Dyestuff process

A new overall method of producing chlorinated or brominated compounds of 2-(haloaryl)-4,5-diamino chrysazines from chrysazine without the need for isolation of intermediates at any point during the reaction; and to the novel products produced thereby, which products are good blue dyes having excellent build-up in heavy shades and are intended for dyeing cellulose acetate, cellulose triacetate, polyesters, and the like.

This application relates to and has for its object a new overall method of 
producing chlorinated or brominated compounds of 2-(haloaryl)-4,5-diamino 
chrysazines from chrysazine without the need for isolation of intermdiates 
at any point during the reaction; and to the novel products produced 
thereby, which products are good blue dyes having excellent build-up in 
heavy shades and are intended for dyeing cellulose acetate, cellulose 
triacetate, polyesters, and the like. 
The new dyestuffs of the present invention are represented by the following 
formula (I): 
##STR1## 
wherein Y is H, OH, lower alkoxy (C.sub.1 -C.sub.4 alkoxy groups such as 
methoxy, ethoxy, propoxy, and butoxy), lower alkyl (C.sub.1 -C.sub.4 alkyl 
such as methyl, ethyl, propyl, or butyl), chlorine or bromine and Y' is OH 
or lower alkoxy; A is H, lower alkyl, lower alkoxy, Cl or Br (lower alkoxy 
and lower alkyl being as previously defined); X is Cl or Br; Z is Cl or 
Br; and n is 0-2. 
It is known from Indian Journal of Chemistry, Volume 9, Pages 1060 to 1063, 
that 2-(p-anisyl)-1,5-diamino-4,8-dihydroxyanthraquinone can be prepared 
from the corresponding 3,7-disulfonic acid and the production of 
3-(p-anisly)-1,5-diamino-4,8-dihydroxy-anthraquinone by arylation of the 
corresponding dinitro compound in the presence of boric acid followed by 
reduction with sodium hydrosulfide is also disclosed. U.S. Pat. No. 
3,631,184 discloses 
3-(3-bromo-4-hydroxyphenyl)-1,5-diamino-4,8-dihydroxyanthraquinone and a 
brominated derivative thereof useful for dyeing polyester fibers. Further, 
U.S. Pat. No. 3,549,667 claims the arylation of 
1,5-dihydroxy-4,8-dinitroanthraquinone in the presence of boric acid to 
produce the corresponding 3-(hydroxy-or alkoxy-phenol) substituted 
compound which can then be reduced to the corresponding monoamino or 
diamino derivative using sodium hydrosulfide as the reducing agent. 
The only prior art which is known to relate to the production of 
3-aryl-1,8-diamino-4,5-dihydroxyanthraquinones is U.S. Pat. No. 3,265,460. 
This patent relates particularly to 
3-aryl-1,5-diamino-4,8-dihydroxyanthraquinones wherein the aryl group 
contains at least one hydroxy or alkoxy substituent and up to two other 
substituents, one of which may be chloro. In its broader aspects, this 
patent discloses 
aryl-.alpha.,.alpha.-diamino-.alpha.,.alpha.-dihydroxyanthraquinones. 
However, the only method of producing such dyes disclosed in this patent 
is by arylation of diaminodihydroxyanthraquinone disulfonic acids. This 
method works very well in a case of arylation of the 
1,5-diamino-4,8-dihydroxy-configuration, but not in the case of the 
1,8-diamino-4,5-dihydroxy-configuration. Even in Example 3 of the patent 
which describes arylation of a mixture 1,8-diamino-4,5-dihydroxy- and 
1,5-diamino-4,8-dihydroxyanthraquinone disulfonic acids, it is believed 
that only the 1,5-diamino-4,8-dihydroxy-configuration arylates 
effectively. Arylation of the 1,8-diamino-4,5-dihydroxyanthraquinone alone 
in the manner of Example 3 of the patent results in a dyestuff which has 
poor sublimation properties in contrast to the statement in the patent 
that the dyestuffs provided thereby have excellent sublimation properties. 
It is an object of the present invention to provide a new class of dyes 
having excellent build-up properties in heavy shades and useful for dyeing 
cellulose acetate, cellulose triacetate, polyesters, and the like. It is a 
further object of the present invention to provide a novel method by which 
such dyes can be prepared. Other objects will be apparent from the ensuing 
discussion of the invention. 
One aspect of the present invention is the provision of a method for 
preparing the compounds of formula I from chrysazine in an efficient 
manner which avoids the necessity for the isolation of intermediates at 
any point during the reaction. This method is illustrated by the following 
series of equations: 
##STR2## 
In the foregoing equations R' is H, OH, lower alkoxy or lower alkyl; R is 
H or lower alkyl and R" is H, lower alkyl, or lower alkoxy. Y, Y', X, A, Z 
and n are as defined above. 
In the first step, chrysazine (II) is nitrated with mixed acid in the 
presence of boric acid giving dinitrochrysazine (III) using 2 to 3 moles 
of nitric acid per mold of chrysazine. Preferably, mixed nitric-sulfuric 
acid is used and the reaction is stirred for up to about 5 hours. The 
temperature is between about 10.degree. C. and about 35.degree. C. 
although elevated temperatures varying up to about 50.degree. C. can be 
employed. Preferably, the reaction is conducted at between about 
10.degree. and about 30.degree. C. in the presence of boric acid as 
outlined in U.S. Pat. No. 3,082,218. 
The dinitrochrysazine resulting from the dinitration step is then arylated 
to give the 2-aryl-dinitrochrysazine compound shown in the formula (IV). 
The aryl compound (IIIa) is a phenol or an alkoxy benzene which may have 
lower alkoxy and/or lower alkyl substituents as shown in the formula 
(IIIa). Arylation is accomplished by lowering the temperature of the 
dinitrochrysazine to between about 0.degree. and about 25.degree. C, and 
then adding the phenolic (or alkoxybenzene) compound. The reaction mixture 
is maintained at 0.degree. to 25.degree. C. for from about 30 minutes to 
several hours. 
The hydroxy- or alkoxy- compounds which may be employed in the arylation 
are exemplified by the following: phenol, cresols, anisoles, phentols, 
resorcinols, catechol, resorcinol- and cathecholmono and di -methyl, 
-ethyl, and -propyl, ethers, and the like. 
The resultant mixture containing 2-aryl-dinitro-chrysazine is halogenated 
by adding chlorine or bromine to the mixture. The usual amount of halogen 
is from 1 to 2 moles, and if desired, an excess of about 2% over 2 moles 
may be employed. A small catalytic amount of iodine or ferric chloride may 
be introduced to the halogenation mixture. Halogenation is usually 
conducted at reduced temperatures in the range of 0.degree. to 40.degree. 
C., preferably 5.degree. to 30.degree. C. The resultant mixture contains 
2-haloaryl-dinitro chrysazine (V). 
The mixture containing 2-haloaryl-dinitrochrysazine is then reduced 
directly by any known manner capable of converting nitro groups to amino 
groups. One suitable reduction system is concentrated or fuming sulfuric 
acid or a mixture of sulfur and oleum. A minimum of 2 moles of sulfur to 
an excess of about 4 moles of sulfur is employed, the temperature of 
reduction being higher than room temperature, e.g., 35.degree. to 
90.degree. C. and preferably 60.degree. to 75.degree. C. 
The resultant reaction mixture containing 2-haloaryl-diaminochrysazine (VI) 
can be isolated by drowning in water, filtering, washing and drying. 
Alternatively, the compound depicted by formula (VI) can be further 
halogenated in the same reactor at a temperatue in the range of 20.degree. 
to 80.degree. C using, if desired, the same halogenation system employed 
in the production of the compound of formula (V). It is noteworthy that 
the first halogenation step does not affect the anthraquinone nucleus due 
to the presence of nitro groups thereon. However, halogenation of the 
reduction product of compound (V), i.e., compound (VI), results in the 
addition of halogen directly to the anthraquinone moiety, evidently as a 
result of the presence of amino groups thereon. The halogenated product 
[compound (VII)] can be isolated in the manner described above.

The following examples are intended to further illustrate the present 
invention. 
EXAMPLE 1 
To a flask containing 24 g. (0.1 mole) chrysazine, 16g. (0.25 mole) boric 
acid and 100 ml. sulfuric acid 100% was added at 25.degree.-30.degree. C, 
36.14 g. mixed acid (33% HNO.sub.3 -67% H.sub.2 SO.sub.4). The mixture was 
stirred at 25.degree.-30.degree. C for 1 hour and cooled to 0.degree. C. 
11g. (0.102 mole) anisole was added dropwise at 0.degree.-10.degree. C. 
The mixture was stirred for 30 minutes followed by bromination for 2 hours 
at 5.degree.-10.degree. C employing 31.2 g. (0.19 mole) bromine in the 
presence of 0.1 g. iodine. To this brominated mixture was then added, at 
5.degree.-50.degree. C. with occasional cooling, 200 g. fuming sulfuric 
acid containing 65% SO.sub.3 and reduced at 65.degree.-75.degree. C. with 
12 g. (0.375 mole) sulfur for 1 hour. It was then cooled to 30.degree. C. 
and the product further brominated with 15.5 g. (0.096 mole) bromine for 
18 hours. 
The resulting mixture was drowned in 2 1. water at 25.degree.-55.degree. C. 
and heated to 90.degree. C. The hot slurry was filtered, washed with water 
to neutrality yielding 280 g. wet cake of 
2-(3,5-dibromo-4-methoxy-phenyl)-4,5-diamino-bromochrysazine. 
The paste was admixed with 6 g. Marasperse, CB (partially desulfonated 
sodium lignosulfonade, dispersant, American Can Co.). 
A dyebath was prepared consisting of 100 ml. water at 130.degree. F., 1 ml. 
Aviton T Sol 10% (long chain hydrocarbonsulfonate, Dupont), 25 ml. 
Dowicide A Sol 10% sodium o-phenyl-phenolate, 20 ml. monosodium phosphate 
sol 10% and 4% dyestuff as the above prepared dispersion based on the 
weight of the fiber. The bath was diluted to 300 ml. Dacron polyester 
skein was immersed in the dyebath at 150.degree.-160.degree. F. and the pH 
adjusted to 6-6.5. The bath was raised to the boil and maintained at that 
temperature for 11/2 hours. The skein was rinsed at 160.degree. F., soaped 
at 160.degree. F. with 1% Igepon T-51 (sodium N-methyl-oleoyltaurate) and 
1% soda ash, rinsed and dried. A full dark blue dyeing was obtained which 
had excellent light fastness, sublimation properties and good exhaust. 
EXAMPLE 2 
To a flask containing 24 g. (0.1 mole) chrysazine and 16 g. (0.259 mole) 
boric acid dissolved in 100 ml. sulfuric acid 100% was added at 
25.degree.-30.degree. C. 26.35 g. mixed acid (49% HNO.sub.3, 46% H.sub.2 
SO.sub.4). The mixture was stirred at 30.degree. C. for 2 hours, then 
cooled to 0.degree. C. to which was then added 11 g. (0.102 mole) anisole 
at 0.degree.-9.degree. C. It was held at this temperature for 50 minutes. 
This mixture was then brominated with 34.8 g. (0.155 mole) bromine at 
9.degree.-25.degree. C. for 11/2hours in the presence of 0.1 g. iodine. To 
the mixture was added dropwise at 10.degree.-60 .degree. C. with 
occasional cooling, 200 g. fuming sulfuric acid followed by addition of 12 
g. (0.375 mole sulfur. The mixture was stirred at 60.degree.-68.degree. C 
for 1 hour. The resulting mixture was cooled to 12.degree. C., and the 
oleum was destroyed with ice water and cooling at 10.degree.-45.degree. C. 
To the sulfuric acid solution was then added 15.5 g. (0.096 mole) bromine 
to brominate, and after bromination the solution was drowned in 1. 7 1. of 
water, filtered, washed neutral and dried. The product has structure: 
##STR3## 
Br = 34.9%. After dispersion, the dyestuff dyed polyester fiber in blue 
shades having excellent build-up in heavy shades. 
EXAMPLE 3 
To a flask containing 24 g. chrysazine and 14 g. boric acid dissolved in 
100 ml. sulfuric acid 100% was added dropwise at 12.degree.-20.degree. C., 
25.5 g. mixed acid (49% HNO.sub.3, 46% H.sub.2 SO.sub.4). The mixture was 
stirred at 24.degree. C. overnight, then cooled to 0.degree. C. 12 g. 
anisole was added at 0.degree.-10.degree. C. Bromination was carried out 
at 10.degree.-17.degree. C. employing 31.2 g. (0.19 mole) bromine in the 
presence of 2 g. FeCl.sub.3 for 3 hours. 200 g. fuming sulfuric acid was 
then introduced to the brominated mixture at 17.degree.-60.degree. C. 
with occasional cooling. 14 g. sulfur was then added portionwise at 
60.degree. C. After 2 hours the reduction mixture was drowned in water, 
filtered and washed with water to neutrality. The product has the formula: 
##STR4## 
A dyeing on polyester fiber gave a birght blue shade having excellent 
build-up in heavy shades. 
EXAMPLE 4 
Example 1 was repeated with the exception that in place of the original 
bromination 21.3 g. (0.3 mole) chlorine was passed through the mixture. 
After reduction with sulfur the mixture was further chlorinated with 14.18 
g. (0.2 mole) to give the corresponding 
2-(3,5-dichloro-4-methoxyphenyl)-4,5-diamino-chlorochrysazine dyestuff. 
EXAMPLE 5 
Example 3 was repeated with the exceptions that instead of using 12 g. 
anisole, 6 g. anisole and 6 g. o-cresol were employed and 0.1 g. iodine 
was used as catalyst instead of the 2 g. FeCl.sub.3. The product was a 
mixture of the two dyes: 
##STR5## 
EXAMPLE 6 
The procedure of Example 1 was followed with the exception that 16. g. 
(0.124 mole) o-methoxyphenol was substituted for the anisole, 2 g. 
FeCl.sub.3 was substituted for the iodine catalyst and 3.2 g. was used in 
the final bromination at 50.degree. C. for 3 hours instead of at room 
temperature for 18 hours. 
The producst has the following structure: 
##STR6## 
EXAMPLE 7 
Attempt to Prepare 2-Aryl Diaminochrysazines by the Procedure Shown in 
Example 3 of the Allied Chemical Patent, U.S. Pat. No. 3,265,460 
The arylation procedure of Example 1 of U.S. Pat. No. 3,265,460 was 
repeated using 4,5-diamino-2,7-disulfo-chrysazine, a component of the 
starting material named in Example 3 of the patent. The resultant dyestuff 
dyed polyester a blue shade of very poor sublimation fastness thus showing 
that the purported arylation had not occurred.