Process for the catalytic decarboxylative cross-ketonization of aryl and aliphatic carboxylic acid

Patent metadata

Field	Value
Publication number	US-11708317-B2
Application number	US-202017131021-A
Country	US
Kind code	B2
Filing date	Dec 22, 2020
Priority date	Jun 16, 2017
Publication date	Jul 25, 2023
Grant date	Jul 25, 2023

Abstract

The present invention pertains to a process for the cross-ketonization (Piria reaction) between an aryl carboxylic acid and an aliphatic carboxylic acid using a metal-based compound and a slight or a moderate excess of aryl carboxylic acid. A good selectivity, up to 99 mol %, can be achieved. The aryl aliphatic ketone can be used for the preparation of surfactants and other downstream products.

First claim

The invention claimed is:

1. A process for the preparation of at least one end compound from at least one aryl aliphatic ketone K,
said aryl aliphatic ketone K being an aryl aliphatic ketone of formula (I)

wherein Ar represents an aryl radical and Rn represents a C 3 -C 27 aliphatic group,
said process comprising
synthesizing the aryl aliphatic ketone K through a process for the catalytic decarboxylative cross-ketonisation of aryl- and aliphatic carboxylic acids comprising the steps of:
a) Providing a mixture containing:
i) an aryl carboxylic acid,
ii) an aliphatic carboxylic acid,
iii) a metal-containing compound;

in which the number of moles of the metal in the mixture is at least equal to 90% of the sum of the number of moles of aryl carboxylic acid and the number of moles of aliphatic carboxylic acid divided by the valency of the metal,
said mixture being substantially free of any added solvent;
b) heating the mixture at a temperature sufficient to form metal carboxylates;
c) further heating the mixture at a temperature sufficient to form a dialiphatic ketone and an aryl aliphatic ketone K;
d) adding to the reaction mixture of step c):
i) aryl carboxylic acid in an amount which corresponds substantially to the amount of aryl carboxylic acid consumed during the formation of the aryl aliphatic ketone K in step c);
ii) aliphatic carboxylic acid in an amount which corresponds substantially to the amount of aliphatic carboxylic acid consumed during the formation of the aryl aliphatic ketone K and the dialiphatic ketone in step c);

maintaining the mixture at a temperature sufficient to continue forming the dialiphatic ketone and the aryl aliphatic ketone K;
e) optionally repeating step d),

causing the aryl aliphatic ketone K to react in accordance with a single or multiple chemical reaction scheme involving at least one reagent other than the aryl aliphatic ketone K, wherein at least one product of the chemical reaction scheme is the end compound product that is not further caused to be chemically converted into another compound.

2. The process according to claim 1 , wherein the aryl aliphatic ketone K is caused to react directly with at least one reagent chosen from the list consisting of ammonia, primary or secondary amines and mixtures of at least one aldehyde with ammonia or with at least one primary or secondary amine, thereby obtaining an intermediate or an end compound that is not further caused to be chemically converted into another compound.

3. The process according to claim 2 , wherein an intermediate is obtained and the so-obtained intermediate further reacts with a reagent selected from the group consisting of alkylating agents, acrylate derivatives, hydrogen and hydrogen peroxide.

4. The process according to claim 1 , wherein the aryl aliphatic ketone K is caused to react directly with at least one reagent chosen from the list consisting of sulfonating agents, diesters derived from tartaric acid, phenol and other aromatic mono- or polyalcohols, anilines, formaldehyde, polyols, acrylates derivatives, acrylonitrile, and hydroxylamine, thereby obtaining an intermediate or an end compound.

5. The process according to claim 4 , wherein an intermediate is obtained and the so-obtained intermediate further reacts with a reagent selected from the group consisting of ethylene and/or propylene oxide, sodium hydroxide and hydrogen, thereby obtaining an end compound.

6. The process according to claim 1 , wherein the aryl aliphatic ketone K is engaged in a sulfonation reaction.

7. The process according to claim 6 , wherein the sulfonation is conducted using SO 3 as sulfonating agent, thereby obtaining a sulfonic acid.

8. The process according to claim 7 , wherein the obtained sulfonic acid is neutralized using an aqueous solution of XOH or X(OH) 2 , wherein X can be Li, Na, K, Cs, NH 4 , triethanolammonium, Mg or Ca in order to obtain a sulfonate salt.

9. The process according to claim 8 , wherein the aryl aliphatic ketone K is of formula (I′)

wherein Ar represents an aryl radical and R′ n represents a C 2 -C 26 aliphatic group and the sulfonate salt is of formula (XXIII)

10. A compound of formula (XXIII)

wherein Ar represents an aryl radical and R′ n represents a C 2 -C 26 aliphatic group.

11. The compound of claim 10 , wherein Ar represents a phenyl group.

12. The compound of claim 10 , wherein R′ n is selected from the group consisting of C 5 -C 16 alkyl and C 5 -C 16 alkenyl groups.

13. The compound of claim 10 , wherein Ar represents a phenyl group and R′ n is a C 5 -C 16 alkyl group.

14. The process according to claim 1 , wherein the metal of the metal-containing compound is Fe or Mg.

15. The process according to claim 1 , wherein the aryl aliphatic ketone K is condensed with glycerol to afford at least one intermediate as a mixture of 2 isomers of formulae (XXIXa) and (XXIXb)

16. The process according to claim 15 , wherein the at least one intermediate as a mixture of the 2 isomers (XXIXa) and (XXIXb) is condensed with m+n equivalents of alkylene oxide consisting of m equivalents of propylene oxide and/or n equivalents of ethylene oxide wherein m and n are integers ranging from 0 to 50 provided at least one of m and n is of at least 1, in order to afford the non-ionic surfactants as a mixture of 2 isomers (XXXa) and (XXXb):

17. A compound of formula (XXXa) or (XXXb), or a mixture thereof,

wherein
Ar represents an aryl radical,
Rn represents a C 11 -C 27 aliphatic group,
m and n are integers ranging from 0 to 50, provided at least one of m and n is of at least 1.

18. The compound of formula (XXXa) or (XXXb), or mixture thereof according to claim 17 , wherein Ar represents a phenyl group.

19. The compound of formula (XXXa) or (XXXb), or mixture thereof according to claim 17 , wherein Rn is selected from the group consisting of C 7 -C 17 alkyl and C 7 -C 17 alkenyl groups.

20. The compound of formula (XXXa) or (XXXb), or mixture thereof according to claim 17 , wherein Ar represents a phenyl group and Rn represents a C 7 -C 17 alkyl group.

Assignees

• Rhodia Operations

Inventors

• Back Olivier
• Marion Philippe

Classifications

• C07C45/48 Primary

  involving decarboxylation · CPC title

• C07C49/76

  Ketones containing a keto group bound to a six-membered aromatic ring (compounds having a keto group being part of a condensed ring system and being bound to a six-membered aromatic ring C07C49/657 - C07C49/757) · CPC title

• C07C51/265

  having alkyl side chains which are oxidised to carboxyl groups · CPC title

• C07C51/38

  by decarboxylation · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title