Method for preparing carbonyl sulfone

Patent metadata

Field	Value
Publication number	US-12351548-B2
Application number	US-202017780699-A
Country	US
Kind code	B2
Filing date	Nov 27, 2020
Priority date	Nov 29, 2019
Publication date	Jul 8, 2025
Grant date	Jul 8, 2025

Abstract

Disclosed is a method for preparing β-carbonyl sulfones. The method comprises: by taking an α-carbonyl diazo compound and sodium arylsulfinate as reaction substrates, cheap silver nitrate as an optimal catalyst, 1,10-phenanthroline as a ligand, and potassium persulfate as an oxidant, carrying out coupling reaction in a mixed solvent of acetonitrile and water to obtain a β-carbonyl sulfones compound. Compared with the prior art, the method has the following advantages: a wide range of reaction substrates, short reaction time, a relatively high reaction yield, a mild reaction condition, etc. In the present invention, non-toxic and harmless reagents are used as reaction raw materials, so that it has no harm to the environment and satisfies the requirements of contemporary green chemistry development. Post-reaction treatment is relatively simple, and is convenient for separation and purification. In addition, the reaction can achieve gram-scale synthesis, and lays a foundation for actual applications.

First claim

The invention claimed is:

1. A method for preparing a β-carbonyl sulfone, comprising: reacting an α-carbonyldiazo compound with a sodium arylsulfinate, an N,N-bidentate compound as a ligand, a peroxide as an oxidant, in the presence of a metal compound as a catalyst, in a mixed solvent of an organic solvent and water, to obtain the β-carbonyl sulfone,
wherein the α-carbonyldiazo compound has the following chemical formula:

R 1 is selected from the group consisting of methyl, ethyl and hydrogen; R 2 is alkoxy;
the sodium arylsulfinate has the following chemical formula:

Ar is benzene or substituted benzene;
the β-carbonyl sulfone has the following chemical formula:

the metal compound is a silver compound or a copper compound;
the peroxide is potassium persulfate, sodium persulfate or ammonium persulfate; and
the N,N-bidentate compound is 1,10-phenanthroline, 2,2′-bipyridine, 4,7-dimethoxy-1,10-phenanthroline, 4,7-diphenyl-1,10-phenanthroline, or 3,8-dibromo-1,10-phenanthroline.

2. The method according to claim 1 , wherein the reaction is conducted at 40 to 90° C., for 4 to 12 hours.

3. The method according to claim 1 , wherein a molar ratio of the catalyst to the sodium arylsulfinate is 1:10; a molar ratio of the oxidant to the sodium arylsulfinate is from 0.2:1 to 2:1; and a molar ratio of the ligand to the sodium arylsulfinate is 10:1; and a molar ratio of thea-carbonyldiazo compound to the sodium arylsulfinate is 2:1.

4. The method according to claim 1 , wherein the reaction is conducted in the air.

5. The method according to claim 1 , wherein the organic solvent is acetonitrile.

Assignees

• Univ Soochow

Inventors

• Wan Xiaobing
• Wang Hanghang
• Zheng Yonggao
• Lian Pengcheng
• Li Jingjing

Classifications

• C07C2523/50

  Silver · CPC title

• C07C315/06

  Separation; Purification; Stabilisation; Use of additives · CPC title

• C07J41/0038

  with an androstane skeleton, including 18- or 19-substituted derivatives, 18-nor derivatives and also derivatives where position 17-beta is substituted by a carbon atom not directly bonded to a further carbon atom and not being part of an amide group · CPC title

• C07J31/006

  not covered by C07J31/003 · CPC title

• C07D333/16

  by oxygen atoms · CPC title