Transfer hydroformylation for the production of oxygenates

Patent metadata

Field	Value
Publication number	US-11512035-B2
Application number	US-201917275846-A
Country	US
Kind code	B2
Filing date	Aug 20, 2019
Priority date	Sep 17, 2018
Publication date	Nov 29, 2022
Grant date	Nov 29, 2022

Abstract

The present disclosure provides a method for forming oxygenates from olefins which includes hydroformylation of aldehydes as a formyl source alternative to syngas. In at least one embodiment, a hydroformylation process is performed at low-temperature and at or near ambient pressure for the conversion of olefins into aldehydes, thus reducing the formation of by-products such as via double bond or skeletal isomerization of the feedstock; or via further conversion of the formed aldehydes and alcohols. In at least one embodiment, the use of gaseous olefinic products (e.g., ethylene) instead of strained olefins (e.g., norbornene) improves the control equilibria in transfer hydroformylation reactions.

First claim

The invention claimed is:

1. A method for preparing aldehydes, comprising:
contacting a C x aldehyde, a C y olefin, and a metal catalyst in a reaction vessel while maintaining a reaction temperature of 120° C. or less and a pressure of 150 psig or less, wherein x is an integer of from 3 to 41 and y is an integer of from 2 to 40; and
obtaining a C y+1 aldehyde product and a C x−1 alkene product,
wherein the C y olefin is a linear alpha olefin.

2. The method of claim 1 , wherein the alkene product consists essentially of linear alkenes.

3. The method of claim 1 , wherein the reaction temperature is from 80° C. to 100° C.

4. The method of claim 1 , wherein the reaction pressure is at or near ambient pressure.

5. The method of claim 1 , wherein the method is free of introducing syngas into the reaction vessel.

6. The method of claim 1 , wherein the method is free of introducing carbon monoxide into the reaction vessel.

7. The method of claim 1 , wherein the alkene product is ethylene.

8. The method of claim 1 , wherein the aldehyde is represented by formula (I):

wherein each of R 1 and R 2 is independently hydrogen, alkoxide, or substituted or unsubstituted hydrocarbyl, and each of R 3 and R 4 is independently hydrogen, or substituted or unsubstituted hydrocarbyl.

9. The method of claim 8 , wherein R 1 and R 2 are hydrogen.

10. The method of claim 8 , wherein R 3 and R 4 is independently hydrogen or C 1 to C 5 alkyl.

11. The method of claim 8 , wherein each of R 3 and R 4 is hydrogen.

12. The method of claim 1 , wherein the C 2 -C 40 olefin is represented by formula (II):

where each of R 5 , R 6 , R 7 , and R 8 is independently hydrogen, or substituted or unsubstituted hydrocarbyl group.

13. The method of claim 1 , wherein the metal catalyst is represented by formula (III):
M[L] n X  (III)

wherein M is a group 9 metal, L is any suitable ligand capable of coordinating a group 9 metal, and n is an integer of from 1 to 10.

14. The method of claim 13 , wherein M is Rh or Co.

15. The method of claim 14 , wherein the metal catalyst is selected from Rh 4 (CO) 12 , Rh 6 (CO) 16 , (acetylacetonato)dicarbonylrhodium(I), chlorodicarbonylrhodium dimer, chlorobis(ethylene)rhodium dimer, HRh(CO) 4 , HRh(CO)PPh 3 , [RhCOD(OMe)] 2 , [Rh(CO) 2 (acetylacetonato)].

16. The method of claim 14 , wherein the metal catalyst is selected from Co(acac) 3 , HCo(CO) 4 , and HRh(CO)(PPh 3 ) 3 .

17. The method of claim 1 , wherein the alkene product is represented by formula (IV):

wherein each of R 1 and R 2 is independently hydrogen, alkoxide, or substituted or unsubstituted hydrocarbyl; and each of R 3 and R 4 is independently hydrogen, or substituted or unsubstituted hydrocarbyl.

18. The method of claim 17 , wherein R 1 and R 2 of formula (IV) is hydrogen.

19. The method of claim 1 , wherein the aldehyde product is represented by formula (V):

wherein each of R 5 and R 6 is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group.

20. The method of claim 19 , wherein at least one of R 5 and R 6 is C 1 to C 38 alkyl.

21. The method of claim 20 , wherein at least one of R 5 and R 6 is C 1 to C 10 alkyl.

22. The method of claim 21 , wherein at least one of R 5 and R 6 is C 1 to C 5 alkyl.

23. The method of claim 19 , wherein at least one of R 5 and R 6 is C 10 to C 38 alkyl.

24. The method of claim 23 , wherein at least one of R 5 and R 6 is C 20 to C 38 alkyl.

25. The method of claim 24 , wherein at least one of R 5 and R 6 is C 30 to C 38 alkyl.

26. The method of claim 19 , wherein R 5 is hydrogen and R 6 is C 10 to C 38 alkyl.

27. The method of claim 26 , wherein R 6 is C 30 to C 38 alkyl.

28. The method of claim 1 , wherein the aldehyde is propanal and the aldehyde product is heptanal.

29. The method of claim 1 , wherein the aldehyde is propanal and the aldehyde product is norbornal.

30. The method of claim 1 , wherein the aldehyde is propanal and the aldehyde product is a tridecanal.

31. A method for preparing aldehydes, comprising:
1) contacting:
a) a C x aldehyde, where x is an integer of from 3 to 41, represented by formula (I):

wherein each of R 1 and R 2 is independently hydrogen, alkoxide, or substituted or unsubstituted hydrocarbyl, and each of R 3 and R 4 is independently hydrogen, or substituted or unsubstituted hydrocarbyl;
b) a C y linear alpha olefin, where y is an integer of from 2 to 40, represented by formula (II):

where each of R 5 , R 6 , R 7 , and R 8 is independently hydrogen, or substituted or unsubstituted hydrocarbyl group; and
c) a metal catalyst represented by formula (III): M[L] n (III)

wherein M is a group 9 metal, preferably Rh or Co, L is any suitable ligand capable of coordinating a group 9 metal, and n is an integer of from 1 to 10;

in a reaction vessel at a reaction temperature of from 80° C. to 100° C. and a reaction pressure of 150 psig or less; and
2) obtaining:
i) a C y+1 aldehyde product represented by formula (V):

wherein each of R 5 and R 6 is as defined above; and
ii) a C x−1 alkene product represented by formula (IV):

wherein each of R 1 , R 2 , R 3 and R 4 is as defined above.

32. The method of claim 31 , where the method is free of introducing syngas and or carbon monoxide into the reaction vessel.

33. The method of claim 31 , wherein the alkene product is ethylene.

34. The method of claim 31 , wherein each R 1 and R 2 is hydrogen, each R 3 and R 4 is independently hydrogen or C 1 to C 5 alkyl, each R 5 and R 6 is C 1 to C 5 alkyl, and M is Rh or Co.

35. The method of claim 31 , wherein the metal catalyst is selected from Rh 4 (CO) 12 , Rh 6 (CO) 16 , (acetylacetonato)dicarbonylrhodium(I), chlorodicarbonylrhodium dimer, chlorobis(ethylene)rhodium dimer, HRh(CO) 4 , HRh(CO)PPh 3 , [RhCOD(OMe)] 2 , [Rh(CO) 2 (acetylacetonato)], Co(acac) 3 , HCo(CO) 4 , and HRh(CO)(PPh 3 ) 3 .

36. The method of claim 31 , wherein the aldehyde is propanal and the aldehyde product is heptanal, norbornal, tridecanal, or a mixture thereof.

37. The method of claim 31 , wherein the alkene product consists essentially of linear alkenes.

38. The method of claim 1 , wherein the metal catalyst is selected from Rh 4 (CO) 12 , Rh 6 (CO) 16 , (acet

Assignees

• Carpenter Alex
• Wiersum Andrew
• Martens Luc
• Exxonmobil Chemical Patents Inc

Inventors

• Carpenter Alex
• Wiersum Andrew
• Martens Luc

Classifications

• C07C45/69 Primary

  by addition to carbon-to-carbon double or triple bonds · CPC title

• C07C2602/42

  the bicyclo ring system containing seven carbon atoms · CPC title