GB742740A - Improvements in the production of carboxylic acids, their esters and anhydrides - Google Patents
Improvements in the production of carboxylic acids, their esters and anhydridesInfo
- Publication number
- GB742740A GB742740A GB15945/53A GB1594553A GB742740A GB 742740 A GB742740 A GB 742740A GB 15945/53 A GB15945/53 A GB 15945/53A GB 1594553 A GB1594553 A GB 1594553A GB 742740 A GB742740 A GB 742740A
- Authority
- GB
- United Kingdom
- Prior art keywords
- nickel
- iodide
- ammonium
- phosphonium
- bromide
- 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
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Carboxylic acids, anhydrides and esters are made by treating saturated aliphatic alcohols or their ethers or aliphatic monocarboxylic acid esters with CO, optionally in admixture with H2, at elevated temperatures and pressures in the presence of a complex compound of nickel bromide or iodide with a quaternary ammonium and/or phosphonium halide. Complex compounds used may be of formula [A4N]2.Ni.X4, where A is a saturated hydrocarbon radicle of 1-4 C atoms, an aralkyl or cycloalkyl radicle or 2 of the A's form an alkylene radicle of 5-7 C atoms and X is Br or I or the quat. ammonium radicle may be replaced by a benzyl or alkyl pyridinium radicle. Typical of specified ammonium complexes are triethyl butyl ammonium nickel bromide iodide, diethyl dibutyl ammonium nickel iodide, trimethyl cyclohexyl ammonium nickel bromide, benzyl pyridinium nickel iodide and diethyl pyrrolidinium nickel iodide. Phosphonium complexes described are triaryl alkyl phosphonium nickel bromides where the alkyl radicle has 1-6 C atoms and the aryl group is a benzene residue, e.g. phenyl, tolyl or xylyl. The complexes may be formed during the reaction from the nickel bromide or iodide or nickel and the free halogen and the quat. ammonium or phosphonium halide. Preferred temperatures are 70-250 DEG C. and pressures over 50, especially 200-700 atmospheres are preferred. The CO used may be pure or contain other gases such as N2, H2, CO2 or CH4. When mixed gases are used the minimum concentration of CO is 10 per cent. With an excess of CO over H2, e.g. with at least 60 volumes of CO and at most 40 volumes of H2 the main products are carboxylic acids, esters and anhydrides. With higher concentrations of hydrogen a greater tendency to the production of aldehydes is observed. The feed gases should be substantially free of H2S. Products may be worked up in conventional fashion the complex being recovered unchanged and suitable for reuse. Preferably 0.01-2 per cent of Ni in the complex form calculated on starting material is used. Solvents, e.g. hydrocarbons, esters, ethers, N-alkyl lactams or reaction products, may be present. Specified alcohols are methanol, ethanol, propanols, butanols, ethylene glycol, propylene glycol, butanediols and mixtures of alcohols obtained by olefine hydration. Specified ethers are dimethyl and dipropyl ether. Acetates and propionates are mentioned as suitable esters. In examples (1) methyl acetate with CO in the presence of a mixture of triphenyl butyl phosphonium nickel tetrabromide or triphenyl ethyl phosphonium nickel tetra iodide or tritolyl butyl phosphonium nickel tetra bromide or iodide and N-methyl pyrrolidone yield acetic anhydride; (2) dimethyl ether with CO in the presence of triphenyl n-propyl phosphonium nickel tetra bromide or tritolyl butyl phosphonium nickel bromide or the corresponding iodides admixed with N-methyl pyrrolidone yields acetic anhydride; methyl acetate with CO in the presence of (3) tetramethyl ammonium nickel iodide; (4) tetraethyl ammonium nickel iodide; (5) tetraethyl ammonium nickel bromo iodide; (6) tetraethyl ammonium nickel bromide; (7), (8) and (9) trimethyl butyl ammonium nickel iodide; and (10) tetramethyl ammonium nickel iodide + triphenyl butyl phosphonium nickel bromide admixed with N-methyl pyrrolidone yield acetic anhydride; (11) methanol with CO and triphenyl ethyl phosphonium nickel iodide or triphenyl butyl phosphonium nickel bromo iodide or tritolyl ethyl phosphonium nickel iodide or triphenyl butyl phosphonium nickel bromide or tetraethyl ammonium nickel iodide or trimethyl propyl ammonium nickel bromo iodide or trimethyl butyl ammonium nickel iodide yield methyl acetate and acetic acid; (12) methyl acetate with CO and H2 and a mixture of tetramethyl ammonium iodide, nickel iodide and N-methyl pyrrolidone yields acetic anhydride; (13) butane diol 1,4 with CO and tetramethyl ammonium nickel iodide yields mainly adipic acid with some d -valero-lactone and valeric acid and in (14) butane diol-1,4 with CO and a mixture of nickel, iodine, bismuth, triethylamine and ethyl iodide yields adipic acid.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE742740X | 1952-06-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB742740A true GB742740A (en) | 1956-01-04 |
Family
ID=6646201
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB15945/53A Expired GB742740A (en) | 1952-06-11 | 1953-06-10 | Improvements in the production of carboxylic acids, their esters and anhydrides |
Country Status (2)
Country | Link |
---|---|
CH (1) | CH316745A (en) |
GB (1) | GB742740A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2506760A1 (en) * | 1981-05-28 | 1982-12-03 | Halcon Sd Group Inc | PROCESS FOR PRODUCING ACETIC ACID BY CATALYTIC TRANSPOSITION OF METHYL FORMIATE |
FR2527599A1 (en) * | 1982-05-28 | 1983-12-02 | Halcon Sd Group Inc | PROCESS FOR THE PREPARATION OF ACETIC ACID IN THE PRESENCE OF HYDROGEN |
EP0476333A2 (en) * | 1990-09-21 | 1992-03-25 | Hoechst Aktiengesellschaft | Process for simultaneous production of acetic acid and acetanhydride |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5196138A (en) * | 1989-06-30 | 1993-03-23 | Cyprus Foote Mineral Company | Preparation of mixed lithium amide reagents |
CA2018790A1 (en) * | 1989-10-11 | 1991-05-11 | Smith, (W.) Novis, Jr. | Mixed lithium amides and reagent compositions thereof |
-
1953
- 1953-06-10 GB GB15945/53A patent/GB742740A/en not_active Expired
- 1953-09-22 CH CH316745D patent/CH316745A/en unknown
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2506760A1 (en) * | 1981-05-28 | 1982-12-03 | Halcon Sd Group Inc | PROCESS FOR PRODUCING ACETIC ACID BY CATALYTIC TRANSPOSITION OF METHYL FORMIATE |
FR2527599A1 (en) * | 1982-05-28 | 1983-12-02 | Halcon Sd Group Inc | PROCESS FOR THE PREPARATION OF ACETIC ACID IN THE PRESENCE OF HYDROGEN |
EP0476333A2 (en) * | 1990-09-21 | 1992-03-25 | Hoechst Aktiengesellschaft | Process for simultaneous production of acetic acid and acetanhydride |
EP0476333A3 (en) * | 1990-09-21 | 1992-11-25 | Hoechst Aktiengesellschaft | Process for simultaneous production of acetic acid and acetanhydride |
Also Published As
Publication number | Publication date |
---|---|
CH316745A (en) | 1956-10-31 |
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