Method for purifying phenylhydrazine-beta-carboxylate compound

Abstract

The present invention provides a method of separating and removing the impurities contained in a colature of a phenylhydrazine-beta-carboxylate compound (I) effectively, and preventing the loss of the phenylhydrazine-beta-carboxylate compound, to thereby obtain the purified phenylhydrazine-beta-carboxylate compound (I) having less impurities. The method for purifying the phenylhydrazine-beta-carboxylate compound (I) comprises the steps of mixing the colature of the phenylhydrazine-beta-carboxylate compound (I), water and an organic solvent capable of being separated from the water, at the present of acid, and then separating the mixture into an oil layer having the phenylhydrazine-beta-carboxylate compound (I) and a water-containing layer.

Description

Background of the invention

[0001] The present invention relates to a method for purifying a phenylhydrazine-β-carboxylate compound represented by formula (I) [hereinafter sometimes referred to as phenylhydrazine-β-carboxylate compound (I)]:

[0002] [Chemical formula 1]

[0003]

[0004] Where R 1 Represents hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, alkoxy group, aryl group, aralkyl group, aryloxy group, aralkoxy group or carboxyalkyl group, R 2 Represents an alkyl group having 1 to 4 carbon atoms.

[0005] It is known that the phenylhydrazine-β-carboxylate compound (I) can be used as an intermediate material for the production of medical and agricultural chemicals. For example, it is known that the phenylhydrazine-β-carboxylate compound (I) is produced, for example, by reacting a phenylhydrazine compound with a halide alkyl carbonate, and the formed phenylhydrazine-β-carboxylate compound (I ) Contains different impurities. As a method of purifyin...

Examples

Embodiment

[0068] Hereinafter, examples of the present invention will be shown, but the present invention is not limited thereto. It should be noted that in the examples, 2-(2-methoxyphenyl)hydrazine-1-carboxylic acid methyl ester [the compound represented by formula (I)] was analyzed and calculated by high performance liquid chromatography, wherein R 1 Is methoxy, R 2 Is the content of methyl], 2-(2-methoxyphenyl)hydrazine-2-carboxylic acid methyl ester [the compound represented by formula (II), where R 1 Is methoxy, and R 2 Is the content of methyl] and o-methoxyphenylhydrazine [the compound represented by formula (III), where R 1 Is the content of methoxy].

reference example 1

[0070] Put a mixed solution of 159.46g of 17.97g (0.13mol) of o-methoxyphenylhydrazine, 141.49g of toluene, 55.32g (3.07mol) of water, and 20.79g (0.13mol) of sodium hydroxide in a 300mL flask 25% by weight of the aqueous solution and stirred at 3°C ​​for 0.1 hour. After stirring, while stirring and maintaining the obtained liquid mixture at 3°C, 11.36 g (0.12 mol) of methyl chlorocarbonate was added dropwise within 0.5 hours. Further, the mixture was stirred at 3°C ​​for 0.5 hour, then heated to 65°C, and stirred at 65°C for 0.5 hour. After stirring, the stirring was stopped, and the mixture was allowed to stand at 65°C for 0.2 hours to perform oil-water separation, and thereafter, 16.13 g of water was added to the obtained oil layer and stirred at 65°C for 0.5 hours. After stirring, the stirring was stopped, and the mixture was subjected to oil-water separation by standing at 65°C for 0.2 hours, after which 101.62 g of toluene was added to the obtained oil layer, and the mix...

Embodiment 1

[0072] The content of the crude product (i) (6.30g) [2-(2-methoxyphenyl)hydrazine-1-carboxylate: 2.51mmol, 2-(2-methoxy The content of methyl phenyl)hydrazine-2-carboxylate: 0.23 mmol] was stirred, 0.41 g (0.56 mmol) of 5 wt% hydrochloric acid was added, and the mixture was stirred at 65°C for 1 minute. After stirring, the mixture was subjected to oil-water separation by allowing it to stand at 65°C for 1 minute. While maintaining the temperature at 65°C, the obtained oil layer was stirred, 0.29 g of water was added and stirred at 65°C for 1 minute. After stirring, the mixture was subjected to oil-water separation by allowing it to stand at 65°C for 1 minute, and 6.18 g of an oil layer (A) was recovered. The oil layer (A) was analyzed by high performance liquid chromatography, and it was determined that the content of methyl 2-(2-methoxyphenyl)hydrazine-1-carboxylate in the oil layer (A) was 7.76 wt% ( 2.44 mmol), and the content of methyl 2-(2-methoxyphenyl)hydrazine-2-carbo...

Background of the invention

[0001] The present invention relates to a method for purifying a phenylhydrazine-β-carboxylate compound represented by formula (I) [hereinafter sometimes referred to as phenylhydrazine-β-carboxylate compound (I)]:

[0002] [Chemical formula 1]

[0003]

[0004] Where R 1 Represents hydrogen atom, alkyl group, cycloalkyl group, alkenyl group, aralkyl group, alkoxy group, aryl group, aralkyl group, aryloxy group, aralkoxy group or carboxyalkyl group, R 2 Represents an alkyl group having 1 to 4 carbon atoms.

[0005] It is known that the phenylhydrazine-β-carboxylate compound (I) can be used as an intermediate material for the production of medical and agricultural chemicals. For example, it is known that the phenylhydrazine-β-carboxylate compound (I) is produced, for example, by reacting a phenylhydrazine compound with a halide alkyl carbonate, and the formed phenylhydrazine-β-carboxylate compound (I ) Contains different impurities. As a method of purifyin...

Examples

Embodiment

[0068] Hereinafter, examples of the present invention will be shown, but the present invention is not limited thereto. It should be noted that in the examples, 2-(2-methoxyphenyl)hydrazine-1-carboxylic acid methyl ester [the compound represented by formula (I)] was analyzed and calculated by high performance liquid chromatography, wherein R 1 Is methoxy, R 2 Is the content of methyl], 2-(2-methoxyphenyl)hydrazine-2-carboxylic acid methyl ester [the compound represented by formula (II), where R 1 Is methoxy, and R 2 Is the content of methyl] and o-methoxyphenylhydrazine [the compound represented by formula (III), where R 1 Is the content of methoxy].

reference example 1

[0070] Put a mixed solution of 159.46g of 17.97g (0.13mol) of o-methoxyphenylhydrazine, 141.49g of toluene, 55.32g (3.07mol) of water, and 20.79g (0.13mol) of sodium hydroxide in a 300mL flask 25% by weight of the aqueous solution and stirred at 3°C ​​for 0.1 hour. After stirring, while stirring and maintaining the obtained liquid mixture at 3°C, 11.36 g (0.12 mol) of methyl chlorocarbonate was added dropwise within 0.5 hours. Further, the mixture was stirred at 3°C ​​for 0.5 hour, then heated to 65°C, and stirred at 65°C for 0.5 hour. After stirring, the stirring was stopped, and the mixture was allowed to stand at 65°C for 0.2 hours to perform oil-water separation, and thereafter, 16.13 g of water was added to the obtained oil layer and stirred at 65°C for 0.5 hours. After stirring, the stirring was stopped, and the mixture was subjected to oil-water separation by standing at 65°C for 0.2 hours, after which 101.62 g of toluene was added to the obtained oil layer, and the mix...

Embodiment 1

[0072] The content of the crude product (i) (6.30g) [2-(2-methoxyphenyl)hydrazine-1-carboxylate: 2.51mmol, 2-(2-methoxy The content of methyl phenyl)hydrazine-2-carboxylate: 0.23 mmol] was stirred, 0.41 g (0.56 mmol) of 5 wt% hydrochloric acid was added, and the mixture was stirred at 65°C for 1 minute. After stirring, the mixture was subjected to oil-water separation by allowing it to stand at 65°C for 1 minute. While maintaining the temperature at 65°C, the obtained oil layer was stirred, 0.29 g of water was added and stirred at 65°C for 1 minute. After stirring, the mixture was subjected to oil-water separation by allowing it to stand at 65°C for 1 minute, and 6.18 g of an oil layer (A) was recovered. The oil layer (A) was analyzed by high performance liquid chromatography, and it was determined that the content of methyl 2-(2-methoxyphenyl)hydrazine-1-carboxylate in the oil layer (A) was 7.76 wt% ( 2.44 mmol), and the content of methyl 2-(2-methoxyphenyl)hydrazine-2-carbo...

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