JPH0112741B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [] [In the formula, , a cyano group, and a methylthio group. ] Novel trans-2,2-dimethyl-
The present invention relates to 3-(p-substituted phenyl)-cyclopropanecarboxylic acid (hereinafter sometimes abbreviated as the compound of the present invention) and a method for producing the same. Various synthetic pyrethroids have been developed by modifying the structure of the natural insecticidal ingredient pyrethrin and have been used as household insecticides mainly targeting sanitary pests, but in recent years, pyrethroids that are chemically stable even in the natural environment have been discovered. There are great expectations for synthetic pyrethroids as agricultural insecticides because they have excellent insecticidal efficacy and suitable residual efficacy against various agricultural and horticultural pests. The present invention provides a synthetic intermediate for a substituted phenylcyclopropanecarboxylic acid ester insecticide and acaricide, which is a type of synthetic pyrethroid, and a method for producing the same. For example, the general formula [] [In the formula, X represents the same meaning as above. ] The esters can be derived from carboxylic acid esters shown by the following, and these esters have excellent control over sanitary pests such as houseflies and mosquitoes, as well as various agricultural and horticultural pests that damage crops such as rice, vegetables, fruit trees, and cotton. have an effect. Moreover, the compound of the present invention has the general formula []
In addition to the carboxylic acid esters shown above, it is also useful as a synthetic intermediate for various substituted phenylcyclopropane carboxylic acid derivatives. Conventionally, known compounds similar to the compound of the present invention have the general formula [] [In the formula, X' is a hydrogen atom, a chlorine atom, a fluorine atom,
Represents a methyl group or a methoxy group. ] The carboxylic acid shown by [Collection of Czechoslovak Chemical] and its production method are known.
Communication, 24 , 2460 (1959) and Ibid., 25 , 1815 (1960)]. There is also a report on 2,2-dimethyl-3-(3',4'-methylenedioxyphenyl)-cyclopropanecarboxylic acid [Insect Control Science Vol. 27...
From page 51]. However, the compound of the present invention represented by the above general formula [] in which the benzene ring is substituted with a specific group is not known and is a new compound that has not been described in any literature. Representative examples of the compounds of the present invention are shown in Table 1.

【table】

[Table] The compounds of the present invention represented by the general formula [] are:
General formula [] [In the formula, X represents the same meaning as above, and R represents a lower alkyl group. ] p-substituted cinnamate ester represented by the general formula [′] [In the formula, Hal represents a halogen atom. ] is reacted with a halogenated isopropyltriphenylphosphonium represented by the formula in the presence of a base selected from the group consisting of sodium hydride, sodium amide and n-butyllithium to form a compound of the general formula [] [In the formula, X and R represent the same meanings as above. ] It can be produced by obtaining a carboxylic acid ester represented by the following and hydrolyzing it. To explain the raw material compound used in the above production method, the p-substituted cinnamate ester represented by the general formula [] is a linear or branched alkyl ester having about 1 to 5 carbon atoms, preferably methyl or ethyl. An ester is used, which is prepared by the known method of condensing an aromatic aldehyde and an acetate in the presence of an alcoholate (Org-
Synth, Collective Volume, p252~). Further, the halogenated isopropyltriphenylphosphonium represented by the general formula ['] can be produced by reacting triphenylphosphine with the halogenated isopropyl, and the halogen atom in the general formula ['] is a chlorine atom,
Examples include bromine atom and iodine atom, with iodine atom being particularly preferred. Next, to explain the production method of the present invention, the reaction of isopropyltriphenylphosphonium halide with a base is performed using a base in an equimolar to slightly excess amount (molar ratio of about 1.0 to 1.3) as the molar ratio of the raw materials. The reaction is carried out in an organic solvent such as tetrahydrofuran, diethyl ether, dimethyl sulfoxide, dimethoxyethane, or an aliphatic hydrocarbon, preferably under an inert gas atmosphere such as nitrogen, argon, or helium. Regarding the reaction temperature, when using a highly active base such as n-butyllithium, a temperature of 0°C to around room temperature (about 20°C) is sufficient, and the reaction is completed in several minutes to several hours. When using sodium chloride or sodium amide, it is necessary to heat the reaction system.
The reaction is usually carried out at a temperature near the boiling point of the reaction solvent. Furthermore, the ring-forming reaction between the reaction product (ylide compound) of the above-mentioned phosphonium salt and a base and the p-substituted cinnamate ester is carried out using a predetermined amount of the cinnamate ester or the p-substituted cinnamate ester, preferably under an inert gas atmosphere, as in the above reaction. The reaction is carried out, for example, by dropping a solution into the above reaction mixture, and the reaction temperature is preferably from 0° C. to around room temperature, and the reaction is completed in several tens of minutes to several hours. The above general formula obtained by the above reaction operation []
The carboxylic acid ester represented by (removes triphenylphosphine)
The desired compound of the present invention can be obtained by making the mixture acidic by adding an acid such as hydrochloric acid or sulfuric acid. The manufacturing method of the present invention will be specifically explained in Examples below. Example 1 Production of trans-2,2-dimethyl-3-(p-t-butylphenyl)cyclopropanecarboxylic acid (invention compound No. 7) using n-butyllithium as a base 45.4 g of Isopropyltriphenylphosphonium iodide was added, and 66 ml of 15% n-butyllithium-hexane solution was added dropwise at room temperature under a stream of dry nitrogen. After dropping, stir for 30 minutes under nitrogen atmosphere, then 21.8g of p
A solution of -t-butyl cinnamic acid methyl ester dissolved in 30 ml of tetrahydrofuran was added dropwise.
After the addition was completed, the mixture was stirred and reacted for another 1.5 hours.
A potassium hydroxide solution (6 g of potassium hydroxide, 50 ml of methyl alcohol, 20 ml of water) was added under ice cooling. 50% solution of insoluble triphenylphosphine
After stirring at °C for 2 hours, methyl alcohol was distilled off under reduced pressure. 200 ml of water and 300 ml of ethyl ether were added to this residue, and the aqueous layer was further washed with ethyl ether. 1N hydrochloric acid was added to the resulting aqueous layer to make it acidic. The precipitated crystals were extracted with 500 ml of ethyl ether, the ether layer was washed with water and then dried over anhydrous sodium sulfate, and the ethyl ether was distilled off under reduced pressure to obtain 20.9 g (yield: 85%) of crystals.
This crystal was recrystallized from n-hexane with a melting point of 148
The title compound was obtained at ~150°C. Nuclear magnetic resonance absorption spectrum; δ, ppm, CCl ₄ ; 0.92 (3H, S), 1.28 (9H, S), 1.37 (3H, S),
1.98 (1H, d, J = 6.0Hz), 2.57 (1H, d, J
= 6.0Hz), 6.99 (2H, d, J = 8.0Hz), 7.22
(2H, d, J = 8.0Hz), 11.06 (1H, S) Example 2 Production of the present invention compound No. 7 using sodium amide Sodium amide was added to 50 ml of tetrahydrofuran.
0.51 g and 4.8 g of isopropyltriphenylphosphonium iodide were added, and the mixture was heated to reflux under a nitrogen atmosphere. After 10 minutes, the mixed solution became a homogeneous reddish-brown solution. This solution was further heated under reflux for 2 hours and then allowed to cool. A solution of 1.85 g of pt-butylcinnamic acid methyl ester dissolved in 10 ml of tetrahydrofuran was added to the mixture at room temperature, and the mixture was allowed to react for an additional hour. This reaction mixture was subjected to a hydrolysis reaction according to Example 1 to obtain the desired title compound 1.6.
g (yield 77%). The nuclear magnetic resonance absorption spectrum of the compound obtained here was the same as that obtained in Example 1. Example 3 Production of compound No. 7 of the present invention using sodium hydride 6 g of sodium hydride and 48 g of isopropyltriphenylphosphonium iodide were added to 500 ml of tetrahydrofuran, and the mixture was heated under reflux for 8 hours under a nitrogen atmosphere. After cooling, a solution of 9.3 g of pt-butyl cinnamic acid methyl ester dissolved in 20 ml of tetrahydrofuran was added and stirred for 3 hours to react. This mixed solution was subjected to a hydrolysis reaction according to Example 1 to obtain 9.9 g of the desired title compound.
was obtained (yield 94.7%). The nuclear magnetic resonance absorption spectrum of the obtained compound was the same as that obtained in Example 1. Example 4 Production of trans-2,2-dimethyl-3-(p-trifluorobutylphenyl)-cyclopropanecarboxylic acid (invention compound No. 11) 45.4 g of isopropyltriphenylphosphonium iodide (in 200 ml of tetrahydrofuran) 0.105 mol) and 66 ml at room temperature (21℃) under a stream of dry nitrogen.
15% n-butyllithium-hexane solution (n-
Butyl lithium (0.105 mol) was added dropwise. After the completion of the dropwise addition, after stirring for another 30 minutes under nitrogen atmosphere, methyl p-trifluoromethylcinnamate 23.0
g (0.10 mol) in tetrahydrofuran (30 ml) was added dropwise. After the dropwise addition was completed, the reaction was continued with stirring for an additional 1.5 hours, and then a potassium hydroxide solution (6 g of KOH, 50 ml of methanol, 20 ml of water) was added under ice cooling.
After removing insoluble triphenylphosphine from the reaction system, the solution was stirred at 50°C for 2 hours, and then methanol was distilled off under reduced pressure. To this residue were added 200 ml of water and 300 ml of ethyl ether, and the aqueous layer was further washed with ethyl ether. The resulting aqueous layer was made acidic by adding 1N hydrochloric acid. The precipitated crystals are ethyl ether 500
ml, the ether layer was washed with water, dried over anhydrous sodium sulfate, ethyl ether was distilled off under reduced pressure, and the melting point was determined.
20.6 g of crystals (yield: 80%) were obtained at 83.0-85.0°C. Nuclear magnetic resonance absorption spectrum: δ, ppm, CCl ₄ 0.95 (3H, S), 1.42 (3H, S), 1.95 (1H, d,
J = 6.0Hz), 2.68 (1H, d, J = 6.0Hz), 7.18
(2H, d, J=8.0Hz), 7.47 (2H, d, J=8.0
Hz), 11.10 (1H, S) The following reaction materials were the same as in Example 4 (however, the corresponding compound was used for p-substituted methyl cinnamate), reaction solvent (tetrahydrofuran), reaction conditions, and post-treatment as listed in Table 2. The compound of the present invention was produced. The results are shown in Table 2.

【table】

【table】

[Table] *Attribution of NMR absorption in the compounds of the present invention


It has been confirmed that the following known compounds can be similarly produced by the production method of the present invention. trans-2,2-dimethyl-3-(p-chlorophenyl)-cyclopropanecarboxylic acid Reaction yield 87%, melting point 139-141°C trans-2,2-dimethyl-3-(p-methylphenyl)-cyclopropanecarboxylic acid Acid Reaction yield 85%, melting point 140-142°C Trans-2,2-dimethyl-3- of the present invention
(p-substituted phenyl)-cyclopropanecarboxylic acid has the following reaction formulas [A] to [D] [In the formula, X has the same meaning as above, Hal represents a halogen atom, M represents an alkali metal, and R ¹ is a group

Eliminate [expression]. ] The ester derivatives can be derived from various agricultural and horticultural pests such as sanitary pests such as houseflies and mosquitoes, as well as various agricultural and horticultural pests such as leafhoppers, leafhoppers, fall armyworms, peach aphids, apple spider mites, citrus spider mites, two-spotted spider mites, and false red spider mites. [Applicant's Japanese Patent Application No. 53-38968, No. 53-
No. 112107 and the application specification dated June 26, 1978 (title of the invention: "Novel carboxylic acid ester, process for producing the same, and insecticide and acaricide containing the same")].

Claims (1)

[Claims] 1. General formula [] In the formula, X represents a substituent selected from the group consisting of tert-butyl group, trifluoromethyl group, and trimethylsilyl group. trans-2,2-dimethyl-3-
(p-substituted phenyl)cyclopropanecarboxylic acid. 2 General formula [] In the formula, X represents a substituent selected from the group consisting of a tertiary butyl group, a trifluoromethyl group, and a trimethylsilyl group, and R represents a lower alkyl group. p-substituted cinnamate ester represented by the general formula [] By reacting isopropyltriphenylphosphonium iodide represented by the formula in the presence of a base selected from the group consisting of sodium hydride, sodium amide and n-butyllithium, the general formula [] [In the formula, X and R represent the same meanings as above. ] A general formula characterized by obtaining a carboxylic acid ester represented by and hydrolyzing it [] [In the formula, X represents the same meaning as above. ] Trans-2,2-dimethyl-3- represented by
A method for producing (p-substituted phenyl)-cyclopropanecarboxylic acid.