Unsymmetric bisphosphite

Patent metadata

Field	Value
Publication number	US-9556096-B2
Application number	US-201314435007-A
Country	US
Kind code	B2
Filing date	Sep 27, 2013
Priority date	Oct 12, 2012
Publication date	Jan 31, 2017
Grant date	Jan 31, 2017

Abstract

An unsymmetric bisphosphite of the formula (1)

a process for preparation thereof, a reaction thereof with metals to give mixtures containing complexes of the unsymmetric bisphosphite and the metal, and a use thereof as a catalytically active composition in hydroformylation reactions, where the hydroformylation-active composition contains, as well as the complex of metal and unsymmetric bisphosphite, unbound bisphosphite and at least one further component.

First claim

The invention claimed is:

1. A compound of formula (1):

2. A process for preparing a compound of claim 1 , comprising:
i) oxidatively coupling 2,4-dimethylphenol to obtain 3,3′,5,5′-tetramethyl-2,2′-dihydroxybiphenyl;
ii) oxidatively coupling 3-tert-butyl-4-hydroxyanisole to obtain 5,5′-dimethoxy-3,3′-di-tert-butyl-2,2′-dihydroxybiphenyl;
iii) reacting 3,3′,5,5′-tetramethyl-2,2′-dihydroxybiphenyl from i) with PCl 3 to obtain a phosphorochloridite derivative under inert gas atmosphere;
iv) reacting at least 2 equivalents of the phosphorochloridite derivative from iii) with 1 equivalent of the 5,5′-dimethoxy-3,3′-di-tert-butyl-2,2′-dihydroxybiphenyl from ii) under inert gas atmosphere.

3. The process according to claim 2 ,
wherein a solvent mixture is present during the reacting iv).

4. The process according to claim 3 , wherein the solvent mixture comprises at least two solvents selected from the group consisting of an organic nitrogen compound, an organic ester, and an aromatic compound.

5. The process according to claim 4 ,
wherein the organic nitrogen compound is at least one compound selected from the group consisting of a nitrile, an amine, and an amide.

6. The process according to claim 2 ,
further comprising v), removing the compound (1) in solid form and suspending the compound (1) in an aprotic solvent mixture, recrystallizing the compound (1) in an aprotic solvent mixture, or suspending and recrystallizing the compound in an aprotic solvent mixture.

7. A compound of formula (2):

wherein M is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, and M may enter into additional bonds.

8. A compound of the formula (3):

wherein M is selected from the group consisting of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, and Pt.

9. The compound according to claim 8 , wherein M is Rh.

10. A mixture comprising a compound of formula (2) and/or (3), and a compound of formula (1) not bonded to M.

11. A composition comprising a mixture of claim 10 ,
and a further component selected from the group consisting of bases, organic amines, buffer solutions, epoxides, and ion exchangers.

12. The composition according to claim 11 , wherein the organic amine has an 2,2,6,6-tetramethylpiperidine unit.

13. The composition according to claim 11 , wherein the further component is a di-4-(2,2,6,6-tetramethylpiperidinyl) sebacate.

14. A process for hydroformylating an unsaturated compound or a mixture of unsaturated compounds, comprising:
a) initially charging a compound of claim 1 ,
b) introducing a gas mixture comprising carbon monoxide and hydrogen; and
c) adding an unsaturated compound or a mixture of unsaturated compounds.

15. The process according to claim 14 ,
wherein the unsaturated compound or mixture thereof are selected from the group consisting of:
hydrocarbon mixtures from steamcracking plants;
hydrocarbon mixtures from catalytically operated cracking plants;
hydrocarbon mixtures from oligomerization operations;
hydrocarbon mixtures comprising polyunsaturated compounds; and
unsaturated carboxylic acid derivatives.

16. The process according to claim 14 ,
wherein the mixture comprises unsaturated compounds having 2 to 30 carbon atoms.

17. The process according to claim 14 ,
wherein the mixture comprises unsaturated compounds having 2 to 8 carbon atoms.

18. The process according to claim 15 ,
wherein the unsaturated carboxylic acid derivatives are selected from fatty acid esters.

Assignees

• Evonik Degussa Gmbh

Inventors

• Christiansen Andrea
• Franke Robert
• Fridag Dirk
• Hess Dieter
• Dyballa Katrin Marie
• Hannebauer Bernd

Classifications

• B01J31/0237

  Amines · CPC title

• C07F9/6571

  having phosphorus and oxygen atoms as the only ring hetero atoms · CPC title

• B01J31/0209

  Esters of carboxylic or carbonic acids · CPC title

• C07F9/65683

  the ring phosphorus atom being part of a phosphine · CPC title

• C07F9/65746 Primary

  the molecule containing more than one cyclic phosphorus atom · CPC title