Patent GB-615363-A (GB)
Title: Manufacture of polymeric nitrogen-containing compounds
IPC: C08G73/02
Filed: 1946-07-31
Abstract: Polyaminophenyl carbinols suitable for use as intermediates in the production of dyestuffs and anion-exchange resins are obtained by subjecting a primary aromatic amine, having at least two of the positions ortho or para to the amino groups free from substituents, and carbon monoxide to a temperature above 150 DEG  C. and a pressure exceeding 1000 atmospheres in the presence of a mineral acid catalyst.  Suitable amines are aniline, o- and p-toluidine, m- or p-phenylene diamine, benzidine, p-chloraniline, p-bromaniline, ethyl anthranilate and p,p1-diaminodiphenylmethane, and part or all of the amine may be replaced by its N-formyl derivative.  Catalysts include nitric, phosphoric, hydrochloric, hydrofluoric and sulphuric acids and salts of such acids with the primary amine which is used in the reaction.  Preferred temperatures are 200-300 DEG  C. and pressures 2000 to 4000 atmospheres.  The amine and catalyst are put in a preferably corrosion resisting vessel, carbon monoxide is injected and the vessel heated, preferably with agitation. Alternatively, a continuous flow process may be employed.  On cooling and releasing the pressure, a liquid or solid mixture of products is obtained, separable by fractional distillation, dissolution or extraction with acids of different strength.  Water or benzene may be present during the reaction.  The product usually contains 3 to 6 molecules of original amine per molecule. In examples, aniline and hydrochloric acid are reacted for 15 hours at 250 DEG  C. with carbon monoxide at 3000 atmospheres to yield a solid 90 per cent soluble in N/10 HCl. Hydrolysis of the ester groups of the product yields an amphoteric water-, acid- and alkali-soluble compound.ALSO:Poly amino-phenyl carbinols suitable for use as intermediates in the production of dyestuffs and anion exchange resins are obtained by subjecting a primary aromatic amine, having at least two of the positions ortho or para to the amino groups free from substituents, and carbon monoxide to a temperature above 150 DEG  C. and a pressure exceeding 1000 atmospheres in the presence of a mineral acid catalyst.  Suitable amines are aniline, o- and p-toluidine, m- or p-phenylene diamine, benzidine, p-chloraniline, p-bromaniline, ethyl anthranilate and p,p1-diaminodiphenylmethane, and part or all of the amine may be replaced by its N-formyl derivative.  Catalysts include nitric, phosphoric, hydrochloric, hydrofluoric and sulphuric acids and salts of such acids with the primary amine which is used in the reaction. Preferred temperatures are 200 DEG -300 DEG  C. and pressures 2000 to 4000 atmospheres.  The amine and catalyst are put in a preferably corrosion resisting vessel, carbon monoxide is injected and the vessel heated, preferably with agitation. Alternatively, a continuous flow process may be employed.  On cooling and releasing the pressure, a liquid or solid mixture of products is obtained, separable by fractional distillation dissolution, or extraction with acids of different strength. Water or benzene may be present during the reaction.  The product usually contains 3 to 6 molecules of original amine per molecule. In examples: (1) aniline and hydrochloric acid are reacted for 15 hours at 250 DEG  C. with carbon monoxide at 3000 atmospheres to yield a solid 90 per cent soluble in n/10 HCl; hydrolysis of the ester groups of the product yields an amphoteric water-, acid- and alkali-soluble compound.