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Process for synthesis of intermediates useful for preparing 1,3,4-triazine derivatives

A mixture, diethyl technology, used in the preparation of amino compounds by condensation/addition reactions, the preparation of hydrazones, organic chemical methods, etc., can solve the problems of complex side reactions in harmful oxidation reactions

Inactive Publication Date: 2018-07-31
FMC CORP
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

A disadvantage of this method is the conversion involved from diethyl malonate to diethyl ketomalonate, which is an inherently deleterious oxidation reaction and involves undesirably complex side reactions

Method used

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  • Process for synthesis of intermediates useful for preparing 1,3,4-triazine derivatives
  • Process for synthesis of intermediates useful for preparing 1,3,4-triazine derivatives
  • Process for synthesis of intermediates useful for preparing 1,3,4-triazine derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] Example 1 - Preparation of DMP using Cl-DEM

[0021]

[0022] 9.9 g of diethyl 2-chloromalonate were dissolved in 50 g of acetonitrile. The reaction solution was heated to 60°C. During reflux, 13.3 g of 41% methylhydrazine were added dropwise to the solution at 60°C. The reaction was monitored by gas chromatography ("GC"). After the reaction was completed within 4 hours (residual diethyl 2-chloromalonate < 1% in the reaction, determined by gas chromatography), water and toluene were added to extract the product. The toluene phase was concentrated to give 8.3 g of diethyl 2-(2-methylhydrazono)malonate as an oil. The purity is 71.3%. The yield was 58.6%.

Embodiment 2

[0023] Example 2 - Preparation of DMP using diBr-DEM

[0024]

[0025] 13.6 g of 41% methylhydrazine were dissolved in 13.6 g of ethanol. At 20°C to 40°C, 13.2 g of diethyl 2,2-dibromomalonate was added dropwise to the solution. The reaction was monitored by GC. After the reaction was completed within 6 hours (<1% diethyl 2,2-dibromomalonate remaining in the reaction, determined by gas chromatography), water and toluene were added to extract the product. The toluene phase was concentrated to give 7.7 g of diethyl 2-(2-methylhydrazono)malonate as an oil. The purity is 81.6%. The yield was 77.7%.

Embodiment 3

[0026] Example 3 - Preparation of DMP using Br-DEM

[0027]

[0028] 11 g of 41% methylhydrazine were dissolved in a mixture of 30 g ethanol and 1.2 g acetic acid. At 50°C to 60°C, 10 g of diethyl 2-bromomalonate was added dropwise to the solution. The reaction was monitored by GC. After the reaction was complete within 2 hours (diethyl 2-bromomalonate <1%, determined by gas chromatography), water and toluene were added to extract the product. The toluene phase was concentrated to give 8.5 g of diethyl 2-(2-methylhydrazono)malonate as an oil. The purity is 74.5%. The yield was 78.9%.

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Abstract

A process for the synthesis of the intermediate useful for the preparation of 1,3,4-triazines, are disclosed.

Description

technical field [0001] The present invention relates to a process for the synthesis of intermediates useful in the preparation of 1,3,4-triazines, more specifically 2-(2-methylhydrazinylidene)malonic acid 1, 3-diethyl ester. Background technique [0002] 1,3,4-Triazine-based derivatives are a subgroup of triazines, and many of them exhibit herbicidal activity and have been synthesized and widely used to protect crops against weeds. Recently, SHIBAYAMA, Atsushi et al. reported novel 1,3,4-triazine-based derivatives in WO 2012 / 002096A. [0003] 1,3-Diethyl 2-(2-methylhydrazono)malonate (“DMP”) is an important intermediate for the preparation of 1,3,4-triazine-based derivatives and is mainly used to form 1,3,4-triazine ring. For DMP preparation, diethyl malonate is often used as starting material and is first converted to diethyl ketomalonate. Then, the obtained diethyl ketomalonate was reacted with methylhydrazine to obtain DMP. A disadvantage of this process is the conve...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C209/60C07C69/38
CPCC07C249/16C07C251/76C07B43/00
Inventor 许胜许宜晖
Owner FMC CORP