Unlock instant, AI-driven research and patent intelligence for your innovation.

A kind of method of synthesizing 2-sulfonyl ketone compound

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, high requirements, and difficult separation of metal catalysts, and achieves the effects of good substrate adaptability and simple reaction operation.

Active Publication Date: 2016-03-02
HUAWEI TEHCHNOLOGIES CO LTD
View PDF1 Cites 0 Cited by
  • 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

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • A kind of method of synthesizing 2-sulfonyl ketone compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0039] Formula 1

[0040] (1) Add 1.2g (10mmol) of acetophenone, 1.04g of hydroxylamine hydrochloride, 2.3mL of pyridine, and 20ml of ethanol into a 50ml round bottom flask. After the mixture was reacted at 60° C. for 2 to 4 hours, TLC detected that the reaction was complete, and the resulting mixed solution was extracted three times with ethyl acetate, and the organic phases were combined, washed with 30% hydrochloric acid solution, washed with saturated saline, and dried under reduced pressure to obtain White solid acetophenone oxime 1.3 g (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 successively added into a sealed pressure vessel under nitrogen protection. 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 ethyl ...

Embodiment 2

[0045] Formula 2

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

[0047](2) 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 Ethyl chloride (15ml) was successively added into a sealed pressure vessel under nitrogen protection. 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 w...

Embodiment 3

[0051] Formula 3

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

[0053] (2) The implementation steps are 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 tetrabutylammonium iodide, tert Add 128.5 mg of butyl hydroperoxide (1.0 mmol, 70% aqueous solution), and add the solvent into the flask to react at 80° C. for 10 to 12 hours. After the TLC detection reaction is finished, use column chromatography (eluent ratio: sherwood oil to ethyl acetate volume ratio 4:1) to separate and obtain 1-phenyl 2-p-bromobenzenesulfonyl ketone (structural formula such as formula 3 ) 122.1 mg (72% yield).

[0055] Product characterization: mp120℃; 1 HNMR (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 CNMR (125MHz, CDCl 3 ) δ 187.9, 137.7, 1...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

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 invention relates to the technical field of organic synthesis, in particular to a method for synthesizing 2-sulfonyl ketones. Background technique [0002] 2-sulfonyl ketones are mainly used in natural products, medicine and important organic synthesis intermediates. For example, the structural unit of 2-sulfonyl ketones can undergo a variety of functional group conversions, and can be used to synthesize a variety of important organic compounds such as alkenes, disubstituted acetylenes, vinyl sulfones, allenes, and hydropyrans. It has a wide range of applications in organic synthesis. Applications. [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 relea...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(China)
IPC IPC(8): C07C315/00C07C317/24
Inventor 李小青许响生唐裕才
Owner HUAWEI TEHCHNOLOGIES CO LTD