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Method for synthesizing difluoro methyl triazoline-ketone and sulfentrazone

A technology for difluoromethyltriazolinone and difluoromethylation, which is applied in the field of synthesis of organic fluorine compounds, can solve the problems of affecting product quality and yield, generating formamide impurities, poor atom economy and the like, and achieves operation The effect of convenience, less side reactions and high product quality

Inactive Publication Date: 2015-02-04
ZHEJIANG ZHUJI UNITED CHEM
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, there are many problems in this process, such as excessive triethylamine or pyridine to produce a large amount of waste water; consumption of 2 equivalents of methanesulfonyl chloride, poor atom economy; low yield, etc.
US5990315 discloses soluble salts such as quaternary ammonium salts and quaternary phosphonium salts to catalyze sulfonylation reactions. This method solves direct sulfonylation, but the catalyst is more expensive and the yield is low
US7169952 discloses the direct sulfonylation reaction catalyzed by high-boiling amides and tertiary amines such as DMF. This method solves the problem of direct sulfonylation reaction by using cheap catalysts, but produces formamide impurities, which affects product quality and yield

Method used

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  • Method for synthesizing difluoro methyl triazoline-ketone and sulfentrazone
  • Method for synthesizing difluoro methyl triazoline-ketone and sulfentrazone
  • Method for synthesizing difluoro methyl triazoline-ketone and sulfentrazone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Example 1: Add 17.9g 1-phenyl-3-methyl-1,2,4-triazolin-5-one, 115mL toluene, 6.9g potassium carbonate, 6.2g potassium hydroxide and 22mL to a 500mL reaction flask water, heated and refluxed for dehydration. Add 130mL DMSO, heat up and distill toluene to an internal temperature of 145-150°C. Pass difluorochloromethane until the reaction raw material content is lower than 0.5%. Stop the reaction, drop to room temperature and filter with suction, and wash the filter cake with DMSO. The filtrate was precipitated, slurred with water, filtered, rinsed with water, and dried to obtain 20.1 g of the product.

Embodiment 2

[0036] Example 2: Add 15g of 1-phenyl-3-methyl-1,2,4-triazolin-5-one, 45mL of toluene, 6.4g of potassium carbonate, 5.3g of potassium hydroxide and 12mL of water into a 500mL reaction flask , heating and reflux dehydration. Add 120mL of DMF, heat up and distill the toluene to an internal temperature of 145-150°C. Pass difluorochloromethane until the reaction raw material content is lower than 0.5%. Stop the reaction, drop to room temperature and filter with suction, and wash the filter cake with DMF. The filtrate was precipitated, slurred with water, filtered, rinsed with water, and dried to obtain 17.5 g of the product.

Embodiment 3

[0037] Example 3: Add 21.4g 1-(4-chlorophenyl)-3-methyl-1,2,4-triazolin-5-one, 115mL toluene, 10.6g potassium carbonate, 6.2g to a 500mL reaction flask Potassium hydroxide and 23mL of water were heated and refluxed for dehydration. Add 165mL DMSO, heat up and distill toluene to an internal temperature of 145-150°C. Pass difluorochloromethane until the reaction raw material content is lower than 0.5%. Stop the reaction, drop to room temperature and filter with suction, and wash the filter cake with DMSO. The filtrate was desolvated, slurred with water, filtered, rinsed with water, and dried to obtain 24 g of the product. 1 HNMR (500MHz, DMSO-d6) 7.84 (2H, dd, J = 9Hz), 7.56 (2H, dd, J = 9Hz), 7.52 (1H, t, J = 57Hz), 2.42 (3H, s); MS ( [M] + ): 259.1.

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Abstract

The invention discloses a method for synthesizing difluoro methyl triazoline-ketone and sulfentrazone. The method comprises the following steps: taking 1-aryl-3-methyl-1H-1,2,4-triazole-5-ketone as a raw material, dehydrating and salifying by an aprotic solvent under synergism of an alkali metal hydroxide and alkali carbonate to obtain an intermediate (II), using an aprotic polar solvent for solvent displacement, performing difluoro methylation to obtain difluoro methyl triazoline-ketone (III), steps of chlorination, nitrification, reduction and methyl sulfonylation are carried out to obtain N-(2,4-dichloro-5-(4-difluoro methyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole-1-group)phenyl) methanesulfonamide target product. The method has the beneficial effect that the integral technology is simple, the reaction condition is mild, technology is safe, yield is high, product quality is high, and the method is benefit for industrial production.

Description

technical field [0001] The invention relates to a method for synthesizing organic fluorine compounds, in particular to a method for synthesizing difluoromethyltriazolinone and sulfentrazone. Background technique [0002] Sulfentrazone is a herbicide belonging to the class of difluoromethyltriazolinones. The chemical name is N-(2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole -1-yl)phenyl)methanesulfonamide. Its chemical structural formula is shown below: [0003] [0004] 1-phenyl-4-difluoromethyl-3-methyl-1H-1,2,4-triazol-5-one (IIIa) is the main intermediate in the synthesis of sulfentrazone. US5438149 discloses the preparation method of the intermediate: using difluorochloromethane as the difluoromethylation reagent, potassium carbonate as the acid-binding agent, and DMF as the reaction solvent, reacting in a closed autoclave at a temperature of 160-200°C. High temperature and high pressure reaction has many disadvantages in industrial ...

Claims

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Application Information

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IPC IPC(8): C07D249/12
CPCC07D249/12
Inventor 王唐君俞建娣郭群震虞小华蔡国平陈邦池
Owner ZHEJIANG ZHUJI UNITED CHEM
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