DE2522174A1 - 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 ver application Addendum to patent application P 24 61 432.2 - (HOE 74 / F 396) The present The invention relates to new basic azo dyes, processes for their preparation and their use.

In continuation of the inventive concept of patent application P 2z G1 432.2, new dyes were found which are free from sulfonic acid groups and have the general formula (I) correspond, in which D (+) the radical of an aromatic or heterocyclic diazo component which contains a quaternary nitrogen atom, h an aromatic radical or together with the formula member - (NR) - a heterocyclic radical, R is hydrogen, an optionally substituted lower alkyl radical, a Aralkyl or cycloalkyl radical and X) is 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, Halogen acetamides, ß-halogen propionitriles, halohydrins, alkylene oxides, acrylic acid amide, 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 Rq and R5 together represent substituents which complemented a fused aromatic ring, n denotes the number 0 or 1 and X () denotes an anion. Such quaternary compounds can be derived from amines of the pyridine, pyrazole, imidazole, triazole, tetrazole, oxazole, thiazole, selenazole, oxdiazole, thiadiazole, pyrimidine or triazine series, and also the quinoline, indazole series , Benzimidazole, benzisothiazole, arylguanazole, naphthimidazole, benzoxazole, naphthoxazole, benzthiazole or naphthothiazole series.

Quaternary amines of the formulas (VI) and (via) are also suitable where 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-, SO, -, -CONH-, -OCO- or -SO2NH group, m is O or 1 and X () is an anion and the benzene radical a can contain further substituents, for example halogen atoms, alkoxy, aryloxy, alkyl, trifluoromethyl, nitro, alkylsulphone, arylsulphone, 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 remainder R stands for hydrogen or a methyl, ethyl, propyl or butyl radical, the other substituents, such as Halogen atoms, hydroxy, cyano, acyloxy, carbalkoxy, carbamoyl, dialkylamino, Alkoxy, trifluoromethyl, acyl, carbinic acid ester, alkylsulfon, sulfamoyl or May contain aryloxy groups. R can also be a cycloalkyl, for example a Cyclohexyl radical, an aralkyl, for example a benzyl or phenethyl radical, or an aryl radical, for example an optionally substituted phenyl radical, sen.

Together with the formula residue - (NR) - A can also be a 1,6- (1,2,3,4-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 5 alkyl-5 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 nitrosyl sulfuric 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 other known ones, the coupling rate influencing buffer substances or catalysts, such as dimethylformamide, Pyridine or its salts.

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 Formula (III) can be obtained.

The procedure b. is especially for amines of the formula (X) in which n, Y, Rq and R5 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-5 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 into consideration.

Alkyl halides, aralkyl halides, Halogenacetamides, ß-halopropionitriles, halohydrins, alkylene oxides, acrylic sureamide, 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, methyl benzenesulfonate, 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 nitrocarbon, such as benzene, toluene, xylene, tetrachloro-thane, chloroform, carbon retrachloride, 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 one Solvent, an excess of the alkylating agent can also be used.

Depending on the number of nitrogen atoms that can be alkylated in the outlet, s -arstoffs one or more alkyl groups are introduced into the dye molecule. The alkylation is at elevated 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 of one as the anion X strong acid, for example sulfuric acid or its half-ester, an arylsulfonic acid or a hydrohalic acid. These anions introduced according to the method can also 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 are obtained in the form of their double salts with zinc or cadmium halides.

Of the dyestuffs of the invention, dyestuffs of the formula XII are in particular preferred in which D is the radical of a heterocyclic or aromatic heterocyclic diazo component which contains a quaternary nitrogen atom in the heterocyclic ring, A is an aromatic radical or, together with the formula member - (ER) -a heterocyclic radical, R is hydrogen, an optionally substituted alkyl radical, an aralkyl - Or cycloalkyl radical and X (-) denote an anion, in particular dyes of the formula XIII in which Y represents a remainder, which together with the remainder added to a thiazolium, benzthiazolium, pyrazolium, indazolium, triazolium, guanazolium, pyridinium or quinolinium radical, A denotes the phenyl radical, which is replaced by chlorine, methyl, ethyl, methoxy, ethoxy, Carboxylic acid alkyl ester groups of 2 to 5 carbon atoms or acetylamino groups can be substituted, R is hydrogen, an alkyl radical of 1 to 4 carbon atoms,, ß-hydroxyethyl, ß-chloroethyl, a-chloro-hydroxy-propyl, ß-acetoxyethyi - or represents the benzyl radical, +) ß-cyanoethyl-R3 represents the methyl or ethyl radical and X (-) represents an anion.

Dyes of the formula XIV are also preferred in which E represents a radical which, together with the radical R3 - N and the benzene nucleus, adds to an imidazolium, pyrazolium or triazolium radical.

represents hydrogen, methyl or chlorine and A, R, R3 and X () the for formula (XIII) have given meaning.

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; or acid modified polyamide or polyester fibers, but especially for dyeing, printing and mass dyeing (spin dyeing) of polyacrylonitrile or fibers containing polyvinylidenecyanide. The ones available on these fibers Colorations are usually very strong and generally have good light and lightness Wet fastness properties, for example good washing, fulling, over-dyeing, carbonization, chlorine and perspiration fastness, as well as good decatur, steaming, ironing, rubbing and dissolving agents telfastnesses. The dyes are generally resistant to a change in pH of the dyebath largely undetectable and can therefore be used in weakly acidic as well as in a strongly acidic bath. They are also at temperatures Above 100 ° C, as used in high-temperature dyeing, resistant.

The dyes make wool complete under normal dyeing conditions reserved.

Coloring 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 fort: from powders, which optionally control agents, such as Use inorganic salts, dextrin and possibly other additives. It is advantageous to use concentrated aqueous, but easier to handle Solutions of Dyes that contain about 20 to 60% dye, one or more several lower aliphatic carboxylic acids such as formic acid, acetic acid, propionic acid or lactic acid, and optionally other additives, such as water-soluble polyvalent Alcohols, their ethers or esters, polyethers, aliphatic carboxamides, lactams, Lactones, nitriles, dimethyl sulfoxide, diacetone alcohol, dioxane, tetrahydrofuran or Contain urea and 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 amount of pig used in paper printing could become.

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 25 parts by volume of water and 3½ parts by volume of dimethyl sulfate are added at 50-60 ° C. with stirring over the course of about 1 hour . The mixture is stirred for about 2 hours at 50-60 ° C. (pH 7.5-8.5), 2.5 parts by weight of kieselguhr and 2.5 parts by weight of activated carbon are added, and the mixture is filtered off with suction and washed with 120 parts by volume of hot water. The filtrate is mixed with 120 parts by volume of 30% hydrochloric acid and cooled to 0 ° C. After adding 75 parts by weight of ice, diazotization is carried out by rapidly adding 52 parts by volume of 5N sodium nitrite solution Run the diazo solution into a mixture of 36.75 parts by weight of N-methyl N-F openyl- (3) -aniline and 1000 parts by volume of water. After stirring for 2 hours, the dye is precipitated with 25 parts by volume of approximately 64% zinc chloride solution. The precipitated dye is filtered off with suction, washed with 5% sodium chloride solution and dried at 50.degree. 70 parts by weight of dye of the formula are obtained which dissolves with orange color in water and 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, and polyacrylonitrile fibers from a weakly acidic bath in light- and wet-fast orange tones.

The dye can also be obtained by coupling diazotized 1-methyl-5-chloro-7-aminobenzimidazole with N-methyl-N-propenyl- (3, -aniline and subsequent quaternization of the resulting Produce azo dye.

Example 2 18.7 parts by weight of N-methyl-benzthiazolon-2-hydrazone and 35 parts by weight of 3-methyl-N-ethyl-N-propenyl- (3) -aniline are in 1200 parts by volume Water and 320 parts by volume of 5N hydrochloric acid entered. At 400 you then drop one 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 precipitated dye is filtered off with suction. The moist dye filter cake will Dissolved hot in 4000 parts by volume of water and after adding activated carbon and kieselguhr clarified. The filtrate is mixed with 200 parts by weight of table salt and 40 parts by volume of approx. 64% zinc chloride solution added. The dye that separates out in crystalline form is filtered off with suction, washed with 5% sodium chloride solution and then at 60.degree dried.

flan contains 25 parts by weight of dye of the formula which dissolves with blue color in water and 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, and polyacrylonitrile fibers in lightfast and wetfast Shades of blue.

The coupling component used is heated for several hours under pressure or without pressure of equimolar amounts of 3-methyl-N-ethyl-aniline and 3-chlorine -propene- (1) in the presence of acid-binding agents such as tertiary aliphatic or aromatic anines, 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, direthylformamide, dimethyl sulphoxide, glycol, glycol ethers or esters, performed will.

Example 3 11 parts by weight of 2-amino-thiazole are in 30 parts by volume Dissolved 95% sulfuric acid. At 0-50C with 30 parts by weight 42.3 pointer Diazotized nitrosylsulfuric acid and stirred for 50 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 14.7 parts by weight N-methyl-N-propenyl (3) -aniline is added, the coupling starting immediately. It is stirred for 3 hours until the coupling reaction is complete, with 1000 parts by volume Diluted water and adjusted to OH 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 15 parts by volume of dimethyl sulfate in 25 parts by volume of chlorobenzene is then added dropwise over 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 80-900 ° C. (approx. 6-8 hours). The reaction mixture is cooled to 25 ° C., the deposited dye is filtered off with suction, washed with 200 parts by volume of chlorobenzene and then dried at 50 ° C. 33 parts by weight of dye of the formula are obtained which can optionally be cleaned by redissolving in water. The dye dissolves with a blue-violet color in water and aliphatic carboxylic acids such as acetic or formic acid, if necessary also in mixtures of these acids with other solvents, many alcohols, glycol monoethers, ketones, carboxamides or carboxylic acid esters, and dyes polyacrylonitrile fibers in light- and wet, red-tinged blue tones. The quaternization of the dye can also be carried out in other organic solvents, such as toluene, xylene, chloroform, acetonitrile, or in an aqueous medium. If, instead of dimethyl sulfate, equimolar amounts of diethyl sulfate are used, the dye of the formula is obtained If epichlorohydrin is used instead of dimethyl sulfate and the quaternization is carried out in glacial acetic acid at about 50 ° C., the dye of the formula is obtained after precipitation with zinc chloride Example 4 A solution containing 27 parts by weight of 4-acetaminophenacyl-trimethyl ammonium chloride, 50 parts by volume of water and 100 parts by volume of 5N hydrochloric acid is refluxed for 60 minutes to saponify the acetyl group. The resulting solution is cooled to 0 ° C., diazotized at 0 ° -50 ° C. with 20 parts by volume of 5N sodium nitrite solution, stirred for 30 minutes while the excess nitrite remains and the excess nitrite is then reduced with sulfamic acid. The diazo solution is clarified with kieselguhr and 16.1 parts by weight of N-ethyl-N-propenyl- (3) -aniline are added while stirring. After stirring for 1 hour, 150 parts by volume of water, diluted with 50 parts by weight of sodium chloride, are added and the dye is precipitated as zinc chlorine salt by dropping in 20 parts by volume of 64% zinc chloride solution. After drying at 60 ° C., 20 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 introduced into 36 parts by volume of water and, after 30 minutes, 48 parts by volume of 95% sulfuric acid are added so that the temperature does not exceed 30 ° C. After cooling to 0 ° C., nitrosylsulfuric acid is diazotized with 93.6 parts by weight of 41% nitrosylsulfuric acid at 0 ° -50 ° C. The mixture is stirred for 30 minutes with a constant excess of nitrite and the diazotization mixture is then added dropwise at 5-100 ° C. to a receiver containing 4S, 3 parts by weight of N-ethyl-N-propenyl- (3) -aniline in 200 parts by volume of OOC water, 100 parts by volume of 5N sulfuric acid and 3 parts by weight of sulfamic acid. After stirring for 1 hour, the mixture is diluted with 500 parts by volume of water at 0 ° C. and part of the mineral acid is neutralized with 110 parts by volume of 33% strength sodium hydroxide solution. The coupling mixture is then poured into a solution of 2000 parts by volume of water and 200 parts by weight of crystalline. Sodium acetate and adjusts to a pH of 5-6 with sodium hydroxide solution. After several hours of stirring, the dye becomes of the formula sucked off.

For quaternization, the moist dye is used in 300 parts by volume Stirred water and 15 parts by weight of nagnesiuin oxide. At 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 at 30 ° C. for 3 hours until the quaternization reaction has ended ist1 which is advantageously followed with a thin-layer chromatogram. The quaternization mixture 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 poured into a mixture of 18C0 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, if necessary, purified by reprecipitation.

100 parts by weight of dye are obtained, which is dissolved in dilute vinegar and formic acid with red color dissolves and polyacrylonitrile fibers in light- and wet-fast Shades of red.

Example 6 32.64 parts by weight of 4-chloro-3-nitrophenyl-trimethylammonium methyl sulfate are at 90 - 9500 within 20 minutes in a mixture of 125 parts by volume Water, 20 parts by weight of iron powder and 0.5 parts by weight of glacial acetic acid added, which is refluxed for 30 minutes to etch the iron.

The mixture is then stirred at 9500 for 1 hour, 5.3 parts by weight of calcined sodium carbonate are added, and the filtrate is filtered at 90 ° C. 90 parts by volume of 5N hydrochloric acid are added, the mixture is cooled to 0 ° C. and 20 parts by volume of 5N sodium nitrite solution are added over the course of 15 minutes , Stirred for 30 places, the excess nitrite is destroyed with sulfamic acid and then the resulting diazo solution is clarified with kieselguhr. A solution of 17 parts by weight of 2-chloro-N-propenyl (3) aniline in 100 parts by volume of glacial acetic acid is added to the diazo solution. After 2 hours of stirring, it is diluted with 600 parts by volume of water, then the dye is precipitated with 15 parts by volume of 64.7 parts of zinc chloride solution, filtered off with suction, washed with 5% sodium chloride solution and dried at 600, 29 parts by weight of the formula are obtained which 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% acetic acid stirred and dissolved in 5000 parts by volume of water. Then you go with 100 parts by weight washed yarn made of polyacrylonitrile staple fiber at 600C in the dye bath, increased the temperature slowly to 1000C and stains for 1 hour at boiling temperature. Afterward allowed to cool slowly to about 700C, rinsed and dried.

A clear reddish yellow coloration with very good light and wet fastness properties.

If acid-modified polyester fibers are used as the dyed material, so a reddish-tinged yellow coloration with too good fastness properties is also obtained.

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

Dye hue ZnCl4-- red 2 ZnCl4-- yellowish red 2 CH3SO4- red CH3SO4- wine red CH3SO4- red dye hue CH3SO4- Bordo CH3SO4- Bordo Cl- bluish red CH3SO4- violet CH3SO4- violet ZnCl4-Bordo 2 dye color N = CH! ~ CH = CIT2 ZnC1483 Bordo 7 / OH3 - 2 CH3 cr 2 CH3 3 ditto ~ dA / C4E9 ZnC1489 Bordo 2CH = CH2 2 CH3 OH3 r '3 ZnC1 E, RC - NW R LI- 4 red-tinged XIC SS o MN = LZ> 2 5, 2 blue / - - ai2-CH = C OH ditto 3 - ZnOl Ea reddish - CH2-- CH = CN2 2 blue CH3 3 OH 2 5 ditto ZnOl red ticking OH> 3 CH2- CM 2 - blue 3 cH2 CH2 CH2 red-tinged blue CHZ-CH = CH, 2 Dye hue = NS N = NO ZEC11 CH Z2 ° l / Ke3 blue OH3- N \ Iz, - 2 OH3 ditto Ä7N $ 0) 'CH = Cll ZnCl4 blue CIIZ - CH OH 1 3 W> @ C - N = NX a ~ CH = CH 2 OH 13th N s CN = N- N 3 ZnC1'43 blue H C 50 S CH CH ~ CH = C H2 Ci 'C 3 2 CH, ditto ON4NCH3 CH3S04 blue CH2 ~ CH C: H2 Dye hue CH j3 OH e N - CH, SO1C OH3 34 blue , (DC - N = NO CH3SO4 <3 'CH -CH-CHZ same as S 02115 ZnOl4 blue blue CH3 Cff2 CH = CH2 2 OH I H3 @ G - Nffi NUN 3 24 blue H3C CH3 CH2 ~ CH = CH2 2 0113 OH ditto N, 3 OH3SO e blue 4th OH2-. CH = CH2 I '3 CIZ3 N $ 1 0 - N = N'ffi N0113 ZnCl4 blue CII C - N = N- N. 4 Blue 3 CH3 CH3 CE - CH = CHS 2 3 OH Hc N cH, s4 blue 3 to (; - N = NO N / C, H, 25 1305 OH 2CH = CH2 Dye hue C1 ZnC14S? reddish -N = N- NK- CH, - CII = CII2 ZnCl ee H, CN-CH, 3 '3 CH3 ditto VNH- CII2 ~ CH = CH2 ZnC14 golden yellow 3- 2 CH3 Cl 4 golden yellow H3C ~ NN N = Nq N = NNH ---. Ai2 CH = CH2 golden yellow 011 3 COOCH3 Cl Ol N = NI-CH2- CH = CH2 LnO; 4 golden yellow hT = N- .TH ~ 4 CB = CHZ H3C-N-CH3 V§3 CE3 C2. 01113 3 - ZnCl golden yellow H3C \ N = NH ~ CH2 ~ CH = Ch? 2 2 CX3 CH3 3 > = r? CEIZ- CH = CH2 ZI GO1dEeSb - 22 2 7 N-0H E3C-N T-CH3 C1 lC H Dye hue Cl = N = N 4N 2-CH = CH2 ZnCl4 golden yellow COOCH 4- H CN N- CK3 2 3 <C z 3 COOCH) H CX 1 3 HC = N \ OH5 ZnCl4 | s 4 = ~~~~~~~~ golden yellow HC = N-CH2-cH = cHS 2 Number4 ditto e N - CH2CH2CST 2 golden yellow CH2 CH = C112 U 2 ditto g N - 2 2 CH2OH N CH2 Zn0l Go N2H = C% 2 light yellow ditto 5 N, CH2CH2C1 ZnCl 5 golden yellow - mB2f 4 CH2-CH-CH2 sICH3 ZnOl 0 orange --CR, - C - = v 0112 CH = CH2 2 OH7 II - ) OH 3 Dye hue CH, 3 = 2H5 ZnC1 3 red. H30-N1-CH2-O 4WN N - (/ CiIZ- CH = CH 4 OH3 O OH3 2 CH3 Br rotstichigcsrOtSt H CN-0H2-C / = <3 / 2H5 2 catch 3 1 NNWCll2, CH = CH2 2 1I CH CII, CH3 O OH CH3 N ~ 4 red t ie iges II3C- (H2G N = NQ-g / s 2. Orange CH3 0 CR2-'CH = CH2 3 \ N-CH2-CN o N = N e, CII: 4 red-tinged - OH2- = CH3 2 orange Cl = N = N e CHZ 2 C16 orange H3C-} It @ N-CH3 0 II OH Orane ditto N 2 5 ZnCl4 CH2 - CH - CHS 2 2 ditto 9 S CH2- CH = CH2 Clg Orange 91 h A - Dye hue CH X3C-N ON @ j 3 CH3 ~ CXSCH = CIt2 2 OH3 OH3 to C1, -CH = CII2 2 C1 2 N ) H2CH = CHS 2 H30 ') ¼0H3 3 ditto, 1fflH- OI- CH = CH ZnCl Orange 2 2 OH C1 68 orange I 3 4 3 / \ <=> NN = CE2- CH = CtT2 2 CH3 CH3 ditto e C2H5 SnC14eg Orange ditto - r; 4th CK, g aI = CH2 2 OH 1 N ZnCl 3 orange 4th æ @NIN Orange NN -CR3 - H2-CE = c.H2 Dye hue OH (3 6N ZnC1463 orange HO g <N - N 9 tE- CH2-CH = CHS ~ ~ = NN = N 2 CH CH, O - N-OH3 1, CH3 ZnC1463 orange HN = C ON = N OH2-1C11 = CH2 22 CH3 OH 4th ditto e 0H2-OH-OH2Cl ZnOl LC Orange CH2-CH = CH2 2 OH2¼ ~ ditto e, CH2 e ZnOl4 orange ai2-CH = CJ2 ditto O, CH2-CH2-OCOCH3 ZnOl4 orange EI-CH-CHZ 2 2 04H9 ZnCl4 ditto ffiNMM 2 Orals 5I2 "CH = CH2 Dye hue Cl. yellowish = N = ff4 N / CH3 ZnC1 c red NN 4 - - OH CH2 ~ CH = CH2 1 'ON 8 N-OH C / ZnOl red ditto o 'C2H5 L5 red 1 OH - CH = C . ditto 4 o C2E) 01e red t CH2-CII = CH2 CH CR, - = CN - NON 2 5 - HC - N r CH2 - CH = CH2 I, OH3 3 jl ZnOl4 & red ditto g 3 cH3 - OH2 CH2CH2 2 CH3 ditto 9 "CH2 t ZnC14oe red CH3 to 2 3 2-OH = C112 CH3 1 3 HC N HC S 'N t N tHH CH3S04 Red CH3 CH2-cH = cII2 ditto Wed (-> reddish 0113504 blue CH2 CH2-CII = CH2 HC CH oo a N = NI c2H5 ZnCl4 orange / NC H3C / \ No - N = N / \ N ---- 2 --- CH2-CH = CEIZ CH3 Cl r - \ CH2 CH2 ee N === N; t ZnClq red HQC, CII, red 2 H30 - \\ o OH3 K CH . C NX CH2-CH2-CN ZnC14 blue NN N - N g / - CRZ-CH = CH 2 CH3

Claims (6)

Claims 1. Basic azo dyes which are free from sulfonic acid groups, with the general formula (I) in which D (+) is the radical of an aromatic or heterocyclic diazo component which contains 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 radical or mean cycloalkyl radical and an 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 and and xt) 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 diazo 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 hydrazone 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 R are the same .5 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 denotes the number 0 or 1 and X) denotes an anion and W is a hydrogen atom or a benzenesulfonyl radical, under the meaning of oxidizing agents with an azo component of the claim 2 mentioned and defined formula III couples. 4. Use of those mentioned and defined in claim 1 or of 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. Powder 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 AnsDruch 1 or according to claims 2 or 3 produced dyes.