JPH0768199B2 - Glycine ester derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to the general formula [I] useful as a synthetic intermediate for insecticidal and acaricidal compounds. [In the formula, R and R ′ are the same or different and each represents a lower alkyl group. ] It is related with the N-propargyl-N-alkoxycarbonyl glycine ester shown by these.

More specifically, the present invention has the general formula [II] [In the formula, R ₁ represents a lower alkyl group, a lower alkenyl group or a lower alkynyl group, and R ₂ represents Represents a group represented by. Here, R ₃ represents a hydrogen atom or a methyl group, R ₄ represents a methoxyiminomethyl group, a 2,2-dimethylvinyl group or a 2,2-dihalovinyl group, R 4
₅ represents a methyl group, a methoxy group, a halogen atom or a 3,4-methylenedioxy group, and n represents 1 or 2. ] It is related with the useful synthetic intermediate in manufacture of the pyrethroid type compound shown by these.

<Prior Art> The compound represented by the general formula [II] has excellent insecticidal and acaricidal activity. [In the formula, R ₁ represents the same meaning as described above. ] The general formula [IV] derived from 1-substituted-2,4-dioxoimidazolidine represented by [In the formula, R ₁ represents the same meaning as described above. Alcohol compound with the general formula (V) R ₂ -COOH (V) [represented by the formula], R ₂ are as defined above. ] It is known that it can be obtained by reacting with a carboxylic acid represented by or a reactive derivative thereof (US Pat. No. 4,176,189).

By the way, 1-substituted-2,4 represented by the above general formula [III]
As a method for producing -dioxoimidazolidine, a method of reacting an N-substituted-α-amino acid with potassium cyanate or urea is known (Chemical Review Vol. 46,
407 and 413, 1950).

<Problems to be Solved by the Invention> However, in the above-mentioned method for producing 1-substituted-2,4-dioxoimidazolidine, for example, when the substituent is a propargyl group, N-propargylglycine, which is difficult to obtain as an industrial raw material, is produced. There was a problem that it had to be used.

<Means for Solving Problems> Therefore, the inventors of the present invention have formulas that are raw material compounds of insecticides and acaricides. As a result of an examination on a method for producing 1-propargyl-2,4-dioxoimidazolidine represented by the formula, it was found that the compound represented by the general formula [I] is a very useful synthetic intermediate, and the present invention was completed. It was

That is, the present invention relates to a compound represented by the above general formula [I] (hereinafter referred to as the compound of the present invention). The production method of the compound of the present invention is described below.

The compound of the present invention has the general formula [VII] [In the formula, R and R'represent the same meaning as described above. ] It can manufacture by making N-alkoxy carbonyl glycine ester shown by these and propargyl halide react in the presence of a base.

In this reaction, propargyl halide is represented by the general formula [VI
I] is used in an amount of 1 to 10 equivalents and a base of 1 to 1.5 equivalents based on 1 equivalent of the N-alkoxycarbonylglycine ester. The reaction is usually carried out in an inert solvent, and examples of such a solvent include alcohols such as methanol, ethanol and t-butanol, ethers such as tetrahydrofuran and 1,2-dimethoxyethane, benzene, toluene and the like. Aromatic hydrocarbons, dimethylsulfoxide, N, N-dimethylformamide (DMF) and the like, or a mixture thereof. As the base used,
Examples thereof include sodium hydride and potassium t-butoxy. The reaction temperature is usually -30 to 120 ° C, and the reaction time is 15 minutes to 10 hours. Further, this reaction is preferably carried out in a nitrogen atmosphere.

The compound of the present invention thus obtained has the general formula [VIII] by reacting it with aqueous ammonia or ammonia gas. [In the formula, R represents the same meaning as described above. ] The amide compound of formula [VI] can be derived, and the amide compound can be converted to the compound of formula [VI] by reacting with a base.

The above two-step reaction can be carried out continuously in one container without isolating the compound represented by the general formula [VIII].

The N-alkoxycarbonylglycine ester represented by the general formula [VII], which is a starting material for producing the compound of the present invention, can be prepared by the method described in Chemische Berichite Vol. 114, pp. 173-189 (1981). Obtainable.

<Example> The production method of the compound of the present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.

Example 1 5.0 g of N-methoxycarbonylglycine methyl ester
It was dissolved in 30 ml of DMF, 1.5 g of sodium hydride (60% oily) was added under ice cooling under a nitrogen atmosphere, and the mixture was stirred for 20 minutes. Then, 6.0 g of propargyl bromide was added dropwise over 15 minutes, and the mixture was further stirred for 40 minutes. The reaction solution was poured into ice water, sodium chloride was added to saturate, and the aqueous layer was washed with hexane. Next, the aqueous layer was extracted twice with 100 ml of ether, the ether layers were combined, dried over magnesium sulfate and the solvent was distilled off to obtain 3.9 g of N-propargyl-N-methoxycarbonylglycine methyl ester.

N ¹⁸ _D 1.4891 Example 2 3.0 g of N-methoxycarbonylglycine methyl ester
After dissolving in 30 ml of DMF, 820 mg of sodium hydride (60% oily) was added under ice cooling under a nitrogen atmosphere, and the mixture was stirred for 20 minutes. Next, 2.3 g of propargyl chloride was added dropwise over 10 minutes, and the mixture was further stirred for 40 minutes. The reaction solution was poured into ice water, sodium chloride was added to saturate, and the aqueous layer was washed with hexane. Next, the aqueous layer was extracted twice with 100 ml of ether, the ether layers were combined and dried over magnesium sulfate, and then the solvent was distilled off to obtain 1.95 g of N-propargyl-N-methoxycarbonylglycine methyl ester.

Example 3 100 g of N-methoxycarbonylglycine ethyl ester
After dissolving in 600 ml of DMF, 25 g of sodium hydride (60% oily) was added under ice cooling under a nitrogen atmosphere. After stirring the reaction solution for 2 hours, 81.3 g of propargyl bromide was added dropwise to the reaction solution over 2 hours. After further stirring for 1 hour, the reaction solution was poured into water and the aqueous layer was washed with hexane. Then extract from the aqueous layer three times with ether, combine the ether layers, wash with water,
After drying over magnesium sulfate, the solvent was distilled off to obtain 79.8 g of N-propargyl-N-methoxycarbonylglycine ethyl ester.

Next, an example in which the compound represented by the formula (VI) is produced from the compound of the present invention will be shown as a reference example.

Reference Example 1 N-propargyl-N-methoxycarbonylglycine
To 20 ml of a methanol solution containing 650 mg of methyl ester, 700 mg of 28% sodium methoxide (methanol solution) was added, and ammonium gas was blown into the solution at room temperature. After stirring at room temperature for 2 hours, the mixture was heated under reflux for 30 minutes. Then, the mixture was cooled to room temperature, neutralized with hydrogen chloride gas and concentrated to remove inorganic salts, and then the solvent was distilled off from the solution to obtain 510 mg of N-propargyl-2,4-dioxoimidazolidine.

Reference Example 2 N-propargyl-N-methoxycarbonylglycine
3.0 g of methyl ester was dissolved in 40 ml of 28% ammonia water,
It was kept under pressure (10 to 13 Kg / cm ² ) at 100 to 110 ° C. for 1 hour.
Then, the solvent was distilled off, and the residue was subjected to silica gel column chromatography (elution solvent; ethyl acetate: methanol = 5: 1) to give 1-propargine-2,4-dioxoimidazolidine.
0.65 g was obtained.

Reference Example 3 (i) 3.9 g of N-propargyl-N-methoxycarbonylglycine methyl ester was added to a mixed solution of 100 ml of 28% aqueous ammonia and 10 ml of methanol, and the mixture was stirred at room temperature for 10 hours. Then, the solvent was distilled off, and the residue was treated by silica gel column chromatography to obtain 3.0 g of N-propargyl-N-methoxycarbonylglycinamide.

mp 77-80 ° C. (ii) N-propargyl-N-methoxycarbonylglycinamide 2.0 g was added to a mixed solution of 5 ml of methanol and 2.5 ml of 20% sodium hydroxide aqueous solution, and kept at 70 ° C. for 1 hour. After cooling to room temperature, it was neutralized with concentrated hydrochloric acid and concentrated to dryness under reduced pressure. After extraction with acetonitrile to remove sodium chloride, the solvent was distilled off from the solution to give 1-propargyl-2,4-
1.4 g of dioxoimidazolidine was obtained.

mp 124-125 ° C. <Effect of the invention> The compound of the present invention is a synthetic intermediate useful for producing insecticidal and acaricidal compounds, and an insecticidal and acaricidal compound can be easily obtained by way of the compound of the present invention. It can be manufactured.

Claims (1)

[Claims] 1. A general formula [In the formula, R and R ′ are the same or different and each represents a lower alkyl group. ] N-propargyl-N-alkoxycarbonyl glycine ester shown by these.