Methods of using homogenous rhodium catalysts with N-heterocyclic carbene ligands for the hydroformylation of olefins and substituted olefins

Patent metadata

Field	Value
Publication number	US-9765005-B2
Application number	US-201414481528-A
Country	US
Kind code	B2
Filing date	Sep 9, 2014
Priority date	Sep 9, 2014
Publication date	Sep 19, 2017
Grant date	Sep 19, 2017

Abstract

A method of using homogenous rhodium catalysts comprising N-heterocyclic carbene ligands for the hydroformylation of olefins and substituted olefins is provided. In some aspects, the methods provided herein relate to the hydroformylation of allyl alcohol to 4-hydroxybutaldehyde in the presence of a rhodium catalyst which contains one or more N-heterocyclic carbene ligands of the formula:

wherein R 1 , R 2 , R 3 , and R 4 are defined herein.

First claim

What is claimed is:

1. A method for the hydroformylation of a terminal alkene (C≦12) or a substituted terminal alkene (C≦12) to make an aldehyde, comprising:
reacting the terminal alkene (C≦12) or the substituted terminal alkene(C≦12) with carbon monoxide (CO) and hydrogen (H 2 ) in a reaction mixture comprising a rhodium complex and an N-heterocyclic carbene ligand to produce an aldehyde (C≦13) or a substituted aldehyde (C≦13) at a H 2 /CO pressure from about 40 psi to about 600 psi;
wherein the reaction mixture further comprises a first auxiliary ligand, wherein the first auxiliary ligand is a phosphine (C≦30), a diphosphine (C≦50), a phosphite (C≦30), a diphosphite (C≦50), or a substituted version of any of these groups;
wherein the N-heterocyclic carbene ligand is selected from the group consisting of

2. The method of claim 1 , wherein the terminal alkene (C≦12) or substituted terminal alkene (C≦12) is allyl alcohol.

3. The method of claim 1 , wherein the aldehyde (C13) or substituted aldehyde (C≦13) is 4-hydroxybutyraldehyde.

4. The method of claim 1 , wherein the rhodium complex is a rhodium (I) complex with no halide ligands.

5. The method of claim 1 , wherein the rhodium complex is Rh(CO) 2 (acac), Rh(CO) 2 COD, Rh(CO) 2 (PPh3), or RhOAc.

6. The method of claim 1 , wherein the first auxiliary ligand is:

7. The method of claim 1 , wherein the reaction mixture further comprises a second auxiliary ligand, wherein the second auxiliary ligand is a phosphine (C≦30), a diphosphine (C≦50), a phosphite (C≦30), a diphosphite (C<50), or a substituted version of any of these groups.

8. The method of claim 7 , wherein the second auxiliary ligand is:

9. The method of claim 1 , wherein the method further comprises adding a solvent to the reaction mixture.

10. The method of claim 1 , wherein the reaction mixture comprising a rhodium complex and an N-heterocyclic carbene ligand produces an aldehyde (C≦13) or a substituted aldehyde (C≦13), wherein the reacting step also makes a 2-methyl aldehyde (C≦13), wherein the ratio of aldehyde (C≦13) to the 2-methyl aldehyde (C≦13) made in the reacting step is at least 10:1.

11. The method of claim 1 , further comprising heating the reaction mixture to a temperature from about 50 ° C. to about 110 ° C.

12. The method of claim 1 , where the ratio of H 2 to CO is approximately 1:1.

13. The method of claim 1 , wherein the molar ratio of the rhodium complex to the first auxiliary ligand in the reaction mixture is from about 1:0.1 to about 1:100.

14. The method of claim 1 , wherein the molar ratio of the rhodium complex to the first auxiliary ligand in the reaction mixture is from about 1:1 to about 1:2.

15. The method of claim 1 , wherein the hydroformylation is performed in a solvent system selected from the group consisting of an alcohol (C≦20), an ether (C≦20), toluene, cyclohexane, methyl t-butyl ether, isopropanol or a mixture thereof.

Assignees

• Lyondell Chemical Tech Lp
• Lyondell Chemical Tech Lp

Inventors

• Mandimutsira Beaven S
• White Daniel F
• Salisbury Brian A

Classifications

• B01J2540/10

  Non-coordinating groups comprising only oxygen beside carbon or hydrogen · CPC title

• B01J2531/822

  Rhodium · CPC title

• B01J31/2273

  with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes · CPC title

• B01J31/2404

  Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring · CPC title

• B01J2540/225

  comprising perfluoroalkyl groups or moieties · CPC title