Claims
- 1. A polyazo of the formula I
- where
- m is 0 or 2,
- n is 1,
- p is from 1 to 2,
- q is from 0 to 1,
- X is nitro,
- R.sup.1 and R.sup.2 are identical or different and each is independently of the other hydrogen or C.sub.1 -C.sub.4 -alkoxy,
- R.sup.3 is hydrogen,
- R.sup.4 and R.sup.5 are identical or different and each is independently of the other hydroxyl or amino,
- R.sup.6 is hydrogen, C.sub.1 -C.sub.4 -alkyl, halogen, nitro, hydroxysulfonyl, sulfamoyl, C.sub.1 -C.sub.4 -monoalkylsulfamoyl, C.sub.1 -C.sub.4 -dialkylsulfamoyl or C.sub.1 -C.sub.4 -alkylsufonyl,
- R.sup.7 is hydrogen, halogen, nitro or hydroxysulfonyl and
- Y is a radical of the formula ##STR180## where R.sup.8 is hydrogen, hydroxyl, halogen, nitro or hydroxysulfonyl,
- R.sup.9 is hydrogen, halogen, nitro or hydroxysulfonyl,
- R.sup.10 is hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or hydroxysulfonyl and
- R.sup.11 is hydrogen, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, halogen or carboxyl, and the
- ring A or unfused or fused with an unsubstituted or nitro-or hydroxysulfonyl-substituted benzo ring, in the free form or as a copper, chromium, iron, cobalt or nickel complex.
- 2. A polyazo dye as claimed in claim 1, wherein, m is 0, q is 0, and R.sup.1 and R.sup.2 are each hydrogen.
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 3827447 |
Aug 1988 |
DEX |
|
Parent Case Info
This application is a continuation of application Ser. No. 07/389,799, filed on Aug. 4, 1989, now abandoned. ##STR3## where ms is 0, 1 or 2,
CH-A-571,599, DE-A-2,024,047, DE-A-2,162,419 and EP-A-45,868 describe polyazo dyes which are similar to those of the formula I. However, instead of the --S(O).sub.m -- linkage they have an amino linkage.
It is an object of the present invention to provide novel polyazo dyes which should be easily accessible and have advantageous application properties.
We have found that this object is achieved by the dyes of the above formula I.
All the alkyl groups appearing in the compounds according to the invention can be not only straight-chain but also branched.
R.sup.1, R.sup.2, R.sup.3, R.sup.10 and R.sup.11 are each for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy.
R.sup.1, R.sup.2, R.sup.10 and R.sup.11 are each further for example, like R.sup.6, methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.
R.sup.1, R.sup.2, R.sup.3, R.sup.6 and R.sup.11 are each further for example (like R.sup.7, R.sup.8 and R.sup.9) fluorine, chlorine or bromine, the preferred halogens being chlorine and bromine.
R.sup.3 is further for example formylamino, acetylamino, propionylamino, butyrylamino or isobutyrylamino.
R.sup.6 is further for example monomethylsulfamoyl, dimethylsulfamoyl, monoethylsulfamoyl, diethylsulfamoyl, monopropylsulfamoyl, dipropylsulfamoyl, monoisopropylsulfamoyl, diisopropylsulfamoyl, monobutylsulfamoyl, dibutylsulfamoyl, methylsufonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl or butylsulfonyl.
The indices p and q can each also be fractions of whole numbers, in which case mixtures of polyazo dyes are present.
It will be readily understood that if the polyazo dyes of the formula I contain one or more hydroxysulfonyl groups the salts thereof also come within the scope of the present invention.
These salts can be metal or ammonium salts. Metal salts are in particular the lithium, sodium or potassium salts. Ammonium salts for the purposes of the present invention are those salts which have either unsubstituted or substituted ammonium cations. Substituted ammonium cations are for example monoalkyl-, dialkyl-, trialkyl-, tetraalkyl- or benzytrialkyl-ammonium cations or those cations which are derived from nitrogenous five- or six-membered saturated heterocycles, such as pyrrolidinium, piperidinium, morpholinium, piperazinium or N-alkyl-piperazinium cations or N-monoalkyl- or N,N-dialkyl-substituted products thereof. Alkyl here is to be understood as meaning in general straight-chain or branched C.sub.1 -C.sub.20 -alkyl which may be substituted by hdyroxyl groups and/or interrupted by oxygen atoms.
Preference is given to polyazo dyes of the formula Ia ##STR5## where R.sup.3 is hydrogen and R.sup.1, R.sup.2, R.sup.4, R.sup.5, R.sup.6, R.sup.7, X, Y, m, n, p, q and the ring A are each as defined above.
Preference is further given to polyazo dyes of the formula I where m is 0 or 2, q is 0, X is nitro, R.sup.1 and R.sup.2 are each hydrogen and R.sup.3 is hydrogen or nitro.
Particular preference is given to such polyazo dyes of the formula I where m is 0.
If R.sup.3 is hydrogen, X is nitro and n is 1, preference is given in particular to those dyes of the formula I where the nitro group (X) is ortho and the hydroxysulfonyl group para to the --S(O).sub.m -- linkage or the nitro group (X) is para and the hydroxysulfonyl group ortho to the --S(O).sub.m -- linkage.
Preference is further given to the copper, chromium, iron or cobalt complexes of the polyazo dyes of the formula I, of which the corresponding iron or chromium complexes must be mentioned in particular.
The polyazo dyes according to the invention can be obtained in a conventional manner.
For example, an aminophenol of the formula III ##STR6## where R.sup.6 and R.sup.7 and the ring A are each as defined above, can be diazotized and coupled with a coupling component of the formula IV ##STR7## where R.sup.4 and R.sup.5 are each as defined above, forming a monoazo compound of the formula V ##STR8## where R.sup.4, R.sup.5, R.sup.6, R.sup.7 and the ring A are each as defined above.
Thereafter an aniline derivative of the formula ##STR9## where R.sup.1, R.sup.2, R.sup.3, X, m and n are each as defined above, can be diazotized and coupled with the above-described monoazo compound V.
If desired, an amine of the formula VI
This example of a method of preparation need not of course be adhered to; that is, it is also possible to vary the coupling sequence. For instance, first the aniline derivative II can be diazotized and coupled with the coupling component IV and the resulting reaction product can then be coupled with a previously diazotized aminophenol III.
The metallization, ie. the preparation of the respective copper, chromium, iron, cobalt or nickel complexes of the polyazo dyes I, is likewise effected in a conventional manner, for example by treating the polyazo dye with the corresponding metal salts, for example with iron(III) chloride, iron(II) sulfate, copper sulfate or chromium(III) formate, in aqueous solution at from 80.degree. to 105.degree. C. and at pH 4-6.
The aminophenols III and the coupling component IV are compounds known per se.
The present invention further provides aniline derivatives of the formula II ##STR10## where m is 0, 1 or 2,
For examples of the radical R.sup.1, R.sup.2 and R.sup.3, see the lists given above.
The novel aniline derivatives of the formula II, which are useful diazo components for preparing polyazo dyes of the formula I or indeed other azo dyes, can be obtained in a conventional manner.
For example, a nitro compound of the formula VII ##STR11## where R.sup.1 and R.sup.2 are each as defined above, can be reacted with an alkali metal sulfide to give a thiophenol derivative VIII ##STR12## where M.sup..sym. is an alkali metal cation and R.sup.1 and R.sup.2 are each as defined above.
This thiophenol derivative VIII produces by reaction with the chlorobenzene derivative of the formula IX ##STR13## where R.sup.3, X and n are each as defined above, the novel aniline derivative of the formula II (where m=0). By oxidization of these thio compounds, for example with hydrogen peroxide, it is possible to obtain the corresponding sulfoxides (II, m=1) or sulfones (II, m=2).
Another way of preparing those aniline derivatives of the formula II where m is 2 comprises for example reacting a sulfinate of the formula X ##STR14## where R.sup.1 and R.sup.2 are each as defined above, L is C.sub.1 -C.sub.4 -alkanoyl and M.sup..sym. is an alkali metal cation, with the chlorobenzene derivative IX to form a sulfone of the formula XI ##STR15## where L, R.sup.1, R.sup.2, R.sup.3, X and n are each as defined above. By hydrolytic elimination of the protective group L it is then possible to arrive at the target product of the formula I (where m =2). In some cases, the hydrolytic elimination of the protective group L already takes place during the formation of the sulfone; that is, the sulfone XI is not intermediately isolated.
The sulfinates X are obtainable for example by reduction from the corresponding sulfonyl chlorides.
The components of the formulae VII, VIII, IX and X are in general compounds known per se.
In what follows, some aniline derivatives of the formula II and suitable aminophenol derivatives of the formula III are given as examples.
Aniline derivatives of the formula II are for example: ##STR16##
Aminophenols of the formula III are for example: ##STR17##
The polyazo dyes according to the invention are suitable in an advantageous manner for dyeing leather.
US Referenced Citations (12)
Foreign Referenced Citations (2)
| Number |
Date |
Country |
| 191126 |
Aug 1986 |
EPX |
| 3263 |
Jan 1891 |
GBX |
Non-Patent Literature Citations (1)
| Entry |
| El-Ezbawy et al, Chemical Abstracts, vol. 113, No. 78227a (1990). |
Continuations (1)
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Number |
Date |
Country |
| Parent |
389799 |
Aug 1989 |
|
Patent Grant
5104979
