Production of two esters using homogeneous catalyst

Patent metadata

Field	Value
Publication number	US-9493395-B2
Application number	US-201514680595-A
Country	US
Kind code	B2
Filing date	Apr 7, 2015
Priority date	Apr 7, 2015
Publication date	Nov 15, 2016
Grant date	Nov 15, 2016

Abstract

Disclosed is a process for preparing two esters by reacting an aldehyde with an alcohol in the presence of a ruthenium complex compound as a catalyst. The process is particularly useful for preparing ethyl acetate and n-butyl acetate, isobutyl acetate, or 2-ethylhexyl acetate in high yield by coupling acetaldehyde with n-butanol, i-butanol, or 2-ethylhexanol.

First claim

We claim:

1. A process for preparing two ester compounds, comprising:
contacting an aldehyde with an alcohol at an aldehyde-to-alcohol molar ratio of greater than 2:1 and up to 25:1 in the presence of a ruthenium complex compound at conditions effective to produce two ester compounds.

2. The process according to claim 1 , wherein the aldehyde-to-alcohol molar ratio ranges from 4:1 to 25:1.

3. The process according to claim 1 , wherein the aldehyde-to-alcohol molar ratio ranges from 8:1 to 25:1.

4. The process according to claim 1 , wherein the aldehyde-to-alcohol molar ratio ranges from 12:1 to 25:1.

5. The process according to claim 1 , wherein the ruthenium complex compound comprises [Ru 2 (CO) 4 (μ-H)(C 4 Ph 4 COHOCC 4 Ph 4 )].

6. The process according to claim 1 , which is carried out in the absence of a hydrogen acceptor.

7. The process according to claim 1 , wherein the aldehyde and the alcohol contain 1 to 12 carbon atoms.

8. The process according to claim 7 , wherein the aldehyde comprises acetaldehyde.

9. The process according to claim 7 , wherein the alcohol comprises n-butanol, i-butanol, or 2-ethylhexanol.

10. The process according to claim 7 , wherein the two ester compounds comprise (a) ethyl acetate and (b) n-butyl acetate, isobutyl acetate, or 2-ethylhexyl acetate.

11. The process according to claim 1 , which has an aldehyde conversion of at least 95%.

12. The process according to claim 1 , which has a combined selectivity for the two ester compounds of at least 80%.

13. The process according to claim 1 , which has a combined selectivity for the two ester compounds of at least 90%.

14. The process according to claim 1 , which has a combined selectivity for the two ester compounds of at least 95%.

15. A process for preparing ethyl acetate and n-butyl acetate, isobutyl acetate, or 2-ethylhexyl acetate, the process comprising:
contacting acetaldehyde with an alcohol selected from n-butanol, i-butanol, or 2-ethylhexanol at an aldehyde-to-alcohol molar ratio of greater than 2:1 and up to 25:1 in the presence of a ruthenium complex compound at conditions effective to produce ethyl acetate and n-butyl acetate, isobutyl acetate, or 2-ethylhexyl acetate.

16. The process according to claim 15 , wherein the aldehyde-to-alcohol molar ratio ranges from 4:1 to 25:1.

17. The process according to claim 15 , wherein the aldehyde-to-alcohol molar ratio ranges from 8:1 to 25:1.

18. The process according to claim 15 , wherein the aldehyde-to-alcohol molar ratio ranges from 12:1 to 25:1.

19. The process according to claim 15 , wherein the ruthenium complex compound comprises [Ru 2 (CO) 4 (μ-H)(C 4 Ph 4 COHOCC 4 Ph 4 )].

20. The process according to claim 15 , which is carried out in the absence of a hydrogen acceptor.

21. The process according to claim 15 , which has an aldehyde conversion of at least 95%.

22. The process according to claim 15 , which produces ethyl acetate and n-butyl acetate.

23. The process according to claim 22 , which has a combined selectivity for ethyl acetate and n-butyl acetate of at least 80%.

24. The process according to claim 15 , which produces ethyl acetate and isobutyl acetate.

25. The process according to claim 24 , which has a combined selectivity for ethyl acetate and isobutyl acetate of at least 80%.

26. The process according to claim 15 , which produces ethyl acetate and 2-ethylhexyl acetate.

27. The process according to claim 26 , which has a combined selectivity for ethyl acetate and 2-ethylhexyl acetate of at least 80%.

Assignees

• Eastman Chem Co

Inventors

• Janka Mesfin Ejerssa
• Hembre Robert Thomas
• Testerman Stephanie Rollins

Classifications

• C07C67/44 Primary

  by oxidation-reduction of aldehydes, e.g. Tishchenko reaction · CPC title

• C07C67/39

  by oxidation of groups which are precursors for the acid moiety of the ester · CPC title