Basic dyestuffs free of sulphonic acid groups contain an indoline group the 2-position of which is connected through a vinylene group to the N-atom of a 2,3-dihydro-4H-1,4-benzoxazine group. The dyestuffs are useful for the dyeing of leather, paper and plastics and, particularly, polyacrylonitrile or acid-modified polyester fibres.

This invention relates to basic dyestuffs free of sulphonic acid groups. 
The invention provides compounds of formula I 
##STR1## 
in which R is--hydrogen; halogen; cyano; nitro; C.sub.1-4 alkyl which is 
unsubstituted or mono-substituted by phenyl, monochlorophenyl or mono 
(C.sub.1-4 alkyl)phenyl; C.sub.1-4 alkoxy which is unsubstituted or 
mono-substituted by phenyl; phenoxy; acetyl or di-(C.sub.1-4 
alkyl)sulphonylamino, 
R.sub.o --is hydrogen, C.sub.1-4 alkyl or C.sub.1-4 alkoxy, or 
R and R.sub.o together form a group of formula --O--CH.sub.2 --O--, 
--O--CH.sub.2 --CH.sub.2 --O--, --O--CH.sub.2 --O--CH.sub.2 --, 
--CH.sub.2).sub.4 or --CH.sub.3).sub.3, in which the asymmetric 
--O--CH.sub.2 --O--CH.sub.2 -- group may be connected in either of both 
possible ways, 
R.sub.1 --and R.sub.2 are independently linear C.sub.1-4 alkyl, 
R.sub.3 --is allyl, unsubstituted C.sub.1-4 alkyl or C.sub.1-4 alkyl 
monosubstituted by hydroxy, phenyl, carbonamido, cyano or C.sub.1-4 
alkoxy, 
R.sub.4 --is hydrogen, cyano, carboxyl, C.sub.1-4 alkyl, carbonamido or 
--COO--(C.sub.1-4)alkyl, 
D--is a group of formula II or III 
##STR2## 
in which R.sub.5 is hydrogen, C.sub.1-4 alkyl, phenyl unsubstituted or 
substituted by one or two groups selected from methoxy, chloro, methyl or 
dimethylamino, or --COO--(C.sub.1-4 alkyl), 
R.sub.6 and R.sub.8 are independently hydrogen or C.sub.1-4 alkyl, 
R.sub.7 is hydrogen, C.sub.1-4 alkyl, phenyl or --COO--(C.sub.1-4 alkyl), 
or 
R.sub.7 and R.sub.5 together with the carbon atoms to which they are 
attached form an unsubstituted cyclopentyl or cyclohexyl ring, 
R.sub.9 is hydrogen, halogen, C.sub.1-4 alkyl, C.sub.1-4 alkoxy, amino, 
di(C.sub.1-4 alkyl) amino, C.sub.2-5 acylamino, --NH--SO.sub.2 
--(C.sub.1-4 alkyl), --NH--SO.sub.2 --phenyl or a benzoylamino group 
unsubstituted or substituted by one or two chlorine atoms or one or two 
C.sub.1-4 alkyl groups, 
X is oxygen or sulphur, and 
A is an anion. 
Preferred significances of the groups R-R.sub.10 and X are as follows: 
R: hydrogen, halogen, unsubstituted alkyl, unsubstituted or 
phenyl-substituted alkoxy, phenoxy or dialkylsulphonylamino 
R.sub.o : hydrogen 
R.sub.4 : hydrogen 
R.sub.5 : hydrogen, alkyl or phenyl 
R.sub.7 : hydrogen, alkyl or phenyl 
R.sub.9 : hydrogen, halogen, alkyl, alkoxy, amino-, di-alkylamino, 
acylamino, or benzoylamino; more preferably hydrogen, amino, acylamino or 
alkoxy. 
X: oxygen. 
By halogen is meant fluorine, chlorine, bromine and iodine, preferably 
chlorine. 
Where any of R, R.sub.1, R.sub.2, R.sub.6, R.sub.7, R.sub.8 and R.sub.9 are 
alkyl, they are, independently, preferably methyl. Where R is alkoxy it is 
preferably methoxy, where R is phenyl-substituted alkoxy it is preferably 
benzyloxy, and where R is dialkylsulphonylamino it is preferably 
dimethylsulphonylamino. 
Where R.sub.3 is alkyl it is preferably methyl, ethyl or propyl, and where 
R.sub.3 is substituted alkyl it is preferably 2-hydroxyethyl, 
2-hydroxypropyl, 2-cyanoethyl or 2-carboxamidoethyl. 
Where R.sub.5 is alkyl it is preferably methyl or ethyl, more preferably 
methyl. 
Where R.sub.9 is alkoxy it is preferably methoxy, and where R.sub.9 is 
acylamino it is preferably acetylamino. 
Preferably R is R.sub.a where R.sub.a is hydrogen, chloro, methyl, methoxy, 
phenoxy, benzyloxy or dimethylsulphonylamino, more preferably R.sub.b 
where R.sub.b is hydrogen, chloro or methoxy. 
R.sub.3 is preferably R.sub.3a where R.sub.3a is methyl, ethyl, propyl, 
allyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl or 
2-carboxamidoethyl, more preferably methyl. 
R.sub.5 is preferably R.sub.5a where R.sub.5a is hydrogen, methyl ethyl or 
phenyl, more preferably R.sub.5b where R.sub.5b is hydrogen, methyl or 
phenyl. 
R.sub.6 and R.sub.8 are preferably R.sub.6a and R.sub.8a where R.sub.6a and 
R.sub.8a are independently hydrogen or methyl, more preferably hydrogen. 
R.sub.7 is preferably R.sub.7a where R.sub.7a is hydrogen, methyl or 
phenyl, more preferably R.sub.7b where R.sub.7b is hydrogen or methyl. 
R.sub.9 is preferably R.sub.9a where R.sub.9a is hydrogen, chloro, methyl, 
methoxy, ethoxy, amino, acetylamino, dimethylamino or benzoylamino, more 
preferably R.sub.9b where R.sub.9b is hydrogen, amino, acetylamino or 
methoxy. 
A preferred group of compounds of formula I are those of formula IV 
##STR3## 
in which R.sub.a and R.sub.3a are as defined above, and D.sub.1 is a group 
of formula II.sub.a or III.sub.a 
##STR4## 
in which R.sub.5a, R.sub.6a, R.sub.7a, R.sub.8a and R.sub.9a are as 
defined above. 
Particularly preferred are those of formula V 
##STR5## 
in which R.sub.b, R.sub.5b, R.sub.7b and R.sub.9b are as defined above. 
The invention also provides a process for the preparation of compounds of 
formula I characterized by (A) the reaction of a compound of formula VI 
##STR6## 
with a compound of formula VII or VIII 
##STR7## 
in the presence of an acid of formula HA, or (B) the reaction of a 
compound of formula IX 
##STR8## 
with a compound of formula X or XI 
##STR9## 
in which Z is =O, =N--R.sub.11, or =N.sup..sym. HR.sub.11 A.sup..crclbar., 
and R.sub.11 is hydrogen 
or C.sub.1-4 alkyl, 
in the presence of a Lewis acid. 
Process variant (A) may be carried out in conventional manner, for example 
in water or organic solvents or a mixture thereof at a temperature from 
room temperature to 80.degree. C., preferably 50.degree.-70.degree. C. 
Preferably the acid used is hydrochloric acid. Process variant (B) is also 
conventional and may be carried out in an organic solvent, for example 
chlorobenzene or toluene, from room temperature to 80.degree. C., 
preferably at 50.degree.-70.degree. C. Preferred Lewis acids are 
phosphorus oxychloride and aluminium chloride. 
The compounds of formulae VI and IX are known, and those of formulae VII, 
VIII, X and XI are either known (for example from German Patent 2 234 468) 
or may be prepared in analogous manner to known compounds. 
The anion A.sup..crclbar. in compounds of formula I may be a 
non-chromophoric organic or inorganic anion, for example chloride, 
bromide, sulphate, bisulphate, methylsulphate, aminosulphate, perchlorate, 
lactate, succinate, tartrate, malate, methane sulphonate or benzoate; or 
may be a complex anion for example of boric, citric, glycollic, 
diglycollic or adipic acids. 
The anion A.sup..crclbar. may be exchanged for other anions for example 
with the aid of an ion-exchange resin or by reaction with salts or acids. 
Such reaction may take place in more than one step, for example through 
the hydroxide or bicarbonate, or according to French Pat. Nos. 2 028 725 
or 2 028 726. 
The compounds of formula I are dyestuffs and are useful for the dyeing of 
cationically dyeable substrates such as leather, paper and plastics, and 
particularly for the dyeing or printing of textile substrates containing 
or consisting of fibres of homopolymers or copolymers of acrylonitrile or 
asymmetric dicyanoethylene, or of acid-modified polyamides or polyesters. 
Such polyamides and polyesters are described in Belgian Pat. No. 706 104 
and U.S. Pat. No. 3 379 723 respectively. 
The compounds may be worked up by conventional means into solid or liquid 
compositions, for example by granulation or by dissolving in a suitable 
solvent, optionally in the presence of additives such as stabilisers or 
solubilising agents such as urea. Such preparations may be obtained for 
example as described in French Pat. Nos. 1 572 030 and 1 581 900 or German 
patent publications 2 001 748 and 2 001 816. 
Textile material may be dyed in neutral or acidic aqueous media at 
temperatures of from 60.degree.-100.degree. C. at atmospheric pressure or 
at temperatures over 100.degree. C. under pressure. Alternatively, dyeing 
may be carried out in organic solvents, for example as described in German 
patent publication No. 2 437 549. 
The dyeings obtained from compounds of formula I on the above substrates 
show good light fastness. The dyestuffs have good compatibility with other 
basic dyes, and have advantageously low compatibility numbers (K-values). 
The dyes have good exhaust power on the above substrates, giving dyeings 
with good fastness to washing, sweat, sublimation, pleating, decatising, 
ironing, water, seawater, dry cleaning, overdyeing and solvents. The 
dyestuffs are resistant to hydrolysis, have good water solubility and give 
deep level dyeings.