Method for preparing perfluoroalkyl sulfinate ester

Patent metadata

Field	Value
Publication number	US-11840504-B2
Application number	US-202117205937-A
Country	US
Kind code	B2
Filing date	Mar 18, 2021
Priority date	Sep 19, 2018
Publication date	Dec 12, 2023
Grant date	Dec 12, 2023

Abstract

The present invention discloses a method for preparing a perfluoroalkyl sulfinate ester. The method includes reacting an α-carbonyldiazo compound and a sodium perfluoroalkyl sulfinate, in an organic solvent, in the presence of anhydrous copper acetate as an optimal catalyst and tert-butyl hydroperoxide (TBHP) as a green oxidant, to obtain the perfluoroalkyl sulfinate ester. Compared to the prior art, the present method has the advantages of a wide range of reaction substrates, a short reaction time, a high reaction yield, and mild reaction conditions. The reaction does not require pre-activation of sodium perfluoroalkyl sulfinate, which can participate in the reaction directly, making reaction operations simple. The present method uses TBHP as a green oxidant and produces tert-butanol and water after reaction. Moreover, the present method avoids using a bromide or a chloride as a reaction material, and thus avoids formation of a large amount of a halide salt.

First claim

The invention claimed is:

1. A method for preparing a perfluoroalkylsulfinate ester, comprising:
reacting an α-carbonyldiazo compound with a sodium perfluoroalkylsulfinate in the presence of a transition metal compound as a catalyst, with a peroxide as an oxidant, in an organic solvent, to obtain the perfluoroalkylsulfinate ester,
wherein the α-carbonyldiazo compound has the following chemical structural formula:

R 1 is selected from the group consisting of naphthyl, thienyl, alkyl, alkoxy, and phenol; or R 1 is

 R 2 is selected from the group consisting of hydrogen, methyl, ethyl, tert-butyl, methoxy, phenyl, fluorine, chlorine, bromine, trifluoromethyl, hydroxyl, acetoxy, and p-toluenesulfonyloxy;
wherein the sodium perfluoroalkylsulfinate is

wherein the transition metal compound is selected from the group consisting of a copper compound, a cobalt compound, and an iron compound;
wherein the peroxide is hydrogen peroxide or tert-butyl hydroperoxide (TBHP); and
wherein the perfluoroalkylsulfinate ester has the following chemical structural formula:

 n is 1 to 8.

2. The method according to claim 1 , wherein the reaction of the α-carbonyldiazo compound with the sodium perfluoroalkylsulfinate is conducted at 50 to 90° C., for 1 to 6 hours, in the air; the transition metal compound is a copper compound; the organic solvent is petroleum ether, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, nitro methane, acetonitrile, or ethyl acetate.

3. The method according to claim 2 , wherein the reaction is conducted at 60° C., in the air, for 1 hour; the copper compound is anhydrous copper acetate; and the organic solvent is ethyl acetate.

4. The method according to claim 3 , further comprising after the reaction is complete, diluting with ethyl acetate, removing ethyl acetate, and conducting silica column chromatography to obtain the perfluoroalkylsulfinate ester.

5. The method according to claim 1 , wherein a molar ratio of the catalyst to the α-carbonyldiazo compound is 1:10; a molar ratio of the oxidant to the α-carbonyldiazo compound is 5:1; and a molar ratio of the sodium perfluoroalkylsulfinate to the α-carbonyldiazo compound is 3:1.

Assignees

• Univ Soochow

Inventors

• Wan Xiaobing
• Wang Hanghang

Classifications

• C07C313/04 Primary

  Sulfinic acids; Esters thereof · CPC title