# US 2018/0022764 A1 · Process for the alkoxycarbonylation of ethylenically unsaturated compounds with monophosphine ligands

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- Number: US 2018/0022764 A1
- Document ID: US20180022764A1
- Status: Published application
- Kind: A1
- Application number: 15/649,743
- Filed: 2017-07-14
- Published: 2018-01-25
- Earliest claimed: 2016-07-19
- Assignees: Evonik Degussa GmbH
- Applicants: Evonik Degussa GmbH
- Inventors: Kaiwu DONG; Ralph JACKSTELL; Matthias BELLER; Dirk FRIDAG; Dieter HESS; Katrin Marie DYBALLA; Frank GEILEN; Robert FRANKE
- Web page: https://patentgrep.com/patent/US20180022764A1

## CPC

- C07F 9/5045: {Complexes or chelates of phosphines with metallic compounds or metals}
- C07C 67/38: by addition to an unsaturated carbon-to-carbon bond
- C07F 15/0066: {without a metal-carbon linkage}
- C07D 403/14: containing three or more hetero rings
- C07D 405/14: containing three or more hetero rings
- 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 an ethylenically unsaturated compound; b) adding a monophosphine ligand and a compound which comprises Pd, or adding a complex comprising Pd and a monophosphine ligand; c) adding an aliphatic alcohol; d) supplying CO; e) heating the reaction mixture, the ethylenically unsaturated compound being reacted to form an ester; where the monophosphine ligand is a compound of formula (I) where R1 is selected from —(C1-C12)-alkyl, —O—(C1-C12)-alkyl, —O—(C6-C20)-aryl, —(C6-C20)-aryl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —(C3-C20)-heteroaryl; R2 is selected from —(C6-C20)-aryl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —(C3-C20)-heteroaryl; R3 is —(C3-C20)-heteroaryl; and R1, R2 and R3 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

Process comprising the following process steps:
a) introducing an ethylenically unsaturated compound;
b) adding a monophosphine ligand and a compound which comprises Pd, or adding a complex comprising Pd and a monophosphine ligand;
c) adding an aliphatic alcohol;
d) supplying CO;
e) heating the reaction mixture, the ethylenically unsaturated compound being reacted to form an ester;
where the monophosphine ligand is a compound of formula (I)
where
R1 is selected from —(C1-C12)-alkyl, —O—(C1-C12)-alkyl, —O—(C6-C20)-aryl, —(C6-C20)-aryl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —(C3-C20)-heteroaryl;
R2 is selected from —(C6-C20)-aryl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocyclo-alkyl, —(C3-C20)-heteroaryl;
R3 is —(C3-C20)-heteroaryl;
and R1, R2 and R3 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, —(C1-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.

### Claim 2 (depends on 1)

Process according to claim 1,
wherein R1 is selected from —(C1-C12)-alkyl, —(C6-C20)-aryl, —(C3-C12)-cycloalkyl, —(C3-C20)-heteroaryl.

### Claim 3 (depends on 1)

Process according to claim 1,
wherein R2 is selected from —(C6-C20)-aryl, —(C3-C12)-cycloalkyl, —(C3-C20)-heteroaryl.

### Claim 4 (depends on 1)

Process according to claim 1,
wherein R1 and R2, if they are —(C3-C20)-heteroaryl, are selected from heteroaryl groups having five to ten ring atoms.

### Claim 5 (depends on 1)

Process according to claim 1,
wherein R1 and R2, if they are —(C3-C20)-heteroaryl, are selected from furyl, thienyl, pyrrolyl, imidazolyl, pyridyl, pyrimidyl, indolyl.

### Claim 6 (depends on 1)

Process according to claim 1,
wherein R3 is selected from heteroaryl groups having five to ten ring atoms.

### Claim 7 (depends on 1)

Process according to claim 1,
wherein R3 is selected from furyl, thienyl, pyrrolyl, imidazolyl, pyridyl, pyrimidyl, indolyl.

### Claim 8 (depends on 1)

Process according to claim 1,
wherein R1, R2 and R3 may each independently be substituted by one or more substituents selected from —(C1-C12)-alkyl, —(C6-C20)-aryl, —(C6-C20)-aryl-(C1-C12)-alkyl, —(C6-C20)-aryl-O—(C1-C12)-alkyl.

### Claim 9 (depends on 1)

Process according to claim 1,
wherein the monophosphine ligand is selected from compounds of one of the formulae (1), (2), (7) to (9) and (11) to (14):

### Claim 10 (depends on 1)

Process according to claim 1,
wherein the ethylenically unsaturated compound is selected from ethene, propene, 1-butene, cis- and/or trans-2-butene, isobutene, 1,3-butadiene, 1-pentene, cis- and/or trans-2-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 2-methyl-2-butene, hexene, tetramethylethylene, heptene, 1-octene, 2-octene, di-n-butene, and mixtures thereof.

### Claim 11 (depends on 1)

Process according to claim 1,
wherein the ethylenically unsaturated compound comprises 8 to 12 carbon atoms.

### Claim 12 (depends on 1)

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)palladium(II), bis(dibenzylideneacetone)palladium, bis(acetonitrile)dichloro-palladium(II), palladium(cinnamyl) dichloride.

### Claim 13 (depends on 1)

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

### Claim 14 (depends on 1)

Process according to claim 1,
wherein the alcohol in process step c) is selected from methanol and ethanol.