Fibre-reactive azo dyestuffs containing a halotriazinyl radical and a non-reactive triazinyl radical

Azo dyes of the formula ##STR1## wherein D is benzene, naphthalene, benzoylaminobenzene, azobenzene or stilbene, which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenoxy, alkanoylamino of 1 to 6 carbon atoms, benzoylamino, amino, alkylamino of 1 to 4 carbon atoms, phenylamino, alkoxycarbonyl of 1 to 5 carbon atoms, alkylcarbonyl of 1 to 5 carbon atoms, nitro, cyano, acetyl, carbamoyl, ureido, hydroxy, carboxy, halogen or sulfo, and which contains a dihalo-s-triazinylamino or a monohalo-s-triazinylamino radical substituted by an alkyl, aryl, alkylthio, arylthio, hydroxy, alkoxy, aryloxy, -NH.sub.2, alkylamino, arylamino or heterocyclic amino group, wherein the halo-s-triazinylamino radical is bonded directly or via methylene to a ring carbon of D, and the amino group, by which the halo-s-trazinyl radical is bonded to a carbon atom in D is optionally substituted at the nitrogen atom by C.sub.1-4 -alkyl or -sulfoalkyl, R is hydrogen or alkyl of 1 to 4 carbon atoms, and R.sub.1 and R.sub.2, independently of one another, have the same meaning as those substituents referred to above of monohalo-s-triazinyl radicals in D; or a heavy metal complex thereof, are especially suitable for dyeing cotton fabric according to the exhaustion dyeing method and produce dyeings which have good fastness properties.

The present invention relates to azo dyes of the formula 
##STR2## 
in which D is the radical of an aromatic diazo component, which can have 
additional substituents and can itself contain an azo bridge, and which 
contains a halo-s-triazinylamino group, R is hydrogen or alkyl having 1 to 
4 carbon atoms and R.sub.1 and R.sub.2, independently of one another, are 
unreactive substituents. 
The radical D is an aromatic radical which can itself contain an azo group, 
or is a radical which is derived from a compound of the anthraquinone, 
nitroaryl, phthalocyanine or stilbene series, or the like. In particular, 
D is a radical of the benzene or naphthalene series. 
The radical D can contain the substituents conventionally present in azo 
dyes. In particular, the radical D contains sulfonic acid groups. Examples 
of substituents, additional to these, which the radical D can contain are 
alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, 
isopropyl, butyl, isobutyl, sec.-butyl and tert.-butyl, alkoxy groups 
having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, 
butoxy, isobutoxy, sec.-butoxy and tert.-butoxy, phenoxy, acylamino groups 
having 1 to 6 carbon atoms, such as acetylamino, propionylamino and 
benzoylamino, amino groups, such as --NH.sub.2, methylamino, ethylamino 
and phenylamino, carboxylic acid ester groups, such as methoxycarbonyl and 
ethylcarbonyl, the nitro, cyano, acetyl, carbamyl, ureido, hydroxyl and 
carboxyl groups, and halogen, such as fluorine, chlorine and bromine. 
If the radical D contains complex-forming groups, such as hydroxyl, 
carboxyl, amino and sulfo, in the o-position to the azo group, the heavy 
metal complexes of the azo dyes of the formula (1) also form part of the 
invention. 
Preferred complex-forming heavy metals are chromium, cobalt, nickel, 
copper, iron and manganese. 
The radical D contains a halo-s-triazinylamino group. This can be a 
dihalo-s-triazinyl group, for example 2,4-difluoro-, 2,4-dichloro- and 
2,4-dibromo-s-triazinyl-6-amino or a monohalo-s-triazinyl group, for 
example 4-fluoro-, 4-chloro- and 4-bromo-s-triazinyl-6-amino, which are 
substituted in the 2-position by an aryl or alkyl radical, for example a 
phenyl, methyl or ethyl radical, or by the radical of an aliphatic or 
aromatic mercapto compound, bonded via the sulfur atom, or the hydroxyl 
compound, bonded via the oxygen atom, or especially by a --NH.sub.2 group, 
or the radical of an aliphatic, heterocyclic or aromatic amino compound, 
bonded via the nitrogen atom. 
The amino group, by which the halo-s-triazinyl radical is bonded to a 
carbon atom in D can be substituted at the nitrogen atom, for example by 
alkyl, such as methyl or ethyl, or sulfoethyl. The halo-s-triazinylamino 
group can be bonded directly to an aromatic carbon atom in D, or can be 
bonded thereto via an alkylene group, for example a methylene group. 
The substituent R in formula (1) can be methyl, ethyl, propyl, isopropyl, 
butyl, isobutyl, sec.-butyl or tert.-butyl or, preferably, hydrogen. 
Suitable unreactive substituents R.sub.1 and R.sub.2 are the same radicals 
as those referred to above as substituents in the 2-position of 
monohalo-s-triazinyl radicals in D, ie. aryl and alkyl radicals, such as 
phenyl, methyl and ethyl, or radicals of aliphatic or aromatic mercapto 
compounds, bonded via the sulfur atom, or of hydroxyl compounds, bonded 
via the oxygen atom, or, in particular, the --NH.sub.2 group or radicals 
of aliphatic, aromatic or heterocyclic amino compounds, bonded via the 
nitrogen atom. 
Preferred azo dyes are those of the formula 
##STR3## 
in which D.sub.1 is a benzene or naphthalene radical which can be 
substituted further, X is a fluoro-s-triazinyl or chloro-s-triazinyl 
group, R.sub.3 is hydrogen or alkyl having 1 to 4 carbon atoms, R is 
hydrogen or alkyl having 1 to 4 carbon atoms and R.sub.1 and R.sub.2, 
independently of one another, are unreactive substituents. 
The benzene or naphthalene radical D.sub.1 can be substituted further, for 
example by the substituents mentioned above as possible substituents of D 
in formula (1). 
Especially preferred azo dyes of the formula (2) are those in which X is a 
monofluoro-s-triazinyl or monochloro-s-triazinyl group, R.sub.3 is 
hydrogen or methyl, R is hydrogen or methyl, and R.sub.1 and R.sub.2, 
independently of one another, are unsubstituted or substituted hydroxyl or 
amino groups. 
Other preferred azo dyes are those of the formula 
##STR4## 
in which D.sub.1 is a sulfobenzene radical, a sulfobenzene-CH.sub.2 -- 
radical, which can be substituted by methoxy, or a 
sulfonaphthalene-CH.sub.2 -- radical, Y is fluorine or chlorine, Z is 
amino, C.sub.1-4 -alkylamino or N,N-di-C.sub.1-4 -alkylamino, in which the 
alkyl radicals can be substituted by hydroxyl or sulfo, or is 
cyclohexylamino, or is phenylamino which can be substituted in the phenyl 
nucleus by methyl, methoxy, ethoxy, chlorine, carboxyl, sulfo, 
.beta.-sulfatoethylsulfonyl, acetylamino, oxaloamino or ureido, or is 
morpholino, benzthiazolyl-2-amino, thiazolyl-2-amino or 
4-methyl-5-sulfobenzthiazolyl-2-phenylamino, or is N--C.sub.1-2 
-alkyl-N-phenylamino, in which the alkyl radical can be substituted by 
hydroxyl, or is C.sub.1-4 -alkoxy or C.sub.1-2 -alkoxy-C.sub.1-2 -alkoxy, 
R.sub.3 is hydrogen or methyl, R is hydrogen or methyl and R.sub.1 and 
R.sub.2, independently of one another, are hydroxyl, methoxy, isopropoxy, 
phenoxy, amino, .beta.-hydroxyethylamino, N,N-di-.beta.-hydroxyethylamino, 
.beta.-sulfoethylamino, .beta.-carboxyethylamino, 
N-methyl-N-.beta.-sulfoethylamino, phenylamino, sulfophenylamino, 
carboxyphenylamino, sulfo-carboxyphenylamino, N-methyl-N-phenylamino or 
morpholino. 
An important sub-group of the azo dyes of the formula (3) comprises the azo 
dyes of the formula 
##STR5## 
in which Y, Z, R.sub.1 and R.sub.2 are as defined for formula (3). 
Amongst the azo dyes of the formula (4), those of the formula 
##STR6## 
in which Y and Z are as defined for formula (4), are of particular 
importance. Preferably, Y in formula (5) is fluorine. 
Valuable dyes having the structure defined by formula (5) are those of the 
formulae 
##STR7## 
Since the azo dyes of the formula (1) contain a halo-s-triazinylamino group 
in the radical D, they are reactive. 
Reactive or fibre-reactive radicals are to be understood as meaning 
radicals which are able to react with the hydroxyl groups of cellulose, or 
with the amino groups of natural or synthetic polyamides, to form covalent 
chemical bonds. 
To prepare an azo dye of the formula (1), a diazotized diazo component of 
the formula 
EQU D--NH.sub.2, (7) 
a coupling component of the formula 
##STR8## 
a trihalo-s-triazine of the formula 
##STR9## 
and the compounds of the formulae 
EQU R.sub.1 --H (10) 
and 
EQU R.sub.2 --H (11) 
are coupled, and condensed, with one another and a halo-s-triazinyl radical 
is introduced into the radical D, which must still contain an amino group 
capable of acylation. 
If the radical D of the diazo components of the formula (7) contains a 
complex-forming group in the ortho-position to the --NH.sub.2 group, the 
azo dyes obtained can be reacted with heavy metal donors. 
Preferred diazo components of the formula (7) are those of the benzene 
series or naphthalene series. 
Since the individual process steps referred to above, namely coupling and 
multiple condensation, can be carried out in different sequences and, 
where appropriate, can in part also be carried out simultaneously, a 
plurality of embodiments of the process are feasible. The starting 
materials to be used for each component reaction follow from formula (1). 
In general, the reaction is carried out in stepwise succession, the 
sequence of the simple reactions between the individual reactants of the 
formulae (7) to (11) and the halo-s-triazine, which is being introduced 
into the radical D, being optional. 
The following are the most important embodiments of the process: 
1. A coupling component of the formula (8) is condensed with a 
trihalo-s-triazine of the formula (9), the resulting primary condensation 
product is coupled with a diazotised diazo component of the formula (7), 
the monoazo compound is condensed with the compounds of the formulae (10) 
and (11), and the resulting condensation product is condensed with a 
dihalo-s-triazine or trihalo-s-triazine, after which a halogen atom of the 
triazine can be replaced by an unreactive substituent by condensation with 
a compound which contains easily detachable hydrogen. 
2. A compound which contains easily detachable hydrogen, a 
trihalo-s-triazine and a diazo component of the formula (7) are condensed 
and the secondary condensation product is diazotised and is coupled with 
the tertiary condensation product obtained from a coupling component of 
the formula (8), a trihalo-s-triazine of the formula (9) and the compounds 
of the formulae (10) and (11). 
3. A coupling component of the formula (8) is condensed with a 
trihalo-s-triazine of the formula (9), the primary condensation product is 
condensed with the compounds of the formulae (10) and (11), the resulting 
condensation product is coupled with a diazotised diazo component of the 
formula (7) and the monoazo compound is condensed with a dihalo-s-triazine 
or a trihalo-s-triazine, after which a halogen atom of the triazine can be 
replaced by an unreactive substituent by condensation with a compound 
which contains easily detachable hydrogen. 
If the halo-s-triazinyl group to be introduced into the radical of the 
diazo component is to be a fluoro-s-triazinyl group, it is advantageous 
first to proceed as above, then to isolate the monoazo compound, 
redissolve this in an aqueous alkaline solution, for example a sodium 
hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide or 
sodium carbonate solution, react it with cyanuric fluoride and then, if 
desired, replace a fluorine atom on the triazine radical by an unreactive 
substituent by condensation with a compound which contains easily 
detachable hydrogen. 
Suitable compounds which contain easily detachable hydrogen are, in 
particular, hydroxyl, mercapto and amino compounds. 
In the preferred process for the preparation of the compounds of the above 
formulae (6) and (6a), 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid is 
condensed with cyanuric chloride, the primary condensation product is 
condensed with morpholine, the secondary condensation product is coupled 
with diazotised 1-amino-3-acetylaminobenzene-6-sulfonic acid, the residual 
chlorine atom on the triazine is replaced by hydroxyl by means of 
hydrolysis, the acetyl group is detached by saponification and the 
resulting amino compound is condensed with cyanuric fluoride and lastly 
with ethanolamine or o-toluidine. 
In accordance with the method of preparation described above, the azo dyes 
of the formula (1) can be prepared by using diazo components or coupling 
components which already contain reactive radicals. 
In many cases, however, it is also possible to introduce reactive radicals 
subsequently into the azo dyes of the formula (1). This can be done after 
coupling or, where relevant, after metallisation. The reactive radical is 
introduced by acylating the diazo component, which in addition to the 
amino group to be diazotised contains a further amino group which can be 
acylated or a group which can be converted, for example by reduction or 
hydrolysis, into an amino group which can be acylated, such as the nitro 
group or the acetylamino group or, where the reactive radical is 
introduced subsequently, by acylating the corresponding aminoazo dye which 
contains an amino group which can be acylated. 
In a further embodiment, the azo dyes of the formula (1) can be obtained by 
carrying out the coupling with a coupling component of the formula (8) and 
subjecting the condensable --N(R)H group, in the coupling component, to 
condensation with a compound of the formula 
##STR10## 
In the examples which follow, the preparation of the intermediates is not 
described in every case, but the method by which they are prepared follows 
directly from what has been stated above. 
Examples of starting materials which can be used to prepare the azo dyes of 
the formula (1) are: 
DIAZO COMPONENTS OF THE FORMULA (7) 
1,3-Diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-4,6-disulfonic acid, 
1,4-diaminobenzene-2-sulfonic acid, 1,4-diaminobenzene-2,5- or 
-2,6-disulfonic acid, 1,4-diamino-2-chlorobenzene-5-sulfonic acid, 
1,4-diamino-2-methylbenzene-5-sulfonic acid, 
1,3-diamino-4-methylbenzene-6-sulfonic acid and their monoacetyl 
derivatives, 3-(3'- or 4'-aminobenzoylamino)-1-aminobenzene-6-sulfonic 
acid, 1-(4'-aminobenzoylamino)-4-aminobenzene-2,5-disulfonic acid, 
4-nitro-2-aminophenol-6-sulfonic acid, 
2,6-diaminonaphthalene-4,8-disulfonic acid, 
1-amino-4-methoxy-5-aminomethyl-benzene-6-sulfonic acid, 
2-amino-5-aminomethyl-naphthalene-1-sulfonic acid, 
4-amino-4'-acetylamino-azo-benzene-3-sulfonic acid, 
4-amino-4'-nitrostrilbene-2,2'-disulfonic acid and 
1-amino-3-N-methylaminomethyl-benzene-6-sulfonic acid. 
COUPLING COMPONENTS OF THE FORMULA (8) 
1-Amino-8-naphthol-3,6-disulfonic acid, 1-amino-8-naphthol-4,6-disulfonic 
acid, 2-amino-5-naphthol-7-sulfonic acid, 
1-amino-8-naphthol-2,4-disulfonic acid, 1-amino-8-naphthol-4-sulfonic 
acid, 2-amino-8-naphthol-6-sulfonic acid, 2-amino-6-naphthol-8-sulfonic 
acid, 1-amino-5-naphthol-7-sulfonic acid, 
2-amino-8-naphthol-3,6-disulfonic acid, 2-amino-5-naphthol-7,1-disulfonic 
acid, 2-N-methylamino-5-naphthol-7-sulfonic acid and 
2-N-methylamino-8-naphthol-6-sulfonic acid. 
TRIHALO-S-TRIAZINES OF THE FORMULA (9) 
Cyanuric fluoride, chloride and bromide. 
COMPOUNDS OF THE FORMULAE (10) AND (11) 
Ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, 
isopropylamine, butylamine, dibutylamine, isobutylamine, sec.-butylamine, 
tert.-butylamine, hexylamine, methoxyethylamine, ethoxyethylamine, 
methoxypropylamine, chloroethylamine, hydroxyethylamine, 
dihydroxyethylamine, hydroxypropylamine, aminoethanesulfonic acid, 
.beta.-sulfatoethylamine, benzylamine, cyclohexylamine, aniline, o-, m- 
and p-toluidine, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- and 3,5-dimethylaniline, o-, 
m- and p-chloroaniline, N-methylaniline, N-ethylaniline, 
N-.beta.-hydroxyethylaniline, 3- and 4-acetylaminoaniline, o-, m- and 
p-nitroaniline, o-, m- and p-aminophenol, 2-methyl-4-nitroaniline, 
2-methyl-5-nitroaniline, 2,5-dimethoxyaniline, 3-methyl-4-nitro-aniline, 
2-nitro-4-methylaniline, 3-nitro-4-methylaniline, o-, m- and p-anisidine, 
o-, m- and p-phenetidine, naphthyl-1-amine, naphthyl-2-amine, 
2-amino-1-hydroxynaphthalene, 1-amino-4-hydroxynaphthalene, 
1-amino-8-hydroxynaphthalene, 1-amino-2-hydroxynaphthalene, 
1-amino-7-hydroxynaphthalene, orthanilic acid, metanilic acid, sulfanilic 
acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, 
anthranilic acid, m- and p-aminobenzoic acid, 2-aminotoluene-4-sulfonic 
acid, 2-aminotoluene-5-sulfonic acid, p-aminosalicyclic acid, 
1-amino-4-carboxy-benzene-3-sulfonic acid, 
1-amino-2-carboxy-benzene-5-sulfonic acid, 
1-amino-5-carboxybenzene-2-sulfonic acid, naphthyl-1-amine-2-, -3-, -4-, 
-5-, -6-, -7- and -8-sulfonic acid, naphthyl-2-amine-1-, -3-, -4-, -5-, 
-6-, -7- and -8-sulfonic acid, naphthyl-1-amine-2,4-, -2,5-, -2,7-, -2,8-, 
-3,5-, -3,6-, -3,7-, -3,8-, -4,6-, -4,7-, -4,8- and -5,8-disulfonic acid, 
naphthyl-2-amine-1,5-, -1,6-, -1,7-, -3,6-, -3,7-, -4,7-, -4,8-, -5,7- and 
-6,8-disulfonic acid, naphthyl-1-amine-2,4,6-, -2,4,7-, -2,5,7-, -3,5,7-, 
-3,6,8- and -4,6,8-trisulfonic acid, naphthyl-2-amine-1,3,7-, -1,5,7-, 
-3,5,7-, -3,6,7-, -3,6,8- and -4,6,8-trisulfonic acid, 2-, -3- and 
4-aminopyridine, 2-aminobenzthiazole, 5-, 6- and 8-aminoquinoline, 
2-aminopyrimidine, morpholine, piperidine, piperazine, water, methanol, 
ethanol, propanol, isopropanol, n-butanol, isobutanol, sec.-butanol, 
tert.-butanol, hexanol, cyclohexanol, .beta.-methoxyethanol, 
.beta.-ethoxyethanol, .gamma.-methoxypropanol, .gamma.-ethoxypropanol, 
.beta.-ethoxy-.beta.-ethoxyethanol, glycollic acid, phenol, o-, m- and 
p-chlorophenol, o-, m- and p-nitrophenol, o-, m- and p-hydroxybenzoic 
acid, o-, m- and p-phenolsulfonic acid, phenol-2,4-disulfonic acid, 
.alpha.-naphthol, .beta.-naphthol, 1-hydroxynaphthalene-8-sulfonic acid, 
2-hydroxynaphthalene-1-sulfonic acid, 1-hydroxynaphthalene-5-sulfonic 
acid, 1-hydroxynaphthalene-4-sulfonic acid, 1-hydroxynaphthalene-6- and 
-7-sulfonic acid, 2-hydroxynaphthalene-6-, -7- and -8-sulfonic acid, 
2-hydroxynaphthalene-4-sulfonic acid, 2-hydroxynaphthalene-4,8- and 
-6,8-disulfonic acid, 1-hydroxynaphthalene-4,8-disulfonic acid, 
2-hydroxynaphthalene-3,6-disulfonic acid, methanethiol, ethanethiol, 
propanethiol, isopropanethiol, n-butanethiol, thioglycollic acid, 
thiophenol, .alpha.-thionaphthol and .beta.-thionaphthol. 
Examples of compounds which can be used as acylating agents for introducing 
a halo-s-triazine radical into the radical D are 2,4,6-trichloro, 
2,4,6-tribromo- and 2,4,6-trifluoro-s-triazine, and 4,6-dichloro-, 
4,6-dibromo- and 4,6-difluoro-s-triazines, which are substituted in the 
2-position by an aryl or alkyl radical, for example a phenyl, methyl or 
ethyl radical, or by the radical of an aliphatic or aromatic mercapto 
compound, bonded via the sulfur atom, or of a hydroxyl compound, bonded 
via the oxygen atom, or especially by a --NH.sub.2 group or by the radical 
of an aliphatic, heterocyclic or aromatic amino compound, bonded via the 
nitrogen atom. 
The 2-substituted 4,6-dihalo-s-triazines are obtained, for example, by 
reacting a trihalo-s-triazine with the amino, hydroxy or mercapto 
compounds mentioned above. 
The substituent in the 2-position of the triazine radical can also be 
introduced after coupling or after metallising. Accordingly, for example, 
one of the amino, hydroxy or mercapto compounds mentioned above can be 
subsequently condensed with a dihalo-s-triazine radical which is already 
bonded to the azo dye of the formula (1). This possibility must also be 
considered, inter alia, in the process for the preparation of the azo dyes 
of the formula (1), described above. 
The compounds, containing easily detachable hydrogen, which have been 
mentioned above are in particular to be understood as meaning compounds 
which contain reactive hydrogen bonded via a hetero-atom. Suitable 
compounds of this type are, in particular, the amino, hydroxy and mercapto 
compounds mentioned above. 
Examples of aminoazo dyes, into which the reactive radicals can be 
introduced after coupling, are the coupling products of the diazo 
components of the formula (7), mentioned above, with coupling components 
of the formula (8). 
Further important azo dyes of the formula (1) are those which possess a 
monohalotriazine radical which is bonded via an amino group and which in 
addition to the halogen atom contains an amino group bonded to the 
triazine ring, a further reactive radical, in particular a halotriazine 
radical, being bonded to this amino group. If the second, additional 
reactive radical is a halotriazine radical, it is preferably bonded to the 
first triazine radical via the radical of an alkylenediamine or 
arylenediamine. The fibre-reactive amino group which is present, 
additionally to the halogen atom, on the monohalotriazine radical 
accordingly preferably has the structure 
##STR11## 
in which R.sub.4 and R.sub.5 are hydrogen or alkyl having 1 to 4 carbon 
atoms, A.sub.1 is an alkylene or arylene radical, Z.sub.1 is a halogen 
atom, for example a fluorine, chlorine or bromine atom, and Z.sub.2 is a 
halogen atom or an amino, alkoxy, aryloxy, alkylthio or arylthio group. 
A.sub.1 can be a relatively short-chain or relatively long-chain alkylene 
radical, for example an ethylene or hexylene radical, but is preferably a 
benzene radical, for example an m- or p-phenylene radical, and especially 
a phenylenesulfonic acid radical. Examples of amino, alkoxy, aryloxy, 
alkylthio or arylthio groups Z.sub.2 are the radicals of the amino, 
hydroxy and mercapto compounds mentioned above. 
In a particular embodiment, Z.sub.2 in formula (13) is identical with the 
chromogenic radical of the azo dye of the formula (1). 
The condensation of 2,4,6-trihalo-s-triazines with diazo components and 
coupling components, and with amino, hydroxy and mercapto compounds, is 
preferably carried out in aqueous solution or suspension, at a low 
temperature and at an acidic, neutral or slightly alkaline pH, under 
conditions such that in the finally obtained azo dye of the formula (1) 
there remains, as a detachable radical, a halogen atom of the triazine 
ring present in the radical D. Advantageously, the hydrogen halide set 
free during the condensation is neutralised continuously by addition of 
aqueous alkali metal hydroxide, carbonate or bicarbonate. 
The condensations are, for example, carried out with cyanuric halides, such 
as cyanuric chloride, at about 0.degree. to 10.degree. C. in an acid or 
neutral medium, with 1,3,5-triazine-dihalides at about 10.degree. to 
50.degree. C. in a neutral medium, and with 1,3,5-triazine-monohalides at 
70.degree. to 100.degree. C. in a neutral medium. The reaction is carried 
out at the lowest temperature, for example 0.degree. to 60.degree. C., 
compatible with the reactivity of the components, and at a pH value of the 
aqueous solution of 1 to at most 9, in the presence of buffer salts, such 
as alkali metal salts of polybasic inorganic acids or organic acids, as 
mineral acid acceptors, for example in the presence of the sodium salts of 
the phosphoric acids, of carbonic acid or of acetic acid. 
The coupling components which contain the s-triazinylamino groups according 
to the definition given, possessing the unreactive substituents R.sub.1 
and R.sub.2, are obtained, for example, by stepwise reaction of 1 mol of 
cyanuric chloride with 1 mol of the corresponding coupling component 
containing a --N(R)H group and with 1 mol each of a compound of the 
formula (10) and a compound of the formula (11). 
The diazotisation of the diazo components of the formula (7) is as a rule 
effected by treatment with nitrous acid in an aqueous solution, containing 
a mineral acid, at a low temperature, whilst the coupling to the coupling 
components of the formula (8) is carried out at a slightly acid, neutral 
or slightly alkaline pH value. 
If the radical D in formula (1) contains a complex-forming group, for 
example a hydroxyl or carboxyl group or an alkoxy group, such as a methoxy 
group, in the orthoposition to the azo group, the azo dyes obtained can, 
either before or after their conversion to reactive dyes, be converted to 
their heavy metal complexes, for example to the copper, chromium, nickel 
or cobalt complexes. The reaction with a heavy metal donor is accordingly 
carried out at any suitable stage of the reaction sequence, for example 
before or after the reaction with the compounds of the formulae (10) and 
(11). 
For this purpose, the metal donors used are, for example, salts containing 
the said metals as the cation, such as chromium sulfates, cobalt acetates, 
cobalt sulfate, copper sulfate and copper acetate. In some cases, it is 
advantageous to use complex metal compounds, for example in the form of 
metal-ammine complexes, such as copper-ammine sulfates obtained from 
copper sulfate and ammonia, pyridine or monoethanolamine, or in the form 
of compounds which contain one of the said metals in a complex anion, for 
example complex chromium compounds of organic hydroxycarboxylic acids, 
such as salicylic acid, or complex cobalt or copper compounds of the 
alkali metal salts of aliphatic aminocarboxylic acids or hydroxycarboxylic 
acids, such as of glycine, of lactic acid and especially of tartaric acid, 
for instance sodium copper-tartrate. 
The treatment with the metal donor can be carried out by methods known per 
se, for example at room temperature or moderately elevated temperature if 
the starting dyes are easily metallisable, or, if dealkylation must take 
place simultaneously with metallisation, by heating to temperatures of 
between 50.degree. and 120.degree. C. in an open vessel, for example under 
reflux, or, where necessary, in a closed vessel under pressure. The pH 
conditions are determined by the nature of the metallising process 
employed; for example, coppering with copper sulfate is carried out under 
acid conditions and coppering with copper-tetramine sulfate is carried out 
under alkaline conditions. If desired, a solvent, for example alcohol, 
dimethylformamide or the like, can be added for the metallisation. 
The metal complex compounds obtainable can contain one atom of metal, bound 
as a complex, per one or two azo dye molecules. For example, when using 
copper compounds and nickel compounds as the metal donor, compounds which 
contain one atom of metal per azo dye molecule are preferably obtained, 
whilst when using chromium and especially when using cobalt, the 1:2 
compounds are easily obtainable and particularly valuable. 
Instead of the o,o'-dihydroxy-azo dyes, the corresponding 
o-alkoxy-o'-hydroxy-azo dyes can also be used as starting materials; in 
that case, the alkyl group of the o-alkoxy radical is detached during 
metallisation and the metal complexes obtained are the same as those 
obtained from the o,o'-dihydroxy dyes. 
The azo dyes of the formula (1) can be isolated and converted to useful dry 
dye formulations. Preferably, they are isolated at as low a temperature as 
possible by salting out and filtration. After having been filtered off, 
the dyes can be dried, if desired after addition of extenders and/or 
buffers, for example after addition of a mixture of equal parts of 
monosodium phosphate and disodium phosphate; preferably, drying is carried 
out under reduced pressure and without using excessively high 
temperatures. In some cases, the dry formulations according to the 
invention can be obtained direct, ie. without intermediate isolation of 
the dye, by spray-drying of the complete reaction mixture. 
The azo dyes of the formula (1), and their heavy metal complexes, are novel 
compounds; they are useful for dyeing and printing very diverse materials, 
for example silk, leather, wool, synthetic high-molecular weight polyamide 
and high-molecular weight polyurethane fibres, and polyhydroxylic 
materials, for example cellulosic materials of fibrous structure, such as 
linen, cellulose, regenerated cellulose, cotton and the like. 
The azo dyes of the formula (1) are used to dye nitrogen-containing fibres, 
for example high-molecular weight polyamides, high-molecular weight 
polyurethanes, silk, leather and especially wool, for instance from a 
weakly acid, neutral or weakly alkaline bath, with or without addition of 
the conventional assistants, such as ethylene oxide adducts of 
high-molecular weight amines, and especially for dyeing cellulosic 
materials, in particular cotton, for example by exhaustion, using a long 
liquor, from an alkaline aqueous bath which can have a high salt content, 
and especially by pad-dyeing, in which the goods are impregnated with an 
aqueous dye solution, which can also contain salt, and the dyes are fixed 
after an alkali treatment, or in the presence of alkali, with or without 
use of heat. 
The reactive dyes can also be used for printing, especially of cotton, but 
also of nitrogen-containing fibres, for example wool or silk, or union 
fabrics containing wool. 
The dyeings and prints are distinguished by interesting and valuable, very 
pure and brilliant shades. They have good stability to acids and alkalis 
and good resistance to synthetic resin finishes, good lightfastness and, 
especially on cotton, excellent wetfastness. The high degree of fixing, 
and the easy removability of non-fixed dye, also warrant mention. 
To improve the wetfastness properties, it is advisable to rinse the dyes 
and prints obtained thoroughly with cold and hot water, where appropriate 
with addition of a dispersant which assists the diffusion of any non-fixed 
dye. 
In the examples which follow, parts are by weight unless stated otherwise, 
percentages are by weight and temperatures are in degrees centigrade. 
Parts by weight bear the same relation to parts by volume as that of the 
gram to the cubic centimeter.

EXAMPLE 1 
31.9 parts of H-acid are stirred into 100 parts of water and neutralised 
with sodium hydroxide. This solution is added dropwise to a suspension 
consisting of 18.5 parts of finely milled cyanuric chloride in 70 parts of 
water and 70 parts of ice. The reaction mixture is stirred for 1 to 2 
hours and kept at 0.degree. to 5.degree. C., by addition of ice, until a 
clear solution has formed. 
21.8 parts of 3-aminoacetanilide-4-sulfonic acid are diazotised in the 
usual manner and then coupled with the cyanurated H-acid, the coupling 
mixture being neutralised in the course of 2 hours with sodium hydroxide 
solution, and the temperature being raised to 20.degree.-25.degree. C. 
8.3 parts of morpholine are added dropwise to the resulting suspension of 
the monoazo dye. The pH is brought to 7.5 by adding sodium hydroxide 
solution, the temperature is raised to 35.degree.-40.degree. C. and the 
mixture is stirred for 1 hour. A clear solution is obtained. 
The chlorine still remaining on the triazine ring is split off by adding 20 
parts by volume of concentrated sodium hydroxide solution and then 
stirring for two hours at 95.degree. to 100.degree. C. 
To saponify the acetyl group, 30 parts of sodium hydroxide (5% of the 
volume) are added and the mixture is stirred for 4 hours at 95.degree. to 
100.degree. C. 
The reaction solution is neutralised with concentrated hydrochloric acid 
and the dye is precipitated with sodium chloride, filtered off and dried. 
It has the formula 
##STR12## 
molecular weight 698. 
If the chlorine which remains on the triazine ring is replaced by 
diethanolamine, the compound of the formula 
##STR13## 
molecular weight 785 is obtained. 
EXAMPLE 2 
13.2 parts of aminodifluorotriazine are suspended in a fine form in 200 
parts of water and 100 parts of ice. A neutral solution of 69.8 parts of 
dye I, obtained in Example 1, in 1,000 parts of water is added. Acylation 
takes place on stirring for two hours at 15.degree. to 20.degree. C., The 
reaction mixture is kept at pH 7 by dropwise addition of dilute sodium 
hydroxide solution. The resulting reactive dye is precipitated with sodium 
chloride, filtered off and dried. 
The product dyes cellulose fibres, by the method specified in Dyeing 
Instruction I, in brilliant red shades having good fastness properties. 
The dyeings are easily dischargeable to white. 
EXAMPLE 3 
If, in place of the aminodifluorotriazine employed in Example 2, a 
corresponding amount of the primary condensation product of cyanuric 
chloride and aniline-2,5-disulfonic acid is used, the dye obtained dyes 
cellulose fibres, by the printing process specified in Dyeing Instruction 
II, in red shades having good fastness properties. The very good print 
obtained on regenerated cellulose is particularly noteworthy. 
EXAMPLE 4 
46 parts of the secondary condensation product of 1 mol of 
2-aminobenzenesulfonic acid, 1 mol of trifluorotriazine and 1 mol of 
1,3-diaminobenzene-4-sulfonic acid are diazotised in the conventional 
manner. The diazo suspension is added to a solution, cooled to 0.degree. 
C., of the sodium salt of 66 parts of the tertiary condensation product of 
1 mol of cyanuric chloride, 1 mol of 
1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 1 mol of 
1-aminobenzene-3-sulfonic acid and 1 mol of aminobenzene, in 600 parts of 
water and 40 parts of sodium carbonate. After completion of coupling, the 
dye is precipitated by adding sodium chloride, and is filtered off and 
dried. 
The novel dye has the following structure: 
##STR14## 
The product dyes cellulose fibres, by the method specified in Dyeing 
Instruction I, in brilliant red shades having good fastness properties. 
The dyed materials can be discharged to white. 
If, in Examples 1 to 4, H-acid is replaced, as the coupling component, by 
1-amino-8-hydroxynapthalene-4,6-disulfonic acid (K-acid), 
2-amino-5-hydroxynaphthalene-7-sulfonic acid (J-acid), 
2-N-methylamino-5-hydroxynaphthalene-7-sulfonic acid or 
2-amino-8-hydroxynaphthalene-6-sulfonic acid (.gamma.-acid), the reactive 
dyes obtained again dye cellulose fibres, by the methods specified in 
Dyeing Instructions I and II, in red shades having good fastness 
properties. 
The table which follows lists further dyes which have the general formula 
##STR15## 
can be prepared analogously to Examples 1 to 4, and have comparably good 
properties. All the dyes shown in the table which follows dye cotton in 
red shades. 
TABLE 
__________________________________________________________________________ 
No. 
S T Ar R.sub.1 R.sub.2 
__________________________________________________________________________ 
##STR16## 
##STR17## 
##STR18## 
##STR19## N(CH.sub.2 CH.sub.2 
OH).sub.2 
2 " " " N(CH.sub.2 CH.sub.2 OH).sub.2 
" 
3 " " " OH " 
4 " " " NH.sub.2 " 
5 " " " OCH.sub.3 " 
6 " " " 
##STR20## " 
7 " " " 
##STR21## " 
8 " " " NHCH.sub.2 CH.sub.2 OH 
" 
9 " " " NHCH.sub.2 CH.sub.2 SO.sub.3 
" 
10 " " " 
##STR22## " 
11 " " " NHCH.sub.2 CH.sub.2 COOH 
" 
12 " " " " 
##STR23## 
13 " " " 
##STR24## " 
14 " " " 
##STR25## " 
15 " " " NHCH.sub.2 CH.sub.2 SO.sub.3 
" 
16 
##STR26## 
##STR27## 
##STR28## N(CH.sub.2 CH.sub.2 OH).sub.2 
N(CH.sub.2 CH.sub.2 
OH).sub.2 
17 " " " 
##STR29## " 
18 
##STR30## " 
##STR31## N(CH.sub.2 CH.sub.2 OH).sub.2 
##STR32## 
19 " 
##STR33## 
" " " 
20 
##STR34## " " " " 
21 
##STR35## 
##STR36## 
" " 
##STR37## 
22 " " " " 
##STR38## 
23 H.sub.2 N 
##STR39## 
##STR40## 
##STR41## OH 
24 
##STR42## 
##STR43## 
##STR44## OH 
##STR45## 
25 
##STR46## " " " " 
26 
##STR47## " " " " 
27 
##STR48## " " " " 
28 
##STR49## " " " " 
29 
##STR50## " 
##STR51## " " 
30 
##STR52## " " " " 
31 
##STR53## " " " " 
32 OCH.sub.3 
##STR54## 
" " " 
33 OC.sub.2 H.sub.5 
" " " " 
34 OCH(CH.sub.3).sub.2 
##STR55## 
##STR56## " " 
35 OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.3 
" 
##STR57## " " 
36 
##STR58## " 
##STR59## " N(CH.sub.2 CH.sub.2 
OH).sub.2 
37 " 
##STR60## 
" " " 
38 
##STR61## " 
##STR62## " " 
39 
##STR63## " 
##STR64## NH.sub.2 " 
40 
##STR65## " 
##STR66## " " 
__________________________________________________________________________ 
EXAMPLE 5 
9.6 parts by volume of trigenortriazine (sic) are added dropwise at 
0.degree. C. to a well-stirred solution of 69.8 parts of the intermediate 
dye prepared in Example 1, No. I. The pH is kept at 5.5 by simultaneously 
adding sodium hydroxide solution. After completion of the condensation, 
6.6 parts by volume of 2-amino-ethanol are added all at once, the pH is 
kept at 7.5 by adding more sodium hydroxide solution, and the mixture is 
slowly warmed to room temperature. When the condensation is complete, the 
dye of the formula 
##STR67## 
is isolated by adding NaCl, in the conventional manner. The product dyes 
cotton in a brilliant red shade which has good fastness properties and is 
easily dischargeable. 
Further, equally good dyes of the same shade are obtained by proceeding as 
described in Example 5, except that in place of ethanolamine an equivalent 
amount of one of the following amines is used: ammonia, methylamine, 
dimethylamine, ethylamine, diethylamine, diethanolamine, taurine, 
methyltaurine, n-butylamine, aniline, cyclohexylamine, N-methylaniline, 
N-ethylaniline, 2-anilinoethanol, o-toluidine, m-toluidine, p-toluidine, 
m-chloroaniline, p-chloroaniline, o-anisidine, p-anisidine, p-phenetidine, 
p-aminobenzoic acid, aniline-3-sulfonic acid, aniline-4-sulfonic acid, 
3-amino-acetanilide, 4-amino-acetanilide, 3-amino-phenyl-oxamic acid, 
3-aminophenylurea, 4-aminophenylurea, morpholine, 2-aminobenzthiazole, 
2-amino-thiazole and dehydrothio-p-toluidine-5-sulfonic acid. 
DYEING INSTRUCTION I 
2 parts of the dye obtained according to Example 1 and 0.5 part of sodium 
m-nitrobenzenesulfonate are dissolved in 100 parts of water. The resulting 
solution is used to impregnate a cotton fabric to a wet pick-up of 75% of 
its weight, which is then dried. 
The fabric is then impregnated with a solution, at 20.degree., which 
contains 5 grams of sodium hydroxide and 300 grams of sodium chloride per 
liter; thereafter it is squeezed off to 75% wet pick-up and the dyed 
fabric is steamed for 30 seconds at 100.degree. to 101.degree., rinsed, 
soaped for quarter of an hour in a boiling 0.3% solution of a non-ionic 
detergent, rinsed and dried. 
DYEING INSTRUCTION II 
2 parts of the dye obtainable according to Example 1 are dissolved in 100 
parts of water. 
The solution is added to 1,900 parts of cold water, 60 parts of sodium 
chloride are added and 100 parts of a cotton fabric are introduced into 
this dyebath. 
The temperature is raised to 40.degree. and after 30 minutes 4 parts by 
volume of 30% strength sodium hydroxide solution, 10 parts of calcined 
sodium carbonate and a further 60 parts of sodium chloride are added. The 
temperature is then kept at 40.degree. for 30 minutes, after which the 
dyed fabric is rinsed, soaped for 15 minutes in a boiling 0.3% solution of 
a nonionic detergent, rinsed and dried.