JPS63238066A - Production of imidazolidine derivative - Google Patents

Abstract

PURPOSE:To readily obtain the titled compound useful as a synthetic intermediate for pyrethroid compound having insecticidal and acaricidal activity, by reacting an amide compound readily obtainable as an industrial raw material with a base. CONSTITUTION:An amide compound shown by formula I (R is lower alkyl) is used as a raw material and reacted with a base such as sodium hydroxide, sodium methoxide or ammonia to give the aimed compound. The amounts of the amide compound shown by formula I and the base used are >=1 equivalent base based on 1 equivalent compound shown by formula I. When ammonia is used as the base, the reaction is ordinarily carried out under several kg/ cm<2>-100kg/cm<2> pressure. The compound shown by formula I is obtained by amidating an ester compound shown by formula II (R' is lower alkyl) and the compound shown by formula II is prepared by reacting a compound shown by formula III with a propargyl halide.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention is directed to l-propargyl-2,4-dioquinimidazolidine C represented by the formula CI), hereinafter referred to as compound CI]. ).

More specifically, the present invention is based on the general formula [■] [wherein R1 represents a lower alkyl group, lower aldenyl group or lower alkynyl group, and represents a group represented by R7]. Here R1
represents a hydrogen atom or a methyl group, and R1 is a methoxyiminomethyl group, a 2.2-dimethylvinyl group, or a 2.2-dimethylvinyl group.
-dihalobinyl group, R5 represents a methyl group, methoxy group, halogen atom or 8,4-methylenedioxy group, and n does not represent 1 or 2; ] <Prior art> Regarding the production method of compound CI), which is a useful synthetic intermediate in the production of pyrethroid compounds, the compound represented by the above general formula (II) has excellent insecticidal and acaricidal activity. It has the general formula (Ill) [wherein, l
ri has the same meaning as above. ] An alcohol compound represented by the general formula (ffl [wherein R8 represents the same meaning as above]) derived from the t-4-substituted-2,4-dioxoimidazolidine and the general formula [ma]^ -COOHm [In the formula, R1 represents the same meaning as above.] It is known that it can be obtained by reacting with a carboxylic acid represented by the following formula or a reactive derivative thereof (IFF No. 4
No. 176189).

By the way, 1-substituted- represented by the above general formula ([[I)]
As a method for producing 2,4-dioquinoimidazolidine, N
A method is known in which an f + & substituted α-amino acid is reacted with potassium cyanate or urea (Chemica
l Review Volume 46, Pages 4 and 41
3, 1950).

<Problems to be Solved by the Invention> However, in the method for producing 1-; There was a problem in that it was necessary to use a very pure N-propargylglycine.

Means for Solving the Problems> Therefore, the back of the present invention is to develop a manufacturing method for the compound CI'l, which is a raw material for insecticides and acaricides. The present inventors have discovered that a compound CI) can be obtained by reacting an amide compound represented by °C0] with a 1Ji group, in which R represents a lower alkyl group, and a compound CI) can be obtained.

In the method of the present invention, the base is usually used in an amount of 1 equivalent or more to 1 equivalent to 1 equivalent of the amide compound 'ri711 represented by the general formula [■].
Examples of bases used include hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and barium hydroxide; alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide; and ammonia. is kicked out. When using ammonia as the base, add 4 to the usual number! /cti -100
React under the pressure of castle 4d. The reaction temperature is usually 10-2
In the range of 00°C, the reaction time is in the range of 15 minutes to 5 hours. The reaction is usually carried out in an inert solvent, such as water, alcohols such as methanol and ethanol, ethers such as dioxane and tetrahydrofuran, or mixtures thereof.

After the reaction is completed, it is usually neutralized using an acid such as chloride water blade gas, hydrochloric acid, or sulfuric acid, and after distilling off the solvent, extraction is performed using an alcohol such as methanol or ethanol, acetonitrile, acetone, etc. By doing so, inorganic salts are removed, concentration is performed, and if necessary, processing operations such as recrystallization and chromatography are performed.

The amide compound represented by the general formula [■] which is the starting material for this reaction is represented by the general formula [■] [wherein R represents the same meaning as above and RI represents a lower alkyl group. ] It can be obtained by amidating the ester compound shown below. The amidation reaction is carried out using alcohols such as methanol and ethanol as a solvent, and
This can be carried out by reacting a large excess of aqueous ammonia at a temperature of 100° C. under normal pressure or by blowing ammonia gas. This amidation reaction can be promoted by adding an alkoxide.

The amide compound represented by the general formula [■] obtained by the above reaction can be used as a raw material compound for the method of the present invention without being isolated or purified.

Furthermore, the compound represented by the general formula [R] is represented by the general formula [R].
ν厘] [Wherein, R and klf represent the same meanings as above. ] Compound (Chemische Berich
te, Vol. 114, pp. 178-189, 1981) and propargyl halide.

<Examples> The method of the present invention will be specifically explained below using Examples, but the present invention is not limited thereto.

Example 1 N-propargyl-N-methoxycarbonylglycinamide 2. 20% hydroxylation of Of with methanol 5) I
The mixture was added to a mixture with 2.5 ml of a Jium aqueous solution and kept at 70°C for 1 hour. After cooling to room temperature, the mixture was neutralized with concentrated hydrochloric acid and evaporated to dryness under reduced pressure.

After extracting with acetonitrile to remove the salt, the solvent was distilled off from the r solution to obtain 1.42 of 1-propargyl-2°4-dioquinimidazolidine.

mp 124-125°C Example 2 Methanol solution of sodium methoxide 0.52 80
ml IcN-methoxycarbonylglycinamide 1.
51 was added and kept at 70°C for 1 hour.

The mixture was then cooled to room temperature, neutralized with concentrated hydrochloric acid, and then the solvent was distilled off. The residue was extracted with acetonitrile, the inorganic salts were removed, and the solvent was distilled off from the solution to obtain 1-propargyl-2.
, 0.96f of 4-dioxoimidazolidine was obtained.

Example 8 N-f lopargyl-N-methoxycarbonylglycine
Methyl ester 650μ methanol solution 20g/2
8% sodium methoxide (methanol solution) 7001
119 was added, and ammonia gas was blown in at room temperature. After stirring at room temperature for 2 hours, the mixture was heated under reflux for 30 minutes. The mixture was then cooled to room temperature, neutralized with hydrogen chloride gas, concentrated, the inorganic salts were removed, and the solvent was distilled off from the liquid to give N-propargyl-2,4-dioquinimidazolidine 510■ .

Example 4 N-propalyl-N-methoxycarbonylglycine
Methyl ester a, or 28% ammonia water 40 m
Dissolve in l and pressurize (l Oml 8Kv'ctjly,
The temperature was kept at too~110°C for 1 hour. Then, the solvent was distilled off, and the mixture was subjected to silica gel column chromatography (elution solvent: ethyl acetate: methanol (25:1)), and 0.65 t of l-propargyl-2,4-dioxoimidazolidine was added to 14 ft.

Next, the general formula [)1] which is the raw material compound of the method of the present invention
A manufacturing example of the compound represented by is shown in Reference Example.

Reference example (11N-methoxycarbonylglycine methyl ester 5.Of I) was dissolved in 80 g of MF, and under a nitrogen atmosphere,
While cooling with water, 1.5 f of sodium hydride (60% oil) was added and stirred for 20 minutes. Next, propargyl bromide 6,
Of was added dropwise over 15 minutes, and the mixture was further stirred for 40 minutes. The reaction solution was diluted with ice water, saturated with sodium chloride, and the aqueous layer was washed with hexane. Next, add ether l 00 from the aqueous layer.
ml twice, the ether layers were combined, dried over magnesium sulfate, the solvent was distilled off, and N-propargyl-
N-methoxycarbonylglycine methyl ester 8.9
I got 2.

n" 1.4891 (11) Add 8.9f of N-propargyl-N-methoxycarbonylglycine methyl ester to a mixture of 100ml of 28% aqueous ammonia and 10ml of methanol,
The mixture was stirred at room temperature for 10 hours.

Then, the solvent was distilled off and the residue was treated with silica gel column chromatography to obtain N-propargyl-N-methoxycarbonylglycinamide 8. Of is changed to fzI.

ntp77-80C <Effects of the Invention> According to the method of the present invention, l-proparzel 2゜4, which is an acid-containing intermediate necessary for insecticidal and acaricidal compounds, is obtained from easily available raw material compounds as raw materials. - Dioquinimidazolidines can be produced.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R represents a lower alkyl group. ] A method for producing 1-propargyl-2,4-dioxoimidazolidine, which comprises reacting an amide compound represented by the following with a base.