Azo dyes having a quaternized heterocyclic diazo component radical and an optionally substituted aryloxyalkyl substituent on the amino group of the coupling component radical

Basic dyes free from sulfo groups of the formula ##STR1## in which Q signifies an unsubstituted or substituted phenyl or naphthyl radical, PA0 R.sub.1 and R.sub.2 signify hydrogen, unsubstituted or substituted alkyl, phenyl or cycloalkyl, PA0 R.sub.3 signifies hydrogen, unsubstituted or substituted alkyl or phenyl, PA0 the Z containing group signifies a heterocyclic diazo radical containing a quaternary ammonium group, PA0 R.sub.4 signifies unsubstituted or substituted alkyl, alkenyl, cycloalkyl or alkoxy, PA0 x signifies 1 to 3, PA0 A.crclbar. signifies an anion, and PA0 D signifies an unsubstituted or substituted phenylene or naphthylene radical are useful for dyeing and printing homo- and co-polymers of acrylonitrile and asymmetrical dicyanoethylene and synthetic polyamides and polyesters modified to contain acid groups. The obtained dyeings are level and fast to light and wet treatments.

The invention relates to basic azo compounds free from sulphonic acid 
groups. 
The invention provides compounds of formula I, 
##STR2## 
in which Q signifies a radical of the formula 
##STR3## 
R signifies hydrogen; hydroxy; halogen; alkyl or alkoxy of 1 to 4 carbon 
atoms, unsubstituted or substituted by halogen, hydroxy, cyano, phenyl or 
phenoxy; cycloalkyl of 5 or 6 carbon atoms, unsubstituted or substituted 
by alkyl of 1 to 4 carbon atoms; cyano; nitro; trihalomethyl; 
trifluoromethyl; phenoxy; naphthyloxy, phenylazo; or a radical of the 
formula --CORo, 
##STR4## 
--SO.sub.2 --Ro, --SO.sub.2 --NH--Ro, 
##STR5## 
--O--CO--NH--Ro, --O--CO--N(Ro).sub.2, --SO.sub.2 --N(Ro).sub.2, 
--CO--NH--Ro,--OSO.sub.2 N(Ro).sub.2, --CO--N(Ro).sub.2, --NH--CO--Ro, 
##STR6## 
in which the Ro's, independently, signify C.sub.1-4 alkyl or phenyl, and 
X signifies --CO-- or --SO.sub.2 --; 
R.sub.1 and R.sub.2, which may be the same or different, signify hydrogen; 
alkyl of 1 to 4 carbon atoms, unsubstituted or substituted by halogen, 
C.sub.1-4 alkoxy or phenoxy; phenyl; or C.sub.5-6 cycloalkyl; 
R.sub.3 signifies hydrogen; alkyl of 1 to 12 carbon atoms, unsubstituted or 
substituted by halogen, hydroxy, cyano, phenyl, phenoxy, C.sub.1-4 
alkoxycarbonyl, C.sub.1-4 alkylcarbonyloxy, C.sub.1-4 alkoxy, 
phenylcarbonyloxy (benzoyloxy), 
##STR7## 
or --CON(Ra).sub.2 in which the Ra's, independently, signify hydrogen or 
C.sub.1-4 alkyl; or phenyl; 
Z signifies a residue which together with the nitrogen atom forms an 
unsaturated heterocyclic ring containing at least five ring atoms, which 
may be carbon, oxygen, sulphur or further nitrogen atoms, which ring 
optionally has an aromatic carbocyclic or heterocyclic ring fused thereto 
and is, along with any ring fused thereto, optionally substituted by 
substituents selected from alkyl of 1 to 4 carbon atoms and alkoxy of 1 to 
4 carbon atoms, each unsubstituted or substituted by phenyl, hydroxy, 
--CONH.sub.2, cycloalkyl of 5 or 6 carbon atoms, cyano or halogen; 
cycloalkyl of 5 or 6 carbon atoms, unsubstituted or substituted by 
C.sub.1-4 alkyl, C.sub.1-4 alkoxy or halogen; phenyl or phenoxy, each 
unsubstituted or substituted by cyano, nitro, C.sub.1-4 alkyl, C.sub.1-4 
alkoxy or halogen; halogen; nitro; cyano; trifluoromethyl; a radical of 
the formula --CO--Ro, 
##STR8## 
--NH--SO.sub.2 --Ro, --CO--NHRo, --CO--N(Ro).sub.2, --NH--CO--Ro, 
--SO.sub.2 --Ro, --SO.sub.2 --N(Ro).sub.2 or --SO.sub.2 --NHRo, in which 
Ro is as defined above; or phenylazo; the 
##STR9## 
group being free from water-solubilizing groups and containing at least 
one quaternary nitrogen atom, and being bound to the azo group through a 
carbon atom, 
R.sub.4 signifies a C.sub.1-8 alkyl, C.sub.2-8 alkenyl or C.sub.1-4 alkoxy 
radical, each unsubstituted or substituted by halogen, hydroxy, cyano, 
phenyl, phenoxy, cycloalkyl of 5 or 6 carbon atoms, alkoxy of 1 to 4 
carbon atoms or the group --CONH.sub.2 ; or a cycloalkyl radical of 5 or 6 
carbon atoms, unsubstituted or substituted by C.sub.1-4 alkyl; or the 
group 
##STR10## 
y signifies 1, 2, 3, 4 or 5, and, where y signifies 2 or more, the R's may 
be the same or different, 
x signifies 1, 2 or 3, 
A.sup..crclbar. signifies an organic or inorganic anion, and 
D signifies a phenylene or naphthylene radical, each further unsubstituted 
or further substituted by 1 or 2 substituents selected from C.sub.1-4 
alkoxy, C.sub.1-4 alkyl and halogen. 
Any heterocyclic ring in 
##STR11## 
is preferably of 5 or 6 ring atoms and preferably contains 1, 2 or 3 
heteroatoms. 
As examples of radicals 
##STR12## 
may be given thiazolyl, isothiazolyl, thiadiazolyl, triazolyl, imidazolyl, 
indazolyl, oxazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, 
benzothiazolyl, oxadiazolyl, quinoxalinyl, cinnolinyl, quinolinyl, 
phthalazinyl, pyrazolyl, benzoxazolyl and benzimidazolyl derivatives. 
Preferred examples of 
##STR13## 
are the triazolyl, pyridinyl, benzothiazolyl, quinolinyl and indazolyl 
derivatives, more preferably the triazolyl, pyridinyl and benzothiazolyl 
derivatives and most preferably the triazolyl derivatives. 
In the compounds of formula I, where Q signifies a naphthalene radical, 
such radical is preferably unsubstituted. 
The preferred compounds of Formula I are those wherein 
R.sub.1 is hydrogen, C.sub.1-4 alkyl or phenyl, 
R.sub.2 is hydrogen, 
R.sub.3 is hydrogen; C.sub.1-4 alkyl or C.sub.1-4 alkyl substituted by 
phenoxy, phenyl, C.sub.1-4 alkoxycarbonyl or benzoyloxy, 
R.sub.4 is C.sub.1-4 alkyl; C.sub.1-4 alkyl substituted by phenyl, hydroxy 
or --CONH.sub.2 ; or C.sub.1-4 alkoxy, 
##STR14## 
is a triazolyl, pyridyl, benzothiazolyl, quinolyl or indazolyl 
derivative, preferably a triazolyl, pyridyl or benzothiazolyl derivative, 
most preferably a triazolyl derivative, 
D is phenylene, naphthylene or phenylene substituted in a position ortho to 
the azo radical by C.sub.1-4 alkyl, C.sub.1-4 alkoxy or halo, and 
Q is phenyl, naphthyl, phenyl substituted by 1 or 2 R's or phenyl 
substituted by 3, 4 or 5 halo substituents. 
As examples of anions A.sup..crclbar. may be given the halides, such as 
chloride, bromide or iodide, sulphate, bisulfate, methylsulphate, 
aminosulphate, perchlorate, carbonate, bicarbonate, phosphate, 
phosphormolybdate, phosphortungstenate, phosphortungstenmolybdate, 
formate, benzenesulphonate, naphthalenesulphonate, 
4-chlorobenzenesulphonate, oxalate, maleinate, acetate, propionate, 
lactate, succinate, chloroacetate, tartrate, malate, methanesulphonate or 
benzoate ions, or complex anions such as zinc chloride double salts, e.g. 
ZnCl.sub.3.sup..crclbar.. The preferred anions are the halide preferably 
chloride, methylsulphate ZnCl.sub.3.sup..crclbar. and acetate ions. 
Even more preferred are the compounds of Formula I wherein 
R.sub.1 is hydrogen, methyl or phenyl, 
R.sub.2 is hydrogen, 
R.sub.3 is methyl, ethyl, butyl, phenoxyethyl, benzyl, ethoxycarbonylethyl 
or benzoyloxyethyl, 
R.sub.4 is methyl, ethyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, 
2-carbamoylethyl or methoxy, 
##STR15## 
is a triazolyl, pyridyl or benzothiazolyl derivative, especially a 
triazolyl derivative, 
D is phenylene, naphthylene or phenylene substituted in a position ortho to 
the azo radical by methyl, methoxy or chloro, 
Q is phenyl, naphthyl, phenyl substituted by 3, 4 or 5 chloro substituents 
or phenyl substituted by 1 or 2 substituents selected from chloro, 
C.sub.1-4 alkyl, benzyl, nitro, cyano, phenylsulfonyl, methylsulfamoyl, 
dimethylsulfamoyl, trifluoromethyl, methoxycarbonyl, methylcarbamoyl, 
methoxy, phenoxy, benzoyloxy, phenylazo, benzamido, phenylcarbamoyloxy, 
dimethylcarbamoyloxy, N-methyl-N-phenylcarbamoyloxy, methylsulfonyl, 
dimethylsulfamoyloxy, phenoxymethyl, benzoyl or hydroxy (especially 
phenyl, naphthyl, phenyl substituted by 2, 3, 4 or 5 chloro substituents, 
phenyl monosubstituted by one of the aforementioned substituents or phenyl 
substituted by hydroxy and by benzoyl), and x is 1 or 2. 
Thus, the preferred compounds of Formula I' when P is a group of Formula 
(a), or an isomer thereof of formula (b) or (c), are those wherein 
R.sub.8 is C.sub.1-4 alkyl or C.sub.1-4 alkyl substituted by phenyl, 
hydroxy or carbamoyl, 
R.sub.9 is C.sub.1-4 alkyl or C.sub.1-4 alkyl substituted by phenyl, 
hydroxy or carbamoyl, and 
R.sub.10 is hydrogen, C.sub.1-4 alkyl or C.sub.1-4 alkyl substituted by 
phenyl, 
especially those of the group wherein 
R'.sub.1 is hydrogen or C.sub.1-4 alkyl, 
R'.sub.2 is hydrogen, 
R'.sub.3 is C.sub.1-4 alkyl or C.sub.1-4 alkyl substituted by phenoxy, 
R'.sub.7 is hydrogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy, 
B is 1,4-phenylene, 
Q' is phenyl, naphthyl, phenyl substituted by 3, 4 or 5 chloro substituents 
or phenyl substituted by 1 or 2 substituents selected from halo, nitro, 
cyano, phenylsulfonyl, C.sub.1-4 alkylsulfamoyl, di-(C.sub.1-4 
alkyl)sulfamoyl, (C.sub.1-4 alkoxy)carbonyl, (C.sub.1-4 alkyl)carbamoyl, 
C.sub.1-4 alkoxy, benzoyl, phenoxy, benzoyloxy, phenylazo, benzamido, 
phenylcarbamoyloxy, di-(C.sub.1-4 alkyl)carbamoyloxy, N-C.sub.1-4 
alkyl-N-phenylcarbamoyloxy, C.sub.1-4 alkylsulfonyl, di-(C.sub.1-4 
alkyl)sulfamoyloxy, trifluoromethyl, C.sub.1-4 alkyl or phenyl(C.sub.1-4 
alkyl), and 
x is 1, 
and particularly those of the immediately preceding group wherein 
A.sup..crclbar. is chloride, ZnCl.sub.3.sup..crclbar., methylsulfate or 
acetate or wherein 
R.sub.8 is methyl, 
R.sub.9 is methyl, and 
R.sub.10 is hydrogen. 
Even more preferred compounds of Formula I' when P is a group of Formula 
(a), or an isomer thereof of Formula (b) or (c), are those wherein 
R'.sub.1 is hydrogen or C.sub.1-4 alkyl, 
R'.sub.2 is hydrogen, 
R'.sub.3 is methyl or ethyl, 
R'.sub.7 is hydrogen 
R.sub.8 is methyl, 
R.sub.9 is methyl, 
R.sub.10 is hydrogen, 
B is 1,4-phenylene, 
Q' is phenyl, 2-naphthyl, phenyl substituted by 1 to 5 chloro substituents 
or phenyl monosubstituted by nitro, cyano, phenylsulfonyl, 
methylsulfamoyl, dimethylsulfamoyl, methoxycarbonyl, methylcarbamoyl, 
methoxy, phenoxy, benzoyloxy, phenylazo, benzamido, phenylcarbamoyloxy, 
dimethylcarbamoyloxy, N-methyl-N-phenylcarbamoyloxy, methylsulfonyl, 
dimethylsulfamoyloxy, trifluoromethyl, methyl or benzyl (especially those 
wherein when Q' is monosubstituted phenyl, the substituent is in the para 
position), and 
x is 1, 
especially those of this group wherein A.sup..crclbar. is chloride, 
ZnCl.sub.3.sup..crclbar., methylsulfate or acetate. 
The invention also provides a process for the production of compounds of 
formula I, characterised by quaternising a compound of formula II, 
##STR16## 
in which Z, D, R.sub.1, R.sub.2, R.sub.3 x and Q are as defined above, by 
reaction with a compound of formula III, 
EQU R.sub.4 --A III 
in which R.sub.4 is as defined above, and A corresponds to A.sup..crclbar., 
above, or by addition reaction of an R.sub.4 yielding epoxide or vinyl 
compound with a compound of formula II, in the presence of water and with 
neutralization employing an acid HA. 
The quaternisation with a compound of formula III may be carried out in 
conventional manner. Suitably, the reaction is carried out in an inert 
solvent, in an aqueous suspension or, where liquid under the reaction 
conditions, in an excess of the compound of formula III. Where necessary, 
the reaction can be carried out at elevated temperatures and in a buffered 
medium. As examples of preferred quaternising agents of formula III may be 
given methyl or ethyl chloride, bromide or iodide, alkyl sulphates, such 
as dimethyl sulphate, or benzyl chloride. As examples of other 
quaternising agents may be given acrylic acid amide hydrochloride, such as 
CH.sub.2 .dbd.CH--CO--NH.sub.2 /HCl, chloroacetic acid amide, or epoxides 
such as ethylene oxide and propylene oxide, and epichlorohydrins, in the 
presence of an acid of the formula HA. 
Preferred compounds of formula I are compounds of formula I', 
##STR17## 
in which P signifies a radical of the formula 
##STR18## 
in which R.sub.8 signifies an alkyl radical of 1 to 4 carbon atoms or 
alkenyl radical of 2 to 4 carbon atoms, unsubstituted or substituted by 
hydroxy, halogen, cyano, phenyl or the group --CONH.sub.2 ; or a 
cyclohexyl radical, unsubstituted or substituted by C.sub.1-4 alkyl, 
R.sub.9 signifies an alkyl radical of 1 to 4 carbon atoms, unsubstituted or 
substituted by hydroxy, halogen, cyano, phenyl or the group --CONH.sub.2 ; 
a cyclohexyl radical, unsubstituted or substituted by C.sub.1-4 alkyl; or 
a phenyl radical, unsubstituted or substituted by halogen, C.sub.1-4 alkyl 
or C.sub.1-4 alkoxy, 
R.sub.10 signifies hydrogen or one of the significances of R.sub.9, above, 
a radical of the formula 
##STR19## 
in which R.sub.11 signifies C.sub.1-4 alkoxy, C.sub.1-4 alkyl or 
C.sub.2-4 alkenyl, each unsubstituted or substituted by hydroxy, halogen, 
cyano, phenyl or the group --CONH.sub.2, 
R.sub.12 signifies phenyl; halogen; nitro; cyano; C.sub.1-4 alkyl or 
C.sub.1-4 alkoxy; 
q signifies 0, 1 or 2; and where q signifies 2, the R.sub.12 's may be the 
same or different, a radical of the formula 
##STR20## 
in which R.sub.13 signifies a C.sub.1-4 alkyl radical, R.sub.14 signifies 
halogen, nitro, cyano, trifluoromethyl, C.sub.1-4 alkylsulphonyl or, 
di-(C.sub.1-14 alkyl)sulfamoyl or phenylsulphonyl, 
R.sub.11 is as defined above, and 
q is a defined above, and when q signifies 2, the R.sub.14 's may be the 
same or different; 
a radical of the formula 
##STR21## 
in which R.sub.8, R.sub.9, R.sub.14 and q are as defined above; and when 
q signifies 2, the R.sub.14 's may be the same or different; 
or a radical of the formula 
##STR22## 
in which R.sub.8 is as defined above, either R.sub.16 and R.sub.17, which 
may be the same or different, each signifies hydrogen; halogen; C.sub.1-4 
alkyl or C.sub.1-4 alkoxy, unsubstituted or substituted by phenyl, 
hydroxy, --CONH.sub.2, cycloalkyl of 5 or 6 carbon atoms, cyano or 
halogen; phenoxy; or a radical of the formula --CO--Ro, 
##STR23## 
--NH--SO.sub.2 --Ro, --CO--NH--Ro, --CON(Ro).sub.2, --NH--CO--Ro, 
--SO.sub.2 --Ro, --SO.sub.2 --NH--Ro or --SO.sub.2 --N(Ro).sub.2 ; in 
which Ro is as defined above, 
or R.sub.16 and R.sub.17 are on adjacent carbon atoms and are linked to 
form a --CH.dbd.CH--CH.dbd.CH-- linkage; 
R'.sub.3 signifies hydrogen; or a C.sub.1-4 alkyl radical, unsubstituted or 
substituted by phenyl, halogen, C.sub.1-4 alkoxy, phenoxy, C.sub.1-4 
alkylcarbonyloxy, phenylcarbonyloxy, cyano or 
N,N-di(C.sub.1-4)alkylcarbamoyl, 
either B signifies a 1,4-phenylene radical, and 
R'.sub.7 is in a position of said radical ortho to the --N.dbd.N-- group 
and signifies hydrogen; halogen; C.sub.1-4 alkyl or C.sub.1-4 alkoxy, 
or B signifies a naphthylene radical, preferably a 1,4-naphthylene radical, 
and 
R'.sub.7 signifies hydrogen; 
R'.sub.1 and R'.sub.2 which may be the same or different, each signifies 
hydrogen, phenyl, or C.sub.1-4 alkyl, 
Q' signifies an unsubstituted naphthyl radical, an unsubstituted phenyl 
radical, or a phenyl radical substituted by up to 5 halogen atoms or up to 
two substituents selecting from nitro; halogen; hydroxy; cyano; 
trihalomethyl; trifluoromethyl; alkyl or alkoxy of 1 to 4 carbon atoms, 
unsubstituted or substituted by phenyl or phenoxy; phenylazo; cyclohexyl; 
benzoyloxy; phenylcarbamoyloxy; a group --CORo, 
##STR24## 
--SO.sub.2 --Ro, --SO.sub.2 --NH--Ro, --SO.sub.2 --N(Ro).sub.2, 
--CO--NH--Ro, --CO--N(Ro).sub.2, O--CO--N(Ro).sub.2 or --NH--CO--Ro, in 
which Ro is as defined above; 
##STR25## 
in which X is as defined above, x signifies 1, 2 or 3, preferably 1; 
A.sup..crclbar. is as defined above, preferably a halide 
ZnCl.sub.3.sup..crclbar. methylsulfate ion or acetate ion. 
As will be appreciated, formulae (b) and (c), above, are isomeric forms of 
formula (a). For convenience, only one formula will be given hereinafter, 
it being understood to embrace the isomers. Mixtures of the isomers are 
obtained when producing the compounds. 
In the compounds of formula I', P preferably signifies a radical (a) or an 
isomer (b) or (c) thereof, a radical (d) or a radical (g). Most preferably 
P signifies a radical (a) or an isomer (b) or (c) thereof. 
In radical (a), or isomer (b) or (c) thereof, R.sub.8 preferably signifies 
an alkyl radical of 1 to 4, more preferably 1 or 2, carbon atoms, 
unsubstituted or substituted by phenyl, e.g. a benzyl radical, hydroxy, 
e.g. 2-hydroxyethyl and 2-hydroxypropyl, or the group --CONH.sub.2, e.g. 
2-carboxyamidoethyl (2-carbamoylethyl). R.sub.8 most preferably signifies 
a methyl radical. R.sub.9 preferably signifies an unsubstituted C.sub.1-4, 
more preferably C.sub.1-2, alkyl radical, or a C.sub.1-4, more preferably 
C.sub.1-2, alkyl radical substituted by phenyl, e.g. benzyl and 
phenylethyl, hydroxy, e.g. 2-hydroxyethyl and 2-hydroxypropyl, or the 
group --CONH.sub.2, e.g. 2-carbamoylethyl. Most preferably R.sub.9 
signifies a methyl radical. R.sub.10 preferably signifies a hydrogen atom, 
a phenyl radical, a cyclohexyl radical, an unsubstituted C.sub.1-4, more 
preferably C.sub.1-2, alkyl radical, or a C.sub.1-4 alkyl, more preferably 
C.sub.1-2, alkyl radical substituted by phenyl, e.g. a benzyl radical. 
R.sub.10 most preferably signifies a hydrogen atom. 
Where P signifies a radical (a), or an isomer (b) or (c) thereof, R'.sub.3 
preferably signifies an alkyl radical of 1 to 4 carbon atoms, 
unsubstituted or substituted by phenoxy, e.g. 2-phenoxyethyl, phenyl, e.g. 
benzyl, C.sub.1-4 alkoxycarbonyl, e.g. 2-ethoxy carbonylethyl, or 
phenylcarbonyloxy, e.g. 2-phenylcarbonyloxyethyl. R'.sub.3 more preferably 
signifies an unsubstituted C.sub.1-4 alkyl, particularly a methyl or 
ethyl, radical. Most preferably, R'.sub.3 signifies an ethyl radical. 
R'.sub.2 preferably signifies a hydrogen atom. R'.sub.1 preferably 
signifies a hydrogen atom, or a C.sub.1-4 alkyl radical, e.g. a methyl 
radical. R'.sub.1 most preferably signifies a hydrogen atom or a methyl 
radical, particularly a hydrogen atom. B preferably signifies a phenylene 
radical. R'.sub.7 preferably signifies a hydrogen atom, a C.sub.1-4 alkyl 
radical or a C.sub.1-4 alkoxy radical. More preferably R.sub.7 signifies a 
hydrogen atom or a methyl radical and, most preferably, signifies a 
hydrogen atom. Q' preferably signifies an unsubstituted naphthyl radical, 
preferably a 2-naphthyl radical, an unsubstituted phenyl radical or a 
phenyl radical substituted by up to 5 halogen atoms, preferably chlorine 
atoms, or by up to two substituents, which may be the same or different, 
selected from halogen, e.g. chlorine, nitro, cyano, phenylsulfonyl, 
--SO.sub.2 NH(C.sub.1-4 alk), preferably --SO.sub.2 NHCH.sub.3, --SO.sub.2 
N(C.sub.1-4 alk).sub.2, preferably --SO.sub.2 N(CH.sub.3).sub.2, 
##STR26## 
preferably 
##STR27## 
O--Co--N(C.sub.1-4 alkyl).sub.2, preferably 
##STR28## 
C.sub.1-4 alkoxy, preferably methoxy, phenoxy, phenylcarbonyloxy, 
phenylazo, phenylcarbonylamino, phenylaminocarbonyloxy, 
##STR29## 
preferably N,N-dimethylaminocarbonyloxy, N(C.sub.1-4 
alk)-N-phenylaminocarbonyloxy, preferably 
N-methyl-N-phenylaminocarbonyloxy, C.sub.1-4 alkylsulphonyl, preferably 
methylsulphonyl, di-(C.sub.1-4)alkylaminosulphonyloxy, preferably 
dimethylaminosulphonyloxy, trifluoromethyl, unsubstituted C.sub.1-4 alkyl, 
preferably methyl, or C.sub.1-4 alkyl substituted by phenyl, preferably 
benzyl. Where Q signifies a phenyl radical substituted by up to two such 
substituents it is generally only monosubstituted. Where Q is 
monosubstituted, the substituent is preferably in the para-position. The 
most preferred significances of Q' are 2-naphthyl, unsubstituted phenyl 
and phenyl substituted by up to 5 halogen atoms, preferably chlorine 
atoms. A.sup..crclbar. preferably signifies a Cl.sup..crclbar., 
ZnCl.sub.3.sup..crclbar., CH.sub.3 SO.sub.4.sup..crclbar., or acetate ion. 
x preferably signifies 1. 
Where P signifies a radical of formula (d), R.sub.11 preferably signifies 
an alkyl radical of 1 to 4, preferably 1 or 2, carbon atoms or an alkoxy 
radical of 1 to 4 carbon atoms, preferably a methoxy radical. R.sub.11 
most preferably signifies a methyl radical. R.sub.12 preferably signifies 
hydrogen, a C.sub.1-4 alkyl radical, preferably a methyl radical, 
C.sub.1-4 alkoxy radical, preferably a methoxy radical, or a halogen atom, 
preferably chlorine. R.sub.12 most preferably signifies hydrogen. q 
preferably signifies 1. R'.sub.3 preferably has a significance as given 
above, when P signifies (a), more preferably an alkyl radical or 1 to 4 
carbon atoms, most preferably a methyl or ethyl radical. R'.sub.2 
preferably signifies a hydrogen atom. R'.sub.1 preferably has a 
significance as given above, when P signifies (a), more preferably methyl 
or hydrogen, and most preferably a hydrogen atom. B preferably signifies a 
phenylene radical. R'.sub.7 preferably has a significance as given above, 
when P signifies (a), more preferably a hydrogen atom or an alkyl radical 
of 1 to 4 carbon atoms, e.g. methyl, most preferably hydrogen. Q' 
preferably has a significance as given above, where P signifies (a), more 
preferably an unsubstituted 2-naphthyl or phenyl radical, or a phenyl 
radical substituted by up to 5 halogen, preferably chlorine, atoms. 
A.sup..crclbar. preferably signifies Cl.sup..crclbar., 
ZnCl.sub.3.sup..crclbar., CH.sub.3.sup..crclbar. SO.sub.4 or an acetate 
ion, and x preferably signifies 1. 
Where P signifies a radical of formula (g), R.sub.8 preferably signifies an 
alkyl radical of 1 to 4, preferably 1 or 2, carbon atoms, unsubstituted 
or substituted by -CONH.sub.2, e.g. 2-carbamoylethyl. R.sub.8 more 
preferably signifies a methyl or ethyl radical, most preferably a methyl 
radical. R.sub.16 and R.sub.17, which may be the same or different, each 
preferably signify hydrogen; chlorine, C.sub.1-4 alkoxy, preferably 
methoxy, unsubstituted or substituted by phenyl, e.g. benzyloxy; C.sub.1-4 
alkylcarbonyl, preferably methylcarbonyl; C.sub.1-4 alkylaminocarbonyl, 
preferably methylaminocarbonyl; phenylcarbonylamino; C.sub.1-4 
alkylsulphonylamino, preferably methylsulphonylamino; phenoxy; 
di-C.sub.1-4 (di-C.sub.1-4 alkylsulfamoyl), preferably 
dimethylaminosulphonyl; or phenylsulphonyl, or R.sub.16 and R.sub.17 are 
on adjacent carbon atoms and form a --CH.dbd.CH--CH.dbd.CH-- linkage. Most 
preferably one of R.sub.16 and R.sub.17 signifies hydrogen, the other 
methoxy. R.sub.3 ' preferably has one of the significances given above, 
when P signifies (a), more preferably a methyl or ethyl radical. R.sub.2 ' 
preferably signifies a hydrogen atom. R.sub.1 ' preferably has a 
significance given above when P signifies (a), more preferably methyl or 
hydrogen. B preferably signifies a phenylene radical. R.sub.7 preferably 
has a significance given above, when P signifies (a), more preferably 
methyl or hydrogen, most preferably hydrogen. Q' preferably has a 
significance given above, where P signifies (a), most preferably an 
unsubstituted 2-naphthyl radical, an unsubstituted phenyl radical or a 
phenyl radical substituted by up to 5 halogen, preferably chlorine, atoms. 
X preferably signifies 1 and A.sup..crclbar. preferably signifies 
Cl.sup..crclbar., ZnCl.sub.3.sup..crclbar., CH.sub.3 
SO.sub.4.sup..crclbar. or an acetate ion. 
Thus, the preferred compounds of Formula I' when P is a group of Formula 
(g) are those where 
R.sub.8 is C.sub.1-4 alkyl or C.sub.1-4 alkyl substituted by carbamoyl, and 
each of R.sub.16 and R.sub.17 is independently hydrogen; C.sub.1-4 alkoxy; 
C.sub.1-4 alkoxy substituted by phenyl; C.sub.1-4 alkylcarbonyl; C.sub.1-4 
alkylcarbamoyl; benzamido; C.sub.1-4 alkylsulfonylamino; phenoxy or 
phenylsulfonyl or 
R.sub.16 and R.sub.17 taken together are --CH.dbd.CH--CH.dbd.CH--, 
especially those of this group wherein 
R.sub.1 ' is hydrogen or methyl, 
R.sub.2 ' is hydrogen, 
R.sub.3 ' is methyl or ethyl, 
R.sub.7 ' is hydrogen or methyl, 
B is 1,4-phenylene, 
Q is phenyl, naphthyl or phenyl substituted by 1 to 5 chloro substituents, 
and 
x is 1. 
Representative compounds of formula I' are those in which x signifies 1, 
R.sub.2 ' signifies hydrogen, R.sub.1 ' signifies a hydrogen atom or an 
alkyl radical of 1 to 4 carbon atoms, and P signifies a radical of the 
formula 
##STR30## 
in which R.sub.8 ' and R.sub.9 ', which may be the same or different, each 
signifies an alkyl radical of 1 to 4 carbon atoms, unsubstituted or 
substituted by phenyl, hydroxy or --CONH.sub.2 ; 
R.sub.10 ' signifies a hydrogen atom, an alkyl radical of 1 to 4 carbon 
atoms, a phenyl (C.sub.1-4)alkyl radical or a phenyl radical; 
a radical of the formula 
##STR31## 
in which R.sub.11 ' signifies C.sub.1-4 alkyl; 
R.sub.12 ' signifies hydrogen; halogen; C.sub.1-4 alkyl or C.sub.1-4 
alkoxy; 
a radical of the formula 
##STR32## 
in which R.sub.13 ' signifies hydrogen or an alkyl radical of 1 to 4 
carbon atoms, 
R.sub.1 ' is as defined above, and 
R.sub.14 ' signifies hydrogen; 
a radical of the formula 
##STR33## 
in which R.sub.8 ', R.sub.14 ' and R.sub.9 ' are as defined above, or a 
radical of the formula 
##STR34## 
in which either R.sub.16 ' and R.sub.17 ', which may be the same or 
different, each signifies hydrogen; C.sub.1-4 alkyl or C.sub.1-4 alkoxy, 
unsubstituted or substituted by phenyl or phenoxy; 
or R.sub.16 ' and R.sub.17 ' are on adjacent carbon atoms and are linked to 
form a --CH.dbd.CH--CH.dbd.CH-- linkage; and 
R.sub.8 ' is as defined above. 
Still further preferred compounds of formula I are the compounds of the 
formula I", 
##STR35## 
in which P' signifies a radical of formula 
##STR36## 
or an isomer thereof, 
##STR37## 
R.sub.53 signifies a hydrogen atom, a methyl radical, a phenyl radical or a 
benzyl radical. 
R.sub.54 and R.sub.55, independently, signify an unsubstituted alkyl 
radical of 1 to 4 carbon atoms, preferably a methyl or ethyl radical, or 
an alkyl radical of 1 to 4 carbon atoms substituted by a hydroxy radical 
or the group --CONH.sub.2, 
R.sub.57 signifies a hydrogen atom or an alkoxy radical of 1 to 4 carbon 
atoms, preferably a methoxy radical, 
R.sub.59 signifies an alkyl radical of 1 to 4 carbon atoms, preferably a 
methyl or ethyl radical, unsubstituted or substituted by the group 
--CONH.sub.2, 
R.sub.60 signifies an alkyl or alkoxy radical of 1 to 4 carbon atoms, 
preferably a methyl or ethyl radical, 
R.sub.62 signifies an alkyl radical of 1 to 4 carbon atoms, preferably a 
methyl radical, 
R.sub.63 signifies a hydrogen atom or a group (C.sub.1-4 alk).sub.2 
NSO.sub.2 --, preferably (CH.sub.3).sub.2 NSO.sub.2 --, 
R.sub.64 signifies an alkyl radical of 1 to 4 carbon atoms, preferably a 
methyl radical, 
R.sub.65 and R.sub.66, which may be the same or different, each signify an 
alkyl radical of 1 to 4 carbon atoms, preferably a methyl radical, 
B signifies a 1,4-phenylene radical, unsubstituted or substituted in the 
ortho position to the azo group by alkyl of 1 to 4 carbon atoms, 
preferably methyl, 
R.sub.50 signifies an alkyl radical of 1 to 4 carbon atoms, unsubstituted 
or substituted by phenyl, 
R.sub.51 signifies a hydrogen atom or an alkyl radical of 1 to 4 carbon 
atoms, preferably a methyl radical, 
Q" signifies an unsubstituted naphthyl, preferably a 2-naphthyl, radical, 
an unsubstituted phenyl radical, a phenyl radical substituted by up to two 
substituents, preferably one substituent, selected from hydroxy, halogen, 
preferably chlorine, C.sub.1-4 alkoxycarbonyl, preferably methoxycarbonyl, 
phenoxy, phenylcarbonyl, cyclohexyl, alkyl of 1 to 4 carbon atoms, 
preferably methyl, unsubstituted or substituted by up to three halogen 
atoms or by a phenyl radical; or Q" signifies a phenyl radical substituted 
by up to 5 halogen atoms, preferably chlorine atoms, and A.sup..crclbar. 
is as defined above, preferably chloride, ZnCl.sub.3.sup..crclbar., 
methylsulfate or acetate. 
In the compounds of formula I", P' preferably signifies a radical of 
formula (a"), (b") or (c"), most preferably a radical of (a"). 
Representative of the compounds of formula I" are the compounds of formula 
Ia", 
##STR38## 
in which R.sub.54 and R.sub.55 are as defined above, 
R.sub.50a signifies an unsubstituted alkyl radical of 1 to 4 carbon atoms, 
preferably a methyl, ethyl or butyl radical; 
R.sub.51a signifies hydrogen or a methyl radical, 
Q.sub.a " signifies an unsubstituted naphthyl radical, an unsubstituted 
phenyl radical, a phenyl radical substituted by up to two methyl radicals, 
a phenyl radical substituted by up to five halogen atoms, preferably 
chlorine atoms; or a 3-hydroxy-4-phenylcarbonylphenyl radical, and 
A.sup..crclbar. is as defined above, preferably a ZnCl.sub.3.sup..crclbar., 
Cl.sup..crclbar., CH.sub.3 SO.sub.4.sup..crclbar. or acetate ion. 
As examples of alkyl and alkoxy radicals of 1 to 4 carbon atoms may be 
given methyl, ethyl, n-propyl, isopropyl and n-butyl and the corresponding 
alkoxy radicals. Unless otherwise stated, the preferred such radicals are 
methyl, ethyl, methoxy and ethoxy, methyl and methoxy being most 
preferred. By the term halogen, as used herein, is meant chlorine, bromine 
and iodine; chlorine and bromine being preferred, chlorine being most 
preferred. 
The compounds of formula I are useful as dyes. They may be converted into 
dyeing preparations, e.g. into stable, liquid or solid dyeing 
preparations, in conventional manner, e.g. by grinding or granulating or 
dissolving in conventional dyestuff solvents, if necessary with the 
addition of assistants such as stabilizers. Such preparations may be 
produced, for example, in accordance with French Pat. Nos. 1,572,030 and 
1,581,900. 
The compounds of formula I may be used in the dyeing and printing of 
textile substrates, whether in fibre, yarn or fibric form, which consist 
of or comprise homopolymers or co-polymers of acrylonitrile or 
asymmetrical dicyanoethylene. The dyeing of such substrates may be carried 
out in conventional manner. 
The compounds of formula I may also be used for dyeing or printing 
substrates of synthetic polyamide or synthetic polyester fibres, modified 
by the introduction of acid groups. Polyamides of this type are described 
in Belgian Pat. No. 706,104 and polyester fibres of this type are 
described in U.S. Pat. No. 3,379,723. The dyeing of such substrates may be 
carried out in conventional manner. It is advantageous to dye in an 
aqueous, neutral or acid medium, at from 60.degree. C. to the boil or at 
temperatures above 100.degree. C. under pressure. 
The dyeings obtained with the compounds of formula I are level, have stable 
light fastness as well as good wet fastness properties, e.g. to washing, 
perspiration, sublimation, pleating, decatizing, pressing, steam, water, 
sea water, dry cleaning, crossdyeing and solvents. The dyes are well 
soluble in water, show good compatibility with salt, good stability to 
boiling, good pH stability and partly reserve fibres other than those on 
which they are dyeable. Further, they possess good power of build-up in 
combination with other basic dyes. 
The compounds, which have good solubility in organic solvents, may also be 
used for the dyeing of natural or synthetic resins in the mass, being 
incorporated therein in conventional manner, e.g. by intimate admixture 
therein, for example by milling, optionally with the use of a solvent. 
It has been found that mixtures of two or more of the compounds of the 
present invention or of one of the compounds of the present invention amd 
other cationic dyes can be used with advantage.