Patent GB-438793-A (GB)
Title: Improvements in the manufacture and production of amines
IPC: D03D51/20
Filed: 1934-05-15
Abstract: High molecular aliphatic amines containing more than 10 carbon atoms are prepared by the catalytic hydrogenation in the liquid phase of the corresponding nitriles, preferably in the presence of ammonia, at temperatures above 50 DEG  C. and pressures of at least 25 atmospheres.  Nitriles specified are lauric, myristic, palmitic, stearic, montanic and oleic nitriles, nitriles of the mono- and di-carboxylic acids resulting from the oxidation of paraffin wax &c., and mixtures of nitriles of the fatty acids of coconut oil; substituents such as amino or hydroxy groups may be present in the nitriles.  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)], and 356,731; 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 manufacture of such assistants or of pharmaceutical preparations.  Examples describe the preparation of (1) a mixture of mono- and di-stearylamines by the hydrogenation of stearic nitrile in cyclohexane at 100 DEG  C. and 25 or 200 atmospheres in the presence of a catalyst prepared by reducing basic cobalt carbonate with hydrogen; lauric nitrile under the same conditions gives mono- and di-dodecylamines; (2) stearylamine by treating stearic nitrile, cyclohexane and liquid ammonia with hydrogen at 100 DEG  C. and under 200 atmospheres pressure using the catalyst of (1); (3) dodecylamine from lauric nitrile and hydrogen at 100 DEG  C. and 150--200 atmospheres using the catalyst of (1); (4) stearyl- and distearyl-amines by treatment with hydrogen under 300 atmospheres pressure and at 270 DEG  C. of a solution of stearic nitrile and ammonia in cyclohexane, using a catalyst obtained by heating to 350 DEG  C. the precipitation product of mixed copper and manganese nitrates with sodium bicarbonate and bleaching earth; (5) a mixture of mono-and di-dodecylamines by the hydrogenation of lauric nitrile in cyclohexanol at 50--55 DEG  C. and 200 atmospheres using a reduced nickel catalyst activated with chromic acid.  The samples furnished under Sect. 2 (5) comprise: (A) mixed amines prepared by hydrogenation of the nitriles of coconut oil fatty acids at 100 DEG C. and 200 atmospheres in the presence of ammonia p  and the catalyst of (2) above; (B) oleylamine obtained by treatment of oleic nitrile with ammonia and hydrogen at 80--100 DEG  C. and 100 atmospheres using the catalyst of (2) above; (C) dodecylamine from lauric nitrile using hydrogen containing ammonia at 100 DEG  C. and 200 atmospheres in the presence of the catalyst of (2) above; (D) mixed amines prepared by hydrogenation of coconut oil nitriles at 125 DEG  C. and 100 atmospheres using a catalyst obtained by precipitating mixed copper and manganese nitrates with sodium bicarbonate, adding cobalt carbonate, and reducing with hydrogen; (E) a mixture of amines obtained from nitriles of the formula R.NH.CH2.CH2.CN (wherein R is the alkyl radicle of the fatty acids of palm kernel oil, the nitriles being prepared by the process of Specification 404,744) using hydrogen and ammonia at 100 DEG  C. and 200 atmospheres in the presence of the catalyst of (1) above; (F) hydroxyoctadecylamine by hydrogenation of hydroxystearic nitrile in cyclohexane at 110 DEG  C. and 100 atmospheres using the catalyst of (1) above.  Specifications 282,083, [Class 2 (iii)], 357,152, 369,690, [Group III], and 388,874 also are referred to.  The Specification as open to inspection under Sect. 91 also describes the use of primary or secondary amines of low boiling-point in lieu of ammonia and mentions in this connection methylamine, ethylamine, diethylamine, propylamine, butylamine, piperidine and cyclohexylamine.  It also states that the nitriles employed may contain 8--28 carbon atoms and refers in addition to capric nitrile and dipropylacetic nitrile; carboxylic groups are mentioned as further substituents in the nitrile molecule.  The Specification also adverts to the use of (1) room temperature and atmospheric pressure; (2) certain solvents which react with the amines formed, the nitriles employed, or intermediate reaction products; (3) cobalt catalysts prepared by decomposing cobalt formate or reducing cobaltous hydroxide or cobalt carbonate with hydrogen; when using cobalt catalysts the presence of ammonia or amines may be dispensed with and temperatures of below 300 DEG  C. employed.  It also includes an example describing the preparation of cyclohexyldodecylamine by treating lauric nitrile and cyclohexanol with hydrogen at 230 DEG  C. and 250 atmospheres in the presence of a catalyst prepared by heating basic cobalt carbonate at 350 DEG  C. This subject-matter does not appear in the Specification as accepted. Nitriles.--High molecular aliphatic nitriles containing an even number of carbon atoms may be prepared by treating naturally-occurring fatty acids, e.g. those of coconut oil, or their derivatives with ammonia in the presence of dehydrating catalysts. Another method consists in treating the acid amides with thionyl chloride; e.g. stearic nitrile is thus obtained from stearic amide. Nitriles containing an uneven number of carbon atoms may be prepared by interaction of the appropriate alkyl halides with alkali metal cyanides.  Hydroxystearic nitrile is obtained by adding sulphuric acid to oleic acid nitrile and cautiously saponifying the sulphuric ester obtained.ALSO:High-molecular aliphatic amines containing more than 10 carbon atoms are prepared by the catalytic hydrogenation in the liquid phase of the corresponding nitriles, preferably in the presence of ammonia, at temperatures above 50 DEG  C., and pressures of at least 25 atmospheres.  Nitriles specified are lauric, myristic, palmitic, stearic, montanic and oleic nitriles, nitriles of the mono- and dicarboxylic acids resulting from the oxidation of paraffin wax &c., and mixtures of nitriles of the fatty acids of coconut oil; substituents such as amino or hydroxy groups may be present in the nitriles.  As hydrogenating gas, hydrogen alone or in admixture with nitrogen, carbon monoxide or hydro-carbons may be employed. Hydrogenating catalysts mentioned are nickel, cobalt, copper and the catalysts described in Specifications 255,884 [Class 1 (i)], and 356,731; 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 manufacture of such assistants or of pharmaceutical preparations. Examples describe the preparation of (1) a mixture of mono-and di-stearylamines by the hydrogenation of stearic nitrile in cyclohexane at 100 DEG  C. and 25 or 200 atmospheres in the presence of a catalyst prepared by reducing basic cobalt carbonate with hydrogen; lauric nitrile under the same conditions gives mono-and di-dodecylamines; (2) stearylamine by treating stearic nitrile, cyclohexane and liquid ammonia with hydrogen at 100 DEG  C. and under 200 atmospheres pressure using the catalyst of (1); (3) dodecylamine from lauric nitrile and hydrogen at 100 DEG  C. and 150--200 atmospheres using the catalyst of (1); (4) stearyl and distearyl-amines by treatment with hydrogen under 300 atmospheres pressure and at 270 DEG  C. of a solution of stearic nitrile and ammonia in cyclohexane, using a catalyst obtained by heating to 350 DEG  C. the precipitation product of mixed copper and manganese nitrates with sodium bicarbonate and bleaching earth; (5) a mixture of mono- and di-dodecylamines by the hydrogenation of lauric nitrile in cyclohexanol at 50--55 DEG  C. and 200 atmospheres using a reduced nickel catalyst activated with chromic acid.  The samples furnished under Sect. 2 (5) comprise (A) mixed amines prepared by hydrogenation of the nitriles of coconut oil fatty acids at 100 DEG  C. and 200 atmospheres in the presence of ammonia and the catalyst of (2) above; (B) oleylamine obtained by treatment of oleic nitrile with ammonia and hydrogen at 80--100 DEG  C. and 100 atmospheres using the catalyst of (2) above; (C) dodecylamine from lauric nitrile using hydrogen containing ammonia at 100 DEG  C. and 200 atmospheres in the presence of the catalyst of (2) above; (D) mixed amines prepared by hydrogenation of coconut oil nitriles at 125 DEG  C. and 100 atmospheres using a catalyst obtained by precipitating mixed copper and manganese nitrates with sodium bicarbonate, adding cobalt carbonate, and reducing with hydrogen; (E) a mixture of amines obtained from nitriles of the formula R.NH.CH2.CH2.CN (wherein R is the alkyl radicle of the fatty acids of palm kernel oil, the nitriles being prepared by the process of Specification 404,744, [Group IV]) using hydrogen and ammonia at 100 DEG  C. and 200 atmospheres in the presence of the catalyst of (1) above; (F) hydroxyoctadecylamine by hydrogenation of hydroxystearic nitrile in cyclohexane at 110 DEG  C. and 100 atmospheres using the catalyst of (1) above. Specifications 282,083, [Class 1 (i)], 357,152, 369,690; and 388,874, [Group IV], also are referred to.  The Specification as open to inspection under Sect. 91 also describes the use of primary or secondary amines of low boiling-point in lieu of ammonia and mentions in this connection methylamine, ethylamine, diethylamine, propylamine, butylamine, piperidine and cyclohexylamine.  It also states that the nitriles employed may contain 8--28 carbon atoms and refers in addition to capric nitrile and dipropylacetic nitrile; carboxylic groups are mentioned as further substituents in the nitrile molecule.  The Specification also adverts to the use of (1) room temperature and atmospheric pressure; (