DE2516687A1 - Basic azo dyes free from sulphonic acid gas - for dyeing or printing natural and synthetic fibre textiles - Google Patents

Abstract

The novel basic azo dyes free from sulphonic acid gps. are of formula (I): D(+)-N=N-A-NR-CH2-C(Z)=CH2 X(-) (I) (where D(+) is the radical of an aromatic or heterocyclic diazotisation component contg. a quaternary N atom. A is an aromatic radical or with -NR- forms a heterocyclic radical, R is H opt. substd. lower alkyl, or aralkyl or cycloalkyl, X(-) is an anion, Z is H, halogen, or lower alkyl). Used for dyeing/printing of natural or synthetic fibre textiles. (I) may be in powder or liq. form.

Description

Basic azo dyes, process for their preparation and their use Addition to patent application P 24 61 432.2 (HOE 74 / P 396) The present invention relates to new basic azo dyes, processes for their preparation and their use.

In a continuation of the inventive concept of patent application P 24 61 432.2, new dyes were found which are free from sulfonic acid groups and have the general formula (I) in which the radical of an aromatic or heterocyclic diazo component containing a quaternary nitrogen atom, A is an aromatic radical or, together with the formula member - (NR) - a heterocyclic radical, R is hydrogen, an optionally substituted lower alkyl radical, an aralkyl or cycloalkyl radical and mean an anion.

The new dyes can be obtained in such a way that a. the diazonium compound of a quaternary amine of the formula (II) wherein D (+) and X (-) have the meaning given above, with a coupling component of the formula (III) wherein A and R have the meaning given above, coupling, or that b. an azo dye of the formula (IV) where D is the remainder of a diazo component and A and R are as defined above, treated with alkylating agents.

The quaternary amines of the formula used for procedure a) (II) can be obtained by treating suitable aromatic or heterocyclic amines with alkylating agents, for example Alkyl halides, aralkyl halides, Haloacetamides, ß-halopropionitriles, halohydrins, alkylene oxides, acrylic sureamide, Alkyl esters of sulfuric acid or organic sulfonic acids can be obtained.

Suitable quaternary amines of the formula (II) are, for example, those of the formula (V) where R3 is an optionally substituted alkyl or aralkyl radical, Y is a divalent atom or a divalent group required to complete a 5- or 6-membered ring, R4 and R5 are identical or different and each is hydrogen or an alkyl radical or R4 and R5 together represent substituents which add to a fused aromatic ring, n is the number 0 or 1 and X () is an anion. Such quaternary compounds can be derived from amines of the pyridine, pyrazole, imidazole, triazole, tetrazole, oxazole, thiazole, selenazole, oxdiazole, thiadiazole, pyrimidi.n or triazine series, and also of the quinoline, Derive indazole, benzimidazole, benzisothiazole, arylguanazole, naphtimidazole, benzoxazole, naphthoxazole, benzthiazole or naphthothiazole series.

Quaternary amines of the formulas (VI) and (VII) are also suitable where: 'n R6 is an optionally substituted alkyl or aralkyl radical, K is a 5- or 6-membered heterocyclic ring, for example a pyridinium, triazolium, pyrazolium or thiazolium radical and an anion and the benzene radical a further substituents, such as halogen atoms, alkoxy -, aryloxy, alkyl, trifluoromethyl, nitro, alkylsulfone, arylsulfone, cyano or acyl groups.

Finally, quaternary amines of the formulas (VIII) and (IX) are suitable wherein R7, R8 and R optionally substituted lower alkyl groups, Alk a straight-chain or branched lower alkylene radical, B a -0-, -S-, -CO-, -SO2, -CONII-, -OCO- or -SO4NH- group, m 0 or 1 and X is an anion and the benzene radical a can contain further substituents, for example halogen atoms, alkoxy, hryloxy, alkyl, trifluoromethyl, nitro, alkylsulfone, arylsulfone, cyano or acyl groups.

The azo component of the formula (III) is secondary or tertiary Amines of the benzene or naphthalene series into consideration. The radical R here stands for hydrogen or a methyl, ethyl, propyl or butyl radical, the other substituents, such as Halogen atoms, pydroxy, cyano, acyloxy, carbalkoxy, carbamoyl, dialkylamine, Alkoxy, trifluoromethyl, acyl, carbamic acid ester, alkylsulfonic, sulfamoyl or May contain aryloxy groups. R can also be a cycloalkyl, for example a Cyclohexylret, an aralkyl, for example a benzyl or phenethyne st, or an aryl radical, for example an optionally substituted phenyl radical, be.

Together with the remainder of the formula - (NR) - A can also be a 1,6- (t, 2,3,4-tetrahydro) -quinolinylen- or -7,8-benzoquinolynylene radical, a 1,6-benzomorpholynylene radical or a 1,3-indolynylene radical be.

The remainder can also contain substituents, such as, for example Halogen atoms, alkyl, alkoxy, carbalkoxy, alkylsulfonyl, carbamoyl, sulfamyl, Amino, trifluoromethyl, acyl or acylamino groups.

The diazotization of the amines of the formula (II) can be carried out by known methods for example by means of alkyl nitrite and an inorganic acid, for example Hydrochloric acid, sulfuric acid or phosphoric acid, or by means of nitrosylsulfuric acid take place.

The coupling with the azo components of the formula (III) can likewise in a manner known per se, e.g. in a neutral to acidic medium, if necessary in the presence of sodium acetate or others knowna the coupling rate influencing buffer substances or catalysts, such as dimethylformamide, Pyridine or its salts.

The for procedure b. used starting dyes of Formula IV can be prepared by coupling the diazotized amines of the formula D-NH2 with the coupling components or by condensation of the amines with the corresponding p-nitroso compounds of Formula (IIT) can be obtained.

The procedure b. is especially for amines of the formula (.X) in which n, Y, R4 and RF have the meaning given for formula (V), are suitable. As amines of the formula (X) are in particular those of the pyridine, pyrazole, imidazole, triazole, tetrazole, oxazole, thiazole, selenazole, oxdiazole> thiadiazole, pyrimidine or triazine series, and also the quinoline series , Indazole, benzimidazole, benzisothiazole, arylguanazole, naphthimidazole, benzoxazole, benzthiazole or naphthothiazole series.

Alkyl halides, aralkyl halides, Halogenacetamides, ß-halopropionitriles, halohydrins, alkylene oxides, acrylic acid amide, Alkyl esters of sulfuric acid or alkyl esters of organic sulfonic acids into consideration.

Suitable alkylating agents are, for example, methyl chloride, methyl bromide or iodide, ethyl bromide or iodide, propyl bromide or iodide, benzyl chloride, chloroacetamide, ß-chloropropionitrile, ethylene chlorohydrin, dimethyl sulfate, benzene sulfonic acid methyl ester, p-Toluenesulfonic acid methyl, ethyl, propyl or butyl ester. The alkylation advantageously takes place in an inert organic solvent, for example in a hydrocarbon, chlorinated hydrocarbon or nitro hydrocarbon, such as benzene, toluene, xylene, tetrachloroethane, chloroform, carbon tetrachloride, mono- or Dichlorobenzene or nitrobenzene, in an acid amide or acid anhydride, such as dimethylformamide, N-methylacetamide or acetic anhydride, in dimethyl sulfoxide or in a ketone, such as acetone or methyl ethyl ketone. Instead of an organic solvent can an excess of the alkylating agent can also be used.

Depending on the number of alkylatable nitrogen atoms in the starting dye one or more alkyl groups are introduced into the dye molecule. The alkylation is used at increased temperature, if necessary with the addition of acid-binding agents, such as magnesium oxide, magnesium carbonate, soda, calcium carbonate or sodium bicarbonate and, if necessary, under pressure. The most favorable conditions in each case can easily be determined by a preliminary test.

If appropriate, the alkylation can also be carried out in water.

Some of the new dyes can be obtained by modifying the abovementioned processes by using a hydrazone or benzenesulfonylhydrazone of the general formula in which Y, R3> R4, R5 and n have the meaning given for formula (V) and W is a hydrogen atom or a benzenesulfonyl radical, couples with an azo component of the formula (III) under the action of oxidizing agents.

The new dyes preferably contain the remainder as anion X () a strong acid, for example sulfuric acid or its half-ester, a Arylsulfonic acid or a hydrohalic acid. These were introduced in accordance with the procedure Anions can also be replaced by anions of other acids, for example phosphoric acid, Acetic acid, oxalic acid, lactic acid or tartaric acid can be replaced. The dyes can also be obtained in the form of their double salts with zinc or cadmium halides will.

Among the new dyes of this invention are the compounds of the general formula in which Y represents a remainder, sr is together with the remainder added to a thiazolium, benzthiazolium, pyrazolium, indazolium, triazolium, guanazolium or quinolinium radical, A denotes the phenylene radical which is substituted by chlorine, methyl, ethyl, methoxy, thoxy, carboxylic acid alkyl ester groups from 2 to 5 C atoms or acetylamino groups can be substituted, R is hydrogen, an alkyl radical of 1 to 4 carbon atoms, ß-cyano, ß-hydroxyethyl, ß-chloroethyl, ß-chloro-γ-hydroxypropyl, ß-acetoxyethyl or represents the benzyl radical, R3 represents the methyl or ethyl radical and an anion.

In particular, the dyes of the formula (XiiI) should be emphasized in which E represents a radical which, together with the radical R3 and the benzene nucleus is added to an imidazolirium, pyrazolinium or triazolyl radical, T1 stands for hydrogen or chlorine and A, R, R3 and X () have the meanings given for formula (XII), furthermore the dyes of the formula in which B denotes a single bond or a - (CH2) k-CO group, in which k denotes 1, 2 or 3, in particular 2 or 3, T2 denotes hydrogen, chlorine, bromine or the trifluoromethyl group and A and R and X (-) have the meanings given for formula (XIII).

The novel dyes of the present invention are useful for dyeing or printing on tannin cellulose fibers, silk, leather or fully synthetic Fibers such as acetate silk, polyamide fibers or acid modified polyamide or polyester fibers, but especially for dyeing, printing and mass dyeing (pin dyeing) of polyacrylonitrile or fibers containing polyvinylidenecyanide.

The dyeings available on these fibers are usually very strong and generally have good light and wet fastness properties, for example good washing, Fulling, over-dyeing, carbonizing, chlorine and welding fastness, as well as good decatur, Damping, ironing, rubbing and solvent fastness properties. The dyes are generally largely insensitive to a change in the pH of the dyebath and can therefore be used in both weakly acidic and strongly acidic baths.

They are also at temperatures above 1000C, as they are in high-temperature dyeing applied consistently. Wool is made by the dyes under normal dyeing conditions fully reserved.

The dyeing is generally carried out in an aqueous medium at the boiling point or in closed vessels at temperatures above 100 ° C. and under pressure. The dyes can also be used from organic solvents.

To prepare the aqueous dye baths and printing pastes you can use the Dyes in the form of powders, which optionally contain adjusting agents, such as, for example Use inorganic salts, dextrin and possibly other additives. However, it is advantageous to use concentrated aqueous solutions which are easier to handle Solutions of the dyes containing about 20 to 60% dye, one or more lower aliphatic Carboxylic acids such as formic acid, acetic acid, propionic acid or lactic acid, as well optionally further additives, such as water-soluble polyhydric alcohols, their ethers or esters, polyethers, aliphatic carboxamides, lactams, lactones, nitriles, Dimethyl sulfoxide, diacetone alcohol, dioxane, tetrahydrofuran or urea as well Contain water.

To prepare the dyebaths that only use organic solvents, for example Contain chlorinated hydrocarbons, it is advantageous to use concentrated solutions, which use the dye as a free base or as a salt of a monobasic organic acid, Chlorinated hydrocarbons, organic acids, or polar organic solvents contain.

The new dyes form with anionic precipitants such as Clay, tannin or heteropolyacids, real pigments, - those used in paper printing can be.

The following examples serve to illustrate the invention.

Example 1 45.4 parts by weight of 5-chloro-7-amino-1-methylbenzimidazole are mixed with 7.5 parts by weight of magnesium oxide in 125 parts by volume of water and at 50-600C with stirring for approx.

38.8 parts by volume of dimethyl sulfate are added for 1 hour. One stirs about 2 hours at 50-600G (pH 7.5-8.5), gives 2.5 parts by weight of kieselguhr and 2.5 Parts by weight of activated charcoal are added, suctioned off and washed with 120 parts by volume of hot water after.

The filtrate is mixed with 120 parts by volume of 30% hydrochloric acid and cooled to 000. After adding 75 parts by weight of ice, the rapid addition of 52 parts by volume of 5N sodium nitrite solution is diazotized. After a slight excess of nitrite has been destroyed with a little amidosulfonic acid, the yellow-brown, clear diazo solution is left in a mixture of 47.25 parts by weight of 3-methyl-N-ethyl-N [2-methyl-propenyl- (3)] aniline in 500 ml Pour in parts by volume of water and 50 parts by volume of 5N hydrochloric acid. After stirring for 2 hours, the mixture is diluted with 750 parts by volume of water and the dye is filled with 125 parts by weight of sodium chloride and 25 parts by volume of approx. 64% strength zinc chloride solution. The precipitated dye is filtered off with suction, washed with 5% sodium chloride solution and dried at 50.degree. 75 parts by weight of dye of the formula are obtained -which are red in water and aliphatic carboxylic acids such as acetic or formic acid, optionally also in mixtures. These acids dissolve with other solvents such as alcohols, glycol-ono-ethers, ketones, carboxamides or carboxylic acid esters, and dyes polyacrylnitrite fibers from weakly acidic baths in light- and wet-fast emergency tones.

The dye can also be removed from diazotized by cupping 1-methyl-5-chloro-7-aminobenzimidazole with 3-methyl-N-ethyl-N- [2-methyl-propenyl- (32-aniline and then produce quaternization of the azo dye thus obtained.

Example 2 18 parts by weight of N-methyl-benzothiazolen-2-hydrazone and 32.2 parts by weight of N-methyl-N- [2-methyl-propenyl- (3)] - aniline are converted into 1200 parts by volume Water and 320 parts by volume of 5N hydrochloric acid entered. One then drips in at 40 ° C Solution of 80 parts by weight of anhydrous ferric chloride in 400 parts by volume Water is added and the mixture is subsequently stirred at 40 ° C. until the reaction has ended (approx. 6 hours). The resulting solution is then diluted with 4000 parts by volume of water is clarified at 60-70 ° C after adding activated carbon and kieselguhr. The filtrate will with 200 parts by weight of table salt and 50 parts by volume of approx. 64% zinc chloride solution offset. The dyestuff which separates out in crystalline form is filtered off with suction with 5% strength Washed saline solution and then dried at 60.

30 parts by weight of dye of the formula are obtained which are blue in water as well as aliphatic carboxylic acids, such as acetic or formic acid, optionally also in mixtures of these acids with other solvents, such as alcohols, glycol monoethers, ketones, carboxamides or carboxylic acid esters, these acids with other solvents, such as alcohol-resistant Shades of blue.

The coupling component used is by heating for several hours under pressure or without pressure of equimolar amounts of N-methyl-ani lin and 3-chloro -2 -methy 1-propen- (1) in the presence of acid-binding agents such as tertiary aliphatic or aromatic amines, magnesium oxide, magnesium carbonate, soda, sodium bicarbonate, Calcium oxide or calcium carbonate. If necessary, the implementation can also in water or other suitable solvents, such as toluene, chlorobenzene, Xylene, dimethylformamide, dimethyl sulfoxide, glycol, glycol ethers or esters will.

Example 3 11 parts by weight of 2-amino-thiazole are in 30 parts by volume 95 of the above sulfuric acid dissolved. With 0-SOG, it is 42.3% strength with 30 parts by weight Diazotized nitrosylsulfuric acid and stirred for 30 minutes with excess nitrite. The diazotization mixture is poured onto 250 parts by volume of ice water and coated with activated charcoal and kieselguhr clarified. Then the diazo solution is 16 parts by weight N-N-ethyl-N- [2-methyl-propenyl (3) -aniline is added, the coupling starting immediately. Stirring is continued for 3 hours until the coupling reaction has ended, with 2000 parts by volume Diluted water and adjusted to pH 6-7 with sodium hydroxide solution.

The unusual dye of the formula is isolated. The moist dye is dehydrated azeotropically with 500 parts by volume of chlorobenzene and the resulting solution is clarified with activated carbon and kieselguhr. A catalytic amount of magnesium oxide is added to the filtrate. At 40 ° C., a solution of 10 parts by volume of dimethyl sulfate in 25 parts by volume of chlorobenzene is then instilled in the course of 30 minutes, and the mixture is stirred for 1 hour.

at 40-50 ° C., slowly heated to 80 ° C. and stirred until the end of the quaternization reaction at 80-90 ° C. after approx. (6-8 hours). The reaction mixture is cooled to 25 ° C., the deposited dye is isolated and dried at 50 ° C. 25 parts by weight of dye of the formula are obtained which, if necessary, can be stimulated by dissolving it again in water. The dye dissolves with a blue-violet color in water and aliphatic carboxylic acids, such as acetic or formic acid, optionally also in mixtures of these acids with a: '- their solvents, such as alcohols, glycol monoethers, ketones, carboxamides or carboxylic acid esters, and dyes polyacrylonitrile fibers in light- and wet-fast reddish blue tones.

The quaternization of the dye can also occur in other organic Solvents such as toluene, xylene, chloroform, acetonitrile, or in an aqueous medium be performed.

Example 4 A solution containing 27 parts by weight of 4-acetaminophenacyl-trimethylammonium chloride, Contains 50 parts by volume of water and 100 parts by volume of 5N hydrochloric acid, takes 60 minutes refluxed to saponify the acetyl group. The solution obtained is cooled to OOC, diazotized at 0-5 ° C with 20 parts by volume of 5N sodium nitrite solution, 30 Stirred minutes with a remaining excess of nitrite and then the excess of nitrite withdrawn with sulfamic acid.

The diazo solution is clarified with kieselguhr and 17.5 parts by weight of N-ethyl-N - [2-methyl-propenyl (3)] -aniline are added while stirring. After stirring for 1 hour, the mixture is diluted with 150 parts by volume of water, mixed with 50 parts by weight of sodium chloride and the dye is deposited as zinc chlorine salt by dropping 20 parts by volume of 64% zinc chloride solution. After drying at 60 ° C, 40 parts by weight of dye of the formula are obtained which dyes polyacrylonitrile fibers in shades of orange with good light and wet fastness properties from a weakly acidic dyebath.

Example 5 27.7 parts by weight of 3-amino-1,2,4-triazole are used in 36 Parts by volume of water entered and after 30 minutes with 48 parts by volume of 95% Sulfuric acid is added so that the temperature does not exceed 30.degree. After cooling down the mixture is diazotized to 0 ° C. at 0-5 ° C. with 93.6 parts by weight of 41% strength nitrosylsulfuric acid. The mixture is stirred for 30 minutes with a remaining excess of nitrite and then added dropwise at 5-100C the diazotization mixture in a template of 56.7 parts by weight of 3-methyl-N-ethyl-N- [2-methylpropenyl- (3)] - aniline in 200 parts by volume of water of 000, 100 parts by volume of 5N sulfuric acid and 3 parts by weight Amidosulfonic acid. After stirring for 1 hour, 500 parts by volume of water are added diluted by 000 and part of the mineral acid with 110 parts by volume of 33% sodium hydroxide solution neutralized. Afterward.

The coupling mixture is poured into a solution of 2000 parts by volume of water and 200 parts by weight of crystalline sodium acetate and the pH is adjusted to 5-6 with sodium hydroxide solution. After several hours of stirring, the dye becomes of the formula separated from the aqueous phase.

The wet dye is used for quaternization; n 300 parts by volume Stirred water and 15 parts by weight of magnesium oxide. Rei 25 -30 ° C is then left Add 80 parts by volume of dimethyl sulfate dropwise, keeping the pH at 8-10 will. The mixture is subsequently stirred for 3 hours at 30 ° C. until the quaternization reaction has ended is what is advantageously followed with a thin layer chromatogram. The quarter mix is then adjusted to pH 3 with dilute hydrochloric acid, with 2000 parts by volume of water diluted and heated to 90 ° C until solution has occurred.

The dye solution obtained is in a mixture of 1800 parts by volume Water, 150 parts by weight of common salt and 80 parts by volume of 64% zinc chloride solution poured.

The deposited dye of the formula is isolated and optionally purified by reprecipitation. 100 parts by weight of dye are obtained which dissolve in dilute acetic and formic acid with a red color and dyes polyacrylonitrile fibers in lightfast and wetfast red tones.

Example 6 32.65 parts by weight of 4-chloro-3-nitrophenyl-trimethylammonium methyl sulfate are converted into a mixture of 125 at 90 - 95 ° C within 20 minutes Parts by volume of water, 20 parts by weight of iron powder and 0.5 parts by weight of glacial acetic acid entered, which is refluxed for 30 minutes to etch the iron.

The mixture is then stirred at 9500 for 1 hour, with 5.3 parts by weight of carcinated Sodium carbonate is added, and the mixture is filtered at 90.degree.

90 parts by volume of 5N hydrochloric acid are added to the filtrate Cooled 0 ° C, within 15 minutes with 20 parts by volume of 5N sodium nitrite solution added, stirred for 30 minutes, the excess nitrite destroyed with sulfamic acid and then the diazo solution obtained in this way is clarified with kieselguhr. The diazo solution is poured at 10-1500 into a template of 18.15 parts by weight of 2-chloro-N- [2-methyl-propenyl - (3)] - aniline in 200 parts by volume of water. After stirring for 1 hour, the dye becomes separated by adding 12 parts by volume of 64% zinc chloride solution, sucked off, washed with 5% Roch salt solution and dried at 60 ° C.

36 parts of dye of the formula are obtained dissolves in water and dilute acetic acid with a golden yellow color.

1 part by weight of dye is mixed with 2 parts by weight of 50% strength acetic acid stirred and dissolved in 5000 parts by volume of water.

Then 100 parts by weight of washed polyacrylonitrile staple fiber yarn are used at 60 ° C in the dyebath, increase the temperature slowly to 100 ° C and dye 1 hour at boiling temperature. It is then allowed to cool slowly to about 70.degree rinses and dries. A clear, reddish-tinged yellow coloration with very good results is obtained Light and wet fastness.

The table below contains further dyes according to the invention and the shades of the dyeings on polyacrylonitrile fibers.

Dye hue CH i3 - N - Ns ~ OH ~ ZnCl 89 red li CN = N N4N 2 5 2 HC - N C112-C = CH2 OH CH3 CH3 CH3 ON - N-CH 3 1 @ II 11 = 02H5 ZnCl red HN = C 'CN = N N1 OH 2- i wCH2 2 CH3 3 cH3 - - CH Ii 11 / C2H OH3S040 Red H3C-N 8 hT-N = N4N 5 3 4N \ H2 "2 OH cH2-cI = CH2 N 3 CH3 C1 = N = N-, CH3 01135040 white red H3C-NX 0+ / N-0H3 0112-C = CH2 N H3 N CH, SO, O red N = Ni I LC 011 50 red I 3 CHQ C5z3 Dye hue C1 OH3 - OH 50 Bordo -N = cH CK-SOI8f H3 (7- N () N- OH3 OH3 CtI3 ditto 43 - rJ = 02115 CH f; 0 (3 Bordo - N 4- CK, LII CIf3 C1 OC, H, ° C 5 W> C1 bluish , N - N9NH- CII2-C-CT2 red 113 CN OH '113 N10CH3 H3 -23 CH / L V7 LVVVI13 N = NN½, CH3 CH, SO, violet M¼N1 OH cEI3 0112 0113504 Cl N 'OH3 CH3 0 N = N NW02115 011350 purple CII, -C% H, 4 0113 ClI3 II -1 = N N91; 'Zn20l4 Bordo N \ cI7 ai2-Ce 0117) cII2-C1 = 01L9 (. 3 CH3 3 Dye hue N = NN - ZnOl4 Bordo ÄMN + N 'CH3 -C - CH CH3 CH3 ditto 43 z C4} 19 ZnC14C3 Bordo 'rC CH3 CH3 3 OH3 OH 1 3 ZnCL 3 HG - N; N -C 4: ~ red; sti chi Se o C - e C Ne Ns 5 2 Blue CH3 OH 3 red tinged ditto NW, CII3 blue & B1 2 OH3 I13 ditto t3 'C2H5 ZnCl,' rotschis - 4 - blue 0117 2 ) 2 2 0113 , C2I-Ig - - N = Ng T / 3 ZnC14 r or; stichiges uc - sCH2 - IC = CH2 2 CIf3 Cfl2CI2CONH2 110 -N -CII, -CONB, / jnCl4 ti2-CrI2-CONH2 HC - 5> 2 zCI12-Ct 011 ZnCl G9 blue 2 Dye hue cE13-1TS N = N o zC2H5 ZnC14e3 blue CII, -C = CS, 0113 2 CH3 ditto N 02115 ZnCl Bla ' 4th - CII -C = OH 2 0113 2 2 CH3 OH 3 lT 0 - 2 5 ZnC146 £ 3 blue N (: v N 2 5 ~~~~~ S CH3 CZ C = CII2 CH3 0H3 1 3 N 11 000) ON = N iTN3001T CH, blue 3 5 OH3 C-Ei = N 21 nlz-F- 2 2 OH3 ditto N OH3 OH SO blue -N. 34 CH2-1 -CH2 CIl3 ditto -CHZ -CN CIiQ S01 ditto 9 (CY = CH CH3S04 blue OH 3 01112 CII (OI1) 0ll2Ol X 63> - N = N e XCJI2 to ZnCld blue NM) 115020 CH-C-CIIz 011 Dye hue CH st CK, NC - N = nu CH3So463 CHSO - N = N 0H3 H5C2C3 E H2- | CH2 21 CH3 ditto v; N½02H5 4 blue Cii I OH3 11s OH I v - N = N OH3 ZnOl blue H NNN 4 3 CH CH2-C = CTI 3 4th ditto N \ OH3 CH3Sole blue C'T2-. C (CH2 GE3 OH l H3 N OH , (3 C - N = NQ = ZnOfl P3 blue 3 CM 3 CF3 t çI2 2 0113 CH 1-3 H3O OH5 OH e blue 3 C-N = 34 0 - N = NOW 2 H - 3 c1I -C = C'lf, 1H3 CH2-CI12-OEI IN / \ M112-0112-CoNH2 + ZnCl4 0 C - N = NN ZCIi2-cl {2-ccN} I2 02N S CE.IZ Cll2-C 2 blue CH3 CH3 Dye hue C1 GoldEelS """-CN ZnC1 83 4); Ü01N -> = / CH2 iCII golden yellow H30-11OH3 H2-1 = 3. 0112 2 CH3 ditto - C1I2- | CH2 ZnC149 golden yellow OH3 CH3 2 CH3 C1 H3, C-Q + «3bN = N9NH C} I2- 1- = CH2 ZnCl4 golden yellow 1 Ic 01I2 0113 0000113 CLIs 2 COOCIi Cl C1 ZnCl1 golden yellow w, ZllCS ob - = 113 CE3 CH3 0113 OH3 0113 3 OH 0F3 } I3Ct - NX CH-0 - OH 2 t 2 2 - 2t2 2 CH3 CH3 CIf3 Cl N = NI'tIt- - ZnGl4 2- - lD E 2-r-cII2 2 1I3C l N-CH7 Cl 0113 ) \\ 0) 6O9844 / 1137 ditto.-H ZnCi4 ditto - CIIM red 0113 2 Dye hue C1 yellowish 1 IsrR ~ -C = CH Znbl Orange \ CII 2 H3C-! CH 2 2 4 9 C / 3 COOCH3 11 0H3 110 = N Z1iC1 CH) Zn0l4 golden yellow 1 to N 4 N = NQ-; G21I5 4 KC = N / CH -f - eLt 2 OH3 ZnCl4 ditto 43 ~ CH2CH2CN 2 golden yellow 2 2 21 2 CH3 OH OH OH - golden yellow ditto <NNci $ 2 ZnCl40 2 "2 2 CH3 ditto <3 CH2CH2Cl ZnCl463 golden yellow CII2- C = CIX2 2 0113 OH7 ZnCl eo-Oic ne ) 4 H7C-N-CH -C -fY '= IN O NIil-cII2 - ;; t2 2 CII 0 OH 3 3 Dye hue CH, l E3 2 5 03 red-tinged H 0-lT-OH - lTN - prange 3i 2 - 0112-C = CH2 2 CH3 0 C; IZ-C "C'rl2 2 OH3 3 CHs 3 13r ZnC1 83 orange H CN-CE2-CN t3 = OH2 0 = 0112 2 3 1 "1r OH3 0oll CTI3 ¢ CH3 ZnC1 4th E CN- (HC) 2-C oN - N e N, CX3 2 orange '7 1 L LcrK, -c-cHz cK o I OH3 qi% T-OH2-1N = Nc 'ZnOl orange 4th O CEi, -C = CZ 21 = CH2 2 CII3 3 Cl XN = Ne N -C = OI - CN 2 2 010 orange HC-Nt @ N-OH 1 3 OH3 C 3 H ditto e sCH2-C = ClI2 reddish - OH2C = CH2 2 orange OH3 ditto 9 Cua- c - cw C19 Orangec = cg " 1 Cl OH3 Dye hue OH N K s N) = N oC2H5 ZnCl49 orange O'H3: H, C'A2-C = CI-f 2 3 CH3 Cl C2H) ZnCl} orange 04N N CH2O = OH2 2 CH, CH3 I. H3, CN-CH3 cH3 3 to 3 ditto - (2I2-C = CH2 ZnCl,! Sç orange dito to the 2nd CH Cl ZnCl. where orange 3yz n H3C-N / ^ = hTH-CR, -C "CH 2 3 3 3 ditto o ~ C o 5 ZnC14eX3 Oranxe Y- Ci = 0112 - CIZ3 C. CK , 7 æ N ZnC} orange \ N »N ~ No N CH C = CH 2 I CHo-C = CH3 1130 - Ç r CH ß XM2-CI-T-cN ZnClo 3 5 N = << orange CH3 Dye hue OH I. ZnCl rots.t; ichiges KC @ <orange N NT rnr- CH, -CZCK2 2 CH CH 0.113 3 CH, N-CH3 red t 1 chiges 1 n II ZnC1.rcOH IiN = C CN = W-3 CH-C --- OH2 2 3 c113 Oh reddish 4th ditto 6 CH2-CH-CH2Cl ZnCl Orange N 2 \ CH C - Cp 2 CH3 CH2 reddish ditto e "-0 = 011 ZnCl4 orange 2 -C-CII, 2 CIl3 rotst 1 chiges ditto e / CH2.CH2-OCOCH3 Zncl i Orange C112CI = CIT2 2 CI, .3 2 CVID ZnC14 rotichies n / or ange ditto <N 2 CH - C = Cliz 2 1 (, Tt3 Dye hue Cl L IOOI CH ZnCl eo no-t; = OH ZnCl4 3C-N "CH2CjC1? 2 2 0 11 3iX ditto N 25 ZnCl4 CEI, -C = CIT 2 CII3 2 1 v cIf3 ditto e / C4Hg 01e red CEIZ-C-CfI, ci3 CH3 0113 = CH2 ditto 8 4 ZuC1 59 Red 2 CH3 N - 02115 Zncl4 red II O C- ~ N e NN 2 HG 3 IC CTT C113 £ 13 ditto / \ NWCH3 7JnCll; Red > = / CtI -Ce 2 2 CH3 C1i3 0f13 nx c Ci r rl ZnClq RoL \ N / F c 2 "5 N-CI1, -C = 0f12 II ClI3 OH 3 H3 110 L. ' 11 (0 - I'T 5 110 - N '- w Red i> ot CT! 3 013 0J13 - 2. 2 011.3 6O9SI4 / 1137

Claims (6)

Claims 1. Basic azo dyes which are free from sulfonic acid groups, with the general formula (I) in which the radical of an aromatic or heterocyclic diazo component containing a quaternary nitrogen atom, A is an aromatic radical or, together with the formula member - (NR) - is a heterocyclic radical, R is hydrogen, an optionally substituted lower alkyl radical, an aralkyl or cycloalkyl radical and a Mean anion. 2. Process for the preparation of the dyes mentioned and defined in claim 1, characterized in that either a. the diazonium compound of a quaternary amine of the formula (II) wherein D (+) and X (-) have the meaning given in claim 1, with a coupling component of the formula (III) wherein A and R have the meaning given in claim 1, coupling, or that b. an azo dye of the formula (IV) wherein D is the remainder of a diazoic component and A and R are as defined in claim 1, treated with alkylating agents. 3. Process for the preparation of the azo dyes mentioned and defined in claim 1, characterized in that a hyd ^ a.zor or benzenesulfonylhydrazone of the general formula is used where R3 is an optionally substituted alkyl or aralkyl radical, Y is a divalent atom or a divalent group required to complete a 5- or 6-membered ring, R4 and R5 are identical or different and each is hydrogen or an alkyl radical or R4 and R5 together represent substituents which add to a fused aromatic ring, n is the number O or 1 and X @X (-) is an anion and W is a hydrogen atom or a benzenesulfonyl radical, under the action of oxidizing agents with an azo component of those mentioned in claim 2 and defined formula III couples. 4. Use of those mentioned and defined in claim 1 or Dyes produced according to claims 2 or 3 for dyeing or printing Textile material made from natural or synthetic fibers 5. Use the in claim 1 mentioned and defined or the dyes prepared according to claims 2 or 3 for dyeing or printing textile material made of synthetic containing acid groups Fibers. 6. Powdery or liquid dye preparation for dyeing or printing of textile material made of natural or synthetic fibers, containing one or several of those mentioned and defined in claim 1 or according to claims 2 or 3 produced dyes.