IP Library › Granted Patent US 9,605,011

Granted Patent B2

US 9,605,011 · App. 15/141,130 · Granted Mar 28, 2017

Monophosphite compounds having an ether group

Inventors: Katrin Marie Dyballa (Recklinghausen, DE); Robert Franke (Marl, DE)

Assignee: EVONIK DEGUSSA GMBH

C07F9/65744 B01J31/185 B01J31/22 C07C45/50 C07F9/65742 C07F15/008 B01J2231/321 B01J2531/822

View Patent ↗

Loading inventors, assignments & file history…

Monitor This Case

Get email alerts when status or documents change.

Order Certified Copies

Most orders are placed with the USPTO same day — all within 24 business hours.

Order via The Patent Place →

Pre-filled with this patent's details

Quick Facts

Patent No.: US 9,605,011
App. No.: 15/141,130
Granted: Mar 28, 2017
Kind: B2

External Links

USPTO Patent Center↗ Full Patent PDF↗

Abstract

Novel monophosphite compounds having an ether group, and a process for preparing these compounds, which are especially suitable for use as ligands in hydroformylation reactions.

Claims (106)

1. Compound having one of the two general structures I and II:

where W is selected from:

—(C 1 -C 12 )-alkyl, —CH 2 OCH 3 (MOM), —CH 2 OCH 2 C 6 H 5 (BOM),

—CH 2 OCH 2 CH 2 OCH 3 (MEM), —CH 2 OCH 2 CH 2 Si(CH 3 ) 3 (SEM), —CH 2 SCH 3 (MTM), —CH 2 SC 6 H 5 (PTM), —CH 2 CN, —CF 2 CHCl 2 , —CH 2 CH 2 Cl, —CH 2 CH 2 Br, -2-tetrahydropyranyl, —CH(OC 2 H 5 )CH 3 , —CH 2 COC 6 H 5 , —CH 2 COC 6 H 4 -4-Br, —CH 2 -c-C 3 H 5 , —CH 2 CH═CH 2 , —CH 2 CH═C(CH 3 ) 2 , -c-C 6 H 11 , —CH 2 C 6 H 5 , —CH 2 C 6 H 3 -2,4-(CH 3 ) 2 , —CH 2 C 6 H 4 -4-OCH 3 , —CH 2 C 6 H 4 -o-NO 2 , —CH 2 C 4 H 6 -p-NO 2 , —CH 2 C 6 H 3 -2,6-Cl 2 , —CH 2 C 6 H 3 -3,4-Cl 2 , —CH 2 -9-anthryl, —CH 2 -4-pyridyl, —Si(CH 3 ) 3 , —Si(CH 3 ) 2 C(CH 3 ) 3 ;

where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from:

—CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —SO 3 Na, —NO 2 , —CN, —NH 2 , —N[(C 1 -C 12 )-alkyl] 2 ;

where X and Y are each independently selected from:

—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, —(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-COO—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-CONH—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-CON[(C 1 -C 12 )-alkyl] 2 , —(C 4 -C 20 )-heteroaryl, —(C 4 -C 20 )-heteroaryl-(C 1 -C 12 )-alkyl, —(C 5 -C 8 )-cycloalkyl, —(C 5 -C 8 )-heterocycloalkyl, —(C 6 -C 20 )-aryl-CO—(C 6 -C 20 )-aryl;

where Z is selected from:

—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 1 -C 12 )-alkyl-O—(C 6 -C 20 )-aryl,

—(C 4 -C 20 )-heteroaryl-, —(C 6 -C 20 )-aryl-CO—(C 6 -C 20 )-aryl-, —(C 6 -C 20 )-aryl-(C 6 -C 20 )-aryl-,

and where the alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl groups mentioned may be substituted.

2. Compound according to claim 1 ,

where X and Y are each independently selected from:

—(C 1 -C 12 )alkyl-, —(C 6 -C 20 )-aryl-, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl-, —(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl-, —(C 4 -C 20 )-heteroaryl and —(C 5 -C 8 )-cycloalkyl.

3. Compound according to claim 1 ,

where Z is selected from:

—(C 1 -C 12 )-alkyl-, —(C 6 -C 20 )-aryl-, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl-, —(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl- and —(C 6 -C 20 )-aryl-(C 6 -C 20 )-aryl-.

4. Compound according to claim 1 ,

where W is selected from:

—(C 1 -C 12 )-alkyl, —CH 2 -c-C 3 H 5 , -c-C 6 H 11 , —CH 2 C 6 H 5 , —CH 2 C 6 H 3 -2,4-(CH 3 ) 2 , —CH 2 C 6 H 4 -4-OCH 3 , —CH 2 -9-anthryl, —CH 2 -4-pyridyl.

5. Compound according to claim 1 , having the general structure III:

where W is selected from:

—(C 1 -C 12 )-alkyl, —CH 2 OCH 3 (MOM), —CH 2 OCH 2 C 6 H 5 (BOM), —CH 2 OCH 2 CH 2 OCH 3 (MEM), —CH 2 OCH 2 CH 2 Si(CH 3 ) 3 (SEM), —CH 2 SCH 3 (MTM),—CH 2 SC 6 H 5 (PTM), —CH 2 CN, —CF 2 CHCl 2 , —CH 2 CH 2 Cl, —CH 2 CH 2 Br, -2-tetrahydropyranyl, —CH(OC 2 H 5 )CH 3 , —CH 2 COC 6 H 5 , —CH 2 COC 6 H 4 -4-Br, —CH 2 -c-C 3 H 5 , —CH 2 CH═CH 2 , —CH 2 CH═C(CH 3 ) 2 , -c-C 6 H 11 , —CH 2 C 6 H 5 , —CH 2 C 6 H 3 -2,4-(CH 3 ) 2 , —CH 2 C 6 H 4 -4-OCH 3 , —CH 2 C 6 H 4 -o-NO 2 , —CH 2 C 4 H 6 -p-NO 2 , —CH 2 C 6 H 3 -2,6-Cl 2 , —CH 2 C 6 H 3 -3,4-Cl 2 , —CH 2 -9-anthryl, —CH 2 -4-pyridyl, —Si(CH 3 ) 3 , —Si(CH 3 ) 2 C(CH 3 ) 3 ;

where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from:

—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl, —Cl, —F, —Br, —I, —COO—(C 1 -C 12 )-alkyl, —CONH—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-CON[(C 1 -C 12 )-alkyl] 2 , —CO—(C 1 -C 12 )-alkyl, —CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —SO 3 Na, —NO 2 , —CN, —NH 2 , —N[(C 1 -C 12 )-alkyl] 2 ;

and where R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 are each independently selected from:

—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl, —Cl, —F, —Br, —I, COO—(C 1 -C 12 )-alkyl, CONH—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-CON[(C 1 -C 12 )-alkyl] 2 , —CO—(C 1 -C 12 )-alkyl, —CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —SO 3 Na, —NO 2 , —CN, —NH 2 , —N[(C 1 -C 12 )-alkyl] 2 .

6. Compound according to claim 1 , wherein the compound has a structure selected from L1, L2 and L3:

7. Process for preparing a compound having one of the two general structures I and II:

where W is selected from:

—(C 1 -C 12 )-alkyl, —CH 2 OCH 3 (MOM), —CH 2 OCH 2 C 6 H 5 (BOM), —CH 2 OCH 2 CH 2 OCH 3 (MEM), —CH 2 OCH 2 CH 2 Si(CH 3 ) 3 (SEM), —CH 2 SCH 3 (MTM), —CH 2 SC 6 H 5 (PTM), —CH 2 CN, —CF 2 CHCl 2 , —CH 2 CH 2 Cl, —CH 2 CH 2 Br, -2-tetrahydropyranyl, —CH(OC 2 H 5 )CH 3 , —CH 2 COC 6 H 5 , —CH 2 COC 6 H 4 -4-Br, —CH 2 -c-CH 3 H 5 , —CH 2 CH═CH 2 , —CH 2 CH═C(CH 3 ) 2 , -c-C 6 H 11 , —CH 2 C 6 H 5 , —CH 2 C 6 H 3 -2,4-(CH 3 ) 2 , —CH 2 C 6 H 4 -4-OCH 3 , —CH 2 C 6 H 4 -o-NO 2 , —CH 2 C 4 H 6 -p-NO 2 , —CH 2 C 6 H 3 -2,6-Cl 2 , —CH 2 C 6 H 3 -3,4-Cl 2 , —CH 2 -9-anthryl, —CH 2 -4-pyridyl, —Si(CH 3 ) 3 , —Si(CH 3 ) 2 C(CH 3 ) 3 ;

where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from:

—H, —(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —(C 6 -C 2 )-aryl, —Cl, —F, —Br, —I, —COO—(C 1 -C 12 )-alkyl, —CONH—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-CON[(C 1 -C 12 )-alkyl] 2 , —CO—(C 1 -C 12 )-alkyl, —CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —SO 3 Na, —NO 2 , —CN, —N[(C 1 -C 12 )-alkyl] 2 ;

where X and Y are each independently selected from:

—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-O—(C 1 -C 12 )-alkyl, —(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-COO—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-CONH—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-CON[(C 1 -C 12 )-alkyl] 2 ; —(C 4 -C 20 )-heteroaryl, —(C 4 -C 20 )-heteroaryl-(C 1 -C 12 )-alkyl, —(C 5 -C 8 )-cycloalkyl, —(C 5 -C 8 )-heterocycloalkyl, —(C 6 -C 20 )-aryl-CO—(C 6 -C 20 )-aryl;

and where Z is selected from:

—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 1 -C 12 )-alkyl-O—(C 6 -C 20 )-aryl, —(C 4 -C 20 )-heteroaryl-, —(C 6 -C 20 )-aryl-CO—(C 6 -C 20 )-aryl-, —(C 6 -C 20 )-aryl-(C 6 -C 20 )-aryl-;

where the process comprises the following steps:

a) initially charging a reactant,

b) adding an alkylating reagent,

c) adding a compound containing phosphorus and chlorine,

d) obtaining a product.

8. Process according to claim 7 , wherein an intermediate having a structure of formula 40 is formed

where W is selected from:

—(C 1 -C 12 )-alkyl, —CH 2 OCH 3 (MOM), —CH 2 OCH 2 C 6 H 5 (BOM),

—CH 2 OCH 2 CH 2 OCH 3 (MEM), —CH 2 OCH 2 CH 2 Si(CH 3 ) 3 (SEM), —CH 2 SCH 3 (MTM), —CH 2 SC 6 H 5 (PTM), —CH 2 CN, —CF 2 CHCl 2 , —CH 2 CH 2 Cl, —CH 2 CH 2 Br, -2-tetrahydropyranyl, —CH(OC 2 H 5 )CH 3 , —CH 2 COC 6 H 5 , —CH 2 COC 6 H 4 -4-Br, —CH 2 -c-C 3 H 5 , —CH 2 CH═CH 2 , —CH 2 CH═C(CH 3 ) 2 , -c-C 6 H 11 , —CH 2 C 6 H 5 , —CH 2 C 6 H 3 -2,4-(CH 3 ) 2 , —CH 2 C 6 H 4 -4-OCH 3 , —CH 2 C 6 H 4 -o-NO 2 , —CH 2 C 4 H 6 -p-NO 2 , —CH 2 C 6 H 3 -2,6-Cl 2 , —CH 2 C 6 H 3 -3,4-C 2 , —CH 2 -9-anthryl, —CH 2 -4-pyridyl, —Si(CH 3 ) 3 , —Si(CH 3 ) 2 C(CH 3 ) 3 ;

and where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from:

—CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —SO 3 Na, —NO 2 , —CN, —NH 2 , —N[(C 1 -C 12 )-alkyl] 2 .

9. Process according to claim 7 , wherein the reactant used is a compound having a structure of formula 20

where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from:

—H, —(C 1 -C 12 )-alkyl, —O—(C 2 -C 12 )-alkyl, —O—(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl, —Cl, —F, —Br, —I, —COO—(C 1 -C 12 )-alkyl, —CONH—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl-CON[(C 1 -C 12 )-alkyl] 2 , —CO—(C 1 -C 12 )-alkyl,

—CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —SO 3 Na, —NO 2 , —CN, —NH 2 , —N[(C 1 -C 12 )-alkyl] 2 ;

and wherein the compound containing phosphorus and chlorine is a chlorophosphite having a structure of formula 50

where X and Y are each independently selected from:

10. Process according to claim 7 , wherein the reactant used is a compound having a structure of formula 20

where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from:

—CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —SO 3 Na, —NO 2 , —CN, —NH 2 , —N[(C 1 -C 12 )-alkyl] 2 ;

and wherein the compound containing phosphorus and chlorine is a chlorophosphite having a structure of formula 60

where Z is selected from:

—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 1 -C 12 )-alkyl-O—(C 6 -C 20 )-aryl,

—(C 4 -C 20 )-heteroaryl-, —(C 6 -C 20 )-aryl-CO—(C 6 -C 20 )-aryl-, —(C 6 -C 20 )-aryl-(C 6 -C 20 )-aryl-.

11. Process according to claim 7 , wherein an intermediate having a structure of formula 30 is formed

where W is selected from:

—(C 1 -C 12 )-alkyl, —CH 2 OCH 3 (MOM), —CH 2 OCH 2 C 6 H 5 (BOM),

and where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from:

—CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —SO 3 Na, —NO 2 , —CN, —NH 2 , —N[(C 1 -C 12 )-alkyl] 2 .

12. Complex comprising a metal atom or ion and at least one compound according to claim 1 .

13. Complex according to claim 12 , wherein the metal atom or ion is selected from the group comprising Rh, Ru, Co and Ir.

14. A process for the hydroformylation of (C 2 -C 24 ) olefins, comprising:

introducing a compound having one of the two general structures I and II:

where W is selected from:

—(C 1 -C 12 )-alkyl, —CH 2 OCH 3 (MOM), —CH 2 OCH 2 C 6 H 5 (BOM),

—CH 2 OCH 2 CH 2 OCH 3 (MEM), —CH 2 OCH 2 CH 2 Si(CH 3 ) 3 (SEM), —CH 2 SCH 3 (MTM), —CH 2 SC 6 H 5 (PTM), —CH 2 CN, —CF 2 CHCl 2 , —CH 2 CH 2 Cl, —CH 2 CH 2 Br, -2-tetrahydropyranyl, —CH(OC 2 H 5 )CH 3 , —CH 2 COC 6 H 5 , —CH 2 COC 6 H 4 -4 Br, —CH 2 -c-C 3 H 5 , —CH 2 CH═CH 2 , —CH 2 CH═C(CH 3 ) 2 , -c-C 6 H 11 , —CH 2 C 6 H 5 , —CH 2 C 6 H 3 -2,4-(CH 3 ) 2 , —CH 2 C 6 H 4 -4-OCH 3 , —CH 2 C 6 H 4 -o-NO 2 , —CH 2 C 4 H 6 -p-NO 2 , —CH 2 C 6 H 3 -2,6-Cl 2 , —CH 2 C 6 H 3 -3,4-Cl 2 , —CH 2 -9-anthryl, —CH 2 -4-pyridyl, —Si(CH 3 ) 3 , —Si(CH 3 ) 2 C(CH 3 ) 3 ;

where R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from:

—CO—(C 6 -C 20 )-aryl, —COOH, —OH, —SO 3 H, —SO 3 Na, —NO 2 , —CN, —NH 2 , —N[(C 1 -C 12 )-alkyl] 2 ;

where X and Y are each independently selected from:

where Z is selected from:

—(C 1 -C 12 )-alkyl, —(C 6 -C 20 )-aryl, —(C 6 -C 20 )-aryl-(C 1 -C 12 )-alkyl, —(C 1 -C 12 )-alkyl-O—(C 6 -C 20 )-aryl,

—(C 4 -C 20 )-heteroaryl-, —(C 6 -C 20 )-aryl-CO—(C 6 -C 20 )-aryl-, —(C 6 -C 20 )-aryl-(C 6 -C 20 )-aryl-,

and where the alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl groups mentioned may be substituted;

or a complex according to claim 12 .

15. Process according to claim 14 , wherein the hydroformylation reaction comprises the following steps:

a) initially charging an olefin,

b) adding said complex,

or said compound and a compound containing a metal atom or metal ion,

c) feeding in H 2 and CO,

d) heating the reaction mixture, with conversion of the olefin to an aldehyde.

16. Compound according to claim 5 , wherein the compound has a structure selected from L1, L2 and L3:

17. Complex comprising a metal atom or ion and at least one compound according to claim 5 .

18. Complex according to claim 17 , wherein the metal atom or ion is selected from the group comprising Rh, Ru, Co and Ir.

19. The compound of claim 1 , wherein, when W is the —(C 1 -C 12 )-alkyl group, the —(C 1 -C 12 )-alkyl group is selected from -Me, —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH(CH 3 ) 2 , or —C(CH 3 ) 3 .

20. The compound of claim 4 , wherein, when W is the —(C 1 -C 12 )-alkyl group, the —(C 1 -C 12 )-alkyl group is selected from -Me, —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH(CH 3 ) 2 , or —C(CH 3 ) 3 .

21. The compound of claim 5 , wherein, when W is the —(C 1 -C 12 )-alkyl group, the —(C 1 -C 12 )-alkyl group is selected from -Me, —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH(CH 3 ) 2 , or —C(CH 3 ) 3 .

22. The process of claim 7 , wherein, when W is the —(C 1 -C 12 )-alkyl group, the —(C 1 -C 12 )-alkyl group is selected from -Me, —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH(CH 3 ) 2 , or —C(CH 3 ) 3 .

23. The process of claim 8 , wherein, when W is the —(C 1 -C 12 )-alkyl group, the —(C 1 -C 12 )-alkyl group is selected from -Me, —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH(CH 3 ) 2 , or —C(CH 3 ) 3 .

24. The process of claim 11 , wherein, when W is the —(C 1 -C 12 )-alkyl group, the —(C 1 -C 12 )-alkyl group is selected from -Me, —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH(CH 3 ) 2 , or —C(CH 3 ) 3 .

25. The process of claim 14 , wherein, when W is the —(C 1 -C 12 )-alkyl group, the —(C 1 -C 12 )-alkyl group is selected from -Me, —CH 2 CH 3 , —CH 2 CH 2 CH 3 , —CH(CH 3 ) 2 , or —C(CH 3 ) 3 .

Assignments (2)

CHANGE OF NAME Recorded Mar 29, 2020

From: EVONIK DEGUSSA GMBH

To: EVONIK OPERATIONS GMBH

Reel/Frame 052254/0052 →

ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 8, 2016

From: DYBALLA, KATRIN MARIE, DR.; FRANKE, DR.ROBERT, PROF

To: EVONIK DEGUSSA GMBH

Reel/Frame 040597/0745 →

Priority Claims (1)

DE 10 2015 207 864 · Apr 29, 2015 · national

Continuity (1)

Related Publication 20160318960A1 · Nov 3, 2016