Preparation of anthraquinoid disperse dyes

An improvement in the process for the preparation of dispersed dyes of compounds of the formula ##STR1## where X is >O or >NH and R is C.sub.1 -C.sub.12 -alkyl, C.sub.2 -C.sub.6 -hydroxyalkyl, alkoxyalkyl of 3 to 12 carbon atoms in total, C.sub.5 -C.sub.8 -cycloalkyl, phenoxy-C.sub.2 - or-C.sub.3 -alkyl, phenyl-C.sub.1 -C.sub.4 -alkyl or phenyl-C.sub.1 -C.sub.4 -alkoxy-C.sub.2 - or -C.sub.3 -alkyl, by reacting a compound I where R is H with an amine of the formula R-NH.sub.2 in a liquid under the influence of heat, wherein the reaction is carried out in water, in the presence or absence of a cationic or non-ionic surfactant. Very pure dyes are obtained with a high space/time yield.

The present invention relates to a process for the preparation of 
anthraquinoid disperse dyes. 
U.S. Pat. Nos. 3,835,154, 2,753,356 and 2,628,963 disclose that dyes of the 
formula 
##STR2## 
where A is alkyl, alkoxyalkyl, hydroxyalkyl, phenoxyalkyl or 
phenylaminoakyl, are obtained by reacting a compound of the formula I 
where A is H with an amine of the formula A--NH.sub.2 in an organic 
solvent. These processes have the disadvantages that expensive organic 
solvents or solvent mixtures which must be worked up for economic and 
ecological reasons are required, and the starting materials must be dry 
and in milled form. 
German Pat. No. 1,073,661 discloses that 
1-imino-3-oxo-4,7-diamino-5,6-phthaloyl-dihydroisoindole reacts with an 
aliphatic amine in an inert solvent, eg. methanol, or in excess to give a 
compound of the formula 
##STR3## 
where A' is an aliphatic radical, by replacement of the .dbd.NH group. 
It is an object of the present invention to provide an improved, simple and 
inexpensive process for the preparation of anthraquinoid disperse dyes of 
the formula given below, in which dyes of good quality are obtained in a 
high yield, and which does not pollute the environment. 
We have found that this object is achieved by a process for the preparation 
of anthraquinoid disperse dyes of the formula 
##STR4## 
where X is .dbd.O or .dbd.NH and R is C.sub.1 -C.sub.12 -alkyl, C.sub.2 
-C.sub.6 -hydroxyalkyl, alkoxyalkyl of 3 to 12 carbon atoms in total, 
C.sub.5 -C.sub.8 -cycloalkyl, phenoxy-C.sub.2 -or-C.sub.3 -alkyl, 
phenyl-C.sub.1 -C.sub.4 -alkyl or phenyl-C.sub.1 -C.sub.4 -alkoxy-C.sub.2 
- or -C.sub.3 -alkyl, by reacting a compound of the formula 
##STR5## 
with an amine of the formula 
EQU R--NH.sub.2 (V), 
where X and R have the above meanings, in a liquid under the influence of 
heat, wherein the improvement is that the reaction is carried out in 
water. 
The products are useful disperse dyes which give light-fast, 
sublimation-fast and laundering-fast brilliant greenish blue dyeings on 
synthetic hydrophobic fibers. 
The process gives very pure dyes of the formula (III) with a high 
space/time yield. In contrast to the process disclosed in German Pat. No. 
1,073,661, in the process of the present invention virtually exclusively 
products of the formula (III) are obtained from compounds of the formula 
(IV) where X is &gt;NH. 
The process according to the present invention is substantially more 
economical than the known processes, since expensive solvents are not 
necessary and accordingly do not have to be recovered. Another advantage 
is that the starting materials (IV) are used in the form of the moist 
filter residue from the synthesis process. 
R can be C.sub.1 -C.sub.12 -alkyl, C.sub.2 -C.sub.6 -hydroxyalkyl, 
alkoxy-alkyl of 3 to 12 carbon atoms in total, C.sub.5 -C.sub.8 
-cycloalkyl, phenoxy-C.sub.2 - or -C.sub.3 -alkyl, phenyl-C.sub.1 -C.sub.4 
-alkyl or phenyl-C.sub.1 -C.sub.4 -alkoxy-C.sub.2 - or -C.sub.3 -alkyl. 
Specific examples are: 
1. C.sub.1 -C.sub.12 -alkyl, in particular C.sub.1 -C.sub.8 -alkyl: methyl, 
ethyl, n- and i-propyl, n- and i-butyl, sec.-butyl, pentyl, hexyl, octyl, 
2-ethylhexyl, decyl and dodecyl; 
2. Hydroxyalkyl: 2-hydroxyethyl, 2- and 3-hydroxy-propyl, 
1-hydroxybut-4-yl, 2-hydroxybut-3-yl and 6-hydroxy-hex-1-yl; 
3. Alkoxyalkyl of 3 to 12 carbon atoms in total: 2-methoxyethyl, 
2-ethoxyethyl, 2-n- and -i-propoxyethyl, 2-n- and -i-butoxyethyl, 
2-(2'-ethylhexoxy)-ethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-n- and 
-i-propoxypropyl, 3-n- and -i-butoxypropyl, 3-(2'-ethylhexoxy)-propyl and 
3-(n-octoxy)-propyl; 
4. Cycloalkyl: cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; 
5. Phenalkyl: benzyl, 2-phenethyl, 3-phenylpropyl, 2-phenylpropyl, 
4-phenylbutyl and 3-phenylbutyl; 
6. Phenoxy-C.sub.2 - or -C.sub.3 -alkyl: phenoxyethyl and phenoxypropyl; 
7. Phenalkoxy-alkyl: benzyloxyethyl, 2-benzyloxypropyl and 
3-benzyloxypropyl. 
R is preferably C.sub.2 - or C.sub.3 -hydroxyalkyl or alkoxy-alkyl of 3 to 
12 carbon atoms in total. 
In general, the process is carried out by introducing the compound of the 
formula (IV) or a mixture of compounds of the formula (IV) where X is &gt;O 
and &gt;NH into a mixture of water and the amine R--NH.sub.2 and warming the 
suspension to the desired temperature. The reaction as a rule takes place 
rapidly and quantitatively at from 70.degree. to 100.degree. C., and is 
preferably carried out at from 80 .degree. to 100.degree. C., in 
particular from 90.degree. to 100.degree. C. 
Depending on the amine (V) used and on the temperature, the reaction time 
is from 0.5 to 10 hours, in most cases from 2 to 5 hours. Below 80.degree. 
C., the reaction proceeds very slowly. 
Provided the mixture is stirrable before, during and after the reaction, 
the amount of water required for a successful reaction is not critical. 
Preferably the amount by weight of water is from 4 to 6 times the weight 
of (IV). 
The amine V is used in not less than the stoichiometrically required 
amount, and as a rule in excess, advantageously in an amount of from 1.2 
to 3 moles per mole of (IV). 
The reaction can also be carried out in the presence of not more than 60% 
by weight, based on (IV), of a cationic or non-ionic surfactant. From 10 
to 40% by weight, based on (IV), is in general sufficient if the presence 
of the surfactant accelerates the reaction. 
Examples of suitable cationic surfactants are ammonium salts of the formula 
##STR6## 
where R.sup.1 is C.sub.4 -C.sub.20 -alkyl, preferably C.sub.8 -C.sub.20 
-alkyl, and R.sup.2 and R.sup.3 are each C.sub.1 -C.sub.4 -alkyl, 
preferably methyl, or R.sup.1 and R.sup.3 are each C.sub.8 -C.sub.20 
-alkyl and R.sup.2 is C.sub.1 -C.sub.4 -alkyl, preferably methyl, or 
R.sup.1 is phenyl-C.sub.1 -C.sub.4 -alkyl, R.sup.2 is C.sub.1 -C.sub.4 
-alkyl and R.sup.3 is phenyl or C.sub.1 -C.sub.20 -alkyl, or R.sup.1 is 
C.sub.8 -C.sub.20 -alkyl or phenyl-C.sub.1 -C.sub.4 -alkyl and 
##STR7## 
is pyridinium, and X.sup..crclbar. is equivalent of an anion. 
Suitable non-ionoc surfactants include adducts of ethylene oxide or 
propylene oxide/ethylene oxide with a C.sub.2 -C.sub.6 -alkanediol or a 
C.sub.3 -C.sub.6 -alkanepolyol having not more than 5 hydroxyl groups, and 
adducts of ethylene oxide with a C.sub.4 -C.sub.20 -alkylphenol. 
However, the above surfactants are generally not required in the process 
according to the present invention. 
The reaction mixture is worked up in the conventional manner by separating 
off the product from the mother liquor by filtration or centrifugation and 
washing it with warm water. The mother liquor, which contains the excess 
of amine and, where relevant, a surfactant, can be reused four or more 
times as the reaction medium.

In the Examples which follow and illustrate the process according to the 
present invention, parts and percentages are by weight. 
EXAMPLE 1 
300 parts of 96% pure 1,4-diaminoanthraquinone-2,3-dicarboximide (formula 
IV, X=O) were heated to 80.degree. C. in a mixture of 150 parts of the 
reaction product of 1 mole of nonylphenol with 14 moles of ethylene oxide 
and 1,300 parts of water, with stirring. 200 parts of 
3-methoxypropylamine were added at the above temperature, and the mixture 
was refluxed (98.degree.-100.degree. C.) for 3 hours. 100 parts of 
methoxypropylamine were then added, and the mixture was refluxed for a 
further 2 hours. The suspension was then brought to 75.degree. C. by the 
addition of 500 parts of cold water, and was filtered with suction. The 
material on the filter was washed with warm water (about 60.degree. C.). 
Yield: 1,050 parts of moist presscake containing 349.7 parts of the dye of 
the formula III where X=O and R=--(CH.sub.2).sub.3 --OCH.sub.3), which 
dyes polyester in brilliant greenish blue hues. 
EXAMPLE 2 
A mixture of 300 parts of 1,4-diaminoanthraquinone-2,3-dicarboximide 
(formula IV, X=O) in the form of a 46.2% strength aqueous presscake, 1,000 
parts of water and 300 parts of 3-methoxypropylamine was heated to the 
reflux temperature (98.degree.-100.degree. C.), with stirring, and was 
refluxed for 5 hours. The suspension was cooled to 70.degree. C. and 
filtered with suction, and the material on the filter was washed with warm 
water of 60.degree. C. Yield: 1,013 parts of moist presscake containing 
345.3 parts of the dye of the formula III where X=O and 
R=--(CH.sub.2).sub.3 --OCH.sub.3), which dyes polyester in brilliant 
greenish blue hues. 
EXAMPLE 3 
A mixture of 325 parts of a moist filter cake, which contained 150 parts of 
1,4-diaminoanthraquinone-2,3-dicarboximide, and 700 parts of water and 150 
parts of 3-ethoxypropylamine was refluxed (98.degree.-100.degree. C.) for 
5 hours. The suspension was cooled to 70.degree. C. and filtered with 
suction, and the material on the filter was washed with warm water. Yield: 
598 parts of presscake containing 184.8 parts of the dye of the formula 
III where X=O and R=--(CH.sub.2).sub.3 --OC.sub.2 H.sub.5), which dyes 
polyester in brilliant greenish blue hues. 
EXAMPLE 4 
The procedure followed was as described in Example 3, but 
3-isopropoxypropylamine was used instead of 3-ethoxypropylamine. The 
presscake isolated contained 189.3 parts of the dye of the formula III 
where X=O and R=--(CH.sub.2).sub.3 --OCH(CH.sub.3).sub.2. 
EXAMPLE 5 
The procedure followed was as described in Example 3, but a mixture of 50 
parts of 3-methoxypropylamine and 100 parts of 3-isopropoxypropylamine was 
used instead of 3-ethoxypropylamine. The presscake isolated contained 
182.6 parts of a mixture of dyes of the formula III where X=O and 
R=--(CH.sub.2).sub.3 --OCH.sub.3 or --(CH.sub.2).sub.3 
--OCH(CH.sub.3).sub.2. 
EXAMPLE 6 
The procedure followed was as described in Example 3, but ethanolamine was 
used instead of 3-ethoxypropylamine. The presscake isolated contained 
164.7 parts of the dye of the formula III where X=O and R=--CH.sub.2 
-CH.sub.2 -OH. 
EXAMPLE 7 
30 parts of a mixture of 1,4-diaminoanthraquinone-2,3-dicarboximide and 
1-hydroxy-3-amino-4,7-diamino-5,6-phthaloylisoindolenine in the form of 
the moist filter cake were introduced into a mixture of 9 parts of the 
adduct of ethylene oxide with nonylphenol (14:1 moles), 130 parts of water 
and 30 parts of 3-methoxypropylamine, and the mixture was refluxed 
(98.degree.-100.degree. C.) for 6 hours. The suspension was cooled to 
75.degree. C. and filtered with suction, and the material on the filter 
was washed with warm water. Yield: 68.8 parts of presscake containing 37.2 
parts of a mixture consisting virtually only of dyes of the formula III 
where X=O or &gt;NH and R=--(CH.sub.2).sub.3 --OCH.sub.3. The dye mixture 
dyes acetate and polyester in brilliant greenish blue hues. 
EXAMPLE 8 
300 parts of 94.1% pure 1,4-diaminoanthraquinone-2,3-dicarboximide (formula 
IV, X=O) were introduced, at room temperature with stirring, into a 
mixture of 1,300 parts of water, 150 parts of the adduct of 14 moles of 
ethylene oxide with 1 mole of nonylphenol, 100 parts of 
methoxypropylamine, 100 parts of ethoxypropylamine, and 100 parts of 
isopropoxypropylamine. The suspension was refluxed (98.degree.-100.degree. 
C.) for about 4 hours. The temperature was then brought to 75.degree. C. 
by cooling and by addition of 500 parts of cold water, and the suspension 
was filtered with suction. Yield: 1,098 parts of presscake containing 
372.5 parts of a mixture of dyes of the formula III where X=O and 
R=--(CH.sub.2).sub.3 --OCH.sub.3, --(CH.sub.2).sub.3 -OC.sub.2 H.sub.5 or 
--(CH.sub.2).sub.2 --O--CH(CH .sub.3).sub.2, which dyes polyester and 
acetate in brilliant greenish blue hues. 
EXAMPLE 9 
150 parts of 96% pure 1,4-diaminoanthaquinone-2,3-dicarboximide (formula 
IV, X=O) were introduced into a mixture of 50 parts of an adduct of 
ethylene oxide with nonylphenol (14:1 moles), 600 parts of water and 150 
parts of 3-isopropoxypropylamine, and the mixture was heated at 
98.degree.-100.degree. C. under its autogeneous pressure. After 7 hours, 
the suspension was cooled to room temperature and filtered with suction. 
The material on the filter was washed with warm water (about 60.degree. 
C.). Yield: 575 parts of a presscake containing 188.5 parts of the dye of 
the formula III where X=O and R=--(CH.sub.2).sub.3 --O--CH(CH 
.sub.3).sub.2, which dyes polyester in brilliant greenish blue hues.