JPS5920660B2 - Cyclopropane carboxylic acid ester derivatives, method for producing cyclopropane carboxylic acid ester derivatives, insecticide containing cyclopropane carboxylic 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, R, R2 represents a methyl group or a chloro atom, and R3 represents a hydrogen atom or a methyl group).

R4 represents a methylene or ethylene group;
V), (Vt). Here ι is l~
5, m is an integer of 2 to 6, n is an integer of 1 to 3, R7 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a halomethyl group, a lower alkoxy group, and R8 represents hydrogen. Represents an atom or a methyl group.

Further, R6 represents a hydrogen atom, a cyano group or an ethynyl group.
), its optical and geometrical isomers, its production method, and an insecticide characterized by containing this compound as an active ingredient. Various alcohol components of chrysanthemum acid esters have been studied and put into practical use.
It is susceptible to oxidative decomposition due to light, which has limited its 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, compounds with structures similar to naturally occurring organic compounds, mainly consisting of carbon, hydrogen, oxygen, and nitrogen, are advantageous as future insecticidal ingredients and L7. It is thought that. 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 on various sanitary pests and agricultural and horticultural pests due to its insecticidal component L7, but has no toxicity to warm-blooded animals. I learned that it is extremely stable against light compared to conventional pyrethroids. The present invention was completed based on the above findings. The compound represented by the above formula (1) used as an active ingredient in the present invention is prepared according to the general method for producing esters according to the general formula (wherein A is 0, NH,
S, R,, R2 represents a methyl group or a chloro atom 1
7. R3 represents a hydrogen atom or a methyl group.

R4 represents a methylene or ethylene group, R5 represents an alkyl group, an alkenyl group, a haloalkyl group, a haloalkenyl group, an alkoxyalkyl group and the general formula (), ([[),
0V), (V), (VD. Here, t is an integer of 1 to 5, m is an integer of 2 to 6, n is an integer of 1 to 3, and R7 is a hydrogen atom, a lower It represents an alkyl group, a lower alkenyl group, a halogen atom, a methyl group, or a lower alkoxy group, and R8 represents a hydrogen atom or a methyl group.

) or its reactive derivative represented by the general formula (where R6 represents a hydrogen atom, a cyano group, or an ethynyl group).

) or a reactive derivative thereof. Examples of reactive derivatives of carboxylic acids include acid halides, acid anhydrides, lower alkyl esters, and alkali metal salts. Examples of reactive derivatives of alcohol 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. (
1) 3'-phenoxy-α'-cyanobenzyl 2,2
-dimethyl-3-n-propyloxymethyl (2) ρ
Rho cyclopropanecarboxylate Nl.548l3'-Phenoxy-α'-cyanobenzyl 2,2-dimethyl-3-isobutoxymethylcyclo(3) CH-
．． Propane carboxylate N26l. 55233'
-Phenoxy-α'-cyanobenzyl 2,2-dimethyl-3-ethoxyethylcyclopro(4)rμm
ρ"-Pancarboxylate Nl.54693'-Phenoxy-α'-cyanobenzyl 2,2-dimethyl-3
-cyclohexyloxymethy(5)R,r, cyclopropanecarboxylate Nl. 575O3'-Phenoxy-α'-cyanobenzyl 2,2-dichloro-3-(4-methylphenoxymethy(6) CH
,9H3)-cyclopropanecarboxylate Nl. 59O4 3'-phenoxy-α'-cyanobenzyl 2,2,3
-trimethyl-3-methoxymethylzig・(7)ropro0
Pancarboxylate N2Ol. 5327D'-Phenoxybenzyl 2,2-dichloro 3-
Methyl-3-(3-methyl-2-buteny(8)
Ruaminoethyl)-cyclopropanecarboxylate
Nl. 56853'-Phenoxy-α'-ethynylbenzyl 2-methyl-2-chloroo-3-(4-promobe(9)r,IT-ndylthiomethyl)cyclopropanecarboxylate
Nl. 6O343-Phenoxybenzyl 2,3-dimethyl-2-chloro-3-(2,2-dichlorovinyl-(10)oxymethyl)-cyclopropanecarboxylate Nl. 56523'-Phenoxy-α'-cyanobenzyl 2-methyl-2-chloro-3-(3
-Methylzig(11)pentylmethylaminoethyl)-cyclopropanecarboxylate Nl. 59l9
3-Phenoxybenzyl 2,2-dimethyl-3-(
1-Methoxyethylthioethyl)-cyclopropanecarboxylate Nl. 567O (12) 3'-phenoxy-α'-ethynylbenzyl 2,2-dimethyl-3-(4-isopropenyl-2-cyclohexenylaminoethyl)-zig (13) Ha Ha Jn- Lopropanecarboxylate Nl. 59863'-Phenoxy-α'-cyanobenzyl 2,2-dichloro-3-methyl-3-(2,6-dimethyl-4-
Trifluoromethylphenylthio(14)ClC'methyl)-cyclopropanecarboxylate Nl. 6l
733'-phenoxy-α'-ethynylbenzyl 2,2
-dichloro- 3 -methyl- 3 -( 3 -(
15) ρH- ρ, Methoxydig-0-butoxymethyl)-cyclopropanecarboxylate Nl. 56853'-Phenoxybenzyl 2,3-dimethyl-2-chloro-3-(2,3,
4,5,6-Bender (16) "Chloroanilinoethyl)-dig0p0pancarboxylate Nl.586l3'-Phenoxy-α'-ethynylbenzyl 2,2,3-trimethyl-3-(2
-Fluoro-3-bromopropylthioethyl)-cyclopropanecarboxylate Nl. 5638(17) 3'-phenoxy-α'-ethynylbenzyl 2-methyl-2-chloro-3-(α-methyl-3-isopropylbenzyloxyethyl)-(18) ,, u cyclopropanecarboxylate Nl. 59723'-Phenoxybenzyl 2,2-dimethyl-3-
(1-methyl-n-butylaminomethyl): (1
9) RuTnjρ''-Cyclopropanecarboxylate Nl.57943'-Phenoxy-α'-cyanobenzyl 2,2-dichloro-3-(3,4-dimethylcyclo{(20)heptylthioethyl)-cyclopropanecarboxylate Nl .59l53'-Phenoxy-α'-cyanobenzyl 2-methyl-2-chloro-3-(2
-Ethoxye・(21)toxymethyl)-zig07'O
Pancarboxylate N26l. 55633'-Phenoxy-α'-ethynylbenzyl 2,2-dichloro-
3-(3-chloromethyl-2-butenylaminomethyl)-cyclopropanecarboxylate Nl. 56
O8(22) 3'-phenoxy-α'-ethynylbenzyl 2,2-
Dimethyl-3-(4-chloromethylthi(23)
Cl, C! , Chlohexylmethylthiomethyl)-cyclopropanecarboxylate Nl. 59223'-Phenoxybenzyl 2,2-dichloro-3-(4-ethyl-2
-cyclopentenylo(24)xyethyl)-cyclopropanecarboxylate n peta 1.56573'
-Phenoxy-α'-cyanobenzyl 2,2,3-trimethyl-3-(4-Tert.
25) CH,Clcyanilinoethyl)-cyclopropanecarboxylate N26l. 6O8O3'-phenoxy-α'-cyanobenzyl 2,3-dimethyl-2
-Chloro- 3-cyclopropy(26) p-rumethylthiomethylcyclopropanecarboxylate Nl.
56543'-Phenoxy-α'-ethynylbenzyl 2
, 2-dichloro-3-methyl-3-(3-bromomethylbenzyloxyethyl)-cyclopropanecarboxylate Nl. 6l44(27) 3'-Phenoxy-α'-cyanobenzyl 2,3-dimethyl-2-chloro3-(l-methyl(28
)CH. C[-allylthioethyl)-cyclopropanecarboxylate N2Bl. 57293'-Phenoxy-α'-ethynylbenzyl 2,2,3-trimethyl-3-(α-
Methyl-2,4-dichlorobenzylaminomethyl)-cy(29)ρ Chlopropanecarboxylate Nl. 6lO53'-phenocow cybenzyl 2,2,3-trimethyl-
3-(5-allyl-3-cyclohexeε(3
0) Nylthiomethyl)-cyclopropanecarboxylate Nl. 58l73-Phenoxybenzyl 2-methyl-2-chloro-3-cyclopentylaminomethyl dig-(31)propanecarboxylate N2Bl. 57753'-Fenobeef-alpha'-ethynylbenzyl 2,3-dimethyl-2-chloro-3-(4-chlorocyclohexyloxyethyl)-cyclopropanecarboxylate Nl. 582O(32) 3'-phenoxy-α'-ethynylbenzyl 2,2-dichloro-3-(2,2,2-trif(33)f,
rι fluoroethylaminoethyl)-cyclopropanecarboxylate Nl. 567l 3'-Phenoxy-α'-cyanobenzyl 2,2-dimethyl-3-n-butoxymethylcyclo: (34) C'ρ' Propanecarboxylate Nl. 55483'-Phenoxy-α'-cyanobenzyl 2,2-dichloro-
3-Methyl-3-ethylthioe(35)ρloha r[Jrqj thylcyclopropanecarboxylate N26l. 57l53'-Phenoxy-α'-ethynylbenzyl 2,3-dimethyl-2-chloro-3-(3,4-dimethoxy-4-cycloheptenylaminomethane) (36) ρ, ρ
(notyl)-cyclopropanecarboxylate Nl. 598
33'-Phenoxybenzyl 2,2-dichloro-3-
(2-Methyl-4-isopropylphenylthiomethyl)-cyclopropanecarboxylate Nl. 6Ol
l(37) 3-phenoxybenzyl 2,2,3-trimethyl-
3-Cyclopropoxyethylcyclop(38)lopanecarboxylate N2Bl. 54263'-Phenoxy-α'-ethynylbenzyl 2,2-dimethyl-3-n
-Amyloxymethy(39)cyclopropanecarboxylate Nl. 56O33'-Phenoxybenzyl 2,2-dichloro-3-
Methyl ~ 3-isopropylaminomethyl. (40)ρ
H- ρj Cyclopropanecarboxylate n Kasumi 1.55403'-Phenoxybenzyl 2-methyl-2-chloro-3-phenylthioethylcyclopropy(41)
Carboxylate Nl. 57l93'-Phenoxy-α'-cyanobenzyl 2-methyl-
2-chloro- 3-(2,6)-difluoro-
3-Methoxy-4-allylanilinomethyl)cyclopropanecarboxylate N2Ol. 6O23D (42) 3'-phenoxybenzyl 2,2-dichloro-3-
Methyl-3-(3-vinyl-4-ethoxy-6
-methylbenzyloxymethyl)cyclo(43)propanecarboxylate 201.5984n D3'-Phenoxy-α'-cyanobenzyl 2,2,3-
Trimethyl-3-(α-methylbendi(44)haN
VrUρl ruthioethyl)cyclopropanecarboxylate n
to Sl. 597O3'-Phenoxybenzyl 2-methyl-2-chloro-3-(2-fluoro-3
-Trifluoromethyl-4-isopropenylcyclopentyl (45)thiomethyl)cyclopropanecarboxylate Nl. 58693'-Phenoxy-α'-cy1benzyl 2,2-dichloro-3-methyl-3-(
2-Methyl-3.(46)-allylcyclobutylmethoxyethyl)cyclopropanecarboxylate Nl
．． 594l3'-Phenoxybenzyl 2,2-dimethyl-3-(3,6,7-trichloro-4-trifluoromethyl-5-isopropoxycyclohebutylmethylaminomethyl)cyclopropanecarboxylate N2
Bl. 6O2O(47) 3'-phenoxy-α'-ethynylbenzyl 2,2-dichloro-3-methyl-3-(3-cy(48)
) CH9cι CH. CIQO pentenylthioethyl)DIGO propanecarboxylate N2Bl. 579
53'-phenoxy-α'-cyanobenzyl 2,3-
Dimethyl-2-k00-3-(3-chloromethyl-4,6-dimethyl-5-bromo-3-(49)
CH,. ρ, cycloheptenyloxymethyl) cyclopropane carboxylate Nl. 59323'-Phenoxybenzyl 2-methyl-2-chloro-3
-(2-methylallyloxymethyl)-(50)
c'C' cyclopropane carboxylate Nl. 55673'-Phenoxy-α'-cyanobenzyl 2,2-dichloro-3-methyl-3-(4-chlorof(5
1) ρH.

butoxymethyl)cyclopropanecarboxylate N
l. 56O53'-Phenoxy-α'-cyanobenzyl 2-methyl-2-chloro-3-(2-fluoromethyl-3-bromoallylthioethyl)cyclopropanecarboxylate Nl. 578l'' 3-Phenoxy-α-cyanobenzyl 2,2-dichloro-3-methyl-3-(2-fluoro-3,6-dimethoxy-4-ethylbenzylaminoethyl)cyclopropanecarboxylate The compound of the present invention is novel is a compound,
It is solid or liquid at room temperature and is generally easily soluble in organic solvents.

Therefore, it can be used as an insecticide for spraying in the form of emulsions, oils, powders, wettable powders, aerosols, etc. It can also be used as an insecticide for fumigation such as mosquito coils by mixing with wood flour or other suitable base materials. can do. In addition, when this active ingredient is dissolved in a suitable organic solvent [7] and soaked in a mount or dissolved in a suitable solvent and heated and evaporated with a suitable heating element, it is used as an electric mosquito repellent, just like a mosquito coil. This shows the effect of The compound of the present invention is more stable to light than conventional pyrethroids and can also be used as an agricultural and horticultural insecticide. In addition, N-octylbicycloheptenedicarboximide (trade name MGK-26
4), mixture of N-octylbicycloheptenedicarboximide and arylsulfonate (trade name MGK-
5026), octachlorodipropyl ether, piperonyl butoxide, etc., the insecticidal effect can be further enhanced.

The compounds of the present invention may also be used with other insecticides such as Sumithion, D.
DVP, organic phosphorus agents such as diazinon, carbamates such as 1-naphthyl-N-methyl carbamate, 3,4-dimethylphenyl-N-methyl carbamate, pyrethrin, allethrin, phthalthrin, flamethrin,
Conventional pyrethroid insecticides such as phenotrin, permethrin, cypermethrin, decametrin, fuenvalerate, fuenpropanate, insecticides such as pattern, galuecuron, rannate, or acaricides, fungicides, nematicides, and 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% white light solution 4 of the above-mentioned compound example (54) of the present invention, 0.2% and biperonyl butoxide 0.8%
white light solution 03), 0.1% and phthalthrine 0.1%
For the white light solution (C) and the 0.2% white light solution of Areschili and Phthalthrin, the falling and turning rates of house flies were determined, and the relative effectiveness of the test drugs was calculated [7, furthermore, 24
The mortality rate after hours was determined as follows.

Test Example 2 Insecticidal test by fumigation Mosquito coils containing 0.5% of the insecticidal ingredient were prepared and tested for their effectiveness in making adult Culex mosquitoes fall and roll over.

This experiment was published in Insect Control Science Vol. 16 (1951), p. 176.
The relative effectiveness of the incense sticks was calculated according to the method of Nagasawa, Katsuta et al. and was as follows. The sample drug number is the same as that of the active ingredient example above. Test Example 3 Insecticidal test by microdropping method Allethrin and the compound of the present invention were added with pipenyl butoxide in an amount twice the amount of the active ingredient, respectively, to make an acetone solution of a predetermined concentration, and the solution was applied to the thorax of an adult house fly using a microsyringe. The relative insecticidal power against allethrin and the synergistic effect with piperonyl butoxide were investigated from the insect mortality rate 24 hours after application to the backboard, and the results were as follows.

Examples of the present invention will be shown below. The compound names are the same as those in the active ingredient examples above. Example 1 4.2 g of 2,2-dimethyl-3-n-butoxymethylcyclopropanecarboxylic acid chloride was added to 15 g of dry benzene.
When 4.7 g of 3-phenoxy-α-cyanobenzyl alcohol dissolved in 20 ml of dry benzene is added thereto, and dry pyridine 3W11 is further added as a condensation aid, crystals of pyridine hydrochloride are precipitated.

After leaving it overnight at room temperature in a sealed stopper L7, remove the crystals of pyridine hydrochloride.
After separation, the benzene solution was dried with sulfuric acid and the benzene was distilled off under reduced pressure to obtain 14 g of 3'-phenoxy-α5-cyanobenzyl 2,2-dimethyl-3-n-butoxymethylcyclopropanecarboxylate. Example 2 6.6 g of 2,3-dimethyl-2-chloro-3-(3,4-dimethoxy-4-cycloheptenylaminomethyl)-cyclopropanecarboxylic acid and 3-phenoxy-α-ethynylbenzyl alcohol4. 6g to 150ml of benzene
and add 5 ml of concentrated sulfuric acid while stirring the solution vigorously.

Heat to reflux while stirring and remove water produced by azeotropy 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 aqueous sodium bicarbonate and brine, and the benzene was distilled off under reduced pressure to give 3'-phenoxy-α7-ethynylbenzyl 2,3-dimethyl-2-chloro3-(3,4-
8.8 g of dimethoxy-4-cycloheptenylaminomethyl)-cyclopropanecarboxylate was obtained. Example 3 7.2 g of sodium salt of 2,2-dichloro-3-(2-methyl-4-isopropylphenylthiomethyl)-cyclopropanecarboxylic acid and 4.5 g of 3-phenoxybenzyl chloride are added to 50 ml of benzene. Dissolve and reflux 3
After reacting in a nitrogen stream for an hour, the reaction solution was cooled and the precipitated salt was separated from P. After washing thoroughly with brine, it was dried over sulfuric acid, and the benzene was distilled off under reduced pressure to form 3'-phenoxybenzene. 8.7 g of 2,2-dichloro-3-(2-methyl-4-isopropylphenylthiomethyl)-cyclopropanecarboxylate was obtained.

Example 4 8.2 g of methyl ester of 2,2-dichloro-3-methyl-3-(butomomethylbenzyloxyethyl)-cyclopropanecarboxylic acid and 4.6 g of 3-phenoxy-alpha-ethynylbenzyl alcohol were added to 150 g of methyl benzyl alcohol. 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. The ether solution was washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over nitric acid, and the ether was distilled off under reduced pressure to give 3'-phenoxy-α7-ethynylbenzyl 2,2- Dichloro-
10.1 g of 3-methyl-3-(3-bromomethylbenzyloxyethyl)-cyclopropanecarboxylate was obtained. Example 5 3.4 g of 2,2,3-trimethyl-3-methoxymethylcyclopropanecarboxylic acid anhydride and 3-phenoxy-alpha
- Mix 4.7 g of cyanobenzyl alcohol, gradually add 8 g of 98% sulfuric acid while stirring, react at 80-100°C for 3 hours, then dissolve in ether, wash the ether solution thoroughly with sodium bicarbonate solution and saline solution. It was dried over salt solution and the ether was distilled off under reduced pressure to obtain 5.5 g of 3-phenoxy-α-cyanobenzyl 2,2,3-trimethyl-3-methoxymethyl cycloprocarboxylate. .

Example 6 4.7 g of 2-methyl-2-chloro-3-cyclopentylaminomethylcyclopropanecarboxylic acid is dissolved in 50 d of dimethylformamide, and 5.4 g of 3-phenoxybenzyl bromide is added thereto.

Add triethylamine 4WL1 while stirring at 60-80°C.
After reacting for 3 hours, the ether solution was dissolved in ether, the ether solution was thoroughly washed with dilute hydrochloric acid, aqueous sodium bicarbonate, and brine, dried over nitric acid, and the ether was distilled off under reduced pressure to give 3''-phenoxybenzyl 2-methyl. 7.2 g of -2-chloro-3-cyclopentylaminomethylcyclopropanecarboxylate was obtained.Example 7 1.5 g of metallic sodium was dissolved in 50 ml of absolute ethanol, and 100 ml of anhydrous toluene was added thereto.

Remove ethanol and toluene under reduced pressure in a nitrogen stream,
100 d of 1,2-dimethoxyethane was added to the precipitated sodium ethoxide, and further Dt-cis, trans-2
, 12.0 g of ethyl ester of 2-dimethyl-3-(n-propyloxymethyl)cyclopropanecarboxylic acid was added thereto, and the mixture was heated under reflux for 12 hours.

After the isomerization is completed, 1,2-dimethoxyethane is distilled off under reduced pressure, and 100 WII of water is added to the residue to perform ether extraction. 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,
Dt-trans-2,2-dimethyl-3-(n-propyloxymethyl)cyclopropanecarboxylic acid ethyl ester (boiling point 123-127°C/260Hg fraction) 9
．． 2g was obtained. Add 4.8 g of this ethyl ester to 20 g of acetic acid.
ml and 4.1 g of the obtained carboxylic acid was hydrolyzed in 20N of 35% aqueous hydrochloric acid solution according to the method of Example 1.
3'-Phenoxy-α5-cyanobenzyl was obtained by reacting with 4.7 g of phenoxy-α-cyanobenzyl alcohol.
Dt-trans-2,2-dimethyl-3-(n-propyloxymethyl)cyclopropanecarboxylate7.
4g was obtained.

Example 8 dt-cis,trans-2,2,3-trimethyl-3-
Precise distillation was repeated on 18.0 g of ethyl ester of methoxymethylcyclopropanecarboxylic acid.
/1711Hg fraction) 6.8g (5-Dt-cis-2
,2,3-trimethyl-3-methoxymethylcyclopropanecarboxylic acid ethyl ester (boiling point 88℃/13m
1.7 g of m1 {g fraction) were obtained.

The latter ethyl ester was treated as in Example 7 to give 3'
-Phenoxy-α5-cyanobenzyl Dt-cis-2
, 2,3-trimethyl-3-methoxymethylcyclopropanecarboxylate was obtained. Hereinafter, the symbol A will be added after the compound number to indicate that the acid moiety is the Dt-trans form, and the symbol B will be added to indicate that the acid moiety is the Dt-cis form.

Example 9 Dt-trans-2,2 obtained in Example 7
-4.1 g of dimethyl-3-(n-propyloxymethyl)cyclopropanecarboxylic acid in 50 methanol
The solution was dissolved at ℃, and a solution prepared by dissolving 5.2 g of t-(4-tolyl)-2-phenethylamine in 25 d of methanol was added to form a salt.

Cool to room temperature and leave for 2 hours, and collect precipitated crystals. The crystals were further recrystallized with methanol to obtain 3.4 g of crystals. Add 20% of 10% caustic soda solution to this crystal.
After adding and suspending, t-(4-tolyl)-2-phenethylamine is recovered by ether extraction. After acidifying the aqueous layer with hydrochloric acid and extracting with methylene chloride, the solvent was distilled off and t-
1.4 g of trans-2,2-dimethyl-3-(n-propyloxymethyl)cyclopropanecarboxylic acid was obtained.
[α]-41' (Chloroform) Optical purity 93% 1.2 g of this carboxylic acid was reacted with 1.4 g of 3-phenoxy-α-cyanobenzylbamide according to the method of Example 6 to give 3'-phenoxy-41' (chloroform). α5-Cyanobenzyl t-trans-2,2-dimethyl-3-(n-propyloxymethino(ha)cyclopropanecarboxylate 1.7g)
I got it.

Note that this compound exhibited approximately twice the insecticidal activity as compared to the ester of the Dt-trans form.

Hereinafter, the symbol C will be added after the compound number to indicate that the acid moiety is the t-trans form.

Example 10 Dt-cis-2,2, obtained in Example 8
4.0 g of 3-trimethyl-3-methoxymethylcyclopropanecarboxylic acid was dissolved in 40-methanol at 50°C, and d-(4-tolyl)-2-phenethylamine 5.
．． 1g of methanol 25? Add the dissolved liquid.

The precipitated salt was subjected to the same operation as in Example 9 to obtain d-cis-2,2,3-trimethyl-3-methoxymethyl dig0
1.3 g of propanecarboxylic acid was obtained. Reference Example 1 White kerosene was added to 0.2 parts of the compound (1) of the present invention, and the total amount was 1 part.
0.2% oil solution is obtained as 00 parts.

Reference Example 2 White kerosene was added to 0.2 parts of the compound of the present invention (2) and 0.8 parts of piperonyl butoxide, and the total was mixed to 100 parts to obtain an oil solution.

Reference Example 3 Solpol SM-200 (
10 parts of Toho Chemical (registered trademark) and 70 parts of xylene were added and mixed and dissolved with stirring to obtain a 20 (fl) emulsion.

Reference Example 4 0.4 parts of the compound (8) of the present invention, 0.1 part of resmethrin, and 1.5 parts of octachlorodipropyl ether were dissolved in 28 parts of refined kerosene, filled into an aerosol container, and a valve part was attached. The propellant (
70 parts of liquefied petroleum gas) is charged under pressure to obtain an aerosol.

Reference Example 5 Compound (14) of the present invention 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.
A mosquito coil is obtained by uniformly mixing 0g of the product and using a known method.

Reference Example 6 Compound (21) of the present invention (0.4 g). MGK-50261
．． 0g as base material for mosquito coil 98.

A mosquito coil was obtained by uniformly mixing 6 g of the product and using a known method.

Reference Example 7 3 parts of the compound of the present invention (32) and 97 parts of clay are thoroughly ground and mixed to obtain a 3% powder.

Reference Example 8 40 parts of the present compound (38), 35 parts of diatomaceous earth, clay 2
0 parts of lauryl sulfonate, and 2 parts of carboxymethyl cellulose are ground and mixed to obtain a wettable powder.

Test Example 4 Large number of green peach aphids [Reference Example 3. Among the emulsions obtained by
13), (17), (21), (24), (29), (
32), (36), (41), (44), (48), (
50), (51), (54), (1)-A, (10)-
100 tons of each emulsion containing B, (22)-C, (28)-B and (37)-A diluted 1000 times with water.
/Scattered per counter.

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 5 Among the emulsions obtained in Reference Example, compounds of the present invention (1) and (3)
), (4), (5), (7), (11), (14), (
19), (23), (26), (34), (39), (
42), (45), (49), (52), (53), (
1) -C, (6)-B, (18)-A, (27)-B and (43)-C in a 2000 times diluted solution. Dip the fresh leaves in the chemical solution for about 5 seconds, and after drying the chemical solution. Ten healthy larvae of armyworm were released in a cage.

The test insects were released twice, once on the day of soaking the fresh leaves, and once 5 days later.
The insect mortality rate after 24 hours was determined. Test Example 6 One day before applying the insecticidal active ingredient to potted fava beans, one tree was infested with about 200 aphids.

Claims (1)

[Claims] 1. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I
) (In the formula, A is O, NH, S, R, R_2 represents a methyl group or a chloro atom, R_3 represents a hydrogen atom or a methyl group. R_4 represents a methylene or ethylene group, and R_5 represents an alkyl group. , alkenyl group, haloalkyl group, haloalkenyl group, alkoxyalkyl group and general formula (II), (I
II), (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.▼・・・・・・(I
V) ▲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 3, and R_7 is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a halomethyl group,
It represents a lower alkoxy group, and R_4 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, R_2 represent a methyl group or a chloro atom, R_3 represents a hydrogen atom or a methyl group, R_4 represents a methylene or ethylene group, and R_5 represents an alkyl group, an alkenyl group, a haloalkyl group, a haloalkenyl group, Alkoxyalkyl group and general formula (II), (I
II), (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.▼・・・・・・(I
V) ▲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 3, and R_7 is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a halomethyl group,
It represents a lower alkoxy group, and R_3 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. 3. The cyclopropanecarboxylic acid ester derivative and its optical and geometric isomers according to claim 2, which are compounds represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼. 4. The cyclopropanecarboxylic acid ester derivative and optical and geometric isomers thereof according to claim 2, which is a compound represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼. 5. The cyclopropanecarboxylic acid ester derivative and optical and geometric isomers thereof according to claim 2, which is a compound represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼. 6. The cyclopropane carbon derivative and its optical and geometric isomers according to claim 2, which is a compound represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼. 7. The cyclopropane carboxylic acid ester derivative and its optical and geometric isomers according to claim 2, which are compounds represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼. 8. The cyclopropane carboxylic acid ester derivative and its optical and geometric isomers according to claim 2, which is a compound represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼. 9 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(VII
I) (In the formula, A is O, NH, S, R, R_2 represents a methyl group or a chloro atom, R_3 represents a hydrogen atom or a methyl group. R_4 is a methylene or ethylene haloalkyl group, a haloalkenyl group, Alkoxyalkyl group and general formula (II),
Indicates a group represented by (III), (IV), (V), or (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 from 1 to 3, R_7 represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a halomethyl group, or a lower alkoxy group, and R_3 represents a hydrogen atom or a methyl group. ) Carboxylic acids or their reactive derivatives and general formulas ▲ Numerical formulas, chemical formulas, tables, etc. ▼
) (where R_4 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 alcohol or its reactive derivative represented by ▼. ...(I) (Here, A, R_1
, R_2, R_3, R_4, R_5, and R_6 have the same meanings as above. ) A method for producing a cyclopropanecarboxylic acid ester derivative and its optical and geometric isomers. 10 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・( I
) (In the formula, A is O, NH, S, R, R_2 represents a methyl group or a chloro atom, R_3 represents a hydrogen atom or a methyl group. R_4 represents a methylene or ethylene group, and R_5 represents an alkyl group. , alkenyl group, haloalkyl group, haloalkenyl group, alkoxyalkyl group and general formula (II), (I
II), (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.▼・・・・・・(I
V) ▲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 3, and R_7 is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a halogen atom, a halomethyl group,
It represents a lower alkoxy group, and R_3 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. 11 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(VII
) (Here, R_1, R_2, R_3, R_4, R_5
, R_6 represent the same meaning as the above-mentioned item 10. 11. The insecticide according to claim 10, which contains the cyclopropanecarboxylic acid ester derivative represented by ) and its optical and geometric isomers. 12. The insecticide according to claim 11, which contains a cyclopropanecarboxylic acid ester derivative represented by the formula ▲numerical formula, chemical formula, table, etc.▼ and its optical and geometric isomers. 13. The insecticide according to claim 11, characterized in that it contains a cyclopropanecarboxylic acid ester derivative represented by the formula ▲A mathematical formula, a chemical formula, a table, etc.▼ and its optical and geometric isomers. 14. The insecticide according to claim 11, which contains a cyclopropanecarboxylic acid ester derivative represented by the formula ▲ including mathematical formulas, chemical formulas, tables, etc., and its optical and geometric isomers. 15. The insecticide according to claim 11, characterized in that it contains a cyclopropanecarboxylic acid ester derivative represented by the formula ▲numerical formula, chemical formula, table, etc.▼ and its optical and geometric isomers. 16. The insecticide according to claim 11, characterized in that it contains a cyclopropanecarboxylic acid ester derivative represented by the formula ▲ Numerical formula, chemical formula, table, etc. ▼ and its optical and geometric isomers. 17. The insecticide according to claim 11, characterized in that it contains a cyclopropanecarboxylic acid ester derivative represented by the formula ▲numerical formula, chemical formula, table, etc.▼ and its optical and geometric isomers.