Preparation method of N-benzenesulfonyl-4-halogen-2-nitroaniline

A technology for benzenesulfonylaniline and nitroaniline, which is applied in the preparation of sulfonic acid amides, organic chemistry, etc., can solve the problems of harsh reaction conditions, long reaction routes, low process yields, etc., and achieves reduction of the reaction risk factor and reduction Production cost, the effect of simple reaction operation

Active Publication Date: 2022-03-11
SHANDONG FIRST MEDICAL UNIV & SHANDONG ACADEMY OF MEDICAL SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Synthesized in the prior art N -Benzenesulfonyl-4-halogen-2-nitroaniline has the disadvantages of harsh reaction conditions, low process yield, and long reaction route

Method used

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  • Preparation method of N-benzenesulfonyl-4-halogen-2-nitroaniline
  • Preparation method of N-benzenesulfonyl-4-halogen-2-nitroaniline
  • Preparation method of N-benzenesulfonyl-4-halogen-2-nitroaniline

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] synthetic compound N -Benzenesulfonyl-4-bromo-2-nitroaniline

[0037] compound N- Benzenesulfonylaniline (0.2 mol), pyridine (0.3 mol), copper nitrate trihydrate (0.3 mol), tetrabutylammonium bromide (0.4 mol) were added to 200 mL of 1,2-dichloroethane, After the raw materials are dissolved, the reaction system is heated to 95°C-105°C, generally 100°C, and the reaction process is monitored by LCMS and HPLC. When the reaction time reaches 12h, it is processed. The reaction solution was poured into 1 times the volume of ice water, and the pH was adjusted to pH = 6. A large amount of solids precipitated, extracted three times with 100 mL of 1,2-dichloroethane each time, combined the organic phases, dried over anhydrous sodium sulfate, and filtered. 1,2-Dichloroethane to wash the filter cake. The filtrate was removed in vacuo to give 54.3 g of compound N -Benzenesulfonyl-4-bromo-2-nitroaniline, yield 76%, HPLC purity 95%.

[0038] compound N The H NMR spectrum of -ben...

Embodiment 2

[0045] For embodiment 2 and embodiment 3 embodiment 1, changed the consumption of copper nitrate trihydrate; Wherein embodiment 3 then reduced the consumption of copper nitrate trihydrate, and reaction yield was reduced. Embodiment 4 increases the consumption of copper nitrate trihydrate, and the resulting reaction yield and embodiment 1 reduce slightly.

[0046] Compared with Example 1, Embodiment 4 reduces the consumption of pyridine, slows down the reaction rate of this step reaction, and makes the reaction yield decrease to some extent. For Example 5 and Example 11, the amount of pyridine was increased, so that the reaction yield did not rise.

[0047] Compared with embodiment 1, embodiment 6 to embodiment 8 replace pyridine with different bases; compared with pyridine, potassium acetate, potassium tert-butoxide, and cesium carbonate all promote the generation of side reactions, which also reduce the reaction yield. Rate.

[0048] Compared with embodiment 1, embodiment 9...

Embodiment 11

[0050] synthetic compound N -Benzenesulfonyl-4,5-dichloro-2-nitroaniline

[0051] compound N -Benzenesulfonyl-3-chloroaniline (0.2 mol), potassium acetate (0.3 mol), copper nitrate trihydrate (0.3 mol), tetrabutylammonium chloride (0.4 mol) were added to 200 mL of 1,2-di In ethyl chloride, after the raw materials are dissolved, the reaction system is heated to 95°C-105°C, generally 100°C, and the reaction process is monitored by LCMS and HPLC. When the reaction time reaches 12 h, it is processed. The reaction solution was poured into 1 times the volume of ice water, and the pH was adjusted to pH = 6. A large amount of solids precipitated, extracted three times with 100 mL 1,2-dichloroethane each time, combined the organic phases, dried over anhydrous sodium sulfate, and filtered. 1,2-Dichloroethane to wash the filter cake. The filtrate was removed in vacuo to give 44.4 g of compound N -Benzenesulfonyl-4-chloro-2-nitroaniline, yield 71%, HPLC purity 95%.

[0052] compound ...

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Abstract

According to the preparation method of the N-benzenesulfonyl-4-halogen-2-nitroaniline, provided by the invention, the N-benzenesulfonyl-4-halogen-2-nitroaniline can be further hydrolyzed to generate the 4-halogen-2-nitroaniline. The 4-halo-2-nitroaniline is an important organic synthesis intermediate, has a wide application prospect, and can be mainly used for preparing medicines such as maribavir, triclabendazole and the like and synthesizing various substituted benzimidazole, quinazolinone derivatives and the like. However, in the prior art, synthesis of N-benzenesulfonyl-4-halogen-2-nitroaniline has the defects of harsh reaction conditions, low process yield and relatively long reaction route. The invention relates to the technical field of synthesis of medical intermediates, which comprises the following steps: dissolving N-benzenesulfonyl aniline in 1, 2-dichloroethane, and reacting with a nitrate source and tetrabutyl ammonium halide in the presence of alkali to obtain N-benzenesulfonyl-4-halo-2-nitroaniline. The synthetic route is mild in reaction condition, simple in reaction and post-treatment process operation, low in reaction danger coefficient, low in production cost and suitable for industrial large-scale production.

Description

technical field [0001] The invention relates to the technical field of chemical intermediate synthesis, in particular to a N - Preparation method of benzenesulfonyl-4-halo-2-nitroaniline. Background technique [0002] N -Benzenesulfonyl-4-halo-2-nitroaniline can be further hydrolyzed to generate 4-halo-2-nitroaniline. And 4-halo-2-nitroaniline is an important organic synthesis intermediate with broad application prospects, mainly used in the preparation of maribavir, triclabendazole and other drugs and in the synthesis of various substituted benzos Imidazole, quinazolinone derivatives, etc. Synthesized in the prior art N -Benzenesulfonyl-4-halogen-2-nitroaniline has the disadvantages of harsh reaction conditions, low process yield and long reaction route. Contents of the invention [0003] The purpose of the present invention is to provide a N - The preparation method of benzenesulfonyl-4-halo-2-nitroaniline, the preparation method does not use highly polluting reage...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C303/40C07C311/21
CPCC07C303/40C07C311/21Y02P20/55
Inventor 夏成才于晓
Owner SHANDONG FIRST MEDICAL UNIV & SHANDONG ACADEMY OF MEDICAL SCI
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