Title:
CONTINUOUS-FLOW CLEAN PRODUCTION PROCESS FOR PYRAZOLONE SERIES PRODUCTS
Document Type and Number:
WIPO Patent Application WO/2019/085876
Kind Code:
A1
Abstract:
The present invention discloses a continuous-flow clean production process for pyrazolone series products, comprising reacting an aromatic amine with an aqueous sulfuric acid solution for 0.5-2 h to obtain an aromatic amine sulfate solution; simultaneously introducing the aromatic amine sulfate solution and a sodium nitrite into a pre-mixer solution for mixing, and then introducing the mixture into a continuous flow reactor for a diazotization reaction; adding the generated diazonium salt to an aqueous ammonium sulfite solution and an aqueous ammonium hydrogen sulfite solution in sequence for a reduction reaction; upon completion of the reduction reaction, adding a sulfuric acid solution for a hydrolyzation reaction at 70-120°C; carrying out neutralization after the hydrolyzation reaction, the pH being controlled between 2 and 5, and then carrying out a condensation reaction with diethylamine at 40-70°C for 1-3 h, cooling the solution to 10-40°C, followed by filtration and drying to give a pyrazolone product; and subjecting the mother liquor to extraction with a solvent or decolorization with activated carbon, followed by concentration by evaporation, gradient cooling at stages, and separation by crystallization, to give ammonium sulfate and sodium sulfate. The present invention has fewer side reactions, a high diazotization yield, and is capable of producing a series of products.
Inventors:
QING JIU (CN)
YU XINNAN (CN)
XUE JINQUAN (CN)
LIU FANG (CN)
ZHU XIAOGANG (CN)
ZHOU XINJIAN (CN)
ZHU AIHUA (CN)
SHI CHUNMING (CN)
YU XINNAN (CN)
XUE JINQUAN (CN)
LIU FANG (CN)
ZHU XIAOGANG (CN)
ZHOU XINJIAN (CN)
ZHU AIHUA (CN)
SHI CHUNMING (CN)
Application Number:
PCT/CN2018/112589
Publication Date:
May 09, 2019
Filing Date:
October 30, 2018
Export Citation:
Assignee:
NANTONG ACETIC ACID CHEMICAL CO LTD (CN)
NANTONG LIYANG CHEMICAL CO LTD (CN)
NANTONG LIYANG CHEMICAL CO LTD (CN)
International Classes:
C07D231/26; C01C1/24; C01D5/00
Foreign References:
| RU2235091C1 | 2004-08-27 | |||
| CN106565534A | 2017-04-19 | |||
| RU2075476C1 | 1997-03-20 | |||
| DE3416204A1 | 1985-11-07 | |||
| CN101367763A | 2009-02-18 | |||
| CN107827821A | 2018-03-23 |
Other References:
GAN, LIGUANG ET AL.: "Preparation of Phenylhydrazine Sulfate and 1-Phenyl-2, 3-Dimethyl-4-Amino- Pyrazolone-5 through Ammonium Salt Reduction", ACTA PHARMACEUTICAL SINICA, no. 2, 2 March 1966 (1966-03-02), pages 151, ISSN: 0513-4870
"Northwest Second Synthetic Pharmaceutical Factory", SHAANXI CHEMICAL INDUSTRY, no. 7, 30 June 1975 (1975-06-30), pages 36 - 37, ISSN: 1671-3206
JIN, PING ET AL.: "Synthesis and Application of 1- (4'-sulfophenyl)-3-methyl-5-pyrazolone", ACETALDEHYDE ACETIC ACIDE CHEMICAL INDUSTRY, no. 7, 5 July 2015 (2015-07-05), pages 12 - 16, ISSN: 2095-5960
"Northwest Second Synthetic Pharmaceutical Factory", SHAANXI CHEMICAL INDUSTRY, no. 7, 30 June 1975 (1975-06-30), pages 36 - 37, ISSN: 1671-3206
JIN, PING ET AL.: "Synthesis and Application of 1- (4'-sulfophenyl)-3-methyl-5-pyrazolone", ACETALDEHYDE ACETIC ACIDE CHEMICAL INDUSTRY, no. 7, 5 July 2015 (2015-07-05), pages 12 - 16, ISSN: 2095-5960
Attorney, Agent or Firm:
SANHE INTERNATIONAL IP ATTORNEYS (GP) (CN)
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