Preparation method for substituted pyridine dicarboxylic acid derivative

A technology of dipicolinic acid and derivatives, which is applied in the field of preparation of substituted dipicolinic acid derivatives, can solve the problems of a large number of waste liquids, harsh process conditions, complicated preparation processes, etc., and achieves the effect of improving yield

Inactive Publication Date: 2019-03-15
SHENYANG SCIENCREAT CHEM
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0007] The present invention aims at the problems that the existing preparation of 5-methoxymethyl-2,3-pyridinedicarboxylic acid requires that the reaction system be anhydrous, the process conditions are harsh and the preparation process is complicated, and a large amount of waste liquid will be produced, which is not environmentally friendly. Provide a kind of preparation method of 5-methoxymethyl-2,3-pyridine dicarboxylic acid derivative

Method used

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  • Preparation method for substituted pyridine dicarboxylic acid derivative
  • Preparation method for substituted pyridine dicarboxylic acid derivative
  • Preparation method for substituted pyridine dicarboxylic acid derivative

Examples

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Embodiment 1

[0048] This embodiment provides a preparation method of substituted dipicolinic acid derivatives, comprising the following preparation steps:

[0049] (1) Put 0.418mol 5-methylpyridine-2,3-dicarboxylate diethyl into 2.090mol 1,2-dichloroethane, start stirring, heat up to 80°C, add 0.004mol azobisiso Mix butyronitrile and 0.250mol bromine, control the same temperature and add bromine dropwise to the 1,2-dichloroethane solution of 5-methylpyridine-2,3-dicarboxylate, keep warm after the dropwise addition After 2 hours, the temperature was lowered to obtain a solution of 5-bromomethylpyridine-2,3-dicarboxylic acid diethyl ester;

[0050](2) Transfer the solution of diethyl 5-bromomethylpyridine-2,3-dicarboxylate into a pressure vessel, feed trimethylamine gas to 6 atm, start stirring, keep at 20°C for 5 hours, and add additional Trimethylamine keeps pressure 6atm, and reaction finishes, is distilled to pH=7, adds 183 gram waters, layering, organic phase continues to be used in st...

Embodiment 2

[0053] (1) Add 0.418mol 5-methylpyridine-2,3-dicarboxylate to 12.540mol chlorobenzene, start stirring, heat up to 100°C, mix 0.021mol dimethyl azobisisobutyrate and 0.418 mol bromosuccinimide is mixed, and bromosuccinimide is put into the chlorobenzene solution of 5-methylpyridine-2,3-dicarboxylate at the same temperature, and the reaction is kept for 6 hours after the addition is completed. , cooling to obtain a solution of 5-bromomethylpyridine-2,3-dicarboxylic acid dimethyl ester;

[0054] (2) Transfer the solution of dimethyl 5-bromomethylpyridine-2,3-dicarboxylate into a pressure vessel, feed trimethylamine gas to 4.5atm, start stirring, keep 35°C for 3.5 hours, and make up the reaction process Add trimethylamine to keep the pressure at 4.5atm, the reaction is over, distill to pH=9, add 40 grams of water, separate layers, the organic phase continues to be used for step (1) synthesis, and obtains 134 grams of water phase, which is the 70% quaternary ammonium made Saline s...

Embodiment 3

[0057] (1) Add 0.418mol 5-methylpyridine-2,3-dicarboxylate into 7.106mol chloroform, start stirring, heat up to 60°C, mix 0.012mol azobisisobutylimidazoline hydrochloride and 0.335 mol of sodium hypochlorite was mixed, and sodium hypochlorite was added dropwise into the chloroform solution of 5-methylpyridine-2,3-dicarboxylate under control of the same temperature. , a chloroform solution of dimethyl 3-dicarboxylate;

[0058] (2) Transfer the solution of dimethyl 5-chloromethylpyridine-2,3-dicarboxylate into a pressure vessel, add triethylamine, start stirring, keep at 120°C for 1.5 hours, and add triethylamine during the reaction process Keep pressure 2.5atm, reaction finishes, distills to pH=8, adds 57 gram waters, layering, organic phase continues to be used in step (1) synthesis, obtains 115 gram water phases, is the 50% quaternary ammonium salt aqueous solution ( Contains quaternary ammonium salt 0.167mol);

[0059] (3) Add 1.003mol sodium hydroxide and 5.016mol methano...

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Abstract

The invention provides a preparation method for a substituted pyridine dicarboxylic acid derivative, belongs to the technical field of organic synthesis, and can solve the problems that the existing preparation method for preparing 5-methoxyl methyl-2,3-dipicolinic acid requires no water in a reaction system, process conditions are rigorous, a preparation flow is complicated, in addition, a largeamount of waste liquid can be produced, and the preparation method is not environment-friendly. According to the preparation method provided by the invention, water is not required to be removed in amethylating process; synthesizing is performed by adding an alkaline in the existence of water; then, acidifying and filtering are performed in a water-containing organic phase, so that the yield of the product can be improved when the product is refined. Meanwhile, because of the existence of the water, the mixture of the product, namely, the 5-methoxyl methyl-2,3-dipicolinic acid and an organicsalt, is directly obtained after filtering; and by the method, a solvent of a filtered waste liquid can be recovered for cycle use, so that the wastewater amount in the method is remarkably less thanthat in the prior art. In addition, the product contains the organic salt, but the product quality can meet the use in preparation of imidazolinone series of compounds.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a preparation method of substituted pyridinedicarboxylic acid derivatives. Background technique [0002] Substituted dipicolinic acid is an intermediate for preparing imidazolinone series compounds. The synthetic routes of imidazolinone series compounds in the prior art are all carried out using substituted dipicolinic acid and its derivatives as raw materials. [0003] 5-methoxymethyl-2,3-pyridinedicarboxylic acid (CAS No. 143382-03-0), its structural formula is as follows: [0004] [0005] 5-methoxymethyl-2,3-pyridinedicarboxylic acid is an intermediate of the herbicide imazamox, and its preparation methods currently include cyclization hydrolysis and cyclization oxidation. [0006] The inventor finds that there are at least the following problems in the prior art: the preparation of 5-methoxymethyl-2,3-pyridinedicarboxylic acid in the prior art requi...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D213/80C07D213/803
CPCC07D213/80C07D213/803
Inventor 程春生林洋杨兆国王永峰孟宪梅李全国李子亮卢丙增
Owner SHENYANG SCIENCREAT CHEM
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