CA1152094A - Cyclopropane carboxylic acid esters - Google Patents
Cyclopropane carboxylic acid estersInfo
- Publication number
- CA1152094A CA1152094A CA000330476A CA330476A CA1152094A CA 1152094 A CA1152094 A CA 1152094A CA 000330476 A CA000330476 A CA 000330476A CA 330476 A CA330476 A CA 330476A CA 1152094 A CA1152094 A CA 1152094A
- Authority
- CA
- Canada
- Prior art keywords
- parts
- formula
- bromine
- chlorine
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (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
Abstract Cyclopropanecarboxylic acid esters of the formula in which X1 is fluorine, chlorine or bromine, and Y is methoxy, methyl, fluorine, chlorine or bromine;
processes for producing them, and their use in combating pests.
processes for producing them, and their use in combating pests.
Description
Case 5-11781/1+2/A
The present invention relates to cyclopropanecarboxylic acid esters, to processes for producing them, and to their use in combating pests.
The cyclopropanecarboxylic acid esters have the formula /CzCH-CH - CH-C-O-CH-t~ \--0--~ ~ ~
Xl /C\ C
in which Xl is fluorine, chlorine or bromine, and Y is methoxy, methyl, fluorine, chlorine or bromine.
Compounds of the formula I which are of particulaLr importance by virtue of their action are those in whi.ch Xl i9 fluorine, chlorine or bromine, and Y is p-methoxy, p-methyl, p-fluorine, p-chlorine or p-bromine.
' ' : . ', ' ~15'~
The present invention relates to cyclopropanecarboxylic acid esters, to processes for producing them, and to their use in combating pests.
The cyclopropanecarboxylic acid esters have the formula /CzCH-CH - CH-C-O-CH-t~ \--0--~ ~ ~
Xl /C\ C
in which Xl is fluorine, chlorine or bromine, and Y is methoxy, methyl, fluorine, chlorine or bromine.
Compounds of the formula I which are of particulaLr importance by virtue of their action are those in whi.ch Xl i9 fluorine, chlorine or bromine, and Y is p-methoxy, p-methyl, p-fluorine, p-chlorine or p-bromine.
' ' : . ', ' ~15'~
2 --The compounds of the formula I are produced by methods known per se, i-or example as follows:
CH~
1) Xl C
~C=CH-CH - CH-COOH C
Xl H3 CH3+ X-CH-I~ y~O~i~ i (II) (III) acid-binding ~ I
CH3 agent 2) Xl C
~C=CH-CH - CH-COX ~C . y ~C~+ HO-CH--~ \~_o_~ X.
CH~
1) Xl C
~C=CH-CH - CH-COOH C
Xl H3 CH3+ X-CH-I~ y~O~i~ i (II) (III) acid-binding ~ I
CH3 agent 2) Xl C
~C=CH-CH - CH-COX ~C . y ~C~+ HO-CH--~ \~_o_~ X.
3 CH3 1~ ~Y
(IV) (V) acid-binding . agent _ 3) Xi C
~C=CH-CH- CH-COOH111 Xl ~C~ + HO-CH--~ \~_o_~ X.
H3 CH31~ /Y 1~ ~Y
(II) (V) water-bindin~
agent CH
(IV) (V) acid-binding . agent _ 3) Xi C
~C=CH-CH- CH-COOH111 Xl ~C~ + HO-CH--~ \~_o_~ X.
H3 CH31~ /Y 1~ ~Y
(II) (V) water-bindin~
agent CH
4) Xl C 3 ~C=CH-CH - CH-COOR C
1~C~ ~ HO-CH--~ o_~ X-CH3 CH3 ~ ~Y
~VI) -ROH
- ~ I
_ . ., . . . _ . . .
- -_ .
~ ~S ~ 9 ~
In the formulae II to VI, the symbols Xl and Y have the meanings given under the formula I.
In the formulae III and IV, X is a halogen atom, particularly chlorine or bromine, and in the formula VI, R is Cl-C4 alkyl, especially methyl or ethyl. Suitable acid-binding agents for the processes 1 and 2 are in particular tertiary amines such as trialkylamine and pyridine, also hydroxides, oxides, carbonates and bicarbonates of alkali metals and alkaline-earth metals, as well as alkali metal alcoholates, such as potassium tert-butylate and sodium methylate. The water-binding agent used for Process 3 can be, for example, dicyclo-hexylcarbodiimide. The processes 1 to 4 are perform,ed at a reaction temperature of between -10 and 120C, usually between 20 and 80C, under normal or elevated pressure and preferably in an inert solvent or diluent.
Suitable solvents or diluents are, for example, ethers and ethereal compounds such as diethyl ether, diFropyl ether, dioxane, dimethoxyethane and tetrahydrofuran;
amides such as N,N-dialkylated carboxylic acid amides;
aliphatic, aromatic and halogenated hydrocarbons, par.-ticularly benzene, toluene, xylenes, chloroform and chlorobenzene; nitriles such as acetonitrile; dimethyl-sulfoxide, and ketones such as acetone and methyl ethyl ketone.
The starting materials of the formulae II to VII
are known, or they can be produced by methods analogous to known methods.
If the starting materials used for producing the compounds of the formula I are not homogeneous op~ically active materials, the said compounds are obtained as mixtures of various optically active isomers. The diif-ferent isomeric mixtures can be separated by known methods into the individual isomers. It is to be understood that the term 'compounds of the formula I' embraces both the individual isomers and the mixtures thereo.E.
The compounds of the formula I are suitable for combating various animal and plant pests.
The compounds of the formula I are particularly suitable for combating 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. The compounds of the formula I are su-itable in particular for combating insects that damage plants, especially insects that damage plants by eating, in crops of ornamental plants and useful plants, particularly in cotton crops (for example against Spodoptera lit~oralis and Heliothis virescens), and in crops of vegetables (for example against Leptinotarsa decemlineata and Myzus persicae). Active substances of the formula I have a very good action also against flies, such as Musca domestica, and against mosquito larvae.
The acaricidal and insecticidal action can be s~lbstan-tially broadened and adapted to suit given circumstclnces by the addition of other insecticides and/or acaricides.
Suitable additives are for example: organic phosphorus compounds; nitrophenols and derivatives thereof; for-mamidines; ureas; other pyrethrin-like compounds; as well as carbamates and chlorinated hydrocarbons.
Compounds of the formula I are combined particularly advantageously also with substances which have a syner-gistic or intensifying effect on pyrethroids. Exampl~s of such compounds are, inter alia, piperonylbutoxide, propynyl ethers, propynyl oximes, propynyl carbamates and .. . . . ..
1~5~
propynyl phosphonates, 2-(3,4-methylenedioxyphenoxy)-3,6,9-trioxaundecane (Sesamex or Sesoxane), S,S,S-tributylphosphorotrithioates and 1,2-methylenedioxy 4-(2-(octylsulfinyl)-propyl)-benzene.
~ ompounds 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, wetting 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 the active substances of the form.ula I
with suitable carriers, optionally with the addition. of dispersing agents or solvents which are inert to the active substances. The active substances can be obtained and used in the following forms:
olid preparations: dusts, scattering agents, granules (coated, impregnated and homogeneous granules);
liguid preparations-.
a) water-dispersible concentrates of active substance:
wettable powders, pastes or emulsions;
b) solutions.
The content of active substance in the compositi.ons described is between 0.1 and 95%; it is to be mentioned in this respect that with application from an aeroplane, or from other suitable devices, concentrations of UE) to 99.5% or even the pure active substance can be used.
The active substances of the formula I can be formu-lated for example as follows (parts are by weight):
. .... ..
115~4 Dusts The following substances are used to produce a) a
1~C~ ~ HO-CH--~ o_~ X-CH3 CH3 ~ ~Y
~VI) -ROH
- ~ I
_ . ., . . . _ . . .
- -_ .
~ ~S ~ 9 ~
In the formulae II to VI, the symbols Xl and Y have the meanings given under the formula I.
In the formulae III and IV, X is a halogen atom, particularly chlorine or bromine, and in the formula VI, R is Cl-C4 alkyl, especially methyl or ethyl. Suitable acid-binding agents for the processes 1 and 2 are in particular tertiary amines such as trialkylamine and pyridine, also hydroxides, oxides, carbonates and bicarbonates of alkali metals and alkaline-earth metals, as well as alkali metal alcoholates, such as potassium tert-butylate and sodium methylate. The water-binding agent used for Process 3 can be, for example, dicyclo-hexylcarbodiimide. The processes 1 to 4 are perform,ed at a reaction temperature of between -10 and 120C, usually between 20 and 80C, under normal or elevated pressure and preferably in an inert solvent or diluent.
Suitable solvents or diluents are, for example, ethers and ethereal compounds such as diethyl ether, diFropyl ether, dioxane, dimethoxyethane and tetrahydrofuran;
amides such as N,N-dialkylated carboxylic acid amides;
aliphatic, aromatic and halogenated hydrocarbons, par.-ticularly benzene, toluene, xylenes, chloroform and chlorobenzene; nitriles such as acetonitrile; dimethyl-sulfoxide, and ketones such as acetone and methyl ethyl ketone.
The starting materials of the formulae II to VII
are known, or they can be produced by methods analogous to known methods.
If the starting materials used for producing the compounds of the formula I are not homogeneous op~ically active materials, the said compounds are obtained as mixtures of various optically active isomers. The diif-ferent isomeric mixtures can be separated by known methods into the individual isomers. It is to be understood that the term 'compounds of the formula I' embraces both the individual isomers and the mixtures thereo.E.
The compounds of the formula I are suitable for combating various animal and plant pests.
The compounds of the formula I are particularly suitable for combating 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. The compounds of the formula I are su-itable in particular for combating insects that damage plants, especially insects that damage plants by eating, in crops of ornamental plants and useful plants, particularly in cotton crops (for example against Spodoptera lit~oralis and Heliothis virescens), and in crops of vegetables (for example against Leptinotarsa decemlineata and Myzus persicae). Active substances of the formula I have a very good action also against flies, such as Musca domestica, and against mosquito larvae.
The acaricidal and insecticidal action can be s~lbstan-tially broadened and adapted to suit given circumstclnces by the addition of other insecticides and/or acaricides.
Suitable additives are for example: organic phosphorus compounds; nitrophenols and derivatives thereof; for-mamidines; ureas; other pyrethrin-like compounds; as well as carbamates and chlorinated hydrocarbons.
Compounds of the formula I are combined particularly advantageously also with substances which have a syner-gistic or intensifying effect on pyrethroids. Exampl~s of such compounds are, inter alia, piperonylbutoxide, propynyl ethers, propynyl oximes, propynyl carbamates and .. . . . ..
1~5~
propynyl phosphonates, 2-(3,4-methylenedioxyphenoxy)-3,6,9-trioxaundecane (Sesamex or Sesoxane), S,S,S-tributylphosphorotrithioates and 1,2-methylenedioxy 4-(2-(octylsulfinyl)-propyl)-benzene.
~ ompounds 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, wetting 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 the active substances of the form.ula I
with suitable carriers, optionally with the addition. of dispersing agents or solvents which are inert to the active substances. The active substances can be obtained and used in the following forms:
olid preparations: dusts, scattering agents, granules (coated, impregnated and homogeneous granules);
liguid preparations-.
a) water-dispersible concentrates of active substance:
wettable powders, pastes or emulsions;
b) solutions.
The content of active substance in the compositi.ons described is between 0.1 and 95%; it is to be mentioned in this respect that with application from an aeroplane, or from other suitable devices, concentrations of UE) to 99.5% or even the pure active substance can be used.
The active substances of the formula I can be formu-lated for example as follows (parts are by weight):
. .... ..
115~4 Dusts The following substances are used to produce a) a
5% dust and b) a 2% dust:
a) 5 parts of active substance, and parts of talcum;
b) 2 parts of active substance, 1 part of highly dispersed silicic acid, and 97 parts of talcum.
The active substance is mixed and ground with the carriers.
Granulate The following ingredients 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, and 91 parts of kaolin (particle size 0.3 - O.i3 mm).
The active substance is mixed with epichlorohydrin and dissolved in 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The solution thus obtained is sprayed onto kaolin, and the acetone is subsequently evaporated off in vacuo.
Wettable ~owders The following constituents are used to produce a) a 40% wettable powder, b) and c) a 25~/9 wettable powder and d) a 10% wettable powder:
a) 40 parts of active substance, parts of sodium lignin sulfonate, 1 part of sodium dibutyl-naphthalene sulfonate, and .. . , . . . . ,.. . ~ . .. _ . . ,.. . . . . _ , ........... . .
, .
~15~:(39 54 parts of silicic acid;
b) 25 parts of active substance, 4.5 parts of calcium lignin sulfonate, 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutyl-naphthalene sulfonate, 19.5 parts of silicic acid, 19.5 parts of Champagne chalk, and 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 mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, and 46 parts of kaolin; and d) 10 parts of active substance, 3 parts of a mixture of the sodium salts o:E
saturated fatty alcohol sul~ates, parts of naphthalenesulfonic acid/
formaldehyde condensate, and 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 to obtain wettable powders which can be diluted with water to give suspensions of the concentration desired.
Emulsifiable concentrates The following substances are used to produce a) a 10% emulsifiable concentrate, b) a 25% emulsifiable .. . . . . . . .. . .. . .. . . .. . ..... . ... . .. . ....... . .. .
concentrate 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 alkyl-arylsulfonate calcium salt, parts of dimethylformamide, and 43.2 parts of xylene;
b) 25 parts o~ active substance, 2.5 parts of epoxidised vegetable oil, parts of alkylarylsulfonate/fatty alcohol polyglycol ether mixture, parts of dimethylformamide, and 57.5 parts of xylene; and c) 50 parts of active substance, 4.2 parts of tributylphenol-polyglycol ether, 5.8 parts of calcium-dodecylbenzenesulfonate, parts of cyclohexanone, and parts of xylene.
Emulsions of the required concentration can be prepared from these concentrates by dilution with water.
SPrays The following constituents are used to produce a) a 5% spray and b) a 95% spray:
a) 5 parts of active substance, 1 part of epichlorohydrin, and 94 parts of ligroin (boiling limites 160-190C);
b) 95 parts of active substance, and parts of epichlorohydrin.
The invention is further illustrated by the Examples which follow.
~s~
Example 1 a) Production of a-prop-l-ynyl-3-p-chlorophenoxybenzyl alcohol A Grignard solu~ion, freshly prepared from 4 g of magnesium and 20 g of ethyl bromide in 20 ml of tetra-hydrofuran, is slowly added at 0C to a solution of 8 g of methylacetylene in 100 ml of tetrahydrofuran, and the mixture i5 stirred under argon for 15 minutes. There is then added dropwise to this mixture at 0 to 5C a solution of 33.6 g of o-p-chlorophenoxybenzaldehyde in 100 ml of tetrahydrofuran. After being stirred for 14 hours at room temperature, the reactîon mixture is cooled to 0C with 50 g of ice; 25 ml of conc. hydrochloric acid is subsequently slowly added, and extraction is performed with ether. The ether extract is washed twice with water and twice with saturated sodium chloride solution; it is then dried over sodium sulfate, filtered, and concentrated by evaporation. The product is chromatographed through silica gel with ethyl acetate/hexane (1:4) as the eluant to thus obtain the compound of the formula HO-C~ -o-t~
c having a re~ractive index of n20 = 1.5844.
b) Production of Prop-l-ynYl-3-phenoxybenzyl-2,2-dimethyl-3-(2',2'-dichlorovinYl)-cYclopropane-l-carboxyla~e A solution of 4.5 g of a-prop-1-ynyl-3-p-chlorophenoxy-benzyl alcohol in 20 ml of toluene is added dropwise to an ice-cooled solution of 3.82 g of 2,2-dimethyl-3-(2',2'-~15;~
dichlorovinyl)-cyclopropanecarboxylic acid chloride and 1.8 ml of pyridine in 50 ml of toluene. The reaction mixture is stirred for 14 hours at room temperature, and ether is then added. The ether extract is washed once with water, once with 2N hydrochloric acid and three times with a saturated sodium chloride solution;
it is subsequently dried over sodium sulfate, filtered, and concentrated by evaporation. The product is chromato-graphed through silica gel with ether/hexane (1:3) as the eluant. There is obtained the compound of the formula C-CH-CH -CH-C00-CH--~ .-o-.
Cl/ ~ ¢ ~ C
3 3 C'C-CH
as a diastereoisomeric mixture having a refractive index of n20 = 1.5712.
The following compounds are obtained in an analogous manner:
~ C~ ~ Cl ca3 ca3 'C~C-C~3 \C-C~CH -c~-Coo C~ T~ ' ' 20 C~3 ca3 C~C- ~
\c-c~-ca-ca-coo-c~-T~ il~-T il 20 ¢ ~ -F = ~ = 1,5291 3 3 C-~-Ca3 . , . ~ . .. ., .. . .. . .. . .. , , . . . , . , ., . . . .. . .. .... , .. . , _ . . .. .. . . ..
.. ...
l15z~9~
/C\ ~ / 3 C~3 C~3 C~C-CH3 C~
/c3~a-c~ coo-~-ti `d--I~ = 1,5581 Ca3 Ca3 C~C-C83 Br r,c-c~-ca -ca-coo-ls-t li- l i~_ClnD = 1,5397 ca3 ca3 C~C-CH3 C~CH-C8 -cH-coo-cH~ li-o-t~ 1,5832 Ca3 Ca3 C C-C~3 Br ,c-c~-c~ -c~-coo ca t li t l'_ F nD ' 1,5740 C~3 C~3 C C-C~3 \c-CH-CH -CH-COO-CH-t il- t il nD - 1,5981 Br \ ¢ ~ Br ~3 ~3 ~-C~
l,`c-ca-ca -ca-coo-l ~l li I~ ,li Br nD0 3 1,5819 C~3 3 C-C-C~3 115ZO9~L
F
,cYc~-ca - ca--coo--c~--~ \ --o-- ~ 1, 5400 C~I3 CH3 C~-CH3 - F
~C-CH-CH -CH-COO-CH-~ il-- i~ i~ nD ' 1, 5420 C3~ . .
~C-CH-CH -CH-COO-CH~ -O-î~ ~il-F n20 = 1,5598 ~C-CH-CH-CH-C00-CH-i~ -iSS \i ~ = 1,5695 3 3 ~=~-Ca3 Br ~C-CH-CH-CH-C00-CH~ il--i~ ~il nD ~ 1,5850 C~3 C~3 ~ -CH3 Example 2 a) Insecticidal stomach-Poison action Cotton plants were sprayed with a 0.05% aqueous active-substance emulsion (obtained from a 10% emulsi-fiable concentrate). After drying of the coating, larvae of Spodoptera littoralis in the L3-stage and of -, . .. :
.
1 ~5;;~9 Heliothis virescens in the L3 stage were placed on~o the cotton 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 ~eliothis virescens larvae.
Example 3 Acaric;dal action Phaseolus vulgaris plants 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 and 7 days, by examination under a binocular microscope, of the living larvae 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 l were effective in the above test against adults, larvae and eggs of Tetranychus urticae.
Example 4 a) RhipicePhalus burs_ For each concentration, 5 adult ticks and 50 tick larvae, respectively, were counted into a small glass test tube, and immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion from a dilution series of 100, 10, 1 and .. . . .. .
~15~(~99 O.1 ppm of test substance. The tubes were then sealed with a standardised cotton plug, and inverted so that the active-substance emulsion could be absorbed by the cotton wool.
The evaluation in the case of the adults was made after 2 weeks and in the case of the larvae after 2 days. There were two repeats for each test.
b) Boophilus microplus (larvae~
With a dilution series analogous to that of Test A, tests were carried out with 20 sensitive larvae and OP-resistant larvae, respectively (resistance is with respect to diazinon compatibility).
Compounds according to Example 1 were effective in these tests against adults and larvae of Rhipicephalus bursa and against sensitive and OP-resistant larvae~
respectively, of Boophilus microplus.
. ..
' ~ ' ' ,
a) 5 parts of active substance, and parts of talcum;
b) 2 parts of active substance, 1 part of highly dispersed silicic acid, and 97 parts of talcum.
The active substance is mixed and ground with the carriers.
Granulate The following ingredients 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, and 91 parts of kaolin (particle size 0.3 - O.i3 mm).
The active substance is mixed with epichlorohydrin and dissolved in 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The solution thus obtained is sprayed onto kaolin, and the acetone is subsequently evaporated off in vacuo.
Wettable ~owders The following constituents are used to produce a) a 40% wettable powder, b) and c) a 25~/9 wettable powder and d) a 10% wettable powder:
a) 40 parts of active substance, parts of sodium lignin sulfonate, 1 part of sodium dibutyl-naphthalene sulfonate, and .. . , . . . . ,.. . ~ . .. _ . . ,.. . . . . _ , ........... . .
, .
~15~:(39 54 parts of silicic acid;
b) 25 parts of active substance, 4.5 parts of calcium lignin sulfonate, 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1), 1.5 parts of sodium dibutyl-naphthalene sulfonate, 19.5 parts of silicic acid, 19.5 parts of Champagne chalk, and 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 mixture (1:1), 8.3 parts of sodium aluminium silicate, 16.5 parts of kieselguhr, and 46 parts of kaolin; and d) 10 parts of active substance, 3 parts of a mixture of the sodium salts o:E
saturated fatty alcohol sul~ates, parts of naphthalenesulfonic acid/
formaldehyde condensate, and 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 to obtain wettable powders which can be diluted with water to give suspensions of the concentration desired.
Emulsifiable concentrates The following substances are used to produce a) a 10% emulsifiable concentrate, b) a 25% emulsifiable .. . . . . . . .. . .. . .. . . .. . ..... . ... . .. . ....... . .. .
concentrate 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 alkyl-arylsulfonate calcium salt, parts of dimethylformamide, and 43.2 parts of xylene;
b) 25 parts o~ active substance, 2.5 parts of epoxidised vegetable oil, parts of alkylarylsulfonate/fatty alcohol polyglycol ether mixture, parts of dimethylformamide, and 57.5 parts of xylene; and c) 50 parts of active substance, 4.2 parts of tributylphenol-polyglycol ether, 5.8 parts of calcium-dodecylbenzenesulfonate, parts of cyclohexanone, and parts of xylene.
Emulsions of the required concentration can be prepared from these concentrates by dilution with water.
SPrays The following constituents are used to produce a) a 5% spray and b) a 95% spray:
a) 5 parts of active substance, 1 part of epichlorohydrin, and 94 parts of ligroin (boiling limites 160-190C);
b) 95 parts of active substance, and parts of epichlorohydrin.
The invention is further illustrated by the Examples which follow.
~s~
Example 1 a) Production of a-prop-l-ynyl-3-p-chlorophenoxybenzyl alcohol A Grignard solu~ion, freshly prepared from 4 g of magnesium and 20 g of ethyl bromide in 20 ml of tetra-hydrofuran, is slowly added at 0C to a solution of 8 g of methylacetylene in 100 ml of tetrahydrofuran, and the mixture i5 stirred under argon for 15 minutes. There is then added dropwise to this mixture at 0 to 5C a solution of 33.6 g of o-p-chlorophenoxybenzaldehyde in 100 ml of tetrahydrofuran. After being stirred for 14 hours at room temperature, the reactîon mixture is cooled to 0C with 50 g of ice; 25 ml of conc. hydrochloric acid is subsequently slowly added, and extraction is performed with ether. The ether extract is washed twice with water and twice with saturated sodium chloride solution; it is then dried over sodium sulfate, filtered, and concentrated by evaporation. The product is chromatographed through silica gel with ethyl acetate/hexane (1:4) as the eluant to thus obtain the compound of the formula HO-C~ -o-t~
c having a re~ractive index of n20 = 1.5844.
b) Production of Prop-l-ynYl-3-phenoxybenzyl-2,2-dimethyl-3-(2',2'-dichlorovinYl)-cYclopropane-l-carboxyla~e A solution of 4.5 g of a-prop-1-ynyl-3-p-chlorophenoxy-benzyl alcohol in 20 ml of toluene is added dropwise to an ice-cooled solution of 3.82 g of 2,2-dimethyl-3-(2',2'-~15;~
dichlorovinyl)-cyclopropanecarboxylic acid chloride and 1.8 ml of pyridine in 50 ml of toluene. The reaction mixture is stirred for 14 hours at room temperature, and ether is then added. The ether extract is washed once with water, once with 2N hydrochloric acid and three times with a saturated sodium chloride solution;
it is subsequently dried over sodium sulfate, filtered, and concentrated by evaporation. The product is chromato-graphed through silica gel with ether/hexane (1:3) as the eluant. There is obtained the compound of the formula C-CH-CH -CH-C00-CH--~ .-o-.
Cl/ ~ ¢ ~ C
3 3 C'C-CH
as a diastereoisomeric mixture having a refractive index of n20 = 1.5712.
The following compounds are obtained in an analogous manner:
~ C~ ~ Cl ca3 ca3 'C~C-C~3 \C-C~CH -c~-Coo C~ T~ ' ' 20 C~3 ca3 C~C- ~
\c-c~-ca-ca-coo-c~-T~ il~-T il 20 ¢ ~ -F = ~ = 1,5291 3 3 C-~-Ca3 . , . ~ . .. ., .. . .. . .. . .. , , . . . , . , ., . . . .. . .. .... , .. . , _ . . .. .. . . ..
.. ...
l15z~9~
/C\ ~ / 3 C~3 C~3 C~C-CH3 C~
/c3~a-c~ coo-~-ti `d--I~ = 1,5581 Ca3 Ca3 C~C-C83 Br r,c-c~-ca -ca-coo-ls-t li- l i~_ClnD = 1,5397 ca3 ca3 C~C-CH3 C~CH-C8 -cH-coo-cH~ li-o-t~ 1,5832 Ca3 Ca3 C C-C~3 Br ,c-c~-c~ -c~-coo ca t li t l'_ F nD ' 1,5740 C~3 C~3 C C-C~3 \c-CH-CH -CH-COO-CH-t il- t il nD - 1,5981 Br \ ¢ ~ Br ~3 ~3 ~-C~
l,`c-ca-ca -ca-coo-l ~l li I~ ,li Br nD0 3 1,5819 C~3 3 C-C-C~3 115ZO9~L
F
,cYc~-ca - ca--coo--c~--~ \ --o-- ~ 1, 5400 C~I3 CH3 C~-CH3 - F
~C-CH-CH -CH-COO-CH-~ il-- i~ i~ nD ' 1, 5420 C3~ . .
~C-CH-CH -CH-COO-CH~ -O-î~ ~il-F n20 = 1,5598 ~C-CH-CH-CH-C00-CH-i~ -iSS \i ~ = 1,5695 3 3 ~=~-Ca3 Br ~C-CH-CH-CH-C00-CH~ il--i~ ~il nD ~ 1,5850 C~3 C~3 ~ -CH3 Example 2 a) Insecticidal stomach-Poison action Cotton plants were sprayed with a 0.05% aqueous active-substance emulsion (obtained from a 10% emulsi-fiable concentrate). After drying of the coating, larvae of Spodoptera littoralis in the L3-stage and of -, . .. :
.
1 ~5;;~9 Heliothis virescens in the L3 stage were placed on~o the cotton 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 ~eliothis virescens larvae.
Example 3 Acaric;dal action Phaseolus vulgaris plants 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 and 7 days, by examination under a binocular microscope, of the living larvae 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 l were effective in the above test against adults, larvae and eggs of Tetranychus urticae.
Example 4 a) RhipicePhalus burs_ For each concentration, 5 adult ticks and 50 tick larvae, respectively, were counted into a small glass test tube, and immersed for 1 to 2 minutes in 2 ml of an aqueous emulsion from a dilution series of 100, 10, 1 and .. . . .. .
~15~(~99 O.1 ppm of test substance. The tubes were then sealed with a standardised cotton plug, and inverted so that the active-substance emulsion could be absorbed by the cotton wool.
The evaluation in the case of the adults was made after 2 weeks and in the case of the larvae after 2 days. There were two repeats for each test.
b) Boophilus microplus (larvae~
With a dilution series analogous to that of Test A, tests were carried out with 20 sensitive larvae and OP-resistant larvae, respectively (resistance is with respect to diazinon compatibility).
Compounds according to Example 1 were effective in these tests against adults and larvae of Rhipicephalus bursa and against sensitive and OP-resistant larvae~
respectively, of Boophilus microplus.
. ..
' ~ ' ' ,
Claims (7)
1. A cyclopropanecarboxylic acid ester of the formula (I) in which X1 is fluorine, chlorine or bromine, and Y is methoxy, methyl, fluorine, chlorine or bromine.
2. A compound according to Claim 1, wherein X1 is fluorine, chlorine or bromine, and Y is p-methoxy, p-methyl, p-fluorine, p-chlorine or p-bromine.
3. The compound according to Claim 2 of the formula .
4. The compound according to Claim 2 of the formula .
5. A process for producing a compound according to claim 1, which pro-cess comprises reacting a compound of the formula in the presence of an acid-binding agent, with a compound of the formula wherein X1 and Y have the meanings given in claim 1, and X is a halogen atom.
6. A method of combating various animal and plant pests, which compri-ses applying to a locus a pesticidally effective amount of a compound accord-ing to claim 1.
7. A method according to claim 6 for combating insects, and represen-tatives of the order Acarina.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH699078 | 1978-06-27 | ||
| CH6990/78-9 | 1978-06-27 | ||
| CH2558/79-6 | 1979-03-19 | ||
| CH255879 | 1979-03-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1152094A true CA1152094A (en) | 1983-08-16 |
Family
ID=25690764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000330476A Expired CA1152094A (en) | 1978-06-27 | 1979-06-25 | Cyclopropane carboxylic acid esters |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0008331B1 (en) |
| CA (1) | CA1152094A (en) |
| DE (1) | DE2961873D1 (en) |
| IL (1) | IL57658A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4389412A (en) * | 1979-03-30 | 1983-06-21 | Kuraray Company, Ltd. | Substituted cyclopropanecarboxylic acid esters and pesticidal compositions containing the same as active ingredient |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5813522B2 (en) * | 1974-10-24 | 1983-03-14 | 住友化学工業株式会社 | Insecticide and acaricide containing new cyclopropane carboxylic acid ester |
-
1979
- 1979-06-25 EP EP79102084A patent/EP0008331B1/en not_active Expired
- 1979-06-25 CA CA000330476A patent/CA1152094A/en not_active Expired
- 1979-06-25 DE DE7979102084T patent/DE2961873D1/en not_active Expired
- 1979-06-26 IL IL57658A patent/IL57658A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IL57658A (en) | 1982-07-30 |
| EP0008331B1 (en) | 1982-01-20 |
| IL57658A0 (en) | 1979-10-31 |
| EP0008331A1 (en) | 1980-03-05 |
| DE2961873D1 (en) | 1982-03-04 |
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