Patent GB-606037-A (GB)
Title: Aryl amines and process of making the same
IPC: C23F11/14
Filed: 1946-01-08
Abstract: Compounds of the general formula <FORM:0606037/IV(b)/1> (where the group <FORM:0606037/IV(b)/2> is bound to the carbon atom of the benzene ring in the ortho- or para-position to the phenolic hydroxyl group, R1 represents hydrogen or an alkyl or an alkylene radical containing from one to ten carbon atoms, R2 represents an alkyl or an alkylene radical containing from one to ten carbon atoms, or R1 and R2 when taken together with the nitrogen atom form a saturated heterocyclic ring, and Rn represents the radical R taken n times where R represents hydrogen, halogen or hydroxy radicals or alkoxy, alkyl or alkylene radicals containing not more than six carbon atoms and n is one or two) are prepared by hydrolysing compounds of the general formula <FORM:0606037/IV(b)/3> where the groups <FORM:0606037/IV(b)/4> R, R1 and R2 and n have the significance indicated above and R3 represents an alkyl radical containing not more than six carbon atoms or an aryl radical containing not more than seven carbon atoms.  The hydrolysis may be effected in alkaline or acid medium, e.g. in the presence of a mineral medium.  In examples: (1) 2-diethylamino-methyl-4-aminophenol is prepared by treating 2 - diethylaminomethyl - 4 - acetylaminophenol with boiling hydrochloric acid and adding ammonia and may be converted to its dihydrochloride; (2), (3), (10) 2-di-n-butylaminomethyl-and 2-di-n-hexylaminomethyl-4-aminophenol are prepared by refluxing 2-di-n-butylamino-methyl-4-acetylaminophenol with hydrochloric acid and 2-di-n-hexylaminomethyl-4-acetyl-aminophenol with hydrobromic or hydrochloric acids; (4) 2-di-n-octylaminomethyl-4-amino-phenol is prepared by refluxing 2-di-n-octyl-aminomethyl - 4 - benzoylaminophenol with hydrochloric acid; (5), (6) 2-N-piperidylmethyl-, 2 - N - pyrrolidinylmethyl-, 2 - N - morpholinyl - methyl- and 2 - N - thiomorpholinylmethyl - 4 - aminophenol are prepared by refluxing the corresponding 2 - substituted - 4 - acetylamino - phenol with hydrochloric acid; (7), (9) 2-ethyl-butylaminomethyl- and 2-n-butylaminomethyl-4-aminophenol are prepared by refluxing 2-ethylbutylaminomethyl- and 2-n-butylamino-methyl-4-acetylaminophenol with sulphuric and hydrobromic acid respectively; (8), (11), (13) 2-ethylaminomethyl-, 2-iso-butylaminomethyl-and 2 - a  - methylallylaminomethyl - 4 - amino - phenol are prepared by refluxing the corresponding 2 - substituted - 4 - acetylaminophenol with hydrochloric acid; (12), (15), (16) 2-diethylaminomethyl- and 2-diethylaminomethyl-4-bromo-5-aminophenol and 2 : 4-dihydroxy-5-N-piperidylmethylaniline are prepared by heating 2-diethylaminomethyl- and 2-diethylamino-methyl-4-bromo-5-acetylaminophenol and 2 : 4-dihydroxy-5-N-piperidylmethylacetanilide with hydrochloric acid; (14), (18) 2-diethylamino-methyl-4-chloro- and 2-diethylaminomethyl-4-tert-butyl-6-aminophenol are prepared by heating the corresponding 2 : 4-substituted-6-acetyl-aminophenol with hydrochloric acid; (17), (19), 920) 2-diethylaminomethyl-4-amino-6-methyl, 2-diallylaminomethyl-4-amino-6-allyl- and 2-diethylaminomethyl - 4 - amino - 6 - methoxy - phenol are prepared by heating 2-diethylamino-methyl - 4 - propionylamino - 6 - methylphenol, 2 - diallylaminomethyl - 4 - acetylamino - 6 - allyl - phenol and 2-diethylaminomethyl-4-p-toluyl-amino-6-methoxyphenol with hydrochloric acid.  The 31 - diethylaminomethyl - 41 - hydroxyanilo derivatives of acridines, quinolines and pyridines are prepared by reacting 9-chloracridines, 4-chloroquinolines and 4-chloropyridines with 2 - diethylaminomethyl - 4 - aminophenol, e.g. 2-methoxy-6-chloro-9-(31-diethylaminomethyl-41 -hydroxyanilo)-acridine may be prepared and its dihydrochloride. 4-(21 : 41-dihydroxy-51-N-piperidylmethylanilino)-quinoiine is prepared by reacting 4-chloroquinoline and 2 : 4-dihydroxy-5-N-piperidylmethylaniline.  Acylaminophenols of the general formula <FORM:0606037/IV(b)/5> where R, R1, R2, R3 and n have the significance indicated above are prepared by condensing a primary or secondary amine of the formula <FORM:0606037/IV(b)/6> with formaldehyde and an acylaminophenol wherein at least the ortho- or paraposition to the phenolic hydroxyl group is unsubstituted.  In examples: (1) 2-diethylaminomethyl-4-acetylaminophenol is prepared by heating p-acetylaminophenol, formaldehyde and diethylamine; (3) 2 - di - n - hexylamino - methyl-4-acetylaminophenol is prepared by reacting di-n-hexylamine, paraformaldehyde and p-acetylaminophenol; (6) 2-N-morpholinyl-methyl-4-acetaminophenol is prepared by reacting morpholine, formaldehyde and p-acetaminophenol.  The Specification as open to inspection under Sect. 91 refers generally to the preparation of compounds of the general formula given above, where R1, R2 and n have the significance indicated above, R represents hydrogen, halogen, hydroxy, alkoxy, lower alkyl and lower alkylene radicals, from the corresponding acylaminophenols of the above general formula, where R3 represents a lower alkyl or aryl radical.  This subject-matter does not appear in the Specification as accepted.ALSO:An azo dye is prepared by diazotising 2-diethylaminomethyl-4-aminophenol and coupling with b -naphthol.