Preparation of 4-amino-2,4-dioxobutanoic acid

Patent metadata

Field	Value
Publication number	US-9290443-B2
Application number	US-201414489329-A
Country	US
Kind code	B2
Filing date	Sep 17, 2014
Priority date	Mar 14, 2013
Publication date	Mar 22, 2016
Grant date	Mar 22, 2016

Abstract

A process for synthesizing 4-amino-2,4-dioxobutanoate involves reacting a dialkyl oxalate with an alkoxide in ethanol to form a reaction mixture, and afterward adding an alkyl cyano acetate to the reaction mixture and allowing a reaction to proceed under conditions suitable to form a first reaction product of the formula diethyl 2-cyano-3-hydroxy-butenedioate, and then isolating the diethyl 2-cyano-3-hydroxy-butenedioate, and afterward reacting the diethyl-2-cyano-3-hydroxy-butenedioate with an aqueous hydroxide under conditions suitable to form 4-amino-2,4-dioxobutanoate. The 4-amino-2,4-dioxobutanoate may be acidified into 4-amino-2,4-dioxobutanoic acid.

First claim

What is claimed is:

1. A process for synthesizing 4-amino-2,4-dioxobutanoate, comprising:
reacting a dialkyl oxalate with an alkoxide in an alcoholic solvent to form a reaction mixture, and afterward
adding an alkyl cyanoacetate to the reaction mixture and allowing a reaction to proceed under conditions suitable to form a first reaction product of the formula diethyl 2-cyano-3-hydroxy-butenedioate,
isolating said first reaction product of diethyl 2-cyano-3-hydroxy-butenedioate,
reacting said first reaction product of diethyl 2-cyano-3-hydroxy-butenedioate with aqueous hydroxide under conditions suitable to form 4-amino-2,4-dioxobutanoate.

2. The process of claim 1 further comprising acidifying said 4-amino-2,4-dioxobutanoate to form 4-amino-2,4-dioxobutanic acid.

3. The process of claim 1 wherein said dialkyl oxalate is diethyl oxalate.

4. The process of claim 1 wherein said alkyl cyanoacetate is ethyl cyanoacetate.

5. The process of claim 1 wherein said alkoxide is sodium ethoxide.

6. The process of claim 1 wherein said alcoholic solvent is ethanol.

7. The process of claim 1 wherein said alkoxide is selected from the group consisting of sodium ethoxide, potassium ethoxide, lithium ethoxide, cesium ethoxide and calcium ethoxide.

8. A process for synthesizing 4-amino-2,4-dioxobutanoate, comprising:
reacting a dialkyl oxalate with an alkoxide in a first suitable solvent to form a reaction mixture, and afterward
adding an alkyl cyanoacetate to the reaction mixture, and afterward
extracting the reaction mixture with a suitable organic solvent and water to form an organic layer and an aqueous layer,
then separating the aqueous layer from the organic layer,
then acidifying the aqueous layer and extracting the acidified aqueous layer with additional suitable organic solvent to form a second aqueous layer and a second organic layer,
then isolating diethyl-2-cyano-3-hydroxy-butenedioate from the second organic layer,
then reacting the diethyl-2-cyano-3-hydroxy-butenedioate with an aqueous hydroxide under conditions suitable to form 4-amino-2,4-dioxobutanoate.

9. The process of claim 8 further comprising acidifying said 4-amino-2,4-dioxobutanoate to form 4-amino-2,4-dioxobutanic acid.

10. The process of claim 8 , wherein the suitable organic solvent for extracting the reaction mixture is dichloromethane.

11. The process of claim 8 wherein the first and second organic layers are combined, and the diethyl-2-cyano-3-hydroxy-butenedioate is isolated from the combined organic layers.

12. The process of claim 8 wherein said alkoxide is selected from the group consisting of sodium ethoxide, potassium ethoxide, lithium ethoxide, cesium ethoxide and calcium ethoxide.

13. The process of claim 8 wherein said dialkyl oxalate is diethyl oxalate.

14. The process of claim 8 wherein said alkyl cyanoacetate is ethyl cyanoacetate.

15. The process of claim 8 wherein said alkoxide is sodium ethoxide.

16. The process of claim 8 wherein said first suitable solvent is ethanol.

17. The process of claim 8 wherein said alkoxide is selected from the group consisting of sodium ethoxide, potassium ethoxide, lithium ethoxide, cesium ethoxide and calcium ethoxide.

Assignees

• Los Alamos Nat Security Llc
• New Mexico Highlands University

Inventors

• Unkefer Pat J
• Martinez Rodolfo A
• Glass David R

Classifications

• C07C253/30

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

• C07C255/23

  containing cyano groups and carboxyl groups, other than cyano groups, bound to the same unsaturated acyclic carbon skeleton · CPC title

• C07C231/065 Primary

  By hydration using metals or metallic ions as catalyst · CPC title

• C07C235/80

  having carbon atoms of carboxamide groups and keto groups bound to the same carbon atom, e.g. acetoacetamides · CPC title