GB2216538A - Triphenodioxazine dyes with sulphonate ester groups - Google Patents

Abstract

Novel triphenodioxazine dyes of the formula: <IMAGE> wherein each of T<1> and T<2>, independently, represents H, C1, Sr, F SO3H or an optionally substituted alkyl or aryl radical; (A)n represents n substituents A each of which, independently, is lower alkyl, lower alkoxy, C1, SO3H or COOH and n is 0 or 1; R represents an optionally substituted hydrocarbon radical, preferably sulphonated aryl; R<1> represents hydrogen or an optionally substituted hydrocarbon radical; X represents O, S, or NR<2> wherein R<2> is H or optionally substituted alkyl; Y represents an optionally substituted alkylene, aralkylene or arylene radical, and Z represents an aromatic radical devoid of cellulose-reactive groups, preferably a diaminotriazinyl radical whereof one of the amino groups is alphatic or cycloaliphatic and the other is sulphonated arylamino. The dyes preferably contain at least two SO3H groups. The dyes impart bright blue shades to celluloisic substrates, esp paper.

Description

TRIPHENODIOXAZINE DYES This invention relates to triphenodioxazine dyes, to methods for their manufacture and to their use for dyeing cellulosic substrates.

According to the invention, there are provided triphenodioxazine dyes of the formula:

T1 and T2 wherein each of T and T , independently, represents H, Cl, Br, F, SO3H or an optionally substituted alkyl or aryl radical; (A) n represents n substituents A each of which, independently, is lower alkyl, lower alkoxy, Cl, SO3H or C00H and n is 0 or 1; R represents an optionally substituted hydrocarbon radical; R1 represents hydrogen or an optionally substituted hydrocarbon radical; 2 2 X represents 0, S, or NR wherein R is H or optionally substituted alkyl; Y represents an optionally substituted alkylene, aralkylene or arylene radical, and Z represents an aromatic radical devoid of cellulose-reactive groups.

The terms "lower alkyl" and "lower alkoxy" as used herein refer to alkyl and alkoxy groups having from 1 to 6 carbon atoms.

In general, lower alkyl and lower alkoxy groups having from 1 to 4 carbon atoms are preferred.

Preferred dyes contain at least two S03H groups.

Examples of optionally substituted alkyl radicals which may be represented by T1 and T2 particularly include lower alkyl radicals. Examples of optionally substituted aryl radicals which may be so represented particularly include optionally substituted phenyl radicals, for example phenyl, sulphophenyl, methylphenyl, dimethylphenyl, disulphophenyl, methoxyphenyl, dimethoxyphenyl, chlorophenyl, dichlorophenyl, methylchlorophenyl, methoxymethylphenyl, methoxychlorophenyl, aminophenyl and acetylaminophenyl. It is preferred that T1 and T2 are both chlorine.

In the groups (A)n, n is preferably 0 but when n is 1, A is preferably S03H.

The optionally substituted hydrocarbon radicals represented by R and R1 include optionally substituted alkyl, cycloalkyl, aralkyl and aryl radicals. In the case of R, the preferred radicals are optionally substituted aryl radicals, especially sulphonated aryl radicals, for example those mentioned with reference to T1 and T2.

As examples of atoms or groups represented by R1 there may be mentioned H, methyl, ethyl, phenyl, 3- and 4-nitrophenyl, 3- and 4-sulphophenyl, benzyl, 3- and 4-sulphobenzyl, CH2S03H, beta-hydroxyethyl and beta-sulphatoethyl.

X is preferably NR2 and R2 is preferably hydrogen.

The radicals represented by Y are preferably alkylene or aralkylene radicals and as typical examples there may be mentioned ethylene, 1,2- and 1,3-propylene, 2-hydroxy-1,3-propylene, 1- and 2-phenyl-1,3-propylene, 2-(4' -sulphophenyl)-1 ,3-propylene, 1,4-, 2,3and 2,4-butylene, 2-methyl-1 ,3-propylene, 2-methyl-2,4-pentylene, 2, 2-dimethyl-1 ,3-propylene, -1-phenylethylene, 1-chloro-2 ,3-propylene, 1,6- and 2,5-hexylene, 2,3-diphenyl-1,4-butylene, 1 (methoxycarbonyl) - 1,5-pentylene, 1-carboxy-1,5-pentylene, 2,7-heptylene, 3-methyl1,6-hexylene, -CH2CH2OCH2CH2-, -CH2CH2SCH2CH2-, -CH2CH2SS CH2CH2-,

R1 may be linked to both nitrogen atoms in the structure:: ,NOR1 - Y - NR2-. As examples of such a grouping there may be mentioned

Y is preferably a linear or branched chain alkylene radical containing from 2 to 6 carbon atoms and optionally containing one or more hydroxy or alkoxy substituents, for example an ethylene or propylene group optionally containing one hydroxy or methoxy substituent.

The aromatic radical represented by Z is preferably an aromatic nitrogen heterocycle.

Suitable aromatic nitrogen heterocycles devoid of cellulose-reactive groups include quinoxaline systems, pyrimidine systems and pyridine systems. Especially preferred groups Z however are triazine groups containing no cellulose-reactive substituents.

The group Z may be unsubstituted, but preferably contains one or more non-reactive substituents. Suitable non-reactive substituents are amino groups, optionally substituted alkyl or aryl amino groups, acylamino groups, hydroxyl groups, alkylthio and arylthio groups and alkoxy and aryloxy groups.

Preferred forms of these groups include lower (i.e. C1 4) 1-4 alkoxy, e.g. methoxy, ethoxy, n-propoxy and iso-propoxy, butoxy and lower alkoxy lower alkoxy, e.g. beta-methoxy-ethoxy, beta-ethoxyethoxy; phenoxy and sulphophenoxy; amino lower alkylamino, e.g.

methylamino, ethylamino, butylamino, di(lower alkyl) amino, e.g.

dimethylamino, diethylamino, methylethylamino, dibutylamino and groups of the latter two types in which the alkyl groups are substituted in particular by OH, CN or S03H, e.g. beta-hydroxyethylamino, di(beta-hydroxyethyl)amino, beta-cyanoethylamino, di(beta-cyanoethyl)amino, beta-sulphoethylamino, beta-hydroxypropylamino, (beta-hydroxybutyl)ethylamino and (beta-hydroxyethyl) methylamino; cycloalkylamino, e.g. cyclohexylamino; cyclic amino, e.g. morpholino or piperazino; naphthylamino substituted by 1, 2 or 3 S03H groups and optionally substituted phenylamino groups.

As a particularly preferred form of the optionally substituted phenylamino groups there may be mentioned groups of the formula:

where G is H, methyl, ethyl, w -sulphomethyl, beta-carboxyethyl, beta-hydroxyethyl or beta-cyanoethyl; and U and V are each independently selected from H, C00H, S03H, CH3, C2H5, OCH3, OC2H5, Cl, Br, CN, N02, NHCOCH3, NH2, phenylamino and methylamino.

As specific examples of such groups there may be mentioned anilino, o-, m- or -sulphoanilino, o-, m- and -carboxyanilino, 4- and 5-sulpho-2-carboxyanilino, 4- and 5-sulpho-o-tolylamino, 2,4-, 2,5- and 3,5-disulphoanilino, 2,4-dicarboxyanilino, 4- and 5-sulpho-2-methoxyanilino, N-methyl-o-, m- and p-sulphoanilino, N- -sulphomethylanilino, N- (beta-hydroxyethyl) -3-sulphoanilino.

An especially preferred group Z is the triazine group of formula (II):

wherein S and S may be independently hydrogen or any of the non-reactive substituents described above. It is usually preferred 1 2 that one of S and S is an arylamino especially a sulphonated arylamino and that the other is a non aryl group e.g. OH, NH2, optionally substituted primary or secondary alkylamino or a cyclo aliphatic amino group such as cyclohexylamino, morpholino or piperidino.

Preferred sulphonated arylamino groups are sulphoanilino groups, the group 3-sulphoanilino- (derived from metanilic acid) being especially preferred. Thus an especially preferred group Z is:

wherein S is preferably an aliphatic amino group, for example a primary or secondary alkyl amino group containing a total of from 1 to 8 carbon atoms, or a cyclic aliphatic amino group such as morpholino- or piperidino-. The alkyl groups may be substituted preferably by OH.

The invention further provides a process for the manufacture of dyes of formula (1) which comprises reacting the corresponding dyebase (i.e. a compound of formula I wherein both symbols Z now represent hydrogen and the other symbols have the meanings given above) with an aromatic ring heterocycle which contains at least one halogen atom attached to a carbon atom of the heterocyclic nucleus, followed by the subsequent conversion of any residual cellulose-reactive groups to non-reactive groups.

Thus the aromatic ring heterocycle may possess a single halide group and the desired non-reactive groups, in which case the dyestuff of the present invention is manufactured directly.

Preferably, however the aromatic ring heterocycle possesses two or three halide groups so that the first stage of the manufacture is the reaction of the dyebase with one of the halide groups of the aromatic ring heterocycle followed by subsequent conversion of the remaining one or two halide groups to the desired non-reactive groups.

For example, if the group Z in the dye is the triazine group of formula (II) having non-reactive substituents S and S2, the dye may be prepared by reaction of the dyebase with cyanuric chloride followed by reaction of the first remaining chloride group with the appropriate nucleophile S (i.e. the appropriate amine, alcohol, thiol, etc. or water or ammonia) to form the group S under relatively mild conditions, followed in turn by the reaction of the second remaining chloride group under more forcing conditions with 2 the appropriate nucleophile to form the group S2. Preferably, however the dye is prepared by reaction with a triazine derivative from cyanuric chloride in which one of the chloride atoms has been replaced by the appropriate group S .The one remaining halogen atom in the product is then replaced by reaction with the appropriate nucleophile to form the substituent Reaction of the dyebase with the aromatic ring heterocycle can conveniently be carried out by stirring a mixture of the reactants in an aqueous medium at a suitable temperature which may for example be from OOC to 600C. Subsequent reaction of remaining halogen atom(s) with the appropriate nucleophile(s) will in general take place under more forcing conditions, for example at a temperature of from 300C to 1000C. It is generally preferred to add an acid-binding agent during the course of the reaction to maintain the pH within the limits 8 to 11.

The dyebase (the compound of formula (I) wherein both symbols Z now represent hydrogen and the other symbols have the meanings given above) may itself be prepared by reacting 2,3,5,6-tetrachloro-1,4-benzoquinone (or a corresponding compound wherein T1 and T2 have the other meanings given above) with 2 moles of a diamine of the formula:

and heating the resulting dianilide in the presence of a strongly acid condensing agent, for example oleum, to effect ring closure.

The dyes prepared as described above may be isolated by any conventional means, for example by spray drying or precipitation and filtration. The dyes contain sulphonic acid groups which confer water-solubility and they may be isolated with such groups in the free acid form. However, it is usually found more convenient to isolate the dyes in the form of salts particularly alkali metal salts, especially sodium.

The dyes of the present invention are water-soluble dyes useful for the coloration of cellulosic materials, especially paper on which they give attractive and bright blue shades with or without the use of size. Because of their high tinctorial strength, the amount of dye used to achieve quite deep shades is small, resulting in relatively economic dyeing. The light fastness and fastness to food solvents such as milk and cooking oil of the dyed paper is excellent.

Claims (2)

1. Triphenodioxazine dyes of the formula:

T1 and T2 wherein each of T and T , independently, represents H, Cl, Br, F, S03H or an optionally substituted alkyl or aryl radical; (A) n represents n substituents A each of which, independently, is lower alkyl, lower alkoxy, Cl, SO3H or COOH and n is 0 or 1; R represents an optionally substituted hydrocarbon radical; R1 R1 represents hydrogen or an optionally substituted hydrocarbon radical; 2 2 X represents 0, S, or NR wherein R is H or optionally substituted alkyl; Y represents an optionally substituted alkylene, aralkylene or arylene radical, and Z represents an aromatic radical devoid of cellulose-reactive groups.

2. A method of dyeing paper which comprises applying thereto a triphenodioxazine dye as defined in claim 1.