Process for the carbonylation of an ethylenically unsaturated compound and catalyst therefore
A process for the carbonylation of an ethylenically unsaturated compound with carbon monoxide and a co-reactant. The carbonylation reaction is carried out in the presence of a novel catalyst involving: a) a source of a group VIII metal; b)a bidentate diphosphine of formula I, wherein R 1 represents a bivalent radical that together with the phosphorus atom to which it is attached is an optionally substituted 2-phospha-tricyclo[3.3.1.1{3,7}]- decyl group or a derivative thereof in which one or more of the carbon atoms are replaced by heteroatoms (“2-PA” group); wherein R 2 and R 3 independently represent univalent radicals of up to 20 atoms or jointly form a bivalent radical of up to 20 atoms; and wherein A 1 and A 2 independently represent optionally substituted alkylene groups and R represents an optionally substituted aromatic group; and, c) a source of anions.
1. A process for the carbonylation of an ethylenically unsaturated compound with carbon monoxide and a co-reactant in the presence of a catalyst comprising:
a) a source of a group VIII metal;
b) a bidentate diphosphine of formula I,
wherein R 1 represents a bivalent radical that together with the phosphorus atom to which it is attached is an optionally substituted 2-phospha-tricyclo[3.3.1.1{3,7}]-decyl group or a derivative thereof in which one or more of the carbon atoms are replaced by heteroatoms (“2-PA” group); wherein R 2 and R 3 independently represent univalent radicals of up to 20 atoms or jointly form a bivalent radical of up to 20 atoms; and wherein A 1 and A 2 independently represent optionally substituted alkylene groups and R represents an optionally substituted aromatic group; and,
c) a source of anions.
2. A catalyst comprising:
a) a source of palladium or rhodium;
b) a bidentate diphosphine of formula I,
wherein R 1 represents a bivalent radical that together with the phosphorus atom to which it is attached is an optionally substituted 2-phospha-tricyclo[3.3.1.1{3,7}]-decyl group or a derivative thereof in which one or more of the carbon atoms are replaced by heteroatoms (“2-PA” group); wherein R 2 and R 3 independently represent univalent radicals of up to 20 atoms or jointly form a bivalent radical of up to 20 atoms; and wherein A 1 and A 2 independently represent optionally substituted alkylene groups and R represents an optionally substituted aromatic group; and,
c) a source of anions.
3. The catalyst of claim 2 wherein R 2 and R 3 together with the phosphorus atom form a 2-PA group identical to R 1 .
4. The catalyst of claim 3 wherein the bidentate diphosphine is 1,2-P,P′-[di-(2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3.7}decyl)-methylene]-benzene.
5. The catalyst of claim 2 wherein the source of anions is a carboxylic acid.
6. The process of claim 1 wherein the catalyst is a catalyst comprising:
a) a source of palladium or rhodium;
b) a bidentate diphosphine of formula I,
wherein R 1 represents a bivalent radical that together with the phosphorus atom to which it is attached is an optionally substituted 2-phospha-tricyclo[3.3.1.1{3,7}]-decyl group or a derivative thereof in which one or more of the carbon atoms are replaced by heteroatoms (“2-PA” group); wherein R 2 and R 3 independently represent univalent radicals of up to 20 atoms or jointly form a bivalent radical of up to 20 atoms; and wherein A 1 and A 2 independently represent optionally substituted alkylene groups and R represents an optionally substituted aromatic group; and,
c) a source of anions.
7. The process of claim 1 wherein a carboxylic acid is used as a reaction diluent.
8. A process for the preparation of a carboxylic acid and its corresponding carboxylic anhydride comprising the following steps:
a) carbonylation of an ethylenically unsaturated compound with carbon monoxide and water to yield a carboxylic acid, said carbonylation being carried out in the presence of a catalyst comprising:
i) a source of a group VIII metal;
ii) a bidentate diphosphine of formula I,
wherein R1 represents a bivalent radical that together with the phosphorus atom to which it is attached is an optionally substituted 2-phospha-tricyclo[3.3.1.1{3,7}]-decyl group or a derivative thereof in which one or more of the carbon atoms are replaced by heteroatoms (“2-PA” group); wherein R2 and R3 independently represent univalent radicals of up to 20 atoms or jointly form a bivalent radical of up to 20 atoms; and wherein A1 and A2 independently represent optionally substituted alkylene groups and R represents an optionally substituted aromatic group; and,
iii) a source of anions; and
b) carbonylation of an ethylenically unsaturated compound with carbon monoxide and the carboxylica acid obtained in step a) in the presence of a catalyst to yield a carboxylic anhydride.
9. The process of claim 8 wherein the catalyst in step b) is a catalyst comprising:
i) a source of group VIII metal;
ii) a phosphorus containing ligand; and
iii) a source of anions.
10. The process of claim 9 wherein the source of anions iii) is the carboxylic acid prepared in step a).
11. The process of claim 8 wherein the carboxylic acid as prepared in step a) is used as a reaction diluent in both step a) and step b).
12. The process of claim 9 wherein the phosphorus containing ligand of ii) is a bidentate diphosphine.
13. The process of claim 12 wherein the bidentate diphosphine ligand of ii) is 1,2-P,P′-di(2-phospha-1,3,5,7-tetramethyl-6,9,10-trioxatricyclo[3.3.1.1{3,7}decyl)-methylene]-benzene.