Process for preparing cyanoacetates

Patent metadata

Field	Value
Publication number	US-11976024-B2
Application number	US-202217838897-A
Country	US
Kind code	B2
Filing date	Jun 13, 2022
Priority date	Dec 12, 2019
Publication date	May 7, 2024
Grant date	May 7, 2024

Abstract

This invention relates to a process for producing cyanoacetates involving contacting a salt of an alkyl, alkenyl, alkynyl or aryl formyl acetate with a hydroxyl amine acid under appropriate conditions and for a time sufficient to yield a cyanoacetate.

First claim

What is claimed is:

1. A process for the preparation of a cyanoacetate, steps of which comprise:
(a) contacting an alkyl, alkenyl, alkynyl or aryl acetate with an alkyl, alkenyl, alkynyl or aryl formate in the presence of a base and for a time sufficient to form a salt of an alkyl, alkenyl, alkynyl or aryl formyl acetate;
(b) optionally, separating therefrom the so formed salt of the alkyl, alkenyl, alkynyl or aryl formyl acetate;
(c) contacting the so formed salt of the alkyl, alkenyl, alkynyl or aryl formyl acetate with a hydroxyl amine acid under appropriate conditions and for a time sufficient to yield a cyanoacetate;
(d) optionally, separating therefrom the so formed cyanoacetate.

2. The process of claim 1 , wherein the conditions of step (a) comprise in an organic polar solvent or an organic polar protic solvent.

3. The process of claim 1 , wherein the conditions of step (a) comprise at room temperature.

4. The process of claim 1 , wherein the alkyl, alkenyl, alkynyl or aryl acetate is selected from methyl acetate, ethyl acetate, propyl acetates, butyl acetates, pentyl acetates, hexyl acetates, heptyl acetates, octyl acetates, allyl acetate, propargyl acetate, phenyl acetate, phenethyl acetate, or benzyl acetate.

5. The process of claim 1 , wherein the alkyl, alkenyl, alkynyl or aryl formate is selected from methyl formate, ethyl formate, propyl formates, butyl formates, pentyl formates, hexyl formates, heptyl formates, octyl formates, allyl formate, propargyl formate, phenyl formate, phenethyl formate, or benzyl formate.

6. The process of claim 1 , wherein the basic conditions are formed from sodium hydride, potassium hydride, sodium alkoxide, potassium alkoxide, and combinations thereof.

7. The process of claim 1 , wherein the salt of an alkyl, alkenyl, alkynyl or aryl formyl acetate is selected from the sodium or potassium salt of the enol structure of methyl formyl acetate, ethyl formyl acetate, propyl formyl acetates, butyl formyl acetates, pentyl formyl acetates, hexyl formyl acetates, heptyl formyl acetates, octyl formyl acetates, allyl formyl acetate, propargyl formyl acetate, phenyl formyl acetate, phenethyl formyl acetate, or benzyl formyl acetate.

8. The process of claim 1 , wherein the hydroxyl amine acid is selected from hydroxyl amine hydrochloride or hydroxyl amine sulfur trioxide.

9. The process of claim 1 , wherein the cyanoacetate is a C 1-20 alkyl cyanoacetate, a C 6-20 aryl cyanoacetate, a C 7-20 alkaryl cyanoacetate or a C 7-20 aralkyl cyanoacetate, any of which may be substituted by one or more hydroxyl groups or C 1-20 alkyl ether groups.

10. The process of claim 1 , wherein the cyanoacetate is a C 1-20 alkyl cyanoacetate, wherein the C 1-20 alkyl may contain one or more points of unsaturation and may be substituted and/or interrupted by one or one heteroatoms or heteroatom-containing groups, or substituted by halogens or substituted or interrupted by halogen-containing groups.

11. 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 cyanoacetates, and combinations thereof.

12. The process of claim 1 , wherein the cyanoacetate is a C 6-20 aryl cyanoacetate.

13. The process of claim 1 , wherein the cyanoacetate is phenyl cyanoacetate.

14. The process of claim 1 , wherein the cyanoacetate is a C 7-20 aralkyl cyanoacetate selected from phenethyl cyanoacetate, benzyl cyanoacetate, or toluyl cyanoacetate.

15. The process of claim 1 , wherein step (b) is substantially free from starting materials and/or by-products.

16. The process of claim 1 , wherein step (d) is substantially free from starting materials and/or by-products.

17. A process for the preparation of a cyanoacetate, steps of which comprise:
(i) contacting a salt of an alkyl, alkenyl, alkynyl or aryl formyl acetate with a hydroxyl amine acid under appropriate conditions and for a time sufficient to yield a cyanoacetate;
(ii) optionally, separating therefrom the so formed cyanoacetate.

18. A process for the preparation of a cyanoacetate, steps of which comprise:
(i) contacting an alkyl, alkenyl, alkynyl or aryl acetate with an alkyl, alkenyl, alkynyl or aryl formate with a base and for a time sufficient to form a salt of an alkyl, alkenyl, alkynyl or aryl formyl acetate, and after which mixing therewith a hydroxyl amine acid under appropriate conditions and for a time sufficient to yield a cyanoacetate;
(ii) optionally, separating therefrom the so formed cyanoacetate.

19. The process of claim 17 , wherein the hydroxyl amine acid is selected from hydroxyl amine hydrochloride or hydroxyl amine sulfur trioxide.

Assignees

• Henkel Ag & Co Kgaa

Inventors

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

Classifications

• C07C253/30 Primary

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

• C07C227/18

  by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters · CPC title

• C07C253/08

  by addition of hydrogen cyanide or salts thereof to unsaturated compounds · CPC title

• C07C253/14

  by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups · CPC title

• C07C253/00 Primary

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