DE2600490A1 - REACTIVE COLORS - Google Patents

Description

PATENT LAWYERS

DR.-ING. H. FINCKE DIPL-ING. H. BOHR DIPL.-ING. S. STAEGER Dr.rer.nat.R.Kneißl

8 Mönchen s, January 8, 1976 Müllerstrasse 31 Fernruf: (089) * 266060 Telegrams: Claims Munich Telex: 523903 Claim d

Folder 23901 - Dr. K / by ICI Case Dd. 27546

IMPERIAL CHEMICAL INDUSTRIES LTD. London, UK

Reactive dyes

Priority: 13-1.75 - Great Britain

The invention relates to reactive dyes, in particular to reactive dyes of the 6,13-dichlorotriphendioxazine series, which have fluorotriazine groups.

According to the invention, dyes of the formula:

_D 7

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7600490 4

suggested, in which D stands for the remainder of a colored compound of the 6,13-dichlorotriph.endioxaziii series, η stands for 1 or 2, R is an optionally substituted amino group, an optionally etherified hydroxyl group, an optionally etherified thiol group or an optionally substituted hydrocarbon group

is radical and R 'is a hydrogen atom or an optionally substituted alkyl radical. The N-atoin, which connects D and the triazine ring, is preferably bonded to a carbon atom in D, although it can also be bonded via other groups such as SOo ₁ .

The substituents on the group R can include atoms or groups reactive with cellulose. With the phrase "with cellulose reactive "means that these groups can react with cellulose to form a covalent bond.

It is usually desirable that the dye molecule as a whole contains at least one sulfonic acid group, and it is usually preferred that a sufficient number of sulfonic acid groups be present so that the dye, Sufficient water solubility is granted, especially in the presence of alkalis.

Examples of R 'are C ^ _ ^ - alkyl groups, especially methyl, and substituted alkyl groups such as sulfomethyl

η or hydroxyethyl. In general, it is preferred that Ή.

stands for hydrogen.

Examples of the groups R are the following groups. In the case of substituted amino groups, this includes class for example mono- and dialkylamino groups, in which the alkyl groups preferably contain at most 4 carbon atoms, where there may also be substituents, such as hydroxyl or alkoxy groups, and phenylamino and eaphthylamino groups, the preferably sulfonic acid substituents

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b υ υ 4 ο υ

keep. In the case of substituted hydroxyl or thiol groups this class includes, for example, alkoxy and alkylthio groups, and preferably those with a low molecular weight, i.e. those with up to 4 carbon atoms, and phenoxy, phenylthio, naphthoxy or naphthylthio groups.

As specific examples of each of these classes, the following are intended are mentioned: methylamino, ethylamino, dirnethylami— no, ß-hydroxyethylamino, di- (ß-hydroxyethyl) amino, ß-chloroethylamino, Cyclohexylamino, anilino, sulfophenylamino, disulfophenylamino, N-Methylsulfophenylamino, N-ß-Hydroxyäthylsulfophenylamino, Mono-, di- and trisulfonaphthylamino, suIf oo-tolylamino, Carboxyphenylamino and sulfocarboxyphenylamino, N-w-sulfomethylphenylamino, methoxy, ithoxy and butoxy, phenoxy, Methylphenoxy and chlorophenoxy and phenylthio.

Examples of E, provided it is an optionally substituted hydrocarbon radical are alkyl groups such as methyl or ethyl, substituted alkyl groups such as trichloromethyl, Aryl groups such as phenyl or substituted aryl groups such as sulfophenyl or chlorophenyl.

The groups R can also carry groups or atoms with Cellulose are reactive. It should be noted that such groups or atoms in addition to the F atom of the formula (1), which is also an atom reactive with cellulose, may be present. For example, group E can be a Be alkoxy, aryloxy, alkylamino or arylamino groups, in which the alkyl or aryl group is optionally substituted, for example by a sulfonic acid group, and an -NH group have, which directly 'or through a CO group to a homocyclisch.es, heterocyclisch.es or mixed homocyclischheterocyclisches Is bonded free-radically, the at least one bonded to the core, cellulose-reactive substituent having.

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ORIGINAL INSPECTED

Examples of this are the following:

2,2,5,3-tetrafluorocyclobutylcarbonyl, 2,3,3-trifluorocyclobutenylcarbonyl, 2,2,3,3-tetrafluorocyclobutyl acryloyl, 2,3-dichlorochinoxaline-5- or -6-sulfonyl, 2,3-Dichlorocliinoxalin-5- or -6-carbonyl, 2,4-dichloroquinazoline-6- or -7-sulfonyl, 2,4,6-trichloroquinazoline-7- or -8-sulfonyl, 2,4,7- or 2,4,8-trichloroquinazoline-6-sulfonyl, 2,4-dichloroquinazoline-6-carboriyl,

1, ^ - dichlorophthalazine-G-carbonyl,

4,5-dichloropyridaz ~ 6-on-1-yl,

2,4-difluoro-5-chloropyrimid-6-yl,

2, ^ - dichloropyrimidine - ^ - carbonyl,

2-methylsulfonyl-5> -chloro-6-methylpyrimid-4-yl, 4- (4 ', 5'-dichloropyridaz-6'-one-1'-yl) benzoyl, 4 ~ (^' j 5 '-dich .loropyridaz-6'-one-1'-yl) phenylsulfonyl, and in particular s-triazin-2-yl and pyrimidin-2-yl or -4-yl radicals, which are attached to at least one of the remaining 2-, 4- and 6-positions have the following: a bromine or preferably a chlorine atom, a sulfonic acid group, a Thiocyana.to group, an aryloxy or arylthio group which contains an electronegative substituent, such as

Sulfophenoxy, sulfophenylthio, nitrosulfophenoxy, disulfophenoxy and sulfonaphthoxy; or a group of the formula: '

- ^s - <(V ¹ (2)

where Y is a group of atoms which form a 5- or 6-membered heterocyclic ring is capable, which can carry substituents or form part of a fused ring system; .or a quaternary ammonium or Pyridinium group; or a group of the formula:

609829/0843

-S-C-If

2 5
where R and R each represent the same or different alkyl,

2 5 cycloalkyl, aryl or aralkyl groups or R and R ^ together with the nitrogen atom form a 5- or 6-membered heterocyclic ring; or a group of the formula:

wherein R and Έ / can be the same or different and each represent a hydrogen atom or an alkyl, aryl or aralkyl group.

In those cases where the pyrimidine ring or the triazine ring Bearing only one such reactive substituent, the ring may have a non-reactive substituent on the remaining ones Have carbon atoms.

A non-reactive substituent is a group formed by, a covalent bond is bonded to a carbon atom of the triazine or pyrimidine nucleus, this covalent bond is not broken under the conditions used to apply the reactive dye. Examples for such non-reactive substituents are the optionally substituted amino, optionally etherified hydroxyl or thiol or optionally substituted alkyl groups which are free of atoms reactive with cellulose, as described above, for example for R has been described.

The group R can also have chromophoric properties, that is, they differ from a colored compound with a

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Can derive amino, hydroxyl or thiol substituents. If the color associated with R is different from the one which is linked to D, then the resulting dyes can have valuable intermediate hues. the chromophoric group contributed by R may be the same or nearly the same as that contributed by D. will.

Examples of colored compounds from which the radical D is derived are any colored compounds that are derive from 6,13-dichlorotriphendioxazine.

Find examples of such 6,13-dichlorotriphendioxazines in GB-FSen 1 34-9 513 and 1 368 158 and in GB-FA 4-576 / 74-, which are generally reactive dyes of the 6,13-dichlorotriphendioxazine series describe.

A preferred general class of dyes of the invention can be expressed by the formula:

Cl H- ZNYX U (SO-H).
3 b (SO H) Cl

X-Y-N -Z «.

1?

represent where

6 6 6

(R) represents m substitution groups R, where each R is independently halogen, C ^ ^ -alkyl, Cj ^ -alkoxy or COOH, m is 0 to 3,
a + b stands for 1 to 4-,

X stands for a direct bond or a connecting atom or a connecting group,

X for an optionally substituted connecting group of the aromatic, araliphatic or aliphatic series, or X and Y together form a direct bond,

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Z and Z 'each independently of one another for H or ■■■■■■ F

stand

'di

and R and R / have the meanings given above.

A particularly preferred general class of dyes is formed by those compounds of formula (5) in which m = 0, a = b = 1 and each X is at the p-position to the heterocyclic Nitrogen atom is bound, so these are dyes of the formula:

R '

Z-N-Y-X,

Vji

SOJfI

^ "SO_H / ^^ / ~ X-Y-N-Z

wherein X, Y, R ', Z and Z ^{1 have} the meanings given above.

Examples of atoms or groups represented by X are 0, S, CH ₂ , CO, CH = CH, NHCONH, NHCH ₂ CH ₂ NH, N = N

Il

NH (X ¹ = C1, OH or

N N

and preferably NH.

Preferred types within these general classes, the

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the formulas (5) and (6) are defined are those wherein

(a) X and I together form a direct bond;

(b) Y is a benzene or naphthalene compound group which is optionally substituted, in particular by 1, 2 or 3 groups of the formula S (XH, especially when such groups are combined with an X which represents ΉΚ , and

(c) Y is an aliphatic or araliphatic ^ linking group is, each of which can optionally be substituted.

Examples of such groups are ethylene, 1,2- and 1,3-propylene, 2-hydroxy-1,3-propylene, 1- and 2-phenyl, 1,3-propylene, 2-0'-sulfophenyl) -1 , 3-propylene, 1,4-, 2,3- and 2,4-butylene, 2-kethyl-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-methyl-1,6-hexylene, -CH ₂ GH ₂ OCH ₂ CH ₂ , -CH ₂ CH ₂ SCH ₂ CH ₂ -, -

- N N- CH ₂ CH ₂ -,

-CH

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With these types it is also preferred that X be IiH stands.

In the case of types (c) in which X is a substituted amino group, the group bonded to the nitrogen of X can, in addition to the group T, to both nitrogen atoms in the structure ■
pen are:

Structure -X-Y-IiR - be bound. Examples of such groups

CH - CH-

rp

It is often more preferred that E 'in the formula (6) stands for H.

Further structural features of preferred types of the invention Dyes are derived from compounds referred to below, to intermediates to explain the production of the invention Dyes can be used.

The invention further relates to a process for the preparation of dyes of the formula (1), apart from those in which E stands for an optionally substituted hydrocarbon radical, which is carried out by adding η mol of cyanuric fluoride in any order with 1 mol of an amino-6, 13-dichlorotriphendioxazins of the formula D (NR ¹ H) and η mol of a compound

implementation of the formula EH, where n, E, R 'and D are those given above Have meanings, but R is something other than an optionally substituted hydrocarbon radical.

If η stands for 1 in the above procedure, then it is possible to

that the amino-6,13-dichlorotriphendioxazine DNR'H more than one

Group NE'H may contain, i.e. that D is a 6,13-dichlorotriphendioxazine radical is that one or more additional

Groups NE'H which are not involved in the reaction with cyanuric

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rid or the intermediate

be used.

Such is the preferred general class in making of dyes of the formula (5) used in the process

rp

dete amino-6,13-dichlorotriphendioxazine D (ES H) is a compound of the formula (5) in which both Z and Z ^{1 are} H. This can be reacted with 1 mol of cyanuric fluoride and 1 col of compound RH, a compound of the formula (5) being obtained in which one of the symbols Z and Z ^{1 stands} for

and the other is H, that is to say a compound of the formula (1) in which η is 1 and the group D comprises a group MH. Alternatively, reaction with 2 moles of cyanuric fluoride and 2 moles of a compound EH gives a compound of formula (5) i wherein both Z and Z ^{1 are}

stand, i.e. that is to say a compound of the formula (1) in which η is 2.

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The process is expediently carried out by adding cyanuric fluoride to an aqueous solution of one of the compounds D (IiIrH) ₁₁ or EH at a temperature of from 0 to 10 ° C. and after the first fluorine atom of the cyanuric fluoride has been replaced by the The other compound is added radically to the compound at a somewhat higher temperature of 20 ° to 50 ° C. In some cases it has proven advantageous to dissolve the cyanuric fluoride in a water-immiscible solvent before it is added to the aqueous solution of the colored compound. Any water-immiscible solvent that does not react with cyanuric fluoride is suitable, such as benzene, toluene, chlorobenzene, chloroform, carbon tetrachloride, ethylene dichloride and trichlorethylene. The condensations are preferably carried out at a pH of 4 to 10, using an acid-binding agent, such as sodium hydroxide, carbonate or bicarbonate, is added to the hydrofluoric acid in their infrequent initiation to neutralize during the condensation.

The dyes prepared by the above methods can be prepared by the usual isolation methods for water-soluble Reactive dyes are isolated, for example by salting out and filtering off or by spray drying the Reaction mixtures in which the dye has been prepared.

In the above procedure, it has often been found to be beneficial to use compound EH and not compound D (NR ^ H) in the first stage.

Examples of compounds of the formula RH are the hydroxy, thio and amino compounds, of which the special Derive examples of R given above.

Dyes of the formula (i) in which R represents an optionally substituted Hydrocarbon radical can be obtained by using an amino-GjiJ-dichlorotriphendioxa-

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zin of the formula D (NR'H) with η mol \. / *, where R is

an optionally substituted hydrocarbon radical is implemented.

moron)

Lie Anino-5, "13-dich.lorotriphendioxazine of the formula

those used in the above method can be obtained by conventional means, including in general 1 mole of 2,3,5,6-tetrachloro-1,4-benzoquinone with 2 moles of a liamine is condensed and the resulting dianilide is heated in the presence of a strongly acidic condensing agent such as oleum to bring about the ring closure. For example, the reactive dyes of the preferred general class represented by the formula (5) is, from an amino-6,13-dichlorotriphendioxazine of the formula (5), wherein both Z and Z 'are H, which "compound" is in turn obtained thereby is that you 2,3,5-6-tetrachloro-1,4-benzoquinone with 2 mol of diamine

X-Y-NH (7)

S ⁷

wherein X, Y, R, R 'and m have the meanings given above and s is 0, 1 or 2, condensed and the resulting "dianilide in the presence of a strongly acidic Kon Densant, such as oleum, condensed to bring about ring closure. Further groups SO, H can during this ring closure stage are introduced.

Examples of diamines of the formula (7) »those for the preparation of amino-S ^ J-dichlorotriphendioxazines and further of Reactive dyes of the formula (5) in which X and Y together Form a direct bond, that's them. above preferred dyes of type (a) can be used

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stated in GB-PS 134-9513.

Similarly, examples of diamines are of the formula (7), in which Y is an optionally substituted benzene or naphthalene group represents to be found in GB-PS 1368153, while Examples of diamines of the formula (7)? v; orin Y for one aliphatic or araliphatic group in the GE-PA ^ 576 / 74- can be found. These diamines give amino-6,13-dichlorotriphendioxazine intermediates, which can be used in the preparation of the preferred above dyes of types (b) and (c).

It may prove desirable to take steps to prevent hydrolysis of the fluorine atom on the triazine nucleus of the dyes of the formula (1) to be kept low during storage of the dye or in dyebaths or in Printing pastes containing the dye can occur. There is an appropriate stabilization measure in mixing in the dye certain compositions which have pH in the range 4-7, preferably in the range from 6-7, like e.g. alkali metal hydrogen phosphate and mixtures of alkali metal N, IT-diethylan: inobensol sulfonate with the corresponding free sulfonic acid. Mixtures of dyes of the formula (1) and a stabilizer, which reduces the tendency to hydrolysis represent a further aspect of the invention.

The fluorotriazine dyes of the present invention can be used to dye a wide variety of textile materials containing hydroxyl or amino groups, such as materials made of wool, silk, polyamide and natural or regenerated cellulose, such as cotton or viscose rayon. The conventional methods can be used for this used for dyeing such materials with water-soluble Beactive dyes are known. In the case of cellulose are they preferably carried out together with a

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lunr; with an acid-binding agent such as caustic soda, or sodium carbonate, phosphate, silicate or bicarbonate, applied, this treatment being applied to the textile materials can be used before, during or after the application of the dye.

The fluorotriazine dyes according to the invention are distinguished by their high rate of reactivity with cellulose and by an exceptionally stable triazine / cellulose bond. Although the new dyes have the high reactivity, so far only the dichloro-s-triazine or sulfato-ethylsulfone dyes was intrinsic, but they do not tend to break the fiber / dye bond like axes Lei these dyes normally under acidic bsw. alkaline conditions is determined.

The dyes according to the invention dye textiles in bright red, reddish blue or blue shades and often result Colors that are brighter and deeper than similar dyes that are other reactive Groups included.

The invention is illustrated in more detail by the following examples, in which all parts and percentages are expressed by weight are.

example 1

1.49 parts of cyanuric fluoride are added rapidly to a neutral solution of 2.79 parts of 3,5-disulfoaniline in 60 parts of water and 10.5 parts of η Katriumhydroxidlösung at 0-5 ⁰ C. This mixture is stirred for 5 min at 0-5 ⁰ C, the pH being kept at 4-4.5. The mixture is then made into a solution of 3 »94 parts of triphendioxazine of the formula:

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Cl

added in 2000 parts of water at room temperature and at a pH of 9.0-9.5. The mixture is stirred for a further hour at 25 ° C., the pH being kept in the range from 9.0-9.5 by adding 21 parts of η aqueous sodium hydroxide solution. The pH is adjusted to 7.0 by adding 2 η aqueous hydrochloric acid. 1000 parts of iatrium acetate trihydrate are then added and the mixture is kept at 25 ° for 20 hours. touched. The precipitated product is filtered off and dried ^{at 30 ° C. in vacuo.} The product, which is a dark blue powder, dyes cellulose textiles in attractive, bright blue shades with high color strength and very good fastness to light and washing.

Dyes of similar hue are obtained by repeating the procedure of Example 1 with the 3,5-disulfoaniline is replaced by an equivalent amount of one of the following substances:

example Amine 2 2-sulfoaniline 3 2,3-dicarboxyaniline 4- 2,5-disulfoaniline 5 2,4 - DiSuIf oaniline 6th .2-Carboxy-4-sulfoaniline 7th 2-carboxy-4-, 5-disulfoaniline 8th· 4 ~ chloro-3-sulfoaniline 9 4-methyl-2-sulfoaniline 10 2,4-dicarboxyaniline 11 2-carb oxy-5-sulfoaniline

- 15 -

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Example Amirt

12 4-Amino-3,5-disulfoaniline

13 2-Amino-1-sulfonaphthalene

14 2-amino-1,5-disulfonaphthalene

15 2-amino-3,6,8-trisulfonaphthalene

16 N-sulfomethyl-3-sulfoaniline

Example 1?

Following the procedure of Example 1, a triphendioxazine dye base of the formula (6), wherein Z = Z = H, R ⁷ = H, X = ITH and Y = CH ₂ CH (OSO ₅ H) CH _{2, is made} with the condensate of cyanuric fluoride and 3,5-sisulfoaniline are reacted to obtain a product which dyes cellulosic textile materials in bright blue shades.

Dyes with a similar hue are obtained if the 3,5-ßisulfoanilin in Example I7 by an equivalent amount one of the following substances is replaced:

Example amine

18th 2,5-disulfoaniline

19 2-carboxyaniline

20 2-sulfoaniline

21 2-Carboxy ~ 4 ~ sulfoaniline

22 2,4-disulfoaniline

23 2,3-dicarboxyaniline

24 4-chloro-3-sulfoaniline

25 4-methyl-2-sulfoaniline

26 2,4-dicarboxyaniline

27 2-Carboxy-5-sulfoaniline

28 2-Amino-1-sulfonaphthalene

29 2-amino-1,5-disulfonaphthalene

30 '2-amino-3 ₅ 6,8-trisulfonaphthalene

31 2-Amino-3,5- <iicarboxyaniline

32 N-sulfomethyl-3-sulfoaniline

33 4-Amino-3,5-cisulfoaniline

6 0 9 8-2 9IiSO 8-43

2 6 O0 49

Example 54

According to the procedure of Example 1, a triphen

dioxazine of the formula (6), in which J is -N N-

^ ⁰ V

1
and Z = Z = H reacted with a condensate of cyanuric fluoride and 3,5-disulfoaniline, a product being obtained which dyes cellulose textiles in bright blue shades.

Dyes with a similar hue are obtained when the 3,5-disulfoaniline in Example 34 is replaced by an equivalent Amount of one of the following substances is replaced:

Example amine

35 2,5-disulfoaniline

36 2-carboxy-4-sulfoaniline

37 2-amino-3,6,8-trisulfonaphthalene

38 2-Amino-1-sulfonaphthalene

39 2-carboxy-5-sulfoaniline

Example 40

Following the procedure of Example 1, a triphendioxazine dye base is made of the formula (6), in which Z = Z = H, Ir = H,

XY = -NH-GHo - \ j - reacted with a condensate of cyanuric fluoride and 3 »5-disulfoaniline, a product being obtained which dyes cellulose textile materials in bright blue shades.

Dyes with a similar hue are obtained when the 3 »5-disulfoaniline of Example 40 is replaced by an equivalent Amount of one of the following substances is replaced:

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26G0490

Example amine

41 2-sulfoaniline

42 2,5-disulfoaniine

43 2,4-Msulfoaniline

44 2,4-dicarboxyaniline

45 4-chloro-3-sulfoaniline

46 2-Amino-1-sulfonaphthalene

47 2-Amino-1,5-disulfonaphthalene

48 2-amino-3,6,8-trisulfonaphthalene

49 4-methyl-2-sulfoaniline

Example 50

Following the procedure of Example 1, a triphendioxazine dye base is made of the formula (6), in which Z = Z = H,

R ^ = H and X-Y = -NH- / _} - with the condensate of cyanuric fluo-

SO H

rid and 3,5-3isulfoaniline within a pH range of to 7 »5 implemented, a product being obtained which Dyes cellulose textiles in bright blue shades that are greener than in Examples 1-59 «

Dyes with a similar shade to that in the example are obtained when the 315-disulfoaniline in example is replaced by one of the following:

Example amine

51 2-sulfoaniline

52 2,5-disulfoaniline

53 2-Garboxyaniline

54 2-Carboxy-4-sulfoaniline

55 2-carboxy-5-sulfoaniline

56 2-carboxy-4,5-disulfoaniline

57 2,3-dicarboxyaniline

58 2,4-dicarboxyaniline

59 4-chloro-3-sulfoaniline

6 0 9 $ 7 9 ¹ ^ O &% 3

■ Example Amiη

60 4-methyl-2-sulfoaniline

61 2-Amino-1-sulfonaphthalene

62 2-amino-1,5-disulfonaphthalene

63 2-Amino-3,6,8-trisulfonaphthalene

Example 64-

The dye base used in Example 50 is ^{reacted with an excess of cyanuric fluoride at 0} ° C. and at pH 4-6, and the resulting difluorotriazinyl pigment is reacted with an equivalent amount of 3-sulfoaniline at pH 7 and at 25-35 ° C. A product is obtained which dyes cellulosic textile materials in bright blue shades similar to those of Example 50.

Dyes of similar hue are obtained when the 3-sulfoaniline of Example 64 is replaced by any of the following Substances is replaced:

example Anun 65 4-sulfoaniline 66 4-carb oxyaniline 67 3-carboxyaniline 68 ammonia 69 Methylamine 70 Ethylamine 71 n-butylamine 72 ß-sulfoethylamine 73 aniline 74- -p-toluidine 75 p-chloroaniline 76 2-methyl-5-sulfoaniline 77 N-sulfomethylaniline 78 N-methyl-3-sulfoaniline 79 Morpholine

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Example aniline

80 2-aniino-4,6,8-trisulfonaphthalene

81 dimethylamine

62 2-AmXnO- ² J-, 8-disulfonaphthalene

83 2-amino-6,8-disulfonaphthalene

84-2-amino-5,7-disulfonaphthalene

85 4-sulfobenzylamine

86 N-methyl taurine

87 N-methyl-ß-alanine

88 M- (n-butyl) amine

89 Di- (ß-hydroxyethyl) amine

90 ß-hydroxyethylamine

91 β-hydroxypropylamine

92 diethylamine

Example 93

If the dye base used in Example 50 with a Excess of 2,4-difluoro-6-methoxytriazine instead of Cyanuric fluoride is reacted, then a product is obtained, which dyes cellulosic fabrics in bright blue shades similar to those of Example 64.

Example 94

When the 2,4-mfluoro-6-methoxytriazine of Example 93 is replaced by an equivalent amount of 2,4-difluoro-6-n-butoxytriazine, then a product is obtained which is cellulose textiles colors in bright blue shades similar to Example 93.

Example 95

Following the procedure of Example 50, a triphendioxazine dye base is made of formula (6), where Z = Z '= H, IT = CH, and X-Y = -NH - / _ \ - with the condensate of cyanuric

^^ S0 H

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fluoride and 3ι5-disulfoaniline implemented, with a product which dyes cellulosic fabrics in bright blue shades similar to those of Example 50.

Dyes with a similar hue are obtained when the 3,5-disulfoaniline of Example 95 is replaced by one of the the following substances are replaced:

Example amine

96 2-sulfoaniline

97 2,5-disulfoaniline

98 2-Carboxy-4-sulfoaniline

99 2,3-dicarboxyaniline

Example 100

Following the procedure of Example 50, a triphendioxazine dye base is made of the formula (6), in which Z = Z = H,

? / = C.Kq and XT = \ __ / ~~ ²¹ ^ t ^ - ^eni condensate of cyanuric

SOJfI

fluoride and 3,5-disulfoaniline reacted, whereby a product which dyes cellulosic fabrics in bright blue shades similar to those of Example 50.

Dyes of similar hue are obtained when the 3,5-disulfoaniline of Example 100 is replaced by any of the following Substances is replaced:

Example amine

101 2-sulfoaniline

102 2,3-disulfoaniline

103 2 ~ Carboxy-4-sulfoaniline

104 2-carboxy-4,5-disulfoaniline

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is

Example 105

Following the procedure of Example 50, a triphendioxazine dye base, whose main component is the formula

1 7
(6), wherein Z = Z = H, R = H and X and Y represent a direct bond, reacted with the condensate of cyanuric fluoride and 3,5-disulfoaniline in a manner similar to Example 50. A product is obtained which dyes cellulose in bright reddish-blue shades.

Dyes with a similar hue as in Example 105 are obtained if the 3ί5-disulfoaniline in Example 105 is replaced by one of the following:

Example Nurse 106 2,5-disulfoaniline 107 2-sulfoaniline 103 2-carboxy-4-sulfoaniline 109 2,3-dicarboxyaniline

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Claims (1)

PATENT CLAIMS ; 1. Dyes of the formula: where D stands for the remainder of a colored compound of the 6,13-dichlorotriphendioxazine series, η stands for Λ or 2, R stands for an optionally substituted amino group, an optionally etherified hydroxyl group, an optionally etherified thiol group or an optionally substituted hydrocarbon - n
is a hydrogen radical and R is a hydrogen atom or an optionally substituted alkyl radical. 2. Dyes according to claim "1, characterized in that that they contain at least one group of the formula SCUE. 3. Dyestuffs according to Claim 1, characterized in that R stands for a hydrogen atom. 4. Dyes according to one of claims 1 to 3 »characterized in that R is a mono- or di-CU ^ -alkyl amino group stands in which the alkyl group or alkyl groups are optionally substituted by OH or C / _ ^ - alkoxy. 5. Dyestuffs according to one of claims 1 to 3 · » characterized in that R stands for an optionally substituted phenylamino or kaphthylamino group. 6. Dyestuffs according to Claim 5 _5, characterized in that one or more groups of the formula SO ^ H are present as substituents in the phenylamino or naphthylamino groups. - 23 60.9829 / 0843 7. Dyes according to any one of claims 1 to 3, characterized characterized in that R is a CU ^ alkoxy or a Phenoxy group. 5. Dyes after. Claim 2, characterized in that the formula: have, in which (R) represents m substitution groups R, where each 6th
R is independently halogen, C ^ _ ^ - alkyl, C ^ _ ^ - alkoxy, or GOOH, m stands for 0 to 3, a + b stands for 1 to 4-, X stands for a direct bond or a connecting atom or a connecting group, Y for an optionally substituted connecting group of aromatic, araliphatic or aliphatic series, or X and T together form a direct bond, Z and Z 'each independently of one another for H or -f ^N stand, R has the meanings given in one of claims 1 or 4 to 7 and R 'has the meanings given in one of claims 1 or 3. 609829 / 08A3 Dyes according to Claim 8, characterized in that they have the formula: wherein X, Y, R, Z and Z ^{1 have} those in claim. 8 have given meanings. Dyestuffs according to Claim 8 or 9, characterized in that X stands for NH. Dyes according to one of Claims 8 or 9, characterized in that X and Y together form a direct bond are. Dyestuffs according to one of Claims 8 to 10, characterized in that Y represents a benzene or naphthalene compound group which is optionally substituted by up to three groups of the formula SO ^ H. Dyestuffs according to one of Claims 8 to 10, characterized characterized in that Y represents an optionally substituted aliphatic or araliphatic group. Process for the preparation of the dyes according to Claim 1, with the exception of those in which R is an optionally substituted one Hydrocarbon radical, characterized in that one η mol of cyanuric fluoride in any Sequence with 1 mole of an amino-6,13-dichloro triphendioxazins of the formula D (IR H) and η mol of one 7 Reacts compound of the formula RH, where n, R, R ⁽ and D have the meanings given in claim 1). - 25 - 60 9 829/0843 15. Process for the preparation of the dyes according to claim 1, wherein R is an optionally substituted hydrocarbon radical, characterized in that 1 mol of an amino-6,13-dichlorotriphendioxazine of the formula D (IiE ⁷ H) _n with η mol converts, where R is an optionally substituted hydrocarbon radical and D, R and η have the meanings given in claim 1. 16. Dye mixture, characterized in that there is a. A dye according to claim 1 and a stabilizer which has the pH of the mixture in the range of 4 to 7 holds. 17. Dye mixture according to claim 16, characterized in that that the stabilizer consists of a mixture of acidic alkali metal phosphates. 18. Dye mixture according to claim 16, characterized in that that the stabilizer consists of a mixture of an alkali metal N, N-diethylaminobenzene sulfonate and the corresponding free sulfonic acid. 19. "Use of the dyes according to claim 1 for dyeing or printing on a textile material using an acid binder. ^{D! PL} "'· ° - - 26 - 609829/0843