DE1218092B - Process for the production of metal-free azo dyes - Google Patents

Description

Process for the preparation of metal-free azo dyes The present invention relates to a process for the preparation of new valuable dyes of the general composition In this formula, F denotes the radical of a metal-free azo dye, A a five- or six-membered carbocyclic or heterocyclic ring, X hydrogen or a substituent, Y hydrogen, halogen or an organic radical, "hal" a halogen atom, W a sulfonamide group, m a whole Number and n is an integer from 1 to 3.

The metal-free azo dyes can be both the series of the mono- al s also belong to the polyazo dyes.

In the dyes of the general formula (I), the remainder is by definition bound to the dye molecule via a sulfonamide group ..

Possible substituents X include: optionally substituted alkyl, aralkyl and aryl radicals, sulfonic acid, carboxylic acid, halogen substituents, such as chlorine and bromine substituents, and also nitro, hydroxy, alkoxy, cyano, sulfone and optionally substituted sulfonamide groups, acid ester groups such as sulfonic acid and carboxylic acid ester groups and the like. In the event that Y represents an organic radical, this can be of any type, e.g. B. an alkyl, aralkyl, aryl or acylamino group, an alkyl or arylsulfonylamino group, and also residues of aliphatic and aromatic hydroxy or mercapto compounds. Of course, Y can also be used for the remainder of a colored component, i.e. H. that is, of any dye.

. The new dyes of the formula (I) can, depending on the nature of their substituents, be either water-soluble or sparingly soluble or insoluble in water. The radical F can contain the usual substituents in azo dyes, such as sulfonic acid, carboxylic acid, optionally substituted sulfonamide, sulfone, alkylamino, aralkylamino, arylamino, acylamino, nitro, cyano, halogen, hydroxy, Alkoxy, azo groups and the like. The dyes can also contain other fixable groups, such as mono- or dihalotriazinylamino, mono-, di- or trihalopyriinidinylamino, esterified sulfonic acid, oxalkylamide and oxyalkylsulfone groups, sulfofluoride, haloalkylamino and haloacylamino Have urethane, unsaturated haloalkyl urethane, isocyanate groups and the like .

The new dyes can be obtained by either a) metal-free aminoazo dyes which have reactive hydrogen on the amino group with compounds of the formula wherein A is a five- or six-membered carbo- or heterocyclic ring, X is hydrogen or a substituent, Y is hydrogen, halogen or an organic radical, "hal" is a halogen radical and n is an integer from 1 to 3 , and those in ring A are Contain sulfonic acid halide group, or b) sulfonic acid halides of metal-free azo dyes with compounds of the above formula which have an amino group with reactive hydrogen in ring A, to give metal-free azo dyes of the general formula where A, X, Y, "hal" and n have the meaning given above, F is the radical of a metal-free azo dye, W is a sulfonylamino or sulfonamide group and m is an integer from 1 to 3 will.

According to a variant of this process, the dyes can also be built up in such a way that one diazo and one coupling component, at least one of which is the group has, converted to metal-free azo dyes of the formula (I).

Depending on the number of sulfonic acid halide groups in the dyestuff radical or in the dyestuff precursors which are suitable for the conversion reaction, one or more groupings of the general formula (II) can be incorporated into the dyestuffs. In the majority of cases, the number will not exceed m = fourth

Some of the starting products of the formula (II) are known from the literature (compare, for example, Angewandte Chemie, 1960, 72, p. 973). From these, some of the products which can be used for the various implementation methods can be obtained by subsequent introduction of the corresponding reactive groups, e.g. B. build up by sulfochlorination. In general, however, it is advantageous to add the desired groups, e.g. B. nitro, amino or acylamino groups, even before the ring closure z. B. to introduce the quinoxaline derivative in the aromatic no A of the o-arylenediamino compound. In this case you go z. B. of a 1,2-diaminobenzenesulfonic acid or a triaminobenzene compound (with at least two o-amino groups) or a substituted or acylated derivative on the amino group in question, this reacts with oxalic acid to form a quinoxaline ring and converts the free Hydroxy groups, optionally after a modification of the substituents contained in No A , into halogen substituents, e.g. B. in the case of a nitro group after reduction.

One of the two halogen substituents in the pyrazine ring can be in the precursors or after the dyes have formed can be modified into the remainder of an organic compound by reacting at this point, for example, with aliphatic, aromatic or heterocyclic amino, hydroxy or mercapto compounds.

From the large number of dyes obtainable according to the process, such products are particularly easily accessible which differ from amino group-containing azo dyes of the benzene-azo-benzene- ' benzene-azo-naphthalene, benzene-azo-aminopyrazole and -pyrazolone series, such as the hetero-azo -aryl series, by reaction with the compounds of the formula (II) which have a sulfonic acid chloride group in the aryl nucleus A, aling.

There is no need to look more closely at the large number of starting components that can be used enter into.

The new dyes are extremely valuable products that can be used for The most diverse applications are excellently suited. As water-soluble compounds you find preferred interest in dyeing nitrogenous and hydroxyl-containing groups Textile materials, especially native and regenerated cellulose, wool, Silk, synthetic polyamide and polyurethane fibers. Thanks to the reactive halogen substituents With a pyrazine residue, the products are particularly suitable as reactive dyes for Dyeing of cellulose materials according to the ones that have recently become known for this purpose Techniques.

The dyeings obtainable with the new dyes are generally distinguished by good to very good fastness properties, in particular excellent wet fastness properties. In comparison with the dye of the formula known from German Auslegeschrift 1 112 229, Table V, No. 3 obtained with the new dye of the formula much deeper color prints on cotton. EXAMPLE 1 46 parts of the monoazo dye obtained by coupling diazotized 2-aminonaphthalene-4,8-disulfonic acid onto 3-methylaminotoluene are dissolved in 300 parts of water at 50 ° C. at pH 7 to 8 and in the presence of excess sodium acetate or calcium carbonate at 50 to 70 'C in portions with a total of 30 to 35Teilen finely powdered 2,3 - dichloroquinoxaline - 6 - sulphonyl chloride of melting point 86 offset to 87'C and stirred at this temperature until a sample no longer shows color on acidification envelope.. The resulting dye of the formula is salted out, filtered off with suction, washed and dried.

Cotton fabric is impregnated with a solution at 20 to 25 ° C. which contains 20 g of the above dye and 0.5 g of a nonionic wetting agent (e.g. a polyoxyethylated oleyl alcohol) and 150 g of urea and 15 g of sodium bicarbonate per liter of liquor . The fabric is then squeezed between two rubber rollers to a moisture content of about 100 () / o. After intermediate drying at 50 to 60 ° C , the mixture is heated to 140 ° C for 10 minutes and the resulting dye is rinsed thoroughly with hot water and treated at the boil for 20 minutes with a solution containing 5 g of Marseille soap and 2 g of soda per liter. After rinsing and drying, a strong reddish yellow coloration with good wet, rub and lightfastness is obtained.

The table below lists the diazo components, coupling components and the reactive component linkable to the amino group, from which dyes can be synthesized analogously to the information in this example, the color shades of which - obtained by one of the application processes described - are also shown in the table. Abbreviation for the reactive component: C = 2,3-dichloroquinoxaline-6-sulfochloride Diazo component, coupling component, reactive color component 2-aminonaphthalene-4,8-disulfonic acid 1-methylamino-3-methoxybenzene C yellow 1-aminobenzene-2-sulfonic acid 2-methylamino-5-hydroxynaphthalene- C orange 7-sulfonic acid 1-Amino-4-acetylaminobenzene-6-sulf.o-2-methylamino-5-hydroxynaphthalene- C scarlet acid 7-sulfonic acid 1,3-diaminobenzene-4-sulfonic acid 1- (2 ', 4'-dichlorotriazine-l', 3 ', 5'-yl- C red 6'-amino) -8-hydroxynaphthalene-3,6-di- sulfonic acid Example 2 In the solution of 36.5 parts of the sodium salt of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid in 100 parts of water, 33.5 parts of finely powdered 2,3-dichloroquinoxaline-8-chloro-6- sulfonic acid chloride and 12 parts whiting chalk and the mixture stirred at 500C until no free amino group can be detected. After condensation with 600 parts of water and addition of 12 parts of soda, the reaction mixture is slowly mixed with 17.5 parts of diazotized 2-aminobenzenesulfonic acid, dissolved in 200 parts of water, at 5 to 10 ° C. The instantly formed dye of the formula is salted out when the final pH value is 7 , filtered off with suction, washed with dilute sodium chloride solution and dried at 40 to 50 ° C. in vacuo. It dyes materials made of cotton or regenerated cellulose, wool or synthetic polyamide fibers by one of the processes described above in clear blue-tinged red shades of good wet, rub and lightfastness.

If, in this example, the reactive component used is 2,3-dichloroquinoxaline-8-cyano-6-sulfonic acid chloride, a similarly red dye is obtained. A similar result is obtained when 44 parts of 2,3-dibromoquinoxaline-6-sulfonic acid bromide are used instead of 33.5 parts of 2,3-dichloroquinoxaline-8-chloro-6-sulfonic acid chloride.

If one proceeds, as stated above, but uses 30 parts of finely powdered 2,3-dichloroquinoxaline-6-sulfonic acid chloride as reactive component, so that equivalent amounts of the amino group-containing coupling or diazo components mentioned below are acylated and coupled with the indicated diazo or coupling components, valuable reactive dyes are also obtained in this way. Diazo component, coupling component, color shade 1-aminobenzene-2-sulfonic acid 1-hydroxy-8- (3'-aminobenzoylamino) -naphthalene- red 3,6-disulfonic acid 2-aminonaphthalene-1-sulfonic acid 1-hydroxy-8- (3'-aminobenzoylamino) -naphthalene- bluish- 3,6-disulfonic acid red 2-aminonaphthalene-1-sulfonic acid 1-hydroxy-8- (4'-aminobenzoylamino) -naphthalene- bluish- 3,6-disulfonic acid red 2-aminonaphthalene-l-sulfonic acid 2- (3'-aniinobenzoylamino) -5-hydroxy-naphthalene - reddish- 1,7-disulfonic acid orange 1-aminobenzene-2-sulfonic acid 2- (3'-aminobenzoylamino) -5-hydroxy-naphthalene-orange 1,7-disulfonic acid 1,3-diaminobenzene-4-sulfonic acid, 2-acetylamino-5-hydroxynaphthalene-7-sulfonic acid, orange Example 3 To the solution of 26.1 parts of the sodium salt of 2-amino-5-hydroxynaphthalene-7-sulfonic acid in 400 parts of water are one, 32 parts of finely powdered 2,3-dichloroquinoxaline-6-sulfonic acid chloride and stirred under constant becoming blunt free Hydrochloric acid with soda solution to pH 5 for 2 hours at 45 to 50 ° C until no free amino group can be detected. The acylation product formed is added after the addition of 28 parts of sodium bicarbonate at 40 "C with 22.5 parts of diazotized sodium salt of 1-amino-4-methoxybenzene-2-sulfonic acid. The thus formed red reactive dye of the formula which is present in a volume of 1000 parts is precipitated by adding 100 parts of sodium chloride, filtered off, washed and dried. Materials made of cellulose fibers can be dyed with this dye in the presence of soda as an acid-binding agent at 40 "C from a long liquor, in the cold dwell process, by heat setting at 140 ° C or after printing in the presence of conventional thickeners by a quick fix of one minute at 1032C (steam colored or printed.

If one proceeds as indicated above, but uses the starting component listed in the table below, one also obtains a valuable reactive dye which dyes cellulosic materials in the indicated shade. Diazo component, coupling component, color shade p-sulfanilic acid 1-hydroxy-7- (4'-nitro-black phenylazo) -ß-amino- naphthalene-3,6-di- sulfonic acid (reduced) Example 4 The solution of 68.8 parts of the trisodium salt of 1-hydroxy-2-azo- (2'-sulfobenzene) -8- (3 '# aminobenzoylamino) -naphthalene-3,6-disulfonic acid in 500 parts of water is mixed with 10 parts of calcium carbonate and 32 parts of finely powdered 2,3- dichloro -7- methylquinoxaline-6-sulfonic acid chloride (melting point 103 ° C.) are added and the mixture is stirred at 50 ° C. until no more aminoazo dye can be detected. The reactive dye formed of the formula is salted out, filtered off and dried. It dyes cellulose materials in clear blue-tinged red tones using one of the processes described above. Likewise valuable reactive dyes are obtained when using 30 parts of 2,3-dichloroquinoxaline-6-sulfonic acid chloride or 34 parts of 2,3-dichloro-5,7-dimethylquinoxaline-6-sulfonic acid chloride instead of 32 parts of 2,3-dichloro-7- methyl-6-sulfonic acid chloride. Example 5 In the solution of 68.8 parts of the trisodium salt of 1-hydroxy-2-azo- (4'-sulfobenzene) -8-amino-7-azo- (4 "-aminobenzene) -naphthalene-3,6-disulfonic acid , obtained by acidic coupling of diazotized 4-nitroaniline to 1-hydroxy-8-arninonaphthalene-3,6-disulfonic acid, alkaline coupling of the monoazo dye with diazotized aniline-4-sulfonic acid and reduction of the nitro group with sodium sulfide in 500 parts of water, 10 parts of calcium carbonate and 30 parts of finely powdered 2,3-dichloroquinoxaline-6-sulfonic acid chloride are added, and the mixture is stirred at 50 ° C. until no more aminodisazo dye can be detected by chromatography, and the reactive dye formed of the formula is salted and dries it in a vacuum at 50'C. On cellulose fabrics with soda as an acid-binding agent, it provides strong black prints with very good wet fastness in steaming times of 1 to 8 minutes.

If the procedure is as above, however, instead of the 68.8 parts of the aminodisazo dye mentioned, 70.3 parts of the trisodium salt of 1-hydroxy-2-azo- (2'-sulfo-4'-aminobenzene) -8-amino-7- azo- (4 "-aminobenzene) -naphthalene-3,6-disulphonic acid and instead of 30 parts 60 parts 2,3-dichloroquinoxaline-6-sulphonic acid chloride, a disazo dye containing two reactive groups is obtained which dyes cellulose fabric in wetfast, greenish blue shades .

Claims (2)

Claims: 1. A process for the preparation of metal-free azo dyes, characterized in that either a) metal-free amino azo dyes which have reactive hydrogen on the amino group with compounds of the formula where A is a five- or six-membered carbo- or heterocyclic ring, X is hydrogen or a substituent, Y is hydrogen, halogen or an organic radical, "hal" is a halogen radical and n is an integer from 1 to 3 and the group in ring A is a sulfonic acid halide group or b) sulfonic acid halides of metal-free azo dyes with compounds of the above formula which have an amino group with reactive hydrogen in ring A , to give metal-free azo dyes of the general formula where A, X, Y, "hal" and n have the meaning given above, F is the radical of a metal-free azo dye, W is a sulfonylamino or sulfonamide group and m is an integer from 1 to 3 . 2. Modification of the process for the preparation of the metal-free azo dyes obtainable according to claim 1 , characterized in that a diazo compound with a coupling component, of which at least one is the group has, to metal-free azo dyes of the formula converts, in which F, W, X, hal, A, Y and n have the meaning given in claim 1. When the application was announced, a coloring table with explanations was laid out.