GB719919A - Improvements in the production of aliphatic oxygen compounds - Google Patents
Improvements in the production of aliphatic oxygen compoundsInfo
- Publication number
- GB719919A GB719919A GB31365/52A GB3136552A GB719919A GB 719919 A GB719919 A GB 719919A GB 31365/52 A GB31365/52 A GB 31365/52A GB 3136552 A GB3136552 A GB 3136552A GB 719919 A GB719919 A GB 719919A
- Authority
- GB
- United Kingdom
- Prior art keywords
- mixture
- cobalt
- carbon monoxide
- hydrogen
- give
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/54—Preparation of carboxylic acid anhydrides
- C07C51/56—Preparation of carboxylic acid anhydrides from organic acids, their salts, their esters or their halides, e.g. by carboxylation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Aliphatic oxygen compounds are obtained by the action of carbon monoxide on saturated aliphatic alcohols containing up to 4 carbon atoms, or their ethers with saturated alcohols, at elevated temperatures and under super-atmospheric pressure in the presence of a complex compound of a cobalt halide of general formula Q2CoX4 in which Q is an organic quaternary ammonium or phosphonium radical and in which X stands for a chlorine, bromine or iodine ion, at least two of which are bromine or iodine ions. Suitable catalysts are, for example, [(C2H5)3(C4H9)N]2CoBr4, [(C2H5)2(C4H9)2N]2 CoI4, [(C3H7)4N]2CoBr2I2 [(CH3)3(C6H4)N]2CoBr4, [(C5H5N)(C4H9)]2CoBr4, [(C5H5N)(C6H5CH2)]2CoI4 and the corresponding phosphonium compounds. In particular, the triaryl alkyl phosphonium cobalt bromides, in which the alkyl group contains from 1 to 6 carbon atoms and the aryl group is phenyl or a homologue thereof, are suitable. The catalysts may be formed in situ, for example, by adding to the starting material a cobalt halide and an organic quaternary ammonium or phosphonium halide. Preferably the reaction is carried out between 70 DEG and 250 DEG C. and at pressures above 50 atmosphere. The carbon monoxide may be pure or mixed with other gases such as nitrogen, methane, carbon dioxide and hydrogen. The reaction may be carried out continuously or otherwise. Preferably a concentration of 0.01 and 1 per cent of cobalt based on starting materials is used. In the examples: (a) methanol is treated with a mixture of carbon monoxide and hydrogen in the presence of di-(butyl-pyridinium) cobalt tetrabromide [(C5H5N(C4H2)]2.CoBr4 to give methyl acetate and acetaldehyde dimethylacetal; (b) methanol is treated with a mixture of carbon monoxide and hydrogen in the presence of dibutyl dipyridinium cobalt tetrabromide, triethyl butyl ammonium cobalt tetrabromide and pyridine to give a mixture of methyl acetate, acetic acid, acetaldehyde dimethyl acetal and a small amount of acetaldehyde; (c) methanol is treated with a mixture of carbon monoxide and hydrogen in the presence of triethyl butyl ammonium cobalt tetrabromide to give methyl acetate, acetic acid and acetaldehyde dimethyl acetal; if pure carbon monoxide is used a mixture of methyl acetate and acetic acid is obtained; (d) methanol is heated with a mixture of carbon monoxide and hydrogen in the presence of triphenyl butyl phosphonium cobalt tetrabromide to give a mixture of acetic acid, methyl acetate and acetaldehyde dimethyl acetal; (e) n-butanol is treated with a mixture of carbon monoxide and hydrogen in the presence of trimethyl butyl ammonium cobalt tetrabromide to give n-butyl valerate and n-valeric acid; (f) butane diol-1,4 is treated with a mixture of carbon monoxide and hydrogen in the presence of triethyl butyl ammonium monoxide and hydrogen in the presence of triethyl butylammonium cobalt tetrabromide to give d -valerolactone, n-valeric acid and adipic acid; similar results are obtained if a mixture of anhydrous cobalt bromide and triphenyl butylphosphonium bromide [(C6H5)3(C4H9)P]Br is used as catalyst; (g) methanol is treated with a mixture of carbon monoxide and hydrogen in the presence of a mixture of cobalt bromide and triphenyl ethyl phosphonium iodide to give acetic acid with some methyl acetate; (h) butane-diol 1.4 is treated with a mixture of carbon monoxide and hydrogen in the presence of triphenyl ethyl phosphonium cobalt diodide dibromide to give a mixture of adipic acid and n-valeric acid; and (j) a solution of dimethyl ether in N-methyl pyrrolidone is treated with a mixture of carbon monoxide and hydrogen in the presence of [(C2N5)4N]2CoBr2I2 to give acetic anhydride; (k) methanol is treated with a mixture of carbon monoxide and hydrogen in the presence of triethyl methyl ammonium cobalt dibromide dichloride to give a mixture of acetic acid and methyl acetate; a similar result is obtained if a mixture of triethyl methyl ammonium chloride and anhydrous cobalt iodide is used as catalyst.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE719919X | 1951-12-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB719919A true GB719919A (en) | 1954-12-08 |
Family
ID=6627317
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB31365/52A Expired GB719919A (en) | 1951-12-18 | 1952-12-11 | Improvements in the production of aliphatic oxygen compounds |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB719919A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0129332A1 (en) * | 1983-05-21 | 1984-12-27 | BP Chemicals Limited | Process for preparing carboxylic-acid anhydrides |
-
1952
- 1952-12-11 GB GB31365/52A patent/GB719919A/en not_active Expired
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0129332A1 (en) * | 1983-05-21 | 1984-12-27 | BP Chemicals Limited | Process for preparing carboxylic-acid anhydrides |
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