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Method for synthesizing 2-sulfonyl ketone compounds

A technology for sulfonyl ketones and compounds, which is applied in the field of synthesizing 2-sulfonyl ketone compounds, can solve the problems of waste of raw materials, excessive requirements, dangerous production and the like, and achieves the effects of good substrate adaptability and simple reaction operation.

Active Publication Date: 2014-11-19
HUAWEI TEHCHNOLOGIES CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] At present, 2-sulfonyl ketones are mainly prepared from 2-bromoacetophenone (or 2-chloroacetophenone) and sodium sulfinate through sulfonation reaction under alkaline conditions. In this case, strong base and ionic liquid are required, which leads to high requirements on the reaction equipment. At the same time, a large amount of heat is released during the reaction process, which is likely to cause production hazards. A large amount of inorganic salts are produced in this process, resulting in waste of raw materials. , but also caused environmental pollution
[0004] In recent years, new methods for the preparation of 2-sulfonyl ketones with metal catalysts (such as copper and iron) have been widely studied, but the use of metal catalysts and their difficult separation in medicinal chemistry limit the use of such methods. Wide application in the field of medicine

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Formula 1

[0040] (1) Add 1.2 g (10 mmol) of acetophenone, 1.04 g of hydroxylamine hydrochloride, 2.3 mL of pyridine, and 20 mL of ethanol to a 50 mL round bottom flask. After the mixture was reacted at 60°C for 2 to 4 hours, TLC detected the end of the reaction. The resulting mixed solution was extracted three times with ethyl acetate. The organic phases were combined, washed with 30% hydrochloric acid solution, washed with saturated brine, dried and then removed under reduced pressure to obtain 1.3 g of white solid acetophenone oxime (95% yield).

[0041] (2) 1.08g (8mmol) of acetophenone oxime, 153mg (0.8mmol) of cuprous iodide, 2.5g (24mmol) of sodium bisulfite, 1.6g (16mmol) of acetic anhydride and 1,2-dichloroethane (15ml) were sequentially added into a sealed pressure vessel under the protection of nitrogen. The mixture was heated and reacted in an oil bath at 120°C for 12 hours. After the reaction was detected by TLC, the reaction solution was diluted with eth...

Embodiment 2

[0045] Formula 2

[0046] (1) Add 1.38 g (10 mmol) of 4-fluoroacetophenone, 1.04 g of hydroxylamine hydrochloride, 2.3 mL of pyridine, and 20 mL of ethanol into a round bottom flask. After the mixture was reacted at 60°C for 2 to 4 hours, TLC detected the end of the reaction. The resulting mixed solution was extracted three times with ethyl acetate. The organic phases were combined, washed with 30% hydrochloric acid solution, washed with saturated brine, dried and then removed under reduced pressure to obtain 1.42 g of 4-fluoroacetophenone oxime as a white solid (93% yield).

[0047] (2) Mix 1.22g (8mmol) of 4-fluoroacetophenone oxime, 153mg (0.8mmol) of cuprous iodide, 2.5g (24mmol) of sodium bisulfite, 1.6g (16mmol) of acetic anhydride and 1,2-bis Chloroethane (15ml) was sequentially added into a sealed pressure vessel under the protection of nitrogen. The mixture was heated and reacted in an oil bath at 120°C for 12 hours. After the reaction was detected by TLC, the reacti...

Embodiment 3

[0051] Formula 3

[0052] (1) The implementation steps are the same as step (1) in the first embodiment.

[0053] (2) The implementation steps are the same as step (2) in the first embodiment.

[0054] (3) 80.5 mg (0.5 mmol) of N-(1-styryl)acetamide, 188.3 mg (0.75 mmol) of p-bromobenzenesulfonyl hydrazide, 36.9 mg (0.1 mmol) of tetrabutylamine iodide, tertiary 128.5 mg (1.0 mmol, 70% aqueous solution) of butyl hydroperoxide, and the solvent was added to the flask to react at 80°C for 10-12 hours. After the reaction is detected by TLC, column chromatography (eluent ratio: petroleum ether to ethyl acetate volume ratio 4:1) is used to separate 1-phenyl-2-p-bromobenzenesulfonyl ketone (the structural formula is as formula 3). ) 122.1 mg (72% yield).

[0055] Product characterization: mp120℃; 1 H NMR(500MHz, CDCl 3 )δ7.92(d,J=7.4Hz,2H), 7.75(d,J=8.6Hz,2H), 7.68(d,J=8.5Hz,2H), 7.63(t,J=7.4Hz,1H) ,7.48(t,J=7.8Hz,2H),4.75(s,2H). 13 C NMR(125MHz, CDCl 3 )δ187.9, 137.7, 135.6, 134.5, 132...

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Abstract

The invention discloses a method for synthesizing 2-sulfonyl ketone compounds. The method comprises the following steps: mixing substituted N-vinyl acetamide, sulfohydrazide compounds, a catalyst, an oxidant and a solvent to obtain a mixed liquid; and reacting for 2-12 hours at 20-120 DEG C; and then, decompressing to remove the solvent and separating to obtain the 2-sulfonyl ketone compounds, wherein the catalyst is organic amine salt, the oxidant is peroxide and the molar ratio of the sulfohydrazide compound to the substituted N-vinyl acetamide is (1-3):1. The invention provides a new route for synthesizing the 2-sulfonyl ketone compounds. By taking N-vinyl acetamide and the sulfohydrazide compounds as raw materials, the substrate is good in adaptability and corresponding 2-sulfonyl ketone compounds can be synthesized by various substituents. The method is mild in reaction condition, safe and environmental friendly and free from exhaust gases.

Description

Technical field [0001] The present invention relates to the technical field of organic synthesis, in particular to a method for synthesizing 2-sulfonyl ketone compounds. Background technique [0002] 2-sulfonyl ketone compounds are mainly used in natural products, medicines and important organic synthesis intermediates. For example, 2-sulfonyl ketone structural units can undergo a variety of functional group conversions, and can be used to synthesize a variety of important organic compounds such as olefins, disubstituted acetylenes, vinyl sulfones, allenes, and hydropyrans. They are widely used in organic synthesis. Applications. [0003] At present, 2-sulfonyl ketones are mainly prepared from 2-bromoacetophenone (or 2-chloroacetophenone) and sodium sulfinate through sulfonation under alkaline conditions. In most cases Strong bases and ionic liquids are needed for the next step, which leads to excessively high requirements on the reaction equipment. At the same time, a lot of hea...

Claims

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Application Information

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IPC IPC(8): C07C315/00C07C317/24
Inventor 李小青许响生唐裕才
Owner HUAWEI TEHCHNOLOGIES CO LTD
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