Process for double carbonylation of allyl alcohols to corresponding diesters

Patent metadata

Field	Value
Publication number	US-9850194-B2
Application number	US-201615378514-A
Country	US
Kind code	B2
Filing date	Dec 14, 2016
Priority date	Dec 16, 2015
Publication date	Dec 26, 2017
Grant date	Dec 26, 2017

Abstract

The invention relates to a process for doubly carbonylating allyl alcohols to the corresponding diesters, wherein a linear or branched allyl alcohol is reacted with a linear or branched alkanol (alcohol) with supply of CO and in the presence of a catalytic system composed of a palladium complex and at least one organic phosphorus ligand and in the presence of a hydrogen halide selected from HCl, HBr and HI.

First claim

The invention claimed is:

1. Process for doubly carbonylating allyl alcohols to diesters, comprising: reacting, in a single step, a linear or branched allyl alcohol with a linear or branched alkanol with supply of CO and in the presence of a catalytic system composed of a palladium complex and at least one organic phosphorus ligand and in the presence of a hydrogen halide selected from HCl, HBr and HI, wherein both the allyl portion and the alcohol portion of the allyl alcohol are reacted with the CO.

2. Process according to claim 1 ,
characterized in that the allyl alcohols are compounds of the general formula (1):

where R 1 , R 2 and R 3 are independently hydrogen or a C 1 to C 10 alkyl radical and R′ is hydrogen, or a saturated branched or unbranched, aliphatic, cycloaliphatic or cycloaliphatic-aliphatic hydrocarbyl radical having up to 12 carbon atoms, in which C—C bonds may be interrupted by oxygen or the —O—CO— group, or a phenyl radical, where the phenyl radical may be substituted as follows: C 1 - to C 10 -alkyl- or C 1 - to C 10 -alkoxy groups.

3. Process according to claim 1 ,
characterized in that the alkanols are compounds of the general formula ROH where R is a C 1 - to C 20 -alkyl, a C 1 to C 20 -cycloalkyl or a C 7 - to C 11 -aralkyl group.

4. Process according to claim 1 ,
characterized in that the reaction is conducted in the liquid phase at a temperature of 70 to 250° C.

5. Process according to claim 1 ,
characterized in that reaction is conducted under a pressure of 2 to 100 bar.

6. Process according to claim 1 ,
characterized in that the palladium complex is formed in situ proceeding from a pre-complex, using, as palladium source, palladium-containing salts and complexes as precursor.

7. Process according to claim 6 ,
characterized in that the palladium complex is selected from the group comprising Pd acetate, Pd acetylacetonate, Pd halides, Pd-halogen-1,5-cyclooctadienes, Pd nitrates, Pd oxide and diammonium hexachloropalladate.

8. Process according to claim 1 ,
characterized in that the phosphine ligands have a mono- or bidentate structure, preferably selected from the group comprising
L1—(9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphine),
L2—10,10′-(oxybis(2,1-phenylene))bis(10H-phenoxaphosphinine),
L3—2,2′-((9,9-dimethyl-9H-xanthene-4,5-diyl)bis(tert-butylphosphinediyl))dipyridine,
L4—(oxybis(2,1-phenylene))bis(tert-butyl(phenyl)phosphine),
L5—4,6-bis(diphenylphosphinyl)-10H-phenoxazine,
L6—1,3-bis((diphenylphosphinyl)methyl)benzene,
L7—(oxybis(2,1-phenylene))bis(di-tert-butylphosphine),
L8—(oxybis(2,1-phenylene))bis(di-o-tolylphosphine),
L9—bis(2-(diphenylphosphinyl)-5-methylphenyl)methane,
L10—1,2-bis((di-tert-butylphosphinyl)methyl)benzene,
L11—di(1-adamantyl)-n-butylphosphine,
L12—1-(2-(diphenylphosphinyl)benzyl)-1H-pyrrole.

9. Process according to claim 1 ,
characterized in that the hydrogen halide used is hydrogen chloride.

10. Process according to claim 1 ,
characterized in that the ratio of palladium to hydrogen halide is in the range from 1:3 to 1:30.

11. Process according to claim 1 ,
characterized in that a metal halide is added to the reaction, where the ratio of halide to hydrogen halide is in the range from 1:1 to 5:1.

Assignees

• Evonik Degussa Gmbh

Inventors

• Li Haoquan
• Liu Jie
• Beller Matthias
• Jackstell Ralf
• Franke Robert
• Dyballa Katrin Marie

Classifications

• C07C67/38 Primary

  by addition to an unsaturated carbon-to-carbon bond · CPC title