Patent GB-943264-A (GB)
Title: Improvements relating to heterocyclic dyestuffs, their production and use
IPC: C09B62/04
Filed: 1960-07-08
Abstract: The invention comprises dyes of formula <FORM:0943264/C3/1> where D is the residue of an amino dye bound to a C atom of tetrameric cyanogen by amino nitrogen, A is the residue of a nitrogenous base bound to a C atom of tetrameric cyanogen by amino nitrogen, W is a water-solubilizing anionic salt-forming group attached to D and A, m-1 is the number of amino nitrogens of A bound to C atoms of tetrameric cyanogen, n is 1 or 2, m and p are 1, 2 or 3, q is an integer of from 1 to 7, the sum of n, (m-1) and (p-1) being 4. The dyes are made by treating tetrameric cyanogen chloride, or a derivative thereof which contains at least one mobile chlorine atom, with an acylatable amino dye, or dye intermediate which, in addition to the acylatable amino group, contains a substituent which enables dye formation, and if the reaction products contain mobile chlorine atoms, optionally reacting with other organic compounds having at least one acylatable amino group and, if necessary, forming the dye, from the intermediates, by conventional methods. Advantageously the dyes contain acid water-solubilizing groups such as carboxylic and sulphonic acid groups, which groups may either be present in the dye or amine portion of the molecule. Nitro, azo, anthraquinone and phthalocyanine dyes are mentioned.  They may contain complexed heavy metals, e.g. Cr, Co, Cu, Ni and Fe. 1,1- and 1,2-complexes are described. Different dye molecules may be in the 1,2-complexes. Indicated metal dyes are of the o-nitroso-hydroxyaryl, phthalocyanine, o,o1-dioxyazo, o-carboxy-o1-hydroxy-azo and o-hydroxy-o1-aminoazo series. Metallization is effected after reaction with the cyanogen halide. Indicated azo-dyes are of the p-aminoaryl mono- and poly-azo series, mentioned being benzene-azo-benzene and -naphthalene, naphthalene-azo-naphthalene, benzene- or naphthalene-azo-5-hydroxy- or -amino-pyrozole, benzene- or naphthalene-azo-acylacetarylamide or benzene- or naphthalene-azo-2,4-dihydroxy-quinoline series with an acylatable amino group in the diazo or coupling component residue. o-Aminoazo dyes, e.g. those from o-sulphodiazo-benzene and -diphenyl compounds and naphthylamines, coupling o to an amino group, may also be used provided they contain an acylatable group. Indicated substituents which may be present in the products are halogen, lower alkyl and alkoxy, phenoxy, nitro, acylamino, carboxyl, sulphonic acid, carbamyl, sulphonyl, alkylsulphonyl, arylsulphonyl, 1,2-sulphomethyleneoxy and 1,2-dioxino groups. Anthraquinone dyes used advantageously contain sulphonic acid groups and have the acylatable group in an external position as a substitutent, e.g. in an arylamino or aryloxy group, especially a phenylamino group, and there may be more than one of such external groupings present. Preferably the amino phenylamino groups are in a - or 1,4 or 1,5 position and other indicated substituents for the phenyl group are low alkyl or alkoxy, phenoxy or phenyl-thioether groups all of which are advantageously in the 2,6-position with regard to the anthraquinone link. Phthalocyanines used may be metal-free or contain such metals as Cu, Co, Ni and Sn.  The benzo radicles may contain substituents, e.g. halogen, phenyl, sulphonic acid, carboxyl, sulphamyl and carbamyl groups. The acylatable amino groups may be bound direct to a benzo radicle or via a divalent bridging member, e.g. phenylene, cophenylene, So2-phenylene, NH-phenylene, CON (R)-phenylene, So2N(R)-phenylene, (R = H or alkyl), O-phenylene, S-phenylene, CH2-phenylene, So2O-phenylene, alkylene and So2N(R)-alkylene. Advantageously several sulphonic acid groups are present in the phthalocyanine products. The cyanogen chloride may contain 1-3 amino radicles.  The dyes, when containing mobile chlorine in the product react with materials containing hydroxy or amino groups, e.g. cellulosic fibres, fixing being effected by heating, preferably in the presence of an acid-binding agent. The products which are free from mobile chlorine atoms dye wool from a neutral to weak acid bath. Leather may also be coloured. The material may be treated with cyanogen chloride, or with a diazo or coupling component containing the cyanogen chloride residue, and the dye formed on the fibre.  Insoluble products may be used for colouring lacquers, acyl celluloses, synthetic resins, cellulose and paper. Numerous examples are provided of the preparation of the dyes and their use in colouring processes, a variety of colours being obtained.  Both mono- and dis-azo dyes are given, the latter type being derived from dis-azo dyes or obtained by combining two molecules of a mono-azo dye in the final product.  Tetrazo dyes are likewise made by combining two molecules of a dis-azo dye in one molecule of the product.  The use of heterocyclic reactants, e.g. a benzothiazole derivative and high-molar weight reactants, e.g. 3-amino-pyrene disulphonic acids, is exemplified in the preparation of azo dyes. Metal complexes are also obtained in the examples and phthalocyanine- and anthraquinone-azo dyes prepared.ALSO:Dyes of formula <FORM:0943264/D1-D2/1> where D is the residue of an amino dye bound to a C atom of tetrameric cyanogen by amino nitrogen, A is the residue of a nitrogenous base bound to a C atom of tetrameric cyanogen by amino nitrogen, W is a water-solubilising anionic salt-forming group attached to D and A, m-1 is the number of amino nitrogens of A bound to C atoms of tetrameric cyanogen, n is 1 or 2, m and p are 1, 2, or 3, q is 1-7, the sum of n(m-1) and (p-1) being 4, may be formed on textile fibres.  Thus the material to be coloured may be treated with a derivative of tetrameric cyarogen chloride, containing more than one reactive substituent, and then with an appropriate dye e.g. cellulose, after alkali treatment, may be treated with the reaction product of tetrameric cyanogen chloride, having one to two mols of amine, and the product with a dye containing an acylatable amino group the last treatment being in the presence of an acid binding agent.  When the tetrameric cyanogen chloride reaction product has aromatically bound diazotisable amino groups or radicals containing a carbon atom which can be coupled by aromatic diazo compounds, an azo dye may be formed on the fibre in the usual way.  The materials may also be pad dyed with a substantive azo component and treated with an aryldiazonium compound containing a radical derived from tetrameric cyanogen chloride, the dyeing being fixed by heating or with acid-binding agents.  Textile fibres containing hydroxyl or amino groups e.g. cellulose, wool, leather and synthetic polypeptide fibres are mentioned.  Indicated dyes are of the nitro, azo, anthraquinone and phthalocyanine series.  The dyes may be metal-free or contain heavy metals such as chromium, cobalt, copper, nickel or iron in a complex linkage.  Metal-containing dyes indicated are of the o-nitrosohydroxyaryl, phthalocyanine, o,o1-dioxyazo,o-carboxy-o1-hydroxyazo and o-hydroxy-o1-aminoazo series.  A variety of colours is obtained.  For the reagents used in the preparation of the dyes, which may also be used as substantive dyes, see Division C4.