A/en not_active Expired
- 1975-10-31 IT IT2893075A patent/IT1045594B/en active
- 1975-10-31 AT AT832075A patent/AT345033B/en not_active IP Right Cessation
- 1975-11-01 JP JP50132074A patent/JPS5173123A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| FR2289485A1 (en) | 1976-05-28 |
| IT1045594B (en) | 1980-06-10 |
| BR7507163A (en) | 1976-08-10 |
| DE2548450A1 (en) | 1976-05-13 |
| TR19005A (en) | 1978-02-22 |
| FR2289485B1 (en) | 1979-07-13 |
| GB1523736A (en) | 1978-09-06 |
| AU8613075A (en) | 1977-05-05 |
| IL48386A0 (en) | 1975-12-31 |
| IL48386A (en) | 1978-09-29 |
| ATA832075A (en) | 1977-12-15 |
| AT345033B (en) | 1978-08-25 |
| JPS5173123A (en) | 1976-06-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |