Light assisted, catalyst-free oxidation of aldehydes to carboxylic acids using carbon dioxide

Patent metadata

Field	Value
Publication number	US-12043595-B2
Application number	US-202217886023-A
Country	US
Kind code	B2
Filing date	Aug 11, 2022
Priority date	Aug 13, 2021
Publication date	Jul 23, 2024
Grant date	Jul 23, 2024

Abstract

Method for visible-light driven oxidation of aldehydes to carboxylic acid using carbon dioxide (CO2) as the oxidant in the absence of any catalyst are provided. In the disclosed process, aldehydes, when reacted with CO2 in an organic solvent, either in a batch reactor or in a continuous flow reactor, under conditions of ambient temperature and pressure, using a readily available household LED lamp, yield corresponding carboxylic acids along with the formation of carbon monoxide (CO) in the effluent gas.

First claim

We claim:

1. A light assisted, catalyst-free photochemical process for oxidation of aldehydes using carbon dioxide, the process comprising:
oxidizing an aldehyde with CO 2 dissolved in a solvent under light irradiation in a batch or continuous flow photoreactor at a reaction temperature from 20° C. to 40° C. and a reaction pressure from 1 bar to 5 bar for an irradiation time from 1 hour to 24 hours to obtain a carboxylic acid product with formation of gaseous carbon monoxide as a co-product; and
purifying the carboxylic acid product.

2. The process of claim 1 , wherein the aldehyde is selected from:
aromatic aldehydes substituted with an electron donating group or an electron deficient group; or
aliphatic aldehydes.

3. The process of claim 1 , wherein the aldehyde is an aryl aldehyde of Formula (I):

where R is selected from the group consisting of hydrogen, halogen, methyl, ethyl, propyl, butyl, amyl, isopropyl, isobutyl, phenyl, tolyl, biphenyl, benzyl, and naphthyl.

4. The process of claim 1 , wherein the light irradiation comprises irradiating with a light source having a wavelength greater than 420 nm.

5. The process of claim 4 , wherein the light source is a household LED light having a power from 10 W to 50 W.

6. The process of claim 1 , wherein the solvent is selected from the group consisting of water, acetonitrile, dimethylformamide, dimethylsulfoxide, tetrahydrofuran, and mixtures thereof.

7. The process of claim 6 , wherein the solvent comprises acetonitrile.

8. The process of claim 1 , wherein the irradiation time is from 1 hour to 15 hours.

9. The process of claim 1 , wherein the reaction temperature is from 25° C. to 35° C. and a pressure of CO 2 in the photoreactor is 1 atmosphere.

10. The process of claim 1 , wherein the purifying comprises performing column chromatography on the carboxylic acid product in a silica gel bed.

11. The process of claim 1 , wherein the process results in a yield of the carboxylic acid product from 30% to 97% determined on the basis of isolated carboxylic acid.

Assignees

• Council Scient Ind Res

Inventors

• Jain Suman Lata
• Khan Shafuir Rehman
• Aniya Vineet
• Kumari Alka
• Saini Sandhya
• Khatri Praveen Kumar
• Ray Anjan

Classifications

• C07C51/47

  by solid-liquid treatment; by chemisorption · CPC title

• C07D333/40

  Thiophene-2-carboxylic acid · CPC title

• C07D307/68

  Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen · CPC title

• C07C201/12

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

• C07C51/15 Primary

  by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis · CPC title