Bidentate diphosphoramidites with a piperazine group as ligands for hydroformylation

Patent metadata

Field	Value
Publication number	US-9908910-B2
Application number	US-201615381722-A
Country	US
Kind code	B2
Filing date	Dec 16, 2016
Priority date	Dec 21, 2015
Publication date	Mar 6, 2018
Grant date	Mar 6, 2018

Abstract

The invention relates to Rh, Ru, Co and Ir complexes comprising bidentate diphosphoramidites as ligands and to the use thereof as catalysts for the hydroformylation of olefins. The invention also relates to a process for preparing an aldehyde from an olefin using the complexes or ligands mentioned.

First claim

The invention claimed is:

1. Complex comprising Rh, Ru, Co or Ir and a compound of one of the general formulae (I) and (II)

where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 are each independently selected from —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —O—(C 6 -C 20 )-aryl, halogen, —COO—(C 1 -C 12 )-alkyl, —CONH—(C 1 -C 12 )-alkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 6 -C 20 )-aryl, —COOH, —OH, —N[(C 1 -C 12 )-alkyl] 2 ;
and R 2′ , R 3′ , R 4′ , R 5′ , R 6′ , R 7′ , R 8′ , R 9′ , R 12′ , R 13′ , R 14′ , R 15′ , R 16′ , R 17′ , R 18′ , R 19′ are each independently selected from —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —O—(C 6 -C 20 )-aryl, halogen, —COO—(C 1 -C 12 )-alkyl, —CONH—(C 1 -C 12 )-alkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 6 -C 20 )-aryl, —COOH, —OH, —N[(C 1 -C 12 )-alkyl] 2 .

2. Complex according to claim 1 ,
comprising Rh.

3. Compound according to claim 1 ,
characterized in that R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 are each independently selected from —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —O—(C 6 -C 20 )-aryl, -halogen.

4. Complex according to claim 1 ,
characterized in that R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 are each independently selected from —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —O—(C 6 -C 20 )-aryl.

5. Complex according to claim 1 ,
characterized in that R 2′ , R 3′ , R 4′ , R 5′ , R 6′ , R 7′ , R 8′ , R 9′ , R 12′ , R 13′ , R 14′ , R 15′ , R 16′ , R 17′ , R 18′ , R 19′ are each independently selected from —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —O—(C 6 -C 20 )-aryl, -halogen.

6. Complex according to claim 1 ,
characterized in that R 2′ , R 3′ , R 4′ , R 5′ , R 6′ , R 7′ , R 8′ , R 9′ , R 12′ , R 13′ , R 14′ , R 15′ , R 16′ , R 17′ , R 18′ , R 19′ are each independently selected from —H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —O—(C 6 -C 20 )-aryl.

7. Complex according to claim 1 ,
characterized in that R 1 , R 2 , R 4 , R 7 , R 9 , R 10 , R 11 , R 12 , R 14 , R 17 , R 19 , R 20 are each H.

8. Complex according to claim 1 ,
characterized in that R 2′, R 4′ , R 7′ , R 9′ , R 12′ , R 14′ , R 17′ , R 19′ are each H.

9. Complex according to claim 1 ,
characterized in that the compound of one of the formulae (I) and (II) is selected from the compounds (4), (5), (6) and (7)

10. A process for hydroformylation, comprising: introducing the complex according to claim 1 as a catalyst.

11. Process for preparing an aldehyde, comprising the process steps of:
a) initially charging an olefin,
b) adding a complex according to claim 1
and a catalyst precursor comprising an Rh, Ru, Co or Ir complex,

c) feeding in hydrogen and carbon monoxide,
d) heating the reaction mixture, with conversion of the olefin to an aldehyde.

12. Process according to claim 11 ,
characterized in that the catalyst precursor comprises a ligand selected from acetylacetonate, acetate and chloride.

13. Process according to claim 11 ,
characterized in that the catalyst precursor is Rh(acac)(CO) 2 .

14. Process for preparing an aldehyde, comprising the process steps of:
a) initially charging an olefin,
b) adding a compound of one of the formulae (I) and (II) according to claim 1 and a catalyst precursor comprising an Rh, Ru, Co or Ir complex,
c) feeding in hydrogen and carbon monoxide,
d) heating the reaction mixture, with conversion of the olefin to an aldehyde.

15. Process according to claim 14 ,
characterized in that the catalyst precursor comprises a ligand selected from acetylacetonate, acetate and chloride.

16. Process according to claim 14 ,
characterized in that the catalyst precursor is Rh(acac)(CO) 2 .

Assignees

• Evonik Degussa Gmbh

Inventors

• Dyballa Katrin Marie
• Franke Robert
• Fridag Dirk
• Hess Dieter
• Geilen Frank
• TORRES Galina Morales
• Selent Detlef
• Boerner Armin

Classifications

• C07F9/650952

  having the nitrogen atoms in the positions 1 and 4 · CPC title

• C07C45/505

  Asymmetric hydroformylation · CPC title

• C07F9/657154

  Cyclic esteramides of oxyacids of phosphorus · CPC title

• C07F15/008 Primary

  without a metal-carbon linkage · CPC title

• C07F9/650958

  Chemistry & Metallurgy · mapped topic