Patent GB-627069-A (GB)
Title: Manufacture of polyazo dyestuffs of the pyrazolone series
IPC: C09B35/48
Filed: 1947-01-10
Abstract: Metallizable polyazo dyestuffs, of the general formula <FORM:0627069/IV (c)/1> wherein X represents a CO or CS group, Y an alkyl (e.g. methyl), phenyl, carboxyl or converted carboxyl (e.g. ester or amide) group, B the radical of a simple or complex polynuclear tetrazotized aromatic diamine (which may be further substituted) and A the radical of any desired coupling component (which may also contain one or more azo groups), are manufactured by coupling a tetrazotized polynuclear aromatic diamine successively in either order, in a slightly acid, neutral or slightly alkaline medium, on the one hand with a monoazo dyestuff from one molecular proportion of the nitrated diazo compound of 1-amino-2-naphthol-4-sulphonic acid and a condensation product of phosgene or thiophosgene with two molecular proportions of a 1-phenyl-5-pyrazolone compound of the general formula <FORM:0627069/IV (c)/2> and on the other hand with any desired further coupling component (which may contain one or more azo groups); or by coupling the tetrazotized diamine in either order with any desired coupling component (which may contain one or more azo groups) and with the aforesaid condensation product of urea or thiourea with the 1-phenyl-5-pyrazolone of the general formula above, and coupling the resulting dyestuff with an equimolecular proportion of the nitrated diazo compound of 1-amino-2-naphthol-4-sulphonic acid; or (when the radical A imparts sufficient solubility) by the action of phosgene and thiophosgene on a mixture of equimolecular proportions of two aminoazo dyestuffs obtained by coupling a 1-phenyl-5-pyrazolone of the general formula above with, in one case, the nitrated diazo compound of 1-amino-2-naphthol-4-sulphonic acid, and, in the other case, the one-sided coupling product of a tetrazotized polynuclear aromatic diamine and any desired coupling component (which may contain one or more azo groups), the reaction being continued until the primary amino groups disappear.  Suitable polynuclear aromatic diamines are the 4 : 41-diamino compounds of diphenyl, diphenylmethane, diphenyl sulphide, diphenylamine, diphenyl sulphone, benzophenone, diphenylurea and stilbene, the p-aminobenzoyl derivatives of these compounds and of m- and p-phenylenediamine, and nuclear substitution products of the foregoing, e.g. their alkyl, halogen, hydroxy, alkoxy, acylamino, carboxy or sulphonic acid derivatives.  The coupling component corresponding to A may be an enolic or an aromatic hydroxy, amino or hydroxyamino coupling component, or an azo compound capable of further coupling, examples of each type being specified.  The products dye cellulose fibres in orange, red, Bordeaux, brown and brown-violet tints, and may be treated in substance or on the fibre with agents yielding metals, e.g. copper or chromium. Examples illustrate the three alternative processes, and a table gives the properties of further dyestuffs. The Specification as open to inspection under Sect. 91 comprises also the manufacture of dyestuffs in which (a) X in the general formula above represents a cyanuryl radical; (b) the linkage -NH-X-NH- is connected in m-positions relative to the pyrazolone nuclei; (c) the linkage -NH-X-NH- is replaced by -Zn-NH-X-NH-Znwhere Z represents -C6H4-, -NH-CO-C6H4- or -CH =CH-C6H4- (the phenylene radical in each case being attached in the 1 : 3- or preferably 1 : 4-positions), and n is zero or one.  Additional examples and lists of components illustrate these features.  This subject-matter does not appear in the Specification as accepted.