US4076949A
Expired / Lapsed
US
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Process for the preparation of oxalate esters
Assignee: Atlantic Richfield Co
•
Filing: 1977-05-09
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Granted: 1978-02-28
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Expires: 1997-05-09
Abstract
Abstract A process for the preparation of oxalate esters by reacting an alcohol with a mixture of carbon monoxide and oxygen in the presence of a catalytic mixture of:
Inventors
- 👤 Lee R. Zehner
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 21:19
CPC Classifications
C; C07; C07C; C07C69/00; C07C69/34; C07C69/36; C07C67/00; C07C67/36
Claims Analysis
Total Claims: 35
Claim 1
Independent Claim
155 words
A process for the preparation of oxalate esters of an alcohol which comprises reacting a monohydric saturated aliphatic, alicyclic or aralkyl alcohol containing from 1 to 20 carbon atoms and which may contain other substituents which do not interfere with the reaction, with a mixture of carbon monoxide and oxygen at a pressure of between about 500 psig to 5000 psig and at a temperature in the range of about 40° C. to 150° C. in the presence of an effective amount of a catalytic mixture of (a) a palladium, rhodium, platinum, copper or cadmium metal salt compound or mixtures thereof, (b) an aliphatic, cycloaliphatic aromatic or heterocyclic amine or ammonia, (c) a copper (I), copper (II), iron (II) or iron (III) oxidant salt compound and (d) from about 0.1 to 40 weight percent of an ammonium or substituted ammonium salt compound with a counterion other than a halide, and recovering the desired oxalate ester.
Claim 2
Dependent Claim
155 words
A process for the preparation of oxalate esters of an alcohol which comprises reacting a monohydric saturated aliphatic, alicyclic or aralkyl alcohol containing from 1 to 20 carbon atoms and which may contain other substituents which do not interfere with the reaction, with a mixture of carbon monoxide and oxygen at a pressure of between about 500 psig to 5000 psig and at a temperature in the range of about 40° C. to 150° C. in the presence of an effective amount of a catalytic mixture of (a) a palladium, rhodium, platinum, copper or cadmium metal salt compound or mixtures thereof, (b) an aliphatic, cycloaliphatic aromatic or heterocyclic amine or ammonia, (c) a copper (I), copper (II), iron (II) or iron (III) oxidant salt compound and (d) from about 0.1 to 40 weight percent of an ammonium or substituted ammonium salt compound with a counterion other than a halide, and recovering the desired oxalate ester.
Claim 3
Dependent Claim
22 words
A process according to claim 1 wherein the alcohol is a monohydric saturated aliphatic alcohol containing from 1 to 8 carbon atoms.
Claim 4
Dependent Claim
23 words
A process according to claim 2 wherein the alcohol is selected from the group consisting of methanol, ethanol, propanol, a butanol and octanol.
Claim 5
Dependent Claim
11 words
A process according to claim 3 wherein the alcohol is methanol.
Claim 6
Dependent Claim
11 words
A process according to claim 3 wherein the alcohol is ethanol.
Claim 7
Dependent Claim
11 words
A process according to claim 3 wherein the alcohol is 2-propanol.
Claim 8
Dependent Claim
16 words
A process according to claim 3 wherein the alcohol is normal butyl, iso-butyl or sec-butyl alcohol.
Claim 9
Dependent Claim
34 words
A process according to claim 1 wherein the metal salt compound is selected from the group consisting of palladium, rhodium, platinum and cadmium, halides, oxalates, sulfates and acetates and copper halides or mixtures thereof.
Claim 10
Dependent Claim
37 words
A process according to claim 8 wherein the metal salt compound is selected from palladium iodide, palladium sulfate, palladium chloride, palladium bromide, platinum acetate, platinum chloride, platinum bromide, copper iodide, cadmium chloride, cadmium iodide, and rhodium chloride.
Claim 11
Dependent Claim
14 words
A process according to claim 9 wherein the metal salt compound is palladium iodide.
Claim 12
Dependent Claim
14 words
A process according to claim 9 wherein the metal salt compound is palladium sulfate.
Claim 13
Dependent Claim
14 words
A process according to claim 9 wherein the metal salt compound is copper iodide.
Claim 14
Dependent Claim
26 words
A process according to claim 1 wherein the amine is a primary, secondary or tertiary amine employed in concentrations of from 0.1 to 10 weight percent.
Claim 15
Dependent Claim
20 words
A process according to claim 13 wherein the amine is employed in concentrations of from 0.3 to 4 weight percent.
Claim 16
Dependent Claim
11 words
A process according to claim 13 wherein the amine is triethylamine.
Claim 17
Dependent Claim
29 words
A process according to claim 1 wherein the oxidant salt compound is a copper (I), copper (II), iron (II), or iron (III) halide, oxalate, sulfate, acetate, naphthenate or trifluoroacetate.
Claim 18
Dependent Claim
14 words
A process according to claim 16 wherein the oxidant salt is copper (I) iodide.
Claim 19
Dependent Claim
14 words
A process according to claim 16 wherein the oxidant salt is copper (II) sulfate.
Claim 20
Dependent Claim
13 words
A process according to claim 16 wherein the oxidant salt is copper oxalate.
Claim 21
Dependent Claim
26 words
A process according to claim 1 wherein the ammonium salt compound is selected from the group consisting of ammonium and substituted ammonium sulfates, trifluoroacetates and acetates.
Claim 22
Dependent Claim
14 words
A process according to claim 20 wherein the ammonium salt compound is triethylammonium sulfate.
Claim 23
Dependent Claim
15 words
A process according to claim 19 wherein the ammonium salt compound is triethylammonium hydrogen sulfate.
Claim 24
Dependent Claim
22 words
A process according to claim 1 wherein the ammonium salt compound is employed in concentrations of from 2 to 20 weight percent.
Claim 25
Dependent Claim
75 words
A process according to claim 1 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 said amine base in the catalytic mixture, said acid being of a strength stronger than water and such that the anion will not substantially complex with the metal salt or oxidant salt compound in said catalytic mixture.
Claim 26
Dependent Claim
12 words
A process according to claim 24 wherein said acid is sulfuric acid.
Claim 27
Dependent Claim
46 words
A process according to claim 1 wherein the reaction is carried out in the presence of a catalytic amount of an organic mono- or poly-dentate ligand or coordination complex selected from the group consisting of alkyl, aryl and halogen substituted phosphines, arsines, stibines and halide salts.
Claim 28
Dependent Claim
14 words
A process according to claim 26 wherein the ligand or coordination complex is triphenylphosphine.
Claim 29
Dependent Claim
15 words
A process according to claim 26 wherein the ligand or coordination complex is lithium iodide.
Claim 30
Dependent Claim
30 words
A process according to claim 1 wherein the pressure is between about 900 psig and 2200 psig and the temperature is in the range of 60° C. to 100° C.
Claim 31
Dependent Claim
47 words
A process according to claim 1 wherein the alcohol is selected from the group consisting of methanol, ethanol, 2-propanol and butanol, the metal salt compound is palladium iodide, the amine is triethylamine, the oxidant salt is copper (II) sulfate, and the ammonium salt compound is triethylammonium sulfate.
Claim 32
Dependent Claim
19 words
A process according to claim 30 wherein a catalytic amount of lithium iodide is added to the reaction mixture.
Claim 33
Dependent Claim
18 words
A process according to claim 1 wherein air is employed as a source of oxygen for the reaction.
Claim 34
Dependent Claim
13 words
A process according to claim 1 wherein the metal salt compound is supported.
Claim 35
Dependent Claim
59 words
A process according to claim 1 wherein the alcohol is n-butyl alcohol, the metal salt compound is palladium iodide, the amine is triethylamine employed in excess over the required quantities of said amine base, the oxidant salt is copper (I) iodide, and the amine salt compound is triethylammonium sulfate which is formed upon the addition of concentrated sulfuric acid.
References Cited (Backward Citations)
US3393136A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-02-27 | 1981-08-29 | 1982-02-28 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-02-27 | 1985-08-29 | 1986-02-28 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-02-27 | 1989-08-29 | 1990-02-28 | $7700.00 | Window Closed / Lapsed |