Production method of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole

A technology of trifluoromethylphenyl and trifluoromethylaniline, applied in the field of preparation of 5-amino-3-cyano-1-pyrazole, which can solve the problem of low product quality and high salt content in waste acid Easy to deal with, easy to recycle, and cost-saving

Active Publication Date: 2020-01-10
台州达辰药业有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0007] The purpose of the invention is to solve the waste acid amount and / or salt content in the existing 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl) pyrazole preparation process The shortcomings of being difficult to handle and low product quality; the invention provides a preparation method of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole , using nitrosyl sulfuric acid as a diazotization reagent, diazotization of 2,6-dichloro-4-trifluoromethylaniline in an organic system, and then reacting with ethyl 2,3-dicyanopropionate High-purity 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole prepared by coupling and cyclization

Method used

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  • Production method of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole
  • Production method of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole
  • Production method of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Example 1: Add 150 g of sulfuric acid solution of 40% mass concentration of nitrosylsulfuric acid to a 1L four-necked bottle, start stirring, and then add 2,6-dichloro-4-trifluoromethyl to the constant pressure dropping funnel A mixed solution of 60g of aniline and 180g of dichloroethane is added dropwise at a temperature of 10-30°C, and the drop is completed in 1-2 hours. After the drop is completed, it is kept at 10-30°C for 2 hours; the diazo solution is added dropwise to 400g of ice-water bath, Control the temperature ≤ 15°C, keep it warm for 0.5 hours after dripping, let it stand for stratification, separate the water layer, add 50g of ethyl 2,3-dicyanopropionate dropwise, control the temperature at 0-30°C, and drop it at 0-30°C after dripping Stir at 30°C for 5 hours; add 300g of toluene to extract, separate layers, extract the water layer with 100g*2 toluene, combine the toluene layer, add 200g of ammonia water with a concentration of 18% dropwise, and add dropwis...

Embodiment 2

[0032] Example 2: Add 180 g of sulfuric acid solution of nitrosylsulfuric acid with a mass concentration of 30% to a 1L four-necked bottle, start stirring, and then add 2,6-dichloro-4-trifluoromethyl to the constant pressure dropping funnel A mixed solution of 60g of aniline and 240g of n-hexane, add dropwise at a temperature of 10-30°C, drop in 1-2 hours, and keep warm at 10-30°C for 3 hours after dropping; add the diazo solution dropwise into a 500g ice-water bath, and control the temperature ≤15°C, keep warm for 0.5 hours after dripping, let stand to separate the layers, separate the water layer, add 46g of ethyl 2,3-dicyanopropionate dropwise, control the temperature at 0-30°C, add drops at 0-30°C after dripping Insulate and stir for 6 hours; add 350g toluene to extract, separate layers, extract the water layer with 100g*2 toluene, combine the toluene layer, add 250g of ammonia water with a mass concentration of 15% dropwise, control the temperature at 0-15°C and add dropwi...

Embodiment 3

[0033] Example 3: Add 200 g of sulfuric acid solution of nitrosylsulfuric acid with a mass concentration of 25% to a 1L four-necked bottle, start stirring, and then add 2,6-dichloro-4-trifluoromethyl to the constant pressure dropping funnel A mixed solution of 60g of aniline and 300g of n-heptane, add dropwise at a temperature of 10-30°C, drop it in 1-2 hours, and keep it warm at 10-30°C for 5 hours; ≤15°C, keep warm for 0.5 hours after dripping, let stand to separate layers, separate the water layer, add 50g of ethyl 2,3-dicyanopropionate dropwise, control the temperature at 0-30°C and add dropwise, dropwise at 0-30°C Insulate and stir for 5 hours; add 350g toluene for extraction, separate layers, extract the water layer with 100g*2 toluene, combine the toluene layer, add 300g of ammonia water with a mass concentration of 12% dropwise, and add dropwise at 0-15°C with temperature control. Heat at 0-10°C for 10 hours, filter with suction, wash and dry to obtain 78.6g of finishe...

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Abstract

The invention provides a production method of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole. The production method of the 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole comprises the following steps: (1) adding nitrosyl sulfuric acid into a four-necked bottle, and adding mixed liquid of 4-amino-3,5-dichlorobenzotrifluoride and an organic solvent dropwise to produce diazonium liquid; (2) adding the diazonium liquid back into ice water, conducting stirring, standing for layering, separating out a water layer, and adding ethyl 2,3-dicyanopropionate dropwise for coupling; and (3) conducting toluene extraction and combining, adding ammonium hydroxide dropwise for cyclization, and conducting filtering, washing and drying to obtain a finished product. According to the production method of the 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole, the yield is high, the quality is good, single impurity is lower than or equal to 0.1%, the level ofdifficulty of treating three waste is effectively lowered, discharge of the three waste is reduced, and the cost is low.

Description

technical field [0001] The invention belongs to the field of medicine and chemical industry, and specifically relates to a preparation method of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole. Background technique [0002] 5-Amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole, referred to as pyrazole ring, is a synthetic high-efficiency insecticide "fipronil" (English name : fipronil, trade name: sharp proton, Regent, etc.) important intermediates, first developed and put into production by the French company Rhône-Planck, its molecular formula H 5 CIF 3 N 4 , MP: 132-141°C, CAS No.: 120068-79-63, soluble in methanol, ethanol, acetone, dichloroethane and ethyl acetate, etc., the product is light yellow or white crystal. [0003] The structural formula of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole is shown in the following formula (A): [0004] [0005] There are many synthetic patent reports of 5-amino-3-cyano-1-(2,6-...

Claims

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Application Information

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Patent Type & AuthorityApplications(China)
IPC IPC(8): C07D231/38
CPCC07D231/38
Inventor姜礼进蔡青峰缪炳林
Owner台州达辰药业有限公司