US4041068A
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Synthesis of oxalate esters by catalytic oxidative carbonylation of borate esters
Assignee: Atlantic Richfield Co
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Filing: 1976-06-29
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Granted: 1977-08-09
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Expires: 1996-06-29
Abstract
Abstract A process for the preparation of oxalate esters by the catalytic oxidative carbonylation of orthoborate, metaborate and polyborate esters or mixtures thereof with carbon monoxide and oxygen or an oxygen-containing gas in the presence of a metal salt catalyst, an amine base and at least a catalytic amount of an alcohol. Preferably a catalytic amount of particular metal oxidizing salts are employed along with a catalytic amount of an amine salt compound which may be formed in situ by the addition of an acid. Alternatively various counterions and ligands of the metal salt catalysts may be employed.
Inventors
- 👤 Lee R. Zehner
- 👤 John G. Zajacek
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 15:54
CPC Classifications
C; C07; C07C; C07C69/00; C07C69/34; C07C69/36; C07C67/00; C07C67/36
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
133 words
A process for the preparation of oxalate esters which comprises reacting under substantially anhydrous conditions in orthoborate ester having the formula ##STR4## wherein R is alkyl or aralkyl groups which may contain substituents which do not interfere with the reaction, with carbon monoxide and oxygen at a pressure of between about 500 psi and 3000 psi and at a temperature in the range of about 50° C. to 200° C. in the presence of an effective amount of a catalyst selected from the group consisting of palladium, platinum and rhodium salt compounds and a catalytic amount of an aliphatic, cycloaliphatic, aromatic or heterocyclic amine, and a catalytic amount of a monohydric aliphatic, alicyclic or aromatic alcohol which may contain substituents which do not interfere with the reaction, and recovering the desired oxalate ester.
Claim 2
Dependent Claim
133 words
A process for the preparation of oxalate esters which comprises reacting under substantially anhydrous conditions in orthoborate ester having the formula ##STR4## wherein R is alkyl or aralkyl groups which may contain substituents which do not interfere with the reaction, with carbon monoxide and oxygen at a pressure of between about 500 psi and 3000 psi and at a temperature in the range of about 50° C. to 200° C. in the presence of an effective amount of a catalyst selected from the group consisting of palladium, platinum and rhodium salt compounds and a catalytic amount of an aliphatic, cycloaliphatic, aromatic or heterocyclic amine, and a catalytic amount of a monohydric aliphatic, alicyclic or aromatic alcohol which may contain substituents which do not interfere with the reaction, and recovering the desired oxalate ester.
Claim 3
Dependent Claim
27 words
A process according to claim 1 wherein the catalyst salt compound is selected from the group consisting of palladium, platinum and rhodium, halides, oxalates, sulfates and acetates.
Claim 4
Dependent Claim
27 words
A process according to claim 2 wherein the catalyst is selected from palladium chloride, palladium iodide, palladium oxalate, palladium sulfate, palladium acetate, platinum chloride and rhodium chloride.
Claim 5
Dependent Claim
12 words
A process according to claim 3 wherein the catalyst is palladium iodide.
Claim 6
Dependent Claim
20 words
A process according to claim 1 wherein the amine is employed in concentrations of from 0.1 to 5 weight percent.
Claim 7
Dependent Claim
11 words
A process according to claim 5 wherein the amine is triethylamine.
Claim 8
Dependent Claim
20 words
A process according to claim 1 wherein the alcohol is employed in concentrations of from 0.1 to 50 weight percent.
Claim 9
Dependent Claim
21 words
A process according to claim 7 wherein the alcohol is selected from the group consisting of methyl alcohol and ethyl alcohol.
Claim 10
Dependent Claim
12 words
A process according to claim 8 wherein the alcohol is methyl alcohol.
Claim 11
Dependent Claim
37 words
A process according to claim 1 wherein the reaction is carried out in the presence of a catalytic amount of a copper (II) or iron (III) oxidant salt compound and an ammonium or substituted ammonium salt compound.
Claim 12
Dependent Claim
22 words
A process according to claim 10 wherein the oxidant salt compound is copper (II) or iron (III) oxalate, sulfate, acetate or trifluoroacetate.
Claim 13
Dependent Claim
14 words
A process according to claim 11 wherein the oxidant salt is copper (II) sulfate.
Claim 14
Dependent Claim
14 words
A process according to claim 11 wherein the oxidant salt is copper (II) oxalate.
Claim 15
Dependent Claim
14 words
A process according to claim 11 wherein the oxidant salt is iron (III) sulfate.
Claim 16
Dependent Claim
14 words
A process according to claim 10 wherein the ammonium salt compound is triethylammonium sulfate.
Claim 17
Dependent Claim
67 words
A process according to claim 10 wherein the ammonium or substituted ammonium salt compound is formed in situ upon the addition of an acid to the reaction mixture containing an excess of amine over the required quantities of amine base, said acid being of a strength stronger than water and such that the anion will not complex with the metal salt catalyst or metal oxidant salt compound.
Claim 18
Dependent Claim
12 words
A process according to claim 16 wherein said acid is sulfuric acid.
Claim 19
Dependent Claim
12 words
A process according to claim 16 wherein said acid is boric acid.
Claim 20
Dependent Claim
49 words
A process according to claim 1 wherein the reaction is carried out in the presence of a cocatalytic amount of an organic mono- or poly-dentate ligand or co-ordination complex of the metal catalyst selected from the group consisting of alkyl, aryl and halogen substituted phosphines, arsines, stibines and iodides.
Claim 21
Dependent Claim
15 words
A process according to claim 19 wherein the ligand or co-ordination complex is lithium iodide.
Claim 22
Dependent Claim
31 words
A process according to claim 1 wherein the pressure is between about 900 psi and 2200 psi and the temperature is in the range of about 100° C. to 135° C.
Claim 23
Dependent Claim
28 words
A process according to claim 21 wherein the orthoborate ester is trimethyl borate, the catalyst is palladium iodide, the amine is triethylamine and the alcohol is methyl alcohol.
Claim 24
Dependent Claim
27 words
A process according to claim 22 wherein a catalytic amount of a copper (II) sulfate, triethyl ammonium sulfate and lithium iodide is added to the reaction mixture.
Claim 25
Dependent Claim
28 words
A process according to claim 21 wherein the orthoborate ester is triethyl borate, the catalyst is palladium iodide, the amine is triethylamine and the alcohol is ethyl alcohol.
Claim 26
Dependent Claim
25 words
A process according to claim 24 wherein a catalytic amount of a copper (II) sulfate, boric acid, and lithium iodide is added to reaction mixture.
Claim 27
Dependent Claim
20 words
A process according to claim 1 wherein an oxygen-containing gas is employed as a source of oxygen for the reaction.
Claim 28
Dependent Claim
11 words
A process according to claim 1 wherein the catalyst is supported.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-08-08 | 1981-02-07 | 1981-08-09 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-08-08 | 1985-02-07 | 1985-08-09 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-08-08 | 1989-02-07 | 1989-08-09 | $7700.00 | Window Closed / Lapsed |