CH578031A5 - Yellow-orange-red basic azo dyes - free from water-solubilising gps - Google Patents

Abstract

Title cpds. of formula (I):- (where two of the Z gps. are -NR'R" and one Z gp. is -NR'R", -OR'", or -S-R", R', R" and R'" each being H, aryl, alkyl, cycloalkyl or aliphatic gp.., R' and R" being able to form a ring contng. the N atom of the amino gp. and the gps. -NR'R" being the same or different; Y is -CN or -CONH2; D is the residue of an aromatic or heterocyclic diazo cpd.; >=1 Z gp. and/or D contains an opt. cationic basic gp.), are prepd. by coupling, quaternisation or condensation and when Y is -CN, opt. converting the -CN gp. to the -CONH2 gp. Cpds. are used for colouring PVC cyanide, polyamides, polyesters etc., paints, pigments, etc.

Description

  

  
 



   The present invention relates to a process for the preparation of new, free of acidic, water-solubilizing groups of basic azo dyes of the formula DN - NA wherein D is the residue of an aromatic or heterocyclic diazo component and A is the residue of a 2, e-diamino-pyridine bonded in the 3-position, which carries an organic radical bonded via a nitrogen, oxygen or sulfur atom in the 6-position, and in which this radical and / or D contains basic, optionally cationic groups.



   In particular, it relates to the manufacture of dyes of the formula
EMI1.1
 where D 'is the radical of an aromatic or heterocyclic diazo component and R ,, R2, R3, R4 and R5 each represent hydrogen or an aryl, aralkyl, cycloalkyl radical or an aliphatic radical, where R, with R2 and R3 with R4 denote Can form amine nitrogen-containing ring and Q each is an optionally quaternized amino, hydrazino, etherified hydroxylamino or pyridine group, bonded directly or via a bridge, and p and q each denote 1 or 2, where, when p and q are both 1, D 'is a heterocycle with a quaternized ring nitrogen atom, and wherein Z is an oxygen or sulfur atom or an imino group of the formula
EMI1.2
 is where R6 is hydrogen, aryl, aralkyl, cycloalkyl or an aliphatic radical,

   which can be linked with R5 or with Q The basic radical Q can be bonded directly to the aromatic or heterocyclic nucleus of the diazo component. But it can also be attached to a substituent, e.g. B. sit an alkyl or alkoxy group of the diazo component or be linked to the dye molecule via an alkylenecarbonyl, carbonyloxy, carbonylamino, alkylenecarbonyloxy or alkylenecarbonylamino bridge.



  The basic group Q can also form a ring together with R5 and Z, for example a piperazine residue.



   Aryl, aralkyl and cycloalkyl radicals are preferably understood to mean radicals of the benzene series, benzyl and cyclohexyl radicals. With aliphatic radicals are meant primarily alkyl radicals with up to 8 carbon atoms, which can be interrupted by oxygen, sulfur atoms or nitrogen groups.



   Preferred dyes of the formula given are those in which D 'is a radical of the benzene series or a nitrogen-containing heterocyclic radical and dyes in which Rt, R2, R3 and R4 are hydrogen atoms.



   According to the invention, the new dyes are prepared by coupling.



   This is based on diazo and coupling components, of which at least one component already contains a basic group. These basic groups are generally introduced before the coupling by reacting a corresponding coupling or diazo component, which has a reactive atom or group instead of the basic group, with amines, etherified hydroxylamines, hydrazines, pyridinecarboxylic acid chlorides or aminocarboxylic acid chlorides.



  Possible reactive groups are: halogen atoms, in particular chlorine or bromine, benzenesulfonic acid ester groups, such as p-toluenesulfonates and benzenesulfonates, low molecular weight, d. H. Alkylsulfonic acid ester and alkylsulfuric acid half-ester groups containing 1 to 4 carbon atoms, such as methyl sulfate and methanesulfonate, hydroxyl and amino groups. Diazotized amines of the formula are thus coupled
EMI1.3
 with coupling components of the formula
EMI1.4
 where D ', R1, R2, R3, R4, R5, Z, q, p and Q have the meanings mentioned above.



   The basic groups Q are e.g. B. those of the formula
EMI1.5
 in question, in which R 1 and R 2 are hydrogen or an alkyl, in particular with 1-4 C atoms, aralkyl; in particular benzyl or cycloalkyl, in particular cyclohexyl radical, R'3 is hydrogen or an alkyl, aralkyl, cycloalkyl or alkoxy radical or an amino group and in which the nitrogen atom with R'1 and or R'2 and or R'3 is part of a heterocyclic ring can form. X is an anion and n is 1 or 2.



  These radicals can be derived, for example, from the amines, hydroxylamines and hydrazines mentioned below. The anions can be such strong inorganic acids, e.g. B. chloride, bromide, iodide, nitrate, sulfate, especially hydrogen sulfate and phosphate, especially dihydrogen phosphate. But there are also anions of organic acids, which are understood to mean aryl and alkyl sulfonates and carbonates, in particular benzenesulfonate and its derivatives substituted with nitro, chlorine, bromine, C1 to C4 alkyl and C4 to C4 alkoxy groups, C , -C4-alkylsulfonates, anions of aliphatic carboxylic acids with 1 to 4 carbon atoms and benzoates, where the benzene ring can carry the same substituents as in the case of the benzenesulfonates.

  Of particular importance are the anions of the low molecular weight, i.e. H. Alkylsulfuric acid half-esters containing 1 to 4 carbon atoms. The dyes can also be present as double salts with heavy metal halides, in particular with zinc and cadmium halides.



   Examples of such anions are: benzenesulfonate, p-toluenesulfonate, p-methoxybenzenesulfonate, methanesulfonate, ethanesulfonate, formate, acetate, chloroacetate, propionate, lactate, tartrate, benzoate, methyl benzoate, methyl sulfate, ethyl sulfate, ZnC13- and CdCl-sulfate.



   Preferred basic radicals of the formula given are those in which R '", R'2 and R'3 are low molecular weight alkyl radicals, in particular methyl radicals.



   The basic groups can also contain pyridine residues
EMI2.1
 where R'4 is an alkyl radical, in particular having 1 to 4 carbon atoms, cycloalkyl, in particular cyclohexyl, or aralkyl, in particular benzyl, and X and n are the same as above. The diazotized amines are derived, for example, from amines of the naphthol series and, in particular, from amines of the benzene series. The benzene nucleus can here except with the basic groups mentioned, for.

  B. carry the following substituents: halogen atoms, in particular chlorine or bromine, nitro; Cyano, thiocyano, trifluoromethyl, alkyl, alkoxy, aryloxy, alkyl mercapto, aryl mercapto, alkoxycarbonyl, aryloxycarbonyl, alkoxycarbonyloxy, aryloxycarbonyloxy, alkoxysulfonyl, aminosulfonyloxy, carboxylic acid amide, sulfonamide and acylamino radicals and phenylazo groups, it being possible for the phenyl nucleus to be substituted by chlorine, nitro, alkyl and alkoxy groups.



   By alkyl and alkoxy are meant low molecular weight radicals with 1 to 4 carbon atoms, preferably methyl and methoxy. Acyl is understood to mean residues of aliphatic and aromatic carboxylic, sulfinic and sulfonic acids, in particular benzoyl (optionally substituted on the benzene nucleus), benzenesulfonyl, benzylsulfonyl and residues of alkylsulfonic acids containing at most 4 carbon atoms and aliphatic carboxylic acids. The sulfonic and carboxamide groups and the aminosulfonyloxy radicals can carry one or two alkyl groups on the nitrogen, which alkyl groups can also be linked to form a ring.



   Aminobenzenes suitable as aromatic diazo components can be substituted, for example, according to the following equation:
EMI2.2
   Rt is hydrogen, bromine, a thiocyano, alkoxysulfonyl, alkoxycarbonyl, hydroxy, alkyl mercapto, aryl mercapto, alkoxycarbonyloxy, aminosulfonyloxy, acylamino group or, preferably, chlorine, a nitro, cyano, acyl, sulfon amide -, carboxamide, alkoxy or aryloxy group. R2 is hydrogen, a carboxamide or preferably an alkoxycarbonyl or aminosulfonyloxy group.

  R3 is hydrogen, bromine, a thiocyano, alkoxycarbonyl, alkoxy, aryloxy or acylamino group or preferably chlorine or a nitro, cyano, acyl, sulfonamide, carboxamide, trifluoromethyl or phenylazo group, the phenyl nucleus of which is in turn alkyl -, alkoxy, nitro groups and chlorine can be substituted. R4 is hydrogen, bromine, a nitro, cyano, thiocyano, acyl, carboxamide, alkoxy, aryloxy or acylamino group or, preferably, chlorine, a sulfonamide, alkoxycarbonyl, trifluoromethyl or alkyl group. R5 is in particular hydrogen, chlorine or bromine, a nitro, cyano, thiocyano, acyl, alkoxycarbonyl, trifluoromethyl or alkyl group. Acyl, alkyl and alkoxy here mean the same as above.



   Examples of acyl radicals are: benzoyl, 4-chlorobenzoyl, 4-methylbenzoyl, benzenesulfonyl, 4-methylbenzenesulfonyl, acetyl, propionyl, chloroacetyl or methylsulfonyl radicals.



   It should also be noted that never 2 strongly electrophilic, i.e. H.



  electron-attracting substituents such as nitro or acyl groups may be in the o-position to one another. However, this is possible with halogen atoms, cyano and alkoxycarbonyl groups. In the o-position to strongly electrophilic substituents there are preferably hydroxyl, alkoxy, alkyl groups or halogen atoms.



   From the series of useful diazo components of the benzene series, the following may be mentioned, for example: aniline, 1-amino-3- or -4-chlorobenzene, 1-amino-4-bromobenzene, 1-amino-2-, -3- or -4- methylbenzene, 1-amino-2-, -3- or -4-nitrobenzene, 1-amino-4-cyanobenzene, 1-aminobenzene-3- or -4-methylsulfone, 1-amino-2-chlorobenzene-4-methylsulfone, 1-amino-2,5-dicyanobenzene, 1-amino-4-carbethoxybenzene, 1-amino-2,4- or -2,5-dichlorobenzene, 1-amino-2,4-dibromobenzene, 1-amino-2- methyl-4- or -6-chlorobenzene, 1-amino-2-trifluoromethyl-4-chlorobenzene, 1-amino-2-cyano-4-chlorobenzene, 1-amino-2-cyano-4-nitrobenzene, 1-amino 2-carbomethoxy-4-chlorobenzene, 1-amino-2-methanesulfonyl-4-chlorobenzene, 1-amino-2-carbomethoxy-4-nitrobenzene,

   1-amino-2-phenoxy-4-nitrobenzene, 1-amino-2-chloro-4-cyanobenzene, 1-amino-2-chloro-4-nitrobenzene, 1-amino-2-methoxy-4-nitrobenzene, 1- Amino-2-chloro-4-carbethoxybenzene, 1-amino-2,4-dinitrobenzene, 1-amino-2,4-dicyanobenzene, 1-amino-2,6-dichloro-4-cyanobenzene, 1-amino-2, 6-dichloro-4-nitrobenzene, 1-amino-2,5- or -2,6-dichlorobenzene-4-sulfonic acid dimethylamide, 1-amino-2-chlorobenzene-4-sulfonic acid dimethylamide, 1-amino-2,6- dibromobenzene-4-sulfonic acid amide, 1-amino-2,4-dinitro-6-chloro- or -6-bromobenzene, 1-amino-2,4-dicyano-6-chlorobenzene, 1-amino-2,4,6- trichlorobenzene or tribromobenzene, 1-aminobenzene-3- or -4-sulfonic acid amide, 1-aminobenzene-3- or 4-sulfonic acid-N-methyl- or diethylamide, 4-aminoazobenzene,

   4-amino-2'-chloro-azobenzene, 4-amino-2 ', 4'-dichloro-azobenzene,
4-amino-3'-chloroazobenzene,
4-amino-2'-nitro-azobenzene,
1-amino-nitrobenzene-2-methylsulfone,
1-aminobenzene-4-carboxylic acid-s-methoxyethyl ester,
4-amino-3-nitro-azobenzene,
4-amino-3'-nitro-azobenzene,
4-amino-2-methyl-azobenzene,
4-amino4'-methoxy-azobenzene,
4-amino-3-nitro-2'-chloro-azobenzene,
4-Amino-3-nitro4'-chloroazobenzene,
4-Amino-3-nitro-2: 4dichloroazobenzene,
4-amino-3-nitro-4'-methoxy-azobenzene,
4-aminodiphenyl and
2- or 4-aminodiphenyl ethers.



   Another group of suitable diazo components are ethyl ethers of aminophenols which contain one of the basic groups Q mentioned in the ss-position of the ethoxy, and z. B. derive from
4-nitro-2-aminophenol 4,6-dinitro-2-aminophenol
6-nitro-4-chloro-3-aminophenol 4-nitro-3-aminophenol 5-methanesulfonyl-2-aminophenol 5-nitro-2-aminothiophenol 4-chloro-2-aminophenol-5-sulfonic acid-N-methylamide, with group Q in particular trimethylammonium chloride, Triethylammonium chloride, pyridinium chloride, N-methylpiperidinium chloride and N-methylmorpholinium chloride occur as well as the residues of the amines, hydrazines and hydroxylamines mentioned below, from which the group Q can be derived.



   Also suitable diazo components are the condensation products of phenyl chloride or bromide with the same amines, hydrazines and hydroxylamines, such as. B.



  Phenacyltrimethylammonium chloride, phenacyltriethylammonium chloride.



   The diazo components can, however, also be derived from any diazotizable heterocyclic amines without acidic, water-solubilizing groups. These amines originate, for example, from the thiazole, benzothiazole; Naphthothiazole, isothiazole, benzisothiazole, imidazole, benzimidazole, thiadiazole, pyridine, quinoline, indazole, selenazole; Oxazole, oxdiazole, benzoxazole; Pyrazole or triazole series. The nitrogen-containing heterocycles can be quaternized, the representatives mentioned in the description of the basic radicals being possible anions.



   In addition to the basic groups Q, the following are possible as substituents of these diazo components: phenyl and phenylazo groups, where the phenyl rings can carry further substituents such as chlorine, nitro, alkyl, alkoxy and alkyl mercapto radicals each with 1 to 4 carbon atoms, sulfamoyl , Trifluoromethyl, nitro, cyano, thiocyano, aralkyl, especially benzyl, cycloalkyl, especially cyclohexyl, and alkyl, alkoxy, alkylmercapto, alkylsulfonyl, alkoxycarbonyl, alkanoyl and N, N-dialkylsulfonamide groups, especially those Residues with 1-4 C atoms.



     Preference is given to the diazo components which have a heterocyclic five-membered ring with 2 or 3 heteroatoms, especially one nitrogen and one or two sulfur, oxygen or nitrogen atoms as heteroatoms, in particular the amines of thiazole; Benzthiazole, isothiazole; Benzisothiazole and thiadiazole series.



   Preferred substituents of these diazo components are: halogen, in particular chlorine or bromine, nitro; Cyano-, trifluoromethyl; Alkyl and alkoxycarbonyl radicals each having 1 to 4 carbon atoms, phenyl and the substituted phenyl radicals mentioned above.



   Examples of such heterocyclic diazo components 2-aminothiazole, 2-amino-3-methyl-thiazolium chloride, 2-amino-5-nitrothiazole, 2-amino-5-methylsulfonyl-thiazole, 2-amino-5-cyanthiazole, 2-amino-4-methyl- 5-nitrothiazole, 2-amino4-methylthiazole, 2-amino4-phenylthiazole, 2-amino444'-chloro) -phenylthiazole, 2-amino4- (cnitro) -phenylthiazole, 3-aminopyridine, 3-aminoquinoline, 3-aminopyrazole, 3- Amino-1-phenylpyrazole, 3-aminoindazole, 3-amino-1, 2,4-triazole, 3-amino-1- (4¯methoxyphenyltpyrazole, 2-aminobenzothiazole, 2-amino-6-methylbenzthiazole, 2-amino-6 methoxybenzthiazole, 2-amino-6-chlorobenzthiazole, 2-amino-6-cyanobenzothiazole, 2-amino-6-nitrobenzthiazole, 2-amino-6-carboethoxybenzthiazole, 2-amino-6-methylsulfonylbenzthiazole, 2-amino-1,3 , 4-thiadiazole,

   2-amino-1, 3,5-thiadiazole, 5-amino-3- (2'-, 3'- or 4-pyridyl) -1,2,4-thiadiazole, 2-amino4-phenyl- or -4- methyl-1,3,5-thiadiazole, 2-amino-5-phenyl-1,3,4-thiadiazole.



   The coupling component is a 3-cyano4,6-diaminopyridine substituted in the 2-position. The two amino groups are preferably not further substituted. In the 2-position there are aliphatic and aromatic amino, oxy and mercapto groups. Such compounds can be prepared by reacting the 2-bromo-3-cyano4,6-diaminopyridine with a primary or secondary amine, a hydroxy or mercapto compound.



   Examples of amines that are suitable for preparing the coupling components are: naphthylamine, aniline and its derivatives, such as 1-amino-3-chlorobenzene, 1-amino-4-carbethoxybenzene, 1-amino-2,4-dicyanobenzene, 1 - Amino-2-methoxy4-nitrobenzene, 1-amino-2-methanesulfonyl-4-chlorobenzene, methylaminobenzene-, ethylaminobenzene, 1-methylamino-3-chlorobenzene, 142'-chloroethoxy) -2-amino4-nitrobenzene, 1 - (2 ' -Chloroethoxy) -2-amino4,6-dinitrobenzene, 142'-chloroethoxy) -2-amino-5-methanesulfonylbenzene, 1 (2'-chloroethoxy 3-amino4-chloro-6-nitrobenzene.



   Primary and secondary aliphatic amines such as methyl, ethyl, isopropyl; Methoxyethyl, methoxypropyl; Dimethyl; Dimethylaminopropyl; Chloroethyl; Ethanol, diet hanoli propanol, benzyl or cyclohexylamine, morpholine, pyrrolidine, piperidine and piperazine.



   As alcohols are z. B. called: Ethanol, propanol, isopropanol, butanol, 2-ethoxyethanol, 2-dimethylaminoethanol, cyclohexanol, benzyl alcohol, phenol and its substituted derivatives such as dimethylaminophenol.



   Examples of mercapto compounds are: ethyl mercaptan, thiophenol.



   In those diazo and coupling components which contain a reactive atom or group, e.g. B. chlorine, bromine, sulfonic acid ester, alkyl sulfate, Hy droxyl or amino groups, as discussed below, basic groups can be introduced by condensation before coupling.



   Components with quaternizable nitrogen atoms can be treated with quaternizing agents before or after the coupling.



   Instead of a single diazo component, it is also possible to use a mixture of two or more of the diazo components according to the invention and instead of a single azo component a mixture of two or more of the azo components according to the invention.



   The diazotization of the diazo components mentioned can be carried out by methods known per se, for. B. with the help of
Mineral acid, especially hydrochloric acid, and sodium nitrite or z. B. with a solution of nitrosylsulfuric acid in concentrated sulfuric acid.



   The coupling can also be carried out in a manner known per se, e.g. B. in neutral to acidic agents, optionally in the presence of sodium acetate or similar, the coupling speed influencing buffer substances or catalysts, such as. B. pyridine, respectively. its salts, are made.

 

   As compounds from which the group Q can be derived, z. B. the following mentioned: Amines: primary and secondary such as methyl, ethyl, isopropyl, methoxyethyl, methoxypropyl, dimethyl, diethyl; Ethylphenyl; Diethanol, porpanol, benzyl, cyclohexylamine, pyrrolidine, piperidine, piperazine, morpholine, tertiary such as trimethylamine, triethylamine, dimethylaniline, triethanolamine, pyridine, picoline, lutidine, N-methyl-piperidine, N-methyl-piperazine, N-methylmorpholine , Quinoline or pyrimidine.



  Hydrazines: N-methylhydrazine, N, N-dimethylhydrazine, N, N'-diethylhydrazine, N, N, N'-trimethylhydrazine, N, N, N, N'-tetramethylhydrazine, N-aminopiperidine, N-aminopyrrolidine, 1,5 -Diazabicyclo (0,3,3) octane.



  Etherified hydroxylamines:
EMI4.1
 Carboxylic acid chlorides
EMI4.2

EMI4.3
   The implementation of z. B. a halogen or sulfatoalkyl group containing disazo or coupling component with the amine, hydrazine or etherified hydroxylamine is done in a neutral solvent, for. B. in chlorobenzene, alcohols or aqueous alcohol mixtures or dimethylformamide, or without a solvent, conveniently at an elevated temperature in an excess of the hydroxylamine and optionally with the addition of catalysts, eg. B. NaJ.



   The acylation of an acylatable hydroxyl or amino group-containing diazo or coupling components with the carboxylic acid chlorides mentioned is preferably carried out in the presence of acid-binding agents such as alkali and alkaline earth acetates, hydrogen carbonates and carbonates or pyridine in an organic or organic-aqueous medium by methods known per se carried out.



   Those new dyes which contain a quaternized nitrogen atom can also be obtained in such a way that the corresponding dyes which contain a non-quaternized amino; Contain hydrazino or etherified hydroxylamino group or nitrogen-containing heterocyclic group, quaternized by treatment with alkylating agents. As such alkylating or quaternizing agents can be, for. B. use: esters of strong mineral acids, especially low molecular weight sulfuric acid esters, or organic sulfonic acids, e.g. B. dimethyl sulfate, diethyl sulfate, alkyl halides, e.g. B. methyl chloride, bromide or iodide, aralkyl halides, e.g. B. benzyl chloride, esters of low molecular weight, d. H. 1 to 4 carbon atoms containing alkanesulfonic acids, such as. B.

  Methyl ester of methane; Ethane or butanesulfonic acid, and esters of benzenesulfonic acids, which may have additional substituents, e.g. B. methyl, ethyl, propyl or butyl esters of benzenesulfonic acid, of 2- or 4-methylbenzenesulfonic acid, 4-chlorobenzenesulfonic acid or 3- or 4-nitrobenzenesulfonic acid.



   The alkylation is conveniently carried out by heating in an inert organic solvent, for example hydrocarbons such as benzene, toluene or xylene, halogenated hydrocarbons such as carbon tetrachloride, tetrachloroethane, chlorobenzene, o-dichlorobenzene, or nitrohydrocarbons such as nitromethane, nitroaphthalene or nitrobenzene. Acid anhydrides, acid amides or nitriles, such as acetic anhydride, dimethylformamide or acetonitrile or even dimethyl sulfoxide, can also be used as solvents in the alkylation. Instead of a solvent, it is also possible to use a large excess of alkylating agent. In this case, however, care must be taken that the mixture does not heat up excessively, as the reaction is strongly exothermic.

  Nevertheless, in most cases, especially in the presence of organic solvents, it is necessary to heat the reaction mixture from the outside in order to start the reaction. In special cases, the alkylation can also be carried out in an aqueous medium or using an alcohol, possibly in the presence of small amounts of potassium iodide.



   If necessary, the dye salts are expediently purified by dissolving them in water, with any unreacted starting dye being able to be filtered off as an insoluble residue. The dye can be deposited again from the aqueous solution by adding water-soluble salts, for example sodium chloride.



   The dye salts obtained can contain the anions introduced according to the process. However, these can also be subsequently replaced by other anions specified above.



   The dyes or dye salts obtained according to the invention with an optionally quaternized amino, hydrazinoverätherten hydroxylamino groups or nitrogen-containing heterocyclic group are suitable for dyeing and printing a wide variety of fully synthetic fibers, such as. B. of polyvinyl chloride, polyamide; Polyurethane fibers, also of fibers made from polyesters of aromatic dicarboxylic acids, such as. B. of polyacrylonitrile fibers of polyethylene terephthalate fibers, but especially of polyacrylonitrile fibers of polyvinylidene anide fibers (Darvan).



   Polyacrylonitrile fibers are primarily understood to be polymers containing more than 80 oils, e.g. B. 80 to 95 o / o acrylonitrile; in addition, they contain 5 to 20/0 vinyl acetate, vinyl pyridine, vinyl chloride, vinylidene chloride, acrylic acid,. Acrylic acid esters, methacrylic acid, methacrylic acid esters, etc. These products are z. B. sold under the following brand names: Acrilan 1656 (The Chemstrand Corporation, Decatur, Alabama, USA), Acrilan 41 (The Chemstrand Corporation), Creslan (American Cyanamid Company), Orlon 44 (Du Pont), Crylor HH (Soc. Rhodiaceta SA , France), Leacril N (Applicazioni Chimice Societä per Azioni, Italy), Dynel (Union Carbide Chem.

  Corp.), Exlan (Japan Exlan Industry Co., Japan), Vonnel (Mitsubishi, Japan), Verel (Tennessee Eastman, USA), Zefran (Dow Chemical, USA), Wolcrylon (Agfa Film Factory, Wolfen), Ssaniw (USSR) and also Orlon 42 Dralon, Courtelle etc.



   On these fibers, which can also be dyed in a mixture with one another, the new dyes give intense and level dyeings with good lightfastness and good all-round fastness properties, in particular good washing and perspiration; Sublimation, anti-crease, decatur, bracket; Rubbing, carbonizing, water, chlorinated water, sea water, dry cleaning, over-dyeing and solvent fastness. The novel dyes according to the invention have u. a. also good stability in a larger pH range, good affinity e.g. B.



  in aqueous solutions of different pH values and good bench fastness. Another advantage is the good reserve for wool and other natural polyamide fibers as well as cotton. The colors are characterized by bright nuances.



   The quaternized, water-soluble dyes are generally not very sensitive to electrolytes and show e.g. T. an extremely good solubility in water or polar solvents. The quaternized, water-soluble dyes are generally colored in an aqueous, neutral or acidic medium, at the boiling point under atmospheric pressure or in a closed vessel under elevated temperature and pressure.



   They can also be applied to the fiber materials by printing. For this purpose, a printing paste is used, for example, which contains the dye in addition to the auxiliaries customary in printing. They are also suitable for the mass coloration of polymerization products of acrylonitrile, as well as other plastic, optionally dissolved masses, in lightfast and washable shades, furthermore for the coloration of oil paints or varnishes, or finally also for the coloration of cellulose, regenerated cellulose , Paper and especially stained cotton.

 

   Those among the new dyes whose basic residue contains non-quaternized nitrogen atoms and which are not or only slightly water-soluble are expediently in finely divided form and with the addition of dispersants such as soap, sulphite cellulose liquor or synthetic detergents, or a combination of different wetting or dispersing agents used. In the
As a rule, it is advisable to convert these dyes into a dye preparation which contains a dispersant and finely divided dye in such a form that a fine dispersion is formed when the dye preparations are diluted with water. Such dye preparations can in a known manner, for. B. obtained by grinding the dye in highly effective grinding devices in dry or wet form with or without the addition of dispersants during the grinding process.

  They are also suitable for dyeing and printing a wide variety of semi-synthetic and fully synthetic fibers, such as. B. of cellulose acetate, polyolefin, z. B.



  modified polypropylene, polyester, polyvinyl chloride, polyamide or polyurethane fibers, but in particular polyacrylonitrile fibers.



   To achieve strong colorations, it has proven to be expedient to carry out the dyeing process at higher temperatures, for example at the boiling point.



   A dispersant is advantageously added and the dyebath is made slightly acidic, for example by adding a weak acid, e.g. B. acetic acid.



   The present dyes can also be applied by printing. For this purpose one uses z. B. a printing ink which, in addition to the auxiliaries customary in printing, such as wetting agents and thickeners, contains the finely dispersed dye, optionally in a mixture with other dyes.



   In the following examples, unless otherwise stated, parts by weight are percentages percentages by weight, and temperatures are given in degrees Celsius.



  Regulation 1
10.65 parts of 2-bromo-3-cyano-4,6-diaminopyridine, 10 parts of alcohol and 16 parts of 700 / above aqueous ethylamine are heated in an autoclave at 100 "for 4 hours.



   Excess amine and the other volatile constituents are evaporated in vacuo and the residue, which is the compound of the formula
EMI6.1
 contains, is used as a coupling component without further purification.



  Regulation 2
10.65 parts of 2-bromo-3-cyano-4,6-diaminopyridine and 24 parts of aniline are heated at 140 for 4 hours. The mixture is cooled, adjusted to pH 7-8 with sodium hydroxide solution and the excess aniline is driven off with steam. The unusual product of the formula
EMI6.2
 is separated and used as a coupling component without purification.



  Regulation 3
4.26 parts of 2-bromo-3-cyano-4,6-diaminopyridine are dissolved in 120 parts of hot methyl alcohol. 3 parts of sodium methylate are added and the mixture is boiled under reflux until the starting substance can no longer be detected in the thin-layer chromatogram. The solvent is removed in vacuo, the residue is stirred with ice water, the insoluble product is separated off by filtration, the filter cake is washed with cold water and dried. The compound has the formula
EMI6.3
 Regulation 4
6.4 parts of 2-bromo-3-cyano-4,6-diaminopyridine, 14.5 parts of phenol and 2.5 parts of potassium carbonate are heated at 140 ° until no more starting substance can be detected in thin-layer chromatograms. The mixture is poured into water and adjusted to pH 9 with sodium hydroxide solution.

  The precipitated compound of the formula
EMI6.4
 is filtered off, washed with water and dried.



  Regulation 5
8.4 parts of 2-chloro-3-cyano-4,6-diaminopyridine and 20 parts of 3-dimethylamino-1-propylamine are heated at 100 "for 6 hours. Excess amine is evaporated in vacuo and the viscous residue, which contains the compound the formula
EMI6.5
 contains, is used as a coupling component.



  example 1
4.57 parts of 4-aminophenacyltrimethylammonium chloride, obtained by reacting 4-aminophenacyl chloride with trimethylamine, are dissolved in 20 parts of water, and 8 parts by volume of concentrated hydrochloric acid are added to the entire solution. The solution is diazotized at 0-5 "by adding 5 parts by volume of 4N sodium nitrite solution. The diazo solution is diazotized at 0-5" to a solution of 4.5 parts of 2-anilino-3-cyano-4,6-diaminopyridine in 30 parts Alcohol added. The coupling mixture is made Congo-neutral by adding sodium acetate solution. After the coupling has ended, the mixture is diluted with 100% above sodium chloride solution.



  The dye is filtered off, dissolved in hot water and, after the solution has been filtered, salted out of the filtrate.



  The unusual dye of the formula
EMI7.1
 is filtered off and dried. It dyes polyacrylonitrile fibers in red-yellow shades with excellent fastness properties.



  Example 2
3.54 parts of 5-amino-3-phenyl-1,2,4-thiadiazole are dissolved in 20 parts by volume of formic acid. At 0 to 5, 1.4 parts of sodium nitrite are added and the mixture is stirred for 30 minutes. Then 0.05 parts of sulfamic acid are added. Then 6.9 parts of 3 (3'Cyan4: G'diaminopyridin-2 '-) - aminopropyl.91- trimethylammonium methosulfate are added and rinsed with 10 parts by volume of formic acid. The mixture is slowly heated to 60 and stirred at this temperature for 2 hours. The paste is diluted with water, dissolved while hot and, after filtering the solution from the filtrate, salted out with sodium chloride and zinc chloride.



   The unusual dye of the formula
EMI7.2
 is filtered off and dried. It dyes polyacrylonitrile fibers in reddish yellow shades with very good fastness properties.



   The coupling component is obtained by alkylating the intermediate described in instruction 5 with dimethyl sulfate in a chlorobenzene solution.



   Further dyes of the formula are obtained in an analogous manner
EMI7.3
 in which the symbols D, A, B, C, E and X have the meaning given in Table 1.
EMI8.1
  

 

  Table 1
EMI9.1


<tb> <SEP> D <SEP> s <SEP> A
<tb> <SEP> 3
<tb> <SEP> NH2
<tb> <SEP> (<SEP> CHD <SEP>) <SEP> (CI,
<tb> <SEP>)) <SEP> L
<tb> <SEP> (02H5) <SEP> 3NOH2CO <SEP> NH2
<tb> <SEP> NH,
<tb> <SEP> / <SEP> NH2
<tb> <SEP> (<SEP> CH3 <SEP>) <SEP> 2N <SEP> WH2 <SEP> <
<tb> <SEP> NHCOGH3
<tb> <SEP> (<SEP> C2H5 <SEP>) <SEP> 2 <SEP> ss <SEP> CH2C <SEP> NH2
<tb> <SEP> CO <SEP> 2H5
<tb> NCH2OON = N <SEP> NH2
<tb> <SEP> CH3
<tb> ¸ ;;

  ; 2OO x N = N <SEP> NH2
<tb> <SEP> H <SEP> N
<tb> <SEP> (<SEP> C3H7 <SEP>) <SEP> 3 <SEP> 2 <SEP> 3OH2OM · <SEP> NH2
<tb> 0 <SEP> 2NU
<tb> <SEP> CóH4CQCH2NX <SEP> NH2
<tb> <SEP> CH3
<tb> <SEP> 3
<tb> <SEP> 02Ne
<tb> <SEP> OH3) <SEP> NH2
<tb> <SEP> oC6H4C C2H4 <SEP> (<SEP> 3
<tb> Table 1
EMI10.1


<tb> B <SEP> C <SEP> E <SEP> X <SEP> color
<tb> NH2 Piperidyl CN Br golden yellow NH2 NHC6H5 CN Cl golden yellow NH2 NHC2H4OC6H5 CN Cl 'yellow NH2 N (C4H9) 2 CN Cl golden yellow NH2 NHCH2CON (CH3) 2 CN Cl orange NH2 OCH3 CN CH3COO golden yellow NH2 NHC2H4OH CN Cl NH2 yellow Cl orange NH2 NHC6H4Cl (m) CN Br orange
EMI11.1

 l <SEP>
<tb> <SEP> iNOH <SEP> NH2
<tb> <SEP> CH,
<tb> <SEP> -7
<tb> <SEP> N-OH <SEP> 200 <SEP> NH2
<tb> <SEP>
<tb> <SEP> CH3
<tb> <SEP> (OH3) <SEP>), SCH2C <SEP> NHC4H8OH
<tb> <SEP> (<SEP> CH3 <SEP>) <SEP> 3NCH2CGw
<tb> <SEP>

   (O2H5) 3NO2H4HNOO <SEP> NH2
<tb> <SEP> 3) <SEP> 3 <SEP> 2E4CCCO <SEP> NH2
<tb> <SEP> OH3N- <SEP> 4 <SEP> 2 V <SEP> NH2
<tb> <SEP> 02N
<tb> <SEP> 1 <SEP> NH,
<tb> <SEP> oc2x; Nw
<tb> <SEP> ÇN <SEP> 21140001140 <SEP> 20 <SEP> NH2
<tb> <SEP> CH
<tb> <SEP> 2NX
<tb> <SEP> C2H4 <SEP> N (OH <SEP>) <SEP> 2 <SEP> NH2
<tb> <SEP> OCH3
<tb> <SEP> 00113
<tb>
EMI12.1

 B <SEP> C <SEP> E <SEP> X <SEP> color tone
<tb> NH2 SC6H5 CN Cl yellow NH2 OCH (CH3) 2 CN Br yellow NHCH (CH3) 2 NHCH (CH3) 2 CN Cl orange NH2 NHC6H4CH3 (p) CN I golden yellow NH2 N (CH3) 2 CN CH3SO4 golden yellow NH2 NHC2H4Cl CN C7H7CO3 yellow NH2 NHC2H4C6Hs CN CH3SO3 orange NHC6Hs NHC6H5 CN Cl yellow NH2 OC6Hs CN CH3SO3 yellow
EMI13.1


<tb> <SEP> D <SEP> · <SEP> A
<tb> CSHg <SEP> 2N;

  ; H4O <SEP> 2s <SEP> NH2
<tb> <SEP> OC <SEP> H
<tb> <SEP> 49
<tb> (<SEP> CH3 <SEP>) <SEP> 3NCH2Co {CH2icE3 <SEP> NH2
<tb> <SEP> OH3
<tb> (CH,), N-N = HC- <SEP> NH2
<tb> (C2t5) 2 <SEP> {<SEP> C2H4HN <SEP> 2 <SEP> 0 <SEP> NH2
<tb> I <SEP> L <SEP> L <SEP> 4 <SEP> L <SEP> 42 ·
<tb> <SEP> CH3
<tb> <SEP> C1
<tb> N-O <SEP> H <SEP> ENT <SEP> S <SEP> NH2
<tb> <SEP> 24 <SEP> 2 <SEP> NH2
<tb> <SEP> NHCOC11 <SEP> N <SEP> STILL,
<tb> <SEP> L
<tb> <SEP> OH2C6115
<tb> <SEP> CH.

  <SEP> -N <SEP> = N \ <SEP> N
<tb> <SEP> CH = CH / <SEP> NH,
<tb> <SEP> C1
<tb> <SEP> Ü <SEP> NH2
<tb> <SEP> 0113 <SEP> ¯ <SEP> N-CH
<tb> <SEP> 3 <SEP> ssCH / <SEP> 3
<tb>
EMI14.1


<tb> B <SEP> C <SEP> E <SEP> X <SEP> color
<tb> NH2 NH-cyclohexyl CN HSO4 yellow NH2 SC2H5 CN Cl yellow NH2 NHC6H13 CN CH3SO4 yellow NH2 pyrrolidinyl CN I orange NH2 OC2H4C6H5 CN Cl yellow NHC3H6OCH (CH3) 2 NHC3H6OCH (CH3) 2 CNHC5 yellow NH2 CH2 NHC8H17 CN CH3SO4 yellow
EMI15.1


<tb> <SEP> · <SEP> NHC6H5
<tb> t
<tb> <SEP> <<SEP> NHC6Hs
<tb> <SEP> 3 <SEP> WN <SEP> / <SEP> 3
<tb> <SEP> (<SEP> 2 <SEP> 2 <<SEP> NH2
<tb> <SEP> cH3
<tb> <SEP> NH
<tb> <SEP> cyclo
<tb> <SEP> hexyl
<tb> <SEP> S02N11C2114 <SEP> X <SEP> ff <SEP> 2 <SEP> 5
<tb> <SEP> (X <SEP> NH2
<tb> <SEP> CW
<tb> <SEP> Q <SEP>} <SEP> NH2
<tb> <SEP> I (C113) 3
<tb> <SEP> 3
<tb> <SEP> 0113 <SEP>

   NHC2H4C6H5
<tb> <SEP> 4-nitrophenyl <SEP> NH2
<tb> <SEP> 5-nitrothiazolyl-2- <SEP> NH2
<tb> <SEP> CNitro - trifluor- <SEP> nTHCH <SEP> STHCH
<tb> <SEP> methylphenyl <SEP> 2 <SEP> 2
<tb>
EMI16.1


<tb> B <SEP> C <SEP> E <SEP> X <SEP> color
<tb> NHC2Hs NHC2Hs CN CH3SO4 yellow
NH2 Morpholino CN I yellow NHCH (CH3) 2 NHCH (CH3) 2 CN C2H5SO4 yellow NH2 N (C2H5) 2 CN CH3SO4 orange NH2 OC6H4CH3Cm) CN CH3SO4 yellow NHC2H5 NHC2H5 CN Br orange
EMI16.2


<tb> NH2 <SEP> NHC3H6N, <SEP> (<SEP>;) 2 <SEP> CN <SEP> Cl <SEP> orange
<tb> <SEP> CH2 <SEP> C; H5
<tb> NH2 <SEP> NHC <SEP> 11 <SEP> N <SEP> (<SEP> CN <SEP> C2H5S04 <SEP> ruby
<tb> <SEP> 3 <SEP> NHC.H;

  ; N (CH, <SEP> 61 <SEP> 30113) 2
<tb> <SEP> OH
<tb> N (CH3) 2 <SEP> N <SEP> (OH <SEP>) <SEP> CN <SEP> Cl <SEP> scarlet
<tb> <SEP> 32
<tb>
EMI17.1


<tb> D <SEP> A
<tb> D 4 (4'-nitrophenyl) azophenyl 2-chloro-4-nitrophenyl 2,5-dichloro-4 dimethylamino sulfonylphenyl
4-phenylazophenyl
4-nitro-2 thiocyanphenyl
5-nitro-7-bromo
2,1-benz isothiazolyl-3 2,6-dichloro-4-nitrophenyl
5-acetyl-3 nitrothiophenyl
3-butylthio-1,2,4 thiadiazolyl-5
4- (2'-hydroxy-5 'methylphenyl) azophenyl
6-methylsulfonyl benzthiazolyl-2
1-anthraquinonyl
5-chloro-2-methyl thiophenyl
EMI17.2
  
EMI18.1


<tb> <SEP> B <SEP> OH <SEP> E <SEP> X <SEP> y¸ton
<tb> <SEP> NH2 <SEP> iNHC <SEP> H <SEP> N <SEP> 4 <SEP> 9 <SEP> CN <SEP> Br <SEP> orange
<tb> <SEP> 2 <SEP> 4 <SEP> \, <SEP> 2X5
<tb> <SEP> OC ,:

  : K9
<tb> <SEP> N (C2Hs) 2 <SEP> N (C2Hs) 2 <SEP> CN <SEP> CH3SO3 <SEP> scarlet
<tb> <SEP> NH2 <SEP> NHC6H4OC2H4N (CH3) 3 (-p) <SEP> CN <SEP> CH3SO4 <SEP> orange
<tb> <SEP> N (CH3) 2 <SEP> N (CH3) 2 <SEP> CN <SEP> C6HsSO3 <SEP> golden yellow
<tb> <SEP> NHC3H6N (CH3) 3 <SEP> NH-cyclohexyl <SEP> CN <SEP> CH3SO4 <SEP> orange
<tb> NH2 <SEP> SC2H4N (C2Hs) 3 <SEP> CN <SEP> Br <SEP> red
<tb> NH2 <SEP> NHC2H4N (C2Hs) 3 <SEP> CN <SEP> I <SEP> orange
<tb> N (CH3) 2 <SEP> N (CH3) 2 <SEP> CN <SEP> CH3SO3 <SEP> ruby
<tb> <SEP> NHC2H4N (C2Hs) 3 <SEP> NHC6Hs <SEP> CN <SEP> Br <SEP> reddish <SEP> yellow
<tb> <SEP> nCE:

  <SEP> 11 <SEP> CC <SEP> 114iN (CH7) 2
<tb> <SEP> NH2 <SEP> 2 <SEP> 4 <SEP> 2 <SEP> CN <SEP> cN <SEP> Br <SEP> orange
<tb> <SEP> C2H4COOC2H5
<tb> <SEP> N (CH3) 2 <SEP> N (CH3) 2 <SEP> CN <SEP> Cl <SEP> scarlet
<tb> <SEP> /
<tb> <SEP> 02114 <SEP> N <SEP> 11 <SEP> 0
<tb> <SEP> NH2 <SEP> i <SEP> CN <SEP> 1/3 <SEP> PO4 <SEP> scarlet
<tb> <SEP> 04119
<tb> <SEP>. <SEP>. <SEP>.
<tb>



   <SEP> piperidino <SEP> piperidino <SEP> CN <SEP> Cl <SEP> yellow
<tb>
EMI19.1


<tb> D <SEP> A
<tb> n
<tb> 2-ethoxycarbonyl4-nitrophenyl 1-naphthyl 6-bromo-2-cyano4nitrophenyl 1 -methyl4- nitroimidazolyl-52-methoxy-5nitrophenyl 2,6-dichloro-aminosulfonylphenyl 4-azophenyl-2nitrophenyl 2,4-dicyanophenyl 5,6-dichlorobenzthia 2 3-methyl4-nitro 1,2-isothiazolyl-5 5-thiocyanthiazolyl-2 2-methyl4nitrophenyl 2,4-dinitrophenyl
EMI19.2
  
EMI20.1


<tb> <SEP> B <SEP> | <SEP> C <SEP> 1 <SEP> E <SEP> X <SEP> x <SEP> | <SEP> hue
<tb> NH2 <SEP> NHC6H4NHCOCH2N (CH3) 3l (-m) <SEP> CN <SEP> HSO4 <SEP> scarlet
<tb> N (CH3) 2 <SEP> N (CH3) 2 <SEP> CN <SEP> CH3SO3 <SEP> orange
<tb> NH2 <SEP> NHC2H4N <9 <SEP> CN <SEP> Cl <SEP> ruby
<tb> <SEP> Approx
<tb> <SEP> 3
<tb> NHCH (CH3) 2 <SEP> NHCH (CH3) 2 <SEP> CN <SEP> 1/2 <SEP> SO4 <SEP>

   Scarlet fever
<tb> NHC3H6N (CH3) 3 <SEP> NHC2H4C6H5 <SEP> CN <SEP> CH3SO4 <SEP> yellow
<tb> NH2 <SEP> NHC6H4CH2N (CH3) 3 (-p) <SEP> CN <SEP> Cl <SEP> orange
<tb> N (CH3) 2 <SEP> N (CH3) 2
<tb> <SEP> CN <SEP> Cl <SEP> red
<tb> NH2 <SEP> liTtt ^ C <SEP> 11 <SEP> CN <SEP> C <SEP> orange
<tb> <SEP> ^ <SEP> 2 <SEP> 4 <SEP> 2 <SEP> 5 <SEP> CN <SEP> C2HsSO4 <SEP> orange
<tb> NH2
<tb> NH <SEP> 1N (CH) 2
<tb> <SEP> CN <SEP> CH3SO4 <SEP> orange
<tb> pyrrolidino <SEP> pyrrolidino
<tb> <SEP> CN <SEP> C7H7SO3 <SEP> ruby
<tb> NHC3H6N (CH3) 3 <SEP> NHC3H6N (CH3) 3
<tb> <SEP> CN <SEP> CH3SO4 <SEP> orange
<tb> NH2 <SEP> OC2H4N (C2Hs) 3
<tb> <SEP> CN <SEP> C2HsSO4 <SEP> yellow
<tb> NH2 <SEP> NHC3H6H (CH3) 3
<tb> <SEP> CN <SEP> Cl <SEP> red
<tb>
EMI21.1


<tb> D <SEP> A
<tb> 444-chlorophenyl) - azo-2-methoxy-5methylphenyl 4-methoxy-2nitrophenyl 2-methyl-5nitrophenyl

   4-Ethylaminosulfonylphenyl 5-phenyl-1,3,4thiadiazolyl-2 2-ethoxy4nitrophenyl 2,6-dibromo4nitrophenyl 2,4,5-trichlorophenyl 1-methylbenztriazolyl42-cyano4nitrophenyl 5-nitroindazolyl-3 2,6-dicyan4nitrophenyl
EMI21.2
  
EMI22.1


<tb> B <SEP> 13 <SEP> C <SEP> E <SEP> | <SEP> X <SEP> l <SEP> color tone
<tb> N (CH3) 2 <SEP> N (CH3) 2 <SEP> CN <SEP> Cl <SEP> scarlet
<tb> <SEP> X ,, TiTC <SEP> H <SEP> ss
<tb> <SEP> NH2 <SEP> 2 <SEP> 41 <SEP> CN <SEP> CH3COO <SEP> orange
<tb> <SEP> OH
<tb> N (C2Hs) <SEP> N (C2H5) 2 <SEP> CN <SEP> Cl <SEP> yellow
<tb> NH2 <SEP> NHC2M4N <SEP> (02115) 2 <SEP> CN <SEP> Br <SEP> orange
<tb> <SEP> 011011
<tb> <SEP> 2465
<tb> N (CH3) 2 <SEP> N (CH3) 2 <SEP> CN <SEP> Cl <SEP> reddish
<tb> <SEP> yellow
<tb> NH2 <SEP> NHCH2Mj0113 <SEP> CN <SEP> C7H7SO3 <SEP> orange
<tb> <SEP> CX3
<tb> NH2 <SEP> SC2H4N (C2Hs) 3 <SEP> CN <SEP> 1/3 <SEP> PO4 <SEP> yellow
<tb> NH2 <SEP> iNHC

   <SEP> 2I; 4N <SEP> H <SEP> CH3 <SEP>) <SEP> 2
<tb> <SEP> 2432
<tb> <SEP> CN <SEP> Ltl <SEP> j <SEP> CN <SEP> HSO4 <SEP> yellow
<tb> <SEP> OCH
<tb> NHC2Hs <SEP> NHC2H5 <SEP> CN <SEP> Cl <SEP> yellow
<tb> NH2 <SEP> N11C <SEP> 3 <SEP> 6 <SEP> (011) 2
<tb> <SEP> CN <SEP> 6 <SEP> 1 <SEP> / <SEP> cN <SEP> C2H5SO4 <SEP> scarlet
<tb> <SEP> 11
<tb> <SEP> L
<tb> <SEP> N (CH3) 2 <SEP> N (CH3) 2 <SEP> CN <SEP> Cl <SEP> orange
<tb> NH2 <SEP> NHC3E6N (C2E5) 2 <SEP> CN <SEP> HCO3 <SEP> ruby
<tb> <SEP> OC2H ,,
<tb>
EMI23.1


<tb> D <SEP> A
<tb>
5-nitro-2,1 benzisothiazolyl-3 NH2
4-butylsulfonyl- NH phenyl NH2
3-pyridyl NH2 5-phenyl-1,2,4-NH triazolyl-3 2
EMI24.1


<tb> B <SEP> 13 <SEP> c <SEP> E <SEP> X <SEP> I <SEP> color
<tb> <SEP> B <SEP> c <SEP> E <SEP> x <SEP> color tone
<tb> <SEP> NH2 <SEP> NHC2H4N (C2Hs) 3 <SEP> CN <SEP> Cl <SEP> ruby
<tb> <SEP> NH2

   <SEP> 1N7 <SEP> does <SEP> N <SEP> 11 <SEP> N (0H) <SEP> 2 <SEP> CN <SEP> Cl <SEP> orange
<tb> <SEP> / <SEP> v <SEP> 2
<tb> <SEP> NH2 <SEP> NHC6H4CH2N (CH3) 3 (p) <SEP> CN <SEP> Br <SEP> yellow
<tb> <SEP> NHC, H, <SEP> X (C. <SEP> -i <SEP> 2 <SEP> cN <SEP> a <SEP> yellow
<tb> <SEP> NH2 <SEP> NHO2HAN (02115) 2 <SEP> e <SEP> 1 <SEP> 5 <SEP> CNCN <SEP> Cl <SEP> yellow
<tb> <SEP> CH (C; t <SEP>)
<tb> example 3
2.76 parts of 4-nitroaniline are made into a paste with 8 parts by volume of concentrated hydrochloric acid and stirred into a mixture of 80 parts of ice and water. The suspension is diazotized at 0-5 with 5 parts by volume of 4N sodium nitrite solution. The diazo solution is added to a solution of 4.68 parts of 2-dimethylaminopropylamino-3-cyano-4,6-diaminopyridine in 20 parts of alcohol.

  After the coupling has ended, the mixture is adjusted to pH 8.9 with sodium hydroxide solution. The precipitated dye is filtered off, washed with water and dried. It dyes polyacrylonitrile fibers in red-yellow shades with excellent fastness properties. Further dyes of the formula are obtained in an analogous manner
EMI24.2
 where the symbols D, A, B, C and E have the meaning given in the table below.
EMI25.1


<tb>



   <SEP> D <SEP> A
<tb> <SEP> D <SEP> A
<tb> <SEP> (0113) <SEP> STCt <SEP> Ce <SEP> NH2
<tb> <SEP> L <SEP> L
<tb> CO- <SEP> C = '2CO <SEP> 00y <SEP> NH2
<tb> <SEP> I
<tb> <SEP> Approx
<tb> <SEP> C
<tb> <SEP> I
<tb> <SEP> NHp
<tb> 06115 <SEP> OH <SEP>? Tt <SEP>; ¸i0CH3 <SEP> CO
<tb> <SEP> 2 <SEP> 2
<tb> <SEP> OCH <SEP> 2 <SEP> C
<tb> <SEP> '2 "6'
<tb> (04119) <SEP> 2N11402 <SEP> NH2
<tb> / <SEP>
<tb> <SEP> 3 <SEP> to <SEP> NH2
<tb> <SEP> ra
<tb> <SEP> CH2-NS
<tb> (<SEP> Crz <SEP> C <SEP> s <SEP> CC <g = yv <SEP> NH2
<tb> <SEP> 3
<tb> <SEP> CCW
<tb> (0113) <SEP> 2SCZ;

  ; 2 '<SEP> NH2
<tb> <SEP> cH.3
<tb> 0,
<tb> <SEP> NHC6H5
<tb> <SEP> N <SEP> 11 <SEP> 0
<tb> <SEP> C, uCII2N <SEP> H
<tb> Table 2
EMI26.1


<tb> B <SEP> | <SEP> ss <SEP> C <SEP> E <SEP> color tone
<tb> NH2 Pyrrolidino CN golden yellow NH2 NHC4H9 CN golden yellow NH2 OCH (CH3) 2 CN yellow NH2 NHC5H4OCH3 (m) CN yellow NH2 SC6H3Cl2 (2,5) CN yellow NH2 NHCH2C6H5 CN orange NH2 NHC3H6OCH3 CN orange NHC2H5 NHC2H5 orange
EMI27.1


<tb> D <SEP> A
<tb>
EMI27.2
 NH2 NH2 NH2 NH-cyclohexyl
NH2 NH2 NH2 NHC6H13 NH2 NH2 NHCH3
EMI28.1


<tb> <SEP> 13 <SEP> C <SEP> | <SEP> E <SEP> | <SEP> hue
<tb> NH2 <SEP> NSCH2 <SEP> 4 <SEP> CN <SEP> orange
<tb> NH2 OC6H3 (CH3) 2 (3,4) CN yellow NH2 SC6H13 CN yellow NHCH (CH3) 2 NHCH (CH3) 2 CN reddish yellow NH2 NHC4H8OH CN yellow
NH2 N (C2H4OCOCH3) 2 CN orange
NHC6H5 NHC6H5 CN orange
N (CH3) 2 N (CH3) 2 CN

   orange
NH2 OC2H4C6H5 CN yellow NH2 Thiomorpholino CN orange N (CH3) 2 N (CH3) 2 CN orange
EMI29.1


<tb> D <SEP> A
<tb> 2-Bromo-4- NH2 nitrophenyl 4-phenylazo- NH2 phenyl 4-chloro-2- NH2 cyanophenyl 6-nitrobenz- NH2 thiazolyl-2 4-ethoxy- NH2 carbonylphenyl 2-methyl4- NH2 nitrophenyl 4- [4 ' -Nitro- NH2 phenyl-] azophenyl 2,6-dichloro4- äthylsulfonyl- NH2 phenyl 3-phenyl-1,2,4- NH2 thiadiazolyl 4-diphenyl NH2 5-chloroindazolyl-3 NH2 5-acetyl-3-nitrothiophenyl-2 NHC2H4N (CH3) 2 5-methylsulfohylthiazolyl-2 3-phenoxysulfonylphenyl quinolinyl-8 4-butylaminocarbonyl
EMI29.2
  
EMI30.1


<tb> B <SEP> 1 <SEP> C <SEP> | <SEP> E <SEP> | <SEP> hue
<tb> NH2 <SEP> NHC3H6N (CH3) 2 <SEP> CN <SEP> orange
<tb> NH2 <SEP> NHC2H4N (C2Hs) 2 <SEP> CN <SEP> orange
<tb> NH2 <SEP> NHC6Ht2NH2 <SEP> CN <SEP> reddish
<tb> <SEP> yellow
<tb> <SEP> OCH
<tb> NH2 <SEP> n'HC <SEP> a <SEP>

   CN <SEP> scarlet
<tb> <SEP> 2 <SEP> 4
<tb> <SEP> 3
<tb> NH2 <SEP> NHC4 <SEP> 8N <<SEP> CN <SEP> golden yellow
<tb> <SEP> CC <SEP> 11
<tb> <SEP> 49
<tb> NH2 <SEP> NHC24N <SEP> CN <SEP> orange
<tb> NH2 <SEP> NHC2H4N <9 <SEP> CN <SEP> orange
<tb> NH2 <SEP> NHC3H6N <SEP> X <SEP> CN <SEP> orange
<tb> <SEP> 3 <SEP> u <SEP>
<tb> NH2 <SEP> N11O <SEP> 11 <SEP> N <SEP> 4NO <SEP> CN <SEP> orange
<tb> <SEP> 2 <SEP> 4 <SEP> \ W
<tb> NH2 <SEP> NEC, H, <SEP> N <SEP> H <SEP> NCB,

   <SEP> CN <SEP> golden yellow
<tb> <SEP> 4 <SEP> Lf <SEP> 3
<tb> <SEP> NH2 <SEP> NHC6H4CH2N (CH3) 2 (m) <SEP> CN <SEP> yellow
<tb> <SEP> NH <SEP> NHC6H4OC2H4N (C2H5) 2 (p)
<tb> <SEP> 2 <SEP> CN <SEP> orange
<tb> <SEP> N (CH3) 2 <SEP> N (CH3) 2 <SEP> CN <SEP> ruby
<tb> <SEP> NHCH (CH3) 2 <SEP> NHCH (CH3) 2 <SEP> CN <SEP> red
<tb> <SEP> CN <SEP> yellow
<tb> <SEP> NHC2H5 <SEP> NHC2Hs
<tb> <SEP> CN <SEP> orange
<tb> <SEP> NHCH3 <SEP> NHCH3
<tb> <SEP> NHC2H4N (C2H5) 2 <SEP> NHC2H4N (C2H5) 2 <SEP> CN <SEP> golden yellow
<tb>
EMI31.1


<tb> D <SEP> A
<tb> 2-Ethyl-5- NH2 nitrophenyl 2-chloro4- NH2 nitrophenyl 2-ethoxycarbonyl- NH2 4-nitrophenyl 4-w-dimethylamino-NH2 acetylphenyl
EMI32.1

 B <SEP> C <SEP> E <SEP> color tone
<tb> NHC3H6N (CH3) 2 NHC6Hs CN yellow
NH2 OC2H4N (CH3) 2 CN yellow
NH2 SC2H4N (C2Hs) 2 CN yellow
NH2

   NHC3H6N (CH3) 2 CN golden yellow example 4
3.83 parts of the dye described in Example 3 are dissolved in 150 parts of hot chlorobenzene. 1.9 parts of dimethyl sulfate, dissolved in 10 parts of chlorobenzene, are added dropwise and the reaction mixture is stirred at 95-100 for 3 hours. After cooling, the suspension is filtered off. The filter residue is dissolved in hot water and, after filtering the solution from the filtrate, salted out with sodium chloride and zinc chloride. The unusual one
Dye of the formula
EMI32.2
 is filtered off and dried. It dyes polyacrylonitrile fibers in red-yellow shades with excellent fastness properties.

  In an analogous manner, further dyes are obtained by alkylating the dyes of the formula designated below
EMI32.3
 with the alkylating agents indicated in the penultimate column of the table.



  Table III
EMI33.1


<tb> <SEP> D <SEP> i <SEP> A <SEP> X
<tb> D <SEP> A
<tb> <SEP> (o2a5) <SEP> 2N0H20O · <SEP> NH2
<tb> <SEP> C2H4NHC <SEP> · <SEP> WHCe <SEP> NH2
<tb> <SEP> N02 <SEP> N-11O <SEP> 2 <SEP> NH2
<tb> <SEP> yL02H4N.110 <SEP> nI \> <SEP> N11oH2ĸjl
<tb> <SEP> N <SEP> | i <SEP> NH2
<tb> <SEP> \ <SEP> s
<tb> <SEP> TN <SEP> NH2
<tb> <SEP> H
<tb> <SEP> C> C01-HCL- <SEP> NH2
<tb> <SEP> (<SEP> CH <SEP>) <SEP> No <SEP> HCç <SEP> NH2
<tb> <SEP> OH
<tb> <SEP> NH2
<tb> <SEP> 1N <SEP> N-CH
<tb> <SEP> 3
<tb> <SEP> N (CH3) 2
<tb> <SEP> N <SEP> SH
<tb> Table III
EMI34.1


<tb> <SEP> alkylation <SEP> B <SEP> C <SEP> E <SEP> color
<tb> medium
<tb> NH2 NHCH3 CN C6HsCH2CI golden yellow NH2 NHC6Hs CN C7H7SO3CH3 golden yellow NH2 NHCH2C6H5 CN C4H9Br golden yellow NHC2H5 NHC2Hs CN <RTI

    ID = 34.4> C2Hsl reddish orange NH2 N (CH3) 2 CN (CH3) 2SO4 golden yellow NH2 OC6H13 CN (CH3) 2CHBr yellow NH2 OC6H4OCH3 (p) CN (C2H5) 2SO4 yellow NH2 piperidino CN (CH3) 2SO4 yellow NH2 NHC6H CN (CH3) 2SO4 yellow N (CH3) 2 N (CH3) 2 CN (CH3) 2SO4 yellow
EMI35.1


<tb> <SEP> D <SEP> A
<tb> <SEP> I
<tb> N = N <SEP> NIl2
<tb> CU = Cw
<tb> 2,6-dichloro 4
<tb> nitrophenyl
<tb> 4-Phenylazo-2- <SEP> NfiC <SEP> H0 <SEP> HN
<tb> nitrophenyl <SEP> 2 <SEP> 4
<tb> <SEP> 2,5-dichloro4
<tb> <SEP> dimethylamino
<tb> <SEP> sulfonylphenyl <SEP> NH2
<tb> <SEP> 5-chloro-2- <SEP> RTHC <SEP> 3I-I / 1 <SEP> OC
<tb> <SEP> phenoxyphenyl <SEP> NEC <SEP> 2 <SEP> E4 <SEP> <SEP> C <SEP> 0ts,>
<tb> Dyes with similarly good properties are obtained if the dyes listed in Table 2 are quaternized with one of the following quaternizing agents:

  Dimethyl sulfate, diethyl sulfate, ethyl iodide, butyl bromide, benzyl chloride, 2-chloroethanol, 2-chloropropionic acid ethyl ester, 2-bromopropionic acid amide, p-toluenesulfonic acid methyl ester and benzene sulfonic acid ethyl ester.
EMI36.1





  l <SEP> - <SEP> F
<tb> l <SEP> 1 <SEP> 1: <SEP> t <SEP> medium <SEP> I; <SEP> hue
<tb> <SEP> NH2 <SEP> OC6H5 <SEP> CN <SEP> (CH3) 2SO4 <SEP> yellow
<tb> <SEP> NH2 <SEP> 1 \ J110 <SEP> 21140 <SEP> CN <SEP> (CH3) 2SO4 <SEP> orange
<tb> <SEP> NHC2Hs <SEP> NHC2H5 <SEP> CN <SEP> (C2Hs) 2SO4 <SEP> red
<tb> <SEP> NHC <SEP> 2E'4 <SEP> 6F <SEP> 0011 <SEP> 3 (p)
<tb> <SEP> NH2 <SEP> Cv <SEP> 3 <SEP> CN <SEP> C7H7S03CH3 <SEP> orange
<tb> <SEP> 3
<tb> <SEP> N (CH3) 2 <SEP> N (CH3) 2
<tb> <SEP> CN <SEP> C7H7SO3C2Hs <SEP> yellow
<tb> example 5
1.5 parts of sodium nitrite are sprinkled into 18 parts of concentrated sulfuric acid at 0-10.

  The mixture is heated to 65 "until everything has dissolved, then cooled to 0 and 20 parts by volume of a mixture of glacial acetic acid and propionic acid in a ratio of 4: 1 are added dropwise. A solution of 2 parts 2- Aminothiazole in 20 parts by volume of a mixture of glacial acetic acid and propionic acid (4: 1) was added dropwise and the reaction mixture during 3
Stirring is continued for hours at 0-5 ". 1.5 parts of urea are added in portions to this diazo solution. The diazo solution obtained in this way is added to a solution of 3.54 parts of 2-ethylamino-3-cyano-4,6-diaminopyridine in 20 parts of alcohol The mixture is stirred for a further 10 hours and adjusted to pH 8 with sodium hydroxide solution.

  The precipitated dye is filtered off, washed with water and dried.



   2.88 parts of the dye obtained above are dissolved in 150 parts of hot nitrobenzene. 1.9 parts of dimethyl sulfate, dissolved in 10 parts of nitrobenzene, are added dropwise and the reaction mixture is stirred for a further 3 hours at 95-100. After cooling, the suspension is filtered off.



   The filter residue is dissolved in hot water and, after filtering the solution from the filtrate, salted out with sodium chloride and zinc chloride.



  The unusual dye of the formula
EMI36.2
 is filtered off and dried. It dyes polyacrylonitrile fibers 60 in brilliant orange shades with excellent fastness properties. In an analogous manner, further quaternized dyes are obtained by alkylating the dyes of the formula given below
EMI36.3
 with the alkylating agents specified in the penultimate column. Table IV
EMI37.1


<tb> D <SEP> A
<tb> Benzthiazol-2 NH2 1, 3,4-thia-NH2 diazolyl-2 1,2,4-thia-NH2 diazolyl-5 pyridine-3 NH2 4- (6'-methyl-2'-NH benzthiazolyl) phenyl 3-methyl-1,2-NH2 isothiazolyl-5
1,2,4-triazolyl-3 NH2 Benz-2,1-iso- NH2 thiazolyl-3 thiazolyl-2 NH2 6-methoxybenz- NH2 thiazolyl-2 5-methyl-1,3,4- NH2 thiazolyl-2 2- Methoxy- NH2 pyridyl4 i-phenyl- NH2 pyrazolyl-5 4-methyl- NH2 thiazolyl-2 2-methylquinolinyl4 3-methylpyrazolyl-5 NH2 3-methylthio- <RTI

    ID = 37.2> NIl 1,2,4-thiadia-2 zolyl-5 Table IV
EMI38.1


<tb> <SEP> alkylation <SEP> B <SEP> C <SEP> E <SEP> color
<tb> medium
<tb> NH2 NHCH3 CN (C2H5) 2SO4 scarlet NH2 NHC2H4C5H5 CN C7H7SO3CH3 orange NH2 OC6H3 CN C6H5SO3CH3 yellow NH2 SCH3 CN C4H9Br yellow
NH2 NHC2H4OH CN BrCH2CONH2 orange
NH2 NHC4H9 CN (CH3) 2SO4 orange
NH2 NHcyclohexyl CN (CH3) 2SO4 yellow
NH2 piperidino CN (CH3) 2SO4 red
NH2 N (CH3) 2 CN (CH3) SO4 orange NH2 OCH3 CN C6H5SO3C2H5 orange
NH2 SC6Hs CN (C2H5) 2SO4 yellow
NH2 N (C2H5) 2 CN (CH3) 2SO4 scarlet
NH2 NHC6H5 CN ClC2H4OH yellow
NH2 NHC6H5 CONH2 ClCH2CH2COOC2H5 orange
NHCH (CH3) 2 NHCH (CH3) 2 CN (CH3) 2SO4 scarlet
NH2 NHC6H13 CN (CH3) 2SO4 yellow
NH2 OC6H13 CN (C2H5) 2SO4 yellow coloring instructions
1 part of the dye obtained in Example 1 is dissolved in 2000 parts of water with the addition of 4 parts of 40% acetic acid,

   1 part of crystallized sodium acetate and 10 parts of anhydrous sodium sulfate dissolved. 100 parts of dried polyacrylonitrile staple fiber yarn are placed in this dyebath at 60, the temperature is increased to 100 "within half an hour and the dye is dyed for one hour at boiling temperature. The dyeing is then rinsed thoroughly and dried.



   PATENT CLAIM I
Process for the preparation of basic azo dyes which are free from acidic water-solubilizing groups and of the general formula
DN = NA, where D is the residue of an aromatic or heterocyclic diazo component and A is the residue of a 2,4-diamino-pyridine bonded in the 3-position and an organic bond in the 6-position via a nitrogen, oxygen or sulfur atom Bears radical, and in which this radical and / or D contains a basic group with a quaternizable or quaternized nitrogen atom, characterized in that a diazotized amine of the formula D-NH2 is coupled to a pyridine of the formula HA.



   SUBCLAIMS
1. Process according to claim I for the preparation of basic azo dyes of the formula
EMI39.1
 where D 'is the radical of an aromatic or heterocyclic diazo component and Rl, R2, R3, R4 and R5 each represent hydrogen or an aryl, aralkyl, cycloalkyl radical or an aliphatic radical, where R, with R2 and R3 with R4 represent the amine nitrogen containing ring and Q each is an optionally quaternized amino, ilydrazino, etherified hydroxylamino or pyridine group bonded directly or via a bridge, and p and q each denote 1 or 2, where, when p and q are both 1, D ' is a heterocycle having a quaternized ring nitrogen atom, and wherein Z is an oxygen or sulfur atom or an imino group of the formula
EMI39.2
 is

   wherein R6 is hydrogen, aryl, aralkyl, cycloalkyl or an aliphatic radical which can be linked to R5 or to Q, characterized in that a diazotized amino compound of the formula (Qss, D '-NR2 q -1 with a Coupling component of the formula
EMI39.3
 implements.



   2. The method according to claim I and dependent claim 1, characterized in that amines of the benzene series or amines of nitrogen-containing heterocycles are used as the diazo component.



   3. The method according to dependent claim 1, characterized in that one starts from coupling components of the formula given, in which Rt, R2, R3 and R4 are each hydrogen.



   4. The method according to claim I and dependent claim 1, characterized in that one starts from coupling components of the formula given in dependent claim 1, in which R5 and R6 are hydrogen, radicals of the benzene series, benzyl, cycloalkyl or alkyl radicals with at most 8 carbon atoms which are optionally interrupted by oxygen, nitrogen or sulfur atoms and which can be linked to one another directly or via an oxygen, sulfur or nitrogen atom to form a ring containing the amine nitrogen.

 

   5. The method according to claim I and dependent claim 1 for the preparation of azo dyes of the formula given, in which the basic group Q is a group of the formula
EMI39.4
 is, where R'1 and R'2 are hydrogen or an alkyl, aralkyl or cycloalkyl radical, R'3 is hydrogen or an alkyl, aralkyl, cycloalkyl or alkoxy radical or an amino group, and where N with R'1 and / or R'2 and / or R'3 can form part of a heterocyclic ring, X is an anion and n is 1 or 2, characterized in that diazotized amines and coupling components are used, at least one component containing a radical Q of the above formula.



   6. The method according to claim I and dependent claim 1 for the preparation of azo dyes, in which the basic group Q is a group of the formula

** WARNING ** End of DESC field could overlap beginning of CLMS **.



   

 

Claims (1)

** WARNING ** Beginning of CLMS field could overlap end of DESC **. Staining instructions 1 part of the dye obtained in Example 1 is dissolved in 2000 parts of water with the addition of 4 parts of 40% strength acetic acid, 1 part of crystallized sodium acetate and 10 parts of anhydrous sodium sulfate. 100 parts of dried polyacrylonitrile staple fiber yarn are placed in this dyebath at 60, the temperature is increased to 100 "within half an hour and the dye is dyed for one hour at boiling temperature. The dyeing is then rinsed thoroughly and dried. PATENT CLAIM I Process for the preparation of basic azo dyes which are free from acidic water-solubilizing groups and of the general formula DN = NA, where D is the residue of an aromatic or heterocyclic diazo component and A is the residue of a 2,4-diamino-pyridine bonded in the 3-position and an organic bond in the 6-position via a nitrogen, oxygen or sulfur atom Bears radical, and in which this radical and / or D contains a basic group with a quaternizable or quaternized nitrogen atom, characterized in that a diazotized amine of the formula D-NH2 is coupled to a pyridine of the formula HA. SUBCLAIMS 1. Process according to claim I for the preparation of basic azo dyes of the formula EMI39.1 where D 'is the radical of an aromatic or heterocyclic diazo component and Rl, R2, R3, R4 and R5 each represent hydrogen or an aryl, aralkyl, cycloalkyl radical or an aliphatic radical, where R, with R2 and R3 with R4 represent the amine nitrogen containing ring and Q each is an optionally quaternized amino, ilydrazino, etherified hydroxylamino or pyridine group bonded directly or via a bridge, and p and q each denote 1 or 2, where, when p and q are both 1, D ' is a heterocycle having a quaternized ring nitrogen atom, and wherein Z is an oxygen or sulfur atom or an imino group of the formula EMI39.2 is wherein R6 is hydrogen, aryl, aralkyl, cycloalkyl or an aliphatic radical which can be linked to R5 or to Q, characterized in that a diazotized amino compound of the formula (Qss, D '-NR2 q -1 with a Coupling component of the formula EMI39.3 implements. 2. The method according to claim I and dependent claim 1, characterized in that amines of the benzene series or amines of nitrogen-containing heterocycles are used as the diazo component. 3. The method according to dependent claim 1, characterized in that one starts from coupling components of the formula given, in which Rt, R2, R3 and R4 are each hydrogen. 4. The method according to claim I and dependent claim 1, characterized in that one starts from coupling components of the formula given in dependent claim 1, in which R5 and R6 are hydrogen, radicals of the benzene series, benzyl, cycloalkyl or alkyl radicals with at most 8 carbon atoms which are optionally interrupted by oxygen, nitrogen or sulfur atoms and which can be linked to one another directly or via an oxygen, sulfur or nitrogen atom to form a ring containing the amine nitrogen. 5. The method according to claim I and dependent claim 1 for the preparation of azo dyes of the formula given, in which the basic group Q is a group of the formula EMI39.4 is, where R'1 and R'2 are hydrogen or an alkyl, aralkyl or cycloalkyl radical, R'3 is hydrogen or an alkyl, aralkyl, cycloalkyl or alkoxy radical or an amino group, and where N with R'1 and / or R'2 and / or R'3 can form part of a heterocyclic ring, X is an anion and n is 1 or 2, characterized in that diazotized amines and coupling components are used, at least one component containing a radical Q of the above formula. 6. The method according to claim I and dependent claim 1 for the preparation of azo dyes, in which the basic group Q is a group of the formula EMI40.1 which is bonded to the dye molecule directly or via a carbonyloxy or carbonylamino group and in which R'4 is an alkyl, cycloalkyl or aralkyl radical, X is an anion and n is 1 or 2, characterized in that one of diazotized amines and coupling components starts, where at least one component contains a radical Q of the formula given. 7. The method according to claim I and dependent claim 1, characterized in that one of coupling components of the formula EMI40.2 where Z 'is a piperidine, morpholine, pyrrolidine or piperazine radical bonded via a ring nitrogen atom, wherein, if the diazo component does not contain any basic groups, Z' must be a piperazine radical. 8. A process for the preparation of azo dyes according to claim I and dependent claim 1, wherein D or D 'is a heterocyclic radical of the formula EMI40.3 where R'5 is an alkyl, cycloalkyl or aralkyl radical and X is an anion, characterized in that one of diazotized amines of the formula EMI40.4 where R'5 and X- have the meaning given, starts. 9. The method according to subclaims 5, 6 and 8, characterized in that one starts from compounds in which R '>, R'2, R'3. R'4 and R'5 denote alkyl radicals having 1 to 4 carbon atoms, preferably methyl radicals. 10. The method according to claim I and dependent claim 1, characterized in that one starts with diazotized amines of the thiazole, benzthiazole, thiadiazole, isothiazole or benzisothiazole series with an optionally quaternary ring nitrogen atom. 11. The method according to claim I and dependent claim 1, characterized in that one starts from diazotized amines of the benzene series, which can carry one or more of the following substituents: halogen atoms, in particular chlorine or bromine, nitro, cyano, thiocyano, trifluoromethyl , Alkyl, alkoxy, aryloxy, alkyl mercapto, aryl mercapto, alkoxycarbonyl, aryloxycarbonyl, aryloxycarbonyloxy, alkoxysulfonyl, aminosulfonyloxy, sulfonamide, carboxamide, acyl and acylamino radicals and phenylazo groups with, where the Nitro, alkyl and alkoxy groups can be substituted. PATENT CLAIM 11 Use of the dyes obtained by the process according to claim I which contain a basic group with a quaternizable nitrogen atom for the preparation of dyes with quaternized cationic groups, characterized in that they are quaternized with an alkylating or aralkylating agent. SUBCLAIMS 12. Use according to claim II, characterized in that an azo dye of the formula EMI40.5 where D ', R1, R2, R3, R4, R5 and Z have the meanings given and at least 1 radical Q or D' contain a non-quaternized nitrogen atom, quaternized by treatment with alkylating agents. 13. Use according to patent claim 11, characterized in that the alkylating or aralkylating agent used is low molecular weight sulfuric acid esters, alkyl halides, aralkyl halides, corresponding esters of low molecular weight alkanesulfonic acids or corresponding esters of benzenesulfonic acids.