Process for preparing [5-amino-2-(2-hydroxyethylamino)-phenyl](2-hydroxyethyl)sulphone

A process for preparing the sulphone of the formula ##STR1## consists in reductive cleavage of disazo/disazoxy dyestuffs of the formula ##STR2## in which B is a direct bond or a bridging member and PA1 v, w, x, y, independently of one another, are 0 or 1, PA2 x+y being 0 or 1 and v+w being 0 or 1.

[5-Amino-2-(2-hydroxyethylamino)phenyl](2-hydroxyethylsulphone of the 
formula (1) is an important intermediate in the synthesis of dyestuffs, in 
particular in the synthesis of reactive dyestuffs, as described, for 
example, in DE-A 3,512,340 or U.S. Pat. No. 4,577,015. 
U.S. Pat. No. 5,107,025 describes a preparation process based on the 
catalytic reduction of monoazo/azoxy compounds. Removal of (1) and the 
particular diazo components to be reused in accordance with the process is 
not optimal. This is mainly due to the solubility product of the betaine 
of the diazo component in water. 
Accordingly, the invention relates to a novel process for preparing 
[5-amino-2-(2-hydroxyethylamino)phenyl]-(2-hydroxyethyl)sulphone of the 
formula (1) 
##STR3## 
characterized in that disazo/disazoxy dyestuffs of the formula (5) 
##STR4## 
in which B is a direct bond or a bridging member, such as, for example, 
CH.sub.2, CH.sub.2 CH.sub.2, SO.sub.2, CO, O, CH.dbd.CH, NHCONH, OCH.sub.2 
CH.sub.2 O, NH or N(C.sub.1 -C.sub.4 -alkyl) , preferably CH.sub.2 
CH.sub.2 or CH.dbd.CH, and 
v, w, x, y, independently of one another, are 0 or 1, 
x+y being 0 or 1 and v+w being 0 or 1, 
are reductively cleaved to give the diamino compound of the formula (2) 
##STR5## 
and 2 equivalents of the formula (1), and the resulting diamino compound 
of the formula (2), after acidification and precipitation, is separated 
off as a sparingly water-soluble doubled betaine, a sparingly 
water-soluble betaine being understood to mean one having a solubility of 
0.0 g/l to 1 g/l (25.degree. C.). 
The almost quantitatively precipitated and removed (2) is reused in the 
synthesis. The compound of the formula (1) which remains in solution can 
either be isolated by concentrating or else directly further reacted in 
this form. 
The reduction of the disazo/disazoxy dyestuffs of the formula (5) to (1) 
and (2) can take place by methods such as described in U.S. Pat. No. 
5,107,025 and by R. Schroter in, Handbuch fur preparative Methoden der 
organischen Chemie, Houben-Weyl, Volume XI, Part 1, page 522 to 531. 
According to these references, reduction with sodium dithionite or 
D-glucose or else catalytic reduction with hydrogen are particularly 
advantageous. Suitable catalysts for these reductions are in particular 
Raney nickel, palladium/carbon or platinum compounds. The reduction is 
preferably carried out in water at temperatures of between 20.degree. and 
80.degree. C. and under neutral pH conditions, preferably between pH 5 to 
pH 8. Catalytic reduction with-hydrogen is in general carried out at 
pressures of 10 to 100 atm, preferably 30 to 80 atm, in particular at 50 
to 70 atm, in an autoclave suitable therefor. 
In a particular embodiment of the process, disazo/disazoxy dyestuffs of the 
formula (5a) 
##STR6## 
in which B is CH.sub.2 CH.sub.2 or CH.dbd.CH and 
v, w, x, y, independently of one another, are 0 or 1, 
v+w being 0 or 1 and x+y being 0 or 1, 
are reduced to give (1) and diamino compounds of the formula (2a ) 
##STR7## 
In a further particular embodiment of the process, the compounds of the 
formula (1) are obtained by reduction of the disazo/disazoxy dyestuffs of 
the formula (5), which in turn can be obtained by tetrazotizing diamino 
compounds of the formula (2) 
##STR8## 
in which B is a direct bond or a bridging member such as, for example, 
CH.sub.2, CH.sub.2 CH.sub.2, SO.sub.2, CO, O, CH.dbd.CH, NHCONH, OCH.sub.2 
CH.sub.2 O, NH or N(C.sub.1 -C.sub.4 -alkyl), coupling the 
tetrazoniumcompounds onto 2 equivalents of 
2-(2-hydroxyethyl)mercapto-N-(2-hydroxyethyl)aniline of the formula (3) 
##STR9## 
and oxidizing the resulting disazo compounds of the formula (4) 
##STR10## 
to disazo/disazoxy dyestuffs of the formula (5) 
##STR11## 
in which v, w, x and y, independently of one another, are 0 or 1, 
v+w being 0 or 1 and 
x+y being 0 or 1. 
A particular embodiment of this process consists in the use of diamino 
compounds of the formula (2a) 
##STR12## 
in which B is CH.sub.2 --CH.sub.2 or CH.dbd.CH. 
The doubled betaine of (2a) has only low water solubility of about 0.5 g/l 
at 25.degree. C. 
Sulpho-containing diamino compounds have the advantage that the process, 
i.e. diazotization, coupling, oxidation and reduction, can be carried out 
in an aqueous reaction medium. Azo coupling of tetrazotized diamino 
compounds (2) onto two equivalents (3) is preferably carried out at 
temperatures of between 0.degree. and 30.degree. C. and a pH of preferably 
0.5 to 5.0. For this reaction the use of emulsifiers or coupling 
accelerators, such as, for example, urea, may be advantageous. Dyestuffs 
(4) are obtained as crystalline compounds and can therefore be isolated by 
filtration. Since the coupling reaction in most cases gives relatively 
uniform products, (4) can also be oxidized directly, without intermediate 
isolation, to give disazo/disazoxy dyestuffs (5). 
The oxidizing agents used can be, for example, hydrogen peroxide, 
perborates, persulphates, persulphonic acids or peroxides of alkali metal 
and alkaline earth metals, if appropriate in the presence of suitable 
catalysts. 
In a particularly preferred embodiment of the process, hydrogen peroxide in 
the presence of catalytic amounts (0.001 to 2% by weight, relative to (4)) 
of tungstates and/or vanadates, in particular alkali metal tungstates 
and/or alkali metal vanadates, has proven to be an advantageous oxidizing 
agent. 
Oxidation is in general carried out in aqueous medium at 20.degree. to 
100.degree. C., preferably 40.degree. to 90.degree. C., and at a pH of 4 
to 8. The reaction passes through the corresponding sulphoxide compounds 
as intermediates. 
The disazo/disazoxy dyestuffs (5) can be isolated as yellow to red 
crystalline compounds and can be additionally purified by 
recrystallization from water or water/alcohol mixtures. 
After reduction, a two-component solution is obtained from which, after 
separating off the catalyst, the diamino compound (2) can be made to 
precipitate by acidification with mineral acids, such as, for example, 
sulphuric acid or hydrochloric acid and separated off almost 
quantitatively as doubled betaine by filtration or pressing. Compound (1) 
remains in the acid filtrate and can then be isolated or neutralized and 
directly further reacted as a solution. The removed diamino compound (2) 
can be tetrazotized and reused in the next synthesis sequence. 
The formulae given for the intermediates and disazo dyestuffs are those of 
the free acids. In general, the salts are used or obtained in the 
preparation, in particular the alkali metal salts, such as, for example, 
sodium salts, potassium salts or lithium salts.

EXAMPLE 1 
54 g of 4,4'-diaminostilbene-2,2'-disulphonic acid are stirred in 300 ml of 
water, 100 g of ice and 60 ml of conc. hydrochloric acid and then 
tetrazotized by addition of 70 ml of a 30% strength by volume aqueous 
sodium nitrite solution. The suspension is stirred at 5.degree. C. for 1 
hour. Excess nitrite is removed by addition of sulphamic acid after the 
reaction has ended. A solution of 65 g of 
2-(2-hydroxyethylmercapto)-N-(2-hydroxyethyl)aniline in 50 ml of water/15 
ml of conc. hydrochloric acid is then added. After 30 minutes, the pH is 
brought from 0.5-0.8 to 1.5 at about 10.degree. C. over a period of 1 hour 
with sodium carbonate solution, and the resulting mixture is stirred for 2 
hours. It is then stirred at 10.degree. to 15.degree. C. and pH 2.0 to 2.5 
for 6 to 8 hours. The precipitated intermediate of the structure 
##STR13## 
(.lambda..sub.max =481 nm) is isolated by suction filtration, and the 
moist paste is directly further reacted. However, isolation of the 
intermediate can also be dispensed with, and the coupling mixture can 
directly be oxidized. 
For oxidation, the moist paste is suspended in 400 ml of water, the 
suspension is brought to pH 5.0with sodium. carbonate solution, and 0.2 g 
of sodium tungstate is added. The reaction mixture is heated to 60.degree. 
C. Without any further addition of heat, about 100 ml of a 30% strength 
aqueous hydrogen peroxide solution are then slowly metered in, as a result 
of which the temperature rises to about 70.degree. to 75.degree. C. owing 
to the heat of reaction and a solution is formed. During the reaction, the 
pH is kept constant at 5.0 with sodium carbonate solution. After an 
additional stirring phase of 1 hour at 75.degree. C., the mixture is 
slowly cooled to 20.degree. C. the precipitated dyestuff is isolated and 
dried to give about 100 g of a salt-containing product of the structure 
##STR14## 
(.lambda..sub.max =440 nm (H.sub.2 O)), the structure given including 
possible disazoxy compounds. Drying can also be dispensed with, and the 
moist dyestuff paste can directly be further reacted by suspending it in 
250 ml of water at pH 7, adding 0.2 g of Raney nickel catalyst, and 
reducing the mixture in an autoclave at 50 to 70 atm with 4.5 to 4.7 times 
the equimolar amount of hydrogen. 
This may result in heating of the suspension to 40.degree. to 50.degree. C. 
After letdown and removal of the catalyst by filtration, a clear, pale 
brownish solution is obtained. It is heated to 60.degree. C. and brought 
to a pH of 1.0 with dilute sulphuric acid. This results in almost 
quantitative crystallization of the 4,4'-diaminostilbene-2,2'-disulphonic 
acid as the betaine. It is filtered off with suction while Hot and washed 
with 50 ml of cold water. Drying gives about 40 g of 
4,4'-diaminostilbene-2,2'-disulphonic acid. 
The filtrate combined with the wash water contains the desired 
[5-amino-2-(2hydroxyethylamino)phenyl]-(2-hydroxyethyl) sulphone of the 
formula 
##STR15## 
Content analysis of the 350 ml of solution is performed by means of 
diazotization. It shows that about 55 g of product of the above formula 
are in solution. Comparison by TLC shows that this compound is identical 
to a sample of the substance prepared by the method of EP 153,599. After 
neutralization, the above solution can be used for dyestuff synthesis. 
EXAMPLE 2 
54 g of 2,2'-(1,2-ethanediyl)bis[5-aminobenzenesulphonic acid] are stirred 
in 300 ml of water, 100 g of ice and 60 ml of conc. hydrochloric acid and 
then tetrazotized by addition of 70 ml of a 30% strength by volume aqueous 
sodium nitrite solution. The suspension is stirred at 5.degree. C. for 1 
hour. Excess nitrite is removed by addition of sulphamic acid after the 
reaction has ended. A solution of 65 g of 
2-(2-hydroxyethylmercapto)-N-(2-hydroxyethyl)aniline in 50 ml of water/15 
ml of conc. hydrochloric acid is then added. After 30 minutes, the pH is 
brought from 0.5-0.8 to 1.5 at about 10.degree. C. over a period of 1 hour 
with sodium carbonate solution, and the resulting mixture is stirred for 2 
hours. It is then stirred at 10.degree. to 15.degree. C. and pH 2.0 to 2.5 
for 6 to 8 hours. The precipitated intermediate of the structure 
##STR16## 
(.lambda..sub.max =440 nm) is isolated by suction filtration, and the 
moist paste is directly further reacted. However, isolation of the 
intermediate can also be dispensed with, and the coupling mixture can 
directly be oxidized by the following procedure: 
For oxidation, the moist paste is suspended in 400 ml of water, the 
suspension is brought to pH of 6.5 with sodium carbonate solution, and 0.2 
g of sodium tungstate is added. The reaction mixture is heated to 
60.degree. C. Without any further addition of heat, about 100 ml of a 30% 
strength aqueous hydrogen peroxide solution are then slowly metered in, as 
a result of which the temperature rises to about 70.degree. to 75.degree. 
C. owing to the heat of reaction and a solution is formed. During the 
reaction, the pH is kept constant at 5.0 with sodium carbonate solution. 
After an additional stirring phase of 1 hour at 75.degree. C., the mixture 
is cooled to 20.degree. C., the salted-out dyestuff is isolated and dried 
to give about 100 g of a salt-containing product of the structure 
##STR17## 
(.lambda..sub.max =395,435 (sh) nm (H.sub.2 O)), the structure given 
including possible disazoxy compounds. 
Drying can also be dispensed with, and the moist paste can directly be 
further reacted. 
The moist dyestuff paste is suspended in 250 ml of water, 0.2 g of Raney 
nickel catalyst is added, and the mixture is reduced in an autoclave at 50 
to 70 atm with 4.5 to 4.7 times the equimolar amount of hydrogen. 
This may result in exothermic heating of the suspension to 40.degree. C. 
After the end of the reaction, the catalyst is filtered off, and the 
remaining aqueous solution is heated to 80.degree. C. The pH is brought to 
1.0 with dilute sulphuric acid, resulting in almost quantitative 
precipitation of the 2,2'-(1,2-ethanediyl)bis[5-aminobenzenesulphonic 
acid] as the dibetaine. It is filtered off with suction at 60.degree. C. 
and washed with 50 ml of cold water. After tetrazotization, the removed 
diamino compound can be reused in the next synthesis sequence. 
The filtrate combined with the wash water contains the desired 
[5-amino-2-(2-hydroxyethylamino)phenyl]-(2-hydroxyethyl) sulphone, which 
can now be analyzed and reacted as described in Example 1.