Phosphorous compounds useful as ligands and compositions and methods regarding them

Patent metadata

Field	Value
Publication number	US-9308527-B2
Application number	US-201514657532-A
Country	US
Kind code	B2
Filing date	Mar 13, 2015
Priority date	Mar 17, 2014
Publication date	Apr 12, 2016
Grant date	Apr 12, 2016

Abstract

This describes bidentate ferrocene-linked phosphine-phosphoramidate compounds. Hydroformylation catalyst compositions and methods of hydroformylation using the compounds are also disclosed. Methods of making the compounds are also disclosed.

First claim

The invention claimed is:

1. A compound having a structure of general formula (I):

Wherein:
R 1 and R 2 are independently selected from substituted and unsubstituted, aryl, alkyl, aryloxy or cycloalkyl groups containing from 1 to 40 carbon atoms; and
R 6 and R 7 are independently selected from substituted and unsubstituted, aryl, alkyl, 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
R 3 , R 4 , R 5 , R 8 , and R 9 are independently selected from hydrogen and substituted and unsubstituted alkyl, cycloalkyl and aryl groups containing 1 to 20 carbon atoms.

2. The compound of claim 1 , wherein R 1 and R 2 are independently selected from substituted and unsubstituted C 6 -C 14 aryl groups.

3. The compound of claim 1 , wherein R 1 and R 2 are independently selected from substituted and unsubstituted phenyl groups.

4. The compound of claim 1 , wherein R 1 and R 2 are independently selected from phenyl groups having at least one substitution located in a meta-configuration with respect to the phosphorus, said substitution being independently selected from trifluoromethyl, trichloromethyl, cyano, sulfonic acid ester groups, carboxylic acid groups, carboxylic acid ester groups, salts of carboxylic acids, salts of sulfonic acids, quaternary ammonium groups, halogen atoms, and nitro groups.

5. The compound of claim 1 , wherein each R 6 and R 7 group is independently selected from C 1 -C 4 alkyl groups and trimethylsilyl.

6. The compound of claim 1 , wherein R 8 and R 9 are both hydrogen.

7. The compound of claim 1 , wherein at least one of R 8 and R 9 is independently selected from substituted and unsubstituted C 6 -C 14 aryl groups.

8. The compound of claim 7 , wherein one of R 8 and R 9 is hydrogen.

9. The compound of claim 1 , wherein at least one of R 8 and R 9 is independently selected from phenyl groups having at least one substitution, such substitution being independently selected from amine groups, ether groups, alkyl groups, aryl groups, trifluoromethyl, trichloromethyl, cyano, sulfonic acid ester groups, carboxylic acid groups, carboxylic acid ester groups, salts of carboxylic acids, salts of sulfonic acids, quaternary ammonium groups, halogen atoms, and nitro groups.

10. The compound of claim 9 , wherein one of R 8 and R 9 is hydrogen.

11. The compound of claim 1 , wherein at least one of R 3 , R 4 and R 5 is independently selected from alkyl groups having branching at the alpha carbon and arylmethyl groups.

12. The compound of claim 11 , wherein two of R 3 , R 4 and R 5 are independently selected from methyl and hydrogen.

13. The compound of claim 1 , wherein at least two of R 3 , R 4 and R 5 are independently selected from methyl and hydrogen.

14. The compound of claim 10 , wherein:
R 1 and R 2 are independently selected from phenyl groups having at least one substitution located in a meta-configuration with respect to the phosphorus, said substitution being independently selected from trifluoromethyl, trichloromethyl, cyano, sulfonic acid ester groups, carboxylic acid groups, carboxylic acid ester groups, salts of carboxylic acids, salts of sulfonic acids, quaternary ammonium groups, halogen atoms, and nitro groups; and
at least two of R 3 , R 4 and R 5 are independently selected from methyl and hydrogen; and
each R 6 and R 7 group is independently selected from C 1 -C 4 alkyl groups and trimethylsilyl.

15. The compound of claim 14 , wherein at least one of R 3 , R 4 and R 5 is independently selected from alkyl groups having branching at the alpha carbon and arylmethyl groups.

16. The compound of claim 4 , wherein:
at least two of R 3 , R 4 and R 5 are independently selected from methyl and hydrogen; and
each R 6 and R 7 group is independently selected from C 1 -C 4 alkyl groups and trimethylsilyl.

17. The compound of claim 16 , wherein one of R 3 , R 4 and R 5 is selected from alkyl groups having branching at the alpha carbon and arylmethyl groups.

18. A catalyst composition comprising:
a transition metal selected from the Group VIII metals and rhenium; and
a compound having a structure of general formula (I):

Wherein:
R 1 and R 2 are independently selected from substituted and unsubstituted, aryl, alkyl, aryloxy or cycloalkyl groups containing from 1 to 40 carbon atoms; and
R 6 and R 7 are independently selected from substituted and unsubstituted, aryl, alkyl, 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
R 3 , R 4 , R 5 , R 8 , and R 9 are independently selected from hydrogen and substituted and unsubstituted alkyl, cycloalkyl and aryl groups containing 1 to 20 carbon atoms.

19. The catalyst composition of claim 18 , further comprising a solvent.

20. The catalyst composition of claim 18 , wherein:
at least one of R 8 and R 9 is independently selected from phenyl groups having at least one substitution, such substitution being independently selected from amine groups, ether groups, alkyl groups, aryl groups, trifluoromethyl, trichloromethyl, cyano, sulfonic acid ester groups, carboxylic acid groups, carboxylic acid ester groups, salts of carboxylic acids, salts of sulfonic acids, quaternary ammonium groups, halogen atoms, and nitro groups; and
one of R 8 and R 9 is hydrogen.

21. The catalyst composition of claim 18 , wherein:
R 1 and R 2 are independently selected from phenyl groups having at least one substitution located in a meta-configuration with respect to the phosphorus, said substitution being independently selected from trifluoromethyl, trichloromethyl, cyano, sulfonic acid ester groups, carboxylic acid groups, carboxylic acid ester groups, salts of carboxylic acids, salts of sulfonic acids, quaternary ammonium groups, halogen atoms, and nitro groups; and
at least two of R 3 , R 4 and R 5 are independently selected from methyl and hydrogen; and
each R 6 and R 7 group is independently selected from C 1 -C 4 alkyl groups and trimethylsilyl.

22. The catalyst composition of claim 21 , wherein at least one of R 3 , R 4 and R 5 is independently selected from alkyl groups having branching at the alpha carbon and arylmethyl groups.

23. The catalyst composition of claim 18 , wherein:
R 1 and R 2 are independently selected from phenyl groups having at least one substitution located in a meta-configuration with respect to the phosphorus, said substitution being independently selected from trifluoromethyl, trichloromethyl, cyano, sulfonic acid ester groups, carboxylic acid groups, carboxylic acid ester groups, salts of carboxylic acids, salts of sulfonic acids, quaternary ammonium groups, halogen atoms, and nitro groups;
at least two of R 3 , R 4 and R 5 are independently selected from methyl and hydrogen; and
each R 6 and R 7 group is independently selected from C 1 -C 4 alkyl groups and trimethylsilyl.

24. A process for preparing at least one aldehyde, comprisin

Assignees

• Eastman Chem Co

Inventors

• How Rebecca
• Clarke Matt
• Hembre Robert Thomas
• Ponasik James A
• Tolleson Ginette S

Classifications

• C07C45/50 Primary

  by oxo-reactions · CPC title

• C07F17/02

  of metals of Groups 8, 9 or 10 of the Periodic Table · CPC title

• B01J31/22 Primary

  Organic complexes · CPC title

• B01J31/20

  Carbonyls · CPC title

• B01J2531/822

  Rhodium · CPC title