1,4-Di(hydroxy- or amino-)-2-[alkoxycarbonylmethylene(oxy or amino)phenyl(oxy)]anthraquinones. Disperse dyestuffs for synthetic textile materials, especially aromatic polyesters.

This invention relates to disperse anthraquinone dyestuffs which are 
valuable for colouring synthetic textile materials, in particular aromatic 
polyester textile materials. 
According to the invention there are provided the disperse anthraquinone 
dyestuffs free from sulphonic acid and carboxylic acid groups which are of 
the formula: 
##STR1## 
wherein T.sup.1 and T.sup.2 are each independently hydrogen, hydroxy, 
amino or N-lower alkylamino; 
L.sup.1 and L.sup.2 are each independently hydroxy, amino or N-lower 
alkylamino; 
X is a direct link or an oxygen atom; 
Y is an oxygen atom or an amino group, 
R is an optionally substituted hydrocarbon radical; 
Z is a --COOR, nitrile or carboxylic acid amide group, 
AND THE ANTHRAQUINONE NUCLEUS CAN CONTAIN UP TO THREE CHLORINE OR BROMINE 
ATOMS. 
Throughout this Specification the terms "lower alkyl" and "lower alkoxy" 
are used to denote alkyl and alkoxy respectively containing from 1 to 4 
carbon atoms. 
As examples of N-lower alkylamino represented by T.sup.1, T.sup.2, L.sup.1 
and L.sup.2 there may be mentioned methylamino, ethylamino, n-propylamino 
and n-butylamino. 
It is preferred that both T.sup.1 and T.sup.2 are hydrogen atoms. 
The optionally substituted hydrocarbon radicals represented by R are 
preferable optionally substituted alkyl, cycloalkyl or phenyl radicals. As 
examples of substituted phenyl radicals represented by R there may be 
mentioned tolyl, xylyl, chlorophenyl, bromophenyl and anisyl. As examples 
of cycloalkyl represented by R there may be mentioned cyclopentyl and 
cyclohexyl. It is however preferred that R is an optionally substituted 
alkyl radical, and, above all, an optionally substituted lower alkyl 
radical. As examples of alkyl radicals represented by R there may be 
mentioned n-hexyl, 2-ethyl-n-hexyl, n-octyl and n-decyl, but more 
especially lower alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl 
and sec-butyl. As examples of substituted lower alkyl radicals represented 
by R there may be mentioned hydroxy lower alkyl such as 
.beta.-hydroxyethyl, lower alkoxy lower alkyl such as .beta.-ethoxyethyl 
and .gamma.-methoxypropyl, and phenyl lower alkyl such as benzyl and 
.beta.-phenylethyl. 
The carboxylic acid amide groups represented by Z are preferably of the 
formula: 
##STR2## 
wherein U is hydrogen, lower alkyl or phenyl, and V is hydrogen or lower 
alkyl. 
Preferably Z is a --COOR group. 
According to a further feature of the invention there is provided a process 
for the manufacture of the anthraquinone dyestuffs of the invention which 
comprises reacting on anthraquinone compound, of the formula: 
##STR3## 
with a halogeno ester of the formula: 
##STR4## 
wherein T.sup.1, T.sup.2, L.sup.1, L.sup.2, X, Y, R and Z have the 
meanings stated, W is a chlorine or a bromine atom, and tha anthraquinone 
nucleus can contain up to three chlorine or bromine atoms. 
The process of the invention can be conveniently carried out, for example, 
by heating the said anthraquinone compound and the halogenoester together 
in the presence of an acid-binding agent and an inert liquid medium, which 
can be water or an organic liquid or a mixture thereof. The resulting 
dyestuff is then isolated in conventional manner, for example by filtering 
off the precipitated dyestuff, or by adding a liquid in which the dyestuff 
is insoluble and then filtering off the dyestuff. 
If desired the liquid medium can comprise a basic organic liquid such as 
pyridine or quinoline, in which case it is not necessary to additionally 
include an acid-binding agent. 
As examples of acid-binding agent there may be mentioned sodium or 
potassium carbonates. 
As examples of organic liquids there may be mentioned chlorobenzene, 
toluene, xylene, dichlorobenzene, dimethylformamide and 
dimethylsulphoxide. 
As specific examples of the halogeno esters there may be mentioned diethyl 
chloromalonate, dimethyl bromomalonate, ethyl chloroacetoacetate, methyl 
chloro-cyanoacetate, and ethyl chloro-carboxamidoacetate. 
The anthraquinone compounds used as starting materials in the process of 
the invention are themselves known compounds and are prepared by 
conventional methods of synthesis. As specific examples of the said 
compounds there may be mentioned 1-(amino- or 
hydroxy-)-2-(p-hydroxyphenoxy)-4-(amino- or hydroxy-)anthraquinone, 
1-(amino-, methylamino- or hydroxy-)-2-(m- or p-hydroxyphenyl)-4-(amino- 
or hydroxy-)-anthraquinone, 1-(amino- or hydroxy-)-2-(m- or 
p-aminophenoxy)-4-(amino- or hydroxy-)-6-(or -7-) (chloro- or bromo-) 
anthraquinone and 
1:5-dihydroxy-4:8-diamino-2-(p-hydroxyphenyl)anthraquinone. 
Alternatively the anthraquinone dyestuffs of the invention which contains 
from 1 to 3 chlorine or bromine atoms can be obtained by chlorination or 
bromination of the corresponding dyestuffs which do not contain such 
atoms. Such chlorinated or brominated derivatives can be obtained by 
treating the corresponding dyestuffs which do not contain such atoms with 
chlorine or bromine in the presence of a halogenation catalyst such as 
iodine and in a liquid medium such as chlorobenzene or nitrobenzene. 
The anthraquinone dyestuffs of the invention when dispersed in aqueous 
medium are valuable for colouring synthetic textile materials (such as 
cellulose acetate, polyamide and aromatic polyester textile materials) by 
aqueous dyeing, padding or printing processes using the methods and 
conditions which are conventionally employed in colouring such textile 
materials. The said anthraquinone dyestuffs are especially valuable for 
colouring aromatic polyester textile materials as the dyestuffs have 
excellent build up and dyeing properties on such textile materials, and 
the resulting colourations have very good to excellent fastness to the 
tests conventionally applied to such textile materials, in particular to 
light, to wet treatments, to perspiration and to dry heat tests. The 
dyestuffs also have the valuable property that any unfixed dyestuff can 
readily be removed from the surface of the textile material by treatment 
in an aqueous solution of an alkali, for example a 0.2% w/w solution of 
sodium hydroxide, at a temperature in the region of 80.degree. C. 
The said anthraquinone dyestuffs can also be used for mass colouring 
synthetic materials, or can be applied to synthetic textile materials by 
the process of transfer printing, this being optionally carried out under 
humid conditions or at reduced air pressures.

The invention is illustrated but not limited by the following Examples in 
which the parts and percentages are by weight. 
EXAMPLE 1 
A mixture of 13.8 parts of 
1-amino-2-(p-hydroxyphenoxy)-4-hydroxyanthraquinone, 5.6 parts of 
potassium carbonate and 15 parts of water are heated for 2 hours at 
150.degree. C whilst distilling off the water. 15 Parts of 
dimethylformamide are added and the mixture stirred for 15 minutes at 
100.degree. C. 9.6 Parts of diethyl chloromalonate are finally added and 
stirring continued for 1 hour at 100.degree. C. The mixture is cooled to 
10.degree. C, 400 parts of methanol added, and the precipitated solid is 
filtered off, washed with water and dried. 
After crystallisation from ethyl acetate the 
1-amino-2-[p-(bis(ethoxycarbonyl)methoxy)phenoxy]-4-hydroxyanthraquinone 
melts at 122.degree. C. 
When dispersed in aqueous medium the dyestuff dyes aromatic polyester 
textile materials in red shades, and any unfixed dyestuff on the surface 
of the textile material is readily removed by washing in an 0.2% aqueous 
solution of sodium hydroxide at 80.degree. C. The resulting coloured 
textile material has very good to excellent fastness to the tests 
conventionally applied to such textile materials. 
EXAMPLE 2 
A mixture of 25 parts of 
1-amino-2-p-hydroxyphenoxy-4-p-toluenesulphonamidoanthraquinone, 4.32 
parts of potassium carbonate and 100 parts of water are heated, with 
stirring, for 2 hrs. at 150.degree. C, whilst distilling off the water. 
The resultant solid is cooled to 65.degree. C, 70 parts of 
dimethylformamide are added and finally 12.2 parts of 
chlorodiethylmalonate. The temperature is raised to 85.degree. C for 2 
hours, then cooled to 55.degree. C and 150 parts of methanol are added. 
The precipitate so formed is filtered off, washed with methanol and with 
water, and dried to give 24.5 parts of 
1-amino-2-[p-bis(ethoxycarbonyl)methoxy]phenoxy-4-p-toluenesulphonamidoant 
hraquinone, m.p. 170.degree. C. 
Hydrolysis of this product is carried out in 98% w/w sulphuric acid at 
20.degree. to yield the desired 1,4-diamino-2-[p-bis 
(ethoxycarbonyl)methoxy]phenoxyanthraquinone, m.p. 92.degree.-95.degree. 
C. 
When dispersed in aqueous medium the dyestuff colours aromatic polyester 
textile material in bluish red shades, and any unfixed dyestuff on the 
surface of the textile material is readily removed by washing in a 0.2% 
w/w aqueous solution of sodium hydroxide at 80.degree. C. The resultant 
coloured textile material has very good fastness to the tests 
conventionally applied to such textile materials. 
EXAMPLE 3 
A mixture of 17.9 parts of 
1-amino-2-(m-hydroxy)phenoxy-4-hydroxyanthraquinone, 3.5 parts of 
potassium carbonate and 20 parts of water is heated for 2 hours at 
150.degree. C whilst distilling off the water. 20 Parts of 
dimethylsulphoxide are added and the mixture is stirred at 100.degree. C 
for 30 minutes. 10 Parts of ethylchlorocyanoacetate are finally added and 
stirring continued for 1 hour at 100.degree. C. The mixture is cooled to 
room temperature, 400 parts of methanol are added and the precipitated 
solid is filtered off, washed with water and dried to give 12 parts of 
1-amino-2-[m(.alpha.-ethoxycarbonyl-.alpha.-cyano)methoxy]phenoxy-4-hydrox 
y anthraquinone as a dark red solid. 
When applied to polyester as described in Example 2 it yields bright red 
shades with good alkali clearing and fastness properties. 
EXAMPLE 4 
A mixture of 3.6 parts of 
1,5-diamino-4,8-dihydroxy-2-(p-hydroxyphenyl)anthraquinone, 1.4 parts of 
potassium carbonate and 10 parts of water is heated at 
110.degree.-120.degree. C for 2 hours, then cooled to 95.degree. C. 6 
Parts of dimethylformamide and 3.9 parts of chlorodiethylmalonate are 
added and the reaction mixture is stirred for 1/2 hour. The solution is 
cooled to room temperature, 75 parts of methanol are added and the 
precipitate so formed is filtered off, washed with water and dried. 2.9 
Parts of 1,5-diamino-4,8-dihydroxy-2-[p-bis(ethoxycarbonyl)methoxy] 
phenylanthraquinone, a dark blue solid, m.p. 195.degree.-200.degree. C, 
are obtained. 
When dispersed in aqueous medium the dyestuff colours aromatic polyester 
textile material in reddish blue shades which exhibit very good fastness 
properties. 
The invention is further exemplified by the dyes shown in Table I, which 
are prepared by methods similar to those described above. 
The table headings T, T.sup.2, L.sup.1, L.sup.2, X, Y, R and Z have the 
meanings hereinbefore stated. 
TABLE I 
______________________________________ 
Ex. 
No. T.sup.1 
T.sup.2 
L hu 1 
L hu 2 
X Y R Z Shade 
______________________________________ 
5 H H NH.sub.2 
OH O para CH.sub.3 
CO.sub.2 CH.sub.3 
Red 
O 
6 H H NH.sub.2 
OH O para phenyl 
CO.sub.2 -- 
Red 
O phenyl 
7 H H NH.sub.2 
OH O meta n-C.sub.3 H.sub.7 
CO.sub.2 nC.sub.3 H.sub.7 
Red 
O 
8 H H NH.sub.2 
NH.sub.2 
O para CH.sub.3 
CO.sub.2 CH.sub.3 
Blu- 
O ish- 
Red 
______________________________________