Copper-complex formazan compounds having a fiber-reactive group of the vinylsulfone series, suitable as dyestuffs

Copper complex formazan compounds of the general formula (1) ##STR1## in which A and B both independently of one another denote a benzene or naphthalene ring, both of which can be substituted by substitutents customary in fiber-reactive dyestuffs, these substituents being, in particular, the groups Z which confer water-solubility and fiber-reactive groups --SO.sub.2 --Y shown in formula (1); PA1 Z is a group which confers water-solubility, such as a carboxy of sulfo group, and can be bonded to A, B and R; PA1 m is the number 1, 2, 3 or 4; PA1 R is an aryl radical, for example phenyl or naphthyl, which can be substituted by one or two groups Z of the above meaning and/or by halogen, lower alkyl and/or lower alkoxy, or is a lower alkyl radical, which can be substituted by halogen, sulfo and/or carboxy; PA1 the group --SO.sub.2 --Y can be bonded to A and B; PA1 n is the number 1 or 2; PA1 Y is vinyl or an ethyl group, which is substituted in the .beta.-position by a substituent which can be eliminated by alkali; PA1 X is an oxygen atom or a carbonyloxy or sulfo group; PA1 M is hydrogen or a salt-forming metal, such as an alkali metal. The copper complex formazan compounds of the formula (1) are particularly suitable as fiber-reactive dyestuffs for dyeing materials containing hydroxy groups and/or carboxamide groups, such as, for example, wool and synthetic polyamide fiber materials, and in particular cellulose fiber materials, such as cotton, which they dye in deep fast shades.

The invention relates to the technical field of fiberreactive dyestuffs. 
Copper complex formazan dyestuffs of the triphenylformazan type having a 
fiber-reactive group from the vinylsulfone series which are capable, for 
example, of dyeing cellulose fiber materials in green to blue shades are 
known, for example, from British Patent No. 1,194,504 and U.S. Pat. Nos 
4,370,145 and 4,757,135. 
Novel copper complex formazan compounds which, for example, are capable of 
dyeing cellulose fiber materials in claret-colored and violet shades have 
now been found with the present invention These novel formazan compounds 
correspond to the general formula (1) 
##STR2## 
in which: A can be substituted by one or two groups Z, which is defined 
below, and/or by the group shown of the formula --SO.sub.2 --Y, which is 
defined below, and is a phenylene radical or a naphthylene radical, both 
of which can be substituted by substituents, such as, for example, one 
substituent, these belonging to the following group of substituents: 
halogen, such as fluorine, chlorine and bromine, alkyl having 1 to 5 bon 
atoms, such as methyl and ethyl, alkoxy having 1 to 5 carbon atoms, such 
as methoxy and ethoxy, alkylsulfonyl having 1 to 4 carbon atoms, which can 
be substituted, such as, for example, by hydroxy or sulfo, such as, for 
example, methylsulfonyl, ethylsulfonyl, .beta.-hydroxyethylsulfonyl and 
.beta.-sulfoethylsulfonyl, phenylsulfonyl, sulfamoyl, sulfamoyl which is 
mono- or disubstituted by alkyl having 1 to 4 carbon atoms, 
cycloalkylsulfamoyl having a cycloalkyl radical having 5 to 8 carbon 
atoms, such as, for example, cyclohexylsulfamoyl, nitro, alkanoylamino 
having 2 to 5 carbon atoms, such as acetylamino and propionylamino, 
benzoylamino, which can be substituted by 1 or 2 substituents from the 
group comprising sulfo, carboxy, chlorine, methyl, ethyl, methoxy and 
ethoxy, alkanoylamino having 2 to 5 carbon atoms, which is substituted, 
such as, for example, by sulfo, carboxy and/or hydroxyl, such as, for 
example, succinylamido, alkylsulfonylamino having 1 to 4 carbon atoms, 
phenylsulfonylamino, (.beta.-sulfatoethyl)sulfonylamino and 
N-methyl-N-(.beta.-sulfatoethylsulfonyl)-amino; 
the group X and the N atom are bonded to the aromatic nucleus of A in the 
ortho-position relative to one another; 
B has one of the meanings of A and can be identical to A or different from 
A; 
the O atom and the N atom are bonded to the aromatic nucleus of B in the 
ortho-position relative to one another; 
R is an aryl radical, such as a phenyl or naphthyl radical, which can be 
substituted by one or two groups Z, which is defined below, and/or by 
substituents, such as one or two substituents, which belong to the 
following group of substituents: halogen, such as fluorine, chlorine and 
bromine, alkyl having 1 to 5 carbon atoms, such as methyl and ethyl, and 
alkoxy having 1 to 5 carbon atoms, such as methoxy and ethoxy, or 
R is a straight-chain or branched alkyl radical having 1 to 6, preferably 1 
to 4, carbon atoms, such as the methyl, ethyl and propyl radical, which 
can be substituted by halogen, such as chlorine, bromine and fluorine, 
sulfo and/or carboxy , such as, for example, the trifluoromethyl group; 
Z is a group which confers water-solubility, such as, for example, the 
sulfo, carboxy and phosphonic acid group, and of these preferably the 
sulfo group, as a substituent on A, B and R, if appropriate in addition to 
the abovementioned substituents of A, B and R, and is contained in the 
formazan molecule one to four times, according to the definition of m 
below, and is bonded to an aromatic carbon atom or to an aliphatic carbon 
atom of A, B and R or a substituent thereof, such as, for example, also to 
an aromatic carbon atom via a methylene or ethylene bridge, preferably, 
however, to an aromatic carbon atom, it being possible for Z, if it is 
contained in the molecule 2, 3 or 4 times, to have different meanings 
within the abovementioned meanings; 
m is the number 1, 2, 3 or 4, preferably 1, 2 or 3; 
Y is the vinyl group or ethyl group, which contains a substituent in the 
.beta.-position, which can be eliminated by means of an alkali, the group 
--SO.sub.2 --Y, as a substituent on A and B if appropriate in addition to 
the abovementioned substituents of A and B, being contained in the 
formazan molecule once or twice, according to the definition of n below, 
and being bonded to an aromatic carbon atom of A and B or to an aliphatic 
carbon atom of a substituent thereof, such as, for example, also to an 
aromatic carbon atom via a methylene or ethylene bridge, but preferably to 
an aromatic carbon atom, it being possible for the groups --SO.sub.2 --Y, 
if they are contained in the molecule twice, to have different meanings 
within the abovementioned meanings; 
n is the number 1 or 2; 
X is an oxygen atom or a carbonyloxy group of the formula --CO--O--, or a 
group of the formula --SO.sub.3.sup.(-) bonded only to the radical A; and 
M.sup.(+) is a hydrogen atom or an alkali metal or the equivalent of a 
divalent metal, such as an alkaline earth metal, for example of calcium or 
magnesium, preferably a hydrogen atom, and in particular sodium, potassium 
or lithium. 
The compounds of the general formula (1) according to the invention can be 
either in acid form or in the form of their salts, in particular the 
abovementioned alkali metal and alkaline earth metal salts. They are used, 
preferably in the form of the alkali metal salts, for dyeing (including 
printing) materials containing hydroxy groups, amino groups and/or 
carboxamide groups, in particular fiber materials. 
Preferably, A is a benzene nucleus which can be substituted by, in addition 
to the group Z and/or the group --SO.sub.2 --Y, where Y is preferably the 
vinyl group and particularly preferably the .beta.-sulfatoethyl group, a 
substituent from the group comprising chlorine, bromine, nitro, methyl, 
ethyl, methoxy, ethoxy, methylsulfonyl, ethylsulfonyl, sulfamoyl, 
N,N-dimethylsulfamoyl, phenylsulfonyl, .beta.-hydroxyethylsulfonyl, 
.beta.-sulfoethylsulfonyl, acetylamino, benzoylamino, succinylamino, 
(.beta.-sulfato-ethylsulfonyl)-amino and 
N-methyl-N-(.beta.-sulfatoethyl-sulfonyl)-amino. Preferably, B is the 
benzene ring which can be substituted by, in addition to Z and/or a group 
--SO.sub.2 --Y, where Y is preferably the vinyl group and particularly 
preferably the .beta.-sulfatoethyl group, one or two substituents from the 
group comprising chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, 
methylsulfonyl, ethylsulfonyl, sulfamoyl, N,N-dimethylsulfamoyl, 
phenylsulfonyl, .beta.-hydroxyethylsulfonyl, .beta.-sulfoethylsulfonyl, 
acetylamino, benzoylamino, succinylamino, 
(.beta.-sulfato-ethylsulfonyl)-amino and 
N-methyl-N-(.beta.-sulfatoethylsulfonyl)-amino. 
.beta.-Substituents of the ethyl radical which can be eliminated by means 
of an alkali to form the vinyl group in the radical Y are, for example, a 
halogen atom, such as a chlorine or bromine atom, an alkanoyloxy group 
having 2 to 5 carbon atoms, such as the acetoxy group, an aroyloxy group, 
such as the benzoyloxy or sulfobenzoyloxy group, an arylsulfonyloxy group, 
such as the p-methylphenylsulfonyloxy group, a lower dialkylamino group, 
such as the dimethylamino or diethylamino group, a phosphato group, a 
thiosulfato group or a sulfato group. Preferably, Y is the vinyl group and 
in particular the .beta.-sulfatoethyl group. 
Particularly preferred compounds of the general formula (1) are those in 
which A denotes a naphthylene or phenylene radical which can be 
substituted by--in addition to the groups Z and/or --SO.sub.2 --Y 
mentioned--1 or 2, preferably one, substituent from the group comprising 
chlorine, bromine, nitro, methyl, ethyl, methoxy, ethoxy, methylsulfonyl, 
ethylsulfonyl, .beta.-sulfoethylsulfonyl, sulfamoyl and 
N,N-dimethylsulfamoyl, and B denotes a naphthylene or phenylene radical 
which can substituted by--in addition to the groups Z and/or --SO.sub.2 
--Y--1 or 2 substituents from the group comprising chlorine, methyl, 
ethyl, methoxy, ethoxy, methylsulfonyl, ethylsulfonyl and nitro. Z here is 
preferably a sulfo group, one or two of which are bonded to A and/or one 
or two of which are bonded to B, and the group --SO.sub.2 --Y is bonded to 
A or to B or, in the case where n is 2, to A and B. 
Preferably, n is the number 1, and the group --SO.sub.2 --Y is 
preferably bonded to B. Compounds of the general formula (1) which are 
furthermore preferred are those in which R is methyl, ethyl, phenyl or 
naphthyl, preferably methyl or phenyl. Particularly preferred compounds of 
the formula (1) are those in which A denotes the phenylene radical, which 
can be substituted by a methyl, ethyl, methoxy, ethoxy, nitro, 
.beta.-sulfoethylsulfonyl, methylsulfonyl or ethylsulfonyl group or a 
chlorine atom, B denotes the phenylene radical, which is substituted by a 
group --SO.sub.2 --Y, m represents the number 1, 2 or 3, Z denotes the 
sulfo group and is bonded to A and/or B, X denotes the oxy or carbonyloxy 
radical and M and Y have the abovementioned particularly preferred 
meanings. 
Those copper complex formazan compounds according to the invention which 
correspond to the following general formulae (1a) (1b) and (1c) can be 
singled out in particular: 
##STR3## 
In these formulae: R.sup.1 is a hydrogen atom or a sulfo group, but at 
least one R.sup.1 is a sulfo group; 
R.sup.2 is hydrogen or .beta.-sulfatoethylsulfonyl; 
R* is hydrogen, sulfo, chlorine, methylsulfonyl, ethylsulfonyl, carboxy , 
nitro or methyl; 
R is methyl or phenyl; 
X has the abovementioned meaning and is preferably carbonyloxy or oxy; 
Y has one of the abovementioned particularly preferred meanings; 
M is hydrogen or an alkali metal, such as sodium, potassium or lithium. 
The substituents "sulfo", "carboxy ", "phosphato", "thiosulfato" and 
"sulfato" include both the acid form thereof and the salt form thereof. 
Accordingly, sulfo groups denote groups corresponding to the general 
formula --SO.sub.3 M, carboxy groups denote groups corresponding to the 
general formula --COOM, phosphato groups denote groups corresponding to 
the general formula --OPO.sub.3 M.sub.2, thiosulfato groups denote groups 
corresponding to the general formula --S--SO.sub.3 M and sulfato groups 
denote groups corresponding to the general formula --OSO.sub.3 M, in each 
case where M has the abovementioned meaning. 
The present invention furthermore relates to processes for the preparation 
of the abovementioned and defined compounds of the general formula (1). 
The processes comprise reacting an aromatic hydrazone compound of the 
general formula (2) 
##STR4## 
in which A, R and Z have the abovementioned meanings, 
X.sup.1 represents the hydroxy , carboxy or sulfo group, 
Y.sup.1 has one of the meanings given for Y or is the .beta.-hydroxyethyl 
group, 
n' denotes the number zero or 1, 
m' denotes the number zero, 1, 2 or 3, 
Q is a hydrogen atom or a substituent which can replaced by azo coupling, 
such as, for example, the carboxy group (which is obtainable from the 
corresponding starting compound where Q is carbalkoxy by alkaline 
hydrolysis), the group X.sup.1 and the amino group being bonded to A in 
the ortho-position relative to one another, 
with the diazonium compound of an aromatic amine of the general formula (3) 
##STR5## 
in which B, Z and Y.sup.1 have one of the abovementioned meanings, the 
hydroxy group and the amino group being bonded to B in the ortho-position 
relative to one another, 
m" represents the number zero, 1 or 2 and 
n" denotes the number zero or 1, 
the sum of (m'+m") being equal to the meaning of m and the sum of (n'+n") 
being equal to the meaning of n, in the presence of a copper-donating 
agent, 
and, in the case where one or both of the groups Y.sup.1 represent the 
.beta.-hyiroxyethyl group, converting this (these) group(s) in the copper 
formazan compound formed into the .beta.-sulfatoethylsulfonyl-copper 
complex formazan compound according to the invention by procedures 
analogous to known procedures by means of a sulfating agent, such as 
sulfuric acid or amidosulfonic acid in pyridine. 
The customary procedure analogous to known procedures for the preparation 
of metal complex formazan compounds can be used in the synthesis of the 
compounds (1) according to the invention. Preferably, the process 
according to the invention is carried out at a pH of 3 to 8, in particular 
4.5 to 6, and at a temperature between about 0.degree. C. and 30.degree. 
C., it also being possible for the reaction temperature to be increased up 
to 60.degree. C. during the coupling step. The reaction components can be 
added as desired, but the process can be carried out particularly easily 
as a three-component reaction. 
Examples of copper-donating compounds are the simple and complex salts of 
copper, such as, for example, copper sulfate, copper chloride, copper 
acetate or copper carbonate, and the copper salts of salicylic acid or 
tartaric acid. 
If the copper salts of mineral acids are used, the reaction is 
advantageously carried out in the presence of an acid-buffering agent, 
such as, for example, an alkali metal or alkaline earth metal hydrox-ide 
or carbonate or an alkali metal salt of a lower alkanecarboxylic acid, 
such as acetic acid, or a basic alkali metal salt of phosphoric acid. 
These alkali metal or alkaline earth metal compounds are, in particular, 
the sodium, potassium, lithium and calcium compounds, and preferably, for 
example, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium, 
lithium and potassium carbonate, calcium carbonate, sodium bicarbonate, 
sodium acetate, disodium hydrogen phosphate, trisodium phosphate and 
magnesium oxide. 
The copper-donating agent is used in equimolar amounts, so that one copper 
atom is present per compound of the formula (1) to be formed. The coupling 
reaction and metallization usually already proceed to completion at room 
temperature, but a reaction temperature of up to 60.degree. C. can also be 
chosen. 
The compounds (1) according to the invention can be prepared, for example, 
by a procedure in which a hydrazone compound of the general formula (2) is 
dissolved in water with an alkali, such as sodium hydroxide solution or 
sodium carbonate, at room temperature; the pH is preferably kept at 5 to 
7. The diazonium salt solution of the amine of the general formula (3) is 
then added. The reaction is preferably carried out at a pH between 4 and 
7, in particular between 4.5 and 6. It is preferably carried out at a 
reaction temperature of not more than 20.degree. C., in particular not 
more than 15.degree. C. The equimolar amount of the copper-donating agent, 
for example as copper sulfate in aqueous solution, is added at the same 
time as, i.e. also--together with--or after the addition of the diazonium 
compound. The metallization reaction is also advantageously carried out at 
a pH of 4 to 6, in particular 4.5 to 6. The metallization and coupling 
reaction take place simultaneously. The metallization reaction proceeds 
relatively rapidly. Before isolation of the metal complex formazan 
compound prepared, however, it is advantageous to heat the reaction 
solution up to 60.degree. C. and to clarify it by means of kieselguhr. The 
batch is then brought to a pH of 5 to 6 and the compound according to the 
invention is isolated from the synthesis solution in the customary manner, 
for example by salting out by means of an electrolyte, such as sodium 
chloride or potassium chloride. If appropriate, the compound (1) can also 
be isolated by evaporation of the solution, such as, for example, spray 
drying. In this case, it is advisable, if the reaction has not gone to 
completion, for residual ionic copper to be eliminated by customary 
methods such as are known from the literature for the precipitation of 
copper ions, for example by means of oxalic acid, stearic acid, 
trimercapto-triazine, sodium sulfide and agents having a similar action; 
ion exchangers, for example, are also useful for this. 
Aldehydes which are used according to the invention as starting compounds 
are, in particular, methylglyoxal and phenylglyoxal. 
Numerous aromatic amino compounds of the general formula X-A-NH.sub.2 which 
are used as starting compounds for the corresponding aromatic hydrazines 
are described in the literature. Examples of such aromatic amines are 
2-aminophenol, 2-aminophenol-4- or -5-sulfonic acid, 2-aminophenol-3,5-or 
-4,6-disulfonic acid, 2-aminophenol-4- or -5-sulfonamide, 
4-ethylsulfonyl-2-aminophenol, 4-ethylsulfonyl-6-sulfo-2-amino-phenol, 
4-methylsulfonyl-6-sulfo-2-aminophenol, 
6-acetylamino-2-aminophenol-4-sulfonic acid, 
6-chloro-2-aminophenol-4-sulfonic acid, 6-nitro-2-aminophenol-4-sulfonic 
acid, 4-chloro-2-aminophenol-6-sulfonic acid, 
4-nitro-2-amino-phenol-6-sulfonic acid, 4-methyl-2-aminophenol-6-sulfonic 
acid, 6-succinylamino-2-aminophenol-4-sulfonic acid, 
6-sulfobenzoylamino-2-aminophenol-4-sulfonic acid, 
6-methyl-4-sulfo-2-aminophenol, 4- or 5-methyl=2-amino-phenol, 4- or 5- or 
6-chloro-2-aminophenol, 4-sulfo-6-carboxy-2-aminophenol, 
4-methoxy-2-aminophenol, 5-methylsulfonyl-2aminopheno, 
1,4-diethylsulfamoyl-6-sulfo- 
2-aminopheno-1,4-bromo-6-sulfo-2-aminophenol, 4- or 
5-(N-.beta.-hydroxyyethyl)sulfamoyl-2-aminophenol, 
4-(N-methyl-N-.beta.-sulfatoethylsulfonyl)-amino-6-sulfo-2-aminophenol, 
4-(N-.beta.-sulfato-1-amino=2-naphthol-4- or -6-sulfonic acid, 
1-amino-2-naphthol-3,6- or -4,6- or 4,7-disulfonic acid, 
6-nitro-1-diazo-2-naphthol-4-sulfonic acid, 
4-(.beta.-sulfatoethylsulfonyl)-2-aminophenol and derivatives thereof 
which are substituted in the 6-position by chlorine or nitro or methyl, 
5-(.beta.-sulfatoethylsulfonyl)-2-aminophenol, 
4-(.beta.-sulfatoethylsulfonyl)-6-sulfo-aminophenol, 
the.beta.-hydroxyethylsulfonyl derivatives of these 
.beta.-sulfatoethylsulfonyl compounds, 
4-(N-methyl-N-.beta.-sulfoethylsulfonyl)-amino-6-sulfo-2-aminophenol, 
4-(N-methyl-N-.beta.-sulfoethylsulfonyl)-amino-6-sulfo-2-aminophenol, 
4-(N-.beta.-sulfoethylsulfonyl)-amino-2-aminophenol, 
4-(.beta.-sulfoethylsulfonyl)-2-aminophenol and derivatives thereof which 
are substituted in the 6-position by chlorine or nitro or methyl, 
5-(.beta.-sulfoethylsulfonyl)-2-aminophenol, 
4-(.beta.-sulfatoethylsulfonyl)-6-sulfoaminophenol, 2-amino-benzoic acid, 
4- or 5-sulfo-2-amino-benzoic acid, 5-nitro-2-amino-benzoic acid, 
5-chloro-2-amino-benzoic acid, 5-methoxy-2-amino-benzoicacid, 
5-sulfamoyl-2-amino-benzoic acid, 5-methylsulfamoyl-2-amino-benzoic acid, 
5-phenylsulfamoyl-2-amino-benzoic acid, 
2-amino-4-(.beta.-hydroxyethylsulfonyl)-benzoic acid, 
2-amino-4-(.beta.-sulfatoethylsulfonyl)-benzoic acid, 2-amino-5-(.beta. 
-hydroxy-ethylsulfonyl)-benzoic acid, 
2-amino-5-(.beta.-sulfatoethylsulfonyl)-benzoic acid, aniline-2-sulfonic 
acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, 5- and 
4-methyl-aniline-2-sulfonic acid, 2,4-dimethyl-aniline-6-sulfonic acid, 
4,5-dimethyl-aniline-2-sulfonic acid, 2-methyl-aniline-4,6-disulfonic 
acid,4-methyl-aniline-2,5-disulfonic acid, 4- and 
5-methoxy-aniline-2-sulfonic acid, 4-methoxy-5-chloro-aniline-2-sulfonic 
acid, 4,5-dimethoxy-aniline-2-sulfonic acid, 4- and 
5-ethoxyaniline-2-sulfonic acid, 4- and 5-hydroxy-aniline-2-sulfonic acid, 
5-hydroxy-aniline-2,4-disulfonic acid, 4and 5-carboxy-aniline-2-sulfonic 
acid, 4-hydroxy-3-carboxy-aniline-2-sulfonic acid, 4- and 
5-nitro-aniline-2-sulfonic acid, 2,4-dinitro-aniline-6-sulfonic acid, 
5-nitro-4-chloro-aniline-2-sulfonicacid, 4-fluoro-aniline-2-sulfonic acid, 
3-, 4- and 5-chloro-aniline-2-sulfonic acid, 
4,5-dichloro-aniline-2-sulfonic acid, 2,4-dichloroaniline-6-sulfonic acid, 
2,4,5-trichloro-aniline-2sulfonic acid, 
4-chloro-5-carboxy-aniline-2-sulfonic acid, 
2,5-dichloro-4-nitro-aniline-6-sulfonic acid, 4and 
5-bromo-aniline-2-sulfonic acid, 2,4- and 3,4-dibromo-aniline-6-sulfonic 
acid, 4- and 5-iodo-aniline-2sulfonic acid, 4- and 
5-acetamino-aniline-2-sulfonic acid, 1-naphthylamine-2-sulfonic acid, 
2-naphthylamine-1-sulfonic acid, 1-naphthylamine-2,4-disulfonic acid, 
1-naphthylamine-2,5-disulfonic acid, 2-naphthylamine-1,5-disulfonic acid, 
2-naphthylamine-1,7-disulfonic acid, 2-naphthylamine-3,6-disulfonic acid, 
2-naphthylamine-3,7-disulfonic acid, 1-naphthylamine-2,4,7-trisulfonic 
acid, 2-naphthylamine-3,6,8-trisulfonic acid and 
2-naphthylamine-1,5,7-trisulfonic acid, 
2-amino-4-(.beta.-hydroxyethylsulfonyl)-benzenesulfonic acid, 
2-amino-4-(.beta.-sulfatoethylsulfonyl)-benzenesulfonic acid, 
2-amino-4-(.beta.-hydroxyethylsulfonyl)-benzene-1,5-disulfonic acid, 
2-amino-4-(.beta.-sulfatoethylsulfonyl)-benzene-1,5-disulfonic acid, 
2-amino-.beta.-(2-hydroxyethylsulfonyl)-benzenesulfonic acid and 
2-amino-5-(.beta.-sulfatoethylsulfonyl)-benzenesulfonic acid. 
The ortho-hy-droxy-arylamines having the formula radical B which are used 
as diazo components in the synthesis of the compounds (1) according to the 
invention are, for example, all those compounds mentioned for the 
derivatives having the formula radical A which are o-aminophenol and 
o-amino-naphthol derivatives. 
The hydrazone compounds of the formula (2) where Q is hydrogen which are 
used as the starting compound are obtained from the corresponding phenyl- 
and naphthylhydrazines --which can in turn be prepared in a manner which 
is customary and known per se, for example from the corresponding 
diazonium compounds with salts of sulfurous acid, the intermediate 
N-sulfonic acids being hydrolyzed with mineral acids--by reaction with the 
corresponding aldehyde of the general formula R--CO--CHO, where R has the 
abovementioned meaning. 
The hydrazone compounds of the general formula (2) where Q is the carboxy 
group mentioned, which can be split off, can preferably be obtained in a 
manner which is customary per se when a methylene compound which can be 
coupled in two positions and contains the structural portion of the 
formula radical R--CO-- is coupled with the diazonium compound of an 
aromatic amino compound of the general formula (4) 
##STR6## 
in which Y.sup.1, n', A, X.sup.1, Z and m' have the abovementioned 
meanings. Examples of methylene compounds which can be coupled in two 
positions and which, after coupling has taken place, still contain an 
optionally modified carboxy group on the methine carbon are the 
benzoylacetic esters, such as methyl benzoylacetate or ethyl 
benzoylacetate, benzoylacetone or the benzoylacetic acid esters in which 
the benzene radicals are substituted by carboxy sulfo, nitro and/or 
chlorine, and moreover the acetylacetic esters, such as methyl 
acetylacetate and ethyl acetylacetate, acetylacetone, the butyrylacetic 
acid esters, such as, for example, the methyl and ethyl esters, the 
propionylacetic acid esters, such as, for example, the methyl and ethyl 
esters, and moreover acetylacetic acid, benzoylacetic acid, 
acetylacetamide and benzoylacetamide. When the alkaline hydrolysis of the 
ester group has taken place, the hydrazone of the formula (2), if this 
contains a group in which Y.sup.1 represents the .beta.-hydroxyethyl 
group, can be esterified to the sulfato compound by means of sulfuric acid 
or sulfuric acid containing sulfur trioxide. 
The copper complex formazan compounds according to the invention (called 
compounds (1) below) have useful dyestuff properties. They are preferably 
used for dyeing (in the general sense) materials containing hydroxy, amino 
and/or carboxamide groups, for example in the form of sheet-like 
structures, such as paper and leather, or in bulk, such as polyamide and 
polyurethane, and in particular those materials in fiber form. 
The present invention accordingly also relates to the use of the compounds 
(1) for dyeing (including bulk dyeing and dyeing by printing) these 
materials and processes for dyeing such materials by a procedure which is 
customary per se, in which a compound (1) is used as the coloring agent. 
The materials are preferably used in the form of fiber materials, in 
particular in the form of textile fibers. 
Materials containing hydroxy groups are naturally occurring or synthetic 
materials containing hydroxy groups, such as, for example, cellulose fiber 
materials or regenerated products thereof and polyvinyl alcohols. 
Cellulose fiber materials are preferably cotton, but also other plant 
fibers, such as linen, hemp, jute and ramie fibers; regenerated cellulose 
fibers are, for example, viscose staple and filament viscose. 
Examples of materials containing carboxamide groups are synthetic and 
naturally occurring -polyamides and polyurethanes, in particular in the 
form of fibers, for example wool and other animal hair, silk, leather, 
polyamide 6,6, polyamide 6, polyamide 11 and polyamide 4. 
The compounds (1) can be applied to and fixed on the substrates mentioned, 
in particular on the fixed materials mentioned, by the use techniques 
known for watersoluble dyestuffs, and in particular for fiber-reactive 
dyestuffs. 
Very good color yields are thus obtained with them on cellulose fibers by 
the exhaustion processes from a long liquor using the most diverse 
acid-binding agents and if appropriate neutral salts, such as, for 
example, sodium chloride or sodium sulfate. Dyeing is carried out at 
temperatures between 40.degree. and 100.degree. C., if appropriate at 
temperatures of up to 120.degree. C., under pressure, if appropriate in 
the presence of customary dyeing auxiliaries, in an aqueous bath. A 
procedure can be followed here in which the material is introduced into 
the hot bath, this is gradually heated up to the desired dyeing 
temperature and the dyeing process is brought to completion at this 
temperature. The neutral salts which accelerate the exhaustion of the 
dyestuff can also be added to the bath, if desired, only after the actual 
dyeing temperature has been reached. 
Excellent color yields are likewise obtained by the padding process on 
cellulose fibers, it being possible for fixing to be carried out in the 
customary manner by batching at room temperature or elevated temperature, 
for example up to about 60.degree. C., by steaming or with dry heat in the 
customary manner. 
Deep prints with a good contour status and a clear white ground are 
likewise obtained by the customary printing processes for cellulose 
fibers. The result of the prints depends on varying fixing conditions to 
only a minor degree. The printing processes can be one-phase processes, in 
which the material is printed with a printing paste containing, for 
example, sodium bicarbonate or another acid-binding agent and the compound 
(1) and the compound (1) is fixed on the fiber by subsequent steaming at 
101.degree. to 103.degree. C., or can be two-phase processes, in which the 
material is printed, for example, with a neutral or weakly acid printing 
ink which contains the compound (1) and the compound (1) is then fixed on 
the material by passing the printed material through a hot alkaline bath 
containing electrolyte or by over-padding with an alkaline padding liquor 
containing electrolyte and subsequent batching of this over-padded 
material or subsequent steaming or subsequent treatment with dry heat. The 
degrees of fixing obtained with the compounds (1) are high both in dyeing 
and in printing. 
Hot air of 120.degree. to 200.degree. C. is used for fixing by means of dry 
heat by the customary thermofixing processes. In addition to the customary 
steam of 101 to 103.degree. C., it is also possible to use superheated 
steam and pressurized steam of temperatures of up to 160.degree. C. 
The acid-binding agents which effect fixing of the compounds (1) on the 
cellulose fibers are, for example, water-soluble basic salts of alkali 
metals and similarly alkaline earth metals with inorganic or organic acids 
or compounds which liberate alkali under the influence of heat. The alkali 
metal hydroxides and alkali metal salts of weak to medium-strength 
inorganic or organic acids may be mentioned in particular, alkali 
compounds preferably meaning the sodium and potassium compounds. Examples 
of such acid-binding agents are sodium hydroxide, potassium hydroxide, 
sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, 
sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium 
trichloroacetate, water-glass and trisodium phosphate. 
The compounds (1) are bonded chemically to the fibers by the treatment of 
the compounds (1) with the acid-binding agents, if appropriate under the 
action of heat; the cellulose dyeings in particular exhibit excellent 
wetfastness properties after the customary after-treatment by rinsing to 
remove non-fixed portions of dyestuff. 
As regards the coloristic properties of the compounds (1), it should be 
mentioned in particular that they are distinguished by a good stability in 
printing pastes and padding liquors, also in the presence of alkali, by a 
very good absorption capacity from a long liquor, by a good buildup and 
high rate of fixing in the customary dyeing and printing processes in 
particular at lower temperatures (i.e. room temperature up to 50.degree. 
C.), by an equal depth of color in dyeing on cotton and regenerated 
cellulose fibers, by a level result of the dyeings and prints produced 
with them and also by a uniform result of dyeings from a long liquor when 
various amounts of electrolytes are added. 
The dyeings on polyurethane fibers and polyamide fibers are usually carried 
out from an acid medium. Thus, for example, acetic acid and/or ammonium 
sulfate or acetic acid and ammonium acetate or sodium acetate can be added 
to the dyebath in order to obtain the desired pH. Addition of customary 
leveling agents, such as, for example, based on a reaction product of 
cyanuric chloride with three times the molar amount of an 
aminobenzenesulfonic acid and/or an aminonaphthalenesulfonic acid or based 
on a reaction product of, for example, stearylamine with ethylene oxide, 
is advisable for the purpose of achieving a usable levelness of the 
dyeing. As a rule, the material to be dyed is introduced at a temperature 
of about 40.degree. C. into the initially weakly alkaline bath and is 
agitated therein for some time, the dyebath is then brought to a weakly 
acid, preferably weakly acetic acid, pH and the actual dyeing is carried 
out at a temperature between 60 and 98.degree. C. However, the dyeings can 
also be performed at the boiling point or at temperatures of up to 
120.degree. C. (under pressure). After-treatment in an ammoniacal bath can 
then be carried out. 
The dyeings and prints produced with the compounds (1) are distinguished by 
claret-red to navy blue color shades. In particular, the dyeings and 
prints on cellulose fiber materials, as already mentioned, have a high 
depth of color and good fastnesses to light, fastnesses to light when wet 
and fastnesses to light in the presence of perspiration, a good fastness 
to hypochlorite bleaching and fastness to chlorinated water, good fastness 
to ironing, over-dyeing and rubbing and moreover good fastnesses to 
washing, milling, alkali, acid and perspiration. Non-fixed portions of 
dyestuff can be washed out of the fiber material again easily and 
completely, which is an essential precondition for the good wet-fastnesses 
of the dyeing obtainable. The dyeings are moreover stable towards the 
customary synthetic resin finishes. Some of the compounds (1) are 
comparable in the purity of the color shade and important fastness 
properties to reactive dyestuffs of the azo series, but in some cases are 
superior in essential fastnesses, such as, for example, the fastness to 
light. 
The following Examples serve to illustrate the invention. The parts 
mentioned therein are parts by weight. The percentage data are percentages 
by weight, unless noted otherwise. Parts by weight bear the same relation 
to parts by volume as the kilogram to the liter. The compounds described 
by way of their formulae in the Examples are shown in the form of the free 
acids; they are in general prepared and isolated in the form of their 
sodium or potassium salts and used for dyeing in the form of their salts. 
The starting compounds and components mentioned in the form of the free 
acid in the following Examples, in particular the Tabular Examples, are 
employed in the synthesis as such or in the form of their salts, 
preferably alkali metal salts. 
The absorption maxima (.lambda..sub.max) in the visible range stated for 
the compounds according to the invention were determined with the aid of 
the alkali metal salts thereof in aqueous solution. In the Tabular 
Examples, the .lambda..sub.max values are in parentheses with the 
indication of the color shade; the wavelength quoted is in nm.

EXAMPLE A 
225 parts of 6-chloro-2-aminophenol-4-sulfonic acid are diazotized in 800 
parts of a mixture of ice and water in the customary manner; the batch is 
then brought to a pH of 6 and stirred into a solution of 192 parts of 
ethyl benzoylacetate in 1000 parts of water and 90 parts by volume of a 
concentrated sodium hydroxide solution at 0.degree. to 10.degree. C., 
while maintaining a pH of 8 to 9. Thereafter, the mixture is acidified to 
a pH of 5 with hydrochloric acid and the compound of the formula 
##STR7## 
which has precipitated is isolated and then dissolved in 2000 to 3000 
parts of water at a pH of 7 and a temperature of 50.degree. C. The 
carbethoxy group in this compound is hydrolyzed to the carboxy group by 
addition of 100 parts by volume of a concentrated sodium hydroxide 
solution at a pH between 10 and 12 for one hour. The carboxy-hydrazone 
compound is precipitated by subsequently adjusting the pH of this batch to 
4 to 5. It is obtained in a high yield and purity by filtration. 
EXAMPLE B 
A carboxy-hydrazone compound used as the starting compound for the 
preparation of copper complex formazan compounds according to the 
invention is prepared as follows: 297 parts of 
4-(.beta.-hyiroxyethylsulfonyl)-2-aminophenol-6-sulfonic acid are 
diazotized in a mixture of 1000 parts of ice and water in the customary 
manner. The diazonium salt suspension is then brought to a pH of 5 with 
sodium carbonate and added to a solution of 192 parts of ethyl 
benzoylacetate in a mixture of 1000 parts of water and 90 parts by volume 
of a concentrated sodium hydroxide solution; the reaction is carried out 
at a pH of 9 and a temperature of 0.degree. to 10.degree. C. Subsequent 
ester hydrolysis is carried out at a pH of 10 to 12 and a temperature of 
50.degree. C. over a reaction time of to 4 hours, after addition of a 
corresponding amount of concentrated sodium hydroxide solution. The batch 
is then brought to a pH of 2 to 3. The phenylhydrazone compound which has 
precipitated is isolated and dried and then introduced into three times 
the amount by weight of sulfuric acid or up to 20% strength oleum at a 
temperature of not more than 20.degree. C. The batch is subsequently 
stirred for some time and then poured onto ice, and the phenylhydrazone of 
the formula 
##STR8## 
which has precipitated is isolated, if appropriate after addition of an 
electrolyte salt, such as sodium chloride. 
EXAMPLE 1 
The aqueous solution of the diazonium salt of 37.7 parts of 
4-(.beta.-sulfatoethyl-sulfonyl)-6-sulfo-2-aminophenol is added to an 
aqueous solution of pH 6.5 to 7 of 40 parts of the carboxy-hydrazone 
starting compound of Example A at 5.degree. to 15.degree. C., and 100 
parts by volume of an aqueous 1molar copper sulfate solution is then 
slowly added at 10.degree. to 15.degree. C. in the course of 15 minutes, 
while maintaining a pH of between 4.0 and 6.5. The reaction mixture is 
subsequently stirred for a further hour, to bring the coupling reaction to 
completion, and if appropriate is heated to 40 to 50.degree. C., the batch 
is stirred for a further hour and clarified with kieselguhr and the copper 
complex formazan compound formed is precipitated out of the filtrate with 
sodium chloride, filtered off, washed with dilute aqueous sodium chloride 
solution and dried. A dark electrolyte-containing powder of the alkali 
metal salt (sodium salt) of the compound of the formula 
##STR9## 
is obtained. It is very suitable as a dyastuff and dyes, for example, 
cotton and regenerated cellulose fibers from a long liquor in the presence 
of an acid-binding agent at a high rate of fixing in bluish-tinged claret 
shades. The dyeing after-treated in the customary manner (for example by 
boiling treatment for 10 minutes in an aqueous bath containing a nonionic 
detergent and rinsing with water) has good light- and wet-fastnesses, of 
which the good fastness to washing, milling and perspiration, the good 
fastness to chlorine water, the fastness to light when wet and the 
fastness to light in the presence of perspiration can be singled out in 
particular. The good stability of prints towards acid hydrolysis is also 
worth mentioning. 
EXAMPLE 2 
The .beta.-sulfatoethylsulfonyl-copper complex formazan compound according 
to the invention is converted into the corresponding vinylsulfonyl 
compound thereof by a procedure in which 9 parts by volume of a 
concentrated aqueous sodium hydroxide solution are added to the synthesis 
solution obtained from Example 1 and the mixture is stirred at 15.degree. 
to 25.degree. C. for some time, or in which the aqueous synthesis solution 
is heated to 50.degree. to 55.degree. C., a solution of 21 parts of sodium 
carbonate in 76 parts of water is added in the course of 5 to 10 minutes 
and the mixture is stirred at a pH of 9.2 for a further 30 to 40 minutes 
for complete reaction. 20 parts by volume of a 17% strength aqueous 
hydrochloric acid are then added at 50.degree. to 55.degree. C. and the pH 
is brought to 6.5. The vinylsulfonyl compound according to the invention, 
which exhibits an absorption maximum at 575 nm in aqueous solution, is 
isolated from the synthesis solution in the customary manner, for example 
by spray drying. It also has very good dyestuff properties and dyes, for 
example, cotton and regenerated cellulose fibers or wool by the 
application and fixing processes customary for fiberreactive dyestuffs 
giving the good properties stated for the compound of Example 1 according 
to the invention. 
The vinylsulfonyl-copper formazan compound according to the invention can 
also be prepared by a procedure analogous to that of Example 1, by using 
the equivalent amount of the diazonium salt of 
4-vinylsulfonyl-6-sulfo-2aminophenol instead of the aqueous diazonium salt 
solution of 4-(.beta.-sulfatoethylsulfonyl)-6-sulfo-2-aminophenol used in 
that example. 
EXAMPLE 3 
To prepare the .beta.-thiosulfatoethylsulfonyl-copper complex formazan 
compound according to the invention having the structure of the compound 
of Example 1 according to the invention, a procedure analogous to that of 
Example 1 can be followed, using 
4-(.beta.-thiosulfatoethylsulfonyl)-6-sulfo-2-aminophenol as the diazo 
component. However, to prepare the .beta.-thiosulfatoethylsulfonyl 
compound according to the invention, it is also possible to start from the 
solution, obtained from the synthesis, of the vinylsulfonyl compound of 
Example 2 and adding 37.5 parts of crystalline sodium thiosulfate to this 
at a pH of 6.8 to 7.2 and a temperature of 70.degree. to 75.degree. C. To 
bring the reaction to completion, the batch is stirred for about 4 hours, 
while maintaining a pH of between 5.7 and 6.2 by means of acetic acid, and 
is then clarified by kieselguhr and filtration and the 
.beta.-thiosulfatoethylsulfonyl compound according to the invention is 
precipitated by addition of potassium chloride in an amount of 15%, based 
on the volume of the filtrate. The mixture is cooled, while stirring, and 
the compound which has precipitated is filtered off with suction and 
dried. 
The .beta.-thiosulfatoethylsulfonyl compound according to the invention is 
obtained as the alkali metal salt, predominantly the potassium salt, in 
the form of a dark powder containing electrolyte salt. It has an 
absorption maximum at 576 nm, exhibits very good dyeing properties and 
dyes, for example, cotton in strong claret-colored shades with the good 
fastness properties mentioned for the compound according to the invention 
of Example 1. 
EXAMPLE 4 
30 parts of the carboxy-hydrazone compound obtainable by a coupling 
reaction of the diazonium salt of 4-sulfo-2aminophenol on ethyl 
acetoacetate and subsequent alkaline hydrolysis of the ester group are 
suspended in 250 parts of water and the compound is dissolved with 
concentrated aqueous sodium hydroxide solution at a pH of 6.5 to 7. An 
aqueous solution of the diazonium salt of 37.7 parts of 
4-(.beta.-sulfatoethylsulfonyl)-6-sulfo-2-aminophenol is then added at a 
pH of about 6 and a temperature of 5.degree. to 15.degree. C., 25 parts of 
crystalline copper sulfate, if appropriate in the form of an aqueous 
solution, are then added and the pH is kept between 4.5 and 6.5. The batch 
is heated to 30.degree. to 40.degree. C. and stirred for about a further 4 
hours, the synthesis solution is clarified at a pH of 5.5 and the compound 
according to the invention is isolated in the customary manner, for 
example by spray drying or salting out. 
The copper complex formazan compound of the formula (written in the form of 
the free acid) 
##STR10## 
according to the invention exhibits very good dyestuff properties and 
dyes, for example, cellulose fiber materials in deep, clear, blue-violet 
color shades with good light- and wet-fastnesses by the customary 
application and fixing methods for fiber-reactive dyestuffs. 
The copper complex formazan compound according to the invention of Example 
4 can also be prepared by reacting 26 parts of the hydrazone compound 
obtainable from 2-hydroxy-5-sulfo-phenylhydrazine and methylglyoxal with 
the diazonium salt of 
4-(.beta.-sulfatoethylsulfonyl)-6-sulfo-2-aminophenol by a procedure 
analogous to that described in Example 4. 
EXAMPLE 5 
The aqueous solution of the diazonium salt of 29.7 parts of 
4-(.beta.-sulfatoethylsulfonyl)-2-aminophenol are added to 43 parts of a 
carboxy-hydrazine compound in the form of an aqueous neutral solution 
(about 400 parts) and obtainable by known procedures by a coupling 
reaction of diazotized aniline-2,5-disulfonic acid with ethyl 
benzoylacetate at a pH of 13 and subsequent alkaline hydrolysis of the 
ester group. The reaction is carried out at a pH of 4.5 to 6.5 and a 
temperature of 10 to not more than 20.degree. C. Thereafter, 100 parts by 
volume of an aqueous 1-molar copper sulfate solution are slowly added at a 
temperature between 10.degree. and 15.degree. C. and the pH is still kept 
at 4.5 to 6.5. The mixture is subsequently stirred for a few hours and, 
after clarifying filtration at a pH of 5, the resulting copper complex 
formazan compound according to the invention is isolated in the customary 
manner. The sodium salt of the compound of the formula 
##STR11## 
is obtained in the form of a powder containing electrolyte. 
The compound according to the invention exhibits very good fiber-reactive 
dyestuff properties and dyes the materials mentioned in the description, 
such as, for example, cellulose fiber materials or naturally occurring or 
synthetic polyamide fiber materials, in bluish-tinged claret-colored 
shades with a good depth of color and good fastness properties by the 
application and fixing methods customary for fiber-reactive dyestuffs. 
EXAMPLE 6 
To prepare a copper complex formazan compound according to the invention, 
the procedure followed is according to the procedure of Example 5, but 32 
parts of the phenylhydrazone obtainable from 2,5-disulfo-phenylhydrazine 
and methylglyoxal are used as the starting substance. The compound 
according to the invention has, written in the form of the free acid, the 
formula 
##STR12## 
It is isolated as the alkali metal salt and has good dyestuff properties. 
For example, cellulose fiber materials in deep red-violet shades with good 
fastness properties are obtained. 
EXAMPLE 7 
250 parts of an aqueous diazonium salt solution of 37.7 parts of 
4-(.beta.-sulfatoethylsulfonyl)-6-sulfo-2-aminophenol and 100 parts by 
volume of an aqueous 1 molar copper sulfate solution (the diazonium salt 
solution and the copper sulfate solution can also be combined beforehand) 
are added simultaneously to about 250 parts of an aqueous solution of pH 
5.5 to 6.5 of 55 parts of the phenylhydrazone starting compound of Example 
B in the course of 15 minutes, while maintaining a temperature of between 
about 5.degree. and 20.degree. C., preferably 10.degree. to 15.degree. C., 
and a pH of between 4.5 and 6.5. The reaction mixture is subsequently 
stirred at 15.degree. to 25.degree. C. for about a further hour and is 
then heated to 40.degree. to 50.degree. C. When no further diazonium salt 
is detectable, the batch is brought to a pH of 5 and clarified by means of 
kieselguhr and filtration and the copper formazan compound according to 
the invention is precipitated from the filtrate with the aid of sodium 
chloride. It is filtered off and the residue is washed with dilute aqueous 
sodium chloride solution and dried. 
The alkali metal salt of the compound of the formula 
##STR13## 
according to the invention, which has very good fiberreactive dyestuff 
properties and dyes, for example, cellulose fiber materials, such as 
cotton, in deep violet shades with good fastness properties, in particular 
good light-fastnesses, is obtained. 
EXAMPLE 8 
To prepare a copper complex formazan compound according to the invention, 
the procedure followed is as according to the procedure of Example 7, but 
the diazonium salt employed is that of 22.5 parts of 
6-chloro-2-aminophenol-4-sulfonic acid. The compound according to the 
invention synthesized has, written in the form of the free acid, the 
formula 
##STR14## 
and dyes, in particular, cellulose fiber materials, such as cotton, in 
deep claret-colored shades of good light- and wet-fastnesses, such as, for 
example, good fastnesses to washing and good fastnesses to alkaline and 
acid perspiration, by the application and fixing methods customary in the 
art. 
EXAMPLE 9 
A neutral aqueous solution (about 250 parts) of 40 parts of a 
carboxy-phenylhydrazone (obtainable by coupling 2-amino-4-sulfo-benzoic 
acid onto ethyl benzoylacetate and subsequent alkaline hydrolysis of the 
ester group) is used as the starting substance and the aqueous diazonium 
salt solution, rendered weakly acid, of 37.7 parts of 
4-(.beta.-sulfatoethylsulfonyl)-6-sulfo-2-aminophenol is added at a 
temperature of 5.degree. to 15.degree. C. and a pH of 5, and 100 parts by 
volume of an aqueous 1 molar copper sulfate solution are then added 
continuously in the course of 5 minutes at 10.degree. to 15.degree. C. 
while maintaining a pH of between 4.5 and 6.5. The mixture is subsequently 
stirred for a further 10 to 12 hours at 20.degree. C. to bring the 
coupling reaction to completion, and the reaction mixture is then heated 
to 40.degree. to 50.degree. C., subsequently stirred for a further hour 
and clarified by means of kieselguhr and filtration at a pH of 12.5. The 
copper complex formazan compound according to the invention is 
precipitated out of the filtrate by means of sodium chloride and isolated. 
It has, written in the form of the free acid, the formula 
##STR15## 
and dyes, for example, cotton and regenerated cellulose fibers in pure 
bluish-tinged claret shades from a long liquor by the fixing conditions 
customary for fiberre-active dyestuffs. The dyeings and prints 
after-treated in the customary manner by soaping for 10 minutes and 
rinsing with water exhibit good light- and wet-fastness properties. 
The copper complex formazan compound according to the invention can also be 
prepared by using 35 parts of a phenylhydrazone obtainable from 
2-carboxy-5-sulfophenylhydrazine and phenylglyoxal as the starting 
substance. 
EXAMPLES 10 TO 236 
Further copper complex formazan compounds according to the invention are 
described in the following Tabular Examples with the aid of the formula 
radicals of the general formula (A) 
##STR16## 
They can prepared in the manner according to the invention, for example 
analogously to the above Embodiment Examples, from the starting compounds 
which can be deduced from the components of the corresponding Tabular 
Example. They have very good dyestuff properties and produce, on the 
materials mentioned in the description, in particular cellulose fiber 
materials, by the application and fixing processes customary in the art 
for fiberreactive dyestuffs, deep dyeings and prints in the color shade 
stated for the particular Tabular Example for dyeing on cotton (the 
figures stated in parentheses after the color shade indicate the 
absorption maximum of the compound according to the invention in nm, 
measured in aqueous solution). 
In the table, the radicals --B.sup.1 --O-- are represented by the 
abbreviations (I), (II) and (III); these have the following meaning: 
(I) is: 1-oxy-4-(.beta.-sulfatoethylsulfonyl)-6-sulfophen-2-yl 
(II) is: 1-oxy-4-(.beta.-sulfatoethylsulfonyl)-phen-2-yl 
(III) is: 1-oxy-5-(.beta.-sulfatoethylsulfonyl)-phen-2-yl. 
The abbreviation VS represents the .beta.-sulfatoethylsulfonyl group. 
__________________________________________________________________________ 
Ex. 
Radical --A.sup.1 --X-- 
Radical R 
Radical -O-B.sup.1 - 
Color shade 
__________________________________________________________________________ 
10 1-oxy-4-sulfo-6- 
phenyl 
(II) bluish-tinged 
chloro-phen-2-yl claret (528) 
11 1-oxy-4-sulfo-6- 
phenyl 
(III) reddish-tinged 
chloro-phen-2-yl navy blue (584) 
12 1-oxy-4-sulfo-6- 
phenyl 
(I) bluish-tinged 
chloro-phen-2-yl claret (576) 
13 1-oxy-4-sulfo- 
phenyl 
(I) bluish-tinged 
phen-2-yl claret (575) 
14 1-oxy-4-sulfo- 
phenyl 
(II) bluish-tinged 
phen-2-yl claret (567) 
15 1-oxy-4-sulfo- 
phenyl 
(III) reddish-tinged 
phen-2-yl navy blue (581) 
16 1-oxy-4,6-disulfo- 
phenyl 
(I) reddish-tinged 
phen-2-yl violet (582) 
17 1-oxy-4,6-disulfo- 
phenyl 
(II) reddish-tinged 
phen-2-yl violet (576) 
18 1-oxy-4,6-disulfo- 
phenyl 
(III) reddish-tinged 
phen-2-yl navy blue (590) 
19 1-oxy-4-sulfo-6- 
phenyl 
(I) bluish-tinged 
nitro-phen-2-yl violet (585) 
20 1-oxy-4-sulfo-6- 
phenyl 
(II) bluish-tinged 
nitro-phen-2-yl violet (577) 
21 1-oxy-4-sulfo-6- 
phenyl 
(III) reddish-tinged 
nitro-phen-2-yl navy blue 
22 1-oxy-5-sulfo- 
phenyl 
(I) reddish-tinged 
phen-2-yl navy blue 
23 1-oxy-5-sulfo- 
phenyl 
(II) reddish-tinged 
phen-2-yl navy blue 
24 1-oxy-5-sulfo- 
phenyl 
(III) reddish-tinged 
phen-2-yl navy blue 
25 1-oxy-4-ethyl- 
phenyl 
(I) reddish-tinged 
sulfonyl-6-sulfo- violet 
phen-2-yl 
26 1-oxy-4-ethyl- 
phenyl 
(II) reddish-tinged 
sulfonyl-6-sulfo- violet 
phen-2-yl 
27 1-oxy-4-ethyl- 
phenyl 
(III) reddish-tinged 
sulfonyl-6-sulfo- navy blue 
phen-2-yl 
28 1-oxy-4-methyl- 
phenyl 
(I) reddish-tinged 
sulfonyl-6-sulfo- violet 
phen-2-yl 
29 1-oxy-4-methyl- 
phenyl 
(II) reddish-tinged 
sulfonyl-6-sulfo- violet 
phen-2-yl 
30 1-oxy-4-(.beta.-sul- 
phenyl 
(I) reddish-tinged 
fatoethylsulfon- violet 
yl)-6-sulfo-phen- 
2-yl 
31 1-oxy-4-(.beta.-sulfo- 
phenyl 
(I) reddish-tinged 
ethylsulfonyl)-6- violet 
sulfo-phen-2-yl 
32 1-oxy-4-(.beta.-sulfo- 
phenyl 
(II) reddish-tinged 
ethylsulfonyl)-6- violet 
sulfo-phen-2-yl 
33 1-oxy-4-(.beta.-sulfo- 
phenyl 
(III) reddish-tinged 
ethylsulfonyl)-6- navy blue 
sulfo-phen-2-yl 
34 1-oxy-4-(.beta.-sulfo- 
phenyl 
(I) reddish-tinged 
ethylsulfonyl)- violet 
phen-2-yl 
35 1-oxy-5-(.beta.-sulfo- 
phenyl 
(I) reddish-tinged 
ethylsulfonyl)- violet 
phen-2-yl 
36 1-oxy-4-sulfo-6- 
phenyl 
(I) reddish-tinged 
carboxy-phen-2-yl violet 
37 1-oxy-4-sulfo-6- 
phenyl 
(II) reddish-tinged 
carboxy-phen-2-yl violet 
38 1-oxy-4-sulfo-6- 
phenyl 
(III) reddish-tinged 
carboxy-phen-2-yl navy blue 
39 1-oxy-4-sulfo-6- 
phenyl 
(I) bluish-tinged 
acetylamino- violet 
phen-2-yl 
40 1-oxy-3,5-disulfo- 
phenyl 
(I) greenish-tinged 
phen-2-yl blue 
41 1-oxy-3,5-disulfo- 
phenyl 
(II) greenish-tinged 
phen-2-yl blue 
42 1-oxy-3,5-disulfo- 
phenyl 
(III) greenish-tinged 
phen-2-yl navy blue 
43 1-oxy-4-chloro-6- 
3-sulfo- 
(I) reddish-tinged 
sulfo-phen-2-yl 
phenyl violet 
44 1-oxy-4-nitro-6- 
3-nitro- 
(I) bluish-tinged 
sulfo-phen-2-yl 
phenyl violet 
45 1-oxy-4-methyl-6- 
phenyl 
(I) bluish-tinged 
sulfo-phen-2-yl violet 
46 1-oxy-3-chloro-5- 
phenyl 
(I) bluish-tinged 
sulfo-phen-2-yl green 
47 1-oxy-3-nitro-5- 
phenyl 
(I) bluish-tinged 
sulfo-phen-2-yl green 
48 1-oxy-3-sulfo-5- 
phenyl 
(I) bluish-tinged 
methylsulfonyl- green 
phen-2-yl 
49 1-oxy-4-dimethyl- 
2-carboxy- 
(I) reddish-tinged 
sulfamoyl- phenyl violet 
phen-2-yl 
50 1-oxy-4-(3'-sulfo- 
2,6-di- 
(I) reddish-tinged 
phenyl-sulfonyl)- 
fluoro- violet 
phen-2-yl phenyl 
51 1-oxy-4-sulfo-6- 
phenyl 
(I) bluish-tinged 
(4'-sulfo- violet 
benzoylamino)- 
phen-2-yl 
52 1-oxy-4-sulfo-6- 
phenyl 
(II) bluish-tinged 
(4'-sulfo- violet 
benzoylamino)- 
phen-2-yl 
53 1-oxy-4-sulfo-6- 
phenyl 
(III) reddish-tinged 
(4'-sulfo- navy blue 
benzoylamino)- 
phen-2-yl 
54 2-oxy-4-sulfo-6- 
phenyl 
(I) bluish-tinged 
nitro-naphth-1-yl green 
55 2-oxy-3,6-disulfo- 
phenyl 
(I) bluish-tinged 
naphth-1-yl green 
56 1-oxy-4-(N-methyl- 
phenyl 
(I) reddish-tinged 
N-.beta.-sulfatoethyl- violet 
sulfonyl)-amino- 
phen-2-yl 
57 1-oxy-4-sulfo-6- 
phenyl 
(I) reddish-tinged 
(.beta.-carboxy- blue 
propionylamino)- 
phen-2-yl 
58 1-oxy-4-sulfo-6- 
phenyl 
(II) reddish-tinged 
(.beta.-carboxy- blue 
propionylamino)- 
phen-2-yl 
59 1-oxy-4-sulfo-6- 
phenyl 
(III) reddish-tinged 
(.beta.-carboxy- navy blue 
propionylamino)- 
phen-2-yl 
60 1-oxy-4-phosphono- 
phenyl 
(I) reddish-tinged 
phen-2-yl violet 
61 1-oxy-4-carboxy-6- 
phenyl 
(II) reddish-tinged 
sulfo-phen-2-yl violet 
62 1-oxy-4-sulfamoyl- 
phenyl 
(I) reddish-tinged 
phen-2-yl violet 
63 1-oxy-4-sulfo- 
phenyl 
1-oxy-4-(.beta.- 
bluish-tinged 
phen-2-yl sulfatoethyl- 
violet 
sulfonyl)-6- 
nitro-phen-2-yl 
64 1-oxy-4-sulfo-6- 
phenyl 
1-oxy-4-(.beta.- 
reddish-tinged 
chloro-phen-2-yl sulfatoethyl- 
violet 
sulfonyl)-6- 
chloro-phen- 
2-yl 
65 1-oxy-4,6-disulfo- 
phenyl 
1-oxy-4-(.beta.- 
reddish-tinged 
phen-2-yl phosphatoethyl- 
violet 
sulfonyl)- 
phen-2-yl 
66 1-oxy-4,6-disulfo- 
phenyl 
1-oxy-4-(.beta.- 
reddish-tinged 
phen-2-yl phenylsulfon- 
violet 
yloxy-ethyl- 
sulfonyl)-phen- 
2-yl 
67 1-oxy-4,6-disulfo- 
phenyl 
1-oxy-4-(.beta.- 
reddish-tinged 
phen-2-yl propionyloxy- 
violet 
ethylsulfonyl)- 
phen-2-yl 
68 1-oxy-4,6-disulfo- 
phenyl 
1-oxy-4-(.beta.- 
reddish-tinged 
phen-2-yl dimethylamino- 
violet 
ethylsulfonyl)- 
phen-2-yl 
69 1-oxy-4-sulfo-6- 
methyl 
(I) reddish-tinged 
chloro-phen-2-yl violet 
70 1-oxy-4-sulfo-6- 
methyl 
(II) reddish-tinged 
chloro-phen-2-yl violet 
71 1-oxy-4-sulfo-6- 
methyl 
(III) reddish-tinged 
chloro-phen-2-yl navy blue 
72 1-oxy-4-sulfo- 
trifluoro- 
(I) reddish-tinged 
phen-2-yl methyl violet 
73 1-oxy-4-sulfo- 
methyl 
(II) reddish-tinged 
phen-2-yl violet 
74 1-oxy-4-sulfo- 
methyl 
(III) bluish-tinged 
phen-2-yl violet (565) 
75 1-oxy-4-sulfo- 
ethyl (I) reddish-tinged 
phen-2-yl violet 
76 1-oxy-4-sulfo- 
n-propyl 
(I) reddish-tinged 
phen-2-yl violet 
77 1-oxy-4-sulfo- 
methyl 
(I) reddish-tinged 
phen-2-yl violet (573) 
78 1-oxy-4,6-disulfo- 
methyl 
(I) bluish-tinged 
phen-2-yl violet 
79 1-oxy-4,6-disulfo- 
methyl 
(II) bluish-tinged 
phen-2-yl violet 
80 1-oxy-4,6-disulfo- 
methyl 
(III) bluish-tinged 
phen-2-yl violet 
81 1-oxy-4-sulfo-6- 
methyl 
(I) bluish-tinged 
nitro-phen-2-yl violet 
82 1-oxy-4-sulfo-6- 
methyl 
(II) bluish-tinged 
nitro-phen-2-yl violet 
83 1-oxy-4-sulfo-6- 
methyl 
(III) reddish-tinged 
nitro-phen-2-yl navy blue 
84 1-oxy-5-sulfo- 
methyl 
(I) bluish-tinged 
phen-2-yl violet 
85 1-oxy-5-sulfo- 
methyl 
(II) bluish-tinged 
phen-2-yl violet 
86 1-oxy-5-sulfo- 
methyl 
(III) bluish-tinged 
phen-2-yl violet 
87 1-oxy-4-ethyl- 
methyl 
(I) reddish-tinged 
sulfonyl-6-sulfo- violet 
phen-2-yl 
88 1-oxy-4-ethyl- 
methyl 
(II) reddish-tinged 
sulfonyl-6-sulfo- violet 
phen-2-yl 
89 1-oxy-4-ethyl- 
methyl 
(III) reddish-tinged 
sulfonyl-6-sulfo- navy blue 
phen-2-yl 
90 1-oxy-4-methyl- 
methyl 
(I) reddish-tinged 
sulfonyl-6-sulfo- violet 
phen-2-yl 
91 1-oxy-4-(.beta.- 
methyl 
(I) reddish-tinged 
sulfatoethylsul- violet 
fonyl)-6-sulfo- 
phen-2-yl 
92 1-oxy-4-(.beta.-sulfo- 
methyl 
(I) reddish-tinged 
ethylsulfonyl)-6- violet 
sulfo-phen-2-yl 
93 1-oxy-4-(.beta.-sulfo- 
methyl 
(II) reddish-tinged 
ethylsulfonyl)-6- violet 
sulfo-phen-2-yl 
94 1-oxy-4-(.beta.-sulfo- 
methyl 
(III) reddish-tinged 
ethylsulfonyl)-6- navy blue 
sulfo-phen-2-yl 
95 1-oxy-4-(.beta.-sulfo- 
methyl 
(I) reddish-tinged 
ethylsulfonyl)- violet 
phen-2-yl 
96 1-oxy-5-(.beta.-sulfo- 
methyl 
(I) reddish-tinged 
ethylsulfonyl)- violet 
phen-2-yl 
97 1-oxy-4-sulfo-6- 
methyl 
(I) reddish-tinged 
carboxy-phen-2-yl violet 
98 1-oxy-4-sulfo-6- 
methyl 
(II) reddish-tinged 
carboxy-phen-2-yl violet 
99 1-oxy-4-sulfo-6- 
methyl 
(III) reddish-tinged 
carboxy-phen-2-yl navy blue 
100 
1-oxy-4-sulfo-6- 
methyl 
(II) reddish-tinged 
acetylamino-phen- violet 
2-yl 
101 
1-oxy-3,5-disulfo- 
methyl 
(I) bluish-tinged 
phen-2-yl violet 
102 
1-oxy-3,5-disulfo- 
methyl 
(II) bluish-tinged 
phen-2-yl violet 
103 
1-oxy-3,5-disulfo- 
methyl 
(III) navy blue 
phen-2-yl 
104 
1-oxy-4-chloro-6- 
methyl 
(I) reddish-tinged 
sulfo-phen-2-yl violet 
105 
1-oxy-4-nitro-6- 
methyl 
(I) bluish-tinged 
sulfo-phen-2-yl violet 
106 
1-oxy-4-methyl-6- 
methyl 
(I) bluish-tinged 
sulfo-phen-2-yl violet 
107 
1-oxy-3-chloro-5- 
methyl 
(I) greenish-tinged 
sulfo-phen-2-yl blue 
108 
1-oxy-3-nitro-5- 
methyl 
(I) greenish-tinged 
sulfo-phen-2-yl blue 
109 
1-oxy-3-sulfo-5- 
methyl 
(I) greenish-tinged 
methylsulfonyl- blue 
phen-2-yl 
110 
1-oxy-4-dimethyl- 
methyl 
(I) reddish-tinged 
sulfamoyl-phen- violet 
2-yl 
111 
1-oxy-4-(3'-sulfo- 
methyl 
(I) reddish-tinged 
phenyl-sulfonyl)- violet 
phen-2-yl 
112 
1-oxy-4-sulfo-6- 
methyl 
(I) reddish-tinged 
(4'-sulfobenzoyl- violet 
amino)-phen-2-yl 
113 
1-oxy-4-sulfo-6- 
methyl 
(II) reddish-tinged 
(4'-sulfobenzoyl- violet 
amino)-phen-2-yl 
114 
1-oxy-4-sulfo-6- 
methyl 
(III) reddish-tinged 
(4'-sulfobenzoyl- navy blue 
amino)-phen-2-yl 
115 
2-oxy-4-sulfo-6- 
methyl 
(I) bluish-tinged 
nitro-naphth-1-yl green 
116 
2-oxy-3,6-disulfo- 
methyl 
(I) bluish-tinged 
naphth-1-yl green 
117 
1-oxy-4-(N-methyl- 
methyl 
(I) bluish-tinged 
N-.beta.-sulfatoethyl- violet 
sulfonyl)-amino-6- 
sulfo-phen-2-yl 
118 
1-oxy-4-sulfo-6- 
methyl 
(I) bluish-tinged 
(.beta.-carboxy- violet 
propionylamino)- 
phen-2-yl 
119 
1-oxy-4-sulfo-6- 
methyl 
(II) bluish-tinged 
(.beta.-carboxy- violet 
propionylamino)- 
phen-2-yl 
120 
1-oxy-4-sulfo-6- 
methyl 
(III) bluish-tinged 
(.beta.-carboxy- violet 
propionylamino)- 
phen-2-yl 
121 
1-oxy-4-sulfo- 
1-naphthyl 
(I) bluish-tinged 
phen-2-yl violet 
122 
1-oxy-4-sulfo- 
sulfo- 
(II) bluish-tinged 
phen-2-yl naphth- violet 
1-yl 
123 
1-carbonyloxy-4- 
phenyl 
(II) bluish-tinged 
sulfo-phen-2-yl claret (524) 
124 
1-carbonyloxy-4- 
phenyl 
(III) bluish-tinged 
sulfo-phen-2-yl claret (538) 
125 
1-carbonyloxy-5- 
phenyl 
(I) bluish-tinged 
sulfo-phen-2-yl claret 
126 
1-carbonyloxy-5- 
phenyl 
(II) bluish-tinged 
sulfo-phen-2-yl claret 
127 
1-carbonyloxy-5- 
phenyl 
(III) bluish-tinged 
sulfo-phen-2-yl claret 
128 
1-carbonyloxy- 
phenyl 
(I) bluish-tinged 
phen-2-yl claret 
129 
1-carbonyloxy-4- 
phenyl 
(I) bluish-tinged 
methoxy-phen-2-yl claret 
130 
1-carbonyloxy-5- 
phenyl 
(I) bluish-tinged 
chloro-phen-2-yl claret 
131 
1-carbonyloxy-4- 
phenyl 
(I) bluish-tinged 
nitro-phen-2-yl claret 
132 
1-carbonyloxy-4- 
phenyl 
(I) bluish-tinged 
carboxy-phen-2-yl claret 
133 
1-carbonyloxy-5- 
phenyl 
(I) bluish-tinged 
acetylamino- claret 
phen-2-yl 
134 
1-carbonyloxy-4- 
methyl 
(I) bluish-tinged 
sulfo-phen-2-yl claret (524) 
135 
1-carbonyloxy-4- 
methyl 
(II) bluish-tinged 
sulfo-phen-2-yl claret (519) 
136 
1-carbonyloxy-4- 
methyl 
(III) bluish-tinged 
sulfo-phen-2-yl claret (534) 
137 
1-carbonyloxy-5- 
methyl 
(I) bluish-tinged 
sulfo-phen-2-yl claret 
138 
1-carbonyloxy-5- 
methyl 
(II) bluish-tinged 
sulfo-phen-2-yl claret 
139 
1-carbonyloxy-5- 
methyl 
(III) bluish-tinged 
sulfo-phen-2-yl claret 
140 
1-carbonyloxy- 
methyl 
(I) bluish-tinged 
phen-2-yl claret 
142 
1-carbonyloxy-4- 
methyl 
(I) bluish-tinged 
methoxy-phen-2-yl claret 
143 
1-carbonyloxy-5- 
methyl 
(I) bluish-tinged 
chloro-phen-2-yl claret 
144 
1-carbonyloxy-4- 
methyl 
(I) bluish-tinged 
nitro-phen-2-yl claret 
145 
1-carbonyloxy-4- 
methyl 
(I) bluish-tinged 
N-(.beta.-sulfato- claret 
ethylsulfonyl)- 
amino-phen-2-yl 
146 
1-carbonyloxy-4- 
methyl 
(I) bluish-tinged 
(.beta.-sulfatoethyl- claret 
sulfonyl)-phen- 
2-yl 
147 
1,4-disulfo- 
phenyl 
(I) bluish-tinged 
phen-2-yl claret (528) 
148 
1,4-disulfo- 
phenyl 
(III) bluish-tinged 
phen-2-yl claret (538) 
149 
1,5-disulfo- 
phenyl 
(I) bluish-tinged 
phen-2-yl claret 
150 
1,5-disulfo- 
phenyl 
(II) bluish-tinged 
phen-2-yl claret 
151 
1,5-disulfo- 
phenyl 
(III) bluish-tinged 
phen-2-yl claret 
152 
1-sulfo-phen-2-yl 
phenyl 
(I) bluish-tinged 
claret 
153 
1-sulfo-phen-2-yl 
phenyl 
(II) bluish-tinged 
claret 
154 
1-sulfo-phen-2-yl 
phenyl 
(III) bluish-tinged 
claret 
155 
1-sulfo-5-methoxy- 
phenyl 
(III) bluish-tinged 
phen-2-yl claret 
156 
1-sulfo-5-carboxy- 
phenyl 
(I) bluish-tinged 
phen-2-yl claret 
157 
1-sulfo-4-carboxy- 
phenyl 
(II) bluish-tinged 
phen-2-yl claret 
158 
1-sulfo-4-chloro- 
phenyl 
(I) bluish-tinged 
phen-2-yl claret 
159 
1,4-disulfo- 
methyl 
(I) bluish-tinged 
phen-2-yl claret 
160 
1,4-disulfo- 
methyl 
(III) bluish-tinged 
phen-2-yl claret 
161 
1,5-disulfo- 
methyl 
(I) bluish-tinged 
phen-2-yl claret 
162 
1,5-disulfo- 
methyl 
(II) bluish-tinged 
phen-2-yl claret 
163 
1,5-disulfo- 
methyl 
(III) bluish-tinged 
phen-2-yl claret 
164 
1-sulfo-phen-2-yl 
methyl 
(I) bluish-tinged 
claret 
165 
1-sulfo-phen-2-yl 
methyl 
(II) bluish-tinged 
claret 
166 
1-sulfo-phen-2-yl 
methyl 
(III) bluish-tinged 
claret 
167 
1-sulfo-5-methoxy- 
methyl 
(I) bluish-tinged 
phen-2-yl claret 
168 
1-sulfo-5-carboxy- 
methyl 
(I) bluish-tinged 
phen-2-yl claret 
169 
1-sulfo-4-carboxy- 
methyl 
(II) bluish-tinged 
phen-2-yl claret 
170 
1-sulfo-4-chloro- 
methyl 
(I) bluish-tinged 
phen-2-yl claret 
171 
1-oxy-4-VS-6- 
phenyl 
(II) bluish-tinged 
sulfo-phen-2-yl claret 
172 
1-oxy-4-VS-6- 
phenyl 
(III) bluish-tinged 
sulfo-phen-2-yl claret 
173 
1-oxy-4-VS-6- 
phenyl 
1-oxy-4-sulfo- 
bluish-tinged 
sulfo-phen-2-yl phen-2-yl 
claret 
174 
1-oxy-4-VS-6- 
phenyl 
1-oxy-4,6-di- 
reddish-tinged 
sulfo-phen-2-yl sulfo-phen- 
violet 
2-yl 
175 
1-oxy-4-VS-6- 
phenyl 
1-oxy-4-sulfo- 
reddish-tinged 
sulfo-phen-2-yl 6-acetylamino- 
violet 
phen-2-yl 
176 
1-oxy-4-VS-6- 
phenyl 
1-oxy-4-sulfo- 
reddish-tinged 
sulfo-phen-2-yl 6-(.beta.-carboxy- 
violet 
propionylamino)- 
phen-2-yl 
177 
1-oxy-4-VS-6- 
phenyl 
1-oxy-4-sulfo- 
bluish-tinged 
sulfo-phen-2-yl 6-nitro-phen- 
violet 
2-yl 
178 
1-oxy-4-VS-6- 
phenyl 
1-oxy-4-ethyl- 
reddish-tinged 
sulfo-phen-2-yl sulfonyl-6- 
violet 
sulfo-phen- 
2-yl 
179 
1-oxy-4-VS- 
phenyl 
1-oxy-4,6- 
reddish-tinged 
phen-2-yl disulfo-phen- 
violet 
2-yl 
180 
1-oxy-4-VS- 
phenyl 
(I) reddish-tinged 
phen-2-yl violet 
181 
1-oxy-5-VS- 
phenyl 
(I) reddish-tinged 
phen-2-yl violet 
182 
1-oxy-5-VS- 
phenyl 
1-oxy-4,6- 
reddish-tinged 
phen-2-yl disulfo-phen- 
violet 
2-yl 
183 
1-sulfo-5-VS- 
methyl 
1-oxy-4-sulfo- 
bluish-tinged 
phen-2-yl phen-2-yl 
claret 
184 
1-oxy-4-VS-6- 
methyl 
(II) reddish-tinged 
sulfo-phen-2-yl violet 
185 
1-oxy-4-VS-6- 
methyl 
(III) bluish-tinged 
sulfo-phen-2-yl violet 
186 
1-oxy-4-VS-6- 
methyl 
1-oxy-4-sulfo- 
reddish-tinged 
sulfo-phen-2-yl phen-2-yl 
violet 
187 
1-oxy-4-VS-6- 
methyl 
1-oxy-4,6-di- 
reddish-tinged 
sulfo-phen-2-yl sulfo-phen- 
violet 
2-yl 
188 
1-oxy-4-VS-6- 
methyl 
1-oxy-4-sulfo- 
reddish-tinged 
sulfo-phen-2-yl 6-acetylamino- 
violet 
phen-2-yl 
189 
1-oxy-4-VS-6- 
methyl 
1-oxy-4-sulfo- 
reddish-tinged 
sulfo-phen-2-yl 6-(.beta.-carboxy- 
violet 
propionyl- 
amino)-phen-2- 
yl 
190 
1-oxy-4-VS-6- 
methyl 
1-oxy-4-sulfo- 
bluish-tinged 
sulfo-phen-2-yl 6-nitro-phen- 
violet 
2-yl 
191 
1-oxy-4-VS-6- 
methyl 
1-oxy-4-ethyl- 
reddish-tinged 
sulfo-phen-2-yl sulfonyl-6- 
violet 
sulfo-phen-2- 
yl 
192 
1-oxy-4-VS- 
methyl 
1-oxy-4,6-di- 
reddish-tinged 
phen-2-yl sulfo-phen-2-yl 
violet 
193 
1-oxy-4-VS- 
methyl 
(I) reddish-tinged 
phen-2-yl violet 
194 
1-oxy-5-VS- 
methyl 
(I) bluish-tinged 
phen-2-yl violet 
195 
1-oxy-5-VS- 
methyl 
1-oxy-4,6-di- 
bluish-tinged 
phen-2-yl sulfo-phen- 
violet 
2-yl 
196 
1-carbonyloxy- 
phenyl 
(I) bluish-tinged 
4-VS-phen-2-yl claret 
197 
1-carbonyloxy- 
phenyl 
1-oxy-4,6-di- 
bluish-tinged 
4-VS-phen-2-yl sulfo-phen-2- 
claret 
yl 
198 
1-carbonyloxy- 
phenyl 
1-oxy-4-sulfo- 
bluish-tinged 
4-VS-phen-2-yl phen-2-yl 
claret 
199 
1-carbonyloxy- 
phenyl 
1-oxy-4-sulfo- 
bluish-tinged 
4-VS-phen-2-yl 6-chloro- 
claret 
phen-2-yl 
200 
1-carbonyloxy- 
phenyl 
1-oxy-4- bluish-tinged 
4-VS-phen-2-yl methyl-sul- 
claret 
fonyl-6-sulfo- 
phen-2-yl 
201 
1-carbonyloxy- 
phenyl 
1-oxy-4-sulfo- 
bluish-tinged 
4-VS-phen-2-yl 6-acetylamino- 
claret 
phen-2-yl 
202 
1-carbonyloxy- 
phenyl 
1-oxy-4-sulfo- 
bluish-tinged 
4-VS-phen-2-yl 6-(.beta.-carboxy- 
claret 
propionyl- 
amino)-phen-2-yl 
203 
1-carbonyloxy- 
phenyl 
2-oxy-4,6-di- 
bluish-tinged 
4-VS-phen-2-yl sulfo-naphth- 
violet 
1-yl 
204 
1-carbonyloxy-5- 
phenyl 
1-oxy-4,6-di- 
bluish-tinged 
VS-phen-2-yl sulfo-phen- 
claret 
2-yl 
205 
1-carbonyloxy-5- 
phenyl 
1-oxy-4-sulfo- 
bluish-tinged 
VS-phen-2-yl phen-2-yl 
claret 
206 
1-carbonyloxy-4- 
methyl 
(I) bluish-tinged 
VS-phen-2-yl claret 
207 
1-carbonyloxy-4- 
methyl 
1-oxy-4,6-di- 
bluish-tinged 
VS-phen-2-yl sulfo-phen-2- 
claret 
yl 
208 
1-carbonyloxy-4- 
methyl 
1-oxy-4-sulfo- 
bluish-tinged 
VS-phen-2-yl phen-2-yl 
claret 
209 
1-carbonyloxy-4- 
methyl 
1-oxy-5-sulfo- 
bluish-tinged 
VS-phen-2-yl 6-chloro-phen- 
claret 
2-yl 
210 
1-carbonyloxy-4- 
methyl 
1-oxy-4- bluish-tinged 
VS-phen-2-yl methyl-sul- 
claret 
fonyl-6-sulfo- 
phen-2-yl 
211 
1-carbonyloxy-4- 
methyl 
1-oxy-4-sulfo- 
bluish-tinged 
VS-phen-2-yl 6-acetylamino- 
claret 
phen-2-yl 
212 
1-carbonyloxy-4- 
methyl 
1-oxy-4-sulfo- 
bluish-tinged 
VS-phen-2-yl 6-(.beta.-carboxy- 
claret 
propionyl- 
amino)-phen- 
2-yl 
213 
1-carbonyloxy-4- 
methyl 
2-oxy-4,6-di- 
bluish-tinged 
VS-phen-2-yl sulfo-naphth- 
claret 
1-yl 
214 
1-carbonyloxy-5- 
methyl 
1-oxy-4,6-di- 
bluish-tinged 
VS-phen-2-yl sulfo-phen-2-yl 
claret 
215 
1-carbonyloxy-5- 
methyl 
1-oxy-4-sulfo- 
bluish-tinged 
VS-phen-2-yl phen-2-yl 
claret 
216 
1-sulfo-4-VS- 
phenyl 
(I) bluish-tinged 
phen-2-yl claret 
217 
1-sulfo-4-VS- 
phenyl 
(II) bluish-tinged 
phen-2-yl claret 
218 
1-sulfo-4-VS- 
phenyl 
(III) bluish-tinged 
phen-2-yl claret 
219 
1-sulfo-4-VS- 
phenyl 
1-oxy-4-sulfo- 
bluish-tinged 
phen-2-yl phen-2-yl 
claret 
220 
1-sulfo-4-VS- 
phenyl 
1-oxy-4,6-di- 
bluish-tinged 
phen-2-yl sulfo-phen- 
claret 
2-yl 
221 
1-sulfo-4-VS- 
phenyl 
1-oxy-4-sulfo- 
bluish-tinged 
phen-2-yl 6-chloro- 
claret (537) 
phen-2-yl 
222 
1-sulfo-5-VS- 
phenyl 
1-oxy-4-sulfo- 
bluish-tinged 
phen-2-yl 6-chloro- 
claret 
phen-2-yl 
223 
1-sulfo-5-VS- 
phenyl 
(I) bluish-tinged 
phen-2-yl claret 
224 
1-sulfo-5-VS- 
phenyl 
1-oxy-6-acet- 
bluish-tinged 
phen-2-yl ylamino- claret 
phen-2-yl 
225 
1-sulfo-5-VS- 
phenyl 
1-oxy-4,6-di- 
bluish-tinged 
phen-2-yl sulfo-phen- 
claret 
2-yl 
226 
1-sulfo-5-VS- 
phenyl 
1-oxy-4-sulfo- 
bluish-tinged 
phen-2-yl phen-2-yl 
claret 
227 
1-sulfo-4-VS- 
methyl 
(I) bluish-tinged 
phen-2-yl claret 
228 
1-sulfo-4-VS- 
methyl 
(II) bluish-tinged 
phen-2-yl claret 
229 
1-sulfo-4-VS- 
methyl 
(III) bluish-tinged 
phen-2-yl claret 
230 
1-sulfo-4-VS- 
methyl 
1-oxy-4-sulfo- 
bluish-tinged 
phen-2-yl phen-2-yl 
claret (536) 
231 
1-sulfo-4-VS- 
methyl 
1-oxy-4,6-di- 
bluish-tinged 
phen-2-yl sulfo-phen- 
claret 
2-yl 
232 
1-sulfo-4-VS- 
methyl 
1-oxy-4-sulfo- 
bluish-tinged 
phen-2-yl 6-chloro- 
claret 
phen-2-yl 
233 
1-sulfo-5-VS- 
methyl 
1-oxy-4-sulfo- 
bluish-tinged 
phen-2-yl 6-chloro- 
claret 
phen-2-yl 
234 
1-sulfo-5-VS- 
methyl 
(I) bluish-tinged 
phen-2-yl claret 
235 
1-sulfo-5-VS- 
methyl 
1-oxy-6-acet- 
bluish-tinged 
phen-2-yl ylamino-phen- 
claret 
2-yl 
236 
1-sulfo-5-VS- 
methyl 
1-oxy-4,6-di- 
bluish-tinged 
phen-2-yl sulfo-phen-2-yl 
claret 
__________________________________________________________________________ 
USE EXAMPLE 1 
An aqueous bath which consists of 0.25 part by volume of a 60% strength 
aqueous acetic acid, 0.15 part of a commercially available leveling 
auxiliary for wool and 0.3 part of ammonium sulfate in 400 parts of water 
is prepared for the purpose of dyeing 10 parts of a yarn of wool. This 
wool is wetted thoroughly in the bath at a temperature of 30.degree. to 
40.degree. C. and a pH of the bath of 5 to 5.2. A solution of 0.2 part of 
the vinylsulfonyl-copper complex formazan dyestuff of Example 2 in 20 
parts of water is then introduced into the bath, while stirring. The wool 
is still agitated in the bath, the temperature is left at 30.degree. to 
40.degree. C. for 5 minutes, the dyebath is then heated to 85.degree. C. 
in the course of 40 minutes, dyeing is continued at this temperature for 
10 minutes and the dyebath is then heated to the boiling point in the 
course of 10 minutes. Dyeing is continued at the boil for 1 hour. The bath 
is then cooled to 80.degree. C. The dyestuff used has been absorbed very 
well onto the wool. After-treatment of the dyed woollen yarn can therefore 
take place in the same bath. Ammonia is added to a pH of 8 to 8.5,and the 
material is treated at this pH and at a temperature of 80.degree. C. for 
15 minutes. It is removed, rinsed with hot and cold water and dried. A 
deep claret dyeing with the good use and fabrication properties mentioned 
in Example 2 is obtained. 
USE EXAMPLE 2 
An aqueous padding liquor which contains, per liter, 40 g of the copper 
formazan dyestuff according to the invention of Example 9, 100 g of urea, 
30 g of anhydrous sodium sulfate and 16 ml of an aqueous 32.5 % strength 
sodium hydroxide solution is prepared for dyeing a cotton fabric. The 
cotton fabric is padded at room temperature with a liquor pick-up of 80% 
of the weight of the cotton fabric, wound onto a beam, wrapped in a 
plastic film and left to lie at room temperature for 24 hours. During this 
time, the dyestuff is fixed. After soaping and rinsing in the customary 
manner, a deep brilliant claret dyeing which has the good use and 
fabrication properties mentioned in Example 9 is obtained. 
USE EXAMPLE 3 
An aqueous dyebath which contains, in 2000 parts by volume, 5 parts of the 
copper formazan dyestuff according to the invention of Example 4, 100 
parts of sodium chloride, 10 parts of anhydrous sodium carbonate and 4 
parts by volume of a 32.5% strength aqueous sodium hydroxide solution as a 
solution is prepared for dyeing a cotton fabric. 100 parts of a cotton 
fabric are introduced into this dyebath and dyed at a temperature of 
40.degree. C. for between 60 and 90 minutes. After soaping and rinsing in 
the customary manner, a deep brilliant violet dyeing with the good use and 
fabrication properties mentioned in Example 4 is obtained. 
USE EXAPLE 4 
A printing paste which contains, per 1000 parts, 30 parts of the copper 
formazan dyestuff according to the invention of Example 9, 50 parts of 
urea, 375 parts of water, 500 parts of a neutral 4% strength aqueous 
alginate thickener, 15 parts of sodium bicarbonate and 10 parts of the 
sodium salt of m-nitrobenzoic acid is used for printing a mercerized 
cotton fabric. The cotton fabric is printed with this printing paste in 
the customary manner and, after drying, is steamed with steam of 
101.degree. to 103.degree. C. for 10 to 15 minutes. After this fixing 
operation, the fabric is finished in the customary manner by rinsing with 
cold and hot water, by soaping at the boiling point and renewed rinsing 
with water and by subsequent drying. A deep brilliant claret-colored print 
of good light- and wet-fastnesses is obtained. 
USE EXAMPLE 5 
A solution of 30 parts of the copper formazan dyestuff according to the 
invention of Example 9 in 200 parts of water at 70.degree. C. is stirred 
into 500 parts of a neutral or weakly acid 4% strength alginate thickener. 
The thickened dyestuff solution is made up to 1000 parts with water. A 
fabric of mercerized cotton is printed in the customary manner with the 
printing paste thus prepared, and is then dried and passed through a hot 
aqueous fixing bath, which contains, in 1000 parts of water, 100 parts of 
sodium chloride, 150 parts of anhydrous sodium carbonate, 50 parts of 
anhydrous potassium carbonate and 70 parts by volume of a 33% strength 
aqueous sodium hydroxide solution, at 90.degree. to 105.degree. C. in 
order to fix the dyestuff. Fixing is already effected here within a few 
seconds, so that the printed fabric can be passed through very rapidly. 
After this fixing treatment, the fabric is finished in the customary 
manner by rinsing with cold water and by hot washing, renewed rinsing with 
water and drying. A level, claret-colored print sample of good light- and 
wet-fastnesses is obtained. 
USE EXAMPLE 6 
An aqueous padding liquor which contains, per 1000 parts by volume, 40 
parts of the copper formazan dyestuff according to the invention of 
Example 9, 95 parts by volume of waterglass, 5 parts of a commercially 
available leveling auxiliary and 28.5 parts by volume of an aqueous 32.5% 
strength sodium hydroxide solution is prepared for dyeing a cotton fabric. 
The cotton fabric is padded at room temperature at a liquor pick-up of 80% 
of the weight of the cotton fabric, wound onto a beam, wrapped in plastic 
film and left to stand at room temperature for 24 hours. During this time, 
the dyestuff is fixed. After soaping and rinsing in the customary manner, 
a deep brilliant claret-colored dyeing of good light- and wet-fastnesses 
is obtained. 
USE EXAMPLE 7 
An aqueous dyebath which contains, in 2000 parts by volume, 6 parts of the 
copper formazan dyestuff according to the invention of Example 1, 10 parts 
of anhydrous sodium sulfate, 10 parts of anhydrous sodium carbonate and 4 
parts by volume of a 32.5% strength aqueous sodium hydroxide solution, is 
prepared for dyeing a cotton fabric. 100 parts of a cotton fabric are 
introduced into this dyebath and dyed at a temperature of 60.degree. C. 
for between 60 and 90 minutes. After soaping and rinsing in the customary 
manner, a deep bluish-tinged claret dyeing with the good fastness 
properties mentioned in Example 1 is obtained. 
USE EXAMPLE 8 
If the procedure followed is one of the procedures according to the present 
invention for dyeing and printing wool or synthetic polyamide materials or 
cellulose fiber materials, for example analogously to Use Examples 1 to 7, 
and other copper complex formazan dyestuffs according to the invention 
described in the embodiment and Tabular Examples 1 to 236 are used for 
this, according to the invention, as the dyestuff, strong dyeings and 
prints with good fastnesses and the color shades mentioned for these 
dyestuffs are likewise obtained.