Patent GB-421718-A (GB)
Title: Improvements in the manufacture and production of amines and amides
Filed: 1933-04-26
Abstract: Amines or amides are obtained by treating carboxylic acids or their anhydrides, esters or amides at about 200--400 DEG  C. with a mixture of hydrogen and ammonia in the presence of a hydrogenation catalyst. The process may be modified in that (a) a primary or secondary amine may be used instead of or in addition to ammonia, or (b) a nitrogenous compound which yields ammonia or is reduced to a primary or secondary amine under the reaction conditions may be used instead of or in addition to ammonia or a primary or secondary amine, or (c) a non-nitrogenous compound which reacts under the reaction conditions with hydrogen and ammonia (or an amine) to form a primary or secondary amine may be present.  The reaction may be effected at atmospheric or raised pressure and in the liquid or vapour phase. The carboxylic acids or derivatives treated may be of the aliphatic, cycloaliphatic, aromatic or heterocyclic series; specified carboxylic acids or derivatives are acetic acid; propionic acid; butyric acid; valeric acid; caproic acid; caprylic acid; nonoic acid; capric acid; lauric acid; myristic acid; pentadecylic acid; palmitic acid; margaric acid; stearic acid; arachidic acid; behenic acid; lignoceric acid; cerotic acid; melissic acid; montanic acid; fatty acid mixtures obtainable by oxidizing paraffin hydrocarbons; acrylic acid; crotonic acid; vinylacetic acid; methacrylic acid; nonylenic acid; undecylenic acid; oleic acid; elaidic acid; linoleic acid; linolenic acid; erucic acid; sorbic acid; cyclopentanecarboxylic acid; hexahydrobenzoic and other naphthenic acids; camphoric acid; decahydronaphthoic acid; benzoic acid; toluic acids; ethylbenzoic acids; 1-naphthoic acid; phenanthrene-10-carboxylic acid; anthracene monocarboxylic acids; phenylacetic acid; cinnamic acid; oxalic acid; maleic acid; adipic acid; phthalic acid; anthracene and phenanthrene polycarboxylic acids; furanecarboxylic acid; picolinic acid and other pyridinecarboxylic acids; oxy-, amino-, nitro-, keto- and aldehydocarboxylic acids such as lactic, ricinoleic, mandelic, salicylic, pyroracemic, levulic, benzoylacetic, glyoxalic, aminoacetic, a -aminopropionic, phenylaminoacetic, cyanacetic and cyanopropionic acids; esters of the acids specified with methyl, ethyl, propyl, butyl, nonyl, octodecyl or oleyl alcohol or with ethylene glycol, hexanediol, glycerol, benzyl alcohol, hexahydrobenzyl alcohol, cyclohexanol, phenol, resorcinol, or sorbitol, including naturally occurring esters such as coco-nut oil, peanut oil, palm kernel oil, soya bean oil, olive oil, castor oil, train oil and tallow. Polycarboxylic acids and keto-and aldehydo-carboxylic acids yield polyamines; thus, levulic acid may be converted into 2 : 5-diaminopentane.  Oxycarboxylic acids may yield mono- or poly-amines.  Nitro- and cyano-carboxylic acids yield polyamines. Specified primary and secondary amines for use in modification (a) above are methyl, ethyl, propyl, butyl, nonyl, undecyl, stearyl and oleyl amines, ethylenediamine, cyclohexylamine, aniline, N-monoalkylanilines, 2 - tetrahydronaphthylamine, diethylamine, dibutylamine, dibenzylamine, cyclohexylmethylamine, piperidine, decahydroquinoline, primary or secondary alkylolamines such as ethanolamine, and aminoacids such as b -aminopropionic acid. Specified nitrogenous compounds for use in modification (b) above are acetonitrile, propionitrile, valeronitrile, palmitonitrile, benzyl cyanide, hydrocyanic acid, butyronitrile, nonylenic acid nitrile, stearonitrile, lauronitrile, benzonitrile, phenylacetonitrile, mandelic acid nitrile, ammonium carbonate, urea, aldehydeammonias, oximes such as acetaldoxime and benzaldoxime, nitro compounds such as nitromethane, nitrobenzene and nitrophenols, and hydrogenizable heterocyclic tertiary amines such as pyridine, quinoline, and isoquinoline; thus a mixture of lauronitrile and methyl butyrate may be converted into butyldodecylamine.  Specified non-nitrogenous compound for use in modification (c) above are alcohols, phenols, ketones and aldehydes; in particular, the alcohols and phenols specified above may be present, or the following ketones or aldehydes:--acetone, methylethyl ketone, methylundecyl ketone, benzophenone, cyclohexanone, acetaldehyde, propionaldehyde, butyraldehyde, oenanthic aldehyde, oleic aldehyde, phenylacetaldehyde and benzaldehyde; thus, if a mixture of acetone, ethylamine and a carboxylic acid or derivative is treated, isopropylethylamine is first formed from the acetone and ethylamine, and then reacts with the carboxylic acid or derivative; a mixture of palm kernel oil and acetaldehyde yields, with ammonia and hydrogen, a mixture of primary, secondary and tertiary amines useful as a wetting, emulsifying or washing agent in the textile industry, either as such or after treatment with alkylene oxides.  Specified hydrogenation catalysts are (a) copper, cobalt, nickel, iron, platinum, ruthenium, rhodium, palladium, osmium and iridium, and their alloys; (b) oxides, sulphides and other compounds containing oxygen or sulphur of metals of the sixth periodic group and sulphides of metals of the eighth periodic group, such as tungsten oxide, molybdenum oxide, tungsten disulphide, and molybdenum disulphide, or mixtures thereof such as mixtures of sulphides of tungsten and/or molybdenum with sulphides or iron, cobalt or nickel; (c) salts and complex compounds of tungstic and/or molybdic acid such as their alkali or alkaline earth salts, phosphotungstic and phosphomolybdic acids, and complex compounds of chromium oxide or trioxide with tungstic or molybdic acid; the metallic catalysts specified may be taken as oxides, hydroxides or salts, e.g. carbonates, nitrates, formates or acetates, which are reduced in the reaction.  Specified substances which may be added to the catalysts are compounds of metals (other than metals of the sixth periodic group) the oxides of which are not reducible under the reaction conditions, such as oxides hydroxides, phosphates, carbonates and nitrates of alkali metals, barium carbonate, aluminium phosphate or silicate, calcium oxide, strontium oxide, magnesium oxide, aluminium oxide, zinc oxide, zinc phosphate, cadmium oxide, manganous oxide, vanadium oxide, titanium oxide, zirconium oxide, cerium oxide, thorium oxide and silicon hydroxide or silica gel. Specified catalytic compositions contain (a) copper, aluminium and barium; (b) cobalt, aluminium and an alkali metal; (c) nickel, magnesium and silicon; (d) copper, chromium, titanium and aluminium; (e) copper and manganese; (f) nickel (or cobalt), copper, and manganese (or aluminium); (g) nickel (or cobalt), molybdenum and tungsten; (h) nickel sulphide and tungsten disulphide or molybdenum sulphide; (i) iron sulphide and molybdenum sulphide; (j) cobalt sulphide and tungsten disulphide. Specified supports for the catalysts are pumice, bleaching earth, kieselguhr, china clay, and charcoal.  The catalyst or one component of the catalytic composition is preferably preheated before use; thus, alumina may be heated to 800--900 DEG  C. and then mixed with a hydrogenating metal.  The hydrogen used in the reaction may contain diluents such as nitrogen, carbon dioxide or steam; thus, the waste gases from the synthesis of ammonia may be used.  In the examples: (1) methyl stearate is treated with ammonia and hydrogen in the presence of a catalyst prepared by mixing preheated alumina with basic cobalt carbonate and reducing the product in hydrogen; stearylamine and distearylamine are obtained; (2) acetic anhydride is treated with ammonia and hydrogen in the presence of a catalyst prepared by precipitating copper and manganese carbonates on to bleaching earth, and heating the mixture; ethylacetamide is the principal product; (3) capric acid and aniline are treated with hydrogen in the presence of a catalyst prepared by adding sodium bicarbonate to a solution of aluminium, barium and cobalt nitrates, and drying and reducing the precipitate; the product contains cyclohexylamine, dicyclohexylamine, cyclohexyldecylamine and other unspecified amines, as well as a substituted capric amide; (4) capric acid and butylamine are treated with hydrogen in the presence of the catalyst used in example 3; the product contains di- and tri-butylamine, butyldecylamine, other unspecified amines, and alkylated capric amides; (5) and (6) as in examples 1, except that the catalysts described in examples 3 and 2 respectively are used; (7) ethyl acetate is treated with ammonia and hydrogen in the presence of the catalyst used in example 3; di- and tri-ethylamine and ethylacetamide are obtained; (8) nonylenic acid methyl ester is treated with ammonia and hydrogen in the presence of the catalyst used in example 2 supported on pumice; nonyleneamine and nonylamines are obtained; (9) ethyl benzoate is treated with ammonia and hydrogen in the presence of the catalyst used in example 2; benzylamine and dibenzylamine are obtained; (10) capric acid and dibutylamine are treated with hydrogen in the presence of the catalyst used in example 3; tributylamine, butyldecylamine, and dibutyldecylamine are obtained; (11) lauric acid and ethylenediamine are treated with hydrogen in the presence of the catalyst used in example 2; a mixture of unspecified amines is obtained; (12) octodecyl butyrate is treated with ammonia and hydrogen in the presence of the catalyst used in example 2; a mixture of unspecified amines is obtained; (13) as in example 1, except that a catalyst prepared by heating basic cobalt carbonate is used; (14) coco-nut oil is treated with ammonia and hydrogen in the presence of the catalyst of example 13; a mixture of primary and secondary amines is obtained; (15) methyl laurate is treated with ammonia and hydrogen in the presence of a catalyst prepared by adding sodium bicarbonate to a solution of copper, aluminium and barium nitrates, and drying and reducing the precipitate; dodecylamine