Synthetic method of 2-amino-4-aryl-5-methylthiothiazole compound

A technology of methylthiothiazole and compounds, which is applied in the field of organic chemical synthesis, can solve the problems of poisonous and harmful use, low yield, high cost, etc., and achieve the effects of mild reaction conditions, short process lines, and high yield

Active Publication Date: 2017-04-19
HUAIHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] Although the above method can be used to prepare 2-amino-4-aryl-5-methylthiothiazole compounds, there are many shortcomings: the raw materials used in the synthesis process are not easy to obtain, and the cost is high; the use of toxic and harmful organic solvents, Or the yield is low, or the post-processing is cumbersome, etc.

Method used

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  • Synthetic method of 2-amino-4-aryl-5-methylthiothiazole compound
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  • Synthetic method of 2-amino-4-aryl-5-methylthiothiazole compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0017] Embodiment 1: Synthesis of 2-amino-4-(p-nitrophenyl)-5-methylthiothiazole

[0018] (a) Weigh p-nitroacetophenone (6.52g, 39.5mmol), dissolve it in a round bottom flask adding 40% hydrobromic acid (20ml) and dimethyl sulfoxide (20ml) mixture, seal it, avoid Light, the mixture was heated to 40°C, reacted for 10 hours, and cooled. Add ether (20ml) and isopropanol (20ml) to a round bottom flask, refrigerate and stand overnight, a large amount of precipitate precipitates, filter, wash with dichloromethane, and dry to obtain α-bromo-p-nitroacetophenone dimethyl Sulfonium salt, white crystal, weighing 12.16g, yield 80%, melting point 119-123°C.

[0019] (b) Take the sulfonium salt (0.5g, 1.3mmol) prepared by the above steps, add water (5ml) to dissolve, add thiourea (0.1g, 1.3mmol), stir at room temperature for 3 hours, then add ethanol (5ml), and heat up to React at 90°C for 12 hours. Cool in an ice-water bath, store in refrigerator overnight, precipitate out, filter with ...

Embodiment 2

[0020] Embodiment 2: Synthesis of 2-amino-4-(p-chlorophenyl)-5-methylthiothiazole

[0021] (a) Weigh p-chloroacetophenone (6.11g, 39.5mmol) in a round bottom flask, add dimethyl sulfoxide (10ml) and hydrobromic acid (20ml), seal it, avoid light, and heat the mixture to 60°C, react for 8 hours, and cool. Add ether (20ml) and isopropanol (20ml) to a round bottom flask, refrigerate and stand overnight, a large amount of precipitate precipitates, filter, wash with dichloromethane, and dry naturally to obtain α-bromo-p-chloroacetophenone dimethyl Sulfonium salt, white crystal, weighing 10.35g, yield 70%, melting point 124-128°C.

[0022] (b) Take the sulfonium salt (0.50g, 1.3mmol) obtained in step (a), add water (10ml) to dissolve, add thiourea (0.2g, 2.6mmol), stir at room temperature for 3 hours, add ethanol (5ml), The temperature was raised to 70° C. for 10 hours. After cooling, it was left to stand in the refrigerator overnight, and no precipitate was precipitated. It was e...

Embodiment 3

[0023] Example 3: Synthesis of 2-amino-4-(p-fluorophenyl)-5-methylthiothiazole

[0024] (a) Weigh p-fluoroacetophenone (5.45g, 39.5mmol), dissolve it in a round-bottom flask adding 40% hydrobromic acid (20ml) and dimethyl sulfoxide (20ml) mixture, seal it, and avoid light , The mixture was heated to 30°C, reacted for 12 hours, and cooled. Add ether (20ml) and isopropanol (20ml) to a round bottom flask, refrigerate and stand overnight, precipitate precipitate, filter, wash with dichloromethane, dry to obtain α-bromo-p-fluoroacetophenonyl dimethyl Sulfonium salt, white crystal, weighing 8.49g, yield 60%, melting point 120-124°C.

[0025] (b) Weigh the α-bromo-p-fluoroacetophenonyl dimethylsulfonium salt (0.50g, 1.4mmol) obtained in step (a), add water (10ml) to dissolve, add thiourea (0.55g, 7.2 mmol), stirred at room temperature for 3 hours, then added ethanol (5 ml), and heated to 60°C for 14 hours. Cool and store in refrigerator overnight, no precipitate was precipitated, ...

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Abstract

The invention belongs to the field of organic chemical synthesis technology and relates to an efficient and simple method for synthesis of a 2-amino-4-aryl-5-methylthiothiazole compound. The method of the invention comprises the following synthesis steps: (1) dissolving aryl ethylketone in a DMSO / HBr mixed system, heating and reacting to prepare alpha-bromoacetophenone dimethylsulfonium salt; and (2) dissolving the sulfonium salt prepared in the step (1) into water, adding thiourea, and stirring at room temperature; and adding ethanol, continuously heating and reacting to prepare 2-amino-4-aryl-5-methylthiothiazole.

Description

technical field [0001] The invention belongs to the technical field of organic chemical synthesis, and relates to a method for efficiently and conveniently synthesizing 2-amino-4-aryl-5-methylthiothiazole compounds. Specifically, it relates to the synthesis method of the compound of formula I. [0002] [0003] Where: R is NO 2 , F, Cl, Br, H, CH 3 Background technique [0004] Sulfuryl thiazole compounds are a class of heterocyclic compounds with various biological and pharmacological activities such as anticancer, analgesic and anti-inflammatory, antibacterial and antiviral. Iriuchijima etc. have disclosed that 2-methylsulfinyl-1-acetophenone is reacted with thiourea as a raw material to synthesize 2-amino-4-phenyl-5-methylthiothiazole (Iriuchijima S, Hasegawa K, JP 7777061 , (1975); Chem.Abstr., (1977) 87, 201513), studies have shown that the compound has important biological and pharmacological activities such as bactericidal, antiviral and cytotoxic activities. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D277/54
CPCC07D277/54
Inventor 曹志凌吴巧陈静朱丹丹马晓冬滕文琪宋晓凯刘玮炜史大华陶传洲赵跃强唐丽娟王建殷龙朱荟龙
Owner HUAIHAI INST OF TECH
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