Methyl-iodide-free carbonylation of an alcohol to its homologous aldehyde and/or alcohol

Patent metadata

Field	Value
Publication number	US-9714206-B2
Application number	US-201414585915-A
Country	US
Kind code	B2
Filing date	Dec 30, 2014
Priority date	Dec 30, 2014
Publication date	Jul 25, 2017
Grant date	Jul 25, 2017

Abstract

Disclosed is a process for the reductive carbonylation of a low molecular weight alcohol to produce the homologous aldehyde and/or alcohol. The process includes conducting the reaction to produce the aldehyde in the presence of a catalyst complex composed of cobalt, an onium cation and iodide in a ratio of 1:2:4 with a phosphine ligand. A ruthenium co-catalyst is used in the production of the homologous alcohol. The reductive carbonylation reaction does not require an additional iodide promoter and produces a crude reductive carbonylation product substantially free of methyl iodide.

First claim

We claim:

1. A catalyst composition comprising:
a complex of cobalt, iodide, and an onium cation or an alkali metal cation of the general formula Y 2 CoI 4 , wherein Y is said onium cation or said alkali metal cation: and
a phosphine ligand of the general formula

wherein phosphorus atoms P are bridged by 2 to 6 atoms of R 17 , wherein R 17 is selected from the group consisting of substituted or unsubstituted alkylene, cycloalkylene, arylene, and biarylene, each having up to 22 carbon atoms; wherein a heteroatom, optionally, can substitute for one or more of said carbon atoms, wherein said heteroatom is selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorus; and
R 16 is selected from the group consisting of substituted or unsubstituted alkyl, alkoxy, cycloalkyl, aryl, and aryloxy, each having up to 20 carbon atoms.

2. The catalyst composition according to claim 1 , wherein said onium cation is of the general formula (I) or (II):

wherein X is selected from the group consisting of phosphorus (P) and nitrogen (N), R 1 is methyl, and R 2 , R 3 , and R 4 are independently selected from alkyl having up to 12 carbon atoms and aryl, wherein said aryl is selected from only one of the group consisting of phenyl, tolyl, xylyl, and mesityl; R 5 is methyl and R 6 , R 7 , R 8 , R 9 , and R 10 are hydrogen.

3. The catalyst composition according to claim 1 , wherein said phosphine ligand is of the general formula

wherein R 18 is selected from the group consisting of a hydrogen radical and a hydrocarbon radical having up to 17 carbon atoms, wherein said hydrocarbon radical can be substituted with at least one substituent selected from the group consisting of alkyl, alkoxy, cycloalkyl, aryl, aryloxy, dialkylphosphinomethyl, and diarylphosphinomethyl; and
R 19 is selected from the group consisting of hydrogen radical, and substituted or unsubstituted alkyl, alkoxy, cycloalkyl, aryl, and aryloxy, each having up to 8 carbon atoms.

4. The catalyst composition according to claim 3 , wherein R 16 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, tert-butoxy, phenyl, tolyl, xylyl, mesityl, phenoxy, tolyl-oxy, xylyl-oxy, and mesityl-oxy;
R 18 is selected from the group consisting of hydrogen radical, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, tert-butoxy, phenyl, tolyl, xylyl, mesityl, phenoxy, tolyl-oxy, xylyl-oxy, mesityl-oxy, dimethylphosphinomethyl, diethylphosphinomethyl, di-n-propylphosphinomethyl, di-iso-propylphosphinomethyl, di-n-butylphosphinomethyl, di-iso-butylphosphinomethyl, di-tert-butylphosphinomethyl, dimethoxyphosphinomethyl, diethoxyphosphinomethyl, di-n-propoxyphosphinomethyl, di-iso-propoxyphosphinomethyl, di-n-butoxyphosphinomethyl, di-iso-butoxyphosphinomethyl, di-tert-butoxyphosphinomethyl, diphenylphosphinomethyl, ditolylphosphinomethyl, and dixylylphosphinomethyl; and
R 19 is a hydrogen radical.

5. The catalyst composition according to claim 1 , wherein said phosphine ligand is selected from the group consisting of 1,2-bis(diphenylphosphino)ethane; 1,4-bis(diphenylphosphino)butane; 1,6-bis(diphenylphosphino)hexane; 1,2-bis(diphenylphosphino)benzene; bis(diphenylphosphinomethyl)biphenyl; 1,3-bis(diphenylphosphino)propane; 1,1,1-tris(diphenylphosphinomethyl)ethane; 1,1,1-tris(diethylphosphinomethyl)ethane; 1,3-bis(dicyclohexylphosphino)propane; 1,3-bis(dimethylphosphino)propane; 1,3-bis(diisopropylphosphino)propane; 1,3-bis(di-tert-butylphosphino)propane; (2-butoxy-2-((diphenylphosphino)methyl)propane-1,3-diyl)bis(diphenylphosphine); 1,8-bis(diphenylphosphino)naphthalene; bicyclo[2.2.1]heptane-2,7-diylbis(diphenylphosphine); 1,3-bis(diphenylphosphino)cyclohexane; 1,3-bis(diphenylphosphino)cyclopentane; and 1,3-bis(diphenylphosphino)cyclobutane.

6. The catalyst composition according to claim 1 , wherein said onium cation is selected from the group consisting of methyltriphenylphosphonium, methyltributylphosphonium, methyltrioctylphosphonium, and 1-methylpyridinium; wherein said phosphine ligand is selected from the group consisting of 1,3-bis(diphenylphosphino)propane, 1,1,1-tris(diphenylphosphinomethyl)ethane, and 1,1,1-tris(diethylphosphinomethyl)ethane; and wherein the molar ratio of said phosphine ligand to said cobalt (phosphine ligand:cobalt) ranges from 0.025:1 to 2:1.

7. A process for the preparation of a crude reductive carbonylation product comprising contacting hydrogen, carbon monoxide, and an alcohol having 1 to 3 carbon atoms in the presence of a catalyst composition to form said crude reductive carbonylation product comprising homologous aldehyde equivalents in a higher mole percent than homologous acid equivalents or homologous alcohol equivalents, each based on the total moles of said homologous aldehyde equivalents, said homologous acid equivalents, and said homologous alcohol equivalents:
wherein said catalyst composition comprises a complex of cobalt, iodide, and an onium cation or an alkali metal cation of the general formula Y 2 CoI 4 , wherein Y is said onium cation or said alkali metal cation and a phosphine ligand, wherein said phosphine ligand is of the general formula

wherein phosphorus atoms P are bridged by 2 to 6 atoms of R 17 , wherein R 17 is selected from the group consisting of substituted or unsubstituted alkylene, cycloalkylene, arylene, and biarylene, each having up to 22 carbon atoms; wherein a heteroatom, optionally, can substitute for one or more of said carbon atoms, wherein said heteroatom is selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorus:
wherein R 16 is selected from the group consisting of substituted or unsubstituted alkyl, alkoxy, cycloalkyl, aryl, and aryloxy, each having up to 20 carbon atoms: and
wherein said crude reductive carbonylation product comprises less than 1 weight percent of methyl iodide, based on the total weight of said crude reductive carbonylation product.

8. The process according to claim 7 , wherein said onium cation is of the general formula (I) or (II):

wherein X is selected from the group consisting of phosphorus (P) and nitrogen (N), R 1 is methyl, and R 2 , R 3 , and R 4 are independently selected from alkyl having up to 12 carbons and aryl, wherein said aryl is selected from only one of the group consisting of phenyl, tolyl, xylyl, and mesityl; R 5 is methyl and R 6 , R 7 , R 8 , R 9 , and R 10 are hydrogen.

9. The process according to claim 7 , wherein said phosphine ligand is of the general formula

wherein R 18 is selected from the group consisting of a hydrogen radical and a hydrocarbon radical having up to 17 carbon atoms, wherein said hydrocarbon radical may be substituted with at least one substituent selected from the group consisting of alkyl, alkoxy, cycloalkyl aryl, aryloxy dialkylphosphinomethyl, and diarylphosphinomethyl; and
R 19 is selected from the group consisting of a hydrogen radical, and a substituted or uns

Assignees

• Eastman Chem Co

Inventors

• Vetter Andrew James
• Penney Jonathan Michael
• Norman David William

Classifications

• B01J31/2409 Primary

  with more than one complexing phosphine-P atom · CPC title

• C07C45/49 Primary

  by reaction with carbon monoxide · CPC title

• C07C29/16

  by oxo-reaction combined with reduction · CPC title

• C07C53/08

  Acetic acid (pyroligneous acid C10C; preparation of vinegar C12J) · CPC title

• C07C45/50

  by oxo-reactions · CPC title