FORM2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10; rule 13)
1. Title of the invention -"NOVEL REACTIVE DYES, THERE MIXTURES AND
PROCESSES THEREOF"
2. Applicant(s)
(a) NAME : COLOURTEX INDUSTRIES LIMITED
(b) NATIONALITY : An Indian Company
(c) ADDRESS : Survey No 91, Paikee Bhestan, Navasari-Surat Road, Surat - 395 023,
Gujarat (India)
3. PREAMBLE TO THE DESCRIPTION
The following specification particularly describes the invention and the manner in which it is to be performed:

Field of the Invention
The present invention relates to polyazo reactive dyes comprising of stilbene or diaminodiphenylsulfone derivatives and processes for the preparation thereof. Background of the invention and prior art
Diaminodiphenyl derivatives of the formula (4) are very widely used and well known intermediate in the dyestuff chemistry. These intermediates are mainly explored for the synthesis of Direct and Acid Dyes.

X= -CH=CH-; S02; -NH-S02-; -NHCO-; -CO-... etc.
As such these intermediates has very limited or no utilization in the synthesis of
Reactive Dyes. Some of the following patent literatures represent the some specific
reactive dye molecules based on these intermediates.
US patent 6013775 discloses polyazo compounds which are useful as dyes for dyeing
material or synthetic substrates and is provide by the formula

Where one of the two radicals XI and X2 is hydroxyl and the other is amino,
p and q are each independently of the other 0 or 1,
Dl and D2 are each independently of the other a radical of the formula


And B is a bridge member are prepared using novel sulfonamide intermediates and
are useful as dyes for dyeing natural or synthetic substrates. It is further disclosed that
Bis
-S02-NH-A1-NH-S02-)-S02-N(Alk)-A1-NH-S02-,-S02-N(Alk)-A,-N(Alk)-S02-,
-S02-N(Alk)-A1-0-S02-, -S02-0-A1-0-S02-, -S02-N(Alk)- S02-N(Alk)-S02-, -S02-
NH-A2-NH-S02-,-S03- or S02,
Further column 17 & 18 disclose compound of the formula,

Most closest prior art US2008047079 discloses polyazo dyes of the formula

Wherein T is a radical of the general formula

wherein B is a bridging element of the formula
-NH-, -CO-, -S02-, -CH=CH-, -CH2-CH2-, -NH-CO-, -NH-S02-,-S02-NH-S02- or a
direct bond. The main objective of US2008047079 is to provide better solution for

dyeing leather to overcome issue with most commonly used acid and direct dyes with polyazo reactive dyes which can have good affinity and fixation on leather. Although claim 11 of US2008047079 mentioned general formula 1 which is very wide and in subsequent claims it was limited to specific substituents and in particular with radical T it disclosed only -NH-, -NH-CO- and -NH-SO2-. Other patent literature discloses use of these intermediate in the synthesis of Bis, tris, tetra and poly azo Direct and Acid dyes such as; EPOO13750; US5272259; US4390470; US2056539; EP0498217; US5785718; US4169832; EP2022828 and US5431723.
Objects of the Invention:
It is an object of the present invention to provide bis, tris, tetra and poly azo reactive dyes based on derivatives of 4, 4'-diaminostilbene-2, 2'-disulphonic acid; 4:4'-Diaminodiphenylsufone and 3:3'-Diamino diphenyl sulfone of the respective formula
(1) to obtain novel black, blue, red, brown and yellow reactive dyes with very deeper
shades and overall good fastness properties particularly washing fastness and light
fastness.
It is another object of the present invention to provide reactive azo dyes based on
derivatives of 4,4'-diaminostilbene-2,2,-disulphonic acid; 4:4'-
Diaminodiphenylsufone and 3:3'-Diamino diphenyl sulfone of the respective formula
(2) with excellent fastness properties especially washing fastness and light fastness.
It is yet another object of the present invention to provide reactive azo dyes based on
derivatives of 4,4'-diaminostilbene-2,2'-disulphonic acid; 4:4'-
Diaminodiphenylsufone and 3:3'-Diamino diphenyl sulfone of the respective formula
(3) with excellent fastness properties and very good build up.
It is a further object of the present invention to provide a process for the preparation of compounds of formula (1), Formula (2) and Formula (3).
It is a further object of the present invention to apply as single dye or as mixture, or in combination with other compatible dyestuffs containing vinylsulfone and/or

heterocyclic reactive groups, preferably applied in dichromatic or trichromatic combinations, to achieve very deep shades, and excellent fastness properties.
Summary of the invention:
According to an aspect of the present invention there is provided polyazo dyes of the formula (1) and mixtures thereof,

Where, A= 4,4'-diaminostilbene-2,2'-disulphonic acid;
4:4'-Diaminodiphenylsufone;
3:3'-Diaminodiphenylsulfone X & Y are same or different in combination of followings l-Amino-8-Hydroxy naphthalene-3:6-disuIphonic acid. l-Amino-7-Hydroxy naphthalene-3:6-disulphonic acid. l-Amino-7-Hydroxy naphthalene-6-sulphonic acid. 7-Amino-l-naphthol-3-sulfonic acid (Gamma acid) N-Methyl-Gamma acid
2-Amino-5-hydroxy-7-naphthalenesulfonic acid (J acid) l-Hydroxy-6-(methylamino)-3-naphthalenesulfonic acid (N-methyl J-acid) l-Hydroxy-6-(2'-Carboxy ethyl amino)-3-naphthalenesulfonic acid l-Hydroxy-6-(2'-sulfo ethyl amino)-3-naphtha!enesuIfonic acid And similar N-substituted alkyl derivatives. l:3-Diamino benzene (m- phenylenediamine) 1:4-Diamino benzene (p- phenylenediamine) l:4-Diamino benzene sulphonic acid (PPDSA) l:3-Diamino benzene sulphonic acid (MPDSA) l:3-Diamino benzoic acid

2:4-Diamino toluene
3:4-Diamino toluene
1:3-Dihydroxy benzene,
1:5/l :8-Diamino naphthalene
1:5/l :8-Dihydroxy naphthalene
and similar diamino, amino hydroxy and dihydroxy benzene and naphthalene
derivatives;
wherein X and Y are not simultaneously l-Amino-8-Hydroxy naphthalene-3:6-
disulphonic acid (H acid);
R1 & R2 = Amino benzene or naphthalene derivatives containing at least one or more
vinylsulphone reactive group with or without -SO3H, alkyl, alkoxy and halo
substituent on benzene or naphthalene ring.
R3 & R5= May be same or different in combination of CI; F; C1-C4 Alkoxy, -NH2, -
NHCN, -C1-C4 alkylamine, Alkyl amino sulfone derivatives, alkyl amino acids, alkyl
amino sulphonic acid derivatives etc.
R4&R6=N,CH,C-C1.
According to another aspect of the present invention there is provided polyazo dyes
of the formula (2) and mixtures thereof,

(2)
According to another aspect of the present invention there is provided polyazo dyes of the formula (3) and mixtures thereof,

According to yet another aspect of the invention there is provided a process for the
preparation of compounds of formula (1), formula (2) and formula (3).
Detailed Description of the present invention
The present invention describes a new and unique class of polyazo dyes comprising
of stilbene or diaminodiphenylsulfone derivatives, processes for preparing said dyes,
and methods for applying these dyes to fibers.
In its most basic embodiment the dyes of the present invention have the structure of
formula (4)

X= -CH=CH-; S02; -NH-S02-; -NHCO-; -CO-... etc.
which is further substituted with azo groups and amino groups which are further
substituted.
According to one embodiment, there is provided polyazo dyes based on the formula
(1), formula (2) and formula (3),


Where, A= 4,4'-diaminostilbene-2,2'-disuIphonic acid; (DASDSA)
4:4'-Diaminodiphenylsufone;(4,4,-DADPS) 3,3'-Diaminodiphenylsulfone(3,3'-DADPS)
X & Y are same or different in combination of followings
l-Amino-8-Hydroxy naphthalene-3:6-disulphonic acid. (H acid)
l-Amino-7-Hydroxy naphthalene-3:6-disulphonic acid.
l-Amino-7-Hydroxy naphthaIene-6-sulphonic acid.
7-Amino-l-naphthol-3-sulfonic acid (Gamma acid)
"N-Methyl-Gamma acid
2-Amino-5-hydroxy-7-naphthalenesulfonic acid (J acid)
l-Hydroxy-6-(methylamino)-3-naphthalenesulfonic acid (N-methyl J-acid)
l-Hydroxy-6-(2'-Carboxy ethyl amino)-3-naphthalenesulfonic acid
l-Hydroxy-6-(2'-suIfo ethyl amino)-3-naphthalenesulfonic acid
And similar N-substituted alkyl derivatives.
1:3-Diamino benzene (m- phenylenediamine)
l:4-Diamino benzene (p- phenylenediamine)

2:5-Diamino benzene sulphonic acid (PPDSA)
2:4-Diamino benzene sulphonic acid (MPDSA)
1:3-Diamino benzoic acid
2:4-Diamino toluene
3:4-Diamino toluene
l:3-Dihydroxy benzene,
1:5/1:8-Diamino naphthalene
1:5/l :8-Dihydroxy naphthalene
and similar diamino, amino hydroxy and dihydroxy benzene and naphthalene
derivatives;
wherein in formula (1), X and Y are not simultaneously l-Amino-8-Hydroxy
naphthalene-3:6-disulphonic acid (H acid);
R1 & R2 = Amino benzene or naphthalene derivatives containing at least one or more
vinylsulphone reactive group with or without -SO3H, alkyl, alkoxy and halo
substituent on benzene or naphthalene ring.
R3 & R5= May be R3 & R5 are same or different in combination of CI; F; C1-C4
Alkoxy, -NH2, -NHCN, -C1-C4 alkylamine, Alkyl amino sulfone derivatives, alkyl
amino acids, alkyl amino sulphonic acid derivatives etc.
R4&R6=N,CH,C-C1.
The poly azo dyes of formula 1 are preferably selected from formula (!')

Where, A= 4,4'-diaminostilbene-2,2'-disulphonic acid; (DASDSA) 4:4'-Diaminodiphenylsufone;(4,4'-DADPS) 3:3'-Diaminodiphenylsulfone(3,3'--DADPS)

R7, R8, R9 and R10 = May be same or different in combination of -H, -S03H, alkyl and halo.
R11 = -CH2CH2COOH, -CH2CH2CN, -CH2CH2CONH2, -CH2COOH, -CH2CH2S03H, -CH2CH(CH3)COOH, -CH2CH2OS03H, -CH2CH2COCH3, -CH2CH2COOC2H5; and also their mixtures with each or one another.
In another embodiment, there is provided a process for the preparation of compounds of formula (1), formula (2) and formula (3).
While diamino diphenyl derivative as described by formula (4) is tetraazotized and coupled with mono azo dyes obtained by coupling of diamino, amino hydroxyl or dihydroxy benzene & naphthalene derivatives with diazotized primary aromatic amine containing at least one vinylsulphone reactive group under appropriate condition to get novel reactive dyes of formula (1) having very high optical density and excellent build up and all around fastness properties.

In another embodiment, Bisazo amino/hydroxyl intermediate may be linked to suitable chromophores through a suitable heterocyclic reactive intermediate which may or may not be prior substituted or subsequently condensed with any of the

substituent described as R3 and/or R5 to get novel reactive dyes of formula (2) having very excellent build up and all around fastness properties.
The following examples of linking compounds serve to illustrate this embodiment without in any way limiting the range of possible linking components: cyanuric chloride, cyanuric fluoride, trifluoro chloropyrimidine, trifluoro pyrimidine. STEP-1


In yet another embodiment, diamino diphenyl derivative as described by formula (4) may be linked with diamino, amino hydroxy! or dihydroxy benzene & naphthalene derivatives through a suitable bifunctional intermediate heterocyclic reactive intermediate which may or may not be prior substituted or subsequently condensed with any of the substituent described as R4.
The following examples of linking compounds serve to illustrate this embodiment without in anyway limiting the range of possible linking components: cyanuric chloride, cyanuric fluoride, trifluoro chloropyrimidine, trifluoro pyrimidine. This is further coupled with diazotized amino benzene or naphthalene derivatives containing at least one or more vinylsulphone reactive group to get novel reactive dyes of formula (3) having very high optical density and excellent build up and all around fastness properties.



All novel reactive dyes described as formula(l), formula(2) and formula(3) can be applied as single dye or as mixtures or in combination with other compatible dyestuffs containing vinylsulfone and/or heterocyclic reactive groups, preferably applied in dichromatic or trichromatic combinations, to achieve very deep shades, and excellent fastness properties.
Application:
The present invention provides a process for dyeing from aqueous bath and printing
of fiber materials with the dyes of the present invention.
In particular, cellulose, natural cellulose fibers such as cotton, linen or hemp,
especially cotton, and regenerated cellulose such as viscose or lyocell, polyamide
fibers such as nylon 6, nylon 6.6 or protein fibers such as wool, silk or leather are
preferred fiber materials.
The dyes are also suitable for dyeing and printing of fiber blends containing the
mentioned cellulose, polyamide or protein fiber materials.
The dyes of the invention can be applied to and fixed on the fiber material in various
ways, in particular in the form of aqueous dye solutions and print pastes. They are
suitable for known application techniques which are established for the application of
reactive dyes, in particular exhaust method, padding method, whereby the material is
impregnated with aqueous, salt containing or salt free solutions of the dyes, and fixed
after alkali treatment or in presence of alkali with or without heating, and printing
methods, conventional or digital (ink jet) printing.

After fixing, the dye and prints are rinsed and thoroughly washed with cold or hot
water containing auxiliary agents such as detergents or surfactants that promote the
wash-off of unfixed portions.
Coloration in deep shades is often a challenge, especially when high fastness to
washing, contact and perspiration is concerned. All known dyes have limitations in
this respect.
The present dyes are of from Yellow to Black colour and are especially suitable for
dyeing in deep shades, applied as single dye or as mixture in the present invention, or
in combination with other compatible dyestuffs containing vinylsulfone and/or
heterocyclic reactive groups, preferably applied in dichromatic or trichromatic
combinations, while exhibiting superior properties in coloration technology compared
to known mixtures of state of the art, with regard to achieving very deep shades, and
excellent fastness properties.
Examples of suitable alkali used for fixation include alkali hydroxide, alkali
carbonate, alkali silicate, of which sodium hydroxide, sodium carbonate, sodium
silicate are preferred.
The amount of dye applied in the dyebath can vary according to the desired depth of
shade, generally an amount of 0.01 to 10 % per weight of fabric is suitable, and in
particular 0.2 to 8% per weight of fabric is preferred.
The dyebath may contain additions of auxiliaries such as inorganic salt, preferably
sodium chloride or sodium sulfate, to support the exhaustion of the dyes onto the
fiber material, and in padding process urea, and in printing applications thickening
pastes such as alginate thickenings.
In exhaust dyeing process, the preferred procedure is dyeing from an aqueous batch,
in the presence of 20-100 g/L salt, sodium chloride or sodium sulfate, and a liquor
ratio of 1:2 to 1:50, preferably 1:3 to 1:30, at a dyebath pH of 7-13, preferably 9-11,
and at a temperature of 40-90°C, preferably 70-90 °C.
The dyeing obtained with the dyes of the present invention has excellent fixation
yield and excellent build-up. The obtained dye-fiber bond is of high stability not only

in the acid but also in the alkaline range, also good light fastness and very good wash
fastness, even in deep shades, as well as good contact fastness to water and
perspiration.
Moreover, the dyeing obtained with the dyes of the first part of the present invention
represents formula (1) are dischargeable and can be applied in discharge printing.
Leather is dyed using dyeing procedure described in US2008047079 for comparative
study.
Example: 1
(A) 28.8 parts of 2-[(4-Aminophenyl)suIfonyl]ethyl hydrogensulfate (p-VS ester) are introduced into 400 parts of ice-water and 15 parts of 30% Hydrochloric acid with small amount of wetting agent under efficient stirring, cool the reaction mass to 0-5°C with ice. A solution of 7.3 parts of Sodium Nitrite in 25 parts of water is added slowly in 10-15 minutes. Check reaction mass for excess of nitrite and stir for 2 hrs. After two hrs excess nitrite is destroyed by addition sulfamic acid. Add 32 parts of 1-amino-8-hydroxy naphthaIene-3,6-disulphonic acid at 0-5°C and stir for 4-5 hrs at 0-5°C until coupling is complete.
(B) 34.5 parts of 4-Amino-3-sulfophenyl-2'-sulfatoethylsuIfone (SulphoVS ester) are introduced into 400 parts of ice-water and 15 parts of 30% Hydrochloric acid with small amount of wetting agent under efficient stirring, cool the reaction mass to 0-5°C with ice. A solution of 7.3 parts of Sodium Nitrite in 25 parts of water is added slowly in 10-15 minutes. Check reaction mass for excess of nitrite and stir for 2 hrs. After two hrs excess nitrite is destroyed by addition sulfamic acid. Add 24 parts of 2-amino-5-hydroxy-7- naphthalenesulphonic acid at 0-5°C and stir for 4-5 hrs at 0-5°C until coupling is complete.
(C) 15.2 parts of 3,3'-Diaminodiphenylsulfone are charged into 400 parts of water, stir for 15-30 minutes and slowly adjust pH 7-7.5 with caustic soda lye to obtain clear solution. Add 7.3 parts of sodium nitrite and stir to dissolve. This solution is added slowly over a period of 2-3 hrs in 800 parts ice and 30 parts of 30% Hydrochloric acid keeping temperature below 5°C with ice as needed. After completion of addition

continue stirring at 0-5°C with excess of nitrite for another 2 hrs. Destroy excess nitrite with sulfamic acid.
(D) Add coupling mass (A) to above tetra azo solution (C) at 0-5°C in 30 minutes. Stir further 30 minutes at 0-5°C temperature and then adjust pH 2.5-3.0 with 20% soda ash solution. Stir further at this pH and let temperature raises up to 10-15°C till coupling is completed. When first coupling is completed again cool down to 5-10°C and add coupling mass (B) in 30 minutes at 5-10°C, stir for further 30 minutes without adjusting pH. After 30 minutes raise pH up to 6.0-6.5 with 20% soda ash solution and maintain at this pH till completion of coupling. Finally dye of formula (1-A) is isolated by filtration after salting out or by drying reaction mass at low temperature.

(1-A)
The product (1-A) obtained as dark blue powder which dyes cotton in very deep navy
blue shade with good all around fastness properties.
ExampIe-2:
The dyestuffs of the formula 1 are synthesized using same method as described in
Example-1 to get following dyes described in table shown as Figure 1:

Example-3:
(A) 28.8 parts of 2-[(4-Aminophenyl)sulfonyl]ethyl hydrogen sulfate are introduced into 400 parts of ice-water and 15 parts of 30% Hydrochloric acid with efficient stirring, cool the reaction mass to 0-5°C with ice. A solution of 7.3 parts of Sodium Nitrite in 25 parts of water is added slowly in 10-15 minutes. Check reaction mass for

excess of nitrite and stir for 2 hrs. After two hrs excess nitrite is destroyed by addition sulfamic acid. Add 18.6 parts of 2,4-diaminobenzene sulphonic acid at 0-5°C and stir for 4-5 hrs at 0-5°C until coupling is complete.
(B) 19 parts of 4s4'-DiaminostiIbene-3,3'-disulphonic acid are charged into 400 parts of water, stir for 15-30 minutes and slowly adjust pH 7-7.5 with caustic soda lye to obtain clear solution. Add 7.3 parts of sodium nitrite and stir to dissolve. This solution is added slowly over a period of 2-3 hrs in 800 parts ice and 30 parts of 30% Hydrochloric acid keeping temperature below 5°C with ice as needed. After completion of addition continue stirring at 0-5°C with excess of nitrite for another 2 hrs. Destroy excess nitrite with sulfamic acid.
(C) Add solution (A) to above tetra azo solution (B) at 0-5°C in 30 minutes. Stir further 5-6 hrs maintaining 0-5°C temperature and then adjust pH 6-6.5 with 20% soda ash solution. Stir further at this pH and temperature till coupling is completed. Finally dye of formula (1-B) is isolated by filtration after salting out or by drying reaction mass at low temperature.

(1-B)
The product (1-B) obtained as orange coloured powder which dyes cotton in very
deep orange shade with good all around fastness properties.
ExampIe-4:
The dyestuffs of the formula 1 are synthesized using same method as described in
Example-1 to get following dyes described in table shown as Figure 2:


Example-5:
(A) 86.3 parts of 4-Amino-3-sulfophenyl 2-sulfatoethyl sulfone are introduced into 800 parts of ice-water and 30 parts of 30% Hydrochloric acid with efficient stirring, cool the reaction mass to 0-5°C with ice. A solution of 17 parts of Sodium Nitrite in 50 parts of water is added slowly in 10-15 minutes. Check reaction mass for excess of nitrite and stir for 2 hrs. After two hrs excess nitrite is destroyed by addition sulfamic acid. Add 26 parts of 1,3-diaminobenzene at 0-5°C and stir for 5-6 hrs at 0-5°C until coupling is complete.
(B) 72 parts of 2-[(4-AminophenyI)sulfonyl]ethyl hydrogen sulfate are introduced into 1000 parts of ice-water and 37 parts of 30% Hydrochloric acid with efficient stirring, cool the reaction mass to 0-5°C with ice. A solution of 18 parts of Sodium Nitrite in 50 parts of water is added slowly in 15-30 minutes. Check reaction mass for excess of nitrite and stir for 2 hrs. After two hrs excess nitrite is destroyed by addition sulfamic acid. Add 80 parts of l-amino-8-hydroxy naphthalene-3,6-disuIphonic acid at 0-5°C and stir for 5-6 hrs at 0-5°C until coupling is complete.
(C) 95 parts of 4,4'-Diaminostilbene-3,3'-disulphonic acid are charged into 1000 parts of water, stir for 15-30 minutes and slowly adjust pH 7-7.5 with caustic soda lye to obtain clear solution. Add 37 parts of sodium nitrite and stir to dissolve. This solution is added slowly over a period of 2-3 hrs in 1200 parts ice and 150 parts of 30% Hydrochloric acid keeping temperature below 5°C with ice as needed. After completion of addition continue stirring at 0-5°C with excess of nitrite for another 2 hrs. Destroy excess nitrite with sulfamic acid.
(D) Add solution (A) to above tetra azo solution (B) at 0-5°C in 30 minutes. Stir further 30 minutes and then maintaining 0-5°C temperature slowly adjust pH up to 3.5 to 4.0 with 20% sodium carbonate solution. Stir further at this pH for another 7-8 hrs and let temperature rises up to 20-25°C till coupling is completed. Check with TLC and it should show very little presence of solution (A) when OK proceed further for second coupling.

(E) Cool reaction mass (D) to 10°C with ice and slowly charge solution (B) in 30 minutes and further stir at 5-10°C for 30 minutes and then adjust pH 6.0-6.5 with 20% sodium carbonate solution. Maintain at this temperature and pH for 6-7 hrs for completion of coupling. Finally dye of the formula 1-C is isolated by filtration after slating out or directly dried.

The product (1-C) obtained as black powder and dyes cotton in very deep black shade
with excellent build up and good fastness properties.
Example-6:
The dyestuffs of the formula 1 are synthesized using same method as described in
Example-1 to get following dyes described in table shown as Figure 3:

Example-7:
(A) 55.9 parts of Cyanuric Chloride slurry is prepared by charging under stirring in
600 parts of water at 0-5°C. To this slurry slowly charge solution of 94.8 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid dissolved in 800 ml of water under neutral conditions in 2 hrs. Stir further 3-4 hrs at 0-5°C and check TLC to ensure absence of l-amino-8-hydroxynaphthalene-3,6-disulfonic acid. Slowly charge 83.5 parts of 2-[(4-Aminophenyl)sulfonyl]ethyl hydrogen sulfate and stir for another 5-6 hrs at 25-30°Cand adjust pH 3 with 20% sodium carbonate solution. Then slowly raise pH up to 5 - 5.5 and temperature also rises up to 45°C and further stir for 2 hrs for completion of condensation.

(B) 57 parts of 4,4'-Diaminostilbene-3,3,-disulphonic acid are charged into 800 parts of water, stir for 15-30 minutes and slowly adjust pH 7-7.5 with caustic soda lye to obtain clear solution. Add 21.3 parts of sodium nitrite and stir to dissolve. This solution is added slowly over a period of 2-3 hrs in 1200 parts ice and 90 parts of 30% Hydrochloric acid keeping temperature below 5°C with ice as needed. After completion of addition continue stirring at 0-5°C with excess of nitrite for another 2 hrs. Destroy excess nitrite with sulfamic acid.
Now, charge reaction mass (A) to tetraazo (B) at 0-5°C in 30-40 minutes without adjusting pH further stir for 30 minutes and then adjust pH to 3.5-4 with 20% sodium carbonate solution and maintain pH and temperature for 1-2 hrs. After 2 hrs again adjust pH to 6.5-7.0 with 20% sodium carbonate solution and stir for 1-2 hrs at 0-5°C at this pH. Check for TLC and spot test for completion of coupling. When coupling is completed product of formula 2-A is either isolated by filtration after slating out or directly dried.

The product (2-A) obtained as blue powder and dyes cotton in bright blue shade with
excellent fixation yield of 80% on exhaust dyeing with excellent build up and ISO
105 C03 washing fastness- staining on cotton 4 and on polyamide 4-5.
Example-8:
The dyestuffs of the formula 2 are synthesized using same method as described in
Example-7 to get following dyes described in table shown as Figure 4:


Example-9: Product synthesized in Eample-7 and 8 were further condensed with 2-(methylamino)ethanesulphonic acid maintaining 7.5 pH at 85-90°C monitor condensation reaction by TLC and when OK clarify the reaction mass and spray dried.
The product (2-B) obtained blue powder and dyes cotton in bright blue shade with excellent fixation yield which provide excellent build up and good fastness properties.

Here, in place of 2-(methylamino)ethanesulphonic acid, Cyanamide, Mercaptoacetic acid, 2-Amino ethanesulphonic acid, ammonia, Cl-C4alkyl amine, etc were used and products were evaluated.
Example-10:
(A) 94.8 parts of l-amino-8-hydroxynaphthalene-3,6-disulfonic acid are dissolved
in 800 ml of water under neutral conditions, and the solution is cooled down to 0-5. 42 parts of 2,4,6-trifluoro-l,3,5-triazine are added drop wise at this temperature in the course of 20 minutes, during which the pH of the reaction solution is kept weakly acid to Congo red by the simultaneous addition of 2N sodium hydroxide solution. After addition of a mixture of 83.5 parts of 2-[(4-Aminophenyl)sulfonyl]ethyl hydrogen sulfate in 500 parts of water which has been adjusted to pH 5 the pH of the

reaction mixture is initially briefly kept weakly acid to Congo red and then at 5-6 by the constant addition of 2N sodium hydroxide solution. At the same time the temperature is raised to 20-25°C in the course of 2 to 3 hours.
(B) 57 parts of 4,4'-Diaminostilbene-3,3'-disulphonic acid are charged into 800 parts of water, stir for 15-30 minutes and slowly adjust pH 7-7.5 with caustic soda lye to obtain clear solution. Add 21.3 parts of sodium nitrite and stir to dissolve. This solution is added slowly over a period of 2-3 hrs in 1200 parts ice and 90 parts of 30% Hydrochloric acid keeping temperature below 5°C with ice as needed. After completion of addition continue stirring at 0-5°C with excess of nitrite for another 2 hrs. Destroy excess nitrite with sulfamic acid.
(C) Now, charge reaction mass (A) to tetra azo solution (B) to coupled at 0-10°C and pH 6.5. After the coupling reaction at pH 8 has ended the reaction mixture is clarified and the resultant reactive dye of the formula (2-C) is isolated at pH 7 by filtration after slating it out from reaction mass or directly dried.

(2-C)
The product (2-C) obtained as blue powder and dyes cotton in bright blue shade with
excellent build up and good fastness properties.
Example-ll:
The dyestuffs of the formula 2 are synthesized using same method as described in
Example-9 to get following dyes described in table shown as Figure 5:


Example-12:
(A) 55.9 parts of Cyanuric Chloride slurry is prepared by charging under stirring
in 600 parts of water at 0-5°C. To this slurry slowly charge solution of 94.8 parts of l-amino-8-hydroxynaphthalene-3,6-disulfonic acid dissolved in 800 ml of water under neutral conditions in 2 hrs. Stirr further 3-4 hrs at 0-5°C and check TLC to ensure absence of l-amino-8-hydroxynaphthalene-3,6-disulfonic acid.
(B) 85.4 parts of 2-[(4-Aminophenyl)sulfonyl]ethyl hydrogen sulfate are
introduced into 500 parts of ice-water and 65 parts of 30% Hydrochloric acid with
efficient stirring, cool the reaction mass to 0-5°C with ice. A solution of 21 parts of
Sodium Nitrite in 50 parts of water is added slowly in 15-30 minutes. Check reaction
mass for excess of nitrite and stir for 2 hrs. After two hrs excess nitrite is destroyed
by addition sulfamic acid.
Add this diazo solution to solution (A) at 0-5°C and stir for 30 minutes and raise pH up to 6.5-7.0 and check spot test for completion of coupling reaction. After coupling test is ok use this reaction mass for further condensation.
(C) Add 57 parts of 4,4,-Diaminostilbene-3,3'-disulphonic acid in to above
coupling mass and stir 2-3 hrs at room temperature at pH 3.0 and then slowly raise
pH up to 5.0-5.5 and also raise temperature up to 40-45°C, stir further for 2-3 hrs and
confirm completion of condensation by TLC. On completion of condensation product
of the formula 3(A) is isolated by filtration after slating out from reaction mass or
directly dried.


The product of the formula (3-A) is obtained as red powder and dyes cotton in very
deep bright red shade having fixation yield of 82% on exhaust dyeing and ISO 105
C03 washing fastness -staining on cotton 4 and on polyamide 4-5.
Example-13:
The dyestuffs of the formula 3 are synthesized using same method as described in
Example-11 to get following dyes described in table shown as Figure 6:

Example-14:
(A) 94.8 parts of l-amino-8-hydroxynaphthaIene-3,6-disulfonic acid are dissolved
in 800 ml of water under neutral conditions, and the solution is cooled down to 0-5°C. 42 parts of 2,4,6-trifluoro-l,3,5-triazine are added drop wise at this temperature in the course of 20 minutes, during which the pH of the reaction solution is kept weakly acid to Congo red by the simultaneous addition of 2N sodium hydroxide solution. After addition of a mixture of 57 parts of 4,4'-Diaminostilbene-3,3'-disulphonic acid in 500 parts of water which has been adjusted to pH 6-6.5 the pH of the reaction mixture is initially briefly kept weakly acid to Congo red and then at 5-6 by the constant addition of 2N sodium hydroxide solution. At the same time the temperature is raised to 20-25°C in the course of 2 to 3 hours.

(B) 85.4 parts of 2-[(4-AminophenyI)suIfonyl]ethyI hydrogen sulfate are introduced into 500 parts of ice-water and 65 parts of 30% Hydrochloric acid with efficient stirring, cool the reaction mass to 0-5°C with ice. A solution of 21 parts of Sodium Nitrite in 50 parts of water is added slowly in 15-30 minutes. Check reaction mass for excess of nitrite and stir for 2 hrs. After two hrs excess nitrite is destroyed by addition sulfamic acid.
Add this diazo solution to solution (A) at 0-5°C and stir for 30 minutes and raise pH up to 6.5-7.0 and check spot test for completion of coupling reaction. After the coupling reaction at pH 8 has ended the reaction mixture is clarified and the resultant reactive dye of the formula (3-B) is isolated at pH 7 by filtration after slating it out from reaction mass or directly dried.

(3-B)
The product (3-B) obtained as blue powder and dyes cotton in bright red shade with
excellent build up and good fastness properties.
Example-15:
The dyestuffs of the formula 2 are synthesized using same method as described in
Example-13 to get following dyes described in table shown as Figure 7:


Comparative Examples
1. The following dyestuffs are used as comparative examples: DYE-1 is known from US2008/0047079 Al, example 1. DYE-2 is known from US2008/0047079 Al, example 2. DYE-3 is from Example 5 DYE-4 is from Example 6 DYE-5 is from Example 6



DYE-5
In the following table advantages of the dyestuffs of the present invention are
illustrated.
In the table, ISO105-C06 is 60 °C washing fastness and ISO 105 B02 fastness is
Color Fastness to Light. All fastness tests are obtained from dyeing in 1/1 standard
depth with dyes of the present invention of formula in comparison with structural
similar known dyestuffs. In the fastness test, the staining of adjacent cotton and
polyamide fabric is assessed. On the assessment scale used, 5 denote to no staining
whatsoever and 1 denotes to substantial staining.
Fixation yield refers to the degree of fixation on cotton relative to the total amount of
dyestuff applied in the dye bath in exhaust dyeing, carried out according to the dyeing
examples 1 and 2.

Shade Fixation Wash fastness (ISO 105 C06) CO/PA Light fastness (ISO 105 B02)
DYE-1 Olive 60% 4/4 2-3
DYE-2 Olive 65% 4/4-5 3
DYE-3 Black 82% 3-4/4-5 5
DYE-4 Black 70% 4/3-4 3-4
DYE-5 Black 70% 4/4-5 3-4
The table shows that fastnesses and fixation yields and Light fastness of the dyes of the present invention are superior compared to similar dyes of closest the state of the art. In particular DYE-3 which represents Example-5 of present invention having one

additional chromophore resulting in more deeper dyeing shade and also shows
significant improvement in fixation yield on cotton fabrics and light fastness.
2. The following dyestuffs are used as comparative examples: DYE-6 is known from US2000/6013775 example 1. D YE-7 is from Example 1.

In the following table advantages of the dyestuffs of the present invention are
illustrated.
In the table, ISO105-C06 is 60 °C washing fastness and ISO 105 B02 fastness is
Color Fastness to Light. All fastness tests are obtained from dyeing in 1/1 standard
depth with dyes of the present invention of formula in comparison with structural
similar known dyestuffs. In the fastness test, the staining of adjacent cotton and
polyamide fabric is assessed. On the assessment scale used, 5 denote to no staining
whatsoever and 1 denotes to substantial staining.
Fixation yield refers to the degree of fixation on cotton relative to the total amount of
dyestuff applied in the dye bath in exhaust dyeing, carried out according to the dyeing
examples 1 and 2.

Shade Fixation Wash fastness (ISO 105 C06) CO/PA Light fastness (ISO 105 B02)
DYE-6 Navy 60% 3/4 2-3
DYE-7 Navy 70% 4/4-5 3-4
The table shows that fastnesses and fixation yields and Light fastness of the dyes of
the present invention are superior compared to similar dyes of closest the state of the
art.
Dyeing Example 1:
100 parts per weight of cotton fabric is introduced at a temperature of 60 °C into a
dyebath containing 800 parts of water, 30 parts per weight of sodium chloride, and 5
parts per weight of the dyestuff of Example 1-6. After 30 min at 60°C, 10 parts per
weight of sodium carbonate is added, and the dyeing temperature is maintained at 60
°C for another 45 min. The dyed fabric is then rinsed in a fresh bath of 2000 parts
warm water, neutralized by adding 1 part per weight of acetic acid, and soaped in
another fresh bath of 2000 parts of water in presence of a conventional detergent for 5
min. at 95°C, and dried. A dyeing with excellent fixation yield and overall good
fastness property is obtained.
Dyeing Example 2:
100 parts per weight of cotton fabric is introduced at a temperature of 80 °C into a
dye bath containing 1000 parts of water, 60 parts per weight of sodium chloride, and
5 parts per weight of the dyestuff of example 7-14. Start heating at 1.5°C/minute and
raise temperature up to 80°C and after 10 minutes at 80°C, add 15 parts per weight of
sodium carbonate, the dyeing temperature is maintained at 80 °C for 60 min, then the
dyed fabric is rinsed and soaped in the same manner as outlined in dyeing example 1.
A deep dyeing with excellent fixation yield with overall good fastness property is
obtained.


We claim:
1. A polyazo dye of the formula 1.
(1)
Where, A= 4,4'-diaminostilbene-2,2,-disulphonic acid; (DASDSA) 4:4'-Diaminodiphenylsufone;(4,4'-DADPS) 3:3,-Diaminodiphenylsulfone(3,3'--DADPS)
X & Y are same or different in combination of followings,
l-Amino-8-Hydroxy naphthalene-3:6-disulphonic acid. (H acid)
l-Amino-7-Hydroxy naphthalene-3:6-disulphonic acid.
l-Amino-7-Hydroxy naphthalene-6-sulphonic acid.
7-Amino-l-naphthoI-3-sulfonic acid (Gamma acid)
N-Methyl-Gamma acid
2-Amino-5-hydroxy-7-naphthalenesulfonic acid (J acid)
l-Hydroxy-6-(methylamino)-3-naphthalenesulfonic acid (N-methyl J-acid)
l-Hydroxy-6-(2'-Carboxy ethyl amino)-3-naphthalenesulfonic acid
l-Hydroxy-6-(2'-sulfo ethyl amino)-3-naphthalenesulfonic acid
And similar N-substituted alkyl derivatives.
l:3-Diamino benzene (m- phenylenediamine)
1:4-Diamino benzene (p- phenylenediamine)
2:5-Diamino benzene sulphonic acid (PPDSA)
2:4-Diamino benzene sulphonic acid (MPDSA)
l:3-Diamino benzoic acid
2:4-Diamino toluene
3:4-Diamino toluene
1:3-Dihydroxy benzene,
1:5/l :8-Diamino naphthalene
1:5/l :8-Dihydroxy naphthalene

and similar diamino, amino hydroxy and dihydroxy benzene and naphthalene
derivatives;
wherein X and Y are not simultaneously l-Amino-8-Hydroxy naphthalene-
3:6-disulphonic acid. (H acid);
R & R = Amino benzene or naphthalene derivatives containing at least one
or more vinylsulphone reactive group with or without -SO3H, alkyl, alkoxy
and halo substituent on benzene or naphthalene ring;
R3 & R5= May be R3 & R5 are same or different in combination of CI; F; Cl-
C4 Alkoxy, -NH2, -NHCN, -C1-C4 alkylamine, Alkyl amino sulfone
derivatives, alkyl amino acids, alkyl amino sulphonic acid derivatives etc;R4
&R6-N,CH,C-C1;
and their mixtures with each or one another.
2. The poly azo dyes as claimed in Claim 1 wherein the compound of formula 1 is preferably of formula (1')

Where, A= 4,4'-diaminostilbene-2,2'-disulphonic acid; (DASDSA) 4:4'-Diaminodiphenylsufone;(4,4'-DADPS) 3:3'-Diaminodiphenylsulfone(3,3'-DADPS)
R7, R8, R9 and R10 = May be same or different in combination of -H, -SO3H,
alkyl and halo;
R11 = -CH2CH2COOH, -CH2CH2CN, -CH2CH2CONH2, -CH2COOH, -
CH2CH2SO3H, -CH2CH(CH3)COOH, -CH2CH2OS03H, -CH2CH2COCH3, -
CH2CH2COOC2H5;


and their mixtures with each or one another. 3. A poly azo dye of formula (2),
(2)
Where, A= 4,4'-diaminostilbene-2,2'-disulphonic acid; (DASDSA)
4:4'-Diaminodiphenylsufone;(4,4,-DADPS) 3:3*-DiaminodiphenylsuIfone(3,3'--DADPS)
X & Y are same or different in combination of followings,
l-Amino-8-Hydroxy naphthalene-3:6-disulphonic acid. (H acid)
l-Amino-7-Hydroxy naphthalene-3:6-disulphonic acid.
l-Amino-7-Hydroxy naphthalene-6-sulphonic acid.
7-Amino-l-naphthol-3-suIfonic acid (Gamma acid)
N-Methyl-Gamma acid
2-Amino-5-hydroxy-7-naphthalenesulfonic acid (J acid)
l-Hydroxy-6-(methylamino)-3-naphthalenesuIfonic acid (N-methyl J-acid)
l-Hydroxy-6-(2'-Carboxy ethyl amino)-3-naphthalenesulfonic acid
l-Hydroxy-6-(2'-sulfo ethyl amino)-3-naphthalenesulfonic acid
And similar N-substituted alkyl derivatives; 1:3-Diamino benzene (m-
phenylenediamine)
1:4-Diamino benzene (p- phenylenediamine)
2:5-Diamino benzene sulphonic acid (PPDSA)
2:4-Diamino benzene sulphonic acid (MPDSA)
l:3-Diamino benzoic acid
2:4-Diamino toluene
3:4-Diamino toluene

1:3-Dihydroxy benzene, 1:5/l :8-Diamino naphthalene 1:5/l :8-Dihydroxy naphthalene
and similar diamino, amino hydroxy and dihydroxy benzene and naphthalene derivatives;
R1 & R2 = Amino benzene or naphthalene derivatives containing at least one or more vinylsulphone reactive group with or without -SO3H, alkyl, alkoxy and halo substituent on benzene or naphthalene ring;
R3 &R5 are same or different and is selected from CI; F; C1-C4 Alkoxy, -NH2, -NHCN, -C1-C4 alkylamine, Alkyl amino sulfone derivatives, alkyl amino acids, alkyl amino sulphonic acid derivatives etc; R4&R6=N,CH,C-C1; and their mixtures with each or one another. 4. A poly azo dye of formula (3),

Where, A= 4,4'-diaminostilbene-2,2'-disulphonic acid; (DASDSA) 4:4'-Diaminodiphenylsufone;(4,4'-DADPS) 3:3'-DiaminodiphenylsuIfor]e(3,3'-DADPS)
X & Y are same or different in combination of followings,
l-Amino-8-Hydroxy naphthalene-3:6-disulphonic acid. (H acid)
l-Amino-7-Hydroxy naphthalene-3:6-disulphonic acid.
1 -Amino-7-Hydroxy naphthalene-6-suiphonic acid.
7-Amino-l-naphthol-3-sulfonic acid (Gamma acid)
N-Methyl-Gamma acid
2-Amino-5-hydroxy-7-naphthalenesulfonic acid (J acid)

l-Hydroxy-6-(methylamino)-3-naphthaIenesulfonic acid (N-methyl J-acid)
l-Hydroxy-6-(2'-Carboxy ethyl amino)-3-naphthalenesulfonic acid
l-Hydroxy-6-(2'-su!fo ethyl amino)-3-naphthalenesulfonic acid
And similar N-substituted alkyl derivatives.
1:3-Diamino benzene (m- phenylenediamine)
1:4-Diamino benzene (p- phenylenediamine)
2:5-Diamino benzene sulphonic acid (PPDSA)
2:4-Diamino benzene sulphonic acid (MPDSA)
l:3-Diamino benzoic acid
2:4-Diamino toluene
3:4-Diamino toluene
l:3-Dihydroxy benzene,
1:5/l :8-Diamino naphthalene
1:5/l :8-Dihydroxy naphthalene
and similar diamino, amino hydroxy and dihydroxy benzene and naphthalene
derivatives;
are Amino benzene or naphthalene derivatives containing at least one or more vinylsulphone reactive group with or without -S03H, alkyl, alkoxy and halo substituent on benzene or naphthalene ring;
R3 & R5 are same or different and is selected from CI; F; C1-C4 Alkoxy, -NH2, -NHCN, -C1-C4 alkylamine, Alkyl amino sulfone derivatives, alkyl amino acids, alkyl amino sulphonic acid derivatives etc; R4&R6-N,CH,C-CI; and their mixtures with each or one another. 5. A process for dyeing and printing fiber materials which comprises treating the fiber materials with dyes of formula (1), formula (2) and formula (3) as claimed in any of the preceding claims.

6. The process as claimed in claim 5, wherein the fiber material is selected from cellulose fibers, cotton or regenerated cellulose, viscose or Lyocell, a polyamide fiber, nylon 6 or nylon 66 or a protein fiber, wool or silk.