# US 11,028,110 B2 · Process for the alkoxycarbonylation of alcohols

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- Number: US 11,028,110 B2
- Document ID: US11028110B2
- Status: Granted
- Kind: B2
- Application number: 15/649,770
- Filed: 2017-07-14
- Published: 2018-01-25
- Granted: 2021-06-08
- Earliest claimed: 2016-07-19
- Assignees: Evonik Operations GmbH
- Applicants: Evonik Degussa GmbH
- Inventors: Kaiwu Dong; Ralf Jackstell; Helfried Neumann; Matthias Beller; Dirk Fridag; Dieter Hess; Katrin Marie Dyballa; Frank Geilen; Robert Franke
- Web page: https://patentgrep.com/patent/US11028110B2

## CPC

- C07F 9/5045: {Complexes or chelates of phosphines with metallic compounds or metals}
- C07C 67/36: by reaction with carbon monoxide or formates (C07C67/02, C07C67/03, C07C67/10 take precedence)
- C07C 67/38: by addition to an unsaturated carbon-to-carbon bond
- C07D 471/00: 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
- C07F 15/0066: {without a metal-carbon linkage}
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)

## 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) where m 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; and R1, 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.

## Claims

### Claim 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;
R1, R2, R3, R4 are each independently selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —(C6-C20)-aryl or —(C3-C20)-heteroaryl, where each is substituted or unsubstituted; and
at least one of the R1, R2, R3, R4 radicals is a —(C3-C20)-heteroaryl radical; wherein
the substituents are 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 or halogen.

### Claim 2 (depends on 1)

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

### Claim 3 (depends on 1)

The process according to claim 1, where at least two of the R1, R2, R3, R4 radicals are a —(C3-C20)-heteroaryl radical.

### Claim 4 (depends on 1)

The process according to claim 1,
where the R1 and R3 radicals are each a —(C3-C20)-heteroaryl radical.

### Claim 5 (depends on 1)

The process according to claim 1,
where the R1 and R3 radicals are each a —(C3-C20)-heteroaryl radical;
and R2 and R4 are each independently selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl or —(C6-C20)-aryl.

### Claim 6 (depends on 1)

The process according to claim 1,
where the R1 and R3 radicals are each a —(C3-C20)-heteroaryl radical;
and R2 and R4 are each independently selected from —(C1-C12)-alkyl.

### Claim 7 (depends on 1)

The process according to claim 1,
where R1, R2, R3, R4, 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.

### Claim 8 (depends on 1)

The process according to claim 1,
wherein the first alcohol in process step a) is a compound of formula (IV)
where R5 is selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl or —(C6-C20)-aryl;
and R6 and R7 are each independently selected from —H, —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl or —(C6-C20)-aryl and wherein not more than one of the radicals R6 and R7.

### Claim 9 (depends on 8)

The process according to claim 8,
wherein R5 is —(C1-C12)-alkyl.

### Claim 10 (depends on 8)

The process according to claim 8,
where R6 and R7 are each independently selected from —H, —(C1-C12)-alkyl or —(C6-C20)-aryl.

### Claim 11 (depends on 1)

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.

### Claim 12 (depends on 1)

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.

### Claim 13 (depends on 1)

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

### Claim 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)

### Claim 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.