Molecular catalysts for selective hydrogenolysis of amides

Patent metadata

Field	Value
Publication number	US-11111257-B2
Application number	US-201916409522-A
Country	US
Kind code	B2
Filing date	May 10, 2019
Priority date	May 14, 2018
Publication date	Sep 7, 2021
Grant date	Sep 7, 2021

Abstract

A compound by the name 1,1,1-tris(di(3,5-dimethoxyphenyl)phosphino-methyl)ethane. The compound can be represented by the structure of formula (I):

The compound is useful as a ligand for ruthenium to form an organometallic complex. The complex is an active catalyst for the hydrogenolysis of amides to form amines and optionally alcohols.

First claim

We claim:

1. A compound having the structural formula (I):

2. A method of making the compound of claim 1 , the method comprising contacting bis(3,5-dimethoxyphenyl)phosphine with 1,1,1-tris(bromomethyl)ethane in the presence of a base.

3. An organometallic compound having the structural formula (II):

wherein
Ar represents a 3,5-dimethoxyphenyl group, and
L represents a ligand selected from trimethylenemethane, allyl, methylallyl, ethylene, cyclooctadiene, acetylacetonate, and acetate.

4. The compound according to claim 3 , wherein L comprises trimethylenemethane.

5. A method of preparing the organometallic compound of claim 3 , the method comprising contacting a Ru-containing compound with a compound having the structural formula (I):

6. The method of claim 5 , wherein the Ru-containing compound is selected from Ru(acac) 3 , [Ru(COD)(methylallyl) 2 ], Ru(NBD)(methylallyl) 2 , Ru(ethylene) 2 (methylallyl) 2 , [(COD)RuCl 2 ] n , RuCl 3 , [(PPh 3 ) 3 Ru(H)(CO)Cl], or [(cymanthren)RuCl 2 ] 2 .

7. The method of claim 6 , wherein the Ru-containing compound comprises [Ru(COD)(methylallyl) 2 ].

8. A catalyst composition comprising the organometallic compound of claim 3 , and an acid.

9. A catalyst composition comprising the organometallic compound of claim 4 , and an acid.

10. The catalyst composition of claim 8 , wherein the acid is selected from HNTf 2 , methanesulfonic acid, B(C 6 F 5 ) 3 , or Al(OTf) 3 .

11. The catalyst composition of claim 9 , wherein the acid is selected from HNTf 2 , methanesulfonic acid, B(C 6 F 5 ) 3 , or Al(OTf) 3 .

12. A process for hydrogenolysing an amide, the process comprising:
contacting an amide with hydrogen in the presence of an organometallic catalyst comprising a central metal and a tridentate ligand at conditions effective to form an amine and optionally an alcohol,
wherein the central metal comprises ruthenium, and
wherein the tridentate ligand has the structural formula (I):

13. The process of claim 12 , which is carried out in the absence of an added acid.

14. The process of claim 12 , which is carried out in the presence of an acid.

15. The process of claim 14 , wherein the acid is selected from HNTf 2 , methane sulfonic acid, B(C 6 F 5 ) 3 , and Al(OTf) 3 .

16. The process of claim 12 , wherein the catalyst comprises a compound having the structural formula (IIa):

wherein Ar represents a 3,5-dimethoxyphenyl group.

17. The process of claim 13 , wherein the catalyst comprises a compound having the structural formula (IIa):

wherein Ar represents a 3,5-dimethoxyphenyl group.

18. The process of claim 14 , wherein the catalyst comprises a compound having the structural formula (IIa):

wherein Ar represents a 3,5-dimethoxyphenyl group.

19. The process of claim 15 , wherein the catalyst comprises a compound having the structural formula (IIa):

wherein Ar represents a 3,5-dimethoxyphenyl group.

20. The process of claim 12 , wherein the amide comprises δ-valerolactam, N-hexylhexanamide, N-methyldecylamide, or N-dimethyldecylamide.

Assignees

• Eastman Chem Co

Inventors

• Klankermayer Jürgen
• Westhues Stefan
• Leitner Walter
• Hembre Robert Thomas

Classifications

• B01J2231/643

  of R2C=O or R2C=NR (R= C, H) · CPC title

• B01J31/2291

  Olefins · CPC title

• C07F9/5027 Primary

  Polyphosphines · CPC title

• C07F15/0046

  Ruthenium compounds · CPC title

• B01J31/0271

  also containing elements or functional groups covered by B01J31/0201 - B01J31/0231 · CPC title