CA1132603A - Pesticidal phenoxybenzyl cyclopropanecarboxylate derivatives - Google Patents
Pesticidal phenoxybenzyl cyclopropanecarboxylate derivativesInfo
- Publication number
- CA1132603A CA1132603A CA296,701A CA296701A CA1132603A CA 1132603 A CA1132603 A CA 1132603A CA 296701 A CA296701 A CA 296701A CA 1132603 A CA1132603 A CA 1132603A
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-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Case 5-109800/1+2/B/= Canada Pesticidal Phenoxybenzyl Cyclopropanecarboxylate Derivatives Abstract of the Disclosure Cyclopropanecarboxylic acid esters of the formula wherein R1 represents hydrogen, methyl, cyano or ethynyl, X represents chlorine or bromine, Y represents halogen, methyl or trifluoromethyl, processes for their manufacture and their use in pest control.
Description
~3Z6t)3 The present invention relates to cyclopropanecarboxylic acid esters, to a process for their manufacture and to their use in pest control.
The cyclopropanecarboxylic acid esters have the formula X Br O y I \C / I
Br C/ \ R
wherein Rl represents hydrogen, methyl, cyano or ethynyl, X
represents chlorine or bromine, Y represents halogen, methyl or trifluoromethyl.
By halogen is meant fluorine, chlorine, bromine or iodine, especially fluorine or chlorine.
The compounds of the formula I are prepared by methods which are known per se, for example as follows: .
. X Br 1) X-C - CH-CH - CH-COOH ~ Z CIH
Br ~ \ R
~II) (III) acid acceptor ~ I
X Br I I Y
The cyclopropanecarboxylic acid esters have the formula X Br O y I \C / I
Br C/ \ R
wherein Rl represents hydrogen, methyl, cyano or ethynyl, X
represents chlorine or bromine, Y represents halogen, methyl or trifluoromethyl.
By halogen is meant fluorine, chlorine, bromine or iodine, especially fluorine or chlorine.
The compounds of the formula I are prepared by methods which are known per se, for example as follows: .
. X Br 1) X-C - CH-CH - CH-COOH ~ Z CIH
Br ~ \ R
~II) (III) acid acceptor ~ I
X Br I I Y
2) X-C-CH-CH - CH-COZ ~ HO-CH- ~ o Br R
3 3 (IV) (V) acid acceptor - 2 - _ '~IJ;f'~
' . ' ,' . ' '' ''' ' '` .''. ". . ' '~' ':',, . ' ..
' ' ': , `' '' ' , ,~ .' , ; ' ' . .
~L~L3Z6~3 X Br Y
3) X-C - CH-CH - CH-COOH + HO-CH ~ O
Br / \ R
(II) (V) hydrophilic agent X Br y
' . ' ,' . ' '' ''' ' '` .''. ". . ' '~' ':',, . ' ..
' ' ': , `' '' ' , ,~ .' , ; ' ' . .
~L~L3Z6~3 X Br Y
3) X-C - CH-CH - CH-COOH + HO-CH ~ O
Br / \ R
(II) (V) hydrophilic agent X Br y
4) X-C-CH-CH - CH-COOR ~ HO-CH ~ ~
Br / \ Rl -(VI) (V) -P~OH
~ I
X ~ bromination
Br / \ Rl -(VI) (V) -P~OH
~ I
X ~ bromination
5) x/c CH-CH - CH-CooC~ ~ ~ ~ I
- / \C
(VII) In the formulae III, V and VII, Rl and Y are as defined in formula I.
In the formulae III and IV, Z represents a halogen atom, especially a chlorine or bromine atom, and in formula VI R represents Cl-C4alkyl, especially methyl or ethyl.
Suitable acid acceptors for processes 1 and 2 are in particular tertiary amines, such as trialkylamine and pyridi-ne, and also hydroxides, oxides, carbonates and bicarbonates of alkali metals and alkaline earth metals, and in addition alkali metal alcoholates, for example potassium tert.-butyl-ate and sodium methylate. As hydrophilic agent for process 3, dicyclohexylcarbodiimide can be used for example. Processes ~, . . .... . .
- - , : :: , ., . , ., . -.
~13; :~
1 to 5 are carried out at a reaction temperature between -10 and 120C, usually between 20 and 80C~ under normal or elevated pressure and preferably in an inert solvent or di-luent. Examples of suitable solvents or diluents are: ether and ethereal compounds, for example diethyl ether, dipropyl ether, dioxane, dimethoxy ethane and tetrahydrofurane; amides, such as N,N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, especially benæene~ toluene, ,.y-lenes, chloroform and chlorobenzene; nitriles, such as ace-tonitrile~ dimethyl sulphoxide; and ketones, such as acetone and methyl ethyl ketone.
The starting materials of the formulae II to VII are ~nown or they can be prepared by methods analogous to known ones.
The compounds of the formula I are in ~he form of a mi~ture of different optically active isomers i~ individual opti-cally active starting materials are not used in the reaction.
The different isomer mixtures can be separated into the in-dividual isomers by known methods. The compound o the for-mula I is to be understood as comprising both the indivi-dual isomers and the mixtures thereof.
The compounds of the formula I are suitable or controlling a variety of animal and plant pests. In particular, the com-pounds of the formula I are suitable for controlling insects, phytopathogenic mites and ~icks, for example of the orders:
Lepidoptera~ Coleoptera, ~omoptera, Heteroptera, Diptera, Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonap~era, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenopt~ra In particular, the compounds of the formula I are suitable or controlling insects which are harmful to plants, especial-ly insects which damage plants by eating a in ornamentals and crops of useful plants, especially in cotton plantations (e.g. Spodoptera littoralis and Heliothis virescens) and in vegetable crops (for example Leptinotarsa decemlineata . .
, . . . . . .. . . . .
, " ~ .... -~ .
, ~: ., , , . . :
.. ~ . . ., ,- ~. . -.
:. . , , ,,, ~
: .. , .:...... . . .
'. ; ' : . , '~' .:
~i3~6~3 and Myæus persicae).
The active compounds of the formula I also have a very good action against flies, for example Musca domestica 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, ~ormamidines, 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)-396,9-trioxaundecane (Sesamex or Sesoxane), S,S,S-tributylphosphorotrithioate, 1,2-Methy-lenedioxy-4(2-(octylsulphonyl)-propyl)-benzene.
The compounds of the ormula 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 liquid and correspond to the substances conventionally used in the art of formulation, for example natural or regenerat~d sub-stances, solvents, dispersants, wetting agents, tacki~iers, thickeners, binders and/or fertilisers.
The compositions of the present invention are manuac-tured in known m~nner by homogeneous1y mixing and/or grin-~ing active substances of the formula I with the suitable carriers, with or without the addition of di.spersants or solvents which are inert to the active substances.
The compounds of the formula I may be processed to the following formulations:
. . .
, -. .
,- ":, , ., ~` ~
~13Z6.~)3 Solid formulations:
Dusts, tracking powders and granules (coated granules~
impregnated granules and homogene~us granules).
Liquid formulations:
a) active substarlces which are dispersable in water:
wettable powders, pastes and emulsions;
b) solutions.
The content of active substance in the above described compositions is generally between 0.1% and 95%, though con-centrations of up to 99.5% or even pure active substance, can also be used if the compositions are applied from an air-craft or other appropriate application devices.
The compounds (active substances) of the formula I can, for example, be formulated as follows (throughout the pre-sent specification all parts and percentages are by weight):
Dusts __ , 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 o highly disperse silicic acid, 97 parts of talc.
The active substances are mixed with the carriers and ground.
Gra The following substances are used to produce 5%
granules:
parts o~ active subs~ance 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether,
- / \C
(VII) In the formulae III, V and VII, Rl and Y are as defined in formula I.
In the formulae III and IV, Z represents a halogen atom, especially a chlorine or bromine atom, and in formula VI R represents Cl-C4alkyl, especially methyl or ethyl.
Suitable acid acceptors for processes 1 and 2 are in particular tertiary amines, such as trialkylamine and pyridi-ne, and also hydroxides, oxides, carbonates and bicarbonates of alkali metals and alkaline earth metals, and in addition alkali metal alcoholates, for example potassium tert.-butyl-ate and sodium methylate. As hydrophilic agent for process 3, dicyclohexylcarbodiimide can be used for example. Processes ~, . . .... . .
- - , : :: , ., . , ., . -.
~13; :~
1 to 5 are carried out at a reaction temperature between -10 and 120C, usually between 20 and 80C~ under normal or elevated pressure and preferably in an inert solvent or di-luent. Examples of suitable solvents or diluents are: ether and ethereal compounds, for example diethyl ether, dipropyl ether, dioxane, dimethoxy ethane and tetrahydrofurane; amides, such as N,N-dialkylated carboxamides; aliphatic, aromatic and halogenated hydrocarbons, especially benæene~ toluene, ,.y-lenes, chloroform and chlorobenzene; nitriles, such as ace-tonitrile~ dimethyl sulphoxide; and ketones, such as acetone and methyl ethyl ketone.
The starting materials of the formulae II to VII are ~nown or they can be prepared by methods analogous to known ones.
The compounds of the formula I are in ~he form of a mi~ture of different optically active isomers i~ individual opti-cally active starting materials are not used in the reaction.
The different isomer mixtures can be separated into the in-dividual isomers by known methods. The compound o the for-mula I is to be understood as comprising both the indivi-dual isomers and the mixtures thereof.
The compounds of the formula I are suitable or controlling a variety of animal and plant pests. In particular, the com-pounds of the formula I are suitable for controlling insects, phytopathogenic mites and ~icks, for example of the orders:
Lepidoptera~ Coleoptera, ~omoptera, Heteroptera, Diptera, Acarina, Thysanoptera, Orthoptera, Anoplura, Siphonap~era, Mallophaga, Thysanura, Isoptera, Psocoptera and Hymenopt~ra In particular, the compounds of the formula I are suitable or controlling insects which are harmful to plants, especial-ly insects which damage plants by eating a in ornamentals and crops of useful plants, especially in cotton plantations (e.g. Spodoptera littoralis and Heliothis virescens) and in vegetable crops (for example Leptinotarsa decemlineata . .
, . . . . . .. . . . .
, " ~ .... -~ .
, ~: ., , , . . :
.. ~ . . ., ,- ~. . -.
:. . , , ,,, ~
: .. , .:...... . . .
'. ; ' : . , '~' .:
~i3~6~3 and Myæus persicae).
The active compounds of the formula I also have a very good action against flies, for example Musca domestica 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, ~ormamidines, 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)-396,9-trioxaundecane (Sesamex or Sesoxane), S,S,S-tributylphosphorotrithioate, 1,2-Methy-lenedioxy-4(2-(octylsulphonyl)-propyl)-benzene.
The compounds of the ormula 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 liquid and correspond to the substances conventionally used in the art of formulation, for example natural or regenerat~d sub-stances, solvents, dispersants, wetting agents, tacki~iers, thickeners, binders and/or fertilisers.
The compositions of the present invention are manuac-tured in known m~nner by homogeneous1y mixing and/or grin-~ing active substances of the formula I with the suitable carriers, with or without the addition of di.spersants or solvents which are inert to the active substances.
The compounds of the formula I may be processed to the following formulations:
. . .
, -. .
,- ":, , ., ~` ~
~13Z6.~)3 Solid formulations:
Dusts, tracking powders and granules (coated granules~
impregnated granules and homogene~us granules).
Liquid formulations:
a) active substarlces which are dispersable in water:
wettable powders, pastes and emulsions;
b) solutions.
The content of active substance in the above described compositions is generally between 0.1% and 95%, though con-centrations of up to 99.5% or even pure active substance, can also be used if the compositions are applied from an air-craft or other appropriate application devices.
The compounds (active substances) of the formula I can, for example, be formulated as follows (throughout the pre-sent specification all parts and percentages are by weight):
Dusts __ , 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 o highly disperse silicic acid, 97 parts of talc.
The active substances are mixed with the carriers and ground.
Gra The following substances are used to produce 5%
granules:
parts o~ active subs~ance 0.25 parts of epichlorohydrin, 0.25 parts of cetyl polyglycol ether,
- 6 ~
.. ..
. ~
.: : - , . ; ~ ~
~ 3 3.50 parts of polyethy]ene glycol, 91 parts of kaolin (~article size 0.3-0.8 mm).
The active substance is mixed with epichlorohydrin and the mixture is dissolved 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 eva~orated in vacuo.
Wettable powders:
The following constituents are used for 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 ligninsulphona~e, 1 part of sodium dibutylnaphthalenesulphonat2 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 o isooctylphenoxy-polyoxyethylene-ethanol, 1,7 parts of Champagne chalk/hydroxyethyl cellulose ~ixture (1:1)~
8.3 parts of sodium aluminium silicate, 16 5 parts of kieselguhr~
46 parts o Icaolin;
d~ 10 parts of active substance~
~, ............... .
.. ..
. ~
.: : - , . ; ~ ~
~ 3 3.50 parts of polyethy]ene glycol, 91 parts of kaolin (~article size 0.3-0.8 mm).
The active substance is mixed with epichlorohydrin and the mixture is dissolved 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 eva~orated in vacuo.
Wettable powders:
The following constituents are used for 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 ligninsulphona~e, 1 part of sodium dibutylnaphthalenesulphonat2 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 o isooctylphenoxy-polyoxyethylene-ethanol, 1,7 parts of Champagne chalk/hydroxyethyl cellulose ~ixture (1:1)~
8.3 parts of sodium aluminium silicate, 16 5 parts of kieselguhr~
46 parts o Icaolin;
d~ 10 parts of active substance~
~, ............... .
7 -..
'' ' : ' ' '., " ' ' ~ .': .
': ' : : ~ :
'' , ' ' ' ~ '' ' ` 1~32603 3 par~s of a mixture of the sodium salts o saturated fatty alcohol sulphates, parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.
The active substances are homogeneously mixed with the additives in suitable mixers and the ~ixture is then ground in appropriate mills and rollers. Wettable powders are ob-tained which can be diluted with water to give suspensions of tlle 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 par~s of ~ylene;
b) 25 parts of active substance, 2,5 parts of epoxidised vegetable oil, parts of allcylarylsulphonate/fatty alcohol polyglycol ether mixture, parts of dimethyl form2mide, 57~5 parts of xylene;
c) 50 parts of active sub~tance, 4~2 parts of tributylphenol-polyglycol ether, 5~8 parts of cylcium dodecylbenzenesulphonate, parts of cyclohexanene, parts of xylene.
, ~ .
.. . . , . ... .. , . . . ... . . . . ~ . .
:
~13Z~i~3 By diluting these concentrates with water it is possible to obtain emulsions of the required concentration.
Sprays:
The following ingredients are used to prepare a) a 5a/0 spray, and b) a 95% spray:
a) 5 parts o acti.ve substance, 1 part of epichlorohydrln, 94 parts of ligroin (boiling range 160-190C);
b) 95 parts of active substance, parts of epichlorohydrin, The invention is further il.lustrated by the fnllowing Examples.
9 _ , ,,, .. , .. ,, , , , , . . .. ~ . .
,, - . . ~ ... . . . .. . .
i. -1~3Z~;~3 Example 1 Preparation of a-cyano-m-(3-tri1uoromethylphenoxy)-benzyl 3-(2',2'-dichloro-1',2'-dibromoethyl)-2,2-dimethylcyclopro-panecarboxylate 14.5 g of ~-cyano-m-(3-triEluoromethylphenoxy)-benzyl 3-(2'2'-dichloroviny~-2,2-dimethylcyclopropanecarboxylate are dissolved in 100 ml o carbon tetrachloride. To this solution are then added dropwise 4.77 g of Br2 at 20-30C. Th~ reac-tion mixture is stirred for 2 hours and the carbon tetrachlo-ride distilled off, yielding the compound o the ormula - -Cl 0 CN
Cl-C - CH-CH - C~-C-o-~H ~ _0 ~ CF3 C~3 CH3 , with a refractive index o n40: 1.5823 (isomer mixture).
The following compounds are also prepared in analogous manner:
Cl Br O
Cl- C - CH-CH - CH-C-O-CH~-O~
nD : 1.56B8 ~isomer mixture) , . . A .
''1, , . . ' . ' ' ' ' " ' ' ' ' ' '' ' ~ ;'' ~'~ ' ' .
' .
' ' f ~IL3Z&iO3 Cl Br 0 Br\ C~ ' ~ ~ C 1 n40 1.5689 isomer mixture Cl Br 0 Cl-C - CH-CH - CH-C~0-CH- ~ 0 ~ CF ~ trans Br > \ CN ~ ~ n40 : 1,5439 Cl Br 0 / \ Cl CE13 CH3 nD :1,5799 + ~rans Cl Br 0 - / \ Cl n40 : 1.5695 Cl Br Cl- C - CH - CH~ ~CH C2C 2 ~ ~ ~ nD : 1.5809 .. .. , . .. , .. , ~ . . . . .
':
'; ' : `
;' , ' , : ~ , ~
~3Z6~)3 Cl Br CH3 CH3 n20 : 1,5790 Cl Br Cl-C - CH - CH - CH-C02CH2 ~ n20 : 1,5~10 Br CH3 CH3 ~ F
Cl- C - CH-CH - CH-C02CH ~ F nD9 : 1,5641 Br / C CN
Cl Br Cl-C - CH - C \ ~CH C02CH ~ ~ nD9: 1.5656 Cl Br Cl-C - CH - CH - CH-C02CH ~
Bx \C CN ~ o~F nD : 1 ~ 5 658 .
: - .
- i : ' ~ : .
, ,, ~ .
' ~ ~\ ~
~3;Z6~3 ClBr Cl-C-CH-C \ /H C 2 2 ~ \ ~ Cl nD : 1,5854 Br Br C 3 3 nD : 1,5900 Br Br F
Br- C - CH-CH - CH-C0 CH2 ~ ~ nD : 1.5832 Br Br Br-C - CH - CH - CH-C02CH2 ~ Cl Br /C~ \o ~ n40 : 1.6025 .- CH3 CH3 .
. .
Br Br Br-C - CN - CH - CH-C02CH ~ ~0 Br \/C / CN Y ~ nD : 1.5855 ' ~` ~ ~
~ 3~0 3 xample 2 Inse~ticidal stomach pois~n action Cotton plants were sprayed with a 0.05% aqueous emulsion of active substance (obtained from a 10% emulsifiable concen-trate). After the spray coating had dried, the cotton plants were populated with Spodoptera littoralis and Heliothis vi-rescens in the L3-stage. The text was carried out at 24C
and 60% relative humidity.
In this te9t, the compounds of Example 1 exhibited a good in-secticidal stomach poison action against Spodoptera and He-liothis larvae. -Example 3 hction against Chilo suppressalis .. . . . .
Rice seedlings of the variety Caloro were transplanted into plastic pots (6 plants per pot~ having a diameter of 17 cm at the top and reared to a helght of about 60 cm. In~sta-tion with Chil~ suppressalis larvae (Ll-stage, 3 to 4 mm in length) took place two days after the addition of active substance in granule form (rate of application: 8 kg of ac-tive ingredient per hectare) to the paddy water. Evaluation of the insecticidal action was made 10 days after addition of the granules. In this test, the ompounds of Example 1 acted against Chilo suppressalis.
. . .
, , :
, ll~Z~;~3 Example 4 .
Acaricidal action .
Twe~ve hours before the test for acaricidal action, Phaseolus vulgaris plants were populated with an infested piece of leaf from a mass culture of Tetranychus urticae. The mobile stages which had migrated to the plants were sprayed with the emulsified test preparations from a chromatography ato-miser in such a way that the spray broth did not run off. The number of livi.ng and dead larvae, adults and eggs was eva-luated under a stereoscopic microscope after 2 and 7 days -- `~- ~ and the result expressed in percentage values. During the test run, the plants stood in greenhouse compartments at In this test, the compounds of Example 1 acted against adults, larvae and eggs of Tetranychus urticae.
Exampl.e 5 . .
A~tion against ticks A) Rhipicephalus bursa Five adult ticks and 50 tick larvae were counted into each of a number of test tubes and immersed for 1 to 2 ~inutPs in 2 ~1 of an aqueous emulsion containing a concentration of 100, 10, 1 or 0.1 pp~ of test substance. Each test tube was then . ~ , " ", ~ , "
i, ~, . .. .
, . . . . .
,: ' . ,~ - ' : ' ~ 3 sealed with a cotton~wool plug and placed on its head to enable the cotton wool to absorb the active substance emul-sion, Evaluati~n of the action against adults was made after 2 weeks and of that against larvae after 2 days. Each test was repeated twice.
B) Boophilus microplus (larvae) Test were carried out with 20 OP-sensitive and 20 OP-resist-ant larvae using aqweous emulsions similar to those used in Test A. (The resistance refers to the tolerance towards dia-zinone). The compounds of Exampl-s 1 acted in these tests against adults and larvae of f~hipicepllalus bursa and OP-sen-sitive and OP-resistant larvae of Boophilus microplus.
xample_6 Action against Erysiphe graminis on Hordeum vulgare Barley plants about 8 m in height were sprayed with a spray broth (0,05% of active ingredientJ prepared from a wettable powder of the active compound. 48 hours later, the treated plants were dusted with conldia of the fungus. The infected barley plants were stood in a greenhouse at about 22C and the fungus attack was evaluated after 10 days. In this test, the compounds o~ Example 1 acted against Erysiphe graminis.
.";, ' ' . ' - ~: ' .
'' ' : ' ' '., " ' ' ~ .': .
': ' : : ~ :
'' , ' ' ' ~ '' ' ` 1~32603 3 par~s of a mixture of the sodium salts o saturated fatty alcohol sulphates, parts of naphthalenesulphonic acid/formaldehyde condensate, 82 parts of kaolin.
The active substances are homogeneously mixed with the additives in suitable mixers and the ~ixture is then ground in appropriate mills and rollers. Wettable powders are ob-tained which can be diluted with water to give suspensions of tlle 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 par~s of ~ylene;
b) 25 parts of active substance, 2,5 parts of epoxidised vegetable oil, parts of allcylarylsulphonate/fatty alcohol polyglycol ether mixture, parts of dimethyl form2mide, 57~5 parts of xylene;
c) 50 parts of active sub~tance, 4~2 parts of tributylphenol-polyglycol ether, 5~8 parts of cylcium dodecylbenzenesulphonate, parts of cyclohexanene, parts of xylene.
, ~ .
.. . . , . ... .. , . . . ... . . . . ~ . .
:
~13Z~i~3 By diluting these concentrates with water it is possible to obtain emulsions of the required concentration.
Sprays:
The following ingredients are used to prepare a) a 5a/0 spray, and b) a 95% spray:
a) 5 parts o acti.ve substance, 1 part of epichlorohydrln, 94 parts of ligroin (boiling range 160-190C);
b) 95 parts of active substance, parts of epichlorohydrin, The invention is further il.lustrated by the fnllowing Examples.
9 _ , ,,, .. , .. ,, , , , , . . .. ~ . .
,, - . . ~ ... . . . .. . .
i. -1~3Z~;~3 Example 1 Preparation of a-cyano-m-(3-tri1uoromethylphenoxy)-benzyl 3-(2',2'-dichloro-1',2'-dibromoethyl)-2,2-dimethylcyclopro-panecarboxylate 14.5 g of ~-cyano-m-(3-triEluoromethylphenoxy)-benzyl 3-(2'2'-dichloroviny~-2,2-dimethylcyclopropanecarboxylate are dissolved in 100 ml o carbon tetrachloride. To this solution are then added dropwise 4.77 g of Br2 at 20-30C. Th~ reac-tion mixture is stirred for 2 hours and the carbon tetrachlo-ride distilled off, yielding the compound o the ormula - -Cl 0 CN
Cl-C - CH-CH - C~-C-o-~H ~ _0 ~ CF3 C~3 CH3 , with a refractive index o n40: 1.5823 (isomer mixture).
The following compounds are also prepared in analogous manner:
Cl Br O
Cl- C - CH-CH - CH-C-O-CH~-O~
nD : 1.56B8 ~isomer mixture) , . . A .
''1, , . . ' . ' ' ' ' " ' ' ' ' ' '' ' ~ ;'' ~'~ ' ' .
' .
' ' f ~IL3Z&iO3 Cl Br 0 Br\ C~ ' ~ ~ C 1 n40 1.5689 isomer mixture Cl Br 0 Cl-C - CH-CH - CH-C~0-CH- ~ 0 ~ CF ~ trans Br > \ CN ~ ~ n40 : 1,5439 Cl Br 0 / \ Cl CE13 CH3 nD :1,5799 + ~rans Cl Br 0 - / \ Cl n40 : 1.5695 Cl Br Cl- C - CH - CH~ ~CH C2C 2 ~ ~ ~ nD : 1.5809 .. .. , . .. , .. , ~ . . . . .
':
'; ' : `
;' , ' , : ~ , ~
~3Z6~)3 Cl Br CH3 CH3 n20 : 1,5790 Cl Br Cl-C - CH - CH - CH-C02CH2 ~ n20 : 1,5~10 Br CH3 CH3 ~ F
Cl- C - CH-CH - CH-C02CH ~ F nD9 : 1,5641 Br / C CN
Cl Br Cl-C - CH - C \ ~CH C02CH ~ ~ nD9: 1.5656 Cl Br Cl-C - CH - CH - CH-C02CH ~
Bx \C CN ~ o~F nD : 1 ~ 5 658 .
: - .
- i : ' ~ : .
, ,, ~ .
' ~ ~\ ~
~3;Z6~3 ClBr Cl-C-CH-C \ /H C 2 2 ~ \ ~ Cl nD : 1,5854 Br Br C 3 3 nD : 1,5900 Br Br F
Br- C - CH-CH - CH-C0 CH2 ~ ~ nD : 1.5832 Br Br Br-C - CH - CH - CH-C02CH2 ~ Cl Br /C~ \o ~ n40 : 1.6025 .- CH3 CH3 .
. .
Br Br Br-C - CN - CH - CH-C02CH ~ ~0 Br \/C / CN Y ~ nD : 1.5855 ' ~` ~ ~
~ 3~0 3 xample 2 Inse~ticidal stomach pois~n action Cotton plants were sprayed with a 0.05% aqueous emulsion of active substance (obtained from a 10% emulsifiable concen-trate). After the spray coating had dried, the cotton plants were populated with Spodoptera littoralis and Heliothis vi-rescens in the L3-stage. The text was carried out at 24C
and 60% relative humidity.
In this te9t, the compounds of Example 1 exhibited a good in-secticidal stomach poison action against Spodoptera and He-liothis larvae. -Example 3 hction against Chilo suppressalis .. . . . .
Rice seedlings of the variety Caloro were transplanted into plastic pots (6 plants per pot~ having a diameter of 17 cm at the top and reared to a helght of about 60 cm. In~sta-tion with Chil~ suppressalis larvae (Ll-stage, 3 to 4 mm in length) took place two days after the addition of active substance in granule form (rate of application: 8 kg of ac-tive ingredient per hectare) to the paddy water. Evaluation of the insecticidal action was made 10 days after addition of the granules. In this test, the ompounds of Example 1 acted against Chilo suppressalis.
. . .
, , :
, ll~Z~;~3 Example 4 .
Acaricidal action .
Twe~ve hours before the test for acaricidal action, Phaseolus vulgaris plants were populated with an infested piece of leaf from a mass culture of Tetranychus urticae. The mobile stages which had migrated to the plants were sprayed with the emulsified test preparations from a chromatography ato-miser in such a way that the spray broth did not run off. The number of livi.ng and dead larvae, adults and eggs was eva-luated under a stereoscopic microscope after 2 and 7 days -- `~- ~ and the result expressed in percentage values. During the test run, the plants stood in greenhouse compartments at In this test, the compounds of Example 1 acted against adults, larvae and eggs of Tetranychus urticae.
Exampl.e 5 . .
A~tion against ticks A) Rhipicephalus bursa Five adult ticks and 50 tick larvae were counted into each of a number of test tubes and immersed for 1 to 2 ~inutPs in 2 ~1 of an aqueous emulsion containing a concentration of 100, 10, 1 or 0.1 pp~ of test substance. Each test tube was then . ~ , " ", ~ , "
i, ~, . .. .
, . . . . .
,: ' . ,~ - ' : ' ~ 3 sealed with a cotton~wool plug and placed on its head to enable the cotton wool to absorb the active substance emul-sion, Evaluati~n of the action against adults was made after 2 weeks and of that against larvae after 2 days. Each test was repeated twice.
B) Boophilus microplus (larvae) Test were carried out with 20 OP-sensitive and 20 OP-resist-ant larvae using aqweous emulsions similar to those used in Test A. (The resistance refers to the tolerance towards dia-zinone). The compounds of Exampl-s 1 acted in these tests against adults and larvae of f~hipicepllalus bursa and OP-sen-sitive and OP-resistant larvae of Boophilus microplus.
xample_6 Action against Erysiphe graminis on Hordeum vulgare Barley plants about 8 m in height were sprayed with a spray broth (0,05% of active ingredientJ prepared from a wettable powder of the active compound. 48 hours later, the treated plants were dusted with conldia of the fungus. The infected barley plants were stood in a greenhouse at about 22C and the fungus attack was evaluated after 10 days. In this test, the compounds o~ Example 1 acted against Erysiphe graminis.
.";, ' ' . ' - ~: ' .
Claims (8)
1. A cyclopropanecarboxylic acid ester of the formula wherein R1 represents hydrogen, methyl, cyano or ethynyl, X
represents chlorine or bromine, and Y represents halogen, methyl or trifluoromethyl.
represents chlorine or bromine, and Y represents halogen, methyl or trifluoromethyl.
2. The compound as claimed in claim 1 of the formula
3. The compound as claimed in claim 1 of the formula
4. The compound as claimed in claim 1 of the formula
5. The compound as claimed in claim 1 of the formula
6. A process for the manufacture of a compound as claimed in claim 1 which comprises a) reacting a compound of the formula wherein X is as defined in claim 1 and Z represents a halo-gen atom, in the presence of an acid acceptor, with a compound of the formula wherein R1 and Y are as defined in claim 1, or b) brominating a compound of the formula wherein R1, X and Y are as defined in claim 1.
7. A method of controlling a variety of animal and plant pests at a locus, comprising applying to the locus a pesticidally effective amount of a compound according to claim 1.
8. A method as claimed in claim 7 wherein the pests to be controlled are insects and representatives of the order Acarina.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH169077A CH625396A5 (en) | 1977-02-11 | 1977-02-11 | Pesticides |
| CH1690/77 | 1977-02-11 | ||
| CH9347/77 | 1977-07-28 | ||
| CH934777A CH627921A5 (en) | 1977-07-28 | 1977-07-28 | Pesticides |
| CH185/78 | 1978-01-09 | ||
| CH18578A CH636074A5 (en) | 1978-01-09 | 1978-01-09 | Cyclopropanecarboxylates, their preparation and use, and pesticides prepared therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1132603A true CA1132603A (en) | 1982-09-28 |
Family
ID=27171886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA296,701A Expired CA1132603A (en) | 1977-02-11 | 1978-02-10 | Pesticidal phenoxybenzyl cyclopropanecarboxylate derivatives |
Country Status (22)
| Country | Link |
|---|---|
| JP (1) | JPS53101341A (en) |
| AU (1) | AU524179B2 (en) |
| BE (1) | BE863838A (en) |
| BG (1) | BG31062A3 (en) |
| BR (1) | BR7800808A (en) |
| CA (1) | CA1132603A (en) |
| DD (1) | DD134720A5 (en) |
| DE (1) | DE2805193A1 (en) |
| EG (1) | EG13058A (en) |
| ES (1) | ES466861A1 (en) |
| FR (1) | FR2380247A1 (en) |
| GB (1) | GB1589955A (en) |
| GR (1) | GR71685B (en) |
| IL (1) | IL54008A0 (en) |
| IT (1) | IT1093629B (en) |
| MX (1) | MX5905E (en) |
| NL (1) | NL7801591A (en) |
| NZ (1) | NZ186449A (en) |
| OA (1) | OA05881A (en) |
| PL (1) | PL111166B1 (en) |
| PT (1) | PT67634B (en) |
| TR (1) | TR20011A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2960827D1 (en) * | 1978-06-27 | 1981-12-03 | Ciba Geigy Ag | Tetrahalogen-ethylcyclopropane carboxylic acid esters, process for their preparation and their use as herbicides |
| JPS55115859A (en) * | 1979-02-27 | 1980-09-06 | Sumitomo Chem Co Ltd | Carboxylic ester, its preparation, insecticide and acaricide with low toxicity to fish comprising it as active constituent |
| FR2469403A1 (en) * | 1979-11-14 | 1981-05-22 | Roussel Uclaf | ESTERS OF HETEROCYCLIC ALCOHOLS, PROCESSES FOR THEIR PREPARATION AND COMPOSITIONS CONTAINING THEM |
| DE3004092A1 (en) * | 1980-02-05 | 1981-08-13 | Bayer Ag, 5090 Leverkusen | SUBSTITUTED 3- (1,2-DIBROM-ALKYL) - 2,2-DIMETHYL-CYCLOPROPAN-1-CARBONIC ACID ESTERS, METHODS AND INTERMEDIATE PRODUCTS FOR THEIR PRODUCTION AND THEIR USE IN PEST CONTROL |
| US4331682A (en) * | 1980-03-14 | 1982-05-25 | Ciba-Geigy Corporation | Cyclopropanecarboxylic acid-α-haloethynyl-m-phenoxybenzyl esters and their use for combating insect pests |
| WO1981002892A1 (en) * | 1980-04-10 | 1981-10-15 | Dainippon Jochugiku Kk | Cyclopropanecarboxylic acid ester derivatives,process for their preparation,and insecticidal and acaricidal composition containing such as effective ingredients |
| US4376785A (en) | 1980-06-19 | 1983-03-15 | Sumitomo Chemical Company, Limited | Cyclopropanecarboxylates and a low fish toxic insecticide and/or acaricide containing them |
| FR2512815B1 (en) * | 1981-04-16 | 1989-04-14 | Roussel Uclaf | NOVEL DERIVATIVES OF CYCLOPROPANE CARBOXYLIC ACID, THEIR PREPARATION METHOD, THEIR APPLICATION TO THE CONTROL OF PESTS |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1512955A (en) * | 1974-08-12 | 1978-06-01 | Nat Res Dev | Cyclopropane carboxylic esters |
| CA1100991A (en) * | 1976-02-16 | 1981-05-12 | Willy Meyer | Esters |
| FR2364884A1 (en) * | 1976-09-21 | 1978-04-14 | Roussel Uclaf | Fungicidal bactericidal cyclopropane carboxylic acid derivs. - are intermediates in prepn. of insecticidal, acaricidal, nematocidal and antifungal ester(s) |
-
1978
- 1978-02-08 TR TR20011A patent/TR20011A/en unknown
- 1978-02-08 PT PT67634A patent/PT67634B/en unknown
- 1978-02-08 DE DE19782805193 patent/DE2805193A1/en not_active Withdrawn
- 1978-02-09 FR FR7803673A patent/FR2380247A1/en active Granted
- 1978-02-09 DD DD78203632A patent/DD134720A5/en unknown
- 1978-02-09 IL IL54008A patent/IL54008A0/en unknown
- 1978-02-09 OA OA56402A patent/OA05881A/en unknown
- 1978-02-09 GR GR55411A patent/GR71685B/el unknown
- 1978-02-09 BG BG038631A patent/BG31062A3/en unknown
- 1978-02-10 IT IT20193/78A patent/IT1093629B/en active
- 1978-02-10 ES ES466861A patent/ES466861A1/en not_active Expired
- 1978-02-10 BR BR7800808A patent/BR7800808A/en unknown
- 1978-02-10 JP JP1480178A patent/JPS53101341A/en active Pending
- 1978-02-10 CA CA296,701A patent/CA1132603A/en not_active Expired
- 1978-02-10 NZ NZ186449A patent/NZ186449A/en unknown
- 1978-02-10 NL NL7801591A patent/NL7801591A/en not_active Application Discontinuation
- 1978-02-10 BE BE185055A patent/BE863838A/en unknown
- 1978-02-10 PL PL1978204554A patent/PL111166B1/en unknown
- 1978-02-10 MX MX786839U patent/MX5905E/en unknown
- 1978-02-10 AU AU33184/78A patent/AU524179B2/en not_active Expired
- 1978-02-10 GB GB5546/78A patent/GB1589955A/en not_active Expired
- 1978-02-11 EG EG86/78A patent/EG13058A/en active
Also Published As
| Publication number | Publication date |
|---|---|
| GB1589955A (en) | 1981-05-20 |
| NZ186449A (en) | 1980-05-27 |
| MX5905E (en) | 1984-08-23 |
| GR71685B (en) | 1983-06-21 |
| TR20011A (en) | 1980-06-16 |
| PL111166B1 (en) | 1980-08-30 |
| BR7800808A (en) | 1979-01-02 |
| AU524179B2 (en) | 1982-09-02 |
| ES466861A1 (en) | 1979-06-01 |
| PT67634A (en) | 1978-03-01 |
| JPS53101341A (en) | 1978-09-04 |
| BG31062A3 (en) | 1981-10-15 |
| DE2805193A1 (en) | 1978-08-17 |
| IT7820193A0 (en) | 1978-02-10 |
| IL54008A0 (en) | 1978-04-30 |
| IT1093629B (en) | 1985-07-19 |
| FR2380247A1 (en) | 1978-09-08 |
| PT67634B (en) | 1979-07-17 |
| DD134720A5 (en) | 1979-03-21 |
| OA05881A (en) | 1981-05-31 |
| PL204554A1 (en) | 1978-11-06 |
| BE863838A (en) | 1978-08-10 |
| NL7801591A (en) | 1978-08-15 |
| EG13058A (en) | 1980-12-31 |
| FR2380247B1 (en) | 1981-04-30 |
| AU3318478A (en) | 1979-08-16 |
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