Anthraquinone compounds represented by the following formula are useful as dyes: ##STR1## wherein Y stands for a hydrogen atom or a nitro group, Z stands for an oxygen or sulfur atom when Y stands for a hydrogen atom, but Z stands for an oxygen atom when Y stands for a nitro group, R.sub.1 stands for a hydrogen atom or a lower alkyl group, R.sub.3 stands for a halogen atom or a group R.sub.2 wherein R.sub.2 stands for an amino, substituted or unsubstituted lower alkylamino, substituted or unsubstituted arylamino, substituted or unsubstituted alkoxy, substituted or unsubstituted aryloxy, substituted or unsubstituted alkylthio, substituted or unsubstituted arylthio group, or a group ##STR2## Q stands for a nitrogen atom or carbon atom bearing a halogen atom when R.sub.3 stands for a halogen atom, but Q stands for a nitrogen atom when R.sub.3 stands for a group R.sub.2, X stands for a halogen atom, the group ##STR3## links to the benzene ring in the 3'- or 4'-position, and M stands for an alkali metal or hydrogen atom.

BACKGROUND OF THE INVENTION 
It has already been known that dyes having a halogenotriazine group or a 
halogenopyrimidine group react with cellulose fibers in the presence of an 
acid-binding agent, and numerous dyes have been used actually as reactive 
dyes. These dyes are characterized in that they have a good wet fastness 
and light fastness and that dyeings therewith have an excellent brightness 
in color shade. 
However, among reactive dyes for dip dyeing there have been no blue dyes 
with excellent fastnesses and brightness which are characteristics of this 
kind of dyes, and so it is intensively desired that such dyes which can 
dye cellulose fibers deep blue by dip dyeing method should be developed. 
SUMMARY OF THE INVENTION 
The dyes of formula (1) used in the present invention give very strong 
bright, fast, deep blue dyeings when cellulose fibers are dip-dyed. 
The dyes give very strong bright dyeings with a wide range of color when 
they are mixed with other dyes. 
These dyes are suitable for padding and printing too. 
These are new, and the dyeings with them are very bright and display an 
excellent build-up property, as compared with reactive dyes obtained by 
using bromamine acid (1-amino-4-bromoanthraquinone-2-sulfonic acid) as a 
starting material, when cellulose fibers are dip-dyed. Color Index 
Reactive Blue 5 and color Index Reactive Blue 2 as typical examples of the 
prior reactive dyes are compared with the dyes of formula (1) in the 
following table. 
__________________________________________________________________________ 
Color Bright- 
Shade ness Build-up 
__________________________________________________________________________ 
property 
Dyes used in the present invention 
##STR4## consider- ably more reddish 
very strong brighter 
100 much better 
##STR5## a little more reddish 
very strong brighter 
100 much better 
a visual 
depth of 
shade on 
a visual depth 
C.I. Reactive Blue 5 standard 
standard 
dyeing at 
of shade on the 
2 % o.w.f. 
dyeing at 8 % 
is used as 
o.w.f. is used 
a standard 
as a standard 
and defined 
and defined 
to be 100. 
to be 100. 
C.I. Reactive Blue 2 more darker 
100 a little 
greenish better 
__________________________________________________________________________ 
In obtaining the data given in the foregoing table, the dyeing process used 
was as follows: 
Fifty parts of cotton knitted goods were immersed in a solution containing 
a certain amount of dyes, 60 parts of anhydrous sodium sulfate in 1,000 
parts of water and treated at 80.degree. C for 30 minutes. Then 20 parts 
of sodium carbonate were added to the solution and dyeing was carried out 
at the same temperature for 60 minutes. The dyed goods were washed with 
water, soaped thoroughly with Scourol #900 (a nonionic surface active 
agent manufactured by Kao Soap Co., Ltd.), washed with water and dried. 
In order to measure build-up property the following procedure was used: 
Dyeing was carried out with C.I. Reactive Blue 5 at 2% o.w.f. and dyeing 
with other dyes was also done so as to obtain the same depth of shade as 
one with C.I. Reactive Blue 5. Then dyeing with each dye was carried out 
in four times the former concentration and the dyeings thus obtained were 
visually assessed. 
DETAILED DESCRIPTION OF THE INVENTION 
The dyes of formula (1) in the present invention may be manufactured by 
either of the following two methods, herein referred to as Process I and 
Process II. 
In Process I, anthraquinone compounds of formula (1) are manufactured by 
reacting a compound of the formula: 
##STR6## 
wherein Q, X and R.sub.3 have the meanings given above, with an 
anthraquinone compound of the formula: 
##STR7## 
wherein Y, Z, R.sub.1 and M have the meanings given above, and wherein the 
group 
##STR8## 
links to the benzene ring in the 3'- or 4'-position. 
In Process II, anthraquinone compounds of the formula: 
##STR9## 
wherein Y, Z, R.sub.1, R.sub.2, X and M have the meanings given above, and 
wherein the group 
##STR10## 
links to the benzene in the 3'- or 4'-position, are manufactured by 
reacting a triazine compound of the formula: 
##STR11## 
wherein X has the meaning given above, with an anthraquinone compound of 
formula (3) and a compound of the formula: 
EQU R.sub.2 H (6) 
wherein R.sub.2 has the meaning given above, in an arbitrary order. In 
Process I the reaction of compounds of formula (2) with anthraquinone 
compounds of formula (3) is carried out in a conventional way, preferably 
in the presence of acid-binding agents such as sodium carbonate. When a 
2,4,6-trihalogeno-1,3,5-triazine is used as a compound of formula (2), the 
reaction may be carried out by dissolving 1 mole of a compound of formula 
(3) at pH 6-7.0 in an adequate solvent such as water and adding 1 mole of 
the said triazine at 10.degree. C or below, preferably 0-7.degree. C. When 
a 2,4,5,6-tetrahalogenopyrimidine or a compound of formula (2) wherein 
R.sub.3 = R.sub.2 is used as a compound of formula (2), the reaction is 
preferably effected at little higher temperature, for example, 30 - 
50.degree. C at pH 6-9 in water. 
Process II is shown by either one of the following chemical reactions 
herein referred to as Process IIa and Process IIb. 
In Process IIa, the following chemical reaction occurs: 
##STR12## 
In Process IIb, the following chemical reaction occurs: 
##STR13## 
These reactions are preferably carried out in the presence of an 
acid-binding agent by the conventional methods. The reaction of compounds 
of formula (5) with compounds of formula (3) and the reaction of compounds 
of formula (5) with compounds of formula (6) are conducted at 10.degree. C 
or below, preferably 0 - 7.degree. C, and the next reaction of compounds 
of formula (7) with compounds of formula (6) and the reaction of compounds 
of formula (8) with compounds of formula (3) are suitably conducted at a 
little higher temperature, for example 30 - 50.degree. C. 
Compounds of formula (7) and (8) may be used in the following reaction with 
or without separating from the reaction solution. Anthraquinone compounds 
thus obtained can be isolated in the form of powder from the reaction 
solution by salting-out, filtration and drying, or by spray-drying the 
reaction solution. The anthraquinone compounds are very readily soluble in 
water when they are in the form of an alkali metal salt such as sodium or 
potassium. 
As examples of compounds of formula (2) there may be mentioned, for 
example, 2,4,5,6-tetrachloropyrimidine, 2,4,5,6-tetrabromopyrimidine, 
2,4,6-trichlorotriazine, 2,4,6-tribromotriazine, 2,4-dichlorotriazine or 
2,4-dibromotriazine substituted with R.sub.2 at the 6-position. 
Compounds of formula (2) where R.sub.3 stands for R.sub.2 can be prepared 
by reacting a 2,4,6-trihalogenotriazine with a compound of the formula 
(6). As examples of compounds of formula (3) there may be mentioned, for 
example, sodium 1,4-diamino-2-(m or 
p-aminophenoxy)-anthraquinone-3-sulfonate, sodium 1,4-diamino-2-(m- or 
p-N-methylaminophenoxy) anthraquinone-3-sulfonate, sodium 
1,4-diamino-2-(m- or p-amino- phenoxy)-5-nitroanthraquinone-3-sulfonate, 
sodium 1,4-diamino-2-(m- or 
p-N-methylaminophenoxy)-5-nitroanthraquinone-3-sulfonate, sodium 
1,4-diamino-2-(m or p-aminophenylthio)-anthraquinone-3-sulfonate, sodium 
1,4-diamino-2-(m or p-N-methylaminophenylthio)-anthraquinone-3-sulfonate. 
Examples of compounds of formula (5) include 2,4,6-trichlorotriazine and 
2,4,6-tribromotriazine. 
As examples of compounds of formula (6) there may be, for example, ammonia, 
substituted or unsubstituted alkylamine such as methylamine, ethylamine, 
propylamine, butylamine, glycine, methoxypropylamine, ethanolamine, 
ethanolamine sulfonate, taurine, dimethylamine, diethylamine, 
diethanolamine, morpholine, substituted or unsubstituted arylamine such as 
aniline, o, m or p-chloroaniline, o, m or p-toluidine, o, m or 
p-anisidine, o, m or p-phenetidine, o, m or p-sulfoaniline, 2,4-, 2,5-or 
3,5-disulfoaniline, o, m or p-carboxyaniline, 4 or 
5-sulfo-2-carboxyaniline, 2 or 5-sulfo-3-carboxyaniline, 2- or 
3-sulfo-4-carboxyaniline, 4,5 or 6-sulfo-methylaniline, 2- or 
3-sulfo-4-methylaniline, 3-methyl-4-sulfoaniline, 
2,4-disulfo-6-methylaniline, 3,5-disulfo-4-methylaniline, 2- or 
3-sulfo-4-methoxyaniline, 5-sulfo-2-methoxyaniline, 2- or 
6-sulfo-3-chloroaniline, 3 or 5-sulfo-2-chloroaniline, 2 or 
3-sulfo-4-chloroaniline, N-methylaniline, 2-, 3- or 
4-sulfo-N-methylaniline, 2- or 3-sulfo-4-acetylaminoaniline, 2- or 
4-sulfo-3-acetylaminoaniline. 
2-, 3-, 4-, 5-, 6-, 7- or 8-sulfo-.alpha.-naphthylamine, 1-, 5-, 6-, 7- and 
8- .beta.-naphthylamine, 3,8-, 4,6-, 4.7-, 4.8- or 
3,6-disulfo-.alpha.-naphthylamine and 1,5-, 4,8-, 3.6- or 
6.8-disulfo-.beta.-naphthylamine, substituted or unsubstituted alcohol 
such as methanol, ethanol, n- or iso-propanol, n-, iso,sec- or 
tert-butanol, ethyleneglycolmonomethylether, ethyleneglycolmonoethylether, 
ethyleneglycolmonobutylether, diethylenglycolmonomethylether and 
.gamma.-methoxy-n-butanol, substituted or unsubstituted phenols such as 
phenol, o-, m- or p-chlorophenol, o-, m- or p-cresol, o-, m- or 
p-methoxyphenol, o-, m- or p-nitrophenol, o-, m- or p-sulfophenol and o-, 
m- or p- carboxyphenol, substituted or unsubstituted alkylthiol such as 
methylmercaptane, ethylmercaptane and butylmercaptane, 
.beta.-hydroxyethylmercaptane, arylthiol such as thiophenol, o-, m- or 
p-methylthiophenol and o-, m- or p-methoxythiophenol, 2,6-diaminopyridine 
and 2-mercaptobenzothiozole. 
With a view towards economy in manufacture of compounds and the dyeing 
property of compounds, one preferred class of the anthraquinone compounds 
of the present invention includes the dyes of formula (1) wherein Y and Z 
have the meanings given above, R.sub.1 stands for a hydrogen atom or an 
alkyl group having 1 to 4 carbon atoms, R.sub.3 stands for a chlorine or 
bromine atom or R.sub.2, wherein R.sub.2 stands for an amino, alkylamino 
having 1 to 4 carbon atoms, --NHCH.sub.2 COOH, --NHCH.sub.2 CH.sub.2 
CH.sub.2 OCH.sub.3, --NHCH.sub.2 CH.sub.2 OH, --NHCH.sub.2 CH.sub.2 
OSO.sub.3 H, --NHCH.sub.2 CH.sub.2 SO.sub.3 H, --N(CH.sub.3).sub.2, 
--N(C.sub.2 H.sub.5).sub.2, --N(CH.sub.2 CH.sub.2 OH).sub.2, 
##STR14## 
anilino, chloroanilino, toluidino, anisidino, phenetidino, 
acetoaminoanilino, monosulfoanilino, disulfoanilino, carboxyanilino, 
##STR15## 
alkoxy having 1 to 4 carbon atoms, --OCH.sub.2 CH.sub.2 OCH.sub.3, 
--OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3, --OC.sub.2 H.sub.4 
OC.sub.2 H.sub.5, --OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2 
CH.sub.3, 
##STR16## 
phenoxy, chlorophenoxy, methylphenoxy, methoxyphenoxy, nitrophenoxy, 
sulfophenoxy, carboxyphenoxy, methylthio, ethylthio, butylthio, --SC.sub.2 
H.sub.4 OH, phenylthio, methylphenylthio, methoxyphenylthio, 
##STR17## 
Q stands for a nitrogen atom or carbon atom bearing a chlorine or bromine 
atom when R.sub.3 stands for a chlorine or bromine atom, but Q stands for 
a nitrogen atom when R.sub.3 stands for a group R.sub.2, X stands for a 
chlorine or bromine atom, M stands for a hydrogen, sodium or potassium 
atom. 
A second preferred class of the anthraquinone compounds of the present 
invention comprises the dyes of formula (1) wherein Y, Z, R.sub.1, 
R.sub.2, R.sub.3, X and M have the meanings given in the above preferred 
class, and Q stands for a nitrogen atom. A third preferred class of the 
anthraquinone compounds of the present invention comprises the dyes of 
formula (1) wherein Y, R.sub.1, R.sub.2, R.sub.3, X, Q and M have the 
meanings given in the second preferred class, Z stands for an oxygen atom. 
A fourth preferred class of the anthraquinone compounds of the present 
invention comprises the dyes of formula (1) wherein Y, Z, R.sub.2, 
R.sub.3, X, Q and M have the meanings given in the third preferred class 
and R.sub.1 stands for a hydrogen atom. 
A fifth preferred class of the anthraquinone compounds of the present 
invention comprises the dyes of formula (1) wherein Y, Z, R.sub.1, X, Q 
and M have the meanings given in the third preferred class, and R.sub.3 
stands for R.sub.2 and R.sub.2 stands for an amino, --NHCH.sub.2 CH.sub.2 
OH, --NHCH.sub.2 CH.sub.2 SO.sub.3 H, 
##STR18## 
monosulfoanilino, disulfoanilino, carboxyanilino, 
##STR19## 
methoxy, --OCH.sub.2 CH.sub.2 OCH.sub.3 or --OCH.sub.2 CH.sub.2 OCH.sub.2 
CH.sub.3. 
A sixth preferred class of the anthraquinone compounds of the present 
invention comprises the dyes of formula (1) where Z, R.sub.1, R.sub.2, 
R.sub.3, X, Q and M have the meanings given in the fifth preferred class 
and Y stands for a hydrogen atom. 
A seventh preferred class of the anthraquinone compounds of the present 
invention comprises the dyes of formula (1) wherein Z, R.sub.1, R.sub.2, 
R.sub.3, X, Q and M have the meanings given in the fifth preferred class 
and Y stands for a nitrogen group. 
The present invention includes, for example, the following dyeing 
processes: dip-dyeing, padding or printing of cellulose fibers or their 
mixed spun fibers by using the anthraquinone compounds of formula (1) in 
the presence of acid-binding agents. 
Naturally anthraquinone compounds of formula (1) can be used for dyeing in 
a mixture among themselves and also with any other dyes. 
As acid-binding agents used in dyeing there may be mentioned, for example, 
sodium hydrocarbonate, sodium metaphosphate, sodium phosphate, sodium 
ortho-or meta-silicate, sodium carbonate, sodium hydroxide and the like. 
In case the dyeing process of the present invention is applied to dyeing 
treatment with a relatively long liquor-to-goods ratio such as a 
batch-wise dip dyeing, the bath is usually prepared with an inorganic salt 
such as sodium chloride or sodium sulfate and the dye, and after the 
dyeing is preferably carried out for 10 - 60 minutes while heating at 30 - 
100.degree. C, an acid-binding agent is added to the bath and then the 
dyeing is continued for 20 - 60 minutes while heating at 30 - 100.degree. 
C. In this case an acid-binding agent may be added at the beginning of the 
dyeing, and moreover, after the dyeing is carried out at a neutral 
condition, fixation of dyes may be done in another bath containing an 
acid-binding agent. 
In case the dyeing process of the present invention is applied to dyeing 
treatment with a little shorter liquor-to-goods ratio such as padding, the 
dye-bath is usually prepared with the dye, an acid-binding agent, a 
penetrating agent and, if necessary, urea, and after fibers are immersed 
in the bath for a short time, the fibers are squeezed, allowed to stand at 
room temperature or under heating or steamed or dry-heated for a short 
time. Alternatively, fibers can be first immersed in a solution of an 
acid-binding agent and then padded in a neutral bath, or after padding in 
a neutral bath, fibers can be treated in a solution of an acid-binding 
agent which is saturated with an inorganic salt and then allowed to stand 
or heat-treated. 
In case the dyeing process of the present invention is applied to printing 
treatment, fibers are printed with a colour paste usually containing 
sodium alginate or an emulsion paste as a thickener, the dye, an 
acid-binding agent, urea and the like, then dried intermediately, and 
heat-treated or allowed to stand at room temperature or under heating to 
fix the dyes on the fibers. If desired, fibers which are immersed in a 
solution of an acid-binding agent are printed with a neutral colour paste 
or overprinted and then the fibers can be allowed to stand or 
heat-treated. 
Fibers dyed by such dip-dyeing, padding or printing treatment can be 
slightly washed with water and then usually treated with a fixing agent in 
the market for anionic dyes, preferably, a fixing agent of 
polyethylenepolyamines.

The following examples serve to illustrate the present invention but they 
are not intended to limit it thereto. 
In the examples part(s) and % are by weight. 
EXAMPLE 1 
A mixture of 43 parts of disodium salt of 
1,4-diaminoanthraquinone-2,3-disulfonic acid, 30 parts of 
p-acetylaminophenol, 11 parts of potassium carbonate and 80 parts of 
dimethylformamide was stirred at 140.degree. C for 3 hours. This reaction 
solution was poured into 1000 parts of water. The mixture was filtered to 
remove insoluble components. 300 parts of sodium chloride was added to the 
filtrate and was filtered again. The cake was washed with 500 parts of a 
20% aqueous solution of sodium chloride. The cake thus obtained was 
dissolved in 450 parts of water and 130 parts of hydrochloric acid was 
added to the solution. The solution was heated to 95.degree. C and stirred 
for 10 hours. After cooling the solution was filtered to obtain 
1,4-diamino-2-(4'-aminophenoxy)anthraquinone-3-sulfonic acid. 4 parts of 
sulfanilic acid were added to 200 parts of water and the solution was 
adjusted to pH 7 with soda ash. 4.1 parts of cyanuric chloride were added 
to the solution at 0.degree. C, the reaction was continued for 1 hour and 
after the solution was neutralized, excess cyanuric chloride was removed 
by filtration. To the filtrate there were added 9 parts of 
1,4-diamino-2-(4'-aminophenoxy) anthraquinone-3-sulfonic acid, the 
solution was kept at 35 - 40.degree. C, a 10% solution of soda ash was 
added and the reaction was carried out for 2 hours while adjusting the pH 
to 5 - 7. 60 parts of sodium chloride were added to the reaction solution. 
The dye precipitated was filtered and dried. There was obtained 13 parts 
of a dye represented by the following formula: 
##STR20## 
.mu. max. : 580 m.mu. in pure water 
Elemental analysis values 
(Sample purified by column chromatography was used) 
______________________________________ 
Found Calculated 
______________________________________ 
C 46.20% 46.18% 
H 2.40% 2.39% 
N 13.01% 13.01% 
Cl 4.70% 4.71% 
S 8.50% 8.49% 
______________________________________ 
EXAMPLE 2 
A dye-bath was prepared by using 1 part of the dye of formula (9), 60 parts 
of anhydrous sodium sulfate and 1000 parts of water. 50 parts of cotton 
knitted goods were immersed into the dye-bath and treated at 80.degree. C 
for 30 minutes. Then 20 parts of sodium carbonate were added to the 
dye-bath and dyeing was continued at the same temperature for 60 minutes. 
After washing with water the dyed goods were soaped thoroughly with 
Scourol #900 (a nonionic surface active agent manufactured by Kao Soap 
Co., Ltd.), washed with water and dried. The dyed goods thus obtained were 
bright reddish blue. 
EXAMPLE 3 
In a similar manner as described in Example 1, 
1,4-diamino-2-(3'-aminophenoxy)-anthraquinone-2-sulfonic acid was 
manufactured by using 1,4-diaminoanthraquinone-2,3-disulfonic acid and 
metaacetylaminophenol. 4.5 parts of this anthraquinone compound were added 
to 100 parts of water and the solution was adjusted to pH 6.5 with a 10% 
aqueous solution of sodium carbonate. Then ice was added to cool the 
solution to 0.degree. C and 1.9 parts of cyanuric chloride was added. The 
reaction was carried out at 0 - 3.degree. C for 1 hour while adjusting the 
solution to pH 5 - 6by using a 10% aqueous solution of sodium carbonate. 
After removing insoluble components, 20 parts of sodium chloride were 
added to the solution and the dye precipitated was filtered and dried. The 
resultant compound was represented by the formula: 
##STR21## 
.lambda. max. : 578 m.mu. (in pure water) 
Elemental analysis values 
(Sample purified by column chromatograph was used) 
______________________________________ 
Found Calculated 
______________________________________ 
C 46.41 % 46.39 % 
H 2.18 % 2.18 % 
N 14.05 % 14.12 % 
Cl 11.82 % 11.93 % 
S 5.36 % 5.38 % 
______________________________________ 
EXAMPLE 4 
A dyebath was prepared by using 1 part of the dye of formula (10), 50 parts 
of anhydrous sodium sulfate and 1000 parts of water. 50 parts of spun 
rayon were immersed into the dyebath and treated at 30.degree. C for 30 
minutes. Then 20 parts of sodium carbonate were added and dyeing was 
conducted at the same temperature for 60 minutes. A reddish blue dyeing 
was obtained by treating in a similar manner as described in Example 2. 
EXAMPLE 5 
A solution of 43 parts of disodium 
1,4-diaminoanthraquinone-2,3-disulfonate, 25 parts of p-aminothiophenol 
and 8 parts of sodium bicarbonate in 500 parts of water was stirred at 
25.degree. C for 3 hours. To the reaction solution there were added 100 
parts of sodium chloride and the precipitate thus obtained was filtered 
and dried. 
The compound of the following formula was obtained. 
##STR22## 
A solution of 80 parts of methanol and 2 parts of sodium bicarbonate was 
cooled to 0.degree. C and 4.45 parts of cyanuric chloride were added to 
the solution. After the reaction was carried out at 0 - 3.degree. C for 1 
hour, a solution of 9.5 parts of the said anthraquinone compound in 200 
parts of water was added to the reaction solution and adjusted to pH 6.5 
with a 10% solution of soda ash. Then the solution was heated to 
35.degree. C and the reaction was continued for 1 hour while adjusting the 
pH to 5 - 6. To the reaction solution there were added 60 parts of sodium 
chloride and the dye thus obtained was filtered and dried. 
The dye is represented by the formula: 
##STR23## 
.lambda. max. : 656 m .mu. (in a 20% aqueous solution of pyridine) 
Elemental Analysis values 
(Sample purified by column chromatography was used) 
______________________________________ 
Found Calculated 
______________________________________ 
C 47.58 % 47.49 , % 
H 2.74 % 2.64 % 
N 13.75 % 13.85 % 
Cl 5.80 % 5.85 % 
S 10.58 % 10.55 % 
______________________________________ 
EXAMPLE 6 
A cotton cloth was immersed into a solution which was prepared by mixing 20 
parts of the dye of formula (12), 200 parts of urea and 740 parts of water 
and adding 20 parts of a 10% thickener of sodium alginate and 20 parts of 
sodium carbonate. Then the cloth was squeezed so as to weight twice as 
much as the original, subjected to intermediate drying, and then to 
heat-treatment at 160.degree. C for 2 minutes. 
The dyed cloth was washed and soaped to obtain a greenish blue dyeing. 
EXAMPLE 7 
4.5 parts of sodium 
1,4-diamino-2-(4'-aminophenoxy)-anthraquinone-3-sulfonate were added to 
100 parts of water and to this solution there was added a solution of 2.3 
parts of 2-carboxymethylamino-4,6-dichlorotriazine in 100 parts of water. 
While maintaining the solution at 40.degree. C and adjusting it to pH 6.5 
- 7.5 with a 10% solution of sodium carbonate the reaction was carried 
out. After completion of the reaction, the dye obtained was salted out by 
adding sodium chloride, filtered off and dried. 
The dye was represented by the formula: 
##STR24## 
.lambda. max. : 580 m.mu. (in pure water) 
Elemental Analysis Value 
(Sample purified by column chromatography was used) 
______________________________________ 
Found Calculated 
______________________________________ 
C 45.72 % 45.77 % 
H 2.46 % 2.44 % 
N 14.91 % 14.95 % 
Cl 5.40 % 5.42 % 
S 4.85 % 4.88 % 
______________________________________ 
EXAMPLE 8 
20 parts of the dye of formula (13), 2 parts of Liponox OCS (a non-ionic 
penetrating agent manufactured by Lion Fat & Oil Co., Ltd.), 20 parts of 
sodium carbonate, 200 parts of urea and 505 parts of water were mixed and 
to this solution there were added 250 parts of a 10% solution of sodium 
alginate to prepare a colour paste. A cotton cloth was printed with the 
colour paste, subjected to intermediate drying, then steamed at 
102.degree. C for 2 minutes, washed with water, treated at 60.degree. C 
for 20 minutes in a bath which was prepared with 2 parts of Suprefix WF 
New (a fixing agent of polyamines made by Nippon Senka Co., Ltd.) and 1000 
parts of water, washed with water and dried. There was thus obtained a 
very bright, deep reddish blue dyeing. 
EXAMPLE 9 
A dye-bath was prepared with 1.2 parts of the dye of formula (9), 0.8 part 
of C.I. Reactive Blue 71 and 60 parts of anhydrous sodium sulfate in 1000 
parts of water. 50 parts of a cotton knitted cloth were immersed in the 
bath and treated at 80.degree. C for 30 minutes. 20 parts of sodium 
carbonate were then added to the bath and dyeing was carried out at the 
same temperature for 60 minutes. After the dyed cloth was washed with 
water it was thoroughly soaped and dried. 
The dyed cloth thus obtained had a very good bright, deep blue colour. 
EXAMPLE 10 
6 parts of the dye of formula (10) were dissolved in 200 parts of water. 
While keeping at 35 - 40.degree. C, 0.35 part of methylamine in the form 
of a 40% aqueous solution were added to the said solution. The reaction 
was carried out for 3 hours while adjusting the pH to 6.5 - 7.5 with a 10% 
soda ash aqueous solution. 25 parts of sodium chloride were added to 
precipitate the dye, which was filtered off and dried. 
The dye thus obtained was represented by the formula: 
##STR25## 
It dyed cotton fibers reddish blue. .lambda. max. : 579 m.mu. (in pure 
water) 
Elemental Analysis Value 
(Sample purified by column chromatography was used)* 
______________________________________ 
Found Calculated 
______________________________________ 
C 48.75 % 48.85 % 
H 2.89 % 2.88 % 
N 16.57 % 16.62 % 
Cl 6.06 % 6.02 % 
S 5.40 % 5.43 % 
______________________________________ 
*Note : 
adsorbent used : activated almina 
solvent used : n-butanol : pyridine : 
= 1 : 1 : 1 
EXAMPLE 11 
The dyes represented by the formula: 
##STR26## 
wherein Z, R.sub.1, R.sub.3, the linkage position of 
##STR27## 
Q and X are described in the following table, were obtained in a similar 
manner as used in Example 1, 3, 5, 7 and 10 and they gave fast dyeings 
having colour shades mentioned in the table. 
__________________________________________________________________________ 
Linkage posi- 
tion of 
No. 
Z 
R.sub.1 R.sub.3 
##STR28## Q X 
Colour 
__________________________________________________________________________ 
1 S H Cl 4' N Cl 
Greenishblue 
2 S H Br 4' N Br 
" 
3 S H Cl 4' 
##STR29## 
Cl 
" 
4 S CH.sub.3 Cl 4' N Cl 
" 
5 S CH.sub.2 CH.sub.3 
NH.sub.2 4' N Cl 
" 
6 S CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 
NHCH.sub.2 CH.sub.3 3' N Cl 
" 
7 S H NHCH.sub.2 CH.sub.2 CH.sub.3 
4' N Cl 
" 
8 S CH.sub.3 NHCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 
3' N Cl 
" 
9 S H NHCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 
3' N Cl 
" 
10 S CH.sub.2 CH.sub.3 
Cl 3' CCl Cl 
" 
11 S H NHCH.sub.2 CH.sub.2 OH 
3' N 3' 
" 
12 S H NHCH.sub.2 CH.sub.2 OSO.sub.3 Na 
4' N Cl 
" 
13 S H NHCH.sub.2 CH.sub.2 SO.sub.3 Na 
4' N Cl 
" 
14 S CH.sub.3 
##STR30## 4' N Cl 
" 
15 S H 
##STR31## 4' N Cl 
" 
16 S CH.sub.2 CH.sub.3 
##STR32## 3' N Cl 
" 
17 S CH.sub.3 
##STR33## 4' N Cl 
" 
18 S H 
##STR34## 3' N Cl 
" 
19 S H 
##STR35## 3' N Br 
" 
20 S H 
##STR36## 4' N Cl 
" 
21 S CH.sub.3 
##STR37## 3' N Cl 
" 
22 S H 
##STR38## 4' N Cl 
" 
23 S H 
##STR39## 4' N Br 
" 
24 S H 
##STR40## 4' N Cl 
" 
25 S H 
##STR41## 4' N Cl 
" 
26 S H 
##STR42## 3' N Cl 
" 
27 S H 
##STR43## 3' N Cl 
" 
28 S H 
##STR44## 3' N Cl 
" 
29 S CH.sub.3 
##STR45## 4' N Cl 
" 
30 S H 
##STR46## 4' N Cl 
" 
31 S H 
##STR47## 4' N Cl 
" 
32 S H 
##STR48## 3' N Cl 
" 
33 S H 
##STR49## 4' N Cl 
" 
34 S H 
##STR50## 4' N Cl 
" 
35 S H 
##STR51## 4' N Cl 
" 
36 S H 
##STR52## 4' N Cl 
" 
37 S H 
##STR53## 3' N Cl 
" 
38 S H 
##STR54## 3' N Cl 
" 
39 S H 
##STR55## 3' N Cl 
" 
40 S H OCH.sub.2 CH.sub.2 CH.sub.3 
3' N Cl 
" 
41 S H OCH(CH.sub.3).sub.2 4' N Cl 
" 
42 S H OCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 
4' N Cl 
" 
43 S CH.sub.3 OCH.sub.2 CH.sub.2 OCH.sub.3 
4' N Cl 
" 
44 S CH.sub.2 CH.sub.3 
OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 
4' N Cl 
" 
45 S CH.sub.2 CH.sub.2 CH.sub.3 
##STR56## 4' N Cl 
" 
46 S H 
##STR57## 4' N Cl 
" 
47 S CH.sub.3 
##STR58## 4' N Cl 
" 
48 S H 
##STR59## 4' N Cl 
" 
49 S CH.sub.3 
##STR60## 3' N Cl 
" 
50 S H 
##STR61## 3' N Cl 
" 
51 S H 
##STR62## 4' N Cl 
" 
52 S CH.sub.3 SCH.sub.3 4' N Cl 
" 
53 S H SCH.sub.2 CH.sub.2 OH 
4' N Cl 
" 
54 S H SCH.sub.2 CH.sub.3 3' N Cl 
" 
55 S H SCH.sub.2 CH.sub.2 CH.sub.3 
3' N Cl 
" 
56 S H 
##STR63## 4' N Cl 
" 
57 S H 
##STR64## 4' N Cl 
" 
58 S H 
##STR65## 3' N Cl 
" 
59 O H Cl 4' CCl Cl 
Reddishblue 
60 O H Br 3' N Br 
" 
61 O CH.sub.3 NH.sub.2 4' N Cl 
" 
62 O CH.sub.2 CH.sub.3 
NHCH.sub.2 CH.sub.2 OH 
4' N Cl 
" 
63 O H 
##STR66## 4' N Cl 
" 
64 O CH.sub.3 NHCH.sub.2 CH.sub.2 SO.sub.3 Na 
4' N Br 
" 
65 O H NHCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 
4' N Cl 
" 
66 O H NHCH.sub.2 CH.sub.2 OSO.sub.3 Na 
4' N Cl 
" 
67 O CH.sub.2 CH.sub.3 
NHCH.sub.2 CH.sub.2 CH.sub.3 
3' N Cl 
" 
68 O H 
##STR67## 3' N Cl 
" 
69 O H 
##STR68## 4' N Cl 
" 
70 O CH.sub.3 
##STR69## 4' N Cl 
" 
71 O H 
##STR70## 3' N Cl 
" 
72 O CH.sub.2 CH.sub.2 CH.sub.3 
##STR71## 4' N Cl 
" 
73 O H 
##STR72## 4' N Cl 
" 
74 O H 
##STR73## 4' N Cl 
" 
75 O H 
##STR74## 4' N Cl 
" 
76 O H NHCH.sub.3 4' N Cl 
" 
77 O H 
##STR75## 4' N Cl 
" 
78 O H 
##STR76## 4' N Cl 
" 
79 O H 
##STR77## 4' N Cl 
" 
80 O H 
##STR78## 4' N Cl 
" 
81 O H 
##STR79## 3' N Cl 
" 
82 O H 
##STR80## 4' N Br 
" 
83 O CH.sub.3 
##STR81## 4' N Cl 
" 
84 O H 
##STR82## 4' N Cl 
" 
85 O H 
##STR83## 4' N Cl 
" 
86 O H 
##STR84## 3' N Cl 
" 
87 O H 
##STR85## 3' N Cl 
" 
88 O H 
##STR86## 4' N Cl 
" 
89 O H 
##STR87## 4' N Cl 
" 
90 O H 
##STR88## 3' N Cl 
" 
91 O H 
##STR89## 4' N Cl 
" 
92 O CH.sub.3 OCH.sub.3 4' N Cl 
" 
93 O H CH.sub.2 CH.sub.2 OCH.sub.3 
3' N Cl 
" 
94 O H 
##STR90## 4' N Cl 
" 
95 O H OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 
4' N Cl 
" 
96 O H OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 
4' N Cl 
" 
97 O H 
##STR91## 4' N Br 
" 
98 O H 
##STR92## 4' N Cl 
" 
99 O H 
##STR93## 4' N Cl 
" 
100 
O H 
##STR94## 4' N Cl 
" 
101 
O H 
##STR95## 4' N Cl 
" 
102 
O CH.sub.2 CH.sub.3 
##STR96## 3' N Cl 
" 
103 
O H 
##STR97## 4' N Cl 
" 
104 
O H 
##STR98## 4' N Cl 
" 
105 
O H 
##STR99## 4' N Cl 
" 
106 
O H OCH.sub. 3 4' N Cl 
" 
107 
O H Cl 4' N Cl 
" 
108 
O H SCH.sub.3 4' N Cl 
" 
109 
O CH.sub.3 SCH.sub.2 CH.sub.3 4' N Br 
" 
110 
O H SCH.sub.2 CH.sub.2 OH 
3' N Cl 
" 
111 
O H SCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 
4' N Cl 
" 
112 
O H 
##STR100## 3' N Cl 
" 
113 
O H 
##STR101## 4' N Cl 
" 
114 
O H 
##STR102## 4' N Cl 
" 
115 
O H NHCH.sub.3 4' N Cl 
" 
116 
O H NHCH.sub.2 H.sub.5 4' N Cl 
" 
117 
O H NHCH.sub.2 CH.sub.2 OH 
4' N Cl 
" 
118 
O H 
##STR103## 4' N Cl 
" 
119 
O H NH.sub.2 4' N Cl 
" 
120 
O H 
##STR104## 4' N Cl 
" 
121 
O H 
##STR105## 4' N Cl 
" 
122 
O H 
##STR106## 4' N Cl 
" 
123 
O H 
##STR107## 4' N Cl 
" 
124 
O H 
##STR108## 3' N Cl 
" 
125 
O H 
##STR109## 4' N Cl 
" 
126 
O H 
##STR110## 4' N Cl 
" 
127 
O H 
##STR111## 4' N Cl 
" 
128 
O H 
##STR112## 3' N Cl 
" 
129 
O H 
##STR113## 4' N Cl 
"-130 O H 
3'SNRCl4"# 
131 
O H 
##STR115## 4' N Cl 
" 
132 
O H 
##STR116## 3' N Cl 
" 
133 
O H NHCH.sub.2 CH.sub.2 SO.sub.3 Na 
4' N Cl 
" 
134 
O H 
##STR117## 4' N Cl 
" 
135 
O H OC.sub.2 H.sub.4 OC.sub.2 H.sub.5 
3' N Cl 
" 
__________________________________________________________________________ 
EXAMPLE 12 
1.9 parts of metanilic acid were added to 100 parts of water and the 
mixture was adjusted to pH 6.5 - 7.0 with soda ash. To this there was 
added ice to cool it to 0.degree. C and added 2.0 parts of cyanuric 
chloride followed by stirring for one hour at 0 - 5.degree. C. The 
solution was adjusted to pH 6.5 - 7.0 with a 10% sodium carbonate aqueous 
solution and filtered to remove excess cyanuric chloride. To the filtrate 
there were added 4.9 parts of the anthraquinone compound of the following 
formula: 
##STR118## 
The reaction was continued at 35 - 40.degree. C for one hour while keeping 
the pH to 6.0 - 7.0. After completion of the reaction 20 parts of sodium 
chloride were added and the precipitate was salted-out, filtered and 
dried. 
The compound thus obtained had the following formula: 
##STR119## 
.lambda. max. : 590 m.mu. (in a 20% pridine-water) 
______________________________________ 
Elemental analysis of the compound purified by thin-layer 
chromatography (Solvent ; butanol : pridine : water = 
1 : 1 : 1) 
Found Calculated 
______________________________________ 
C 43.45 % 43.58 % 
H 2.24 % 2.13 % 
N 14.10 % 14.03 % 
Cl 4.39 % 4.45 % 
S 7.99 % 8.02 % 
______________________________________ 
The compound of the formula (16) used in this example was obtained by the 
following procedure: 
A mixture of 200 parts of 90% sulfuric acid, 16 parts of boric acid and 
35.2 parts of 1,4-diamino-2,3-dichloro-5-nitroanthraquinone was stirred at 
80.degree. C for 2 hours to form a boric acid ester. 
To a solution containing 1000 parts of water, 300 parts of sodium carbonate 
and 38 parts of sodium sulfite there was added dropwise a sulfuric acid 
solution of the above boric acid ester while maintaining the temperature 
at 10 -15.degree. C by adding ice. After adding the pH was adjusted to 
10.0 with a 10% caustic soda solution. The temperature was raised slowly 
to 80.degree. C, followed by stirring one hour. The colour of the solution 
changes from yellow green to blue. The solution was then filtered hot for 
removing insoluble components. 300 parts of sodium chloride were added to 
the filtrate and the crystal precipitated was filtered off. The crystal is 
disodium, 1,4-diamino-5-nitroanthraquinone - 2,3-disulfonate. A mixture of 
49 parts of 1,4-diamino-5-nitroanthraquinone-2,3-disulfonic acid, 30 parts 
of p-acetylaminophenol, 6.9 parts of potassium carbonate and 80 parts of 
dimethylformamide was stirred at 110.degree. C for 4 hours. After 
completion of the reaction, the reaction mixture is poured into 1000 parts 
of water and mixed with 300 parts of sodium chloride. The precipitate was 
salted out and filtered off. All the cake containing water was added to 
350 parts of water and then 100 parts of conc. hydrochloric acid was added 
to hydrolyze at 95.degree. C for 10 hours. After cooling the precipitate 
was filtered to obtain the compound of formula (16). 
Example 13 
5 parts of the compound of the formula: 
##STR120## 
were dissolved at pH 6.5 - 7.0 in parts of water. The temperature cooled 
down to 0 - 3.degree. C by adding ice, 2.0 parts of cyanuric chloride were 
added and the reaction was carried out at 0 - 5.degree. C for one hour. 
The pH was adjusted to 6.5 with a 10% sodium carbonate solution and the 
reaction mixture was filtered to remove excess cyanuric chloride. 20 parts 
of sodium chloride were added to the filtrate followed by salting-out, 
filtering and drying. 
The compound thus obtained was represented by the formula: 
##STR121## 
.lambda. max. 588 m.mu. 
Elemental Analysis 
______________________________________ 
Sample purified by thin layer chromatography (Solvent; 
butanol : pyridine : water = 1 : 1 : 1) was used. 
Found Calculated 
______________________________________ 
C 35.01 % 34.89 % 
H 2.43 % 2.38 % 
N 19.39 % 19.43 % 
Cl 7.01 % 7.04 % 
S 6.29 % 6.34 % 
______________________________________ 
Example 14 
A solution containing 80 parts of methanol and 2 parts of sodium 
bicarbonate was cooled down to 0.degree. C and 4.45 parts of cyanuric 
chloride were added. After the reaction was continued at 0 - 3.degree. C 
for one hour a solution of 10.2 parts of the compound of the formula: 
##STR122## 
and 200 parts of water was added and the pH was adjusted to 6.5 with a 10% 
sodium carbonate solution. The temperature was raised to 35.degree. C and 
the reaction was carried out for one hour while keeping pH 6 - 7 with a 
10% sodium carbonate. 
The reaction mixture was filtered to remove insoluble components and the 30 
parts of sodium chloride were added and the precipitate was filtered off 
and dried. Thus, there was obtained the dye of the formula: 
##STR123## 
.lambda. max. 591 m.mu. (in a 20% pyridine aqueous solution) 
Elemental Analysis 
(Sample purified by thin layer chromatography was used) 
______________________________________ 
Found Calculated 
______________________________________ 
C 46.10 % 46.19 % 
H 2.68 % 2.62 % 
N 15.02 % 15.09 % 
Cl 5.44 % 5.47 % 
S 4.95 % 4.93 % 
______________________________________ 
EXAMPLE 15 
A solution of 5 parts of the compound of formula (16) in 100 parts of water 
was mixed with a solution of 2.3 parts of 
2-carboxymethylamino-4,6-dichlorotriazine in 100 parts of water and the 
temperature was maintained at 40.degree. C. The reaction was carried out 
keeping pH 6.5 - 7.5 with a 10% sodium carbonate solution. After 
completion of the reaction, the precipitate was salted out, filtered and 
dried. Thus there was obtained the dye of the formula: 
##STR124## 
.lambda. max. 590 m.mu. (20 % pyridine-water) 
Elemental Analysis 
(Sample purified by chromatography was used) 
______________________________________ 
Found Calculated 
______________________________________ 
C 44.85 % 44.88 % 
H 2.29 % 2.24 % 
N 16.73 % 16.75 % 
Cl 5.27 % 5.31 % 
S 4.83 % 4.79 % 
______________________________________ 
EXAMPLE 16 
5 parts of the compound of formula (16) were added to 200 parts of water 
and dissolved by adjusting the pH to 6.5. The temperature was cooled down 
to 3.degree. C or below and 1.9 parts of cyanuric chloride were added. The 
reaction mixture was stirred for one hour at 3.degree. C or below. After 
completion of the reaction 1.9 parts of metanilic acid were added. The 
reaction mixture was stirred for one hour at 30 - 35.degree. C, 
maintaining the pH at 6.5 - 7.0 with a 10% sodium carbonate aqueous 
solution. 25 parts of sodium chloride were added to the reaction mixture 
and the precipitate ws filtered off and dried. Thus there was obtained the 
anthraquinone compound of formula (17). 
EXAMPLE 17 
A dyebath was prepared with 1 part of the dye of formula (17), 80 parts of 
anhydrous sodium sulfate and 1,000 parts of water. 50 parts of knitted 
cotton cloth were immersed into the bath, treated for 30 minutes at 
80.degree. C. Then 20 parts of sodium carbonate were added and dyeing was 
carried out for 60 minutes at the same temperature. After washing with 
water, the dyed product was soaped thoroughly with Scourole No. 900 (a 
nonionic surface active agent manufactured by Kao soap Co., Ltd.) washed 
with water and dried. Thus there was obtained a bright blue dyeing. 
EXAMPLE 18 
50 parts of spun rayon were immersed into a bath containing 1 parts of the 
dye of formula (19), 50 parts of anhydrous sodium sulfate and 1,000 parts 
of water, treated for one half hour at 30.degree. C and then 20 parts of 
sodium carbonate were added and dyeing was carried out 1 hour at the same 
temperature. The dye product was treated in the same manner as in Example 
17. Thus there was obtained a bright blue dyeing. 
EXAMPLE 19 
Cotton cloth was immersed into a bath containing a mixture of 20 parts of 
the dye of formula (21), 200 parts of urea and 740 parts of water, 20 
parts of a 10% sodium alginate thickner and 20 parts of sodium carbonate. 
The cloth was squeezed so as to weigh twice as much as the original cloth, 
subjected to intermediate drying and heat-treatment at 160.degree. C for 2 
minutes. The dyed cloth was washed with water and soaped to obtained a 
bright blue dyeing 
EXAMPLE 20 
A colour paste was prepared by mixing 20 parts of the dye of formula (22) 
with 2 parts of Liponox OCS (a nonionic penetrating agent manufactured by 
Lion Fat & Oil Co., Ltd.) 20 parts of sodium carbonate, 200 parts of urea 
and 505 parts of water, adding 250 parts of 10% sodium alginate aqueous 
solution to this and stirring well. Cotton cloth was printed with the 
colour paste, dried intermediately, steamed for two minutes at 102.degree. 
C, washed with water, treated at 60.degree. C for 20 minutes in a bath 
containing 2 parts of Suprafix WF New (a polyamine fixing agent 
manufactured by Nippon Senka Co., Ltd.) and 1,000 parts of water, washed 
with water and dried. 
Thus a bright blue print was obtained. 
EXAMPLE 21 
5.1 parts of the formula (16) were dissolved in 200 parts of water by 
adjusting the pH to 6 - 7 with a 10% sodium carbonate aqueous solution. 
Then 2.2 parts of 2,4,5,6-tetrachloropyrimidine were added and the 
reaction mixture was heated to 55.degree. C and stirred for 4 hours at the 
same temperature while keeping the pH to 5 - 6 with a 10% sodium carbonate 
aqueous solution. 
To the reaction mixture there were added 20 parts of sodium chloride. The 
precipitate was salted out, filtered off and dried. The resultant compound 
was represented by the formula: 
##STR125## 
.lambda. max. 590 m.mu. (in 20% pyridine water) 
Elemental Analysis 
(Sample purified by chromatography was used: solvent, butanol : pyridine : 
water = 1 : 1 : 1 
______________________________________ 
Found Calculated 
______________________________________ 
C 42.59 % 42.76 % 
H 1.92 % 1.78 % 
N 12.33 % 12.47 % 
S 4.67 % 4.75 % 
Cl 15.68 % 15.81 % 
______________________________________ 
EXAMPLE 22 
100 parts of cotton knitted cloth were immersed into a bath containing 2 
parts of the dye of formula (23) and 4,000 parts of water. The bath was 
heated to 40.degree. C and 110 parts of anhydrous sodium sulfate and 30 
parts of sodium carbonate were added. 
Then the temperature was raised in the course of 30 minutes and maintained 
for 20 minutes. 100 parts of anhydrous sodium sulfate and 50 parts of 
sodium carbonate were added. The bath was boiled for 1 hour. After cooling 
the dye cloth was taken out, washed well with water and dried. Thus a 
bright reddish blue dyeing was obtained. 
EXAMPLE 23 
The dyes represented by the formula: 
##STR126## 
wherein Z, R.sub.1, R.sub.3 and X are described in the following table, 
were obtained in a similar manner as used in Example 12, 13, 14, 15 and 
16. They gave fast blue dyeings. 
__________________________________________________________________________ 
Linkage posi- 
tion of 
No. 
R.sub.1 
R.sub.3 
##STR127## Q X 
__________________________________________________________________________ 
1 H Cl 4' CCl Cl 
2 H Br 3' N Br 
3 CH.sub.3 
NH.sub.2 4' N Cl 
4 CH.sub.2 CH.sub.3 
NHCH.sub.2 CH.sub.2 OH 
4' N Cl 
5 H 
##STR128## 4' N Cl 
6 CH.sub.3 
NHCH.sub.2 CH.sub.2 SO.sub.3 Na 
4' N Br 
7 H NHCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 
4' N Cl 
8 H NHCH.sub.2 CH.sub.2 OSO.sub.3 Na 
4' N Cl 
9 CH.sub.2 CH.sub.3 
NHCH.sub.2 CH.sub.2 CH.sub.3 
4' N Cl 
10 H 
##STR129## 3' N Cl 
11 H 
##STR130## 4' N Cl 
12 CH.sub.3 
##STR131## 4' N Cl 
13 H 
##STR132## 3' N Cl 
14 CH.sub.2 CH.sub.3 
##STR133## 4' N Cl 
15 H 
##STR134## 3' N Cl 
16 H 
##STR135## 4' N Cl 
17 H 
##STR136## 4' N Cl 
18 H 
##STR137## 4' N Cl 
19 H 
##STR138## 4' N Cl 
20 H 
##STR139## 3' N Cl 
21 H 
##STR140## 4' N Cl 
22 H 
##STR141## 4' N Cl 
23 H 
##STR142## 4' N Cl 
24 H 
##STR143## 4' N Cl 
25 H 
##STR144## 3' N Cl 
26 H 
##STR145## 3' N Cl 
27 H 
##STR146## 4' N Cl 
28 H 
##STR147## 4' N Cl 
29 H 
##STR148## 3' N Cl 
30 H 
##STR149## 4' N Cl 
31 H OCH.sub.3 4' N Cl 
32 H OCH.sub.2 CH.sub.2 OCH.sub.3 
3' N Cl 
33 H 
##STR150## 4' N Cl 
34 H OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3 
4' N Cl 
35 H OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3 
4' N Cl 
36 H 
##STR151## 4' N Br 
37 H 
##STR152## 4' N Cl 
38 H 
##STR153## 4' N Cl 
39 H 
##STR154## 4' N Cl 
40 H 
##STR155## 3' N Cl 
41 H 
##STR156## 4' N Cl 
42 H 
##STR157## 4' N Cl 
43 CH.sub.3 
##STR158## 3' N Cl 
44 H NHCH.sub.3 4' N Cl 
45 H NHCH.sub.2 CH.sub.2 OH 
4' N Cl 
46 H SCH.sub.3 3' N Cl 
47 H SCH.sub.2 CH.sub.2 OH 
4' N Cl 
48 H SCH.sub.2 CH.sub.3 4' N Cl 
49 H SCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3 
4' N Cl 
50 H 
##STR159## 3' N Cl 
51 H 
##STR160## 4' N Cl 
52 H 
##STR161## 3' N Cl 
53 H NH.sub.2 4' N Cl 
54 H 
##STR162## 4' N Cl 
55 H NH.sub.2 4' N Cl 
__________________________________________________________________________