Acid disazo dyes as well as sulphonamides as their intermediate product

The present invention relates to novel disazo dyes of the formula I ##STR2## where one of the two radicals X.sup.1 and X.sup.2 is hydroxyl and the other is amino,
R.sup.1 is hydrogen, hydroxysulfonyl or a radical of the formula CO--Ar, CO--Alk, SO.sub.2 --Ar, SO.sub.2 --Alk, SO.sub.2 --OAr, ##STR3## R.sup.2 is hydrogen or R.sup.2 and R.sup.1 together are a radical of the formula
CO--NZ.sup.1 --CO
or ##STR4## R.sup.3 is hydrogen, hydroxysulfonyl, C.sub.1 -C.sub.4 -alkyl, halogen or a radical of the formula SO.sub.2 --OAr, SO.sub.2 --N(Ar)Alk or SO.sub.2 --NHAr or R.sup.3 and R.sup.2 together are a radical of the formula CO--NZ.sup.1 --Y,
R.sup.4 is hydrogen, hydroxysulfonyl, pyrrolidinylsulfonyl, piperidinylsulfonyl, morpholinylsulfonyl or a radical of the formula CO--Ar, CO--OAlk, CO--NHAr, CO--N(Ar)Alk, CO--N(Alk).sub.2, SO.sub.2 --Alk, SO.sub.2 --OAr, SO.sub.2 --N(Alk).sub.2, SO.sub.2 --NHAlk, SO.sub.2 --N(Ar)Alk or SO.sub.2 --NHAr,
R.sup.5 is hydrogen, C.sub.1 -C.sub.4 -alkyl, halogen or hydroxysulfonyl, and
R.sup.6, R.sup.7 and R.sup.8 are each independently of the others hydrogen, C.sub.1 -C.sub.4 -alkyl, halogen, cyano, nitro, hydroxysulfonyl, pyrrolidinylsulfonyl, piperidinylsulfonyl, morpholinylsulfonyl or a radical of the formula CO--Ar, CO--OAr, CO--OAlk, CO--N(Ar)Alk, CO--N(Alk).sub.2, SO.sub.2 --Ar, SO.sub.2 --Alk, SO.sub.2 --CH.sub.2 CH.dbd.CH.sub.2, SO.sub.2 --CH.dbd.CH.sub.2, SO.sub.2 --C.sub.2 H.sub.4 --Q, SO.sub.2 --OAr, SO.sub.2 --N(Alk).sub.2, SO.sub.2 --NHAlk, SO.sub.2 --N(Ar)Alk, SO.sub.2 --NHAr, ##STR5## where Alk is C.sub.1 -C.sub.8 -alkyl which may be interrupted by from 1 to 3 oxygen atoms in ether function or by 1 sulfur atom or 1 sulfonyl group and may be substituted by hydroxyl, C.sub.1 -C.sub.4 -alkanoyloxy, benzoyloxy, sulfato, halogen, cyano, carbamoyl, carboxyl, hydroxysulfonyl, phenoxy, phenyl or hydroxysulfonylphenyl, or is C.sub.5 -C.sub.8 -cycloalkyl,
Ar is phenyl or naphthyl, and each of these radicals may be substituted by C.sub.1 -C.sub.4 -alkyl, phenyl-(C.sub.1 -C.sub.4)-alkyl, halogen, C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkoxy-(C.sub.1 -C.sub.4)-alkyl, phenoxy, hydroxyl, carboxyl, C.sub.1 -C.sub.4 -alkanoylamino with or without interruption by 1 oxygen atom in ether function in the alkyl chain, benzoylamino, hydroxysulfonyl, pyrrolidinylsulfonyl, piperidinylsulfonyl, morpholinylsulfonyl or a radical of the formula SO.sub.2 --Alk, SO.sub.2 --CH.sub.2 CH.dbd.CH.sub.2, SO.sub.2 --CH.dbd.CH.sub.2, SO.sub.2 --C.sub.2 H.sub.4 --Q, SO.sub.2 --NHAlk, SO.sub.2 --N(Alk).sub.2, SO.sub.2 --G, SO.sub.2 --OG, SO.sub.2 --NHG or SO.sub.2 --N(Alk)G,
Y is methylene or carbonyl,
Z.sup.1 is hydrogen or a radical of the formula Alk or Ar,
Z.sup.2 is hydrogen or hydroxysulfonyl,
Q is hydroxyl or an alkali-detachable group, and
G is phenyl which may be substituted by C.sub.1 -C.sub.4 -alkyl, carboxyl, hydroxysulfonyl or C.sub.1 -C.sub.4 -alkanoylamino or is naphthyl which may be substituted by hydroxysulfonyl,
and at least one of the radicals R.sup.1, R.sup.2, R.sup.3, R.sup.4 or R.sup.5 and at least one of the radicals R.sup.6, R.sup.7 or R.sup.8 are not hydrogen,
sulfonamides as their intermediates and also the use of the novel dyes for dyeing natural or synthetic substrates.
It is an object of the present invention to provide novel disazo-based acid dyes having advantageous application properties.
We have found that this object is achieved by the acid disazo dyes of the formula I defined at the beginning.
If R.sup.3 and R.sup.2 together are a radical of the formula CO--NZ.sup.1 --Y, this radical can be bonded to the ring positions of R.sup.2 and R.sup.3 via Y or CO, or vice versa.
Any alkyl appearing in the abovementioned formula I may be straight-chain or branched.
Any substituted alkyl appearing in the abovementioned formula generally contains 1 or 2 substituents.
Any alkyl appearing in the abovementioned formulae with interruption by oxygen atoms in ether function is preferably alkyl interrupted by 1 or 2 oxygen atoms in ether function.
Any substituted phenyl appearing in the abovementioned formulae generally contains from 1 to 3 substituents.
R.sup.3, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and Alk are each for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, fluorine, chlorine or bromine.
Alk may also be for example pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, octyl, 2-ethylhexyl, isooctyl (the above designation isooctyl is a trivial name derived from the oxo process alcohols--cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 1, pages 290 to 293, and Vol. A 10, pages 284 and 285), 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 2- or 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 2-methylthioethyl, 2-ethylthioethyl, 2- or 3-methylthiopropyl, 2- or 3-ethylthiopropyl, 2- or 4-methylthiobutyl, 2- or 4-ethylthiobutyl, 2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2- or 3-methylsulfonylpropyl, 2- or 3-ethylsulfonylpropyl, 2- or 4-methylsulfonylbutyl, 2- or 4-ethylsulfonylbutyl, chloromethyl, 2-chloroethyl, 2- or 3-chloropropyl, benzyl, 1- or 2-phenylethyl, 2-, 3- or 4-hydroxysulfonylbenzyl, 2-(2-,3- or 4-hydroxysulfonylphenyl)ethyl, 3-benzyloxypropyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, cyanomethyl, 2-cyanoethyl, 2- or 3-cyanopropyl, carbamoylmethyl, 2-carbamoylethyl, 2- or 3-carbamoylpropyl, 2-acetyloxyethyl, 2- or 3-acetyloxypropyl, 2-isobutyryloxyethyl, 2- or 3-isobutyryloxypropyl, carboxylmethyl, 2-carboxylethyl, 2- or 3-carboxylpropyl, hydroxysulfonylmethyl, 2-hydroxysulfonylethyl, 2- or 3-hydroxysulfonylpropyl, 2-sulfatoethyl or 2- or 3-sulfatopropyl.
Ar may also be for example phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-propylphenyl, 2-, 3- or 4-isopropylphenyl, 2-, 3- or 4-butylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-phenoxyphenyl, 2-, 3- or 4-methoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-isobutoxyphenyl, 2,4-dimethoxyphenyl, 2-, 3- or 4-formylaminophenyl, 2-, 3- or 4-acetylaminophenyl, 2-, 3- or 4-propionylaminophenyl, 2-, 3- or 4-methoxyacetylaminophenyl, 2-, 3- or 4-chlorophenyl, 2-, 3- or 4-carboxyphenyl or 2-, 3- or 4-hydroxysulfonylphenyl, 2-, 3- or 4-benzoylaminophenyl, 2-, 3- or 4-pyrrolidinylsulfonylphenyl, 2-, 3- or 4-piperidinesulfonylphenyl, 2-, 3- or 4-morpholinylsulfonylphenyl, 2-, 3- or 4-methylsulfonylphenyl, 2-, 3- or 4-carboxymethylsulfonylphenyl, 2-, 3- or 4-vinylsulfonylphenyl, 2-, 3- or 4-(2-hydroxyethyl)sulfonylphenyl, 2-, 3- or 4-(2-sulfatoethyl)sulfonylphenyl, 2-, 3- or 4-ethylsulfamoylphenyl, 2-, 3- or 4-(2-hydroxyethyl)sulfamoylphenyl, 2-, 3- or 4-bis(2-hydroxyethyl)sulfamoylphenyl, naphth-1-yl, naphth-2-yl, 2-hydroxysulfonylnaphth-1-yl, 5-hydroxysulfonylnaphth-1-yl or 5-hydroxysulfonylnaphth-2-yl.
Z.sup.1 is, as Alk may also be, for example cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
Q is hydroxyl or an alkali-detachable group. Such groups are for example chlorine, bromine, C.sub.1 -C.sub.4 -alkylsulfonyl, phenylsulfonyl, OSO.sub.3 H, SSO.sub.3 H, OP(O) (OH).sub.2, C.sub.1 -C.sub.4 -alkylsulfonyloxy, phenylsulfonyloxy, C.sub.1 -C.sub.4 -alkanoyloxy, C.sub.1 -C.sub.4 -dialkylamino, cyanoamino or a radical of the formula ##STR6## where W.sup.1, W.sup.2 and W.sup.3 are each independently of the others C.sub.1 -C.sub.4 -alkyl or benzyl and An.sup..crclbar. is in each case one equivalent of an anion. Suitable anions include for example fluoride, chloride, bromide, iodide, mono-, di- and trichloroacetate, methylsulfonate, phenylsulfonate or 2- or 4-methylphenylsulfonate.
R.sup.1 and R.sup.4 are each for example benzoyl, 2-, 3- or 4-methylbenzoyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylbenzoyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl or butylsulfonyl.
R.sup.1 may also be for example 5-methyl-, 5-ethyl-, 5-propyl-, 5-butyl- or 5-phenyl-1,3,4-oxadiazol-2-yl, 3-methyl-, 3-ethyl-, 3-propyl-, 3-butyl- or 3-phenyl-1,2,4-oxadiazol-5-yl, phenylsulfonyl, 2-, 3- or 4-methylphenylsulfonyl or 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dimethylphenylsulfonyl.
R.sup.3, R.sup.6, R.sup.7 and R.sup.8 are, as R.sup.1 and R.sup.4 may also be, for example phenoxysulfonyl or 2-, 3- or 4-methylphenoxysulfonyl.
R.sup.3, R.sup.4, R.sup.6, R.sup.7 and R.sup.8 may each also be for example N-phenyl-N-methylsulfamoyl, N-phenyl-N-ethylsulfamoyl, N-phenyl-N-propylsulfamoyl, N-phenyl-N-butylsulfamoyl, phenylsulfamoyl or 2-, 3- or 4-methylphenylsulfamoyl.
R.sup.4, R.sup.6, R.sup.7 and R.sup.8 may each also be for example dimethylsulfamoyl, diethylsulfamoyl, dipropylsulfamoyl, dibutylsulfamoyl, N-methyl-N-ethylsulfamoyl, bis(2-hydroxyethyl)sulfamoyl, bis(carboxymethyl)sulfamoyl, bis(2-carboxyethyl)sulfamoyl, methylsulfamoyl, ethylsulfamoyl, propylsulfamoyl, isopropylsulfamoyl, butylsulfamoyl, 2-hydroxyethylsulfamoyl, carboxymethylsulfamoyl or 2-carboxyethylsulfamoyl.
R.sup.4, R.sup.6, R.sup.7 and R.sup.8 may each also be for example dimethylcarbamoyl, diethylcarbamoyl, dipropylcarbamoyl, dibutylcarbamoyl, N-methyl-N-ethylcarbamoyl, bis(2-hydroxyethyl)carbamoyl, bis(carboxymethyl)carbamoyl, bis(2-carboxyethyl)carbamoyl, N-phenyl-N-methylcarbamoyl, N-phenyl-N-ethylcarbamoyl, N-phenyl-N-propylcarbamoyl or N-phenyl-N-butylcarbamoyl.
R.sup.4 may also be for example methylcarbamoyl, ethylcarbamoyl, propylcarbamoyl, isopropylcarbamoyl, butylcarbamoyl, 2-hydroxyethylcarbamoyl, carboxymethylcarbamoyl or 2-carboxyethylcarbamoyl.
R.sup.6, R.sup.7 and R.sup.8 may each also be for example 2-hydroxyethylsulfonyl, 2-chloroethylsulfonyl, 2-sulfatoethylsulfonyl or 2-acetyloxyethylsulfonyl.
The radicals ##STR7## conform for example to the formulae ##STR8##
Since the disazo dyes of the formula I contain a plurality of hydroxysulfonyl groups and optionally also carboxyl groups, their salts are likewise encompassed by the invention.
Suitable salts are 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 with either unsubstituted or substituted ammonium cations. Substituted ammonium cations are for example monoalkyl-, dialkyl-, trialkyl-, tetraalkyl- or benzyltrialkyl-ammonium cations or those cations derived from nitrogenous five- or six-membered saturated heterocycles, such as pyrrolidinium, piperidinium, morpholinium or piperazinium cations or their N-monoalkyl- or N,N-dialkyl-substituted products. Alkyl is here in general to be understood as meaning straight-chain or branched C.sub.1 -C.sub.20 -alkyl which may be substituted by from 1 to 3 hydroxyl groups and/or interrupted by from 1 to 4 oxygen atoms in ether function.
Preference is given to disazo dyes of the formula I containing 3, 4 or 5, in particular 3 or 4, hydroxysulfonyl groups.
Preference is further given to disazo dyes of the formula I containing 1 or 2 carboxyl groups.
Preference is further given to disazo dyes of the formula I containing 2 hydroxysulfonyl groups, 2 hydroxyl groups and optionally 1 carboxyl group.
Preference is further given to disazo dyes of the formula I where Alk is C.sub.1 -C.sub.6 -alkyl which may be interrupted by 1 or 2 oxygen atoms in ether function or by 1 sulfonyl group and may be substituted by hydroxyl, C.sub.1 -C.sub.4 -alkanoyloxy, sulfato, chlorine, cyano, carboxyl, hydroxysulfonyl, phenyl or hydroxysulfonylphenyl.
Preference is further given to disazo dyes of the formula I where Ar is phenyl which may be substituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, carboxyl, C.sub.1 -C.sub.4 -alkanoylamino, methoxyacetylamino, hydroxysulfonyl or a radical of the formula SO.sub.2 --CH.dbd.CH.sub.2, SO.sub.2 --C.sub.2 H.sub.4 --Q, SO.sub.2 --NHAlk, SO.sub.2 --N(Alk).sub.2, SO.sub.2 --G, SO.sub.2 --OG, SO.sub.2 --NHG or SO.sub.2 --N(Alk)G.
Preference is further given to disazo dyes of the formula II ##STR9## where R.sup.9 is a radical of the formula SO.sub.2 --CH.dbd.CH.sub.2, SO.sub.2 --CH.sub.2 CH.dbd.CH.sub.2, SO.sub.2 --C.sub.2 H.sub.4 Q, pyrrolidinylsulfonyl, piperidinylsulfonyl, morpholidinylsulfonyl or a radical of the formula SO.sub.2 --N(Alk).sub.2, SO.sub.2 --NHAlk, SO.sub.2 --N(Ar)Alk or SO.sub.2 --NHAr,
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, X.sup.1 and X.sup.2 are each as defined above, and R.sup.9 is in the 3- or 4-position.
Particular preference is given to disazo dyes containing a radical of the formula SO.sub.2 --CH.dbd.CH.sub.2, SO.sub.2 --CH.sub.2 CH.dbd.CH.sub.2 or SO.sub.2 --C.sub.2 H.sub.4 --Q, especially those dyes which contain a radical of the formula SO.sub.2 --C.sub.2 H.sub.4 --Q.sup.1, where Q.sup.1 is an alkali-detachable group.
Emphasis is given to dyes of the general formula III ##STR10## where R.sup.10 is a radical of the formula SO.sub.2 --CH.dbd.CH.sub.2, SO.sub.2 --CH.sub.2 CH.dbd.CH.sub.2 or SO.sub.2 --C.sub.2 H.sub.4 --Q,
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, X.sup.1 and X.sup.2 are each as defined above, and R.sup.10 is in the 3- or preferably 4-position.
Particular preference is further given to disazo dyes of the formula I where R.sup.6, R.sup.7 or R.sup.8 is a radical of the formula SO.sub.2 --N(Alk).sub.2, SO.sub.2 --NHAlk, SO.sub.2 --N(Ar)Alk, SO.sub.2 --NHAr or pyrrolidinylsulfonyl, piperidinylsulfonyl or morpholinylsulfonyl. Disazo dyes of the formula I where R.sup.3 and/or R.sup.7 is a radical of the formula SO.sub.2 --N(Ar)Alk or SO.sub.2 --NHAr are of particular importance. Emphasis is given to the dyes of the general formulae IV and V ##STR11## where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 R.sup.6, R.sup.7, R.sup.8, X.sup.1, X.sup.2, Alk and Ar are each as defined above and the sulfonamide group is in the 3-position or preferably in the 4-position.
Particular preference is given to dyes of the formula I where R.sup.3 and/or R.sup.7 are each a radical of the formula SO.sub.2 --N(Ar)Alk, where Ar contains a radical of the formula SO.sub.2 --C.sub.2 H.sub.4 --Q, SO.sub.2 --CH.dbd.CH.sub.2 or SO.sub.2 --CH.sub.2 CH.dbd.CH.sub.2. Preference is further given to dyes of the formulae IV and V where Ar is a phenyl or naphthyl group which is substituted by a radical of the formula SO.sub.2 --CH.sub.2 --CH.sub.2 --Q, SO.sub.2 --CH.dbd.CH.sub.2 or SO.sub.2 --CH.sub.2 --CH.dbd.CH.sub.2. Emphasis is given in particular to dyes of the formula IVa ##STR12## where R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are each as defined above, the ring A may be benzofused,
Alk is C.sub.1 -C.sub.8 -alkyl with or without interruption by from 1 to 3 oxygen atoms in ether function or by 1 sulfur atom or 1 sulfonyl group and with or without substitution by hydroxyl, C.sub.1 -C.sub.4 -alkanoyloxy, benzoyloxy, sulfato, halogen, cyano, carbamoyl, carboxyl, hydroxysulfonyl, phenyl or hydroxysulfonylphenyl, or is C.sub.5 -C.sub.8 -cycloalkyl,
U.sup.1 is hydrogen, C.sub.1 -C.sub.4 -alkyl, unsubstituted or C.sub.1 -C.sub.4 -alkoxy- or phenyl-substituted, or halogen, and
U.sup.2 is a radical of the formula SO.sub.2 --CH.dbd.CH.sub.2 or SO.sub.2 --C.sub.2 H.sub.4 --Q, where Q is hydroxyl or an alkali-detachable group,
and the sulfonamide radical is in the 3- or 4-position.
Particular preference is further given to dyes of the formula IVb ##STR13## where R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are each as defined above, the ring A.sup.1 may be benzofused and may be substituted by hydroxysulfonyl, carboxyl, C.sub.1 -C.sub.4 -alkyl, chlorine or C.sub.1 -C.sub.4 -alkoxy,
Alk is C.sub.1 -C.sub.8 -alkyl with or without interruption by from 1 to 3 oxygen atoms in ether function or by 1 sulfur atom or 1 sulfonyl group and with or without substitution by hydroxyl, C.sub.1 -C.sub.4 -alkanoyloxy, benzoyloxy, sulfato, halogen, cyano, carbamoyl, carboxyl, hydroxysulfonyl, phenyl or hydroxysulfonylphenyl, or is C.sub.5 -C.sub.8 -cycloalkyl,
and the sulfonamide radical is in the 3- or 4-position. Preference is given especially to dyes of formula IVb where the ring A is mono- or disubstituted by carboxyl or hydroxysulfonyl.
Preference is further given to disazo dyes of the formulae Ia to In ##STR14## where T.sup.1 is Alk or Ar, T.sup.2 is hydrogen or hydroxysulfonyl, and X.sup.1, X.sup.2, R.sup.3, R.sup.4, R.sup.6, R.sup.7, R.sup.8, Y, Z.sup.1, Alk and Ar are each as defined above.
Preference is further given to disazo dyes of the formulae I and also Ia to In where R.sup.6 and R.sup.8 are each hydrogen and R.sup.7 is a radical R.sup.9 which is as defined above, and in particular a radical of the formula SO.sub.2 --N(Ar)Alk, where Ar and Alk are each as defined above.
Preference is further given to disazo dyes of the formulae I and also Ia to In containing a radical of the formula SO.sub.2 --CH.dbd.CH.sub.2 or in particular SO.sub.2 --C.sub.2 H.sub.4 --Q where Q is as given above and denotes in particular sulfato, chlorine or acetyloxy.
Preference is further given to disazo dyes of the formula I where R.sup.1, R.sup.6, R.sup.7 or R.sup.8 is an oxadiazole radical and especially of the formulae II, III, IV, IVa and IVb where R.sup.1 is an oxadiazole radical.
Particular preference is given to disazo dyes of the formulae Ia, Ib (including in particular those where X.sup.1 =OH and X.sup.2 =NH.sub.2), If, Ih, Ij, Ik, Im and In.
Of particular importance are mixtures of dyes of the formula Ic where X.sup.1 is hydroxyl and X.sup.2 is amino and Id where Y is carbonyl. Of these, particularly suitable mixtures are those where R.sup.6 and R.sup.8 are each hydrogen and R.sup.7 is a radical of the formula SO.sub.2 --N(Ar)Alk where Ar and Alk are each as defined above.
Particular preference is further given to mixtures of dyes Ic and Id where the dyes of the formulae Ic and Id are present in a weight ratio of from 30:70 to 70:30.
In addition, preference is given to disazo dyes of the formula I in which the substituents are selected from a combination of the above-recited preferred substituents.
The novel disazo dyes of the formula I are obtainable in a conventional manner.
For example, they can be obtained by diazotizing an aniline of the formula VI ##STR15## where R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are each as defined above, in a conventional manner and coupling the resulting diazonium salt with a naphthalene of the formula VII ##STR16## where X.sup.1 and X.sup.2 are each as defined above.
The resulting monoazo dye of the formula VIII ##STR17## where R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, X.sup.1 and X.sup.2 are each as defined above, can then be coupled with a diazonium salt derived from an aniline of the formula IX ##STR18## where R.sup.6, R.sup.7 and R.sup.8 are each as defined above.
It will be appreciated that the dyes can also be obtained by the reverse sequence, by diazotizing D.sup.2 --NH.sub.2 and coupling with the naphthalene of the formula VII and then diazotizing D.sup.1 --NH.sub.2 and coupling with the resulting dye.
The dyes of the formula I according to the invention are advantageously useful for dyeing natural or synthetic substrates, in particular wool, leather or polyamide.
The dyeings obtained have black and blue to navy shades and good lightfastness and also good wetfastness properties.
The novel dyes can be applied alone and mixed with one another or else mixed with other dyes.
The present invention further encompasses a process for dyeing wool at a pH of from 3 to 7 by using disazo dyes containing an SO.sub.2 --C.sub.2 H.sub.4 --Q.sup.1 radical. The prior art azo class reactive dyes require special dyeing processes for wool. It has now been found that the novel reactive dyes, especially those of the formula III where R.sup.10 is a radical of the formula SO.sub.2 --C.sub.2 H.sub.4 --Q.sup.1, lead to excellent dyeing results by conventional wool-dyeing methods under acidic conditions.
The present invention further provides sulfonamides of the formula X ##STR19## where the ring A may be benzo-fused,
Alk is C.sub.1 -C.sub.8 -alkyl which may be interrupted by from 1 to 3 oxygen atoms in ether function or by 1 sulfur atom or 1 sulfonyl group and may be substituted by hydroxyl, C.sub.1 -C.sub.4 -alkanoyloxy, benzoyloxy, sulfato, halogen, cyano, carbamoyl, carboxyl, hydroxysulfonyl, phenyl or hydroxysulfonylphenyl, or is C.sub.5 -C.sub.8 -cycloalkyl,
U.sup.1 is hydrogen, C.sub.1 -C.sub.4 -alkyl which may be substituted by C.sub.1 -C.sub.4 -alkoxy or phenyl, or is halogen, and
U.sup.2 is a radical of the formula SO.sub.2 --CH.dbd.CH.sub.2 or SO.sub.2 --C.sub.2 H.sub.4 --Q, where Q is hydroxyl or an alkali-detachable group
and the sulfonamide is in the 3- or 4-position.
The present invention further provides sulfonamides of the formula XI ##STR20## where n is 1 or 2,
Alk is C.sub.1 -C.sub.8 -alkyl which may be interrupted by from 1 to 3 oxygen atoms in ether function or by 1 sulfur atom or 1 sulfonyl group and may be substituted by hydroxyl, C.sub.1 -C.sub.4 -alkanoyloxy, benzoyloxy, sulfato, halogen, cyano, carbamoyl, carboxyl, hydroxysulfonyl, phenyl or hydroxysulfonylphenyl, or is C.sub.5 -C8-cycloalkyl
and the sulfonamide is in the 3- or 4-position.
As regards exemplification of the substituents Alk, U.sup.1 and U.sup.2, the observations made above refer.
The novel sulfonamides of the formula X are obtainable in a conventional manner.
For example, they can be obtained by reacting an anilinesulfonic acid of the formula XII ##STR21## where the ring A, Alk and U.sup.1 are each as defined above, with 4-acetylaminobenzenesulfonyl chloride and converting the resulting sulfonamide, for example with thionyl chloride or chlorosulfonic acid, into the corresponding sulfonyl chloride of the formula XIII ##STR22## where the ring A, Alk and U.sup.1 are each as defined above. Reducing the sulfonyl chloride group gives the sulfinic acid, which, for example by reaction with ethylene oxide, can be made to yield the compound of the formula XIV ##STR23## where the ring A, Alk and U.sup.1 are each as defined above.
The sulfonamides of the formula X are obtained by customary deacetylation and/or esterification reactions.
The novel sulfonamides of the formula XI are likewise obtainable in a conventional manner.
For example, they can be obtained by reacting a naphthalenesulfonic acid of the formula XV ##STR24## where n and Alk are each as defined above, with 4-acetylaminobenzenesulfonyl chloride and deacetylating the resulting sulfonamide in a conventional manner.
The sulfonamides of the formulae X and XI are useful intermediates for dye synthesis, especially for synthesizing the disazo dyes of the formula I.

The Examples which follow illustrate the invention.
EXAMPLE 1
46.8 g of the red dye of the formula ##STR25## were dissolved in 200 ml of water at pH 7 (sodium hydroxide solution) and at room temperature. To the solution was added, simultaneously with sodium bicarbonate, the suspension of a diazonium salt prepared as follows:
35.8 g of the diazo component of the formula ##STR26## were dissolved in 200 ml of water at pH 11 and then admixed with 31 ml of 23% strength by weight aqueous sodium nitrite solution. The solution was then stirred out onto 100 ml of 18.5% strength by weight hydrochloric acid cooled with ice to 0.degree. C. The mixture was subsequently stirred at from 0 to 5.degree. C. for 1 h, and excess nitrous acid was then destroyed.
The reaction mixture was subsequently stirred at pH 6.5-7 for 2 h. Thereafter the mixture was spray-dried.
This gave 89.5 g of the dye of the formula ##STR27##
The black powder still comprised about 35 g of sodium chloride and 4 g of water. The dye forms a blue solution in water and dyes wool in a navy shade having excellent lightfastness.
The absorption spectrum in water has a maximum at 600 nm (pH about 4).
EXAMPLE 2
a) 24 g of 2-aminodiphenyl sulfone were stirred overnight with 110 ml of 30% strength by weight hydrochloric acid and 0.1 g of an acidic wetting agent. A little ice was then added to cool down to 0.degree. C., and 31.5 ml of 23% strength by weight aqueous sodium nitrite solution were added dropwise. The diazotization was complete after a further two hours of stirring. Excess nitrous acid was destroyed with sulfamic acid.
The resulting diazonium salt solution was admixed over 90 min of very thorough stirring with 31.9 g of 1-amino-8-hydroxy-naphthalene-3,6-disulfonic acid dissolved in 200 ml of water at pH 5.8. This gave a suspension of the red dye of the formula ##STR28## b) 33 g of the diazo component of the formula ##STR29## were dissolved in 450 ml of water and 1 g of an alkaline wetting agent at 50.degree. C. and at pH 11 (sodium hydroxide solution). To the solution were added 35 ml of 23% strength by weight aqueous sodium nitrite solution, and the mixture was then poured onto a mixture of 300 ml of water and 40 ml of concentrated hydrochloric acid. The mixture was subsequently stirred at from 40 to 45.degree. C. for 4 h. Excess nitrous acid was then destroyed.
c) The reaction mixtures described in a) and b) were then combined and the pH of the mixture was adjusted to 6-7.5 with dilute sodium hydroxide solution. The mixture was subsequently stirred for 1 h, adjusted to pH 9 and stirred overnight. The resulting blue suspension was heated to 70.degree. C. and the dye of the formula ##STR30## was precipitated with concentrated hydrochloric acid and filtered off with suction. Drying left 88 g of a black powder which dyes wool and polycaprolactam fabric in a navy to black shade (.lambda..sub.max in water: 582 nm; shoulder at 626 nm).
EXAMPLE 3
a) 38.0 g of the diazo component of the formula ##STR31## were added to 100 ml of 18.5% strength by weight hydrochloric acid a little at a time and stirred in overnight at room temperature. The mixture was then cooled down to 0.degree. C. with ice and admixed with 31.5 ml of 23% by weight aqueous sodium nitrite solution. Excess nitrous acid was destroyed after stirring for one hour.
b) 31.9 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid were dissolved in 600 ml of water at pH 6 (sodium hydroxide solution). This solution was added with very thorough stirring to the diazonium salt suspension described under a), which had been diluted with 600 ml of water beforehand. The coupling mixture was stirred overnight at from 20 to 25.degree. C. The pH of the mixture was then adjusted to 4 with sodium acetate.
c) 24.5 g of the diazo component of the formula ##STR32## were stirred for 1 h at from 30 to 60.degree. C. with 30.5 g of concentrated hydrochloric acid and 300 ml of water. The mixture was then admixed with 0.7 g of an acidic wetting agent and thereafter 35 ml of 23% strength by weight aqueous sodium nitrite solution were added dropwise over 10 min, and subsequently stirred at 30.degree. C. for 2 h. Excess nitrous acid was then destroyed and the diazonium salt solution was poured into the coupling mixture described under b). The pH of the 2nd coupling reaction was raised to 6-6.5 with sodium bicarbonate and the coupling was completed by stirring overnight.
The dye of the formula ##STR33## was precipitated with hydrochloric acid. Filtering off with suction and drying left 104.5 g of a black powder which gives a blue solution in water (.lambda..sub.max : 577 nm) and dyes polycaprolactam and wool in a navy shade having good fastness properties.
EXAMPLE 4
33 g of the diazo component of the formula ##STR34## were dissolved in 450 ml of water at 80.degree. C. and pH 11 (sodium hydroxide solution). The solution was admixed with 0.5 g of an acidic wetting agent and 35 ml of 23% strength by weight sodium nitrite solution. The suspension obtained was stirred out onto a mixture of 300 ml of water and 40 ml of concentrated hydrochloric acid. The mixture was subsequently stirred at from 35 to 40.degree. C. for 4 h. Excess nitrous acid was then destroyed and the pH of the suspension was raised to 1.6 with sodium bicarbonate. Thereafter 31.9 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, dissolved in 150 ml of water at pH 5.8 - 6, were added dropwise over 1.5 h. The temperature was 30-35.degree. C. The reaction mixture was stirred overnight at pH 2 and was then mixed with a diazonium salt solution prepared as follows:
24.5 g of the diazo component of the formula ##STR35## were diazotized similarly to Example 3.
The coupling with the above-described red intermediate of the formula ##STR36## was carried out by gradually raising the pH of the mixture to 7.5 with dilute sodium hydroxide solution, subsequently stirring it at pH 7.5 for 30 min and then adjusting it with sodium hydroxide solution to pH 9.
The dye of the formula ##STR37## was precipitated by acidifying the reaction mixture to pH 0.5 and additionally adding sodium chloride. Filtering off with suction drying left 144 g of a black powder still comprising about 50 g of salt.
The dye dissolved in water at about pH 4 has a UV-VIS maximum at 575 nm. It dyes wool, polyamide and leather in a fast blue to navy shade.
EXAMPLE 5
61.1 g of the red dye of the formula ##STR38## were dissolved at room temperature in 500 ml water at pH 6-7 (sodium bicarbonate). 22.2 g of 4-aminophthalic N-(3-hydroxypropyl)imide were then diazotized by dissolving in 33 ml of concentrated hydrochloric acid and water, cooling with ice to -3.degree. C. and adding 31 ml of 23% strength by weight aqueous sodium nitrite solution. After subsequent stirring at 0-5.degree. C. for 20 min excess nitrous acid was destroyed with sulfamic acid. The resulting diazonium salt solution was added over 30 min to the above-prepared solution in such a way that the pH of the reaction mixture could be held continuously within the range from 6 to 7.8 with sodium bicarbonate. The resulting blue dye solution was spray-dried at pH 6.5. This gave a black powder of the dye of the formula ##STR39##
It gives a blue solution in water and dyes wool and polyamide in a bright blue to bluish black shade having excellent wetfastness properties.
The absorption maximum in water at about pH 4 is 590 nm.
EXAMPLE 6
37.5 g of the diazo component of the formula ##STR40## were dissolved in 250 ml of water at pH 10 (sodium hydroxide solution) and thereafter admixed with 31.5 ml of 23% strength by weight aqueous sodium nitrite solution. The mixture was stirred out onto 100 ml of the 18.5% strength by weight hydrochloric acid which had been cooled down to -2.degree. C. with ice in such a way that the temperature was .ltoreq.5.degree. C. Initially this produced a solution, from which the diazonium salt separated as a precipitate. After 60 min of stirring at 0-5.degree. C. excess nitrous acid was destroyed. A freshly prepared aqueous solution of 38.5 g of 83.2% by weight 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid was then added dropwise over 1.5 h and the temperature of the reaction mixture was raised to 22.degree. C. Stirring overnight gave a thick suspension of the dye of the formula ##STR41## (This dye dissolves on high dilution in water with a red color, the solution having an absorption maximum at 517 nm at pH 3-4 and an absorption maximum at 549 nm at pH 10.)
The mixture was then neutralized with sodium hydroxide solution and admixed with the diazonium salt of 1-aminoanthraquinone, which had been diazotized in a conventional manner in sulfuric acid with nitrosylsulfuric acid and had been isolated in crystalline form following precipitation with ice. At pH 5-8 the diazonium salt was coupled to form the blue dye of the formula ##STR42##
Titrating the reaction mixture, precipitating the dye with potassium chloride, filtering off with suction, washing with aqueous potassium chloride solution and drying left 165 g of a black powder having a dye content of about 61% as potassium salt.
The dye gives a blue solution in water (.lambda..sub.max : 604 nm and 400 nm at pH .about.4) and dyes wool in a strong dark blue shade having excellent fastness properties.
EXAMPLE 7
43.5 g of the diazo component of the formula ##STR43## were dissolved in 400 ml of water under weakly acidic conditions (sodium bicarbonate). The mixture was then cooled down to 0.degree. C., and 27 ml of 30% strength by weight hydrochloric acid were added, followed by 31.5 ml of 23% strength of aqueous sodium nitrite solution. The mixture was subsequently stirred at 5.degree. C. for 2 h. Excess nitrous acid was then destroyed and the mixture was stirred out onto a freshly prepared precipitation of 38.5 g of 83.2% strength by weight 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid of pH<1. The reaction mixture was stirred overnight at room temperature. This gave the red dye of the formula ##STR44##
The absorption maximum of an aqueous solution (pH 3-4) has a maximum at 518 nm, and the maximum at pH 7.9 is at 546 nm.
A mixture of 10.3 g of 3-aminophthalic N-(.sub.2 -hydroxyethyl)imide and 10.3 g of 4-aminophthalic N-(2-hydroxyethyl)imide dissolved in 35 ml of concentrated hydrochloric acid and 75 ml of water at 0-5.degree. C. was then diazotized in a conventional manner with sodium nitrite. Following the destruction of excess nitrous acid the diazonium salt solution was added to the above-described red coupling mixture. The mixture was then neutralized by stirring with sodium bicarbonate.
The result obtained was a deep blue solution of the dyes of the formulae ##STR45##
The dye mixture dyes wool in a navy shade having good light- and wetfastness properties.
The dyes listed in the tables below are obtained in a similar manner.
TABLE 1______________________________________ #STR46## Ex. Hue on No. Q wool______________________________________ - 8 blue 7## - 9 blue 8## - 10 blue 9## - 11 blue 0## - 12 blue 1## - 13 blue 2## - 14 blue 3## - 15 blue 4## - 16 blue 5## - 17 blue 6## - 18 blue 7## - 19 blue58##______________________________________
TABLE 2__________________________________________________________________________ #STR59## -Ex. No. Q E.sup.1 E.sup.2 Hue on wool__________________________________________________________________________ 20 H H bluish black - 21 H H bluish black - 22 H H bluish black - 23 H H bluish black - 24 H H bluish black - 25 H H bluish black - 26 H H bluish black - 27 NHCOCH.sub.3 H bluish black - 28 H H bluish black - 29 H H bluish black - 30 CH.sub.3 H bluish black - 31 CH.sub.3 CH.sub.3 bluish__________________________________________________________________________ black
TABLE 3__________________________________________________________________________ #STR72## -Ex. No. Q E Hue on wool__________________________________________________________________________ 32 H navy # - 33 H navy # - 34 H navy # - 35 H navy # - 36 H navy # - 37 H navy # - 38 H navy # - 39 H navy # - 40 H navy # - 41 H navy # - 42 H navy # - 43 H navy # - 44 H navy # - 45 H navy # - 46 H navy # - 47 H navy # - 48 CH.sub.3 navy - 49 CH.sub.3 navy - 50 CH.sub.3 navy__________________________________________________________________________
TABLE 4__________________________________________________________________________ #STR92## -Ex. No. E.sup.1 E.sup.2 E.sup.3 Q Hue on wool__________________________________________________________________________ 51 H CH.sub.3 CH.sub.3 bluish black - 52 H H H bluish black - 53 H CH.sub.3 CH.sub.3 bluish black - 54 H H CH.sub.3 bluish black - 55 CH.sub.3 CH.sub.3 H bluish black - 56 H H H bluish black - 57 H H H bluish black - 58 H H H bluish black - 59 H H H bluish black - 60 H H H bluish black - 61 NHCOCH.sub.3 H OCH.sub.3 bluish black - 62 NHCOCH.sub.3 H OCH.sub.3 bluish black - 63 H H H bluish black - 64 H H H bluish black - 65 H H CH.sub.3 bluish black - 66 H H CH.sub.3 bluish black - 67 H H CH.sub.3 bluish black - 68 H H H bluish black - 69 H H CH.sub.3 bluish black - 70 CH.sub.3 H CH.sub.3 bluish black - 71 CO.sub.2 H H H bluish black - 72 H CH.sub.3 H bluish black - 73 H CH.sub.3 H bluish black - 74 H H H bluish black__________________________________________________________________________
TABLE 5__________________________________________________________________________ #STR117## -Ex. No. E.sup.1 E.sup.2 E.sup.3 Hue on wool__________________________________________________________________________ 75 H H reddish blue - 76 Cl H reddish blue - 77 CN H dark blue - 78 CO.sub.2 CH.sub.3 SO.sub.3 H H reddish blue 79 CO.sub.2 C.sub.2 H.sub.5 SO.sub.3 H H reddish blue 80 CN SO.sub.3 H H reddish blue - 81 Br H reddish blue - 82 H SO.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub.3 SO.sub.3 H reddish blue 83 H SO.sub.2 CH.sub.2 CH.sub.2 OH SO.sub.3 H reddish blue 84 H SO.sub.2 CH.sub.2 CH.sub.2 OCHO SO.sub.3 H reddish blue 85 H SO.sub.2 CH.dbd.CH.sub.2 SO.sub.3 H reddish blue 86 H SO.sub.2 CH.sub.2 CH.sub.2 Cl SO.sub.3 H reddish blue 87 H SO.sub.2 CH.sub.2 CH.dbd.CH.sub.2 SO.sub.3 H reddish blue 88 H SO.sub.2 C.sub.2 H.sub.5 SO.sub.3 H reddish blue 89 H SO.sub.2 C.sub.6 H.sub.5 SO.sub.3 H reddish blue 90 SO.sub.3 H SO.sub.2 C.sub.6 H.sub.5 H reddish blue 91 SO.sub.3 H SO.sub.2 N(C.sub.2 H.sub.5).sub.2 H reddish blue - 92 SO.sub.3 H H reddish blue - 93 COC.sub.6 H.sub.5 Cl SO.sub.3 H reddish blue__________________________________________________________________________
TABLE 6__________________________________________________________________________ #STR123## -Ex. Hue on No. E.sup.1 E.sup.2 E.sup.3 wool__________________________________________________________________________ 94 SO.sub.3 H CH.sub.2 CH.sub.2 OH H blue 95 SO.sub.3 H CH.sub.2 CH.sub.2 OCH.sub.3 H blue 96 SO.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 H blue 97 SO.sub.3 H CH.sub.3 H blue 98 SO.sub.3 H C.sub.2 H.sub.5 H blue - 99 H H blue ## - 100 H H blue ## - 101 SO.sub.3 H C.sub.4 H.sub.8 OH(n) H blue 102 SO.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 H blue - 103 H H blue ## - 104 H CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH H blue 105 H CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H blue 106 H CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub.3 H blue 107 SO.sub.3 H CH.sub.2 CH.sub.2 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H blue 108 SO.sub.3 H C.sub.2 H.sub.5 Cl blue 109 SO.sub.3 H C.sub.2 H.sub.4 OH Cl blue 110 H CH.sub.2 CO.sub.2 H H blue - 111 H H blue7##__________________________________________________________________________
TABLE 7__________________________________________________________________________ #STR128## -Ex. Hue on No. E.sup.3 Y E.sup.1 E.sup.2 wool__________________________________________________________________________ 112 SO.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 ,1 reddish ,1 blue - 113 SO.sub.3 H CO CH.sub.2 CH.sub.2 OCH.sub.3 ,1 reddish ,1 blue - 114 H CO #STR131## ,1 reddish ,1 blue - 115 H CO #STR133## ,1 reddish ,1 blue - 116 SO.sub.3 H CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 ,1 reddish ,1 blue - 117 SO.sub.3 H CH.sub.2 C.sub.2 H.sub.5 ,1 dark ,1 blue - 118 SO.sub.3 H CO CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 (n) ,1 reddish ,1 blue - 119 SO.sub.3 H CO CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 ,1 dark ,1 blue - 120 SO.sub.3 H CO CH.sub.2 C.sub.6 H.sub.5 ,1 reddish ,1 blue - 121 SO.sub.3 H CO CH.sub.2 C.sub.6 H.sub.5 ,1 dark ,1 blue - 122 SO.sub.3 H CH.sub.2 C.sub.4 H.sub.9 ,1 dark ,1 blue - 123 CH.sub.3 CO #STR142## ,1 dark ,1 blue - 124 CH.sub.3 CO #STR144## ,1 dark ,1 blue - 125 H CH.sub.2 CH.sub.2 CH.sub.2 OH ,1 dark ,1 blue - 126 H CO CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OH ,1 dark ,1 blue - 127 H CH.sub.2 #STR148## blue149##__________________________________________________________________________
TABLE 8__________________________________________________________________________ #STR150## -Ex. No. E.sup.1 E.sup.2 E.sup.3 E.sup.4 Hue on wool__________________________________________________________________________128 NO.sub.2 H CH.sub.3 H grayish blue 129 NO.sub.2 H CH.sub.3 CH.sub.3 grayish blue 130 NO.sub.2 CH.sub.3 CH.sub.3 H grayish blue 131 NO.sub.2 CH.sub.3 OCH.sub.3 H grayish blue 132 NO.sub.2 H OCH.sub.3 H grayish blue 133 NO.sub.2 H OC.sub.2 H.sub.5 H grayish blue 134 NO.sub.2 H OC.sub.4 H.sub.9 H grayish blue 135 NO.sub.2 CH.sub.3 H CH.sub.3 grayish blue 136 NO.sub.2 H C.sub.2 H.sub.5 H grayish blue 137 NO.sub.2 H OCH.sub.3 NHCOCH.sub.3 grayish blue 138 SO.sub.2 O--C.sub.6 H.sub.5 H OCH.sub.3 H grayish blue 139 SO.sub.2 C.sub.2 H.sub.4 OH H CH.sub.3 CH.sub.3 grayish blue 140 SO.sub.2 CH.sub.2 CH.dbd.CH.sub.2 H OCH.sub.3 H grayish blue 141 SO.sub.2 CH.dbd.CH.sub.2 H CH.sub.3 CH.sub.3 grayish blue 142 SO.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub.3 H CH.sub.3 CH.sub.3 grayish blue 143 SO.sub.2 N(CH.sub.3).sub.2 H OCH.sub.3 H grayish blue 144 SO.sub.2 CH.dbd.CH.sub.2 H NHCOCH.sub.3 H grayish blue 145 SO.sub.2 CH.sub.2 CH.sub.2 OH H NHCOCH.sub.3 H grayish blue__________________________________________________________________________
TABLE 9__________________________________________________________________________ #STR151## -Ex. No. E.sup.1 E.sup.2 Q Hue on wool__________________________________________________________________________ 146 CH.sub.2 CH.sub.2 OSO.sub.3 H H reddish blue - 147 CH.sub.2 CH.sub.2 OCOCH.sub. 3 H reddish blue - 148 C.sub.2 H.sub.5 H reddish blue - 149 CH.sub.2 CH.sub.2 OCHO SO.sub.2 N(CH.sub.3 ).sub.2 reddish blue - 150 CH.sub.2 CH.sub.2 OCOCH.sub. 3 SO.sub.2 N(CH.sub.3).sub.2 reddish blue - 151 CH.sub.3 SO.sub.2 NHCH.sub.2 CH.sub.2 OH reddish blue - 152 CH.sub.2 CH.sub.2 OH H reddish blue - 153 CH.sub.2 CH.sub.2 OH H reddish blue - 154 CH.sub.2 CH.sub.2 OH H reddish blue - 155 CH.sub.2 CH.sub.2 OH SO.sub.2 N(CH.sub.3 ).sub.2 reddish blue - 156 CH.sub.2 CH.sub.2 OH SO.sub.2 N(CH.sub.3 ).sub.2 reddish blue - 157 CH.sub.3 SO.sub.2 N(C.sub.2 H.sub.5).sub.2 reddish blue - 158 C.sub.2 H.sub.5 H reddish blue - 159 C.sub.2 H.sub.5 SO.sub.2 N(CH.sub.3).sub.2 reddish blue - 160 CH.sub.2 CH.sub.2 OSO.sub.3 H H reddish blue - 161 CH.sub.3 SO.sub.3 H reddish blue - 162 C.sub.2 H.sub.5 SO.sub.3 H reddish blue - 163 C.sub.2 H.sub.5 SO.sub.3 H reddish blue - 164 OH #STR170## reddish blue__________________________________________________________________________
TABLE 10__________________________________________________________________________ #STR172## - Hue Ex. on No. E.sup.1 E.sup.2 E.sup.3 E.sup.4 E.sup.5 wool__________________________________________________________________________ 165 CO.sub.2 CH.sub.3 SO.sub.2 OC.sub.6 H.sub.5 H SO.sub.3 H ,1 blu- ,1 ish ,1 black - 166 CO.sub.2 CH.sub.3 SO.sub.3 H H H ,1 blu- ,1 ish ,1 black - 167 CO.sub.2 CH.sub.3 SO.sub.3 H H H ,1 redd- ,1 ish ,1 blue - 168 CO.sub.2 CH.sub.3 SO.sub.3 H H H ,1 redd- ,1 ish ,1 blue - 169 CO.sub.2 CH.sub.3 SO.sub.3 H H ,1 redd- ,1 ish ,1 blue - 170 CO.sub.2 CH.sub.3 SO.sub.2 N(CH.sub.3).sub.2 SO.sub.3 H H ,1 redd- ,1 ish ,1 blue - 171 CO.sub.2 CH.sub.3 SO.sub.2 N(C.sub.2 H.sub.5).sub.2 H SO.sub.3 H ,1 blu- ,1 ish ,1 black - 172 CN SO.sub.2 N(CH.sub.3).su b.2 SO.sub.3 H H ,1 redd- ,1 ish ,1 blue - 173 Br SO.sub.2 N(CH.sub.3).sub.2 SO.sub.3 H H ,1 redd- ,1 ish ,1 blue - 174 SO.sub.2 N(C.sub.2 H.sub.4 OH).sub.2 SO.sub.3 H H ,1 redd- ,1 ish ,1 blue - 175 #STR185## SO.sub.3 H H ,1 redd- ,1 ish ,1 blue - 176 #STR188## SO.sub.3 H H ,1 redd- ,1 ish ,1 blue - 177 CO.sub.2 CH.sub.3 SO.sub.3 H CH.sub.3 H ,1 blu- ,1 ish ,1 black - 178 CO.sub.2 CH.sub.3 SO.sub.3 H H CH.sub.3 ,1 blu- ,1 ish ,1 black - 179 H H TR193## SO.sub.3 H ,1 dark ,1 blue__________________________________________________________________________
TABLE 11__________________________________________________________________________ #STR195## -Ex. No. E.sup.1 E.sup.2 E.sup.3 E.sup.4__________________________________________________________________________ Hue on wool 180 H NO.sub.2 H CH.sub.2 CH.sub.2 OH reddish blue 181 H NO.sub.2 H CH.sub.2 CH.sub.2 CH.sub.2 OH reddish blue 182 H NO.sub.2 H CH.sub.2 C.sub.6 H.sub.5 reddish blue 183 H NO.sub.2 H (CH.sub.2).sub.2 OCH.sub.3 reddish blue 184 H NO.sub.2 H (CH.sub.2).sub.3 OCH.sub.3 reddish blue 185 H NO.sub.2 H (CH.sub.2).sub.3 O(CH.sub.2).sub.2 OCH.sub.3 reddish blue - 186 H NO.sub.2 H reddish blue - 187 H NO.sub.2 H reddish blue - 188 H NO.sub.2 H reddish blue - 189 SO.sub.2 C.sub.6 H.sub.5 H H reddish blue - 190 H H 200## reddish blue - 191 SO.sub.2 C.sub.6 H.sub.5 CH.sub.3 H reddish blue - 192 SO.sub.3 H H C.sub.4 H.sub.9 reddish blue - 193 SO.sub.2 C.sub.6 H.sub.5 H SO.sub.3 H C.sub.4 H.sub.9 reddish blue - 194 H SO.sub.3 H C.sub.4 H.sub.9 reddish blue - 195 SO.sub.2 C.sub.6 H.sub.5 H SO.sub.2 CH.sub.2 CO.sub.2 H C.sub.2 H.sub.4 OH reddish blue 196 SO.sub.2 C.sub.6 H.sub.5 H SO.sub.2 CH.sub.2 CO.sub.2 H CH.sub.2 C.sub.6 H.sub.5 reddish blue 197 SO.sub.2 C.sub.6 H.sub.5 H SO.sub.2 CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 reddish blue - 198 H SO.sub.2 CH.sub.2 CO.sub.2 H CH.sub.2 C.sub.6 H.sub.5 reddish blue - 199 H SO.sub.2 --O--C.su b.6 H.sub.5 H reddish blue - 200 H SO.sub.2 --O--C.su b.6 H.sub.5 H reddish blue - 201 H H C.sub.2 H.sub.4 OH reddish blue - 202 H H C.sub.4 H.sub.9 reddish blue - 203 H H CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 reddish blue - 204 H H C.sub.4 H.sub.9 reddish blue - 205 H SO.sub.2 N(C.sub.2 H.sub.4 OH).sub.2 H CH.sub.2 C.sub.6 H.sub.5 reddish blue 206 H SO.sub.2 N(C.sub.2 H.sub.4 OCH.sub.3).sub.2 H CH.sub.2 C.sub.6 H.sub.5 reddish blue 207 H SO.sub.2 N(C.sub.2 H.sub.4 OCH.sub.3).sub.2 H CH.sub.2 C.sub.6 H.sub.5 reddish blue 208 SO.sub.3 H SO.sub.2 N(C.sub.2 H.sub.5).sub.2 H CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 reddish blue 209 SO.sub.3 H SO.sub.2 N(C.sub.2 H.sub.5) 2 H CH.sub.2 C.sub.6 H.sub.5 reddish blue - 210 SO.sub.3 H H CH.sub.2 C.sub.6 H.sub.5 reddish blue - 211 SO.sub.3 H H CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 reddish blue - 212 H H C.sub.2 H.sub.5 reddish blue - 213 H H CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 reddish blue - 214 H H CH.sub.2 C.sub.6 H.sub.5 reddish blue - 215 H H C.sub.4 H.sub.9 reddish blue - Hue on wool/ .sub.max [nm] at pH 4 216 SO.sub.2 OC.sub.6 H.sub.5 H H CH.sub.2 C.sub.6 H.sub.5 reddish blue - 217 SO.sub.2 OC.sub.6 H.sub.5 H H reddish blue - 218 CH.sub.3 H #STR219## reddish blue - 219 H SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 392 and 593 220 H SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5 392 and 594 221 H SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H CH.sub.2 C.sub.6 H.sub.5 392 and 593 222 H SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 392 and 594 223 H SO.sub.2 CH.sub.2 CH.sub.2 Cl H CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 392 and 594 224 H SO.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub.3 H CH.sub.2 CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5 392 and 593 - 225 H SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H 393 and 591 - 226 H SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H 393 and 591 - 227 H SO.sub.2 CH.dbd.CH .sub.2 H 394 and 595 - 228 H SO.sub.2 CH.sub.2 CH.sub.2 OCOCH.sub .3 H reddish blue - 229 H SO.sub.2 CH.sub.2 CH.sub.2 Cl H reddish blue - 230 SO.sub.3 H SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H C.sub.4 H.sub.9 reddish blue - 231 SO.sub.3 H SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H reddish blue - 232 SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H H CH.sub.2 CH.sub.2 OH reddish blue 233 H H SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H CH.sub.2 C.sub.6 H.sub.5 reddish blue 234 H NO.sub.2 H (CH.sub.2).sub.5 CO.sub.2 H reddish blue - 235 H SO.sub.2 CH.sub.2 CH.sub.2 OSO.sub.3 H H reddish__________________________________________________________________________ blue
TABLE 12__________________________________________________________________________ #STR228## -Ex. No. E.sup.1 E.sup.2 Hue on wool__________________________________________________________________________236 CH.sub.2 CH=CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.4 H.sub.9 reddish blue - 237 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 reddish blue - 238 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 reddish blue - 239 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 reddish blue - 240 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 reddish blue - 241 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 reddish blue - 242 CH.sub.2 C.sub.6 H.sub.5 reddish blue - 243 C.sub.2 H.sub.4 OH reddish blue - 244 C.sub.3 H.sub.6 OH reddish blue - 245 C.sub.4 H.sub.8 OH reddish blue - 246 CH.sub.2 C.sub.6 H.sub.5 reddish blue - 247 C.sub.2 H.sub.4 OH reddish blue - 248 C.sub.4 H.sub.9 reddish blue__________________________________________________________________________
TABLE 13__________________________________________________________________________ #STR241## -Ex. No. E.sup.1 E.sup.2 E.sup.3 Hue on wool__________________________________________________________________________ 249 H H reddish blue - 250 H H reddish blue - 251 H SO.sub.2 CH.sub.3 blue - 252 H SO.sub.2 CH.sub.2 CO.sub.2 H blue - 253 SO.sub.2 OC.sub.6 H.sub.5 H H reddish blue 254 SO.sub.2 OC.sub.6 H.sub.5 CH.sub.3 H reddish blue 255 SO.sub.2 OC.sub.6 H.sub.5 H H reddish blue - 256 H H blue ## - 257 H H blue ## - 258 H H blue 48## - 259 H H SO.sub.2 OC.sub.6 H.sub.5 blue 260 Cl H SO.sub.2 OC.sub.6 H.sub.5 blue 261 H CH.sub.3 SO.sub.2 OC.sub.6 H.sub.5 blue__________________________________________________________________________
TABLE 14__________________________________________________________________________ #STR249## -Ex. No. E.sup.1 E.sup.2 E.sup.3 E.sup.4 E.sup.5 E.sup.6 E.sup.7 Hue on wool__________________________________________________________________________ 262 H H H CH0## .sub.3 H SO.sub.3 H bluish black - 263 H H H CH.sub.3 H H bluish black - 264 H CH.sub.3 H CH.sub.3 H SO.sub.3 H bluish black - 265 H CH.sub.3 H CH.sub.3 H H dark blue - 266 H CH.sub.3 CH.sub.3 CH.sub.3 H SO.sub.3 H bluish black - 267 Cl H SO.sub.2 O--C.sub.6 H.sub.5 CH.sub.3 OCH.sub.3 H SO.sub.3 H bluish black 268 H H SO.sub.2 O--C.sub.6 H.sub.5 CH.sub.3 H CH.sub.3 SO.sub.3 H bluish black - 269 H H CH.sub.3 CH.sub.3 H H bluish black - 270 H H CH.sub.3 CH.sub.3 H H dark blue - 271 H H CH.sub.3 CH.sub.3 H H dark blue__________________________________________________________________________
TABLE 15__________________________________________________________________________ #STR258## -Ex. No. E.sup.1 E.sup.2 E.sup.3 E.sup.4 Hue on wool__________________________________________________________________________ 272 H H TR259## blue 60## - 273 H CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 blue - 274 H H CH.sub.2 C.sub.6 H.sub.5 blue - 275 H H CH.sub.2 C.sub.6 H.sub.5 blue - 276 H CH.sub.3 #STR264## blue 65## - 277 H H #STR266## blue 67## - 278 Cl H #STR268## blue 69## - 279 H H #STR270## blue 71## - 280 H H TR272## blue 73## - 281 H H C.sub.4 H.sub.9 blue - 282 H H C.sub.3 H.sub.6 OCH.sub.3 blue__________________________________________________________________________
TABLE 16__________________________________________________________________________ #STR276## -Ex. No. E.sup.1 E.sup.2 E.sup.3 E.sup.4 Hue on wool__________________________________________________________________________ 283 H H SO277## .sub.3 H reddish blue - 284 CH.sub.3 CH.sub.3 SO.sub.3 H reddish blue - 285 CH.sub.3 H H reddish blue - 286 H H H reddish blue - 287 H H H reddish blue - 288 H H H reddish blue - 289 CH.sub.3 H H reddish blue - 290 H H H reddish blue - 291 H H H reddish blue - 292 H H H reddish blue - 293 H H H reddish blue - 294 H H H reddish blue__________________________________________________________________________
TABLE 17__________________________________________________________________________ #STR289## -Ex. No. E.sup.1 E.sup.2 E.sup.3 Hue on wool__________________________________________________________________________ 295 H CH.sub.3 blue 90## - 296 Cl H blue 91## - 297 H H blue 92## - 298 H H blue 93## - 299 H CH.sub.3 blue 94## - 300 H H blue 95## - 301 H H blue 96## - 302 H H blue 97## - 303 H H blue 98## - 304 H H blue 99## - 305 H H blue300##__________________________________________________________________________
TABLE 18__________________________________________________________________________ #STR301## -Ex. No. E.sup.1 E.sup.2 E.sup.3 E.sup.4 Hue on wool__________________________________________________________________________ 306 H NO.sub.2 H C.sub.4 H.sub.9 blue 307 H C.sub.6 H.sub.5 SO.sub.2 H C.sub.2 H.sub.5 blue - 308 H H C.sub.2 H.sub.5 blue - 309 H H C.sub.2 H.sub.5 blue - 310 H (C.sub.2 H.sub.5).sub.2 N--SO.sub.2 C.sub.2 H.sub.5 ,1 bluish ,1 black - 311 H (C.sub.2 H.sub.5).sub.2 N--SO.sub.2 C.sub.2 H.sub.5 ,1 bluish ,1 black - 312 H CH.sub.2 .dbd.CH--SO.sub.2 H C.sub.2 H.sub.5 blue 313 H HOCH.sub.2 CH.sub.2 --SO.sub.2 H C.sub.2 H.sub.5 blue 314 H CH.sub.3 CO.sub.2 C.sub.2 H.sub.4 --SO.sub.2 H C.sub.2 H.sub.5 blue 315 H ClCH.sub.2 CH.sub.2 --SO.sub.2 H CH.sub.3 blue 316 H CH.sub.2 .dbd.CH--SO.sub.2 H CH.sub.3 blue - 317 H H CH.sub.3 blue - 318 H H C.sub.2 H.sub.5 blue - 319 H H C.sub.2 H.sub.5 blue - 320 H H C.sub.2 H.sub.5 blue - 321 H H C.sub.2 H.sub.5 blue - 322 H C.sub.2 H.sub.5 O.sub.2 C H C.sub.2 H.sub.5 blue 323 H CSTR311## .sub.2 H.sub.5 blue - 324 H C.sub.2 H.sub.5 blue - 325 H C.sub.2 H.sub.5 blue 326 H SO314## .sub.2 CH.sub.2 CO.sub.2 H CH.sub.3 ,1 bluish ,1 black - 327 H SO.sub.2 CH.sub.2 CO.sub.2 H C.sub.2 H.sub.5 ,1 bluish ,1 black - 328 H SO.sub.2 CH.sub.2 CO.sub.2 H CH.sub.3 ,1 bluish ,1 black - 329 H SO.sub.2 CH.sub.2 CO.sub.2 H CH.sub.3 ,1 bluish ,1 black - 330 C.sub.6 H.sub.5 --SO.sub.2 H CH.sub.3 ,1 bluish ,1 black - 331 C.sub.6 H.sub.5 --SO.sub.2 H C.sub.2 H.sub.5 ,1 bluish ,1 black - 332 H TR320## C.sub.2 H.sub.5 ,1 bluish ,1 black - 333 H TR322## CH.sub.3 ,1 bluish ,1 black - 334 CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3 CH.sub.3 blue 335 CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3 C.sub.2 H.sub.5 blue 336 CO.sub.2 C.sub.2 H.sub.5 H CO.sub.2 C.sub.2 H.sub.5 CH.sub.3 blue 337 CO.sub.2 C.sub.2 H.sub.5 H CO.sub.2 C.sub.2 H.sub.5 C.sub.2 H.sub.5 blue 338 CO.sub.2 CH.sub.3 H CO.sub.2 C.sub.3 H.sub.7 CH.sub.3 blue 339 CO.sub.2 CH.sub.3 H CO.sub.2 C.sub.6 H.sub.5 CH.sub.3 blue 340 CO.sub.2 CH.sub.3 H CO.sub.2 C.sub.6 H.sub.5 CH.sub.3 blue__________________________________________________________________________
TABLE 19__________________________________________________________________________ #STR324## -Ex. No. E.sup.1 E.sup.2 E.sup.3 Hue on wool__________________________________________________________________________341 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 reddish blue 342 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CH.sub.2 C.sub.6 H.sub.5 reddish blue 343 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 reddish blue 344 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 reddish blue 345 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3 (CH.sub.2).sub.3 OCH.sub.3 reddish blue 346 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 (CH.sub.2).sub.3 OCH.sub.2 C.sub.6 H.sub.5 reddish blue 347 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3 C.sub.6 H.sub.5 reddish blue - 348 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3 reddish blue - 349 HOCH.sub.2 CH.sub.2 CH.sub.3 blue 26## - 350 H.sub.2 C.dbd.CH C.sub.2 H.sub.5 blue 27## - 351 HOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 blue 28## - 352 CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 reddish blue - 353 HOC.sub.2 H.sub.4 CH.sub.3 reddish blue - 354 HOC.sub.2 H.sub.4 C.sub.2 H.sub.5 reddish blue - 355 HO.sub.2 CCH.sub.2 C.sub.2 H.sub.5 reddish blue - 356 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CH.sub.2 CO.sub.2 H reddish blue__________________________________________________________________________
TABLE 20__________________________________________________________________________ #STR333## -Ex. No. E.sup.1 E.sup.2 E.sup.3 Hue on wool__________________________________________________________________________357 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3 H reddish blue 358 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 H reddish blue 359 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.3 H.sub.7 H reddish blue - 360 CH.sub.3 H reddish blue - 361 C.sub.2 H.sub.5 H reddish blue - 362 CH.sub.3 H reddish blue - 363 C.sub.2 H.sub.5 H reddish blue - 364 HO.sub.2 CCH.sub.2 CH.sub.3 H reddish blue 365 (HOCH.sub.2 CH.sub.2).sub.2 N CH.sub.3 H reddish blue 366 HOCH.sub.2 CH.sub.2 NH CH.sub.3 H reddish blue 367 HOCH.sub.2 CH.sub.2 NH C.sub.2 H.sub.5 H reddish blue 368 HO.sub.2 CCH.sub.2 NH C.sub.2 H.sub.5 H reddish blue 369 HO.sub.2 CCH.sub.2 CH.sub.2 NH CH.sub.3 H reddish blue 370 HO.sub.2 CCH.sub.2 CH.sub.2 NH C.sub.2 H.sub.5 H reddish blue 371 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3 CH.sub.3 reddish blue__________________________________________________________________________
TABLE 21__________________________________________________________________________ #STR338## -Ex. No. E.sup.1 E.sup.2 E.sup.3 E.sup.4 E.sup.5 Hue on wool__________________________________________________________________________ 372 HO.sub.2 CCH.sub.2 CH.sub.3 H SO.sub.3 H bluish black - 372 HO.sub.2 CCH.sub.2 C.sub.2 H.sub.5 H SO.sub.3 H bluish black - 374 HOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 H SO.sub.3 H bluish black - 375 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3 H H blue - 376 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 H H blue - 377 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3 H H reddish blue - 378 HO.sub.3 SOCH.sub. 2 CH.sub.2 C.sub.2 H.sub.5 H H reddish blue - 379 HO.sub.3 SOCH.sub. 2 CH.sub.2 C.sub.2 H.sub.5 SO.sub.2 N(C.sub.2 H.sub.4 OCH.sub.3).sub.2 H reddish blue - 380 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 COC.sub.6 H.sub.5 H H reddish blue 381 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 COC.sub.6 H.sub.5 Cl H reddish blue 382 CH.sub.2 .dbd.CH CH.sub.3 SO.sub.2 C.sub.6 H.sub.5 H SO.sub.3 H bluish black 383 CH.sub.2 .dbd.CH C.sub.2 H.sub.5 SO.sub.2 C.sub.6 H.sub.5 H SO.sub.3 H bluish black - 384 C.sub.2 H.sub.5 SO.sub.2 C.sub.6 H.sub.5 H H blue - 385 (HOC.sub.2 H.sub.4).sub.2 N CH.sub.3 H SO.sub.3 H bluish black - 386 CH.sub.2 .dbd.CHCH.sub.2 CH.sub.3 H SO.sub.3 H bluish black - 387 CH.sub.2 .dbd.CHCH.sub.2 C.sub.2 H.sub.5 H SO.sub.3 H bluish black - 388 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CO.sub.2 C.sub.6 H.sub.5 H H blue 389 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CO.sub.2 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 H H blue 390 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CO.sub.2 CH.sub.2 CH.sub.2 OC.sub.6 H.sub.5 H H blue 391 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CO.sub.2 CH.sub.3 H H blue - 392 C.sub.2 H.sub.5 H H reddish blue__________________________________________________________________________
TABLE 22__________________________________________________________________________ #STR353## -Ex. No. E.sup.1 E.sup.2 E.sup.3 Y Hue on wool__________________________________________________________________________393 HOCH.sub.2 CH.sub.2 NH CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 CO blue 394 (HOCH.sub.2 CH.sub.2).sub.2 N CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 CO blue - 395 CH.sub.3 CO blue # - 396 C.sub.2 H.sub.5 CO blue # - 397 HOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CO blue # - 398 CH.sub.2 .dbd.CHCH.sub.2 C.sub.2 H.sub.5 CO blue # - 399 CH.sub.2 .dbd.CHCH.sub.2 C.sub.2 H.sub.5 CH.sub.2 blue - 400 HO.sub.3 SOCH.sub.2 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.2 OCH.sub.3 CH.sub.2 blue 401 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 C.sub.6 H.sub.5 CH.sub.2 blue 402 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CO blue 403 HO.sub.3 SOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CH.sub.2 C.sub.6 H.sub.5 CO blue 404 HO.sub.2 CCH.sub.2 CH.sub.3 CH.sub.2 CH.sub.2 C.sub.6 H.sub.5 CO blue - 405 HO.sub.2 CCH.sub.2 C.sub.2 H.sub.5 CH.sub.2 blue - 406 HO.sub.2 CCH.sub.2 CH.sub.3 CH.sub.2 blue - 407 HO.sub.2 CCH.sub.2 CH.sub.3 CO blue # - 408 HO.sub.2 CCH.sub.2 C.sub.2 H.sub.5 CO blue # - 409 CH.sub.3 CO blue # - 410 HOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CO blue # - 411 HOCH.sub.2 CH.sub.2 C.sub.2 H.sub.5 CH.sub.2 blue - 412 H.sub.2 C.dbd.CH C.sub.2 H.sub.5 CH.sub.2 blue__________________________________________________________________________
EXAMPLE 413
a) 16.9 g of the diazo component of formula ##STR370## were dissolved in 30 ml of water at pH 3.5 using 5.9 g of sodium bicarbonate, and the solution was then cooled down with ice to 0.degree. C. and admixed with 12.6 ml of 36% strength hydrochloric acid. The suspension was then diazotized with 18.3 ml of 3.33 N aqueous sodium nitrite solution. The resulting diazonium salt mixture was mixed with a freshly precipitated suspension of 20.5 g of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid monosodium salt (pH about 1) after excess nitrous acid had been destroyed. The mixture was coupled overnight to obtain a suspension of the red dye of the formula ##STR371## b) The suspension obtained was adjusted to pH 10 at room temperature and the resulting solution was stirred at pH 10 for 3.5 h. The pH was then adjusted to 7, 0.06 mol of the conventionally prepared diazonium salt of diethyl 2-aminoterephthalate was added in the form of a solution, and the mixture was subsequently stirred for 3 h at pH 6-7. The resulting blue dye was precipitated with sodium chloride at pH 6-6.5 and isolated in a conventional manner.
Drying left 50 g of the dye of the formula ##STR372## which still comprised a total of 16 g of sodium chloride and water of crystallization. The dye forms a blue solution in water with absorption maxima in the visible region at 396 and 582 nm and a shoulder at 625 nm.
Dark blue to bluish black dyeings are obtained on wool according to the customary dyeing methods for anionic wool dyes. The buildup capacity and also the wet- and lightfastness properties on wool are excellent.
EXAMPLE 414
The dye described in Example 413 a) as a suspension was neutralized. Then 0.06 mol of the diazonium salt solution of diethyl 2-aminoterephthalate was added while the pH of the coupling solution was maintained at from 5.5 to 7.0 using sodium bicarbonate. The ready-prepared coupling mixture was spray-dried at pH 6.5, affording the dye of the formula ##STR373## as a bluish black powder (together with the salts formed in the course of the reaction) in the form of the sodium salt. The powder forms a blue solution in water (.lambda..sub.max in water: 397 and 585 nm, shoulder at 626 nm) and dyes wool according to the dyeing processes customary for wool dyes (acetic acid to formic acid medium) in a blue to bluish black shade having excellent light- and wetfastness properties.
EXAMPLE 415
a) The dye described in 413 a) as a suspension was neutralized.
Then 0.06 mol of the diazonium salt of 4-aminodiphenyl sulfone (diazotized in water in a conventional manner with hydrochloric acid and sodium nitrite) was added and the pH of the coupling mixture was maintained at 5-7. The mixture was subsequently stirred for 1 h at pH 6.5 and thereafter spray-dried, affording a black powder comprising 51 g of the dye of the formula ##STR374## in the form of the sodium salt (.lambda..sub.max in water: 600 nm, at pH 4-6). The dye dyes wool in a deep bluish black shade having excellent wetfastness properties and good lightfastness.
b) However, on adjusting the blue reaction solution to pH 10 and subsequently stirring it at room temperature for 4 h, the resulting novel dye of the formula ##STR375## was readily precipitated with sodium chloride at pH 6.5. This dye dyes wool according to the customary dyeing processes (acetic-formic acid medium) in a dark blue to black shade having excellent wetfastness properties, similarly to the dye described under a). Blue dyeings are obtained on leather (.lambda..sub.max in water: at pH .about.4 to 5: 392 and 596 nm)
EXAMPLE 416
The dye described in Example 413 a) as a suspension was neutralized at room temperature. Then 0.06 mol of the diazonium salt of the formula ##STR376## was added in the form of an aqueous solution and the pH of the coupling reaction was held within the range from 5.5 to 7.5 using sodium bicarbonate, affording a solution of the dye of the formula ##STR377##
Spray drying at a pH from about 6 to 6.5 gave a black powder which forms a blue solution in water. The absorption spectrum in the visible region had maxima at 394 nm and 584 nm and also a shoulder at about 620 nm.
Adjusting the dye solution to pH 10 and stirring at room temperature for 4 h yielded the novel dye of the formula ##STR378## (.lambda..sub.max in water at pH 4-6: 581 nm, shoulder at about 618 nm). This dye could be precipitated with sodium chloride at pH 6-7.5 and isolated in a conventional manner.
Both dyes dye wool in a dark blue to navy shade having excellent wet- and lightfastness properties. The exhaustion capacity is good.
EXAMPLE 417
a) 29.6 g of the diazo component of the formula ##STR379## were dissolved using 72 ml of 18.5% strength by weight hydrochloric acid. Ice was added, followed at 0-7.degree. C. by 37.5 ml of 23% strength aqueous sodium nitrite solution. The mixture was subsequently stirred at 0-7.degree. C. for 30 min, excess nitrous acid was destroyed, and then 46 g of an aqueous solution, adjusted to pH 6, of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid were added dropwise over 1.5 h with very thorough stirring, and the mixture was subsequently stirred overnight, affording the red dye of the formula ##STR380## as a thick suspension. The dye gives a red solution in water and has an absorption maximum at 518 nm in the visible spectrum.
b) Then a diazonium salt solution was added, which had been prepared as follows: 17.7 g of the diazo component of the formula ##STR381## were diazotized with water, dilute hydrochloric acid and sodium nitrite and also a little glacial acetic acid in a conventional manner at from 10 to 20.degree. C. The reaction mixture was neutralized with dilute sodium hydroxide solution, affording the dye of the formula ##STR382## which was precipitated with sodium chloride and then isolated in a conventional manner. The black powder dissolves in water with a reddish blue color (.lambda..sub.max : 570 nm, shoulder at 625 nm) and dyes wool (acetic- to formic-acid medium) in a deep reddish blue shade having very good lightfastness.
The dyes listed in the table which follows are obtained in a similar manner.
TABLE 23 - ##STR383## Ex. No. E.sup.1 E.sup.2 E.sup.3 E.sup.4 E.sup.5 E.sup.6 Hue on wool 418 H C.sub.6 H.sub.5 SO.sub.2 SO.sub.3 H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.2 CH.sub.3 reddish blue 419 H ##STR384## SO.sub.3 H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.2 CH.sub.3 reddish blue 420 H ##STR385## H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.2 CH.sub.3 reddish blue 421 CH.sub.3 ##STR386## CH.sub.3 CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.2 CH.sub.3 reddish blue 422 H ##STR387## H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.2 CH.sub.3 reddish blue 423 H ##STR388## H CO.sub.2 C.sub.2 H.sub.5 H CO.sub.2 CH.sub.2 CH.sub.3 reddish blue 424 H ##STR389## H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.2 CH.sub.3 reddish blue 425 H ##STR390## H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.2 CH.sub.3 reddish blue 426 H ##STR391## H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3 blue 427 H ##STR392## H CO.sub.2 C.sub.2 H.sub.5 H CO.sub.2 C.sub.2 H.sub.5 blue 428 H C.sub.6 H.sub.5 OSO.sub.2 H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3 blue 429 H C.sub.6 H.sub.5 OSO.sub.2 H CO.sub.2 C.sub.3 H.sub.7 H CO.sub.2 CH.sub.3 blue 430 H C.sub.6 H.sub.5 OSO.sub.2 H CO.sub.2 CH.sub.3 H CO.sub.2 C.sub.3 H.sub.7 blue 431 H ##STR393## H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3 blue 432 CH.sub.3 ##STR394## H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3 blue 433 H ##STR395## H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3 reddish blue 434 C.sub.6 H.sub.5 SO.sub.2 H H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3 blue 435 C.sub.6 H.sub.5 SO.sub.2 SO.sub.3 H H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3 blue 436 C.sub.6 H.sub.5 SO.sub.2 H SO.sub.3 H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3 dark blue 437 C.sub.6 H.sub.5 SO.sub.2 SO.sub.3 H H CO.sub.2 C.sub.2 H.sub.5 H CO.sub.2 C.sub.2 H.sub.5 dark blue 438 ##STR396## SO.sub.3 H H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3 dark blue 439 ##STR397## H H CO.sub.2 C.sub.2 H.sub.5 H CO.sub.2 C.sub.2 H.sub.5 dark blue 440 ##STR398## H H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3 dark blue 441 C.sub.6 H.sub.5 CO Cl H CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3 blue 442 CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3 ##STR399## SO.sub.3 H H reddish blue 443 CO.sub.2 CH.sub.3 H CO.sub.2 CH.sub.3 ##STR400## H H reddish blue 444 CO.sub.3 CH.sub.3 H CO.sub.2 CH.sub.3 ##STR401## H H reddish blue 445 H ##STR402## H ##STR403## H H reddish blue 446 H (CH.sub.3).sub.2 N--SO.sub.2 H ##STR404## H H reddish blue 447 H ##STR405## H ##STR406## SO.sub.3 H H navy 448 CH.sub.3 ##STR407## H ##STR408## SO.sub.3 H H navy 449 H (C.sub.2 H.sub.5).sub.2 N--SO.sub.2 H ##STR409## H SO.sub.3 H navy 450 H ##STR410## H ##STR411## H H blue 451 H ##STR412## H ##STR413## H H reddish blue 452 H C.sub.6 H.sub.5 OSO.sub.2 H ##STR414## H H reddish blue 453 H CH.sub.2 .dbd.CHSO.sub.2 H ##STR415## H H navy 454 H CH.sub.2 .dbd.CHSO.sub.2 H ##STR416## H H navy 455 H CH.sub.2 .dbd.CHCH.sub.2 SO.sub.2 H ##STR417## H H navy 456 H CH.sub.2 .dbd.CHSO.sub.2 H ##STR418## H H navy 457 H CH.sub.2 .dbd.CHSO.sub.2 H ##STR419## H H navy 458 H C.sub.6 H.sub.5 SO.sub.2 H ##STR420## H H reddish blue 459 H C.sub.6 H.sub.5 SO.sub.2 H ##STR421## H H reddish blue 460 H C.sub.6 H.sub.5 SO.sub.2 SO.sub.3 H ##STR422## H H reddish blue 461 H ##STR423## H ##STR424## H H reddish blue 462 ##STR425## H H ##STR426## H H reddish blue 463 ##STR427## H H ##STR428## H H reddish blue 464 CH.sub.3 HO.sub.3 SOCH.sub.2 CH.sub.2 SO.sub.2 CH.sub.3 ##STR429## H H navy 465 H CH.sub.3 O.sub.2 C H ##STR430## SO.sub.3 H H reddish blue 466 H ##STR431## H ##STR432## SO.sub.3 H H reddish blue 467 SO.sub.3 H (C.sub.2 H.sub.5).sub.2 NSO.sub.2 H ##STR433## H H reddish blue 468 SO.sub.3 H ##STR434## H ##STR435## H H reddish blue
EXAMPLE 469
225 g of 1-aminonaphthalene-3-sulfonic acid were dissolved in 800 ml of water at pH 7 (sodium hydroxide solution) and 50.degree. C. 258 g of 4-acetaminobenzenesulfonyl chloride were then added a little at a time with very thorough stirring while the pH of the mixture was maintained within the range from 6.0 to 7.2 by the simultaneous addition of 60 g of sodium carbonate. The mixture was subsequently stirred at pH 7 for 1 hour, then adjusted to pH 9 with sodium hydroxide solution and admixed with 160 g of dimethyl sulfate added dropwise over 15 min while the reaction pH was maintained at >8 to 9 using sodium hydroxide solution. The resulting suspension was subsequently stirred at 45-50.degree. C. for 2 h, then 100 ml of 25% strength by weight aqueous ammonia solution were added, and the dye was precipitated with 250 g of sodium chloride and filtered off with suction. The filter residue was taken up with 300 ml of methanol and 500 ml of water, the mixture was admixed with 135 g of concentrated sulfuric acid and stirred for 6 h under evaporative cooling. Methanol was then distilled off with a little water, the suspension was stirred overnight until cold, the precipitate was isolated on a suction filter, washed with a little ice-cold, highly dilute hydrochloric acid and dried to leave 350 g of the diazo component of the formula ##STR436##
The H--NMR spectrum recorded in hexadeuterodimethyl sulfoxide showed the --N--CH.sub.3 signal at 3.18 ppm (singlet of the CH.sub.3 protons).
EXAMPLE 470
225 g of 1-aminonaphthalene-3-sulfonic acid were reacted with 258 g of 4-acetaminosulfonyl chloride similarly to Example 469 and alkylated with dimethyl sulfate, and then excess dimethyl sulfate was destroyed with ammonia. Sodium hydroxide solution was then used to render the reaction mixture strongly alkaline (pH >12 to about 13), and the mixture was stirred at 80 to 100.degree. C. for 5 h while the pH was held at >12. Thereafter it was slowly acidified with hydrochloric acid to a pH of about 1 to 1.5 and cooled down to room temperature. After stirring overnight the resulting suspension was filtered off with suction and washed once with very dilute hydrochloric acid, affording the diazo component of the formula ##STR437## in similar yield and comparable purity.
The following compounds are obtained in a similar manner:
__________________________________________________________________________Ex. No. E__________________________________________________________________________ 471 472 CHTR438## .sub.3 (S., 3.14 ppm) and C.sub.2 H.sub.5 - 473 474 CH.sub.3 (S., 3.18 ppm) C.sub.2 H.sub.5 - 475 476 CH.sub.3 (S., 3.06 ppm) C.sub.2 H.sub.5 - 477 478 CH.sub.3 C.sub.2 H.sub.5 - 479 singlet at 3.05 ppm__________________________________________________________________________
EXAMPLE 480
250 g of N-ethylaminobenzene-4-sulfonic acid were stirred together with 800 ml of water and adjusted to pH 7 at 50-55.degree. C. using sodium hydroxide solution. Then 306 g of 4-acetaminobenzenesulfonyl chloride were added a little at a time with vigorous stirring while the reaction mixture pH was maintained within the range from 6 to 7.5 using sodium carbonate. The mixture was subsequently stirred for 1 h, then adjusted to pH 12.5-14 and subsequently stirred under evaporative cooling at a pH >12.5 to 13 for 7 h during which further sodium hydroxide solution was added. The mixture was then acidified with hydrochloric acid at pH 1 and 70.degree. C., cooled down to room temperature and allowed to crystallize overnight. The precipitated product was filtered off with suction and washed with cold dilute hydrochloric acid. Drying left 400 g of the diazo component of the formula ##STR443##
The H--NMR spectrum of the product shows the protons of the C.sub.2 H.sub.5 group as a quartet at 3.51 ppm (quartet of the --CH.sub.2 -- group) 0.9 ppm (triplet of the --CH.sub.3 -- group) recorded in dimethyl sulfoxide.
Favorable results are also obtained with the following dyes:
__________________________________________________________________________Dye No.__________________________________________________________________________ F1 navy .sub.max : 587 nm - F2 .sub.max : 598 nm - F3 navy .sub.max : 600 nm - F4 .sub.max : 596.5 nm - F5 greenish blue - F6 .sub.max : 584 nm - F7 .sub.max : 587 nm shoulder: 620 nm - F8 .sub.max : 584 nm shoulder: .about.615 nm - F9 navy .sub.max : 600 nm - F10 .sub.max : 584 nm - F11 .sub.max : 596 nm - F12 .sub.max : 598 nm - F13 .sub.max : 597 nm - F14 .sub.max : 594 nm - F15 navy 58## - F16 bluish black - F17 .sub.max : 596 nm - F18 navy .sub.max : 598 nm - F19 .sub.max : 597 nm - F20 navy 63## - F21 .sub.max : 581 nm shoulder .about.618 nm - F22 .sub.max : 583 nm shoulder at 620 nm - F23 .sub.max : 582 nm shoulder 625 nm - F24 .sub.max : 599 nm - F25 .sub.max : 582 nm - F26 .sub.max : 594 nm - F27 .sub.max : 597 nm - F28 .sub.max : 595 nm - F29 .sub.max : 594 nm - F30 navy 73## - F31 dark blue - F32 navy .sub.max : 580 nm - F33 dark blue .sub.max : 579 nm 401 nm shoulder 622 nm - F34 .sub.max : 572 nm shoulder .about.625 nm reddish blue - F35 .sub.max : 395 nm 582 nm shoulder 623 nm - F36 bluish black - F37 .sub.max : 402 nm 574 nm navy shoulder .about.625 nm - F38 navy 81## - F39 navy 82## - F40 dark blue - F41 dark blue - F42 reddish blue - F43 reddish blue - F44 navy 87## - F45 navy 88## - F46 navy 89## - F47 .sub.max : 576 nm shoulder 615 nm - F48 .sub.max : 585 nm shoulder .about.620 nm - F49 .sub.max : 576 nm shoulder .about.615 nm - F50 .sub.max : 594 nm - F51 .sub.max : 594 nm - F52 .sub.max : 599 nm - F53 .sub.max : 599 nm - F54 dark blue - F55 navy 98## - F56 navy 99## - F57 .sub.max : 596 nm - F58 .sub.max : 597 nm - F59 .sub.max : 600 nm - F60 .sub.max : 574 nm shoulder .about.615 nm - F61 .sub.max : 598 nm - F62 .sub.max : 598 nm - F63 .sub.max : 598 nm - F64 .sub.max : 598 nm - F65 .sub.max : 575 nm navy - F66 .sub.max : 584 nm shoulder 620 nm - F67 .sub.max : 583 nm shoulder 625 nm - F68 .sub.max : 583 nm shoulder 625 nm - F69 .sub.max : 615 nm - F70 .sub.max : 615 nm - F71 .sub.max : 584 nm shoulder .about.625 nm - F72 reddish blue - F73 dark blue - F74 dark blue - F75 navy 18## - F76 navy 19## - F77 navy 20## - F78 .sub.max : 575 nm (400 nm) shoulder 620 nm navy - F79 .sub.max : 581 nm (397 nm) shoulder 620 nm - F80 .sub.max : 591 nm (405 nm) shoulder 638 nm - F81 navy 24## - F82 reddish navy .sub.max : 560 nm (405 nm) shoulder: about 605 nm - F83 navy 26## - F84 navy 27## - F85 navy 28## - F86 navy 29## - F87 navy 30## - F88 navy 31## - F89 navy 32## - F90 navy533##__________________________________________________________________________

Number	Date	Country
0 043 560	Jan 1982	EPX
0 048 692	Mar 1982	EPX
0 559 617	Feb 1993	EPX
739 468	Jan 1933	FRX
1 558 340	Feb 1969	FRX
1558679	Feb 1969	FRX
34 20 467	Jun 1984	DEX
65 651	Nov 1992	DEX
195 30 176	Aug 1995	DEX
192 048	Oct 1937	CHX
192 050	Oct 1937	CHX
192 049	Oct 1937	CHX
92 14791	Sep 1992	WOX

Acid disazo dyes as well as sulphonamides as their intermediate product

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Entry
Dyes and Pigments 24 (1994) 125-141, Elsevier Science Limited, England, Printed in Great Britain.
Chemical Abstracts, vol. 99, No. 4, Jul. 25, 1983, Abs. No. 23999r, "disazo reactive dyes".