Patent GB-519123-A (GB)
Title: The manufacture of carbazole compounds
IPC: C09B5/28
Filed: 1938-09-15
Abstract: 519,123. Dyes. I.G.FARBENINDUSTRIE AKT.-GES. Sept. 15, 1938, Nos. 26973 and 26974. Convention dates, Sept. 15, 1937, and Aug. 22, 1938. [Class 2 (iii)] Carbazole compounds are manufactured by causing addition compounds of aluminium halides with sulphur dioxide or an alkali bisulphite, which compounds may be prepared in situ, to react upon secondary aromatic amines in which at least one of the aromatic radicles is an acylaminoanthraquinone radicle or an anthraquinone radicle having condensed therewith an acridone or thioxanthone ring and at least one o-position with respect to the secondary amino group is unsubstituted in both radicles. The second aromatic radicle may be an anthraquinone radicle or any other aromatic group, e.g., a benzene, naphthalene, benzanthrone, perylene, pyrene or pyranthrone radicle. The nuclei may contain various substituents, and there may be present several secondary aminogroups. The reaction may be carried out with the addition of a neutral salt, e.g. sodium or potassium chloride. In examples : (1)sulphur dioxide is passed into a mixture of aluminium chloride and sodium chloride, and there is added a condensation product from one molecular proportion of 1:5-diaminoanthraquinone and two of 1-benzoylamino-4-chloroanthraquinone; after which the mixture is heated with further passage of sulphur dioxide ; the product may be purified by treatment with' an alkaline hypochlorite solution and then with bichromate in dilute sulphuric acid solution ; instead of using gaseous sulphur dioxide, the aluminium and sodium chloride may be stirred in an autoclave with liquid sulphur dioxide ; (2) the process of (1) is carried out without the addition of sodium chloride ; (3) aluminium chloride is added gradually to dry sodium bisulphite, and the starting material of (1) is then added in portions; (4) sulphur dioxide is passed into a mixture of aluminium chloride and potassium chloride, and there is added a, condensation product from one molecular proportion of 1:4-dibromobenzene and two of 1-benzoylamino-5-or 4-aminoanthraquinone; (5) the compound of the formula is'treated as in (1) ; (6) sulphur dioxide is passed into a mixture of aluminium chloride, sodium chloride, potassium chloride, and 4-benzoylamino-1:1<1>-dianthrimide ; (7) 5:51-dibenzoylamino-1-1<1>-dianthrimide is treated as in (1) ; the condensation product of equimolecular proportions of 5-amino-1:9-anthrapyrimidine and 1-benzoylamino-5-chloroanthraquinone may be similarly treated ; (8) a mixture of aluminium chloride and sodium chloride is treated with liquid or gaseous sulphur dioxide, and the product is heated with 4-benzoylamino-6'- chloro-1:1<1>-dianthraquinonylamine; (9) the condensation product from one molecular proportion of Bz 1:6-dibromobenzanthrone and two of 1-benzoylamino-5-aminoanthraquinone is 'similarly treated ; (10) the condensation product of symm, tribromobenzene with three molecular proportions of* 1-amino-5-benzoylaminoanthraquinone is similarly treated ; (11) the condensation products from one molecular proportion of dibromodibenzpyrenequinone and two of 1-amino-5- or 4-benzoylaminoanthraquinone are similarly treated ; (12) the trianthrimide from one molecular proportion of - 1:5-dichloranthraquinone and two of 1-amino-5- benzoylaminoanthraquinone is similarly treated ; (13) the tetranthrimide from one molecular proportion of 4:4<1>-dibromo-1:1<1>-dianthrimide and two of 1-amino-5-benzoylaminoanthraquinone is similarly treated ; (14) 4-benzoylamino - 1 - (Bz 1 - benzanthronyl)-aminoanthraquinone, or the condensation product of one molecular proportion of Bz 1:6-dibromobenzanthrone with two of 1-amino-4-benzoylaminoanthraquinone is similarly treated ; (15) the condensing agent from aluminium chloride, sodium chloride and sulphur dioxide is stirred with 1 - benzoylamino - 5 - (#-naphthyl)-aminoanthraquinone, whereby carbazolization is accompanied by substitution by a sulphinic acid radicle, which may be oxidized, e.g. with hydrogen peroxide, to a sulphonic acid group ; 1-benzoylamino - 4 - ((#-naphthyl)-aminoanthra - quinone may be similarly treated ; (16) the condensation product from one molecular proportion of symm. tribromobenzene and three of 1-benzoylamino-4-aminoanthraquinone is treated as in (8) ; (17) the condensation product from one molecular proportion of 1:5-dichloroanthraquinone and two of 5<1>-chloro-4-amino-2:1(N)- anthraquinone-11:2<1>(N)-benzacridone is similarly treated ; (18) the condensation product from one molecular proportion of 1:4:5:8-tetraminoanthraquinone and four of 1-chloro-5- benzoylaminoanthraquinone is similarly treated; (19) 1-benzoylamino-4-(21:51-dichlorophenyl)- aminoanthraquinone is similarly treated. Specifications 297,133, 327,756, [both in Class 2 (iii)], 461,432, and 497,971 are referred to. The Specification as open to inspection under Sect. 91 comprises also the treatment of secondary aromatic amines in which at least one of the aromatic radicles is an anthraquinone radicle having condensed therewith any further nuclei. Reference is also made to the replacement of the sodium chloride employed in the preparation of the condensing agent in example (16) above by other salts, e.g. dry calcium chloride or magnesium chloride. This subject-matter does not appear in the Specification as accepted.