Process for the alkoxycarbonylation of functionalized alkenes

Patent metadata

Field	Value
Publication number	US-9056829-B2
Application number	US-201214240816-A
Country	US
Kind code	B2
Filing date	Aug 31, 2012
Priority date	Sep 1, 2011
Publication date	Jun 16, 2015
Grant date	Jun 16, 2015

Abstract

This invention relates to a process for the alkoxycarbonylation of carboxylic acid functionalized alkenes or esters thereof, said process comprising: (a) reacting (i) a carboxylic acid functionalized alkene or ester thereof; (ii) a catalyst system comprising a source of Pd and a ligand, (iii) a source of anions derived from an acid with a pKa<3, (iv) carbon monoxide, and (v) a hydroxylgroup comprising compound, under conditions wherein an ester carbonylation product is produced, whereby the process is carried out in the initial presence of an ester carbonylation product. The presence of the ester carbonylation product results in stabilization of the catalyst system and prevents the formation of Pd black.

First claim

The invention claimed is:

1. A process for alkoxycarbonylation of carboxylic acid functionalized alkenes and/or esters thereof, said process comprising: (a) reacting (i) a carboxylic acid functionalized alkene and/or ester thereof; (ii) a catalyst system comprising a source of Pd and a ligand, (iii) an acid with a pKa<3, (iv) carbon monoxide, and (v) a hydroxyl group comprising compound, under conditions wherein an ester carbonylation product is produced, whereby the process is carried out in initial presence of the ester carbonylation product.

2. Process according to claim 1 comprising adding an ester carbonylation product.

3. Process according to claim 2 wherein the ester carbonylation product is added prior to adding the catalyst system and/or together with the catalyst system.

4. Process according to claim 1 wherein the ligand is a bidentate diphosphine ligand of formula II:
R 1 R 2 >P 1 —R 5 —X—R 6 —P 2 <R 3 R 4   (II)

wherein P1 and P2 represent phosphorus atoms; R 1 , R 2 , R 3 and R 4 can independently represent the same or different optionally substituted organic group containing a tertiary carbon atom through which the group is linked to phosphorus atom; R 5 and R 6 independently represent optionally substituted lower alkylene groups; and X represents an optionally substituted aromatic group.

5. Process according to claim 4 wherein R 5 and R 6 represent methylene and wherein R 1 , R 2 , R 3 , and R 4 represent tert-butyl.

6. Process according to claim 1 wherein the ligand is α-α′-bis(di-tert-butylphosphino)xylene.

7. Process according to claim 1 wherein the process is a continuous process.

8. Process according to claim 1 wherein the process is repetitive batch process, wherein said repetitive batch process further comprises
(b) recovering the catalyst system from the ester carbonylation product in the presence of the ester carbonylation product; and
(c) repeating (a) wherein at least part of the catalyst system in (a) is the recovered catalyst system obtained in (b).

9. Process according to claim 8 wherein at least 10% (w/w) of the catalyst system in (a) is the recovered catalyst system obtained in (b).

10. Process according to claim 1 wherein the carboxylic functionalized alkene is a pentenoate ester, optionally pentenoate methylester.

11. Process according to claim 1 wherein the source of Pd is at least one selected from the group consisting of a palladium halide, palladium carboxylate and Pd2(dba)3.

12. An ester carbonylation product capable of being used in the process of claim 1 .

Assignees

• Parton Rudy Francois Maria Jozef
• Janssen Michèle Catherine Christianne
• Dsm Ip Assets Bv

Inventors

• Parton Rudy Francois Maria Jozef
• Janssen Michèle Catherine Christianne

Classifications

• C07C69/40

  Succinic acid esters · CPC title

• B01J2531/824

  Palladium · CPC title

• C07C67/62 Primary

  Use of additives, e.g. for stabilisation · CPC title

• B01J2231/321

  Hydroformylation, metalformylation, carbonylation or hydroaminomethylation · CPC title

• C07C69/003

  Esters of saturated alcohols having the esterified hydroxy group bound to an acyclic carbon atom · CPC title