Patent GB-456534-A (GB)
Title: Process for the manufacture of nitrogenous aromatic aldehydes
IPC: C07C47/52
Filed: 1935-05-11
Abstract: N-Halogenalkyl aromatic aminoaldehydes are prepared by treating N-halogenalkyl arylamines with formyl compounds of secondary amines in the presence of a halide or oxyhalide of sulphur or phosphorus. The N-halogenalkyl arylamines may be formed in situ from the corresponding N-hydroxyalkyl arylamines.  The products may be treated to replace the halogen by another substituent, e.g. a hydroxy, alkoxy, sulphonic, amino or substituted amino group. Specified amines for use as starting materials are N-hydroxyethyl, N-hydroxypropyl and N-hydroxybutyl arylamines or their derivatives further substituted on the nitrogen atom, e.g. N-hydroxyethyl-N-methylaniline, N-hydroxyethyl - N - propylaniline, N - hydroxyethyl - N - butylaniline, N - hydroxyethyl - N - benzylaniline, N - di(hydroxyethyl)aniline, N - b -hydroxypropyl - N - methylaniline, N - hydroxyethyl-N-ethyl-m-toluidine, N-hydroxyethyl-N-butyl-m-chloraniline, N-hydroxyethyldiphenylamine, N - hydroxypropyl - N - butylaniline, and N-hydroxybutyl-N-ethylaniline.  Specified formyl compounds are N-methylformanilide and N-formyldiphenylamine.  Specified halides are phosphorus chlorides, phosphorus oxychloride and oxybromide, thionyl chloride, and sulphuryl chloride.  In the examples: (1) N - chlorethyl - N - methyl - p - aminobenzaldehyde is obtained from N-hydroxyethyl-N-methylaniline, N-methylformanilide, and phosphorus oxychloride; N - chlorethyl - N - butyl - p - aminobenzaldehyde is similarly obtainable from N-hydroxyethyl-N-butylaniline; (2) N-di(chlorethyl)-p-aminobenzaldehyde is prepared from N - di(hydroxyethyl)aniline, N - methylformanilide, and phosphorus oxychloride; (3) N - chlorethyl - N - phenyl - p - aminobenzaldehyde is prepared from N-hydroxyethyldiphenylamine, N-methylformanilide, and phosphorus oxychloride; (4) N-chlorethyl-N-butyl-p-amino-o-chlorobenzaldehyde is prepared from N-hydroxyethyl - N - butyl - m - chloraniline, N-methylformanilide, and phosphorus oxychloride; (5) N-chlorethyl-N-methyl-p-aminobenzaldehyde is treated with aqueous or aqueous alcoholic soda solution to yield N-hydroxyethylN - methyl - p - aminobenzaldehyde; (6) N - di-(chlorethyl) - p - aminobenzaldehyde, treated as in example 5, yields p-morpholinobenzaldehyde; (7) N - chlorethyl - N - methyl - p - aminobenzaldehyde is heated with sodium sulphite solution to yield N - sulphoethyl - N - methyl - p - aminobenzaldehyde; N - sulphoethyl - N - benzyl - p - aminobenzaldehyde is similarly obtainable; (8) N-di-(chlorethyl)-p-aminobenzaldehyde, treated as in example 7, yields N-di(sulphoethyl)-p-aminobenzaldehyde; (9) N-di(chlorethyl)-p-aminobenzaldehyde is prepared from N-di(chlorethyl)-aniline, N-methylformanilide, and phosphorus oxychloride; (10) N-b -chloropropyl-N-methyl-p-aminobenzaldehyde is prepared from N-b -hydroxypropyl - N - methylaniline, N - methylformanilide, and phosphorus oxychloride; (11) N - chlorethyl - N - ethyl - p - amino - o - methylbenzaldehyde is prepared from N-hydroxyethyl-N-ethyl-m-toluidine, N-methylformanilide, and phosphorus oxychloride; (12) N-bromethyl-N-methyl-p-aminobenzaldehyde is prepared from N - hydroxyethyl - N - methylaniline, N - methylformanilide, phosphorus oxybromide, and phosphorus oxychloride; the product is then converted into N-methoxyethyl-N-methyl-p-aminobenzaldehyde by reaction with a solution of sodium in methyl alcohol; (13) N-bromethyl-N-methyl-p-aminobenzaldehyde is heated with diethylamine to yield N-diethylaminoethyl-N-methyl-p-aminobenzaldehyde; N-aminoethyl-N - methyl - p - aminobenzaldehyde is similarly obtainable. Specification 311,208, [Class 2 (iii)], is referred to. A sample has been furnished under Sect. 2 (5), of N-chlorethyl-N-ethyl-1-amino-4-naphthaldehyde, prepared from N-hydroxyethyl-N-ethyl-1-naphthylamine, N-methylformanilide, and phosphorus oxychloride.