Highly isoselective catalyst for alkene hydroformylation

Patent metadata

Field	Value
Publication number	US-10144751-B1
Application number	US-201715824347-A
Country	US
Kind code	B1
Filing date	Nov 28, 2017
Priority date	Nov 28, 2017
Publication date	Dec 4, 2018
Grant date	Dec 4, 2018

Abstract

Ligands for use with catalyst compositions used in hydroformylation reactions are described herein. The ligands are used with various octofluorotoluene or hydrocarbon solvents and achieve an increase in isoselectivity with an increase in temperature, an increase in TON with an increase in temperature, and/or will show isoselectivity that is surprisingly high in comparison to the hydroformylation reactions using common solvents.

First claim

The invention claimed is:

1. A process for preparing at least one aldehyde under hydroformylation temperature and pressure conditions, comprising contacting at least one olefin with hydrogen and carbon monoxide in the presence of at least one fluorinated solvent and a transition metal-based catalyst composition comprising a phospholane phosphite ligand represented by the following general formula:

wherein:
R1 and R2 are independently selected from substituted and unsubstituted, aryl, alkyl, aryloxy or cycloalkyl groups containing from 1 to 40 carbon atoms;
R3 and R4 are independently selected from substituted and unsubstituted, aryl, alkyl, alkoxy, trialkylsilyl, triarylsilyl, aryldialkylsilyl diarylalkylsilyl and cycloalkyl groups containing from 1 to 20 carbon atoms, wherein the silicon atom of the alkylsilyl is in the alpha position of the substituent; and
R5 is independently selected from H, or alkyl group.

2. The process of claim 1 , wherein the phospholane phosphite ligand is represented by the following general formula:

3. The process of claim 1 , wherein the fluorinated solvent is octofluorotoluene.

4. The process of claim 1 , wherein the fluorinated solvent is perfluorophenyl octyl ether.

5. The process of claim 1 , wherein the product of the process comprises an iso-selectivity of about 55% to about 80%.

6. The process of claim 4 , wherein the product of the process comprises an iso-selectivity of about 55% to about 77%.

7. The process of claim 1 , wherein the product of the process comprises an iso-selectivity of 55% or greater.

8. The process of claim 1 , wherein the pressure ranges from about 2 atm to about 80 atm.

9. The process of claim 8 , wherein the pressure ranges from about 8 atm to about 20 atm.

10. The process of claim 1 , wherein the pressure is about 8 atm.

11. The process of claim 1 , wherein the pressure is about 20 atm.

12. The process of claim 1 , wherein the temperature ranges from about 40 about 120 degrees Celsius.

13. The process of claim 1 , wherein the temperature ranges from about 50 about 90 degrees Celsius.

14. The process of claim 1 , wherein the temperature is about 50 degrees Celsius.

15. The process of claim 1 , wherein the temperature is about 75 degrees Celsius.

16. The process of claim 1 , wherein the temperature is about 90 degrees Celsius.

17. The process of claim 1 , wherein the olefin comprises propylene.

18. The process of claim 1 , wherein the transition metal based catalyst comprises a rhodium based catalyst.

19. A process for preparing at least one aldehyde under hydroformylation temperature and pressure conditions, comprising contacting at least one olefin with hydrogen and carbon monoxide in the presence of at least one fluorinated solvent and a transition metal-based catalyst composition comprising a phospholane phosphite ligand derived from an achiral biphenol diol component.

20. The process of claim 19 , wherein the phospholane phosphite ligand derived from the achiral biphenol diol component is selected from the following ligands, (A) through (D), represented by their general formulas:

21. The process of claim 19 , wherein the fluorinated solvent is octofluorotoluene.

22. The process of claim 19 , wherein the fluorinated solvent is perfluorophenyl octyl ether.

23. The process of claim 19 , wherein the product of the process comprises an iso-selectivity of about 55% to about 80%.

24. The process of claim 19 , wherein the product of the process comprises an iso-selectivity of 55% or greater.

25. The process of claim 19 , wherein the pressure ranges from about 2 atm to about 80 atm.

26. The process of claim 19 , wherein the temperature ranges from about 40 about 120 degrees Celsius.

27. The process of claim 19 , wherein the olefin comprises propylene.

28. The process of claim 19 , wherein the transition metal based catalyst comprises a rhodium based catalyst.

29. A transition metal-based catalyst composition comprising a phospholane phosphite ligand derived from an achiral biphenol diol component, wherein the ligand is selected from the following ligands, (A) through (D), represented by their general formulas:

Assignees

• Eastman Chem Co

Inventors

• Iu Leo
• Clarke Matthew
• Fontenot Kevin John
• Janka Mesfin Ejerssa

Classifications

• B01J2231/321

  Hydroformylation, metalformylation, carbonylation or hydroaminomethylation · CPC title

• B01J2531/822

  Rhodium · CPC title

• C07F9/6571 Primary

  having phosphorus and oxygen atoms as the only ring hetero atoms · CPC title

• B01J31/1875

  Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof) · CPC title

• C07C45/50 Primary

  by oxo-reactions · CPC title