Patent GB-415945-A (GB)
Title: Manufacture of condensation products from phloroglucinol and aromatic amines
IPC: C07C215/82
Filed: 1934-01-22
Abstract: 415,945. Arylaminophenols. I. G. FARBENINDUSTRIE AKT.-GES., Frankforton-Main, Germany. Jan. 22, 1934, No. 2181. Convention date, Jan. 20, 1933. [Class 2 (iii).] Condensation products of phloroglucinol with aromatic amines, which products still contain at least one hydroxyl group, are manufactured by heating phloroglucinol with an aromatic amine (i.e. any amine containing an aminogroup in an aryl nucleus) in the presence of water, at least a part of which remains in the reaction mixture at the end of the reaction. The reaction, particularly when the amine employed contains a strongly negative substituent, e.g. a nitro-group, may also be effected in the presence of a mineral acid, in which case the proportion of amine and acid and the duration of heating are adjusted so as to avoid the formation of a triarylaminobenzene. The proportion of water used may vary widely, the water of crystallization of the phloroglucinol being sufficient in some cases. The products, in the form of their alkali metal salts, have an affinity for vegetable fibres and may be employed as intermediates for the manufacture of dyestuffs or other organic compounds. In examples : (1) phloroglucinol is refluxed with aniline and water to produce diphenyldiaminohydroxybenzene ; the aniline may be replaced by p- or m-toluidine, p-anisidine or p-chloraniline ; (2) the reaction of (1) is carried out in the absence of water other than the water of crystallization of the phloroglucinol ; (3) phloroglucinol is reacted as in (2) with ptoluidine to produce di-(p-tolylamino)-hydroxybenzene ; (4) the reaction of (2) is carried out in a pressure vessel at 140‹ C. ; (5) the reaction of (3) is similarly carried out ; (6) phloroglucinol is refluxed with aniline oil and dilute hydrochloric acid, yielding the same product as in (1) together with a little 1 : 3 : 5-triphenyltriaminobenzene ; the aniline may be replaced by p-toluidine or p-chloraniline; (7) phloroglucinol is reacted with #-naphthylamine by the method of (6) to produce 1 : 3 : 5-di-(2<1>-naphthylamino)- hydroxybenzene ; (8) phloroglucinol is similarly reacted with m-nitraniline, producing 1 : 3 : 5- di-(3<1>-nitrophenylamino)-hydroxybenzene; (9) p-nitraniline similarly yields 1 : 3 : 5-di-(4<1>- nitrophenylamino)-hydroxybenzene, with or without 1 : 3 : 5-(4'-nitrophenylamino)-dihydroxybenzene, according to the proportion of p-nitraniline employed; in (8) and (9) the amines may be replaced by 4- or 5-nitro-2- aminomethoxybenzene or the corresponding ethoxy- or other alkoxy-compounds, 4- or 5- nitro-2-aminomethylbenzene or the corresponding ethyl- or other alkyl-compounds, or 4- or 6-chloro-3-nitraniline or the corresponding bromine or other halogen compounds; (10) phloroglucinol is refluxed with p-chloraniline and dilute sulphuric acid to produce 1 : 3 : 5-di- (4<1> - chlorophenylamino) - hydroxybenzene and some 1 : 3: 5 - tri - (4<1> - chlorophenylamino) - benzene ; the p-chloraniline may be replaced by 3 : 4- or 2 : 5-dichloraniline or 2 : 4 : 5- trichloraniline, the last two compounds yielding mainly the corresponding arylaminodihydroxybenzenes ; (11) phloroglucinol is refluxed with p-aminoquinoline hydrochloride and water.