Patent GB-522658-A (GB)
Title: Manufacture of nitrogenous naphthalene derivatives
IPC: C09B1/32
Filed: 1938-12-19
Abstract: 522,658. Dyes and dyestuff intermediates. SOC. OF CHEMICAL INDUSTRY IN BASLE. Dec. 19, 1938, Nos. 36899 and 36900. Convention dates, Dec. 20, 1937, and Nov. 23, 1938. [Class 2 (iii)] Naphthalene derivatives are obtained by causing a halogenated naphthalene which contains at least two halogen atoms, at least one of which is in #-position, to react with (a) a compound which contains at least one hydrogen atom attached to nitrogen and contains the radical of a compound capable of being vatted, or (b) one mol. each of two such compounds, or (c) at least two mols. of an aminoacylaminoanthroquinone or 1 mol. each of two different aminoacylaminoanthraquinones. Halogenated naphthalenes specified are 2.6-dibromo-, 2.6-dichloro-, and 1.6-dibromo-2-methoxynaphthalene, and vattable compounds specified are 1-aminoanthraquinone, 1-aminoarylaminoanthraquinones, aminoacylaminoanthraquinones wherein the acyl residue may be the residue of an aliphatic, aromatic, or heterocyclic carboxylic acid, e.g., 1-amino-4 (or 5)-benzoylaminoanthraquinone, 1-amino-5-benzoylamino- 8-methoxy-anthraquinone, 1-amino-5.8-dibenzoylaminoanthraquinone, 1-aminoanthraquinoylaminoanthraquinone (obtained by condensing 1-nitro-5-aminoanthraquinone with anthraquinone-2-carboxylic acid chloride, followed by reduction), further aminopyanthrones, aminodibenzanthrones, amino-1.9-anthrapyrimidines, amino-1.9-anthrapyridines, amino-1.9- isothiazoleanthrones, amino-1.9-pyrazoleanthrones, amino-1.2-anthraquinone-acridones. The reaction may be carried out by heating the components in a diluent such as amyl alcohol, nitrobenzene, or naphthalene, preferably in presence of copper or a copper compound and an acid-binding agent. In examples, 2.6-dibromonaphthalene is reacted with two mols. of (1) 1-aminoanthraquinone, (2) 1-amino-4 (or 5)-benzoylamino-anthraquinone, (3) 1-amino-5-acetylaminoanthraquinone, (4) 1-amino-5-(o-, m-, or p-chlor) - benzoylaminoanthraquinone, (5) 1- amino - 5 - (p-methoxy) - benzoylaminoanthraquinone, (6) 4 (or 5) - aminoanthraquinone- 2. 1 (N)-benzacridone (green or violet tints on cotton), (7) 1-amino-4-anilinoanthraquinone, (8) 1-amino 4-methoxyanthraquinone, (9) aminodibenzanthrone (grey-green tints on cotton), (10) 4- amino-N-methyl-1.9-anthrapyridone, (11) 5- amino-isothiazole-anthrone, (12) 4-aminopyrazole-anthrone, (13) 5-amino-1.9-anthrapyrimidine (blue tints), (14) aminoanthanthrone (prepared by nitrating anthanthrone with 96 per cent. nitric acid and reducing) (brown violet), (15) 2.6-dibromonaphthalene is reacted with 1 mol. 1-amino-5-benzoylaminoanthraquinone, and the product may be reacted with a second mol. of the same compound, or with 1 mol. of 1-amino-4-benzoylaminoanthraquinone; alternatively, 2.6-dibromonaphthalene is reacted simultaneously with 1 mol. each of 1-amino-5- benzoylaminoanthraquinone and 1-amino-4- benzoylaminoanthroquinone or with 1 mol. of the latter, which may be followed by reaction with one mol. of the former, (16) the product from 1 mol. 2.6-dibromonaphthalene and 1- mol. 1-amino-5-benzoylaminoanthraquinone is reacted with 4-amino-1.9 - anthrapyrimidine, (17) 2.6-dibromonaphthalene is reacted with 1 mol. 5-aminoanthraquinone-2.1-(N)-benzacridone, and the product is reacted with 1- aminoanthraquinone (violet), (18) 1.6-dibromo- 2-methoxynaphthalene is reacted with 2 mols. of 1-amino-5-benzoylaminoanthraquinone, or 1- amino-4-benzoylaminoanthraquinone (bluegrey) or 1-aminoanthraquinone (bordeaux); two dyeing examples are also given. 2.6-Dibromonaphthalene is obtained from 2- amino-6-bromonaphthalene or from 2.6-diaminonaphthalene by diazotisation or tetrazotisation and reaction with cuprous bromide. Specifications 307,947 and 318,180, [both in Class 2 (iii)] are referred to.