Claims
- 1. Process for the carbonylation of a conjugated diene by reacting the conjugated diene with carbon monoxide and an hydroxyl group containing compound in the presence of a catalyst system comprising:(a) a source of palladium cations, (b) a diphosphine ligand, and (c) a source of anions, wherein the diphosphine ligand is a ligand having the general formula I X1—R—X2 (I) wherein X1 and X2 represent a cyclic group with at least 5 ring atoms, of which one is a phosphorus atom, and R represents a bivalent aliphatic bridging group, connecting both phosphorus atoms, containing from 2 to 4 atoms in the bridge, which is substituted with at least one substituent or R represents a phenyl group with both phosphorus groups bound to the 1,2-position.
- 2. A process as claimed in claim 1, wherein R represents a bivalent aliphatic bridging group, connecting both phosphorus atoms, containing from 2 to 4 atoms in the bridge, which is substituted with at least two alkyl groups.
- 3. A process as claimed in claim 1, wherein the bridging group is a substituted dimethylene or trimethylene group.
- 4. A process as claimed in claim 1, wherein the carbon-atoms of the bridge, which are connected with the phosphorus atoms, are substituted with alkyl groups.
- 5. A process as claimed in claim 1, wherein the bridging group R is di-substituted in the bridge with two methyl groups.
- 6. A process as claimed in claim 1, wherein both X1 and X2 represent a substituted or non-substituted 9-phosphabicyclononyl group.
- 7. A process as claimed in claim 1, wherein the conjugated diene is 1,3-butadiene.
- 8. A process as claimed in claim 1, wherein the hydroxyl group containing compound is an alkanol with 1 to 20 carbon atoms per molecule or an alkanediol with 2 to 20 carbon atoms per molecule.
- 9. A process as claimed in claim 1, wherein a substoichiometric amount of halide anions is present, based on the amount of palladium cations.
- 10. A process as claimed in claim 9, wherein the source of halide anions is a source of iodide anions.
- 11. A process as claimed in claim 10, wherein the source of halide anions is hydrogen iodide.
- 12. A process as claimed in claim 9, wherein the molar ratio of halide anions versus palladium cations is in the range from 0.001:1 up to 1.5:1.
- 13. A process as claimed in claim 1, wherein the source of anions is derived from a tertiary carboxylic acid with formula (II) wherein R4, R5 and R6 independently represent alkyl or aryl groups.
- 14. A process as claimed in claim 13, wherein at least one of R4, R5 and R6 is a methyl or ethyl group.
- 15. Catalyst system comprising(a) a source of palladium cations; (b) a bidentate diphospine ligand having the general formula I X1—R—X2 (I) wherein X1 and X2 represent a cyclic group with at least 5 ring atoms, of which one is a phosphorus atom, and R represents a bivalent organic bridging group, connecting both phosphorus atoms;(c) a source of anions derived from a tertiary carboxylic acid of the formula (II) wherein R4, R5 and R6 independently represent alkyl or aryl groups; and(d) a substoichiometric amount of halide anions; with the proviso that the catalyst system contains less than 0.5 mole of an anion, other than halide anions, that is the conjugated base of an acid having a pKa less than 3, per mole palladium cations.
- 16. Catalyst system as claimed in claim 15, wherein the bridging group R is substituted with at least one substituent.
Priority Claims (2)
Number |
Date |
Country |
Kind |
00203355 |
Sep 2000 |
EP |
|
00203356 |
Sep 2000 |
EP |
|
CROSS REFERENCE TO RELATED APPLICATION
This application is the National Phase of International Application PCT/NL01/00709 filed Sep. 26, 2001 which designated the U.S., which claims priority to European application 00203356.1, filed Sep. 27, 2000 and application 00203355.3, filed Sep. 27, 2000.
PCT Information
Filing Document |
Filing Date |
Country |
Kind |
PCT/NL01/00709 |
|
WO |
00 |
Publishing Document |
Publishing Date |
Country |
Kind |
WO02/26690 |
4/4/2002 |
WO |
A |
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A |
5495041 |
Sielcken et al. |
Feb 1996 |
A |
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