N.sub.1 -substituted 1H-benzytriazole hydroxyethyl sulfone compounds, a process for their preparation and their use for the preparation of dyestudds

N.sub.1 -substituted 1H-benzotriazole hydroxyethyl sulfone compounds, a process for their preparation and their use for the preparation of dyestuffs. Compounds of the general formula ##STR1## in which R is hydrogen or alkyl which has 1 to 6 carbon atoms and can be substituted by hydroxy, sulfo, carboxy, phosphono and/or cyano, W denotes a divalent, optionally substituted aliphatic radical, (C.sub.5 -C.sub.10)-cycloaliphatic radical which is optionally substituted by alkyl, aliphatic-(C.sub.5 -C.sub.8)-cycloaliphatic radical which is optionally substituted by alkyl, optionally substituted araliphatic radical or optionally substituted aromatic carbocyclic radical, it being possible for the aliphatic radicals in W to be interrupted by hetero groups of the formulae --O--, --S--, --SO.sub.2 --, --CO--, 1,4-piperidino, --NH-- and --N(R')-- in which R' is an alkyl group which has 1 to 6 carbon atoms and can be substituted, or is an alkanoyl group having 2 to 5 C atoms, and/or for the aliphatic radicals and aryl radicals to be attached to one another through such a hetero group, and R* denotes hydrogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 5 carbon atoms, halogen, carboxy or sulfo. They are used as intermediates for the preparation of dyestuffs, such as fiber-reactive triphendioxazine dyestuffs, and can be prepared by reducing the nitro group in a compound of the general formula ##STR2## in which R, R* and W have the abovementioned meaning and A is a hydrogen atom or an acyl radical, to the amino group and diazotizing this amino group, whereupon cyclization takes place to give the benzotriazole, and, if necessary, subsequently eliminating the acyl radical by hydrolysis.

The invention falls within the technical field of intermediates. 
The present invention relates to compounds of the general formula (1) 
##STR3## 
in which 
R is a hydrogen atom or an alkyl group which has 1 to 6 carbon atoms and 
can be substituted by one or two substituents, preferably one substituent, 
belonging to the group comprising hydroxy, sulfo, carboxy, phosphono and 
cyano, 
W denotes a divalent, optionally substituted aliphatic radical, (C.sub.5 
-C.sub.10)-cycloaliphatic radical which is optionally substituted by 
alkyl, aliphatic-(C.sub.5 -C.sub.8)-cycloaliphatic radical which is 
optionally substituted by alkyl, optionally substituted araliphatic 
radical or optionally substituted aromatic-carbocyclic radical, it being 
possible for the aliphatic radicals in W to be interrupted by hetero 
groups, preferably one or two hetero groups, selected from the groups of 
the formulae --O--, --S--, --SO.sub.2 --, --CO--, 1,4-piperidino, --NH-- 
and --N(R')-- in which R' is an alkyl group which has 1 to 6 carbon atoms, 
preferably 1 to 4 carbon atoms, such as, in particular, the methyl or 
ethyl group, and which can be substituted, or is an alkanoyl group having 
2 to 5 carbon atoms, such as the acetyl group, and/or it being possible 
for the aliphatic radicals and aryl radicals to be attached to one another 
through such a hetero group, and 
R* denotes a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, 
preferably 1 to 4 carbon atoms, such as, in particular, methyl and ethyl, 
an alkoxy group having 1 to 5 carbon atoms, preferably 1 to 4 carbon 
atoms, such as, in particular, methoxy or ethoxy, a halogen atom, such as 
fluorine and bromine and, in particular, chlorine, or a carboxy or sulfo 
group, 
and to the use thereof for the preparation of fiber-reactive dyestuffs. 
In the preceding and following text, a carboxy group denotes a group of the 
general formula --COOM, a sulfo group denotes a group of the general 
formula --SO.sub.3 M and a phosphono group denotes a group of the general 
formula --PO.sub.3 M.sub.2 in which 
M denotes a hydrogen atom or an alkali metal, such as sodium, potassium or 
lithium. 
The present invention also relates to a process for the preparation of the 
compounds of the general formula (1), which comprises reducing the nitro 
group in a compound of the general formula (2) 
##STR4## 
in which R, R* and W have the abovementioned meanings and A is a hydrogen 
atom or an acyl radical, such as an alkanoyl radical having 2 to 5 carbon 
atoms, such as the acetyl radical, or is a benzoyl radical, it being 
necessary for A to represent an acyl radical in the event that W denotes 
an aromatic-carbocyclic radical, in a manner which is customary per se and 
analogous to known processes, to give the amino group, and diazotizing the 
compound obtained therefrom of the general formula (3) 
##STR5## 
in which A, R, R* and W have the abovementioned meanings, by a procedure 
of diazotization which is customary per se, for example by means of sodium 
nitrite in an aqueous acid, preferably hydrochloric acid, medium at a 
temperature between -10.degree. C. and +20.degree. C., and, if 
appropriate, in the event that the group A in formula (3) should denote an 
acyl radical, subsequently deacylating the benzotriazole compound of the 
general formula (1) which has been obtained as an acyl derivative to give 
the benzotriazole compound of the general formula (1) analogously to known 
methods, for example in an aqueous medium at a temperature between about 
90.degree. and 100.degree. C. and at a pH higher than 12, such as by means 
of a sodium hydroxide solution containing a three-fold to six-fold amount 
of NaOH, but preferably in an acid, for example hydrochloric acid, aqueous 
medium at a pH value below 2. When the compounds of the formula (3) are 
diazotized, cyclization of the diazonium group formed with the amino group 
in the ortho-position takes place. 
The compounds of the general formula (2) can also be prepared in a manner 
according to the invention by reacting a compound of the general formula 
(4) 
##STR6## 
in which R* has the abovementioned meaning and Hal denotes a fluorine or 
bromine atom or, preferably, a chlorine atom, with a compound of the 
general formula (5) 
##STR7## 
in which A, R and W have the abovementioned meanings, in a solvent 
suitable for these reactants, in the presence of an acid-binding agent and 
at a temperature between 30.degree. and 120.degree. C., preferably between 
70.degree. and 90.degree. C. 
The starting compounds of the general formula (4) are known per se (see, 
for example, German Pat. No. 859,462, Example 5); compounds corresponding 
to the general formula (4) which have not yet been described per se can be 
prepared analogously to the known compounds in the manner familiar to 
those skilled in the art, for example synthesized by nitrating a 
corresponding (.beta.-hydroxyethylsulfonyl)-chlorobenzene compound or by 
reducing a corresponding 4-chloro-3-nitrobenzenesulfochloride compound by 
means of sodium sulfite to give the corresponding sulfinic acid and 
subsequently oxethylating the sulfinic acid to give the 
.beta.-hydroxyethylsulfonyl compound. 
Examples of starting compounds corresponding to the general formula (5) are 
1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 
1,5-diaminopentane, 1,6-diaminohexane, 1,2-diaminopropane, 
1,2-diaminobutane, 1,3-diaminobutane, the N-acyl compounds, such as the 
N-acetyl and N-benzoyl compounds, of 1-amino-3-methylaminopropane, 
1,3-diamino-2-methylpropane, 1,3-diamino-2-hydroxypropane, 
1,5-diamino-2-carboxypentane, 1,3-diamino-2-phenylpropane or its 
derivative which is sulfo-substituted in the benzene radical, and also 
compounds corresponding to a general formula (a), (b), (c) and (d) 
EQU H.sub.2 N--(CH.sub.2).sub.2 --X--(CH.sub.2).sub.2 --NH.sub.2(a) 
EQU H.sub.2 N--(CH.sub.3).sub.2 --X--(CH.sub.3).sub.2 --NH.sub.2(b) 
##STR8## 
EQU H.sub.2 N--(CH.sub.2 --CH.sub.2 --NH).sub.n --CH.sub.2 --CH.sub.2 
--NH.sub.2(d) 
in which 
X denotes an oxygen atom, a sulfur atom, a sulfonyl group or a group of the 
formula --NH--, --N(CH.sub.3)-- or --N(COCH.sub.3)--, 
R.sup.1 represents a hydrogen atom or a sulfo group, 
A has the abovementioned meaning, 
n is the number 2, 3 or 4, 
X.sup.1 represents the group --NH-- or an oxygen atom and 
y denotes the number 2 or 3, 
and also 1,3-cyclohexylenediamine, 1,4-cyclohexylenediamine, 
bis-(4-aminocyclohex-1-yl)-methane, 1,8-di-(aminomethyl)-naphthalene, 
1,4-di-(aminomethyl)-benzene, 1,3-di-(aminomethyl)-benzene, 
N,N'-bis-(.beta.-aminoethyl)-1,4-piperidine, 1,4-phenylenediamine, 
1,3-phenylenediamine, 4-aminobenzylamine, 4-aminophenethylamine and the 
corresponding N-monoacyl derivatives of such compounds. Of these, 
1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane and 
1,2-diaminopropane are preferred. 
Since hydrogen chloride is eliminated in the reaction of the compounds (4) 
with the compounds (5), it is necessary to carry out the reaction in the 
presence of an acid-binding agent. Agents suitable for this purpose are 
either inorganic compounds, such as, for example, sodium hydroxide, 
potassium hydroxide, sodium carbonate, calcium carbonate, magnesium oxide, 
sodium acetate or potassium acetate, or organic basic compounds, such as, 
for example, trialkylamines containing alkyl radicals having 1 to 4 carbon 
atoms, such as, for example, trimethylamine and triethylamine, or 
pyridine, quinoline, the picolines and morpholine. The acid-binding agent 
must be present in each case in at least an amount equivalent to the 
monohalogen compound (4). If the amino compound (5) is a compound having 
an adequately basic reaction, such as, for example, ethylenediamine, and 
if this compound is employed in an adequate excess, this compound then 
acts as an acid acceptor, as a result of which the addition of a separate 
inorganic or organic acid-binding agent is unnecessary. 
Examples of suitable solvents which can be used as the reaction medium in 
the reaction of (4) with (5) are water, alkanols having 1 to 4 carbon 
atoms, such as methanol, ethanol, propanol and isopropanol, dioxane, 
toluene, the xylenes, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, 
dimethylformamide or N-methylpyrrolidone. If one of the two reactants (4) 
or (5) or both of them are not completely soluble in the solvent used, the 
reaction takes place partly in suspension, which does not affect it 
adversely. It is also possible, however, to employ the compound (5) as the 
solvent by using it in a sufficient excess. 
If a solvent is used in which the two reactants (4) and (5) are each 
completely soluble, it is suitable to react the compounds (4) and (5) in a 
molar ratio of 1:(1-2.5). Although the use of a larger excess of the 
compound (5) is possible, it affords no further advantage and is therefore 
not advisable. 
If a solvent is used in which one or both of the reactants (4) and (5) are 
not completely soluble, or if excess (5) is used as the solvent, it is 
suitable to react the compound (5) with the compound (4) in an amount by 
weight of 1 to 4 times, relative to the compound (4). Here too, the use of 
a larger excess of (5) is possible but not advisable. 
After being synthesized, the nitro compound of the general formula (2) can 
be isolated in a simple manner by crystallization from this reaction 
mixture and subsequent filtration, optionally after distilling partially 
or completely the solvent or the excess reagent (5), which can 
advantageously be recovered for further reactions, and then mixing the 
eventually concentrated reaction mixture with cold water which, if 
appropriate, contains an electrolyte salt, such as sodium chloride, 
potassium chloride or sodium sulfate. The product which crystallizes out 
in this way can be isolated by filtration, if appropriate after 
acidification with mineral acid. The subsequent reduction of the nitro 
compound (2) to the corresponding amino compound (3) can be carried out in 
a manner known per se by catalytic hydrogenation with hydrogen over known 
catalysts, such as palladium, platinum or Raney nickel, at a temperature 
between 20.degree. and 150.degree. C., preferably between 50.degree. and 
110.degree. C., and under an elevated pressure, for example between 30 and 
100 bar, preferably between 40 and 55 bar, or by reduction by the Bechamp 
method using iron in an acid or alkaline medium, preferably an acid 
medium, for example using iron in ethanol/glacial acetic acid. It is 
particularly advantageous to subject the nitro compound (2) which can be 
obtained from the reaction of the compounds (4) and (5) to catalytic 
hydrogenation directly, without intermediate isolation thereof. This makes 
it possible to reduce energy and effluent costs. The reduction of (2) to 
(3), whether carried out catalytically or by the Bechamp method, is 
appropriately carried out in a suitable solvent, such as water, methanol 
or ethanol, or in a mixture of water and methanol or water and ethanol, 
since this makes it possible to induce the amino compounds (3) to 
crystallize in a simple manner by cooling, if appropriate after 
acidification with mineral acid, in the form of the free amino compounds 
or in the form of salts thereof with mineral acids; if appropriate, they 
can also be salted out with sodium chloride. The subsequent separation is 
then carried out by filtration, and the mother liquors can be re-used for 
subsequent hydrogenation batches and, if appropriate, recycled for this 
purpose. It is also possible to recover the organic solvent from the 
mother liquors by simple distillation under normal pressure. 
The procedures according to the invention make it possible to obtain the 
new compounds of the general formula (1) in good to very good yields. They 
constitute new, valuable intermediates for the preparation of 
fiber-reactive dyestuffs, in particular fiber-reactive triphendioxazine 
dyestuffs, such as, for example, the preparation of dyestuffs of the 
general formula (A) 
##STR9## 
in which W and R* have the abovementioned meanings, M denotes an alkali 
metal and E denotes a hydrogen atom or a sulfo, carboxy, C.sub.1 -C.sub.4 
-alkylsulfonyl or sulfo-C.sub.1 -C.sub.4 -alkylsulfonyl group or a 
.beta.-sulfatoethylsulfonyl group. An example of particularly advantageous 
triphendioxazine dyestuffs corresponding to the general formula (A) are 
dyestuffs in which E is a sulfo group and W is an ethylene or n-propylene 
group; these dyestuffs afford dyeings in clear blue and fast shades on 
cotton by the dyeing procedures customary in the art for fiber-reactive 
dyestuffs. 
The use, according to the invention, of the compounds (1) as intermediates 
for the synthesis of fiber-reactive dyestuffs is carried out, for example, 
by first reacting the compound (1) with a chloronitro compound, for 
example with 2-sulfo-4-nitrochlorobenzene, 
2-(.beta.-sulfoethylsulfonyl)-4-nitrochlorobenzene or 
2-(.beta.-hydroxyethylsulfonyl)-4-nitrochlorobenzene, to give a compound 
of the general formula (6) 
##STR10## 
in which W, R* and E have the abovementioned meanings or E is also a 
.beta.-hydroxyethylsulfonyl group (it being possible to carry out the 
reaction of the amino compound with the chlorobenzene compound analogously 
to the instructions above by a procedure which is known per se), and to 
reduce the nitro group in this compound (6) by a procedure which is known 
per se, such as that described above, for example, to give the amino group 
in the compounds of the general formula (7) 
##STR11## 
in which W, R* and E have the abovementioned meanings. The amino compound 
of the general formula (7) can then be reacted with 
2,3,5,6-tetrachloro-1,4-benzoquinone by a procedure, known per se, of the 
preparation of fiber-reactive triphendioxazine compounds (see, for 
example, European Patent Application Publication No. 0,168,751 A1) with 
oxidative cyclization and simultaneous or subsequent sulfation in sulfuric 
acid containing sulfur trioxide to give the dyestuffs of the formula (A).

EXAMPLE 1 
(a) 530 parts of 2-nitro-4-(.beta.-hydroxyethylsulfonyl)-chlorobenzene are 
introduced slowly, at a temperature between 70.degree. and 80.degree. C., 
into 620 parts of ethylenediamine; the mixture is kept at this temperature 
for some time and is then, after quantitative reaction has been reached, 
stirred into water. The compound of the formula 
##STR12## 
which has been precipitated, is isolated by filtration and dried. It is 
obtained in a good yield and high purity (melting point 
146.degree./147.degree. C.) and gives the following data in .sup.1 H-NMR 
analysis (in d.sub.6 -DMSO using TMS as internal standard): 
.delta.=2.83 ppm (t,2H); 3.44 ppm (m,2H); 3.7 ppm (m,2H); 7.27 ppm (d,1H); 
7.9 ppm (dd,1H); 8.49 ppm (d,1H); mobile protons at 1.7 ppm (NH.sub.2), 
4.8 ppm (OH) and 8.8 ppm (NH). 
(b) The nitro compound obtained under (a) is reduced to the aniline 
compound by hydrogenating 290 parts of the nitro compound in 1200 parts of 
water in the presence of a Pd-on-charcoal catalyst in an autoclave at a 
temperature of up to 100.degree. C. and under a hydrogen pressure of 50 
bar. The catalyst is then filtered off; the amino compound obtained can be 
processed further in the filtrate without further treatment. 
A sample of the aniline compound obtained of the formula 
##STR13## 
is isolated and has a melting point of 169.degree.-172.degree. C. and 
gives the following data in .sup.1 H-NMR analysis (in d.sub.6 -DMSO using 
TMS as internal standard): 
.delta.=2.84 ppm (t,2H); 3.2 ppm (m,4H); 3.6 ppm (m,2H); 6.53 ppm (dd,1H); 
6.96 ppm (d,1h); 7.0 ppm (dd,1H); mobile protons at 4-5 ppm (NH.sub.2,OH) 
and 5.45 ppm (NH). 
(c) 260 parts of 
.beta.-[4-(.beta.-hydroxyethylsulfonyl)-2-aminophenylamino]-ethylamine in 
about 1800 parts of an aqueous solution of hydrochloric acid are 
diazotized in a customary manner at 0.degree. to 5.degree. C. by means of 
an aqueous solution of sodium nitrite. Cyclization takes place immediately 
and quantitatively. A sample of the compound of the formula 
##STR14## 
is isolated and gives the following data in .sup.1 H-NMR analysis (in 
d.sub.6 -DMSO using TMS as internal standard): 
.delta.=3.06 ppm (t,2H); 3.54 ppm (m,2H); 3.7 ppm (m,2H); 4.72 ppm (t,2H); 
8.0 ppm (dd,1H); 8.16 ppm (dd,1H); 8.6 ppm (m,1H); mobile protons (OH, 
NH.sub.2). 
EXAMPLE 2 
(a) 530 parts of 2-nitro-4-(.beta.-hydroxyethylsulfonyl)-chlorobenzene are 
introduced slowly into 750 parts of 1,3-propylenediamine at a temperature 
between 70.degree. and 80.degree. C.; the mixture is kept at this 
temperature for some time and, when quantitative reaction has been 
reached, is then stirred into water. The compound of the formula 
##STR15## 
which is precipitated, is isolated by filtration and dried. It is obtained 
in good yield and high purity, melting point 110.degree./112.degree. C., 
and gives the following data in .sup.1 H-NMR analysis (in d.sub.6 -DMSO 
using TMS as internal standard): 
.delta.=1.7 ppm (m,2H); 2.66 ppm (t,2H); 3.5 ppm (m,4H); 3.68 ppm (m,2H); 
7.25 ppm (d,1H); 7.9 ppm (dd,1H); 8.5 ppm (d,1H); mobile protons 
(NH.sub.2, OH, NH) at approx. 5 ppm. 
(b) The nitro compound obtained under (a) is reduced to the aniline 
compound by hydrogenating 303 parts of the nitro compound in 1200 parts of 
water in the presence of a Pd-on-charcoal catalyst in an autoclave at a 
temperature of up to 100.degree. C. and under a hydrogen pressure of 50 
bar. The catalyst is then filtered off; the resulting amino compound can 
be processed further in the filtrate without further treatment. 
A smaple of the aniline compound obtained of the formula 
##STR16## 
is isolated and gives the following data in .sup.1 H-NMR analysis (in 
d.sub.6 -DMSO using TMS as internal standard): 
.delta.=1.9 ppm (m,2H); 2.88 ppm (t,2H); 3.2 ppm (m,4H); 3.58 ppm (m,2H); 
6.51 ppm (dd,1H); 6.92 ppm (d,1H); 6.96 ppm (dd,1H); mobile protons at 4.9 
ppm (OH), 5.2 ppm (NH.sub.2), 5.74 ppm (NH) and 8.2 ppm (NH.sub.2). 
(c) 260 parts of 
.gamma.-[4-(.beta.-hydroxyethylsulfonyl)-2-aminophenylamino]-n-propylamine 
in about 1800 parts of an aqueous solution of hydrochloric acid are 
diazotized in a customary manner at 0.degree. to 5.degree. C. by means of 
an aqueous solution of sodium nitrite. Cyclizatioin takes place 
immediately and quantitatively. A sample of the compound of the formula 
##STR17## 
is isolated and gives the following data in .sup.1 H-NMR analysis (in 
d.sub.6 -DMSO using TMS as internal standard): 
.delta.=2.24 ppm (m,2H); 2.85 ppm (m,2H); 3.6 ppm (m,4H); 4.92 ppm (t,2H); 
8.04 ppm (dd,1H); 8.27 ppm (d,1H); 8.6 ppm (s,1H); mobile protons 
(OH,NH.sub.2). 
EXAMPLE 3 
132.8 parts of 4-(.beta.-hydroxyethylsulfonyl)-2-nitrochlorobenzene are 
introduced, in the course of 30 minutes, into a solution of 118.8 parts of 
1,4-phenylenediamine in 500 parts by volume of methanol at 65.degree. C. 
and under an atmosphere of nitrogen. Stirring is continued for a further 4 
hours at this temperature, the mixture is allowed to cool to room 
temperature and the reaction product is crystallized out by adding 1000 
parts by volume of ice water 
4-(.beta.-hydroxyethylsulfonyl)-2-nitro-4'-amino-diphenylamine is obtained 
in high yield by filtration with suction and drying. It is N-acylated at 
50.degree. C. with the equimolar amount of acetic anhydride, for ex. in 
glacial acetic acid; this acetamino compound, which has a melting point of 
193.degree./194.degree. C., is then reduced to the anilino compound of the 
formula 
##STR18## 
(m.p.: 183.degree./184.degree. C.) which is converted, by diazotization 
and subsequent acid deacylation in accordance with customary procedures, 
into the compound, according to the invention, of the formula 
##STR19## 
The compound according to the invention has a melting point of 177.degree. 
C. It gives the following data in .sup.1 H-NMR analysis (in d.sub.6 -DMSO 
with TMS as internal standard): 
.delta.=3.6 ppm (t,2H); 3.8 ppm (m,2H); 4.9 ppm (t,OH); 5.7 ppm 
(s,NH.sub.2); 6.8 ppm (d,2H); 7.5 ppm (d,2H); 8.0 ppm (d,1H); 8.1 ppm 
(d,1H); 8.7 ppm (s,1H). 
It is also preferable to use 4-aminoacetanilide as the starting compound 
instead of 1,4-phenylenediamine. In this case, the acid-binding agent used 
is, for example, sodium acetate, triethylamine or triethanolamine; the 
subsequent N-acetylation is consequently unnecessary. 
EXAMPLE 4 
The procedure of Example 3 is used to prepare a compound according to the 
invention, but an equal amount of 1,3-phenylenediamine or, preferably, 
3-aminoacetanilide is employed instead of 1,4-phenylenediamine. The 
compound, according to the invention, of the formula 
##STR20## 
is obtained in this manner. 
USE EXAMPLE 1 
The compound, according to the invention, described in Example (1c) can be 
processed further as follows to give a dyestuff: 
(a) 259 parts of the sodium salt of 5-nitro-2-chlorobenzenesulfonic acid 
are first added, at a temperature of 40.degree. C., to a mixture of 270 
parts of 
5-(.beta.-hydroxyethylsulfonyl)-1-(.beta.-aminoethyl)-benzotriazole in 
1000 parts of water and 500 parts of triethanolamine (the benzotriazole 
compound can also be employed, without further treatment, in the form of 
the solution obtained in accordance with Example 1c)). The mixture is 
heated to 100.degree. to 110.degree. C. in the course of two hours, during 
which part of the water distils off. The mixture is stirred for a further 
10 hours at 115.degree. to 120.degree. C. to achieve quantitative 
reaction, and 3000 parts of water are then added at 100.degree. C., and 
the solution is clarified at 80.degree. to 90.degree. C. On cooling, the 
sodium salt of 
4-[.beta.-(5'-.beta.'-hydroxyethylsulfonylbenzotriazol-1'-yl)-ethylamino]- 
3-sulfonitrobenzene crystallizes out from the aqueous medium in a high 
yield and purity. The nitro compound gives the following data in .sup.1 
H-NMR analysis (in d.sub.6 -DMSO with TMS as internal standard): 
.delta.=3.5 ppm (m,2H); 3.64 ppm (t,2H); 3.95 ppm (m,2H); 4.82 ppm (t,OH); 
5.0 ppm (t,2H); 6.69 ppm (d,1H); 7.57 ppm (t,NH); 7.95 ppm (m,2H); 8.16 
ppm (m,1H); 8.3 ppm (d,1H); 8.57 ppm (d,1H). 
The nitro compound is then reduced to the aniline compound by catalytic 
hydrogenation by dissolving 236 parts of the nitro compound in 1000 parts 
of water and hydrogenating it in the presence of a Pd-on-charcoal catalyst 
in an autoclave at a temperature of up to 100.degree. C. and under a 
hydrogen pressure of 50 bar. The catalyst is then filtered off and the 
filtrate is cooled and acidified. The aniline compound of the formula 
##STR21## 
crystallizes out therefrom in a good yield and high purity. 
(b) 441 parts of the aniline compound obtained under (a) are dissolved in 
2000 parts of water at pH 6.degree. and 60.degree. C. 124 parts of 
chloranil are introduced, the pH being kept at a value of 6.5 by means of 
about 90 parts of sodium bicarbonate and the reaction temperature being 
kept at about 65.degree. C. The mixture is stirred for a further 6 hours 
and the reaction product is then clarified at about 65.degree. C., 
precipitated by means of a little sodium chloride, filtered off with 
suction, washed with 1000 parts of 10% strength aqueous sodium chloride 
solution and dried at 70.degree. C. under reduced pressure. 
(c) 105 parts of the product obtained under (b) are introduced at a 
temperature between 20.degree. and 25.degree. C. into 750 parts of 13% 
strength oleum. The reaction mixture is then stirred for about a further 3 
hours at this temperature; 48 parts of sodium peroxodisulfate are then 
introduced at such a rate that the reaction temperature can be kept at 
20.degree. to 25.degree. C. The mixture is stirred for a further 10 hours 
at this temperature and is then run onto ice, and the compound, according 
to the invention, which has been precipitated is filtered off and 
redissolved in about 1000 parts of water, the pH of which is adjusted to a 
value of 5 with sodium carbonate, and the compound is salted out by means 
of sodium chloride, if necessary after clarifying the solution beforehand 
in a customary manner. 
The triphendioxazine compound according to the invention can also be 
obtained in the form of its sodium salt by evaporating or spray-drying the 
clarified synthesis solution. Expressed in the form of the free acid, it 
has the probable formula 
##STR22## 
(each of the sulfo groups can also be attached in the other ortho-position 
relative to the benzotriazolylethylamino group, but is more probably 
located in the position indicated in the above formula). This compound 
according to the invention possesses good fiber-reactive properties as a 
dyestuff. It dyes the materials mentioned in the description, in 
particular cellulose fiber materials, such as cotton, by the procedures 
which are customary and known in the art for the application and fixation 
of fiber-reactive dyestuffs, in deep, clear, reddish-tinged blue shades 
(corresponding to the color coordinate 13 of the Color Index Hue 
Indication Chart) having good fastness properties such as, in particular, 
good fastness to light of the dry or moist, moistened with drinking water, 
dyeing, good fastness to light in alkaline perspiration, fastness to 
chlorinated water, fastness to hypochlorite, fastness to alkaline 
perspiration, fastness to washing, even in the presence of perborates, 
fastness to wet storage and resistance to acid fading. In aqueous 
solution, it displays an absorption maximum in the visible range at 612 
nm. 
USE EXAMPLE 2 
The compound, according to the invention, described in Example (2c) can be 
processed further as follows to give a triphendioxazine dyestuff: 
An aqueous acid solution, obtained as in Example (2c), of 285 parts of 
5-(.beta.-hydroxyethylsulfonyl)-1-(.gamma.-aminopropyl)-benzotriazole and 
500 parts of triethanolamine is warmed to 40.degree. C. and 259 parts of 
the sodium salt of 5-nitro-2-chlorobenzenesulfonic acid are added. The 
mixture is heated to 100.degree. to 110.degree. C. in the course of two 
hours, during which time part of the water distils off. The mixture is 
stirred at 115.degree. to 120.degree. C. for a further 10 hours in order 
to achieve quantitative reaction, and 3000 parts of water are then added 
at 100.degree. C. and the solution is clarified at 80.degree. to 
90.degree. C. On cooling, the sodium salt of 
4-[.gamma.-(5'-.beta.'-hydroxyethylsulfonylbenzotriazol-1'-yl)-propylamino 
]-3-sulfonitrobenzene crystallizes out from the aqueous medium in a high 
yield and purity. The nitro compound gives the following data in .sup.1 
H-NMR analysis (in d.sub.6 -DMSO with TMS as internal standard): 
.delta.=2.25 ppm (m,2H); 3.32 ppm (m,2H); 3.54 ppm (m,2H); 3.66 ppm (m,2H); 
4.9 ppm (m,OH,2H); 6.9 ppm (d,1H); 7.47 ppm (t,NH); 8.0 ppm (m,2H); 8.20 
ppm (m,1H); 8.37 ppm (d,1H); 8.62 ppm (d,1H). 
The nitro compound obtained in this way can then be reduced to the aniline 
compound of the formula 
##STR23## 
in accordance with the instructions of Example (1a), and the product can 
then be converted in accordance with the instructions of Use Example (1b) 
and (1c) into a valuable blue triphendioxazine dyestuff.