Patent GB-433625-A (GB)
Title: The manufacture of aminoalkylated amines
IPC: C07C209/18
Filed: 1934-02-17
Abstract: N-Aminoalkyl amines are prepared by treating primary or secondary amines with aminoalcohols in the presence of an acid or basic condensing agent.  Suitable acid condensing agents are phosphorus pentoxide, phosphoric acid, boron phosphate and its hydrates, zinc chloride and aluminium chloride; suitable basic condensing agents are basic compounds of the alkali and alkaline earth metals, magnesium, and aluminium.  When a basic condensing agent is used, at least one of the reagents is preferably used in the form of a compound with one of the metals specified, and the amine is preferably taken as an acyl derivative.  A solvent or diluent or an excess of the aminoalcohol may be present.  Examples are given of the preparation of (1) N - diethylaminoethylaniline by heating aniline with b -diethylaminoethanol in the presence of phosphorus pentoxide, zinc chloride, boron phosphate, or potassium hydroxide; or by heating aniline with the sodium compound of the alcohol; or by heating formanilide or acetanilide with the alcohol in the presence of metallic sodium or magnesium oxide; or by heating acetanilide with the sodium compound of the alcohol; the same product, and also bis(N-diethylaminoethyl) aniline, are obtained by heating aniline with b -diethylaminoethanol in the presence of hydrated boron phosphate, the products being separated by acylating the secondary amine with phthalic anhydride; (2) a -diethylaminoethylaminopyridine from a -aminopyridine and b -diethylaminoethanol in the presence of phosphorus pentoxide preferably mixed with quartz sand; (3) 6-chloro-8-diethylaminoethylaminoquinoline from 6-chloro-8-aminoquinoline and b -diethylaminoethanol in the presence of phosphoric acid; (4) 6-methoxy-8-diethylaminoethylaminoquinoline from 6-methoxy-8-aminoquinoline and b -diethylaminoethanol in the presence of phosphorus pentoxide and sand; (5) 6-methoxy-8-diethylaminopropylaminoquinoline from 6-methoxy-8-aminoquinoline and g -diethylaminopropanol in the presence of phosphorus pentoxide; (6) 2-(a -diethylamino-d -pentyl)amino naphthalene from formylb -naphthylamine and the sodium compound of a -diethylamino-d -pentyl alcohol; (7) 6-methoxy - 8 - (a -diethylamino-d -pentyl)aminoquinoline from 6-methoxy-8-formylaminoquinoline and a -diethylamino-d -pentyl alcohol in the presence of sodamide; or from 6-methoxy-8-formylaminoquinoline and the calcium compound of the alcohol; or from the sodium compound of 6-methoxy-8-formylaminoquinoline and the alcohol; or from 6-methoxy-8-aminoquinoline and the aluminium or sodium compound of the alcohol; or from 6-methoxy8-acetylaminoquinoline and the sodium compound of the alcohol; or from 6-methoxy-8-aminoquinoline and the alcohol in the presence of boron phosphate or a hydrated boron phosphate; (8) N-diethylaminoethylbenzylamine from formyl benzylamine and b -diethylaminoethanol in the presence of sodium; (9) 2-(g  - piperidino-b -dimethylpropyl)aminopyridine from 2-formylaminopyridine and g -piperidino-b -dimethylpropanol in the presence of sodium; (10) 4-(g -piperidino-b -dimethylpropyl)aminopyridine from 4-formylaminopyridine and g -piperidino-b -dimethylpropanol in the presence of sodium; (11) N-diethylaminododecylamine from formyldodecylamine and b -diethylaminoethanol in the presence of sodium; (12) N-(a -diethylamino-d -pentyl)aniline from acetanilide and the sodium compound of a -diethylamino-d -pentyl alcohol; (13) N-diethylaminoethylbutylamine from butylamine and b -diethylaminoethanol in the presence of zinc chloride; (14) N-(methyl)(diethylaminoethyl) aniline from methylaniline and b -diethylaminoethanol in the presence of phosphorus pentoxide; (15) 1 : 3-bis-diethylaminoethylaminobenzene from m-phenylenediamine and b -diethylaminoethanol in the presence of phosphorus pentoxide; (16) N-(n-butylaminoethyl)aniline from aniline and b -n-butylaminoethanol in the presence of phosphorus pentoxide, or from formanilide and the alcohol in the presence of sodium; in the first case, N-bis-(n-butylaminoethyl)aniline is obtained as a by-product; (17) N-phenylethylenediamine from aniline and ethanolamine in the presence of aluminium chloride. Reference is made also to the manufacture of N-aminoalkyl derivatives of aminoanthracenes and aminoacridines.