NL8006044A - REACTIVE DYES, METHOD FOR THE PREPARATION THEREOF, AND METHOD FOR COLORING TEXTILE MATERIALS. - Google Patents

Description

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Reactive dyes, process for their preparation as well as process for coloring textile materials.

The invention relates to reactive dyes, in particular to disazo dyes containing a 2,5-disulfo-1,4-phenylene group.

Dyes containing cellulose reactive groups and a 2,5-disulfo-1,4-phenylene group are known, see for example British Patent Specification 1,093,354. Various reactive disazo dyes containing a disulfo-1,3-phenylene group are also described in German Auslegeschrift No. 1,085,629. It has now been found that a new class of reactive dyes containing a 2,5-disulfo-1,4-phenylene group exhibits surprisingly good properties, for example, they often combine high color strength, good build-up and good lightfastness to an extent not was to be expected on the basis of known dyes with a closely related structure.

According to the present invention there are provided reactive dyes of formula 1 wherein Q is a cellulose reactive group, is RH or is a C 1-6 alkyl group optionally substituted with OH, CN, SO 3 H or o 3 O 3, 20 E 1 optionally substituted 1,4 -phenylene or 1,4-naphthylene group, D is a 2,5-disulfo-1,4-phenylene group and E3 is an optionally substituted 1-N-phenylaminonaphthyl group.

The cellulose reactive group, represented by Q.25, can be any group capable of forming a covalent bond with a cellulose substrate. It can be any conventional cellulose reactive group of this type, such as those described in patents and other literature on reactive dyes, for example, British Patent 1,440,948.

As the pre-beds of cellulose reactive groups, mention can be made of aliphatic sulfonyl groups containing a sulfate ester group in the-position relative to the sulfur atom, for example β-sulfatoethylsulfonyl groups, α, β-unsaturated acyl groups of aliphatic carboxylic acids, eg acrylic acid, α -chloroacrylic acid, α-bromoacrylic acid, propiolic acid, maleic acid and mono- and dichloro-maleic acid; also the acyl groups of acids containing a substituent which reacts with cellulose in the presence of an alkali, for example the radical of a halogenated aliphatic acid, such as chloroacetic acid, β-chloro and β-bromopropionic acid and α, β-dichloro and -dibromopropionic acid or radicals of vinylsulfonyl or β-chloroethylsulfonyl or β-sulfato-ethylsulfonyl-endo-methylene-cyclohexane-carboxylic acid. Other examples of cellulose reactive groups include tetrafluorocyclobutylcarbonyl, trifluorocyclobutenylcarbonyl, tetrafluorocyclobutylethenylcarbonyl, trifluorocyclobutenylethenylcarbonyl; activated halogenated 1,3-dicyaaribenzene radicals such as 2,4-dicyano-3,5-difluoro-6-chlorophenyl, 2,4-dicyano-3,5-difluoro-6-nitrophenyl, 2,4-dicyano-3 , 5,6-trifluorophenyl, 2,4-dicyan-3,5,6-tri-chlorophenyl, 2,4,6-tricyan-3,5-difluorophenyl, 2,4,6-tricyan-3,5-dichlorophenyl and heterocyclic groups containing 1, 2 or 3 nitrogen atoms in the heterocyclic ring and at least one 20 cellulose reactive substituent on a carbon atom of the ring.

It should be noted that many reactive groups can be described as both heterocyclic and acyl groups since it consists of an acyl group carrying a heterocyclic substituent. For convenience, in such cases where the heterocyclic ring carries the cellulose reactive substituent, these are commonly referred to as heterocyclic reactive groups in the present application.

As examples of such heterocyclic groups 30 may be mentioned, for example: 2,3-dichloroquinoxaline-5- or -6-sulfonyl, 2,3-dichloroquinoxaline-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-carbonyl, 8006044 t

3-1,4-dichloro-eththalazine-6-carbonyl, 4,5-dichloropyridazone-1-yl-ethylcarbonyl, 2,4-dichloropyrimidin-5-carbonyl, 4 ”(4'-dichloropyridaz-6-on-1T-yl) benzoyl, 5 2-chlorobenzothiazole-6-carbonyl, 3,6-dichloropyrazine-4-carbonyl, 4- (4T, 5'-dichloropyridaz-6'-one-1-yl) phenylsulfonyl; activated 4,6-dihalo-pyridin-2-yl and 2,6-dihalo-pyridin-4-yl groups such as 3,4,5,6,6-tetrafluoropyridin-2-yl, 2.3.5.6-tetrafluoropyridin-4-yl, 2.5. 6-trifluoro-3-cyanopyridin-4-yl, 2.5.6-trichloro-3-cyanopyridin-4-yl, 2,6-difluoro-3-cyano-5-chloropyridin-4-yl, 15 2,6-difluoro-3 , 5-dichloropyridin-4-yl and more particularly triazinyl or pyrimidinyl groups.

Examples of specific pyrimidinyl groups are pyrimidin-2-yl or -4-yl groups with a cellulose reactive atom or group, especially Cl, Br or F in at least one of the other 2, 4 and 6 positions. The 5 position can carry various substituents, such as Cl or CN, which are normally not cellulose reactive as such but which can improve the reactivity of substituents in other positions of the pyrimidine ring. As specific examples of such pyrimidinyl groups may be mentioned: 2.6-dichloropyrimidin-4-yl, 4.6-dichloropyrimidin-2-yl, 2.5.6-trichloropyrimidin-4-yl, 4.5.6-trichloropyrimidin-2-yl, 30 5-chloro-2-methylsulfonyl-6-methylpyrimidin-4-yl, 2,6-dichloro-5-cyanopyrimidin-4-yl, 4,6-dichloro-5-cyanopyrimidin-2-yl, 2,6-difluoro-5-chloropyrimidin-4- yl, 4,6-difluoro-5-chloropyrimidin-2-yl, 2,6-difluoro-5-cyanopyrimidin-4-yl, 4,6-difluoro-5-cyanopyrimidin-2-yl.

8006044 4

Examples of particular triazinyl groups are triazin-2-yl groups with cellulose reactive atoms or groups at one or both of positions 4 and 6. In this case, a wide variety of cellulose reactive atoms or groups are for 5 hands, as activated aryloxy or various groups joined by a sulfur atom, for example SO 2 H, but the preferred reactive atoms or groups are F, Br or, especially Cl; quaternary ammonium groups, such as tri-lower alkyl ammonium, for example, (CH 2) 3 -, and pyridinium groups, especially those derived from pyridine carboxylic acids, especially from nicotinic acid.

The triazinyl groups having only one reactive atom or one reactive group on the nucleus in the 4 or 6 position may have a substituent that is not reactive with cellulose in the remaining 4 or 6 position.

As examples of such non-reactive substituents there may be mentioned alkyl or aryl-thio groups, alkoxy or aryloxy groups and optionally substituted amino groups. ·

Preferred forms of these groups include lower, i.e., C 1-4 alkoxy, for example, methoxy, ethoxy, n-propoxy and iso-propoxy, butoxy, and lower alkoxy, for example, 8-methoxy-ethoxy, β-ethoxyethoxy, phenoxy, and sulfophenoxy; amino; lower alkylamino, for example methylamino, ethyl-amino, butylamino, di (lower alkyl) amino, for example dimethyl-25 amino, diethylamino, methylethylamino, dibutylamino and groups of the latter two types, in which the alkyl groups are substituted, in particular by OH, CN or SO ^ H, for example, β-hydroxyethylamino, di (3-hydroxyethyl) amino, β-cyanoethylamino, di ($ - cyanoethyl) amino, β-sulfoethylamino, β-hydroxypropylamino, 30 (3-hydroxybutyl) ethylamino and ( 3-hydroxyethyl) methylamino; cycloalkylamino, for example cyclohexylamino; cyclic amino, for example morpholino or piperazino; naphthylamino substituted by 1, 2 or 3 SO 2 H groups and optionally substituted phenylamino groups.

As a particularly preferred form of the optionally substituted phenylamino groups, there may be mentioned groups of 8006044 · formula II, wherein GH is methyl, ethyl, ω-sulfomethyl, 3-carboxy, 3-hydroxy or β-cyanoethyl and Z and X are independently selected from H, COOH, SO ^ H, CH ^, C2H5> 0CH3 »0C2H5»

Cl, Br, CN, NO2, NHCOCH2 and g-sulfatoethylsulfonyl.

As specific examples of such groups may be mentioned anilino, o-, m- and p-sulfoanilino, o-, m- and p-carboxyanilino, 4- and 5-sulfo-2-carboxyanilino, 4- and 5-sulfo -o-tolylamino, 2,4-, 2,5- and 3,5-disulfoanilino, 2,4-dicarboxyanilino, 4- and 5-sulfo-2-methoxyanilino, N-methyl-o-, m- and p-sulfoani-10 lino, Ν-ω-sulfomethylanilino and N- (β-hydroxyethyl) -3-sulfoanilino,

If desired, the cellulose reactive group Q may be in the form of formula 3, wherein Ht is an s-triazine core containing a cellulose reactive atom or a cellulose reactive group, Dm is a diamine residue connecting Ht and 0 'through the two. amino groups and Q 'is a cellulose reactive group with the meaning indicated above for Q.

In particular, it is usually preferred that the cellulose reactive group or atom on Ht be F, Br or especially Cl and that Q 'be an s-triazine residue as defined above for Q.

Also, the cellulose-reactive group Q may be in the form of formula 4, wherein Dm and Q 'have the meanings indicated above and Ht * is an s-triazine nucleus free of cellulose-reactive atoms or groups, for example it may be a 2,4- s-triria-25-alkyl group with an optionally substituted amino group in the 6-position.

When Q represents an s-triazine ring containing a halogen atom and a non-reactive substituent, the latter may be the residue of a colored amine, for example from the azo, anthraquinone or phthalocyanine series, but more particularly a residue of formula 1 minus the group Q, so that the dye as a whole contains two residues of formula 1 minus the group Q connected by a halo-s-triazine radical or two such residues connected by the two halo-s-triazine groups and a diamine group Dm as given above. In these dyes, the halogen may be F or Br, but usually 8006044 6 is preferred to be Cl.

As examples of the diamine DmH2 which can provide the residue Dm can be mentioned: heterocyclic diamines, piperazine pre-bedded, 5 aliphatic diamines, for example alkylene, hydroxyalkylene or sulfato-alkylene diamines, in particular those with 2-6 carbon atoms e.g. ethylenediamine 1,2- and 1,3-propylenediamines 1,6-diaminohexane 10 β-hydroxyethylaminoethylamine 2-hydroxy-1,3-diaminopropane 2-sulfato-1,3-diaminopropane other α-ω-diaminoaliphatic compounds, for example triethylene-tetramine 15 di- (g-aminoethyl) ether naphthyleneldiamine sulfonic acids, for example 2,6-diaminonaphthalene-4,8-disulfonic acid 1,5-diaminonaphthalene-3,7-disulfonic acid and diamine derivatives of mono- and dicyclic compounds of the benzene series, for example phenylene diamines and their mono- and disulfonic acids, for example mr- and p-phenylene diamines 1,3-phenylene diamine-5-sulfonic acid and 4,6-disulfonic acid 1,4-phenylene diamine-2-sulfonic acid and 2,5-disulfonic acid, diamines of n formula 5.25 wherein p and q are 0 or 1 and E is a direct bond or a group selected from SO 2, 0, C 1, C 2 H 4 '1511' NHCONH, e.g. 4,4'-diamino stilbene-2,2 ' -disulfonic acid benzidine-2-sulfonic acid and 2,2'-disulfonic acid 3,3T- and 4,4T-diaminophenylurea 4,4, -diamino-diphenylurea-2,2T- and 3,3'-disulfonic acid 4,4'-diaminodiphenylamino- 2-sulfonic acid 4,4'-diaminodiphenylmethane 4,4T-diaminodiphenylmethane-2,2 * -disulfonic acid 4,4'-diaminodiphenyl ether 35 4,4'-diaminodiphenylsulfone 4,4'-diaminodiphenylethan-2,2'-disulfonic acid 8006044 <* 7 and the N-lower alkyl and N, N'-di (lower alkyl) derivatives of the above diamines, for example 4-methylamino- and 4-ethylaminoaniline-3-sulfonic acid N, N'-dimethyl-1,4,4'-diamino diphenylamine-2-sulfonic acid.

As examples of optionally substituted alkyl groups R may be mentioned n-propyl, isopropyl, n-butyl, hydroxyethyl, hydroxypropyl, cyanoethyl, sulfatoethyl, sulfoethyl and especially preferred are ethyl and especially methyl.

As examples of the group E ^ may be mentioned 1,4-phenylene 2-urea-1,4-phenylene 2-acetylamino-1,4-phenylene 2-methyl-1,4-phenylene] 5 2-methyl-5 -methoxy-1,4-phenylene 2,5-dimethyl-1,4-phenylene 3-methyl-1,4-phenylene 2,5-dimethoxy-1,4-phenylene 2-carboxy-1,4-phenylene 20 2-methyl-l , 4-phenylene 3-methoxy-1,4-phenylene 6.7- and 8-sulfo-1,4-naphthylene-6,1-disulfo-1,4-naphthylene 2-dichlorotriazinylamino-1,4-phenylene; In these examples, it is assumed that the azo group is linked to the 1 position of Ej.

As examples of the group E2 can be mentioned: 1-hydroxy-8-N-phenylamino-5-sulfonaphth-2-yl 1-hydroxy-5-N-phenylamino-3-sulfonafth-2-y1 4-N-phenylamino - (6- or 7-) sulfonaphth-1-yl 4-N-phenylamino-5-sulfonaphth-1-yl 4-N-phenylamino-5,7-disulfonaphth-1-yl 1-hydroxy-8-N-phenylamino -3-sulfonaphth-2-yl 35 1-hydroxy-8-N-phenylamino-3,5-disulfonaphth-2-yl 1-hydroxy-8-N-phenylamino-3,6-disulfonaphth-2-yl 8006044 8 1 -hydroxy-8-N-3'-methylphenylamino-3,6-disulfo-2-yl 1-hydroxy-8-N-2 * -methylphenylamino-3,6-disulfonaphth-2-yl 1-hydroxy-8-N -2 ', 5'-dimethylphenylamino-3,6-disulfonaphth-2-yl 1-hydroxy-8-N-3'-methylphenylamino-3,5-disulfonaphth-2-yl 5 1-hydroxy-8-N-4 1'-methoxyphenylamino-3,6-disulfonaphth-2-yl 1-hydroxy-8-N-3'-methoxyphenylamino-3,5-disulfonaphth-2-yl 1-hydroxy-8-N-2 ', 5'- dimethylphenylamino-3,5-disulfonaphth-2-yl 1-hydroxy-5-N-41-methylphenyl amino-3-sulfonaphth-2-yl 1-hydroxy-5-N-3'-methylphenylamino-3-sulfonaphth- 2-yl 10 1-hydroxy-8-N-phenylamino-5-sulfonaphth-2-yl 1-hydroxy-8-N-3'-sulfophenylamino-3,6-d isulfonaphth-2-yl 1-hydroxy-8-N-4Lsulfophenylamino-3,6-disulfonaphth-2-yl 1-hydroxy-8-N-3'-carboxyphenylamino-3,6-disulfonaphth-2-yl 1-hydroxy- 8-N-3'-sulfophenylamino-3,5-disulfonaphth-2-yl 15 1-hydroxy-8-N-2 ', 5'-dimethylphenylamino-3-sulfonaphth-2-yl 1-hydroxy-8-N- phenylamino-3-sulfonaphth-2-yl 1-hydroxy-8-N-3'-carboxyphenylamino-3,5-disulfonaphth-2-yl 1-hydroxy-8-N-2 ', 5'-dimethoxyphenylamino-3,6 -disulfonaphth-2-yl 1-hydroxy-8-N-4'-aminophenylamino-3,6-disulfonaphth-2-yl 20 1-hydroxy-8-N-3'-aminophenylamino-3,6-disulfonafth-2- yl 1-hydroxy-8-N-3'-2 ", 4" -dichloro-s-triazin-6 "-ylamino-phenylamino-3,6-disulfonaphth-2-yl 1-hydroxy-8-N-4'-2", 4 "-dichloro-s-triazin-6" -ylamino-phenylamino-3,6-disulfonaphth-2-yl 25 l-hydroxy-8-N-4'-2 "-chloro-4", 3 "-sulfophenylamino-s-triazin -6 "- ylaminophenylamino-3,6-disulfonaphth-2-yl 1-hydroxy-8-N-4'-2" -chloro-4 "-4" '-sulfophenylamino-s-triazin-6 "-ylamino-phenylamino-3 6-disulfonaphth-2-yl 1-hydroxy-8-4'-2 ", 4" -dichloro-s-triazin-6 "-ylamino-phenylamino-30 3,5-disulfonaphth-2-yl, 4-N-4 Sulf or enyl amino-5-sulfonaphth-1-yl 4-N-4'-aminophenylamino-5-sulfonaphth-1-yl 4-N-4'-2 ", 4" -dichloro-s-triazin-6 "- ylaminophenylamino-5-sulfonaphth-1-yl 35 4-N-4'-2 "-chloro-4", 3 "- sulfophenylamino-s-triazin-6" -ylamino-phenylamino-5-sulfonaphth-1-yl 8 0 06 0 4 4> f 9 4-N-3'-aminopheny lamino-5-sulfonaph-1-yl 4-N-4'-methylphenylamino-5-sulfonaphth-1-y1 4-N-2 ' 5'-dimethyl-enylamino-5-sulfonaphth-1-yl 4-N-21-methylphenylamino-7-sulfonaf th-1-yl 5 4-N-3'-methylphenylamino-6-sulfonaphth-1-yl 4-N 4'-methylphenylamino-5,7-disulfonaphth-1-yl 4-N-4'-methoxyphenylamino-5-sulfonaphth-1-yl 4-N-4'-sulfophenylamino-5-sulfonaphth-1-yl 4-N 4'-amino-3'-sulfophenylamino-5-sulfonaphth-1-yl 4-N-4'-sulfophenylamino-7-sulfonaphth-1-yl.

From the above examples of E2, it will be apparent that this group can carry substituents such as dichlorotriazinylamino which are cellulose reactive. In such cases, dyes of formula 1 will therefore contain a second cellulose reactive group, in addition to those described by Q.

Preferred classes of dyes of formula 1 are those having one or more of the following characteristics: (a) Q is a triazinyl or pyrimidinyl group (b) R is ethyl, methyl or especially H, 20 (c) Ej is a group of formula 6 wherein YH is CH 2 OCH 3 or COOH and XH is CH 3 OCH 3 NH 2 NHCO 3 CH 3 NHCO 2 NH 2 or NHCO 2 CO 2 H 5; wherein the group X is ortho to the azo group; or a group of formula 7, and 25 (d) E2 is a group of formula 8 or 9, wherein the ring A has 0 to 2 substituents, both selected from amino, substituted amino, or especially CH 3, 0CH 3, Cl, COOH or SO3H and the group NH is attached to the 1 or 4 position of the naphthalene core.

Particularly preferred groups E2 conform to formula 10, wherein the ring A has substituents as defined above 1 2 and one of the groups B and B is SO 3 H and the other H.

The present invention also provides a process for the preparation of dyes of formula 1, wherein the diazonium salt of an amine of formula 11 is coupled with a 1-N-phenylaminonaphthalene coupling component E2H, wherein Q, R, rn nan 4 4 10 E and E 'have the meanings indicated above.

1 ^

This reaction can be conveniently carried out in an aqueous medium at 0 to 20 ° C, usually with adjustment of the pH to the range of 6 to 8.

The diazonium salt of the amine of formula 11 can be obtained in a conventional manner, for example, by reacting the amine in an aqueous medium with acid and an alkali metal nitrite at 0 to 5 ° C.

The amines of formula 11 can themselves be obtained by reacting an amine of formula 12 with carbyl sulfate or the compound Qhal, wherein hal is halogen and Q is a cellulose reactive group as defined above for Q, except β -sulfatoethylsulfone.

Carbyl sulfate reacts with amino groups to form a β-sulfatoethylsulfonyl group.

This reaction could be suitably carried out in an aqueous medium, desirably in the presence of an acid-binding material, for example sodium carbonate, bicarbonate or hydroxide, and at a temperature appropriate for the reactivity of the compound Qhal, usually from 0 to 100 ° C.

Specific examples of compounds Qhal will be apparent from the specific examples of Q given above. It is normally preferred that hal be chlorine, for example, Qhal is β-chloropropionyl chloride, cyanuric chloride, methoxydichloro-s-triazine, 2,4,5,6-tetrachloropyrimidine, etc., but in some cases hal may be more suitable way, another halogen, for example fluorine, if this is the cellulose reactive substituent present in Q, for example, Qhal can be 2,4,6-trifluoro-5-chloropyrimidine to introduce the difluoro-5-chloropyrimidinyl group.

When the reactive group Q is to have formula 3 as defined above, the reagent Qhal used in the above reaction has formula 13.

This compound can be obtained by reacting a diamine 35 Dnu ^ with a mole of carbyl sulfate or Qhal as defined above and 1 mole of a s-triazine compound of formula 14, wherein Y is a cellulose reactive substituent. In a preferred case where Ht is a chloro-s-triazinyl group, Y is chlorine, i.e. the above-mentioned s-triazine compound is cyanuric chloride.

The amines of formula 12 can themselves be obtained by coupling the diazonium salt from 4-acetylaminoaniline-2,5-disulfonic acid with a para-coupling amine HE ^ N (R) H under conventional coupling conditions in an acidic aqueous medium and displacing the acetyl group by hydrolysis, usually with hot aqueous alkali.

When the para-coupling amine HEjN (R) H carries a hydrolytically labile group, for example acetylamino or ureido, it will also be hydrolysed and converted to, for example, amino. Dyes in which Ej carries hydrolytically labile substituents are obtained by alternative routes. For example, they can be obtained by coupling the para-coupling amine HEjN (R) H with the diazonium salt of 4-amino-aniline-2,5-disulfonic acid, although this often gives lower yields than the acetylaminodiazonium salts.

As examples of para-coupling amines HEjN (R) H

may be mentioned: aniline 3-acetylaminoaniline 3-ureadoaniline 25 3-methylaniline 2-methylaniline 2,5-dimethylaniline 2-methoxy-5-methylaniline 2-methoxyaniline 30 3-methylaniline 3-acetylamino-6-methoxy anin 1 N -methylaniline N-ethylaniline 3-methyl-1-N-ethylaniline 35 1-naphthylamine-6-, -7- and -8-sulfonic acid and -6,8-disulfonic acid 3-aminoaniline.

8 0 06 0 4 4 12

In the cases where Ej in the amine of formula 12 is substituted by an amino group, in addition to HN (R) -, this group may also be reacted with Qhal or carbyl sulfate, simultaneously with HN (R) -. This provides an intermediate compound for the process of the invention leading to dyes of formula 1 wherein Ej is substituted by a cellulose reactive entity, for example dichlorotriazinylamino, in addition to that provided by Q.N (R) -.

In the particular case where Q is a halogen-10-triazinyl group with the residue of a colored amine of the azo series as a non-reactive substituent, this residue can be formed simultaneously with the process of the invention for coupling to E2H. This is accomplished by taking an amine of formula 11 wherein Q is a triazinyl group with a substituent carrying a diazotizable amino group, the amine being tetrazotated and coupled with 2 moles of coupling component. This procedure is particularly useful when the same coupling component is used for the substituent on Q as for providing E2 in Formula 1.

The invention also provides a second process for the preparation of dyes of formula 1 by reacting carbyl sulfate or a compound of formula Qhal as defined above with a dye base of formula 15. The conditions for this reaction are those described above. 25 for preparing amines of formula 11.

The dye base of formula 15 is obtained by monoacetylation of an amine of formula 12, diazotizing and coupling with a 1-N-phenylaminonaphthalene coupling component E2H and hydrolyzing to remove the acetyl group. Thus, the total route of this second process involves two additional steps, namely, an acetylation and a hydrolysis, compared to the first described process of the invention, and for this reason this route is often unattractive. However, the dye base of formula 15 can be conveniently obtained by diazotizing an amino group of 1,4-phenylenediamine-2,5-disulfonic acid, coupling with 1-N-phenylaminonaphthalene coupling component 8006044 13 nent E ^ H, diazotizing the second amino group of the 1,4-phenylene-diamine residue and coupling to a para-coupling amine HEjN (R) H. Alternatively, 4-acetylaminoaniline-2,5-disulfonic acid can be diazotized and coupled to E2H, and the acetyl group can be removed by hydrolysis in coupling the diazotized 1,4-phenylenediamine-2,5-disulfonic acid with E2H. slowly turns out in any case. The second diazotization and coupling with HEjN (R) H is undertaken as before.

The reactive dyes of formula wherein the cell-10 lulose-reactive group Q is an s-triazine core substituted by a chlorine, bromine or fluorine atom and an amino or substituted amino group may also be obtained by a dye of formula I wherein Q is a dichloro, dibromo or difluoro-s-triazine group to react with ammonia or an amine.

This process can conveniently be carried out by stirring the reagents in an aqueous media, optionally in the presence of a water-soluble organic solvent, at a temperature of 30 to 60 ° C, and preferably maintaining the pH at a value of 5 to 8 by adding an acid binding agent to neutralize the hydrogen halide formed during the reaction. Suitable acid-binding agents are alkali metal hydroxides, carbonates and bicarbonates, or an excess of ammonia or aliphatic amine when this is one of the reagents.

Furthermore, by using a diamine in the ratio of 1 mole diamine to 2 moles of the dichloro, dibromo or difluoro-s-triazinyl dye, the product obtained is of the above type when the dye as a whole contains two groups of formula 1 minus Q, connected via two chlorine, bromine or fluoro-s-triazine groups and a diamine group. In the above-mentioned method, any of the above diamines DmH 2 can be used.

By reacting the dichloro, dibromo or difluoro-s-triazine dye with an diamine DmE 2 in equimolar ratio, the resulting product contains a free amino group and it is possible to react it with carbyl sulfate or a compound of the formula Qhal as defined above, whereby the resulting dye contains a cellulose reactive group of formula 3 as defined above, wherein Ht is chlorine, bromine or fluorotriazinyl.

Dyes of this kind can alternatively be obtained by first reacting the diamine with 1 mole of carbyl sulfate or Qhal and reacting the resulting monoamine with 1 mole of dichloro, dibromo or difluoro-s-triazine dye. In the above reactions in which 1 mole of diamine is reacted with 1 mole of carbyl sulfate or Qhal or with a dye having a dichloro, dibromo or difluoro-s-triazinyl group, it is usually preferred that the diamine has amino groups of different reactivity to minimize additional formation of undesired reaction products from 1 mole of the diamine with 2 moles of the other reagent.

Dyes in which Q is a group of formula 4 as defined above are conveniently obtained by reacting the dichloro, dibromo or difluoro-s-triazine dye with an equimolar amount of diamine Dml ^ followed by reaction to manufacture of the residual halogen at the triazine core by a group that is not reactive with cellulose, for example by reaction with ammonia or an amine, and finally reaction with carbyl sulfate or Qhal as described above.

In the cases where Q is a triazinyl group with quaternary ammonium or pyridinium substituents as a cellulose reactive substituent, these dyes can often be conveniently obtained by reacting the corresponding chlorine, bromine or fluoro-triazinyl dyes with the appropriate tertiary amine or pyridine compound. Such a reaction 30 is normally carried out in aqueous media at 30 to 100 ° C. When Q is a triazinyl group with a SO 2 H substituent as a cellulose reactive substituent, the dyes can be conveniently obtained by reacting the corresponding chlorine, bromine or fluorotriazinyl dyes with an alkali metal sulfite in an aqueous medium. at 30 to 100 ° C.

The dyes prepared by the above methods can be isolated by any suitable means, for example, by spray drying or precipitation and filtration.

The dyes of the invention contain sulfonic acid groups which provide water solubility and they can be isolated with such groups in the free acid form. However, it has usually been found to be easier to isolate the dyes in the form of salts, especially alkali metal salts, especially sodium.

The dyes of the invention can be used to color a wide variety of textile materials containing hydroxyl or amino groups, wool, silk, synthetic polyamides, and natural or regenerated cellulose, for example, cotton or viscous rayon materials, used by conventional methods for coloring such materials with water-soluble reactive dyes, for example in the case of cellulose, they are preferably applied in conjunction with an acid-binding treatment, for example sodium hydroxide, sodium carbonate, phosphate, silicate or dicarbo- which can be applied to the cellulose textile materials before, during or after the application of the dye.

The dyes of the invention are valuable reactive dyes for cellulose. They provide colored textile materials with good wash and light resistance. They are usually characterized by good strength and an ability to build up to high tint depths.

The invention is illustrated by the following examples in which all parts are parts by weight.

Example I

To a solution of 71 parts of the disodium salt 30 of 4-acetylamino-2,5-disulfoaniline in 800 parts of water at 0 to 5 ° C is added 13.8 parts of sodium nitrite, followed by 36 ° Tw HCl to adjust the pH of the mixture to 1.8. The diazotization mixture is stirred at 0 to 5 ° C for one hour, then the excess nitrous acid is removed by adding sulfamic acid. A solution of 30.6 parts of 2,5-dimethoxyaniline in 150 parts of water and 20 parts of 36 ° Tw HCl is added to the above diazonium mixture together with sodium acetate crystals to keep the alkalinity on Congo Red, the mixture is stirred overnight and then filtered. The residue on the filter is resuspended in 300 parts of water, 24 parts of sodium hydroxide granules are added and the mixture is stirred at 85 to 90 ° C for 5 hours. The solution is neutralized to pH 5 by addition of hydrochloric acid, cooled to room temperature and the precipitate filtered off. A solution of 5.9 parts of the thus obtained disodium salt of 4,4T-diamino-2,5-dimetho-10-xy-2 ', 5T-disulfo-1,1'-azobenzene in 100 parts of water is added to a stirred suspension of 2.32 parts of cyanuric chloride, 10 parts of acetone and 20 parts of ice. The mixture is stirred at 0 to 5 ° C for one hour, then the pH is raised to 6.5 to 7 by adding a 2N aqueous sodium carbonate solution. 0.86 parts of sodium nitrite, followed by 36 ° Tw HCl to adjust the pH to 1.8, are added, the mixture is stirred at 0 to 5 ° C for one hour and then excess nitrous acid is removed by addition of sulfamic acid. The above diazonium mixture is added with stirring to a solution of 5.7 parts of the disodium salt of 1N-phenylamino-8-naphthol-3,6-disulfonic acid in 100 parts of water, keeping the pH at 6.5 to 7 by addition of sodium carbonate. The coupling mixture is stirred at 0 to 10 ° C for 2 hours, 3 parts of a buffer mixture consisting of 2 parts of potassium dihydrogen phosphate and 1 part of disodium 25 monohydrogen phosphate are added, followed by a solution of 10 g per 100 ml of sodium chloride. The mixture is filtered and the residue on the filter is then dried.

The dye material thus obtained contains 0.9 atoms of hydrolysable chlorine per azo group. When applied to cellulose textile materials in conjunction with an acid binding agent treatment, the dye exhibits excellent build properties and provides strong black tones with good wash and light resistance.

Example II

To a solution of 21.4 parts of the tetrasodium salt of the dichloro-s-triazinylaminodisazo compound prepared as 8 0 06 0 4 4 η in Example I in 700 din water is stirred a neutral solution of 4.5 parts of the sodium salt of 3-sulfoaniline in 35 parts of water and the mixture is stirred at 40 to 45 ° C for 2 hours, keeping the pH at 6.5 to 7 by adding a 2N aqueous solution of sodium carbonate. Sodium chloride (10 g per 100 ml) is added, the mixture is filtered and the residue on the filter is then dried.

The dye material thus obtained contains 0.5 atoms of hydrolysable chlorine per azo group present. When applied to cellulose textile materials in conjunction with the treatment with an acid binding agent, the dye provides strong black tones with good wash and light resistance. Example III

4-Acetylamino-2,5-disulfoaniline is diazotized, coupled to m-toluidine and the resulting monoazo compound is hydrolyzed according to the method described for Example I.

To a solution of 10.7 parts of the disodium salt of 4,4'-diamino-2-methyl-2,5,5-disulfo-1,1'-azobazene thus obtained in 800 parts of water is thus obtained, a solution of 6.2 parts of 5-cyano-2,4,6-trichloropyrim-20 midine in 30 parts of acetone are added and the mixture is stirred at 20 ° C for one hour, then the pH is raised to 5 by addition of 2N aqueous sodium carbonate solution. The solution is sieved and 1.75 parts sodium nitrite is added to the filtrates at 0 to 10 ° C with stirring, followed by 36 ° Tw HCl to adjust the pH 25 to 1.8. The diazotization is allowed to proceed at 0 to 10 ° C for half an hour and then the excess nitrous acid is removed by adding sulfamic acid. The diazonium mixture is added with stirring to a solution of 11.5 parts of the disodium salt of 1N-phenylamino-8-naphthol-3,6-disulfonic acid in 200 parts of water, keeping the pH at 6.5 to 7 by addition of sodium carbonate. The mixture is stirred at 0 to 10 ° C for 3 hours, sodium chloride solution (10 g per 100 ml) is added, the mixture is filtered and the residue on the filter is then dried. The dye material 35 thus obtained contains 0.9 atoms of hydrolysable chlorine per azo group present.

When applied to cellulose textile materials in conjunction with 8 0 06 0 4 4 18

treatment with an acid binding agent provides the dye with strong black tones, resistant to washing and to light. Example IV

The suspension of 2.32 parts of cyanuric chloride in 10 parts of acetone and 20 parts of ice, used in Example 1, is replaced by a neutral solution of 4.7 parts of the sodium salt of 3-sulfo-N-2 ', 4'- dichloro-s-triazin-6'-ylaniline in 120 parts of water and the condensation of the latter with 4,4'-diamino-2,5-dimethoxy-2 ', 5'-disulfo-1,1'-azobenzene is effected at 10 40 to 45 ° C. The aminomonoazo compound thus obtained is cooled to 0 to 10 ° C, diazotized and coupled to 1-N-phenylamino-8-naphthol-3,6-disulfonic acid by the general method described in Examples I to III.

The dye thus obtained is identical in chemical structure, hue and coloring properties to the dye of Example II.

Example V

A neutral solution of 4.65 parts of the di-sodium salt of 4,4'-diamino-1,1'-diphenyl-2,2'-disulfonic acid in 75 parts of water is added to a stirred suspension of 4.64 parts cyanuric chloride, 20 parts of acetone and 20 parts of ice, and the reaction mixture is stirred at 0 to 5 ° C for 1 hour keeping the pH at 6.5 to 7 by addition of 2N aqueous sodium carbonate solution. The solution of bis-di-25-chloro-s-triazinylamino compound thus obtained is added to a solution of 5.3 parts of a disodium salt of 4,4'-diamino-2-methyl-2 ', 5'-disulfo-1, 1'-Azobenzene (prepared as in Example III) in 200 parts of water and the reaction mixture is heated at 35 to 40 ° C for 1 hour when the reaction is complete. The reaction mixture 30 is cooled to 0 to 5 ° G, diazotized and coupled to 1-N-phenyl-amino-8-hydroxynaphthalene-3,6-disulfonic acid by the method described in the previous examples. 3 parts of buffer mixture consisting of 2 parts of potassium dihydrogen phosphate and 1 part of disodium monohydrogen phosphate followed by sodium chloride solution (15 g per 100 ml) are added, the mixture is filtered and the residue on the filter is then dried.

8006044 19

The dye material thus obtained contains 1.35 parts of hydrolysable chlorine per azo group. When applied to cellulose textile materials in conjunction with the treatment with an acid-binding agent, the dye provides black shades with good resistance to light and washing.

Example VI

5.9 parts of 4,4'-diamino-2,5-dimethoxy-2f, 5'-disullo-1,1'-azobenzene are condensed with an equimolar amount of cyanuric chloride and the resulting dichloro-s-triazinyl-amino -10 monoazo compound is diazotized as described in Example 1. The diazonium salt thus obtained is added with stirring to a solution of 4.4 parts of the sodium salt of 1-N-phenylamino-naphthalene-8-sulfonic acid in 100 parts of water at 0 to 10 ° C, wherein the pH of the mixture is maintained at 5 by adding sodium carbonate. The mixture is stirred at 0 to 10 ° C for 2 hours, 3 parts buffer mixture consisting of 2 parts potassium dihydrogen phosphate and 1 part disodium monohydrogen phosphate, followed by sodium chloride (10 g per 100 ml) are added. The mixture is filtered and the residue on the filter is then dried.

The dye material thus obtained contains 0.9 atoms of hydrolysable chlorine per azo group present. When applied to cellulose textile materials in conjunction with an acid binder treatment, the dye exhibits excellent build properties and provides strong navy blue tones with good wash and light resistance.

Example VII

To a solution of 7.6 parts of the hexasodium salt of the product of Example V in 250 parts of water is added 5 parts of ammonium hydroxide liquid (specific gravity 0.88) and the solution is stirred at 35 to 40 ° for 2 hours. C. Sodium chloride solution (15 g per 100 ml) is added, the mixture is filtered and the residue on the filter is then dried.

The dye material thus obtained contains 0.9 parts of hydrolysable chlorine per azo group present. When applied to cellulosic textile materials in conjunction with an acid-binding treatment, the dye provides black tones with good wash and light resistance.

Example VIII

4,4-diamino-2,5-dimethoxy-2f, 5f-disulfo-1,1'-azo-5-benzene is prepared and condensed with an equimolar amount of cyanuric chloride as in Example 1. To a solution of 6.24 parts of the compound thus obtained in 150 parts of water, a solution of 3.8 parts of methylamine in 15 parts of acetone is added and the solution is stirred at 40 to 45 ° C for 2 hours, keeping the pH 10 at 7 by adding a 2N aqueous sodium carbonate solution. The solution is cooled to 0 to 5 ° C, 6.9 parts of sodium nitrite is added, followed by 36 ° Tw HCl to adjust the pH of the mixture to 1.8, and the diazotization is allowed to proceed for 1 hour at 0 to 10 ° C, after which excess nitrous acid is removed by adding sulfamic acid. The diazonium salt is added to a solution of 4.6 parts of the disodium salt of 1N-phenylamino-8-naphthol-3,6-disulfonic acid in 100 parts of water, keeping the pH at 6.5 to 7 by adding sodium carbonate. The mixture is stirred at 0 to 10 ° C for 2 hours, sodium chloride solution (10 g per 100 ml) is added, the mixture is filtered and the residue on the filter is dried.

The dye material thus obtained contains 0.5 atoms of hydrolysable chlorine per azo group present. When applied to cellulose textile materials in conjunction with an acid binding agent treatment, the dye provides strong black tones with good wash and light resistance.

Table A below gives further examples of novel dyes of the invention obtained by the methods described in the previous examples by preparing the diaminomonoazo compound indicated in column B, condensing it with an equimolar amount of the heterocyclic indicated in column C compound, diazotize the aminomonoazo compound thus obtained and couple with an equimolar amount of the coupling component indicated in column D. When ammonia or an amine is indicated in column E, 8006044 21 is released. either reacting with the reaction product of the materials in columns B and G prior to coupling according to the method of Example VIII, or with the product of the coupling as in Example II (both methods yield essentially equivalent final products). The shade of the dyes is reported in column F of Table A.

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To a neutral solution of 10.78 parts of the pentasodium salt of the product of Example XI in 150 parts of water, a neutral solution of 2.2 parts of the sodium salt of 5-3-carboxypyridine in 30 parts of water is added and the reaction mixture is stirred for 6 hours stirred at 90 ° C keeping the pH at 6.5 to 7 by adding a 2N aqueous solution of sodium hydroxide. Sodium chloride solution (10 g per 100 ml) is added, the mixture is filtered and the residue on the filter is then dried.

When applied to cellulose textile materials in conjunction with an acid-binding agent treatment, the dye provides black shades with good wash and light resistance.

35 Example CLXV

The 2.2 parts of the sodium salt of 3-earboxy-pyridine in 30 parts of water used in example CLXIV are replaced by 0.87 parts of pyridine and the reaction mixture is stirred at 90 ° C for 1 hour. Sodium chloride solution at a concentration of 20 g per 100 ml is added, the mixture is filtered and the residue on the filter is then dried.

When applied to cellulose textile materials in conjunction with an acid binding agent treatment, the dye thus obtained provides black tones with good wash and light resistance. y CLXVI image

The 2.2 parts of the sodium salt of 3-carboxypyridine in 30 parts of water used in example CLXIV are replaced with an aqueous solution of 0.6 parts of trimethylamine in 1.5 parts of water and the reaction stirred at room temperature for 1 hour . Sodium chloride solution at a concentration of 12 g per 100 ml is added, the mixture is filtered and the residue in the filter is then dried.

When applied to cellulose textile materials in conjunction with an acid binder treatment, the dye thus obtained gives black tones with good light and wash fastness.

Example CLXVII

To a solution of 31.2 parts of the disodium salt of 4-aminoaniline-2,5-disulonic acid in 400 parts of water is added 5 concentrated hydrochloric acid to bring the pH to 1.5 and the mixture is stirred at 0 to 5 ° C. 52 parts of 2N aqueous sodium nitrite are added over a period of 5 minutes, stirring is continued for another 15 minutes and excess nitrous acid is removed by addition of sulfamic acid. A suspension of 21 parts of m-urea-aniline hydrochloride, 8 parts of thiourea and 1 part of cetylpyridinium bromide in 200 parts of water is added together with 5 parts of sodium acetate and the mixture is stirred at 0 to 10 ° C for 24 hours. Soda ash is added to bring the pH to 7, sodium chloride solution at a concentration of 20 g per 100 ml is added and the mixture is filtered and the residue on the filter is pressed dry.

To a solution of 5.98 parts of the disodium salt of the diaminomonoazo compound thus obtained in 250 parts of water at 0 to 5 ° C, a solution of 2.32 parts of cyanuric chloride in 20 parts of acetone is added and the mixture is stirred for 1 hour. . 6.25 parts of a 2N aqueous solution of sodium nitrite are added, followed by concentrated hydrochloric acid to bring the pH to 1.8. The mixture is stirred for an hour and the excess nitric acid is removed by addition of sulfamic acid. The above diazonium mixture is added to a stirred neutral solution of 5.48 parts of the disodium salt of 1-N-phenylamino-8-naphthol-3,6-disulfonic acid in 100 parts of water, together with soda ash to adjust the pH at 7 and the coupling mixture is stirred at pH 7 and at 0 to 10 ° C for 3 hours. Sodium chloride-30 solution at a concentration of 10 g per 100 ml is added and the mixture is filtered. The residue on the filter is pasted with 1 part of a mixture consisting of 2 parts of sodium dihydrogen phosphate and 1 part of disodium monohydrogen phosphate and then dried.

The dye material thus obtained contains 1 atom of hydrolysable chlorine per azo group present. When applied to 8006044 45 cellulose textile materials in conjunction with an acid binder treatment, the dye exhibits excellent build properties and provides strong blacks with good wash and light resistance.

5 Example CLXVIII

To a solution of 10.72 parts of the tetra-sodium salt of the dichloro-s-triazinylamino-disazo compound prepared as in the previous example in 250 ml of water is added 24 parts of ammonia (specific gravity 0.88) and the mixture is heated for 3 hours at 35 to 40 ° C. Sodium chloride solution at a concentration of 10 g per 100 ml is added, the mixture is filtered and the residue on the filter is then dried.

The dye material thus obtained contains 0.43 atoms of hydrolysable chloride per azo group present. When applied to cellulose textile materials in conjunction with an acid binding agent treatment, the dye exhibits excellent build properties and provides strong blacks with good wash and light resistance.

Using the method described in Examples CLXVII and CLXVIII, the following dyes obtained from the diaminoazo compound in column B are reacted with the heterocyclic compound of column C, followed by diazotization and coupling with the coupling component in column D and optionally reaction with ammonia / amine from column E. The tint of the dyes on cellulose is given in column F.

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Example CLXXXV

To a solution of 14.3 parts of the disodium salt of 4-amino-4'-N-methylamino-2,5-disulfo-1,1'-azobenzene in 250 parts of water at 0 to 5 ° C is 16.7 parts of a 2N aqueous sodium nitrite solution are added, followed by concentrated hydrochloric acid to adjust the pH to 1. The mixture is stirred at 0-5 ° C for one hour, then the excess nitrous acid is removed by adding sulfamic acid. The above diazonium mixture is added to a neutral solution of 10 27.1 parts of the disodium salt of 1N-phenylamino-8-naphthol-3,6-disulfonic acid in 200 parts of water, together with 2N aqueous sodium carbonate solution to adjust the pH 6.5 to 7 and the mixture is stirred at 0 to 10 ° C for 2 hours. Sodium chloride solution at a concentration of 20 g per 100 ml is added, the mixture is filtered and the residue on the filter is pressed dry. A neutral solution of 8.31 parts of the tetra sodium salt of the N-methylamino-disazo compound, thus obtained, in 800 parts is added to a stirred mixture of 1.75 parts of cyanuric chloride, 20 parts of acetone and 40 parts of ice / water, keeping the pH at 6.5 to 7 by adding 2N aqueous sodium carbonate solution and the mixture is stirred at 0 to 10 ° C for 3 hours. Sodium chloride solution at a concentration of 10 g per 100 ml is added, the mixture is filtered, the residue on the filter is pasted with 0.66 parts of a mixture consisting of 1 part of disodium monohydrogen phosphate and 2 parts of potassium dihydrogen phosphate and then dried.

The dye material thus obtained contains 1 atom of hydrolysable chlorine per azo group present. When applied to cellulose textile materials in conjunction with an acid binding agent treatment, the dye provides strong black tones, identical to the product of Example XVII.

Example CLXXXVI

The 31.2 parts diazonium salt of the disodium salt of 4-aminoaniline-2,5-disulfonic acid prepared as described in Example 167 is added to a neutral solution of 44.3 parts of the 1N-phenylamino-8 disodium salt. naphthol-3.6-8 0 06 0 4 4 49 disulfonic acid in 300 din water together with 3N aqueous sodium carbonate solution to maintain the pH at 6.5 to 7 and the coupling mixture is stirred at 0 to 5 ° for 5 hours C. A portion of the above solution of 1N-phenylamino-y ^ -amino ^, 5'-5-disulfophenylazo-8-naphthol-3,6-disulfonic acid (0.05 µmole) is diazotized at 0 to 5 ° C by adding concentrated hydrochloric acid to adjust the pH to 2, followed by pressing a 5N aqueous sodium nitrite solution to give an excess of nitrous acid. The mixture is stirred for one hour, then excess nitrous acid is removed by adding sulfamic acid.

6.9 parts of 2-methoxy-5-methylaniline are dissolved in 40 parts of water by adding 10 parts of concentrated hydrochloric acid, the solution is cooled to 0 to 5 ° C and its pH is adjusted to 5 to 5.5 by adding 3N aqueous sodium carbonate solution.

The above diazonium mixture is added to the latter solution together with 3N aqueous sodium carbonate solution to maintain the pH at 5 to 5.5 and the mixture is stirred for 6 hours, after which the coupling is complete. To the above solution of aminodisazo compound, thus prepared, a solution of 11.1 parts of cyanuric chloride in 75 parts of acetone is added along with 3N aqueous sodium carbonate solution to maintain the pH of the mixture at 6 to 6.5 and the mixture is adjusted for 2 hours stirred at 0 to 5 ° C. 21 parts of ammonia (specific gravity 0.88) is added and the mixture is stirred at 30 ° C for 3 hours.

Sodium chloride solution at a concentration of 15 g per 100 ml is added, the mixture is filtered and the residue on the filter is then dried. The dye thus obtained is identical in chemical structure, hue and paint properties to the dye of Example XXXIV.

Table C below gives further examples of novel dyes of the invention prepared by the method described in Example CLXXXVI. Dizotated 4-amino-aniline-2,5-disulfonic acid is coupled to a phenylamino naphthalene to provide the aminomonoazo compound indicated in column B. This aminomonoazo compound is diazotized and coupled to the β-coupling amine indicated in column C. The aminodisazo compound thus obtained is condensed with the heterocyclic compound indicated in column D of Table C. When an amine is indicated in column E, it can either be reacted with the reaction product of materials in columns B, C, D or sequentially with the heterocyclic compound in column D and with the reaction product of materials in columns B and C .

The tint of the dyes on cellulose is indicated in column F.

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Example CCXXXIX

To a solution of 12.48 parts of the disodium salt of 4-2 ', 4'-dichloro-s-triazin-6'-ylamino-4'-amino-2,5-dimethoxy-2', 5'- disulfo-1,1'-azobenzene, prepared as in Example 1.5 in 300 parts water, a solution of 9.52 parts of the disodium salt of 4,4'-diamino-2,5-dimethoxy-2 ' 5'-disulfo-1,1'-azobenzene in 250 parts of water is added and the reaction mixture is heated at 40 to 45 ° C for 3 hours, keeping the pH at 7 by adding 2N aqueous sodium carbonate solution. The solution is cooled to 0 to 5 ° C, 2.76 parts of sodium nitrite are added, followed by 36% hydrochloric acid to adjust the pH of the mixture to 1.8. The tetrazotation mixture is stirred at 0 to 10 ° C for 1 hour with excess nitrous acid present, then the latter is removed by addition of sulfamic acid. The mixture is added with stirring to a neutral solution of 18 parts of 1-N-phenylamino-8-naphtho-3,6-disulfonic acid (ie 2 moles) in 700 parts of water at 0 to 10 ° C with the pH at 6. 5 to 7 is kept by adding 2N aqueous sodium carbonate solution. The coupling mixture is stirred at 0 to 10 ° C for 3 hours, sodium chloride solution at a concentration of 18 g per 100 ml is added and the mixture is filtered. The residue on the filter is then dried.

The dye material thus obtained contains 0.25 atoms of hydrolysable chlorine per azo group present. When applied to cellulose textile materials in conjunction with an acid binding agent treatment, the dye provides strong black tones with good resistance to light and washing.

Example CCXL

The 12.48 parts of the disodium salt of 4-2 ', 4'-di-30 chloro-s-triazin-6'-ylamino-4'-amino-2,5-dimethoxy-2', 5'-disulfΟ , 1 '-azobenzene and the 9.52 parts of the disodium salt of 4,4'-di-amino-2,5-dimethoxy-2', 5'-disulfo-1,1'-azobenzene used in example CCXXXIX are replaced by equimolar amounts of the disodium salt of 4-2 ', 4'-dichloro-s-triazin-6'-ylamino-35, 4'-amino-2-methyl-2', 5'-disulfo-1,1'- azobenzene and 4,4'-diamino-2-methyl-1,1,1-azobenzene The dye thus obtained is identical to the product of Example CLXI.

Example CCXLI

The disodium salt of 4,4'-diamino-2-methyl-2 ', 5-disulfo-1,1'-azobenzene used in example CCXXXIX is replaced by an equimolar amount of the disodium salt of 4,4'-diamino- 2-methyl-5-methoxy-21,5'-disulfo-1,1'-azobenzene.

The dye thus obtained is identical to the product of Example CLXII.

8006044

Claims (6)

1. Reactive dyes of formula 1, wherein Q is a cellulose reactive group, is RH or a C 1-6 alkyl group, optionally substituted by 5 OH, CN, SO 3 H or 0 SO 3 H, E 1 an optionally substituted 1,4-phenylene or 1,4-naphthylene group, D is a 2,5-disulfo-1,4-phenylene group, and an optionally substituted 1-N-phenylaminonaphthyl group. 2. Ht * - Dm; - Q1 4 (β: χη ^ Γ ’, -Q- Dyes according to claim 1, characterized in that Q is a triazinyl or pyrimidinyl group. Dyes according to claim 1 or 2, characterized in that R is hydrogen, methyl or ethyl. Dyes according to claim 3, characterized in that R is hydrogen. Dyes according to any one of the preceding conditions, characterized in that Ej is a group of formula 6, wherein Y is H, CH 2 OCH 3 or COOH, and X is H, CH 3, OCH 3, NH 2, NHCO 2 CH 3, NHCO 2 NH 2 or NHCOOC 2 H 5; Wherein the group X is ortho to the azo group. Dyes according to any one of the preceding claims, characterized in that E2 is a group of Formula 8 or 9, in which the rings A have 0 to 2 substituents selected from CH 3> OCH 3, Cl, COOH or SO 3 H and the group NH in Formula 9 attached to the 1 or 4 position. Dyes according to claim 6, characterized in that E_ complies with formula 10, wherein A is substituted as indicated as ^ 1 2 including claim 6 and one of the groups B and B is SO 3 and the other is H. Dyes substantially as described in the description and / or the examples. 9. Process for the preparation of dyes as defined in any one of the preceding claims, characterized in that the diazonium salt of the amine of formula 11 is coupled with a 1-N-phenylaminonaphthalene coupling component E2H, wherein Q, R, E ^ and E2 have the meaning indicated in claim 1. 8006044 Process for the preparation of dyes as defined in any one of claims 1 to 8, characterized in that carbyl sulfate or a compound of formula Qhal is reacted with a dye base of formula 15, wherein D, Ej, 5 and R has the meaning indicated in claim 1 and Q is a cellulose reactive group as defined in claim 1 but different from 8-sulfatoethylsulfone and hal is halogen. 11. A method of coloring cellulose textile materials, characterized in that a dye as described in any one of claims 1 to 8 or as obtained according to the method of claim 9 or 10 is applied together with an acid-binding agent. . 12. Methods and articles essentially as described in the description and / or the examples. 15 / ƒ i 8006044 9 y Qi_n {r) -E1-N = N-D-N = N — Et N— —Ht - Dm— Q * 6 Q 7 so3h "H 0- NH OH flf ^ -iSOjH) ί ^ ΐΓΊ- V 'Ui AJl-L I 8 f SOjH k 10 0 —NH — Cj ^ - (SOjHli4 9 so3h Q — N (R) - Ei - N = N — f \ -NHi V = / S% H SO3H 11, jf \ H — N (R) - Ei — N = N- \ J— NHi hal-Ht— Dm - S05H hall 13 HN (R) —Ε-y — N = N — D —N = N - Ea h 'N 1 5 15 hat NY 14 8 0 060 4 4