JPH0456818B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to esters of cyclopropanecarboxylic acid and unsaturated aliphatic alcohols, methods for producing the same, and pest control compositions containing them. More particularly, the present invention relates to the following general formula () in all isolated isomeric forms or in the form of mixtures thereof: [Here, Y represents hydrogen, fluorine, chlorine or bromine atom, R ₁ represents a saturated or unsaturated linear or branched alkyl group containing 1 to 4 carbon atoms, and R ₂ represents represents a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms, a -C≡N group or a -C≡CH group, each of R ₃ , R ₄ and R ₅ may be the same or different; , a fluorine or chlorine atom, or a linear or branched alkyl group containing 1 to 4 carbon atoms, or an alkynyl group containing 2 to 4 carbon atoms]. . Compounds of formula () can exist in many stereoisomeric forms. In fact, they have two asymmetric carbons in the 1 and 3 positions of the cyclopropane. They also represent the possibility of E/Z isomers with double bonds in the side chains attached to the 1- and 3-position carbons of the cyclopropane. Furthermore, the groups R ₁ , R ₂ , R ₃ , R ₄
and R ₅ can also have one or more asymmetric centers. When R ₁ represents a linear or branched saturated alkyl group, it represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,
Preferably it is an isobutyl group. When R ₁ represents an unsaturated alkyl group, it is preferably an ethylenic group, such as vinyl, 1,1-dimethylallyl; or an acetylenic group, such as ethynyl or propynyl. When R ₂ represents an alkyl group, it is preferably a methyl or ethyl group. When R ₃ , R ₄ or R ₅ represents a linear or branched alkyl group, it is preferably a methyl, ethyl, isopropyl, n-butyl, isobutyl or t-butyl group. When R ₃ , R ₄ or R ₅ represents an alkynyl group,
Preferably it is an ethynyl, propargyl or 2-butynyl group. Among the compounds of formula (), Y, R ₁ , R ₃ ,
R ₄ and R ₅ are as described above, and R ₂ is a hydrogen atom,
In particular, those representing -C≡N or -C≡CH groups may be mentioned. Among the preferred compounds of the invention, in particular:
Examples include those in which R ₄ represents a methyl or ethyl group. In particular, the present invention provides the following general formula ( _A ) (wherein Y, R ₁ , R ₃ , R ₄ and R ₅ have the meanings already indicated, and R' ₂ represents a hydrogen atom or an ethynyl group), and among these, the following general compounds Formula ( _B ) (Here, Y, R ₁ and R' ₂ have the meanings already indicated, R' ₃ represents a linear or branched alkyl group containing 1 to 4 carbon atoms, and R' ₄ represents 1 A linear, branched or cyclic alkyl group containing ~4 carbon atoms or an alkynyl group containing 2 to 4 carbon atoms) is the subject matter. And in particular, the present invention provides the above-mentioned compound corresponding to the formula () in which Y represents hydrogen or a fluorine atom and the configuration of the double bond of the side chain on the 3rd carbon of the cyclopropane is Z or E, respectively. The subject matter is the compound of In addition, the present invention particularly provides examples 1 and 5 of the experimental part.
7, 9, 10, 17, 18, 25, 27, 46, 53 and 56. In addition, the present invention provides the following general formula () in producing the compound of the general formula (). (Here, Y and R ₁ have the meanings already described)
or a functional derivative of this acid with the following general formula () (where R ₂ , R ₃ , R ₄ and R ₅ have the meanings already given) or a functional derivative of this alcohol. The subject matter. here,
Functional derivatives of acids preferably refer to acid chlorides or anhydrides. Functional derivatives of alcohols preferably refer to chloride, bromide or sulphate derivatives of the alcohols. According to a preferred method of carrying out the process of the invention, an acid of formula () is esterified with an alcohol of formula () in the presence of dicyclohexylcarbodiimide and 4-dimethylaminopyridine. The compound of formula () has been disclosed in European Patent Application No.
No. 0038271, No. 0041021, No. 0048186 and No.
It is described in No. 0050534. Some of the compounds of formula () are described in German Patent Application No. 2647366, JP-A-56-147734 or Chem.
Ab. 96 , 197906m. Alcohols of formula () not described in these patent applications can be prepared according to the formula below. The following formula and the following formula A compound having the following is a novel compound. The compounds of formula () exhibit beneficial properties that make it possible to use them for combating parasites.
For example, this includes the control of plant parasites, house parasites and warm-blooded animal parasites. The compounds of the invention can therefore be used for the control of pests, nematodes and parasitic mites which are parasites of plants and animals. The subject of the invention is therefore plant parasites,
Compounds of formula () for use in the control of household parasites and warm-blooded animal parasites. The compounds of formula () can therefore be used, in particular, for the control of pests in the agricultural field, such as larvae of the Aphids, Lepidoptera and Coleoptera. They contain between 10g and 300g of active substance per hectare
It is used in dosages between. The compounds of formula () can also be used to control pests in houses, especially flies, mosquitoes and cockroaches. The compounds of formula () can also be used to combat parasitic pests of animals, such as lice, especially in cattle, sheep and poultry. The compound of formula () can also be used to exterminate mites and nematodes that are plant parasites. The compound of formula () can also be used for the extermination of ticks that are parasites of animals, such as ticks, especially ticks of the Boophilus species, ticks of the Hyalomnia species, and Amblyomnia species. mites, Phipicephalus mites, or all other types of mites or scabies, especially sarcoptic mange.
sarcoptic mite, Psoroptic mite and coryoptic mite
It can be used to exterminate chorioptic mite. They can also be used to control so-called insects. The subject of the invention is also the formula () defined above
A composition for exterminating warm-blooded animal parasites, house parasites, and plant parasites, characterized in that it contains at least one compound having the following. In particular, the subject of the invention is insecticidal compositions containing as active ingredient at least one of the compounds defined above. The present invention also provides a nematicidal composition containing as an active ingredient at least one of the compounds defined above as well as a nematicide composition containing as an active ingredient at least one of the compounds defined above. The subject matter. The subject of the invention is also an acaricide composition for the control of parasites of warm-blooded animals, in particular ticks and other mites, containing at least one of the compounds defined above. . Among the preferred compositions of the invention, especially insecticide compositions, mention may be made in particular of compositions containing the compounds described in the Examples. These compositions are manufactured by conventional methods in the agricultural and chemical industries. One or more other pesticides may be added to these compositions relative to the active substance. These compositions may be powders, granules, suspensions, emulsions, solutions, aerosol solutions,
It can be provided in the form of combustible strips, baits or other formulations commonly used for applications of this type of compound. In addition to the active ingredient, these compositions generally include:
Among these, it contains a carrier and/or a nonionic surfactant that enables uniform dispersion of the components constituting the mixture. The carriers used can be water, alcohols, hydrocarbons or other organic solvents, liquids such as mineral, animal or vegetable oils, powders such as talc, clay, silicates or diatomaceous earth, or combustible solids. It's fine. The insecticide composition according to the invention preferably
Contains 0.005-10% by weight of active substance. According to an advantageous practice, the insecticide compositions of the invention are used in the form of smokable compositions for domestic use. Thus, the insecticide composition according to the invention may consist of a combustible insecticide coil (such as an incense stick) or a non-flammable fibrous base material for the inactive part. In the latter case, the smoke agent obtained after incorporating the active substance is placed in a heating device, such as an electric mosquito repellent. When insecticide coils are used, inert carriers can be used, for example, pyrethrum lees, tab powder (Machilus thumbergii leaf powder), pyrethrum stem powder, cedar needle powder, wood powder (pine powder), etc. (sawdust), starch and coconut shell powder. In that case, the dosage of the active substance is, for example, from 0.03 to
It is 1% by weight. If a non-combustible fibrous carrier is used, the dosage of active substance may be, for example, from 0.03 to 25% by weight. The compositions of the invention for domestic use can also be obtained by preparing a spray oil based on the active ingredient and impregnating a lamp wick with this oil, which is then combusted. The concentration of active ingredient incorporated into this oil is preferably between 0.05 and 25% by weight. Acaricides and nematocides are provided in particular in the form of powders, granules, suspensions, emulsions or solutions. One or more other pesticides may be added to the acaricide and insecticide compositions. For acaricide applications, preferably 1 to 80
% of active ingredient, or foliar spray solutions containing 1 to 500 g of active ingredient are used. Foliar powders containing 0.05-3% active substance can also be used. For nematicides, preferably 300 to 500 g/
A soil treatment solution containing active ingredients is used. The acaricidal and nematicidal compounds according to the invention are:
Doses of 1 to 100 g of active substance per hectare are used. When the control of animal parasites, mites, is a problem, the compounds of the invention are incorporated into fattening compositions in combination with animal fattening nutrient mixtures. The nutrient mixture can vary depending on the species of animal. It includes shellfish, sugars, shell grains, soybean cake, peanut cake, sunflower cake, animal powders such as fishmeal, synthetic amino acids, inorganic salts, vitamins, antioxidants, etc. The subject of the invention is therefore a composition for animal feeding which contains as active ingredient at least one compound of the formula () as defined above. These compositions can be applied by external route, by evaporation, by spraying, by shampooing, by bathing or by painting when attempting to control parasitic mites on animals. They can also be administered by application to the back by a method called the "pour-on" method. It can also be administered by the gastrointestinal route. The present invention also provides on the one hand at least one compound of the general formula () as an active substance, on the other hand chrysanthemum acid and arethrolone, 3,4,5,6-tetrahydrophthalimidomethyl alcohol, 5-benzyl-
Esters with 3-furylmethyl alcohol, 3-phenoxybenzyl alcohol and α-cyano-3-phenoxybenzyl alcohol; 2,2-
Dimethyl-3-(2-oxo-3-tetrahydrothiophenylidenemethyl)cyclopropane-1-
Ester of carboxylic acid and 5-benzyl-3-furylmethyl alcohol; 2,2-dimethyl-3-
(2,2-dichlorovinyl)cyclopropane-1
- Esters of carboxylic acid with 3-phenoxybenzyl alcohol and α-cyano-3-phenoxybenzyl alcohol; 2,2-dimethyl-3-
(2,2-dibromvinyl)cyclopropane-1
-Ester of carboxylic acid and α-cyano-3-phenoxybenzyl alcohol;Ester of 2-p-chlorophenyl-2-isopropylacetic acid and 3-phenoxybenzyl alcohol;2,2-dimethyl-3-( 1,2,2,2-tetrahaloethyl)
Cyclopropane-1-carboxylic acid (where halo represents a fluorine, chlorine or bromine atom) and arethrolone, 3,4,5,6-tetrahydrophthalimidomethyl alcohol, 5-benzyl-3-furylmethyl alcohol, 3- It is characterized by containing at least one pyrethrinoid ester selected from the group consisting of esters with phenoxybenzyl alcohol and α-cyano-3-phenoxybenzyl alcohol (provided that compounds of formula ()) (can exist in all possible stereoisomeric forms thereof, as well as the acid and alcohol moieties of the pyrethrinoid esters mentioned above) are the subject matter of mixtures endowed with insecticidal, acaricidal and nematicidal activity. To increase the biological activity of the compounds of the invention, standard synergists used in such cases, such as 1-(2,5,8-trioxadodecyl)-2-propyl-4, 5-methylenedioxybenzene (piperonyl butoxide), or N-
(2-ethylheptyl)bicyclo[2.2.1]-5-
Heptene-2,3-dicarboxamide, or piperonyl-bis-2-(2'-n-butoxyethoxy)
Can be added to ethyl acetal (Tropital). The subject of the invention is also compositions and mixtures as described above, characterized in that they also contain a pyrethrinoid synergist. The examples below illustrate the invention and do not limit it in any way. Example 1 1R,cis-2,2-dimethyl-3-[1-(△
Z)-3-methoxy-3-oxopropenyl]
Cyclopropanecarboxylic acid (1-(R) or (S)-ethynyl-2-methyl)-2-(ΔE)-pentenyl 4 g of 1R, cis-2,2-dimethyl-3-[1
-(ΔZ)-3-methoxy-3-oxopropenyl]cyclopropanecarboxylic acid, 2.45 g of 4-methyl-4-(ΔE)hepten-1-yn-3-ol (described in Chem.Ab.9619706n) (manufactured by the method of ) and 50 c.c. of dichloromethane, then
4.14g dicyclohexylcarbodiimide and 0.2
A solution of g of 4-dimethylaminopyridine dissolved in 50 c.c. of dichloromethane is introduced. After stirring at 20° C. for 4 hours, filtering, and concentrating the liquid by distillation under reduced pressure, the residue was chromatographed on silica and eluted with a mixture of hexane and isopropyl ether (9/1) to give 1.27 g of the desired amount. Isomer A
and 1.72 g of the desired isomer B were obtained. Isomer A [α] _D = +67° (c = 0.6% chloroform). NMR spectrum (deuterochloroform) 0.87−0.98− attributed to hydrogen of methyl of ethyl
1.1ppm peak, 1.30-1.33ppm peak attributed to paired methyl hydrogen,

The peak at 1.75ppm is attributed to the hydrogen of methyl in [Formula], and the peak at 1.8- is attributed to the hydrogen of methylene in ethyl.
2.2ppm peak, 2.58ppm peak attributed to ethynyl hydrogen, 3.8ppm attributed to methyl hydrogen of methoxyl
peak of,

5.6− attributed to hydrogen in [formula] 5.9ppm peak,

Peaks at 5.9-6.1ppm and 6.5-6.9ppm attributed to hydrogen in [formula], isomer B mp = 56°C [α] _D = +71° (c = 0.5% chloroform) NMR spectrum (deuterochloroform) Ethyl 0.87−0.98− attributed to the hydrogen of methyl
1.1ppm peak, 1.28ppm peak attributed to paired methyl hydrogen,

A peak of 1.73 ppm is attributed to the hydrogen of methyl in [Formula], a peak of 2.5-2.53 ppm is attributed to the hydrogen of acetylene, and a peak of 3.7 ppm is attributed to the hydrogen of methyl of methoxyl.
peak of,

5.6− attributed to hydrogen in [formula] 5.8ppm peak,

Peaks at 5.8-6.0 and 6.5-6.8 ppm attributed to hydrogen in [Formula]. Example 2 1R, cis-2,2-dimethyl-3-[-(△Z)
-3-oxo-3-t-butoxypropenyl]
Cyclopropanecarboxylic acid [1-(RS)-ethynyl-2-methyl]-2-(△E)-pentenyl 2.4 g of 1R,cis-2,2-dimethyl-3-[-
(ΔZ)-3-oxo-3-t-butoxypropenyl]cyclopropanecarboxylic acid, 1.24 g of 4-methyl-4-(ΔE)-hepten-1-yn-3-ol, 50 c.c. Dichloromethane, 2.06 g of dicyclohexylcarbodiimide and 0.1 g of 4-dimethylaminopyridine are mixed and stirred for 1 hour at +10°C and then for 16 hours at 20°C. After filtration, the liquid was concentrated by distillation under reduced pressure and the residue was chromatographed on silica, eluting with a mixture of hexane and isopropyl ether (9/1), 2.42 g of the expected product were obtained. NMR spectrum (deuterochloroform) 0.87−0.98− attributed to hydrogen of methyl of ethyl
1.1 ppm peak, 1.29-1.3 ppm peak attributed to paired methyl hydrogen, 1.5 ppm attributed to t-butyl methyl hydrogen.
peak of,

The peak at 1.75 ppm is attributed to the hydrogen of methyl in [Formula], 2.5-2.53 and 2.52 are attributed to the hydrogen of acetylene.
−2.55ppm peak, 5.6−6.0ppm peak attributed to hydrogen,

Peak at 6.4-6.8ppm attributed to hydrogen in [Formula]. Example 3 1R,cis-2,2-dimethyl-3-[-(△Z)
-3-oxo-3-methoxypropenyl]cyclopropanecarboxylic acid (RS)-1-cyano-2
-Fluoro-3-methyl-2-butenyl Step A: 1-cyano-2-fluoro-3-methyl-2-butenol 16.2 g of 3-methyl-2-fluoro-2-butenal, 44 c.c. of methanol, 90 c.c. of water and 22
Mix cc of acetic acid and add 12.6 g of sodium cyanide little by little at 0°C. The mixture was stirred at 0°C for 5 minutes and then at 20°C for 1 hour, extracted with ethyl ether, and the extract was concentrated to dryness by distillation under reduced pressure.
Methyl-2-butenol was obtained. Step B: 1R, cis-2,2-dimethyl-3-[-
(△Z)-3-oxo-3-methoxypropenyl]cyclopropanecarboxylic acid (RS)-1-cyano-2-fluoro-3-methyl-2-putenyl 2g of 1R,cis-2,2-dimethyl-3 −
[-(△Z)-3-oxo-3-methoxypropenyl]cyclopropanecarboxylic acid, 15 c.c. methylene chloride, 1.4 g 2-fluoro-3-methyl-(RS)-1-cyano-2- butenol and 40
Mix 2 mg of 4-dimethylaminopyridine and
A solution of g of dicyclohexylcarbodiimide dissolved in 10 c.c. of methylene chloride is added at 0°C. Stir at 20°C for 3 hours, filter, concentrate the liquid to dryness by distillation under reduced pressure, and chromatograph the residue on silica, eluting with a mixture of hexane and ethyl acetate (85/15), yielding 2.4 g. The desired ester was obtained. [α] _D = +84° (c = 0.5% chloroform) A number of compounds were prepared according to the method of Example 3.
Its properties are summarized in the table below. These compounds are as follows. 1R, cis-2,2-dimethyl-3-[-(△Z)
-3-oxo-3-t-butoxypropenyl]cyclopropanecarboxylic acid (RS)-1-cyano-2
-Fluoro-3-methyl-2-butenyl, 1R,cis-2,2-dimethyl-3-[-(△Z)
-3-oxo-3-methoxypropenyl]cyclopropanecarboxylic acid-3-methyl-2-butenyl, 1R,cis-2,2-dimethyl-3-[-(△Z)
-3-oxo-3-t-butoxypropenyl]cyclopropanecarboxylic acid 2-fluoro-3-methyl-2-butenyl, 1R,cis-2,2-dimethyl-3-[-(△Z)
-3-oxo-3-methoxypropenyl]cyclopropanecarboxylic acid 2-fluoro-3-methyl-
2-butenyl, 1R, cis-2,2-dimethyl-3-[-(△Z)
-3-oxo-3-methoxypropenyl] 2-propenyl cyclopropanecarboxylate, 1R,cis-2,2-dimethyl-3-[-1-(△
Z)-3-methoxy-3-oxopropenyl]cyclopropanecarboxylic acid α-2-methyl-2-propenyl, 1R,cis-2,2-dimethyl-3-[-1-(△
E)-3-Ethoxy-3-oxo-2-fluoropropenyl]cyclopropanecarboxylic acid α-2-
Methyl-2-propenyl, 1R, cis-2,2-dimethyl-3-[-(△Z)
-3-oxo-3-methoxypropenyl]cyclopropanecarboxylic acid α-2-methyl-2-E-butenyl, 1R,cis-2,2-dimethyl-3-[-(△Z)
-3-oxo-3-methoxypropenyl]cyclopropanecarboxylic acid 2E-butenyl, 1R,cis-2,2-dimethyl-3-[-(△Z)
-3-oxo-3-methoxypropenyl]cyclopropanecarboxylic acid 3,3-dichloropropene, 1R,cis-2,2-dimethyl-3-[-1-(△
Z)-3-methoxy-3-oxopropenyl]cyclopropanecarboxylic acid 2-fluoro-2-(△
Z)-butenyl, 1R,cis-2,2-dimethyl-3-[-1-(△
Z)-3-methoxy-3-oxopropenyl]cyclopropanecarboxylic acid 2-fluoro-2-(△
Z)-butenyl, 1R,cis-2,2-dimethyl-3-[-1-(△
Z)-3-methoxy-3-oxopropenyl]cyclopropanecarboxylic acid [1-(RS)-cyano-
2-methyl]-2-(△E)-pentenyl, 1R, cis-2,2-dimethyl-3-[-(△E)
-2-fluoro-3-oxo-3-ethoxypropenyl]cyclopropanecarboxylic acid 2-fluoro-3-methyl-2-buten-1-yl, 1R,cis-2,2-dimethyl-3-[-(△ E)
-2-fluoro-3-ethoxy-3-oxo-1
-propenyl]cyclopropanecarboxylic acid 1-ethynyl-2-methyl-(△E)-penten-2-yl (isomer A), 1R,cis-2,2-dimethyl-3-[-(△E)
-2-Fluoro-3-oxo-3-ethoxypropenyl]cyclopropanecarboxylic acid 1-ethynyl-2-methyl-(△E)-penten-2-yl (isomer B), 1R, cis-2,2- Dimethyl-3-[-(△Z)
-3-oxo-3-t-butoxypropenyl]cyclopropanecarboxylic acid 1-(RS)-ethynyl-
2-Methylhex-2-(△E)-en-5-ynyl, 1R,cis-2,2-dimethyl-3-[-(△E)
-2-Fluoro-3-oxo-3-ethoxypropenyl]cyclopropanecarboxylic acid (1RS)-ethynyl-2-methylhex-2-(△E)-ene-
5-ynyl, 1R, cis-2,2-dimethyl-3-[-(△Z)
-3-methoxy-3-oxo-1-propenyl]
Cyclopropanecarboxylic acid 1-(RS)-ethynyl-2-methylhex-2-(△E)-en-5-ynyl, 1R,cis-2,2-dimethyl-3-[-(△E)
-3-ethoxy-3-oxo-2-fluoro-1
-propenyl]cyclopropanecarboxylic acid 2-fluoro-2-(△Z)-butenyl, 1R,cis-2,2-dimethyl-3-[-(△E)
-3-ethoxy-3-oxo-2-fluoro-1
-propenyl]cyclopropanecarboxylic acid 2-fluoro-2-(△E)-butenyl, 1R,cis-2,2-dimethyl-3-[-(△E)
-2-Fluoro-3-oxo-3-ethoxypropenyl]cyclopropanecarboxylic acid (RS)-2-
Methyl-2--pentenyl, 1R, cis-2,2-dimethyl-3-[-(△E)
-2-fluoro-3-oxo-3-ethoxypropenyl]cyclopropanecarboxylic acid (RS)-cyano-2-fluoro-3-methyl-2-butenyl, 1R,cis-2,2-dimethyl-3-[- (△E)
-2-fluoro-3-ethoxy-3-oxo-1
-propenyl]cyclopropanecarboxylic acid α-2
-Methyl-2E-butenyl, 1R,cis-2,2-dimethyl-3-[-(△Z)
-3-methoxy-3-oxo-1-propenyl]
Cyclopropanecarboxylic acid (RS)-1-ethynyl-2-fluoro-3-methyl-2-butenyl, 1R,cis-2,2-dimethyl-3-[-(△Z)
-3-ethoxy-3-oxo-1-propenyl]
Cyclopropanecarboxylic acid (RS)-1-ethynyl-2-fluoro-3-methyl-2-butenyl, 1R,cis-2,2-dimethyl-3-[-(△E)
-3-methoxy-3-oxo-2-fluoro-1
-propenyl]cyclopropanecarboxylic acid (RS)
-1-ethynyl-2-fluoro-3-methyl-2
-butenyl, 1R, cis-2,2-dimethyl-3-[-(△E)
-3-ethoxy-3-oxo-2-fluoro-1
-propenyl]cyclopropanecarboxylic acid (RS)
-1-ethynyl-2-fluoro-3-methyl-2
-butenyl, 1R, cis-2,2-dimethyl-3-[-(△E)
-3-methoxy-3-oxo-2-bromo-1-
Propenyl cyclopropanecarboxylic acid (1RS)
-1-ethynyl-2-methyl-2-pentenyl, 1R,cis-2,2-dimethyl-3-[-(△E)
-3-methoxy-3-oxo-2-bromo-1-
Propenyl] cyclopropanecarboxylic acid (RS) -
1-ethynyl-2-methylhex-2-ene-5
-ynyl, 1R, cis-2,2-dimethyl-3-[-(△E)
-3-methoxy-3-oxo-2-chloro-1-
Propenyl cyclopropanecarboxylic acid (1RS)
-1-ethynyl-2-methyl-2-pentenyl, 1R,cis-2,2-dimethyl-3-[-(△E)
-3-methoxy-3-oxo-2-chloro-1-
Propenyl] cyclopropanecarboxylic acid (RS) -
1-ethynyl-2-methylhex-2-ene-5
-ynyl, 1R, cis-2,2-dimethyl-3-[-(△E)
-3-ethoxy-3-oxo-2-bromo-1-
Propenyl cyclopropanecarboxylic acid (1RS)
-1-ethynyl-2-methyl-2-pentenyl, 1R,cis-2,2-dimethyl-3-[-(△E)
-3-ethoxy-3-oxo-2-bromo-1-
Propenyl cyclopropanecarboxylic acid (1RS)
-1-ethynyl-2-methylhex-2-ene-
5-ynyl, 1R, cis-2,2-dimethyl-3-[-(△E)
-3-ethoxy-3-oxo-2-chloro-1-
Propenyl cyclopropanecarboxylic acid (1RS)
-1-ethynyl-2-methyl-2-pentenyl, 1R,cis-2,2-dimethyl-3-[-(△E)
-3-ethoxy-3-oxo-2-chloro-1-
Propenyl cyclopropanecarboxylic acid (1RS)
-1-ethynyl-2-methylhex-2-ene-
5-ynyl, 1R, cis-2,2-dimethyl-3-[-(△E)
-3-t-butoxy-3-oxo-2-bromo-
1-propenyl]cyclopropanecarboxylic acid (1RS)-1-ethynyl-2-methyl-2-pentenyl, 1R,cis-2,2-dimethyl-3-[-(△E)
-3-t-butoxy-3-oxo-2-bromo-
1-propenyl]cyclopropanecarboxylic acid (1RS)-1-ethynyl-2-methylhex-2-
En-5-ynyl, 1R, cis-2,2-dimethyl-5-[-(△E)
-3-t-butoxy-3-oxo-2-chloro-
1-propenyl]cyclopropanecarboxylic acid (1RS)-1-ethynyl-2-methyl-2-pentenyl, 1R,cis-2,2-dimethyl-3-[-(△E)
-3-t-butoxy-3-oxo-2-chloro-
1-propenyl]cyclopropanecarboxylic acid (1RS)-1-ethynyl-2-methylhex-2-
En-5-ynyl, 1R, cis-2,2-dimethyl-3-[-(△Z)
-3-ethoxy-3-oxo-1-propenyl]
1-methyl-2-E- cyclopropanecarboxylate
Pentenyl, 1R, cis-2,2-dimethyl-3-[-(△Z)
-3-ethoxy-3-oxo-1-propenyl]
1-ethynyl-2-methyl-2-E-pentenyl cyclopropanecarboxylate, 1R, cis-2,2-dimethyl-3-[-(△Z)
-3-isopropoxy-3-oxo-1-propenyl]cyclopropanecarboxylic acid 1-ethynyl-
2-Methyl-2-E-pentenyl, 1R, cis-2,2-dimethyl-3-[-(△Z)
-3-methoxy-3-oxo-1-propenyl]
1-ethynyl-2-methyl-2-E-pentenyl cyclopropanecarboxylate, 1R, cis-2,2-dimethyl-3-[-(△Z)
-3-ethoxy-3-oxo-1-propenyl]
1-ethyl-2-methyl-2-E-pentenyl cyclopropanecarboxylate, 1R, cis-2,2-dimethyl-3-[-(△E)
-2-fluoro-3-ethoxy-3-oxo-1
-propenyl]cyclopropanecarboxylic acid 1-ethyl-2-methyl-2-E-pentenyl, 1R,cis-2,2-dimethyl-3-[-(△E)
-2-fluoro-3-methoxy-3-oxo-1
-propenyl] 2-methyl-2-E-pentenyl cyclopropanecarboxylate, 1R, cis-2,2-dimethyl-3-[-(△E)
-2-fluoro-3-ethenyloxy-3-oxo-1-propenyl]cyclopropanecarboxylic acid 2-methyl-2-E-pentenyl, 1R,cis-2,2-dimethyl-3-[-(△E)
-2-fluoro-3-t-butoxy-3-oxo-1-propenyl]cyclopropanecarboxylic acid 2
-Methyl-2-E-pentenyl, 1R, cis-2,2-dimethyl-3-[-(△E)
-2-fluoro-3-ethoxy-3-oxo-1
-propenyl]cyclopropanecarboxylic acid 1-ethynyl-2-methyl-2-E-pentenyl, 1R,cis-2,2-dimethyl-3-[-(△Z)
-3-ethoxy-3-oxo-1-propenyl]
2-methyl-2-E- cyclopropanecarboxylate
Pentenyl, 1R, cis-2,2-dimethyl-3-[-(△E)
-2-fluoro-3-ethoxy-3-oxo-1
-propenyl]cyclopropanecarboxylic acid 1-ethynyl-2-methyl-2-E-pentenyl, 1R,cis-2,2-dimethyl-3-[-(△Z)
-3-methoxy-3-oxo-1-propenyl]
2-methyl-2-E- cyclopropanecarboxylate
Pentenyl, 1R, cis-2,2-dimethyl-3-[-(△E)
-2-fluoro-3-ethoxy-3-oxo-1
-propenyl] 3-methyl-2-pentenyl cyclopropanecarboxylate, 1R, cis-2,2-dimethyl-3-[-(△Z)
-3-ethoxy-3-oxo-1-propenyl]
2-methyl-2-propenyl cyclopropanecarboxylate, 1R, cis-2,2-dimethyl-3-[-(△Z)
-3-isopropoxy-3-oxo-1-propenyl]cyclopropanecarboxylic acid 2-methyl-2
-propenyl, 1R, cis-2,2-dimethyl-3-[-(△E)
-2-fluoro-3-isopropoxy-3-oxo-1-propenyl]cyclopropanecarboxylic acid 2-methyl-2-E-pentenyl, 1R,cis-2,2-dimethyl-3-[-(△Z)
-3-isopropoxy-3-oxo-1-propenyl]cyclopropanecarboxylic acid 2-methyl-2
-E-pentenyl, 1R, cis-2,2-dimethyl-3-[-(△Z)
-2-methyl-2-3-ethenyloxy-3-oxo-1-propenyl]cyclopropanecarboxylate
-E-pentenyl. 1-ethynyl-2-fluoro-3-methyl-2-butenol used as a starting material is produced as follows. 2.5 g of 3-methyl-2-
A solution of fluoro-2-butenol is added at 0°C. Stir at 20°C for 17 hours, add saturated aqueous ammonium chloride solution at 0°C, extract with ether, wash the organic phase with water, concentrate to dryness, and chromatograph the residue on silica in a mixture of hexane and ethyl acetate. After elution with (1/1), 963mg
The expected product was obtained. IR spectrum (chloroform) Absorption at 990 cm ^-1 due to -OH, absorption at 3300 and 3130 cm ^-1 due to C≡CH and C≡C.

【table】

【table】

【table】

[Table] Example 63 Preparation of soluble concentrate Make a homogeneous mixture consisting of the following ingredients. Compound of Example 20 0.25 g Piperonyl butoxide 1.00 g Tween 80 ^* 0.25 g Topanol A ^** 0.1 g Water 98.4 g *Tween 80 = See page 985 of Merch India 9th edition. **Topanol A=2,4-dimethyl-6-t
-Butylphenol. Example 64 Preparation of emulsifying concentrate Mix the following ingredients intimately. Compound of Example 17 0.015g Piperonyl Butoxide 0.5g Topanol A 0.1g Tween 80 3.5g Xylene 95.885g Example 65 Preparation of Emulsifiable Concentrate A homogeneous mixture consisting of the following components was prepared. Compound of Example 7 1.5g Tween 80 20.00g Topanol A 0.1g Xylene 78.4g Example 66 Preparation of Smokable Composition A homogeneous composition consisting of the following ingredients was prepared. Compound of Example 6 0.25g Tab powder ^* 25.00g Cedar leaf powder 40.00g Pine needle powder 33.75g Brilliant Green 0.5g p-Nitrophenol 0.5g *Insecticidal activity of MaChylus thumbergii leaf powder compound of formula () Study on acaricidal activity (a) Study on lethal effect on cockroaches The test was carried out by pipetting acetone solutions of various concentrations onto the bottom of a glass Petri dish and contacting them on the film. The periphery of the Petri dish was pre-covered with a layer of talc to prevent insect escape. Lethal concentration 50 (LC50) was measured. The results obtained are as follows.

[Table] (b) Study of knockdown activity against house flies The test insects were 4-day-old female house flies. The test uses a mixture of acetone (5%) and Isopar L (petroleum solvent) as the solvent (solution volume used, 2 ml per second), sprayed directly into the Cahn-Mars chamber at a concentration of 0.25 g/s. It was carried out by Fifty flies were used per treatment. Tests were performed every minute for up to 10 minutes, then at 15 minutes, and KT50 was determined by conventional methods. The results obtained are as follows.

[Table] (c) Aphis Cracivora
Seven-day-old adults were used and 10 aphids were used for each concentration used. A contact ingestion method was used. Treatments were carried out using a fissure pistol on bean leaves placed in plastic Petri dishes on humidified paper mounts. The treatment consisted of 2 ml of an acetone solution of the test compound (1 ml on each side of the leaf).
ml). Insects were allowed to grow after the leaves dried. The insects were left in contact with the leaves for 1 hour, after which the insects were placed on untreated leaves and mortality was checked at the end of 24 hours. LC50 mg/
It was decided as. The following results were obtained.

【table】

Claims (1)

[Claims] 1. The following general formula () in the form of all isolated isomers or mixtures of these isomers: [Here, Y represents hydrogen, fluorine, chlorine or bromine atom, R ₁ represents a saturated or unsaturated linear or branched alkyl group containing 1 to 4 carbon atoms, and R ₂ represents represents a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms, a -C≡N group or a -C≡CH group, each of R ₃ , R ₄ and R ₅ may be the same or different; , a fluorine or chlorine atom, or a linear or branched alkyl group containing 1 to 4 carbon atoms, or an alkynyl group containing 2 to 4 carbon atoms]. Second-order general formula ( _A ) (Here, Y, R ₁ , R ₃ , R ₄ and R ₅ have the same meaning as defined in claim 1, and R' ₂
represents a hydrogen atom or an ethynyl group. 3rd order general formula ( _B ) (Here, Y, R ₁ and R' ₂ are the second claims.
R′ ₃ represents a linear or branched alkyl group containing 1 to 4 carbon atoms, and R′ ₄ contains 1 to 4 carbon atoms. 3. A compound according to claim 2, which has a linear or branched alkyl group or an alkynyl group containing 2 to 4 carbon atoms. 4 Claims 1 to 4 corresponding to the formula () in which Y represents hydrogen or a fluorine atom, and the configuration of the double bond in the side chain on the 3-position carbon of the cyclopropane is Z or E, respectively. A compound according to any one of Item 3. 5. The compound according to claim 1, wherein the compound name is as follows. 1R, cis-2,2-dimethyl-3-[-1-(△
E)-3-methoxy-3-oxopropenyl]cyclopropanecarboxylic acid 1(R) or (S)-ethynyl-
2-Methyl-2-(△E)-pentenyl, 1R, cis-2,2-dimethyl-3-[-(△Z)
-3-oxo-3-methoxypropenyl] 3-methyl-2-butenyl cyclopropanecarboxylate, 1R,cis-2,2-dimethyl-2-[-(△Z)
-3-oxo-3-methoxypropenyl]cyclopropanecarboxylic acid 2-fluoro-3-methyl-
2-butenyl, 1R, cis-2,2-dimethyl-3-[-(△E)
-3-ethoxy-3-oxo-2-fluoropropenyl]cyclopropanecarboxylic acid α-2-methyl-2-propenyl, 1R,cis-2,2-dimethyl-3-[-(△Z)
-3-oxo-3-methoxypropenyl]cyclopropanecarboxylic acid α-2-methyl-2-E-butenyl, 1R,cis-2,2-dimethyl-3-[-(△E)
-2-fluoro-3-oxo-3-ethoxypropenyl]cyclopropanecarboxylic acid 2-fluoro-3-methyl-2-buten-1-yl, 1R,cis-2,2-dimethyl-3-[-(△ E)
-2-Fluoro-3-oxo-3-ethoxypropenyl]cyclopropanecarboxylic acid (RS)-2-
Methyl-2-pentenyl, 1R, cis-2,2-dimethyl-3-[-(△E)
-2-fluoro-3-ethoxy-3-oxo-1
-propenyl]cyclopropanecarboxylic acid α-2
-Methyl-2-E-butenyl, 1R,cis-2,2-dimethyl-3-[-(△Z)
-3-methoxy-3-oxo-1-propenyl]
1-ethynyl-2-methyl-2-E-pentenyl cyclopropanecarboxylate, 1R,cis-2,2-dimethyl-3-[-(△E)
-2-fluoro-3-ethoxy-3-oxo-1
-propenyl]cyclopropanecarboxylic acid 1-ethynyl-2-methyl-2-E-pentenyl, 1R,cis-2,2-dimethyl-3-[-(△E)
-2-fluoro-3-ethoxy-3-oxo-1
-propenyl]cyclopropanecarboxylic acid 1-ethenyl-2-methyl-(△E)-penten-2-yl, 1R,cis-2,2-dimethyl-3-[-(△Z)
-3-methoxy-3-oxo-1-propenyl]
2-methyl-2-E- cyclopropanecarboxylate
Pentenyl. 6 The following general formula () in the form of all isolated isomers or mixtures of these isomers: [Here, Y represents hydrogen, fluorine, chlorine or bromine atom, R ₁ represents a saturated or unsaturated linear or branched alkyl group containing 1 to 4 carbon atoms, and R ₂ represents represents a hydrogen atom, an alkyl group containing 1 to 4 carbon atoms, a -C≡N group or a -C≡CH group, each of R ₃ , R ₄ and R ₅ may be the same or different; , a fluorine or chlorine atom, or a linear or branched alkyl group containing 1 to 4 carbon atoms, or an alkynyl group containing 2 to 4 carbon atoms]. , the following general formula () (where Y and R ₁ have the meanings given above) or functional derivatives of this acid have the following general formula () (wherein R ₂ , R ₃ , R ₄ and R ₅ have the meanings given above) or a functional derivative of this alcohol. . 7. The process according to claim 6, characterized in that the acid having the formula () is esterified with the alcohol having the formula () in the presence of dicyclohexylcarbodiimide and 4-dimethylaminopyridine. 8. The following general formula () in the form of all isolated isomers or in the form of mixtures of these isomers: [Here, Y represents hydrogen or a fluorine atom, R ₁ represents a linear or branched alkyl group containing 1 to 4 carbon atoms, and R ₂ represents a hydrogen atom, a -C≡N group, or -C≡CH group, each of R ₃ , R ₄ and R ₅ may be the same or different and is a hydrogen or fluorine atom, or 1 to 4
a linear or branched alkyl group containing 2 to 4 carbon atoms, or an alkynyl group containing 2 to 4 carbon atoms] as an active ingredient. , composition for pest control. 9. The composition according to claim 8, which is an insecticidal and acaricidal nematicide composition. 10. The composition according to claim 8, which is an acaricide composition for use in exterminating parasitic mites of warm-blooded animals, particularly ticks and other mites.