Preparation method of carboxylic acids or ketones using ozone, singlet state-oxygen atom or hydroxyl free radical

Patent metadata

Field	Value
Publication number	US-9637438-B2
Application number	US-201514818139-A
Country	US
Kind code	B2
Filing date	Aug 4, 2015
Priority date	Oct 13, 2014
Publication date	May 2, 2017
Grant date	May 2, 2017

Abstract

A preparation method of carboxylic acids or ketones using ozone, singlet state oxygen atom O( 1 D) or hydroxyl free radical is provided. The method includes: filling ozone, singlet state oxygen atom O( 1 D) and/or hydroxyl free radical to cycloalkanes or benzenes at a pre-determined temperature and a pre-determined pressure in the presence or absence of light irradiation to produce carboxylic acids or ketones. The reaction occurs at room temperature and atmospheric pressure without producing harmful side products. The preparation method is a simple, low energy consuming, and eco-friendly method.

First claim

What is claimed is:

1. A method for preparation of ketones, comprising steps of:
providing an oxidant comprising at least one of a singlet state-oxygen atom O( 1 D) and a hydroxyl free radical; and
reacting the oxidant and cycloalkanes at a pre-determined temperature and a pre-determined pressure without using transition metal catalysts or bromide catalysts and without using nitric acid or acetic acid as a solvent to produce cycloketones; wherein the pre-determined temperature is in a range between −10° C. and 50° C., and the pre-determined pressure is in a range between 0.8 atm and 1.2 atm;
wherein the cycloalkanes comprise cyclopentane, cyclohexane, cycloheptane, cyclooctane or a combination thereof; the cycloketones comprise cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone or a combination thereof.

2. The method of claim 1 , wherein the singlet state-oxygen atom O( 1 D) is produced by irradiation of ozone by a light beam having a wavelength between 230 nm and 330 nm.

3. The method of claim 1 , wherein the hydroxyl free radical is produced by reaction of ozone with water, by reaction of a singlet state-oxygen atom O( 1 D) with water, by reaction of hydrogen peroxide with ferrous ions, or by reaction of hydrogen peroxide with cuprous ions.

4. A method for preparation of carboxylic acids, comprising steps of:
providing an oxidant comprising at least one of ozone, a singlet state-oxygen atom O( 1 D), and a hydroxyl free radical; and
reacting the oxidant and the cycloketones prepared by the method of claim 1 at a second pre-determined temperature and a second pre-determined pressure without using transition metal catalysts or bromide catalysts and without using nitric acid or acetic acid as a solvent to produce aliphatic dicarboxylic acids,
wherein the aliphatic dicarboxylic acids comprise glutaric acid, adipic acid, pimelic acid, suberic acid or a combination thereof.

5. The method of claim 4 , wherein the second pre-determined temperature is in a range between −10° C. and 50° C., and the second pre-determined pressure is in a range between 0.8 atm and 1.2 atm;
wherein the method further comprises a step of adding a co-solvent, and
the co-solvent comprises at least one of aluminum oxide, acetonitrile and water.

6. A method for preparation of aromatic ketones, comprising steps of:
providing an oxidant comprising at least one of ozone, a singlet state-oxygen atom O( 1 D) and a hydroxyl free radical produced by reaction of ozone with water, or by reaction of a singlet state-oxygen atom O( 1 D) with water; and
reacting the oxidant and alkylbenzenes at a pre-determined temperature and a pre-determined pressure without using transition metal catalysts or bromide catalysts and without using nitric acid or acetic acid as a solvent to produce aromatic ketones, wherein an alkyl group of the alkylbenzenes comprises two or more carbon atoms;
wherein the alkylbenzenes comprise ethyl benzene or diphenylmethane; and the aromatic ketones comprise acetophenone or benzophenone.

7. The method of claim 6 , wherein the pre-determined temperature is in a range between −10° C. and 50° C., and the pre-determined pressure is in a range between 0.8 atm and 1.2 atm.

8. The method of claim 6 , wherein the singlet state-oxygen atom O( 1 D) is produced by irradiation of ozone by a light beam having a wavelength between 230 nm and 330 nm.

9. A method for preparation of aromatic carboxylic acids, comprising steps of:
providing an oxidant comprising at least one of ozone, a singlet state-oxygen atom O( 1 D), and a hydroxyl free radical; and
reacting the oxidant and benzenes at a pre-determined temperature and a pre-determined pressure without using transition metal catalysts or bromide catalysts and without using nitric acid or acetic acid as a solvent to produce aromatic carboxylic acids, wherein the number of carbon atoms of each substituent of the benzenes is 1;
wherein the benzenes comprise toluene, p-xylene, o-xylene, m-xylene, p-toluic acid, 4-carboxybenzaldehyde or a combination thereof; and the aromatic carboxylic acids comprise benzoic acid, terephthalic acid, phthalic acid, isophthalic acid or a combination thereof.

10. The method of claim 9 , wherein the pre-determined temperature is in a range between −10° C. and 50° C., and the pre-determined pressure is in a range between 0.8 atm and 1.2 atm;
wherein the method further comprises a step of adding a co-solvent; and
the co-solvent comprises at least one of aluminum oxide, acetonitrile and water.

11. The method of claim 9 , wherein the singlet state-oxygen atom O( 1 D) is produced by irradiation of ozone by a light beam having a wavelength between 230 nm and 330 nm.

12. The method of claim 9 , wherein the hydroxyl free radical is produced by reaction of ozone with water, by reaction of a singlet state-oxygen atom O( 1 D) with water, by reaction of hydrogen peroxide with ferrous ions, or by reaction of hydrogen peroxide with cuprous ions.

Assignees

• Nat Univ Tsing Hua

Inventors

• Hwang Kuo-Chu

Classifications

• C07C63/06

  Benzoic acid · CPC title

• C07C49/786

  Benzophenone · CPC title

• C07C63/26

  1,4 - Benzenedicarboxylic acid · CPC title

• B01J19/123

  Ultraviolet light · CPC title

• C07C55/12

  Glutaric acid · CPC title