Patent GB-711039-A (GB)
Title: Nitrogen-containing condensation products of aldehydes
IPC: C07D213/10
Filed: 1950-10-27
Abstract: Resinous nitrogen-containing condensation products are obtained by condensing one or more saturated aliphatic aldehydes and/or one or more aromatic aldehydes containing the aldehyde group in a side chain with more than an equimolecular amount of ammonia, the reaction being effected in the presence of a solvent (for the aldehyde(s)) capable of forming an azeotropic mixture with water formed in the reaction, and removing the water by azeotropic distillation (see Group III). Solvents used are aliphatic, aromatic and naphthenic hydrocarbons or mixtures thereof boiling between 30 DEG  and 160 DEG C., e.g. C6 and C7 hydrocarbon fractions.  In operation, gaseous ammonia, e.g. in amount of 2 to 5 mols. per mol. of aldehyde, is continuously passed at elevated temperatures through the solvent diluted aldehyde(s), and the water formed is removed by azeotropic distillation, unreacted aldehyde(s) and ammonia being recovered from the distillate(s) and re-used.  In examples, nitrogenous resins, suitable for moulding compositions, varnishes and impregnants, are obtained by reaction of ammonia with (1) propionaldehyde, (2, 3) butyraldehyde, and (4) a C11 aldehyde obtained by the OXO synthesis of an olefin-con taining C10 hydrocarbon fraction. Specifications 609,059 and 654,443, [both in Group IV (b)], are referred to.ALSO:Substituted pyridines are obtained by condensing one or more saturated aliphatic aldehydes and/or one or more aromatic aldehydes, containing the aldehyde group in a side chain, with more than an equimolecular amount of ammonia, the reaction being effected in the presence of a solvent (for the aldehyde(s)) capable of forming an azeotropic mixture with water formed in the reaction, and removing the water by azeotropic distillation (see Group III).  Solvents used are aliphatic, aromatic and naphthenic hydrocarbons or mixtures thereof boiling between 30 DEG  and 160 DEG  C., e.g. C6 and C7 hydrocarbon fractions.  In operation, gaseous ammonia, e.g. in amount of 2 to 5 mols. per mol. of aldehyde, is continuously passed at elevated temperatures through the solvent diluted aldehyde(s), and the water formed is removed by azeotropic distillation, unreacted ammonia and aldehyde(s) being recovered from the distillate(s) and re-used.  In examples, substituted pyridines, having boiling-points 260 DEG , 280 DEG  and 320 DEG  C., are obtained by reacting ammonia with (1) propionaldehyde, (2, 3) butyraldehyde, and (4) a C11 aldehyde obtained by the Oxo synthesis of an olefin-containing C10 hydrocarbon fraction. Specifications 609,059 and 654,443 are referred to.ALSO:In making nitrogen-containing condensation products by condensing one or more saturated aliphatic aldehydes and/or one or more aromatic aldehydes containing the aldehyde group in a side chain with more than an equimolecular amount of ammonia (see Groups IV (a), IV (b)), the aldehyde or aldehyde mixture is diluted with a solvent which forms an azeotropic binary or ternary mixture with the water formed during the reaction or with the water and aldehyde.  Aldehydes containing up to 8 carbon atoms in the molecule generally form ternary mixtures with the solvents and water, while higher aldehydes do not usually take part in the azeotropic mixtures.  In operation, gaseous ammonia is continuously passed at elevated temperatures through the solvent diluted aldehyde(s), the water formed being removed by azeotropic distillation.  The distillate separates into two layers, the upper one comprising aldehydes and hydrocarbons (solvent) and the lower one comprising water and aldehyde(s).  The lower layer is freed of aldehyde(s) by treatment with hydrocarbons, e.g. by causing the aqueous layer to flow through a layer of the hydrocarbon(s) used for the dilution and separating it by way of an overflow.  The water remaining contains unreacted ammonia which is recovered by distillation and reused.  Solvents used are aliphatic, aromatic and naphthenic hydrocarbons or mixtures thereof boiling between 30 DEG  and 160 DEG C., e.g. C6 and C7 hydrocarbon fractions.