Process for preparing cyanoacetates

Patent metadata

Field	Value
Publication number	US-12351540-B2
Application number	US-202117503897-A
Country	US
Kind code	B2
Filing date	Oct 18, 2021
Priority date	Apr 18, 2019
Publication date	Jul 8, 2025
Grant date	Jul 8, 2025

Abstract

This invention relates to a process for producing cyanoacetates using asparagine as a precursor to cyanoacetamide, a staring material to form the cyanoacetates.

First claim

What is claimed is:

1. A process for the preparation of a cyanoacetate, steps of which comprise:
(a) contacting asparagine with a halogenating agent in an acidic environment to form cyanoacetamide;
(b) optionally, separating therefrom the so-formed cyanoacetamide;
(c) contacting the so-formed cyanoacetamide with an alcohol, in the presence of a mineral acid to form a cyanoacetate; and
(d) optionally, separating therefrom the so-formed cyanoacetate, wherein the cyanoacetate is a C 1-20 alkyl cyanoacetate, wherein the C 1-20 alkyl may be straight chain or branched, contain one or more points of unsaturation and may be substituted and/or interrupted by one or heteroatoms or heteroatom-containing groups, or substituted by halogens or substituted or interrupted by halogen-containing groups.

2. The process of claim 1 , wherein step (a) is conducted for a time sufficient to yield the cyanoacetamide.

3. The process of claim 1 , wherein step (c) is conducted for a time sufficient to yield the cyanoacetate.

4. The process of claim 1 , wherein step (b) yields cyanoacetamide free from the halogenating agent and acid, and by-products.

5. The process of claim 1 , wherein step (d) yields cyanoacetate free from the cyanoacetamide, the alcohol, and mineral acid, and by-products.

6. The process of claim 1 , wherein the cyanoacetate is a C 1-20 alkyl cyanoacetate selected from methyl cyanoacetate, ethyl cyanoacetate, propyl cyanoacetates, butyl cyanoacetates, pentyl cyanoacetates, octyl cyanoacetates, alkoxy ether alkyl cyanoacetates, allyl cyanoacetate, and combinations thereof.

7. The process of claim 1 , wherein the halogenating agent is selected from trihaloisocyanuric acid, N-halosuccinimide, hypochlorites and N-halo-p-toluenesulfonamide salts.

8. The process of claim 1 , wherein the halogenating agent is selected from tribromoisocyanuric acid or trichloroisocyanuric acid.

9. The process of claim 1 , wherein the halogenating agent is selected from N-chlorosuccinimide or N-bromosuccinimide.

10. The process of claim 1 , wherein the halogenating agent is selected from sodium hypochlorite or calcium hypochlorite.

11. The process of claim 1 , wherein the halogenating agent is N-chloro-p-toluenesulfonamide sodium salt.

12. The process of claim 1 , wherein the acidic environment of step (a) is due to the addition of a citric acid buffer.

13. The process of claim 1 , wherein the acidic environment of step (a) is due to the addition of a citric acid phosphate buffer.

14. The process of claim 1 , wherein the alcohol is an alkyl alcohol, an aryl alcohol, an alkaryl alcohol or an aralkyl alcohol.

15. The process of claim 1 , wherein the alcohol is selected from methanol, ethanol, propanols, proparganols, butanols, pentanols, hexanols, octanols, nonanols, oxononanols, decanols, dodecanols, allanol, cyclohexanol, tetrahydrofurfurol, chloroethanol, 2,2,2-trifluoroethanol, hexafluoroisopropanol, alkoxy ether alkanols, dialkyl siloxanols, or trialkylsilylalkanols.

16. A process for the preparation of a cyanoacetate, steps of which comprise:
(a) contacting asparagine with a halogenating agent in an acidic environment to form cyanoacetamide;
(b) optionally, separating therefrom the so-formed cyanoacetamide;
(c) contacting the so-formed cyanoacetamide with an alcohol, in the presence of a mineral acid to form a cyanoacetate;
(d) optionally, separating therefrom the so-formed cyanoacetate, wherein the alcohol is an aromatic alcohol.

17. The process of claim 1 , wherein the alcohol is selected from phenol, benzyl alcohol or derivatives thereof.

18. The process of claim 1 , wherein the mineral acid used in step (c) is selected from sulfuric acid, sulfurous acid, sulfonic acid, phosphoric acid, phosphorous acid, phosphonic acid, hydrochloric acid or hydrobromic acid.

19. The process of claim 18 , wherein the mineral acid is used in step (c) in an amount of about 0.5 to about 1.5 equivalents to about 1 equivalent of cyanoacetamide.

20. The process of claim 18 , wherein the mineral acid is used in step (c) in an amount of about 0.6 to about 1.2 equivalents to about 1 equivalent of cyanoacetamide.

21. The process of claim 1 , wherein the alcohol in step (c) is used in excess to either or both of the cyanoacetamide and the mineral acid.

22. The process of claim 1 , wherein the cyanoacetate is formed in an amount of about 70% or greater.

23. The process of claim 1 , wherein the cyanoacetate is formed in an amount of about 90% or greater.

24. The process of claim 1 , wherein step (b) is free from the asparagine, halogenating agents, and by-products.

25. The process of claim 1 , wherein step (d) is free from the cyanoacetamide, mineral acid, and/or alcohol, and by-products.

Assignees

• Henkel Ag & Co Kgaa

Inventors

• Duffy Cormac
• O'Sullivan Justine
• Goff Ciara
• Farid Umar
• Ramos Jessica
• Thai Trung King Michael
• Cobo Cardenete Isidro
• Phelan Marisa
• Burns Barry

Classifications

• C07C253/30

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

• C07C253/00 Primary

  Preparation of carboxylic acid nitriles (of cyanogen or compounds thereof C01C3/00) · CPC title

• C07C253/34

  Separation; Purification · CPC title

• C07C255/19

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

• C07C67/20

  from amides or lactams · CPC title