WO 2011/077461

PCT/IN2010/000850

1 DISPERSE AZO DYES
FIELD OF THE INVENTION
The present invention relates to novel disperse dyes and its use thereof.
BACKGROUND OF THE INVENTION
Traditionally, disperse dyes are used for dyeing synthetic fibers and its blend with other fibers such as cellulose, polyurethane, nylon and wool by usual exhaust dyeing, continuous dyeing and printing techniques.
Recently with changing trends, fashion and market requirement consumption of blended fabrics is significantly increased. These new fabrics are made out of micro size fiber using fine denier polyester fiber or blending fiber with polyurethane, nylon and wool. The fastness properties of these new colored fabrics become worse in light fastness and sublimation fastness, particularly washing fastness when dyed or printed with conventional disperse dyes. The fastness properties worsen due to thinning of dyed fiber by using fine denier polyester fiber or blending fiber with polyurethane, nylon and wool. The excellent dyestuff to endure this use is desired in this dyeing and printing field.
IN 190551 and its divisional patents IN 197577 and IN 196765 disclose nionoazo dyes
r . J
containing fluorosulphonyl group. The aforesaid Indian Patents disclose process for colouring synthetic textile material or fiber blend.
The patent application 2 162/KOLNP/2009 which is published as WO 2008/074719 discloses disperse dye mixture comprising (a) two or more disperse dyestuffs of the formula (I).
Thus the prior art discloses azo dye compounds and process for preparation, however does not impart excellent fastness properties particularly Light Fastness and Washing Fastness properties.
OBJECTS OF THE INVENTION
It is an object of the present invention to provide yellow, red and blue disperse azo dyes.

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It is another object of the present invention to provide process for coloration of synthetic textile materials.
It is a further object of the present invention to provide disperse azo dyes with excellent Light Fastness and Washing Fastness properties on the polyester fiber
SUMMARY OF THE INVENTION
According to one aspect of the present invention there is provided disperse dyes of Formula 1.
CH2(CH2)nCOOCH2CN
wherein,
R is'tiydrogen, methyl, hydroxyl orNHR3'
R is hydrogen, chloro or methoxy;
wherein,
D is a group of the formula (2a)

wherein,
X, Y and Z are, independently,.hydrogen, methyl, halogen, cyano or nitro;
Or a group of the formula (2b),

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(2b)

wherein,
o
T is independently hydrogen, halogen, nitro, -S0 2 CH3 or -SCN; and T2 is hydrogen or halogen; Or a group of the formula (2c),


(2c>

Or a group of the formula (2d),

J3

i, J

(2d)

f

\r

wherein,
T3and T4 are independently nitro, acetyl, COOR4 or cyano;
R3 is -COCH 3i-COC2H5, -S0 2CH3 or S0 2CH5;
R4is Ci to C4 unsubstituted alkyl;
n and m are independently 0,1 or 2.
According to yet another aspect of the present invention there is provided processes for preparation of disperse azo dyes of Formula (1) having excellent washing fastness and light fastness on the polyester fiber.

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DETAILED DESCRIPTION OF THE PRESENT INVENTION
The present invention provides new disperse dyes of formula (1) with excellent washing fastness and light fastness.

R8
^CH^CH^COOCHjCN CH2(CH2)nCOOCH2CN
D. . £t—£tm—, £—
..r"-«-i. J—NC (1)
\ //
wherein,
R is hydrogen, methyl, hydroxyl or NHR '
R2 is hydrogen, chloro or methoxy;
wherein,
D is a group of the formula (2a)


. z
wherein,
X, Y and Z are, independently, hydrogen, methyl, halogen, cyano or nitro;
Or a group of the formula (2b),
V- (2b)
wherein,
T1 is independently hydrogen, halogen, nitro, -S0 2 CH3 or -SCN; and
T is hydrogen or halogen;

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Or a group of the formula (2c),


(2c)

Or a group of the formula (2d),


(2d)

wherein,
T and T4 are independently nitro, acetyl, COOR4 or cyano;
R3 is -COCH 3,-COC2H5, -S0 2CH3 or S0 2C2Hs;
R4is Ci to C4 unsubstituted alkyl;
n and m are independently 0,1 or 2.
The present invention further describes processes for syntheses of novel disperse dyes, the preparation of the dye composition and methods for applying these dyes to fibers.
Disperse Azo Dyes are generally prepared by diazotization of primary aromatic amine and subsequently couple with suitable coupling component.
Under appropriate conditions, primary aromatic or heteroaromatic amine can be . successfully diazotized and coupled with specially developed coupling component to get novel disperse dyes of formula (1) respectively. These new disperse dyes possesses -excellent washing and light fastness properties.
The present invention further provides a composition comprising a disperse dye of the present invention and additionally at least on further ingredient conventionally used in colouring application such as a disperse agent and optionally a surfactant or wetting agent.

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The dye composition typically comprises from 10% to 65%, preferably 20% to 50% by weight of the total dye as single component or mixture in solid medium.
Typical examples of dispersing agent are lignosulphonates, naphthalene sulfonic acid/formaldehyde condensates and phenol/cresol/sulphanilic acid/formaldehyde condensates. Typical examples of wetting agent are alkyl aryl ethoxylates which may be sulphonated or phosphate and typical examples of other ingredients which may be present are inorganic salts, de-foamer such as mineral oil or nonanol, organic liquids and buffers. Disperse agents may be present at from 80% to 400% on the weight of the dye mixtures. Wetting agents may be used at from 0.1% to 20% on the weight of the dye mixtures.
The disperse dye or mixtures of disperse dyes of the present invention is milled with suitable dispersing agent using glass beads or sand in an aqueous medium. The compositions may have further additions of dispersing agents, fillers and other surfactants and may be dried, by a technique such as spray drying, to give a solid composition comprising from 15% to 65% by weight of dyestuff.
In case of dyeing with fiber materials, the dyestuffs are milled in water with dispersing agent in usual method and the finished dyes are used for dyeing or printing in the liquid form or the powder form after spray drying of the liquid. The each finished dye is used for dyeing and printing in single or mixtures of two or the more of the present invention dyes.
In case of exhaust dyeing, the polyester fiber, the conjugated fiber and the blend fiber is dyed in excellent fastness by high temperature dyeing, carrier dyeing and continuous dyeing. The dyestuff of formula (1) may be used individually or as a mixture of derivatives of formula (1) for dyeing and printing.
In the case of printing, the polyester fiber, the textile materials are processed in excellent fastness by direct printing or discharge printing.
Embodiment of the present invention will be described in more detail with reference to the following examples, in which parts are by weight unless otherwise stated. The present invention is concretely explained as follows, but the present invention is not limited in these examples.

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The preparation of Dyestuff of formula 1 comprises the following steps:
a) Synthesis of coupling component;
b) Diazotization of aromatic amine;
c) Coupling of diazonium salt with suitable coupling component;
d) Milling with suitable disperse agents, fillers and optionally wetting agents or surfactants.
e) Use it as liquid or spray dry to get final powder sample.
Example-1:
Structural formula (3)
N02
^CjhUCOOCI-kCN
O2N—(\ /)—N=N-^V ,}—N <3)
XC2H4COOCH2CN
The example 1 of structural formula (3) is synthesized in the following method.
Acrylic acid 20.0 g is added into the mixture of DMF (N,N-dimethyformamide) 40.0g and 3-amino acetanilide 15g and heated to 80°C and maintain under continues stirring for 2 hours. After completion of reaction, Chloroacetonitrile (cyanomethylchloride) 19.4 g are added into the reaction mass and heated to 80°C and maintain under continues stirring for 2 hours. On completion of reaction this reaction mass which contains 35 g of this coupler is used for next coupling reaction.
30 ml of 40%nitrosylsulfuric acid is added to the mixture of 19.4 g 2, D-dinitro aniline and 50ml sulfuric acid at 0-5 □ and stirred for 2hr below 5D. After 2 hrs this diazonium salt solution is added to the pre-charged mixture of Ice, water and 35 g of Coupler, N, N-dicyanomethoxycarbonylethyl-3-acetoamideaniline at 0-5 □ . The* reaction mass is stirred for 1 hr below 5□ and filtered. The crystal solid is then washed with chilled water to get

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90% yield of the Dyestuff of formula (3). The A,r|iax (in acetone) of the dyestuffs of formula (3) is 536 ran.
2.0 g of the obtained wet press cake is milled with 2.0 g of naphthalenesulfonic acid-formaldehyde condensate and 50 g of water and 500 g of glass beads (average side is 0.8 mm of diameter.) for 24 hr and after milling, the mass is filtered to separate glass beads.
20 g of the obtained finished liquid is added in 100 ml of water and pH adjusted to 4 with acetic acid. 10 g piece of polyester is added into the dye bath for exhaust dyeing.
The dyeing bath is heated to 135 □ and kept for 40 minutes. After proper rinsing, washing and drying, the dyed material gives deep Rubine shade with excellent washing fastness, light fastness and sublimation fastness.
Fastness properties of the dyed fabrics are evaluated by following test method.
Washing Fastness as per Test Method AATCC 6 1 2A, Light Fastness as per Test Method ISO 105 B02 and Sublimation Test at 180 deg for 30 sec and at 210 deg for 30 sec.
Example 2
The dyestuffs of the formula (4) are synthesized using same methods described in Example-1 to get following dyes described in table:



CH2(CH2)mCOOCH2CN
\ (4)
CH2(CH2)nCOOCH2CN
OoN
N=N

Example Y □ R1 R R m n ^max(nm)
2-1 N02 H NHR H COCH3 0 0 536
2-2 N0 2 H NHR H COCH3 1 1 538
2-3 N02 CI NHRJ H COCH3 0 0 546
2-4 CI CI H H 1 1 430

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2-5 CI Br H H 1 1 429
2-6 CN H CH3 H 1 1 523
2-7 CN H NHR3 H COCH3 0 0 526
2-8 CI H NHR3 H COCH3 1 . 1 .524
2-9 N0 2 H NHR3 OCH3 COCH3 1 1 560
2-10 N0 2 Br NHR OCH3 COCH3 1 1 585
2-11 CN Br NHR3 OCH3 COCH3 1 1 607
2-12 CI Br H H 1 2 433
These dyestuffs show the excellent washing fastness, light fastness and sublimation fastness.
Example-3:
The dyestuffs of the formula (2) are synthesized using same methods described in Example-1 to get following dyes described in table:


,CH2(CH2)mCOOCH2CN
N^ (2)
-N=N
y
\>

■v
CH2(CH2}nCOOCH2CN

Example X Y Z R1 R2 RJ m n Jimax(nm)
3-1 CH3 CN CN NHRJ H COCH3 1 1 522
3-2 CI CN CN NHRj H SO2CH3 1 1 525
3-3 CI N02 H CH3 H 1 1 440
3-4 CI CN CN OH H 1 1 510
These dyestuffs show the excellent washing fastness, light fastness and sublimation fastness.

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Example 4:
The dyestuffs of the formula (1) are synthesized using same methods described in example- 1 to get following dyes described in table:


CH2(CH2)mCOOCH2CN
N- (1)
0-N=N
CHz(CHz)nCOOGHzCN

Example D R1 R2 R* m n Dmax(nm
)
4-1 5:6-dichloroBenzothiazole H H 1 1 515
4-2 6-nitrobenzothiazole H H 1 1 537
4-3 6-chlorobenzothiazole "NHRJ H COCH3 1 1 525
4-4 3,5-dinitro Thiophene CH3 H 1 1 630
4-5 6-nitrobenzoisothiazole NHRJ H COCH3 1 1 605.
These dyestuffs show the excellent washing fastness, light fastness and sublimation fastness.
Comparative Example-l: ■
The following dyes written as Dye 1-5 and Dye 1-38 each, in the Table-1 of. WO2008/074719 is compared with dyes written as Dye Example 2-1 in this patent in washing fastness and sublimation fastness as follows.

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CH2CH2COOCH2CN (Example
02N
CH2CH2COOCH2CN
0,N
CH2CH2COOCH2CN (Dyel-5 in tablelof
C2H5 WO2008/
074719)
2-1 of this patent)

Dye Washing fastness (WF) Sublimation fastness (SF) Light fastness (LF)
Example 2-1 of this patent 4 class 5 class 4-5 class
Comparative Dye 1-5 in Table-1 of W2008/074719 2-3 class 3-4 class 3-4 class
Washing Fastness as per Test MethodAATCC 612A, Light Fastness as per Test Method ISO 105 B02 and Sublimation Test at 180 degfor 30 sec and at 210 degfor 30 sec.
Dye of Example 2-1 of this patent and comparative Dye 1-5 are very similar chemicals only except difference between ethyl group and C2H4COOCH2CN in amino radical and Methpxy group is not there in Example 2-1 but the quality differences are very big especially in washing fastness, also in sublimation fastness and light fastness. This comparative example provides confmnation to the logical approach to introduce two C2H4COOCH2CN substituents to improve washing fastness properties instead of only one in the WO2008/074719. Introduction of two C2H4COOCH2CN substituents gives more excellent washing fastness and also results in the improvement in sublimation fastness and light fastness.
Comparative example 2

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0,N
0,N
/CH2CH2COOCH2CN (Example2
~\ / N\ -4 of this
^ V CH2CH2COOCH2CN patent)
N=N-
^CHjjCHzCOOCHaCN (Dyel-38
\ /)—Nx in tablelof
^—'J C2H5 WO2008/0
74719)

Dye Washing fastness (WF)
AATCC method (Ny) Sublimation fastness (SF) Light fastness (LF)
Example 2-4 of this patent 5 class 5 class 6 class
Comparative dye 1-38 in table lof W2008/074719 2-3 class 3-4 class 5 class
Dye of example 2-4 of this patent and comparative dye 1-38 are very similar chemicals only except difference between ethyl group and C2H4COOCH2CN in amino radical. But the quality differences are very big especially in washing fastness, also in sublimation fastness and light fastness. This comparative example further provide confirmation to the logical approach adopted to get dyestuff with improve washing fastness properties by introducing two C2H4COOCH2CN substituent instead of one C2H4COOCH2CN in the WO2008/074719. In addition to the improvement in washing fastness introduction of two C2H4COOCH2CN substituents gives excellent results with the improvement in sublimation fastness and light fastness.

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CLAIMS
1. Novel Disperse azo dyes of formula (1)
R2
_. , v /GHztGHz)mGOOCHzCN
J—J CHatCHalnGOOGHzGN
R1
wherein,
R 1 is hydrogen, methyl, hydroxyl or NHR3;
R2 is hydrogen, chloro or methoxy;
wherein,
D is a group of the formula (2a)
X—\ V— (2a)
wherein,
X. Y and Z are, independently, hydrogen, methyl, halogen, cyano or nitro;
Or a group of the formula (2b),


(2b)

wherein, .
T1 is independently hydrogen, halogen, nitro, -S0 2 C¾ or-SCN; and

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T2 is hydrogen or halogen; Or a group of the formula (2c),
Orf*l.
(2c)

Or a group of the formula (2d),

T4
J3

(2d)

wherein,
T3 and T4 are independently nitro, acetyl, COOR4 or cyano;
R3 is -COCH 1.,-COC2H5, -S0 2CH3 or -S0 2C2Hk;
.-> do' d A d d J
R4 is Ci to C4 unsubstituted alkyl; n and m are independently 0,1 or 2.
2. Novel disperse azo dyes according to claim 1 in which the compound of formula (1) is of formula (2):


.CH2[CH2)mCOQCH2CN
-N=N—