Patent US3952034A successfully refreshed from Google Patents.
US3952034A
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Carbonylation of olefins and acetylenes
Assignee: Imperial Chemical Industries Ltd
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Filing: 1973-12-03
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Granted: 1976-04-20
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Expires: 1993-12-03
Abstract
Abstract Olefins and acetylenes are carbonylated to a carboxylic acid or ester using a homogenous catalyst system comprising palladium together with iron or a metal of Groups IVA, VA or IIIB, the catalyst being either a polynuclear complex incorporating both metals, or a mixture of a soluble palladium salt and metal halide. Starting with cyclic di-olefins, such as cyclo-octadiene, the product cycloalkenyl carboxylic acid or ester may be cleaved to give acyclic dicarboxylic acids, such as azelaic acid.
Inventors
- 👤 David Thomas Thompson
- 👤 Reginald Jackson
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 14:30
CPC Classifications
C; C07; C07C; C07C67/00; C07C67/36; C07C67/38; B; B01; B01J; B01J31/00; B01J31/16; B01J31/24; B01J31/2404; B01J2231/00; B01J2231/30; B01J2231/32; B01J2231/321; B01J2531/00; B01J2531/02; B01J2531/0213; B01J2531/0219; B01J2531/30; B01J2531/31; B01J2531/40; B01J2531/46; B01J2531/48; B01J2531/50; B01J2531/57; B01J2531/80; B01J2531/82; B01J2531/824; B01J2531/84; B01J2531/842; C07C2601/00; C07C2601/12; C07C2601/14; C07C2601/16; C07C2601/18; C07C2601/20; Y; Y02; Y02P; Y02P20/00; Y02P20/50; Y02P20/582
Claims Analysis
Total Claims: 16
Claim 1
Independent Claim
132 words
A process for the preparation of acyclic dicarboxylic acids in which a. a cyclic olefin selected from the group consisting of cycloalkadienes and alkenylcycloalkenes is carbonylated to a cycloalkenyl carboxylic acid or ester by reaction with carbon monoxide and a hydroxylic compound selected from the group consisting of water, alcohols, and phenols in the presence of a homogeneous catalyst composition including palladium and aluminum, the catalyst composition being a polynuclear organic complex incorporating palladium in combination with aluminum or being a mixture of a soluble palladium compound with a chloride of the further metal, b. the reaction mixture resulting from the above carbonylation reaction is heated to an elevated temperature under alkaline conditions to induce cleavage of the cycloalkenyl ring, and c. the acyclic dicarboxylic acid is isolated from the reaction mixture.
Claim 2
Dependent Claim
132 words
A process for the preparation of acyclic dicarboxylic acids in which a. a cyclic olefin selected from the group consisting of cycloalkadienes and alkenylcycloalkenes is carbonylated to a cycloalkenyl carboxylic acid or ester by reaction with carbon monoxide and a hydroxylic compound selected from the group consisting of water, alcohols, and phenols in the presence of a homogeneous catalyst composition including palladium and aluminum, the catalyst composition being a polynuclear organic complex incorporating palladium in combination with aluminum or being a mixture of a soluble palladium compound with a chloride of the further metal, b. the reaction mixture resulting from the above carbonylation reaction is heated to an elevated temperature under alkaline conditions to induce cleavage of the cycloalkenyl ring, and c. the acyclic dicarboxylic acid is isolated from the reaction mixture.
Claim 3
Dependent Claim
128 words
A process for the preparation of acyclic dicarboxylic acids in which a. a cyclic olefin selected from the group consisting of cycloalkadienes and alkenylcycloalkenes is carbonylated to a cycloalkenyl carboxylic acid or ester by reaction with carbon monoxide and a hydroxylic compound selected from the group consisting of water, alcohols and phenols in the presence of a homogeneous catalyst composition consisting essentially of a mixture of a soluble palladium complex, a halide of aluminum and a substituted phosphine ligand which may constitute part of said palladium complex, b. the reaction mixture resulting from the above carbonylation reaction is heated to an elevated temperature under alkaline conditions without intermediate purification to induce cleavage of the cycloalkenyl ring, and c. the acyclic dicarboxylic acid is isolated from the reaction mixture.
Claim 4
Dependent Claim
128 words
A process for the preparation of acyclic dicarboxylic acids in which a. a cyclic olefin selected from the group consisting of cycloalkadienes and alkenylcycloalkenes is carbonylated to a cycloalkenyl carboxylic acid or ester by reaction with carbon monoxide and a hydroxylic compound selected from the group consisting of water, alcohols and phenols in the presence of a homogeneous catalyst composition consisting essentially of a mixture of a soluble palladium complex, a halide of aluminum and a substituted phosphine ligand which may constitute part of said palladium complex, b. the reaction mixture resulting from the above carbonylation reaction is heated to an elevated temperature under alkaline conditions without intermediate purification to induce cleavage of the cycloalkenyl ring, and c. the acyclic dicarboxylic acid is isolated from the reaction mixture.
Claim 5
Dependent Claim
21 words
A process as claimed in claim 2 in which the cyclic olefin is cyclo-octa-1,5-diene and the dicarboxylic acid is azelaic acid.
Claim 6
Dependent Claim
81 words
In a process for the preparation of carboxylic acids or esters in which an olefinically unsaturated compound is carbonylated by reaction with carbon monoxide and a hydroxylic compound selected from the group consisting of water, alcohols and phenols, the improvement wherein the carbonylation is carried out in the presence of a homogeneous catalyst composition consisting essentially of a mixture of a soluble palladium complex, a halide of aluminum and a substituted phosphine ligand, which optionally constitutes part of said palladium complex.
Claim 7
Dependent Claim
81 words
In a process for the preparation of carboxylic acids or esters in which an olefinically unsaturated compound is carbonylated by reaction with carbon monoxide and a hydroxylic compound selected from the group consisting of water, alcohols and phenols, the improvement wherein the carbonylation is carried out in the presence of a homogeneous catalyst composition consisting essentially of a mixture of a soluble palladium complex, a halide of aluminum and a substituted phosphine ligand, which optionally constitutes part of said palladium complex.
Claim 8
Dependent Claim
22 words
A process as claimed in claim 4 in which the atomic ratio of the aluminum to palladium is from 1:1 to 30:1.
Claim 9
Dependent Claim
25 words
A process as claimed in claim 4 in which the catalyst composition is a mixture of a chlorine-containing palladium compound and a chloride of aluminum.
Claim 10
Dependent Claim
30 words
A process as claimed in claim 4 in which the palladium compound is selected from the group consisting of bis(tri-arylphosphine)palladium dihalide, sodium tetrachloropalladite, π-allylpalladium halide dimer and tri-arylphosphinepalladium dihalide dimer.
Claim 11
Dependent Claim
15 words
A process as claimed in claim 7 in which the palladium compound is bis(triphenylphosphine)palladium dichloride.
Claim 12
Dependent Claim
27 words
A process as claimed in claim 4 in which the concentration of dissolved palladium is from 0.2 × 10.sup. -3 M to 3 × 10.sup. -3 M.
Claim 13
Dependent Claim
22 words
A process as claimed in claim 9 in which the unsaturated compound is selected from the group consisting of octene and styrene.
Claim 14
Dependent Claim
16 words
A process as claimed in claim 9 in which the unsaturated compound is a cyclic olefin.
Claim 15
Dependent Claim
26 words
A process as claimed in claim 11 in which the cyclic olefin is selected from the group consisting of cyclohexene, vinylcyclohexene, cyclo-octadiene, cyclododecene, cyclododecadiene and cyclododecatriene.
Claim 16
Dependent Claim
14 words
A process as claimed in claim 12 in which the cyclic olefin is cyclo-octa-1,5-diene.
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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) | 1979-04-20 | 1979-10-20 | 1980-04-20 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1983-04-20 | 1983-10-20 | 1984-04-20 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1987-04-20 | 1987-10-20 | 1988-04-20 | $7700.00 | Window Closed / Lapsed |