WO1991008265A1

WO1991008265A1 - Azo compounds and their use as dyes, 1-sulpho-6-carboxyl-amino naphthaline, its use as a diazo component and process for the production of these compounds

Info

Publication number: WO1991008265A1
Application number: PCT/EP1990/002019
Authority: WO
Inventors: Hartmut Springer; Kurt Hussong
Original assignee: Hoechst Aktiengesellschaft
Priority date: 1989-12-02
Filing date: 1990-11-26
Publication date: 1991-06-13
Also published as: BR9007891A; DE3939909A1; JPH05501278A; EP0502893A1; KR927003733A

Abstract

The description relates to azo compounds corresponding to formula (1) below, having fibre-reactive properties and making valuable dyes. They can dye hydroxy and/or carbonamide group-containing synthetic and natural materials, especially fibre materials, like wool and especially cellulose fibre materials in bright colours. Formula (1) in which: M is hydrogen or a salt-forming metal like an alkaline metal; K° is a residue of general formulae (2A) or (2B) in which: E is the residue of an intermediate component common in disazo dyes which can act as a coupling and as a diazo component, e.g. the residue of a 1-(aminophenyl) or -amino-naphthyl) pyrazolon, aminonaphthol, anilin or 1-amino naphthalin compound; v is the figure zero or 1; K is the residue of a water-soluble coupling component, preferably from the naphthol, aminonaphthol, anilin, pyrazolon, hydroxypyridon and acetoacetyl arylide series, whereby this coupling component contains 1 or 2 fibre-reactive groups of the vinyl sulphonate series; D is a benzol or naphthalin residue, whereby its substituents R?1 and R2¿ are common ones in azo dyes, e.g. (besides hydrogen) lower alkyl, lower alkoxy, halogen, sulpho and carboxyl; the group -SO¿2?-Y is a fibre-reactive group of the vinyl sulphone series; a is the figure zero, 1 or 2; and k is the number 1 or 2. A description is also given of the compound 2-amino naphthaline-1-sulphonic acid-6-carboxylic acid which may be used as a pre-product in the production of dyes, e.g. as diazo component in the synthesis of dyes of general formula (1).

Description

description

Azo compounds and their use as dyes, 1-sulfo-6-carboxy-2-a ino-naphthalene, its use as a diazo component and process for the preparation of these compounds

The present invention is in the technical field of fiber-reactive azo dyes.

Azo dyes based on di- or trisulfonaphthylamines are well known in the literature, for example from Japanese patent application publications Sho-58-142939, Sho-59-115360 and Sho-59-182859, US Pat. Nos. 3,197,456 , 3 406 163, 3 419 542 and 3 518 245 as well as the British patents 1 341 320 and 1 438 051. The ever increasing demands in the handling of the dyes in the dyeing to achieve brilliant dyeings have made it necessary to use new dyes with improved properties to develop.

With the present invention, new ones have now been made

Azo compounds found which have the general formula (1)

correspond. In this formula:

M is a hydrogen atom or salt-forming metal atom, such as in particular an alkali metal atom, such as sodium, potassium or lithium; K ° is a radical of the general formula (2A) or (2B) , - E - N = N -}. K (2A)

in which

M has the meaning given above, D is a benzene or naphthalene radical,

R ^{1 is} hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy, fluorine, bromine, chlorine, sulfo, carboxy, carbalkoxy of 2 to 5 C. Atoms, such as carbomethoxy and carbethoxy, trifluoromethyl, carbamoyl or N

carbamoyl, preferably hydrogen, methoxy or methyl if D is a benzene ring, or R ^{1 is} hydrogen or sulfo if D is a naphthalene ring,

R ^{2 is} hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy, chlorine, nitro or sulfo, preferably hydrogen, methoxy or methyl, if D means a benzene ring,. or

R ^{2 is} hydrogen or sulfo, if D is a naphthalene radical, Y is the vinyl group or an ethyl group which contains a substituent which can be eliminated by alkaline means to form the vinyl group, a is the number zero, 1 or 2, k the Number 1 or 2,

E is a radical of the general formula (3a), (3b), (3c) or (3d)

means in which

R is hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl, cyano, carboxy, carbalkoxy of 2 to 5 carbon atoms, such as carbomethoxy and carbethoxy, carbamoyl or phenyl, preferably methyl, carboxy, carbomethoxy or carbethoxy,

Q is a benzene or naphthalene residue,

R ^{1 has} one of the abovementioned meanings as a substituent on a benzene radical or is hydrogen or sulfo if Q is a naphthalene radical,

R ^{3 is} hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy, chlorine or sulfo, preferably hydrogen, methoxy, ethoxy or methyl, if one Is benzene, or is hydrogen or sulfo if Q is naphthalene,

R ^{4 is} hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy, bromine, chlorine, trifluoromethyl, sulfo, carboxy or cyano, preferably methyl, methoxy or is sulfo, R "is hydrogen, alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, alkoxy of 1 to 4 carbon atoms, such as

Ethoxy and especially methoxy, chlorine, amino,

Alkylamino of 1 to 4 carbon atoms, such as ethylamino,

Alkanoylamino of 2 to 5 carbon atoms, such as acetylamino and propionylamino, benzoylamino, ureido, N'-phenyl-ureido, N'- (C _] _-C ₄ -alkyl) -ureido, phenylsulfonyl or

Is alkylsulfonyl of 1 to 4 carbon atoms, such as ethylsulfonyl and methylsulfonyl, preferably hydrogen or methoxy,

R ^{c is} hydrogen or ß-sulfatoethylsulfonyl,

M has one of the meanings given above, m denotes the number 1 or 2, n denotes the number zero, 1 or 2 (where n is zero this group represents a hydrogen atom), v is the number zero or 1 and K is the rest is a water-soluble coupling component which contains 1 or 2 groups of the general formula -S0 ₂ -Y with Y of the above meaning, such as, for example, a radical of the general formula (4a), (4b), (4c),

(4d), (4e), (4f), (4g) or (4h)

(4a) (S0 ₃ M) m (4b) (S0 ₃ M) _n

d)

HO -

- (S0 ₂ -Y) _k (4g) I -

is in which

M, m, n, Y, k, R ¹ , R ² , D, R ⁴ , R ⁵ , R and a have one of the meanings mentioned above,

V is a direct, covalent bond or a radical of the formula -NH-CO-phenylene-, -NH-CO-NH-phenylene-, -N (CH ₃ ) -CO-phenylene-, -N (CH ₃ ) -CO- NH-phenylene-, -N (C ₂ H ₅ ) -CO-pheny1en-, -N (C ₂ H ₅ ) -CO-NH-pheny1en-, -NH-CO-alkylene-, -NH-CO-NH- alkylene-, -N (CH ₃ ) -CO-alkylene- or -N (CH ₃ ) -CO-NH-alkylene-, -N (C ₂ H ₅ ) -CO-alkylene- or -N (C ₂ H ₅ ) -C0-NH-alkylene-, in which "alkylene" means a straight-chain or branched alkylene radical of 2 to 6 carbon atoms, preferably 3 carbon atoms,

R 'is hydrogen or alkyl of 1 to 4 carbon atoms, such as

Is methyl or ethyl, or is alkyl of 1 to 4 carbon atoms, such as ethyl, which is substituted by sulfo, carboxy, sulfato, phosphato, hydroxy, methoxy or ethoxy, preferably hydrogen, W is a phenylene radical which is substituted by 1 or 2 substituents from the group alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy, chlorine, carboxy and sulfo can be, or an alkylene of

1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as ethylene, or is an alkylene-phenylene with an alkylene of 2 to 4 carbon atoms, such as methylene-phenylene or ethylene-phenylene, is preferably phenylene or ethylene,

R ^{8 is} hydrogen, alkyl of 1 to 4 carbon atoms, such as methyl, alkoxy of 1 to 4 carbon atoms, such as methoxy, phenyl or cyano-substituted alkyl of 1 to 4 carbon atoms, is preferably methyl and R ^{9 is} hydrogen , Sulfo, sulfoalkyl of 1 to 4 carbon atoms, such as sulfomethyl, carboxy, cyano or preferably carbamoyl.

The formula radical E is to be understood as the radical of a coupling and diazotizable compound according to the general formula HE-NH ₂ .

In the formulas (3b), (4a), (4b) and (4c) the hydroxyl group and the free bond located in the same aromatic nucleus are in the ortho position to one another. The hydroxyl group is preferably bound to the naphthalene radical in the α-position.

Alkaline eliminable substituents of the ethyl group of the radical Y are, for example, halogen atoms, such as the bromine atom and chlorine atom, ester groups of organic carboxylic and sulfonic acids, such as an alkanoyloxy radical of 2 to 5 carbon atoms, for example the acetyloxy group, or a sulfobenzoyloxy, benzoyloxy, phenylsulfonyloxy or tolylsulfonyloxy radical, furthermore, for example, the acidic ester groups of phosphoric acid, sulfuric acid and thiosulfuric acid (phosphato or sulfato or thiosulfato groups), in each case also with alkyl alkyl groups 1 to 4 carbon atoms, such as the dimethylamino and diethylamino group. Y is preferably the vinyl group and in particular the β-sulfatoethyl group.

The groups "sulfo", "carboxy", "thiosulfato", "phosphato" and "sulfato" include both their acid form and their salt form. Accordingly, sulfo groups are groups corresponding to the general formula -SO3M, carboxy groups groups corresponding to the general formula -COOM, thiosulfato groups corresponding to the general formula -S-SO3M, phosphato groups corresponding to the general formula -OPθ M ₂ and sulfato groups corresponding to groups of the general formula -OSO3M , each with M of the meaning given above.

The present invention further relates to a process for the preparation of the azo compounds of the general formula (1) according to the invention, which is characterized in that in the case where K ° is a radical of the general formula (2A), the diazonium compound of an amine of the general formula ( 5)

in which M, E and v have the meanings given above, with a compound of the general formula HK with K the couples the meaning given above, and that in the case of K ° is a radical of the general formula (2B), a compound of the general formula (6)

in which M has the meaning given above, with the diazonium compound of an amine of the general formula (7)

R ¹ IH ₂ N— D t ⁽ CR ₂ ⁾ a— ^S0 2 - ^Y - k ^(?)

R ²

in which D, R ¹ , R ² , Y, a and k have the meanings given above, couples.

The diazotization and coupling reactions of the process according to the invention take place in a customary and well-known manner, so the diazotization is generally preferred at a temperature between -5 ^β C and +15 ^β C and a pH below 2 by means of a strong acid and alkali nitrite aqueous medium and the coupling reaction usually at a temperature between 0 and 30 ^β C and at a pH between 1 and 4.5 in the case of an amino group-containing coupling component and at a pH between 3 and 7.5 in the case of a hydroxy group Coupling component, preferably in an aqueous medium.

The starting compounds of the general formula (5) with v equal to 1 are prepared in a known manner for the diazotization and coupling reactions of l-sulfo-6-carboxy-2-aminonaphthalene as the diazo component and the compound of the general formula HE-NH ₂ as the coupling component. The azo compounds are synthesized in the same way general formula (6) by coupling the diazonium salt of 1-sulfo-6-carboxy-2-aminonaphthalene with 1-amino-8-naphthol-3,6- or -4,6-disulfonic acid analogously to known procedures in a strongly acidic medium.

The starting compounds corresponding to the general formula HE-NH ₂ and the general formula (7) are known and are widely described in the literature.

Starting compounds of the general formula HE-NH are, for example, aniline, 3-methyl-aniline, 3-chloro-aniline, 2,5-dimethyl-aniline, 2,5-di-ethoxy-aniline, 3-methoxy-aniline, 3-methyl 6-methoxy-aniline, 3-ureido-aniline, 3-acetylamino-6-methyl-aniline, 2-amino-4-acetylamino-benzene-1-sulfonic acid, 1-aminonaphthalene, 1-aminonaphthalene-6- or -7- or -8-sulfonic acid, 3-acetylamino-niline, 2-methyl-aniline, 2-methoxy-aniline, 3-benzoylamino-aniline, 2,3-dimethyl-aniline, 3,5-D ^' imethyl-aniline, 2- Methoxy-5-acetylamino niline, 2-chloro-6-methylaniline, 5-chloro-2-methylaniline, 2,6-dichloro-3-methylaniline, 2-methoxy-5-methylaniline, 6- (ß-Sulfatoethylsulfonyl) -! - amino-naphthalene and 7- (ß-Sulfatoethylsulfonyl) -la ino-naphthalene.

Starting compounds of the general formula HK have been extensively described in the literature. Of particular interest are, for example, 1- (4'-β-sulfatoethylsulfonylphenyl) -3-methyl-5-pyrazolone, 1- (4'-ß-sulfatoethylsulfonylphenyl) -3-carboxy-5-pyrazolone, 1- ( 2'-chloro-5'-ß-sulfato-ethylsulfonyl-phenyl) -3-methyl-5-pyrazolone, 1- (2'-chloro-5'-ß-sulfatoethylsulfonyl-phenyl) -3-carboxy-5-pyrazolone , 2- (2'-Methoxy- '-ß-sulfatoethylsulfonylphenyl) -3-carboxy-5-pyrazolone, 2- (2'-methoxy-4 ¹ -ß-sulfatoethylsulfonylphenyl) -3-methyl-5- pyrazolone, 2- (2'-methyl-4'-ß-sulfatoethylsulfonylphenyl) -3-methyl-5-pyrazolone, 2- (2'-methyl-4 ¹ -ß-sulf to¬ ethylsulfonylphenyl) -3 -carboxy-5-pyrazolone, 1- (4 ^! -Ss-Sulfatoethylsulfonyl-phenyl) -3-carbethoxy-5-pyrazolone, 1- (4'-ß-Sulfatoethylsulfonyl-phenylethyl) -4-methyl-6-hydroxy-2-pyridone, 1- (4th '-ß-sulfatoethylsulfonyl-phenylethyl) -3-cyano-4-methyl-6-hydroxy-2-pyridone, 1- (4'-ß-sulfatoethylsulfonyl-phenylethyl) -3-carbamoyl-4-ethyl-6- hydroxy-2-pyridone, 1- (4'-β-sulfatoethylsulfonylphenylethyl) -3-sulfo-4-methyl-6-hydroxy-2-pyridone, 1- (4 ^! -ß-sulfatoethylsulfonylphenylethyl) -3- sulfomethy1-4-methyl-6-hydroxy-2-pyridone, 1- (3'-ß-sulfatoethylsulfonylphenylethyl) -4-methyl-6-hydroxy-2-pyridone, N-acetoacetyl-2-methoxy-5-methyl -4- (ß-sulfatoethylsulfonyl) aniline, N-acetoacetyl-2,5-dimethoxy-4- (ß-sulfatoethylsulfonyl) aniline, N-acetoacetyl-2-methoxy-5- (ß-sulfatoethylsulfonyl) aniline , N-acetoacetyl-4- (ß-sulfatoethylsulfonyl) aniline, N-acetoacetyl-3- (ß-sulfatoethylsulfonyl) aniline, 3- (ß-sulfatoethylsulfonyl) -1-naphthol, 5- or 6- or 7- or 8- (ß-sulfatoethylsulfonyl) -1- naphthol, 4- (ß-sulfatoethylsulfo nyl) -1-naphthol, 6- (ß-sulfatoethylsulfonyl) -2-naphthol, 8- (ß-sulfatoethyl¬ sulfonyl) -2-naphthol, 3,6-di- (ß-sulfatoethylsulfonyl) - 2-naphthol, 2 - [N-Methyl-N- (ß-sulfatoethylsulfony1)] - amino-

6-sulfo-8-naphthol, 3- [N-methyl-N- (ß-sulfatoethylsulfonyl)] - amino-6-sulfo-8-naphthol, 1- (4 * -ß-sulfatoethylsulfonyl-benzoylamino) -3.6 -disulfo-8-naphthol, 1- (4'-ß-sulfatoethyl-sulfonyl-benzoylamino) -4,6-disulfo-8-naphthol, 1- [Y- (ß-chloroethylsulfonyl) propionyl] amino- 3,6-disulfo-8-naphthol,

1- [Y- (β-chloroethylsulfonyl) propionyl] araino-4,6-disulfo-8-naphthol, 1- [N'- (4'-β-chloroethylsulfonylphenyl) -ureido] - 3,6- disulfo-8-naphthol, 1- [N'- (4'-ß-chloroethylsulfonylphenyl) -ureido] -, 6-disulfo-8-naphthol, 2- (4'-ß-sulfato-ethylsulfonyl-benzoylamino) - 6-sulfo-8-naphthol,

3- (4'-ß-Sulfatoethylsulfonyl-benzoylamino) -6-sulfo-8-naphthol, 1- [N'- (4 * -ß-chloroethylsulfonyl-2'-methylphenyl)] - ureido-3,6- disulfo-8-naphthol and 1- [N'- (4'-ß-chloroethylsulfonyl-2'-methoxy-phenyl)] - ureido-3,6-disulfo-8-naphthoil, furthermore azo compounds in which the remainder K is one The rest of the general formula (4h) corresponds. Starting compounds of the general formula (7) are, for example, 2- (β-sulfatoethylsulfonyl) aniline, 3- (β-sulfatoethylsulfonyl) aniline, 4- (β-sulfatoethyl sulfonyl) aniline, 2-carboxy-5- (β- sulfatoethylsulfonyl) aniline, 2-chloro-3- (ß-sulfatoethylsulfonyl) aniline,

2-chloro-4- (ß-sulfatoethylsulfonyl) aniline, 2-ethoxy-4- or -5- (ß-sulfatoethylsulfonyl) aniline, 2-ethyl-4- (ß-sulfatoethylsulfonyl) aniline, 2-methoxy- 5- (ß-sulfatoethylsulfonyl) aniline, 2,4-diethoxy-5- (ß-sulfatoethylsulfonyl) aniline, 2, -dimethoxy-5- (ß-sulfatoethylsulfonyl) aniline, 2,5-dimethoxy -4- (ß-sulfatoethylsulfonyl) aniline, 2-methoxy-5-methyl-4- (ß-sulfatoethylsulfonyl) aniline, 2- or 3- or 4- (ß-thiosulfatoethylsulfonyl) aniline, 2-methoxy-5 - (ß-thiosulfatoethylsulfonyl) aniline, 2-sulfo-4- (ß-phosphatoethylsulfonyl) aniline, 2-sulfo-4-vinylsulfonyl-aniline, 2-hydroxy-4- or -5- (ß-sulfatoethylsulfonyl) aniline , 2-chloro-4- or -5- (ß-chloroethylsulfonyl) aniline, 2-hydroxy-3-sulfo-5- (ß-sulfatoethylsulfonyl) aniline, 3- or 4- (ß-acetoxyethylsulfonyl) aniline, 2-methoxy- 4- [ß- (N-methyl-tauryl) ethylsulfonyl] aniline, 6- or

5- (ß-sulfatoethylsulfonyl) -2-amino-naphthalene, 6- or 7- or 8- (ß-sulfatoethylsulfonyl) -2- mino-naphthalene, 6- (ß-sulfatoethylsulfonyl) -l-sulfo-2-amino- naphthalene, 5- (ß-sulfatoethylsulfonyl) -1-sulfo-2-amino-naphthalene, 8- (ß-sulfatoethylsulfonyl) -6-sulfo-2-amino-naphthalene,

3,4-di- (ß-sulfatoethylsulfonyl) aniline, 2,5-di- (ß-sulfatoethylsulfonyl) aniline and 2,5-bis- ((ß-sulfatoethylsulfonyl) methyl) aniline.

The 1-sulfo-6-carboxy-2- a ino-naphthalene compound used according to the invention for the synthesis of the azo compounds of the general formula (1) is not yet known. The invention thus also relates to this compound, processes for its preparation and its use for the synthesis of dyes, in particular for the synthesis of azo compounds, such as those of the general formula (1). The 1-sulfo-6-carboxy-2-amino-naphthalene according to the invention can be prepared according to the invention by adding 2-naphthol-6-carboxylic acid in a sulfuric acid / sulfur trioxide mixture (oleum) with a sulfur trioxide content of 0 to 35% by weight. -%, preferably in 100% sulfuric acid, at a temperature between -5 ° C and + 40 ° C, preferably at 0 to 10 ° C, first sulfated to 1-sulfo-6-carboxy-2-naphthol, this compound isolated and then reacted at a temperature between 50 and 190 ° C, preferably between 130 and 170 ° C, in an aqueous, alkaline ammonium bisulfite solution in an autoclave.

The intermediate 1-sulfo-6-carboxy-2-naphthol is isolated from the reaction mixture in a conventional manner by carefully stirring the reaction mixture on ice. The precipitated product is suctioned off, suspended in ice water and any sulfuric acid still present is neutralized by means of sodium carbonate by adjusting the suspension to a pH between 4 and 4.5. The connection can then be isolated by suction and drying.

Exchange of the hydroxy group. by the amino group takes place in analogy to the Bucherer reaction.

To do this, the procedure is generally such that the 1-sulfo-6-carboxy-2-naphthol in a 20 to 30 wt .-% aqueous

Ammonium bisulfite solution dissolves and the reaction mixture is reacted in an autoclave under the conditions specified above. After this reaction has ended, the mixture is adjusted to a pH of 1 with hydrochloric acid at room temperature. The mixture is stirred for about 1 hour, during which the sulfo-carboxy-aminonaphthalene compound according to the invention precipitates out as an inner salt and can be isolated. The compounds of the general formula (1) according to the invention - hereinafter referred to as compounds (1) - have fiber-reactive properties and have very valuable dye properties. They “can therefore be used for dyeing (including printing) materials containing hydroxy groups and / or carbonamide groups. For this purpose, the solutions obtained in the synthesis of the compounds (1), optionally after the addition of a buffer substance and optionally also after concentration, can be used directly as a liquid preparation for dyeing.

The separation and isolation of the compounds (1) from the aqueous synthesis solutions can be carried out according to generally known methods for water-soluble compounds, for example by precipitation from the reaction medium using an electrolyte, such as sodium chloride or potassium chloride, or by evaporation of the reaction solution itself, for example by Spray drying. If the latter type of insulation is chosen, it is often advisable to remove any sulfate amounts present in the solutions by precipitation as calcium sulfate and separation by filtration before evaporation.

The present invention therefore also relates to the use of the compounds (1) for dyeing (including printing) hydroxyl- and / or carbonamide-containing materials and processes for their use on these substrates. The materials are preferably used in the form of fiber materials, in particular in the form of

Textile fibers such as yarns, packages and fabrics. This can be done analogously to known procedures. Materials containing hydroxyl groups are of natural or synthetic origin, such as cellulose fiber materials ^' or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton, but also other vegetable fibers, such as linen, hemp, jute and ramie fibers; Regenerated cellulose fibers are, for example, cellulose and viscose rayon.

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

According to the application according to the invention, the compounds (1) can be applied and fixed on the substrates mentioned, in particular on the fiber materials mentioned, by the application techniques known for water-soluble, fiber-reactive dyes, for example by dissolving the compound (1) in solution applies to or brings them into the substrate and fixes them on or in this by the action of heat or by the action of an alkaline agent or by both measures. Such staining and fixing methods have been described in numerous publications (for example in European Patent Application Publication No. 0 181 585-A2). The compounds (1) are distinguished by high degrees of extraction and fixation. In the exhaust process in particular, they deliver dyeings with a high depth of color and a high degree of fixation, even in wide temperature ranges (40 to 80 ° C).

The dyeings according to the invention, particularly on cellulose fiber materials, have good lightfastness both in the dry state of the dyeing and in the wet state, for example moistened with a sweat solution as well as good wet fastness properties, such as good wash fastness properties at 60 to 95 ° C, even in the presence of perborates, acidic and alkaline whale, over-dyeing and perspiration fastness properties, good acid and alkaline perspiration fastness properties, high steam resistance, good acid, water and seawater fastness properties , furthermore good pleating fastness, ironing fastness and rubbing fastness. They also have good acid fading resistance when storing moist, colored material which still contains acetic acid.

The following examples serve to illustrate the invention. The parts are parts by weight, the percentages represent percentages by weight, unless stated otherwise. Parts by weight relate to parts by volume such as kilograms to liters.

The compounds described by formula in these examples are given in the form of the free acids; in general, they are prepared and isolated in the form of their alkali metal salts, such as lithium, sodium or potassium salts, and used in the form of their salts for dyeing. Likewise, the starting compounds and components mentioned in the following examples, in particular table examples, in the form of the free acid can be used as such or in the form of their salts, preferably alkali metal salts, in the synthesis.

The absorption maxima (λ _max ) in the visible range specified for the compounds according to the invention were ^• determined using the alkali metal salts in aqueous solution. Example A

a) 283.6 parts of 2-naphthol-6-carboxylic acid are introduced into 1200 parts of 100% sulfuric acid with stirring and cooling at 5 to 7 ° C. The mixture is then stirred for a further 2 hours at 10 ° C. and then for a further 2 hours at 20 ° C. until no further starting compound is present (can be checked by HPLC analysis). The reaction mixture is then poured onto 2700 parts of ice. A precipitate forms, which is suctioned off and then suspended in ice water. The suspension is adjusted to a pH between 4 and 4.5 with sodium carbonate, the product is filtered off with suction, washed with 10% aqueous sodium chloride solution and dried at 40 ° C. under reduced pressure.

b) 269.2 parts of 1-sulfo-6-carboxy-2-naphthol are in

720 parts of an aqueous, 25% ammonium bisulfite solution in an autoclave at 150 ° C and a pressure of 12 bar stirred for about 8 hours. Then you leave that

Cool the reaction mixture and adjust the pH to 1 with hydrochloric acid at room temperature. The mixture is stirred for a further hour and the compound according to the invention which has precipitated as the inner salt is then isolated in a yield of about 70% of theory

The constitution of the 1-suifo-6-carboxy-2-amino-naphthalene according to the invention is confirmed by the following analyzes:

- ^* Η NMR spectroscopy (d ₆ -DMS0; tetramethylsilane): δ = 7.21 ppm (d, lH), 7.87 ppm (dd, lH), 7.89 ppm (d, lH), 8, 42 ppm (d, 1H), 8.85 ppm (d, 1H);

¹³ C-NMR (d ₆ -DMS0): δ = 167.7 ppm (COOH), δ = 137.1 ppm (C in 6-position), δ = 133.6 ppm (C in 1-position), δ = 122.0-132.1 ppm (remaining aromatic C);

IR spectroscopy (in KBr): v = 1687 cm ^"1 (C = 0);

Elemental analysis: 46.35% C, 3.3% H, 5.1% N

(corresponding to the C: H: N ratio of 11: 9: 1 according to the empirical formula C ^ HgNO ^ S).

Example B

27.0 parts of 1-sulfo-6-carboxy-2-aminonaphthalene are dissolved in a mixture of 30 parts of a 31% aqueous hydrochloric acid and 300 parts of water and with 6.9 parts

Sodium nitrite (in the form of a 40% solution) diazotized.

example 1

The diazonium salt solution from Example B is used, 36.3 parts of 1- (4'-β-sulfatoethylsulfonyl) phenyl-3-methyl-5-pyrazolone are added and the coupling reaction is carried out at 10 ° C. and a pH of 4 through. The azo compound according to the invention is salted out and isolated using sodium chloride. A yellow, electrolyte-containing powder of the alkali metal salt (sodium salt) of the compound of the formula is obtained

⁽ Kmax = 401 nm)

The azo compound according to the invention shows very good fiber-reactive dye properties and, on the fiber materials mentioned in the description, such as in particular cotton, provides brilliant, brilliant yellow dyeings and prints with good fastness properties, of which in particular those, according to the application and fixing methods customary in the art for fiber-reactive dyes Lightfastness can be highlighted.

Example 2

The known coupling component 2- (4 * -ß-sulfatoethylsulfonylphenyl) -azo-3,6-disulfo-l-amino-8-naphthol is obtained in a conventional manner by coupling the diazonium salt from 26 parts of 4- (β-sulfatoethylsulfonyl) - aniline with 33.2 parts of 1-amino-8-naphthol-3,6-disulfonic acid. The solution obtained is then mixed with the diazonium salt solution of 27 parts of 1-sulfo-6-carboxy-2-amino-naphthalene according to Example B and at a pH of 4 to 5 and a temperature of 15 to 20 ° C. Azo connection coupled. The disazo compound according to the invention obtained is salted out with sodium chloride and isolated. A deep blue electrolyte-containing powder of the alkali metal salt (sodium salt) of the compound of the formula is obtained

( ^λ max = ^{612 nm} >

The azo compound according to the invention shows very good fiber-reactive dye properties and, on the fiber materials mentioned in the description, such as in particular cotton, provides vivid, lively navy-blue dyeings and prints with good fastness properties in the application and fixing methods customary in the art for fiber-reactive dyes.

Examples 3 to 32

The following table examples show further azo compounds according to the invention corresponding to the general formula (A) written in the form of the free acid

described with the help of their coupling component HK. They can be prepared in the manner according to the invention, for example according to Examples 1 and 2, by coupling the specified coupling component of the formula HK with the diazonium salt of 1-sulfo-6-carboxy-2-amino-naphthalene and also have very good fiber-reactive properties

Dye properties. They provide strong dyeings and prints on the materials mentioned in the description, such as in particular cellulose fiber materials, using the application and fixing methods customary for fiber-reactive dyes, with the hue specified in the respective table example (here on cotton) with good fastness properties; the values given in brackets are the absorption maxima (λ _max ) in nm.

Example component H-K color

3 1- (4'-ß-sulfatoethylsulfonylphenyl) - yellow 3-carboxy-5-pyrazolone (393)

4 1- (4 * -ß-sulfatoethylsulfonylphenyl) - yellow 3-carbethoxy-5-pyrazolone (395)

5 1- (2'-methoxy-4 ¹ -ß-sulfatoethylsulfonyl-yellow phenyl) -3-methyl-5-pyrazolone

6 1- (2'-methoxy-4'-ß-sulfatoethylsulfonyl-yellow phenyl) -3-carboxy-5-pyrazolone

7 1- (4'-β-sulfatoethylsulfonylphenethyl) - yellow 4-methyl-6-hydroxy-2-pyridone

8 1- (4'-ß-sulfatoethylsulfonylphenethyl) - yellow 3-cyano- -methyl-6-hydroxy-2-pyridone

9 1- (4'-β-sulfatoethylsulfonylphenethyl) yellow 3-carbamoyl-4-methyl-6-hydroxy-2-pyridone

10 1- (4'-β-sulfatoethylsulfonylphenethyl) yellow 3-sulfo-4-methyl-6-hydroxy-2-pyridone

11 N-acetoacetyl-2-methoxy-5-methyl-4- (ß-yellow sulfatoethylsulfonyl) aniline

12 N-acetoacetyl-2,5-dimethoxy-5-methyl-4-yellow (β-sulfatoethylsulfonyl) aniline

13 N-acetoacetyl-2-methoxy-5- (ß-sulfato-yellow ethylsulfonyl) aniline

14 N-acetoacetyl-4- (ß-sulfatoethylsulfonyl) - yellow aniline

15 N-acetoacetyl-3- (ß-sulfatoethylsulfonyl) - yellow aniline HK color component

4- (ß-sulfatoethylsulfonyl) -l-naphthol orange 6- (ß-sulfatoethylsulfonyl) -2-naphthol orange 8- (ß-sulfatoethylsulfonyl) -2- aphthol orange 2- [N-methyl, N- (ß-sulfatoethylsulfonyl) ] - orange amino-6-sulfo-8-aphthol 3- [N-methyl, N- (ß-sulfatoethylsulfonyl)] - red-orange amino-6-sulfo-8-naphthol 1- (4'-ß-sulfatoethylsulfonyl-benzoylamino) - red 3,6-disulfo-8-naphthol 1- (4'-ß-sulfatoethylsulfonyl-benzoylamino) - red 4,6-disulfo-8-naphthol 1- [r- (ß-chloroethylsulfonyl) propionyl] - red amino -3,6-disulfo-8-naphthol 1- [T- (β-chloroethylsulfonyl) propionyl] - red amino-4,6-disulfo-8-naphthol 1-N'- [(4'-β-chloroethylsulfonyl) -phenyl] - bluish ureido-3,6-disulfo-8-naphthol red 1-N ¹ - [('-ß-chloroethylsulfonyl) -phenyl] - red ureido-4,6-disulfo-8-naphthol 2- (' -ß-sulfatoethylsulfonyl-benzoyl-orange amino) -6-sulfo-8-naphthol 3- (4'-ß-sulfatoethylsulfonyl-benzoyl-red-orange amino) -6-sulfo-8-naphthol 1-N "- [(4 ' -ß-chloroethylsulfonyl) -2'-methyl-red phenyl] -ureido-3,6-disulfo-8-naphthol ι _N '- [(4'-ß-chloroethylsulfonyl) -2'-methoxy-red phenyl] -ureido-3,6-disulfo-8-naphthol 2- (3'-ß-sulfatoethylsulfonyl) phenyl azine navy blue 3.6 -disulfo-l-amino-8-naphthol 2- (2'-sulfo-5'-ß-sulfatoethylsulfonyl) - ditto phenylazo-3,6-disulfo-1-amino-8-naphthol Example 33

27 parts of 1-sulfo-6-carboxy-2-amino-naphthalene are diazotized as described in Example B. The acidic diazonium salt solution is mixed with 33.2 parts of 3,6-disulfo-l-amino-8-naphthol, and the coupling reaction is carried out at a temperature between 0 and 5 ° C. and a pH between 1 and 2. Then the hydrochloric acid solution of the diazonium salt prepared in the customary manner from 34.7 parts of 2-sulfo - (β-sulfatoethyl-sulfonyl) aniline is added and the second coupling reaction is carried out at a pH between 4 and 5 and a temperature of about 10 ° C. The synthesized disazo compound according to the invention is salted out of the synthesis solution with sodium chloride, suction filtered and dried. A deep blue electrolyte-containing powder of the alkali metal salt (sodium salt) of the compound of the formula is obtained

CH i ^Δ 0S0 ₃ H (λ _m ma _αv x = 610 nm) '

The azo compound according to the invention shows very good fiber-reactive dye properties and, on the fiber materials mentioned in the description, such as, in particular, cotton, gives bright, brilliant navy-blue dyeings and prints in accordance with the application and fixing methods customary in the art for fiber-reactive dyes.

Claims

Claims:

1. An azo compound according to the general formula (1)

in which mean:

M is a hydrogen atom or a salt-forming one

Metal atom, preferably sodium, potassium or lithium; K ° is a radical of the general formula (2A) or (2B)

- E - N = N - ₇ -. K (2A)

in which M has the abovementioned meaning, D is a benzene or naphthalene radical, R ^{1 is} hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, fluorine, bromine, chlorine, sulfo, carboxy, carbalkoxy of 2 to 5 carbon atoms, trifluoromethyl, carbamoyl or N- (C - ^ - C ^ .- alkyl) carbamoyl if D is a benzene ring, or R is hydrogen or sulfo if D is one

Naphthalene ring means R * ^{* is} hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, nitro or sulfo if D is a benzene ring, or ~ 'r is hydrogen or sulfo if D is one

Naphthalene radical means, Y is the vinyl group or an ethyl group which contains a substituent which can be eliminated by alkaline means to form the vinyl group, a is the number zero, 1 or 2, k is the number 1 or 2, E is a radical of the general formula (3a), (3b), (3c) or (3d)

means in which

R is hydrogen, alkyl of 1 to 4 carbon atoms, cyano, carboxy, carbalkoxy of 2 to 5 carbon atoms, carb ^' amoyl or phenyl, is a benzene or naphthalene radical,

R ^{1 has} one of the abovementioned meanings as a substituent on a benzene radical or is hydrogen or sulfo if it denotes a naphthalene radical,

R ^{3 is} hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine or sulfo if it is a benzene radical, or hydrogen or sulfo if Q is a naphthalene radical,

R ^{4 is} hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, bromine, chlorine, trifluoromethyl, sulfo, carboxy or cyano, c

R is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, amino, alkylamino of 1 to 4 carbon atoms, alkanoylamino of 2 to 5 carbon atoms, benzoylamino, ureido, N'- Phenyl-ureido, N'- (C ^ -C ^ alkyl) -ureido, phenylsulfonyl or

Is alkylsulfonyl of 1 to 4 carbon atoms,

R ^{6 is} hydrogen or β-sulfatoethylsulfonyl,

M has one of the meanings given above, m denotes the number 1 or 2, n denotes the number zero, 1 or 2 (where n is zero this group represents a hydrogen atom), v is the number zero or 1 and

K is the rest of a water-soluble coupling component, the 1 or 2 groups of the general formula

-S0 ₂ -Y with Y contains the meaning given above.

2. A compound according to claim 1, characterized in that K is a radical of the general formula (4a), (4b), (4c), (4d), (4e), (4f), (4g) or (4h)

d)

HO - C CH,

* C R--

I I

CO - NH - D - (S0 ₂ -Y) _k (4g)

is in which

M, m, n, Y, k, R ¹ , R ² , D, R ⁴ , R ⁵ , R and a have one of the meanings mentioned in claim 1,

V is a direct, covalent bond or a radical of the formula -NH-CO-phenylene-, -NH-CO-NH-phenylene-, -N (CH ₃ ) -CO-phenylene-, -N (CH ₃ ) -CO- NH-phenylene-, -NH-CO-alkylene-, -NH-CO-NH-alkylene-, -N (CH ₃ ) -CO-alkylene- or -N (CH3) -CO-NH-alkylene-, wherein "alkylene" means a straight-chain or branched alkylene radical of 2 to 6 carbon atoms,

R ^{7 is} hydrogen or alkyl of 1 to 4 carbon atoms or is alkyl of 1 to 4 carbon atoms which is substituted by sulfo, carboxy, sulfato, phosphato, hydroxy, methoxy or ethoxy, W is a phenylene radical which is represented by 1 or 2

Substituents from the group of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, carboxy and sulfo, or an alkylene of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms, can be substituted , or is an alkylene-phenylene with an alkylene of 2 to 4 carbon atoms,

R ^{8 is} hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, phenyl or alkyl of 1 to 4 carbon atoms substituted by cyano and

R ^{9 is} hydrogen, sulfo, sulfoalkyl of 1 to 4 carbon atoms, carboxy, cyano or carbamoyl.

3. A compound according to claim 1 of the general formula

with M and Y of the meaning given in claim 1.

4. A compound according to claim 1 of the general formula

with M and Y of the meaning given in claim 1.

5. A compound according to claim 1 of the general formula

with M and Y of the meaning given in claim 1.

6. A compound according to at least one of claims 1 to 5, characterized in that Y is the vinyl group or the β-sulfatoethylsulfonyl group.

7. A process for the preparation of an azo compound according to the general formula (1) of claim 1, characterized in that in the case where K ° is a radical of the general formula (2A), the diazonium compound of an amine of the general formula (5)

in which M, E and v have the meanings given in Claim 1, couples with a compound of the general formula HK with K the meaning given in Claim 1, and that in the case of K °, one is a radical of the general formula (2B) Compound of the general formula (6)

in which M has the meaning given in claim 1, with the diazonium compound of an amine of the general formula (7)

R ¹ H ₂ ND [(CR ₂ ) _a -S0 ₂ -Y] _k (7)

R ²

in which D, R, R, Y, a and k have the meanings given in Claim 1, couples.

8. Use of a compound according to the general formula (1) of claim 1 for dyeing (including printing) material containing hydroxyl and / or carbonamide groups, in particular fiber material.

9. A method for dyeing (including printing) material containing hydroxyl and / or carbonamide groups, in particular fiber material, in which a dye is applied to or introduced into the material and fixed by means of heat and / or with the aid of an alkaline agent, characterized that a compound corresponding to the general formula (1) of claim 1 is used as the dye.

10. l-sulfo-6-carboxy-2-amino-naphthalene of the general

formula

in which M is a hydrogen atom or a salt-forming metal atom, preferably an alkali metal atom, and its diazonium salt.

11. A process for the preparation of the aminonaphthalene compound of claim 10, characterized in that 2-naphthol-6-carboxylic acid in a sulfuric acid / sulfur trioxide mixture with a sulfur trioxide content of 0 to 35 wt .-% at a temperature between -5 ° C and + 40 ° C first sulfated to 1-sulf0-6-carboxy-2-naphthol, this compound isolated and then reacted at a temperature between 50 and 190 ° C in an aqueous alkaline ammonium bisulfite solution.

12. Use of a compound of claim 10 for the synthesis of dyes, in particular azo dyes.