Preparation of compounds from levulinic acid

Patent metadata

Field	Value
Publication number	US-10870622-B2
Application number	US-201916555710-A
Country	US
Kind code	B2
Filing date	Aug 29, 2019
Priority date	Jan 30, 2015
Publication date	Dec 22, 2020
Grant date	Dec 22, 2020

Abstract

The present invention provides a method of making carboxylic acids from levulinic acid, such as succinic acid and 3-hydroxypropanoic acid, by reacting levulinic acid with an oxidant such as hydrogen peroxide under acidic or basic conditions.

First claim

What is claimed is:

1. A method of preparing a carboxylic acid, wherein the carboxylic acid is 3-hydroxypropanoic acid, comprising:
forming a reaction mixture comprising levulinic acid, a peroxide oxidant, and a strong base, under conditions suitable to prepare the carboxylic acid.

2. The method of claim 1 , wherein the peroxide oxidant is hydrogen peroxide.

3. The method of claim 2 , wherein the reaction mixture is free of an oxidizing metal catalyst.

4. The method of claim 1 , wherein the strong base is selected from the group consisting of sodium hydroxide and potassium hydroxide.

5. The method of claim 1 , wherein the reaction mixture is at a temperature between about 75° C. and about 200° C.

6. The method of claim 1 , wherein the peroxide oxidant is hydrogen peroxide and the strong base is potassium hydroxide, and wherein the method comprises:
forming the reaction mixture comprising levulinic acid, hydrogen peroxide, and potassium hydroxide, wherein the reaction mixture is at a temperature between about 100° C. and about 150° C., thereby forming the 3-hydroxypropanoic acid.

7. A method of preparing a carboxylic acid, wherein the carboxylic is 3-hydroxypropanoic acid, comprising:
forming a reaction mixture comprising levulinic acid, a peroxide oxidant, and a strong base, wherein the reaction mixture is at a temperature between about 0° C. and about 50° C. such that the product of the forming step is 3-(hydroperoxy)propanoic acid, and the method further comprises:
forming a second reaction mixture comprising the 3-(hydroperoxy)propanoic acid and a hydrogenation agent, under conditions suitable to form the 3-hydroxypropanoic acid.

8. The method of claim 7 , wherein the hydrogenation agent is hydrogen gas and palladium on carbon.

9. The method of claim 7 , wherein the peroxide oxidant is hydrogen peroxide, the strong base is potassium hydroxide, and the hydrogenation agent is hydrogen gas and palladium on carbon, and wherein the method comprises:
forming the reaction mixture comprising levulinic acid, hydrogen peroxide, and potassium hydroxide, wherein the reaction mixture is at about room temperature, thereby preparing 3-(hydroperoxy)propanoic acid; and
forming the second reaction mixture comprising the 3-(hydroperoxy)propanoic acid, hydrogen gas and palladium on carbon, under conditions suitable to form the 3-hydroxypropanoic acid.

10. The method of claim 7 , further comprising prior to the second forming step:
contacting the reaction mixture with an acid such that the pH of the reaction mixture is less than 7.0; and
isolating the 3-(hydroperoxy)propanoic acid via extraction.

11. The method of claim 10 , wherein the acid is selected from the group consisting of hydrofluoric acid, hydrochloric acid, hydrobromic acid, hypochloric acid, sulfuric acid, nitric acid, phosphoric acid, hexafluorophosphoric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, fluoroacetic acid, and trifluoroacetic acid.

12. The method of claim 7 , wherein the peroxide oxidant is hydrogen peroxide, the strong base is potassium hydroxide, and the hydrogenation agent is hydrogen gas and palladium on carbon, and wherein the method comprises:
forming the reaction mixture comprising levulinic acid, hydrogen peroxide, and potassium hydroxide, wherein the reaction mixture is at about room temperature, thereby preparing 3-(hydroperoxy)propanoic acid;
contacting the reaction mixture with hydrochloric acid such that the pH of the reaction mixture is less than 7.0;
isolating the 3-(hydroperoxy)propanoic acid via extraction; and
forming the second reaction mixture comprising the 3-(hydroperoxy)propanoic acid, hydrogen gas and palladium on carbon, under conditions suitable to form the 3-hydroxypropanoic acid.

Assignees

• Univ California

Inventors

• Mascal Mark
• Dutta Saikat
• Wu Linglin

Classifications

• C07C51/285

  with peroxy-compounds · CPC title

• C07C51/367

  by introduction of functional groups containing oxygen only in singly bound form · CPC title

• C07C59/01

  Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups · CPC title

• C07C55/10

  Succinic acid · CPC title

• C07C407/00 Primary

  Preparation of peroxy compounds · CPC title