Reactive dyes containing piperazine

Details Reactive dyes containing piperazine Reactive dyes containing piperazine

2000-01-24

2001-06-19

Powers, Fiona T. (Department: 1626)

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

Organic compounds

Azo

Reexamination Certificate

active

06248871

ABSTRACT:

This invention relates to reactive azo dyes containing piperazine.
EP-A-0126265 discloses a range of reactive azo dyes of the formula (A).
wherein
D is a residue of a benzene- or naphthalenesulphonic acid which is optionally further substituted;
R
1
is hydrogen, C
1-10
-alkyl, cycloalkyl, benzyl or a group C
2
H
4
OR
4
, C
2
H
4
—OC
2
H
4
OR
4
, C
3
H
6
OR
4
or CH(CH
3
)CH
2
OR
4
(in which R
4
is C
1-4
alkyl);
R
2
is a group R
1
or is an optionally substituted sulpho-free, phenyl group;
R
3
is hydrogen, methyl, methoxy, chloro or sulfo and
n is 1 or 2. When n=1, X is at least one reactive group and when n=2, X is a group of the formula
—X
1
—B—X
2
—
 in which each of X
1
and X
2
is a reactive group such as a triazine and B is a linking bridge derived from an amine. In one example (Compound 192), the linking bridge is derived from 2-aminoethylpiperazine. Compound 192 has the formula (20)
It is to be noted especially that the disclosure of EP-A-0126265 explicitly excludes components wherein each of R
1
and R
2
is hydrogen at the same time.
GB-A-1283771 discloses a range of reactive disazo dyes of the formula (B)
where D is a naphthylazo-phenylene or -naphthalene containing at least 3 sulphonic acid groups, R is H or an optionally substituted C
1-4
alkyl group and X is specifically a phenylene, diphenylene or naphthalene nucleus. They offer a degree of fixation over a wide range of liquor to goods ratios and provide shades of very good light fastness.
We have found surprisingly that if in dyes generally of this type, the group X is an asymmetrical amino piperazine derivative thereof as defined below, such dyes, especially when used for exhaust dyeing of cellulosic materials, can exhibit excellent properties, including build-up, aqueous solubility, light-fastness, wash-off and robustness to process variables.
According to one aspect, the present invention provides a dye of the formula (I)
wherein:
each of R
1
, R
2
, R
3
and R
4
, independently, is H or an optionally substituted alkyl group;
each of X
1
and X
2
, independently, is a labile atom or group;
each of x and y, independently, is 0 or 1 and at least one of x and y is 1;
each of a and b, independently, is 2 to 5;
when each of x and y is 1, a>b;
the or each R
5
, independently, is alkyl;
z is zero or is 1 to 4; and
each of D
1
and D
2
, independently, is a monoazo or polyazo chromophore, or a metallized derivative thereof, provided that the dye of the formula I is other than a dye of the formula (20), given above.
In one preferred range of dyes embodying the invention, each of x and y is 1, in which case, more preferably, each of a and b, independently, is 2 or 3.
In an alternatively, even more preferred embodiment, x is 0 and y is 1, in which case, more preferably, b is 2 or 3.
The piperazine nucleus is preferably unsubstituted (z=zero) or substituted in one or both of the 2- and 5- positions, more preferably with methyl or ethyl.
Preferred values of X
1
and X
2
are halogen, especially fluorine and chlorine, and a pyridinium salt, most typically a 3- or 4- carboxy pyridinium salt derived respectively from nicotinic and isonicotinic acid.
Each group R
1
-R
4
, independently, is preferably H or C
1-4
alkyl, for example, methyl, ethyl or propyl, which C
1-4
alkyl group is optionally substituted, for example, by a hydroxy group.
Preferred chromophoric groups D
1
and D
2
are monoazo, disazo and other polyazo dyes, which, more preferably contain at least one sulphonic acid group. Especially preferred dyes contain at least one monoazo or at least one disazo chromophoric group D
1
or D
2
. The groups D
1
and D
2
, even if each is a monoazo or each a disazo chromophore, may be the same as, or different from, one another. The use of different respective chromophores D
1
and D
2
allows the synthesis of a range of new yellows, reds and navies and, for example, when chromophore D
1
would provide a yellow dye and D
2
a blue dye, a new homogenous green dye may be obtained.
In a preferred range of monoazo dyes, each of D
1
and D
2
, independently, is an optionally metallized monoazo chromophore of the formula (i)
A—N═N—E  (i)
wherein:
one of A and E is attached to the reactive triazinylamino group;
A is derived from a diazotizable amine; and
E is derived from a coupling component.
In a preferred range of dyes of the formula (i), A is an optionally substituted aryl group and when A is attached to the triazinylamino group, the attachment may be from the aryl group or from a substituent thereon;
E is an optionally substituted aryl or heteroaryl group and when E is attached to the triazinylamino group the attachment may be from the aryl or heteroaryl group or from a substituent thereon, or E is an acetoacetamidoaryl group wherein the aryl moiety is optionally substituted and wherein the azo linkage in the formula (i), given and defined above, is linked to the methylene group of the acetoacetamidoaryl group and when E is attached to the triazinylamino group the attachment may be from the aryl moiety or from a substituent thereon.
In one, more preferred, range of dyes of formula (i) in which the group A is attached to the triazinylamino group in formula (I), given and defined above,
A is a phenyl or naphthyl group;
which said phenyl or naphthyl group is optionally substituted by an alkyl (preferably C
1-4
alkyl), phenyl, naphthyl or amino- (which may bear a C
1-4
alkyl group), amido- or sulphonamido-phenyl or naphthyl group and A may be attached to the triazinylamino ring from the said substituent alkyl, phenyl or naphthyl group or phenyl or naphthyl moiety of the said substituent;
which said phenyl or naphthyl group of A is additionally optionally substituted by an alkyl (preferably C
1-4
alkyl), alkoxy, (preferably C
1-4
alkoxy) or halo (preferably chloro) group or a carboxylic acid or sulphonic acid group or a salt thereof; and
E is an aryl or heteroaryl group selected from phenyl, naphthyl, pyrazolyl, pyrazolonyl, pyridyl, pyridonyl and pyrimidinyl groups or is an acetoacetamidoaryl group;
which said aryl or heteroaryl group is optionally substituted at least so as to provide the coupling component from which the group E is derived with sufficient electron donating capacity to allow the said coupling (in general, when E is a pyridyl or pyrimidinyl group, the presence of at least one electron donating group is necessary to allow coupling); and
which said aryl moiety of the acetoacetamidoaryl group is optionally substituted preferably by at least one of alkyl, alkoxy, halo, H
2
NCONH, CH
3
CONH or SO
3
H (or a salt thereof), more preferred alkyl and alkoxy being C
1-4
alkyl and C
1-4
alkoxy.
In the above dyes, especially when E is an a-naphthol group, the dye is optionally metallized.
When the group E is a phenyl or naphthyl group, still more preferably this is optionally substituted by an alkyl (preferably C
1-4
alkyl), alkoxy (preferably C
1-4
alkoxy), ureido, acylamino (preferably C
2-5
acylamino), alkyl (preferably C
1-4
alkyl) sulphonyl, halo (preferably chloro), hydroxyl or amino group, which amino group is optionally substituted by at least one (preferably C
1-4
) alkyl group, or is a carboxylic or sulphonic and group or a salt thereof.
When the group E is a pyrazolyl, pyrazolonyl, pyridyl, pyridonyl or pyrimidinyl group, still more preferably this is substituted by a hydroxyl, mercapto or amino group, which amino group is optionally substituted by at least one (preferably Coo) alkyl group.
In one especially preferred range of such dyes, E is an acetoacetamidoaryl group and A is an optionally substituted phenylene group such that at least one of D
1
- and D
2
- is a chromophore of the formula (iv)
wherein:
B is an optionally substituted aryl group;
the or each R
6
, independently, is alkyl, alkoxy, halo, H
2
NCONH, CH
3
CONH or SO
3
H (or a salt thereof);
R
11
is hydrogen or alkyl;
p is zero or
1-4,
more preferably zero or
1-3,
still more preferably 0, 1 or 2, especially 1 or 2.
For the avoidance of doubt it is confirmed that in the above formula (iv

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