# US 12,006,287 B2 · Process for alkoxycarbonylation of ethylenically unsaturated compounds using benzene-based diphosphine ligands and aluminium triflate

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 12,006,287 B2
- Document ID: US12006287B2
- Status: Granted
- Kind: B2
- Application number: 17/530,720
- Filed: 2021-11-19
- Published: 2022-05-26
- Granted: 2024-06-11
- Earliest claimed: 2020-11-24
- Assignees: Evonik Oxeno GmbH
- Applicants: Evonik Operations GmbH
- Inventors: Peter Kucmierczyk; Ricarda Dühren; Dirk Fridag; Johannes Knossalla; Anna Chiara Sale; Ana Markovic; Alexander Brächer; Matthias Beller; Robert Franke
- Web page: https://patentgrep.com/patent/US12006287B2

## CPC

- C07C 67/38: by addition to an unsaturated carbon-to-carbon bond
- B01J 31/0267: {Phosphines or phosphonium compounds, i.e. phosphorus bonded to at least one carbon atom, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, the other atoms bonded to phosphorus being either carbon or hydrogen}
- B01J 31/2239: {Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands}
- B01J 2531/0208: Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
- B01J 2531/824: Palladium
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

Process for alkoxycarbonylation of ethylenically unsaturated compounds using benzene-based diphosphine ligands and aluminium triflate.

## Claims

### Claim 1

Process comprising the process steps of:
a) initially charging an ethylenically unsaturated compound,
b) adding a ligand of formula (I):
where
R1 and R3 are each a —(C3-C20)-heteroaryl radical,
R2 and R4 are each —(C1-C12)-alkyl,
and a compound comprising Pd;
c) pretreating aluminium triflate at least twice by applying a vacuum to reduce pressure and the vacuum applied is broken by flooding with inert gas;
d) adding the pretreated aluminium triflate from c) as a solution, where the ratio of aluminium triflate:ligand is in the range from 2.5 mol:1 mol to 15 mol:1 mol;
e) adding an alcohol;
f) feeding in CO;
g) heating the reaction mixture from a) to f), with conversion of the ethylenically unsaturated compound to an ester.

### Claim 2 (depends on 1)

Process according to claim 1,
where R1, R3 are each selected from furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, furazanyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzofuranyl, indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl.

### Claim 3 (depends on 1)

Process according to claim 1,
where R2 and R4 are terBu.

### Claim 4 (depends on 1)

Process according to claim 1,
wherein the ligand in process step b) has the formula (1):

### Claim 5 (depends on 1)

Process according to claim 1,
wherein the process comprises the additional process step c′):
c′) dissolving the pretreated aluminium triflate from c) in a solvent.

### Claim 6 (depends on 5)

Process according to claim 5,
wherein the solvent used in process step c′) is the same alcohol as in process step e).

### Claim 7 (depends on 1)

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

### Claim 8 (depends on 1)

Process according to claim 1,
wherein the alcohol in process step e) is selected from methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, tart-butanol, 3-pentanol, cyclohexane, phenol, or mixtures thereof.

### Claim 9 (depends on 1)

Process according to claim 1,
wherein the alcohol in process step e) is methanol.