Patent GB-597253-A (GB)
Title: Production of poly-amino compounds
Filed: 1945-06-27
Abstract: N-Acidylated aliphatic polyamines, which may be hydrolysed to the free amines, are prepared by reacting an N - acidyl - amino aliphatic ester of a strong acid with at least m-molecular proportions of an aliphatic compound containing two or more non-tertiary amino groups or a derivative of such a compound containing at least one acidyl-amino group and at least one primary amino or azomethine group, m being equal to the number of hydrogen atoms attached to nitrogen or (in the case of an azo-methine derivative) to the number of azo-methine groups present in said aliphatic compound or derivative thereof, and, when a compound containing an azo-methine group is used, liberating the corresponding aldehyde or ketone from the resulting quaternary compound by hydrolysis.  In this manner, hydrolysable aliphatic acidyl-, tri-, tetra- and higher polyamines may be prepared.  The N-acidyl amino ester starting materials include the phthalimido, succinamido, di-acetamido, benzamido and p-toluene sulphonamido aliphatic esters of those acids which completely dissociate in dilute aqueous solution such as hydrohalic acids and p-toluene sulphonic acid; examples are phthalimido-ethyl, -propyl, -amyl and -decyl chlorides and bromides, phthalimidoethyl p-toluene sulphonate and benzamidoethyl chloride, the phthalimido halide esters being prepared by reacting potassium phthalimide with the appropriate dihalide.  These acidyl-amino esters are reacted with (a) an aliphatic amine containing at least two non-tertiary amino groups, generally by warming the reactants in the presence of a solvent and, if desired, an acid fixing agent in addition to the specified excess of amine; (b) an aliphatic amine containing at least one primary amino group and at least one acidylated-amino group; or (c) an N-benzal-N1-acidyl aliphatic diamine or analogous condensation product of an aldehyde or ketone with an aliphatic diamine or polyamine containing at least one primary amino group and at least one acidyl-amino group, the resulting quaternary compound being decomposed by addition to water.  The N-acidyl polyamines may be hydrolysed by acid or by treatment with hydrazine hydrate followed by mild hydrolysis with hydrochloric acid.  In examples: (1) hexamethylene diamine (10 mols.) is reacted with 6-phthalimido-hexyl chloride or bromide (1 mol.) in butanol and the resulting 1 - phthalimido - 13 - amino - 7 - aza - tridecane isolated and hydrolysed by the hydrazine hydrate method to give 1 : 13-diamino-7-aza-tridecane, and in like manner, 4-phthalimido-butyl chloride and tetramethylene diamine may be reacted to yield 1 : 9-diamino-5-aza-nonane and phthalimido-hexyl bromide and diethylene triamine reacted to yield 1 : 12-diamino-7 : 10-diaza-dodecane; (2) monobenzoyl pentamethylene diamine (5 mols.) and 5-benzoylamino-amyl chloride (1 mol.) are refluxed in butanol and the product hydrolysed in hydrochloric acid to yield 1 : 11-diamino-6-aza-undecane.  In a further illustration, 1 : 13-diamino-7-aza-tridecane is prepared by reacting phthalimido-hexyl bromide with N-benzal-N1-acetyl hexamethylene diamine (obtained by reacting benzaldehyde with N-acetyl hexamethyl diamine), adding the resulting quaternary compound to water and hydrolysing the 1-phthalyl-13-acetyl triamine with hydrochloric acid.  Other starting materials for reaction with the acidylamino esters are (a) ethylene diamine, pentamethylene diamine, decamethylene diamine, N-monomethyl hexamethylene diamine (obtained by reacting N-benzal-N1-acetyl hexamethylene diamine with methyl sulphate and hydrolysing the resulting quaternary compound) and NN1-dimethyl hexamethylene diamine and (b) N-acetyl and N-benzoyl hexamethylene diamines; the N-acidyl diamines may be prepared by reacting excess of the diamine with ethyl acetate or benzoate, for example, ethyl acetate and hexamethylene diamine yield the mono-acetyl and some diacetyl diamine.  The Provisional Specification includes the preparation, by the above methods, of polyamines of the general formula R3.NH-R1-NR4-R2-NHR5, where R1 and R2 are alkylene, cycloalkylene or arylene radicals which may be substituted in the chain, for example, by hydroxy groups, hetero atoms or groups such as -O-, -S-, -N.Alkyl- or by aromatic including nitro-aromatic radicals and R3, R4 and R5 are hydrogen or substituents, a large excess of di- or poly-amine or acidyl derivative thereof being specified. Additional starting materials mentioned are 2-chlorethoxyethyl - phthalimide, 1 - o  - phthalimidomethyl - 4 - o  - brommethyl benzene, 4 : 41 - di-o -amino diphenyl and p-phenylene diamine.  A further preparation of aliphatic triamines is given comprising the hydrogenation of a nitrile in the absence of added ammonia and preferably in the presence of the corresponding diamine; thus, sebacic dinitrile on hydrogenation in the presence of decamethylene diamine and Raney nickel yields 1 : 21-diamino-11-aza-heneicosane.