CS232734B2 - Method of making water-soluble monoazo-compounds - Google Patents

Abstract

Wasserlösliche Monoazoverbindungen mit faserreaktiven Farbstoffeigenschaften der allgemeinen Formel (1) in welcher bedeuten:

D ist eine Gruppe der Formel (2a) oder (2b) in welchen

• M ein Wasserstoffatom oder das Äquivalent eines ein-, zwei- oder dreiwertigen Metalls ist,
• R¹ ist ein Wasserstoffatom, eine Alkylgruppe von 1 - 4 C-Atomen, eine Alkoxygruppe von 1 - 4 C-Atomen oder ein Chloratom;
• R² ist ein Wasserstoffatom, eine Alkylgruppe von 1 - 4 C-Atomen oder eine Alkoxygruppe von 1 - 4 C-Atomen;
• R ist die Methylgruppe, eine Carboxygruppe oder eine Carbalkoxygruppe von 1 - 4 C-Atomen oder eine Alkoxygruppe von 1 - 4 C-Atomen;
• K ist ein Phenylrest oder Naphthylrest, die beide durch 1, 2 oder 3 Substituenten aus der Gruppe Sulfo, Carboxy, Sulfamoyl, Carbamoyl, Alkyl von 1 4 C-Atomen, Alkoxy von 1 - 4C-Atomen und Chlor und gegebenenfalls durch eine Gruppe der Formel -SO₂-Z substituiert sein können, in welcher Z für die β-Hydroxyäthyl-Gruppe steht oder eine Gruppe Y der nachstehend angegebenen Bedeutung ist;
• Y ist die Vinylgruppe oder eine Äthylgruppe, die in β-Stellung einen als Anion alkalisch eliminierbaren Rest enthält, wie beispielsweise eine β-Sulfatoäthyl-Gruppe;
• p steht für die Zahl Null oder 1, ist jedoch zwingend 1, falls der Formelrest K nicht durch die Gruppe -SO₂-Y mit Y der oben genannten Bedeutung substituiert ist.

Die neuen Monoazoverbindungen werden analog bekannten Verfahrensweisen aus den aus Formel (1) ersichtlichen Komponenten (der Pyrazolon-Kupplungskomponente, der Disulfo-di-amino-Verbindung der Formel H₂N-D-NH₂, Cyanurchlorid und der Anilinverbindung, die eine Gruppe -SO₂-Y enthalten kann) hergestellt. Sie liefern beispielsweise auf Cellulosefasermaterialien farbtiefe und echte Färbungen und Drucke.

Description

¹

A process for the preparation of water-soluble monoazo compounds of the general formula 1

used to dye materials containing hydroxy and / or carboxamido groups.

The invention relates to a process for the production of water-soluble monoazo compounds and to their use as fiber-reactive dyes.

New water-soluble, fiber-reactive monoazo compounds which correspond to the general formula 1 have been found.

(I) in which:

D represents a group of formula 2a or 2b

in which

M represents a hydrogen atom or the equivalent of a monovalent, divalent or trivalent metal, such as in particular an alkali metal or an alkaline earth metal such as sodium, potassium and calcium;

R ¹ is hydrogen, alkyl having 1 to 4 carbon atoms such as ethyl and especially methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and especially methoxy, or chlorine;

R ² is hydrogen, alkyl having 1 to 4 carbon atoms such as ethyl and especially methyl, or alkoxy having 1 to 4 carbon atoms, such as ethoxy and especially methoxy, wherein R ¹ and R ² may be mutually the same or different meanings;

R is methyl, carboxy of the formula —COOM wherein

M is as defined above, or a C 2 -C 5 alkoxycarbonyl group, such as a methoxycarbonyl group or an ethoxycarbonyl group;

K is phenyl or naphthyl, both of which may be substituted with 1, 2 or 3 substituents selected from the group consisting of sulfo, carboxy, sulfamoyl, carbamoyl, (C 1 -C 4) alkyl, such as ethyl and in particular methyl, C1-C4alkoxy, such as ethoxy and especially methoxy, and chloro and optionally a group of the formula

-SO2-Z in which

Z is β-hydroxyethyl or Y is as defined below;

Y represents a woolly group or an ethyl group which contains, in the p-position, a residue which is alkali eliminable as an anion, such as a p-thiosulfatoethyl group (corresponding to the formula -CH 2 -CH 2 -S-SO 5 M)

M is as defined above), Mostatoethyl (corresponding to the formula —Cs — CH2 — OPO3M2 where

M is as defined above, a 1-chloroethyl group or a 1-acetyloxyethyl group, or preferably a 3-sulfatoethyl group (corresponding to the formula -CH 2 -CH 2 -OSO 3 M wherein:

M is as defined above);

p is 0 or 1, but necessarily is 1 if the residue K is not substituted by a -SO2-Y group with Y as defined above.

The radical K is preferably a radical of formula 2C or 2D

(2d) in which

R ³ , R ⁴ and X are the same or different from each other; and

R ³ represents hydrogen or halogen, such as chlorine or sulfo group of the formula -SO 3 M with M defined as above, or an alkyl group having 1 to 4 carbon atoms such as methyl group or ethyl group, or an alkoxy group having 1 to 4 carbon atoms such as methoxy or ethoxy,

R ⁴ is hydrogen or halogen, such as chlorine or sulfo group of the formula -SO 3 M with M as above defined or represents alkyl having 1 to 4 carbon atoms such as methyl group or ethyl group, or an alkoxy group having 1 to 4 carbon atoms, as methoxy or ethoxy, and

X represents a hydrogen atom or a sulfo group of the formula -SO 3 M, where M is as defined above, or represents a group of the formula 2e - (SO 2 -Z) _n (2e) wherein

Z is as defined above and n is 0 or 1, and when n is zero or Z is 3-hydroxyethyl, the index p in formula 1 above necessarily represents 1.

The radical K is in particular a mono-, di-or trisulfonaphthyl radical, monosulfophenyl radical, 2,4-disulfophenyl radical, 2,5-disulfophenyl radical, 3,5-disulfophenyl radical, monochlormonosulfophenyl radical, dichlorormonosulfophenyl radical, monomethylmonosulfophenyl radical, monochlormonomethylethyl monosulphonyl radical or 2f

in which

R ^3, R ^4, Z and n have the abovementioned meanings.

The novel azo compounds can exist both in acid form and in the form of their salts. Preferred are the compounds in the form of salts, in particular in the form of alkali metal salts and in the form of alkaline earth metal salts, and are also preferably used in the form of these salts for dyeing (herein and hereinafter are generally understood and include printing) materials containing hydroxyl groups and / or carboxamido groups, in particular fibrous materials.

It is an object of the present invention to provide a process for the preparation of the aforementioned and defined azo compounds of formula (I), comprising:

(fii) in which:

A represents a hydrogen atom or a group of the general formula (a) or (b)

(b)

а

D, R ¹ , R ² , Y and p are as defined above, in the case of an amine of formula II in which A is a group of formula (a), after diazotizing it to a diazonium salt, acts with a compound of formula III (c'l)

R (lit) wherein

R and К have the meanings given above and

В represents a hydrogen atom or a group of formula (b ‘) or (c‘)

H2N — D — N = N— (b ‘) where

D is as defined above, when A is hydrogen then В is a group of formula [c '), if A is a group of formula (а) then В is a hydrogen atom and if A is a group of formula (b) V represents a group of formula (b '), and the reactants are selected such that the resulting azo compound corresponding to the general formula 1 contains at least one group of the above-defined formula -SO 2 Y.

The process according to the invention is illustrated in more detail by the following specific embodiments in which the diazonium compound of the amine of formula 3 is coupled.

in which

R ¹ , R ² , p, D and Y are as defined above, with a pyrazolone derivative of the general formula 4 wherein:

D, R and К are as defined above, reacted with a dichlorotriazine derivative of general formula 6 k

(41 in which

R and K are as defined above, or an ammoazo compound of formula 5

OH k ~ N — K

H-N-D-N-N-ph

in which

R ¹ , R ² , p and Y are as defined above, or a dichlorotriazine derivative of the formula 7

5 (5)

H2N — D — NH2

Ct

K (71 in which

D is as defined above. with a d 'cblortriazine derivative of the above-defined and defined general formula (6) or by reaction of cyanuric chloride (2,4,6-trichloro-1,3,5-triazine), first with a diamino compound of the above-defined general formula

H 2 N-D-NH 2 to give a compound of formula 9 wherein

D, R and K are as defined above, reacted with an amino compound of formula 8

in which

R1, R2, p and Y are as defined above, wherein the reactants are selected such that the resulting azo compound corresponding to formula 1 contains at least one group of the formula -SO2-Y as defined above.

In the starting compounds of formulas 3, 4, 5, 6, 7 and 8, the radical Y (in the radical K can be represented by the radical Z) can also be a β-hydroxyethyl group. The compounds of formula (1) thus obtainable in which Y or Z or both are a β-hydroxyethyl group can be converted by the corresponding esterification or acylating agent analogously to known methods into the corresponding compounds of the invention of formula (1) wherein Y optionally Z represents an ethyl group which is substituted in the .beta.-position with an ester residue. As esterification, sulfation is preferred, i.e. the conversion of the β-hydroxyethyl group to the β-sulfatoethyl group analogously to a number of methods known in the literature, preferably sulfuric acid or sulfuric acid containing sulfuric acid is used as the sulfating agent.

This esterification, preferably sulfation, is necessary when Y in the starting compounds of formulas 3, 6 and 8 is (hydroxymethyl).

The amines of the formula (3) which serve as starting materials can be prepared in analogy to known processes, for example by reaction of a diamine compound of the formula

Cl

Cl

ЛЛNH-D-NH _Z (9) in which

D is as defined above, and this compound is then reacted with an amine of the above-defined general formula (8).

Likewise, the dichlorotriazine derivatives corresponding to the general formula (6) which they serve can be prepared analogously to known processes. as a starting material, for example by reacting cyanuric chloride with an amine of the above-defined general formula (8).

The synthesis of the dichlorotriazine derivative of the general formula (7) can be carried out analogously to known methods, by condensation of the cyanuric chloride with the aminoazo compound of the aforementioned and defined general formula (5) or by reaction. diazonium amine compounds of the above-defined general formula. 9 with a pyrazolone derivative of the above-defined general formula 4.

Both the reaction of cyanuric chloride with an aminoazo compound of formula 5 to form a compound of formula 7, and the reaction of cyanuric chloride with an amino compound of formula 8 to form a compound of formula 6 can be carried out in an organic or aqueous-organic medium. Preferably, the reaction is carried out in an aqueous medium with the addition of acid-binding agents such as alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal bicarbonates or alkali metal or alkaline earth metal hydroxides or alkali metal acetates, the alkali metals and alkali metals The soils are preferably sodium, potassium and calcium. Acid binding agents are also tert ^; linear amines such as pyridine or triethylamine or quinoline. These condensation reactions are carried out at a temperature of 232 ° C to between -10 ° C and 4-40 ° C, preferably between -10 ° C and + 30 ° C, particularly preferably at a temperature between 0 ° C and 10 ° C as well as at a pH between 1.0 and 7.0, preferably between 3.5 and 5.

Reaction of the dichlorotriazinylamino derivatives of the formulas 6, 7 and 9 with the corresponding amino compounds of the formulas 5, 8 and the above defined formula

The H 2 N-D-NH 2 according to the invention to form the compounds of the formula 1 and optionally the intermediates of the formula 3 can also be carried out in an organic or aqueous-organic medium. Preferably, however, it is carried out in an aqueous medium, with the addition of an acid binding agent as described above, as required. The reaction of the amino groups with the chlorine of the triazine compounds in the process of the invention is preferably carried out at a temperature between 10 and 60 ° C, particularly preferably at temperatures between 20 and 50 ° C, and at a pH between 2 and 9, especially between 3 and 8.

The diazotization of the amino compounds of formula (2) or (9) is carried out analogously to known methods, for example in an aqueous-organic, and especially in an aqueous, acidic environment by treatment with nitrous acid. The reaction of the diazonium compounds with the pyrazolone derivatives of the general formula (4) is likewise carried out analogously to known methods, for example in an aqueous-organic but mostly aqueous medium, in a weakly acidic to neutral or very weakly alkaline pH range.

The amino compounds of the general formula 8 with p = 1 which serve as starting materials for the preparation of the compounds according to the invention include, for example:

1-amino-3- (β-sulfatoethylsulfonyl) benzene, 1-amino-2-methoxy-5- (β-sulfatoethylsulfonyl) benzene, 1-amino-2-methoxy-4- (β-sulfatoethylsulfonyl) benzene, 1 -amino-2-methyl-5- (β-sulfatoethylsulfonyl) benzene, 1-amino-2-methyl-4- (β-sulfatoethylsulfonyl) benzene, 1-amino-4-methoxy-5- (4-sulfatoethylsulfonyl) benzene, 1-amino-4-methyl-5- (β-sulfatoethylsulfonyl) benzene, 1-amino-2-methoxy-5-methyl-4- (3-sulfatoethylsulfonyl) benzene, 1-amino-2,5-dimethoxy- 4- (β-sulfato-ethylsulfonyl) -benzene, 1-amino-2,4-dimethoxy-5- ($ - sulfatoethylsulfonyl) benzene,

1-amino-2-methyl-5-methoxy-4- (1,3-sulfatoethylsulfonyl) benzene,

2-chloro-1-amino-5- (β-sulfatoethylsulfonyl) benzene,

4-chloro-1-amino-2-methyl-3- (3-sulfatoethylsulfonyl) benzene,

5-chloro-1-amino-2-methoxy (β-sulfatoethylsulfonylbenzene), as well as the corresponding β-thiosulfatoethylsulfonyl derivatives, β-phosphatoethylsulfonyl derivatives, β-chloroethylsulfonyl derivatives, β-acetoxyethylsulfonyl derivatives, and vinylsulfonyl derivatives of these sulfonyl derivatives further preferably 1-amino-4- (β-sulfethoxyethylsulfonylbenzene) and its corresponding thiosulfatoethyl derivatives, phosphatoethyl derivatives, chloroethyl derivatives, acetoxyethyl derivatives and vinyl derivatives, and optionally β-hydroxyethyl derivatives.

Amino compounds of formula 8 with p = zero, which can serve as starting compounds for the preparation of the compounds of the invention, include, for example:

aniline, 1-aminobenzene-3-sulfonic acid,

1-aminobenzene-3,5-disulfonic acid,

2-aminotoluene,

3-aminotoluene,

4-aminotoluene,

2-aminotoluene-4-sulfonic acid,

2-aminotoluene-5-sulfonic acid,

2-amino-toluene-4,5-disulfonic acid,

2-aminotoluene-4,6-disulfonic acid,

3-aminotoluene-6-sulfonic acid,

4-aminotoluene-2-sulfonic acid,

4-aminotoluene-3-sulfonic acid,

2- ammoanisole,

3-aminoanisole,

4-aminoanisole,

2-aminoanisole-4-sulfonic acid,

2-aminoamsol-5-sulfonic acid,

4-aminoanisole-2-sulfonic acid, 2-chloroaniline-4-sulfonic acid,

2-chloroaniline-5-sulfonic acid,

3-chloroaniline-4-sulfonic acid,

3-chloroaniline-6-sulfonic acid,

4-chloroaniline-3-sulfonic acid, 2,5-dichloroaniline-4-sulfonic acid.

Pyrazolone derivatives which correspond to the general formula 1 and which serve as starting materials for the production of the azo compounds according to the invention include, for example:

1- (2'-sulfo-enyl) -3-methylpyrazol-5-one,

1- (3‘-sulfophenyl) -3-methylpyrazol-5-one,

1- (4‘-sulfophenyl) -3-methylpyrazol-5-one,

1- (2 ', 4'-disulfophenyl) -3-methylpyrazol-5-one,

1- (3 ‘, 5‘-disulfophenyl) -3-methylpyrazol-5-one,

1- (2 ', 5'-sulfonylphenyl) -3-methylpyrazol-5-one, 1- (2'-ch] Or-4'-sulfophenyl) -3-methylpyrazol-5-one, 1- [2' -chloro-5'-sulfophenyl) -3-methylpyrazol-5-one,

1- (2 ', 5'-d: chloro-4'-sulfophenyl) -3-methylpyrazol-5-one; 1- (2'-methyl-4'-sulfophenyl) -3-methylpyrazole-5- he,

1- (4‘-Methyl-2‘-sulfophenyl) -3-methylpyrazol-5-one;

1- (2‘-Methyl-3‘-chloro-4‘-sulfophenyl) -3-methylpyrazol-5-one,

1- (2'-chloro-6'-methyl-4'-sulfophenyl) -3-methylpyrazol-5-one; 1- (3'-carboxyphenyl) -3-methylpyrazol-5-one _;

1- (3‘-Sulfamoylphenyl) -3-methylpyrazol-5-one,

1- (4‘-Sulfamoylphenyl) -3-methylpyrazol-5-one;

1- (6'-sulphonaphth-2'-yl) -3-methylpyrazole-5-one, l- (4 ', 8 ⁱ -clisulfonaft-2'-yl) -3-methylpyrazole-5-one;

1- [5‘, 7‘-disulfonaphth-2‘-yl) -3-methylpyrazol-5-one,

1- (3R, 6R, 8'-Trisulfonaphth-2'-yl) -3-methylpyrazol-5-one.

1- (4 ‘, 6‘, 8 ‘-trisulfonaphth-2‘-yl) -3-methylpyrazol-5-one,

1- (6'-sulfonaphth-Γ-yl) -3-methylpyrazol-5-one,

1- [7'-sulfonaphth-1-yl) -3-methylpyrazol-5-one,

- [3 ‘- (1,6-Sulfethoxyethylsulfonyl) phenyl] -3-methylpyrazol-5-one,

1- [4'- (1'-sulfonylethylsulfonyl) phenyl] -3-methylpyrazol-5-one, 1- [3'- or 4 '- (4-thiosulfatoethylsulfonyl) phenyl] -3-methylpyrazol-5 -one, 1- [3'- or 4 '- [(3-phosphatoethylsulfonyl) phenyl] -3-methylpyrazol-5-one, 1- [3'- or 4' - (3-acetoxyethylsulfonyl) phenyl] -3-methylpyrazol-5-one, 1- [3'- or 4 '- (4-chloroethylsulfonyl) phenyl] -3-methylpyrazol-5-one,

1- [3'- or 4'-i. ₁ H -hydroxyethylsulfonyl) phenyl] -3-methylpyrazol-5-one, furthermore compounds of the above type in which, instead of the methyl group at the 3-position of the pyrazolone ring, a carboxy or methoxycarbonyl or ethoxycarbonyl group, further pyrazol-5-one derivatives, which are substituted in the 3-position of this pyrazole ring by a methyl or carboxy group or a methoxycarbonyl or ethoxycarbonyl group and in each case at the 1-position of the pyrazolone ring are substituted

2-methoxy-5-methyl-4- (β-sulfatoethylsulfonyl) phenyl,

2,5-dimethoxy-4- (β-sulfatoethylsulfonyl) phenyl,

2-methyl-5- (β-sulfatoethylsulfonyl) phenyl,

4-methyl-5- (β-sulfatoethylsulfonyl) phenyl,

2-methoxy-5- (β-sulfatoethylsulfonyl) phenyl,

4-methoxy-5- (β-sulfatoethylsulfonyl) phenyl,

2-methoxy-4- (4-sulfatoethylsulfonyl) phenyl,

2-methyl-4- [β-sulfatoethylsulfonyl) phenyl,

2,4-dimethoxy-5- ($ - sulfatoethylsulfonyl) phenyl,

2-methyl-5-methoxy-4- (O-sulfatoethylsulfonyl) phenyl or a phenyl group in which the sulfatoethylsulfone group is replaced by a β-thiosulfatoethylsulfonyl group, a β-phosphatoethylsulfonyl group, a β-chloroethylsulfonyl group, a β-acetoxyethylsulfonyl group , a β-hydroxyethylsulfonyl group, a 4-hydroxyethylsulfonyl group or a vinylsulfonyl group.

As dramino compounds corresponding to the above general formula

H2N-D-NH2 which can be used as starting materials for the production of the azo compounds of the invention can be mentioned

1,3- diam ^; inobenzene-4,6-disulfonic acid a

1,4-diammobenzene-2,5-disulfonic acid.

The isolation and isolation of the compounds of formula 1 produced by the process of the invention from the reaction mixture can be carried out by generally known methods, such as either precipitation from the reaction mixture with electrolytes such as sodium chloride or potassium chloride, evaporating the reaction solution, e.g. wherein a buffering agent can be added to the reaction solution.

The compounds of the formula I according to the invention are fiber-reactive and have very good dye properties. They can therefore be used for dyeing (including printing) materials containing hydroxyl groups and / or carboxamido groups. Solutions resulting from the synthesis of the compounds according to the invention may also be used, optionally after addition of buffers and optionally after concentration, which are directly supplied as a liquid dye preparation for dyeing.

The compounds of the formula I are thus suitable for dyeing (including printing) materials containing hydroxyl groups and / or carboxamido groups, or methods for their use on such substrates.

These materials are suitable in the form of fibrous materials, in particular in the form of textile fibers, such as yarns, windings and fabrics. It is possible to proceed analogously to the known processes by applying the monoazo compound of the formula I in dissolved form to the substrate or impregnating it and then fixing it to the material or the material, optionally under the effect of heat and / or optionally by the action of alkaline reagents.

Materials containing hydroxyl groups are materials of natural or synthetic origin, such as cellulose fiber materials or regenerated cellulose materials and polyvinyl alcohols.

The cellulosic fibrous materials are preferably cotton, but also other vegetable fibers, such as flax, hemp, jute, and ramie fibers. The regenerated cellulose fibers are, for example, viscose staple and viscose rayon.

Carboxamido-containing materials are, for example, synthetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal fibers, silk, leather, polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4.

The compounds of the formula (1) produced by the process of the invention can be applied and fixed to said substrates, in particular to said fibrous materials, by application techniques known for water-soluble dyes, in particular for water-soluble and fiber-reactive dyes. Such dyeing and fixing procedures are described in the literature in numerous places.

Thus, with these dyes, very good dye yields, as well as excellent color compositions, are obtained on the cellulose fibers by long bath extraction processes using a variety of acid-binding agents and optionally neutral salts such as sodium chloride or sodium sulfate. The dyeing is preferably carried out in a water bath at temperatures between 60 and 105 ° C, optionally at temperatures up to 120 ° C under pressure and optionally in the presence of conventional dyeing aids. This can be done by placing the material in a warm bath and slowly heating the bath to the desired dyeing temperature and completing the dyeing process at this temperature. Neutral salts which accelerate dye uptake can only be added to the bath after the dyeing temperature has been reached.

The dyeing process also achieves excellent dye yields and very good color compositions on the cellulosic fibers, and fixation can be carried out by dwelling at room temperature or at elevated temperature, for example up to about 60 ° C, by steaming or dry heat in the usual manner.

Also, according to conventional printing processes for cellulose fibers, which can be carried out in one phase by, for example, printing with a printing paste containing sodium bicarbonate or other acid binding agent and subsequent steaming at temperatures of 100 to 103 ° C or biphasic, for example by printing with neutral or weakly acidic ink and subsequent fixation. by conducting the printed material with an electrolyte-containing hot alkaline bath or by overprinting the printed material with an electrolyte-containing alkaline bath, followed by a delay or steaming, or by applying dry heat to the overcoated material, color-intensive prints with good contour status and bright white pool are obtained. The quality of these prints remains virtually unaffected by the changing fixation conditions.

Dry heat fixation according to conventional thermofixation procedures uses hot air at a temperature of 120 to 200 ° C. In addition to the usual water steam at a temperature of 101 to 103 ° C, preheated steam and pressure steam at temperatures up to 160 ° C can also be used.

Acid binding agents and agents causing f ^? The xation of the compound of formula 1 into cellulose fibers is, for example, the water-soluble basic salts of alkali metals and optionally alkaline earth metals with inorganic or organic acids or compounds which release alkali in the heat. Particular mention should be made of alkali metal hydroxides and alkali metal salts derived from mild to moderate inorganic or omic acids, of which the alkali metal compounds are preferably sodium and potassium compounds. Such acid-binding agents are, for example, sodium hydrogen carbonate, potassium carbonate, sodium formate, sodium phosphate, sodium phosphate, sodium chloroacetate, water glass or sodium phosphate.

By the action of acid-binding agents on the compounds according to the invention, optionally under the effect of heat, the compounds according to the invention (dyes) - chemically bind to cellulose fibers; on these fibrous materials, the dyeing and printing processes are characterized by a very high fixation yield. The dyeings on cellulose fibers exhibit excellent wet fastness after the usual rinsing action to remove unfixed dye fractions and, moreover, unfixed dye fractions are readily washable due to their good solubility in cold water. .

The dyeing of polyurethane and / or natural or synthetic polyamide fibers is usually carried out from an acid medium. Thus, for example, acetic acid and / or ammonium sulphate and / or acetic acid and ammonium acetate or sodium acetate can be added to the dyeing bath, in order to achieve a useful color uniformity, it is advisable to add conventional leveling aids such as based on the reaction product of cyanuric chloride with a triple molar amount of aminobenzenesulfonic acid and / or aminonaphthalenesulfonic acid, or based on the reaction product, for example, stearylamine with ethylene oxide. Generally, the dyeing material is introduced at a temperature of about 40 ° C into the bath, kept there for some time, the dyeing bath is then adjusted to the desired slightly acidic, preferably by the addition of a slightly acidic pH, by addition of acetic acid, and the dyeing is carried out at between 60 and 98 ° C. The dyeing can also be carried out at boiling temperatures of up to 120 ° C (under pressure).

The dyeings and prints obtained using the compounds of the formula I according to the invention are generally characterized by bright greenish yellow, reddish yellow to yellowish orange shades and a high color intensity. In particular, the dyeing and prints on cellulose fiber materials have very good light fastness and good to very good wet fastness, such as underwear, washboard fastness, water fastness, seawater fastness, color fastness and sweat fastness , also have good pleating stability, ironing resistance and abrasion resistance.

Of particular interest is the use of the compounds of formula 1. according to the invention also for dyeing wool using fiber reactivity. In particular, it is also possible to dye wool with a non-felt finish or a wool with a few felt finish (cf., for example, H. Rath, Lehrbuch der Textilchemie, Springer, Verlag, 3rd edition [1972), pp. 295-299, in particular wool treated with the so-called Hercosette. - by the procedure (page 298); J. Soc. Dyers and Colorists 1972, 93-99, and 1975 33-44) with very good constancy.

The method of dyeing wool is carried out in a customary and known dyeing process by applying the fiber-reactive compound of the formula I preferably first from an acid dye bath having a pH of from about 3.5 to 3.5. 5.5, under pH control by the pull-out process and at the end of the dyeing period, the pH is shifted to a neutral and possibly slightly alkaline range up to a pH of 8.5 in order to achieve a complete reactive bond between the dye 1 . and fiber. At the same time unreactively bound proportion of dye. release.

The method described herein also applies to dyeing fibrous materials of other natural polyamides or of synthetic polyamides and polyurethanes. The dyeing is carried out at temperatures of from 60 to 100 [deg.] C. but can also be carried out in closed apparatuses for dyeing at temperatures up to 106 [deg.] C. Since the water solubility of the compounds of the formula I is very good, The compounds can also be used advantageously in conventional continuous dyeing processes. The color saturation achieved using the compounds of formula (1) according to the invention is very high. Said compounds provide. on fibrous materials, in particular in - reactive dyeing - wool, bright greenish yellow to yellowish orange tints. A high degree of bath depletion can be found at temperatures of 100-105 ° C in dyeing.

In the case of the dyeing achieved by the compounds of the formula I according to the invention, the otherwise customary additional action of ammonia on the dyeed goods can be dispensed with. Surprisingly, the dyes according to the invention have a very good color composition in comparison with the structurally similar known dyes, while achieving brilliant shades in saturated tones. Addition

Claims (1)

they have a very good ability to combine with other fiber-reactive dye wool, which allows a surprisingly uniform coloring of the fibers. It is also possible to uniformly dye wool fiber materials of different provenance with the compounds of the invention. Optionally, leveling aids such as N-methyltaourine can optionally be added to improve egality. Using conventional dyeing aids which have a fiber affinity, the compounds of the invention also provide uniform dyeing on the wool and with a non-felting treatment or with a felting treatment. In light to medium shades, a very good level of wet fastness can be achieved without additional ammonia treatment, although an additional ammonia treatment can be used if desired. In addition to the high light fastness of these wool dyes, very good wet fastness under alkaline conditions and very good fastness in linen at 60 [deg.] C. are to be mentioned as very good wet fastness, even those with high color shades. The following examples serve to illustrate the invention. Parts are by weight parts,%% refers to percent by weight unless otherwise indicated. Parts by weight are relative to parts by volume as kilogram: liter. The compounds described in the examples with. the formulas are given in the form of free acids; in general, these compounds are prepared and isolated in the form of their salts, in particular in the form of sodium or potassium salts, and in the form of salts these compounds are also used for dyeing. They can also be used in the synthesis of the starting materials mentioned in the following examples, in particular the examples summarized in the table, in the form of the free acid, namely. as such or in the form of its salts, preferably alkali metal salts such as sodium or potassium salts. Ex and) A solution of pH 6148 parts of 4 - (. Beta.-3-sulphatoethylsulfonyljaniline in 500 parts of water) is stirred into a suspension of 100 parts of cutane-chloride and 3 parts of a commercial wetting agent in 800 parts of ice and water. between 0 and 5 ° C while maintaining the pH with sodium bicarbonate between 3.5 and 4.5 The conversion of the acylation reaction is 99% or higher. (b) The reaction mixture obtained from the second acylation a) is stirred into a solution having a pH between 6 and 7, which consists of 134 parts of 1,3-diaminobenzene-4,6-disulfonic acid in about 600 parts of water. The reaction mixture is heated to a temperature of 40 ° C and then stirred at a temperature between 40 and 45 ° C while maintaining the pH between 5 'and 6 with sodium bicarbonate until the presence of the diamino compound is virtually no longer possible. C) The reaction mixture obtained from the second acylation reaction according to b) is mixed with the addition of 1000 parts of ice and 150 parts by volume of a 31% aqueous hydrochloric acid solution. Diazotization is accomplished by the addition of an aqueous solution of 35 parts sodium nitrite at a temperature between · 0 and 10 ° C. The diazotization mixture obtained is. then added to a solution with a pH of between 6 and 6.5, which consists of 142 parts of 1- (4'-sulfophenyl) -3-carboxypyrazol-5-one, in about 1100 parts of water, with stirring, using sodium bicarbonate maintains a pH between 4.5 and 6 · throughout the coupling reaction. The reaction mixture was further stirred for some time until the coupling was complete. The monoazo thus prepared according to the invention is isolated in a customary manner, for example by evaporating or drying the neutral solution obtained in the synthesis by spraying or salting out electrolyte salts such as potassium chloride. An electrolyte-containing yellow powder is obtained which contains an alkali metal salt of a compound of the following formula such as a potassium salt: whose CH 2 OSO 4 H HOjS OH N I '= N COQH This azo compound of the invention exhibits very good dye-like properties, in particular very good fiber-reactive dye properties, and provides on the materials described herein, such as, in particular, cellulosic fibrous materials such as cotton by application and fixation methods conventional in the art. in particular by the methods described and used for fiber-reactive dyes, color-intensive, bright greenish-yellow dyes and prints with very good light fastness and good wet fastness, such as