Dyestuffs of the formula ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, m, n, p and X have the meaning given in the description, and their use for dyeing and printing materials containing hydroxyl groups or amide groups, such as textile fibres, filaments and woven fabrics of wool, silk or synthetic polyamide or polyurethane fibres, and for dyeing and printing natural or regenerated cellulose in dyeings and prints which are fast to washing. Blue dyeings and prints which are fast to light and wet processing are obtained.

The present invention relates to reactive dyestuffs of the formula 
##STR2## 
wherein 
R.sub.1 =C.sub.1 -C.sub.4 -alkyl or halogen, 
R.sub.2 =H or C.sub.1 -C.sub.4 -alkyl, 
R.sub.3 and R.sub.4 =H, C.sub.1 -C.sub.4 -alkyl or halogen, 
m, n and p=0 or 1 and 
X=NH.sub.2, where n=0, and NH.sub.2, C.sub.1 -C.sub.4 -alkylamino or 
C.sub.1 -C.sub.4 -dialkylamino, where n=1. 
The alkyl radicals can optionally be substituted. 
Examples of suitable radicals R.sub.1 are CH.sub.3, C.sub.2 H.sub.5, F, Cl 
or Br. 
Suitable radicals R.sub.2 are, in addition to H: CH.sub.3, C.sub.2 H.sub.5, 
CH.sub.2 --CH.sub.2 --OH, CH.sub.2 --CH.sub.2 --OSO.sub.3 H, CH.sub.2 
--COOH, CH.sub.2 --CH.sub.2 --COOH and CH.sub.2 --CH.sub.2 --SO.sub.3 H. 
Suitable radicals R.sub.3 and R.sub.4 are, in addition to H: CH.sub.3, 
C.sub.2 H.sub.5, (CH.sub.2).sub.2 --CH.sub.3, CH(CH.sub.3).sub.2, 
(CH.sub.2).sub.3 --CH.sub.3, CH.sub.2 --CH(CH.sub.3).sub.2, 
C(CH.sub.3).sub.3, Cl and Br. 
Examples of suitable radicals X, where n=1, are, in addition to NH.sub.2 : 
NHCH.sub.3, NHC.sub.2 H.sub.5, NHC.sub.3 H.sub.7, NH--C.sub.4 H.sub.9, 
NH--CH.sub.2 --CH.sub.2 --OH, N(CH.sub.3).sub.2, N(C.sub.2 H.sub.5).sub.2, 
N(CH.sub.3)C.sub.2 H.sub.5, N(CH.sub.3)--CH.sub.2 --CH.sub.2 OH, 
N(CH.sub.2 --CH.sub.2 OH).sub.2 and 
##STR3## 
Particularly preferred dyestuffs within the scope of the formula I are 
those of the formula 
##STR4## 
wherein R.sub.5, R.sub.6 and R.sub.7 =H, CH.sub.3 or C.sub.2 H.sub.5, and 
a sulphonic acid group optionally present in the left-hand part of the 
anthraquinone system can be in the 5-, 6-, 7- or 8-position. 
The new dyestuffs are obtained by a process in which anthraquinone 
compounds containing amino groups, of the formula 
##STR5## 
wherein R.sub.1 to R.sub.4, m, n and p have the abovementioned meaning, 
are subjected to condensation reactions with 2-amino-4,6-difluorotriazine 
or 2-alkylamino- or 2-dialkylamino-4,6-difluorotriazines. 
According to another preparation procedure, the new reactive dyestuffs (I) 
are also obtained by a process in which anthraquinone compounds containing 
amino groups, of the formula (II), are first subjected to condensation 
reactions with cyanuric fluoride to give intermediate products of the 
formula 
##STR6## 
and these products are then reacted with ammonia or compounds which 
release ammonia, monoalkylamines or dialkylamines in a second reaction 
step. 
Suitable compounds for this last stage are, in addition to ammonia itself, 
all the ammonium salts, such as, for example, ammonium chloride, ammonium 
sulphate, ammonium carbonate, ammonium bicarbonate and ammonium nitrate. 
The reaction of the aminoanthraquinone compounds (II) with optionally 
substituted 2-amino-4,6-difluorotriazines is carried out in an aqueous or 
aqueous-organic medium at temperatures of 0.degree.-80.degree., preferably 
10.degree.-50.degree., and at pH values of 3-10, preferably 5-9, in the 
presence of alkaline condensing agents, such as aqueous alkali metal 
carbonate solutions, alkali metal hydroxide solutions or alkali metal 
phosphate solutions. The reaction of aminoanthraquinone compounds (II) 
with cyanuric fluoride is carried out in an aqueous or aqueous-organic 
medium at temperatures of -10.degree. to +30.degree., preferably 
0.degree.-20.degree., and at pH values of 2-8, preferably 3-6. 
The condensation of the difluorotriazinylanthraquinone compounds (III) with 
ammonia, monoalkylamines or dialkylamines is carried out at temperatures 
of 0.degree.-50.degree., preferably 0.degree.-30.degree., and at pH values 
of 7-11, preferably 8-10. 
The new dyestuffs are extremely valuable products which are suitable for 
the most diverse applications. As water-soluble compounds, they are 
preferably of interest for dyeing textile materials containing hydroxyl 
groups or nitrogen, in particular textile materials of natural and 
regenerated cellulose, and furthermore of wool, silk or synthetic 
polyamide or polyurethane fibres. 
The materials mentioned are dyed or printed by the processes customary for 
reactive dyestuffs. Blue dyeings and prints which are fast to light and 
wet processing are obtained.

The temperatures given in the examples are in .degree.C. The formulae of 
the dyestuffs in the description and in the examples are those of the free 
acids. The dyestuffs are generally isolated and used in the form of their 
alkali metal salts, in particular the sodium salts or potassium salts. 
EXAMPLE 1 
15.0 g of 
1-amino-4-(3'-amino-2'-methyl-phenylamino)-anthraquinone-2,5'-disulphonic 
acid are dissolved, at pH 6.5 and at 25.degree., in 220 ml of water. 4.7 g 
of 2-amino-4,6-difluorotriazine are introduced into the solution in the 
course of 15 minutes and the pH value is kept at 6-6.5 with 2 N sodium 
carbonate solution. The course of the reaction is followed by 
chromatography. The mixture is subsequently stirred for several hours 
under the conditions indicated and the dyestuff formed is salted out with 
8% of sodium chloride, filtered off and washed with 8% strength sodium 
chloride solution. The dyestuff of the formula 
##STR7## 
is dried at 45.degree. in vacuo. 
50 g of cotton hanks are dyed in 1 liter of dye liquor containing 1.5 g of 
the above dyestuff by heating the bath to 40.degree. in the course of 30 
minutes, adding 50 g of sodium chloride in several portions and then 
adding 20 g of sodium carbonate and treating the hanks at this temperature 
for 60 minutes. After rinsing, soaping at the boil and drying, a strong, 
blue dyeing with excellent fastness to light and wet processing is 
obtained. 
EXAMPLE 2 
16.0 g of 
1-amino-4-(2',6'-dimethyl-3'-methylaminomethyl-phenylamino)-anthraquinone- 
2,X'-disulphonic acid are dissolved, at pH 7.5 and at 20.degree., in 200 ml 
of water. 4.5 g of 2-amino-4,6-difluorotriazine are added to the solution 
at a constant rate in the course of 20 minutes and the pH value is kept at 
7.0 with 2 N sodium carbonate solution. The reaction is brought to 
completion by subsequently stirring the mixture for several hours. Any 
residues of the reactive component are removed by clarifying the dyestuff 
solution by filtration and the dyestuff is salted out from the filtrate by 
adding 20% of sodium chloride. The precipitate is filtered off, the filter 
cake is washed with 20% strength sodium chloride solution and the 
resulting dyestuff of the formula 
##STR8## 
is dried at 50.degree. in vacuo. 
Cellulose fabric is printed with a printing paste which contains, per 
kilogram, 40 g of the above dyestuff, 100 g of urea, 300 ml of water, 500 
g of alginate thickener and 20 g of sodium carbonate and which has been 
made up to 1 kilogram with water, and the fabric is dried, steamed at 
105.degree. for 5 minutes, rinsed with hot water and then soaped at the 
boil, rinsed and dried. A clear, reddish-tinged blue print of very good 
fastness to wet processing and light is obtained in this manner. 
Cellulose materials can be dyed in the following manner: 
100 g of cotton fabric are padded at room temperature with an aqueous 
solution containing 3% by weight of the above dyestuff, 20 g/liter of 
sodium bicarbonate and 150 g/liter of urea and are intermediately dried, 
heated to 140.degree. for 2 minutes and then rinsed and soaped at the 
boil. The fabric is dyed in clear reddish-tinged blue shades which are 
fast to light and wet processing. 
If the anthraquinone components listed in Table I are subjected to 
condensation reactions with 2-amino-4,6-difluorotriazine in an analogous 
manner, other reactive dyestuffs with which cotton can be dyed or printed 
in the colour shades indicated are obtained. 
TABLE I 
______________________________________ 
No. Anthraquinone component Colour shade 
______________________________________ 
##STR9## blue 
4 
##STR10## blue 
5 
##STR11## blue 
6 
##STR12## reddish-tinged blue 
7 
##STR13## reddish-tinged blue 
8 
##STR14## reddish-tinged blue 
9 
##STR15## blue 
10 
##STR16## blue 
11 
##STR17## Greenish- tinged blue 
12 
##STR18## blue 
13 
##STR19## blue 
14 
##STR20## blue 
15 
##STR21## blue 
16 
##STR22## reddish- tinged blue 
17 
##STR23## reddish- tinged blue 
18 
##STR24## reddish- tinged blue 
19 
##STR25## blue 
20 
##STR26## reddish- tinged blue 
21 
##STR27## blue 
22 
##STR28## blue 
23 
##STR29## blue 
24 
##STR30## blue 
25 
##STR31## blue 
26 
##STR32## blue 
27 
##STR33## reddish- tinged blue 
______________________________________ 
EXAMPLE 28 
18.0 g of 
1-amino-4-(3'-amino-2'-methyl-phenylamino)-anthraquinone-2,5'-disulphonic 
acid are dissolved, at pH 5, in 250 ml of water. After cooling the 
solution to 0.degree.-5.degree., the pH value is adjusted to 3.5 by means 
of dilute hydrochloric acid. 5.8 g of cyanuric fluoride are now added 
dropwise in the course of 5 minutes and the pH value of the solution is 
kept at 3.0-3.5 with 1 N sodium carbonate solution. After the dropwise 
addition, the mixture is subsequently stirred at 0.degree.-5.degree. and 
at pH 3.5 for a further 5-10 minutes and a solution of 2.4 g of ammonium 
chloride in 30 ml of water is then added. The pH value is subsequently 
kept at 8.3-8.5 with sodium carbonate solution. After 4 hours, the 
temperature is allowed to rise to 20.degree., 8% of sodium chloride are 
added gradually and the mixture is stirred for some hours to bring the 
precipitation to completion. The dyestuff of the formula 
##STR34## 
which has precipitated is filtered off, washed with 8% strength sodium 
chloride solution and dried at 45.degree. in vacuo. The resulting dyestuff 
is identical to that of Example 1. 
EXAMPLE 29 
18.0 g of 
1-amino-4-(5'-amino-2',4',6'-trimethylphenylamino)-anthraquinone-2,3'-disu 
lphonic acid are dissolved, at pH 4.5, in 180 ml of water. The solution is 
cooled to 0.degree.-5.degree. and 5.5 g of cyanuric fluoride are added 
dropwise at a constant rate in the course of 5 minutes. During this 
addition, the pH value of the solution is kept at 4.5 by means of 2 N 
sodium carbonate solution. The mixture is subsequently stirred for a 
further 15 minutes under the conditions indicated. When the reaction has 
ended, a solution of 2.4 g of ammonium chloride in 30 ml of water is added 
and the pH value is now kept at 8.3-8.5 with 2 N sodium carbonate 
solution. After about 2-3 hours, the condensation reaction between the 
difluorotriazinyl dyestuff and ammonia has ended. The solution is warmed 
to 20.degree. and the resulting dyestuff of the formula 
##STR35## 
is salted out of it by adding 22% of potassium chloride. The product which 
has precipitated is filtered off, washed with 25% strength potassium 
chloride solution and dried at 40.degree. in vacuo. 
Besides using the dyeing and printing processes mentioned in Examples 1 and 
2, cotton can also be dyed by the following process: 
100 g of cotton fabric are padded on a padder at room temperature using an 
aqueous solution containing 30 g/liter of the dyestuff of Example 29 and 
20 g/liter of sodium carbonate such that the liquor pick-up of the fabric 
is 80% of its dry weight. The fabric is rolled up and kept at 25.degree. 
for 24 hours such that no moisture can escape. The fabric is then rinsed, 
soaped at the boil and dried. A clear, reddish-tinged blue dyeing which 
has very good fastness to light and wet processing is obtained. 
In an analogous manner, other reactive dyestuffs, with which cotton can be 
dyed or printed in the colour shades indicated, can be prepared by 
reacting the anthraquinone components indicated in Table II with cyanuric 
fluoride and subjecting the resulting difluorotriazinyl dyestuffs to 
condensation reactions with ammonia or ammonium chloride. 
TABLE II 
______________________________________ 
No. Anthraquinone component Colour shade 
______________________________________ 
30 
##STR36## reddish- tinged blue 
31 
##STR37## blue 
32 
##STR38## reddish- tinged blue 
33 
##STR39## blue 
34 
##STR40## blue 
35 
##STR41## blue 
36 
##STR42## blue 
37 
##STR43## blue 
______________________________________ 
EXAMPLE 38 
25.0 g of 
1-amino-4-(2',6'-dimethyl-3'-methylaminomethyl-phenylamino)-anthraquinone- 
2,X'-disulphonic acid are dissolved, at pH 7.0 and at 
20.degree.-25.degree., in 250 ml of water. 
7.7 g of 2,4-difluoro-6-methylamino-triazine are introduced into this 
solution in the course of 20-30 minutes and the pH value is kept at 
6.5-7.0 by adding 1 N sodium hydroxide solution. The mixture is 
subsequently stirred for 11/2 hours in order to bring the reaction to 
completion. 22% of sodium chloride are now added to the solution at a 
constant rate in the course of 30 minutes. The dyestuff which has 
precipitated is filtered off, washed with 25% strength sodium chloride 
solution and dried at 45.degree. in vacuo. 
The dyestuff corresponds to the formula 
##STR44## 
and on cellulose fabric gives, by the printing process of Example 2, 
clear, reddish-tinged blue prints which have excellent fastness to light 
and wet processing. 
EXAMPLE 39 
18.0 g of 
1-amino-4-(2',6'-dimethyl-3'-aminomethylamino)-anthraquinone-2,X'-disulpho 
nic acid are dissolved, at pH 7-8 and at 35.degree., in 180 ml of water. A 
solution of 7.2 g of 2-diethylamino-4,6-difluorotriazine in 35 ml of 
acetone is added dropwise at 30.degree.-35.degree. in the course of 30 
minutes and the pH value is kept at 6.5-7.0 with 1 N sodium hydroxide 
solution. After subsequently stirring the mixture for one hour, the 
temperature is increased to 40-45.degree. and the pH value is kept at 7.0 
for a further 2 hours. 
Any residues of the triazine component are filtered off and the filtered 
dyestuff solution is allowed to run into twice the volume of 25% strength 
sodium chloride solution. The dyestuff of the formula 
##STR45## 
which has precipitated is filtered off, washed with 15% strength sodium 
chloride solution and dried at 50.degree. in vacuo. 
Following the printing instructions of Example 2, on cotton and viscose 
staple the dyestuff gives clear reddish-tinged blue prints which are very 
fast to light and wet processing. 
If the anthraquinone components and substituted 
2-amino-4,6-difluorotriazines listed in Table III are subjected to 
condensation reactions in an analogous manner, other reactive dyestuffs 
with which cotton or viscose staple can be printed in the shades indicated 
are obtained. 
TABLE III 
__________________________________________________________________________ 
Anthraquinone Reactive 
No. 
component component Colour shade 
__________________________________________________________________________ 
40 
##STR46## 
##STR47## reddish-tinged blue 
41 
##STR48## 
##STR49## reddish-tinged blue 
42 
##STR50## 
##STR51## reddish-tinged blue 
43 
##STR52## 
##STR53## blue 
44 
##STR54## 
##STR55## blue 
45 
##STR56## 
##STR57## reddish-tinged blue 
46 
##STR58## 
##STR59## reddish-tinged blue 
47 
##STR60## 
##STR61## reddish-tinged blue 
48 
##STR62## 
##STR63## reddish- tinged blue 
49 
##STR64## 
##STR65## reddish- tinged blue 
50 
##STR66## 
##STR67## blue 
51 
##STR68## 
##STR69## blue 
__________________________________________________________________________