Process for the direct alpha-methylenation of ketones

Patent metadata

Field	Value
Publication number	US-11401228-B2
Application number	US-201917293981-A
Country	US
Kind code	B2
Filing date	Nov 18, 2019
Priority date	Nov 20, 2018
Publication date	Aug 2, 2022
Grant date	Aug 2, 2022

Abstract

The invention relates to a process for preparing an α-methylene ketone comprising the step of reacting a ketone with formaldehyde in the presence of a catalyst which is an organic compound comprising at least one acid function or the corresponding salt, ester or amide thereof and at least one amine function or the corresponding ammonium salt, or a zwitterion thereof.

First claim

The invention claimed is:

1. A process for preparing an α-methylene ketone, the process comprising reacting a ketone with formaldehyde in the presence of a catalyst which is an organic compound comprising at least one acid function or the corresponding salt, ester or amide thereof and at least one amine function or the corresponding ammonium salt, or a zwitterion thereof,
wherein the reaction is conducted in the presence of an additional acid and wherein the catalyst is a compound of the general formula (II):

wherein R 1 is H or a hydrocarbon residue which is optionally interrupted by one or more heteroatoms and/or heteroatom(s) containing groups and/or which are optionally substituted with one or more functional groups,
X is an acid function or the corresponding salt, ester or amide, and
L is a linker, which has 1 to 6 atoms between N and X,
wherein any atom of R 1 is optionally attached to any atom of L to form a ring, or the corresponding ammonium salt of the amine function;
or a zwitterion thereof.

2. The process according to claim 1 , wherein the ketone has the general chemical formula (I)

wherein R is a hydrocarbon radical which may be interrupted by one or more heteroatoms and/or heteroatom(s) containing groups and/or which may be substituted with one or more functional groups, and
R′ is H or a hydrocarbon radical which may be interrupted by one or more heteroatoms and/or heteroatom(s) containing groups and/or which may be substituted with one or more functional groups,
wherein R and R′ together with the —C(O)—CH 2 — moiety may form a ring.

3. The process according to claim 2 , wherein in the ketone of formula (I) the R and R′ independently of each other comprise 1 to 30 carbon atoms.

4. The process according to claim 2 , wherein in the ketone of formula (I) the hydrocarbon radicals independently are alkyl which may be linear or branched, alkenyl which may be linear or branched, alkynyl which may be linear or branched, cycloalkyl, or aryl, or combinations of any of these groups.

5. A process for preparing an α-methylene ketone, the process comprising reacting a ketone with formaldehyde in the presence of a catalyst which is an organic compound comprising at least one acid function or the corresponding salt, ester or amide thereof and at least one amine function or the corresponding ammonium salt, or a zwitterion thereof, and also in the presence of an additional acid, wherein the additional acid is selected from the group consisting of HCl, HBr, HI, H 2 SO 4 , HClO 4 , HNO 3 , and H 3 PO 4 .

6. The process according to claim 1 , wherein the catalyst is selected from the group consisting of glycine, valine, serine, methionine, cysteine, proline, sarcosine, β-alanine, phenylalanine, aminomethylphosphonic acid, taurine, methylalanine, isoleucine, and tert-leucine, preferably valine, proline, β-alanine, glycine and methylalanine, more preferably valine, β-alanine, glycine and methylalanine.

7. The process according to claim 1 , wherein the reaction is conducted in the presence of a solvent.

8. The process according to claim 1 , wherein the catalyst is present at an amount of at least 1 mol %, based on the amount of the ketone.

9. The process according to claim 1 , wherein the catalyst is present at an amount of less than 90 mol %, based on the amount of the ketone.

10. The process according to claim 1 , wherein the ketone is present at a concentration of less than 5 mol/1.

11. The process according to claim 2 , wherein the molar ratio of catalyst to further acid is in the range of 0.1 to 3.0.

12. The process according to claim 1 , wherein the formaldehyde is present at an amount of at least 150 mol %, based on the amount of the ketone.

13. The process according to claim 1 , wherein the reaction is conducted at a temperature in the range of 25° C. to 200° C.

14. The process according to claim 7 , wherein the reaction is conducted in the presence of an organic solvent selected from the group consisting of DMSO, THF, methyl-THF, ethylacetate, toluene, benzene, acetone, dimethyl formamide, acetonitrile, alcohols, halogenated solvents, and ketones with the exception of ketones bearing a —CH 2 — moiety next to the carbonyl group.

15. The process according to claim 9 , wherein the catalyst is present at an amount of less than 60 mol %, based on the amount of the ketone.

16. The process according to claim 15 , wherein the catalyst is present at an amount of less than 45 mol %, based on the amount of the ketone.

17. The process according to claim 16 , wherein the catalyst is present at an amount of less than 25 mol %, based on the amount of the ketone.

Assignees

• Rhodia Operations

Inventors

• Back Olivier

Classifications

• C07C49/807

  all halogen atoms bound to the ring · CPC title

• C07C45/75 Primary

  Reactions with formaldehyde · CPC title

• C07C49/794

  having unsaturation outside an aromatic ring · CPC title

• C07C69/738

  Esters of keto-carboxylic acids {or aldehydo-carboxylic acids} · CPC title

• C07C67/343

  by increase in the number of carbon atoms · CPC title