Patent GB-813646-A (GB)
Title: Improvements relating to metallisable disazo dyestuffs, complex copper compounds, thereof, and their use
IPC: C09B45/28
Filed: 1956-06-19
Abstract: The invention comprises dyestuffs of the formula <FORM:0813646/IV (c)/1> wherein A is an aromatic radical of the benzene or naphthalene series containing at least one sulphonic or carboxylic acid group, Ph1 and Ph2 are the same or different p-phenylene radicals which may be substituted, Py1 and Py2 are the same or different radicals of 5-pyrazolones bound to Ph in the 1-position and to the azo group in the 4-position, X is a direct linkage or a divalent bridging group containing carbon, and R is an aromatic radical of the benzene or naphthalene series containing in the o-position to the azo linkage a group capable of forming a copper complex and which may also be the grouping <FORM:0813646/IV (c)/2> The invention also comprises the complex copper compounds of these dyestuffs.  The divalent bridging member X may be a vinylene group, a carbamide or ureido radical, or the radical of a diamide of an aliphatic, aromatic, or heterocyclic polybasic acid such as fumaric, terephthalic or cyanuric acid.  The pyrazolone nuclei may be substituted in the 3-position by aryl or alkyl groups, particularly methyl groups, and the p-phenylene radicals may contain halogen atoms such as chlorine, alkyl groups such as methyl, carboxylic acid groups, or sulphonic acid groups, preferably in the meta positions in regard to X.  The disazo dyes may be obtained by coupling one mole. of an azo component of formula Py1-Ph1-X-Ph2-Py2 in any order with one mole. of a diazonium compound of the formula <FORM:0813646/IV (c)/3> and with one mole. of a diazonium compound of formula R-N=N+. Dyes may be prepared in which X is a diamide radical of formula -NH-Z-NH and is bound with Ph1 and Ph2 by way of styrylene radicals, Z being the radical of carbonic acid or a dicarboxylic acid or the divalent radical of monobasic cyanuric acid, e.g. the dyes may contain in their molecules, the grouping <FORM:0813646/IV (c)/4> The dipyrazolones which may be used in preparing the disazo dyes may be symmetrical or not, both with regard to the two p-phenylene radicals Ph1, Ph2, and to the bridging member. Examples of amines for forming the diazonium component of the first kind are 3- or 4-aminobenzene - 1 - sulphonic or carboxylic acid, 2-methoxy - 2 - chloro or 2 - methyl - 5 - amino - benzene - 1 - sulphonic acid, 5 - amino - 2 - hydroxybenzene - 1 - carboxylic acid, and 1-amino-naphthalene - 3,6- or 3,8- or 4,8 - disulphonic acid.  Examples of amines for making the diazonium component of the second kind are o-hydroxy or o-carboxy amino compounds, e.g. 2-amino-4 or 5-methyl sulphonyl- or ethylsulphonyl-1-hydroxybenzene or its nitro compounds, 1 - hydroxy - 2 - aminobenzene - 4 or 5-sulphonic acid amide, 1-hydroxy-2-aminobenzene-4 or 6-sulphonic acid and further substituted derivatives of the latter such as the 4-nitro-, 4-chloro-, 4- or 6-acetylamino- or -benzoylamino derivatives; 2-aminobenzene-1-carboxylic acid, 2-amino-1-carboxybenzene-4 or 5-sulphonic acid and the corresponding sulphonic acid amides, 1-amino naphthalene-2-carboxylic acid, and 5-acylamino-2-aminobenzoic acid.  Symmetrical disazo dyes may be obtained by using as diazonium compounds of the second type such o-carboxy diazonium compounds as correspond also with those of the first type.  The diazonium compounds are coupled with the dipyrazolones in aqueous medium, if necessary in the presence of organic bases such as pyridine and its homologues.  Disazo dyes containing the grouping -NH-Z-NH- can also be produced by reacting an amino-monoazo dyestuff of formula <FORM:0813646/IV (c)/5> and an amino-monoazo dyestuff of formula R-N=N-Py2-Ph2-Qn2-NH2, wherein n is 0 or 1, and Q1 and Q2 are the same or different, if desired substituted, styrylene radicals, with one mole. of a functional acid derivative corresponding to the radical Z, e.g. phosgene, fumaric or terephthalic dichloride, or cyanuric acid chloride, the third halogen of the latter preferably being replaced by a primary or secondary amino group.  The disazo dyestuffs are yellow to yellow-brown powders which dissolve in hot water, possibly with the addition of sodium carbonate, phosphates, or polyphosphates.  They dye cellulosic fibres by usual methods in full yellow to yellow-brown shades.  The dyeings may be treated in the dyebath or in a fresh bath with coppering agents, e.g. copper sulphate or acetate under neutral or weakly acid conditions.  Copper compounds may be used which are stable to alkalies, such as those obtained by reacting copper sulphate with sodium tartrate in a sodium carbonate alkaline bath.  The coppering treatment improves the wet and light fastness of the dyeings.  If desired, the disazo dyes may be treated in substance to form the complex copper compounds, and the cellulosic fibres may be dyed with these complexes.  In examples, (1) 4-aminodiphenyl - urea - 3 - carboxylic acid - 41 - sulphonic acid is diazotized and then coupled with 1.11 - (411.4111 - diphenylene) - di - [3-methyl-pyrazolone-(5)] to form a yellow-brown dyestuff which is soluble in water and conc. sulphuric acid; similar dyes are made using alternative urea compounds, e.g. 4-aminodiphenyl - urea - 3 - carboxylic acid - 31 - sulphonic (or 21.51-disulphonic) acid, 21- or 41-methyl or chloro-4-aminodiphenyl-urea-3-carboxylic - 31 - sulphonic acid, 4 - amino - 41-hydroxydiphenyl - urea - 3.31 - dicarboxylic acid-51-sulphonic acid, 4 - aminophenyl - 1.11-naphthyl - urea - 3 - carboxylic acid - 31.81-disulphonic acid, or 4-aminophenyl-1.21-naphthyl - urea - 3 carboxylic acid - 41.81- or 61.81-disulphonic acid; (2) a dyestuff of formula <FORM:0813646/IV (c)/6> is prepared by coupling the appropriate dipyrazolone with a diazonium salt dispersion obtained from 4-aminodiphenyl-urea-3 carboxylic acid-31-sulphonic acid; similar dyes may be obtained by using other dipyrazolones, e.g. those in which the bridging group X is the radical of the diamide of fumaric or terephthalic acid or of cyanuric acid mono-anilide or a radical comprising one of these radicals linked to styrylene radicals which are bound to Ph1 and Ph2; an alternative process is described in which diazotized 4-aminodiphenyl-urea-3 carboxylic acid-31-sulphonic acid is coupled with 1-(41-aminophenyl) - 3 - methyl - pyrazolone (5), and the monoazo dyestuff thus formed is reacted with phosgene; (4) the diazonium compound of 4 - amino - 3 - carboxydiphenyl urea - 41 - sulphonic acid is coupled with 1.11-(411.4111-diphenylene) di-[3-methyl-pyrazolone-(5)] and on completion of coupling there is added to the reaction solution the diazonium compound of 4-methylsulphonyl - 2 - amino - 1 - hydroxy - benzene; a yellow-brown powder is obtained, which is soluble in water or concentrated sulphuric acid, and which dyes cotton, regenerated cellulose, hemp, and jute fibres, when after-coppered, in fast yellow shades; similar dyes may be obtained by using other second diazonium components, e.g. those from 5-methyl or ethyl or 4 - methyl sulphonyl - 2 - amino - 1 - hydroxy - benzene, 1 - hydroxy - 2 - amino - benzene - 4 or 6-sulphonic acid, 4-chloro or nitro-2-amino-1-hydroxybenzene - 6 - sulphonic acid, 1.2 - di - azoxide - naphthalene - 4 - sulphonic acid or the 6-nitro derivative, 2-amino-1-carboxybenzene or its 4- or 5-sulphonamide, 5-acetylamino - 2 - amino - 1 - carboxybenzene, and 2 - amino - naphthalene-3-carboxylic acid; (5) diazotized 4 - amino - diphenyl urea - 3 - carboxylic acid-41-sulphonic acid is coupled with a dipyrazolone of the formula <FORM:0813646/IV (c)/7> and the dyestuff is separated from the alkaline solution by the addition of salt; the dyestuff is redissolved in water and then a copper oxideammonia solution is added; the copper complex is salted out; (6) the dyestuff obtained in (5) is dissolved in water containing sodium carbonate and cotton is dipped in the solution, the temperature being raised from 40 DEG  to 95 DEG  C., after which sodium sulphate is added and the dyeing completed, the cotton being dyed in fast reddish-yellow shades; (7) the dyestuff of (1) is dissolved in water containing sodium carbonate and cotton is dyed in the solution, the temperature being raised gradually to 95 DEG  C. and then sodium sulphate is added; the dyed goods are rinsed, and then after-treated in a fresh bath with a solution of copper sulphate in water and acetic acid, the temperature being 70 DEG  C.  Specification 736,166 is referred to.