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One step process for preparing A 1,3-diol

Imported: 23 Feb '17 | Published: 22 Oct '02

John Frederick Knifton, Lynn Henry Slaugh, Paul Richard Weider, Talmadge Gail James, Joseph Broun Powell, Kevin Dale Allen, Timothy Scott Williams

USPTO - Utility Patents

Abstract

The invention provides a process for an improved oxirane hydroformylation catalyst, the improved oxirane hydroformylation catalyst, and a one step process for preparing a 1,3-diol in the presence of such a catalyst. One process for preparing the hydroformylation catalyst involves:

a) forming a complex (A) by contacting a ruthenium(0) compound with a ditertiary phosphine ligand; and

b) forming a complex (B) by subjecting complex (A) to a redox reaction with a cobalt(0) carbonyl compound. This catalyst is used in a one step hydroformylation process for preparing a 1,3-diol, comprising the reaction of an oxirane with syngas at hydroformylation conditions in an inert solvent in the presence of the above hydroformylation catalyst where recovery of product is preferably accomplished via phase separation of a diol rich phase from the bulk reaction liquor.

Description

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a comparison of the in-situ IR spectrum of the invention catalyst (as prepared) with the in-situ IR spectrum of a comparison catalyst (as prepared).

FIG. 2 is a comparison of the in-situ IR spectrum of the HPA absorbance at 1728 cm

−1 over the course of the reaction using a catalyst in accordance with the present invention, as compared to the comparison catalyst.

FIG. 3 is an IR spectrum of catalyst regions of the isolated solid of example 5.

Claims

1. A process for preparing a hydroformylation catalyst which comprises:

2. The process of claim 1, wherein the ditertiary phosphine ligand is of the general formula:

RRP—Q—PR′R′

wherein each group R and R′ independently or jointly is a hydrocarbon moiety of up to 30 carbon atoms, and Q is an organic bridging group of 2 to 4 atoms in length.

3. The process of claim 2, wherein group R or R′ each independently is an alkyl, cycloalkyl, bicycloalkyl or aryl group.

4. The process of claim 3, wherein group R or R′ each independently has up to 20 carbon atoms.

5. The process of claim 2, wherein group Q is composed of carbon atoms.

6. The process of claim 5, wherein Q is an alkylene group of 2, 3 or 4 carbon atoms in length.

7. The process of claim 2, wherein both groups R and/or R′ are part of a bivalent group, forming with the phosphorus atom a phosphacycloalkane of from 5 to 8 atoms, which itself may be part of a multiring system.

8. The process of claim 2, wherein the ditertiary phosphine ligand is selected from any one or more of 1,2-bis(dicyclohexylphosphino)ethane, 1,2-bis(diphenylphosphino)ethane, 1,2-bis(diethylphosphino)ethane, 1-(diethylphosphino)-3-(dibutylphosphino)propane, 1,2-bis(diphenylphosphino)benzene, 1,2-bis(dimethylphosphino)ethane, 1,2-bis(2,4,4-trimethylpentylphosphino)ethane, 1,2-bis(diisobutylphosphino)ethane, 1,2-P,P′-bis(9-phosphabicyclo[3.3.1] and/or [4.2.l]nonyl)ethane, its 1,2-P,P′-propane, or its 1,3-P,P′-propane analogue.

9. The process of claim 1, wherein the ratio of ligand to ruthenium atom varies from 2:1 to 1:2.

10. The process of claim 9, wherein the ratio of ligand to ruthenium atom varies from 3:2 to 2:3.

11. The process of claim 9, wherein the ratio of ligand to ruthenium atom is about 1:1.

12. The process of claim 1, wherein triruthenium(0) dodecacarbonyl is used.

13. The process of claim 1, wherein dicobalt octacarbonyl is used.

14. The process of claim 1, wherein the molar ratio of ruthenium to cobalt varies from 4:1 to 1:4.

15. The process of claim 14, wherein the molar ratio of ruthenium to cobalt varies from 2:1 to 1:3.

16. The process of claim 14, wherein the molar ratio of ruthenium to cobalt varies from 1:1 to 1:2.

17. The process of claim 14, wherein the complex (B) is made by a step-wise method.

18. The process of claim 17, wherein the ruthenium (0) compound is reacted with the ditertiary phosphine ligand in the presence of syngas.

19. The process of claim 17, wherein the ruthenium (0) compound is reacted with the ditertiary phosphine ligand in the presence of a solvent.

20. The process of claim 19, wherein the solvent comprises an ether.

21. The process of claim 19, wherein the solvent is methyl tert.butyl ether.

22. The process of claim 17, wherein the ruthenium (0) compound is reacted with the ditertiary phosphine ligand at a temperature within the range of 90 to 130 C.

23. The process of claim 17, wherein complex (A) is caused to undergo a redox reaction with a cobalt(0) carbonyl compound at a temperature within the range of 90 to 130° C.