Cationic imidazole azo dyes

Details Cationic imidazole azo dyes Cationic imidazole azo dyes

2003-04-10

2004-07-13

Powers, Fiona T. (Department: 1626)

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

Organic compounds

Azo

C534S608000, C008S655000

Reexamination Certificate

active

06762287

ABSTRACT:

The present invention relates to novel cationic imidazole azo dyes, to processes for their preparation and to their use for dyeing textile materials, leather, paper or glass fibres.
The novel imidazole azo dyes correspond to formula
wherein
R
1
, R
1
′, R
2
and R
2
′ are each independently of the others hydrogen, C
1
-C
4
alkyl, halogen or nitro,
R
3
, R
3
′, R
4
and R
4
′ are each independently of the others C
1
-C
4
alkyl unsubstituted or substituted by OH, C
1
-C
4
alkoxy, halogen, CN or phenyl,
R
5
is hydrogen or C
1
-C
4
alkyl,
R
6
is unsubstituted or amino-substituted C
5
-C
12
alkyl;
or unsubstituted or amino-substituted C
5
-C
8
cycloalkyl;
or phenyl-substituted C
1
-C
4
alkyl;
or wherein R
5
and R
6
together with the nitrogen atom linking them form a piperazine ring, which is substituted, at the nitrogen atom that is not bonded to the phenyl group, by C
1
-C
4
-alkyl or phenyl, the alkyl and phenyl radicals mentioned as substituents of the nitrogen atom of the piperazine ring being unsubstituted or substituted by amino,
X
1
, X
2
, X
3
and X
4
are each independently of the others hydrogen, C
1
-C
4
alkyl, C
1
-C
4
alkoxy or halogen,
Y
1
is a bridging member of formula
or —NH—(CH
2
)
6
—NH—, and
X
−
is an anion.
The alkylene groups in the bridging member Y
1
may be straight-chain, branched or cyclic and may also be substituted, for example by halogen, alkoxy or hydroxy. In addition, they may be interrupted by hetero atoms, e.g. O or NR
5
, wherein R
5
is hydrogen or C
1
-C
4
alkyl. Preference is given to a straight-chain or branched C
1
-C
12
alkylene radical. Special preference is given to C
1
-C
6
alkylene radicals, more especially C
2
-C
4
alkylene radicals. Propylene radicals, especially the 1,3-propylene radical, are of particular importance.
Suitable alkylene radicals are e.g. ethylene, 1,3-propylene, 1,2-propylene, 1,2-butylene, 1,4-butylene, 1,6-hexylene, 1,8-octylene, 1,12-dodecylene, 1,4-cyclohexylene, 2-hydroxy-1,3-propylene, 2-chloro-1,3-propylene and 3-oxa-1,5-pentylene.
According to the invention, alkyl radicals are to be understood as being generally straight-chain or branched alkyl radicals, e.g. methyl, ethyl, n- and iso-propyl and n-, sec- or tert-butyl.
Such alkyl radicals may, like the cycloalkyl groups, be mono- or poly-substituted, for example by hydroxy, carboxy, halogen, cyano, amino or C
1
-C
4
alkoxy.
The alkoxy radicals may have e.g. from 1 to 4 carbon atoms, for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy and tert-butoxy. The alkoxy groups also may be substituted, e.g. by the radicals listed as possible substituents for alkyl groups, especially by hydroxy or C
1
-C
4
alkoxy.
Suitable anions X
−
include both inorganic and organic anions, for example halide, such as chloride, bromide or iodide, sulfate, hydrogen sulfate, methyl sulfate, boron tetrafluoride, aminosulfonate, perchlorate, carbonate, bicarbonate, phosphate, nitrate, benzenesulfonate, formate, acetate, propionate, lactate or complex anions, such as the anion of a zinc chloride double salt.
The anion is generally predetermined by the preparation process. Preferably, chlorides, hydrogen sulfates, sulfates, methosulfates, phosphates, formates, lactates or acetates are present. Highly preferred are chlorides.
Halogen is to be understood as being fluorine, bromine, iodine and especially chlorine.
R
1
, R
1
′, R
2
and R
2
′ are preferably each methyl and especially each hydrogen.
R
3
, R
3
′, R
4
and R
4
′ are preferably each ethyl, hydroxyethyl or especially methyl.
X
1
, X
2
, X
3
and X
4
are preferably each methoxy, methyl, chlorine or especially hydrogen.
Y
1
is preferably a bridging member of formula —NH—(CH
2
)
6
—NH—.
R
5
is preferably hydrogen, methyl or ethyl, especially hydrogen or methyl. Preferably, R
5
is hydrogen.
C
5
-C
12
Alkyl radicals R
6
are preferably corresponding unsubstituted or amino-substituted
C
5
-C
8
alkyl radicals and preferably such C
6
-C
8
alkyl radicals.
C
5
-C
8
Cycloalkyl radicals R
6
are preferably corresponding unsubstituted or amino-substituted cyclohexyl radicals.
Phenyl-substituted C
1
-C
4
alkyl R
6
is preferably benzyl.
R
6
is especially preferably unsubstituted or amino-substituted C
5
-C
12
alkyl;
or unsubstituted or amino-substituted C
5
-C
8
cycloalkyl;
or phenyl-substituted C
1
-C
4
alkyl.
More preferably, R
6
is unsubstituted or amino-substituted C
5
-C
8
alkyl;
or unsubstituted or amino-substituted cyclohexyl;
or phenyl-substituted C
1
-C
4
alkyl.
Especially preferred dyes of formula (1) are those of formula
wherein
X
1
, X
2
, X
3
and X
4
are each independently of the others hydrogen, methyl or methoxy, especially hydrogen,
Y
1
is as defined above under formula (1), especially a bridging member of formula —NH—(CH
2
)
6
—NH—, and
X
−
is an anion. As to X
−
the preferences given above apply.
Especially preferred dyes of formula (2) are those of formula
wherein
X
1
and X
2
are each independently of the others hydrogen, methyl or methoxy, especially hydrogen, and
R
5
, R
6
and X
−
are as defined above under formula (2). As to R
5
, R
6
and X
−
the abo preferences apply.
Preferably, in formula (2a) R
5
is hydrogen.
Preferably, in formula (2a) R
6
is unsubstituted or amino-substituted C
5
-C
12
alkyl;
or unsubstituted or amino-substituted C
5
-C
8
cycloalkyl;
or phenyl-substituted C
1
-C
4
alkyl.
The dyes of formulae (1) and (2) can be prepared according to methods known per se (see e.g. EP-A-714 954).
The dyes of formula (1) can be obtained, for example, by reacting a compound of formula
with a diamine of formula
or
NH
2
—(CH
2
)
6
—NH
2
  (4b)
wherein the substituents have the definitions and preferred meanings indicated above. Alternatively, it is also possible to use as compounds of formula (3) those compounds which, instead of the methoxy group indicated, contain halogen, e.g. chlorine, or C
2
-C
4
alkoxy. The compounds of formulae (3), (4a) and (4b) are known or can be prepared in a manner known per se. For example, the compounds of formula (3) can be obtained by diazotising 4-alkoxyanilines, coupling the product with an imidazole and then carrying out alkylation and quaternisation.
The reaction of a compound of formula (3) with a diamine of formula (4a) or (4b) can be carried out, for example, at a temperature of about from 40 to 100° C., preferably from 40 to 70° C., optionally under pressure and/or in an inert gas atmosphere, and in an inert solvent, e.g. in water or aliphatic alcohols, e.g. C
1
-C
8
alcohols, such as methanol, ethanol or especially isopropanol, but more especially in aprotic polar solvents, such as dimethylformamide or dimethyl sulfoxide. In the case of diamines that are liquid under the reaction conditions, it is possible, if desired, to dispense with a solvent.
The dyes of formula (2) can be obtained, for example, in a similar way as given above for the preparation of the compounds of formula (1). However, instead of the diamines of formulae (4a) and (4b) an amine of formula HN(R
5
)R
6
is used.
The dyes of formulae (1) and (2) according to the invention are suitable for dyeing polyacrylonitrile materials and leather, but especially for dyeing paper, since they possess a high substantivity for that substrate. The dyes give dyeings in red shades. The resulting dyeings are distinguished by good fastness properties. The effluents are in most cases completely colourless.
The dyes of formula (1) or (2) may also be used in mixtures with other cationic dyes. Especially preferred dye mixtures are those which contain a dye of formula (1) or a dye of formula (2) and a cationic copper phthalocyanine dye. Using such mixtures there are obtained on paper dyeings in highly attractive neutral shades. Suitable copper phthalocyanine dyes are those dyes which are known from the literature and can be used for the dyeing of paper, especially the dyes described in EP-A-0 184 991, DE-A-3 111 199 and EP-A-0 174 586.
The dyes of formula (1) or (2) can be formulated as a solid or li

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