Acid-catalyzed photocatalyzed oxidation reaction of benzylic C—H bonds of aromatic compound

Patent metadata

Field	Value
Publication number	US-11773045-B2
Application number	US-202218024730-A
Country	US
Kind code	B2
Filing date	Jan 19, 2022
Priority date	Oct 29, 2021
Publication date	Oct 3, 2023
Grant date	Oct 3, 2023

Abstract

Provided is a photo-oxidation reaction of benzylic C—H bonds of an aromatic compound under the catalysis of an acid catalyst. The method aims to synthesize aromatic acids and acetophenones. The acid catalyst is one of Bronsted acids, including one or a mixture of two or more selected from the group consisting of hydrochloric acid, phosphoric acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, and potassium hydrogen sulfate, as well as N-propylsulfonate pyridinium hydrogensulfate, N-butylsulfonate pyridinium hydrogensulfate, N-propylsulfonate pyridinium trifluoromethanesulfonate, N-butylsulfonate pyridinium trifluoromethanesulfonate, N-propylsulfonate pyridinium tetrafluoroborate, and N-butylsulfonate pyridinium tetrafluoroborate. The oxidation reaction is conducted under mild conditions (normal temperature and pressure) using air or oxygen as the oxidant in the presence of recyclable catalyst and solvent.

First claim

What is claimed is:

1. An acid-catalyzed photocatalyzed oxidation reaction of benzylic C—H bonds of an aromatic compound, wherein the liquid-phase oxidation reaction is conducted with oxygen or air as the oxidants using Bronsted acid as the photocatalyst at normal pressure under light irradiation with a wavelength range of 300 nm to 450 nm.

2. The acid-catalyzed photocatalyzed oxidation reaction of benzylic C—H bonds of an aromatic compound according to claim 1 , wherein the Bronsted acid is one or a mixture of two or more selected from the group consisting of an inorganic acid, an organic acid, and an acidic ionic liquid.

3. The acid-catalyzed photocatalyzed oxidation reaction of benzylic C—H bonds of an aromatic compound according to claim 1 , wherein the Bronsted acid is one or a mixture of two or more selected from the group consisting of hydrochloric acid, phosphoric acid, sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, and potassium hydrogen sulfate, as well as N-propylsulfonate pyridinium hydrogensulfate, N-butylsulfonate pyridinium hydrogensulfate, N-propylsulfonate pyridinium trifluoromethanesulfonate, N-butylsulfonate pyridinium trifluoromethanesulfonate, N-propylsulfonate pyridinium tetrafluoroborate, and N-butylsulfonate pyridinium tetrafluoroborate.

4. The acid-catalyzed photocatalyzed oxidation reaction of benzylic C—H bonds of an aromatic compound according to claim 1 , wherein the Bronsted acid is one or a mixture of two or more selected from the group consisting of hydrochloric acid, sulfuric acid, tetrafluoroboric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, acetic acid, and potassium hydrogen sulfate, as well as N-propylsulfonate pyridinium hydrogensulfate, N-butylsulfonate pyridinium hydrogensulfate, N-propylsulfonate pyridinium trifluoromethanesulfonate, N-butylsulfonate pyridinium trifluoromethanesulfonate, N-propylsulfonate pyridinium tetrafluoroborate, and N-butylsulfonate pyridinium tetrafluoroborate.

5. The acid-catalyzed photocatalyzed oxidation reaction of benzylic C—H bonds of an aromatic compound according to claim 1 , wherein the aromatic compound is one selected from the group consisting of methylarenes, ethylarenes, and cumenes that contains at least one benzylic C—H bond.

6. The acid-catalyzed photocatalyzed oxidation reaction of benzylic C—H bonds of an aromatic compound according to claim 1 , wherein the aromatic compound is selected from the group consisting of the methylarenes, the ethylarenes, and the cumenes; the methylarenes are selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, mesitylene, toluene substituted with 1 to 3 halogen atoms, toluene substituted with alkoxy of 1 to 2 C atoms, and trifluoromethyl-substituted toluene; the ethylarenes are selected from the group consisting of ethylbenzene, p-diethylbenzene, ethylbenzene substituted with 1 to 3 halogen atoms, ethylbenzene substituted with alkoxy of 1 to 2 C atoms, trifluoromethyl-substituted ethylbenzene, and nitro-substituted ethylbenzene; and the cumenes are selected from the group consisting of cumene, halogen-substituted cumene, trifluoromethyl-substituted cumene, and nitro-substituted cumene.

7. The acid-catalyzed photocatalyzed oxidation reaction of benzylic C—H bonds of an aromatic compound according to claim 1 , wherein the aromatic compound is selected from the group consisting of the methylarenes, the ethylarenes, and the cumenes; the methylarenes are any one selected from the group consisting of toluene, o-xylene, m-xylene, p-xylene, mesitylene, toluene substituted with 1 to 3 halogen atoms, toluene substituted with alkoxy of 1 to 2 C atoms, trifluoromethyl-substituted toluene, o-tolunitrile, m-tolunitrile, p-tolunitrile, o-toluic acid, m-toluic acid, p-toluic acid, 2-methyl diphenyl, 3-methyl diphenyl, and 4-methyl diphenyl; the ethylarenes are any one selected from the group consisting of ethylbenzene, p-diethylbenzene, ethylbenzene substituted with 1 to 3 halogen atoms, ethylbenzene substituted with alkoxy of 1 to 2 C atoms, trifluoromethyl-substituted ethylbenzene, and nitro-substituted ethylbenzene; and the cumenes are any one selected from the group consisting of cumene, halogen-substituted cumene, trifluoromethyl-substituted cumene, and nitro-substituted cumene.

8. The acid-catalyzed photocatalyzed oxidation reaction of benzylic C—H bonds of an aromatic compound according to claim 1 , wherein the oxidation reaction is conducted in a solvent; the solvent is selected from the group consisting of water, dichloromethane, dichloroethane, benzene, chlorobenzene, acetonitrile, acetone, 2-butanone, and the ionic liquid; and the ionic liquid is one selected from the group consisting of N-propylsulfonate pyridinium hydrogensulfate, N-butylsulfonate pyridinium hydrogensulfate, N-propylsulfonate pyridinium trifluoromethanesulfonate, N-butylsulfonate pyridinium trifluoromethanesulfonate, N-propylsulfonate pyridinium tetrafluoroborate, and N-butylsulfonate pyridinium tetrafluoroborate, or is a mixture of two of the above-described solvents.

9. The acid-catalyzed photocatalyzed oxidation reaction of benzylic C—H bonds of an aromatic compound according to claim 1 , wherein the oxidation reaction is conducted in a solvent, and the solvent is selected from the group consisting of water, the organic solvent, and the ionic liquid, or is a mixture of any two of the above-described solvents.

10. The acid-catalyzed photocatalyzed oxidation reaction of benzylic C—H bonds of an aromatic compound according to claim 1 , wherein the oxidation reaction is conducted in the solvent; the Bronsted acid comprises the inorganic acid; the solvent is selected from the group consisting of water, the organic solvent, or a mixture of water and the organic solvent.

11. The acid-catalyzed photocatalyzed oxidation reaction of benzylic C—H bonds of an aromatic compound according to claim 1 , wherein the oxidation reaction is conducted in the solvent; the Bronsted acid comprises the organic acid; the solvent is selected from the group consisting of the organic solvent and the mixture of the organic solvent and water.

12. The acid-catalyzed photocatalyzed oxidation reaction of benzylic C—H bonds of an aromatic compound according to claim 1 , wherein the oxidation reaction is conducted in the solvent; the Bronsted acid comprises a strongly-acidic ionic liquid; and the solvent is a mixture of one selected from the group consisting of the dichloromethane, the dichloroethane, the benzene, the chlorobenzene, and the chloroform with water.

13. The acid-catalyzed photocatalyzed oxidation reaction of benzylic C—H bonds of an aromatic compound according to claim 1 , wherein the Bronsted acid is used with an amount of 0.1% mol to 20% mol of the aromatic compound.

14. The acid-catalyzed photocatalyzed oxidation reaction of benzylic C—H bonds of an aromatic compound according to claim 1 , wherein the Bronsted acid is used with an amount of 0.5% mol to 5% mol of the aromatic compound.

15. The acid-catalyzed photocatalyzed oxidation reaction of benzylic C—H bonds of an aromatic compound according to claim 7 , wherein a product obtained by photo-oxidation of the methylarenes under acid catalysis is a corresponding substituted or unsubstituted aryl fomic acid; a product obtained by photo-oxidation of the ethylarenes under acid catalysis is a corresponding substituted or unsubstituted acetophenone; and a product obtained by photo-oxidation of the cumenes under acid catalysis is a corresponding acetophenone.

16. The acid-cata

Assignees

• Nanjing University Of Technology

Inventors

• Li Yufeng
• Zhu Hongjun
• Ma Hongfei
• Bu Hongzhong
• Wu Jieqing
• Gu Jiefan
• Chen Jiwei
• Zhang Haoyue
• Wang Chen

Classifications

• C07C51/16 Primary

  by oxidation (C07C51/145 takes precedence) · CPC title

• C07C45/32

  with molecular oxygen · CPC title

• C07C201/12

  by reactions not involving the formation of nitro groups · CPC title

• C07C253/30

  by reactions not involving the formation of cyano groups · CPC title

• C07C51/215 Primary

  of saturated hydrocarbyl groups · CPC title