Monophosphites having an unsymmetric biaryl unit
View Patent ↗Monophosphites having an unsymmetric biaryl structure and metal complexes thereof are provided. The metal complex compositions are useful as hydroformylation catalysts. The metals of the complex include Rh, Ru, Co and Ir. A method of hydroformylation using the metal complex or the metal complex components is also provided.
1. A monophosphite compound of structure (I) or structure (II):
wherein
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl, —S-alkyl, —S-aryl, halogen, COO—(C 1 -C 12 )-alkyl, CONH—(C 1 -C 12 )-alkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —CN, —NH 2 or —N[(C 1 -C 12 )-alkyl] 2 ;
R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 are each independently-H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl, —S-alkyl, —S-aryl, halogen, COO—(C 1 -C 12 )-alkyl, CONH—(C 1 -C 12 )-alkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —NH 2 or —N[(C 1 -C 12 )-alkyl] 2 ;
X and Y are each —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 12 )-cycloalkyl, or —(C 3 -C 12 )-heterocycloalkyl,
wherein the two R radicals in at least one of the four following radical pairs are not the same: R 1 and R 8 , R 2 and R 7 , R 3 and R 6 , R 4 and R 5 ;
and the R 3 and R 4 radicals are not joined to one another via a carbon chain;
wherein when any of R 1 to R 18 comprises any of an alkyl and an aryl group, the alkyl group and the aryl group may optionally be substituted.
2. The monophosphite compound according to claim 1 , wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —S-alkyl or —S-aryl.
3. The monophosphite compound according to claim 1 , wherein R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 are each independently —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —S-alkyl or —S-aryl.
4. The monophosphite compound according to claim 1 , wherein X is —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl or —(C 3 -C 12 )-cycloalkyl.
5. The monophosphite compound according to claim 1 , wherein Y is —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl or —(C 3 -C 12 )-cycloalkyl.
6. The monophosphite compound according to claim 1 , wherein R 1 and R 8 are not the same radical.
7. The monophosphite compound according to claim 1 , wherein X is a radical of formula (X1):
8. The monophosphite compound according to claim 1 ,
wherein X is a radical of formula (X2):
9. The monophosphite compound according to claim 1 , wherein Y is a radical of formula (Y1):
10. The monophosphite compound according to claim 1 , wherein Y is a radical of formula (Y2):
11. The monophosphite compound according to claim 1 , wherein the compound is of structure (I).
12. The monophosphite compound according to claim 1 , wherein the compound is of structure (II).
13. A metal complex, comprising:
the monophosphite compound according to claim 1 ; and
a metal selected from the group consisting of Rh, Ru, Co and Ir.
14. A method for hydroformylation comprising:
conducting the hydroformylation reaction in the presence of a metal complex of claim 13 .
15. The method for hydroformylation of claim 14 , further comprising:
a) charging an olefin to a reaction device;
b) adding the catalyst comprising the metal complex to the reaction device;
or adding a catalyst comprising a monophosphite compound of structure (I) or structure (II):
and a substance having a metal atom selected from the group consisting of Rh, Ru, Co and Ir;
c) feeding H 2 and CO into the reaction device to the olefin and catalyst to obtain a reaction mixture; and
d) heating the reaction mixture to effect conversion of the olefin to an aldehyde;
wherein
R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 17 )-alkyl, —O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl, —S-alkyl, —S-aryl, halogen, COO—(C 1 -C 12 )-alkyl, CONH—(C 1 -C 12 )-alkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —CN, —NH 2 or —N[(C 1 -C 12 )-alkyl] 2 ;
R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 are each independently —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl, —S-alkyl, —S-aryl, halogen, COO—(C 1 -C 2 )-alkyl, CONH—(C 1 -C 12 )-alkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —NH 2 or —N[(C 1 -C 12 )-alkyl];
X and Y are each —(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 3 -C 12 )-cycloalkyl, or —(C 3 -C 12 )-heterocycloalkyl,
wherein the two R radicals in at least one of the four following radical pairs are not the same: R 1 and R 8 , R 2 and R 7 , R 3 and R 6 , R 4 and R 5 ;
and the R 3 and R 4 radicals are not joined to one another via a carbon chain;
wherein when any of R 1 to R 18 comprises any of an alkyl and an aryl group, the alkyl group and the aryl group may optionally be substituted.
16. The method for hydroformylation of claim 15 , wherein the olefin is a monoolefin having 2 to 24 carbon atoms.
17. The method for hydroformylation of claim 15 , wherein the monoolefin is a terminal olefin or an internal olefin.
18. The method for hydroformylation of claim 15 , wherein the catalyst comprises monophosphite compound not complexed to a metal.
19. The method for hydroformylation of claim 15 , wherein the metal is Rh.