Patent GB-439274-A (GB)
Title: Improvements in the manufacture and production of amines
IPC: C07C209/48
Filed: 1934-05-15
Abstract: Amines are prepared by the hydrogenation of nitriles in the presence of primary or secondary amines, preferably in the liquid phase, at a pressure above atmospheric and/or at a temperature above 50 DEG  C. and using base metals or their compounds as catalysts.  A nitrile R.CN in the presence of an amine <FORM:0439274/IV/1> (R and Y representing organic radicles and X an organic radicle or hydrogen) thereby gives rise to products R. CH2 . NH2 and <FORM:0439274/IV/2> Nitriles specified are acetonitrile, propionitrile, succinic acid nitrile, valeronitrile; capronic, caprylic, capric, lauric myristic, palmitic, stearic, montanic and oleic nitriles; nitriles of the fatty acids of coconut, palm kernel, soya bean, castor, sperm and linseed oils and of tallow and hardened train oil; nitriles of the mono- and di-carboxylic acids resulting from the oxidation of waxes; abietic acid nitrile, naphthenic acid nitriles, benzyl cyanide, benzonitrile, cyanodiphenyls, cyanonaphthalenes, picolinic and nicotinic acid nitriles, quinoline carboxylic acid nitriles, salicylic acid nitrile, mandelic nitrile, 3-methoxypropionitrile, amino - acetonitrile, N - dimethyl - 3 - aminopropionitrile and N - dodecyl - 3 - aminopropionitrile.  The nitriles may be prepared by the methods described in Specification 438,793.  The following amines are referred to:--methyl-, dimethyl-, ethyl-, diethyl-, propyl-, butyl-, dibutyl-, octyl-, methyloctyl-, decyl-, dodecyl-and cyclohexyl-amines; aniline and methyl-, ethyl-, butyl- and cyclohexyl-anilines; toluidines, xylidines, benzylamine, naphthylamines, aminotetrahydronaphthalenes, aminodecahydronaphthalenes, piperidine, tetrahydro-quinoline, decahydroisoquinoline, dihydro-indole, carbazole, ethylene and propylene diamines, tetramethylene diamine, N-diethyl-3-aminopropylamine, N - butyl - 3 - aminopropylamine, N-amyl-ethylene diamine, benzidine, piperazine, diethylene triamine, triethylene tetramine, 3-butoxy-propylamine and dianisidine.  As hydrogenating gas, hydrogen alone or in admixture with nitrogen, carbon monoxide or hydrocarbons may be employed.  Hydrogenating catalysts mentioned are nickel, cobalt, copper and the catalysts described in Specifications 255,884, [Class 1 (i)], 356,731 and 421,718; cobalt and copper catalysts containing difficulty reducible metal oxides are especially useful.  The products may themselves be employed as assistants in the textile and related industries or may be used in the preparation of such assistants or of pharmaceutical preparations. Examples describe the preparation of (1) dodecylamine and dimethyldodecylamine by the hydrogenation of lauric nitrile and dimethylamine at 180 DEG  C. and 200 atmospheres in presence of reduced nickel; (2) dimethyloleylamine by allowing oleic nitrile to pass downwards over a basic zinc chromate catalyst in presence of hydrogen and dimethylamine at 275 DEG  C. and 250 atmospheres; (3) dimethyldodecylamine from lauric nitrile and dimethylamine at 180 DEG C. under a hydrogen pressure of 200 atmospheres and in presence of a copper-aluminium oxide catalyst; (4) dibutylstearylamine from stearic nitrile and dibutylamine under the same conditions as (3); (5) dodecylamine and methyldodecylaniline from lauric nitrile and methylaniline under the conditions of (3); (6) N - dodecyl - 3 - n - butoxy - propylamine and dodecylamine from lauric nitrile and 3 - n - butoxy - propylamine under the conditions of (3); (7) b -phenylethylamine and N-dimethyl-b -phenylethylamine from benzyl cyanide and dimethylamine under the conditions of (3); (8) asym - N - dimethyl - 1 : 3 - propylene diamine and N : N<1> - tetramethyl - 1 : 3 - propylene diamine from N - dimethyl - 3 - aminopropionitrile and dimethylamine under the conditions of (3); (9) isobutylamine and dimethylisobutylamine from isobutyric nitrile and dimethylamine under the conditions of (3); (10) dodecylamine and N-dodecyl-diethylene triamine by hydrogenation of lauric nitrile and diethylene triamine at 180 DEG  C. and 200 atmospheres using a nickel catalyst on bleaching earth.  The samples, furnished under Sect. 2 (5) comprise (A) mixed dodecyl- and methyldodecylamines by hydrogenation of lauric nitrile and methylamine at 270 DEG  C. and 200 atmospheres using a tungsten sulphide catalyst prepared according to Specification 379,335; (B) and (C) dodecylamine and cyclohexyldodecylamine respectively by treatment of lauric nitrile and cyclohexylamine at 180 DEG  C. under a hydrogen pressure of 200 atmospheres and in presence of a catalyst prepared by reducing a mixture of nickel carbonate with a little nickel chromate, the products being separated by fractional distillation; (D) and (E) dodecylamine and N-dodecylpiperidine respectively prepared from lauric nitrile and piperidine under the conditions used for samples B and C; (F) a mixture of dodecylamine and diethyldodecylamine from lauric nitrile and diethylamine under the conditions used for samples B and C; (G) a mixture of dodecylamine and methyldodecylamine from lauric nitrile and methylamine at 70 DEG  C. using the catalyst and pressure conditions employed in the case of samples B and C; (H) N - dimethyl - 3 - hydroxy - n - propylamine by treatment with hydrogen of ethylene cyanhydrin and dimethylamine in methanol at 50 DEG  C. and 100 atmospheres using the catalyst employed in the case of samples B and C; (I) mixed oleyl- and methyloleyl-amines from oleic nitrile and methylamine at 110 DEG  C. and a hydrogen pressure of 100 atmospheres using the catalyst employed in (1) above.  The first Provisional Specification states that the cobalt catalysts may be prepared by decomposing cobalt formate or by reducing cobaltous hydroxide or cobalt carbonate with hydrogen.