KR100432403B1 - Asymmetric Triphenylenedioxazine Compound - Google Patents

Abstract

The fiber-reactive asymmetric trifenodioxazine compounds according to the invention are present in the form of free acids or salts as compounds of formula (1) and mixtures thereof. They can be used to dye hydroxyl-containing or nitrogen-containing organic substrates, such as leather or fibrous materials consisting of or comprising natural or synthetic polyamides, or natural or regenerated cellulose, most preferably textiles comprising or comprising cotton; It is used as a reactive dye for printing.

[Formula 1]

Where

Substituents are as defined in claim 1.

Description

Asymmetric Triphenylenedioxazine Compounds

The present invention relates to asymmetric trifenodioxazine compounds containing fiber-reactive groups, methods for their preparation, and their use as fiber-reactive dyes in dyeing or printing processes.

The present invention seeks to provide an asymmetric trifenodioxazine compound which exhibits good fastness when used as a fiber-reactive dye.

The present invention provides, in one embodiment, a compound of Formula 1, a salt thereof, or a mixture thereof:

Formula 1

Where

T ₁ and T ₂ are independently of each other hydrogen, chlorine, bromine, C _1-4 alkyl, C _1-4 alkoxy or phenoxy;

X is -NR ₂ R ₃ or -NR ₁ -Z;

Each R ₁ is independently hydrogen, C _1-4 alkyl or substituted C _1-4 alkyl;

R ₂ and R ₃ are independently of each other hydrogen, C _1-4 alkyl, substituted C _1-4 alkyl or cyclohexyl; or

—NR ₂ R ₃ may additionally include one or two hetero atoms selected from oxygen, nitrogen and sulfur atoms and may also, for example, be amino, sulfo, hydroxyl, alkyl, alkoxy and halogen such as F , Cl or Br) is a 5- or 6-membered heterocyclic ring further substituted or unsubstituted by a group selected from;

R ₄ is hydrogen, halogen, C _1-4 alkyl, C _1-4 alkoxy or carboxyl;

W is an aliphatic, araliphatic, aromatic or cycloaliphatic diamino crosslinker;

Y is fluorine, chlorine or C _1-4 alkoxy;

Each Z is independently a heterocyclic fiber-reactive radical containing at least one labile fluorine or chlorine atom;

m is each independently 1 or 2.

Unless otherwise stated, each alkyl or alkylene group in this description may be linear or branched. In hydroxyl-substituted alkyl or alkylene groups attached to a nitrogen atom, the hydroxyl group is preferably attached to a carbon atom not directly bonded to the nitrogen atom. Each alkyl group may be methyl, ethyl, propyl or butyl; Propyl or butyl groups can be linear or branched. Each alkoxy group may be methoxy, ethoxy, propoxy or butoxy; Propoxy or butoxy groups can be linear or branched.

When halogen is used as a substituent on an alkyl or phenyl group, it can be a fluorine, chlorine or bromine atom, with chlorine being preferred.

T ₁ and T ₂ are preferably chlorine.

When R ₁ is a substituted alkyl group, it is preferably monosubstituted by hydroxyl, chlorine or cyano, preferably hydroxyl or chlorine.

Each R ₁ is preferably R _1a , wherein R _1a is each independently hydrogen, methyl, ethyl or 2-hydroxyethyl. More preferably R ₁ is R _1b , wherein R _1b is each independently hydrogen or methyl. In a particularly preferred embodiment, each R ₁ is hydrogen.

When R ₂ and R ₃ are independently substituted alkyl groups, they are preferably monosubstituted by hydroxyl, halogen, cyano, sulfo, sulfato or carboxyl, more preferably hydroxyl, sulfo or sulfato. .

Preferably, R ₂ and R ₃ are independently of each other R _2a and R _3a , wherein R _2a and R _3a are independently hydrogen, methyl, ethyl, 2-hydroxyethyl, 2-sulfoethyl and 2-sulphatoethyl Or -NR _2a R _3a is pyrrolidone, piperidine or morpholine, or

Wherein R ₅ is hydrogen, methyl, ethyl, 2-hydroxyethyl or 2-aminoethyl. More preferably R ₂ is R _2b , wherein R _2b is hydrogen, methyl, ethyl or 2-hydroxyethyl. Especially preferably, R ₂ and R ₃ are each hydrogen.

R ₄ is preferably R _4a , wherein R _4a is hydrogen, methyl, methoxy or carboxyl, in particular R ₄ is hydrogen.

Y is preferably Y ', where Y' is fluorine, chlorine or methoxy, preferably Y is Y ", where Y" is fluorine or chlorine.

When W is an aliphatic diamino crosslink, it is preferably derived from C _2-6 alkylenediamine which may be unsubstituted or substituted, in which case hydroxyl is a preferred substituent.

When W is an araliphatic diamino crosslinking, one or two substituents are unsubstituted or selected from the group consisting of C _1-4 alkyl, C _1-4 alkoxy, halogen, hydroxyl, sulfo and carboxyl. It is preferred to derive from the accompanying C _1-4 alkylenephenylenediamine.

When W is an aromatic diamino bridge, the phenylene radical is unsubstituted or carries one or two substituents selected from the group consisting of C _1-4 alkyl, C _1-4 alkoxy, halogen, hydroxyl, sulfo and carboxyl. Phenylenediamine or Q-linked diphenylenediamine, in which case Q is a direct bond or, for example, -CH = CH-, -CH ₂ CH _2- , -NH-, -NHCO- and -NHCONH- It is preferably a divalent bridging member selected from the group consisting of

When W is an alicyclic diamino bridge, it is preferably derived from unsubstituted or substituted piperazine. As substituents there may be mentioned C _1-4 alkyl, C _1-4 alkoxy, halogen (eg fluorine or chlorine), hydroxyl, sulfo and carboxyl.

W is preferably W 'wherein W' is -NR _1la -B ₁ -NR _1a- ,

Wherein the nitrogen atom indicated here is bonded to a carbon atom of the triazine ring and B ₁ is C _2-6 alkylene, C _3-6 hydroxyalkylene, phenylene, one or more, for example one or two Aryl groups containing sulfo substituents or araliphatic groups containing said sulfo-substituted aryl groups, preferably

Wherein the carbon atom indicated is bonded to a -NR _1a group linked to the carbon atom of the triazine ring, and R ₆ and R ₇ independently of one another are hydrogen, halogen, hydroxyl, C _1-4 alkyl, C _1-4 alkoxy , Carboxyl or sulfo).

R ₆ is preferably R _6a , wherein R _6a is hydrogen, hydroxyl, chlorine, methyl, methoxy, carboxyl or sulfo.

R ₇ is preferably R _7a , wherein R _7a is hydrogen, methyl, methoxy or sulfo.

B ₁ is preferably B _1a , wherein B _1a is C _2-3 alkylene, C _3-4 hydroxyalkylene or (Where the unspecified bond is a meta or para configuration), particularly preferably B _1b , wherein B _1b is Where the unspecified bond is a meta or para configuration.

When W is an aliphatic crosslinker, -NR _1b -B _1a -NR _1b , wherein B _1a has its aliphatic meaning, or

Is preferably. A - The most preferred group W is W "', wherein W"' is -NR _1b -B _1b -NR _1b.

The reactive radical Z is preferably Z ', where Z' is Monofluoropyrimidinyl radicals of general formula (a)

Is a radical of which Y ₁ is hydrogen, chlorine or cyano; the two Y ₂ groups are the same and each is fluorine or chlorine.

Z is more preferably Z ", wherein Z" is a general formula

Is a radical where Y ₁ ′ is hydrogen or chlorine.

X is preferably X '(where X' is -NR _2a R _3a or -NR _1a -Z '), more preferably X "(where X" is -NHR _2b or -NR _1b -Z " Most preferably -NH ₂ .

It is preferred that m is 1, in which case the sulfo group is preferably at one of the ortho positions for X or -NR ₁ -triazinyl.

In a preferred embodiment of the invention, there is provided a compound of formula 2, a salt thereof, or a mixture thereof:

[Formula 2]

Where

X ', Y ", W', Z 'and R _1b are as defined above.

More preferred in the compound of Formula 2

(1) R _1b is hydrogen;

(2) W 'is W ";

(3) the compound of (1) or (2), wherein Z 'is Z ";

(4) the compound of (3) wherein X 'is X ";

(5) the compound of (2) wherein W 'is W "';

(6) A compound of (5) wherein X 'is -NH ₂ .

The nature of the cations of the sulfo groups and any carboxyl groups additionally present in the compounds of formula (1) is not an important factor when the compounds of formula (1) are in the form of salts, and any preferred non-coloring cations customary in reactive dye chemistry Can be. The essential requirement is that the corresponding salts meet the solubility conditions in water.

Examples of suitable cations include alkali metal ions (eg lithium, sodium or potassium) or unsubstituted or substituted ammonium ions (eg ammonium, mono-, di-, tri- and tetramethylammonium, triethylammonium, and mono- , Di- and triethanol ammonium).

Preferred cations are alkali metal ions and ammonium, of which sodium and / or lithium are particularly preferred.

In general, in either compound of Formula 1, the cations of the sulfo group and any carboxyl group are the same or different and may consist of a mixture of the cations described above. That is, the compound may exist in the form of mixed salts.

In another embodiment, the present invention is characterized in that 1 mol of the compound of formula 3 or a salt thereof is reacted with at least 1 mol or at least 2 mol of the compound Z-Hal, wherein Z is as defined above and Hal is fluorine or chlorine. To provide a method of preparing a compound of Formula 1, a salt thereof or a mixture thereof:

[Formula 3]

Where

X _a is -NR ₂ R ₃ or -NR ₁ -H;

Other substituents are as defined above.

Compounds of formula (1) wherein X is -NR ₂ R ₃ can also be obtained by a method of reacting 1 mol of a compound of formula (4)

[Formula 4]

[Formula 5]

Where

Hal is fluorine or chlorine,

V ₁ is fluorine, chlorine or -WZ,

Y, W, and Z, R ₁ to R ₄ , T ₁ , T ₂ and m are as defined above.

If V ₁ is fluorine or chlorine, the product is subsequently condensed with the compound of the general formula HWZ.

The condensation reaction described above is preferably carried out in a medium having a pH in the range of slightly acidic to weakly alkaline. The temperature at which the amine is reacted with the halogen compound depends on the structure of the halogen compound, for example, a temperature of 50 to 80 ° C. is used when replacing a second chlorine atom of triazine, and a temperature of 0 to 20 ° C. is halopyri. Used for reaction with midines.

Compounds of formula (1) can be isolated by conventional methods, for example by salting the compounds out of the reaction mixture using alkali metal salts, filtering and drying at slightly elevated temperatures under reduced pressure.

Depending on the reaction and isolation conditions, the compound of formula 1 is obtained as a free acid or preferably in the form of a salt, or as a mixed salt comprising, for example, one or more of the above-mentioned cations. However, salts or mixed salts can also be prepared by conventional methods starting from the free acid and vice versa.

When reacted with Z-Hal, a fluorine- and / or chlorine-containing pyrimidine compound, the linkage of the cross-linker W and / or the NR ₁ radical with Z is not immobilized, i. Positional isomers are possible. Positional isomers are also formed by variable substitution in the tripenedioxazine ring backbone. The compound of formula 1 is thus obtained as a mixture of positional isomers depending on the position of the radical Z and with respect to the substitution in the ring skeleton. Separation into individual isomers can in principle be carried out by conventional methods, but generally is not necessary.

Starting compounds of formula (3) are obtained by reacting a compound of formula (6) with a diamine of formula H-W-H in a conventional manner:

[Formula 6]

Where

Substituents are as defined above.

Starting compounds of the formulas (4), (5) and (6) are known or can be prepared by known methods.

The compounds of formula (1) and mixtures thereof are reactive dyes, which are suitable for dyeing or printing hydroxyl-containing or nitrogen-containing organic substrates. Preferred substrates are leather and fibrous materials consisting of or comprising natural or synthetic polyamides, and in particular natural or regenerated cellulose such as cotton, filament viscose or staple viscose. Most preferred substrates are fabrics composed of or comprising cotton.

The compounds of formula (1), salts thereof or mixtures thereof may be used as the only dye in the dyeing solution or printing paste according to all dyeing or printing processes customary for reactive dyes. The dyeing is preferably carried out by an exhaust process from an aqueous medium in the temperature range of 30 to 100 ° C., in particular 50 to 60 ° C. or 80 to 100 ° C. The ratio (dye: base) of the dyeing solution is preferably 6: 1 to 30: 1, preferably 10: 1 to 20: 1.

Compounds of formula (1) provide good absorption and settling values. Part of the dye that is not fixed is easily washed off. The dyeings and printings obtained have good light fastnesses. They also have, for example, good wet fastness and sweat fastness against washing, water, sea water and the like and have good resistance to oxidation and chlorine-containing water, hypochlorite bleaching, peroxide bleaching and perborate-containing detergents. Dyestuffs are made in blue.

The particular yellow color in the dyeing process, given the surprising finding that the compound of formula (1) or a salt thereof, can be used not only as a sole dye in the dyeing or printing process, but also in a low salt concentration bath with good solubility. And dyeing properties (such as general fastness properties, exhaustion values, and solubility in salt baths of low salt concentration) together with the red dye may be used as a mixture comparable to the above use alone. The dyeings obtained provide comparable exhaustion and fixation values as described above for the sole dye.

Particularly preferred dyes from the dye mixtures mentioned above are obtained when the compound of formula 1 is combined with a yellow dye of formula 7 and a red dye of formula 8 below:

[Formula 7]

[Formula 8]

The dye components can be formulated in any desired ratio to obtain the color of the desired dyeing.

Accordingly, in another aspect of the present invention there is provided a dyeing composition comprising (A) a compound of formula 1, (B) a compound of formula 7 and (C) a compound of formula 8 or a salt thereof.

Dyeing using a mixture of the above-mentioned compounds is carried out at a temperature of 40 to 80 ° C., more preferably 50 to 60 ° C. and 0 to 80 g / l, preferably 0 to 50 g / l, more preferably 5 to 20 g / l. , Most preferably salts of 5 to 10 g / l (eg salts of Glauber) at a concentration using an extraction process from an aqueous medium. The ratio of the dyeing solution is preferably 6: 1 to 30: 1, more preferably 10: 1 to 20: 1.

The dyeings obtained from a salt bath comprising a mixture of the compounds of the formulas (1), (7) and (8) (so-called "tricolor salt baths") are blue-brown to brown depending on the relative proportions of the compounds 1, 7 and 8 in the mixture Reddish-brown.

The following examples illustrate the invention. Unless stated otherwise, parts and percentages are by weight and temperatures are expressed in degrees Celsius.

Example 1

140 parts of tripendioxazine compounds of the following formula (9) prepared as described in Example 1 of German Patent Application No. 40 05 551 are charged in 1800 parts of water. Lithium hydroxide is added to adjust the pH of the solution to 5-6. From 75 parts of 2,4-diaminobenzenesulfonic acid and 33 parts of 2,4,6-trifluoropyrimidine, 75 parts of a condensation product of the formula (10) prepared at pH 5 to 6 are added:

[Formula 9]

[Formula 10]

During the condensation reaction carried out at a temperature of 60-70 ° C., lithium hydroxide is added appropriately to maintain the pH at 5-6. After the reaction is completed, the dye formed is salted with sodium chloride, filtered off and dried at 50 ° C. under reduced pressure. The dye (free acid form) has the structure of Formula 11

[Formula 11]

The dye dyes cotton in dark blue shade with good wet fastness properties and high fixation yield.

60 parts of the condensation product of formula 10 are dissolved in 600 parts of water, the pH is maintained at 5 to 6 with lithium hydroxide and reacted with 40 parts of cyanuric chloride at 0 to 5 ° C. to obtain the same dye. The resulting intermediate of Formula 12 is condensed with 100 parts of 2,9-diamino-6,13-dichlorotriphenodioxazindisulfonic acid at 60-70 ° C. and pH 5-6. Additional lithium hydroxide is added to maintain this pH during the reaction. The dye of formula 11 is isolated by salting with sodium chloride, filtering and drying at 50 ° C. under reduced pressure.

[Formula 12]

Example 2

140 parts of the trifenodioxazine compound of the formula (9) used in Example 1 were added to 1800 parts of water. The pH is adjusted to 5-6 with lithium hydroxide. 20 parts of 1,3-diaminobenzene are added, and lithium hydroxide is added to heat the mixture to 60-70 ° C. while maintaining the pH at 5-6. After about 4 hours the reaction is complete. The reaction mixture is then cooled to room temperature and the resulting compound of formula 13 is reacted with 24 parts of 2,4,6-trifluoropyrimidine at 0-5 ° C. Lithium hydroxide is appropriately added to carry out the condensation reaction at pH 5-6. After the reaction is complete, the dye is salted out with sodium chloride, filtered and dried at 50 ° C. under reduced pressure. The dye produced in the form of the free acid has the structure of Formula 14 below.

[Formula 13]

[Formula 14]

The dye dyes cotton in dark blue shade with high fixation yield, and the dyeing has excellent wet fastness properties.

Example 3

The resulting dark blue reaction solution from Example 2, comprising a dye of formula 14, is further reacted with 34 parts of 5-chloro-2,4,6-trifluoropyrimidine. This condensation reaction is carried out at 15 to 20 ° C. while maintaining the pH of the solution at 7 to 8 using lithium hydroxide. After the reaction is complete, the dye is salted out with sodium chloride, filtered and dried at 50 ° C. under reduced pressure. The dye produced in the form of the free acid has the structure of Formula 15.

[Formula 15]

The dye dyes cotton with a reddish-blue tint with high fixation yield. These dyeings have good wet fastness properties.

Examples 4 to 94

The process described in Examples 1 to 3 can further be used to prepare the trifenodioxazine compounds according to the invention. They have the structure of formula 16 wherein the variables are listed in the table below. The sulfo groups in rings A and B are arranged at the ortho position of the radical X or triazinylamino radical (both positions are possible).

[Formula 16]

The diamines used to introduce the crosslinker W into the compound of formula 16 are listed in the W column. Bonding to the triazine ring and radical Z is in each case carried out via an amino group. For asymmetric diamines, no matter what role the synthetic route employed plays, each diamine can be attached to the triazine ring at either end.

In addition, the reactive radicals Z are represented by the symbols Z ₁ to Z ₄ having the following meanings:

Z ₁ is And Z ₃ is ego

Z ₂ is And Z ₄ is to be.

TABLE 1a

Compound of Formula 16

TABLE 1b

TABLE 1c

TABLE 1d

TABLE 1e

TABLE 1f

Table 1g

The dyes of Examples 4 to 94 dye cotton in reddish blue to dark blue shades. The dyeings obtained have very good fastness properties.

The method described above provides the dyes of Examples 1 to 94 as the sodium salt. Depending on the reaction and isolation conditions chosen, or by subsequent means, they can be prepared by conventional methods in the form of free acids or in the form of slightly different salts, or in the form of mixed salts, in which case for example the examples described further It contains one or more cations.

The dyes of the above examples (as free acid or in the form of any salts) are compounds in which unfixed fluorine or chlorine substituents are present in the 2-position of the pyrimidine ring when they involve one of the reactive radicals Z ₁ to Z ₃ And the corresponding compound in which this substituent is present at the 6-position.

In addition, the dyes of Examples 1 to 94 may be mixtures of positional isomers that are considered substituents in the trifenodioxazine ring backbone.

In general, it is preferable to use these synthesized isomer mixtures as such, so separation into individual isomers is not essential, but can be carried out in conventional manner, if necessary.

The absorption maximum λ _max for the dye example is expressed in nm. It was measured in an 8: 2 mixture of dimethylformamide and water.

TABLE 2

Application Example A

10 parts of bleached cotton, 0.3 parts of dye of Example 1 in 100 parts of deionized water and calcining ( V) in a salt bath containing 8 parts of glauber salt at 50 ° C. After standing at 50 ° C. for 30 minutes, 0.4 parts of calcined sodium carbonate was added while maintaining the temperature at 50 ° C. The temperature is raised to 60 ° C. and staining is continued at 60 ° C. for 1 hour. The dyed material is then washed with running cold water for 3 minutes and again with running hot water for 3 minutes. The dyeings are washed by boiling for 15 minutes in 500 parts of deionized water in the presence of 0.25 parts of Marseilles soap. After washing for 3 minutes with running warm water, the dyeings are centrifuged and dried at about 70 ° C. in a drying chamber. The product obtained is a dark blue cotton dyeing with very good fastness properties.

Application Example B

Ten parts of the bleached cotton material are placed in a salt bath comprising 5 parts of calcined glauber salt in 100 parts of deionized water. The salt bath is heated to 50 ° C. for 10 minutes and then 0.5 part of the dye of Example 1 is added. After leaving for 30 minutes at 50 ° C, 1 part of calcined sodium carbonate is added, the temperature is raised to 60 ° C, and the dyeing is continued for another 45 minutes at 60 ° C.

The dyed material is washed with running cold water as described in Application A and then with warm water and washed under boiling. After washing and drying, a dark blue cotton dyeing with very good fastness properties is obtained.

Application C

10 parts of bleached cotton is put in a salt bath containing 0.3 part of the dye of Example 1 and 1.5 parts of calcined glauber salt in 100 parts of deionized water at a temperature of 50 ° C. After standing at 50 ° C. for 30 minutes, 0.4 parts of calcined sodium carbonate was added little by little while maintaining the temperature at 50 ° C. The temperature is raised to 60 ° C. and staining is continued at 60 ° C. for 1 hour. The dyed material is then washed with running cold water for 3 minutes and again with running hot water for 3 minutes. The dye is washed by boiling in 500 parts of deionized water for 20 minutes. After washing for 3 minutes with running warm water, the dyeings are centrifuged and dried at about 70 ° C. in a drying chamber. The product obtained is a dark blue cotton dyeing with very good fastness properties.

Application Example D

10 parts of bleached cotton is placed in a salt bath consisting of 1 part of calcined glauber salt and 100 parts of deionized water. After heating the salt bath to 50 ° C. over 10 minutes, 0.3 parts of a dye mixture consisting of equal parts of the dye of Example 1, the dye of Formula 7 and the dye of Formula 8 is added. 1.0 part of calcined sodium carbonate is added to the salt bath at 50 ° C. over 30 minutes, and then the temperature of the salt bath is raised to 60 ° C. and dyed at this temperature for a further 45 minutes. The dyed cotton is washed with cold water flowing for 3 minutes as in the method of Application Example A, followed by washing with hot water flowing for 3 minutes, followed by boiling. After washing, the dyed cotton is dried at 70 ° C. to give a brown dye. After addition of the Glauber salt and sodium carbonate, the dyeing mixture shows the same color tone through the fixing process.

The method of application can be carried out by dyeing using dyes of other examples, or dye mixtures containing dyes of these other examples. When using the dye mixtures according to Application D, the resulting reddish blue to dark blue dyes or brown dyes have very good fastness properties.

Claims (9)

A compound according to formula 1, a salt thereof or a mixture thereof: Formula 1 Where T ₁ and T ₂ are independently of each other hydrogen, chlorine, bromine, C _1-4 alkyl, C _1-4 alkoxy or phenoxy; X is -NR ₂ R ₃ or -NR ₁ -Z; Each R ₁ is independently hydrogen, C _1-4 alkyl or substituted C _1-4 alkyl; R ₂ and R ₃ are independently of each other hydrogen, C _1-4 alkyl, substituted C _1-4 alkyl or cyclohexyl; or —NR ₂ R ₃ may additionally include one or two hetero atoms selected from oxygen, nitrogen and sulfur atoms and may also, for example, be amino, sulfo, hydroxyl, alkyl, alkoxy and halogen such as F , Cl or Br) is a 5- or 6-membered heterocyclic ring further substituted or unsubstituted by a group selected from; R ₄ is hydrogen, halogen, C _1-4 alkyl, C _1-4 alkoxy or carboxyl; W is an aliphatic, araliphatic, aromatic or cycloaliphatic diamino crosslinker; Y is fluorine, chlorine or C _1-4 alkoxy; Z is independently of each other Monofluoropyrimidinyl radicals of general formula (a) Is a radical of wherein Y ₁ is hydrogen, chlorine or cyano; two Y ₂ are the same and each is fluorine or chlorine; m is each independently 1 or 2. The method of claim 1, m is 1 each, R ₄ is each hydrogen, and T ₁ and T ₂ are each chlorine. The method according to claim 1 or 2, Compound having the formula Formula 2 Where X 'is -NR _2a R _3a or -NR _1a -Z'; Z 'is an expression Monofluoropyrimidinyl radicals of general formula (a) Is a radical of wherein Y ₁ is hydrogen, chlorine or cyano; two Y ₂ are the same and each is fluorine or chlorine; Y ″ is fluorine or chlorine; W 'is -NR _1a -B ₁ -NR _1a- , or Wherein the nitrogen atom indicated is bonded to a carbon atom of the triazine ring and B ₁ is a C _2-6 alkylene, C _3-6 hydroxyalkylene, phenylene, an aryl group containing one or more sulfo substituents, or the Araliphatic groups containing sulfo-substituted aryl groups, preferably or Wherein the carbon atom indicated is bonded to a -NR _1a -group linked to the carbon atom of the triazine ring, and R ₆ and R ₇ independently of one another are hydrogen, halogen, hydroxyl, C _1-4 alkyl, C _1-4 alkoxy , Carboxyl or sulfo); R _1b is hydrogen or methyl; R _1a is hydrogen, methyl, ethyl or 2-hydroxyethyl; R _2a and R _3a are independently of each other hydrogen, methyl, ethyl, 2-hydroxyethyl, 2-sulfoethyl or 2-sulphatoethyl, or -NR _2a R _3a is pyrrolidine, piperidine or morpholine or Wherein R ₅ is hydrogen, methyl, ethyl, 2-hydroxyethyl or 2-aminoethyl. A dye composition comprising a compound according to formula (1), a compound according to formula (7) and a compound according to formula (8), a salt thereof or a mixture thereof as defined in claim 1: Formula 7 Formula 8 A compound of formula 1 as defined in claim 1, characterized in that 1 mol of a compound of formula 3 or a salt thereof is reacted with at least 1 mol or 2 mol of compound Z-Hal, wherein Hal is fluorine or chlorine Or a process for the preparation thereof: Formula 3 Where X _a is -NR ₂ R ₃ or -NR ₁ -H; The remaining substituents are as defined in claim 1. Reacting 1 mol of a compound of Formula 4 or a salt thereof with 1 mol of a compound of Formula 5, and further condensing the product with a compound of Formula HWZ when V ₁ of Formula 5 is fluorine or chlorine A process for the preparation of a compound according to formula 1 as defined in claim 1 wherein X is -NR ₂ R ₃ : Formula 4 Formula 5 Where Hal is fluorine or chlorine; V ₁ is fluorine, chlorine or -WZ; Y, W, Z, R ₁ to R ₄ , T ₁ , T ₂ and m are as defined in claim 1. A dye-containing or nitrogen-containing organic substrate, preferably natural or synthetic polyamide, or natural or regenerated, characterized in that it is dyed or printed using the compound of formula (1) as defined in claim 1 or mixtures thereof. A method of dyeing or printing a leather or fibrous material consisting of or comprising cellulose, more preferably a fabric consisting of or comprising cotton. The method of claim 7, wherein A dyeing or printing method using a dye composition comprising a compound of formula 1, a compound of formula 7 as defined in claim 4 and a compound of formula 8 as defined in claim 4, salts thereof or mixtures thereof. A hydroxyl-containing or nitrogen-containing organic substrate dyed or printed according to the method of claims 7 or 8.