JPS6051453B2 - Substituted cyclopropanecarboxylic acid derivatives - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel substituted cyclopropanecarboxylic acid derivatives, more particularly those having the general formula (I)
RI(I) (wherein X represents a halogen atom, R'' represents a hydrogen atom or a lower alkyl group, and R'' represents a hydrogen atom or a methyl group.

) is related to a substituted cyclopropanecarboxylic acid derivative represented by The purpose of this invention is to provide an intermediate for the synthesis of substituted cyclopropanecarboxylic acid derivatives that have extremely low toxicity to warm-blooded animals and have excellent insecticidal and acaricidal activity. To explain in detail the substituted cyclopropanecarboxylic acid derivative represented by the general formula (I) in the present invention, the -C═CX group is preferably a chlorethynyl group, a promuethynyl group, a fluoroethynyl group, or the like.

Preferred examples of R1 include methyl, ethyl, propyl, octyl and the like. Further, R2 represents a hydrogen atom or a methyl group. Currently, commonly used insecticides that are fast-acting, harmless to humans and livestock, and can be safely used include pyrethrum plant scratches (containing pyrethrin) and synthetic allethrin, an analogue of its active ingredient.

However, despite its excellent usefulness, pyrethrum plant scratches are relatively expensive, and therefore cannot be easily obtained as a raw material for industrially producing insecticides and mites in large quantities. The present inventors synthesized various novel cyclopropanecarboxylic acid derivatives and investigated their biological activities. As a result, they were found to have the general formula (■) (wherein X and R2 are as defined above).

R3- represents a hydrogen atom or a cyano group, and A represents a phenoxyphenyl group or a tetrahydrophthalimide group. The substituted cyclopropanecarboxylic acid derivatives shown in ) exhibit excellent insecticidal effects and have remarkable insecticidal and acaricidal efficacy against flies, mosquitoes, cockroaches, and other sanitary pest insects, agricultural and horticultural pests, and mites. and
It has been found that it has higher insecticidal efficacy and knockdown effect than the corresponding primary chrysanthemum acid ester, has low toxicity to warm-blooded animals including humans, and can be produced at low cost. Among the substituted cyclopropanecarboxylic acid derivatives represented by the general formula (■), those represented by the general formula (■) (wherein R2, R3 and A are as defined above).

), as well as substituted cyclopropanecarboxylic acid derivatives represented by the general formula (■) (wherein R2 and R3 are as defined above).

The substituted cyclopropanecarboxylic acid derivative L shown in ) has particularly excellent insecticidal and acaricidal efficacy. Furthermore, among the substituted cyclopropanecarboxylic acid derivatives represented by the general formula (■), particularly the substituted cyclopropanecarboxylic acid derivatives represented by the general formula (■) (wherein R3 is as defined above).

) has excellent insecticidal and acaricidal efficacy. The general formula (1), (
The substituted cyclopropanecarphonic acid derivatives represented by ■), (■), (■), or (■) are new compounds that have not been described in any literature, and are different from pyrethroid compounds used as insecticides and acaricides. The point is that the β-position of the cyclopropanecarboxylic acid derivative is a -C...CX group.

The substituted cyclopropanecarboxylic acid derivative represented by the general formula (1) of the present invention is a compound useful as an intermediate in producing the substituted cyclopropanecarboxylic acid derivative represented by the general formula (■). That is, the general formula (1
) and the general formula (where R3 and A have the same meanings as in the general formula (■), and B has the same meaning as in the general formula (■) below).

) The substituted cyclopropanecarboxylic acid derivative represented by the general formula (■) can be synthesized by reacting the compound represented by the formula (■). Representative examples of the substituted cyclopancarboxylic acid derivative represented by the general formula (1) of the present invention are shown below. Ethyl 2◆2-dimethyl-3-chloroethynylcyclopropanecarboxylateethyl 2●2-dimethyl-3
-Promoethynyl cyclopropane carboxylate Representative examples of the substituted cyclopropane carboxylic acid derivative represented by the general formula (■) derived from the substituted cyclopropane carboxylic acid derivative represented by the general formula (1) are shown below.

m-phenoxybenzyl 2●2-dimethyl-3-chloroethynylcyclopropanecarboxylatem-phenoxybenzyl1●2,2-trimethyl-3-chloroethynylcyclopropanecarboxylate3,4●5,6-tetrahydrophthalimidomethyl2 ●2-dimethyl-3-
Chlorethynyl cyclopropane carboxylate α-cyano m-phenoxybenzyl 2●2-dimethyl-3-
Chlorethynyl cyclopropane carboxylate The substituted cyclopropane carboxylic acid derivative represented by the general formula (1) of the present invention is represented by the general formula (■) (wherein X and R2 have the same meanings as in the general formula (1)).

) and a cyclopropanecarboxylic acid or its reactive derivative represented by the general formula (■) (where B represents a hydroxyl group, a halogen atom or an arylsulfoxy group, and R1 has the same meaning as in the general formula (1)). ) with alcohol, halide or arylsulfonate. The reactive derivative of cyclopropanecarboxylic acid herein refers to lower alkyl esters, acid halides, acid anhydrides, mixed acid anhydrides, alkali metal salts, or salts of organic tertiary bases. Furthermore, the substituted cyclopropanecarboxylic acid derivative of the present invention can be synthesized, for example, by the method shown in the reaction formula below.

In addition, in the reaction formula, each X and R2 have the same meaning as in general formula (1), and R4 represents a lower alkyl group. Below, a method for synthesizing a novel substituted cyclopropanecarboxylic acid derivative represented by general formula (1), and a substituted cyclopropane represented by general formula (■) from a substituted cyclopropanecarboxylic acid derivative represented by general formula (1) are described. Examples, reference examples, and test examples are shown to clarify the method of synthesizing the carboxylic acid derivative and the insecticidal effect of the substituted cyclopropane carboxylic acid derivative represented by the general formula (■).

Example 1 23.71y of 2.2-dimethyl-3-(2●2-dichlorovinyl)cyclopropanecarboxylic acid ethyl ester was dissolved in 200ml of ethanol, 20.4y of sodium ethylate was added, and the mixture was stirred and refluxed for 6 hours.

As the reaction progressed, crystals were deposited from the contents. After the reaction, unreacted sodium ethylate is neutralized with ethanol-hydrochloric acid, precipitated sodium chloride is filtered off, the filtrate is concentrated under reduced pressure, and then distilled under reduced pressure to obtain 2.
2-dimethyl-3-chloroethynylcyclopropanecarboxylic acid ethyl ester was obtained in a yield of 14.1y1 and 71%. NMR spectrum (60MHz) δTsl. l3(S
)3H;1.18(t)3H;1.21(s)3H;1
．． 56(d) 1H: 1.80(d) 1H: 4.06(q
)2H Example 2 23.7 g of 2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylic acid ethyl ester was dissolved in 200 ml of ethanol, and sodium ethylate 2
0.4f was added and stirred and refluxed for 6 hours.

After the reaction, 100ml of water was added and stirred at room temperature overnight. After the reaction, concentrate the ethanol under reduced pressure and remove the unreacted materials with ether.
After extracting impurities, the aqueous layer was neutralized with hydrochloric acid and extracted with ether.

After distilling off the ether, the extract was allowed to stand to give crystallized 2,2-dimethyl-3-chloroethynylcyclopropanecarboxylic acid having a melting point of 72 to 74°C quantitatively.

This was dissolved in chloroform and 1.2 times the mole (14.3
Thionyl chloride (y) was added dropwise at room temperature, and the mixture was stirred at room temperature for 2 hours. After the reaction, it was concentrated under reduced pressure, and the residue was dissolved in anhydrous benzene, and 1.2 times the mole (24.0y) of m-
Add phenoxybenzyl alcohol, then add a small amount (about 10y) of pyridine and leave at room temperature overnight. After the reaction, it is concentrated under reduced pressure and the residue is purified by column chromatography.

2,2-dimethyl-3-chloroethynylcyclopropanecarboxylic acid m-phenoxybenzyl ester at 21.3
y (yield 60%) was obtained.

NMR spectrum (60MHz) δ♀ Pass 41.1 (s)
6H; 1.61(d) 1H; 1.85(d) 1H; 4.
95 (s) Sha L6.75-7.4 (m) 91 (Example 3
1,2,2-trimethyl-3-(2,2-diclobinyl)cyclopropanecarboxylic acid ethyl ester 2.51y
was dissolved in 20 ml of ethanol, 2.04 y of sodium ethylate was added, and the mixture was stirred and refluxed for 6 hours.

After the reaction, unreacted sodium ethylate was neutralized with ethanol-hydrochloric acid, precipitated sodium chloride was filtered off, the filtrate was concentrated under reduced pressure, and purified by column chromatography. 1・2・2-
1.1y (yield 50%) of trimethyl-3-chloroethynylcyclopropanecarboxylic acid ethyl ester was obtained.

NMR spectrum (60MHz) δ7dePl. O~1.35(m)9H; 1.60~1.
80 (m) 1H; 4.05 (q) 2H mass spectrum (
m/e) 21 Mi 214, 191, 189 s14 Atsushi 141, 105
Reference Example 1 1.91q of 2-dimethyl-3-chloroethynylcyclopropane carbonyl chloride was dissolved in anhydrous chloroform, 1.81J of 3,4,5,6-tetrahydrophthalimidemethanol was added, and 0.80q of pyridine was added. The mixture was left to stand at room temperature for 2 to 3 hours.

Crystals precipitated. After filtration, the filtrate was purified by silica gel column chromatography. 3●4●5●6-tetrahydrophthalimidomethyl 2●2-dimethyl-3-chloroethynyl cyclopropane carboxylate at 2.1
8y (yield 65%) was obtained.

NMR spectrum (60MHz) δ♀? Sl. l5(s), 1.20(s)6H; 1.5
0-1.95 (m) 6H; 2.10-2.50 (m) 4
H; 5.40 (s) 2H Reference Example 1 In Reference Example 1, 3.
4●5,6-tetrahydrophthalimide methanol 1.
α-cyano m-phenoxybenzyl 2,2-dimethyl-3-chloroethynylcyclopropanecarboxylate was obtained in the same manner as in Reference Example 1 except that 2.25q of α-cyano m-phenoxybenzyl alcohol was used instead of 81y. Ta.

NMR spectrum (90rv1Hz) δ7de1s3:1.04-1.24(m)6H:1.5
9-1.70 (m) 1H; 1.83-1.96 (m) 1
H; 6.27, 6.29 (Eachs) 1H; 6.85
~7.40 (m) 9H test example Micro-drop test Predetermined amount of specimen [The compound numbers below are based on the general formula (■
) corresponding to representative examples (3) and (6) of the substituted cyclopropane carboxylic acid derivatives shown in ) were accurately weighed to prepare 1% and 0.1% acetone solutions.

House flies anesthetized with ether (Muscad Omesi)
ca) 1 p' of the above prepared solution was dropped onto the dorsal part of the pronotum of a female adult, placed in a waist-high shear dish with food, covered with a wire mesh lid, and stored at a temperature of 25°C.

After 2 hours, the animals were observed to be alive or dead, and the mortality rate was determined. The results are shown in the table below.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, X represents a halogen atom, R^1 represents a hydrogen atom or a lower alkyl group, and R^2 represents a hydrogen atom or a methyl A substituted cyclopropanecarboxylic acid derivative represented by (representing a group). 2
Claim 1 represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 represents a hydrogen atom or a lower alkyl group, and R^2 represents a hydrogen atom or a methyl group.) Substituted cyclopropanecarboxylic acid derivatives as described in .