CA1123452A - Cyclopropyl carboxylate compounds a process for their manufacture and their use as pesticides - Google Patents
Cyclopropyl carboxylate compounds a process for their manufacture and their use as pesticidesInfo
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- CA1123452A CA1123452A CA304,269A CA304269A CA1123452A CA 1123452 A CA1123452 A CA 1123452A CA 304269 A CA304269 A CA 304269A CA 1123452 A CA1123452 A CA 1123452A
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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)
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- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Cyclopropyl carboxylate compounds in the form of single isomers of combination thereof charaterized in that they have a general formula:-
Description
~.Z3~5Z
CYCLOPROPYL CAR~OXYLATE COMPOUNDS, A PROCESS FOR THEIR MANUFACTVRE `
AND THEIR USE AS PESTICIDES
This invention relates to cyclopropyl carboxylate compounds pos-sessing pesticidal activity, to a process rOr the manufacture and to their use as pesticides. The compounds are related to the so-called ~ -~
synthetic pyrethroids.
United Kingdom Patent Specification 1,413,491 discloses, inter alia, 3-phenoxybenzyl esters and alpha-substituted 3-phenoxybenzyl esters Or 2~2_dimethyl-3-(2~2-dihalovinyl)cyclopropanecarboxylic ~-~
acids; it also disclo~es their u~e as insecticides. Whil3t the high level Or activity Or this class Or compounds against in~ects i~ dis-closed, no mention is made to their activity against Acarines such as the Ixodidae family and the Tetranychidae Pamily.
The Applicant has now Pound a small group of 3-phenoxybenzyl esters and alpha-substituted-3-phenoxybenzyl esters of
CYCLOPROPYL CAR~OXYLATE COMPOUNDS, A PROCESS FOR THEIR MANUFACTVRE `
AND THEIR USE AS PESTICIDES
This invention relates to cyclopropyl carboxylate compounds pos-sessing pesticidal activity, to a process rOr the manufacture and to their use as pesticides. The compounds are related to the so-called ~ -~
synthetic pyrethroids.
United Kingdom Patent Specification 1,413,491 discloses, inter alia, 3-phenoxybenzyl esters and alpha-substituted 3-phenoxybenzyl esters Or 2~2_dimethyl-3-(2~2-dihalovinyl)cyclopropanecarboxylic ~-~
acids; it also disclo~es their u~e as insecticides. Whil3t the high level Or activity Or this class Or compounds against in~ects i~ dis-closed, no mention is made to their activity against Acarines such as the Ixodidae family and the Tetranychidae Pamily.
The Applicant has now Pound a small group of 3-phenoxybenzyl esters and alpha-substituted-3-phenoxybenzyl esters of
2,2_dimethyl-3-(2,2-dihalovinyljcyclopropanecarboxylic acids which not only exhibit high level~ Or insecticidal activity but also have a significant er~ect on acarines, for example Tetranychus urticae (glasshouse red spider mite) and Boophilus microplus (cattle tick).
Accordingly the preqent invention provides cyclopropyl carboxy-late compounds in the form Or single isomers or combinations thereof 20 and having the general formula:- X
c ~a ~ (I) :
.
::~
- : . - ~ . ~ ,..... . ~ : , . - .
., : .. - ,, ~ . .,, , ~, . . . .
2 1~.Z34~
wherein X is a chlorine, bromine or iodine atom and Y i3 a hydrogen atom or a cyano or ethynyl group. Preferably X i~ a chlorine atom.
From formula I it will be apparent that the compounds according to the invention can exist in a number of stereoisomeric forms. Thus in the acid portion of the compounds, the hydrogen atoms carried by carbon atoms 1 and 3 in the cyclopropyl ring can be in a cis or trans relationship and because of asymmetrical substitution at these carbon atoms each cis i~omer can exist in two ~tereoisomeric rorms and each trans isomer can exist in two stereoisomeric forms. The absolute con-figuration of these four stereoisomeric forms can be satisfactorilyderined using the Elliott nomenclature as defined by M. Elliott, A.W.
Farnham, N.F. Janes, P.H. Needham and D.A. Pulman, Nature, 1974, 248, 710. Thus the four stereoisomeric forms are designated ~1R, cis), (1S, cis), (lR, trans) and (1S, trans).
In the acid portion Or the compounds according to the invention the possibility of further stereoisomeric forms occurs by virtue of the asymmetric substitution of the vinylic double bond appearing in the substituent at position 3 on the cyclopropyl ring. The most sat-isfactory method o~ defining stereoisomerism Or this kind is the E~Z
nomenclature of J.E. Blackwood, C.L. Gladys, K.L. Loening, A.E.
Petrarca and J.E. Rush, J.A.C.S./90:2J1968.
In the alcohol portion o~ the compounds according to the inven-tion, when Y represents a cyano or ethynyl group, a further site of asymmetry occurs at the alpha-carbon atom carrying the Y-substituent and the absolute configuration of this carbon atom may be designated R or S in accordance with the sequence rules of R.S. Cahn, C. Ingold, and V. Prelog, Angew. Chem. Int. Ed. 5, 385 (1966). It ~hould be no- ;, ted that the Elliot et al nomenclature and the Blackwood et al nomen-clature are both based on these sequence rules.
Thus the compounds according to the invention can exist in 16 stereoisomeric forms and, whilst all isomers or combinations thereof come within the scope of the invention, it has been found that com-pounds derived from a cyclopropyl carboxylate having a configuration at carbon atoms 1 and 3 in one of the following forms:-(lR, IS cis), or (lR, cis) -- ;
Accordingly the preqent invention provides cyclopropyl carboxy-late compounds in the form Or single isomers or combinations thereof 20 and having the general formula:- X
c ~a ~ (I) :
.
::~
- : . - ~ . ~ ,..... . ~ : , . - .
., : .. - ,, ~ . .,, , ~, . . . .
2 1~.Z34~
wherein X is a chlorine, bromine or iodine atom and Y i3 a hydrogen atom or a cyano or ethynyl group. Preferably X i~ a chlorine atom.
From formula I it will be apparent that the compounds according to the invention can exist in a number of stereoisomeric forms. Thus in the acid portion of the compounds, the hydrogen atoms carried by carbon atoms 1 and 3 in the cyclopropyl ring can be in a cis or trans relationship and because of asymmetrical substitution at these carbon atoms each cis i~omer can exist in two ~tereoisomeric rorms and each trans isomer can exist in two stereoisomeric forms. The absolute con-figuration of these four stereoisomeric forms can be satisfactorilyderined using the Elliott nomenclature as defined by M. Elliott, A.W.
Farnham, N.F. Janes, P.H. Needham and D.A. Pulman, Nature, 1974, 248, 710. Thus the four stereoisomeric forms are designated ~1R, cis), (1S, cis), (lR, trans) and (1S, trans).
In the acid portion Or the compounds according to the invention the possibility of further stereoisomeric forms occurs by virtue of the asymmetric substitution of the vinylic double bond appearing in the substituent at position 3 on the cyclopropyl ring. The most sat-isfactory method o~ defining stereoisomerism Or this kind is the E~Z
nomenclature of J.E. Blackwood, C.L. Gladys, K.L. Loening, A.E.
Petrarca and J.E. Rush, J.A.C.S./90:2J1968.
In the alcohol portion o~ the compounds according to the inven-tion, when Y represents a cyano or ethynyl group, a further site of asymmetry occurs at the alpha-carbon atom carrying the Y-substituent and the absolute configuration of this carbon atom may be designated R or S in accordance with the sequence rules of R.S. Cahn, C. Ingold, and V. Prelog, Angew. Chem. Int. Ed. 5, 385 (1966). It ~hould be no- ;, ted that the Elliot et al nomenclature and the Blackwood et al nomen-clature are both based on these sequence rules.
Thus the compounds according to the invention can exist in 16 stereoisomeric forms and, whilst all isomers or combinations thereof come within the scope of the invention, it has been found that com-pounds derived from a cyclopropyl carboxylate having a configuration at carbon atoms 1 and 3 in one of the following forms:-(lR, IS cis), or (lR, cis) -- ;
3 ~.Z34~Z
give rise to better activity in terms of their acaricidal and in~ec- ~ -ticidal effects.
The cyclopropyl carboxylate of formula I may be prepared by known methods. A convenient process is the reaction of a compound of formula:-X ',;;
H CH = C\
~ F (II) CH3 / / \ \ COZ
with a compound of formula~
0_~/~ '`~ '' Q - ~H ~ (III) wherein X and Y are as defined hereinbefore; one Or the groups Q and ~ -Z repressnts a halogen, preferably a chlorine or bromine atom, and the other represents a hydroxy group. The reaction is preferably car- `~
ried out in the presence of a suitable base, for example a tertiary amine such astriethylamine~ When a particular isomeric form of the compounds according to the invention is required the appropriate ste-reoisomeric starting materials should be selected. Alternatively various isomers or isomer combinations can be isolated by physical'; ~ -~
separation techniques, e.g. fractional crystallization or chromato-graphi¢ methods.
The compounds of the invention are of particular interest as acaricides and insecticides and therefore the invention includes pes-ticidal compositions comprising a compound according to the invention, a surface sctive agent and/or carrier. The invention al~o includes a method for combating acarid and/or insect pests at a locus which comprises applying to the locus an acaricidally-active or in-secticidally-active amount of a compound or composition according to the invention.
25The term "carrier" as used herein means a material, which may be inorganic or organic and of aynthetic or natural origin, with which the active compound is mixed or formulated to facilitate its appllca-;~
3~52 tion to the plant, seed, 30il or other object to be treated, or its storage, transport or handling. The carrier may be a solid or a fluid. Any of the material usually applied in formulatine pesticides may be used as carrier.
Suitable solid carriers are natural and synthetic clays and silicates, for example natural silicas such as diatomaceous earths;
magnesium silicate3, for example, talcs; magnesium aluminium sili-cates, for example, kaolinites, montmorillinites and micas, calcium carbonates; calcium sulphate; synthetic hydrated silicon ox.des and synthetic calcium or aluminium silicates; elements such as for exam-ple, carbon and sulphur; natural and synthetic resin~ such as for example, coumarone resins, polyvinyl chloride and styrene polymers and copolymer~; solid polychlorophenols; bitumen; waxes such as for example, beeswax, paraffin wax, and chlorinated mineral waxes; and 15 solid fertili3ers, for example superphosphates. :-Examples of suitable fluid carriers are water, alcohols, such a~
for example, isopropanol, glycols, ketones such as for example, ace-tone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone;
ether~; aromatic hydrocarbons, such as for example, benzene, toluene and xylene; petroleum fractions such as for example, kerosine, light mineral oils; chlorinated hydrocarbons, such as for example, carbon :
tetrachloride, perchloroethylene, trichloroethane, including lique-fied normally vaporous gaseous compounds. Mixtures of different li-quids are often suitable.
The surface-active agent may be an emulsifying agent or a dis-persing agent or a wetting agent; it may be nonionic or ionic. Any of the surface-active agents usually applied in formulating herbicides or insecticides may be used. Examples of suitable surface-active agent~ are the sodium or calcium salts of polyacrylic acids and lig-30 nin sulphonic acids; the condensation products of fatty acids or ali- ~ :
phatic amines or amides containing at lea3t 12 carbon atoms in the -molecule with ethylene oxide and/or propylene oxide; fatty acid esters of glycerol, sorbitan, sucrose or pentaerythritol; condensates of these with ethylene oxide and/or propylene oxide; condensation :
products of fatty alcohols or alkyl phenols for example p-octylphenol or p-octylcresol, with ethylene oxide and/or propylene oxide;
.. - .. .- -.
~ 23452 sulphates or sulphonates of these condensation products; alkali or alkaline earth metal salts, preferably sodium salts, of sulphuric or sulphonic acid esters con~aining at least 10 carbon atoms in the molecule, for example, sodium lauryl ~ulphate, ~odium secondary alkyl ~ulphates, sodium salts of sulphonated castor oil, and sodium alkyl-aryl sulphonates such as sodium dodecylbenzene sulphonate; and poly-mers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.
The compositions of the invention may be formulated as wettable 10 powders, dusts, granules, solutions, emulsifiable concentrates, emul- -sions, suspension concentrates and aerosols, and will generally con- ;
tain 0.5 to 95~ w, preferably 0.5 to 75S w, of toxicant. Wettable powders are usually compounded to contain 25, 50 or 75% w, of toxi-cant and usually contain, in addition to solid carrier, 3-10% w of a dispersing agent and, where necessary, 0-10S w of stabiliser(s) and/or other additives such as penetrants or stickers. Dusts are usu-ally formulated as a dust concentrate having a similar composition to that of a wettable powder but without a disper~ant, and are diluted in the field with further solid carrier to give a composition usually ` ~!, containing ~-10~ w of toxicant. Granules are usually prepared to have a size between 10 and 100 BS mesh, and may be manufactured by agglomeration or impregnation techniques. GenerallY, granules will contain ~-25S w toxicant and 0-10% w of additives such as stabilisers, slow release modifiers and binding agents. Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, co-solvent, 10-50% w~v toxicant, 2-20% w/v and 0-20% w/v of appropriate additives such as stabilisers, penetrants and corro-sion inhibitors. Suspension concentrates are compounded so as to ob-tain a stable, non-sedimenting, flowable product and usually contain 1-75$ w toxicant, 0.5-15% w of dispersing agents, 0.1-10S w of sus-pending agents such as protective colloids and thixotropic agents, 0-10% w of appropriate additives such as defoamers, corrosion inhibi-tors, stabilisers, penetrants and stickers, and as carrier, water or an orgaDic liquid in which the toxicant is substantially insoluble;
35 certain organic solids or inorganic salts may be dissolved in the ~;
carrier to assist in preventing sedimentation or as anti-freeze agents for water.
The compo~itions of the invention may contain other lngredient~, for example, protecti~e colloids ~uch as gelatin, ~lue, casein, gum, cellulo~e ether~, and polyvinyl alcohol; thixotropic agent~ e.g. ben-tonites, sodium polyphosphates; ~tabilisers quch as ethylene diamine tetra-acetic a¢id, urea, triphenyl phoqphate; other herbioides or pesticideQ; and stickerq, ~or example non-volatile oils.
Aqueous dispersions and emulsions, for example, compo~itions obtained by diluting a wettable powder or an emul~iriable concentrate according to the invention with water, al~o lie within the ~cope of the preqent invention. The qaid emul~ions may be of the water-in-oil or of the oil-in-water type, and may have a thick "mayonnaise"-like con~istency.
The invention iq further illustrated by reference to the fol-lowing Examples:-5 Example 1 Preparation of (RS)alpha-cyano-3-phenoxybenzyl(1S,lR,cis)-(E/Z)3-(2-chloro-2-fluorovinyl)-2,2-dimethylcyclopropane_1-carboxylate (1S,1R,ci )(E/Z)-3-(2-chloro-2-fluorovinyl)-2,2-dimethyl-1-cyclo-propanecarboxylic acid (0.8g), (R,S)-alpha-cyano-3-phenoxybenzylbromide (1.15g) and potasQiUm carbonate were stirred together in acetone (25ml) for 4 hours at room temperature. The product waq treated with water and extracted with ether (3 x 25ml). The ethereal extraats were combined and evaporated to give a crude product which was purified by chromatography u~ing Qilica gel and eluent of toluenehexanone 1:1 to ~
give the deQired product nD= 1.551.
Analy~iQ Calculated for C22H1gN03Cl F: C66.1; H4-8; N3-5 Found : C65.7; H4.9; N3.2 Example 1A Preparation Or starting acid for Example 1 ((1S,1R,ci~) (E/~)-3-(2-chloro-2-fluorovinyl)-2,2-dimethyl-1-cyclo ~ `
39 propanecarboxylic acid) Dichlorofluoromethane was dissolved in 100ml sodium-dried hexane at 0C. The dichlorofluoromethane (7.2g; 0.07mol) ~olution wae added with 3tirring over 20 minutes at 0 C under nitrogen to a fla3k con-taining lOOml dry hexane, potassium tertiary butoxide (7.85g;
35 0.07mol) and triphenylphosphine (18.3g; 0.07mol). The flask was al-lowed to warm to 15C and then a hexane ~olution Or (1S,1R)-ciq-caronaldehyde methyl ester (10.0g; 0.064 mol) added ~ 2~
over 15 minutes. The nitrogen was removed and the flask heated at ;~
55C for 1 hour. The reactants were then aIlowed to stand overnight.
A brown precipitate was then filtered from a brown oil. The oil was distilled to yield 9.2g of a colourless oil and by GLC this was ~hown to be composed of starting aldehyde and 2 higher boiling components.
A saturated solution of sodium metabisulphite iD water was pre- ;
pared. To 50ml of this solution was added 35ml of industrial methyl~
ated spirit and then surficient water to ~orm a olear ~olution. Tbis solution was added to an ether solution of the oil recovered above and the mixture stirred at room temperal;ure for 0.5 hours. GLC
confirmed the formation of a bisulphite-addition oompound and complete removal of aldehyde ~tarting material. The organio layer was separated, washed with water, dried and evaporated to yield 3 3g of ~ -(lS,1R,cis) (E/Z)-3-(2-chloro-2-fluorovinyl~-2,2-dimethyl-1-cyclopro-pane carboxylic acid methyl e~ter (25S yield).
The ester t3.3g) was hydrolysed to the free acid usine ethanol and 2N-sodium hydroxide to yield 2.6g acid (ô4S).
Examples 2-7 The following compounds were prepared using procedures -~imilar to those shown in Examples 1 and lA (see Table I). ~-CN ~l ~' .'' ,'.'`, . .
3~5~
TABLE I
CONFIGURATION AT
EXAMPLE Y _ _ _ __ REFRACTIVE
C and C C Double INDEX
1 3 alphaBond _ _ . .
2 N (lS,1R,ci.~) _ E/Z nD 1.555 3 H ~1S,1R,tran~) _ E/Z nD 1-553 . .
give rise to better activity in terms of their acaricidal and in~ec- ~ -ticidal effects.
The cyclopropyl carboxylate of formula I may be prepared by known methods. A convenient process is the reaction of a compound of formula:-X ',;;
H CH = C\
~ F (II) CH3 / / \ \ COZ
with a compound of formula~
0_~/~ '`~ '' Q - ~H ~ (III) wherein X and Y are as defined hereinbefore; one Or the groups Q and ~ -Z repressnts a halogen, preferably a chlorine or bromine atom, and the other represents a hydroxy group. The reaction is preferably car- `~
ried out in the presence of a suitable base, for example a tertiary amine such astriethylamine~ When a particular isomeric form of the compounds according to the invention is required the appropriate ste-reoisomeric starting materials should be selected. Alternatively various isomers or isomer combinations can be isolated by physical'; ~ -~
separation techniques, e.g. fractional crystallization or chromato-graphi¢ methods.
The compounds of the invention are of particular interest as acaricides and insecticides and therefore the invention includes pes-ticidal compositions comprising a compound according to the invention, a surface sctive agent and/or carrier. The invention al~o includes a method for combating acarid and/or insect pests at a locus which comprises applying to the locus an acaricidally-active or in-secticidally-active amount of a compound or composition according to the invention.
25The term "carrier" as used herein means a material, which may be inorganic or organic and of aynthetic or natural origin, with which the active compound is mixed or formulated to facilitate its appllca-;~
3~52 tion to the plant, seed, 30il or other object to be treated, or its storage, transport or handling. The carrier may be a solid or a fluid. Any of the material usually applied in formulatine pesticides may be used as carrier.
Suitable solid carriers are natural and synthetic clays and silicates, for example natural silicas such as diatomaceous earths;
magnesium silicate3, for example, talcs; magnesium aluminium sili-cates, for example, kaolinites, montmorillinites and micas, calcium carbonates; calcium sulphate; synthetic hydrated silicon ox.des and synthetic calcium or aluminium silicates; elements such as for exam-ple, carbon and sulphur; natural and synthetic resin~ such as for example, coumarone resins, polyvinyl chloride and styrene polymers and copolymer~; solid polychlorophenols; bitumen; waxes such as for example, beeswax, paraffin wax, and chlorinated mineral waxes; and 15 solid fertili3ers, for example superphosphates. :-Examples of suitable fluid carriers are water, alcohols, such a~
for example, isopropanol, glycols, ketones such as for example, ace-tone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone;
ether~; aromatic hydrocarbons, such as for example, benzene, toluene and xylene; petroleum fractions such as for example, kerosine, light mineral oils; chlorinated hydrocarbons, such as for example, carbon :
tetrachloride, perchloroethylene, trichloroethane, including lique-fied normally vaporous gaseous compounds. Mixtures of different li-quids are often suitable.
The surface-active agent may be an emulsifying agent or a dis-persing agent or a wetting agent; it may be nonionic or ionic. Any of the surface-active agents usually applied in formulating herbicides or insecticides may be used. Examples of suitable surface-active agent~ are the sodium or calcium salts of polyacrylic acids and lig-30 nin sulphonic acids; the condensation products of fatty acids or ali- ~ :
phatic amines or amides containing at lea3t 12 carbon atoms in the -molecule with ethylene oxide and/or propylene oxide; fatty acid esters of glycerol, sorbitan, sucrose or pentaerythritol; condensates of these with ethylene oxide and/or propylene oxide; condensation :
products of fatty alcohols or alkyl phenols for example p-octylphenol or p-octylcresol, with ethylene oxide and/or propylene oxide;
.. - .. .- -.
~ 23452 sulphates or sulphonates of these condensation products; alkali or alkaline earth metal salts, preferably sodium salts, of sulphuric or sulphonic acid esters con~aining at least 10 carbon atoms in the molecule, for example, sodium lauryl ~ulphate, ~odium secondary alkyl ~ulphates, sodium salts of sulphonated castor oil, and sodium alkyl-aryl sulphonates such as sodium dodecylbenzene sulphonate; and poly-mers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.
The compositions of the invention may be formulated as wettable 10 powders, dusts, granules, solutions, emulsifiable concentrates, emul- -sions, suspension concentrates and aerosols, and will generally con- ;
tain 0.5 to 95~ w, preferably 0.5 to 75S w, of toxicant. Wettable powders are usually compounded to contain 25, 50 or 75% w, of toxi-cant and usually contain, in addition to solid carrier, 3-10% w of a dispersing agent and, where necessary, 0-10S w of stabiliser(s) and/or other additives such as penetrants or stickers. Dusts are usu-ally formulated as a dust concentrate having a similar composition to that of a wettable powder but without a disper~ant, and are diluted in the field with further solid carrier to give a composition usually ` ~!, containing ~-10~ w of toxicant. Granules are usually prepared to have a size between 10 and 100 BS mesh, and may be manufactured by agglomeration or impregnation techniques. GenerallY, granules will contain ~-25S w toxicant and 0-10% w of additives such as stabilisers, slow release modifiers and binding agents. Emulsifiable concentrates usually contain, in addition to the solvent and, when necessary, co-solvent, 10-50% w~v toxicant, 2-20% w/v and 0-20% w/v of appropriate additives such as stabilisers, penetrants and corro-sion inhibitors. Suspension concentrates are compounded so as to ob-tain a stable, non-sedimenting, flowable product and usually contain 1-75$ w toxicant, 0.5-15% w of dispersing agents, 0.1-10S w of sus-pending agents such as protective colloids and thixotropic agents, 0-10% w of appropriate additives such as defoamers, corrosion inhibi-tors, stabilisers, penetrants and stickers, and as carrier, water or an orgaDic liquid in which the toxicant is substantially insoluble;
35 certain organic solids or inorganic salts may be dissolved in the ~;
carrier to assist in preventing sedimentation or as anti-freeze agents for water.
The compo~itions of the invention may contain other lngredient~, for example, protecti~e colloids ~uch as gelatin, ~lue, casein, gum, cellulo~e ether~, and polyvinyl alcohol; thixotropic agent~ e.g. ben-tonites, sodium polyphosphates; ~tabilisers quch as ethylene diamine tetra-acetic a¢id, urea, triphenyl phoqphate; other herbioides or pesticideQ; and stickerq, ~or example non-volatile oils.
Aqueous dispersions and emulsions, for example, compo~itions obtained by diluting a wettable powder or an emul~iriable concentrate according to the invention with water, al~o lie within the ~cope of the preqent invention. The qaid emul~ions may be of the water-in-oil or of the oil-in-water type, and may have a thick "mayonnaise"-like con~istency.
The invention iq further illustrated by reference to the fol-lowing Examples:-5 Example 1 Preparation of (RS)alpha-cyano-3-phenoxybenzyl(1S,lR,cis)-(E/Z)3-(2-chloro-2-fluorovinyl)-2,2-dimethylcyclopropane_1-carboxylate (1S,1R,ci )(E/Z)-3-(2-chloro-2-fluorovinyl)-2,2-dimethyl-1-cyclo-propanecarboxylic acid (0.8g), (R,S)-alpha-cyano-3-phenoxybenzylbromide (1.15g) and potasQiUm carbonate were stirred together in acetone (25ml) for 4 hours at room temperature. The product waq treated with water and extracted with ether (3 x 25ml). The ethereal extraats were combined and evaporated to give a crude product which was purified by chromatography u~ing Qilica gel and eluent of toluenehexanone 1:1 to ~
give the deQired product nD= 1.551.
Analy~iQ Calculated for C22H1gN03Cl F: C66.1; H4-8; N3-5 Found : C65.7; H4.9; N3.2 Example 1A Preparation Or starting acid for Example 1 ((1S,1R,ci~) (E/~)-3-(2-chloro-2-fluorovinyl)-2,2-dimethyl-1-cyclo ~ `
39 propanecarboxylic acid) Dichlorofluoromethane was dissolved in 100ml sodium-dried hexane at 0C. The dichlorofluoromethane (7.2g; 0.07mol) ~olution wae added with 3tirring over 20 minutes at 0 C under nitrogen to a fla3k con-taining lOOml dry hexane, potassium tertiary butoxide (7.85g;
35 0.07mol) and triphenylphosphine (18.3g; 0.07mol). The flask was al-lowed to warm to 15C and then a hexane ~olution Or (1S,1R)-ciq-caronaldehyde methyl ester (10.0g; 0.064 mol) added ~ 2~
over 15 minutes. The nitrogen was removed and the flask heated at ;~
55C for 1 hour. The reactants were then aIlowed to stand overnight.
A brown precipitate was then filtered from a brown oil. The oil was distilled to yield 9.2g of a colourless oil and by GLC this was ~hown to be composed of starting aldehyde and 2 higher boiling components.
A saturated solution of sodium metabisulphite iD water was pre- ;
pared. To 50ml of this solution was added 35ml of industrial methyl~
ated spirit and then surficient water to ~orm a olear ~olution. Tbis solution was added to an ether solution of the oil recovered above and the mixture stirred at room temperal;ure for 0.5 hours. GLC
confirmed the formation of a bisulphite-addition oompound and complete removal of aldehyde ~tarting material. The organio layer was separated, washed with water, dried and evaporated to yield 3 3g of ~ -(lS,1R,cis) (E/Z)-3-(2-chloro-2-fluorovinyl~-2,2-dimethyl-1-cyclopro-pane carboxylic acid methyl e~ter (25S yield).
The ester t3.3g) was hydrolysed to the free acid usine ethanol and 2N-sodium hydroxide to yield 2.6g acid (ô4S).
Examples 2-7 The following compounds were prepared using procedures -~imilar to those shown in Examples 1 and lA (see Table I). ~-CN ~l ~' .'' ,'.'`, . .
3~5~
TABLE I
CONFIGURATION AT
EXAMPLE Y _ _ _ __ REFRACTIVE
C and C C Double INDEX
1 3 alphaBond _ _ . .
2 N (lS,1R,ci.~) _ E/Z nD 1.555 3 H ~1S,1R,tran~) _ E/Z nD 1-553 . .
4 CR ~1S91R,trans) (B,S) E/Z nD 1.552 :~
CN (lR,ci~) (R,S). E~Z nD 1.550 6 N (lR,cis) _E/Z nD1 1.553 C-CN (lS,1R,~i~) (R,N) E/Z _ _ ~.~
(a) in the preparation of thi-~ compound the acid chloride ~-of (1S,1R,cis)(E/Z)-3-(2-chloro-2-fluorovinyl)-2,2-dimethyl-cyclopropanecarboxylic acid ~a~ reacted with (R,S)-alpha- ~
ethynyl-3-phenoxybenzyl alcohol in the presence o~ r N-methylimidazole.
, ~
.23~Z
TABLE I (Cont~d ) _ EXAMPLE ANALYSIS
__ . ~
2 Calculation for C21H20o3clF C 67-3; H 5-4%
Found: C 67.0; H 5.4g __ _ ___ _ __ . . . .
3 Calculation ~or C21H20o3clF C 6i-3; H 5-4%
_ Found: C 67.5; H 5.4%
4 Calculation for C22H1gNo3ClF C 66.1; H 4-8%
Found: C 66.6; H 5.1%
_ _. _______ _____ .
Calculation for C22H19N03ClF : C 66.1; H 4.8; N 3.5%
Found : C 65.6; H 4.9; N 3.2 __ . _ , ~
6 Calculation for C21H2003ClF C 67-3; H 5-4 Found : C 67.1; H 5.4%
_ ___ .
7(a)Calculation for C23H2003ClF C 69-3; H 5.1 Found : C 69.7; H 5.5 . _ __ _ . .. ~___ .. __ . _____ :, . . .
:'' ;.
_ ~.Z3~5~
Example 8 Acaricidal activity of the cyclopropyl carboxylate composi-tion (a) Activity against one-host cattle tick, Boophilu~ microplus (B.m.) Two to three week old larval ticks were used. In the rearing procedure calves were infe3ted with larval ticks which matured over a three week period. Engorged adult ~emale ticks which detach from the calf were collected and placed in 3" x 1 n gla99 tubes. Egg batches were laid by the females over the next ~ew days and larvae e~erged three weeks later. The cyclopropyl car-boxylates were formulated as solution3 or fine suspensions in acetone containing 10% by weight of polyethylene glycol having an average molecular weight of 400. The formulations contained 0.1~ by weight of the compound to be tested. lml of the above-mentioned 301ution wa~ applied evenly to a filter paper 3ituated inside a petri di~h. After the paper was sufPiciently dry it was folded in half and partly crimped along the outer edge to form a packet. About 80-100 larval ticks (Boophilus microplus) were transferred into the packet which was ~ealed completely. The packets were placed inside an incubator, main-tained at 27C and 80% relative humidity. After 24 hours the packets were opened and the percentage of dead and moribund larYae asses~ed. .;
(b) Activity against elasshouse red spider mite, Tetranychus urticaè
(T.u.) The cyclopropyl carboxylates were formulated as solutions or suspensions in water containing 20S by weight of acetone and -~
0.05~ by weight o~ Triton X100 as wetting agent. The formula-tions contained 0.4~ by weight of the compound to be tested. ;~`
Leaf discs cut from French bean plants were held on moi~t filter paper placed on a lid inside a waxed carton. Prior to te~ting, each leaf disc was infested with 10 adult mites. Tbe mite3 and discs were then 3prayed using a logarithmic spraying machine and held under standard glas house conditions. After 24 hour3 the percentage dead and moribund mites were a~sessed.
., ~ .. . .
~.;Z 3~2 1.
In (a) and (b) the concentration of material expected to kill 50~ of the exposed group Or test speciea was calculated (LC50) and the toxi- -;
city of the compound waa compared with that of the standard (parathion) and expresqed aa a Toxicity Index (T.I.) LC50 of atandard Toxicity Index = ~ X 100 LC50 of teqt Compound The LC50 used for the standard in this calculation was the mean value based on 20 determinations. The results are given in Table II.
For reasona of comparison, aimilar results are included for the known compounds permethrin and cypermethrin which are disclosed in United Kingdom Patent Specification 1,413,491 as Compound P21H and Compound P 21P. :
......
~: , .- ~- .. .:.:, - .
.23~52 TABLE II - ACARICIDAL RESULTS
H CH - C~
>< ~V c~ ~ ~/
CH3 / ` ~ COO - CIH
CH3 H Y \===;/
. . _ . . ._ ~
COMPOUND CONFIGURATION AT . ::
EXAMPLE _ _ . __ _ ~ .
X V Y C1 and C3 Calpha DBunde ~:
_ .
1 Cl F CN (1S,1R,ois) (R,S) E/Z .
_ . . ., . _ ' ': :
Cl F CN (1S,1R,trans) (R,S) E/Z .
: ~ Cl F CN (1R,cis) (R,S) E/Z
_ . . .__ __ .. __ , : cypermethrin Cl Cl CN (1S,1R,cis, (R,S) _ trans) ~ :~
_ __ . __ _ _ _ 2 Cl F H (1S,1R,cis) _ E/Z ::
__ . __ :
: 3 Cl F H (1S,1R,trans) _ E/Z
_ ___ __ __ ,~
: 6 Cl F H (1R,cis) _ E/Z
_. _ _ :. -"'~
permethrin Cl Cl H (1S,1R,cis, _ _ trans) ~ _ __ ... _ . .-- ::
Cl F -C_CN (15,1R,cis) (R,S) _ . : :
~ .:
.. ~
,:~ , ; ~, ~ ,~.`,' :: ~' ::.
: :'~ ."`.` -.' ~, '- , ~' ., 13 ~L~23~52 TABLE II- ACARICIDAL RESULTS (Cont'd) : :
_ _ . _ __ _ __ _ __ _ __ ____ _ TOXICITY INDEX ~ :
EXAMPLE __ __ ~ _ __ _ ~ ___ Boophilus microplus Tetranychus urticae __ __ _______ .
._____ ___. _ _ . . . _ , ..... _ 560 10 :
.. ___ _ ____ _ cypermethrin 21 2 ___ _ __ ___ _ ____ _ _ .. ___ ,:
_ __ ___ _ _ _ ___ ~. .
permethrin 223 1 ~;
_ _ ___ 7 _ _ _ 16 ~Z3~
It will be seen from the above re~ults in Table I that in the :~
Y=CN series, Example~ 1, 4 and 5 all possess superior acaricidal ac-tivity over the known compound cypermethrin and that in the Y=H : :
series, Examples 2, 3 and 6 generally produce better results than the corresponding known compound permethrin. Example 7 also produces better acaricidal effects over permethrin and cypermethrin. :~
''~ ;':
~ '~ ..,'~.
; :.; .
CN (lR,ci~) (R,S). E~Z nD 1.550 6 N (lR,cis) _E/Z nD1 1.553 C-CN (lS,1R,~i~) (R,N) E/Z _ _ ~.~
(a) in the preparation of thi-~ compound the acid chloride ~-of (1S,1R,cis)(E/Z)-3-(2-chloro-2-fluorovinyl)-2,2-dimethyl-cyclopropanecarboxylic acid ~a~ reacted with (R,S)-alpha- ~
ethynyl-3-phenoxybenzyl alcohol in the presence o~ r N-methylimidazole.
, ~
.23~Z
TABLE I (Cont~d ) _ EXAMPLE ANALYSIS
__ . ~
2 Calculation for C21H20o3clF C 67-3; H 5-4%
Found: C 67.0; H 5.4g __ _ ___ _ __ . . . .
3 Calculation ~or C21H20o3clF C 6i-3; H 5-4%
_ Found: C 67.5; H 5.4%
4 Calculation for C22H1gNo3ClF C 66.1; H 4-8%
Found: C 66.6; H 5.1%
_ _. _______ _____ .
Calculation for C22H19N03ClF : C 66.1; H 4.8; N 3.5%
Found : C 65.6; H 4.9; N 3.2 __ . _ , ~
6 Calculation for C21H2003ClF C 67-3; H 5-4 Found : C 67.1; H 5.4%
_ ___ .
7(a)Calculation for C23H2003ClF C 69-3; H 5.1 Found : C 69.7; H 5.5 . _ __ _ . .. ~___ .. __ . _____ :, . . .
:'' ;.
_ ~.Z3~5~
Example 8 Acaricidal activity of the cyclopropyl carboxylate composi-tion (a) Activity against one-host cattle tick, Boophilu~ microplus (B.m.) Two to three week old larval ticks were used. In the rearing procedure calves were infe3ted with larval ticks which matured over a three week period. Engorged adult ~emale ticks which detach from the calf were collected and placed in 3" x 1 n gla99 tubes. Egg batches were laid by the females over the next ~ew days and larvae e~erged three weeks later. The cyclopropyl car-boxylates were formulated as solution3 or fine suspensions in acetone containing 10% by weight of polyethylene glycol having an average molecular weight of 400. The formulations contained 0.1~ by weight of the compound to be tested. lml of the above-mentioned 301ution wa~ applied evenly to a filter paper 3ituated inside a petri di~h. After the paper was sufPiciently dry it was folded in half and partly crimped along the outer edge to form a packet. About 80-100 larval ticks (Boophilus microplus) were transferred into the packet which was ~ealed completely. The packets were placed inside an incubator, main-tained at 27C and 80% relative humidity. After 24 hours the packets were opened and the percentage of dead and moribund larYae asses~ed. .;
(b) Activity against elasshouse red spider mite, Tetranychus urticaè
(T.u.) The cyclopropyl carboxylates were formulated as solutions or suspensions in water containing 20S by weight of acetone and -~
0.05~ by weight o~ Triton X100 as wetting agent. The formula-tions contained 0.4~ by weight of the compound to be tested. ;~`
Leaf discs cut from French bean plants were held on moi~t filter paper placed on a lid inside a waxed carton. Prior to te~ting, each leaf disc was infested with 10 adult mites. Tbe mite3 and discs were then 3prayed using a logarithmic spraying machine and held under standard glas house conditions. After 24 hour3 the percentage dead and moribund mites were a~sessed.
., ~ .. . .
~.;Z 3~2 1.
In (a) and (b) the concentration of material expected to kill 50~ of the exposed group Or test speciea was calculated (LC50) and the toxi- -;
city of the compound waa compared with that of the standard (parathion) and expresqed aa a Toxicity Index (T.I.) LC50 of atandard Toxicity Index = ~ X 100 LC50 of teqt Compound The LC50 used for the standard in this calculation was the mean value based on 20 determinations. The results are given in Table II.
For reasona of comparison, aimilar results are included for the known compounds permethrin and cypermethrin which are disclosed in United Kingdom Patent Specification 1,413,491 as Compound P21H and Compound P 21P. :
......
~: , .- ~- .. .:.:, - .
.23~52 TABLE II - ACARICIDAL RESULTS
H CH - C~
>< ~V c~ ~ ~/
CH3 / ` ~ COO - CIH
CH3 H Y \===;/
. . _ . . ._ ~
COMPOUND CONFIGURATION AT . ::
EXAMPLE _ _ . __ _ ~ .
X V Y C1 and C3 Calpha DBunde ~:
_ .
1 Cl F CN (1S,1R,ois) (R,S) E/Z .
_ . . ., . _ ' ': :
Cl F CN (1S,1R,trans) (R,S) E/Z .
: ~ Cl F CN (1R,cis) (R,S) E/Z
_ . . .__ __ .. __ , : cypermethrin Cl Cl CN (1S,1R,cis, (R,S) _ trans) ~ :~
_ __ . __ _ _ _ 2 Cl F H (1S,1R,cis) _ E/Z ::
__ . __ :
: 3 Cl F H (1S,1R,trans) _ E/Z
_ ___ __ __ ,~
: 6 Cl F H (1R,cis) _ E/Z
_. _ _ :. -"'~
permethrin Cl Cl H (1S,1R,cis, _ _ trans) ~ _ __ ... _ . .-- ::
Cl F -C_CN (15,1R,cis) (R,S) _ . : :
~ .:
.. ~
,:~ , ; ~, ~ ,~.`,' :: ~' ::.
: :'~ ."`.` -.' ~, '- , ~' ., 13 ~L~23~52 TABLE II- ACARICIDAL RESULTS (Cont'd) : :
_ _ . _ __ _ __ _ __ _ __ ____ _ TOXICITY INDEX ~ :
EXAMPLE __ __ ~ _ __ _ ~ ___ Boophilus microplus Tetranychus urticae __ __ _______ .
._____ ___. _ _ . . . _ , ..... _ 560 10 :
.. ___ _ ____ _ cypermethrin 21 2 ___ _ __ ___ _ ____ _ _ .. ___ ,:
_ __ ___ _ _ _ ___ ~. .
permethrin 223 1 ~;
_ _ ___ 7 _ _ _ 16 ~Z3~
It will be seen from the above re~ults in Table I that in the :~
Y=CN series, Example~ 1, 4 and 5 all possess superior acaricidal ac-tivity over the known compound cypermethrin and that in the Y=H : :
series, Examples 2, 3 and 6 generally produce better results than the corresponding known compound permethrin. Example 7 also produces better acaricidal effects over permethrin and cypermethrin. :~
''~ ;':
~ '~ ..,'~.
; :.; .
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Cyclopropyl carboxylate compounds in the form of single isomers or combinations thereof having the following general formula:- (I) wherein X is a chlorine, bromine or iodine atom and Y is a hydrogen atom or a cyano or ethynyl group.
2. Compounds according to claim 1 wherein X is a chlorine atom.
3. Compounds according to claim 1 or 2 wherein they have a config-uration at carbon atoms 1 and 3 of (1R, 1S, cis) or (1R,cis).
4. Process for the manufacture of compounds of the general formula:- (I) which comprises reacting a compound of formula:- (II) with a compound of formula:- (III) wherein X is a chlorine, bromine or iodine atom and Y is a hydrogen atom or a cyano, or ethynyl group; one of the groups Q and Z represents a halogen atom, and the other represents a hydroxy group.
5. A method for controlling acarid and/or insect pests at a locus which comprises applying to the locus an acaridally-active or insecticidally active amount of a compound of the general formula I given in claim 1 or a composition containing an active amount of a compound of said formula I to-gether with a carrier and/or surface active agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB27409/77 | 1977-06-30 | ||
| GB2740977 | 1977-06-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1123452A true CA1123452A (en) | 1982-05-11 |
Family
ID=10259107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA304,269A Expired CA1123452A (en) | 1977-06-30 | 1978-05-29 | Cyclopropyl carboxylate compounds a process for their manufacture and their use as pesticides |
Country Status (15)
| Country | Link |
|---|---|
| EP (1) | EP0000229B1 (en) |
| JP (1) | JPS5412351A (en) |
| AU (1) | AU525337B2 (en) |
| BR (1) | BR7804122A (en) |
| CA (1) | CA1123452A (en) |
| DE (1) | DE2861395D1 (en) |
| DK (1) | DK292478A (en) |
| EG (1) | EG13418A (en) |
| GR (1) | GR64837B (en) |
| IL (1) | IL55027A (en) |
| IT (1) | IT7825089A0 (en) |
| MX (1) | MX5434E (en) |
| NZ (1) | NZ187712A (en) |
| TR (1) | TR20942A (en) |
| ZA (1) | ZA783300B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| FR2591223B1 (en) * | 1985-12-10 | 1988-03-18 | Roussel Uclaf | NOVEL DERIVATIVES OF CYCLOPROPANE CARBOXYLIC ACID SUBSTITUTING IODINE, THEIR PREPARATION AND THEIR APPLICATION TO THE CONTROL OF PESTS OF PLANTS AND ANIMALS |
| FR2601360B2 (en) * | 1986-07-09 | 1988-11-10 | Roussel Uclaf | NOVEL DERIVATIVES OF CYCLOPROPANE CARBOXYLIC ACID SUBSTITUTING IODINE, THEIR PREPARATION, THEIR APPLICATION TO THE CONTROL OF PESTS OF PLANTS AND ANIMALS. |
| DE3671428D1 (en) * | 1985-12-10 | 1990-06-28 | Roussel Uclaf | IODINE-SUBSTITUTED CYCLOPROPANCARBONIC ACID DERIVATIVES, THEIR PRODUCTION, THEIR USE AS PARASITICIDES FOR PLANTS AND ANIMALS, AND COMPOSITIONS CONTAINING THE SAME. |
| GB2187385A (en) * | 1986-03-07 | 1987-09-09 | Shell Int Research | Method of combatting colorado beetles using chemical compounds and compositions containing the chemical compounds |
| JP2546339B2 (en) * | 1988-06-03 | 1996-10-23 | 住友化学工業株式会社 | Ester compounds and their use as insecticides and acaricides |
| FR2641275B1 (en) * | 1988-12-29 | 1991-10-11 | Roussel Uclaf | NOVEL FLUORINATED DERIVATIVES OF ACID 3-ETHENYL 2,2-DIMETHYL CYCLOPROPANE CARBOXYLIC, PROCESS FOR THEIR PREPARATION AND THEIR USE AS PESTICIDES |
| DE4404640C1 (en) * | 1994-02-14 | 1995-02-09 | Siemens Ag | Dental X-ray diagnosis equipment for the preparation of panoramic films of the skull of a patient |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1413491A (en) * | 1972-05-25 | 1975-11-12 | Nat Res Dev | 3-substituted-2,2-dimethyl-cyclopropane carboxylic acid esters their preparation and their use in pesticidal compositions |
| CH608941A5 (en) * | 1973-08-15 | 1979-02-15 | Nat Res Dev | Use of a synthetic pyrethroid as insecticide |
-
1978
- 1978-05-29 CA CA304,269A patent/CA1123452A/en not_active Expired
- 1978-06-08 ZA ZA00783300A patent/ZA783300B/en unknown
- 1978-06-20 EP EP78200056A patent/EP0000229B1/en not_active Expired
- 1978-06-20 DE DE7878200056T patent/DE2861395D1/en not_active Expired
- 1978-06-27 EG EG398/78A patent/EG13418A/en active
- 1978-06-28 GR GR56623A patent/GR64837B/en unknown
- 1978-06-28 BR BR7804122A patent/BR7804122A/en unknown
- 1978-06-28 IT IT7825089A patent/IT7825089A0/en unknown
- 1978-06-28 JP JP7755078A patent/JPS5412351A/en active Pending
- 1978-06-28 TR TR20942A patent/TR20942A/en unknown
- 1978-06-28 MX MX787189U patent/MX5434E/en unknown
- 1978-06-28 NZ NZ187712A patent/NZ187712A/en unknown
- 1978-06-28 AU AU37513/78A patent/AU525337B2/en not_active Expired
- 1978-06-28 DK DK292478A patent/DK292478A/en not_active Application Discontinuation
- 1978-06-28 IL IL55027A patent/IL55027A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| IL55027A (en) | 1981-07-31 |
| EP0000229A1 (en) | 1979-01-10 |
| DE2861395D1 (en) | 1982-01-28 |
| DK292478A (en) | 1978-12-31 |
| EG13418A (en) | 1981-06-30 |
| MX5434E (en) | 1983-08-05 |
| AU3751378A (en) | 1980-01-03 |
| JPS5412351A (en) | 1979-01-30 |
| EP0000229B1 (en) | 1981-12-02 |
| ZA783300B (en) | 1979-09-26 |
| TR20942A (en) | 1983-01-24 |
| GR64837B (en) | 1980-06-04 |
| AU525337B2 (en) | 1982-11-04 |
| NZ187712A (en) | 1980-10-24 |
| BR7804122A (en) | 1979-02-28 |
| IT7825089A0 (en) | 1978-06-28 |
| IL55027A0 (en) | 1978-08-31 |
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