US3923880A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Catalysts and catalytic processes
Assignee: BP Chemicals Ltd
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Filing: 1972-10-10
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Granted: 1975-12-02
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Expires: 1992-10-10
Abstract
Abstract Alcohols and alcohol derivatives are carbonylated to carboxylic acids using as catalyst a cationic complex of rhodium or iridium wherein the anionic moiety of the cationic complex is a radical other than a halide.
Inventors
- 👤 David Jack Westlake
- 👤 Michael John Wriglesworth
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 23:29
CPC Classifications
C; C07; C07C; C07C51/00; C07C51/10; C07C51/12
Claims Analysis
Total Claims: 15
Claim 1
Independent Claim
181 words
A PROCESS FOR THE CARBONYLATION OF AN ALCOHOL OR AN ALCOHOL DERIVATIVE CHOSEN FROM THE GROUP CONSISTING OF ESTERS, SYMMETRICAL ETHERS AND ALKYL HALOGENS CONTAINING FROM 1 TO 20 CARBON ATOMS PER MOLECULE IN THE ALCOHOL MOITY TO PRODUCE A CARBOXYLIC ACID HAVING ONE MORE CARBON ATOM PER MOLECULE THAN THAT IN THE ALCOHOL MOIETY OF THE ALCOHOL OR ALCOHOL DERIVATIVE COMPRISING REACTING SAID ALCOHOL OR SAID ALCOHOL DERIVATIVE WITH CARBON MONOXIDE AT A TEMPERATURE BETWEEN 50* AND 300*C IN THE PRESENCE OF A CATIONIC COMPLEX CATALYST SELECTED FROM THE GROUP CONSISTING OF CATIONIC COMPLEX OF UNIVALENT RHODIUM, UNIVALENT IRIDIUM, TRIVALENT RHODIUM AND TRIVALENT IRIDIUM, CONTAINING A STABILIZING LIGAND SELECTED FROM THE GROUP CONSISTING OF ACETONITRILE, BENZONITRILE, N-BUTYL ISOCYANATE, BENZENE, TOLUENE, HEXAMETHYL BENZENE, AN ARYL PHOSPHITE OR AN ARYL PHOSPHINE, AND WHEREIN THE ANOIC MOIETY IN THE CATIONIC COMPLEX CATALYST IS A RADICAL SELECTED FROM THE GROUP CONSISTING OF PHOSPHATES, SULPHATES, PERCHLORATES, BORATES, IODATES, AND BROMATES, AND OPTIONALLY, A PROMETER SELECTED FROM THE GROUP CONSISTING OF BROMINE, IODINE, A HYDROGEN HALIDE, AN ALKYL HALIDE, AN ARYL HALIDE, AND A METAL HALIDE.
Claim 2
Dependent Claim
181 words
A PROCESS FOR THE CARBONYLATION OF AN ALCOHOL OR AN ALCOHOL DERIVATIVE CHOSEN FROM THE GROUP CONSISTING OF ESTERS, SYMMETRICAL ETHERS AND ALKYL HALOGENS CONTAINING FROM 1 TO 20 CARBON ATOMS PER MOLECULE IN THE ALCOHOL MOITY TO PRODUCE A CARBOXYLIC ACID HAVING ONE MORE CARBON ATOM PER MOLECULE THAN THAT IN THE ALCOHOL MOIETY OF THE ALCOHOL OR ALCOHOL DERIVATIVE COMPRISING REACTING SAID ALCOHOL OR SAID ALCOHOL DERIVATIVE WITH CARBON MONOXIDE AT A TEMPERATURE BETWEEN 50* AND 300*C IN THE PRESENCE OF A CATIONIC COMPLEX CATALYST SELECTED FROM THE GROUP CONSISTING OF CATIONIC COMPLEX OF UNIVALENT RHODIUM, UNIVALENT IRIDIUM, TRIVALENT RHODIUM AND TRIVALENT IRIDIUM, CONTAINING A STABILIZING LIGAND SELECTED FROM THE GROUP CONSISTING OF ACETONITRILE, BENZONITRILE, N-BUTYL ISOCYANATE, BENZENE, TOLUENE, HEXAMETHYL BENZENE, AN ARYL PHOSPHITE OR AN ARYL PHOSPHINE, AND WHEREIN THE ANOIC MOIETY IN THE CATIONIC COMPLEX CATALYST IS A RADICAL SELECTED FROM THE GROUP CONSISTING OF PHOSPHATES, SULPHATES, PERCHLORATES, BORATES, IODATES, AND BROMATES, AND OPTIONALLY, A PROMETER SELECTED FROM THE GROUP CONSISTING OF BROMINE, IODINE, A HYDROGEN HALIDE, AN ALKYL HALIDE, AN ARYL HALIDE, AND A METAL HALIDE.
Claim 3
Dependent Claim
22 words
A process according to claim 1 wherein the stabilizing ligand is selected from the group consisting of triphenyl phosphite and triphenyl phosphine.
Claim 4
Dependent Claim
26 words
A process according to claim 1 wherein the ratio of the stabilizing ligand to the metal atom in the cationic complex catalyst is at least 2:1.
Claim 5
Dependent Claim
91 words
A process according to claim 1 wherein the cationic complex is a complex of univalent rhodium or iridium having the general formula (MLm(CO)nS1)kA wherein M is Rh or Ir, L is the stabilizing ligand, CO is a carbonyl ligand, S is a solvent ligand selected from the group consisting of acetonitrile, benzonitrile, dimethyl sulfoxide, benzene, toluene, and hexamethyl benzene, m, n, and l are integers from 0 to 5 such that n+ m+L 5, A is the anionic moiety and is stable under the reaction conditions, and K is an integer.
Claim 6
Dependent Claim
155 words
A process according to claim 1 wherein the cationic complex is a complex of trivalent rhodium or iridium having the general formulal (MLs(CO)tSuRpXq)kA wherein M is Rh or Ir, L is the stabilizing ligand, CO is a carbonyl ligand, S is a solvent ligand selected from the group consisting of acetonitrile, benzonitrile, dimethyl sulfoxide, benzene, toluene, and hexamethyl benzene, A is the anionic moiety and k is an integer, X is an iodide or bromide ligand, s, t, and u are integers from 0 to 4 such that s + t+ u 4, p and q are integers such that when p 1, q 1, when p 2, q 0, and when p 0, q 2, R is hydrogen or a substituted or unsubstituted alkyl or aryl group such that it contains 1 to 20 carbon atoms when it is an alkyl group and 6 to 20 carbon atoms when it is an aryl group.
Claim 7
Dependent Claim
19 words
A process according to claim 1 wherein the anionic moiety in the cationic complex is a tetra aryl borate.
Claim 8
Dependent Claim
44 words
A process according to claim 1 wherein the cationic complex catalyst is employed in the carbonylation reaction as a solution in a solvent compatible with the reaction system said solvent being selected from aliphatic carboxyliC acids, alcohols, ethers, esters, nitriles, sulpholane and mixtures thereof.
Claim 9
Dependent Claim
45 words
A process according to claim 7 wherein the solvent is selected from the alcohol feedstock being carbonylated, the ether of the alcohol feedstock being carbonylated, the reaction product of the carboxylation reaction, ester of the alcohol feedstock and the carboxylic acid product, acetonitrile and benzonitrile.
Claim 10
Dependent Claim
26 words
A process according to claim 7 wherein the concentration of the cationic complex catalyst in the liquid phase is between 10116 mole/litre and 10 1 mole/litre.
Claim 11
Dependent Claim
15 words
A process according to claim 1 wherein the cationic complex catalyst is formed ''''in situ''''.
Claim 12
Dependent Claim
37 words
A process according to claim 1 wherein a promoter selected from the group consisting of bromine, iodine, a hydrogen halide, an alkyl halide, an aryl halide, and a metal halide, is added to the cationic complex catalyst.
Claim 13
Dependent Claim
33 words
A process according to claim 11 wherein the ratio of the halogen atoms in the promoter to the metal atoms in the cationic complex catalyst is in the range of 1:1 to 3000:1.
Claim 14
Dependent Claim
26 words
A process according to claim 1 wherein the cationic complex catalyst is deposited on a support selected from the group consisting of alumina, silica-alumina and zeolites.
Claim 15
Dependent Claim
22 words
A process according to claim 1 wherein the carbonylation is carried out at a pressure in the range 5 to 3000 p.s.i.g.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1978-12-01 | 1979-06-02 | 1979-12-02 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1982-12-01 | 1983-06-02 | 1983-12-02 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1986-12-01 | 1987-06-02 | 1987-12-02 | $7700.00 | Window Closed / Lapsed |