JPS5920659B2 - Cyclopropanecarboxylic acid ester derivatives, methods for producing cyclopropanecarboxylic acid ester derivatives, insecticides containing cyclopropanecarboxylic acid ester derivatives - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula (wherein A is 0, NH, S, and Rl and R2 represent a methyl group or a chloro atom. R3 represents a methyl group when both Rl and 2 are methyl groups; In other cases, it indicates a hydrogen atom or a methyl atom.
R4 is an alkyl stem, an alkenyl group, a haloalkyl group, a haloalkenyl group, an alkoxyalkyl group, and the general formula ()
, (button, (M, (, (VD). Here, l is an integer of 1 to 5, m is an integer of 2 to 6, n is an integer of l to 2, and R6 is a hydrogen atom. , a lower alkyl group, a lower alkenyl group, a halogen atom, a halomethyl group; a lower alkokyl group; R represents a hydrogen atom or a methyl group; and R5 represents a hydrogen atom, a cyano group, or an ethynyl group).
The present invention relates to a novel cyclopropanecarboxylic acid ester derivative represented by the above formula, its optical and geometric isomers, a method for producing the same, and an insecticide characterized by containing this compound as an active ingredient. Various alcohol components of cyclopcapanecarboxylic acid esters have been studied and put to practical use, but they are susceptible to oxidative decomposition by light and have been restricted in their use outdoors. Recently, research into acid components has become active, and a compound that is more stable to light than conventional pyrethroids by replacing the methyl group with a halogen atom has been discovered. However, when considering issues such as environmental pollution and chronic toxicity, it is thought that compounds containing carbon, hydrogen, oxygen, and nitrogen, which have properties similar to naturally occurring organic compounds, will be advantageous as future insecticidal ingredients. .
As a result of repeated research, the present inventor has found that the compound represented by the above formula (1) has an extremely excellent insecticidal effect as an insecticidal ingredient against various sanitary pests and agricultural and horticultural pests, while having extremely low toxicity to warm-blooded animals. We learned that it is much more stable against light than conventional pyrethroids. The present invention was completed based on the above findings. The compound represented by the above formula (4) used as an active ingredient in the present invention is prepared according to the general method for ester production according to the general formula (wherein A is 0, NH
, S, and Rl and R2 represent a methyl group or a chloro atom. R3 represents a methyl group when both R1 and R2 are methyl groups, but otherwise represents a hydrogen atom or a methyl group. R4 is an alkyl group, an alkenyl group, a haloalkyl group,
Haloalkenyl group, alkoxyalkyl group and general formula (
)6([, (IV), (, (VD), where 2 is an integer of 1 to 5, m is an integer of 2 to 6, n is 1
is an integer of ~2, R6 is a hydrogen atom, a lower alkyl group,
It represents a lower alkenyl group, a halogen atom, a halomethyl group, or a lower alkoxy group, and R represents a hydrogen atom or a methyl group. ) or a reactive derivative thereof, and an alcohol or a reactive derivative thereof represented by the general formula N, (where R represents a hydrogen atom, a cyano group, or an ethynyl group). It can be prepared by dipping. Examples of reactive derivatives of carboxylic acids include acid halides, acid anhydrides, lower alkyl esters, and alkali metal salts. Examples of reactive derivatives of alcohols include chloride. The reaction is carried out in a suitable solvent, optionally in the presence of an organic or inorganic base or acid as a deoxidizer or catalyst, and optionally with heating. What is obtained by conventional synthetic methods is a mixture of optical isomers and geometric isomers, each of which is included in the present invention. Representative examples of the compound represented by the above formula (1) (shown as a mixture of optical isomers and geometric isomers) are as follows, but the present invention is of course not limited to these. 3'-
Phenoxy-d'-cyanobenzyl 2,2,3-trimethyl-3-ethoxycyclopro(3)pancarboxylate N2Ol. 5297D'-Phenoxy-d'
-cyanobenzyl 2,2-dichloro- 3 -Sec
．． Butoxycyclopropyl(4)carboxylate
N2Ol. 548OD'-Phenoxy-d'-cyanobenzyl 2,2-dichloro-3-(4-methylphenoxy)(5)-cyclopropanecarboxylate Nl. 5843D3'-Phenoxy-α'-cyanobenzyl 2,2-dichloro-3-(4-chlorophenoxy)(6)-cyclopropanecarboxylate n 01.58913'-Phenoxy-α'-cyanobenzyl 2,2 -dichloro-3-methyl-3-methoxyzig(7)propanecarboxylate N2Ol. 5258D3'-Phenoxy-α'-cyanobenzyl 2-methyl-
2-chloro-3-(4-methylcyclohexyloxy)-cyclopropanecarboxy W-t N2
Ol. 5736D (8) 3'-phenoxy-α'-cyanobenzyl 2,3-dimethyl-2-chloro-3-benzyl oxy(9) cyclopropanecarboxylate N2Bl. 58253'-Phenoxybenzyl 2,2,3-trimethyl-
3-(3-methyl-2-butenylamine Q1-)-
Cyclopropanecarboxylate N2Ol. 547OD'-Phenoxy-α'-ethynylbenzyl 2,2-dichloro-3-(2-bromoethylthio)

[al
)-cyclopropanecarboxylate N2Ol. 5534D 'Phenoxy-d'-ethynylbenzyl 2-methyl-
2-Chloro-3-cyclopropylmethyl:QO-aminocyclopropanecarboxylate N2Ol. 5452D'-Phenoxybenzyl 2,3 dimethyl-chloro-
3-(2,2-dichlorovinyloxy)cyclopropanecarboxylate n〒 1.5588 Q 3'-phenoxy-a'-cyanobenzyl 2,2,3
-Trimethyl-3-(3-trifluoro-alpha-methylbenzylthio)-cyclopropanecarboxylate N2Ol. 5976D3'-Phenoxybenzyl 2,3-dimethyl-2-chloro-3-(4
-Methoxy-2-zigQωpentenylthio)-cyclopropanecarboxylate N2Ol. 58O5D'-
Phenoxy-α'-cyanobenzyl 2,2-dichloro-3-(1-ethoxyethylamine decoy)cyclopropanecarboxylate N2Ol. 549lD'-Phenoxy-α'-ethynylbenzyl 2-methyl-2-chloro-3-cyclobutyloxy:Q't) Clopropanecarboxylate N2Ol. 5494D3'-Phenoxybenzyl 2,2-dichloro-3-methyl-3-(2,6-dichloro-4-isopropenylanilino)-cyclopropanecarboxylate N2
Bl. 6O33A, 3'-phenoxy-α'-ethynylbenzyl 2,3-
Dimethyl-2-chloro-3-(4-isopyo1
, lopyl-2-cyclohexenyloxy)-cyclopropanecarboxylate N2Ol. 5945D'-phenoxy-α'-cyanobenzyl 2,3-dimethyl-2
-Chloro-3-(2-fluoro4C-C!-3-bromopropylamino)-cyclopropanecarboxylate N2Ol. 5582D'-Phenoxybenzyl 2-methyl-2-chloro-3-(2,3,4,5
,6-pentac:F2υorophenylthio)-cyclopropanecarboxylate N2Ol. 597OD3'-
Phenoxy-d'-ethynylbenzyl 2-methyl-
2-Chloro-3-(2-methoxy-12-ethoxy)-cyclopropanecarboxylate N2Ol
．． 53O9D3'-phenoxy-α'-ethynylbenzyl 2,3-dimethyl-2-chloro-3-(2,
4-dimethylbenzylamino)-cyclopropanecarboxylate N2Ol. 5927D, 3'-phenoxybenzyl 2,2-dichloro-3
-(4-allylcycloheptylamino)-ro"C
H3, cyclopropanecarboxylate N2Ol. 5864D3'-Phenoxy-α'-cyanobenzyl 2,2-dichloro-3-methyl-3-(3-methylcyclopentylmethylthio)-cyclopropanecarboxylate N2Ol. 5793D'-Phenoxybenzyl 2
,2-dichloro-3-methyl-3-allyloxychloropropane 1carboxylate NWl・54503'-phenoxy-α'-cyanobenzyl 2,3-dimethyl-
2-chloro-3-(4-methoxy(2ηdiphenylthio)-cyclopropanecarboxylate N2
Ol. 587lD3'-Phenoxy-α'-ethynylbenzyl 2,2,3-trimethyl-3-(4-
Chloromethylcyclohexylamino)-cyclopropanecarboxylate NWl. 59O5(28) 3'-Phenoxybenzyl 2,2-dichloro-3-methyl-3-(3,4-dimethylbendi(29)ruthio)-cyclopropanecarboxylate N2Ol. 6
O33D3-phenoxy-d'-ethynylbenzyl
2,2-dichloro-3-methyl-3-(3-cyclo:(30)pentenylamino)-cyclopropanecarboxylate N2Ol. 5726D'-Phenoxybenzyl 2,2-dichloro-3-(4-chlorocyclohexylmethylthio](31)-cyclopropanecarboxylateN2Ol.589OD3'-Phenoxy-d'-cyanobenzyl 2-methyl-2-chloro- 3-(α-Methylbendi(32)ruamino)-cyclopropanecarboxylate Nwl.59
l83'-Phenoxy-α'-ethyniJ lebenzyl 2
,2,3-trimethyl-3-(2-methyl-3
-bromoallylthio)-cyclopropanecarboxylate Nwl. 564l(33) 3'-Phenoxybenzyl 2,2,3-trimethyl-3-(3-ethylphenoxy)-zig*(3
4) Propane carboxylate N2Ol. 5677D3'-Phenoxy-α'-ethynylbenzyl 2,2-dichloro-3-methyl-3-(4-Tert.・(35
) Butoxyphenoxy)-cyclopropanecarboxylate N2Ol. 6O53D3'-Phenoxy-α'-
Cyanobenzyl 2,2,3-trimethyl-3-anilinocyclopro G(36) pancarboxylate N
2Ol. 5768D'-Phenoxy-α'-ethynylbenzyl 2,2,3-trimethyl-3-(3-
Chloropropyl 1(37)ruoxy)cyclopropanecarboxylate N2Ol. 55O4D3'-Phenoxybenzyl 2,2-dichloro-3-(3-methylbutylthio)cyclopropanecarboxylate n〒
1. 5531(38)3'-phenoxybenzyl 2
,2,3-trimethyl-3-(1-methoxyethylthio)zig(39) F noropropanecarboxylate N2Bl. 54793'-Phenoxy-d'-cyanobenzyl 2,2,3-
Trimethyl-3-(2,6-difluoro-4-ethoxy-5-vinyl benzyl oxy(40) CH3cy)cyclopropanecarboxylate N2Ol. 6O2OD3'-Phenoxy-d'-ethynylbenzyl 2,2,3
-trimethyl-3-(2-methyl-3-゛(41) Cl, bromocyclobutylmethoxy)cyclopropanecarboxylate n〒 1.54723'-phenoxy-α'
Monoethynylbenzyl 2,2,3-trimethyl-3
-(3-chloro-4-allyl-5-bromomethyl-
3-Cyclohexε(42)cenylthio)cyclopropanecarboxylate N2Ol. 58O5D'-Phenoxybenzyl 2-methyl-2-chloro-3-(2
-Fluoro-3-chloro-1-propenylamino)cyclopropanecarboxylate Nwl. 5567 The compound of the present invention is a new compound, which is solid or liquid at room temperature and is generally easily soluble in organic solvents. As an insecticide for spraying, it can be used as an emulsion, oil, powder, potassium additive, aerosol, etc. It can also be mixed with wood flour or other suitable base material and used as an insecticide for fumigation such as mosquito coils. can do. Also, when used as a so-called electric mosquito repellent, in which the active ingredient is dissolved in an appropriate organic solvent and soaked in a mount, or dissolved in an appropriate solvent and heated and evaporated with an appropriate heating element, it is as good as a mosquito coil. This shows the effect of The compound of the present invention is more stable against light than conventional pyrethroids, and can also be used as an agricultural and horticultural insecticide. In addition, the compound of the present invention includes N-octylbicycloheptenedicarboximide [trade name MG
K-264], a mixture of N-octylbicycloheptenedicarboximide and arylsulfonate [trade name MGK-5026], octachlorodipropyl ether. −
The insecticidal effect can be further enhanced by adding a synergist such as ester or piperonyl butoxide. The compound of the present invention may also be used with other insecticides such as Sumithion, DD.
Organic phosphorus agents such as VP and diazinon. Carbamate agents such as 1-naphthyl-N-methylcarbamate and 3,4-dimethylphenyl-N-methylcarbamate, pyrethrin, allethrin, phthalthrin, flamethrin,
Traditional pyrethroid insecticides such as phenotrin, permethrin 6 cypermethrin, decamethrin, fuenvalerate, fuenpropanate, insecticides such as pattern, galuecuron, rannate, or acaricides, fungicides, nematicides, herbicides By mixing , plant growth regulators, fertilizers, and other agricultural chemicals, a multipurpose composition with excellent efficacy can be obtained, and labor savings and synergistic effects among the drugs can be fully expected. Next, the insecticidal test results of the compounds of the present invention will be shown. Test Example 1 Insecticidal test by spraying 0.2 (fl) of the 47 compounds of the present invention of the above compound examples
white lamp solution (4), 0.2% and piperonyl butoxide 0.8% white lamp solution (day, 0.1% and phthalthrine 0
．． For a 1% white light solution (0, and a 0.2% white light solution of allethrin and phthalthrin), the falling and turning rate of house flies was determined, and the relative effectiveness of the test drug was calculated, and the relative effectiveness of the test drug was calculated.
The mortality rate after hours was determined as follows. Test Example 2 Insecticidal test by fumigation A mosquito coil containing 0.501) as an insecticidal ingredient was prepared and tested for its effectiveness in making adult Culex mosquitoes fall and roll over. This experiment was conducted according to the method of Insect Control Science Vol. 16 (1951, p. 176, Nagasawa, Katsuta et al.), and the relative effectiveness of the incense stick was calculated as follows. Examples of the present invention are shown below. The compound names are the same as those in the active ingredient examples above. Example 1 3.6 g of 2,2,3-trimethyl-3-methoxycyclopropanecarboxylic acid chloride 15ml of dry benzene
When 4.7 g of 3-phenoxy-alpha cyanobenzyl alcohol dissolved in 20 ml of dry benzene is added thereto, and 3d of dry pyridine is added as a condensation aid, crystals of pyridine hydrochloride are precipitated. After sealing the cap and leaving it overnight at room temperature, the pyridine hydrochloride was removed, the benzene solution was dried with nitric acid, and the benzene was distilled off under reduced pressure to obtain 3″-phenoxy-D5-cyanobenzyl 2.
7.0 g of 2,3-trimethyl-3-methoxycyclopropanecarboxylate was obtained. Practical example 2 4.1 g of 2-methyl-2-chloro-3-cycloprobylmethylaminocyclopropanecarboxylic acid and 4.6 g of 3-phenoxy-α-ethynylbenzyl alcohol were dissolved in 150 d of benzene, and the solution was stirred vigorously. Concentrated sulfuric acid 5
Add m1. The mixture is heated to reflux while stirring, and the water produced by azeotropy is removed using a dehydrating agent. Benzene was replenished from time to time and the reaction was carried out for about 4 hours.
The reaction solution was then washed with an aqueous sodium bicarbonate solution and a saline solution, and the benzene was distilled off under reduced pressure to obtain 3''-phenoxy-α''-ethynylbenzyl, 2-methyl-2-chloro-3-cyclopropylmethylaminocyclopropanecarboxylate. 6.9g was obtained. Example 3 2,3-dimethyl-2-chloro-3-(4-methoxy-
6.0 g of sodium salt of 2-cyclopentenylthio)-cyclopropanecarboxylic acid and 4.5 g of 3-phenoxybenzyl chloride were dissolved in 50 ml of benzene and reacted under reflux in a nitrogen atmosphere for 3 hours. After cooling and separating the precipitated salt, it was thoroughly washed with brine and dried over sulfuric acid, and the benzene was distilled off under reduced pressure to obtain 3-phenoxybenzyl 2,3-dimethyl-2-chloro-3- 7.7 g of (4-methoxy-2-cyclopentenylthio)-cyclopropanecarboxylate was obtained. Example 4 6.0 g of methyl ester of 2,3-dimethyl-2-chloro-3-(2,4-dimethylbenzylamino)-cyclopropanecarboxylic acid and 4.6 g of 3-phenoxy-α-ethynylbenzyl alcohol were added to 150 Heat to ℃. When the temperature reaches 150° C., 0.25 g of sodium is added and methanol distillation is started. When the distillation of methanol has stopped, 0.25 g of sodium is further added and the above operation is repeated while keeping the temperature around 150° C. until the theoretical amount of methanol is obtained. The mixture was then cooled and dissolved in ether, and the ether solution was washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over sulfuric acid, and the ether was distilled off under reduced pressure to give 3''-phenoxy-ethynylbenzyl 2,3-dimethyl. 7.8 g of -2-chloro-3-(2,4-dimethylbenzylamino)-cyclopropanecarboxylate was obtained.Example 5 2,2-dichloro-3-(4-chlorophenoxy)-cyclopropanecarboxylate Mix 5.5 g of acid anhydride and 4.7 g of 3-phenoxy-α-cyanobenzyl alcohol, gradually add 8 g of 98% sulfuric acid with stirring, and heat to 80-100°C.
After reacting for 3 hours, it was dissolved in ether, and the ether solution was thoroughly washed with aqueous sodium bicarbonate and brine, dried over sodium sulfate, and the ether was distilled off under reduced pressure to give 3'-phenoxy-α1-cyanobenzyl 2,2. Example 6 7.1 g of -dichloro-3-(4-chlorophenoxy)-cyclopropanecarboxylate was obtained. 4.6 g of 2,2-dichloro-3-methyl-3-allyloxycyclopropanecarboxylate was mixed with dimethyl Dissolve in 50 ml of formamide, and add 5.4 g of 3-phenoxybenzyl bromide. Add 4 ml of trimethylamine while stirring, react at 60-80°C for 3 hours, dissolve in ether, wash the ether solution thoroughly with diluted hydrochloric acid, aqueous sodium bicarbonate, and brine, then dry with sulfur salt.
The ether was distilled off under reduced pressure to obtain 6.9 g of 3''-phenoxybenzyl 2,2-dichloro-3-methyl-3-allyloxycyclopropanecarboxylate. Example 7 1.5 g of sodium metal was obtained. Dissolve in 50 ml of absolute ethanol and add 100 ml of anhydrous toluene. Remove ethanol and toluene under reduced pressure in a nitrogen stream.
100 ml of 1,2-dimethoxyethane was added to the precipitated sodium ethoxide, and De-cis, trans-
11.0 g of ethyl ester of 2,2,3-trimethyl-3-ethoxycyclopropanecarboxylic acid is added and heated under reflux for 12 hours. After the isomerization is completed, 1,2-dimethoxyethane is distilled off under reduced pressure, and ether extraction is performed by adding 100 ml of water to the residue. The ether solution was thoroughly washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and saline, then dried with salt water, and after distilling off the ether,
D2-trans-2,2,3-trimethyl-3-ethoxycyclopropanecarboxylic acid ethyl ester (boiling point 1
9.2 g of 20-124 lC/25 mmHg fraction were obtained. 4.5 g of this ethyl ester was mixed with 20 ml of acetic acid and 3
5(f) Hydrolyzed in 20 ml of an aqueous solution of hydrobromic acid, and 3.9 g of the obtained carboxylic acid was reacted with 4.5 g of 3-phenoxy-d-cyanobenzyl alcohol according to the method of Practical Example 1 to give 3'- Phenoxy-α″-cyanobenzyl dl
7.0 g of -trans-2,2,3-trimethyl-3-ethoxycyclopropanecarboxylate was obtained. Example 8 Precise distillation was repeated on 15.0 g of ethyl ester of d1-cis, trans-2,2-dichloro-3-methyl-3-methoxycyclopropanecarboxylic acid, and dl-trans-2,2-dichloro- Ethyl ester of 3-methyl-3-methoxycyclopropanecarboxylic acid (boiling point 81
0C/17mmHg fraction) 5.8g and De-cis-2
,2-dichloro-3-methyl-3-methoxycyclopropanecarboxylic acid ethyl ester (boiling point 86pC/13
1.7 g of mmHg fraction) was obtained. The latter ethyl ester was treated as in Example 7 to give 3I
-phenoxy-d''-cyanobenzyl D2-cis2,
2-dichloro-3-methyl-3-methoxycyclopropanecarboxylate was obtained. Hereinafter, the symbol A will be added after the compound number to indicate that the acid moiety is the dl-trans form, and the symbol B will be added to indicate that the acid moiety is the De-cis form. Example 9 D2-trans-2,2 obtained in Example 7
, 3.9 g of 3-trimethyl-3-ethoxycyclopropanecarboxylic acid was dissolved in 50 d of methanol at 50°C, and 5.2 g of 2-(4-tolyl)-2 phenethylamine was dissolved therein.
A solution of 25ml of methanol is added to form a salt. Cool to room temperature and leave for 2 hours, then collect the precipitated crystals. The crystals were further recrystallized with methanol to obtain 3.2 g of crystals. Add 20% of 10% caustic soda solution to this crystal.
After suspension, e-(4-trino0-2-phenethylamine is recovered by ether extraction. The aqueous layer is acidified with hydrochloric acid, extracted with methylene chloride, and the solvent is distilled off.
1.4 g of -trans-2,2,3-trityl-3-ethoxycyclopropanecarboxylic acid was obtained. [α]2B-4
6゜(Chloroform) Optical purity 93% This carboxylic acid 1
, 1g was converted into 3-phenoxy-d-
3′-
Phenoxy-d'-cyanobenzyl 2-trans-2
, 1.7 g of 2,3-trimethyl-3-ethoxycyclopropanecarboxylate was obtained. Furthermore, this compound is d
It exhibited approximately twice the insecticidal activity compared to the l-trans form of ester. Hereinafter, the symbol C will be added after the compound number to indicate that the acid moiety is the 2-trans form. Actual example 10 dl-cis-2,2- obtained in Example 8
3.7 g of dichloro-3-methyl-3-methoxycyclopropanecarboxylic acid was dissolved in 40 ml of methanol at 50°C. A solution of 5.1 g of d-(4-trino(ha)-2-phenethylamine) dissolved in 25 d of methanol is added to this. The precipitated salt is subjected to the same operation as in Example 9 to obtain d-cis-2, 1.3 g of 2-dichloro-3-methyl-3-methoxycyclopropanecarboxylic acid was obtained.Reference Example 1 White kerosene was added to 0.2 parts of the compound (1) of the present invention, and the whole was diluted to 1.3 g.
0.2% oil solution is obtained as 00 parts. Reference Example 2 White kerosene is added to 0.2 parts of the compound (2) of the present invention and 0.8 parts of piperonyl butoxide to make a total of 100 parts to obtain an oil agent. Reference Example 3 Solpol SM-200 (
Toho Chemical (registered trademark name) 10 parts and 70 parts of 6xylene were added and mixed and dissolved with stirring to obtain a 20% emulsion. Reference Example 4 0.4 parts of the compound (8) of the present invention, 0.1 part of resmethrin, and 165 parts of octachlorodipropyl ether were dissolved in 28 parts of refined kerosene, filled into an aerosol container, and the valve part was attached. 70 parts of a propellant (liquefied petroleum gas) is pressurized and filled through the tank to obtain an aerosol. Reference Example 5 Compound of the present invention (self) 0.5 g. 0.5g of BHT is used as a base material for mosquito coils such as pyrethrum extract powder, wood flour, starch powder, etc.99.0
g to obtain a mosquito coil by a known method. Reference Example 6 0.4 g of the compound spider of the present invention, 1.0 g of 5MGK-5026, is uniformly mixed with 986 g of a base material for a mosquito coil to obtain a mosquito coil by a known method. Reference Example 7 3 parts of the compound (conversion) of the present invention and 97 parts of clay are thoroughly ground and mixed to obtain a 3% powder. Reference Example 8 Compound C3I4O parts of the present invention, 35 parts diatomaceous earth, 20 parts clay
1 part, 3 parts of lauryl sulfonate, and 2 parts of carboxymethyl cellulose are ground and mixed to obtain a wettable powder. Test Example 3 Compounds of the present invention (2), (4), (7), (9) of the emulsion obtained in Reference Example 3 were applied to a field of radish at the 5-6 leaf stage where a large number of green peach aphids were infested. ), (13), (1
8), (23), (27), (31), (36), (3
9), (41), (43), (46), (2)-A, (
6)-B, (12)-C, (20)-B, (29)-A
and (38)-C in each emulsion containing 100% by water.
The 0-fold diluted solution was sprayed at 100 e/per. A parasitic rate survey two days later showed that the density had decreased to less than 1/10 of the pre-spraying density in each plot. Test Example 4 Among the emulsions obtained in Reference Example 3, compounds of the present invention (1), (
3), (4), (10), (16), (21), (24
), (37), (40), (45), (2)-C, (7
)-A, (15)-B, (26)-A and (44)-
Fresh leaves were immersed in a 2000-fold diluted solution of C for about 5 seconds, and after the solution had dried, they were placed in a shear dish and 10 healthy armyworm larvae were released. The test insects were released twice, once on the day of soaking the fresh leaves and 5 days later, and the mortality rate after 24 hours was determined. Test Example 5 One day before applying the insecticidal active ingredient to potted fava beans, one tree was infested with about 200 aphids. Among the wettable powders obtained in Reference Example 8, (1) and (5)
, (8), (12), (14), (19), (22),
A 4000-fold dilution of (26), (29), and (30) was sprayed on leaves infested with pests using a compressed air spray method per 10 ml/pot, and the degree of damage was observed 2 days later.

Claims (1)

[Claims] 1. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I
) (In the formula, A is O, NH, S, and R and R_2 represent a methyl group or a chloro atom. If R and R_2 are both methyl groups, they represent a methyl group, but in other cases, hydrogen Indicates an atom or methyl group.
R_4 is an alkyl group, an alkenyl group, a haloalkyl group,
Haloalkenyl group, alkoxyalkyl group and general formula (
II), (III), (IV), (V), and (VI). ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・
・・・(II)▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・
・・・(III)▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・
...(IV)▲There are mathematical formulas, chemical formulas, tables, etc.▼...
...(V)▲There are mathematical formulas, chemical formulas, tables, etc.▼...
... (VI) where l is an integer of 1 to 5, m is an integer of 2 to 6, n is an integer of 1 to 2, and R_6 is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, It represents a halomethyl group or a lower alkoxy group, and R_7 represents a hydrogen atom or a methyl group. Further, R_6 represents a hydrogen atom, a cyano group or an ethynyl group. ) and its optical and geometric isomers. 2 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(VII
) (In the formula, R and R_2 represent a methyl group or a chloro atom. R_3 represents a methyl group when both R and R_2 are methyl groups, but otherwise represents a hydrogen atom or a methyl group. R_4 represents a methyl group. Shows alkyl groups, alkenyl groups, haloalkyl groups, haloalkenyl groups, alkoxyalkyl groups, and groups represented by general formulas (II), (III), (IV), (V), and (VI). ▲ Numerical formula, chemical formula, There are tables, etc. ▼...
...(II)▲There are mathematical formulas, chemical formulas, tables, etc.▼...
...(III)▲There are mathematical formulas, chemical formulas, tables, etc.▼・
・・・・・・(IV)▲There are mathematical formulas, chemical formulas, tables, etc.▼・
・・・・・・(V)▲There are mathematical formulas, chemical formulas, tables, etc.▼・
...(VI) where l is an integer from 1 to 5, m is from 2 to 6
, n is an integer of 1 to 2, R_6 is a hydrogen atom,
It represents a lower alkyl group, a lower alkenyl group, a halogen atom, a halomethyl group, or a lower alkoxy group, and R_7 represents a hydrogen atom or a methyl group. Further, R_6 represents a hydrogen atom, a cyano group or an ethynyl group. ) and its optical and geometric isomers according to claim 1. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Cyclopropane carboxylic acid ester derivatives and optical and geometric isomers thereof according to claim 2, which are compounds represented by the following. Cyclopropanecarboxylic acid ester derivatives and optical and geometric isomers thereof according to claim 2, characterized in that they are compounds represented by ▲ where there are mathematical formulas, chemical formulas, tables, etc. ▼. Cyclopropanecarboxylic acid ester derivatives and optical and geometric isomers thereof according to claim 2, characterized in that they are compounds represented by ▲ where there are mathematical formulas, chemical formulas, tables, etc. ▼. Cyclopropanecarboxylic acid ester derivatives and their optical and geometric forms according to claim 2, characterized in that they are compounds represented by ▲ where there are mathematical formulas, chemical formulas, tables, etc. ▼. Cyclopropanecarboxylic acid ester derivatives and optical and geometric isomers thereof according to claim 2, characterized in that they are compounds represented by ▲ where there are mathematical formulas, chemical formulas, tables, etc. ▼. Cyclopropanecarboxylic acid ester derivatives and optical and geometric isomers thereof according to claim 2, characterized in that they are compounds represented by ▲ where there are mathematical formulas, chemical formulas, tables, etc. ▼. Cyclopropanecarboxylic acid ester derivatives and optical and geometric isomers thereof according to claim 2, characterized in that they are compounds represented by ▲ where there are mathematical formulas, chemical formulas, tables, etc. ▼. Cyclopropanecarboxylic acid ester derivatives and optical and geometric isomers thereof according to claim 2, characterized in that they are compounds represented by ▲ where there are mathematical formulas, chemical formulas, tables, etc. ▼. ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(VII
I) (In the formula, A is O, NH, S, R and R_2 represent a methyl group or a chloro atom. R_3 represents a methyl group when both R and R_2 are methyl groups, but in other cases represents a hydrogen atom or a methyl group.R_4 is an alkyl group, an alkenyl group, a haloalkyl group, a haloalkenyl group, an alkoxyalkyl group and a general formula (II), (III), (IV), (V), (VI). Indicates the group represented.▲There are mathematical formulas, chemical formulas, tables, etc.▼...
...(II)▲There are mathematical formulas, chemical formulas, tables, etc.▼...
...(III)▲There are mathematical formulas, chemical formulas, tables, etc.▼・
・・・・・・(IV)▲There are mathematical formulas, chemical formulas, tables, etc.▼・
・・・・・・(V)▲There are mathematical formulas, chemical formulas, tables, etc.▼・
...(VI) where l is an integer from 1 to 5, m is from 2 to 6
, n is an integer of 1 to 2, R_6 is a hydrogen atom,
It represents a lower alkyl group, a lower alkenyl group, a halogen atom, a halomethyl group, or a lower alkoxy group, and R_7 represents a hydrogen atom or a methyl group. ) Carboxylic acids or their reactive derivatives and general formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼・・・・・・(I
X) (Here, R_5 represents a hydrogen atom, a cyano group, or an ethynyl group.) There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by reacting with the alcohol or its reactive derivative ▼.・・・・・・(I)(Here A, R_1,
R_2, R_3, R_4, and R_5 represent the same meanings as above. ) A method for producing a cyclopropanecarboxylic acid ester derivative and its optical and geometric isomers. 12 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・( I
) (In the formula, A is O, NH, S, and R and R_2 represent a methyl group or a chloro atom. R_3 represents a methyl group when both R_1 and R_2 are methyl groups, but in other cases, Represents a hydrogen atom or a methyl group.R_4 is an alkyl group, an alkenyl group, a haloalkyl group, a haloalkenyl group, an alkoxyalkyl group, and is represented by the general formula (II), (III), (IV), (V), or (VI). Indicates the group that is represented.▲Contains mathematical formulas, chemical formulas, tables, etc.▼
・・・・・・(II) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼
・・・・・・(III)▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(IV)▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(V)▲Mathematical formulas, There are chemical formulas, tables, etc. ▼・・・・・・(VI) Here l is an integer from 1 to 5, m is 2
An integer of ~6, n is an integer of 1 to 2, R_6 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a halomethyl group, a lower alkoxy group, and R_7 represents a hydrogen atom or a methyl group. Further, R_5 represents a hydrogen atom, a cyano group or an ethynyl group. ) and its optical and geometric isomers. 13 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(VII
) (In the formula, R and R_2 represent a methyl group, and R_3 represents a methyl group when both R_1 and R_2 are methyl groups, but otherwise represents a hydrogen atom or a methyl group. R_4 represents an alkyl group, an alkenyl group, a haloalkyl group, a haloalkenyl group, an alkoxyalkyl group, and a group represented by the general formula (II), (III), (IV), (V), or (VI). ▲ Numerical formula, chemical formula There are tables, etc.▼
・・・・・・(II) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼
・・・・・・(III)▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(IV)▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(V)▲Mathematical formulas, There are chemical formulas, tables, etc. ▼・・・・・・(VI) Here l is an integer from 1 to 5, m is 2
An integer of ~6, n is an integer of 1 to 2, R_6 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a halomethyl group, a lower alkoxy group, and R_7 represents a hydrogen atom or a methyl group. Further, R_5 represents a hydrogen atom, a cyano group or an ethynyl group. 13. The insecticide according to claim 12, which contains the cyclopropanecarboxylic acid ester derivative shown in ) and its optical and geometric isomers. Claim 13, characterized by containing the cyclopropanecarboxylic acid ester derivative represented by ▲with mathematical formulas, chemical formulas, tables, etc., and its optical and geometric isomers.
Insecticides listed in section. The insecticide according to claim 13, characterized in that it contains a cyclopropanecarboxylic acid ester derivative represented by ▲a mathematical formula, a chemical formula, a table, etc.▼ and its optical and geometric isomers. The insecticide according to claim 13, characterized in that it contains a cyclopropanecarboxylic acid ester derivative represented by ▲a mathematical formula, a chemical formula, a table, etc.▼ and its optical and geometric isomers. The insecticide according to claim 13, characterized in that it contains a cyclopropanecarboxylic acid ester derivative represented by ▲a mathematical formula, a chemical formula, a table, etc.▼ and its optical and geometric isomers. The insecticide according to claim 13, characterized in that it contains a cyclopropanecarboxylic acid ester derivative represented by ▲a mathematical formula, a chemical formula, a table, etc.▼ and its optical and geometric isomers. The insecticide according to claim 13, characterized in that it contains a cyclopropanecarboxylic acid ester derivative represented by ▲a mathematical formula, a chemical formula, a table, etc.▼ and its optical and geometric isomers. The insecticide according to claim 13, characterized in that it contains a cyclopropanecarboxylic acid ester derivative represented by ▲a mathematical formula, a chemical formula, a table, etc.▼ and its optical and geometric isomers. The insecticide according to claim 13, characterized in that it contains a cyclopropanecarboxylic acid ester derivative represented by ▲a mathematical formula, a chemical formula, a table, etc.▼ and its optical and geometric isomers.