Monoazo compounds having vinylsulfone type fiber reactive group and method for dyeing or printing fiber materials using the same

A monoazo compound of the following formula, ##STR1## wherein D is phenylene or naphthylene; X is halogeno, pyridinio or ##STR2## B is --OR.sub.3, --SR.sub.4, ##STR3## in which R.sub.3, R.sub.4, R.sub.5 and R.sub.6 are each hydrogen, alkyl, phenyl, naphthyl or benzyl, r is 0 or 1, and E is O, SO, SO.sub.2, CH.sub.2 or NR.sub.8, in which R.sub.8 is hydrogen or C.sub.1 -C.sub.4 alkyl; R, R.sub.1, R.sub.2 and R.sub.7 are each hydrogen or alkyl; A.sub.1, A.sub.2 and A.sub.3 are each phenylene, naphthylene or alkylene; Z.sub.1, Z.sub.2 and Z.sub.3 are each --SO.sub.2 CH.dbd.CH.sub.2 or --SO.sub.2 CH.sub.2 CH.sub.2 Y, in which Y is a splittable group; and p is 0 or 1; which compound is useful for dyeing or printing fiber materials to obtain a product dyed or printed in a color superior in various fastness properties with superior build-up property.

The present invention relates to improved compounds suitable for use in 
dyeing and printing materials containing hydroxyl group and/or amide 
group, particularly those such as cellulose fiber, natural and synthetic 
polyamide fibers, polyurethane fiber, leather and mixed yarns thereof, to 
obtain a red color fast to light and wetness, as well as application of 
said compounds. 
There are known compounds having a vinyl sulfone type reactive group and a 
monohalogenotriazine type reactive group in one molecule and compounds 
having two vinyl sulfone type reactive groups in one molecule, as 
disclosed in EP 384276, etc. However, they are yet insufficient from the 
viewpoint of dyeing performances such as build-up property, and a further 
improvement of these dyes is waited for. 
A variety of reactive dyes have hitherto been used extensively for dyeing 
and printing fiber materials. Today's level of the technique, however, is 
unsatisfactory from the viewpoint of the high requirements concerning 
applicability to particular dyeing processes and the requirement 
concerning fastness properties of the dyed products which is becoming 
higher. 
For example, the so far known reactive dyes are unsatisfactory in 
solubility, dyeing performances such as build-up property, and fastness 
properties, and it is intensely desired to develop a more improved dye. 
The excellency in build-up property is a very important factor of the dye, 
because today's dyeing processes have become requiring a more and more 
elevated economicity. The present inventors have conducted extensive 
studies with the aim of discovering a novel compound capable of overcoming 
the above-mentioned faults of the known dyes and extensively fulfilling 
the necessary conditions which a dye must fulfill, and as a result, the 
present invention has been accomplished. 
The present invention provides a monoazo compound represented by the 
following formula (I) in the free acid form, 
##STR4## 
wherein D is an unsubstituted or substituted phenylene or naphthylene 
group; X is halogeno, an unsubstituted or substituted pyridinio group or 
##STR5## 
B is --OR.sub.3, --SR.sub.4, 
##STR6## 
in which R.sub.3, R.sub.4, R.sub.5 and R.sub.6 independently of one 
another are each hydrogen, or an unsubstituted or substituted alkyl, 
phenyl, naphthyl or benzyl group, r is 0 or 1, and E is O, SO, SO.sub.2, 
CH.sub.2 or NR.sub.8, in which R.sub.8 is hydrogen or C.sub.1 -C.sub.4 
alkyl; R, R.sub.1, R.sub.2 and R.sub.7 independently of one another are 
each hydrogen, or an unsubstituted or substituted alkyl group; A.sub.1, 
A.sub.2 and A.sub.3 independently of one another are each an unsubstituted 
or substituted phenylene, naphthylene or alkylene group; Z.sub.1, Z.sub.2 
and Z.sub.3 independently of one another are each --SO.sub.2 
CH.dbd.CH.sub.2 or --SO.sub.2 CH.sub.2 CH.sub.2 Y, in which Y is a group 
capable of being split by the action of an alkali; and p is 0 or 1. 
The present invention also provides a process for producing the monoazo 
compound represented by the formula (I), which comprises subjecting a 
compound represented by the following formula (II) in the free acid form, 
##STR7## 
wherein D, R, R.sub.1, A.sub.1, Z.sub.1 and p are as defined above, any 
one of compounds represented by the following formulas (III) to (VII) 
EQU HOR.sub.3 (III) 
EQU HSR.sub.4 (IV) 
EQU HNR5R.sub.6 (V) 
##STR8## 
wherein R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, A.sub.3, Z.sub.3, r 
and E are as defined above, and optionally unsubstituted or substituted 
pyridine or an amine represented by the formula of 
##STR9## 
in which R.sub.2, A.sub.2 and Z.sub.2 are as defined above, to a 
condensation reaction with 2,4,6-trihalogeno-s-triazine in an optional 
order. 
In formula (I), preferable examples of the phenylene and naphthylene 
represented by A.sub.1, A.sub.2 and A.sub.3 include phenylene 
unsubstituted or substituted once or twice by a substituent selected from 
the group consisting of methyl, ethyl, methoxy, ethoxy, chloro, bromo and 
sulfo and naphthylene unsubstituted or substituted by sulfo, of which 
specific examples include the followings: 
##STR10## 
wherein the mark * signifies a bond linking to 
##STR11## 
and the like. 
Among the phenylene and naphthylene represented by A.sub.1, A.sub.2 and 
A.sub.3, phenylene is more preferable, and the groups represented by the 
following formulas: 
##STR12## 
are particularly preferable, wherein the mark * signifies a bond linking 
to 
##STR13## 
As the alkylene represented by A.sub.1, A.sub.2 and A.sub.3, the groups 
represented by the following formulas can be referred to: 
##STR14## 
wherein the mark * signifies a bond linking to 
##STR15## 
alk represents a polymethylene group having 1 to 6 carbon atoms or its 
branched isomer; R' represents hydrogen, chloro, bromo, fluoro, hydroxy, 
sulfato, acyloxy having 1 to 4 carbon atoms, cyano, carboxy, 
alkoxycarbonyl having 1 to 5 carbon atoms or carbamoyl; R" represents 
hydrogen or alkyl having 1 to 6 carbon atoms; the groups alk' 
independently of one another each represents polymethylene having 2 to 6 
carbon atoms or its branched isomer, provided that alk' and R" may be 
taken together to form a ring via a methylene group; n represents 1 to 6; 
and m represents an integer of 1 to 6. 
In formula (a), the polymethylene group represented by alk is preferably 
methylene, ethylene, methylmethylene, propylene or butylene. 
Examples of R" include hydrogen, methyl, ethyl, propyl, isopropyl, butyl, 
isobutyl, sec-butyl, tert-butyl, pentyl, hexyl and the like, among which 
hydrogen is preferable. The polymethylene group represented by alk' is 
preferably ethylene, propylene or butylene. 
The numbers represented by n and m independently of one another are each 2, 
3 or 4, among which 2 is preferable. 
Preferable examples of D include phenylene unsubstituted or substituted 
once or twice by a substituent selected from the group consisting of 
methyl, ethyl, methoxy, ethoxy, chloro, bromo and sulfo and naphthylene 
unsubstituted or substituted by sulfo. Specific examples thereof include 
the followings: 
##STR16## 
wherein the mark ** signifies a bond linking to --N.dbd.N--, and the like. 
Preferable examples of D include the followings: 
##STR17## 
wherein the mark ** signifies a bond linking to --N.dbd.N--. 
Examples of the group capable of being split by the action of an alkali, 
represented by Y, include sulfato, thiosulfato, phosphato acetoxy, halo 
and the like, among which sulfato is preferable. 
As the unsubstituted or substituted alkyl represented by R, R.sub.1, 
R.sub.2 and R.sub.7, alkyl having 1 to 4 carbon atoms are preferable. As 
the substituent, hydroxy, cyano, alkoxy, halo, carbamoyl, carboxy, 
alkoxycarbonyl, alkylcarbonyloxy, sulfo and sulfamoyl are preferable. 
Preferable specific examples of R, R.sub.1, R.sub.2 and R.sub.7 include the 
followings: hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, 
iso-butyl, sec-butyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 
2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, 
3,4-dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 
methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 
3-methoxypropyl, 3-ethoxypropyl, 2-hydroxy-3-methoxypropyl, chloromethyl, 
bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-bromopropyl, 
4-chlorobutyl, 4-bromobutyl, carboxymethyl, 2-carboxyethyl, 
3-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl, carbamoylmethyl, 
2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, 
methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl, 
2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 
4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, 
ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 
3-methylcarbonyloxypropyl, 3-ethylcarbonyloxypropyl, 
4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 
2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, sulfamoylmethyl, 
2-sulfamoylethyl, 3-sulfamoylpropyl and 4-sulfamoylbutyl. Among these 
groups, hydrogen is particularly preferable as R.sub.1, hydrogen, methyl 
and ethyl are particularly preferable as R.sub.2 and R.sub.7, and hydrogen 
and methyl are particularly preferable as R. 
Preferable examples of the unsubstituted or substituted alkyl represented 
by R.sub.3, R.sub.4, R.sub.5 and R.sub.6 include alkyl having 1 to 4 
carbon atoms unsubstituted or substituted once or twice by a substituent 
selected from the group consisting of alkoxy having 1 to 4 carbon atoms, 
sulfo, carboxy, hydroxy, chloro, phenyl, cyano and sulfato. 
Among them, more preferable are methyl, ethyl, n-propyl, iso-propyl, 
n-butyl, iso-butyl, sec-butyl, .beta.-hydroxyethyl, .beta.-sulfatoethyl, 
.beta.-sulfoethyl, .beta.-methoxyethyl, .beta.-ethoxyethyl, 
.beta.-chloroethyl, .beta.-carboxyethyl and the like. 
Preferable examples of the unsubstituted or substituted phenyl represented 
by R.sub.3, R.sub.4, R.sub.5 and R.sub.6 include phenyl unsubstituted or 
substituted once or twice by a substituent selected from the group 
consisting of alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 
carbon atoms, sulfo, carboxy, chloro and bromo. 
Among them, particularly preferable are phenyl, 2-, 3- or 4-sulfophenyl, 
2,4- or 2,5-disulfophenyl, 2-, 3- or 4-carboxyphenyl, 2-, 3- or 
4-chlorophenyl, 2-, 3- or 4-methylphenyl and 2-, 3- or 4-methoxyphenyl. 
Preferable examples of the unsubstituted or substituted naphthyl 
represented by R.sub.3, R.sub.4, R.sub.5 and R.sub.6 include naphthyl 
unsubstituted or substituted once, twice or three times by a substituent 
selected from the group consisting of hydroxy, carboxy, sulfo, alkyl 
having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms and chloro. 
Among them, particularly preferable are 2-, 3-, 4-, 5-, 6-, 7- or 
8-sulfo-1-naphthyl, 1-, 5-, 6-, 7- or 8-sulfo-2-naphthyl, 1,5-, 5,7-, 
6,8-, 4,8-, 4,7-, 3,8-, 4,6-, 3,7- or 3,6-disulfo-2-naphthyl, 4,6,8-, 
2,4,7- or 3,6,8-trisulfo-1-naphthyl, 1,5,7-, 4,6,8- or 
3,6,8-trisulfo-2-naphthyl and the like. 
Preferable examples of the unsubstituted or substituted benzyl represented 
by R.sub.3, R.sub.4, R.sub.5 and R.sub.6 include benzyl unsubstituted or 
substituted once or twice by a substituent selected from the group 
consisting of alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 
carbon atoms, sulfo and chloro. 
Among them, benzyl and 2-, 3- or 4-sulfobenzyl and the like are 
particularly preferable. 
In the present invention, a case that one of R.sub.5 and R.sub.6 is 
hydrogen, methyl or ethyl and the other is phenyl unsubstituted or 
substituted by C.sub.1-4 alkyl, C.sub.1-4 alkoxy, sulfo, carboxy or halo 
is particularly preferable from the viewpoint of dyeing performances. 
When B in formula (I) is a group represented by 
##STR18## 
examples of the compound represented by 
##STR19## 
used for forming such a group include the followings: ammonia; 
aromatic amines such as 1-aminobenzene, 1-amino-2-, -3- or 
-4-methylbenzene, 1-amino-3,4- or -3,5-dimethylbenzene, 1-amino-2-, -3- or 
-4-ethylbenzene, 1-amino-2-, -3- or -4-methoxybenzene, 1-amino-2-, -3- or 
-4-ethoxybenzene, 1-amino-2-, -3- or -4-chlorobenzene, 3- or 
4-amino-phenylmethanesulfonic acid, 2-, 3- or 4-aminobenzenesulfonic acid, 
3-methylaminobenzenesulfonic acid, 3-ethylaminobenzenesulfonic acid, 
4-methylaminobenzenesulfonic acid, 4-ethylaminobenzenesulfonic acid, 
5-aminobenzene-1,3-disulfonic acid, 6-aminobenzene-1,3-disulfonic acid, 
6-aminobenzene-1,4-disulfonic acid, 4-aminobenzene-1,2-disulfonic acid, 
4-amino-5-methylbenzene-1,2-disulfonic acid, 2-, 3- or 4-aminobenzoic 
acid, 5-aminobenzene-1,3-dicarboxylic acid, 
5-amino-2-hydroxybenzenesulfonic acid, 4-amino-2-hydroxybenzenesulfonic 
acid, 5-amino-2-ethoxybenzenesulfonic acid, N-methylaminobenzene, 
N-ethylaminobenzene, 1-methylamino-3- or -4-methylbenzene, 
1-ethylamino-4-chlorobenzene, 1-ethylamino-3- or -4-methylbenzene, 
1-(2-hydroxyethyl)-amino-3-methylbenzene, 3- or 4-methylaminobenzoic acid, 
3- or 4-methylaminobenzenesulfonic acid, 2-aminonaphthalene-1-sulfonic 
acid, 4-aminonaphthalene-1-sulfonic acid, 5-aminonaphthalene-1-sulfonic 
acid, 6-aminonaphthalene-1-sulfonic acid, 7-aminonaphthalene-1-sulfonic 
acid, 8-aminonaphthalene-1-sulfonic acid, 1-aminonaphthalene-2-sulfonic 
acid, 4-aminonaphthalene-2-sulfonic acid, 5-aminonaphthalene-2-sulfonic 
acid, 6-aminonaphthalene-2-sulfonic acid, 7-aminonaphthalene-2-sulfonic 
acid, 7-methylaminonaphthalene-2-sulfonic acid, 
7-ethylaminonaphthalene-2-sulfonic acid, 
7-butylaminonaphthalene-2-sulfonic acid, 
7-isobutylaminonaphthalene-2-sulfonic acid, 8-aminonaphthalene-2-sulfonic 
acid, 4-aminonaphthalene-1,3-disulfonic acid, 
5-aminonaphthalene-1,3-disulfonic acid, 6-aminonaphthalene-1,3-disulfonic 
acid, 7-aminonaphthalene-1,3-disulfonic acid, 8-aminonaphthalene- 
1,3-disulfonic acid, 2-aminonaphthalene-1,5-disulfonic acid, 
3-aminonaphthalene-1,5-disulfonic acid, 4-aminonaphthalene-1,5-disulfonic 
acid, 4-aminonaphthalene-1,6-disulfonic acid, 
8-aminonaphthalene-1,6-disulfonic acid, 4-aminonaphthalene-1,7-disulfonic 
acid, 3-aminonaphthalene-2,6-disulfonic acid, 
4-aminonaphthalene-2,6-disulfonic acid, 3-aminonaphthalene-2,7-disulfonic 
acid, 4-aminonaphthalene-2,7-disulfonic acid, 
6-aminonaphthalene-1,3,5-trisulfonic acid, 
7-aminonaphthalene-1,3,5trisulfonic acid, 
4-aminonaphthalene-1,3,6-trisulfonic acid, 
7-aminonaphthalene-1,3,6-trisulfonic acid, 
8-aminonaphthalene-1,3,6-trisulfonic acid and 
4-aminonaphthalene-1,3,7-trisulfonic acid; and 
aliphatic amines such as methylamine, ethylamine, n-propylamine, 
isopropylamine, n-butylamine, isobutylamine, sec-butylamine, 
dimethylamine, diethylamine, methylethylamine, allylamine, 
2-chloroethylamine, 2-methoxyethylamine, 2-aminoethanol, 
2-methylaminoethanol, bis(2-hydroxyethyl)-amine, 2-acetylaminoethylamine, 
1-amino-2-propanol, 3-methoxypropylamine, 1-amino-3-dimethylaminopropane, 
2-aminoethanesulfonic acid, aminomethanesulfonic acid, 
2-methylaminoethanesulfonic acid, 3-amino-1-propanesulfonic acid, 
2-sulfatoethylamine, aminoacetic acid, methylaminoacetic acid, 
.epsilon.-aminocaproic acid, benzylamine, 2-, 3- or 4-chlorobenzylamine, 
4-methylbenzylamine, N-methylbenzylamine, 2-, 3- or 4-sulfobenzylamine, 
2-phenylethylamine, 1-phenylethylamine and 1-phenyl-2-propylamine. 
Among these compounds, particularly preferable are aniline, 
N-methylaniline, N-ethylaniline, 2-, 3- or 4-chloroaniline, N-methyl-2-, 
-3- or -4-chloroaniline, N-ethyl-2-, -3- or -4-chloroaniline, 2-, 3- or 
4-methylaniline, 2-, 3- or 4-sulfoaniline, aniline-2,4- or -2,5-disulfonic 
acid, 3- or 4-methylaminobenzenesulfonic acid, 3- or 
4-ethylaminobenzenesulfonic acid, 2-, 3- or 4-carboxyaniline, taurine, 
N-methyltaurine, mono- or di-ethanolamine, and the like. 
When B in formula (I) is a group represented by --OR.sub.3, examples of the 
compound represented by R.sub.3 OH, used for forming such a group include 
the followings: 
aromatic compounds such as phenol, 1-hydroxy-2-, -3- or -4-methylbenzene, 
1-hydroxy-3,4- or -3,5-dimethylbenzene, 1-hydroxy-2-, -3- or 
-4-ethylbenzene, 1-hydroxy-2-, -3- or -4-methoxybenzene, 1-hydroxy-2-, -3- 
or -4-ethoxybenzene, 1-hydroxy-2-, -3- or -4-chlorobenzene, 3- or 
4-hydroxyphenylmethanesulfonic acid, 3-hydroxybenzenesulfonic acid, 
4-hydroxybenzenesulfonic acid, 5-hydroxybenzene-1,3-disulfonic acid, 
6-hydroxybenzene-1,4-disulfonic acid, 4-hydroxybenzene-1,2disulfonic acid, 
4-hydroxy-5-methylbenzene-1,2-disulfonic acid, 3- or 4-hydroxybenzoic 
acid, 5-hydroxybenzene-1,3-dicarboxylic acid, 
5-hydroxy-2-ethoxybenzenesulfonic acid, 2-hydroxynaphthalene-1-sulfonic 
acid, 4-hydroxynaphthalene-1-sulfonic acid, 
5-hydroxynaphthalene-1-sulfonic acid, 6-hydroxynaphthalene-1-sulfonic 
acid, 7-hydroxynaphthalene-1-sulfonic acid, 
8-hydroxynaphthalene-1-sulfonic acid, 1-hydroxynaphthalene-2-sulfonic 
acid, 4-hydroxynaphthalene-2-sulfonic acid, 
5-hydroxynaphthalene-2-sulfonic acid, 6-hydroxynaphthalene-2-sulfonic 
acid, 7-hydroxynaphthalene-2-sulfonic acid, 
8-hydroxynaphthalene-2-sulfonic acid, 4-hydroxynaphthalene-1,3-disulfonic 
acid, 5-hydroxynaphthalene-1,3-disulfonic acid, 
6-hydroxynaphthalene-1,3-disulfonic acid, 
7-hydroxynaphthalene-1,3-disulfonic acid, 
8-hydroxynaphthalene-1,3-disulfonic acid, 
2-hydroxynaphthalene-1,5-disulfonic acid, 
3-hydroxynaphthalene-1,5-disulfonic acid, 
4-hydroxynaphthalene-1,5-disulfonic acid, 
4-hydroxynaphthalene-1,6-disulfonic acid, 
8-hydroxynaphthalene-1,6-disulfonic acid, 
4-hydroxynaphthalene-1,7-disulfonic acid, 
3-hydroxynaphthalene-2,6-disulfonic acid, 
4-hydroxynaphthalene-2,6-disulfonic acid, 
3-hydroxynaphthalene-2,7-disulfonic acid, 
4-hydroxynaphthalene-2,7-disulfonic acid, 
6-hydroxynaphthalene-1,3,5-trisulfonic acid, 
7-hydroxynaphthalene-1,3,5-trisulfonic acid and 
4-hydroxynaphthalene-1,3,6-trisulfonic acid; and 
aliphatic compounds such as methanol, ethanol, n-propanol, isopropanol, 
n-butanol, isobutanol, sec-butanol, 2-chloroethanol, 2-methoxyethanol, 
2-ethoxyethanol, 3-methoxypropanol, 3-ethoxypropanol, 
2-hydroxyethanesulfonic acid, 3-hydroxy-1-propanesulfonic acid, 
2-cyanoethanol, 2-sulfatoethanol, glycolic acid, 3-hydroxypropanionic 
acid, benzyl alcohol, 2-, 3- or 4-chlorobenzyl alcohol, 4-methylbenzyl 
alcohol, 2-, 3- or 4-sulfobenzyl alcohol, 2-phenylethanol and 
1-phenyl-2-propanol. When B in formula (I) is a group represented by 
--SR.sub.4, examples of the compound represented by R.sub.4 SH, used for 
forming such a group include compounds having mercapto in place of the 
hydroxy in the above-mentioned compounds. 
When B in formula (I) is 
##STR20## 
wherein r and E are as defined above, a case that r is 1 and E is CH.sub.2 
or O is preferable. 
In the present invention, a case that B is a group represented by 
##STR21## 
is preferable. 
When X is halo, X is preferably chloro or fluoro. When X is a pyridinio 
group having a substituent, examples of said substituent include carboxy, 
carbamoyl, sulfo, halo and unsubstituted or substituted alkyl having 1 to 
4 carbon atoms. As examples of the substituted alkyl, .beta.-hydroxyethyl, 
.beta.-sulfoethyl and the like can be referred to. As the pyridinio group 
represented by X, carboxy- or carbamoyl-substituted pyridinio groups are 
preferable, among which carboxypyridinio is most preferable from the 
viewpoint of dyeing performances. 
Preferable examples of the unsubstituted or substituted pyridine include 
pyridine, 2-, 3- or 4-carboxypyridine, 2-, 3- or 4-carbamoylpyridine, 
3-sulfopyridine, 4-.beta.-sulfoethylpyridine, 
3-.beta.-hydroxyethylpyridine, 4-chloropyridine, 3-methylpyridine, 
3,5-dicarboxypyridine and the like. Among them, 3- or 4-carboxypyridine 
(nicotinic acid and isonicotinic acid) are particularly preferable. 
When X is 
##STR22## 
B is preferably a group represented by 
##STR23## 
The compounds of the present invention exist in the form of a free acid or 
a salt thereof. As the salt, alkali metal salts and alkaline earth metal 
salts are preferable, and sodium salts, potassium salts and lithium salts 
are particularly preferable. 
In the present invention, preferred is one represented by the following 
formula in the free acid form, 
##STR24## 
wherein Z.sub.1, A.sub.1, R.sub.1, D, X and B are as defined above. 
The compounds of the present invention can be produced, for example, in the 
following manner. Thus, a compound represented by the following formula 
(II) in the free acid form: 
##STR25## 
wherein D, A.sub.1, Z.sub.1, R.sub.1, R and p are as defined above, and 
any one of compounds represented by the following formulas (III) to (III) 
EQU HOR.sub.3 (III) 
EQU HSR.sub.4 (IV) 
EQU HNR.sub.5 R.sub.6 (V) 
##STR26## 
wherein R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, A.sub.3, Z.sub.3, r 
and E are as defined above, are subjected to a condensation reaction with 
2,4,6-trihalogeno-s-triazine in an arbitrary order to obtain a compound of 
formula (I) wherein X is halo. The compound thus obtained is subjected to 
a further condensation reaction with an unsubstituted or substituted 
pyridine compound or a compound represented by 
##STR27## 
wherein R.sub.2, A.sub.2 and Z.sub.2 are as defined above, whereby a 
compound of formula (I) wherein X is pyridinio or a group represented by 
##STR28## 
wherein R.sub.2, A.sub.2 and Z.sub.2 are as defined above can be obtained. 
In the present invention, the compound of formula (II) can be obtained by a 
coupling reaction between a compound of the following formula (VIII): 
##STR29## 
and a compound of the following formula (IX): 
##STR30## 
wherein Z.sub.1, A.sub.1, R.sub.1, D, R and p are as defined above. 
Alternatively, the compound of the present invention can be produced in the 
following manner, too. Thus, a compound represented by formula (IX) and 
any one of the compounds represented by formulas (III) to (VII) are 
subjected to a condensation reaction with 2,4,6-trihalogeno-s-triazine in 
an arbitrary order to obtain a compound of the following formula (X): 
##STR31## 
wherein T represents halo; and R, B and p are as defined above. Then, it 
is coupled with a diazo compound of the compound (VIII), whereby there is 
obtained a compound of formula (I) wherein X is halo. If the compound 
obtained above is further condensed with a pyridine compound or a compound 
represented by 
##STR32## 
wherein R.sub.2, A.sub.2 and Z.sub.2 are as defined above, there is 
obtained a compound of formula (I) wherein X is a unsubstituted or 
substituted pyridine or 
##STR33## 
wherein R.sub.2, A.sub.2 and Z.sub.2 are as defined above. 
It is also possible to obtain a compound represented by formula (I) wherein 
X is unsubstituted or substituted pyridinio or 
##STR34## 
wherein R.sub.2, A.sub.2 and Z.sub.2 are as defined above, by subjecting a 
compound represented by formula (IX), any one of the compounds represented 
by formulas (III) to (VII) and a pyridine compound or a compound 
represented by 
##STR35## 
wherein R.sub.2, A.sub.2 and Z.sub.2 are as defined above, to a 
condensation reaction with 2,4,6-trihalogeno-s-triazine to obtain a 
compound represented by the following formula (XI): 
##STR36## 
wherein M is unsubstituted or substituted pyridinio or 
##STR37## 
wherein R.sub.2, A.sub.2 and Z.sub.2 are as defined above, and R, B and p 
are as defined above, followed by coupling it with a diazonium compound of 
a compound represented by formula (VIII). 
As 2,4,6-trihalogeno-s-triazine, cyanuric chloride and cyanuric fluoride 
are particularly preferable. 
In the condensation reaction with 2,4,6-trihalogeno-s-triazine, the order 
of the reactions is not critical. If the yield and quality of compound (I) 
is taken into consideration, it is preferable to react 
2,4,6-trihalogeno-s-triazine firstly with a compound of lower reactivity. 
Although the conditions of the reactions are not critical, it is usual to 
carry out the reaction primarily at a temperature of -10.degree. C. to 
40.degree. C. at pH 2-9, secondarily at a temperature of 0.degree. C. to 
70.degree. C. at pH 2-9 and tertiarily, when a tertiary reaction is 
carried out, at a temperature of 10.degree. C. to 100.degree. C. at pH 
2-9. Thereby, a compound of formula (I) or a salt thereof can be obtained. 
Examples of the compound represented by formula (VIII) include the 
followings: 
1-sulfo-2-aminonaphthalene-5-[N-(4'-.beta.'-sulfatoethylsulfonyl)-phenyl]-s 
ulfonamide, 
1-sulfo-2-aminonaphthalene-5-[N-(3'-.beta.'-sulfatoethylsulfonyl)-phenyl]-s 
ulfonamide, 
1-sulfo-2-aminonaphthalene-5-[N-ethyl-N-(4'-.beta.'-sulfatoethylsulfonyl)-p 
henyl]-sulfonamide, 
1-sulfo-2-aminonaphthalene-5-[N-ethyl-N-(3'-.beta.'-sulfatoethylsulfonyl)-p 
henyl]-sulfonamide, 
1-sulfo-2-aminonaphthalene-5-[N-(2'-methoxy5'-.beta.'-sulfatoethylsulfonyl) 
-phenyl]-sulfonamide, 
1-sulfo-2-aminonaphthalene-5-[N-(2'-methoxy-5'-methyl-4'-.beta.'-sulfatoeth 
ylsulfonyl)-phenyl]-sulfonamide, 
1-sulfo-2-aminonaphthalene-5-[N-(4'-methoxy-3'-.beta.'-sulfatoethylsulfonyl 
)-phenyl]-sulfonamide, 
1-sulfo-2-aminonaphthalene-5-[N-2'-(6'-.beta.'-sulfatoethylsulfonyl)-naphth 
yl]-sulfonamide, 
1-sulfo-2-aminonaphthalene-5-[N-2'-(5'-.beta.'-sulfatoethylsulfonyl)-naphth 
yl]-sulfonamide, 
1-sulfo-2-aminonaphthalene-5-[N-2'-(6'-sulfo-8'-.beta.'-sulfatoethylsulfony 
l)-naphthyl)-sulfonamide, 
1-sulfo-2-aminonaphthalene-5-[N-2'-(.beta.'-sulfatoethylsulfonyl)-ethyl]-su 
lfonamide, 
1-sulfo-2-aminonaphthalene-5-[N-3'-(.beta.'-sulfatoethylsulfonyl)-propyl]-s 
ulfonamide, 
1-sulfo-2-aminonaphthalene-5-{N-2'-[2'-(.beta.'-sulfatoethylsulfonyl)-ethox 
y]-ethyl}-sulfonamide, 
3-sulfo-4-amino-N'-[(3'-.beta.'-sulfatoethylsulfonyl)-phenyl]-benzenesulfon 
amide, 
3-sulfo-4-amino-N'-[(4'-.beta.'-sulfatoethylsulfonyl)-phenyl]-benzenesulfon 
amide, 
3-sulfo-4-amino-N'-ethyl-N'-[(3'-.beta.'-sulfatoethylsulfonyl)-phenyl]-benz 
enesulfonamide, 
3-sulfo-4-amino-N'-ethyl-N'-[(4'-.beta.'-sulfatoethylsulfonyl)-phenyl]-benz 
enesulfonamide, 
3-sulfo-4-amino-N'-[(2'-methoxy-5'-.beta.'-sulfatoethylsulfonyl)-phenyl]-be 
nzenesulfonamide, 
3-sulfo-4-amino-N'-[(2'-methoxy-5'-methyl-4'-.beta.'-sulfatoethylsulfonyl)- 
phenyl]-benzenesulfonamide 
3-sulfo-4-amino-N'-[(4'-methoxy-3'-.beta.'-sulfatoethylsulfonyl)-phenyl]-be 
nzenesulfonamide, 
3-sulfo-4-amino-N'-[2'-(.beta.'-sulfatoethylsulfonyl)-ethyl]-benzenesulfona 
mide, 
3-sulfo-4-amino-N'-[3'-(.beta.'-sulfatoethylsulfonyl)-propyl]-benzenesulfon 
amide, 
3-sulfo-4-amino-N'-{2'-[2'-(.beta.'-sulfatoethylsulfonyl)-ethoxy]-ethyl}-be 
nzenesulfonamide, 
4-sulfo-5-amino-N'-[(3'-.beta.'-sulfatoethylsulfonyl)-phenyl]-benzenesulfon 
amide, 
4-sulfo-5-amino-N'-[(4'-.beta.'-sulfatoethylsulfonyl)-phenyl]-benzenesulfon 
amide, 
4-sulfo-5-amino-N'-ethyl-N'-[(3'-.beta.'-sulfatoethylsulfonyl)-phenyl]-benz 
enesulfonamide, 
4-sulfo-5-amino-N'-ethyl-N'-[(4'-.beta.'-sulfatoethylsulfonyl)-phenyl]-benz 
enesulfonamide, 
4-sulfo-5-amino-N'-[(2'-methoxy-5'-.beta.'-sulfatoethylsulfonyl)-phenyl]-be 
nzenesulfonamide, 
4-sulfo-5-amino-N'-[(2'-methoxy-5'-methyl-4'-.beta.'-sulfatoethylsulfonyl)- 
phenyl]-benzenesulfonamide 
4-sulfo-5-amino-N'-[(4'-methoxy-3'-.beta.'-sulfatoethylsulfonyl)-phenyl]-be 
nzenesulfonamide, 
4-sulfo-5-amino-N'-[2'-(.beta.'-sulfatoethylsulfonyl)-ethyl]-benzenesulfona 
mide, 
4-sulfo-5-amino-N'-[3'-(.beta.'-sulfatoethylsulfonyl)-propyl]-benzenesulfon 
amide, 
4-sulfo-5-amino-N'-{2'-[2'-(.beta.'-sulfatoethylsulfonyl)ethoxy]-ethyl}-ben 
zenesulfonamide, and the like. 
The compounds represented by formula (VIII) can be produced, for example, 
in the following manner. Thus, a condensation reaction between compounds 
of the following formulas (XII) and (XIII): 
##STR38## 
wherein W represents H or a protecting group of amino group, and D, 
A.sub.1 and R.sub.1 are as defined above, is firstly carried out, and 
subsequently, if desired, the product is isolated to obtain a compound of 
the following formula (XIV): 
##STR39## 
which is a precursor of the compound of formula (VIII). The precursor 
(XIV) can be converted to compound (VIII) by a known method. 
Thus, the .beta.-hydroxyethylsulfonyl group can be converted to its ester 
derivative such as sulfato group, phosphato group, thiosulfato group or 
acetoxy group or halogeno such as chloro. As examples of the esterifying 
agent or acylating agent successfully usable for his purpose, the 
corresponding inorganic or organic acids or their anhydrides or halides, 
such as sulfuric acid, sulfur trioxide-containing sulfuric acid, 
chlorosulfonic acid, phosphoric acid, phosphoric acid oxychloride, mixture 
of phosphoric acid and phosphorus pentoxide, acetic anhydride, 
toluenesulfonyl chloride, thionyl chloride and the like can be referred 
to. 
The conversion of .beta.-hydroxyethylsulfonyl group into a vinylsulfonyl 
group can be achieved by treating an analogous ester derivative of 
.beta.-hydroxyethylsulfonyl group in an aqueous medium at pH 10-12, at a 
temperature of 40.degree. C. to 50.degree. C. for a period of 10-20 
minutes. 
As the protecting group W of the amino group, acetyl group and the like can 
be referred to. The protecting group can be split off by a treatment in an 
acidic aqueous medium at a temperature of 50.degree. C. to 90.degree. C. 
Examples of the acid chloride represented by formula (XII), wherein W is 
hydrogen, include the followings: 
2-, 3- or 4-aminobenzenesulfonyl chloride, 
3-methyl-4-aminobenzenesulfonyl chloride, 
3-ethyl-4-aminobenzenesulfonyl chloride, 
2-methyl-5-aminobenzenesulfonyl chloride, 
2-ethyl-5-aminobenzenesulfonyl chloride, 
4-methoxy-3-aminobenzenesulfonyl chloride, 
4-ethoxy-3-aminobenzenesulfonyl chloride, 
2-methoxy-5-aminobenzenesuflonyl chloride, 
2,4-dimethyl-5-aminobenzenesulfonyl chloride, 
2,5-dimethoxy-4-aminobenzenesulfonyl chloride, 
2,4-dimethoxy-5-aminobenzenesulfonyl chloride, 
3-methoxy-6-methyl-4-aminobenzenesulfonyl chloride, 
3-chloro-4-aminobenzenesulfonyl chloride, 
3-bromo-4-aminobenzenesulfonyl chloride, 
3-sulfo-4-aminobenzenesulfonyl chloride, 
4-sulfo-3-aminobenzenesulfonyl chloride, 
2-aminonaphthalene-8-sulfonyl chloride, 
2-aminonaphthalene-6-sulfonyl chloride, 
2-aminonaphthalene-5-sulfonyl chloride, 
1-aminonaphthalene-4-sulfonyl chloride, 
1-sulfo-2-aminonaphthalene-6-sulfonyl chloride, 
6-sulfo-2-aminonaphthalene-8-sulfonyl chloride, 
8-sulfo-2-aminonaphthalene-6-sulfonyl chloride, 
1-sulfo-2-aminonaphthalene-5-sulfonyl chloride, and the like. 
Among these compounds, preferable are 3-sulfo-4-aminobenzenesulfonyl 
chloride, 4-sulfo-3-aminobenzenesulfonyl chloride, 
1-sulfo-2-aminonaphthalene-5-sulfonyl chloride and 
1-sulfo-2-aminonaphthalene-6-sulfonyl chloride. 
Examples of the compound represented by formula (XIII) include the 
followings: 
4-aminobenzene-.beta.-hydroxyethyl sulfone, 
3-aminobenzene-.beta.-hydroxyethyl sulfone, 
2-(.beta.-hydroxyethylsulfonyl)-ethylamine, 
3-(.beta.-hydroxyethylsulfonyl)-propylamine, 
2-[2-(.beta.-hydroxyethylsulfonyl)-ethoxy]ethylamine, 
and the like. 
The compound represented by formula (VIII) can be produced by the following 
method, too. Thus, it can be produced by subjecting a compound of the 
following formula (xv): 
##STR40## 
wherein Z.sub.1, A.sub.1 and R.sub.1 are as defined above, and a compound 
of the above-mentioned formula (XII) to a condensation reaction and 
subsequently, if desired, splitting off the protecting group W of the 
amino group by a treatment in an acidic medium at a temperature of 
50.degree. C. to 90.degree. C. 
Examples of the compound represented by formula (XV) include the 
followings: 
4-aminobenzene-.beta.-sulfatoethylsulfonyl, 
3-aminobenzene-.beta.-sulfatoethylsulfonyl, 
2-(.beta.-sulfatoethylsulfonyl)-ethylamine, 
3-(.beta.-sulfatoethylsulfonyl)-propylamine, 
2-[2-(.beta.-sulfatoethylsulfonyl)-ethoxy]ethylamine, 
and vinyl compounds of these compounds. 
Examples of the compound represented by formula (IX) include the 
followings: 
2-amino-5-naphthol-7-sulfonic acid, 
2-amino-5-naphthol-1,7-disulfonic acid, 
1-amino-5-naphthol-7-sulfonic acid, 
2-amino-8-naphthol-6-sulfonic acid, 
2-amino-8-naphthol-3,6-disulfonic acid, 
2-amino-8-naphthol-4,6-disulfonic acid, 
1-amino-8-naphthol-3,6-disulfonic acid, 
1-amino-8-naphthol-4,6-disulfonic acid, 
2-methylamino-5-naphthol-7-sulfonic acid, 
2-methylamino-8-naphthol-6-sulfonic acid, and the like. 
Among these compounds, 1-amino-8-naphthol-3,6-disulfonic acid and 
1-amino-8-naphthol-4,6-disulfonic acid are preferable. 
The compounds of the present invention have a fiber-reactivity and can be 
used for dyeing or printing hydroxy group- or carbonamide group-containing 
materials. Preferably, the material to be dyed or printed is used in the 
form of a fiber material or a mixed woven material thereof. 
Said hydroxy group-containing material includes natural and synthetic 
hydroxy group-containing materials such as cellulose fiber materials, 
their regenerated products and polyvinyl alcohol. As the cellulose fiber 
material, cotton and other plant fibers such as linen, flax, jute and 
ramie fibers are preferable. As the regenerated cellulose fiber, viscose 
staple and filament viscose can be referred to. 
Said carbonamide group-containing material includes synthetic and natural 
polyamides and polyurethanes. Particularly in the form of a fiber, it 
includes wool and other animal furs, silk, leather, polyamide-6,6, 
polyamide-6, polyamide-11 and polyamide-4. 
The compounds of the present invention can be used for dyeing or printing 
said materials, particularly those such as fiber materials, in a manner 
depending on physical and chemical properties of the material. The manner 
includes, for example, exhaustion dyeing, padding and printing methods. 
For example, the exhaustion dyeing method can be carried out at a 
relatively low temperature in the presence of an acid binding agent such 
as sodium carbonate, sodium tertiary phosphate, sodium hydroxide and the 
like and, if desired, a neutral salt such as sodium sulfate and sodium 
chloride optionally together with dissolving assistants, penetrants or 
level dyeing agents. The neutral salt which can be used for promoting the 
exaustion of the dye may be added either after the intended dyeing 
temperature has been reached or before it, optionally in portions. 
The padding method can be carried out by padding the materials at room or 
elevated temperature, followed by drying and then steaming or dry-heating 
the padded materials to perform dye fixation. 
The printing can be carried out in a one-phase or two-phase manner. The 
one-phase printing may be conducted by printing the fiber-materials with a 
printing paste containing an acid-binding agent such as sodium bicarbonate 
and the like, followed by steaming at a temperature of 100.degree. to 
160.degree. C. The two-phase printing may be conducted by printing the 
fiber materials with a neutral or weakly acidic printing paste, and 
passing the materials through a hot alkaline bath containing an 
electrolyte or over-padding the materials with an alkaline padding liquor 
containing an electrolyte, followed by a steaming or dry-heating 
treatment. 
For the preparation of the printing paste, a paste or emulsifier such as 
sodium aliginate or starch ether is used optionally together with a 
conventional printing assistant such as urea and/or a dispersant. 
As examples of the acid binding agent suitable for fixing the compound of 
the present invention onto cellulose fiber, water-soluble basic salts 
formed between an alkali metal or an alkaline earth metal and an inorganic 
or organic acid or a compound liberating alkali in a heated state can be 
referred to. Particularly, alkali metal salts formed between an alkali 
metal hydroxide and an inorganic or organic acid of weak or medium 
strength are preferable, among which sodium salts and potassium salts are 
most preferable. Examples of such acid binding agent include sodium 
hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, 
sodium formate, potassium carbonate, sodium primary, secondary and 
tertiary phosphates, sodium silicate, sodium trichloroacetate and the 
like. 
The dyeing of synthetic and natural polyamide and polyurethane fibers can 
be carried out by performing exhaustion in an acid or weak acid bath at a 
controlled pH value and then making the bath neutral or in some cases 
alkaline to perform fixation. The dyeing temperature ranges usually from 
60.degree. to 120.degree. C. In order to achieve a level dyeing, there may 
be used a conventional level dyeing agent such as a condensation product 
between cyanuric chloride and 3 times by mole of aminobenzenesulfonic acid 
or aminonaphthalenesulfonic acid or an addition product between 
stearylamine and ethylene oxide. 
The compound of the present invention is characterized in that it exhibits 
excellent performances in dyeing and printing fiber materials. It is 
particularly useful for dyeing cellulose fiber materials, and gives a dyed 
product excellent in light fastness, perspiration-light fastness, wet 
fastnesses such as washing resistance, peroxide-washing resistance, 
perspiration resistance, and hydrolysis resistance and alkali resistance, 
and particularly in abrasion fastness and iron fastness. 
It is further characterized by excellency in build-up, level-dyeing and 
wash-off properties and high solubility as well as high exhaustion and 
fixation percentages. Moreover, it is characterized in that it is hardly 
affected by changes in dyeing temperature and dyeing bath ratio, so that a 
dyed product with a stable quality can be obtained. 
Moreover, the compound of the present invention is characterized in that it 
is resistance to color change at the time of fixing treatment and resin 
treatment of dyed product and resistant to the change due to contact with 
basic substances during storage. 
The present invention will be illustrated in more detail by way of the 
following examples, wherein parts and % are by weight.

EXAMPLE 1 
3-Aminobenzene-.beta.-sulfatoethylsulfonyl (281 parts) was dissolved into 
an aqueous medium at a controlled pH of 5-7. Then, 
1-sulfo-2-aminonaphthalene-5-sulfonyl chloride (321 parts) was slowly 
added thereto, while adjusting temperature to 0.degree.-30.degree. C. and 
pH to 5-7. Further, the reaction was completed under the same conditions 
as above. Then, the product was isolated in the conventional manner to 
obtain 
1-sulfo-2-aminonaphthalene-5-[N-(3'-.beta.'-sulfatoethylsulfonyl)-phenyl]s 
ulfonamide. 
On the other hand, cyanuric chloride (184.5 parts) was successively 
condensed with 1-amino-8-naphthol-3,6-disulfonic acid (319.3 parts) and 
aniline (93 parts) in the conventional manner to obtain a di-condensation 
product shown by the following formula: 
##STR41## 
Then, 
1-sulfo-2-aminonaphthalene-5-[N-(3'-.beta.'-sulfatoethylsulfonyl)-phenyl]- 
sulfonamide (566.6 parts) synthesized above was diazotized to the usual 
manner and coupled firstly with the di-condensation product of the above 
formula and subsequently with nicotinic acid (123 parts). The compound 
thus obtained was salted out with sodium chloride and isolated to obtain a 
monoazo compound represented by the following formula in the free acid 
form: 
##STR42## 
EXAMPLE 2 
Example 1 can be repeated, except that the 
1-sulfo-2-aminonaphthalene-5-[N-(3'-.beta.'-sulfatoethylsulfonyl)-phenyl]- 
sulfonamide, 1-amino-8-naphthol-3,6-disulfonic acid, aniline and nicotinic 
acid used in Example 1 are replaced with the compounds of Column 2, Column 
3, Column 4 and Column 5, respectively, of the following table to obtain 
the corresponding monoazo compounds, and provided that "-" in column 5 
means no use of pyridine derivatives. When used for dyeing, they give dyed 
products of which hues are as shown in Column 6 of the table. 
3 
1 2 3 4 5 6 
1 
##STR43## 
##STR44## 
##STR45## 
##STR46## 
Bluish red 
2 " " 
##STR47## 
" " 
3 " " 
##STR48## 
" " 
4 " " 
##STR49## 
" " 
5 
##STR50## 
##STR51## 
##STR52## 
##STR53## 
Bluish red 
6 " " 
##STR54## 
" " 
7 
##STR55## 
" 
##STR56## 
" " 
8 " " 
##STR57## 
" " 
9 
##STR58## 
##STR59## 
##STR60## 
##STR61## 
Bluish red 
10 
##STR62## 
" 
##STR63## 
" " 
11 
##STR64## 
" 
##STR65## 
" Red 
12 " " " 
##STR66## 
" 
13 
##STR67## 
##STR68## 
##STR69## 
##STR70## 
Red 
14 
##STR71## 
" 
##STR72## 
##STR73## 
Bluish red 
15 " " 
##STR74## 
" " 
16 
##STR75## 
" 
##STR76## 
##STR77## 
" 
17 
##STR78## 
##STR79## 
##STR80## 
##STR81## 
Bluish red 
18 " 
##STR82## 
##STR83## 
" Red 
19 
##STR84## 
" 
##STR85## 
" " 
20 
##STR86## 
##STR87## 
##STR88## 
##STR89## 
Bluish red 
21 
##STR90## 
" 
##STR91## 
" " 
22 
##STR92## 
" 
##STR93## 
-- " 
23 
##STR94## 
##STR95## 
##STR96## 
-- Red 
24 " " 
##STR97## 
" " 
25 
##STR98## 
##STR99## 
##STR100## 
" Orange 
26 " 
##STR101## 
##STR102## 
##STR103## 
" 
27 
##STR104## 
##STR105## 
##STR106## 
##STR107## 
Orange 
28 
##STR108## 
##STR109## 
##STR110## 
" Red 
29 
##STR111## 
##STR112## 
##STR113## 
##STR114## 
Bluish red 
30 " " 
##STR115## 
" " 
31 
##STR116## 
" 
##STR117## 
" " 
32 
##STR118## 
" 
##STR119## 
" " 
33 
##STR120## 
##STR121## 
##STR122## 
##STR123## 
Bluish red 
34 " " 
##STR124## 
" " 
35 " " 
##STR125## 
" " 
36 " " 
##STR126## 
" " 
37 " " 
##STR127## 
" " 
38 
##STR128## 
##STR129## 
##STR130## 
##STR131## 
Bluish red 
39 " " 
##STR132## 
##STR133## 
" 
40 " " 
##STR134## 
" " 
EXAMPLE 3 
Cyanuric chloride (184.5 parts) and methanol (32 parts) were subjected to a 
condensation reaction in the usual manner, and then reacted with 
1-amino-8-naphthol-3,6-disulfonic acid (319.3 parts) in a weakly acidic 
aqueous medium to obtain a di-condensation product shown by the following 
formula: 
##STR135## 
On the other hand, 
1-sulfo-2-aminonaphthalene-5-[N-(3'-.beta.'-sulfatoethylsulfonyl)-phenyl]- 
sulfonamide (566.6 parts) was diazotized in the usual manner and then 
coupled with the di-condensation product shown by the above formula and 
subsequently condensed with nicotinic acid (123 parts). The compound thus 
formed was salted out with sodium chloride and isolated to obtain a 
monoazo compound represented by the following formula in the free acid 
form: 
##STR136## 
EXAMPLE 4 
Example 3 can be repeated, except that the 
1-sulfo-2-aminonaphthalene-5-[N-(3'-.beta.'-sulfatoethylsulfonyl)-phenyl]- 
sulfonamide, 1-amino-8-naphthol-3,6-disulfonic acid, methanol and nicotinic 
acid used in Example 3 are replaced with the compounds of Column 2, Column 
3, Column 4 and Column 5 of the following table, respectively, to obtain 
the corresponding monoazo compounds. When used for dyeing, they give dyed 
products of which hues are as shown in Column 6 of the table. 
3 
1 2 3 4 5 6 
1 
##STR137## 
##STR138## 
HOCH(CH.sub.3).sub.2 
##STR139## 
Bluish red 2 " " HOC.sub.2 H.sub.5 " " 
3 " " 
##STR140## 
" " 
4 " " 
##STR141## 
" " 
5 
##STR142## 
##STR143## 
##STR144## 
##STR145## 
Bluish red 
6 " " 
##STR146## 
" " 
7 
##STR147## 
" " " " 
8 
##STR148## 
" 
##STR149## 
##STR150## 
" 
9 
##STR151## 
##STR152## 
##STR153## 
##STR154## 
Red 
10 
##STR155## 
" 
##STR156## 
" " 
11 
##STR157## 
" " " " 12 " " HOCH(CH.sub.3).sub.2 " " 
13 
##STR158## 
##STR159## 
##STR160## 
##STR161## 
Bluish red 
14 
##STR162## 
" " " " 
15 
##STR163## 
" 
##STR164## 
" " 
16 " 
##STR165## 
##STR166## 
##STR167## 
Yellowish red 
17 
##STR168## 
##STR169## 
##STR170## 
##STR171## 
Bluish red 
18 " " 
##STR172## 
" " 
19 
##STR173## 
" 
##STR174## 
" " 
20 " " 
##STR175## 
" " 
21 
##STR176## 
##STR177## 
##STR178## 
##STR179## 
Bluish red 
22 " " 
##STR180## 
##STR181## 
" 
EXAMPLE 5 
3-Aminobenzene-.beta.-sulfatoethylsulfonyl (281 parts) was dissolved into 
an aqueous medium at a controlled pH of 5-7. Then, 
1-sulfo-2-aminonaphthalene-5-sulfonyl chloride (321 parts) was slowly 
added thereto while controlling the temperature in the range of 0.degree. 
C. to 30.degree. C. and the pH value in the range of 5 to 7, and the 
reaction was completed under the same conditions as above. The product was 
isolated and purified to obtain 
1-sulfo-2-aminonaphthalene-5-[N-(3'-.beta.'-sulfatoethylsulfonyl)-phenyl]- 
sulfonamide. 
On the other hand, cyanuric chloride (184.5 parts) was reacted in the usual 
manner successively with 1-amino-8-naphthol-3,6-disulfonic acid (319.3 
parts) and aniline (93 parts) to obtain a di-condensation product 
represented by the following formula in the free acid form: 
##STR182## 
Then, 
1-sulfo-2-aminonaphthalene-5-[N-(3'-.beta.'-sulfatoethylsulfonyl)-phenyl]- 
sulfonamide (566.6 parts) synthesized above was diazotized in the usual 
manner and coupled with the di-condensation product represented by the 
above formula, and then condensed with 
1-aminobenzene-3-.beta.-sulfatoethyl sulfone (281.3 parts). The compound 
thus obtained was salted out with sodium chloride and isolated to obtain a 
monoazo compound represented by the following formula in the free acid 
form: 
##STR183## 
EXAMPLE 6 
Example 5 can be repeated, except that the 
1-sulfo-2-aminonaphthalene-5-[N-(3'-.beta.'-sulfatoethylsulfonyl)-phenyl]- 
sulfonamide, 1-amino-8-naphthol-3,6-disulfonic acid, aniline and 
3-aminobenzene-.beta.-sulfatoethylsulfone used in Example 5 are replaced 
with the compounds of Column 2, Column 3, Column 4 and Column 5, 
respectively, of the following table to obtain the corresponding monoazo 
compounds. When used for dyeing, they give dyed products of which hues are 
as shown in Column 6 of the table. 
3 
1 2 3 4 5 6 
1 
##STR184## 
##STR185## 
##STR186## 
##STR187## 
Bluish red 
2 " " 
##STR188## 
##STR189## 
" 
3 " " 
##STR190## 
##STR191## 
" 
4 
##STR192## 
" 
##STR193## 
" " 
5 
##STR194## 
##STR195## 
##STR196## 
##STR197## 
Bluish red 
6 " " 
##STR198## 
##STR199## 
" 
7 " " 
##STR200## 
##STR201## 
" 
8 
##STR202## 
" 
##STR203## 
##STR204## 
Red 
9 
##STR205## 
##STR206## 
##STR207## 
##STR208## 
Red 
10 
##STR209## 
##STR210## 
##STR211## 
##STR212## 
11 
##STR213## 
" 
##STR214## 
" " 
12 
##STR215## 
##STR216## 
##STR217## 
##STR218## 
Red 
13 
##STR219## 
##STR220## 
##STR221## 
##STR222## 
" 
14 
##STR223## 
##STR224## 
H.sub.2 N-nC.sub.3 
H.sub.7 
##STR225## 
Bluish red 
15 " " 
##STR226## 
##STR227## 
" 
16 
##STR228## 
##STR229## 
##STR230## 
##STR231## 
Bluish red 
17 " " 
##STR232## 
##STR233## 
" 
18 
##STR234## 
" 
##STR235## 
##STR236## 
" 
19 
##STR237## 
##STR238## 
##STR239## 
##STR240## 
Orange 
20 
##STR241## 
##STR242## 
##STR243## 
##STR244## 
Orange 
21 " 
##STR245## 
##STR246## 
##STR247## 
Bluish red 
22 " " 
##STR248## 
##STR249## 
" 
23 
##STR250## 
##STR251## 
##STR252## 
##STR253## 
Bluish red 
24 
##STR254## 
" 
##STR255## 
##STR256## 
" 
25 " " 
##STR257## 
" " 
26 
##STR258## 
" H.sub.2 NC.sub.2 H.sub.4 SO.sub.3 H " " 
27 
##STR259## 
##STR260## 
##STR261## 
##STR262## 
Bluish red 
28 
##STR263## 
" 
##STR264## 
" " 
29 " " 
##STR265## 
" " 
30 
##STR266## 
##STR267## 
##STR268## 
##STR269## 
Bluish red 
EXAMPLE 7 
Cyanuric chloride (184.5 parts) and methanol (32 parts) were subjected to a 
condensation reaction in the usual manner, and then reacted with 
1-amino-8-naphthol-3,6-disulfonic acid (319.3 parts) in a weakly acidic 
aqueous medium to obtain a di-condensation product represented by the 
following formula in the free acid form: 
##STR270## 
On the other hand, 
1-sulfo-2-aminonaphthalene-5-[N-(3'-'-sulfatoethylsulfonyl)-phenyl]-sulfon 
amide (566.6 parts) was diazotized in the usual manner and coupled with the 
di-condensation product represented by the above formula, and then 
condensed with 3-aminobenzene-.beta.-sulfatoethyl sulfone (281.3 parts). 
The compound thus formed was salted out with sodium chloride and isolated 
to obtain a monoazo compound represented by the following formula in the 
free acid forms: 
##STR271## 
EXAMPLE 8 
Example 7 can be repeated, except that the 
1-sulfo-2-aminonaphthalene-5-[N-(3'-.beta.'-sulfatoethyl-sulfonyl)-phenyl] 
-sulfonamide, 1-amino-8-naphthol-3,6-disulfonic acid, methanol and 
3-aminobenzene-.beta.-sulfatoethyl sulfone used in Example 7 are replaced 
with the compounds of Column 2, Column 3, Column 4 and Column 5, 
respectively, of the following table, to obtain the corresponding monoazo 
compounds. When used for dyeing, they gave dyed products of which hues are 
as shown in Column 6 of the table. 
3 
1 2 3 4 5 6 
1 
##STR272## 
##STR273## 
HOC.sub.2 
H.sub.5 
##STR274## 
Bluish red 2 " " HOCH(CH.sub.3).sub.2 " " 
3 " " 
##STR275## 
" " 
4 " " 
##STR276## 
" " 
5 
##STR277## 
##STR278## 
##STR279## 
##STR280## 
Bluish red 
6 " " 
##STR281## 
##STR282## 
" 
7 
##STR283## 
" 
##STR284## 
" " 
8 " " 
##STR285## 
##STR286## 
" 
9 
##STR287## 
##STR288## 
##STR289## 
##STR290## 
Bluish red 
10 
##STR291## 
" 
##STR292## 
##STR293## 
" 
11 
##STR294## 
##STR295## 
##STR296## 
##STR297## 
Red 
12 
##STR298## 
##STR299## 
##STR300## 
##STR301## 
Red 
13 " 
##STR302## 
##STR303## 
##STR304## 
Bluish red 
14 " " 
##STR305## 
##STR306## 
" 
15 
##STR307## 
" 
##STR308## 
" Red 
16 
##STR309## 
##STR310## 
##STR311## 
##STR312## 
Red 
17 
##STR313## 
" 
##STR314## 
" Bluish red 
18 " " 
##STR315## 
##STR316## 
" 
19 
##STR317## 
##STR318## 
##STR319## 
##STR320## 
Bluish red 
20 
##STR321## 
##STR322## 
##STR323## 
" Orange 
21 
##STR324## 
##STR325## 
##STR326## 
" Bluish red 
22 
##STR327## 
##STR328## 
##STR329## 
##STR330## 
Bluish red 
23 " " 
##STR331## 
##STR332## 
" 
24 
##STR333## 
" 
##STR334## 
##STR335## 
" 
25 
##STR336## 
##STR337## 
##STR338## 
##STR339## 
Bluish red 
Dyeing Example 1 
Each of the monoazo compounds (0.3 part) obtained in Examples 1 to 8 was 
dissolved into water (200 parts). Sodium sulfate (20 parts) and cotton (10 
parts) were added, and the temperature was elevated to 50.degree. C. After 
30 minutes had passed, sodium carbonate (4 parts) was added and dyeing was 
carried out at that temperature for one hour. After completing the dyeing, 
the dyed cotton was washed with water and soaped to obtain a orange- or 
red-colored dyed product of high color depth excellent in fastness 
properties, particularly chlorine fastness, sunlight fastness and 
perspiration-sunlight fastness, and build-up property. 
Dyeing Example 2 
Each of the monoazo compounds (0.3 part) obtained in Examples 1 to 8 was 
dissolved into water (300 parts). Sodium sulfate (30 parts) and cotton (10 
parts) were added, and the temperature was elevated to 60.degree. C. After 
20 minutes had passed, sodium carbonate (5 parts) was added, and dyeing 
was carried out at that temperature for one hour. After completing the 
dyeing, the dyed cotton was washed with water and soaped to obtain a 
orange- or red-colored dyed product of high color depth excellent in 
fastness properties, particularly sunlight fastness and 
perspiration-sunlight fastness, and build-up property. 
Dyeing Example 3 
______________________________________ 
Composition of color paste: 
______________________________________ 
Each of the monoazo 5 parts 
compounds obtained in 
Examples 1 to 8 
Urea 5 parts 
Sodium alginate (5%) stock 
50 parts 
paste 
Hot water 25 parts 
Sodium bicarbonate 2 parts 
Balance 13 parts 
______________________________________ 
A mercerized cotton broad cloth was printed with each color paste. After 
intermediate drying, it was steamed at 100.degree. C. for 5 minutes, 
washed with hot water, soaped, again washed with hot water and dried. 
Thus, there was obtained orange- or red-colored printed products high in 
fixation percentage and excellent in fastness properties, particularly 
sunlight fastness and perspiration-sunlight fastness, and build-up 
property. 
Dyeing Example 4 
Each of the monoazo compounds (25 parts) obtained in Examples 1 to 8 was 
dissolved into hot water and cooled to 25.degree. C. Then, 32.5% aqueous 
solution of sodium hydroxide (5.5 parts) and 50.degree. Be water glass 
(150 parts) were added thereto together with a quantity of water enough to 
give a total quantity of 1,000 parts at 25.degree. C. Immediately after 
it, the resulting solution was used as a padding solution to pad a cotton 
woven fabric. After winding up the padded cotton woven fabric, it was 
tightly sealed with a polyethylene film and stored in a room kept at 
20.degree. C. 
On the other hand, another cotton woven fabric was padded, wound up and 
sealed with a polyethylene film in the same manner as above, and stored in 
a room kept at 5.degree. C. Both the padded fabrics were allowed to stand 
for 20 hours, and the dyed products thus obtained were washed first with 
cold water and then with hot water, soaped in a boiling detergent, again 
washed with cold water and dried. 
Differences in the hue and the color depth between the dyed product stored 
at 20.degree. C. for 20 hours and the dyed product stored at 5.degree. C. 
for 20 hours were measured. As the result, scarce differences were 
obtained between them. By a cold batch up dyeing, dyed products excellent 
in build-up property were obtained therefrom. 
Dyeing Example 5 
Each of the monoazo compounds (25 parts) obtained in Examples 1 to 8 was 
dissolved into hot water and cooled to 25.degree. C. Then, 32.5% aqueous 
solution of sodium hydroxide (10 parts) and anhydrous sodium sulfate (30 
parts) were added thereto together with a quantity of water enough to give 
a total quantity of 1,000 parts at 25.degree. C. Immediately after it, the 
resulting solution was used as a padding solution to pad a viscose rayon 
woven fabric. The padded viscose rayon fabric was wound up, tightly sealed 
with a polyethylene film, and stored in a room kept at 20.degree. C. 
On the other hand, another viscose rayon woven fabric was padded, wound up 
and sealed with a polyethylene film in the same manner as above. It was 
stored in a room kept at 5.degree. C. 
After allowing both the padded fabrics to stand for 20 hours, the dyed 
products thus obtained were washed first with cold water and then with hot 
water, soaped in a boiling detergent, again washed with cold water and 
dried. 
Differences in the hue and the color depth between the dyed product stored 
at 20.degree. C. for 20 hours and the dyed product stored at 5.degree. C. 
for 20 hours were measured. As the result, starce differences were 
observed between them. 
Dyeing Example 6 
Dyeing Example 2 was repeated, except that the amount of sodium carbonate 
was altered from 5 parts in Deying Example 2 to 3 parts. All the monoazo 
compounds used gave dyed products of which qualities were equal to that of 
the dyed product obtained in Dyeing Example 2. 
Dyeing Example 7 
Dyeing Example 2 was repeated, except that the temperature was altered from 
60.degree. C. to 50.degree. C. All the monoazo compounds used gave dyed 
products of which qualities were aqual to that of the dyed product 
obtained in Dyeing Example 2. When the dyeing temperature was 70.degree. 
C., too, the results were similar to the above. 
Dyeing Example 8 
Dyeing Example 2 was repeated, except that the amount of sodium sulfate was 
altered from 30 parts to 15 parts. All the monoazo compounds used gave 
dyed products of which qualities were equal to that of the dyed product 
obtained in Dyeing Example 2.