Reactive azo dyes

Details Reactive azo dyes Reactive azo dyes

2002-11-15

2004-07-13

Powers, Fiona T. (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Azo

C534S612000, C534S631000, C534S634000, C534S635000, C534S636000, C534S642000, C008S547000, C008S549000

Reexamination Certificate

active

06762288

ABSTRACT:

This invention relates to reactive azo dyes containing each of a triazine ring and at least one reactive vinyl sulphone group (or precursor thereof) and at least two azo groups. Such dyes are disclosed in, for example, EP-A-0623655, EP-A-0685532 and EP-A-076469 and typical dyes are as follows:
Example 46 of EP-A-0685532
Example 81 of EP-A-0764694
Example 38 of EP-A-0623655
However, none of the dyes disclosed in the abovementioned documents provide a particularly strong or bright yellow or reddish yellow shade with good migration properties, excellent build-up and good fastness properties.
Thus, the problem addressed by the invention is to provide such a dye capable of giving, particularly on cellulosic fabrics, a strong, bright yellow or reddish yellow shade with good migration properties, excellent build-up and which dyes are particularly easy and economical to produce.
We find surprisingly that it is possible to solve the abovementioned problems by the use of an azo dye containing, on the one hand, a monoazo dye component based on sulpho-J-acid as coupling component and a markedly electron deficient aromatic amine as diazo component and, on the other hand, an azo dye component containing each of a phenylene group and an aromatic group or hetero aromatic group, each dye component being linked, via an amino linkage to a triazine group, the second dye component being so linked via the phenylene group.
Thus, according to one aspect the invention provides an azo dye of the formula (I)
or an alkali metal salt thereof:
wherein: each of R
1
and R
2
independently is hydrogen, optionally substituted C
1-4
alkyl or optionally substituted phenyl;
A is
in which formula (i), c is zero or 1;
in which formula (ii), d is 1, 2 or 3 and a group SO
3
H is ortho to the azo group; and
in which formula (i) or (ii), Y is the group —CH═CH
2
; —CH
2
CH
2
U (wherein U is a leaving group); or —CH
2
CH═CH
2
;
B is fluorine; chlorine; the group OR
3
(in which R
3
is hydrogen, C
1-4
alkyl or phenyl); the group NR
4
R
5
(in which each of R
4
and R
5
independently is hydrogen, C
1-4
alkyl or phenyl; or each of R
4
, R
5
and N together form an optionally substituted aromatic heterocyclic ring); the group
+
NR
6
R
7
R
8
(in which each of R
6
, R
7
and R
8
independently is C
1-4
alkyl or phenyl or each of R
6
, R
7
and R
8
and N together form an optionally substituted aromatic heterocylcic ring); or the group SR
9
(in which R
9
is hydrogen, C
1-4
alkyl or phenyl);
C is an optionally substituted aromatic or heteroaromatic residue;.
D is methyl, methoxy, amino, acylamino or ureido;
a is zero, 1 or 2;
b is zero, 1 or 2 and when b is 2 each D is independent of the other.
Preferably, the substituent D is methyl, methoxy, acylamino or ureido and the substituent B is preferably chlorine or a 3- or 4- carboxypyridinium salt derived respectively from nicotinic and isonicotinic acid.
In the above dye, the group A preferably has the formula
wherein e is —SO
2
CH
2
CH
2
OSO
3
H and f is absent; or
e is —SO
3
H and f is —SO
2
CH
2
CH
2
OSO
3
H.
A preferred azo dye has the formula
wherein each of R
2
, C, D a, b, e and f is as defined above.
More preferably in the azo dye of the formula (I
1
), at least one of the groups SO
3
H or D is ortho to the azo group linking to the group C.
In one range of dyes of the formula (I
1
) which is preferred, a is 1 or 2 and b is zero. More preferably, the group C is a heteroaromatic group, still more preferably a pyridonyl, pyrazolonyl, 2,6-diaminopyridinyl or 4-carboxy-2,6-dihydroxypyridinyl group, or is a hydroxynaphthalene group.
In another range of dyes of the formula (I) which is preferred a is zero or 1, b is 1 or 2 and D, or each D independently, is ureido, (C
1-4
alkyl)carbonylamino, C
1-4
alkoxy or C
1-4
alkylthio.
For such dyes within this other range, a preferred group C has the formula (iv)
wherein : Ar
1
is an aromatic diazo component;
g is zero, 1, 2, 3 or 4;
h is zero, 1, 2 or 3; and
P, or each P independently, is C
1-4
alkyl, nitro, —SO
2
NR
8
(in which R
8
is hydrogen, C
1-4
alkyl or phenyl), carboxyl, cyano, SO
2
Y
1
(in which Y
1
is vinyl, allyl or CH
2
CH
2
V, where V is a leaving grup) or —NHAr
2
[in which Ar
2
is an aromatic residue substituted by at least one group T, the group T, or each group T independently, being selected from cyano, carboxyl, sulphonic acid and SO
2
Y
2
(in which Y
2
is vinyl, allyl or CH
2
CH
2
W (where W is a leaving group)].
More preferably, at least one group P is a group SO
2
Y
1
, where Y
1
is as defined above or a group NHAr
2
substituted by a group T, which group T is the group SO
2
Y
2
, in which Y
2
is as defined above.
Preferred values of Y
1
and Y
2
independently are —CH═CH
2
; —CH
2
—CH═CH
2
; —CH
2
CH
2
Cl, —CH
2
CH
2
Br; —CH
2
CH
2
F; —CH
2
CH
2
OSO
3
H; —CH
2
CH
2
SSO
3
H; —CH
2
CH
2
OCOCH
3
, —CH
2
CH
2
OPO
3
H
2
; —CH
2
CH
2
OCOC
2
H
5
; —CH
2
CH
2
OSO
2
NR
9
(in which R
9
is hydrogen, C
1-4
alkyl or phenyl); and —CH
2
CH
2
OSO
2
R
10
(in which R
10
is hydrogen, C
1-4
alkyl or phenyl).
Most preferably C is the group
Typical azo dyes embodying the invention have the formula
wherein Z is selected from
Another typical azo dye embodying the invention has the formula
An azo dye of the formula (I), given and defined above may be prepared by a process which comprises reacting a triazine dye of the formula (II)
wherein each of R
1
, A and B is as defined above and Hal is a halogen atom;
with an azo dye of the formula (III)
wherein each of a, b, R
2
, C and D is as defined above.
The process is preferably carried out in an aqueous solution at pH 4-6 and at a temperature of at least 30° C.
The triazine dye of the formula (II) may be prepared by diazotising an amine of the formula (IV)
A—NH
2
  (IV)
wherein A is as defined above and coupling the diazotised amine of the formula (IV) to a triazine compound of the formula (V)
wherein each of R
1
and B is as defined above and Hal is a halogen atom, to obtain the triazine dye of the formula (II).
Typically, diazotisation of the amine is carried out in an acid medium at a pH of about 2-5, using, for example, acetic, propionic or hydrochloric acid in the presence of a nitrosating agent, such as nitrosyl sulphuric acid, an alkali metal nitrite (e.g sodium nitrite) or a C
1-4
alkyl nitrite (e.g. methyl nitrite) at a temperature of from −10° C. to 10° C.
The coupling reaction may be carried out by adding the diazotised amine of the formula (IV), to the triazine compound of the formula (V) in water at a temperature of from 0 to 10° C.
The triazine compound of the formula (V), given and defined above, may be prepared by reacting an aminonaphthalenesulphonic acid compound of the formula (VI)
with a cyanuric halide of the formula (VII)
wherein each Hal is a halogen atom and B is as defined above, to form the triazine compound of the formula (V).
The reaction may be carried out by adding the aminonaphthalene sulphonic acid compound of the formula (VI) dropwise to a slurry of the cyanuric halide of the formula (VII) in an ice/water/acetone mixture.
When in the azo dye of the formula (III), a is 1 or 2, b is zero and C is the residue of a heteroaromatic coupling component the azo dye of the formula (III) may be prepared by acylating a diamine of the formula (VIII)
where a is zero, 1 or 2 to form an amine of the formula (IX),
where a is zero, 1 or 2 and Ac is an acyl group, diazotising the amino of the formula (IX) and coupling the diazotised amine to a coupling agent of the formula
C—H
 where C is as defined above to form, after deacetylation, the azo dye of the formula (III).
When, in the azo dye of the formula (III), a is zero or 1, b is 1 or 2 and D, or each D independently, is ureido, (C
1-4
alkyl)carbonyl amino, C
1-4
alkoxy or C
1-4
alkylthio and the Group C is a group (iv)
wherein each of Ar
1
, P, g, and h is as defined above, the azo dye of the formula (III) may be prepared by diazotising an amine of the formula (X)
wherein each of Ar
1
, P, g and h is as defined above,

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