IP Library › Granted Patent US 9,605,010
Granted Patent B2
US 9,605,010 · App. 15/141,069 · Granted Mar 28, 2017

Monophosphite compounds having a methyl group

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Quick Facts
Patent No.
US 9,605,010
App. No.
15/141,069
Granted
Mar 28, 2017
Kind
B2
Abstract

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

Claims (71)

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

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 ;

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 , wherein X and Y are the same radicals.

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

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 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 ;

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 a methylating 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 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 .

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 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 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:

—(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.

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:

—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 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 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 .

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 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 9 , —CN, —NH 9 , —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;

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.

Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 9, 2024
From: EVONIK OPERATIONS GMBH
To: EVONIK OXENO GMBH & CO. KG
Reel/Frame 066242/0585 →
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 Feb 13, 2017
From: DYBALLA, KATRIN MARIE, DR.; FRANKE, PROF. DR. ROBERT
To: EVONIK DEGUSSA GMBH
Reel/Frame 041242/0612 →