Triphenodioxazine dyes which, in the free acid form, have the formula: ##STR1## wherein A is Cl or Br; Y is cyclopentylene, cyclohexylene or (CH.sub.2).sub.x where x is 2, 3 or 4; and PA1 Z is NRCO.sub.2 R.sup.1 or ##STR2## wherein R is H, optionally substituted alkyl or optionally substituted aryl; PA1 R.sup.1 is optionally substituted alkyl, optionally substituted cycloalkyl or optionally substituted aryl; and PA1 R.sup.2 is --CH.dbd.CH--,--CH.dbd.CH--CH.sub.2 --,--(CH.sub.2)--.sub.2-4 or a 1,2-radical of a 5 or 6 membered carbocyclic compound; PA1 or, when Y is cyclopentylene or cyclohexylene, Z may also be H or alkyl, alkoxy, aryl, aryloxy, cycloalkyl, cycloalkoxy or amino, all of which may be optionally substituted.

This invention relates to acid dyes of the triphenodioxazine series. 
Dyes of the triphenodioxazine series are well known and often bear 
sulphonic acid groups making them suitable for colouring various 
substrates e.g. as direct dyes for cellulose such as paper and as acid 
dyes for polyamides such as wool and nylon. 
We have now discovered a novel class of such dyes which show good 
properties e.g. strength of colouration often better than closely related 
known dyes. 
According to the present invention there are provided triphenodioxazine 
dyes which in the free acid form are of the formula: 
##STR3## 
wherein A is Cl or Br; 
Y is cyclopentylene, cyclohexylene or (CH.sub.2).sub.x where x is 2, 3 or 
4; and 
Z is NRCO.sub.2 R.sup.1 or 
##STR4## 
wherein R is H, optionally substituted alkyl or optionally substituted 
aryl; 
R.sup.1 is optionally substituted alkyl, optionally substituted cycloalkyl 
or optionally substituted aryl; and 
R.sup.2 is CH.dbd.CH--, CH.dbd.CH--CH.sub.2 --, (CH.sub.2)--.sub.2-4 or a 
1,2-radical of a 5 or 6 membered carbocyclic compound; 
or, when Y is cyclopentylene or cyclohexylene, Z may also be H or alkyl, 
alkoxy, aryl, aryloxy, cycloalkyl, cycloalkoxy or amino, all of which may 
be optionally substituted. 
As examples of optionally substituted alkyl or aryl groups represented by R 
and R.sup.1, there may be mentioned methyl, ethyl, 1- and 2-propyl, 1- and 
2-butyl, 1-, 2- and 3-hexyl, 1-, 2- and 3-octyl, 2-ethylhexyl, 
2-cyanoethyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-chloropropyl, phenyl, 
tolyl, anisyl, nitrophenyl, sulphophenyl, chlorophenyl, bromophenyl, 
carboxyphenyl, cyanophenyl, acetylaminophenyl, methoxycarbonylphenyl and 
ethoxycarbonylphenyl. 
As examples of groups represented by R.sup.2 there may be mentioned 
--CH.sub.2 CH.sub.2 --, --CH.sub.2 CH.sub.2 CH.sub.2 --, --CH.sub.2 
CH(CH.sub.3)--, --CH.sub.2 CH(C.sub.6 H.sub.5)CH.sub.2 --, --CH.sub.2 
CH(CH.sub.2 C.sub.6 H.sub.5)CH.sub.2 --, --CH.sub.2 CHNH.sub.2 --, 
--CH.sub.2 CH(NHCOCH.sub.3)CH.sub.2 --, --CCl.dbd.CCl--, 1,2-phenylene, 
4-sulpho-1,2-phenylene, 4-methyl-1,2-phenylene, terachloro or 
tetrabromo-1,2-phenylene, 1,2-cyclohexylene, 1,2-cyclohex-1-enylene, 
1,2-cyclohex-4-enylene, 1,2-cyclohexa-1,4-dienylene and 
1,2-cyclohexa-2,4-dienylene. 
Preferred dyes of formula (1) have one or more of the following features: 
(a) A is Cl, 
(b) Y is (CH.sub.2).sub.x with x as 3 or especially 2, or cyclohexylene, 
(c) Z is NRCO.sub.2 R.sup.1, or Z is alkyl when Y is cyclohexylene, 
(d) R is C.sub.1-4 alkyl optionally substituted by Cl or, especially, R is 
H 
(e) R.sup.1 is C.sub.1-12 alkyl or especially C.sub.1-6 alkyl both 
optionally substituted by OH, CN or Cl or R.sup.1 is phenyl optionally 
substituted by C.sub.1-4 alkyl, 
(f) R.sup.2 is --(CH.sub.2).sub.2 or 3, --CH.dbd.CH--, 
--CH.dbd.CH--CH.sub.2 --, 1,2-phenylene, tetrachloro- or 
tetrabromo-1,2-phenylene, 1,2-cyclohexylene, 1,2-cyclohexenylene or 
1,2-cyclohexadienylene. 
The dyestuffs of formula (1) in which Z contains a nitrogen atom linked to 
Y (i.e. those groups defined above which may be linked to all possible Y 
groups) may be conveniently manufactured by reacting an amino 
triphenodioxazine of the formula: 
##STR5## 
with a chloroformate Cl.CO.sub.2 R.sup.1, a dibasic acid R.sup.2 
(COOH).sub.2 or derivative thereof such as acid chloride or anhydride, 
where A, R.sup.1 and R.sup.2 have the meanings given above. 
The reaction is carried out under conventional conditions appropriate for 
the interaction of the above reagents with amino groups. Often this may be 
conveniently performed in aqueous media at room temperature or slightly 
above at a mildly alkaline pH e.g. 8 to 9. In some instances where 
hydrolysis of the reagent is rapid it may be necessary to work in non 
aqueous media. 
The reaction with R.sup.2 (COOH).sub.2 is usually most conveniently 
conducted using the corresponding anhydride which is often the cyclic 
anhydride 
##STR6## 
and is confined to reaction with aminotriphenodioxazines of formula (2) in 
which R is H. The initial reaction product is a dyestuff of formula (1) in 
which Z is --NH--COR.sup.2.COOH. By heating under acidic conditions the 
dyestuffs of formula (1) with Z as 
##STR7## 
are formed. This cyclisation often takes place readily e.g. at 50.degree. 
C. in an aqueous medium of mildly acidic pH e.g. 4-5. In other instances 
higher temperature or use of glacial acetic acid medium may be necessary. 
It is often found that the cyclised product is a superior dye to the 
precursor with Z as NH.COR.sup.2 COOH. In some instances e.g. the dyeing 
of wool or nylon normal dyebath temperatures and pH values would be such 
as to lead to cyclisation. 
Examples of suitable reactants for the above process include: 
ethyl chloroformate 
butyl chloroformate 
cyclohexyl chloroformate 
phenyl chloroformate 
maleic anhydride 
succinic anhydride 
glutaric anhydride 
phthalic anhydride 
tetrachlorophthalic anhydride. 
The aminotriphendioxazines of formula (2) for use in the above process are 
obtained by conventional means e.g. a chloroquinone such as 
tetrachloroquinone of the formula 
##STR8## 
is reacted with 2 moles of a diamine of the formula: 
##STR9## 
e.g. N-4-aminophenyl ethylene diamine or 
N-(4-amino-2-sulphophenyl)ethylene diamine and the resultant dianilide 
cyclised, A, Y and R having the meanings given above. Oleum is often used 
for the cyclisation process which may be accompanied by some sulphonation 
of aromatic groups present. 
The dyes of formula (1) in which Y is not linked to a nitrogen atom in Z 
(i.e. those in which Y can only be cyclohexylene or cyclopentylene) may be 
manufactured by reacting a chloroquinone of formula (3) as given above 
with 2 moles of a diamine of the formula (5): 
##STR10## 
in which Y is cyclohexylene or cyclopentylene and Z is H or alkyl, alkoxy, 
aryl, aryloxy, cycloalkyl, cycloalkoxy or amino, all of which may be 
optionally substituted, and cyclising the resultant dianilide. 
The cyclisation of the dianilide may be carried out under conventional 
conditions e.g. heating in oleum and as previously indicated some 
sulphonation may accompany this step. 
As examples of diamines of formula (5) there may be mentioned: 
N-(4'-amino-2'-sulphophenyl)-4-methylcyclohexylamine, 
N-(4'-amino-2'-sulphophenyl)-4-ethoxycyclohexylamine, 
N-(4'-amino-2'-sulphophenyl)-4-cyclohexyl-cyclohexylamine, 
N-(4'-amino-2'-sulphophenyl)-3-methylcyclopentylamine. 
The dyes of this invention may be isolated in the free acid form but it is 
usually more convenient to have them, at least partially, in the form of 
salts e.g Na, K, Li or NH.sub.4 salts. The dyes all have same solubility 
in water but in instances where this is low it may aid even dyeing to 
convert the isolated dye into a finely divided form and mix it with 
dispersing agent. 
The dyes of this invention are valuable dyes usually of a bright blue hue. 
They may be used as direct dyes for cellulose in the form of fibres or 
paper. They may also be used as acid dyes e.g. for wool or nylon. They can 
be applied by conventional colouration techniques such as printing, 
padding or exhaust dyeing. 
The resulting colouration has good fastness properties and the dyes of the 
present invention frequently show greater tinctorial strength and/or 
better dyeing behaviour than related known triphenodioxazine dyes e.g. 
dyes of formula (1) in which Z is H, alkylamino or acetyl- or 
benzoylamino. They also show advantages over anthraquinone dyes commonly 
used for bright blue dyes.

The invention is illustrated by the following Examples. The initials M.I. 
signify "molecular index" which is the weight of any material containing 
one mole of the pure chemical species named. 
EXAMPLE 1 
To 
3,10-bis-(beta-aminoethylamino)-6,13-dichloro-4,11-disulphotriphenodioxazi 
ne (M.I. 2546; 25 g), in water (350 g) at pH 8.0 and 20.degree., was added 
succinic anhydride (3 g) dissolved in acetone (50 g). The reaction mixture 
was stirred for 1 hour, while maintaining the pH at 8.0, then potassium 
chloride (80 g) was added, and the precipitated carboxyamide filtered off 
and dried (19.6 g). 
The solid was boiled in acetic acid (150 g) for 5 minutes then isolated by 
filtration to give the bis succinimido derivative (9.6 g), .lambda.max 620 
nm. 
The dyestuff gave bright blue shades when applied from mildly acid dyebath 
at 90.degree.-100.degree. C. to nylon which showed excellent fastness to 
washing and to light. 
EXAMPLE 2 
To 
3,10-bis-(beta-aminoethylamino)-6,13-dichloro-4,11-disulphotriphenodioxazi 
ne (M.I. 2131; 42.6 g) in water (400 g) at pH 8.0 and 20.degree., was added 
maleic anhydride (7.8 g) and the reaction mixture stirred for 1 hour while 
maintaining the pH at 8.0. 
Hydrochloric acid was then added to give a pH of 4.0, the solution heated 
to 90.degree. for 1/2 hour, and finally salted to 10% with potassium 
chloride. On cooling the bis maleimide was filtered off, washed with 
potassium chloride solution and oven dried to give the product (18.6 g), 
.lambda.max 620 nm. 
The dyestuff gave clear blue shades on nylon which showed excellent 
fastness to washing and to light. 
EXAMPLE 3 
To 
3,10-bis-(beta-aminoethylamino)-6,13-dichloro-4,11-disulphotriphenodioxazi 
ne (M.I. 2546; 51 g) in water (400 g) at pH 8.0 and 20.degree., was added 
phthalic anhydride (8.9 g) dissolved in acetone (75 g). The reaction 
mixture was stirred for 2 hours, while maintaining the pH at 8.0, then 
potassium chloride (80 g) was added to salt out the carboxyamide. The 
solid was isolated by filtration, washed with potassium chloride and dried 
to give the product, .lambda.max 620, (14 g). 
The above compound was ring closed to give the bis phthalimide by the 
method described in Example 1. 
The carboxyamide and the phthalimide both dyed nylon in clear bright blue 
shades of excellent fastness. 
EXAMPLE 4 
To 
3,10-bis-(beta-aminoethylamino)-6,13-dichloro-4,11-disulphotriphenodioxazi 
ne (M.I. 2546; 25 g) in water (400 g) at pH 8.0 and 20.degree., was added 
tetrachlorophthalic anhydride (8.6 g) dissolved in dimethylformamide (50 
g). The reaction mixture was stirred for 3 hours at room temperature, pH 
8.0, the pH dropped to 4.0 with hydrochloric acid, heated to 90.degree. 
for 10 minutes then cooled and salted to 20% with sodium chloride. The 
tetrachlorophthalimide product (16 g), .lambda.max 620, dyed nylon in 
bright blue shades of excellent fastness to water and to light. 
EXAMPLE 5 
To 
3,10-bis-(beta-aminoethylamino)-6,13-dichloro-4,11-disulphotriphenodioxazi 
ne (M.I. 2546; 25 g) in water (400 g) at pH 8.5, 25.degree., was added 
phenyl chloroformate (5 g) and the reaction mixture stirred at 
25.degree.-30.degree., for 4 hours, while keeping the pH at 8.5. Sodium 
chloride (20 g) was added, the solid isolated by filtration, washed and 
oven dried to give the phenyl urethane dyestuff (14 g), .lambda.max 620. 
The dyestuff dyed nylon in bright blue shades of excellent fastness to 
water and to light. 
EXAMPLE 6 
To 
3,10-bis(beta-aminoethylamino)-6,13-dichloro-4,11-disulphotriphenodioxazin 
e (M.I. 2546; 25 g) in water (400 g) at pH 8.5, was added n-butyl 
chloroformate (4 g) and the reaction mixture stirred for 11/2 hours at 
25.degree.-30.degree., while keeping the pH at 8.5. Sodium chloride (20 g) 
was added, the solid isolated by filtration, washed with water and oven 
dried to give the n-butyl urethane dyestuff (10 g); .lambda.max 618 nm. 
The dyestuff dyed nylon and wool in bright blue shades of excellent 
fastness to water and to light. 
EXAMPLE 7 
To 
3,10-bis(beta-aminoethylamino)-6,13-dichloro-4,11-disulphotriphenodioxazin 
e (M.I. 2546; 25 g) in water (400 g) at pH 8.5, was added cyclohexyl 
chloroformate (4 g) and the reaction mixture stirred for 2 hours at 
25.degree.-30.degree., while keeping the pH at 8.5. Sodium chloride (20 g) 
was added, the solid isolated by filtration, washed with water and oven 
dried to give the cyclohexyl urethane dyestuff (9 g); .lambda.max 620 nm. 
The dyestuff dyed nylon and wool in bright blue shades of excellent 
fastness to water and to light. 
Further Examples of dyestuffs of Formula I were prepared in a similar 
manner and are identified in Table 1 by the substituents A, Y and Z. 
TABLE 1 
______________________________________ 
Ex- 
am- 
ple A Y Z .lambda..sub.max 
______________________________________ 
8 Cl CH.sub.2 CH.sub.2 
NHCOOC.sub.2 H.sub.5 
620 
9 " " NHCOOC.sub.3 H.sub.7 
620 
10 " " NHCOOC.sub.9 H.sub.19 
625 
11 " CH.sub.2 CH.sub.2 CH.sub.2 
##STR11## 615 
12 Br CH.sub.2 CH.sub.2 
NHCOOC.sub.4 H.sub.9 
620 
13 Cl " 
##STR12## 630 
14 " " 
##STR13## 626 
______________________________________ 
EXAMPLE 15 
(a) To 4-chloro-3-sulphonitrobenzene (130 g) in water (2 liters) was added 
cyclohexylamine (75 ml) and sodium carbonate (26.5 g). The reaction 
mixture was heated at 90.degree. for 10 hours, cooled and the solid so 
formed isolated by filtration to give 
4-cyclohexylamino-3-sulphonitrobenzene (120 g). 
(b) The above nitro compound (120 g) in water (3 liters) and palladium 
charcoal (5%; 2 g) was hydrogenated at room temperature and atmospheric 
pressure to give 4-cyclohexylamino-3-sulphoaniline which was filtered to 
remove catalyst but was not isolated. 
(c) To the above solution was added charcoal (150 g) and the reaction 
mixture heated at 50.degree., pH 7.0, for 4 hours. The pH of the solution 
was lowered to 3, salt (20%) added and the derived dianilide isolated by 
filtration to give the product (146 g; M.I. 970). 
(d) The above dianilide (97 g) in 20% oleum (900 g) at 20.degree. was 
stirred for 8 hours. Drowning into ice (5 liters) gave a blue solid which 
was isolated by filtration, washed with saturated brine and oven dried to 
give 
3,10-bis(beta-cyclohexylamino)-6,13-dichloro-4,11-disulphotriphenodioxazin 
e (106 g; M.I. 1500). 
The dyestuff dyed nylon and wool in bright blue shades of excellent 
fastness to water and to light. 
The Examples listed in Table 2 were prepared in a manner similar to Example 
15, the dyestuffs being identified by the substituents A, Y and Z. 
TABLE 2 
______________________________________ 
Example A Y Z .lambda..sub.max 
______________________________________ 
16 Cl cyclohexyl p-methyl 620 
17 " " p-t-butyl 620 
18 " " p-dodecyl 622 
19 " " p-methoxy 620 
20 " " o-cyclohexyl 
618 
21 " " m-methyl 617 
22 " " p-propyl 620 
23 " " p-isopropyl 
620 
24 " " p-n-butyl 621 
25 " " p-isopropoxy 
620 
26 " " p-amyl 619 
27 " " p-hexyl 622 
28 " " p-heptyl 617 
29 " " p-octyl 618 
30 " " p-nonyl 620 
31 " " p-decyl 620 
32 " " p-methoxyethoxy 
620 
33 " cyclopentyl hydrogen 618 
34 " " 3-methyl 620 
35 Br cyclohexyl p-ethyl 620 
______________________________________