Patent GB-820502-A (GB)
Title: Improvements relating to metallisable monoazo dyestuffs, complex heavy metal compounds thereof, and their use
IPC: C09B45/14
Filed: 1956-07-03
Abstract: The invention comprises metallizable monoazo dyes of formula <FORM:0820502/IV(c)/1> wherein A is a benzene radical, B is the radical of a coupling component, X is an hydroxyl or carboxyl group or a group convertible thereto under metallizing conditions in o-position to -N=N-, Y is an hydroxyl or amino group in o-position to -N=N-, R is an alkyl or cycloalkyl radical, n is 1 or 2, and A and B are free from sulphonic acid groups or carboxy groups not taking part in the complex formation, and metal complexes thereof.  The dyes are prepared by coupling a diazotized amine A-NH2 with a coupling component B-H, the components being chosen to give a dye of the above formula.  Specified diazo components are the 3-amino-4-hydroxybenzene-1-alkyl sulphoxides, 5-chloro- or -methyl-4-hydroxy-3-aminobenzene-1-alkyl sulphoxides, 5-hydroxy-4-aminobenzene-1-alkyl sulphoxides and 5-hydroxy-4-amino-2-chloro- or -methyl-1-alkyl sulphoxides (see Group IV (b)), 2-aminobenzoic acids and 2-aminophenols.  Specified coupling components are acetoacetic acid phenylamides, pyrazolones and naphthols having sulphoxide substituents (see Group IV (b)) and acylacetic acid phenylamides, 1-phenyl-5-pyrazolones, p-alkylphenols, and ortho-coupling naphthols and naphthylamines. Both the diazo and coupling components may be further substituted by halogen atoms and alkyl, alkoxy, acylamino, sulphonamide and alkyl- or aryl-sulphonyl groups.  The dyes may be converted by known methods into the copper, nickel, manganese, iron and preferably cobalt and chromium compounds. Preferred complexes are those containing 1 atom of cobalt or chromium to 2 molecules of organic complex former, of which at least one is a monoazo dye of the above formula, and the other is preferably the same or another dye of the above formula, or a metallizable monoazo dye containing no sulphoxide groups, or an uncoloured organic complex former such as an aromatic o-hydroxycarboxylic acid.  The metallization may be carried out in neutral or alkaline medium using chromic acetate, alkali metal chromosalicylates, cobalt sulphate, nitrate or acetate, or hexamine cobaltichloride, or using alkali metal salts of chromic acids in the presence of a reducing sugar. The alkali metal salts of the metallized dyes are obtained by carrying out the metallization in the presence of alkali metal bases or alkaline salts.  The metal complexes dye natural and synthetic polypeptide fibres, in particular wool, in yellow, red, blue, brown and grey shades.  In examples, dyes are prepared from the following components and the cobalt and chromium complexes thereof are also prepared: diazo components:-2 - amino - 1 - hydroxybenzene - 4 - or -5-methyl sulphoxide, 2-amino-1-hydroxy-benzene-4-methyl- or -n-propyl- or -butyl- or -cyclohexyl sulphoxide, 6-chloro- or -methyl-2-amino - 1 - hydroxybenzene - 4 - butyl sulphoxide, 6 - acetylamino - 2 - amino - 1 - hydroxybenzene - 4 - methyl sulphoxide, 4- or 5-nitro-2-aminophenol, 4 - chloro - 2 - aminophenol, 6 - nitro - 4 - methyl - 2 - aminophenol, 2 - aminobenzoic acid and 4-chloro- or 5-nitro-2-aminobenzoic acid; coupling components:-1-(41-methyl sulphoxidophenyl) - 3 - methyl - 5 - pyrazolone, 2 - hydroxynaphthalene - 6 - methyl sulphoxide, acetoacetic acid-4-methyl sulphoxidophenylamide, 1 - (31 - chlorophenyl) - or -phenyl - 3 - methyl - 5 - pyrazolone, 1 - phenyl - 3 - carboxamido - 5 - pyrazolone, 2 - naphthol, beta - naphthylamine, 1 - acetylamino- or -carbomethoxyamino - 7 - naphthol, 3 : 4 - di-methylphenol, 5 : 8 - dichloro - 1 - naphthol and 2-amino-7-methoxy-naphthalene.  Reference has been directed by the Comptroller to Specifications 637,404, 692,073 and 758,016.ALSO:Compounds containing alkyl or cycloalkyl sulphoxide groups are prepared and are used as components in the preparation of azo dyes (see Group IV (c)).  Thus a 4-chloro-3-nitrobenzene-1-alkyl sulphoxide is treated in caustic alkaline medium to replace the chlorine atom by a hydroxyl group, reduced by the Bechamp reaction to a 4-hydroxy-3-aminobenzene-1-alkyl sulphide, reacted with phosgene to give a 5-alkyl mercapto-benzoxazolone, oxidized with hydrogen peroxide in glacial acetic acid to form the alkyl sulphoxide and saponified to give 3 - amino - 4 - hydroxybenzene - 1 - alkyl sulphoxides.  Similarly, the 5-chloro- or -methyl-4-hydroxy - 3 - aminobenzene - 1 - alkyl sulphoxides may be obtained from 4 : 5-dichloro- or 4 - chloro - 5 - methyl - 3 - nitrobenzene - 1 - alkyl sulphoxides.  Specified compounds obtainable by this method are 1-hydroxy-2-aminobenzene-4-methyl, ethyl, n-propyl, butyl and cyclohexyl sulphoxides and 6-chloro- or -methyl-2 - amino - 1 - hydroxybenzene - 4 - butyl sulphoxide. 5-Chloro-2-nitrophenol is reacted with an alkali metal salt of an alkyl mercaptan to give a 5-alkylmercapto-2-nitrophenol which is then treated as above by reduction, phosgenation, oxidation and saponification to give a 5 - hydroxy - 4 - aminobenzene - 1 - alkyl sulphoxide.  Similarly, the 2-chloro- or -methyl-5-hydroxy-4-aminobenzene-1-alkyl sulphoxides may be obtained from 4 : 5-dichloro- or 4-methyl-5-chloro-2-nitrophenols. A specified compound obtainable by this method is 2-amino-1 - hydroxybenzene - 5 - methyl sulphoxide.  Acetoacetic acid alkyl sulphoxidophenylamides, e.g. acetoacetic acid - 4 - methylsulphoxido - phenylamide, are obtained by reacting aminobenzene alkyl sulphoxides with diketenes. 1-(Alkylsulphoxido - phenyl) - 5 - pyrazolones, e.g. 1-(41-methylsulphoxido-phenyl)-3-methyl-5-pyrazolone are obtained by reacting the phenylhydrazines derived from the diazonium compounds of aminobenzene alkyl sulphoxides with diketenes or acylacetic acid alkyl esters.  Alkylsulphoxido - naphthols, e.g. 2 - hydroxynaphthalene-6-methyl sulphoxide are obtained from alkylmercapta-naphthols by acylation, oxidation with hydrogen peroxide and saponification.  In an example, the conversion of 2-nitro-1-chlorobenzene-4-methylsulphoxide, by way of 2 - nitro - 1 - hydroxybenzene - 4 - methyl sulphoxide, 2 - amino - 1 - hydroxybenzene - 4 - methyl sulphide, 5-methyl sulphide-benzoxazolone, and 5-methyl sulphoxide-benzoxazolone to 2 - amino - 1 - hydroxybenzene - 4 - methyl sulphoxide is specified. Reference has been directed by the Comptroller to Specifications 637,404, 692,073 and 758,016, [all in Group IV (c)].