Patent GB-412914-A (GB)
Title: Process for the catalytic synthesis of furfuryl-amines
IPC: C07D307/14
Filed: 1932-10-01
Abstract: Furfurylamines are manufactured by hydrogenating under superatmospheric pressure in the liquid phase and in the presence of a hydrogenating catalyst, a reaction product of an amine (which term includes ammonia and all other compounds containing the group = NH, aliphatic or cyclic) and furfural.  The reaction is preferably carried out at 50--150 atmospheres pressure and 50--200 DEG  C. Suitable catalysts may be prepared by the methods described in Specification 409,732.  In an example, hydrofuramide dissolved in ethanol is hydrogenated in the presence of a nickel catalyst at about 100 DEG  C. and 70--110 atmospheres, producing a mixture of tetrahydro-a -furfurylamine and di-a -furfurylamine. Specification 394,576 is referred to.  The Specification as open to inspection under Sect. 91 comprises in general the manufacture of amines by hydrogenating reaction products or mixtures of amines containing the group = NH with aliphatic or cyclic aldehydes or ketones in general. Additional examples describe the hydrogenation of mixtures of cyclohexylamine and cyclohexanone; cyclohexylamine and n-butyraldehyde; piperidine and n-butyraldehyde; b -phenylethylamine and n-butyraldehyde; and of the following isolated reaction products: hydrobenzamide, in ethanol solution; benzalaniline, in ethanol solution; a -b -cinnamaldoxime, in ether solution; benzaldoxime; cyclohexylbutyraldimine; triacetoneamine.  This subject-matter does not appear in the Specification as accepted.ALSO:Furfurylamines are manufactured by hydrogenating under superatmospheric pressure in the liquid phase and in the presence of a hydrogenating catalyst, a reaction product or a mixture of an amine (which term includes ammonia and all other compounds containing the group = NH, aliphatic or cyclic) and furfural.  The reaction is preferably carried out at 50--150 atmospheres pressure and 50--200 DEG  C.  The furfural and the amine may be mixed just before hydrogenation or may be first isolated as a distinct reaction product.  Suitable catalysts may be prepared by the methods described in Specification 409,732.  Suitable compounds containing the group = NH are: piperidine, ethylamine, aniline, allylamine, ammonia, furfurylamine, p-phenetidine, benzylamine, toluidine, a - or b -naphthylamine, tetrahydrofurfurylamine, cyclohexylamine, dicyclohexylamine, tetrahydronaphthylamines, methylaniline, xylidine, benzidine, tolidine, diethylamine, aminopyridine, dimethylamine, butylamine and vinylamine.  In an example, hydrofuramide dissolved in ethanol is hydrogenated in the presence of a nickel catalyst at about 100 DEG C. and 70--110 atmospheres, producing a mixture of tetrahydro-a -furfurylamine and di-a -furfurylamine.  Specification 394,576, [Group III], is referred to.  The Specification as open to inspection under Sect. 91 comprises in general the manufacture of amines by hydrogenating reaction products or mixtures of amines containing the group = NH with aliphatic or cyclic aldehydes or ketones in general. Additional examples describe the hydrogenation of: (1) a mixture of cyclohexylamine and cyclohexanone, producing dicyclohexylamine; (2) a mixture of cyclohexylamine and n-butyraldehyde, producing N-n-butylcyclohexylamine; (3) a mixture of piperidine and n-butyraldehyde, producing N-n-butylpiperidine; (4) a mixture of b -phenylethylamine and n-butyraldehyde, producing N-mono- and di-n-butyl-b -phenylethylamine; (5) hydrobenzamide, in ethanol solution, producing benzylamine and dibenzylamine; (6) benzalaniline, in ethanol solution, producing benzylaniline; a -b -cinnamaldoxime, in ether solution, producing g -phenylpropylamine.  Other reaction products which may be hydrogenated are: benzaldoxime, cyclohexylbutyraldimine and triacetoneamine.  Other aldehydes and ketones specified are: formaldehyde, crotonaldehyde, acetaldehyde, propionaldehyde, isovaleraldehyde, isocapronic aldehyde, citral, acrolein, ethyl methyl ketone, diethyl ketone, dipropyl ketone, ethyl propyl ketone, phenyl ethyl ketone, benzalacetone, acetophenone, benzophenone, phorone and mesityl oxide.  This subject-matter does not appear in the Specification as accepted.