Process for the alkoxycarbonylation of alcohols

Patent metadata

Field	Value
Publication number	US-11028110-B2
Application number	US-201715649770-A
Country	US
Kind code	B2
Filing date	Jul 14, 2017
Priority date	Jul 19, 2016
Publication date	Jun 8, 2021
Grant date	Jun 8, 2021

Abstract

The invention relates to a process comprising the following process steps:a) introducing a first alcohol, the first alcohol having 2 to 30 carbon atoms;b) adding a phosphine ligand and a compound which comprises Pd, or adding a complex comprising Pd and a phosphine ligand;c) adding a second alcohol;d) supplying CO;e) heating the reaction mixture, the first alcohol reacting with CO and the second alcohol to form an ester;where the phosphine ligand is a compound of formula (I)wherem and n are each independently 0 or 1;R1, R2, R3, R4 are each independently selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —(C6-C20)-aryl, —(C3-C20)-heteroaryl;at least one of the R1, R2, R3, R4 radicals is a —(C3-C20)-heteroaryl radical;andR1, R2, R3, R4, if they are —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —(C6-C20)-aryl or —(C3-C20)-heteroaryl,may each independently be substituted by one or more substituents selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —O—(C1-C12)-alkyl, —O—(C1-C12)-alkyl-(C6-C20)-aryl, —O—(C3-C12)-cycloalkyl, —S—(C1-C12)-alkyl, —S—(C3-C12)-cycloalkyl, —COO—(C1-C12)-alkyl, —COO—(C3-C12)-cycloalkyl, —CONH—(C1-C12)-alkyl, —CONH—(C3-C12)-cycloalkyl, —CO—(C1-C12)-alkyl, —CO—(C3-C12)-cycloalkyl, —N—[(C1-C12)-alkyl]2, —(C6-C20)-aryl, —(C6-C20)-aryl-(C1-C12)-alkyl, —(C6-C20)-aryl-O—(C1-C12)-alkyl, —(C3-C20)-heteroaryl, —(C3-C20)-heteroaryl-(C1-C12)-alkyl, —(C3-C20)-heteroaryl-O—(C1-C12)-alkyl, —COOH, —OH, —SO3H, —NH2, halogen.

First claim

The invention claimed is:

1. A process for forming an ester mixture product having n- and iso-ester components from a corresponding first alcohol substrate and CO and a second alcohol comprising the following process steps:
a) introducing the first alcohol selected from a secondary or tertiary alcohol, having 2 to 30 carbon atoms, to form a reaction mixture;
b) adding a phosphine ligand and a compound which comprises Pd, or adding a complex comprising Pd and the phosphine ligand;
c) adding the second alcohol;
d) supplying CO;
e) heating the reaction mixture, the first alcohol reacting with CO and then the second alcohol to form the ester mixture with the iso- and n-products;
where the phosphine ligand is a compound of formula (I)

where m and n are each independently 0 or 1;
R 1 , R 2 , R 3 , R 4 are each independently selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —(C 6 -C 20 )-aryl or —(C 3 -C 20 )-heteroaryl, where each is substituted or unsubstituted; and
at least one of the R 1 , R 2 , R 3 , R 4 radicals is a —(C 3 -C 20 )-heteroaryl radical; wherein
the substituents are selected from
—(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl, —O—(C 1 -C 12 )-alkyl, —O—(C 1 -C 12 )-alkyl-(C 6 -C 20 )-aryl, —O—(C 3 -C 12 )-cycloalkyl, —S—(C 1 -C 12 )-alkyl, —S—(C 3 -C 12 )-cycloalkyl, —COO—(C 1 -C 12 )-alkyl, —COO—(C 3 -C 12 )-cycloalkyl, —CONH—(C 1 -C 12 )-alkyl, —CONH—(C 3 -C 12 )-cycloalkyl, —CO—(C 1 -C 12 )-alkyl, —CO—(C 3 -C 12 )-cycloalkyl, —N—[(C 1 -C 12 )-alkyl] 2 , —(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 3 -C 20 )-heteroaryl, —(C 3 -C 20 )-heteroaryl-(C 1 -C 12 )-alkyl, —(C 3 -C 20 )-heteroaryl-O—(C 1 -C 12 )-alkyl, —COOH, —OH, —SO 3 H, —NH 2 or halogen.

2. The process according to claim 1 , where the phosphine ligand is a compound of one of the formulae (II) and (III)

3. The process according to claim 1 , where at least two of the R 1 , R 2 , R 3 , R 4 radicals are a —(C 3 -C 20 )-heteroaryl radical.

4. The process according to claim 1 ,
where the R 1 and R 3 radicals are each a —(C 3 -C 20 )-heteroaryl radical.

5. The process according to claim 1 ,
where the R 1 and R 3 radicals are each a —(C 3 -C 20 )-heteroaryl radical;
and R 2 and R 4 are each independently selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl, —(C 3 -C 12 )-heterocycloalkyl or —(C 6 -C 20 )-aryl.

6. The process according to claim 1 ,
where the R 1 and R 3 radicals are each a —(C 3 -C 20 )-heteroaryl radical;
and R 2 and R 4 are each independently selected from —(C 1 -C 12 )-alkyl.

7. The process according to claim 1 ,
where R 1 , R 2 , R 3 , R 4 , if they are a heteroaryl radical, are each independently selected from furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, furazanyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzofuranyl, indolyl, isoindolyl, benzimidazolyl, quinolyl or isoquinolyl.

8. The process according to claim 1 ,
wherein the first alcohol in process step a) is a compound of formula (IV)

where R 5 is selected from —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl or —(C 6 -C 20 )-aryl;
and R 6 and R 7 are each independently selected from —H, —(C 1 -C 12 )-alkyl, —(C 3 -C 12 )-cycloalkyl or —(C 6 -C 20 )-aryl and wherein not more than one of the radicals R 6 and R 7 .

9. The process according to claim 8 ,
wherein R 5 is —(C 1 -C 12 )-alkyl.

10. The process according to claim 8 ,
where R 6 and R 7 are each independently selected from —H, —(C 1 -C 12 )-alkyl or —(C 6 -C 20 )-aryl.

11. The process according to claim 1 ,
wherein the compound comprising Pd in process step b) is selected from palladium dichloride, palladium(II) acetylacetonate, palladium(II) acetate, dichloro(1,5-cyclooctadiene)palla dium(II), bis(dibenzylideneacetone)palladium, bis(acetonitrile)dichloropalladium(II) or palladium(cinnamyl) dichloride.

12. The process according to claim 1 ,
wherein the second alcohol in process step c) is selected from the group consisting of methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, tert-butanol, 3-pentanol, cyclohexanol, and mixtures thereof.

13. The process according to claim 1 ,
wherein the second alcohol in process step c) is a primary alcohol.

14. A process for forming an ester mixture product having n- and iso-ester components from a corresponding first alcohol substrate and CO and a second alcohol comprising the following process steps:
a) introducing the first alcohol selected from a secondary or tertiary alcohol, having 2 to 30 carbon atoms, to form a reaction mixture;
b) adding a phosphine ligand and a compound which comprises Pd, or adding a complex comprising Pd and the phosphine ligand;
c) adding the second alcohol;
d) supplying CO;
e) heating the reaction mixture, the first alcohol reacting with CO and then the second alcohol to form the ester mixture with the iso- and n-products;
where the phosphine ligand is a compound of formula (1)

15. A process for forming an ester mixture product having n- and iso-ester components from a corresponding first alcohol substrate and CO and a second alcohol comprising the following process steps:
a) introducing the first alcohol selected from a secondary or tertiary alcohol, having 2 to 30 carbon atoms, to form a reaction mixture;
b) adding a phosphine ligand and a compound which comprises Pd, or adding a complex comprising Pd and the phosphine ligand;
c) adding the second alcohol;
d) supplying CO;
e) heating the reaction mixture, the first alcohol reacting with CO and then the second alcohol to form the ester mixture with the iso- and n-products; where the phosphine ligand is (α, α′-bis(2-pyridyl)(t-butyl)phosphino)o-xylene and the first alcohol is 3,3-dimethylbutan-2-ol.

Assignees

• Evonik Degussa Gmbh
• Evonik Operations Gmbh

Inventors

• Dong Kaiwu
• Jackstell Ralf
• Neumann Helfried
• Beller Matthias
• Fridag Dirk
• Hess Dieter
• Dyballa Katrin Marie
• Geilen Frank
• Franke Robert

Classifications

• C07C67/36 Primary

  by reaction with carbon monoxide or formates (C07C67/02, C07C67/03, C07C67/10 take precedence) · CPC title

• C07F15/0066

  without a metal-carbon linkage · CPC title

• C07D471/00

  Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 · CPC title

• B01J31/24

  Phosphines {, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands} · CPC title

• C07C69/14

  of monohydroxylic compounds · CPC title