Nitro-diphenylamino-azo-phenyl dyestuffs containing a polyalkyeneoxy group

Disperse dyestuffs of the formula ##STR1## wherein Q.sub.1 and Q.sub.2 are hydrogen or the group V-(A-O).sub.n Z, but do not at the same time represent hydrogen, PA0 A -- denotes an alkylene group, PA0 V -- denotes a direct bond or a bridge member, PA0 Z -- denotes hydrogen, alkyl, aryl, aralkyl or acyl and PA0 N -- denotes an integer from 2-10 and the rings A, B and D can be further substituted. The dyestuffs are suitable for dyeing polyester fibres from an aqueous liquor by the exhaustion process since they are distinguished by a good affinity and build-up power. The dyeings are very clear and display good general fastness properties, such as fastness to light, sublimation and measuring.

The invention relates to nitroaminoazo dyestuffs which are free from 
sulphonic acid groups and of the formula 
##STR2## 
wherein Q.sub.1 and Q.sub.2 independently of one another represent 
hydrogen or the group V-(A-O).sub.n Z, but do not at the same time 
represent hydrogen, 
A denotes an alkylene group, 
V denotes a direct bond or a bridge member, 
Z denotes hydrogen, alkyl, aryl, aralkyl or acyl and 
N denotes an integer from 2-10 and the rings A, B and D can contain further 
non-ionic substituents customary in azo dyestuff chemistry, such as, for 
example, halogen or alkyl, nitro, alkoxy, carboxyl or ester groups and 
carboxyl groups esterified with polyether chains, and the azo group is in 
the m-position or p-position to the secondary amino group on ring B, 
as well as their preparation and use. 
Preferred dyestuffs correspond to the formula 
##STR3## 
wherein R.sub.1 represents H, NO.sub.2, CN, halogen, alkyl, COX.sub.1, 
SO.sub.2 X.sub.2, CONX.sub.3 X.sub.4, SO.sub.2 -NRX.sub.3 X.sub.4, COOZ, 
SCN, OX.sub.1, SX.sub.1 or V-(A-O-).sub.m Z, R.sub.2 represents H, 
NO.sub.2, halogen, alkyl, O-alkyl or aryl, 
R.sub.3, r.sub.4 and R.sub.5 independently of one another represent H, 
alkyl, O-alkyl or halogen, 
R.sub.6 represents H, alkyl, aryl or cycloalkyl, 
R.sub.7 represents H, V-(A-O-).sub.m Z or V-Z and 
R.sub.8 represents H, V-(A-O-).sub.m Z or V-Z and 
X.sub.1 denotes alkyl or aryl, 
X.sub.2 denotes alkyl, aryl or aralkyl, 
X.sub.3 and X.sub.4 independently of one another denote H, alkyl, aryl or 
cycloalkyl, or, conjointly with the N atom, form a 5-membered to 
7-membered saturated heterocyclic structure and 
Z denotes H, alkyl, aryl, aralkyl or cycloalkyl, 
m denotes an integer 2-8 and 
V and A have the abovementioned meaning and the abovementioned alkyl, aryl, 
aralkyl or cycloalkyl radicals can contain further non-ionic substituents 
customary in dyestuff chemistry, 
with the proviso that the azo group is in the m-position or o-position 
relative to the secondary amino group on ring B and that at least one of 
the radicals R.sub.1, R.sub.7 and R.sub.8 independently of one another 
represent the radical V-(A-O-).sub.m Z. 
Within the scope of this invention, alkylene groups are to be understood as 
those with 2 to 8 C atoms, such as, for example, --CH.sub.2 --CH.sub.2 --, 
##STR4## 
Suitable bridge members V are --NY--C.sub.2 H.sub.4 --, 
##STR5## 
--O--, --S--, --NY--, --COO--, --O--CO--O--, --CO--NH--, --NH--CO--NH--, 
--O--CO--NH-- and --SO.sub.2 --NH-- and of these --O-- and --COO-- are 
preferred; in these formulae Y denotes H or alkyl. 
Suitable alkyl radicals R.sub.1 to R.sub.6 and Y are those which have 1 to 
4 C atoms and are preferably unsubstituted. 
Suitable alkyl radicals X.sub.1 to X.sub.4 and Z are those which have 1 to 
8 C atoms and can be further substituted by halogen, cyano, hydroxyl, 
C.sub.1 -C.sub.4 -alkoxy or acyloxy, and acyloxy is to be understood as 
C.sub.1 -C.sub.4 -alkylcarbonyl or benzoyloxy. 
Suitable aryl R.sub.2, R.sub.6, X.sub.1 to X.sub.4 and Z is phenyl, which 
is optionally monosubstituted or disubstituted by C.sub.1 -C.sub.4 -alkyl, 
C.sub.1 -C.sub.4 -alkoxy, halogen, such as fluorine, chlorine or bromine, 
cyano or nitro. 
Suitable cycloalkyl R.sub.6, X.sub.3 to X.sub.4 and Z is cyclopentyl, 
cyclohexyl and cycloheptyl. 
Suitable alkyl radicals R.sub.2 to R.sub.5 are those with 1-4 C atoms. 
Suitable aralkyl X.sub.2 and Z are phenyl-C.sub.1 -C.sub.4 -alkyl radicals 
which can be monosubstituted to trisubstituted in the phenyl nucleus by 
C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy, halogen (such as 
fluorine, chlorine or bromine) or nitro. 
Suitable heterocyclic structures which are formed by X.sub.3 and X.sub.4 
with the inclusion of the N atom of the carboxamide or sulphonamide group 
are pyrrolidine, piperidine and morpholine. However, the new dyestuffs 
preferably do not contain any heterocyclic structures. 
In this invention halogen is understood as fluorine, bromine or, 
preferably, chlorine. 
Preferred dyestuffs are those of the formula (II), wherein 
R.sub.1 represents COO--(C.sub.2 H.sub.4 --O--).sub.m Z or COOZ, 
R.sub.2 represents H, halogen or alkyl, 
R.sub.3 and R.sub.8 represent H, 
R.sub.4 and R.sub.5 independently of one another represent H, alkyl, 
O-alkyl or halogen, 
R.sub.6 represents H, alkyl, aryl or cycloalkyl and 
R.sub.7 represents O--(C.sub.2 H.sub.4 --O--).sub.m Z or V-Z and 
Z denotes H, alkyl, aryl, aralkyl or cycloalkyl and 
m has the abovementioned meaning and the abovementioned alkyl, aralkyl, 
aryl or cycloalkyl radicals can contain further non-ionic substituents 
customary in dyestuff chemistry, such as, for example, have been mentioned 
above, 
with the proviso that the azo group is in the m-position or p-position on 
ring B relative to the secondary amino group and the radical R.sub.7 is in 
the o-position or p-position relative to the azo group and that at least 
one of the radicals R.sub.1 and R.sub.7 contains the group (C.sub.2 
H.sub.4 O).sub.m. 
Amongst these dyestuffs, those of the formula (II) wherein 
R.sub.1 represents COO--(C.sub.2 H.sub.4 --O--).sub.m Z or COOZ, 
R.sub.2 represents H, chlorine or C.sub.1 -C.sub.4 -alkyl, 
R.sub.3 and R.sub.8 represent H, 
R.sub.4 and R.sub.5 independently of one another represent H, 
C.sub.1 -c.sub.4 -alkyl, C.sub.1 -C.sub.4 -alkoxy or chlorine, 
R.sub.6 represents H, C.sub.1 -C.sub.4 -alkyl, phenyl, tolyl or cyclohexyl, 
R.sub.7 represents O--(C.sub.2 H.sub.4 --O--).sub.m Z or O-Z, 
m has the abovementioned meaning and 
Z denotes H, phenyl, phenyl-C.sub.1 -C.sub.4 -alkyl, tolyl, cyclohexyl, 
C.sub.1 -C.sub.8 -alkyl or C.sub.1 -C.sub.8 -aryl which is substituted by 
hydroxyl or phenyl, especially methyl, ethyl, propyl, butyl, pentyl, 
hexyl, heptyl, octyl or 2-hydroxyethyl, as well as the radical 
##STR6## 
in which R.sub.9 denotes H, C.sub.1 -C.sub.4 -alkyl, C.sub.1 -C.sub.4 
-alkoxycarbonyl or benzoyl and 
R.sub.10 denotes H or C.sub.1 -C.sub.4 -alkyl, with the proviso that the 
azo group is in the m-position or p-position on ring B relative to the 
secondary amino group, that the radical R.sub.7 is in the o-position or 
p-position relative to the azo group and that at least one of the radicals 
R.sub.1 and R.sub.7 contains the group (C.sub.2 H.sub.4 O).sub.m, 
are particularly preferred. 
Dyestuffs which are very particularly preferred are those of the formula 
(II) 
wherein 
R.sub.1 represents COO--(C.sub.2 H.sub.4 --O--).sub.m Z or COOZ, 
R.sub.2, r.sub.3, r.sub.4 and R.sub.8 represent H, 
R.sub.5 represents H, methyl, chlorine, methoxy or ethoxy, 
R.sub.6 represents H, methyl, ethyl, propyl, isopropyl, tert.-butyl, phenyl 
or cyclohexyl, 
R.sub.7 represents O--(C.sub.2 H.sub.4 --O--).sub.m Z or O-Z and 
m has the abovementioned meaning and 
Z independently of one another denotes H, methyl, ethyl, n-propyl and 
isopropyl, butyl, pentyl, hexyl, benzyl, phenyl, tolyl, cyclohexyl, 
2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-acetoxyethyl, 
2-hydroxypropyl, 2-hydroxy-3-chloropropyl or 2-methoxybutyl, with the 
proviso that the azo group is in the p-position on ring B relative to the 
secondary amino group, that R.sub.7 is in the o-position or p-position 
relative to the azo group and that at least one of the radicals R.sub.1 or 
R.sub.7 contains the group (C.sub.2 H.sub.4 O).sub.m. 
Further preferred dyestuffs are those of the formula (II), and the 
preferred types derived therefrom, wherein 
R.sub.1 represents H, NO.sub.2 or CN, 
R.sub.2 represents halogen (preferably chlorine), NO.sub.2 or C.sub.1 
-C.sub.4 -alkoxy, 
R.sub.7 represents O--(C.sub.2 H.sub.4 --O--).sub.m Z or O-Z, 
R.sub.8 represents COO--(C.sub.2 H.sub.4 --O--).sub.m Z or COOZ and the 
other radicals and m have the abovementioned meaning, 
with the proviso that the azo group is in the m-position or p-position on 
ring B relative to the secondary amino group, that the radical R.sub.7 is 
in the o-position or p-position relative to the azo group and that at 
least one of the radicals R.sub.7 and R.sub.8 contains the group (C.sub.2 
H.sub.4 O).sub.m. 
"Bulky radicals", such as, for example, tert.-butyl, are preferably in 
those positions where they do not effect any steric hindrance. 
The dyestuffs can be prepared by various processes. One process for the 
preparation of the dyestuffs of the formula (I) consists in diazotising 
amines of the formula 
##STR7## 
wherein Q.sub.1, A and B have the abovementioned meaning and the amino 
group on the ring is in the p-position or m-position relative to the 
secondary amino group, 
and coupling the diazo compound with compounds of the formula 
##STR8## 
wherein D has the abovementioned meaning, 
and subsequently, if desired, converting the phenolic OH group and/or a 
carboxyl group which may be present in nucleus D in a manner which is in 
itself known into the radical Q.sub.2, which has the above meaning. 
A further process for the preparation of the dyestuffs of the formula (I) 
consists in subjecting an aminoazo dyestuff of the formula 
##STR9## 
wherein B, D and Q.sub.2 have the abovementioned meaning and the amino 
group on ring B is in the m-position or o-position relative to the azo 
group, 
to a condensation reaction with an o-nitrohalogenobenzene of the formula 
##STR10## 
wherein A and Q.sub.1 have the abovementioned meaning and Hal represents 
bromine or, in particular, chlorine. 
Examples of suitable diazo components of the formula (III) are: 
2-nitro-4'-aminodiphenylamine, 2-nitro-4-cyano-4'-amino-diphenylamine, 
2,4-dinitro-5-chloro-4'-aminodiphenylamine, 
2-nitro-3,5-dichloro-3'-aminodiphenylamine, 
2-nitro-4-benzoyl-4'-methoxy-3'-aminodiphenylamine, 
2-nitro-4-butyryl-3'-methoxy-4'-aminodiphenylamine, 
2-nitro-4-benzylsulphonyl-4'-aminodiphenylamine, 
2-nitro-4-(2-hydroxyethyl)-sulphonyl-3'-methyl-4'-aminodiphenylamine, 
2-nitro-4-n-butylamino-carbonyl-4'-aminodiphenylamine, 
2-nitro-4-di-n-propyl-aminocarbonyl-4'-aminodiphenylamine, 
2-nitro-4-N-methyl-N-phenylethylaminocarbonyl-4'-amino-diphenylamine, 
2-nitro-4-pyrrolidin-1-yl-carbonyl-4'-methoxy-3-aminodiphenylamine, 
2-nitro-4-N-phenyl-N-methyl-aminocarbonyl-4'-aminodiphenyl-amine, 
2-nitro-4-di-(2-cyanoethyl-)aminocarbonyl-4'-aminodiphenylamine, 
2-nitro-4-methoxycarbonyl-4'-methoxy-3'-aminodiphenylamine, 
2-nitro-4-isopropoxy-carbonyl-4'-aminodiphenylamine, 
2-nitro-4-n-octyloxycarbonyl-4'-methyl-3'-amino-diphenylamine, 
2-nitro-4-(2-methoxyethyl)-carbonyl-4'-aminodiphenylamine, 
2-nitro-4-(2-hydroxyethyl)-carbonyl-4'-aminodiphenylamine, 
2-nitro-4-phenoxycarbonyl-3'-chloro-4'-aminodiphenylamine, 
2-nitro-4-cyclohexyloxycarbonyl-4'-aminodiphenylamine, 
2,6-dinitro-4'-aminodiphenylamine, 
2-nitro-4-carboxy-4'-aminodiphenylamine, 2-nitro-4-carboxy-3'-aminodipheny 
lamine, the 4'-aminodiphenylamine-4-carboxylic acid ester of hexaethylene 
glycol monomethyl ether, the 4'-aminodiphenylamine-4-carboxylic acid 
half-ester of tetraethylene glycol, the 
4'-amino-diphenylamine-4-carboxylic acid half-ester of diethylene glycol, 
4-(4'-aminophenyl)-3-nitro-benzenesulphonic acid N-(2-carboxyphenyl)-amide 
and 4-(4'-aminophenyl)-3-nitrobenzenesulphonic acid 
(3-methoxycarbonyl)-phenyl ester. 
Examples of coupling components (IV) which may be mentioned are: phenol, 
o-, m- and p-cresol, 2-hydroxy-1-tert.butylbenzene, 
2-hydroxy-1,4-dimethylbenzene, 1-hydroxy-2-methoxybenzene, 
1-hydroxy-3-methoxybenzene, 2-chlorophenol, 2-hydroxybiphenyl, 
4-hydroxybenzoic acid methyl ester, 4-hydroxy-benzoic acid n-propyl ester, 
2-hydroxy-benzoic acid isobutyl ester, 2-hydroxybenzoic acid iso-pentyl 
ester, 2-hydroxybenzoic acid phenyl ester, 3-hydroxybenzoic acid ethyl 
ester, 3-hydroxybenzoic acid 2-ethoxy-ethyl ester, 
2-hydroxy-6-methylbenzoic acid methyl ester, 2-hydroxy-4-methyl-benzoic 
acid p-tolyl ester, 2-hydroxy-benzoic acid 2-hydroxy-ethyl ester, 
2-hydroxy-benzoic acid 2-methoxy-ethyl ester, 2-hydroxy-benzoic acid 
n-octyl ester, 2-hydroxy-benzoic acid 2-acetoxy-ethyl ester, 
3-hydroxybenzoic acid benzyl ester, 4-hydroxy-benzoic acid n-pentyl ester, 
4-hydroxybenzoic acid n-pentyl ester, 4-hydroxybenzoic acid 
2-hydroxy-ethyl ester, 4-hydroxybenzoic acid 2-methoxy-ethyl ester, 
3-hydroxy-benzoic acid phenyl ester, the 2-hyroxybenzoate of diethylene 
glycol mono-n-butyl ether, the 2-hydroxybenzoate of hexaethylene glycol 
monomethyl ether, the 4-hydroxybenzoate of diethylene glycol monoethyl 
ether and the 3-hydroxybenzoate of tetraethylene glycol monomethyl ether. 
Examples of substances which are suitable for alkylating the phenolic OH 
group in ring D are: alkylene oxides, such as ethylene oxide, propylene 
oxide, epichlorohydrin and 1,2-butylene oxide; alkyl halides, such as 
methyl chloride, ethyl bromide, butyl chloride, octyl bromide, benzyl 
chloride, 2-ethoxy-2'-chloro-diethyl ether, diethylene glycol monomethyl 
mono-(2-chloroethyl) ether, diethylene glycol mono-(2-chloroethyl) ether, 
triethylene glycol mono-(2-chloroethyl) ether and tetraethylene glycol 
mono-(2-chloroethyl) ether; dialkyl sulphates, such as dimethyl sulphate 
and diethyl sulphate; and esters of aliphatic and aromatic sulphonic 
acids, such as iso-amyl p-toluenesulphonate, n-octyl-p-toluene sulphate, 
the mono-methylsulphonate of glycol mono-(2-methoxyethyl) ether, 
tetra-ethylene glycol mono-p-toluenesulphonate and the 
mono-methylsulphonate of triethylene glycol monoethyl ether. 
The polyethylene glycol derivatives employed for the alkylation can also 
consist of mixtures of homologous compounds. Thus, for example, it is 
possible to employ, in place of the single compound Cl--(C.sub.2 H.sub.4 
--O--).sub.4 CH.sub.3, a mixture Cl--(C.sub.2 H.sub.4 --O--)VCH.sub.3, 
wherein the major proportion in which v = 3, 4 or 5 makes up 70% and the 
remaining 30% are distributed between v = 1, 2, 6, 7 and 8. In a 
corresponding manner, the abovementioned radicals COO--(C.sub.2 H.sub.4 
--O--).sub.m Z and O--(C.sub.2 H.sub.4 --O--).sub.m Z can represent a 
mixture in which m = 0-8. 
Examples of aminoazo dyestuffs of the formula (V) are: diethylene glycol 
mono-4-(4'-aminobenzeneazo)-phenyl ether monoethyl ether, diethylene 
glycol mono-4-(3'-aminobenzeneazo)-phenyl ether monomethyl ether, 
diethylene glycol mono-4-(4'-aminobenzeneazo)-3-methylphenyl monomethyl 
ether, 4'-amino-2-methoxy-5-methyl-azobenzene and the 
mono-4'-amino-4-hydroxyazobenzene-3-carboxylic acid ester of diethylglycol 
monobutyl ether. 
Examples of o-nitrohalogenobenzenes of the formula (VI) are: 
4-chloro-3-nitro-benzoic acid methyl ester, 4-chloro-3-nitro-benzonitrile, 
1,3-dinitro-2-chlorobenzene, the 3-chloro-3-nitrobenzoate of triethylene 
glycol monoethyl ether, 4-chloro-3-nitrobenzenesulphonic acid 
N,N-diethylamide and 4-chloro-3-nitrobenzoic acid. 
The diazotisation of the diazo component (III) is carried out in a manner 
which is in itself known. 
The coupling reaction of the diazotised amines (III) with the phenols (IV) 
is also carried out in a customary manner, preferably in an aqueous 
alkaline medium. 
The condensation reaction of the o-nitrohalogenobenzenes (VI) with the 
aminoazo dyestuffs (V) is also carried out in a manner which is in itself 
known, for example in an aqueous medium with the addition of organic 
solvents, such as alcohols or glycols, in the presence of acid-binding 
agents, such as magnesium oxide, calcium carbonate, alkali metal 
carbonates or alkali metal bicarbonates. The condensation reaction can 
also be carried out under anhydrous conditions, for example in glycol or 
glycol monomethyl ether or dimethylformamide in the presence of tertiary 
amines, such as, for example, tri-n-butylamine or of sodium acetate. 
Temperatures of between 50.degree. and 200.degree. C. and preferably of 
between 80.degree. and 170.degree. C. are employed for the condensation 
reactions. 
The etherification of the azo dyestuffs of the formula (II) wherein R.sub.7 
= OH with the abovementioned alkylating agents in which (A-O).sub.m -Z is 
alkyl is also carried out in a manner which is in itself known, for 
example in an aqueous-alkaline medium or in an alkaline aqueous-organic 
medium. Most advantageously, the reaction is carried out at temperatures 
of 50.degree. to 100.degree. C. and, if necessary, in the case of 
low-boiling alkylating agents (methyl chloride), the reaction is carried 
out in an autoclave. 
The etherification of the dyestuffs of the formula (II) wherein R.sub.7 = 
OH with alkylene oxides is carried out in a manner which is in itself 
known, for example in an aqueous alkaline medium or in an alkaline aqueous 
organic medium or in an organic medium with the addition of alkali or 
basic ion exchangers. The reaction is carried out at temperatures of 
between 50.degree. and 150.degree. C. and in the case of low-boiling 
alkylene oxides is, if necessary, carried out in an autoclave. 
The compounds of the formula (II) are suitable for dyeing and printing 
hydrophobic materials, especially textiles or fibres made of aromatic 
polyesters, such as polyethylene terephthalates and polyesters of 
terephthalic acid and 1,4-bishydroxymethyl-cyclohexane as well as 
cellulose tracetate and cellulose 21/2-acetate and synthetic high 
molecular weight polyamides by the dyeing and printing processes customary 
for these types of fibre. The dyestuffs are preferably employed in the 
form of aqueous formulations which, in the present case, can be prepared 
in a particularly simple manner. 
Above all, however, the new dyestuffs are suitable for dyeing polyester 
fibres from an aqueous liquor by the exhaustion process since they are 
distinguished by a good affinity and build-up power. The resulting dyeings 
are very clear and display good general fastness properties, such as 
fastness to light, sublimation and measuring.