Patent GB-404744-A (GB)
Title: Improvements in the manufacture and production of amino compounds
IPC: C07C255/24
Filed: 1932-08-04
Abstract: Aminonitriles are manufactured by reacting acrylic nitrile with an ammonia base which contains at least one hydrogen atom connected to nitrogen but which is free from alkylol groups, such as ammonia, hydroxylamines, hydrazines, aliphatic, hydroaromatic or aromatic primary or secondary amines, or polyamines of the said kinds, e.g. methyl-, ethyl-, propyl-, butyl-, amyl-, decyl-, dodecyl-, octadecyl- and cyclohexyl-amines, aniline, monomethyl-, ethyl-, propyl- or butyl-anilines, hydroxylamine, N- and O- alkyl- or aryl-hydroxylamines, hydrazine, N-alkyl-, cycloalkyl- or aryl-hydrazines, diethylenetriamine, triethylenetetramine and similar polyamines, also ammonia bases containing reactive groups or atoms such as carboxylic, nitrile, ester or nitro groups or halogen atoms, e.g. aminoacetic acid, N-methylaminoacetic acid, aminocarboxylic nitriles, e.g. aminopropionic nitrile (yielding amines containing two nitrile groups), chlorethylamine, amino-acetic or -propionic esters and nitroaryl-hydroxylamines or -hydrazines.  The reaction may be carried out in the presence of diluents or solvents such as water, mono- or polyhydric alcohols which are liquid under the working conditions, ethers such as diethyl ether or dioxane, ethers of polyhydric alcohols such as ethylene glycol monoalkyl ethers, halogenated aliphatic hydrocarbons such as chloroform, carbon tetrachloride or ethylene chloride, or aliphatic, cycloaliphatic or aromatic hydrocarbons.  Quantities of the reaction components in excess of the theoretical may also act as solvents or diluents. The reaction may proceed at -20 DEG  C. but is usually carried out while warming, e.g. to about 150 DEG  C., or in the case of amines of high molecular weight up to 200 DEG  C.  Preferably temperatures at or about the boiling point of at least one of the reacting compounds are employed, advantageously while working in a closed vessel. The reaction may be accelerated by means of neutral to weakly acid reacting condensation catalysts, e.g. metallic nickel, zinc, cobalt, copper or other metals yielding ammoniates, copper salts such as copper chlorides, sulphate or acetate, and salts of ammonia or amines with strong acids such as the mineral acids. The reaction is preferably carried out in the liquid phase but may also be carried out in the gaseous phase especially with ammonia or amines of low molecular weight.  The products may be reduced to polyamines or the nitrile groups may be saponified or esterified, whilst the amino groups may also enter into reaction, e.g. with acids, alkylene oxides or alkyl acid chlorides.  The products may be employed as intermediates for the production of assistants for the textile and related industries, as solvents, e.g. for albumen, fibrin or sulphur, or as intermediates for other processes.  In examples: (1) acrylic nitrile is heated in an autoclave with anhydrous liquid ammonia yielding 3-aminopropionitrile and iminodi-3-propionitrile, the latter being convertible by means of ethyl alcohol into iminodi-3-propionic diethyl ester which may be converted into piperidone; (2) acrylic nitrile and n-butylamine are allowed to stand at -10 DEG  C., to produce n-butylaminopropionitrile, which may be saponified by means of caustic soda to produce the sodium salt of n-butylaminopropionic acid, or reduced in ethereal solution by means of hydrogen under pressure in the presence of nickel to yield n-butylaminopropylamine, which with oleic acid chloride yields the corresponding oleic amide which on sulphonation yields an assistant for the textile industry; (3) acrylic nitrile is refluxed with di-n-butylamine, producing di-n-butylaminopropionitrile; (4) cyclohexylamine similarly yields cyclohexylaminopropionitrile; (5) acrylic acid and N-ethylaniline are heated in a closed vessel with the addition of sulphuric acid, producing N-phenyl-N-ethylamino-3-propionitrile; (6) acrylic acid is mixed and allowed to stand in the cold with a solution of hydroxylamine in methyl alcohol neutralized or rendered weakly acid with hydrochloric acid, yielding hydroxylamino-N-3-propionitrile; if the reaction is carried out in an alkaline medium, e.g. in the presence of sodium methylate, methoxy-3-propionitrile is also produced; (7) acrylic nitrile is added while cooling to aqueous hydrazine hydrate solution and the water is removed by vacuum distillation, producing a substance which is probably hydrazine-3-propionitrile together with small amounts of the corresponding amide; (8) acrylic nitrile is added slowly, through a reflux condenser, to triethylenetetramine yielding an addition product.  The Provisional Specification comprises the manufacture of aminonitriles from a -b -unsaturated nitriles in general, other nitriles specified being crotonic nitrile, fumaric and maleic dinitriles, cinnamic nitrile and nitrocinnamic nitriles, or from substances yielding a -b -unsaturated nitriles on heating, e.g. allyl cyanide.  In an additional example, crotonic nitrile is heated with anhydrous ammonia to produce amino-3-butyronitrile.