FORM 2
THE PATENTS ACT, 1970
(39 of 1970)
&
The Patents Rules, 2003
COMPLETE SPECIFICATION
(See section 10; rule 13)
1. Title of the invention. - NOVEL VINYLSULFONE INTERMEDIATES AND
REACTIVE DYES 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 INVENTION
The present invention relates to novel vinylsulfone intermediates and reactive dyes and processes thereof.
BACKGROUND OF THE INVENTION
Since their first description in the literature over 50 years ago, compounds bearing
the 2-ethenylsulfonyl substituent have been utilized as fiber reactive dyes. This
substituent, which enables the dye molecule to bind covalently with cellulosic
fibers, may be present either as the 2-ethenylsulfonyl group itself or any of a
number of precursors that readily generate the 2-ethenylsulfonyl group in situ
during the dyeing process. The following may be cited as examples of suitable
precursor substituents without necessarily limiting the possible range of precursor
substituents: 2-sulfatoethylsulfonyl, 2-haloethylsulfonyl, 2-
thiosulfatoethylsulfonyl, 2-quaternaryammoniumethylsulfonyl, and 2-methylsulfonatoethylsulfonyl. For the present purposes all of the precursor substituents are functionally equivalent to the 2-ethenylsulfonyl substituent itself and will be hereinafter referred to as vinyl sulfone substituents or simply VS substituents. The fiber reactive dyes bearing these substituents are referred to as VS reactive dyes.
By far the most numerous group of VS reactive dyes are prepared by diazotizing a primary aromatic or heteroaromatic amine that also contains a VS substituent. This diazonium salt is then reacted with a suitable molecule to form an azo dye. Typical examples of molecules that may be reacted with said diazonium compounds include, without limiting the range of possibilities, aromatic amines, aromatic hydroxy compounds, and activated methylene compounds. These compounds are commonly referred to as coupling components in the art and the reaction sequence is referred to as azo coupling.
A more recent development in this field consists of fiber reactive dyes containing two VS substituents per molecule. These dyes, referred to as bifunctional VS

reactive dyes, exhibit distinctly superior fastness properties compared to the VS reactive dyes containing only one VS substituent per molecule.
Dyes bearing the 2-sulfatoethylsulfone (German patent 965,902) and 2-haloethylsulfone (German patent 966,651) substituents were first described in 1949 although they were not employed as cellulosic fiber reactive dyes until 1956. Subsequently, related reactive dyes having similar substituents on the 2 position of the ethylsulfone such as thiosulfate esters or sulfamate esters have been described in the literature. All dyes of this type are converted to the same reactive intermediate substituent, vinylsulfone, under the basic conditions employed in the dyeing process. Accordingly, for the purposes of the following discussion, the term vinyl sulfone reactive dye will be deemed to include all dyes that generate the reactive intermediate substituent vinyl sulfone as part of the dyeing process regardless of the specific precursors including 2-sulfatoethylsulfone or 2-haloethylsulfone among others.
Since the original disclosures in the patents referenced above, many azo dyes of the vinyl sulfone reactive dye type have been developed. All of these dyes incorporate the vinyl sulfone substituent either as a substituent on the diazonium salt component of the dye or as a pendant substituent that is isolated from the dye chromophore by a linking group.
More recently reactive dyes have been developed that incorporate two vinyl sulfone substituents into the same dye molecule. These dyes are referred to as bis-vinylsulfone dyes to distinguish them from dyes that contain a single vinyl sulfone substituent, which are referred to as mono-vinylsulfone dyes. Like the existing mono-vinylsulfone dyes, all existing bis-vinylsulfone dyes incorporate the vinyl sulfone substituents either as substituents on the diazonium salt component of the dye or as pendant substituents that are isolated from the dye chromophore by a linking group.
Because of their superior fixation and wetfastness properties bis-vinylsulfone dyes have become preferred over the earlier developed mono-vinylsulfone dyes.

The present inventors have surprisingly developed a novel vinyl sulfone reactive dye intermediate having vinyl sulfone substituents bound directly to the aromatic or heteroaromatic nucleus of the coupling component rather than solely incorporating the vinyl sulfone substituent either as a substituent on the diazonium salt component of the dye or as a pendant substituent that is isolated from the dye chromophore by a linking group. This innovation permits preparation of dyes with structure that have not been known hitherto simultaneously possessing superior fastness and affinity for fibre.
OBJECT OF THE INVENTION
It is an object of the present invention to utilize substituted Vinyl Sulphone as coupling component to synthesize more reactive and compact chromophores for reactive dyes which can be further utilized in the synthesis of novel bifunctional vinyl sulfone based reactive dyes.
It is another object of the present invention to provide novel vinyl sulfone reactive dyes that contain two vinyl sulfone substituents per molecule.
It is a further object of the present to provide novel vinyl sulfone reactive dyes that exhibit distinctly superior fastness properties.
SUMMARY OF INVENTION
According to an aspect of the present invention there is provided amino azo vinylsulfone precursor intermediates of formula:


According to another aspect of the present invention there is provided azo bis-vinylsulfone reactive dyes of formula:

DETAILED DESCRIPTION OF THE INVENTION
While primary aromatic and heteroaromatic amines containing VS substituents have been utilized extensively to generate diazonium salts, they have never previously been used as the coupling components in azo coupling reactions.
The present invention describes a new and unique class of azo dyes, processes for preparing said dyes, and methods for applying these dyes to fibers.
Under appropriate conditions, the amine bearing the VS substituent can be successfully utilized as the coupling component in the azo coupling reaction. Consequently, new dyes having very good build up properties, high dyeing strength with overall fastness properties can be synthesized in a very simple manner.
In its most basic embodiment the dyes of the present invention have the structure A-N=N-B where A is a primary diazotizable amine and forms the diazonium salt component of the dye and B is an aromatic or heteroaromatic amine or hydroxy compound bearing a vinyl sulfone substituent bound directly to the aromatic or heteroaromatic nucleus and acting as the coupling component of the dye. Either A or B or both may optionally be further substituted.

In one preferred embodiment, both the diazonium salt component and the coupling component contain VS substituents. The resulting monoazo compound can then be converted into a new diazonium salt and coupled with another suitable substrate molecule to form new and unique bifunctional VS reactive disazo dyes.
Alternatively, the monoazo compound can be reacted with a halogenated anthraquinone compound to generate new and unique bifunctional VS reactive aminoanthraquinone dyes.
In another preferred embodiment, the monoazo compound containing two VS substituents and a free primary amino substituent may be linked to additional chromophores through a suitable bifunctional intermediate. 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, succinyl chloride, maleic anhydride, phthaloyl chloride.
In another preferred embodiment, the amino compound utilized as the diazonium salt precursor may bear two primary amino groups and subsequently couple with two moles of VS substituted amine per mole of diazotized amine. This leads to a bifunctional VS reactive disazo dye in a single step.
In yet another embodiment, the site of the coupling reaction is adjacent to the free amino group of the VS substituted component and the azo group may be cyclized to a triazole function through various methods known to those skilled in the art.
The monoazo dyes so produced can either be utilized as such or further reacted through the remaining free primary amino group on the monoazo dye as per below mentioned scheme,
In another embodiment of the present invention there is provided an amino azo vinylsulfone precursor intermediate for reactive dye of Formula


In an embodiment of the present invention there is provided novel azo vinylsulfone reactive dyes of Formula

In another embodiment of the present invention there is provided vinylsulfone reactive dye prepared by condensing an amino azo vinylsulfone intermediate as claimed in Claim 1 with l-amino-4-haloanthraquinone-2-sulfonic acid.


In another embodiment of the present invention there is provided a vinylsulfone reactive dye prepared by condensing an amino azo vinylsulfone intermediate as claimed in claim 1 with a chlorosulfonated copper phthalocyanine compound.

SCHEME-2:
Preparation of Novel disazo and tetrakisazo vinylsulfone reactive dyes:



The resulting monoazo amino compound D1 can then be converted into a new diazonium salt and coupled with another suitable substrate molecule to form new and unique bifunctional VS reactive disazo dyes. Alternatively, two moles of this new diazonium salt of monoazo compound can be reacted with suitable substrate molecule to form new and unique tetra azo bifunctional reactive dyes.
SCHEME-3:
Preparation of Novel Anthraquinone bifunctional VS reactive dyes:

Hydroxyethyl derivatives of novel bifunctional reactive dyes Intermediate D1/D2 can further reacted with a halogenated anthraquinone compounds and subsequently converted in to corresponding esters to generate new and unique bifunctional VS reactive aminoanthraquinone dyes.

SCHEME-4:
Preparation of Novel polyazo reactive dyes: (DYE-8)

Novel bifunctional reactive dyes Intermediate D can further condensed with substituted cyanuric chloride to generate unique polyazo reactive dyes.
The present invention is described herein below with reference to the following examples, which are only illustrative in nature and should not be construed to limit the scope of the invention in any manner.
EXAMPLES
Examplel: Synthesis of Intermediate D1a:
Charge 57.6 parts of p-Aminophenyl-β-sulfatoethyl sulfone (p-base VS ester) into stirred mixture of 30 parts of Hydrochloric acid (30%) and 400 parts of Ice. On completion of p-base VS ester charging continue stirring for further 2 hours maintaining temperature to 0-5°C. Then add 14.3 parts of Sodium Nitrite as 40% solution at 0-5°C. Stir 1 hour keeping CR and SI paper positive. After 1 hour add sulphamic acid in little portion until SI paper shows negative test. Add 55 parts of p-base VS ester at 0-5 °C. Stir for further 30 minutes at 0-5°C and then adjust pH of the reaction mass to 2-2.5 with soda ash solution. Continue pH adjustment until

it gets stable. When there is no further pH fluctuation raise pH np to 4-4.5 with soda ash solution. Maintain temperature 0-5°C and pH at 4-4.5 till completion of coupling, check coupling test with H-acid spot test there should no colour development on the edge indication absence of diazonium salt solution. Check sample on HPLC for further confirmation and purity- This solution can directly be use for synthesis or this amino azo intermediate can be isolated by salting it out and further filtration to give quantitative yield up to 95% of the theory.
Example-2: Synthesis of the Intermediate D1b:
Intermediate D1b is prepared same as Example 1 using m-Aminophenyl-β-sulfatoethyl sulfone (metabase VS ester) as coupling component instead of parabase VS ester.
Example-3: Synthesis of the Intermediate D1c:
Intermediate Dlc is prepared same as Example 1 using o-Aminophenyl-β-sulfatoethyl sulfone (orthobase VS) ester as coupling component instead of parabase VS ester.
Similarly, other derivatives of D1 are prepared using substituted vinyl sulfone derivatives.
Example-4: Synthesis of the Intermediate I)2:
Intermediate D2 is prepared same as Example 1 using para, meta & ortho base VS ester as coupling component and p-Nitro aniline or p-Anisidine or p-Toluidine as diazocomponent instead of parabase VS ester as listed in the below table.


Derivatives of D2 A position wrt amino group in D2
A position wrt azo group in D2
DZa 4- 3-S03H
DZa
4- 4- SO3H
DZa
4- 4-OCH3
DZa
3- 3-SO3H
DZa
3- 4-SO3H
DZa
3- 4-OCH3
Dzg 2- 3-SO3H
Dzh 2- 4-SO3H
D21 2- 4-OCH3
Example-5: Synthesis of Reactive dyes represented by formula DYE-1; DYE-2 & DYE-3
Charge 400 parts of ice water and add 60 parts of Hydrochloric Acid (30%) and start stirring. Add 15 parts of sodium nitrite in the above reaction mass of Example-1 at 0-5°C and then add slowly this reaction mass to readily prepared chilled Hydrochloric acid and on completion of addition, stir for further 2-3 hours maintaining CR and SI positive and temperature 10 to 15°C. Then destroy excess nitrite by addition sulphamic acid and slowly add 38.2 parts of 1:4-Diaminobenzensulphonic acid at 0-5 °C. Stir this reaction mass for further 6-7 hours. Check coupling test to confirm completion of reaction and ensure absence of coupling component. If coupling test is OK adjust pH of the reaction mass to 5-5.5 with soda ash solution and spray dry the whole reaction mass to get final Dye in good quantitative yield. This Dye when apply on the cellulosic fabrics gives

very good golden yellow shade with excellent build up properties and good washing fastness.
Same method is applied for the synthesis of different derivatives of DYE-1 , DYE-2 and DYE-3 using different Amino azo dyes described under formula D1 and coupling components as listed in the below table.

DYE Derivatives ofD1 R1 R1 Shade Amax
DYE-la D18 ~~ — G. Yellow 409
DYE-lb Dlb -- -_ G. Yellow 415
DYE-lc Dlc -- -- G. Yellow 400
DYE-2a Dla H H Orange 495
DYE-2b Dla H CH2SO3H Scarlet 502
DYE-2c Dla H -CH3 Scarlet 506
DYE-2d Dla H -CH2CH3 Scarlet 508
DYE-2e Dla H -C4H9 Scarlet 507

DYE-2f Dib H H Orange 495
DYE-2g Dib H CH2SO3H Scarlet 502
DYE-2h Dib H -CH3 Scarlet 506
DYE-2i Dib H -CH2CH3 Scarlet 508
DYE-2J Dlb H -C4H9 Scarlet 507
DYE-2k Dlc H H Orange 495
DYE-21 Dic H CH2SO3H Scarlet 502
DYE-2m Dic H -CH3 Scarlet 506
DYE-2n Dlc H -CH2CH3 Scarlet 508
DYE-2o Dlc H -C4H9 Scarlet 507
DYE-2p Dla -CH3 -CH3 Orange
DYE-2q Dla -CH2CH3 -CH2CH3 Orange
DYE-2r Dib -CH3 -CH3 Orange
DYE-2s Dib -CH2CH3 -CH2CH3 Orange
DYE-2t Dlc -CH3 -CH3 Orange
DYE-2u Dlc -CH2CH3 -CH2CH3 Orange
DYE-3a Dla -"~ Red 505
DYE-3b Dlb — ™ Red 510
DYE-3c Dlc — —— Red 505

Example-6: Synthesis of Reactive dyes represented by formula DYE-4; DYE-5 & DYE-6
Charge 400 parts of ice water and add 60 parts of Hydrochloric Acid (30%) and start stirring. Add 15 parts of sodium nitrite in the above reaction mass of Example-l at 0-5°C and then add slowly this reaction mass to readily prepared chilled Hydrochloric acid and on completion of addition, stir for further 2-3 hours maintaining CR and SI positive and temperature 10 to 15°C. Then destroy excess nitrite by addition sulphamic acid and slowly add 19.1 parts of 1:4-Diaminobenzensulphonic acid at 0-5 °C. Stir this reaction mass for further 4-5 hours. Check coupling test to confirm completion of reaction and ensure absence of coupling component. If coupling test is OK adjust pH of the reaction mass to 5-5.5 with soda ash solution and spray dry the whole reaction mass to get final Dye in good quantitative yield. This dye when applied on the cellulosic fabrics gives dull brownish yellow shade.
Same method is applied for the synthesis of different derivatives of DYE-4 , DYE-5 and DYE-6 using different Amino azo dyes described under formula D1 and D2 and coupling components as listed in the below table.


DYE Derivatives of D1 Derivatives
of D2 R1 R2 SHADE
DYE-4a 2Dla — - — D. Yellow
DYE-4b 2D1b — — — D. Yellow
DYE-4c 2D1C — — — D. Yellow
DYE-4d Dla Dib — — Br. Yellow
DYE-4e Dla Dlc — — Br. Yellow
DYE-4f Dlb DJc — — Br. Yellow
DYE-5a 2D,a — H H Scarlet
DYE-5b 2Dla — H CH2S03H Scarlet
DYE-5c 2Dia — H -CH3 Red
DYE-5d 2D,a — H -CH2CH3 Red
DYE-5e 2Dla — H -C4H9 Red
DYE-5f 2Dlb — H H Scarlet
DYE-5g 2Dlb — H CH2SO3H Scarlet
DYE-5h 2D,b — H -CH3 Red
DYE-5i 2Dlb — H -CH2CH3 Red
DYE-5J 2D1b — H -C4H9 Red
DYE-5k 2DtC — H H Scarlet
DYE-5I 2DlC — H CH2SO3H Red
DYE-5m 2Dic — H -CH3 Red

DYE-5n 2Dic — H -CH2CH3 Red
DYE-5o 2Dlc — H -C4H9 Red
DYE-6a 2Dla — — — Navy Blue
DYE-6b 2Dlb — — — Navy Blue
DYE-6c 2D1C — — — Navy Blue
DYE-4g Dta D2a — — R. Yellow
DYE-4h Dla D2b — — R. Yellow
DYE-4i Dla D2c — — R. Yellow
DYE-4J Dla D2d — — R. Yellow
DYE-4k Dla D2e — — R. Yellow
DYE-4I Dla D2t — — R. Yellow
DYE-4m Dlb D2a — — Br. Yellow
DYE-4n DIb D2b — — Br. Yellow
DYE-4o Dlb D2c — — Br. Yellow
DYE-4p D1b D2d — — Br. Yellow
DYE-4q D1b Die ~ -- Br. Yellow
DYE-4r Dlb D2t — — Br. Yellow
DYE-4s Dlc D2a — — R. Yellow
DYE-4t Dlc Dlb — — R. Yellow
DYE-4u Dlc D2C — --- R. Yellow

DYE-4v Dlc D2d — — R. Yellow
DYE-4w Dlc D2e — — R. Yellow
DYE-4x D!c D2e — — R. Yellow
DYE-5p Dia D1b H H Red
DYE-5q Dla Dlc H H Red
DYE-5r Dib Dlc H H Red
DYE-5s Dla Dib H H Scarlet
DYE-5t Dla D2a H H Red
DYE-5u Dla D2b H H Red
DYE-5v Dla D2C H H Red
DYE-5x Dla D26 H H Red
DYE-5y Dla D2C H H Red
DYE-5z Dla D21 H H Red
DYE-5aa Dlb D2a H H Red
DYE-5ab Dib D2b H H Red
DYE-5ac Dla D2C H H Red
DYE-5ad Dib DM H H Red
DYE-5ae Dib D2e H H Red
DYE-5af Dib D2f H H Red
DYE-5ag Dla D2a H -CH3 Red

DYE-5ah
Dla D2b H -CH3 Red
DYE-5ai Dla D2c H -CH3 Red
DYE-5aj Dla D2a H -CH3 Red
DYE-5ak Dla D2e H -CH3 Red
DYE-5al D1a D2f H -CH3 Red
DYE-5am D1b D2a H -CH3 Red
DYE-5an Dib D2b H -CH3 Red
DYE-5ao Dib D2c H -CH3 Red
DYE-5ap Dib Dld H -CH3 Red
DYE-5aq Dib D2t H -CH3 Red
DYE-5ar Dib D2r H -CH3 Red
DYE-6d Dla Dlb — — Navy Blue
DYE-6e D]a D1c ___ Navy Blue
DYE-6f Dib Dlc -- — Navy Blue
DYE-6g Dla D2a — — Navy Blue
DYE-6h Dla D2b — — Navy Blue
DYE-6i D,a D2C — — Navy Blue
DYE-6j Dla D2d — — Navy Blue
DYE-6k Dla D2c — — Navy Blue
DYE-6m Dla D21 -- — Navy Blue

DYE-6n D1b D2a — — Navy Blue
DYE-60 Dib D2b — — Navy Blue
DYE-6p D\1b D2c — — Navy Blue
DYE-6q D1b D2d — — Navy Blue
DYE-6g D1b D2e ... — Navy Blue
DYE-6r D1b D2t — — Navy Blue
Example-7: Synthesis of Reactive dyes represented by formula DYE-7.
Charge 45 parts of sodium bicarbonate in to 250 parts of water and stir for 30 minutes and charge Dla reaction mass as prepared in Example-1 and then charge 73 parts of Bromaminic acid and start heating under stirring. Heat reaction mass to bring temperature up to 75-80°C. Then slowly add 7 parts Cuprous Chloride in small portions maintaining temperature 75-80°C. On completion of addition maintain temperature for further 3 hours. Monitor reaction progress by TLC and on completion of reaction drown to pre-heated mixture of 500 parts of water and 175 parts of 30% hydrochloric acid. Stir drown mass for 30 minutes and filter. Wash with 10% salt solution to remove smaller impurities to get pure product.
Wet press cake is dried and re-slurried in 300 parts of 100% sulphuric acid at <40°C for esterification. Check completion of esterification by TLC and on completion drawn reaction mass into 125 parts of ice and filter and wash with little chilled water. This Wet press cake is further re-slurried in ice water and adjust pH to 4.5-5.0 and spray dried to get final product powder. This Dye-7a gives bright blue shade on Cellulosic fiber when dyed.
Same method is applied for the synthesis of different derivatives of DYE-7 using different amino azo intermediate described under formula D1 and D2 for condensation with Bromaminic acid.

DYE Derivaties of D1 Shade λ, max
DYE-7a Dla Blue 594
DYE-7b Dlb Blue 595
DYE-7c D2a Blue 596
DYE-7d D2b Blue 597
DYE-7e D2c Blue 593
DYE-7f D2d Blue 595
DYE-7g Dze Blue 596
DYE-7h D2l Blue 594
Example-8: Synthesis of Reactive dyes represented by formula DYE-8.1.
Charge 200 parts of Ice, start stirring, add small portion of wetting oil and charge 37 parts of Cyanuric Chloride under stirring for 10-15 minutes keeping temperature 0-5°C. In a another flask charge 200 parts of water and add 64 parts of l-Amino-8-Hydroxy Naphthalene-3:6-Disulfonic acid and adjust pH to 7-7.5 with caustic soda solution. Now add this l-Amino-8-Hydroxy Naphthalene-3:6-Disulfonic acid solution to above prepared solution of cyanuric chloride in 2-3 hours keeping temperature 0-5°C. Continue stirring for another 2 hours and check TLC. Absence of l-Amino-8-Hydroxy NaphthaIene-3:6-Disulfonic acid on TLC confirms completion of reaction.
On completion of Cyanuration add Dla reaction mass at 0-5°C and then slowly raise temperature up to 20-25°C and stir 7-8 hours at this temperature. After that adjust pH to 6.5-7.0 with soda ash solution and spray dry the whole reaction mass to get final product powder. This Reactive dyes when dyed on cellulosic fibers gives bright red shade with good build up and reasonably good washing fastness.

Same method is applied for the synthesis of different derivatives of DYE-8 using

different Amino azo intermediate described under formula D1 and D2 with coupling components as mentioned in below tables.

DYE-8.1 Dl/D2 R5 R6 R7 Shade λ. max
DYE-8.1a Dla -S03H -OH -SO3H Red 522
DYE-8.1b Dlb -SO3H -OH -SO3H Red 521
DYE-8.1 c Dlc -SO3H -OH -SO3H Red 520
DYE-8.1d Dla H -OH -SO3H Orange 482
DYE-8.1 e Dlb H -OH -SO3H Orange 484
DYE-8.1f D1c H -OH -SO3H Orange 480
DYE-8.1 g D1a H -OH -SO3H Scarlet 498
DYE-8.1 h D H -OH -SO3H Scarlet 499
DYE-8.U Dlc H -OH -SO3H Scarlet 495
DYE-8.1J Dla -SO3H -OH -SO3H Orange 481
DYE-8.1k Dlb -SO3H -OH -SO3H Orange 484
DYE-8.11 Dlc -S03H -OH -SO3H Scarlet 482

Example-9: Synthesis of Reactive dyes represented by formula DYE-8:
Charge 200 parts of Ice, start stirring, add small portion of wetting oil and charge 37 parts of Cyanuric Chloride under stirring for 10-15 minutes keeping temperature 0-5°C. In a another flask charge 200 parts of water and add 64 parts of l-Amino-8-Hydroxy Naphthalene-3:6-Disulfonic acid and adjust pH to 7-7.5 with caustic soda solution. Now add this l-Amino-8-Hydroxy Naphthalene-3:6-Disulfonic acid solution to above prepared solution of cyanuric chloride in 2-3 hours keeping temperature 0-5°C. Continue stirring for another 2 hours and check TLC. Absence of l-Amino-8-Hydroxy Naphthalene-3:6-Disulfonic acid on TLC confirms completion of reaction.
On completion of Cyanuration add Dla reaction mass at 0-5°C and then slowly raise temperature up to 20-25°C and stir 7-8 hours at this temperature. After that adjust pH to 6.5-7.0 with soda ash solution.
In another flask charge 400 parts of ice water, 60 parts of Hydrochloric acid (30%) and 60.7 parts of 2-Naphthylamine-l:5-Disulphonic acid (STA, D3) stir to smooth slurry and the charge 14.3 parts of Sodium Nitrite as 40% solution at 0-5 °C. Stir to complete diazotization and then charge this diazonium slat solution to above solution with maintaining pH 5.5-6.5 with soda ash solution. After completion of addition check coupling spot test and ensure completion of coupling reaction. Then adjust pH 6.5-7 with soda ash solution and spray dry the whole reaction mass to get final product powder. This Reactive dyes when dyed on cellulosic fibers gives bright Orange shade with good build up and reasonably good washing fastness.
Same method is applied for the synthesis of different derivatives of DYE-8 using different Amino azo intermediate described under formula D and D with coupling components and Second diazonium compound D as mentioned in below tables.

DYE-8 DVD2 D3 R6 R6 R7 Shade λ max
DYE-8m D1a STA -H -OH -SO3H Orange 483
DYE-8n Dla Tobia's acid -H -OH -SO3H Orange 485
DYE-80 Dla Koach acid -H -OH -SO3H Orange 486
DYE-8p Dla Bronner's Acid H -OH -SO3H Orange 487
DYE-8q Dla p-base ester H -OH -SO3H Orange 482
DYE-8r D,a Sulfo-p-base ester H -OH -SO3H Orange 486
DYE-8s Dla Dib H -OH -SO3H Orange 483
DYE-8t Dla p-cresidine VS H -OH -SO3H Orange 489
DYE-8u Dla o-Anisidine VS H -OH -SO3H Orange 485
DYE-8v Dla Sulfanilic acid -H -OH -SO3H Orange 486
DYE-8w Dla Metanilic acid -H -OH -SO3H Orange 484
DYE-8x Dla Orthanilic acid -H -OH -SO3H Orange 484
DYE-8y Dla STA -SO3H -OH -SO3H Orange 481
DYE-8z Dla Tobia's acid -SO3H -OH -S03H Orange 481

DYE-8aa Dla Koach acid -SO3H -OH -SO3H Orange 482
DYE-8ab Dla Bronner's Acid -SO3H -OH -SO3H Orange 483
DYE-8ac Dla p-base ester -SO3H -OH -SO3H Orange 480
DYE-8ad Dla Sulfo-p-base ester -SO3H -OH -SO3H Orange 480
DYE-8ae Dla Dlb -SO3H -OH -SO3H Orange 481
DYE-8af Dla p-cresidine VS -S03H -OH -SO3H Orange 486
DYE-8ag Dla o-Anisidine VS -SO3H -OH -SO3H Orange 485
DYE-8ah Dla Sulfanilic acid -SO3H -OH -SO3H Orange 483
DYE-8ai D,a Metanilic acid -SO3H -OH -SO3H Orange 481
DYE-8aj Dla Orthanilic acid -SO3H -OH -SO3H Orange 481
DYE-8ak Dla STA -SO3H -OH -SO3H Red 520
DYE-8al Dla Tobia's acid -SO3H -OH -SO3H Red 519
DYE-8am Dla Koach acid -SO3H -OH -SO3H Red 521
DYE-8an Dla Bronner's Acid -SO3H -OH -SO3H Red 521
DYE-8ao Dla p-base ester -SO3H -OH -SO3H Red 518
DYE-8ap Dla Sulfo-p-base ester -SO3H -OH -SO3H Red 519
DYE-8aq DIa D!b -SO3H -OH -SO3H Red 524
DYE-8ar D,a p-cresidine VS -SO3H -OH -SO3H Red 529
DYE-8as Dla o-Anisidine VS -SO3H -OH -SO3H Red 523
DYE-8at Dla Sulfanilic acid -SO3H -OH -SO3H Red 523

DYE-8au Dia Metanilic acid -SO3H -OH -SO3H Red 524
DYE-8av D1a Orthanilic acid -SO3H -OH -SO3H Red 520
DYE-8aw DLh STA -H -OH -SO3H Orange 485
DYE-8ax DIb Tobia's acid -H -OH -SO3H Orange 486
DYE-8ay Dlb Koach acid -H -OH -SO3H Orange 488
DYE-8az Dlb Bronner's Acid H -OH -SO3H Orange 489
DYE-8ba Dlb p-base ester H -OH -SO3H Orange 483
DYE-8bb Dlb Sulfo-p-base ester H -OH -SO3H Orange 488
DYE-8bc Dib D,b H -OH -SO3H Orange 488
DYE-8bd Dlb p-cresidine VS H -OH -SO3H Orange 490
DYE-8be Dlb o-Anisidine VS H -OH -SO3H Orange 486
DYE-8bf Dlb Sulfanilic acid -H -OH -SO3H Orange 486
DYE-8bg Dlb Metanilic acid -H -OH -SO3H Orange 485
DYE-8bh Dlb Orthanilic acid -H -OH -SO3H Orange 485
DYE-8bi Dlb STA -SO3H -OH -SO3H Orange 483
DYE-8bj D1b Tobia's acid -SO3H -OH -SO3H Orange 482
DYE-8bk D™ Koach acid -SO3H -OH -S03H Orange 484
DYE-8bl D1b Bronner's Acid -SO3H -OH -SO3H Orange 486
DYE-8bm Dib p-base ester -SO3H -OH -SO3H Orange 483
DYE-8bn Dib Sulfo-p-base ester -SO3H -OH -S03H Orange 483

DYE-8bo Dlb Dlb -SO3H -OH -SO3H Orange 484
DYE-8bp D1D p-cresidine VS -SO3H -OH -SO3H Orange 486
DYE-8bq D'b o-Anisidine VS -SO3H -OH -SO3H Orange 487
DYE-8br Dlb Sulfanilic acid -SO3H -OH -SO3H Orange 484
DYE-8bs Dib Metanilic acid -SO3H -OH -SO3H Orange 483
DYE-8bt Dib Orthanilic acid -SO3H -OH -SO3H Orange 483
DYE-8bu Dlb STA -SO3H -OH -SO3H Red 522
DYE-8bv Dib Tobia's acid -SO3H -OH -SO3H Red 520
DYE-8bw Dib Koach acid -SO3H -OH -SO3H Red 523
DYE-8bx Dlb Bronner's Acid -SO3H -OH -SO3H Red 524
DYE-8by Dib p-base ester -SO3H -OH -SO3H Red 520
DYE-8bz Dib Sulfo-p-base ester -SO3H -OH -SO3H Red 521
DYE-8ca Dlb Dlb -SO3H -OH -SO3H Red 527
DYE-8cb D,b p-cresidine VS -SO3H -OH -SO3H Red 531
DYE-8cc Dib o-Anisidine VS -SO3H -OH -SO3H Red 526
DYE-8cd Dib Sulfanilic acid -SO3H -OH -SO3H Red 526
DYE-8ce Dib Metanilic acid -SO3H -OH -SO3H Red 526
DYE-8cf Dib Orthanilic acid -SO3H -OH -SO3H Red 522

Example-10: Synthesis bisvinylsulfone reactive dyes containing a copper phthalocyanine chromophore:
Add 143 g. copper phthalocyanine to 650 g. chlorosulfonic acid with agitation over one hour maintaining temperature between 10-20° C. Heat to 143° C. over three hours then hold at 143° C. for two hours. The mixture is poured onto 600 g. ice, stirred for 15 minutes, filtered, and washed with 100 ml. cold water. The wet filter cake is slurried in 1000 ml water at 10° C and 143 g intermediate Dla as prepared in example 1 is added with agitation. The pH of the mixture is adjusted to 3.5 with sodium carbonate, held one hour and then adjusted to pH 7 with sodium hydroxide. The resulting dye can be used as is or isolated by filtration. The compound dyes cotton a brilliant turquoise shade with excellent fastness properties and high exhaustion.
Similarly, other all derivatives of CPC blues are prepared by condensation of different derivatives of D1 with chlorosulphonated CPC as described in Example-10.
Example-ll: Dyeing of cloth with dyes of the invention:
Dissolve 1.0 g. dry weight of the dye prepared according to example 5 in 1000 ml. water at 40° C. add 100 g. scoured cotton cloth to this mixture and agitate for 10 minutes. Next add 40 g. sodium chloride and continue agitation for an additional 10 minutes at 40° C. Raise the temperature of this mixture to 60° C. over 20 minutes and hold at this temperature with agitation for 30 minutes. Add 15.0 g. sodium carbonate and hold at 60° C. for 60 minutes more. The cloth is then removed and rinsed in cold (15-25° C.) water until the rinse water is colourless. The cloth is then dried in at air flow drier at 80-90° C. The resulting cloth is dyed a bright golden yellow colour fast to light and washing.

WE CLAIM:
1. Amino azo vinylsulfone precursor intermediate of formula:

3. The azo vinylsulfone reactive dye as claimed in claim 2, wherein the vinylsulfone precursor is a 2-sulfatoethylsulfone substituent.
4. The azo vinylsulfone reactive dye as claimed in claim 2, wherein the vinylsulfone precursor is 2-haloethylsulfone substituent.

5. The azo vinylsulfone reactive dye as claimed in claim 2, wherein a second vinylsulfone precursor is attached directly to the aromatic nucleus of the diazonium salt component Dl and D2.
6. The azo vinylsulfone reactive dye as claimed in claim 5, wherein the vinylsulfone precursors are 2-sulfatoethylsulfone substituents.
7. The azo vinylsulfone reactive dye as claimed in claim 5, wherein the vinylsulfone precursors are 2-haloethylsulfone substituents.
8. A vinylsulfone reactive dye prepared by condensing an amino azo vinylsulfone intermediate as claimed in Claim 1 with l-amino-4-haloanthraquinone-2-sulfonic acid.

9. A vinylsulfone reactive dye prepared by condensing an amino azo vinylsulfone intermediate as claimed in claim 1 with a chlorosulfonated copper phthalocyanine compound.
10. A disazo vinylsulfone reactive dye prepared by Condensing Cyanurated coupling component with amino azo vinylsulfone reactive dyes intermediate as claimed in Claim 1.


Wherein D and D2 are as described in claim 1 and
R5=H;OH,NH2orS03H; R6 & R7= H or S03H.
11. A Tris-azo and Tetra-azo vinylsulfone reactive dye prepared by Condensing Cyanurated coupling component with Amino azo vinylsulfone reactive dyes intermediate as claimed in Claim 1 and subsequently coupled with diazotized aromatic/heterocyclic amine D .

Wherein D and D are as described in claim 1 and
D3= Substituted Amino Vinylsulfone esters; Amino
benzenesulfonic acid derivatives or Amino
Naphthalenesulfonic acid derivatives.
12. Textile fabrics dyed with a dye as claimed in any one of the preceding claims 2-11.