Patent GB-790904-A (GB)
Title: Improvements relating to metallisable monoazo dyestuffs, complex heavy metal compounds thereof, and their use
IPC: C09B45/14
Filed: 1955-03-03
Abstract: The invention comprises dyestuffs of formula <FORM:0790904/IV (b)/1> where A is a radicle of the benzene series or of a heterocyclic containing a cyclic sulphone residue, B is a naphthalene radicle bound to the azo group in the 1-position containing -NH-D in the 2-position; D is an organic residue containing a group taking part in metal complex formation and X is a substituent ortho to the azo group which forms a metal complex or which can be converted into such a substituent under the metallizing conditions.  The invention also includes heavy metal complexes of the above dyestuffs.  The metal free dyestuffs may be made by diazotizing an appropriate amine and coupling in the 1-position of the necessary 2-amino-naphthalene derivative.  Coupling is effected in a neutral or acid medium at a temperature which in some cases may be as high as 40-80 DEG  C., and stabilizers for the diazo compounds, e.g. naphthalene mono- and di-sulphonic acids and tetrahydro naphthalene sulphonic acids may be present. Specified and indicated diazo components are 5-nitro-4-methyl- or -chloro-, 5- and 4-nitro-, 4,6-dinitro-, 6-nitro-4-chloro-, 6-chloro-4-nitro-, 4-nitro-6-acetylamino-, 6-nitro-4-acetylamino-, 6-nitro-4-methyl-, -tert. butyl- and -tert. amyl-, 5- and 6-nitro - 4 - alkylsulphonyl - and - alkenyl - sulphonyl-, 4-nitro-6-alkylsulphonyl- and -alkenylsulphonyl-, 6-nitro-4-acyl- and 6-acyl-4-nitro-2 - amino - 1 - phenols, 6 - nitro - 2 - amino - 1 - phenol-4-sulphonic acid amides and 4-nitro-2-amino-1-phenol-6-sulphonic acid amides, 4- and 5-alkylsulphonyl-, -alkenylsulphonyl- and -arylsulphonyl-2-amino-1-phenols, 4- and 5-acetyl-, -propionyl- and -butyryl- and 3,4,6-trichloro-2 - amino - 1 - phenols, 4 - nitro - 2 - amino - 1-phenol-5- and -5-sulphonic acids, 6-nitro-2-amino-1-phenol-4-sulphonic acid, 2-amino-1-phenol-4-phenylsulphone-31-sulphonic acid and 4-sulphonic acid N-ethylanilide-411-sulphonic acid, 4-chloro- and 3,4- dichloro-5-nitro-2-amino - 1 - phenol - 6 - sulphonic acids, 6 - nitro - 2 - amino - 1 - phenol - 4 - and 4 - nitro-2 - amino - 1 - phenol - 6 - carboxylic acids, 1-amino - 2 - hydroxy - and - methoxy - 5,4 - hydroxymethylene sulphone, 2 - amino - 3 - hydroxy-6-chloro- and -methylsulphonyl-phenoxthene-S-dioxide and their 3-methylated derivatives.  o-Amino-phenols and -naphthols with little coupling energy may be acylated to the hydroxy group, e.g. with p-toluene sulphochloride before diazotization and the acyl radicle split off after coupling or preferably during metallization.  Ortho groups present in the diazo component which are convertible into hydroxy groups, preferably during metallization are halogen and alkoxyamino groups, the following compounds being indicated for use in this modification of the invention 2-chloro- or -bromo- and 2,5-dichloro- or -dibromo-1-aminobenzenes, 5-alkylsulphonyl-, -alkenylsulphonyl- and -acyl-2-chloro-, 4- and 5-nitro-2-methoxy-, 2,5-dimethoxy- and 5-ethoxy- and -chloro-2-methoxy-1-aminobenzenes and o-alkoxyaminobenzene sulphonic acids.  The N-substituted -2-aminonaphthalenes may contain the following metallizable groups, carboxyl, hydroxy, amino, acylamino, sulphonic acid amide derived from ammonia or a primary amine, sulphonic acid carbacylamide, and carboxylic acid alkyl and aryl sulphonyl amide groups, those specified or indicated being b -carboxy- and -amino-ethyl, alkyl- and aryl-sulphonyl-2-aminoethyl and preferably a phenyl radicle containing one of the above listed metallizable groups in the 2-position and which can contain other substituents, e.g. alkyl, alkoxy, sulphonic and carboxylic acid, sulphonamide and N-substituted derivatives thereof, nitro, acylamino, alkylsulphonyl and halogens, 2-(21-carboxyphenylamino) - naphthalene compounds being particularly preferred, e.g. 2-(21-carboxyphenylamino) -5-, -6-, -7- and -8-methoxy-, -6-bromo- and -tert.-butyl naphthalenes, 2-(21-carboxyphenylamino)-naphthalene-5-, -6- and -7-sulphonic acid amides and -N-methylamides, 2-(21 - carboxy - 41 - acetylamino - and 51 -chlorophenyl) - amino -napthalenes and 2-(21 - carboxyphenylamino) - naphthalene - 5-, -6- and -7-sulphonic acids. Metallization is effected in conventional fashion in substance or on the fibre chromium, cobalt, nickel, iron and manganese being specified metals.  The metal complexes dye nitrogenous fibres and cellulose esters and may be used in the production of dyed films. Metal dyestuffs containing an atom of metal per mol. of dyestuff may easily be obtained in aqueous medium even when sulphonic acid groups are absent.  Examples and a Table are provided illustrating the preparation of the dyestuffs and their chromium and cobalt complexes diazo components used further to those listed above being 4-methylsulphonyl- and 5-nitro-4-methyl- and -ethyl-sulphonyl-2-amino-1-phenols, 2,5-dimethoxy - 1 - aminobenzene - 4 - methyl sulphone, 2 - amino - 1 - phenol - 4 - phenyl sulphone-31-sulphonic acid and its amide, 2-amino - 1 - phenol - 4 - sulphonic acid - (31-chloranilide), 2 - amino - 1 - phenol - 4 - sulphethylanilide - 31 - sulphamide, 2 - aminobenzoic acid methyl ester and 5-nitro-2-aminobenzoic acid, additional coupling components being 2 - (21 - carboxyphenyl) -, - (21 - amino-, acetylamino- and -tolyl- and -methyl-sulphamido - 41 - methyl - sulphonylphenyl) -, - (b -amino- and -carboxy-ethyl)- and -(b -hydroxyethyl)-naphthylamines, the metal complexes dyeing wool in green tints.  Reference has been directed by the Comptroller to Specifications 731,495, 753,261, [both in Group IV (b)], and 755,113.