Monazo compounds having a triozinyl bridging group and two vinylsulfone type fiber reactive groups

A monoazo compound of the following formula, ##STR1## wherein A is phenyl or naphthyl, B.sub.1 and B.sub.2 are each phenylene or naphthylene, R.sub.1 is hydrogen, halogeno, alkyl, alkoxy, ureido or acylamino, R.sub.2 is hydrogen or takes together with R.sub.1 to form benzene, R.sub.3 is hydrogen, alkyl, alkoxy or sulfo, R.sub.4 and R.sub.5 are each hydrogen or alkyl, and Y.sub.1 and Y.sub.2 are each vinyl, sulfatoethyl or the like, which is useful for dyeing hydroxyl group-containing and amide-containing fiber materials to obtain dyed products of excellent fastness properties with excellent build-up property and reproducibility of dyeing irrespective of changes in dyeing temperatures, bath ratio or salt concentration in some degree.

The present invention relates to a monoazo compound, a process for the 
production thereof and a process for dyeing or printing fiber materials 
using the same. More specifically, the present invention relates to a 
monoazo compound having two vinylsulfone type fiber reactive groups per 
molecule, which is particularly useful for dyeing or printing fiber 
materials in a yellow color. 
Many kinds of reactive dyes useful for dyeing or printing fiber materials 
in a yellow color are known. Of these, reactive dyes having a vinylfulfone 
type fiber reactive group are prominent. Particularly, phenyl- or 
naphthyl-azobenzene reactive dyes of this kind have been used much more 
than pyrazolone or pyridone reactive dyes because of their superior dye 
performances with respect to color values and fastness properties of dyed 
products. 
For example, Published Unexamined Japanese Patent Application No. 
96174/1974 discloses a naphthyl-azobenzene yellow reactive dye represented 
by the following formula in a free acid form, 
##STR2## 
wherein Q.sub.1 is hydrogen, methyl or ethyl, Q.sub.2 and Q.sub.3 are each 
hydrogen, methyl, methoxy or sulfo, X is hydrogen, methyl, acetylamino or 
chloro, Y is hydrogen, methoxy or ethoxy, and Z is aliphatic or aromatic 
amino having 1 or 2 sulfo groups. Moreover, in a literature "Kagaku to 
Kougyo" (Science and Industry), Vol. 42, No. 11, a naphthyl-azobenzene 
yellow reactive dye of the following formula, 
##STR3## 
is disclosed, 
However, these known reactive dyes are not yet sufficient to meet the needs 
of a high level of various dye performances. 
In order to find a yellow reactive dye of this kind meeting the needs of a 
high level for various dye performances, the present inventors have 
undertaken extensive studies about substituents on the chromophore of 
phenyl- or naphthyl-azobenzene, and a bridging group between the 
chromophore and the vinylsulfone type fiber reactive group, and as a 
result have found a specific monoazo compound having two vinylsulfone type 
fiber reactive groups per molecule.

The present invention provides a compound of the following formula (I), 
##STR4## 
wherein A is a phenyl or naphthyl group substituted with at least one 
water-solubilizing group, B.sub.1 and B.sub.2 independently of one another 
are each an unsubstituted or substituted phenylene or naphthylene group, 
R.sub.1 is hydrogen, halogeno, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, ureido 
or acylamino, R.sub.2 is hydrogen or taken together with R.sub.1 forms a 
benzene ring unsubstituted or substituted with at least one sulfo, R.sub.3 
is hydrogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy or sulfo, R.sub.4 and 
R.sub.5 independently of one another are each hydrogen or unsubstituted or 
substituted alkyl, and Y.sub.1 and Y.sub.2 independently of one another 
are each vinyl or --CH.sub.2 CH.sub.2 L in which L is a group splittable 
by the action of an alkali, and a process for producing the compound of 
the formula (I), which comprises subjecting any one of a monoazo 
intermediate compound of the following formula (II), 
##STR5## 
wherein A, R.sub.1, R.sub.2 and R.sub.3 are as defined above, an amine 
compound of the following formula (III), 
##STR6## 
wherein B.sub.1, R.sub.4 and Y.sub.1 are as as defined above, and another 
amine compound of the following formula (IV), 
##STR7## 
wherein B.sub.2, R.sub.5 and Y.sub.2 are as defined above, to first 
condensation with a cyanuric halide followed by second and third 
condensations suing the remaining ones. 
The present invention also provides a process for dyeing or printing fiber 
materials, which comprises using the compound of the formula (I). 
In the above formula (I), the phenyl group represented by A may be 
preferably the one represented by the following formula, 
##STR8## 
wherein R.sub.6 and R.sub.7 independently of one another are each 
hydrogen, chloro, methyl or methoxy, p is 0 or 1 and q is 1 or 2, provided 
that p+qis 1 or 2, and the naphthyl may be preferably the one represented 
by the following formula, 
##STR9## 
wherein m is 1 ot 2 and n is 0 or 1, provided that m+n is 2 or 3. 
The phenylene represented by B.sub.1 and B.sub.2 may be unsubstituted or 
substituted with methyl, ethyl, methoxy, ethoxy, halogeno (e.g. chloro, 
bromo etc.), sulfo or carboxy, and the naphthylene may be unsubstituted or 
substituted with one sulfo. Examples thereof are the same as those 
disclosed in Published Unexamined Japanese Patent Application No. 
122549/1984. Of these, preferred are phenylene unsubstituted or 
substituted with methyl or methoxy. 
The halogeno represented by R.sub.1 includes, for example, chloro and 
bromo, and the acyl in the acylamino represented by R.sub.1 includes, for 
example, --COC.sub.1-4 alkyl, --COC.sub.2-4 alkenyl, in which the alkyl 
and alkenyl are unsubstituted or substituted with sulfo, carboxy or 
halogeno, and benzoyl unsubstituted or substituted with sulfo, carboxy, 
methyl or halogeno. Among those represented by R.sub.1, preferred are 
hydrogen, methyl, methoxy, ureido and amino substituted with acetyl, 
propionyl, --COC.sub.2 H.sub.4 COOH, --COCH.dbd.CHCOOH or benzoyl. 
Afternatively, R.sub.1 is preferably taken together with R.sub.2 to form a 
benzene ring which is preferably substituted with one sulfo. 
The alkyl and alkoxy represented by R.sub.3 may be straight or branched, 
and unsubstituted or substituted with chloro or hydroxy. Of these alkyl 
and alkoxy, preferred are those having fewer carbon atoms, particularly 
methyl and methoxy. 
With respect to the combination of R.sub.1, R.sub.2 and R.sub.3, preferred 
are the case where R.sub.1 is hydrogen, chloro, methyl, methoxy, ureido or 
amino substituted with acetyl, propionyl, --COC.sub.2 H.sub.4 COOH, 
--COCH.dbd.CHCOOH or benzoyl, R.sub.2 is hydrogen and R.sub.3 is hydrogen, 
methyl or methoxy, and the case where R.sub.1 is taken together with 
R.sub.2 to form benzene ring substituted with one sulfo, and R.sub.3 is 
hydrogen, methyl or methoxy. 
The alkyl represented by R.sub.4 and R.sub.5 is preferably one having 1 to 
4 carbon atoms, which is unsubstituted or substituted with hydroxy, cyano, 
C.sub.1-4 alkoxy, halogeno, carboxy, carbamoyl, C.sub.1-4 alkoxycarbonyl, 
C.sub.1-4 alkylcarbonyloxy, sulfo, sulfamoyl or the like. Examples thereof 
are the same as disclosed in Published Unexamined Japanese patent 
application No. 122549/1984. Of these alkyl groups, preferred are methyl 
and ethyl. In the present invention, any one of R.sub.4 and R.sub.5 is 
preferably hydrogen. 
The symbol l in --CH.sub.2 CH.sub.2 L which is represented by Y.sub.1 and 
Y.sub.2 denotes a group capable of being split by the action of an alkali, 
and includes various groups known per se, such as sulfato, thiosulfato, 
acetoxy, chloro and the like. Of these groups represented by Y.sub.1 and 
Y.sub.2, preferred is a .beta.-sulfatoethyl group (--CH.sub.2 CH.sub.2 
OSO.sub.3 H), which may be incorporated with a vinyl group 
(--CH.dbd.CH.sub.2). In the present invention, the most preferred is a 
case where both Y.sub.1 and Y.sub.2 denote .beta.-sulfatoethyl. 
Among the monazo compounds represented by the formula (I), preferred are 
those represented by the following formulas (I-1) and (I-2) in each free 
acid form, 
##STR10## 
wherein R.sub.8 is ureido or acetylamino and R.sub.9 is hydrogen, or 
R.sub.8 is methyl and R.sub.9 is methoxy, and R.sub.10 is hydrogen, methyl 
or ethyl, and Y' is vinyl (--CH.dbd.CH.sub.2) or .beta.-sulfatoethyl 
(--CH.sub.2 CH.sub.2 OSO.sub.3 H), and 
##STR11## 
wherein R.sub.11 is hydrogen and R.sub.12 ;l is ureido or acetylamino, or 
R.sub.11 is methoxy and R.sub.12 is methyl, and R.sub.13 is hydrogen, 
methyl or ethyl, and Y' is as defined above. 
The monoazo compound (I) of the present invention can be produced in a 
manner known per se, for example, by subjecting the monoazo intermediate 
compound of the formula (II), the amine compound of the formula (III) and 
another amine compound of the formula (IV) to condensation in an optional 
order with a cyanuric halide such as cyanuric chloride and cyanuric 
fluoride. In this manner, the order to condensation is not particularly 
limited. Considering, however, the yield and quality of the monozao 
compound (I) obtained, it is preferred to use any one of (II), (III), and 
(IV) having the lowest reactivity to the cyanuric halide first of all for 
the condensation with the cyanuric halide. 
A first condensation of any one of (II), (III) and (IV) with the cyanuric 
halide can be carried out in an aqueous medium at a temperature of 
-10.degree. to 50.degree. C., preferably 0.degree. to 30.degree. C., while 
controlling the pH within 1 to 10, preferably 2 to 7. A second 
condensation of any one of remaining two with the first condensate can be 
carried out in an aqueous medium at a temperature of 10.degree. to 
80.degree. C., preferably 20.degree. to 50.degree. C., while controlling 
the pH within 2 to 9, preferably 3 to 6, and a third condensation of the 
last one with the second condensate in an aqueous medium at a temperature 
of 40.degree. to 100.degree. C., preferably 40.degree. to 80.degree. C., 
while controlling the pH within 2 to 9, preferably 3 to 6. 
The monoazo intermediate compound (II) can be prepared by diazotizing an 
aromatic amine compound represented by the following formula (V), 
EQU A--NH.sub.2 (V) 
wherein A is as defined above, followed by coupling with an aniline 
compound represented by the following formula (VI), 
##STR12## 
wherein R.sub.1, R.sub.2 and R.sub.3 are as defined above, the diazotizing 
and coupling being carried out in a conventional manner. 
Preferred examples of the aromatic amine compound (V) are aniline sulfonic 
acids and naphthylamine sulfonic acids, each being represented by the 
following formulas (VII) and (VIII), respectively, in each free acid form, 
##STR13## 
wherein R.sub.6, R.sub.7, p and q are as defined above, and 
##STR14## 
wherein m and n are as defined above. 
The aniline sulfonic acid (VII) includes, for example, aniline-2-, 3- or 4- 
sulfonic acid, 2-amino-4- or 5-sulfobenzoic acid, 4-amino-2-sulfobenzoic 
acid, 4-methylaniline-2- or 3-sulfonic acid, 2-methylaniline-4- or 
5-sulfonic acid, 2- or 4-aminobenzoic acid, 2-methoxyaniline-4- or 
5-sulfonic acid, 4-methoxyaniline-2- or 3-sulfonic acid, 2-methyl-5- or 
6-chloroaniline-4-sulfonic acid, 2-methyl-4-chloroaniline-5- or 6-sulfonic 
acid, 4-chloro-5-methylaniline-2-sulfonic acid, aniline-2,4- 2,5- or 
3,5-disulfonic acid, 2-methylaniline-3,5-, 4,5- or 4,6-disulfonic acid, 
4-methylaniline-2,5-disulfonic acid and the like. 
The naphthylamine sulfonic acid (VIII) includes, for example, 
2-naphthylamine-1,5-, 3,6-, 4,8-, 5,7- or 6,8-disulfonic acid, 
2-naphthylamine-3,6,8- or 4,6,8-trisulfonic acid and the like. 
The aniline compound (VI) includes, for example, m-anisidine, 3-methyl or 
ethylaniline, 2,5-xylidine, 2-ethyl-5-methylanilane, 2-methoxy-5-methyl or 
ethylaniline, 2-ethoxy-5-methyl or ethylanilane, 3-aminoacetanilide, 
3-amino-4-methyl or ethylacetanilide, 3-amino-4-methoxy or 
ethoxyacetanilide, 3-carboxyethylcarbonyl or 
carboxyvinylcarbonylaminoaniline, 2-methyl-5-carboxyethycarbonyl or 
carboxyvinylcarbonylaminoaniline, 3-benzoylaminoaniline, 
2-methyl-5-benzoylaminoaniline, those having a substituent such as chloro, 
methyl, nitro, sulfo or carboxy at o-, m- or p-position of the above 
benzoyl, 2,5-dimethoxyaniline, 3-aminophenylurea, 1-naphthylamine-6-, 7- 
or 8-sulfonic acid, 2-methoxy-1-naphthylamine-6-, 7- or 8-sulfonic acid, 
3-aminoacetanilide-4-sulfonic acid, 3-aminophenylurea-4-sulfonic acid and 
the like. 
All the starting compounds described above may be used in the form of a 
free acid or an alkali or alkaline earth metal salt depending on the 
reaction conditions. 
After completion of the reactions, the monoazo compound (I)-containing 
reaction mixture may be subjected to salting-out in a conventional manner, 
demineralization with a semipermeable membrane, evaporation such as 
spray-drying and the like, if desired, with use of usual axiliary agents 
such as stabilizing agents, dyeing improvers and the like, to provide a 
pulverulent or liquid commercial product. 
The monoazo compound (I) in accordance with the present invention may be in 
the form of a free acid or a salt of an alkali metal or alkaline earth 
metal, preferably in the form of sodium or potassium salt. 
The monoazo compound (I) of the present invention is fiber-reactive and 
useful for dyeing or printing hydroxyl group-containing and amide 
group-containing materials. The materials are favorably in a fibrous form 
including unmixed or mixed fiber spinning. 
The hydroxyl group-containing materials include natural or synthetic 
materials such as cellulose fiber materials, cellulose-containing fiber 
materials, regenerated products thereof and polyvinyl alcohol. Examples of 
the cellulose fiber materials are cotton and other vegetable fibers such 
as linen, hemp, jute and ramie fibers. Examples of the regenerated 
cellulose fibers are viscose staple and filament viscose. Examples of the 
cellulose-containing fiber materials are mixed fiber materials such as 
cellulose/polyester, cellulose/wool, cellulose/acryl and the like. 
The amide group-containing materials include synthetic or natural 
polyamides and polyurethanes. Examples of the materials, particularly in 
the fibrous forms, are wool and other animal furs, silk, leather, 
polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4. 
The dyeing may be carried out in a manner suitable for the reactive group 
of the dyes. 
For example, cellulose fibers can be dyed using the monoazo compound of the 
present invention and an acid binding agent such as sodium hydroxide, 
sodium carbonate, phosphates, silicates or sodium hydrogencarbonate. The 
dyeing may be carried out in a suitable manner, which can be selected from 
conventional ones depending on the physical and chemical properties of the 
fiber materials, and includes, for example, exhaustion dyeing, printing 
and padding including cold-pad-batch-up dyeing. 
The exhaustion dyeing can be carried out at a relatively low temperature in 
the presence of an acid binding agent such as sodium carbonate, trisodium 
phosphate, sodium hydroxide and the like, together with sodium sulfate, 
sodium chloride or the like. 
The printing can be carried out by printing the fibers with a color paste, 
followed by pre-drying and heat-treatment such as steaming. The color 
paste can be prepared in a conventional manner using a thickener or 
emulsion thickener such as sodium alginate, starch ether or the like, and 
an alkali or alkali-generating agent such as sodium carbonate, sodium 
hydrogencarbonate, trisodium phosphate, sodium trichloroacetate and their 
potassium or alkaline earth metal salts, if desired, together with a usual 
printing auxiliary agent such as urea and a dispersing agent. 
The cold-pad-batch-up dyeing can be carried out by padding the fiber 
materials with a padding liquor at ambient temperature, batching up and 
allowing to stand on a roller for 3 hours or more or over night, followed 
by washing with water and drying. 
The dyeing of natural or synthetic polyamide and polyurethane fiber 
materials can be carried out by performing exhaustion in an acid or weak 
acid bath, while controlling the pH value, and then making the bath 
neutral, or in some cases alkaline to perform the 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 aminobenzene-sulfonic acid or amino-naphthalenesulfonic acid, 
or an addition product between stearylamine and ethylene oxide, and the 
like. 
The present monoazo compound (I) can be characterized by excellent dye 
performances in the dyeing and printing of fiber materials, particularly 
cellulose fiber materials. For example, the compound can give a dyed 
product excellent in light fastness, perspiration-light fastness, 
perspiration fastness, acid-hydrolysis fastness, washing fastness, 
chlorine fastness and the like. The monoazo compound (I) can also exhibit 
extremely excellent build-up, level-dyeing and washing-off properties. 
Moreover, when used for the dyeing or printing, the monoazo compound (I) 
is not greatly affected by changes in a dyeing temperature, an amount of 
inorganic salts and bath ratio, so that a dyed or printed product with 
constant quality can be obtained with superior reproducibility. 
The present invention is illustrated in more detail with reference to the 
following Examples, which are only illustrative, but not limitative. In 
Examples, all parts and % are by weight. 
EXAMPLE 1 
Aniline-2,5-disulfonic acid (12.7 parts) was diazotized in a usual manner, 
followed by coupling with 3-aminophenylurea (7.6 parts). The resulting 
intermediate was subjected to a first condensation with cyanuric chloride 
(9.23 parts), followed by a second condensation with 
1-aminobenzene-4-.beta.-sulfatoethylsulfone (14.1 parts). Ultimately, the 
resulting condensate was allowed to react with 
1-aminobenzene-3-.beta.-sulfatoethylsulfone (14.1 parts) at 60.degree. to 
70.degree. C. within a pH of 4 to 5. Salting-out with sodium chloride gave 
a monoazo compound represented by the following formula in a free acid 
form. 
##STR15## 
EXAMPLE 2 
Example 1 was repeated, but the aniline-2,5-disulfonic acid, 
3-aminophenylurea, 1-aminobenzene-4-.beta.-sulfatoethylsulfone and 
1-aminobenzene-3-.beta.-sulfatoethylsulfone which were used in Example 1 
were replaced by the aromatic amine compound shown in Column A of the 
following table which corresponds to the formula (V), the aniline compound 
(VI) shown in Column B, the amine compound (III) shown in Column C and 
another amine compound (IV) shown in Column D, respectively, thereby 
obtaining the corresponding monoazo compound exhibiting a shade shown in 
Column E. 
__________________________________________________________________________ 
A D 
Aromatic 
B C Another 
Run 
amine Aniline Amine amine E 
No. 
compound (V) 
compound (VI) 
compound (III) 
compound (IV) 
Shade 
__________________________________________________________________________ 
1 Aniline-2,5- 
3-Aminophenyl- 
1-Aminobenzene- 
1-Amino- Yellow 
disulfonic 
urea 3-.beta.-sulfato- 
benzene-3-.beta.- 
acid ethylsulfone 
sulfatoethyl- 
sulfone 
1-Amino-2- 
2 " " " methoxybenzene- 
" 
5-.beta.-sulfato- 
ethylsulfone 
1-Amino-4- 
3 " " " methoxybenzene- 
" 
3-.beta.-sulfato- 
ethylsulfone 
1-Aminobenzene- 
1-Aminobenzene- 
4 " " 4-.beta.-sulfato- 
4-.beta.-sulfato- 
" 
ethylsulfone 
ethylsulfone 
5 " " " 1-Amino-2- 
" 
methoxybenzene- 
5-.beta.-sulfato- 
ethylsulfone 
6 " 3-Amino- " 1-Aminobenzene- 
" 
acetanilide 3-.beta.-sulfato- 
ethylsulfone 
7 " " 1-Aminobenzene- 
" " 
3-.beta.-sulfatoethyl- 
sulfone 
8 " 2-Methoxy- 
" " " 
5-methylaniline 
9 " " 1-Aminobenzene- 
" " 
4-.beta.-sulfatoethyl- 
sulfone 
10 " 3-Carboxy- 
1-Aminobenzene- 
" " 
vinylcarboxylamino- 
3-.beta.-sulfato- 
aniline ethylsulfone 
11 " 3-Carboxy- 
" 1-Aminobenzene- 
" 
ethylcarboxylamino- 
4-.beta.-sulfato- 
aniline ethylsulfone 
12 " 2,5-Dimethyl- 
" " " 
aniline 
13 " 2,5-Dimethoxy- 
" " " 
aniline 
14 Aniline-2,4- 
3-Aminophenyl- 
1-Aminobenzene- 
" " 
disulfonic 
urea 4-.beta.-sulfato- 
acid ethylsulfone 
15 " " 1-Aminobenzene- 
1-Aminobenzene- 
" 
3-.beta.-sulfatoethyl- 
3-.beta.-sulfato- 
sulfone ethylsulfone 
16 " " 1-Aminobenzene- 
" " 
4-.beta.-sulfatoethyl- 
sulfone 
17 Aniline-2- 
" " " " 
sulfonic 
acid 
18 Aniline-3- 
3-amino- " " " 
sulfonic 
phenylurea 
acid 
19 Aniline-4- 
" " " " 
sulfonic 
acid 
20 Aniline-3,5- 
" " " " 
disulfonic 
acid 
21 4-Amino-2- 
" " " " 
sulfobenzoic 
acid 
22 Aniline-2,5- 
1-Aminonaphtha- 
" " Raddish 
disulfonic 
lene-6- yellow 
acid sulfonic acid 
23 " 1-Aminonaphtha- 
" " " 
lene-8- 
sulfonic acid 
24 " 3-Amino- " 1-N--Ethylamino- 
Yellow 
phenylurea benzene-3-.beta.- 
sulfatoethyl- 
sulfone 
25 " " 1-N--Ethylamino- 
" " 
benzene-4-.beta.- 
sulfatoethyl- 
sulfone 
26 " " " 1-Aminobenzene- 
" 
4-.beta.-sulfatoethyl- 
sulfone 
27 " " 1-N--Ethylamino- 
1-Aminobenzene- 
" 
benzene-3-.beta.- 
3-.beta.-sulfatoethyl 
sulfatoethyl- 
sulfone 
sulfone 
28 4-Methoxy- 
2-Methoxy- 
" " " 
aniline-2- 
5-methyl- 
sulfonic acid 
aniline 
29 2-Methyl-4- 
1-Amino- " " " 
chloroaniline- 
naphthalene- 
6-sulfonic 
8-sulfonic 
acid acid 
30 4-Methyl- 
3-Amino- 1-Aminobenzene- 
" " 
aniline-2,5- 
phenylurea 
4-vinylsulfone 
disulfonic acid 
31 2-Methyl- 
" 1-Aminobenzene- 
1-Aminobenzene- 
" 
aniline-4,6- 4-.beta.-sulfato- 
3-vinylsulfone 
disulfonic acid ethylsulfone 
32 Aniline-2,5- 
3-Aminoacet- 
" " " 
disulfonic acid 
anilide-4- 
sulfonic acid 
33 " 3-Amino- 2-Aminonaph- 
1-Aminobenzene- 
" 
phenylurea 
thalene-6-.beta.- 
3-.beta.-sulfatoethyl- 
sulfatoethyl- 
sulfone 
sulfone 
34 " " 2-Aminonaphtha- 
" " 
lene-8-.beta.- 
sulfatoethyl- 
sulfone 
35 " " 2-Aminonaphtha- 
" " 
lene-6-.beta.- 
sulfatoethyl- 
sulfone-1- 
sulfonic acid 
36 " " 2-Aminonaptha- 
" " 
lene-8-.beta.- 
sulfatoethyl- 
sulfone-6- 
sulfonic acid 
37 " " 2-Aminonaphtha- 
2-Aminonaphtha- 
" 
lene-6-.beta.- 
lene-6-.beta.- 
sulfatoethyl- 
sulfatoethyl- 
sulfone-1- 
sulfone 
sulfonic acid 
38 " 3-Amino- " 1-Aminobenzene- 
" 
acetanilide 4-.beta.-sulfatoethyl- 
sulfone 
39 " " 2-Aminonaphtha- 
1-Aminobenzene- 
" 
lene-8-.beta.- 
3-.beta.-sulfatoethyl- 
sulfatoethyl- 
sulfone 
sulfone 
40 " 2-Methoxy-5- 
2-Aminonaphtha- 
" " 
methylaniline 
lene-6-.beta.- 
sulfatoethyl- 
sulfone 
41 " " 2-Aminonaphtha- 
" " 
lene-8-.beta.- 
sulfatoethyl- 
sulfone 
42 " 3-Carboxyvinyl- 
2-Aminonaphtha- 
" " 
carbonyl- lene-6-.beta.-sulfato- 
aminoaniline 
ethylsulfone 
43 " 3-Carboxyethyl- 
" 1-Aminobenzene- 
" 
carbonyl- 4-.beta.-sulfatoethyl- 
aminoaniline sulfone 
44 " 2,5-Di- 2-Aminonaphtha- 
1-Aminobenzene-3- 
" 
methylaniline 
lene-5-.beta.- 
.beta.-sulfatoethyl- 
sulfatoethyl- 
sulfone 
sulfone-1- 
sulfonic acid 
__________________________________________________________________________ 
EXAMPLE 3 
2-Naphthylamine-3,6,8-trisulfonic acid (19.2 parts) was diazotized in a 
conventional manner, followed by coupling with 3-aminophenylurea (7.6 
parts). The resulting monoazo intermediate was subjected to condensation 
with cyanuric chloride (9.23 parts) and 
1-aminobenzene-4-.beta.-sulfatoethylsulfone (14.1 parts) in that order. 
The condensate was further subjected to condensation with 
1-aminobenzene-3-.beta.-sulfatoethylsulfone (14.1 parts) at 60.degree. to 
70.degree. C. within a pH of 4 to 5. Salting out with sodium chloride gave 
a monoazo compound represented by the following formula in a free acid 
form. 
##STR16## 
EXAMPLE 4 
Example 3 was repeated, but the 2-naphthylamine-3,6,8-trisulfonic acid, 
3-aminophenylurea, 1-aminobenzene-4-.beta.-sulfatoethylsulfone and 
1-aminobenzene-3-.beta.-sulfatoethylsulfone which were used in Example 3, 
were replaced by the aromatic amine compound shown in Column A of the 
following table, which corresponds to the formula (V), the aniline 
compound (VI) shown in Column B, the amine compound (III) shown in Column 
C and another amine compound (IV) shown in Column D, respectively, thereby 
obtaining the corresponding monoazo compound exhibiting a shade shown in 
Column E. 
__________________________________________________________________________ 
A 
Aromatic 
B C D 
Run 
amine Aniline Amine Another amine 
E 
No. 
compound (V) 
compound (VI) 
compound (III) 
compound (IV) 
Shade 
__________________________________________________________________________ 
2-Naphthyl- 
3-Amino- 
1-Aminobenzene- 
1-Aminobenzene- 
1 amine-3,6,8- 
phenylurea 
3-.beta.-sulfatoethyl- 
3-.beta.-sulfatoethyl- 
Golden 
trisulfone sulfone sulfone Yellow 
acid 
1-Amino-2- 
2 " " " methoxybenzene- 
" 
5-.beta.-sulfatoethyl- 
sulfone 
1-Amino-4- 
3 " " " methoxybenzene- 
" 
3-.beta.-sulfatoethyl- 
sulfone 
1-Aminobenzene- 
1-Aminobenzene- 
4 " " 4-.beta.-sulfatoethyl- 
4-.beta.-sulfatoethyl- 
" 
sulfone sulfone 
2-Naphthyl- 
3-Amino- 
1-Aminobenzene- 
1-Amino-2- 
5 amine-3,6,8- 
phenylurea 
4-.beta.-sulfatoethyl- 
methoxybenzene- 
Golden 
trisulfonic sulfone 5-.beta.-sulfatoethyl- 
Yellow 
acid sulfone 
3-Amino- 1-Aminobenzene- 
6 " acetanilide 
" 3-.beta.-sulfatoethyl- 
" 
sulfone 
1-Aminobenzene- 
7 " " 3-.beta.-sulfatoethyl- 
" " 
sulfone 
2-Methoxy-5- 
8 " methylaniline 
" " " 
1-Aminobenzene- 
9 " " " 4-.beta.-sulfatoethyl- 
" 
sulfone 
3-Carboxy- 
10 " vinylamino 
" " " 
aniline 
2-Naphthyl- 
3-Carboxy- 
1-Aminobenzene- 
1-Aminobenzene- 
11 amine-3,6,8- 
ethylamino- 
3-.beta.-sulfatoethyl- 
4-.beta.-sulfatoethyl- 
Golden 
trisulfonic 
aniline sulfone sulfone yellow 
12 " 2,5-Dimethyl- 
" " " 
aniline 
13 " 2,5-Dimethoxy- 
" " " 
aniline 
2-Naphthyl- 
3-Amino- 
1-Aminobenzene-4- 
14 amine-4,6,8- 
phenylurea 
.beta.-sulfatoethyl- 
" " 
trisulfonic sulfone 
acid 
1-Aminobenzene- 
1-Aminobenzen- 
15 " " 3-.beta.-sulfatoethyl- 
3-.beta.-sulfatoethyl- 
" 
sulfone sulfone 
1-Aminobenzene- 
16 " " 4-.beta.-sulfatoethyl- 
" " 
sulfone 
2-Naphthyl- 
3-Amino- 
1-Aminobenzene- 
1-Aminobenzene- 
17 amine-4,8- 
phenylurea 
4-.beta.-sulfatoethyl- 
3-.beta.-sulfatoethyl- 
Yellow 
disulfonic acid sulfone sulfone 
2-Naphthyl- 
18 amine-1,5- 
" " " " 
disulfonic acid 
2-Naphthyl- 
19 amine-3,6- 
" " " " 
disulfonic acid 
2-Naphthyl- 
20 amine-5,7- 
" " " " 
disulfonic acid 
2-Naphthyl- 
21 amine-6,8- 
" " " " 
disulfonic acid 
2-Naphthyl- 
1-Amino- 
22 amine-4,8- 
naphthalene-6- 
" " " 
disulfonic aicd 
sulfonic acid 
2-Naphthyl- 
1-Amino- 
1-Aminobenzene- 
1-Aminobenzene- 
23 amine-4,8- 
naphthalene-8- 
4-.beta.-sulfatoethyl- 
3-.beta.-sulfatoethyl- 
Yellow 
disulfonic acid 
sulfonic acid 
sulfone sulfone 
2-Naphthyle- 
3-Amino- 1-N--Ethylamino- 
24 amin-3,6,8- 
phenylurea 
" benzene-3-.beta.- 
Golden 
trisulfonic sulfatoethyl- 
yellow 
acid sulfone 
1-N--Ethylamino- 
1-Aminobenzene- 
25 " " benzene-4-.beta.- 
3-.beta.-sulfatoethyl- 
" 
sulfatoethyl- 
sulfone 
sulfone 
1-Aminobenzene- 
26 " " " 4-.beta.-sulfatoethyl- 
" 
sulfone 
1-N--Ethylamino- 
1-Aminobenzene- 
27 " " benzene-3-.beta.- 
3-.beta.-sulfatoethyl 
" 
sulfatoethyl- 
sulfone 
sulfone 
2-Naphthyl- 
2-Methoxy-5- 
1-N--Ethylamino 
1-Aminobenzene- 
28 amine-4,8- 
methylaniline 
benzene-3-.beta.- 
3-.beta.-sulfatoethyl- 
Yellow 
disulfonic acid sulfatoethyl- 
sulfone 
sulfone 
1-Aminonaphtha- 
1-N--Ethylamino- 
29 " lene-8- benzene-3-.beta.- 
" " 
sulfonic acid 
sulfatoethyl- 
sulfone 
2-Naphthyl- 
3-Amino- 
1-Aminobenzene- 
30 amine-3,6,8- 
phenylurea 
4-vinylsulfone 
" Golden 
trisulfonic yellow 
acid 
1-Aminobenzene- 
1-Aminobenzene- 
31 " " 4-.beta.-sulfatoethyl- 
3-vinylsulfone 
" 
sulfone 
2-Naphthyl- 
3-Aminoacet- 
32 amine-4,8- 
anilide-4- 
" " " 
disulfonic acid 
sulfonic acid 
__________________________________________________________________________ 
EXAMPLE 5 
Aniline-2,5-disulfonic acid (12.7 parts) was diazotized in a usual manner, 
followed by coupling with 3-aminoacetanilide-4-sulfonic acid (11.5 parts). 
The resulting intermediate was subjected to a first condensation with 
cyanuric chloride (9.23 parts), followed by a second condensation with 
1-aminobenzene-4-.beta.-sulfatoethylsulfone (14.1 parts). Ultimately, the 
resulting condensate was allowed to react with 
1-aminobenzene-3-.beta.-sulfatoethylsulfone (14.1 parts) at 60.degree. to 
70.degree. C. within a pH of 4 to 5. Salting-out with sodium chloride gave 
a monoazo compound represented by the following formula in a free acid 
form. 
##STR17## 
EXAMPLE 6 
Example 5 was repeated, but the aniline-2,5-disulfonic acid, 
3-aminoacetanilide-4-sulfonic acid, 
1-aminobenzene-4-.beta.-sulfatoethylsulfone and 
1-aminobenzene-3-.beta.-sulfatoethylsulfone which were used in Example 5 
were replaced by the aromatic amine compound shown in Column A of the 
following table which corresponds to the formula (V), the aniline compound 
(VI) shown in Column B, the amine compound (III) shown in Column C and 
another amine compound (VI) shown in Column D, respectively, thereby 
obtaining the corresponding monoazo compound exhibiting a shade shown in 
Column E. In the following table, the symbol Q denotes --SO.sub.2 CH.sub.2 
CH.sub.2 OSO.sub.3 H. 
__________________________________________________________________________ 
A 
Aromatic B C D 
Run amine Aniline Amine Another amine E 
No. compound (V) compound (VI) 
compound (III) compound (IV) Shade 
__________________________________________________________________________ 
##STR18## 
##STR19## 
##STR20## 
##STR21## Yellow 
2 " " 
##STR22## 
##STR23## " 
3 " " 
##STR24## 
##STR25## " 
4 " " 
##STR26## 
##STR27## " 
5 
##STR28## 
##STR29## 
##STR30## 
##STR31## Yellow 
6 " " 
##STR32## 
##STR33## " 
7 " " 
##STR34## 
##STR35## " 
8 " " 
##STR36## 
##STR37## " 
9 
##STR38## 
##STR39## 
##STR40## 
##STR41## Yellow 
10 " " 
##STR42## 
##STR43## " 
11 
##STR44## 
##STR45## 
##STR46## 
##STR47## " 
12 
##STR48## " 
##STR49## 
##STR50## " 
13 
##STR51## 
##STR52## 
##STR53## 
##STR54## Yellow 
14 " 
##STR55## " " " 
15 " 
##STR56## 
##STR57## 
##STR58## " 
16 " " 
##STR59## 
##STR60## " 
__________________________________________________________________________ 
EXAMPLE 7 
2-Naphthylamine-3,6,8-trisulfonic acid (19.2 parts) was diazotized in a 
conventional manner, followed by coupling with 3-aminophenylurea (7.6 
parts). The resulting monoazo intermediate was subjected to condensation 
with cyanuric chloride (9.23 parts) and 
2-aminonaphthalene-6-.beta.-sulfatoethylsulfone-1-sulfonic acid (21.7 
parts) in that order. The condensate was further subjected to condensation 
with 1-aminobenzene-3-.beta.-sulfatoethylsulfone (14.1 parts) at 
60.degree. to 70.degree. C. within a pH of 4 to 5. Salting out with sodium 
chloride gave a monoazo compound represented by the following formula in a 
free acid form. 
##STR61## 
EXAMPLE 8 
Example 7 was repeated, but the 2-naphthylamine-3,6,8-trisulfonic acid, 
3-aminophenylurea, 
2-aminonaphthalene-6-.beta.-sulfatoethylsulfone-1-sulfonic acid and 
1-aminobenzene-3-.beta.-sulfatoethylsulfone which were used in Example 7, 
were replaced by the aromatic amine compound as shown in Column A of the 
following table, which corresponds to the formula (V), the aniline 
compound (VI) as shown in column B, the amine compound (III) as shown in 
Column C and another amine compound (IV) as shown in Column D, 
respectively, thereby obtaining the corresponding monoazo compound 
exhibiting a shade as shown in Column E. 
__________________________________________________________________________ 
A 
Aromatic 
B C D 
Run 
amine Aniline Amine Another amine 
E 
No. 
compound (V) 
compound (VI) 
compound (III) 
compound (IV) 
Shade 
__________________________________________________________________________ 
2-Naphthyl- 
3-Amino- 2-Amino- 1-Aminobenzene- 
amine-3,6,8- 
phenylurea 
naphthalene-6- 
4-.beta.-sulfatoethyl- 
Golden 
1 trisulfonic .beta.-sulfatoethyl- 
sulfone yellow 
acid sulfone-1- 
sulfonic acid 
1-N--Ethylamino- 
2 " " " benzene-3-.beta.- 
" 
sulfatoethyl- 
sulfone 
1-Amino-2-methoxy- 
3 " " " benzene-5-.beta.- 
" 
sulfatoethyl- 
sulfone 
2-Naphthyl- 
3-Amino- 2-Amino- 1-Amino-4-methoxy- 
amine-3,6,8- 
phenylurea 
naphthalene-6- 
benzene-3-.beta.- 
Golden 
4 trisulfonic .beta.-sulfatoethyl- 
sulfatoethyl- 
yellow 
acid sulfone-1- 
sulfone 
sulfonic acid 
2-Amino- 1-Aminobenzene-3- 
naphthalene-5- 
.beta.-sulfatoethyl- 
5 " " .beta.-sulfatoethyl- 
sulfone " 
sulfone-1- 
sulfonic acid 
1-Aminobenzene-4- 
6 " " " .beta.-sulfatoethyl- 
" 
sulfone 
2-Amino- 
7 " " naphthalene-6- 
" " 
.beta.-sulfatoethyl- 
sulfone 
2-Naphthyl- 
3-Amino- 2-Aminonaphtha- 
1-Aminobenzene 
8 amine-3,6,8- 
phenylurea 
lene-6-.beta.-sulfato- 
3-.beta.-sulfato- 
Golden 
trisulfonic ethylsulfone 
ethylsulfone 
yellow 
acid 
2-Aminonaphtha- 
1-Aminobenzene- 
9 " " lene-5-.beta.-sulfato- 
4-.beta.-sulfato- 
" 
ethylsulfone 
ethylsulfone 
1-Aminobenzene- 
10 " " " 3-.beta.-sulfato- 
" 
ethylsulfone 
3-Amino- 2-Aminonaphtha- 
11 " acetanilide 
lene-6-.beta.-sulfato- 
" " 
ethylsulfone-1- 
sulfonic acid 
1-Aminobenzene- 
12 " " " 4-.beta.-sulfatoethyl- 
" 
sulfone 
2-Naphthyl- 
2-Methoxy-5- 
2-Aminonaphtha- 
1-Aminobenzene- 
13 amine-3,6,8- 
methylaniline 
lene-6-.beta.-sulfato- 
3-.beta.-sulfatoethyl- 
Golden 
trisulfonic ethylsulfone-1- 
sulfone yellow 
acid sulfonic acid 
3-Carboxy- 
14 " vinylcarbonylamino 
" " " 
aniline 
3-Carboxy- 
15 " ethylcarbonylamino 
" " " 
aniline 
16 " 2,5-Dimethyl- 
" " " 
aniline 
2-Naphthyl- 
3-Amino- 
17 amine-4,6,8- 
phenylurea 
" " " 
trisulfonic 
acid 
2-Naphthyl- 
3-Amino- 2-Aminonaphtha- 
1-Aminobenzene- 
18 amine-4,6,8- 
phenylurea 
lene-6-.beta.-sulfato- 
4-.beta.-sulfato- 
Golden 
trisulfonic ethylsulfone-1- 
ethylsulfone 
yellow 
acid sulfonic acid 
2-Aminonaphtha- 
19 " " lene-6-.beta.-sulfato- 
" " 
ethylsulfone 
1-Aminobenzene- 
20 " " " 3-.beta.-sulfato- 
" 
ethylsulfone 
2-Naphthyl- 2-Aminonaphtha- 
21 amine-3,6,8- lene-6-.beta.- 
trisulfonic 
" " sulfatoethyl- 
" 
acid sulfone 
2-Naphthyl- 1-Aminobenzene- 
22 amine-4,8- 
" " 3-.beta.-sulfato- 
" 
disulfonic acid ethylsulfone 
2-Naphthyl- 
3-Amino- 2-Aminonaphtha- 
1-Aminobenzene- 
23 amine-1,5- 
phenylurea 
lene-6-.beta.-sulfato- 
3-.beta.-sulfato- 
Golden 
disulfonic acid ethylsulfone 
ethylsulfone 
yellow 
2-Naphthyl- 
24 amine-3,6- 
" " " " 
disulfonic acid 
2-Naphthyl- 1-N--Ethylamino- 
25 amine-3,6,8- 
" " benzene-3-.beta.- 
" 
trisulfonic sulfato- 
acid ethylsulfone 
2-Aminonaphtha- 
26 " " lene-5-.beta.- 
" " 
sulfatoethyl- 
sulfone 
1-N--Ethylamino- 
27 " " " benzene-4-.beta.- 
" 
sulfatoethyl- 
sulfone 
2-Naphthyl- 
3-Amino- 2-Aminonaphtha- 
1-N--Ethylamino- 
amine-3,6,8- 
phenylurea 
lene-5-.beta.- 
benzene-4-.beta.- 
28 trisulfonic sulfatoethyl- 
sulfatoethyl- 
Golden 
acid sulfone-1- 
sulfone yellow 
sulfonic acid 
2-Aminonaphtha- 
1-Aminobenzene- 
29 " " lene-6-vinyl- 
3-.beta.-sulfatoethyl- 
" 
sulfone-1- 
sulfone 
sulfonic acid 
1-N--Ethylamino- 
30 " " " 3-.beta.-sulfato- 
" 
ethylsulfone 
3-Aminoacet- 
2-Aminonaphtha- 
1-Aminobenzene- 
31 " anilide-4- 
lene-6-.beta.- 
3-.beta.-sulfato- 
" 
sulfonic acid 
sulfato- ethylsulfone 
ethylsulfone 
2-Naphthyl- 2-Aminonaphtha- 
32 amine-3,6- 
" lene-5-.mu.- 
" " 
disulfonic acid sulfatoethyl- 
sulfone 
__________________________________________________________________________ 
DYEING EXAMPLE 1 
The monoazo compound obtained in Example 1 (0.3 part) was dissolved in 
water (200 parts), and cotton (10 parts) and sodium sulfate (8 parts) were 
added thereto. The bath was heated up to 60.degree. C. and then sodium 
carbonate (4 parts) was added to the bath. Dyeing was continued for 1 hour 
at that temperature. Thereafter, the cotton was washed with water and 
soaped to obtain a dyed product of a deep yellow color which was excellent 
in various fastness properties. The monoazo compound gave excellent 
reproducibility of the dyeing, irrespective of changes in dyeing 
temperature, bath ratio and salt concentration in some degree. 
DYEING EXAMPLE 2 
Using the monoazo compounds obtained in Examples 2, 5 and 6, dyeing 
procedures similar to that of Dyeing Example 1 are carried out to obtain 
the results similar to those of Dyeing Example 1. 
DYEING EXAMPLE 3 
The monoazo compound obtained in Example 3 (0.3 part) was dissolved in 
water (200 parts), and cotton (10 parts) and sodium sulfate (9 parts) were 
added thereto. The bath was heated up to 60.degree. C., and then sodium 
carbonate (4 parts) was added to the bath. Dyeing was continued for 1 hour 
at that temperature. Thereafter, the cotton was washed with water and 
soaped to obtain a dyed product of a deep yellow color which was excellent 
in various fastness properties. The monoazo compound gave excellent 
reproducibility of the dyeing, irrespective of changes in dyeing 
temperature, bath ratio and salt concentration in some degree. 
DYEING EXAMPLE 4 
Using the monoazo compounds obtained in Examples 4, 7 and 8, dyeing 
procedures similar to that of Dyeing Example 3 are carried out to obtain 
the results similar to those of Dyeing Example 3.