CS232738B2 - Method of water-soluble monoazo-compounds production - Google Patents

Abstract

1. Water-soluble monoazo compounds corresponding to the general formula (1) see diagramm : EP0078009,P28,F4 in which R**1 is a hydrogen atom, a lower alkyl group, a lower alkoxy group or a chlorine atom ; R**2 is a hydrogen atom, a lower alkyl group or a lower alkoxy group ; R**3 is a lower alkyl group which is substituted by a hydroxy group, a lower alkanoylamino group, a sulfato group, a carboxy group or a sulfo group ; R is a hydrogen atom, the carbamoyl group, the cyano group or the sulfo group ; D is the meta- or para-phenylene radical, which is substituted by one or two sulfo groups or by one or two sulfo groups and a lower alkyl group ; X is a chlorine or fluorine atom ; Y is the vinyl group, or an ethyl group which contains bonded in the beta-position a radical which can be eliminated under alkaline conditions as an anion ; the formula moieties R**1, R**2, R**3 and R can be identical to or different from one another.

Description

The present invention relates to a process for the production of water-soluble monoazo compounds, i.e. the technical field of fiber-reactive azo dyes.

From Japanese published file Sho-56-037379 and German published file

(1) in which:

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 1-1 carbon atoms such as ethyl and especially methyl, or alkoxy having 1 to 4 carbon atoms ja features a fiber-reactive dyes which contain a pyridone coupling component.

New valuable water-soluble monoazo compounds have now been found which correspond to the general formula (I) as ethoxy, and in particular methoxy.

R ³ represents a C 1 -C 4 alkyl group such as a methyl or propyl group or, in particular, an ethyl group which is substituted by hydroxy, C 2 -C 5 alkanoylamino, such as propionylamino, and in particular acetylamino, sulfato (general formula -OSO 3 M), carboxy (of the formula —COOM) or a sulfo group (of the formula —SO5M), in these formulas

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

R represents a hydrogen atom or a carbamoyl group or preferably a cyano group, or particularly preferably a sulfo group (of the formula -SO 3 M, where M is as defined above),

D represents a meta- or para-phenyl group which is substituted by one or two sulfo groups or one or two sulfo groups and one alkyl group having 1 to 4 carbon atoms, such as ethyl and in particular methyl,

X represents a chlorine atom or a fluorine atom,

Y represents a vinyl group or an ethyl group which contains an alkali-eliminable anionically bonded moiety, such as a 1-thiosulfatoethyl group (corresponding to the general formula —CH2 —CH2 —S — SO5M with M as defined above), a group (corresponding to the formula -CH2-CH2-OPO3H2 with M as defined above), a 1-chloroethyl group, a β-acetyloxyethyl group and preferably a 1-sulfatoethyl group (corresponding to the formula -CH2-CH2-OSO3M with M as defined above).

General symbols R 1, R ^2, R and R may be mutually the same or different meanings.

Besides the already mentioned preferred compounds of formula 1 may be additionally emphasized are those azo · · according to the invention in which R1 is hydrogen, ^R2 is methoxy or · a methyl group, but preferably represents a hydrogen atom · · and the group Y is -SO3-bound in the meta-position, particularly preferably in the p-position to the amino group. Further, those azo compounds of the invention in which D represents a meta- or para-phenylene group substituted with one or two sulfoamines are to be emphasized. Also preferred are those compounds according to the invention in which Y represents a vinyl group, in particular a β-ulphatsethyl group. Further preferred for R ³ is a C 1 -C 3 alkyl group which is substituted with one sulfo group, one carbsxy group, or C 2 -C 5 alkanesyl amino group.

The terms "lower", as used herein, mean that the alkyl or alkylene moiety contained in the group consists of 1 to 4 carbon atoms.

The novel azo compounds can exist both in acid form and in the form of their salts. Preferred are these azo compounds in the form of salts, in particular in the form of alkali and alkaline earth metal salts, and are also preferably in the form of these salts after use for dyeing (herein and hereinafter to be understood generally and including printing) of materials containing hydroxy and / or carboxamido, 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), which comprises reacting a compound of formula (II):

in which

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

X N ^ N

(A) _X or (b) a

and

D, R ¹ , R 2, X and Y have the meanings given above, in the case of an amine of formula II in which A is a group (a) after its diazotization to a diazonium salt with a compound of formula III

in which

R and R- have the meanings given above and

B represents a hydrogen atom or a group of formula (b ‘) or (c‘) (Ь'У

H _Z NDN = No or X

X —— NH-D ~ №NN where

X and D have the meanings given above, when A represents a hydrogen atom then B represents a group of formula (c), if A represents a group of formula (a) then D represents a hydrogen atom and when A represents a group of formula. (b), then B represents a group of formula (b‘j.

The above process according to the invention can be explained in more detail by means of specific examples, the process being carried out by: the diazonium amine compound of formula

(2) in which

R 1, R 2, D, X and Y are as defined above, coupled with a pyridone derivative of the general formula 3

in which

R @ 3 and R @ 3 are as defined above, or an aminoazo compound of formula 4

in which

D, R ·. and R 3 are as defined above, reacted with a dihalogentriazine derivative of formula 5

in which

R 1, R 2, X and Y are as defined above, or are a dihalogentriazine derivative of formula 6

У)

in which

D, X, R 3 and R 3 are as defined above, reacted with an amino compound of formula 7

^NH Z (7) wherein

R 1, R 2 and Y are as defined above.

In the starting compounds of formulas 2, 5 and 7, Y may also be a β-hydroxyethyl group. The compounds thus obtainable according to the general formula 1, in which Y represents a 3-hydroxyethyl group, can be converted according to the invention into the corresponding compounds of the formula 1 according to the invention in which Y represents an ethyl group which is in beta by analogy with known esterification or acylation reagents. -substituted by an ester group.

The esterification of the sulfation, i.e. converting the .beta.-hydroxyethyl group to the .beta.-sulfatoethyl group analogously to a number of procedures known in the literature, preferably with sulfuric acid or sulfuric acid containing sulfuric acid as the sulfating agent. The sulphation reaction can be carried out in a temperature range between -5 ° C and + 50 ° C, preferably at a temperature between 0 and 10 ° C.

The amines of the formula (2) which serve as starting materials can be prepared analogously to known processes, for example by reacting a diamine compound of the formula H2N — D — NH2, where D is as defined above, with a dihalogentriazine derivative of formula (5) as defined above or cyanuric chloride (2,4,6-trichloro-1,3,5-triazine) or cyanurofluoride (2R, (R, R) - (R, R): 1,3,5 (1, 4-triazine) first) with a diamino compound of the above-defined formula HaN-D-NH 2 to give a compound of formula 8

in which

D and X are as defined above, and then with the amine of the above-defined general formula (7).

Likewise, the analogues of the longhalentriazine corresponding to the general formula (5) can be prepared analogously to known processes and serve as starting materials, for example by reaction with cyanuric chloride. or an amine cyanurfluoride of the above-defined general formula (7).

The synthesis of the dihalogentriazine derivatives of the formula (6) can be carried out analogously to known methods by condensation of the cyanuric chloride or cyanurofluoride with the aminoazo of the aforementioned and defined formula (4) or the reaction of the diazonium amine compound of the above and the defined

the reaction of the cyanuric chloride or cyanurfluoride with the amino compound of formula 4 to form a compound of formula 6, and the reaction of the cyanuric chloride or cyanurfluoride with an amino compound of formula 7 to form a compound of formula 5 can be carried out in an organic or aqueous organic medium. It is preferably carried out in an aqueous medium with the addition of acid-binding agents, such as carbonates. alkali metal or alkaline earth metal, alkali metal or alkaline earth metal hydrogen sulphate or alkali metal or alkaline earth metal hydroxide or alkali metal acetate, the alkali metal and alkaline earth metal being preferably sodium, potassium or calcium. Acid binding agents are also tertiary amines such as pyridine or rrierhylamine or quinoline. These condensation reactions are carried out at a temperature between -10 ° C and +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 i. , 0 and 7.0, preferably between 3.5 and 5.

Reaction of the dihalogeno-triazinylamino compounds of formulas (5), (8) and (8) with the corresponding amino compounds of formula (4), formula (7) and the above-defined formula H 2 N-D-NH 2, according to the invention. of formula 1, optionally to form intermediates of formula 2, can also be carried out in an organic or aqueous-organic medium. Preferably, however, it is carried out in an aqueous medium, optionally adding an acid binding agent such as the above. The reaction of the amino groups with the halogen of the triazine derivatives is carried out preferably at a temperature between 10 and 60 ° C, particularly preferably between 20 and 50 ° C, and at a pH between 2 and 9, in particular between 3 and 8.

The diazotization of the amino compounds of the formula (2) and (8) 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, such as at pH values between 0.5 and 3 and The reaction of the diazonium compounds with the pyridone derivatives of the general formula (3) is likewise carried out analogously to known methods, for example in an aqueous-organic, but mainly aqueous, medium, in a slightly acidic medium. to a neutral or optionally very weakly alkaline pH range, such as at pH values between 4 and 7.5, in particular between 5 and 7, and at a temperature between 5 and 25 ° C.

The amino compounds of formula (7) which serve as starting materials for the preparation of the compounds of the invention are exemplified. for example by the following compounds:

l-amino-3- (/ -sulfatoethylsulf sulfonyl) benzene, l-amino-2-methoxy-5- (/ -su И atoethyysulf onyljbenzen l-amino-2-methoxy-4- ^(/: -sulfatoethylsulf onyl) benzene 1-amino-2-methyl-5- (1-amino-4-methoxy-5- (1-amino-2-methyl-4-methoxy-5- (2-methylsulphonyl) benzene) 1-amino-2-metho (xy-5-methyl-4- (3Sulfaroethylsulfonyl-benzene), 1-ammo-2, 1-amino-4-methyl-5- (N -sulfato-ethylsulfonyl) -benzene, 5-dimethoxy-4- (+ sulfatoethylsulfonyl-benzene), 1-amino-2,4-dimethoxy-5- (t-sulfatoethylsulfonyl) benzene,

1-Amino-2-methyl-5-methoxy-4 - ((Ssulfethoxyethylsulfonyl) benzene,

2-Chloro-1-amine-5- (β-sulfatoethylsulfonyl) benzene

4-Chloro-1-amino-2-methyl-3- (β'-sulfatoethylsulfonyl) benzene

5-chloro-lamino-2-methoxy-4- (β-acetoethylsulfonyl) benzene, as well as 1 optionally corresponding ethoxythioethylsulfonyl, β-phosphatoethylsulfonyl, β-chloroethylsulfonyl, β-acetoxyethylsulfonyl and vinylsulfonyl derivatives and optionally / β-hydroxyethylsulfonyl derivatives of these β'Sulfatoethylsuffonyf compounds, more preferably β-amino-4- (3-suffatoethylsulfonyl) benzene, and its corresponding ω-ω-phosphoromethyl, chloroethyl, acetoxyethyl and vinyl- derivatives and optionally β-hydroxyethyl derivatives.

The pyridone derivatives corresponding to the general formula 3 which serve as starting materials for the preparation of the azo compounds according to the invention are, for example, the following compounds:

1- ((Z-уУгохусШуУ) -4-methyl-6-hydroxy-2-pyridone),

1- (β-Hydroxyethyl) -3-cyano-4-methyl-6-hydroxy-2-pyrrolidone, 1- (S-hydroxy-4-methyl-4-methyl-d) -3-carbamoyl-4-methyl-6-hydroxy -2-pyridone, 1- (- yyrroxyethyl) -4-methyl-6-hydroxy-2-pyrrolidin-3-suffonic acid,

1- {N -sulfatoethyl] -4-methyl-6-hydroxy-2-pyridone,

1- (t-Sulfethoxyethyl) -3-cyano-4-methyl-6-hydroxy-4-pyrrolidone,

1 - ((-sulfaroethyl) -3-carbamoyl-4-methyl-6-hydroxy-2-pyridone,

1- (β-sulfatoethyl) -4-methyl-6-yl-hydroxy-2-pyridone-3-sulfonic acid,

1- (3 Sulfatoethyl) -4-methyl-6-yyrroxy-2-pyridone

1- (β-Sulfatcethyl) --- carbamoyM-methyl-4-hydroxy-Apyricone,

1- (3-sulfatoethyl) -4-methyl-6-yl-hydroxy-2-pyrldone-3-sulfonic acid; 4-methyl-3-cyano-4-methyl-6-hydroxy-2-pyrrolidin-2-yl-2-pyridyl

f-carboxymethyl-3-carbamoyl-4-methyl-6-hydroxy-2-pyridone f-carboxymethyl 4-methyl-6-hydroxy-2-pyridone-3-sulfonic acid,

1- (1-carboxyethyl) -4-methyl-6-hydroxy-2-pyridone,

1- (N-carboxyethyl) -3-cyano-4-methyl-6-yydroxy-2-pyridone,

1- (β-carboxyethyl) -3-carbamyl-4-methyl-6-yyrroxy-2-pyrrolidone,

1- (β-arboxyl) -4-methyl-6-yyrroxy-2-pyridone-2-suffonic acid,

1 - ((4-methylaminoethyl) -4-methyl-6-hydroxy-2-pyrrole),

1- (5S-acylamino) -3-cyano-4-methyl-6-hydroxy-2-pyridone,

1- (4-Chloroethyl-3-carbamoyl-4-methyl-6-yyrroxy-2-pyridone),

- (β-R-aminoethyl) -4- 611111-6-111-4 0x1-2-nyrirone-3-sulfonic acid, and - (R-acetylaminopropyl) -4-methyl-6-hydroxy-2-pyrrolidine,

1- (3-Dimethylaminopropyl) --- cyano-4-methyl-6-liyrroxy-2-pyrrolidinone,

1- (, ^/: 3srety1aminopгopyl) --- carbamoyl carbamoyl-4-methyl-6-hyrroxy-2-pyridone and f - / ^ acetylamincpropyl-4-methyl-6 · hyΓroxy-2-pyгiΓon sulfcnová-3-acid.

The diamino compounds corresponding to the above general formula H 2 N-D-NH 2 which may serve as starting materials for the preparation of the compounds of the invention are, for example, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-S-sulfonic acid, 1,4 -diaminobenzene-2-sulfonic acid, 2,4-diamine-5-sulfonic acid, 2,4-diamine-6-suffonic acid, 2,5-diamino-4-fluorophenoic acid, 1,3-benzoic acid -4,6-bisulfonic acid and 1,4-diminobenzene-2,5-disuccinic acid.

The separation and isolation of the compounds of formula (1) produced by the process of the invention may be carried out by generally known methods, such as either precipitation from the reaction mixture with electrolytes such as sodium chloride or potassium chloride, evaporation of 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.

Accordingly, the present invention also relates to the use of the compounds of the formula I according to the invention 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 methods by applying the mono-compounds 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 with an alkaline active agent.

1.1

Materials containing hydroxyl groups are materials of natural or synthetic origin, such as cellulosic fibrous 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.

Materials containing carboxamido groups 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.

With these dyes, very good dye yields, as well as excellent color compositions, are obtained on 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 gradually 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, possibly also after reaching the temperature at which the dyeing is carried out.

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 a single-phase manner, for example by printing with a printing paste using both sodium bicarbonate or other acid binding agents and subsequent steaming at temperatures. 100 to 103 ° C or biphasic, for example by printing with a neutral or weakly acidic ink and subsequent fixing by guiding the printed material with a hot alkaline electrolyte bath or by overflooding the printed material with an alkaline bath. The electrolyte is followed by a delay or by steaming or dry heat treatment. This overlapped material yields color-intensive prints with a good state of contours and a bright white pool. The quality of these prints remains virtually unaffected by changing fixation conditions.

For dry heat fixation according to conventional thermofixation procedures, hot air at a temperature of 120 to 200 is used. Deň: 32 ° C. In addition to the usual water vapor at a temperature of 101 to 103 ° C, superheated steam and pressure vapor can also be used. temperatures up to 160 ° C.

The acid binding agents and agents for fixing the compound of Formula 1 to cellulosic fibers are, for example, water-soluble alkali metal and optionally alkaline earth metal salts of inorganic 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 organic acids, with sodium and potassium compounds being preferred. Such acid-binding agents are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium formate, sodium phosphate, sodium trichloroacetate, water glass or sodium phosphate.

By treating the compounds of the invention with acid binding agents, optionally. under the effect of heat, the compounds of the invention (dyes) chemically bind to cellulose fibers. In particular, the dyeings on cellulose fibers exhibit excellent wetness after the usual rinsing action to remove unfixed dye fractions. and, moreover, the non-fixed proportions of the dye can be easily washed out because of their good solubility in cold water.

The dyeing of polyurethane or natural or synthetic polyamide fibers is usually carried out from an acid medium. Thus, for example, acetic acid and / or ammonium sulfate and / or acetic acid and ammonium acetate or sodium acetate may be added to the dyeing bath to achieve the desired effect. pH. It is recommended to add conventional leveling aids such as those based on the reaction product of cyanuric chloride with a triple molar amount of aminobenzenesulfonic acid and / or aminonaphthalenesulfonic acid or on the basis of the reaction product, such as stearylamine with ethylene oxide, to achieve a useful color uniformity. As a rule, the coloring material is introduced at a temperature. about 40 ° C to the bath, where it is kept in motion for some time, the dyeing bath is then adjusted to the desired slightly acidic pH, preferably by the addition of acetic acid, and the actual dyeing is carried out at temperatures between 60-98

14.

The dyeing can also be carried out at the boiling point of the dyeing bath, i.e. at temperatures 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 reddish-yellow to yellowish-orange shades and a high color intensity. In particular, dyeing and printing on cellulosic fibrous 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, they also have good pleating stability, ironing stability and abrasion stability.

Of particular importance is the use of the compounds of the formula I according to the invention for dyeing wool using fiber reactivity. In particular, it is also possible to dye wool with a felting finish or a wool with a low felting 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 (page 298), J. Soc., Dyers and Colorists 1972, 93-99, and 1975, 33-34) with very good stability.

The dyeing of the wool is carried out by a conventional and known dyeing method 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 5.5 under control of the pH by the extraction procedure and at the end of dyeing the pH is shifted to the neutral and possibly weakly alkaline pH, up to a pH of 8.5, in order to achieve a complete reactive bond between this dye of formula 1 and the fiber, in particular when the desired high color saturation is desired. At the same time, the non-reactively bound portion of the dye is released.

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 from 60 to 100 ° C, but can also be carried out in closed apparatuses, for dyeing at temperatures up to 106 ° C. Since the water solubility of the compounds of formula (1) is very good, these tp 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 give bright, greenish-yellow to yellowish-orange shades on fibrous materials, in particular in reactive wool dyeing. A high degree of bath depletion can be found at temperatures of 100 to 106 ° C in dyeing.

In the case of the dyes obtained by the compounds of the general formula (1) according to the invention, the otherwise usual additional effect of ammonia on the dyed goods can be dispensed with. In comparison with the structurally similar known dyes, the dyes according to the invention surprisingly show a very good color composition, while achieving brilliant shades even in deep tones. In addition, they exhibit a very good ability to combine with other fiber-reactive dye wool, which allows 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-methyltaurine can optionally be added to improve egality.

Using conventional dyeing aids having a fiber affinity, the compounds of the invention also provide uniform dyeing on wool with a non-felting finish or a low felting finish. In light to medium color shades, even without additional ammonia treatment, a very good level of wet fastness can be achieved, but if appropriate, an additional ammonia treatment can optionally be used. In addition to the high light fastness of these wool dyes, very good wet fastness, in particular excellent sweat fastness under alkaline conditions and very good fastness to the linen at 60 ° C, should also be mentioned, even with dyeing with _; high intensities of 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 kg per liter.

The compounds described in the examples by 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. Likewise, the starting materials mentioned in the following examples, in particular in the table summarized examples, can be used in the synthesis in the form of the free acid, as such or in the form of their salts, preferably alkali metal salts such as sodium or potassium salts.

Example 1

(a) An aqueous solution having a pH of 6-7 56 parts of 1-amino-4- (n -sulfatoethylsulfonyl) benzene in 300 parts of water is poured into a suspension of 38.6 parts of cyanuric chloride and 1 part of a conventional wetting agent in 50 parts of water; 200 parts ice. With sodium bicarbonate, the pH is maintained between 2 and 4 during the acylation reaction, while the mixture is vigorously stirred at a temperature between 0 to 10 ° C. The degree of conversion is greater than 99%.

(b) To produce the diazo component corresponding to formula 2, the monoacylation product suspension obtained in (a) is slowly added with stirring to a neutral solution of 37.5 parts of 1,3-phenylenediamine-4-sulfonic acid in 200 parts of water heated to 40 ° C; in this second condensation reaction, the pH is maintained at 4-5 with sodium bicarbonate.

c) To diazotize the amino compound, 200 parts of ice and 60 parts of 31% aqueous hydrochloric acid are added to the reaction mixture obtained in b). Diazotization is then carried out in a conventional manner by the addition of an aqueous solution of 14 parts of sodium nitrite.

Then 46.5 parts of 1- (3-sulfoethyl) -4-methyl-6-hydroxy-2-pyridone are added, and the pH is maintained between 4.5 and 5.5 with sodium bicarbonate for the coupling reaction.

The monoazo compound thus prepared according to the invention is isolated in a customary manner from the aqueous reaction mixture, for example by evaporating or spray-drying the neutral reaction solution, or by salting, for example with potassium chloride. An electrolyte is obtained containing a yellow powder with a salt of a compound, such as sodium or potassium salt, of a compound of the formula

The absorption maximum of this compound in the visible wavelength range in aqueous solution is at 41 416 nm.

This azo compound of the invention exhibits very good dyeing 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, using techniques known in the art, in particular using the methods described and used for fiber-reactive dyes, color-intensive bright greenish-yellow coloring and prints with good fastness to light and good wet fastness, such as especially good fastness to underwear, washboard, sweat and dyeing .

d) The pyridone derivative used in c) as coupling component can be prepared by known methods by condensing taurine with cyanoacetic acid esters, reacting the reaction product with acetic acid esters in aqueous solution, and then saponifying and decarboxylating the resulting 1- ( (3-sulfoethyl) -3-cyano-4-methyl-6-hydroxy-2-pyridone with sulfuric acid.

Example 2

a] A neutral solution of 54 parts of 1,4-phenylenediamine-2,5-disulfonic acid in 200 parts of water is diazotized with an aqueous solution of 14 parts of sodium nitrite after the addition of 200 parts of ice and 70 parts of 31% hydrochloric acid. 52 parts of 1- (β-sulfoethyl) -3-cyano-4-methyl-6-hydroxy-2-pyridone are then added, maintaining the pH at 5 to 6 with sodium bicarbonate during the coupling reaction.

b) The monoazo compound produced according to a), preferably in the form of a weakly acidic to neutral reaction mixture obtained according to a), is added at 0-5 ° C with stirring to a suspension which has been prepared by adding a solution of 18.4 parts. cyanuric chloride in 80 parts acetone (by slow flow) into a mixture of 100 parts water and 200 parts ice. During the monoacylation reaction of the monoazo compound, the pH is maintained at 4-5 with sodium bicarbonate.

c) The monocondensation product produced according to b) is added to a neutral solution of 56 parts of 1-amino-4- (3-sulfatoethylsulfonyl) benzene in 200 parts water, then the temperature is raised to 35 ° C and the pH during this second condensation reaction. is maintained between 6 and 6.5 with sodium bicarbonate.

The monoazo compound thus prepared is isolated in a conventional manner, for example by salting with sodium chloride. A powder product is obtained which, in addition to the electrolyte, contains an alkali metal salt of the compound of the following formula as the sodium salt of the compound of the formula:

This compound exhibits a maximum at 448 nm in an aqueous solution within the visible range of its absorption.

This azo compound of the invention has very good dye-reactive properties, in particular very good fiber-reactive dye properties, and provides on the materials described herein, such as cellulose fiber materials such as cotton, by application and fixation methods conventional in the art. especially those described and used for fiber-reactive dyes, color-intensive, bright, orange dyeing and prints with good light fastnesses and good wet fastnesses such as especially good fastnesses

in the form of its sodium or potassium salt, for example by salting with sodium chloride or potassium chloride. It has a reddish yellow hue and has similar properties as the colorant of the compound of the invention of Example 2. Absorption. the maximum of this dye according to the invention is at 436 nm.

c) The coupling component used herein under a) is prepared according to known procedures from α-amine, cyanoacetic acid esters and acetic acid esters to give 1- (3-carboxyethyl) -3-cyano-4-methyl-6 hydroxy-2-pyridone, which is converted to 1- (3-carboxyethyl) -2-carbamoyl-4-methyl-6-hydroxy-2-pyridine by partial hydrolysis with concentrated sulfuric acid.

lost in underwear, washboard, sweat and discoloration.

Example 3

a) In order to prepare the monoazo compound as a starting material, the procedure of Example 2aj is followed, but instead of the coupling component 1- (3-carboxyethyl) -3-carbamoyl-4-methyl-6-hydroxy-2- pyridone in an equivalent amount.

b) To the monoacylation reaction mixture obtained as in Example 1a, a monoazo compound obtained from a) above was added at 40 ° C and at a pH between 5 and 6. In this second condensation reaction, a compound of the invention of the formula is obtained

A suspension of 56 parts of 4- _{(1-3'Sulfaloethylsulfonylj} aniline in 300 parts of water was adjusted to pH 4.0 and the solution is cooled to a temperature between -2 ° C and 0. '° C. Under vigorous stirring, then added 32 parts of 2,4,6-trifluoro-1,3,5-triazine [cyanurfluoride], while maintaining the pH at 3.5 with an aqueous solution of sodium bicarbonate, and after a few minutes no amine can be detected. 54 parts of 1,3-phenylenediamine-4,6-disulfonic acid in 250 parts of water are added at a temperature of 10-15 ° C to a neutral aqueous solution, and during this condensation reaction the pH of the reaction mixture is maintained between 4 and 5 with sodium carbonate solution. Then, 100 parts of ice and 60 parts of 31% hydrochloric acid are added and diazotized with an aqueous solution of 14 parts of sodium nitrite, and 42 parts of 1-carboxymethyl-3-cyano-4-methyl-6-hydroxy-2 are added for coupling. -pyridone, and pH s e to adjust to 4.5 to 5.5.

This azo compound of the invention has a visible absorption peak at 429 nm.

The compound exhibits very good fiber-reactive dye properties, and dyes, for example, cellulosic fibrous materials in color-intensive, yellow shades by application and fixation methods customary in the art. The dyeings and prints obtained exhibit very good light fastnesses and very good wet fastnesses, such as good fastness to underwear, washboard, sweat, discoloration and chlorine water bath.

The pyridone derivative used herein as the coupling component is prepared as a 1 [mu] l monoazo compound of the invention so produced, isolated in a conventional manner, for example by spray drying or salting out. It is obtained in the form of an alkali metal salt, such as a sodium or potassium salt. This compound - represented in free acid form - has the following formula

(carboxyethyl) -3-cyano-4-methyl-6-hydroxy-2-pyridone as shown in Example 3, starting from aminocetic acid as the starting material.

Example 5

According to the data contained in Example 1, the azo compound of the invention was synthesized, but 4- (β-sulfatoethylsulfonyl) aniline used in Example 1a was replaced with 60 parts of 4- (β-thiosulfatoethylsulfonyljaniline) after working up the reaction solution and isolation. it comprises an alkali metal salt of a compound of the following formula

Cl

It has very good dyeing properties and provides, for example, cotton using application and fixation methods customary in the art, especially those used for fiber-reactive dyes, color-intensive, green-yellow coloring and prints with good fastness to light and good wet fastnesses, such as good fastness to underwear, washboard and discoloration, as well as good fastness to sweat. The absorption in the visible range is the same as the monoazo compound of the invention of Example 1.

Example 6

For the preparation of the azo compound of the invention, the procedure of Example 2 is followed, but the aqueous solution of 4- (1,3-sulfanoethylsulfonyl) aniline used therein is replaced in Example 2c with a solution of 39 parts of 4-vinylsulfonylaniline in 200 parts by volume of acetone. to the solution of the second condensation product produced according to Example 2b).

After the usual treatment of the reaction solution and isolation, a powder is obtained which, in addition to the electrolyte, contains a salt of the compound below

Ct of the guided alkali metal formula, such as the sodium salt of the compound of the formula

This compound of the invention has a maximum at 448 nm within the visible absorption range.

The compound exhibits very good fiber-reactive dye properties and provides using conventional techniques and fixation methods such as cotton, intensities, orange staining and prints with good light fastness and good wet fastness. The quality of the dyeings obtained with this monoazo compound of the invention is comparable to those obtained using the azo compound of the invention of Example 2.

Example 7

For the production of the monoazo compound according to the invention, the procedure of Example 2 is followed, but the aqueous solution of 4- (4-sulfatoethylsulfonyl) aniline used in paragraph c) is replaced with 46 parts of powdered 4- (3-chloroethylsulfonyljaniline) and added to the solution. of the second condensation product obtained according to Example 2b).

After working up the reaction solution and isolating, a powder is obtained which, in addition to the electrolyte, contains an alkali metal salt of the compound of the following formula

Cl

This compound has very good dyeing properties and dyes, for example, cotton using the application and fixation methods customary in the art for fiber-reactive dyes, in color-intensive orange shades with very good light fastness and very good wet fastness.

Examples 8 to 146

In the following examples, summarized in tabular form, further monoazo compounds of the invention corresponding to formula 1 are described by the individual components from which they are built together with the remainder of the cyanuric chloride or cyanurfluoride. These compounds can be prepared from those amino compounds and cyanuric chloride or cyanurofluoride and the coupling components according to the process of the invention, as described, for example, in one of the process variants of Examples 1 to 7. The prepared compounds are isolated preferably in the form of sodium or potassium salts. The starting compounds mentioned for these compounds are in the form of the free acid when they contain an acid residue.

The monoazo compounds of Examples 8 to 146 of the invention also exhibit very good fiber-reactive dye properties as dyes and provide on the materials described herein, such as, in particular, cellulosic fibrous materials, e.g. the shade given for each example in the cotton dye table.

In Examples 8 to 146, the symbols Z1 to Z6 have the following meanings (wherein, when they contain an acidic group, they are referred to as the free acid):

Z1 = -SO2-CH2-CH2-OSO3H

Z2 = -SO2-CH2-CH2-S-SO3H

Z3 = -SO2-CH2-CH2-Cl

Z4 = -SO2-CH = CH2

Z5 = -SO2-CH2-CH2-O-CO-CH3

Ze = —SO2 — CH2 — CH2 — OPO3H2 Example of diamine of formula X amine of formula 7 pyridone derivative of general formula hue number HzN — D — NH2 of formula 3

X X 'X X > í >> X 4—> 4— · 4— · 4 ~> 4-> Д ti ti ti ti ti ti г — И r— < > N •> N > N > N > N > N > N > Φ > Ф > Ф > CD > CD > Ф > Ф > > > > > > CD CD CD CD CD CD CD tí d ti d · ti ti d φ CD Ф CD CD φ Ф  F — 1 φ  CD Ф ··. Ф Ф φ Ф N N N N N N N

> 4> 4 rd

6 ЯН O O' · - <o r — i o- r — 4 O O

φ cd d.B:

O Д

O

4— »o

WITH

In cd ί3

AND

CM

CD 'С / Г · ’

X 'cd o

Й o

4- (

Д

СЛ

I '

.Ф · -. -.i cd  t Honors d. й d ti  φ φ · »- < S 'φ С (Λ N d ω C / 3 CD φ ό O ti '5 d 'CD .ГЧ> > В 2 WITH O сЗ й ti ti O -5 4-4 Ξ3 4-4 CO ti ti WHAT ti _r сл C / 3

AND

Tfl ά

CD N d

CD

O d в .S S

AND

CO xH cd .s ω сл 'cd> o d o

4-!

Д

СЛ t d Φ N d CD Ю O в s cd В

I CO cd d ω >>

'cd> O d o

0-4

СЛ example of a diamine of formula X amine of formula 7 pyridone derivative of formula hue number H2N — D — NH2 of formula 3

'ÍX '> p + · * 4- » 4- » + -> 4- » 4H ri ri ri ri ri ri 1— < > N > N > N > N > N > N > ф > 0) > Φ > Φ > o> XD > Φ > > > > > > Honors CD ca ca ca CD ca ri ri ri ri ri ri ri ω φ φ φ φ φ φ • <· - < ή; 'Φ φ φ Φ Φ φ N N N N N N N

'I.' * - - ¹

1—1 > ч > ч F — 4 X 1—1 X x r— < X rri дз £ д дз дз rri 4- » 4- » 4- * 4- ^ 4- » 4-> Φ ri a 0 ф ri а § φ ri а о Φ ri a 0 Ф ri and 0 G and g and § 4-5 ýs 4S 4S 45 4S t * ‘ 4S 4 e- ¹ tl z? >> 9 jh X Л х9 x 9 X Ok rH TxQ < of? > Д ώ Л см • М | rri 4->, rri 04 4-> < rri eq ri 1 X3 cq ri ' o x 9? х ф χ Ф X φ X s> * 2> * o χ о х ο х ⁰ X p x 0 X Q x Й 0 а о íri 0 Й O 0 íri 0 S 0 ri Ъ сл p Зё ri £ ω p ri% ω p «1 ri Λ ω p _j X 1.> 4 2; Д řA> * 2; Д AND ^ <9 и 4 rH t CD rH 1 ', what rH 1

the

t CD А Ф лК i cd M <rt 1 ca i ca ri ri ti ri ri ri ri ri and β ω N ri Ф СЛ ф д G ω φ P N 'З ri ω Ф Д and o G ω φ .f4 and φ ri ⁷⁵ ω > 4 Φ x φ x 4> 4 φ; x rO & r * -2 r * £ AS £ r « 0 0 0 _ O _ 0 ri > cd ri P ri '? ri P ri p • f ^ > .ri> S> .ri> S ⁰ § fi • ri and 0 and ° and 2 § o CD ri § ri 0 .2 0 .2 O • 2 0 • S 0 P чч r4 Ό 4 — i Tj ч— ( XJ <w oó ri oó ri CO ri co ri co ri rH C / 3 1 г ω rH 1 rH i И «Р - ω rH 1

ID CD 00 CD rH rH rH rH rH

an example of a diamine of formula X an amine of formula 7 pyridone derivative of general formula shade number H2N — D — NH2 in 3

□ t3 ti r— < > N > N > N > Ф > Ф ΧΦ > > > ti t3 Й 'ti ti Φ 0) Φ CD Φ CD N N N

+ - 1> N> CD>

ti α

CD

N

SX> QD>

«3 t3

CD

Ф

N

ti ti

Ф. cn >>

'03> O ti 0 <1-4 cn t

Φ!

«3 φ

N 3 3 CD rQ O ti p .2 c «3 .p

Ti cn> About you o

T ³ cn 'чЛ ά φ

N and ω о tí

With you t5 co

CM CM

CO Φ

CM M tn CM co CM example of diamine of formula X amine of formula 7 pyridone derivative of general formula hue number H2N — D — NH2 of formula 3 + G) φ

Honors G

4)

4- »G> N

XD

Honors G '> 4

G> N

XD> Honors G

4- »G r-M> N

i Φ

AND

Д

CD

N Й CD rQ

O Д • r4

Honored? 00 honors G г — 4

CD ω 'Cti> o Д o

G CA

I Φ

AND

G CD N G CD Λ O e e Ctí • rH Ό

I 00 Honors G Д CD i

§ « N Д Φ 4Э 4tí Χ5 O t> Ο G O G 8 Д G Д O .S » Д honors • r4 ό g Xtí i CA 00 L 1 СП гЧ » т-Ч

A «j»

Д Ф N t Φ X) o β with honor • яИ Ό i cn r-T

G tD

CA. > 4t <8 §

G ca • нН

A «t .S S I Й U Λ 5 • 9 § § § .SS Ό G i ca oo

CM

σ> O Ή CM CM oo СП СП

Examples of diamines of general formula X amine of formula 7 derivative pyridone of the color number HžN-D-NH ₂ Formula 3 '>>

4- »9> N

4- »

1—4

> Ф> СО 9 Ф > ) Ф > СО 9 Ф> > ф> СО а ф > Ф > а ф £ 4 С-4 Έ5 * ф Ф Ф N N Ю > о

'>> '>> 4- * 4- » а 9 > N > N > Ф > Ф 4— · 4-J > > 9 9 СО а <0 а ) N > N ф ф ф ω N N

>> X O 5- <Ό

Λ

WHAT

4— ·

CD

T r— <

>> o 6

About it

СО. А со

СМ 1 СО см а Τ ' t honors 'Т а а а а а and ф ф ф CD ω N а ф СЛ N а £ чл N а ф ω N а CD ф г-Ч φ ф X) л 'СО . 4tí 4D о о > о О а 'СО Ξ О а 'СО а > з • гН > • гН в О WITH о WITH О 6 сО а СО ч-ч .WITH а СО о о • гН 3 Ч-Ч Й 9 5 Ч-Ч Ί3 1 ω 1 т 9 СО 9 СО ω Ό г СЛ г

СО т it со оо от о гН см СО со со со со со со т т < т

an example of a diamine of the formula X an amine of the formula 7 a pyridone derivative of the general color shade number H? N — D — NH2 of the formula 3

& '>> '>> 4- » \> ч 4- » '>> 4-j tí 4- » tí tí tí P * “< tí tí ) N > N > N. > N > N > N > N > Φ > Φ > Φ > Φ '> » '> ч ) φ > ф > cd > ca > Φ> > Φ > > cd > Honors 4— · th 4— · th > cd > honor tí tí CD honors tí tí > N tí Д Φ φ tí C and) Φ Φ Ф > > CD Φ > > > > Ph CD φ t-i ř-4 Φ Φ N M CD Φ Ф Ф > Q > ω > ω Ю > o > o

4 ~ <and Я

Honors a

M <th o M ¹ ti 'O M < 1 with WITH tí honors • J- * Honors -j-l CD > s L · ! X Ь · ¥ а > 4 1 ÍX 1 ср Д CO ' WHAT

Ttí Φ Ό φ ό Φ Ό >> >>. > >> >> ΪΧ rtí t X Xj O r X _C <О 1 δ ⁴ ? ID 4D 1Л X2 Ю 4D Ю r-t ř-4 Д Λ Си Λ >> WITH ctí íx cd >> rtí Λ Λ 4- »Ф * X φ οχ Φ οχ φ tí v p Τ 's Τ S M 1 rH 7 * н rH f rH?

1 Ч СО ₍ 4 Cd 1 «Я 1 CD CM Honors см й м < Honors Mi tí 1 CM f Honors <γ ΰ м » 1 Honors мГ t tí tí Р ф tí с tí Ti tí tí φ $ ΰ £ p— ‘ 0) tí tí tí φ N t • Р-Н ι — Η Φ сл ф N Й φ сл ř3 СЛ i-н CD N ti Л СЛ Φ N G Л СЛ Ф N ti Φ Ф >> φ ^Л CD >> Φ Ф 42 Λ rQ> ф Х5 rtí \ CQ ХЭ rbí C \ Honors J2 ХЭ Ο 'Honors ь о> О O O O 'Honors о> О 'Honors O tí tí о tí 'Honors tí O tí tí о tí tí

CO M <

M <M <

in CD tx what CD O rH CM cn Ml M < M < Me M < Ю in in in

an example of a diamine of the formula X an amine of the formula 7 a pyridone derivative of the formula hue number H2N — D — NH2 of formula 3

'ix '4—? 'J 'ίχ '_ίΧ. '> 4 4— » '> 4 'ΪΧ '> » 4- » 4ΣΧ 4- * w 3 3 3 4— · 3 4-> 3 Й 3 r — I 4- » 3 4- » 3 3 β > N rtN > Ν ι — 1> Ν ι —— I > Ν JN > Ν > Ν . r ^ * 4 > Ν я > Ν > Ф > Φ> > Φ ►> > Φ > Φ > Φ > ) Φ > > Φ > Φ > Φ £> > Φ > > Φ CD > > Honors CD > > CD honors 3 3 3 φ cd · φ 3 3 3 £ 3 φ 3 Φ ^cd cd ο ³ cd Г! Φ 3 φ φ φ Ν > Рч Φ> Ο > Рч Φ> ο φ Φ Ν Φ F — 4 φ Ν > Рч φ> ω > φ> ω ^φ φ Ν ^φ φ Ν .> Рч Φ> ω > Рч Φ> ω

I β 42

Рч rW

WHAT

AND

X o

S-i T3

ÍX

I cd 42 Рч 03 4 = 1

CO x O

Р-Ч fQ

I cd &

CD 4X1 co

I «o f-t TJ >>

řx · ίχΤ 1 5 5 *? 42 φ ρ> ¥> fj χ Й Χ! Й χ Й ο Φ Д ο Φ d О Щ §? § § Т'С Й 8 § £ 8

CM

AND

00, —X-o r4 S o TJ • 1-4 MM

AND

Ίχ λ 4-> ω ^а ΰ

I о Ζ? Τ2 й

ф

X

О cd Н,, Krf TJ >> 1X

I>. XI + - »φ and l

I and o TJ

Й> φ а

I x X O Рч TJ £ í + - Φ

I λ

4->

Φ

Λ

4- »Φ

X!

»- »

QD >> xs 4- »Φ Φ X o X) t-1 cd

I c o. . i.e

Й >> CD 9 ^ CM i >> X O Рч TJ ^ -xd> 4 X o X2

Рч t

3 ^WITH what ^and có ^and what 4 ň 4 ΰ ^{4 a} 4 CD ^I о TJ 1 £ * S ³ 'ο ^ Ч тз Ф д S ³ £? ´ рч Й> ' Χ3 Д 2 Д >> φ >? £ й ф XIχ XI 43 рч 43 ίχ Φ ω Λ 4- »φ Λ СЛ «> ф а сл >> Ч — ι Φ Ou ω ι ίχ

X o 42

Рч cd

X о

X)

РЧ л £ S '-' t 2 й '??

?. ь

X 2 O

XI

Рч Honors

AND

I >> Λ + j φ a

I р о t3

Рч я * Ί3. ^ x ^ -Xd • ώ г-1 ι

I λ

I a

AND

00.

i гЧ

Г — Н г — Η

О о

ιω

я 4 « СЧ 3 TJ ¹ ad 4 3 1.-4 ³ S Й ω ³ cd φ Ν and φ CD • t — I r — H Φ ω> p Φ ^N ω> гЧ 1 ^ 1 ф «- * < Χ5 'φ 42 4X1 ^rQ 'Φ Ο> O 'Honors O> 3 Ο Я Я О • я 3 * d > е ³ 8 ο 8 O 8 о φ .2 3 o CD ? 5? ? «+ - < Й <сл со 3 СЛ ⁰⁰ Яч

гЧ 'гЧ I гЧ I

CM I φ N cd rQ 0 s s cd cd .3 r — 4 '

4 ω> 4

4Ы 'cd> oЯo

TJ з

T

3е см 3 ¹ .3 ³ Оф Φ ^ф

N 3 Φ & о and .2 й 4, т-Г φ со >>

4x1 '3> О Я о

Ч-Ч сл?

t

Φ N

Φ 42

O .2 й

I со β

.3 φ ω> p

4X1

Md> о я о сл

AND

I я

Φ

N с

ф 32

О

Я я

ТЗ со e C • —I> 4 '03> о я о

Ч-ч сл Й

AND

AND

CM •

φ N φ 42 ο —4 .2 Й · —1 ф со >> 4Ζ • 'Cti> О я о «чи сл Ί

AND

Ω CM * t 3 Φ Ν 3 Φ 43

Ο φ r-H ΈΙ

ΙΩ 02 / Ο 02 / σ> ο ιη ιω ΙΩ Ω ΙΩ what

r-ч см со

CO CO со

-sulfonic acid cd я • гЧ

Φ сл ϊχ Xd 'Ctí> о Я О «+ ч. 2 й

an example of a diamine of the formula X an amine of the formula 7 a pyridone derivative of the formula hue number H2N — D — NH2 of the formula 3

'tx 'tx 4- » + - » > N > N 'tx 'tx > Φ > Φ 4-> 3 4-J 5 > cd > cd > N > N and й φ ω > > É-4 ř-4 ω Φ > CJ Ю

> φ> cd Й > φ> cd Й > Φ > cd й φ > φ> Honors Й Φ Φ φ > > Ή) N φ N í-ч Φ Рч Φ Ю > CJ

and Й and Й • 0 <0 , 0  O Xfl 2 Dři T3 Dr <T5 1 CO X f-4 Honors X) í-4 й К Honor β ⁴ ώ ’É ca tí Honors £ fi ’É honors 7 X 0 tx tx řx Λ tx honors honors CM r * OM CM CM T3 You are CO>, what tx what what Д what Λ X Д X Д x Д X > 4 O > 0 > 0 >> 0 txCD X H Д £ Д £ XI £ Л 1 ц »XJ 4-J Ό 4-J Ό 4-> Ό 4- » 4— · Φ >> 4> 4 Φ tx Ф tx Ф rC Φ Б ^д > ci Θ ^Д > * có with* E 'co 8 ^ CC 6 4- ^ 8 tx tx X> X 1 X 1 X в ° X ⁰ Л X--ч TI ⁰ >> X 5 ⁰ X Рч X O 0 X í-4  * s T 'C <- < O X R- < 3 4- * * p S ω 8 S ω Honors Jj3 & ⁴ CU 0 1 Honors Going rH 1 *, G rH 1 rH 1 ¹ , G rH 1 rH 6 rH

'>>

4- »> N 'tx

4-J

Φ

Honors tx t 1 Honors tx X X X X X X X X3 0 Рч ř-4 Honors O-4 β ° Ctí tM Φ 4-J Φ 4-J Ф T3 Going Ό Clay Ί0 S 6 S 8 S 8 tx » WHAT 1 tx »> 4 1 O T 0 7 0 X3 Д °? Л Ό '·> —1 Díl TJ sjí Ό CD >> co г — 4 1 ÍX CD Tl f-> 4>. 17 ' и * » Oh X ( X Д X CL 4-J 7 ⁴ tx 4-J tx ix 4-J 7 ⁴ 4-J 7 ⁴ X5 Ф XJ S л Ϊ Φ CM 2 <Ň + -> Φ (—4 Й 8 4- » G 8 8 G S £ x tx> g tx X X >> X β 0 X 8 0 x 8 0 X o X 0 X o Dl · WITH 0 0 · Ό О 0 £ O f_ < X 51 * 2 XT ¹ X TJ X Ό p T3 Ίχ о tx eu 1-4 cx β-H г — I 5 β tx honors rj Jxí T β honors H Jti 1 8 CM 1 rH 6 H0N Д '? Д 9

ο δ ο ω <-4 »- <> —4 I — 1 ο ο ω ο · - <Г — 4 ο ω

cd .S φ t tx 'cd> Ο й ο <+ - 4 το

C ω d и-х tí чи ω Φ tx φ φ tx Jtí X 'Honors £ Jtí 0 0 > о Й 8 й O с 'Honors Д > ⁶ § .2 0 8 .2 0 4-4 8 СО> г * 4 0 Д О 3 ω 4-4 co 5 what Dl · 3 _r? Ό ________1 ω

1,4-diaminobenzene-2,5-C11-carboxymethyl-4-methyl-reddish-yellow

disulfonic acid .beta.-6-hydroxy-2-pyridone

CD ID tx

О с x x x x t H H H H H H H H H H H H H

Part of an amine of formula X an amine of formula 7 pyridone derivative of general formula hue number H2N — D — NH2 of formula 3

2? 'Д 4- » '> 4 4- » + - » '> 3 + » +3 Й Й _r —1 3 3 ρΉ > N > N > N XD > N > ф '>> \> p > N > Φ > N > Φ > M XD > ω > cd > C3 + - » 4— · 3 > cd > Cl > φ> cd d honor 3 á Φ 3 φ > 3 > N 3 φ 3 φ та d φ φ > > > > ^φ Φ φ Ca Φ Ca Φ Ca Φ Ca Φ φ N N N > Φ XO > Q

4-J> N> d> cd d

'>> 4- < '>> 4- » 3 3 > N > N > Φ > Φ > > Φ CD 3 3 φ φ > > Ca Рч Φ Φ > G> > Φ

N

AND 03 / CD 1 Honors й ‘Рч Д 1 д Д honors Рч д Рч Рч д а Cd X Honors X CD 44 см 44 О 44 о 44 1 <Рч со 1 Са СО г со I 1 СО TJ ТЗ

^p —f— <г — 4 ooo

Ol a φ N й φ rQ O Й s cd ή co a

СЛ> 4 'Cd> O 3 O Μ

СЛ

honors honors со Ф г Ю honors F Honors 1 «Св Й СМ «ч • honors см й 4 сП 1 Honors ХГ 1 Й см F honors см ~ Г • гН мч Г honors .в A я см .В ф сл >> 44 Ф ф ф д N ф ω £ S ж й £ ф · * Й 3 Ф Д N w S & Ф ф N Й 0) >> 44 й ф N Й Ф й ф СЛ>. Й ф N Й Ф ф СЛ д 44 £ Й -н £ ф ф>. ф д> й £ ф g.S 2 φ g ω ф $ Й £ 0J 'CD & 44 О Д 'Honors О> § * д о 'СО > д о 44 Д О '03 > Д 44 О ’Ζ 'В' й 2> Д 'honors 2> 0 й о 4-4 .S> 6 § .2 о Й о and й 6 о оз 25 , S'g ⁶ § .2 о й в honor О Й О ч-ч г— < Й 6 3 'Honor> О й о й в honor О й о ч-ч й 'J В ° .2 § й о ^{Й й} и о honors Й 'Й • Й> 6 3 .2 § Й О β о Cd Э сл Έ5 1 ТЗ д и а? д i СЛ д а? тз СО Й н? 1 00 гЧ 3 .сл? тз 4. гЧ ч-ч 3 СЛ 1 ? 4 ^ гЧ 3 СЛ д 1 ТЗ ч-ч 00 3 Г СЛ гЧ i S з i сл СО -ч м? Ό ч-ч 4 з а? Д й Д .2 Г ТЗ гЧ t

00 σ) 0 со

гЧ CM 00 00 00 00 οθ

Ю O what what OO ao oO

φ ω н ο

N>

Φ rQ

Ο ti

With you

I.E

4 4— < '> ч 4-> '> 4 4 ~> 4-J 4— · 4- » 4- » 2 Έ ^ ti ti 4- »ti • 4— · 3 ti 1 ti ti r-H ti ι — 1 (—Η г — 4 > Ν > tM Я > Ν > Ν > Ν > Ν > Cd> cd > Φ > cd > φ > Φ > Cd> cd > Φ> honor ) Φ > Φ 'ί>. > Φ > φ > cd ti > Honors α > Honor you > Honor you • 4—1 ti> Τ3 4-> ti > Ν > Honor you > Honor you ti ti φ φ ti ti Φ Φ φ φ φ φ > > φ φ > > > > Έ5 N φ N φ-t φ η φ φ N φ N JU φ с-ч Φ Рч Φ ř- (φ Ю > υ > ω Ю > ω

I I I д rti, α

S 6 S

I 1 I

^ ti о r-H TJ Tfi д А О -н с 'о _Ι TJ >> ΤΙ >> - с

х ^, ¹ X ^е ? >> см X г о >> о >> о >> и X Η X н х Ό О TJ ο TJ о >> Н >> F4 >> н rti TJ rti Tj rti Р '>> 1 • г * ' Sů ⁴ Λ ώ Λ ώ .L «?

ϊ τ — ι ι rH

CD φ Ом φ Ρ <φ λ

. й 1 ti Г ti ’Ф о xtf О ”Ф о 'tj * TJ Л TJ ti · »- < ti · <-4 honors н honors СО £ >? £ >>> »

л >> Λ Λ> г— (X X Г-Н χ >> о >> ο > л О rti И rti Η Л 4-> 4-4 та tť TJ ф> φ >> Φ> О rti 4-4 ’Т * Ο rti 4- <ι • 2 4tí СО 'Honors СО S °? ^C M ι ti >> ti> 4 Έ >> φ гй φ д φ л r-j ω ¹ ti rH ι R В r-Η < rH

ι ι) ι

WHAT Honors . honors , ® « LO ti 4 ti я CM tí T ti T .3 Even you cm AND ti • r- < ti Ф N ti Ф 45 to r ^ ti ti ф -д ΰ ^ω ф >> и d>? Q) ti ti CD «д N ω ti ω φ >> ti Tt ti ω § X ti ti ti d 'N ti ti C / J Ф >> ti Ф N ti Ф ф ω rti 'Honors rQ \ honors & • S 'ti rQ 'Honors O > o _ O> O o> O > ti O ti '5 ti O ti '5 ti o ti 'S ti O with honor • rH ti O <4-4 • ti> 2 c .2 o ‘Ti e o 2 ^e c .2 o with § honors · <—1 '—I 1 § .2 o • rH 8 co • rH ti o <4-4 I.E ’Й (/) TJ <4-4 ? ω 'ti I ± J Ό ti I СЛ XJ <4-4 i d I.E 1 ti ω 00 I.E 4 ti Ч c / 2 СО Д ΓΌ Ttf ti ? СЛ • w I.E t-H rH 1 rH » т-H ' T-i < rH t rH 1

OJ O rH CM 00 Ttl LO CD ts 00 OJ O 00 O) O OJ OJ OJ OJ OJ OJ OJ OJ o rH

an example of a diamine of formula X an amine of formula 7 pyridone derivative of general formula hue number HzN — D — NH2 of formula 3 '>>

4- »Д> N

g> N> Ф>

Д Ф

Ф N

Д> n3> Ф> ca

> t-4

Ф

д> Ф> ca and a)>--Ф> CD

4Д> N> Ф> ca and φ ω N

1 СО СМ 1 cd ™ 1 со СМ 1 Ф ™ X до >> >5> Л Л> гД ř-i X 5 X 5-ч X Í3 X ф (4 со о со о СО О со о Г-ι ДЗ Гн ДЗ Г-Ч Рч Д гч ТЗ ¹ 13 • 13 i Д со >> what 7 >> τί <о хз хз г-L ТЭ 1 г — 1 · ^г “4 £ _. хсо >> со > л CD X СО OF? X хз 1 Л Л Дч ДЗ л g Рч 4-1 tť >> Ч-ч 44 ф о л 4- * S5 Φ О G Φ f- <о S о 4- Cd Ф гЧ З S 44 'CD ф rt 'СО f-i 'Cd X чн Б £ <«Д ч-ч S д й? д ДЗ о ’З о д 4 о д 4 о д о ³ -rt сл t ТЗ СЛ д ТЗ сл 1 13 сл 1 13 сл р >> • ¹ Х> оэ. Т5 оэ.'З / Ё £ 3 O X X Р О о ÍX о х '-' о X '------' 1 1 гН Б р-де т — 1 6 гН Й? - л Т-1 1

> 4 4- » чх 'ίχ 'ΪΧ 4дЗ Д ι — Н д г-Н 4- | Д 4- * Д Д 3 > Ν > N > N > N > 73 > N 73 ) Ф > ф > Ф > ф > Ф > > > Ф > ф > > > ca ф 3> > Ф ca ca д Д ф £ 3 Ф cd £ 3 ca £ 3 £ 3 Ф Д ф ф ф N > Гн Ф > Г-ф Ф Ή! N Ф г-Н ф N > Ϊ-4 Ф > Г-ф > о > О > о ю

д д СО * * * к О СО Ч-ч д д 4 ч U ф ‘ЬЧ ф £ С cd ч-ч cd É СО «* ч cd Й ЬН cd í- · φ S Φ .д О .Д о • I — 1 .Д О .д о • Д ^г— ' .-ч О ο XJ ч-č 1 сл 73 ч-ч 13 р 1 СЛ HI ч-ч • Ie Д3 д 1 СЛ 13 i ТЗ тЗ Д i СЛ ТЗ ч-ч * 73 τ3 τ ω Ό ч-ч 1 л S д со Д TJ1 Д ~ / А со Д ~ гл Д

Τ— < СМ СО τΡ Ю СО 00 СП and ο ο ο Ο ο Ο ο ο О rH гЧ τΗ rH rH τ — 1 i — 1 rH ' rH rH τ — 1

an example of a diamine of formula X an amine of formula 7 pyridone derivative of general formula shade number HN-D-NH2 of formula 3 'X' X '+ titanium> N

'X 4- » 'X 4- » 'X 'X 'X 4- * & X 'X 'X 4- » & ti ti 4- · ti 4— · ti ti ti 4- »ti 4- »ti ti ti Я > N я > N > N > N К > N > N > ω > Ф > Ф > Ф > Ф ) ф > > > ф > Ф > > XD > ф > > Honors Honors > > Honors Honors > > Honors Honors ti ti honors Honors ti ti Honors honors ti fí Ф Ф ti ti Ф CD ti ti Ф Ф > to CD > to Ф Ф Ф N Ф Ф M > to Ф > to CD Ф Ф N Ф Ф N > to Ф > P-1 Ф Ю > CJ > CJ Ю > CD > U

ti o ti o ti O ti o °? X °? X РЛ A * °? X 'X °? X  Т3 Т’Й i Ό 'Т’С 1 Ttí «• p , Ό ’Τ Л о Л o Z — 4 O -> X / —Ч X - X Λχ X r - 0 to r — 0 to i — 0 t0 - <it r— <Cil <- · cl - <Qo «- <Cli ΧΌ ΧΌ X TJ >> Td X 1 X T X i X rti X Д X rti X rti X rti CM rti 00 Д CM , C <N 4- Γ2 4-> rj Φ 1 Φ 1 4 ».ti Ф | 4- »Ь CD i 4— ¹ 'Ф Й? + - * Λ CD X 4— · ' CD> + - F WITH? About CD C CD O CD O CD o X o X O X o X ti d ti d § д ti Д ti >> s л ti Д .2 2 S £ .5 2 2 £ ti θ .ti to 5 Ό ti X .2 2 SS 5 я ÍS 2л ti> р Д О T 1 2д £ ώ 2 rti 5 л X cl ti X d 4- »Д O 4-J ti ti o X those you 4-1 G Q £ 8 £? CD Ž? CD φ 'd Φ Λ и 5 ¹ 2 č WITH φ 'й rH ф Д S ω x and> Λ со >> cd Д H >> Φ Yeah Q X ? ti feL? Д Sx ^ft Wx X d ? b ? G it honors H 4 fi ⁴ ? rti ^S - (-H honors A 4. φ * -> rj 'X CM' X oo rH <1 rH 1 1 'CM rH i i н-ΐ ?  £ rH i ¹ , ti rH 1 '. ti rH i

r — M O 3 O O O ^G i ^G with O F — 1 O WITH O and

honors .s

Ti СЛ X X cd 'O ti o

4-4 ti СЛ

TJ i

i in

Honor you

'Cti> o ti o 4-4 F4 ti СЛ' Cti> o ti o «4-4 ti ω í

L 1 »· Honors ti Д ti ^ -0 Φ СЛ X ti ti <D 5 and o £ СЛ ω x Φ N ti Φ Ф N • гЧ Ф ω X 4Э 'CD O O > O 'Honors ti Д O ti • ti> £ < > s s WITH O with O cd ti CD Ψ4 honors ti Н Н O <FO O TJ <H4 ti СЛ ? «+ - < F ^ 4 73 4 ^ WHAT ti 7 СЛ ъ ω

В в (rH i rH t

—Ι — I ο

Cη Ctí X) ο Λ 'Φ β ο φ X) Ο

Ό • r-4 ø-4> S Λ

CO Φ ω

Σ-4

Ο N>

'β

Φ

Ό

Ο

Φ

Q ί-4 Ν Ν>

Ο Φ ω Λ ο β

g β φ ο Τη Ο Ν>

οι κ Λ ^ζ 9Q υ ι β Λ Λ ο см ΰ Д

3

'>> >> 4- * + · * β β г — 4 r-H > Ν > Ν > Φ > Φ > · > β «Φ β β Φ CD F — Η r-H φ φ Ν Ν

'>> '>> 4- * 4- · 9 β r — Η > Ν > Ν > φ > φ > > β β β β φ Φ > > C-4 S-i Φ Φ > Ο > Ο

'>>

4-J β r — 4> Ν

I I f '> ο + - »9

ΧΝ

'>> 4- * '>> 4- * '>> 4- * '> ^ -Μ 9 β r— < + -> 9 4- » 9 β r — 1 ^re > Ν > Ν > Ν Я > Ν > Ν > φ > Φ > Φ > Φ > Φ > Φ > > > > β β Φ β β Φ > β β > β β β β Φ β β Φ > > Φ Φ > > Τη Τη φ Φ Τη F-n Φ ω Ν Ν Φ Φ χω XD > ω > ο

со · 00 ' со ι Sx <>> 'X X > 4 a.g g «Ie □ č Ρ £ Ρ >> О ^β 7 Тп CU О CD O CD о 9 Д 9 Д 9 Ξ β 2 β 49 9 49 9 β β 4-4 β 4-ч Г — 1 Φ г— 'φ _ > ΰ β >> д β >> 4-J β Q 2 4 2 Т ° φ CD β Λ Τη β Д | JT, β (> 4 • >> 1

4 * 4 4 ^^ 4

ο ο ο Ο ω

CM β Ν β Φ 43 Ο β 1 тЗ f

CO τ-Η β • ^β φ (Λ >> 4t 'β> Ο β Ο

0—4 ω

• Φ t

Ν Ν β β rQ

Ο β

WITH

Ε 3 t CO τΗ

> G Ο * η ω т5 ι

CM ^β φ N β Φ 4D

O β g .β β

R-H >>

4 4 4 β> O β O

4—4 ^{, β} Φ 3 CM β 1 · γΗ

CO β

About $ £ >>

4tí.

\ β> O β o ь-y (Л • Ξ φ

what

4tí 'Honor>

O β O

4-4

CO β φ Ν β Φ

R Ο β • r-4

Ε .2 β

• rH

Φ

Μ >> 4t 'β>

Ο β

Ο

CM ^β

C0

β .5 φ со >>

4t 'β> Ο β

Co <+ - 4 co

XJ β о it WHAT r> what от O rH CM WHAT T it 4tí То CM CM CM CM CM WHAT WHAT WHAT WHAT WHAT WHAT 03 \ r-n> Tn Ю r-H rH rH rH t — 1 rH rH rH rH rH rH

CO as an example of a diamine of formula X amine of formula 7 pyridone derivative of formula hue number HzN — D — NH2 of formula 3

4- » 4-> 4-n β 4- » β β 73 > N 73 73 > ω > CD )CD > CD > > Honors > cd cd rj cd r- · β β CD »- < CD CD ω N CD f — H CD N > Ph CD> ω > Ph Φ

β β β β ¹ O 1. ο !. О • Ο Ттз Τ Ό 5 ¹ 2 5 ¹ Τ5 Ph ¹ - 'Τη * F-t Λ а <? β а O c \ j Ρ СЧ О см Ο oj Рч i Рн < Рн i tn 1 β řx β>? β >> β >> o X ο X о X ο X β O Д ρ β р and ° β Ph • rH Рн • rH Рн β Рн β 73 β Ttí S ъ β Ό Jh 5 β № β 1л со ? -p cd л cd Λ cd д у У >> у у >> ? 43 ? β ? β ? β ГН *> - Ф '-' it 2; φ ± ф - d '7 гЧ? гЧ ГЧ 1

4-J 4-i 4- » β β β 0 i “H 73 73 73 > N > CD > (D > CD > <D > > > > Honors β β CD β and β β CD CD CD CD > > > Ф N ph Ph Рн ω (D CD > u Ю > CD

> cd> cd

0) NJ> (D> cd β

CD

τ · 8 Чф ^ 1 CO WHAT '-' Тн '-' Тн * - ‘Тн r — H Д 9 9 ⁴ β g *? <β &. β ř ». β 4-1 β 4-no ОсмДОомаОСМД CD CD tu 1 .Zu t-ll .LJ f t .Q, & & φ g <& ω Λ & φ, sss £ ”se Tj ± 7 kи * c * 4 kи Ti __J ЧИ S й 7 About 73 71 H N ^E 7 О * Ф 73 71 ?!

CD §

r4

гЧ СЧ 00 ’Ф Ю СО чф ’Ф чф Ф -ф  Ф гЧ гЧ г-1 гЧ гЧ гЧ

Application Example 1:

parts of the compound of the invention [in the form of the sodium salt] of Example 1 are dissolved together with 50 parts of urea in 300 parts of water. The solution obtained is stirred at a temperature below 40 ° C in 400 parts of a neutral, aqueous 4% alginate sparger. 10 parts of sodium carbonate are then added and the whole is supplemented with 4% aqueous alginate sprays to a total of 1000 parts. The mixture is mixed well and the cotton paste is printed with the printing paste which, after drying at 60 ° C, is treated for 5 minutes with saturated steam at a temperature of 100 to 103 ° C in a steaming agretate commercially available. The printing is then completed by rinsing with cold and hot water, washing with neutral detergent and rinsing again in water. After drying of the goods, a color-intensive green-yellow printing with very good light fastness and very good wet fastness is obtained.

Application Example 2

The mercerized cotton fabric is covered with an aqueous dyeing bath at 20 ° C at a bath consumption of <80%, based on the weight of the goods, wherein the dyeing bath contains 20 g sodium salt of the azo compound of Example 1 and 18 g 33%. sodium hydroxide. The woven fabric is wound on a pile, which is sealed in a foil and left to rest for 8 hours at room temperature. The dyeing is then completed by rinsing in cold water, followed by treatment with an aqueous bath containing a small amount of acetic acid and rinsing again in cold and hot water. After drying, a color-intensive greenish-yellow coloring with very good light fastness and very good wet fastness is obtained.

Application Example 3

Per 100 parts of mercerized cotton fabric is caused for 10 minutes at 60 ° C in 3000 parts by volume of an aqueous dye bath containing 5 parts sodium salt of the compound of the invention of Example 1 as well as 150 · parts · anhydrous sodium salt. After 10 minutes of treatment, 15 parts of anhydrous sodium carbonate and 4 parts of 33% sodium hydroxide are added. The dyeing is continued for 60 minutes at 60 ° C. Thereafter, the dyeing process of the dyed fabric is completed in the usual manner, for example as described in Application Example 2. A color-intensive, greenish-yellow coloring with very good light fastness and very good wet fastness is obtained.

Application Example 4

100 parts of wool fabric are placed in an aqueous dyeing bath at 40 ° C consisting of 3,000 parts of water, 2 parts of sodium salt of the compound of the invention described in Example 1, 0.15 parts of an adduct of 12 moles of ethylene oxide with 1 mol of stearylamine. 2 parts ammonium acetate and 2 parts 60% aqueous acetic acid. The temperature of the dyeing bath was raised to boiling temperature over 30 minutes and dyeing was continued for 60 minutes at 100 ° C. Upon usual rinsing and completion of the obtained dyeing of the wool, this wool fabric exhibits a color-intensive, greenish-yellow color shade with very good light fastness and very good color fastness. good wet stability.

Application example 5

It is dyed as described in Application Example 4, but the wool fabric is replaced with 100 parts of ε-polycaprolactam fiber fabric. Color-intensive, greenish-yellow coloring with good durability is also obtained.

According to the above application examples, other monoazo compounds of the present invention may also be used in the dyeing and printing processes described herein in the Examples illustrating the manufacturing process as well as in the Examples summarized in tabular form. In an analogous manner, for example, these dyeing and printing methods as described in Application Examples 1 to 5, with some other dyes of the present invention, also produce very color-intensive dyeings and prints with good light fastness and good wet fastness. which are always given for the respective exemplary embodiments or for the examples summarized in the table.

Claims (11)

OBJECT OF THE INVENTION A process for the preparation of water-soluble monoazo compounds of the general formula 1 dl in which R1 represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group or a chlorine atom, R ² is hydrogen, alkyl having 1 to 4 carbon atoms or alkoxy having 1 to 4 carbon atoms, R3 is C1 -C4 alkyl substituted with hydroxy, C2 -C5 alkanoylamino, sulphate, carboxy or sulpho, R is hydrogen, carbamoyl, cyano or sulfo, D represents a meta- or para-phenylene group which is substituted by one or two sulfo groups or one or two sulfo groups and one alkyl group having 1 to 4 carbon atoms, X represents a chlorine atom or a fluorine atom, Y is vinyl or an ethyl group which contains in - ^ - position linked residue which is alkali-eliminable as the anion, whereby R 1, R ^2, R ³ and R can be identical or different, - characterized - in that the compound of formula II is reacted NH-A (II) wherein A represents a hydrogen atom or a radical of formula (a) or (b) X N ^ b ^ -NH-D-NH ⁰ (a) N or мХ / -SjKx M a D, R 1, R ² , X and Y are as defined above, in the case of an amine of formula II wherein A is a group (a) after its diazotization to the diazonium salt, with a compound of formula III wherein: R and R 3 have the above meanings and B represents a hydrogen atom or a group of the general formula (b ‘) or (c‘j (b‘) h) -D-N-Nr or Л / Ал / x — L JLnh-d-n = wN (c) where D and X have the meanings given above, when A is hydrogen, then B is a group of formula (c'j, if A is a group of formula (a), then B is a hydrogen atom and A is a group of formula (b), then B represents a group of formula (b *). 2. A process as claimed in claim 1, wherein the corresponding compounds of the formulas II - and III are used as starting materials to give compounds of the formula I in which R @ 1 is hydrogen, R @ ² is hydrogen or methoxy or methyl. , -SO2-Y represents a n -sulfatoethylsulfonyl or vinylsulfonyl group and is bonded at the m- or β-position to the amino group on the benzene ring, R3 is known to have a C1-C4 alkyl group substituted by carboxy, sulfo or acetylamino or propionylamino, R represents a sulfo group or a cyano group, D represents a meta- or para-phenyl group. which is substituted with one or two sulfo groups, and M and X have the meanings given in 1. 3. The process according to claim 1, for the preparation of the compounds of the general formula 1 as defined in claim 1, wherein Y is an ethyl group which is substituted in the 3-position by an ester group, preferably a sulphate group, 1 use compounds in which Y is β-hydroxyethyl, and the obtained azo compound corresponding to the general formula 1, in which Y is β-hydroxyethyl, is reacted with an esterifying or acylating agent, preferably a sulfating agent. 4. A process according to claim 1, wherein the corresponding compounds of formulas II and III are used as starting materials to form compounds of formula 1 wherein D is a meta- or para-phenylene group which is substituted by one or two. sulfo groups. 5. A process according to claim 1, wherein the corresponding compounds of formulas II and III are used as starting materials to form compounds of formula 1 wherein -SO2-Y is β-sulfatoethylsulfonyl or vinylsulfonyl which is bound on the benzene ring in the meta- or para-position to the amino group. 6. A process according to any one of claims 1, 2, 4, or 5, wherein the corresponding compounds of formulas II and III are used as starting materials to produce compounds of formula 1 wherein R3 is an alkyl group having 1 to 3 carbon atoms. carbon atoms which is substituted with a sulfo group or a carboxy group. . 7. A process according to any one of claims 1, 4, 5 or 6, wherein the corresponding compounds of the formulas II and III are used as starting materials to give compounds of the formula 1 in which R is a sulfo group or a cyano group. 8. The method according to. claim 1, characterized in that as starting substances · corresponding compounds of the formulas II and III to form a compound of formula CH _of CT or its alkali metal salts. seeing compounds of formulas II and III 9. Process according to claim 1, characterized in that the starting materials are CH _£ SO ₃ H or its alkali metal salts. 10. The process of claim 1, wherein the corresponding compounds of formulas II and III are used as starting materials to form a compound of formula CHfCOOH or its alkali metal salts. 11. Process according to claim 1, characterized in that the starting materials are used as a starting material . * L ^NH Or an alkali metal salt thereof. seeing compounds of formulas II and III to form a compound of formula