The invention is that of a new triphenodioxazine dye of the formula: ##STR1## wherein: ##STR2## K is independently selected from SO.sub.3 H and COOH; W=a substituted or unsubstituted arylene, alkylene or arylene-alkylene group; PA1 Y.sup.1 =Vinyl, .beta.-Sulfatoethyl, .beta.-Thiosulfatoethyl, .beta.-Halogenethyl-group, .beta.-Phosphatoethyl, and PA1 X=H. PA1 R, R.sub.1 and R.sub.2 are independently selected from hydrogen and substituted or unsubstituted alkyl. PA1 T is independently selected from hydrogen, Cl, Br, C.sub.1 to C.sub.6 alkyl, C.sub.1 to C.sub.6 alkoxy, phenyl or phenoxy; and PA1 n is selected from 0, 1 or 2.

BACKGROUND OF THE INVENTION 
1. Technical Field 
This invention is directed to new fiber reactive triphenodioxazine dye. 
2. Background 
Anthraquinone based fiber reactive dyes have been the predominate dye used 
in the coloring of cotton fabdcs in bright blue colors. This dominance of 
the anthraquinone dyes has been threatened over the past decade or so by 
the increasing use of dyes based upon the triphenodioxazine chromophore. 
Examples of the recent patent activity in this triphenodioxazine based dyes 
are: U.S. Pat. No. 4,604,459; U.S. Pat. No. 3,996,221; U.S. Pat. No. 
4,092,478; U.S. Pat. No. 4,400,504; U.S. Pat. No. 4,472,575; U.S. Pat. No. 
4,774,333; U.S. Pat. No. 4,629,788; and EPO 385,120 (Sep. 9, 1990). 
The present invention provides new dioxazine based fiber reactive dyes with 
good fastness properties (light, chlorine and wash fastness), high 
substantivity for cellulosic fibers, high tinctorial strength and a bright 
reddish blue color. In addition, the dyes of the invention are easily 
synthesized from readily available intermediates at low costs. 
SUMMARY OF THE INVENTION 
The invention is that of a new triphenodioxazine dye of the formula: 
##STR3## 
wherein: 
##STR4## 
W=a substituted or unsubstituted arylene, alkylene or arylene-alkylene 
group where the alkylene moiety may be interrupted by a hetero atom 
selected from O, S and N; 
Y.sup.1 =Vinyl, .beta.-Sulfatoethyl, .beta.-Thiosulfatoethyl, 
.beta.-Halogenethyl, .beta.-Phosphatoethyl, and 
X=H. 
K is independently selected from SO.sub.3 H and COOH. 
R, R.sub.1 and R.sub.2 are independently selected from hydrogen and 
substituted or unsubstituted alkyl of 1 to 6 carbons; preferably hydrogen 
and a substituted or unsubstituted C.sub.1 to C.sub.4 alkyl. 
R.sub.2 may also be selected from the group W--SO.sub.2 --Y.sup.1. 
T is independently selected from hydrogen, Cl, Br, C.sub.1 to C.sub.6 
alkyl, C.sub.1 to C.sub.6 alkoxy, phenyl or phenoxy; and 
n is selected from 0, 1 or 2. 
The dyes of the above formula provide dyeing on cotton substrates having a 
bright reddish blue color having good fastness or properties of high 
tinctodal strength. The dyes of the invention may also be used in the 
dyeing of other textiles containing amido and/or hydroxyl groups; 
exemplary materials include regenerated cellulose, synthetic polyamides, 
wool, silk and polyurethane fibers. The dyes of the invention may be 
applied by the standard methods for printing and dyeing textiles with 
fiber reactive dyes.

DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The invention relates to new triphendioxazine reactive dyestuffs of the 
formula: 
##STR5## 
wherein: 
R and R.sub.1 are independently selected from H or a substituted or 
unsubstituted alkyl, preferably hydrogen or a substituted or unsubstituted 
C.sub.1 -C.sub.6 - alkyl, and most preferably hydrogen or a substituted or 
unsubstituted C.sub.1 -C.sub.4 alkyl; 
T is independently selected from H, Cl, Br, a substituted or unsubstituted 
C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, phenyl, or phenoxy; 
##STR6## 
R.sub.2 iS selected from hydrogen or a substituted or unsubstituted 
C.sub.1 to C.sub.6 alkyl or the group W--SO.sub.2 --Y.sup.1 ; preferably 
hydrogen or a substituted or unsubstituted C.sub.1 to C.sub.4 alkyl. 
W is a substituted or unsubstituted arylene, or alkylene, or 
arylene-alkylene group wherein the alkylene group may be interrupted by a 
hetero atom selected from O, S and N, preferably a substituted or 
unsubstituted phenylene or naphthalene group or a substituted or 
unsubstituted C.sub.1 to C.sub.6 alkylene group, wherein said alkylene 
moiety may be interrupted by a hetero atom selected from O, N and S; 
Y.sup.1 =Vinyl, .beta.-Sulfatoethyl, .beta.-Thiosulfatoethyl, 
.beta.-Halogenethyl, .beta.-Phosphato, and X=H. K is independently 
selected from SO.sub.3 H and COOH. n=0, 1 or 2. 
The term "arylene-alkylene" group as used in this specification and the 
claims is intended to mean a phenylene or naphthalene group bonded to one 
or more alkylene groups, e.g. the following illustrations or their 
isomers: 
##STR7## 
Examples of R, R.sub.1 and R.sub.2 are: hydrogen or CH.sub.3, C.sub.2 
H.sub.5, n-C.sub.3 -H.sub.7, n-C.sub.4 H.sub.9, n-C.sub.6 H.sub.13, which 
may be optionally substituted by OH, OCH.sub.3, OC.sub.2 H.sub.5, COOH, 
SO.sub.3 H, OSO.sub.3 H, CN, Cl, or F. 
Examples of the substituents in substituted C.sub.1 -C.sub.4 -alkyl and 
C.sub.1 -C.sub.4 -alkoxy, groups are OH, OCH.sub.3, OC.sub.2 H.sub.5, 
COOH, SO.sub.3 H, OSO23H, CN, Cl, Br or F; preferably OCH.sub.3, OC.sub.2 
H.sub.5 and OSO.sub.3 H. 
Examples of the substituents in a substituted phenyl and phenoxy groups are 
Cl, Br, CH.sub.3, C.sub.2 H.sub.5, OCH.sub.3, SO.sub.3 H, COOH and 
OC.sub.2 H.sub.5. 
Preferably R and R.sub.1 are hydrogen; R.sub.2 is preferably hydrogen, 
CH.sub.3 or C.sub.2 H.sub.5 ; W is preferably phenylene or naphthalene 
which may be substituted by methyl, methoxy, carboxy and sulfo. Y.sup.1 is 
preferably vinyl or sulfatoethyl, X is preferably hydrogen and n is 
preferably 1. 
Exemplary type "Q" groups are: 
2-(.beta.-Sulfatoethylsulfonyl)-phenyl-amino, 
3-(.beta.-Sulfatoethylsulfonyl)-phenyl-amino, 
4-(.beta.-Sulfatoethylsulfonyl)-phenyl-amino, 
2-Carboxy-5-(.beta.-sulfatoethylsulfonyl)-phenyl-amino, 
2-Chloro-3-(.beta.-Sulfatoethylsuifonyl)-phenyl-amino,2-Chloro-4-(.beta.-s 
ulfatoethylsulfonyl)-phenyl-amino, 2-Ethoxy-4- or 
5-(.beta.-sulfatoethylsulfonyl)-phenyl-amino,2-Ethyl-4-(.beta.-sulfatoethy 
lsulfonyl)-phenyl-amino, 
2-Methoxy-5-(.beta.-sulfatoethylsulfonyl)-phenyl-amino, 
2,3-Dimethoxy-5-(.beta.-sulfatoethylsulfonyl)-phenyl-amino, 
2,4-Dimethoxy-5-(.beta.-sulfatoethylsulfonyl)-phenyl-amino, 
2,5-Dimethoxy-4-(.beta.-sulfatoethylsulfonyl)-phenyl-amino, 
2-Methoxy-5-methyl-4-(.beta.-sulfatoethylsulfonyl)-phenyl-amino, 2or 3- or 
4-(.beta.-Thiosulfatoethylsulfonyl)-phenyl-amino, 
2-Methoxy-5-thiosulfatoethylsulfonyl)-phenyl-amino, 
2-Sulfo-4-(.beta.-phosphatoethylsulfonyl)-phenyl-amino, 
2-Sulfo-4-vinylsulfonyl-phenyl-amino, 2-Hydroxy-4- 
or-5-(.beta.-sulfatoethylsulfonyl)-phenyl-amino, 
2-Chloro-4-or-5-.beta.-chloroethylsulfonyl)-phenyl-amino, 
2-Hydroxy-3-sulfo-5-(.beta.-sulfatoethylsulfonyl)-phenyl-amino, 3- or 
4-(.beta.-Acetoxyethylsu lfonyl)-phenyl-amino, 
2-Methoxy-4-[.beta.-(N-methyl-tauryl)ethylsulfonyl]-phenyl-amino 
5-(.beta.-Sulfatoethylsulfonyl)naphth-2-yl-amino, 6- or 7- or 
8-(.beta.-Sulfatoethylsulfonyl)-naphthy-2-yl-amino, 
6-(.beta.-Sulfatoethylsulfonyl)-1-sulfo-naphth-2-yl-amino, 
5-(.beta.-Sulfatoethylsulfonyl)-l-sulfo-naphth-2-yl-amino, 
8-(.beta.-Sulfatoethylsulfonyl)-6-sulfo-naphth-2-yl-amino, 
.beta.-[4-(.beta.'-Sulfatoethylsulfonyl)-phen]-ethylamino, 
.beta.-[-2-Sulfo-4-(.beta.'-sulfatoethylsulfonyl)phen]ethylamino, 
.beta.-(.beta.'-Chloroethylsulfonyl)-ethylamino, .beta.- 
(.beta.'-Sulfatoethylsulfonyl)-ethylamino, 
.beta.-(Vinyisulfonyl)-ethylamino, 
(.beta.'-Chloroethylsulfonyl)-propylamino, 
.gamma.-(.beta.'-Sulfatoethylsulfonyl)-propylamino, 
.gamma.-(.beta.'-Bromoethylsulfonyl)-propylamino, 
.gamma.-(Vinylsulfonyl)-propylamino, 
1-Methyl-1-(.beta.-sulfatoethylsulfonyl)-1-ethylamino, 
.delta.-(.beta.'-Sulfatoethylsulfonyl)-butylamino, 2- 
Methyl-2-(.beta.-chloroethylsulfonyl)-1-propylamino, 
.omega.-(.beta.'-Chloroethylsulfonyl)-pentylamino, 
.beta.-(.beta.'-Chloroethylsulfonyl)-n-hexyalmino, 
N-Methyl-N-[.beta.-(.beta.'chloroethylsulfonyl)-ethyl]-amino, 
N-Ethyl-N-[.beta.-(.beta.'-chloroethyisulfonyl)ethyl]-amino, 
N-n-Propyl-N-[.beta.-(.beta.'chloroethylsulfonyl)-ethyl]-amino, 
N-Carboxymethyl-N-[.beta.-(.beta.'-bromoethylsulfonly)-ethyl]-amino, 
N-Sulfatomethyl-N-[.beta.-(.beta.'-chloroethylsulfonyl)-ethyl]-amino, 
N-(.beta.-Carboxyethyl)-N-[-.gamma.'-(.beta.-chloroethylsulfonyl)-propyl-a 
mino-N-(.beta.-Sulfatoethyl)-N-[.gamma.-(.beta."chloroethylsulfonyl)-propyl 
-amino-N-(.beta.-(.beta.Sulfatoethyl)-N-[,.delta.'(.beta."chloroethylsulfon 
yl)-butyl]-amino, 
N-(.beta.-Ethoxyethyl)-N-[.delta.'-(.beta."-chloroethylsulfonyl)-butyl]-am 
ino, 
N-(.gamma.-Chloropropyl)-N-[.delta.'(.beta."-chloroethylsulfonyl)-butyl]-a 
mino, N-Phenyl-N-[.beta.-(.beta.'-chloroethylsulfonyl)-ethyl]-amino, 
N-(3-Sulfophenyl)-N-[.beta.-(.beta.'-chloroethylsulfonyl)-ethyl]amino, 
N-(4-Sulfophenyl)-N-[.beta.-(.beta.'-chloroethylsulfonyl)-ethyl]-amino, 
Bis-[.beta.-(.beta.'-chloroethylsulfonyl)-ethyl]-amino, 
Bis-[.beta.-(.beta.'-bromoethylsulfonyl)-ethyl]-amino, 
Bis-[.gamma.-(.beta.'-chloroethylsulfonyl)-propyl]-amino, 
Bis-[.delta.-(.beta.'-chloroethyisulfonyl)-butyl]-amino, 
Bis-(.beta.-vinylsulfonyl-ethyl)-amino, 
N-(.beta.-Cyanoethyl)-N-[.gamma.'-.beta."-chloroethylsulfonyl)-propyl]-ami 
no, 
.beta.[.beta.'-(.beta."-Chloroethylsulfonyl)-ethylamino]-ethylamino, 
.beta.[.beta.'(.beta."- Sulfatoethylsulfonyl)-ethylamino]-ethylamino, 
.beta.-[.beta.'(.beta."-Chioroethylsuifonyl)-ethoxy]-ethylamino, 
.beta.-.beta.'-.beta."-Sulfatoethylsulfonyl)-ethoxy]-ethylamino, 
3,4-Di-(.beta.-sulfatoethylsulfonyl)-phenylamino, 
2,5-Di(.beta.-sulfatoethylsulfonyl)-phenylamino, 
4-[.gamma.-(.beta.'Sulfatoethylsulfonyl)-propoxy]-phenylamino, 
2,5-Bis-[(.beta.-sulfatoethylsulfonyl)-methyl], phenylamino, 
N-Methyl-N-[4-(.beta.-sulfatoethylsulfonyl)-phenyl]-amino, 
N-Methyl-N-[3-(.beta.-sulfatoethylsulfonyl)-phenyl]-amino, 
N-Ethyl-N-[4-(.beta.-sulfatoethylsulfonyl)-phenyl]-amino, 
N-Ethyl-N-[3-(.beta.-sulfatoethylsulfonyl)-phenyl]-amino, and halogen 
(chloro, fluoro and bromo). 
Dyestuffs which are preferred having the following general Formula 1A: 
##STR8## 
wherein T.sub.1, R, R.sub.1 and Q have the above mentioned meaning. 
The moiety Q may be represented by the formula: 
##STR9## 
wherein D is independently selected from a covalent bond or a C.sub.1 to 
C.sub.6 alkylene group which may be optionally interrupted by a hetero 
atom selected from O, N and S; Y.sup.1 is defined above, and R.sub.4 is 
selected from H, Cl, Br, C.sub.1 to C.sub.4 alkyl, C.sub.1 to C.sub.4 
alkoxy or phenoxy and R.sub.2 is as previously defined. 
Preferred dyestuffs of Formula 1 are those in which 
##STR10## 
where the benzene ring A can contain further substituents. Examples of 
such substituents are: CH.sub.3, C.sub.2 H.sub.5, OCH.sub.3, OC.sub.2 
H.sub.5, Cl, COOH, and SO.sub.3 H. 
The invention also relates to a process for preparing the dyestuffs of the 
Formula 1 wherein X is hydrogen. This process is characterized in that 
about 1 mole of a triphenodioxazine dyestuff of the Formula 2. 
##STR11## 
preferably in the form of the corresponding lithium salts is condensed 
with about 1 to 1.3 moles of 2,4,6-trichlorotriazine with elimination of 1 
mole hydrochloric acid, preferably using basic lithium compounds such as 
lithium hydroxide or lithium carbonate as acid acceptors, to give the 
triphenodioxazine/dichlorotriazine condensation product, which then is 
reacted with about 1 mole of cyanamide of the Formula 3: 
EQU H.sub.2 N--CN (Formula 3) 
with the elimination of 1 mole of hydrochloric acid. The resulting 
monochloromonocyanamido compound is then reacted with about 1 mole of an 
amine of the Formula 4: 
EQU H--Q (Formula 4) 
with the elimination of 1 mole hydrochloric acid to give the dyestuff of 
Formula 1. In both the last steps, basic alkali such as lithium hydroxide, 
lithium carbonate, sodium hydroxide and sodium carbonate can be used as 
acid acceptors. 
An alternative to the above described process is the reaction of about 1 
mole of 2,4,6-trichloro-triazine with 1 mole of cyanamide of the Formula 
3, to the dichloro-monocyanamido compound of the Formula 5. 
##STR12## 
This compound is then reacted with about 1 mole of amine of the Formula 4 
to give a compound of Formula 6. 
##STR13## 
This compound is then reacted with about 1 mole of triphenodioxazine 
dyestuff of the Formula 2 to give the dye of Formula 1. In all steps 
hydrochloric acid is eliminated, which is neutralized by using a basic 
alkali compounds such as lithium hydroxide, lithium carbonate, sodium 
hydroxide and sodium carbonate. 
An other alternative for preparing the dyestuffs of the Formula 1 is first 
reaction of 1 mole o 2,4,6-trichlorotdazine with 1 mole of cyanamide of 
the Formula 1 to the dichloromonocyanamido compound of Formula 5. This 
compound is then reacted with 1 mole of the triphenodioxazine dyestuff of 
the Formula 2 to give the 
monochloro-monocyanamido-triphendioxazine-triazine compound of Formula 7. 
##STR14## 
Finally the compound of Formula 7 is reacted with approximately 1 mole of 
an amine of the Formula 4. In all steps hydrochloric acid is eliminated, 
which is accepted by using basic alkali compounds such as lithium 
hydroxide, lithium carbonate, sodium hydroxide and sodium carbonate. 
Examples of the H--Q amines are the amines of the above mentioned amine 
radicals Q. 
The preparation of compounds of the Formula 2 is effected by methods known 
to those skilled in the art by condensing 1,4-benzoquinones of the 
formula: 
##STR15## 
wherein 
T has the above mentioned meaning and R.sub.3 is independently selected 
from H, Cl, Br, a substituted or unsubstituted alkyl, a substituted or 
unsubstituted alkoxy or phenoxy, with diaminobenzenes of the formula: 
##STR16## 
wherein R, R.sub.1, and no have the above mentioned meaning, to give a 
compound of the formula: 
##STR17## 
and subsequently cyclizing the diaminobenzene or dianilino compound 10 to 
give the basic dioxazine dyestuff of Formula 2. 
The benzoquinones of Formula 8 are best condensed with the diaminobenzenes 
of the Formula 9 at temperatures of 0.degree.-70.degree. C., preferably 
20.degree.-50.degree. C., and at pH 2-10, preferably pH 5-7, in an aqueous 
or aqueous-organic medium in the presence of alkaline condensing agents. 
It is also possible to work in a purely organic medium in the presence of 
acid-binding agents. The condensation products of the Formula 10 can be 
precipitated by salting out or by acidification. 
Examples of suitable organic mediums are methanol, ethanol, and 
nitrobenzene. Examples of suitable acid-binding agents are sodium 
bicarbonate, sodium carbonate, sodium acetate, potassium acetate, sodium 
hydroxide, potassium hydroxide, sodium phosphates and sodium borate. 
Examples of suitable diaminobenzenes of the Formula 8 are as follows: 
1,4-Diaminobenzene-2-sulfonic acid, 1,4-Diaminobenzene-2-carboxy acid, 1 
-Amino-4-N-methylaminobenzene-3-sulfonic acid, 
1-Amino-4-N-ethylaminobenzene-3-sulfonic acid, 
1,4-Diamono-2-methoxybenzene-5-sulfonic acid, 
1,4-Diamono-2-methylbenzene-5-sulfonic acid, 
1,4-Diaminobenzene-2,5-disulfonic acid, 1,4-Diaminobenzene-2,5-dicarboxy 
acid, 1,4-Diamino-2-carboxybenzene-5-sulfonic acid. 
The cyclization of the dianilino compounds of the Formula 10 can be 
effected by methods known to those skilled in the art; see e.g., U.S. Pat. 
No. 4,604,459 and A.H.M. Renfrew, J.Soc. Dyers Colour, 105 (1989) 262-4, 
GB Patent No. 1,589,915 in particular, at temperatures of 
10.degree.-80.degree. C. in oleum having SO.sub.3 contents of 1-50%, in 
the absence of presence of oxidizing agents such as potassium 
peroxodisulphate, ammonium peroxodisulphate or organic peroxides. 
In general, oleum having an SO.sub.3 content of 5-30% is used in an amount 
of about 5-15 parts by weight per part by weight of the compound of 
Formula 10. 
Under the reactive conditions for cyclization in oleum it is possible to 
sulfonate aliphatic OH groups and sulfonate aromatic rings present in the 
dianilino compounds of the Formula 10; therefore milder conditions must be 
used if undesired sulfonation is encountered. 
The new dyestuffs produce bright reddish blue dyeings on cellulose and 
natural or synthetic polyamide materials. They are distinguished by high 
tinctorial strength. As water-soluble reactive dyestuffs, the new 
dyestuffs are preferably of interest for the dyeing of hydroxyl- and 
amido-containing textile materials, in particular materials in natural and 
regenerated cellulose and synthetic polyamide and polyurethane fibers, 
wool and silk. 
These materials may be dyed or pdnted using the methods which are commonly 
known and customary in industry for water-soluble reactive dyestuffs. The 
dyeing are then light- and wet-fast blue dyeings and prints. 
The temperatures in the Examples are given in .degree.C. The formulae of 
water-soluble reactive dyestuffs in the description and in the Examples 
are shown in the free acid form. In general, the dyestuffs are isolated 
and used in the form of their alkali metal salts, in particular in the 
form of the lithium, sodium or potassium salts. The preferred form of the 
fiber-reactive moiety Y.sup.1 is the .beta.-sulfatoethylsulfonyl group and 
the formula that follow show Y.sup.1 in that form. It will be readily 
apparent to those skilled in the art that equivalent vinyl, phosphato 
thiosulfato etc. group may be used. It will also be apparent to the 
skilled worker that the reaction mixture may be a mixture of fiber 
reactive moieties and depending on the reaction conditions e.g. up to 30% 
of the vinyl moiety and up to about 5% of the non-reactive hydroxy moiety 
may be formed. 
EXAMPLE 1 
21.8 parts of 2,9-diamino-6,13-dichlorotriphenodioxazine- 1,8-disulfonic 
acid is suspended in 1000 parts of water and brought to pH 7.0 by using an 
aqueous solution of 5% LiOH. The reaction mixture is stirred for one hour 
until complete solution. The pH is adjusted with hydrochloric acid to 4.5 
and 7.8 parts of 2,4,6-tdchlorotriazine is added. The reaction mixture is 
stirred for 3 hours at room temperature and the pH maintained at 4.5 using 
an aqueous solution of 5% LiOH. To the resulting pdmary condensation 
product 2.5 parts of cyanamide in form of a 50% aqueous solution is added 
and the pH adjusted to 9.0 using LiOH. The reaction mixture is heated up 
to 45.degree. -40.degree. C. for 3 hours by maintaining the pH. After 
adjusting the pH to 4.0 of the resulting secondary condensation product, 
14.0 pans of 1-amino-3-[.beta.sulfatoethylsulfonyl]-benzene is added. 
After stirring for 6 hours at 80.degree. C. at pH 5.5 the reaction is 
completed. High performance liquid chromatography can be used in all steps 
to indicate the end of each condensation. The resulting dyestuff solution 
is clarified and spray dried. It results in a blue dyestuff powder, which, 
if applied to cotton in one of the methods customary for reactive 
dyestuffs, produces brilliant strongly reddish bluish shades. 
The dyestuff in form of the free acid has the following formula: 
EQU (.lambda.max: 574 nm) 
##STR18## 
EXAMPLE 2 
21.8 pans of 2,9-diamino-6,13-dichlorotriphenodioxazine- 1,8-disulfonic 
acid is suspended in 1000 pans of water and brought to pH 7.0 by using an 
aqueous solution of 5% LiOH. The reamion mixture is stirred for one hour 
until complete solution. The pH is adjusted with hydrochloric acid to 4.5 
and 7.8 pans of 2,4,6-trichlorotriazine is added. The reaction mixture is 
stirred for 3 hours at room temperature and the pH maintained at 4.5 using 
an aqueous solution of 5% LiOH. The resulting primary condensation product 
2.5 parts of cyanamide in form of a 50% aqueous solution is added and the 
pH adjusted to 9.0 using LiOH. The reamion mixture is heated up to 
45.degree. -40.degree. C. for 3 hours by maintaining the pH. After 
adjusting the pH to 4.0 of the resulting secondary condensation product, 
14.0 parts of 1-amino-3-[.beta.-sulfatoethyl-sulfonyl]-5-methoxy-benzene 
is added. After stirring for 6 hours at 80.degree. C. at pH 5.5 the 
reaction is completed. High performance liquid chromatography can be used 
in all steps to indicate the end of each condensation. The resulting 
dyestuff solution is clarified and spray dried. It results in a blue 
dyestuff powder, which, if applied to cotton in one of the methods 
customary for reactive dyestuffs, product brilliant strongly reddish 
bluish shades. The dyestuff in form of the free acid has the following 
formula: 
EQU (.lambda.max: 575 nm) 
##STR19## 
Additional dyestuffs of the following general Formula A. These compound 
shades dye cotton in bright, strong, reddish blue shades are obtained by 
using the procedure of the above examples. 
##STR20## 
Examples 3-31 illustrate compounds of the general Formula A wherein the 
substituents T and Q are as follows: 
EXAMPLES 3-31 
__________________________________________________________________________ 
Ex. 
T Q 
__________________________________________________________________________ 
3 Cl 
##STR21## 
4 Cl 
##STR22## 
5 Cl 
##STR23## 
6 Cl 
##STR24## 
7 Cl 
##STR25## 
8 Cl 
##STR26## 
9 Cl 
##STR27## 
10 Cl 
##STR28## 
11 Cl 
##STR29## 
12 Cl 
##STR30## 
13 Cl 
##STR31## 
14 Br 
##STR32## 
Ex. 
Q T 
__________________________________________________________________________ 
15 Br 
##STR33## 
16 Br 
##STR34## 
17 Br 
##STR35## 
18 Br 
##STR36## 
19 Br 
##STR37## 
20 Cl 
##STR38## 
21 Cl N(CH.sub.2CH.sub.2SO.sub.2CHCH.sub.2).sub.2 
22 Cl 
##STR39## 
23 Cl 
##STR40## 
24 Cl 
##STR41## 
25 Cl 
##STR42## 
26 Cl 
##STR43## 
27 Br 
##STR44## 
28 Cl 
##STR45## 
29 Br 
##STR46## 
30 Cl N[CH.sub.2CH.sub.2CH.sub.2SO.sub.2CH.sub.2CH.sub.2Cl].sub.2 
31 Cl N[CH.sub.2CH.sub.2CH.sub.2SO.sub.2CHCH.sub.2 ].sub.2 
__________________________________________________________________________ 
EXAMPLE 32 
To 6.5 parts of 2,4,6-trichlorotriazine in 50 parts of water and 50 parts 
of ice, 1.5 parts of cyanamide in form of a 50% aqueous solution is added. 
The reaction mixture is stirred for 1.5 hours at 0.degree.-3.degree. C. at 
pH 8.5-9.5. After adjusting the pH to 7.0 of the resulting primary 
condensation product, a suspension of 10.1 parts 1 
-amino-4-[.beta.-sulfatoethylsulfonyl]-benzene in 40 parts of water, which 
was adjusted to pH 4.5 using soda ash, is added. The mixture is stirred 
for 5 hours at 5.degree.-8.degree. C. while the pH is dropping to 1.5. The 
pH of the solution of the resulting secondary condensation product is 
adjusted to 5.5 with soda ash and clarified. This solution is then added 
over 4 hours to a solution of 13.7 parts of 2,9-diamino-6, 
13-dichlorotriphenodioxazine-1,8-disulfonic acid, which was brought to pH 
5.0 using aqueous 5% LiOH. During the addition, the temperature is kept at 
80.degree.-85.degree. C. and the pH at 3.0-3.5. The end of each 
condensation step can be monitored by using the high pedormance liquid 
chromatography. The resulting dyestuff solution is salted out with 15% by 
volume of sodium chloride. After drying and grinding it results in a blue 
dyestuff powder, which, if applied to cotton in one of the methods 
customary for reactive dyestuffs, produces brilliant strongly reddish 
bluish shades. 
The dyestuff in form of the free acid has the following formula: 
EQU (.lambda.max: 588 nm) 
##STR47## 
Further similar reddish blue dyestuffs can be obtained by replacing the 
1,4-Diaminobenzene-3-sulfonic acid by 1,4-Diamino-benzene-3-carboxy acid 
during the chromophore synthesis, and using the procedure of the above 
samples. These compounds have the following general Formula B: 
##STR48## 
Examples 33-44 illustrate compounds of the general Formula B wherein the 
substituents T and Q are as follows: 
EXAMPLE 33-44 
______________________________________ 
Ex. T Q 
______________________________________ 
33 Cl 
##STR49## 
34 Cl 
##STR50## 
35 Cl 
##STR51## 
36 Cl 
##STR52## 
37 Br 
##STR53## 
38 Br 
##STR54## 
39 Cl 
##STR55## 
40 Cl 
##STR56## 
41 Cl 
##STR57## 
42 Cl 
##STR58## 
43 Cl Cl 
44 Br Cl 
______________________________________ 
EXAMPLE 45 
21.8 parts of 2,9-diamino-6,13-dichlorotriphenodioxazine-1,8-disulfonic 
acid is suspended in 1000 parts of water and brought to pH 7.0 by using an 
aqueous solution of 5% LiOH. The reaction mixture is stirred for one hour 
until complete solution. The pH is adjusted with hydrochloric acid to 4.5 
and 7.8 parts of 2,4,6-tdchlorotriazine is added. The reaction mixture is 
stirred for 3 hours at room temperature and the pH maintained at 4.5 using 
an aqueous solution of 5% LiOH. To the resulting pdmary condensation 
product 2.5 parts of cyanamide in form of a 50% aqueous solution is added 
and the pH adjusted to 9.0 using LiOH. The reaction mixture is heated up 
to 45.degree.-40.degree. C. by maintaining the pH. After stirring for 3 
hours the reaction is completed. High performance liquid chromatography 
can be used in all steps to indicate the end of each condensation. The 
resulting dyestuff solution is spray dried. IT results in a blue powder, 
which, if applied to cotton in one of the methods customary for reactive 
dyestuffs, produces brilliant strongly reddish bluish shades. 
The dyestuff in form of the free acid has the following formula: 
EQU (.lambda.max: 582 nm ) 
##STR59## 
The above procedure can be used to produce other dyes having the following 
general Formula C: 
##STR60## 
The above procedure used to prepare a dye in the substituent Q and T are as 
follows: 
EXAMPLE 46 
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Ex. T Q 
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46 Cl Cl 
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Dyes prepared according to the present invention are suitable for the 
dyeing of cellulosic materials such as cotton, linen, viscose, rayon or 
staple fibers. They can be applied by any one of the usual dyeing and 
printing methods for reactive dyestuffs and yield on cellulosic materials, 
in the presence of alkaline agents, brilliant shades having excellent 
fastness properties, and high color yield and reduced cold water bleeding. 
These dyes may also be used on wool, silk or polyamide fibers. 
The dyes of the present invention exhibit an unexpected and highly 
advantageous property in that they can be used at very low salt 
concentration in the dye bath while at the same time providing excellent 
dyeing yield. In the exhaust dyeing method using fiber reactive vinyl 
sulfone type dyes, one necessary auxiliary chemical is an electrolyte 
which is added to the dye bath to force the dye to migrate from solution 
to the fiber. The most commonly used electrolyte is an inorganic salt such 
as sodium sulfate or sodium chloride. In exhaust dyeing procedures, this 
electrolyte is generally employed in amounts from about 20-50 grams per 
liter to about 100 grams per liter of dye bath with the amount of 
electrolyte being proportionally higher as the amount of dye employed in 
the dyeing increases. A few fiber reactive dyes are known which can be 
used at reduced electrolyte concentration. However, some loss in dye yield 
occurs even with these dyes as the salt concentration is decreased in the 
dye bath. Surprisingly the dyes of this invention achieve optimum dye 
yield at a very low salt concentration. After the dyeing process is 
completed, the exhausted dye bath solution is discharged to waste water 
treatment facilities for removal of electrolyte and other residual dye 
bath chemicals. 
The present invention provides a method for the exhaust dyeing of textiles 
using a select class of dyes at significantly lower levels of electrolyte 
in the dye bath with the attendant reduction in raw materials costs, 
reduced chemical discharge to the environment and reduced waste water 
treatment costs. An additional advantage is that the process of the 
invention unexpectedly gives a higher dyeing efficiency as evidenced by 
the achievement of higher dye build up values. 
The advantages and unexpected properties of the dyes of this invention are 
shown in the following comparison of the invention with commercial pdor 
art dioxazine dyes. 
Cotton test fabrics were dyed by the exhaust method at a 2% dye level and a 
liquid ratio of 10 to 1. The dyeing was conducted at 60.degree. C. and in 
addition to the salt component, the dye bath contained 15% by weight soda 
ash and 1% by weight sodium hydroxide. The test specimens were dyed under 
substantially the same conditions and the color yield measured on a 
computer assisted spectrophotonomer with the color yield being measured in 
color density units (CDU). 
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EXHAUST DYEING 
(Color Yield vs Soft Concentration) 
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Example 1 (The Invention) 
Salt g/l 100 50 30 20 10 
CDU 1.067 1.044 1.127 1.094 1.11 
Rel. CDU % 
100 97.8 105.6 102.5 104.6 
C.I. Reactive Blue 198 (Prior Art) 
Salt g/l 100 50 30 20 10 
CDU 0.837 0.795 0.649 0.575 0.481 
Rel. CDU % 
100 90.7 77.5 68.7 57.5 
C.I. Reactive Blue 204 (Prior Art) 
Salt g/l 100 50 30 20 10 
CDU 1.638 1.486 1.376 1.319 1.06 
Rel. CDU % 
100 90.7 84 80.5 64.7 
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The invention may be embodied in other specific forms without departing 
from the spidt or essential characteristics thereof. Through this 
specification and the appended claims, a given chemical name or formula is 
intended to encompass all isomers of said name or formula where such 
isomers exist. The present embodiments are therefore to be considered in 
all respects as illustrative and not restrictive, the scope of the 
invention being indicated by the appended claims rather than by the 
foregoing description; and all changes which come within the meaning and 
equivalency of the claims are therefore intended to be embraced therein.