GB2126598A - Reactive dyestuffs - Google Patents

Abstract

Reactive dyestuffs of the formula: <IMAGE> wherein D is a group confering chromophoric properties. The dyes may be conveniently manufactured and have improved acid bleeding properties.

Description

SPECIFICATION Reactive dyestuffs This invention relates to reactive dyes especially to reactive dyestuffs containing a residue of 1-[2' sulphophenyli-4-dichloro-s-triazinyl piperazine.

It is well known to manufacture reactive dyestuffs i.e. dyestuffs which contain a group which permits a covalent bond to be formed between the dyestuff molecular and a substrate containing active hydrogen atoms such as cellulose. A group commonly employed is the dichloro-s-triazinyl group which will fix to celulose substrates at conveniently low temperatures e.g. ambient to 40"C. However dyes fixed by this group commonly exhibit a problem of "acid-bleeding" i.e. loss of colour under moist acidic conditions and the production of loose dyestuff which can stain other substrates in the vicinity.

Various forms of reactive dyestuffs have been proposed containing dichlorotriazinyl groups and having a reduced tendency to acid bleeding but these are often prone to other disadvantages e.g. they can be difficult to manufacture in suitable form. Dyes in which the dichiorotriazinyl group is linked to a piperazine residue may be seen for example in UK 929426 and 1015932. We have now found a novel structural feature for dichlorotriazinyl-4- reactive dyestuffs which can be conveniently introduced by normal manufacturing methods and leads to reduced problems of acid bleeding.

According to the present invention there are provided reactive dyestuffs of the formula:

wherein D is a group confering the chromophoric properties.

The group D may take various forms.

In one preferred form Disoftheformula: E-N=N- (2) wherein E is the radical of a coupling component EH.

EH may itself be non-chromophoric e.g. 2-naphthol or J acid, the chromophoric properties resulting from the combination of E - N = N with the remainder of the molecule of formula (1). However preferred radicals E are derived from coupling components having chromophoric properties e.g. the coupling components formed by one coupling onto a compound capable of coupling twice. Especially preferred groups of formula (21 are:

where one X is SO3H and the other is H and A is the residue of a diazotisable aromatic amine AN H2.

The amines ANH2 will naturally be those whose derived diazonium salt is capable of coupling ortho to an NH2 group to lead to the structure (3). Specific examples of A will be apparent from examples of ANH2 given below.

Preferred groups for A are naphthyl substituted by 1 to 3 SO3H and phenyl or toll each substituted by 1 to 3 atoms or groups each selected from SO3H, Br, CI, NO2, COOH, CN and SO2NR1R2 have the meanings given below for R in connection with formula (5).

The combinations of substituents on the phenyl or tolyl groups mentioned above will naturally be preferred to be those present in commonly available intermediates e.g. trisulpho ortricarboxy groups are not commonly employed.

A second preferred form for D is: D1 -Y- NH - (4) wherein D1 is the residue of a chromophoric compound and Y is a linking atom or group.

D1 may be from any of the dyestuff series e.g. azo, anthraquinone, phthalocyanine, formazan, nitroarylamine, oxazine, azine, triphenylmethane or xanthene series.

The linking atom or group Y may for example be CO, SO2 or

where R is optionally substituted CIA alkyl e.g. CH3, C2H5, C14 @ cyanoalkyl such as CN.C2H4, CiA hydroxyalkyl such as HOC2H4 or especially H and Z is OH, optionally substituted alkoxy or optionally substituted amino or preferably CI.

It is preferred that Y is SO2 when D1 is of the phthalocyanine series and especially preferred that Y is of formula (5) for all meanings of D1.

Specific illustrations of D1 will be apparent from the examples given below of materials suitable for the manufacture of dyes containing the grouping of formula (4).

As examples of the group Z other than CI or OH there may be mentioned CiA alkoxy e.g. OCH3, OC2H5 and OC4Hs, C1.4 alkoxy substituted by OH, CN, CI, OSO3H, SO3H and Cur 4 alkoxy e.g. HOC2H4O, CH3CHOH.CH2.O, HOC4H8O, CIC2H4O, CN.C2H4O, HO3S.O.C2H4.O, HO3S.C2H4.O, CH3O.C2H4O and C2H5.O.C2H4.O-, amino, C1A alkylamino, e.g. methylamino, ethylamino, butylamino, di-(C1.4 alkyl)amino, e.g. dimethylamino, diethylamino, methylethylamino, dibutylamino and groups of the latter two types in which the alkyl groups are substituted in particular by OH, CN or SO3H, e.g. beta-hydroxyethylamino, di-(beta-hydroxyethyl) amino, beta-cyanoethylamino, di-(beta-cyanoethyl )amino, beta-sulpho ethylamino, beta-hydroxypropylamino, (beta-hydroxybutyl)ethylamino and (beta-hydroxyethyl)-methylamino; cycloalkylamino e.g. cyclohexylamino, naphthylamino substituted by 1, 2 or 3 SO3H groups and optionally substituted phenylamino groups.

As a particularly preferred form of the optionally substituted phenylamino groups there may be mentioned groups otthe tormula:

where G = H, methyl, ethyl, -sulphomethyl, beta-carboxy-, betahydroxy- or beta-cyanoethyl and J and K are each independently selected from H, COOH, SO3H, CH3, C2H5, OCH3, OC2H5, CI, Br, CN, NO2, NHCOCH3.

As specific examples of such groups there may be mentioned anilino, o-, m- and p-sulphoanilino, o-, m and p-carboxyanilino, 4- 4@ and 5-sulpho-2-carboxyanilino, 4- and 5-sulpho-o-tolylamino, 2,4-, 2,5- and 3,5-disulphoanilino, 2,4-dicarboxyanilino, 4- and 5-sulpho-2-methoxyanilino, N-methyl-o-, m- psulphoanilino, N--sulphomethyl anilino, N-(beta-hydroxyethyl)-3-sulphoanilino.

A further preferred form of Z are cyclic amino groups such as morpholino or piperidino.

The dyes of formula (1 ) will have some water solubility in consequence of the SO3H shown. It is often desirable that the dyes have a reasonably high water solubility i.e. at least 5 grams/litre and to this end the SO3H group will often be converted to a salt e.g. sodium or potassium. Frequently water solubilising groups e.g. further suiphonic acid groups or their salts will be present on D to ensure the desired level of solubility.

The present invention further provides a process for the manufacture of dyestuffs of formula (1 ) which comprises reacting dye base of the formula:

with cyanuric chloride.

This reaction may be conveniently carried out in an aqueous medium at temperatures of 0-1 2 C preferably maintaining the pH in the range 7-10 especially 8-9 by the addition of acid binding agents such as sodium carbonate, bicarbonate or hydroxide.

The dyebase of formula (6) may be obtained by methods appropriate to the nature of D.

Thus when D is of the formula (2) the dyebase of formula (6) may be obtained by coupling a coupling component EH with the diazonium salt from

In the case of the preferred groups of formula (2) i.e. those of formula (3) the coupling component EH is of the formula:

where A and X have the meanings given above, and the coupling is conveniently carried out in aqueous media at a mildly alkaline pH and temperatures of 10-30"C.

The coupling component of formula (8) may itself be obtained by coupling H or K acid with the diazonium salt from the amine ANH2 under conventional acidic conditions e.g. at pH 1-2.

As examples of suitable amines of the formula Any2 there may be mentioned: aniline-2,3 and 4-sulphonic acid aniline-2,5-disulphonic acid aniline-3,5-disulphonic acid aniline-2,4-disulphonic acid 4- and 5-sulphoanthranilic acid 2-nitroaniline-4-sulphonic acid 4-nitroaniline-2-sulphonic acid 3-nitroaniline-6-sulphonic acid 5-nitro-2-aminoanisole-4-sulphonic acid 2-methylaniline-4,5-disulphonic acid 2,5-dichloroaniline-4-sulphonic acid 4-methylaniline-2-sulphonic acid 5-chloro-4-methylaniline-2-sulphonic acid 4-methoxyaniline-2-sulphonic acid 4-chloroaniline-3-sulphonic acid 5-acetylaminoaniline-2,4-disulphonic acid anthranilic acid 2-aminoterephthalic acid m-aminobenzoic acid 3-or 4-aminophthalic acid p-aminobenzoic acid 5-nitroanthranilic acid 6-nitro-3-aminobenzoic acid 5-nitro-2-aminoterephthalic acid 1-naphthylamine-4-sulphonic acid 2-naphthylamine-4,8-naphthylamine-4,8-disulphonic acid 2-naphthylamine-6,8-disulphonic acid 2-naphthylamine-5,7-disulphonic acid 2-naphthylamine-1 5-disulphonic acid 2-naphthylamine-1 ,6-disulphonic acid 2-naphthylamine-6,8-disulphonic acid 6-acetylamino-2-naphthylamine-4,8-disulphonic acid 2-naphthylamine-3,6,8-trisulphonic acid 2-naphthylamine-4,6,8-trisulphonic acid 4-aminodiphenyl-3-sulphonic acid 4-amino-4'-nitrodiphenylamine-2'-sulphonic acid 4'-amino-4-sulphobenzanilide 4-amino-2-sulphodiphenyl sulphide 4-amino-2-sulphodiphenyl oxide 4-amino-3-sulphodiphenyl urea 4-amino-4'-nitrostilbene-2,2'-disulphonic acid and dehydrothio-p-toluidine mono- and di-sulphonic acids o-, m- and p-chloroaniline o-, m- and p-bromoaniline 2,4- and 2,5-dichloroaniline 4-chloro-2-trifluoromethylaniline o-, m- and p-nitroaniline 2-chloro-4-nitroaniline 4-chloro-2-nitroaniline 4-chloro-3-nitroaniline 4- and 5-nitro-2-methoxyaniline 4- and 5-nitro-2-methylaniline 3-nitro-4-methoxyaniline 2-nitro-4-methylaniline 3- and 4-benzenesulphonylaminoaniline When D is of the formula (4) the dyebase of formula (6) is obtained by methods appropriate to the linking atom or group Y.

Thus when Y is CO an intermediate containing a carboxylic acid group and group convertable to a diazotisable amino group e.g. nitro or acetylamino is reacted with, for example, thionyl chloride to convert the carboxy group to its chloride. This acid chloride is reacted with the amine of formula (7) under acid conditions and the diazotisable amino group formed by appropriate means e.g. reduction of nitro groups or hydrolysis of acetylamino groups. The resulting product may be diazotised and coupled onto a coupling component to give a dyebase of formula (6) in which D is of the form D1 - Y - NH - (4) in which D1 is an azo chromophoric compound and Y is CO.

This sequence might typically be carried out with meta nitrobenzoic acid.

Similarly compounds containing a SO3H group may have this converted to SO2CI, reacted with the amine of formula (7) and used to produce dyebases of formula (6) in which D1 is an azo chromophore and Y is SO2.

In some instances it may be possible to carry out these reactions on suiphonic acid compounds containing the diazotisable amino group rather than a precursor of this group e.g. the reaction sequence may be performed on 2-aminonaphthalene-1 ,5-disulphonic acid in which the 5-sulpho group is readily converted to its chloride and then reacted with the amine of formula (7), or Tobias acid may be chlorosulphonated (in the 5-position) before reaction with amine of formula (7).

It is not usually possible to carry out the above reaction sequence on carboxy or sulpho groups present on azo chromophoric compounds containing a multiplicity of water solubilising groups since this usually results in low mutual solubility with such compounds and the reagents necessary to form the acid chlorides.

However it is possible to convert sulpho groups on phthalocyanine compounds to the corresponding SO2CI group or introduce such groups directly using chlorosulphonic acid. These groups may be then reacted with the amine of formula (7) to yield dyebases of formula (6) in which D1 is a phthalocyanine chromophore and Y is SO2. It is possible to introduce more than one SO2Ci group per molecule of phthalocyanine and these may all be reacted with amine of formula (7) or only some may be so reacted and the remainder reacted with ammonia or amines other than that of formula (7). This is conveniently achieved by contacting the SO2CI compound with a mixture of amines. By using a deficiency of amines and subsequently treating with water some of the SO2CI groups may be converted to SO3H.It will be appreciated these methods can lead to products containing various molecular species.

The dyebases of formula (6) in which D is of the form D1 -Y- NH - (4) wherein Y is

where Rand Z have the meanings given above are conveniently obtained by reacting the amine of formula (7) with a dichlortriazinyl dyestuff of the formula:

to yield a dyebase of formula (6) in which Z is Cl.

This reaction is conveniently carried out in aqueous media at a pH controlled between 2-6 preferably 3-5.

The temperature for conveniently achieving reaction will usually be in the region of 20-50 C. When Z is other than Cl the product is further reacted with a compound of the formula Z1H, where Z has the meaning given above for Z other than Cl, usually at a temperature of 60-100"C in an aqueous medium at pH controlled in the 5-11 region.

The compound Z1 H used to introduce the group Z when other than CI will typically be water, alcohols such as methanol, ethanol and butanol, ammonia or amines e.g. ethylamine, diethylamine, hydroxyethylamine, di(hydroxyethylamine) cyclohexylamine, morpholine, piperidine, aniline, aniline sulphonic acids and naphthylamine sulphonic acids. Other examples of Z1H will be apparent from the groups Z given above.

The dichlortriazinyl dyestuffs of formula (9) will themselves be obtained by reacting an amino dyestuff D1 - NRH (10) with cyanuric chloride.

This reaction may be conveniently conducted in an aqueous medium at temperatures of 0-10"C usually in the presence of an acid binding agent to neutralise liberated HCI, e.g. the pH controlled in the region of 5-9 especially 6-8.

As examples of amino dyestuffs of formula (10) there may be mentioned the foliowing classes: (i) Anthraquinone compounds oftheformula:

wherein the anthraquinone nucleus may contain an additional sulphonic acid group in thre 5-, 6-, 7-or 8position and V represents a bridging group which is preferably a divalent radical of the benzene series, for example phenylene, diphenylene or 4,4'-divalent stilbene or azobenzene radicals. It is preferred that V should contain one suiphonic acid group for each benzene ring present. R has the meaning stated above.

(ii) Monoazo compounds of the formula:

wherein D1 represents a mono- or di-cyclic aryl radical which is free from azo groups and NHR groups, the -NHR group is preferably attached to the 6-, 7-or 8- position of the naphthalene nucleus, and which may contain a suiphonic acid group in the 5-or 6- position of the naphthalene nucleus.

D1 may represent a radical of the naphthalene or benzene series which is free from azo substituents,for example a stilbene, diphenyl, benzthiazolylphenol or diphenylamine radical. Also in this class are to be considered the related dyestuffs in which the NHR group, instead of being attached to the naphthalene nucleus, is attached to a benzoylamino or anilino group which is attached to the 6-, 7-or 8- position of the naphthalene nucleus.

Particularly valuable dyestuffs are obtained from those wherein D1 represents a sulphonated phenyl or naphthyl radical, especially those which contain a -SO3H group in ortho position to the azo link; the phenyl radical may be further substituted, for example by halogen atoms such as chlorine, alkyl radicals such as methyl, acylamino groups such as acetylamino and alkoxy radicals such as methoxy.

(iii) Disazo compounds of formula (6) wherein D1 stands for a radical of the azobenzene, azonaphthalene or phenylazo-naphthalene series and the naphthalene nucleus is substituted by the NHR group, and optionally by suiphonic acid as in class (ii).

(iv) Mono- or dis-azo compounds of the formula: D1 - N = ND2NHR (13) wherein D1 stands for a radical as defined for class (ii) or class (iii) and D2 is a 1 :4-phenylene or a sulpho-1,4-naphthylene or a stilbene radical; the benzene nuciei in D1 and D2 may contain further substituents such as halogen atoms, or alkyl, alkoxy carboxylic acid and acylamino groups.

(v) Mono- or dis-azo compounds of the formula:

wherein D1 represents an arylene radical such as a radical of the azobenzene, azonaphthalene or phenylazonaphthalene series or, preferably, or at most, dicyclic arylene radical of the benzene or naphthalene series, and K represents the radical of a naphthoi sulphonic acid or the radical of an enolised or enolisable keto-methylene compound (such as an acetoacetarylide, a 5-pyrazolone or a 6-hydroxypyrid-2one having the OH group ortho to the azo group. D1 preferably represents a radical of the benzene series containing a sulphonic acid group.

(vi) Mono- or dis-azo compounds of the formula: D1 - N = N - K2- NHR (14) wherein D1 represents a radical of the types defined for D, in classes (ii) and (iii) above and K2 represents the radical of an enolisable keto-methylene compound such as an acetoacetarylide or a 5-pyrazolone having the -OH group in an alpha-position to the azo group.

(vii) 1:1metal complex, especially the copper complex, compounds of those dyes of formulae (12), (14) and (15) [wherein D1, K and K2 have all the respective meanings stated] which contain a metallisable (for example, a hydroxy, lower alkoxy or carboxylic acid) group ortho to the azo group in D,.

(viii) Phthalocyanine compounds oftheformula:

wherein Pc represents the phthalocyanine nucleus preferably of copper phthalocyanine, represents a hydroxy and/or a substituted or unsubstituted amino group, V1 represents a bridging group, preferably an aliphatic, cycloaliphatic or aromatic group, n represents 1,2 or 3.

(ix) Nitro dyestuffs of the formula:

wherein B1 and B2 represents mono-cyclic aryl nuclei, in nifro group in B1 being ortho to the NH group. (x) Formazan dyestuffs oftheformula:

wherein M is Cu or Ni, D and B are mono or poly nuclear aryl groups in which the links shown are from carbon atoms ortho to each other, the group R1 is an optionally substituted hydrocarbyl group and one of the groups D, B or R' bears a group

(xi) Nitrostilbene dyestuffs of the formula:

wherein n and m are each independently 1 or 2.

(xii) Phenazine dyes of the formula:

wherein n is 1 or 2; R5 is H or optionally substituted CiA alkyl; R6 is optionally substituted C1.4 alkyl, optionally substituted aralkyl or optionally substituted aryl, and the benzene ring A1 can be further substituted, e.g. by Cl, CH3 or OCH3.

(xiii) Triphendioxazine dyes of the formula:

inwhichm=Oor1 andn=Oor1, or

where Alk = an alkylene group preferably of 2-6 carbon atoms.

As particular examples of compounds of classes (i) to (xiii), there may be mentioned: In class (il i-amino-4-(4'-arninoanilino)athraquinone-2:2'-disulphonicacid 1-amino-4-(4'-methylaminoanilino)anthraquinone-2:3'-disulphonic acid 1-amino-4-(3'-amino-2':4':6'-trimethylanilino)anthraquinone-2,5'-disulphonic acid In class (11) 6-amino-i -hydroxy-2-(2'-sulphophenylazo)napththalene-3-sulphonic acid 8-amino-1-hydroxy-2-(2'-sulphophenylazo)naphthalene-3::6-disulphonic acid 7-amino-2-(2';5'-disulphophenylazo)-1-hydroxynaphthalene-3-sulphonic acid 7-methylamino-2-(2'-sulphophenylazo)-l .hydrnxynaphthalene-3-sulphonic acid 7-methylamino-2-(4'-methoxy-2'-sulphophenylazo)-1-hydroxynaphthalene-3-sulphonic acid 8-(3'-aminobenzoylamino)-1-hydroxy-2-(2'-sulphophenylazo)naphthalene-3:6-disulphonic acid 8-amino-1 -hydroxy-2:2'-azonaphthalene-l ':3:5' :6-tetrasulphonic acid 6-amino-1-hydroxy-2(4'-acetylamino-2'-sulphophenylazo)naphthalene-3-sulphonic acid 6-methylamino-1-hydroxy-2-(4'-methoxy-2'-sulphophenylazo)naphthalene-3-sulphonic acid 8-amino-1 -hydroxy-2-phenylazonaphthalene-3:6-disulphonic acid 8-amino-1-hydroxy-2:2'-azonaphthalene-1':3::6-trisulphonic acid 6-amino-1-hydroxy-2-(4'-methoxy-2'-sulphophenylazo)naphthalene-3-sulphonic acid 8-amino-1-hydroxy-2:2'-azonaphthalene-1':3:5'-trisulphonic acid 6-amino-1 -hydroxy-2:2'-azonaphthalene-l ':3:5'-trisulphonic acid 6-methylamino-1 -hydroxy-2:2'-azonaphthalene-l ':3:5'-trisulphonic acid 7-amino-l -hydroxy-2:2'-azonaphthalene-l ':3-disulphonic acid 8-amino-1-hydroxy-2-(4'-hydroxy-3'-carboxyphenylazo)naphthalene-3:6-disulphonic acid 6-amino1-hydroxy-2-(4'-hydroxy-3'-carboxyphenylazo)naphthalene-3:5-disulphonic acid In class (iii) 8-amino-1 -hydroxy-2-[4'-(2"-sulphophenylazo)-2'-methoxy-5'-methylphenylazo]naphthalene-3:6- disulphonic acid 4:4'-bis-(8"-ammino-1"-hydroxy-3":6"-disulpho-2"-naphthylazo)-3::3'-dimethoxydiphenyl 6-amino-1-hydroxy-2-[4'-(2"-sulphophenylazo)-2'-methoxy-5'-methylphenylazo]naphthalene-3:5disulphonic acid In class (iv) 2-(4'-amino-2'-methylphenylazo)naphthalene-4:8-disulphonic acid 2-(4'-amino-2'-acetylaminophenylazo)naphthalene-5:7-disulphonic acid 2-(4'-amino-2'-ureidophenylazo)naphthalene-3:6:8-trisulphonic acid 4-nitro-4'-(4"-methylami nophenylazo)stil bene-2: :2'-disulphonic acid 4-nitro-4'-(4"-amino-2"-methyl-5"-methoxyphenylazo)stilbene-2:2-disulphonic acid 2-(4'-amino-2'-acetylaminophenylazo)naphthalene-4:8-disulphonic acid 4-amino-2-methylazobenzene-2' : 5'-disulphonic acid 4-[4'-(2",5"-disulphophenylazo)-2',5'-dimethylphenylazo]-1-naphthylammine-8-sulphonic acid 4-[4'-(2",5",7"-trisulphonaphth-1"-ylazo)-2',5'-dimethylphenylazo]-1-naphthylamine-6-sulphonic acid 4-[4'-(2",5",7"-trisulphonaphth-1"-ylazo)-2',5'-dimethylphenylazo]-1-naphthylamine-7-sulphonic acid 4-[4'-(2",5",7"-trisulphonaphth-i "-ylazo)naphth-i '-ylazo]-1-naphthylamine-6-sulphonic acid 4-[4'-(2",5"-disulphophenylazo)-6'-sulphonaphth-1-ylazo-1-naphthylamine-8-sulphonic acid 4-[4'-(4"-sulphophenylazo)-2'-sulphophenylazo]-1 -naphthylamine-6-sulphonic acid In class (v) 1-(2',5'-dichloro-4'-sulphophenyl)-3-methyl-4-(3"-amino-4"-sulphophenylazo)-5-pyrazolone 1-(4'-sulphophenyl)-3-carboxy-4-(4"-amino-3"-sulphophenylazo)-5-pyrazolone 1 -(2'-methyl-5'-sulphophenyl)-3-methyl-4-(4"-amino-3"-sulphophenylazo)-5-pyrazolone 1-(2'-sulphophenyl)-3-methyl-4-(3"-amino-4"-sulphophenylazo)-5-pyrazolone 4-amino-4'-(3"-methyl-1"-phenyl-4"-pyrazol-5"-onylazo)-stilbene-2:2'-disulphonic acid 4-amino-4'-(2"-hydroxy-3",6"-disulpho-1"-naphthylazo)-stilbene-2:2'-disulphonic acid 8-acetylamino-1 -hydroxy-2-(3'-amino-4'-sulphophenylazo)-naphthalene-3 :6-disulphonic acid 7-(3'-sulphophenylamino)-1 -hydroxy-2-(4'-amino-2'-carboxyphenylazo)-naphthalene-3-sulphonic acid 8-phenylamino-1 -hydroxy-2-(4'-amino-2'-sulphophenylazo)-naphthalene-3 ::6-disulphonic acid 6-acetylamino-1-hydroxy-2-(5'-amino-2'-sulphophenylazo)-naphthalene-3-sulphonic acid 6-ureido-1-hydroxy-2-(5'-amino-2'-sulphophenylazo)-naphthalene-3-sulphonic acid 8-benzoylamino-1 -hydroxy-2-(5'-amino-2'-sulphophenylazo)-naphthalene-3:6-disulphonic acid 1-(4':8'-disulphonaphth-2'-yl)-3-methyl-4-(5"-amino-2"-sulphophenylazo)-5-pyrazolone 1-(2'-sulphophenyl)-3-carboxy-4-(5"-sulphophenylazo)-5-pyrazolone 1-(2'::5'-dichloro-4'-sulphophenyl)-3-methyl-4-(5"-amino-2"-sulphophenylazo)-5-pyrazolone 5-(3'-amino-4'-sulphophenylazo)-4-methyl-5-cyano-6-hydroxypyrid-2-one 5-(3'-amino-4'-sulphophenylazo)-4-methyl-5-carbonamido-6-hydroxy-N-ethylpyrid-2-one 5-(3'-amino-4'-sulphophenylazo)-4-methyl-6-hydroxypyrid-2-one 5-(3'-amino-4'-sulphophenylazo)-4-methyl-5-cyano-6-hydroxy-N-methylpyridone 5-(4'-amino-3'-su Iphop henylazo )-4-methyl-5-cyano-6-hydroxy-N-ethylpyridone 5-(4'-amino-2',5'-disulphophenylazo)-4-methyl-5-cyano-6-hydroxy-N-ethylpyridone 5-(3-amino-4-sulphophenylazo)-3,4-dimethyl-6-hydroxy-1-n-propylpyrid-2-one 5-(4-amino-2,5-disulphophenylazo)-1 -n-butyl-6-hydroxy-4-methyl-3-sulphomethylpyrid-2-one 5-(3-amino-4-sulphophenylazo)-1 -ethyl-6-hydroxy-4-methyl-3-su Iphopyrid-2-one 5-(3-amino-4-sulphophenylazo)-3-chloro-1-ethyl-6-hydroxy-4-methylpyrid-2-one 5-(3-amino-4-sulphophenylazo)-3-cyano-l -ethyl-6-hydroxy-4-sulphomethylpyrid-2-one 5-(3-amino-4-sulphophenylazo)-3-aminocarbonyl-6-hydroxy-4-methyl-1 -[2-(4-sulphophenyl)ethyl]pyrid-2- one In class (vi) 1-(3'-aminophenyl)-3-methyl-4-(2':5'-disulphophenylazo)-5-pyrazolone 1-(3'-aminophenyl)-3-carboxy-4-(2'-carboxy-4'-sulphophenylazo)-5-pyrazolone 4-amino-4'-[3U-methyl-4"-(2'D: 5"'-disu I phophenyl azo )-1 "-pyrazol-5"-onyl]stilbene-2: 2'-disu Iphonic acid 1-(3'-aminophenyl)-3-carboxy-4-[4"-(2"':5"'-disulphophenylazo)-2"-methoxy-5"-methylphenylazo]-5- pyrazolone In class (viz) The copper complex of 8-amino-1 -hydrnxy-2-(2'-hydroxy-5'-sulphophenylazo)naphthalene-3:6- disulphonic acid The copper complex of 6-amino-1-hydroxy-2-(2'-hydroxy-5'-sulphophenylazo)naphthalene-3-sulphonic acid The copper complex of 6-ammino-1 -hydroxy-2-(2'-hydroxy-5'-sulphophenylazo)naphthalene-3::5- disulphonic acid The copper complex of 8-amino-1,1 '-dihydroxy-2,2'-azonaphthalene-3,4',6,8'-tetrasulphonic acid The copper complex of 8-amino-1 -hydroxy-2-[4'-(2"-sulphophenylazo)-2'-methoxy-5' methylphenylazo]naphthalene-3 :6-disuiphonic acid The copper complex of 6-amino-1-hydroxy-2-[4'-(2":5"-disulphophenylazo)-2'-methoxy-5'- methylphenylazo]naphthalene-3,5-disulphonic acid The copper complex of 1 -(3'-amino-4'-sulphophenyl)-3-methyl-4-[4"-(2"':5"'-disulphophenylazo)-2"- methoxy-5"-methylphenylazo-5-pyrazolone The copper complex of 7-(4'-amino-3'-sulphoanilino)-1-hydroxy-2-[4"-(2"'::5"'-disulphophenylazo)- 2Dmethoxy-5"-methylphenylazo]naphthalene-3-sulphonic acid The copper complex of 6-(4'-amino-3'-sulphoanilino)-1-hydroxy-2-(2"-carboxyphenylazo)naphthalene-3- sulphonic acid In class (villi) 3-(3'-amino-4'-sulphophenyl)sulphamyl copper phthalocyanine tri-3-suiphonic acid 4-(3'-amino-4'-sulphophenyl)sulphamyl copper phthalocyanine tri-4-sulphonic acid 3-(3'- or 4'-aminophenyl)sulphamyl copper phthalocyanine-3-sulphonamide-di-3-sulphonic acid In class (ix) 4-amino-2'-nitro-diphenylamine-3::4'-disulphonic acid In class rx) The copper complex of N-(2-hydroxy-5-sulpho-3-aminophenyl)-N1-(2'-carboxy-4'-sulphophenyl)-ms- phenylformazan The copper complex of N-(2-hydroxy-5-sulpho-3-aminophenyl)-N1-(2'-carboxy-4'-sulphophenyl)-ms-(4"- sulphophenyl)formazan The copper complex of N-(2-hydroxy-5-sulphophenyl)-N1-(2'-carboxy-4'-aminophenyl)-ms-(2"- sulphophenyl)-formazan The copper complex of N-(2-hydroxy-5-sulphophenyl)-N1-(2'-carboxy-4'-aminophenyl)-ms-(2"-chloro-5D- sulphophenyl)formazan The copper complex of N-(2-hydroxy-5-sulphophenyl)-N-(2'-carboxy-4'-sulphophenyl)-ms-(4"- aminophenyl)formazan The copper complex of N-(2-hydroxy-5-sulphophenyl-N1-(2'-carboxy-4'-sulphophenyl)-ms-(4"-amino-2"- sulphophenyl)formazan The copper complex of N-(2-carboxy-4-aminophenyl)-N1-(2'-hydroxy-4'-sulphonaphth-1 "-yl)-ms-(2"- sulphophenyl)formazan In class (xi) 4-amino-4'-nitrostilbene-2,2'-disulphonic acid 4- -(N-methylamino)acetylaminostilbene-2,2'-disulphonic acid In class (xii) Anhydro-9-(4-amino-3-sulphoanilino)-5-anilino-7-phenyl-4sulpho or 2,4-4,11disulphobenz[a]phenazinium hydroxide Anhydro-9-(4-amino-3-sulphoanilino)-5-p-toluidino-7-p-tolyl-2,4-disulphobenz[a]phenazinium hydroxide Anhydro-9-(4-amino-3-sulphoanilino)-5-p-toluidino-7-p-methoxyphenyl-2,4-disulphobenz[a[phenazinium hydroxide Anhydro-3-(4-amino-3-su lphoanilino)-7-N-ethyl-N-(3 or 4-sulphobenzylamino-5-(2, 3 or 4- sulphophenyl)phenazinium hydroxide Anhydro-3-(4-amino-3-sulphoanilino-7-N-ethyl-N-(3 or 4-sulphobenzyl)amino-1 -methyl or methoxy-5-(2sulphophenyl)phenazinium hydroxide Anhydro-3-(4-amino-3-sulphoanilino)-7-N-ethyl-N-(3 or 4-sulphobenzyl)amino-5-(4-chloro, methoxy or methyl-3-sulphophenyl)phenazium hydroxide Anhydro-5-(4-amino-2,5-disulphoanilino)-9-diethylamino-7-phenyl-1 0-sulphobenz[a[phenazinium hydroxide Anhydro-3,7-bis-[N-ethyl-N-(3 or 4-sulphobenzyl)]-5-(3- or 4-amino-4- or 3-sulphophenyl)phenazinium hydroxide Anhydro-3-(4-amino-3-sulphoanilino)-7-N-ethyl-N-(2-sulphoethyl)-amino-5-(2, 3 or 4sulphophenyl)phenazinium hydroxide Anhydro-3-(4-amino-3-sulphoanilino)-7-N-methyl-N-(2-sulphoethyl)-5-(3 or 4-amino-4 or 3sulphophenyl)phenazinium hydroxide.

In class (xiii) 3,1 0-diamino-6,1 3-dichlorotriphendioxazine-4,1 1 -disulphonic acid 3,1 0-bis(4'-amino-3'-sulphoanilino)-6,13-dichlorotriphendioxazine-4,1 1 -disulphonic acid 3,1 0-bis-(4'-amino-2',5'-disu lphoanilino)-6,1 3-dichlorotriphendioxazine-4,1 1 -disulphonic acid 3-(4'-amino-3'-sulphoanilino)-1 0-(4'-amino-2',5'-disulphoanilino)-6,1 3-dichlorntriphendioxazine4,1 1 - disulphonic acid 3,1 0-di-(2'-aminoethylamino)-6,1 3-dichlorotriphendioxazine-4,1 1 -disulphonic acid 3,1 0-bis-(3'-amino-4'-sulphoanilino)-6,1 3-dichlorotriphendioxazine-4,1 1 -disulphonic acid.

In some instances the dyebase of formula (6) in which D is of the form D1 - Y - NH with D' as an azo chromophore and Y as

may be obtained by reacting a coupling component or diazotisable amine bearing a NRH group with cyanuric chloride and the amine of formula (7) and subjecting the resulting compound to appropriate diazotisation/coupling reactions to form an azo compound.

For example H acid may be reacted with cyanuric chloride followed by the amine of fomula (7). This product is then converted to a dyebase of formula (6) by coupling with a diazonium salt from an aromatic amine e.g. such as ANH2 described above or additionally amines which will only couple ortho to the OH group in H acid.

Alternatively, for example cyanuric chloride may be reacted with one of the amino groups in a diamine such as a phenylene diamine sulphonic acid and then with the amine of formula (7). This intermediate may be diazotised and coupled on to any conventional coupling component e.g. J acid to form a dyebase of formula (6).

Where a reaction with Z1 H is necessary for the dyebases of formula (6) where Z is other than CI, this may be carried out immediately before or after the coupling reaction.

The dyestuffs of the present invention are represented e.g. in formula (1) as in their free acid form and may be isolated and used as such. However it is often preferable to isolate and use them with any acid groups partially or totally in the form of salts e.g. Na, K or NH4 salts.

The isolation from the manufacturing processes may be by any convenient method e.g. salting out or spray drying.

It may be found desirable to take steps to minimise the hydrolysis of the chlorine atoms on the triazine nuclei of dyestuffs of formula (1 ) which can occur during storage of the dyestuff or in dyebaths or printing pastes containing the dyestuff. A convenient means of effecting this stabilisation is to mix with the dyestuff certain compositions which tend to keep the pH in the region of 4-7 especially 6 to 7 e.g. mixtures of alkali metal acid phosphates and mixtures of alkali metal N,N-diethylaminobenzene sulphonate and the corresponding free sulphonic acid. Mixtures of the dyestuffs of formula (1 ) and a stabiliser which reduces its tendency to hydrolysis are a further feature of the invention.

The dyestuffs of the present invention may be used for colouring a wide range of materials containing hydroxyl or amino groups, e.g. wool, silk, polyamide and natural or regenerated cellulose, for example, cotton or viscose rayon materials, by the conventional methods used for colouring such materials with water-soluble reactive dyes, e.g. in the case of cellulose they are preferably applied in conjunction with a treatment with an acid-binding agent, e.g. caustic soda, sodium carbonate, phosphate, silicate or bicarbonate, which may be applied to the cellulose textile materials before, during or after the application of the dyestuff.

The process of colouration with the dyestuff of the present invention and textile materials so coloured are further features of the present invention.

The dyestuffs of the present invention are usually characterised by having a good rate of reaction with cellulose substrates e.g. dyeings may be carried out at40 C or below and, in contrast to many dichlorotriazinyl dyes, give coloured material having good resistance to "acid bleeding".

Additionally the new dyestuffs also have a high degree of fixation and are particularly valuable in dyeing by pad-batch methods. Also some of the new dyes show good discharge properties.

The invention is illustrated by the following Examples.

Example 1 A solution of 7.0 g of cyanuric chloride in 70 g of acetone was added dropwise during 15 minutes to a well stirred solution of 13.8 g of 1-amino-8-hydroxy-7-[1 '-sulpho-2'-naphthylazo]-naphthalene-3,6-disulphonic acid in 500 g of water at 0-5 C and pH 6-7. The mixture was stirred at 0-5"C for 2 hours maintaining the pH at 6-7 by addition of 2N sodium carbonate solution as required. 11.55 g of 1-(4'-amino-2'-sulphophenyl)piperazine was added and the mixture was heated to 25"C. The pH of the mixture fell slowly to 4.0 and was maintained at 4-5 by addition of 2N sodium carbonate solution as required. After stirring at 25"C and pH 4-5 for 2 hours reaction was complete and the product isolated by filtration.

A solution of 16.75 g of the dyebase prepared above in 900 g of water at pH 12.0 was added dropwise to a stirred suspension of 4.7 g of cyanuric chloride in 50 g of ice and 50 g of water. The pH of the mixture was maintained at 8-9 by addition of 2N sodium carbonate solution as required and the mixture stirred at 0-5"C for 1 hour after the addition was complete. The pH of the solution was finally adjusted to 6.5 with dilute hydrochloric acid and the condensation product precipitated by addition of sodium chloride. The product was isolated by filtration, intimately mixed with 2 g of sodium diethylametanilate and dried under vacuum at room temperature.

When applied to cellulose textiles in conjunction with an acid binding agent the dyestuff gave bluish red shades with good fastness to washing treatments and good resistance to acid treatments.

Further examples of the invention were prepared by coupling the diazotised amine in colunn II of Table I with the coupling component in column Ill and condensed successively with cyanuric chloride, 1-[4'-amino-2'-sulphophenyl]piperazine and cyanuric chloride in the manner described in Example 1. In the indicated cases it is necessary, after coupling, to hydrolyse the acetylamino group to a free amino group prior to reaction with the first molecule of cyanuric chloride. The shade of the derived dyes are recorded in column IV.

TABLE I I II III IV Example Diazo Component Coupling Component Shade on Cellulose 2 2-naphthylamine-3,6,8 trisulphonic acid m-ureidoaniline Reddish-yeilow 3 4-acetylaminoaniline-2- 1-[4'-sulphophenyl]-3 sulphonic acid * carboxy-5-pyrazolone Orange 4 2-naphthylamine-1,5- 1-[3'-amino-2'-methyl disulphonic acid 5'-sulphophenyl]-3 carboxy-5-pyrazolone Yellow 5 2-naphthylamine-4,8 disulphonic acid m-acetylaminoaniline Reddish-yellow 6 2-naphthylamine-6,8 disulphonic acid 2-methoxy-5-methylaniline Reddish-yellow 7 4-nitro-4'-aminostilbene 2,2'-disulphonic acid m-toluidine Reddish-yellow 8 aniline-2,4-disulphonic 1,3-diaminobenzene-4 acid sulphonic acid Reddish-yellow 9 2-naphthylamine-1 ,5,7- 1-aminoethyl-3-cyano-4- trisulphonic acid methyl-6-hydroxypyrid-2-one Greenish-yellow 10 2-naphthylamine-1 5- 1-aminoethyl-3-carbonamido- disulphonic acid 4-methyl-6-hydroxypyrid-2-one Greenish-yellow 11 aniline-2,5-disulphonic 1-aminoethyl-4-methyl-6- acid hydroxypyrid-2-one Greenish-yellow 12 3-acetylaminoaniline-6- 1 -ethyl-3-carbonaminido-4- sulphonic acid * methyl-6-hydroxypyrid-2-one Greenish-yellow 13 3-acetylaminoaniline-6- 1 -ethyl-3-su Ipho-4-methyl- sulphonic acid * 6-hydroxypyrid-2-one Greenish-yellow 14 orthanilic acid 2-amino-5-hydroxy naphthalene-7-sulphonic acid Orange 15 2-naphthylamine-1 5- 2-N-methylamino-5-hydroxy disulphonic acid naphthalene-7-sulphonic acid Orange 16 4-methoxyaniline-2 2-N-methylamino-5-hydroxy sulphonic acid naphthalene-7-sulphonic acid Scarlet 17 2-naphthylamine-1,5- 2-amino-8-hydroxy disulphonic acid naphthalene-6-sulphonic acid Red TABLE I (Continued) I 111 IV Example Diazo Component Coupling Component Shade on Cellulose 18 6-nitro-2-aminonaphthalene- 1-amino-8-naphthol-3,6- 4,8-disulphonic acid disulphonic acid Bluish-red 19 6-acetylamino-2-amino naphthalene-4,8-disulphonic acid * 2-naphthol-6-sulphonic acid Orange 20 2-naphthol-3,6-disulphonic acid Red * hydrolysed after coupling.

Examples 21 and 22 A solution of 10.7 g of 1-amino-8-naphthol-3,6-disulphonic acid in 200 g of water at pH 7.0 was added dropwise to a suspension of 6.8 g of cyanuric chloride in 100 g of water and 70 g of acetone at 0-5"C. The mixture was stirred at 0-50C for 1 hour and then 8.6 g of 1 [4'-amino-2'-sulphophenyl]-piperazine was added.

After stirring the mixture at pH 1-2 and 250for 15 minutes the pH was raised to 3-4 by addition of 2N sodium carbonate solution as required. The solution was stirred for a further 1 hour at 25"C maintaining the pH at 3-4 by addition of 2N sodium carbonate solution as necessary.

A solution of 10.1 g of 2-naphthylamine-1,5-disulphonic acid in 200 g of water at pH 7.0 and 0-5"C, was acidified by addition of 10 g of hydrochloric acid solution [36 Tw]. The suspension was diazotised by the gradual addition of 17 g of 2N sodium nitrite solution. The diazotised amine was added to the coupling component prepared above and the mixture stirred at 0-5"C and pH 6-7 for 2 hours when coupling was complete. The monoazo compound was precipitated by addition of potassium chloride, isolated by filtration, and dried at 40 C.

A solution of 24.95 g of the monoazo compound prepared above in 400 g of water at 10 C and pH 6-7 was added to a suspension of 5 g of cyanuric chloride in 50 g of ice, 50 g of water and 50 g of acetone at 0-5"C. The mixture was stirred at 0-5"C for 1 hour maintaining the pH at 8-9 by addition of 2N sodium carbonate solution as required. The pH of the solution was finally adjusted to 6.5 with dilute hydrochloric acid and the product precipitated by addition of sodium chloride. The product was isolated by filtration, intimately mixed with 2 g sodium diethylmetanilateand dried undervacuum at room temperature.

When applied to cellulose textiles in conjunction with an acid binding agent the dyestuff gave red shades with good fastness to washing treatments and good fastness to acid treatments.

In place of the 2-naphthylamine-1,5-disulphonic acid used above there may be used an equivalent amount of 2-aminobenzene sulphonic acid (Example 22) which gives red shades with good fastness to washing and acid treatments when applied to cellulose textiles as above.

Example 23 A solution of 41.6 parts of 5-amino-2-chlorobenzene sulphonic acid in 300 parts of water at 0-5"C was acidified with 60 parts of hydrochloric acid (360tow). The mixture was stirred at 0-5"C and diazotised by the gradual addition of 100 parts of 2N sodium nitrite solution.

A solution of 63.8 parts of 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid in 300 parts of water at 10"C and pH 6.5 was added dropwise to the diazo compound above, maintaining the pH at 2-3 by addition of sodium acetate as required. The mixture was stirred at 1 00C, pH 2-3 for 18 hours. The monoazo compound was isolated by filtration and dried.

A solution of 5.14 parts of 1 -(4'-amino-2'-sulphophenyl) piperazine in 100 parts of water and 6 parts of hydrochloric acid (360tow) at 0-5"C was diazotised by the gradual addition of 10 parts of 2N sodium nitrite solution. The diazotised amine was then added to a solution of 10.75 parts of the monoazo compound prepared above in 200 parts of water at 0-5"C and pH 7.0. The mixture was stirred for 2 hours at 0-5"C and pH 6-7 when coupling was complete. The disazo compound was isolated by addition of sodium chloride and filtration.

A suspension of 2.83 parts of cyanuric chloride was stirred in 50 parts of ice and 50 parts of water and a solution of 11.0 parts of the diazo compound prepared above dissolved in 400 parts of water at 10 C and pH 7.0 was added dropwise. The pH of the mixture was maintained at 8-9 by addition of 2N sodium carbonate solution as required and stirred at 0-1-"C for 2 hours. The pH of the solution was finally adjusted to 6.5 with 2N hydrochloric acid and the dyestuff precipitated by addition of sodium chloride and isolated by filtration.

The product was mixed with 2 parts of sodium diethyl metanilate and dried under vacuum at room temperature.

When applied to cellulose textiles the dyestuff gave navy blue shades with good fastness to washing treatments and good resistance to acid treatments.

Examples 24-29 Following the procedure of Example 7 with the 5-amino-2-chlorobenzene sulphonic replaced by an equivalent amount of the amines listed below, further blue reactive dyes were obtained.

Example 24 3-amino-4-chlorobenzene sulphonic acid Example 25 4-amino-2,5-dichlorobenzene sulphonic acid Example 26 2-aminobenzene sulphonic acid Example 27 2-amino-4-methylbenzene sulphonic acid Example 28 2-naphthylamine-1 ,5-disulphonic acid Example 29 4-aminobenzene sulphonic acid.

When applied to cellulose textiles all the dyes gave navy blue shades with good fastness to washing treatments and good resistance to acid treatments.

Examples 30-41 Further examples of the invention can be found in Table II when the dyebase in column II is reacted successively with cyanuric chloride, 1 [4'-amino-2'-sulphophenyl]piperazine and cyanuric chloride by the procedure described in Example 1.

TABLE I 11 111 Example Dyebase Shade on Cellulose 30 1-amino-4-(3'-amino-2',4',6'-trimethylanilino)anthraquinone 2,5'-disuiphonic acid Reddish-blue 31 1-amino-4-(4'-aminoanilino)anthraquinone-2,2'-disulphonic acid Reddish-blue 32 The copper complex of 8-amino-1-hydroxy-2-(2'-hydroxy-5'- sulphophenylazo)naphthalene-3,6-disulphonic acid Blue 33 The copper complex of 6-amino-1-hydroxy-2-[4'-(2",5"- disulphophenylazo)-2'-methoxy-5'-methylphenylazojnaphthalene- 3,5-disulphonic acid Blue 34 3-(3'-amino-4'-sulphophenyl)sulphamyl copper phthalocyanine tri-3-sulphonic acid Turquoise 35 3-(3'-amino-4'-sulphophenyl)sulphamyl copper phthalocyanine tri-4-sulphonic acid Turquoise 36 The copper complex of N-(2-hydroxy-5-sulpho-3-aminophenyl) N'-(2'-carboxy-4'-sulphophenyl)-ms-phenylformazan Blue 37 The copper complex of N-(2-hydroxy-5-sulphophenyl)-N' (2'-carboxy-4'-aminophenyl)-ms-(2"-chloro-5"-sulphophenyl) formazan Blue TABLE II (Continued) I II III Example Dyebase Shade on Cellulose 38 Anhydro-3-(4-amino-3-sulphoanilino)-7-N-ethyl-N (3-sulphobenzylamino)-5-(3-sulphophenyl)phenazium hydroxide Reddish-blue 39 Anhydro-5-(4-amino-2,5-disulphoanilino)-9-diethylamino-7 phenyl-1 0-sulphobenz[a]phenazium hydroxide Reddish-blue 40* 3,1 0-bis-(4'-amino-3'-su lphoanilino)-6,1 3-dichloro triphendioxazine-4,1 1 -disulphonic acid Blue 41 * 3,1 0-di-(2'-aminoethylamino)-6,1 3-dichlorotriphenodioxazine- 4,11-disulphonic acid Reddish-blue * both amino groups reacted.

Claims (1)

1. Reactive dyestuffs of the formula:

wherein D is a group confering chromophoric properties.