A kind of green preparation method of 2-chloro-3-cyanopyridine

A cyanopyridine and green technology, which is applied in the field of green preparation of 2-chloro-3-cyanopyridine, can solve problems such as difficulty in treating phosphorus-containing wastewater and waste acid, achieves low environmental impact, high purity and yield, simple craftsmanship

Active Publication Date: 2021-05-04
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] There are many existing 2-chloro-3-cyanopyridine synthesis routes, one of which is to use 3-cyanopyridine N-oxide as a raw material to react with a chlorination reagent, and most of the chlorination reagents used are trichloroxy Phosphorus, phosphorus pentachloride, thionyl chloride and sulfonyl chloride are mainly used, and there are mainly the following deficiencies: (1) use POCl 3 As a chlorinating agent, direct chlorination under reflux conditions, or add PCl 5 To accelerate the reaction, the molar amount of the chlorinating agent used is not only more than three times the molar amount of the raw material, but also produces a large amount of phosphorus-containing wastewater and waste acid that are difficult to treat

Method used

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  • A kind of green preparation method of 2-chloro-3-cyanopyridine
  • A kind of green preparation method of 2-chloro-3-cyanopyridine

Examples

Experimental program
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Effect test

Embodiment 1

[0022] Take a dry four-neck flask, set up a tail gas absorption device, add 15g (125mmol) 3-cyanopyridine N-oxide and 110mL 1,2-dichloroethane, stir at a low temperature of 0°C to form a homogeneous solution , when T=-5~0℃, add 25.30g (250mmol) triethylamine, continue cooling, add 3.50g (62.5mmol) sodium chloride, 0.78g (6.25mmol) sodium sulfite, 1.13g (5mmol) benzyl Triethylammonium chloride, continued cooling to -15°C, began to slowly add 60mL of 1,2-dichloroethane solution containing 18.52g (62.5mmol) bis(trichloromethyl)carbonate dropwise, and the dropwise addition was completed. The reaction was incubated at this temperature for 16 hours. After the reaction was completed, 40 mL of deionized water was added dropwise and stirred to quench. Separate the layers, wash the organic phase with 60 mL of 10% sodium hydroxide solution, then wash with 60 mL of deionized water, and finally extract the aqueous phase with (60 mL*2) 1,2-dichloroethane, combine the organic layers, add act...

Embodiment 2

[0024] Take a dry four-neck flask, set up a tail gas absorption device, add 15g (125mmol) 3-cyanopyridine N-oxide and 110mL 1,2-dichloroethane, stir at a low temperature of 0°C to form a homogeneous solution , when T=-5~0℃, add 31.63g (312.5mmol) triethylamine, continue cooling, add 1.83g (31.25mmol) sodium chloride, 0.78g (6.25mmol) sodium sulfite, 1.13g (5mmol) benzyl Triethylammonium chloride, continue to cool to -15°C, start to slowly add 60mL of 1,2-dichloroethane solution containing 18.52g (62.5mmol) bis(trichloromethyl)carbonate dropwise, dropwise , keep the reaction at this temperature for 16 hours, after the reaction is complete, add 40 mL of deionized water dropwise and stir to quench. Separate the layers, wash the organic phase with 60 mL of 10% sodium hydroxide solution, then wash with 60 mL of deionized water, and finally extract the aqueous phase with (60 mL*2) 1,2-dichloroethane, combine the organic layers, add activated carbon at 60 Reflux and decolorize at ℃ ...

Embodiment 3

[0026] Take a dry four-neck flask, set up a tail gas absorption device, add 15g (125mmol) 3-cyanopyridine N-oxide and 110mL 1,2-dichloroethane, stir at a low temperature of 0°C to form a homogeneous solution , when T=-5~0 ℃, add 31.63g (312.5mmol) triethylamine, continue cooling, add 3.50g (62.5mmol) sodium chloride, 0.78g (6.25mmol) sodium sulfite, 1.13g (5mmol) benzyl Triethylammonium chloride, continue to cool to -15°C, start to slowly add 60mL of 1,2-dichloroethane solution containing 18.52g (62.5mmol) bis(trichloromethyl)carbonate dropwise, dropwise , keep the reaction at this temperature for 15 hours, after the reaction is complete, add 40 mL of deionized water dropwise and stir to quench. Separate the layers, wash the organic phase with 60 mL of 10% sodium hydroxide solution, then wash with 60 mL of deionized water, and finally extract the aqueous phase with (60 mL*2) 1,2-dichloroethane, combine the organic layers, add activated carbon, and Reflux and decolorize at 60°...

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Abstract

The invention discloses a green preparation method of 2-chloro-3-cyanopyridine, comprising the following steps: taking 3-cyanopyridine N-oxide as a raw material, dissolving it in a certain amount of organic solvent, adding additives , organic base and phase transfer catalyst to form a raw material system, control the appropriate temperature, then dissolve bis(trichloromethyl)carbonate in a certain amount of organic solvent, and slowly add it dropwise to the raw material system for reaction. Simple processing can give 2-chloro-3-cyanopyridine. The preparation method of the invention is simple, the reaction period is short, and the phosphorus-containing reagent is replaced by green chlorination reagent without heavy metal participation. Compared with the prior art, the invention has less environmental pollution, safe operation, low cost and is suitable for industrialized production. This method is applied to the green chlorination reaction of 3-cyanopyridine N-oxide, but not limited to the preparation of 2-chloro-3-cyanopyridine.

Description

technical field [0001] The invention belongs to the field of synthesis of organic intermediates, in particular to a green preparation method of 2-chloro-3-cyanopyridine. Background technique [0002] 2-Chloro-3-cyanopyridine is a common important intermediate in the pharmaceutical industry. It has a wide range of uses and can be used as a raw material to synthesize many drugs with excellent properties, such as the antidepressant mirtazapine and the anti-AIDS drug nevirapine. Anti-inflammatory and analgesic, treating wasting syndrome and other effects, it can also be used as a raw material to synthesize agrochemicals to improve the utilization of feed protein, and can also be used as insecticides and herbicides. [0003] There are many existing 2-chloro-3-cyanopyridine synthesis routes, one of which is to use 3-cyanopyridine N-oxide as a raw material to react with a chlorination reagent, and most of the chlorination reagents used are trichloroxy Phosphorus, phosphorus pentac...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D213/85C07D211/90
CPCC07D211/90C07D213/85
Inventor 戴立言蔡梦露王晓钟陈英奇
Owner ZHEJIANG UNIV
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