DE3037911A1 - Cationic azo dyestuff cpds. with annulated pyridone ring - for dyeing paper and synthetic polymers - Google Patents

Abstract

New cationic azo dyestuffs (I) with an annellated pyridone ring are of formula (I), D is derived from an aromatic-isocyclic or heterocyclic diazo or tetrazo component. R is H, (cyclo)alkyl, ar(alk)yl, a heterocyclic gp. or a -CN, -OH, -COOR4, -CONR4R5, -COR5 or -CONH2 gp. R1 is R, halogen or NO2. R2 and R3 are (cyclo)alkyl, ar(alk)yl, or alkenyl and R3 can also be H. R4 and R5 are (cyclo)alkyl or a heterocyclic gp. and R5 can also be H or R4 and R5 are alkylene, opt. with heteroatom in the chain. Z is a bridge. A(-) is an anion. The (a)cyclic substits. can have other nonionic substits. D is pref. an opt. substd. phenyl, triazolyl, (benzo)thiazolyl or anthraquinonyl gp. or another annellated pyridonyl gp. linked to the azo gp. by a p-phenylene, p,p'-diphenylene, p,p'-diphenyl-amino-carbonyl or p,p'-diphenyl ether gp. (I) are specified for dyeing paper and synthetic polymers (esp. polyacrylonitrile and also acid-modified polyesters and polyamides). They have good fastness are fibre affinity and give very strong, bright (yellow) shades.

Description

Azo dyes, their manufacture and use

for dyeing acid-modified materials and paper The invention relates to azo dyes which are free from carboxylic acid or sulfonic acid groups of the general formula wherein D is the radical of an aromatic-isocyclic or heterocyclic diazo or tetrazo component, R is hydrogen, alkyl, aralkyl, cycloalkyl, aryl, a heterocyclic radical or a group of the formula -CN, -OH, -COOR4, -CO-NR4R51 -COR5 or -CON-i2, R1 hydrogen, halogen, nitro, alkyl, cycloalkyl, aralkyl, ethyl, a heterocyclic radical or a group of the formula -CN, -OH, -COOR4, -CONR4R5, -COR5 or -CONH2 R2 and R3 is alkyl, cycloalkyl, aralkyl, aryl or alkenyl, R3 is also hydrogen, R4 and R5 are alkyl, cycloalkyl, aralkyl, aryl or a heterocyclic radical and R5 is also hydrogen or R4 and R5 are optionally interrupted by heteroatoms, Z is a bridge member and denote an anion, and in which the acyclic and acyclic substituents are further substituted by non-organic radicals.

can.

Examples of aromatic isocyclic radicals D are optionally substituted benzene and naphthalene residues.

Examples of aromatic heterocyclic radicals D are optionally substituted thiazole, isothia zol, quinoline, furan, thiophene, Pyrrole, pyridine, benzthiazole, triazole, thiadiazole, indazole, benzisothiazole, Imidazole and benzimidazole residues.

Examples of nonionic substituents are halogen, e.g. chlorine, Bromine and fluorine, alkoxy radicals such as methoxy and ethoxy, alkyl radicals, e.g. methyl, acylamino radicals, e.g. acetylamino, alkoxycarbonyl radicals, e.g. methoxycarbonyl, nitro, acyloxy radicals e.g. acetoxy, aryloxy residues e.g. phenoxy, carbamyl residues e.g. diethylaminocarbonyl, Amino residues e.g. methylamino, alkylsulfonyl residues, phenoxysulfonyl residues, trifluoromethyl, Alkoxycarbonylamino, dialkylaminosulfamyl, monoalkylaminosulfamyl, Sulfamyl, acyl residues e.g. acetyl, cyano, arylazo residues and aryl residues e.g. phenyl.

The alkyl radicals mentioned preferably have 1-4 carbon atoms, and aryl preferably represents phenyl.

D can also be substituted by groups that contain cationic groups contain. Examples of such groups which can be present as substituents in D are: -SO2-NH-CH2-CH2-Py +, -CO-CH2-Py +, -NH-CO-CH2-Py + -CO-NH-CH2-CH2-CH2-N + (CH3) 3, -CO-O-CH2-CH2-N + (CH3) 3, -O-CH2-CH2-O-CO-CH2-CH2-Py +, -NH-CO-CH2-S + (C2H5) 2, -CO-CH2- S + - (CH2-CH2OH) 2, -O-CH2-CH2-S + - (CH3) -C2H5, -CO-CH2-S + (CH3) -C2H5, -CO-CH2-S + = C- (NH2) 2, -O-CH2-CH2-S + = C- / N- (CH3) 2/2, -NH-CO-CH2-S + - (CH3) -C2H5, -NH-CH = N + (CH3) 2, O = C-NH-CH2-Py +, Ph-N-CO-CH2-Py +, -NH-CO -V +, -O-CH2-CH2-O-CO-V +, = CH = N-N + (CH3) 2, -NH-CO = N-N + (CH3) 3, -O-CH2-CH2-N + - (NH2) - (CH3) 2, -SO2-NH-CH2-CH2-CH2-N + - (NH2) - (CH3) 2, -SO2-CH2-CH2-N + - (NH2) -) CH3) 2, -CO-O-CH2-CH2-N + - (NH2- (CH3) 2, -O-CH2-CH2-O-CO-CH2N + (NH2) - (CH3) 2, -CH2-CH2-N + - (NH2) - (CH3) 2, -NH-CO-CH2-N + (NH2) - ( CH3) 2, -CH2-N + - (NH2) - (CH3) 2, -CH2-NH-CO-CH2N + - (NH2) - (CH3) 2, -CO-CH2CH2-N + (CH3) 3, -SO2-NH-N + ( CH3) 3, -CO-NH-N + (CH3) 3, -O-CH2-CH2-N (CH3) 3, -S-CH2-CH2-N + (CH3) 3, -O-CH2-CH2-N + - (NH2 (- (CH3) 2; -S-CH2-CH2-N + - (NH2) - (CH3) 2, -CO-CH2-N + (CH3) 3, -NH-CO-CH2-N + (CH3) 3, -CO-CH2-P (C4H9 ) 3, -CO-CH2-P + (C4H9) 3, -O-CH2-CH2-P + - (C4H9) 3, -SO2-CH2.CH2-P + (C4H9) 3, -CO-O-CH2-CH2-P + (C4H9 ) 3, -CH2-Py +, -CH2-CH2-N + (CH3) 3, -O-CH2-CH2-Py +, -CO-CH2-W +, -NH-CO-CH2-W +, -CO-CH2-D +, -NH-CO-CH2-D +, -CH2-D +, -O-CH2-CH2-OCH2-CH2-G +, -SO2-NH-CH2-CH2-V +, -SO2-NH2-CH2-CH2-G +, -SO2-NH-CH2-CH2-W +, -CO-CH2-M +, -NH-CO-CH2-M +, -SO2-NH-CH2-M +, -CH2-M +.

3-trimethylammoniumylphenylazo, 4-pyridiniumacetylphenylazo, 4- (pyridinium-1-yl-acetylamino) -phenylazo, 3-trimethylammoniumyl-phenylcarbamoyl and 3-trimethylammoniumylphenyl sulfamyl.

In the above radicals, the symbol Ph stands for the phenyl radical, Py + for the pyridinium radical, M + for the quinolinium radical, V + for the 1-methyl-3-pyridinium-3-yl radical, W + for the 4-N, N-dimethylaminopyridinium-1-yl radical, for the 2-methylpyridinium-1-yl radical and G + for the 1-methylpyridinium-4-yl radical.

D can also be replaced by the rest be substituted.

Examples of optionally substituted alkyl radicals are C1 -C4 alkyl radicals, substituted by hydroxy, methoxy, ethoxy, cyano, carbamoyl, carboethoxy or acetyl could be.

Examples of optionally substituted cycloalkyl radicals are optionally cyclopentyl and cyclohexyl substituted by methyl.

Examples of optionally substituted aralkyl radicals or optionally substituted aryl radicals are benzyl, ß-phenylethyl or phenyl, which are replaced by methyl, Chlorine or methoxy can be substituted.

Examples of optionally substituted heterocyclic radicals are if necessary; 2-pyridyl, 2-thiazolyl, 1-piperidinyl substituted by methyl and 1-morpholinyl.

R4 and R5 together with the 1X atom to which they are attached form e.g. piperidine, morpholine, piperidine which may be substituted by methyl and pyrrolidine.

Alkenyl stands in particular for allyl and methallyl.

Halogen is preferably understood to mean fluorine, chlorine and bromine.

Specific examples for R are hydrogen, methyl, ethyl, n-propyl, n-butyl, ß-hydroxyethyl, B-methoxy (or ethoxy) -ethyl, ß-cyanoethyl, carbethoxymethyl, Acetylmethyl, phenyl, chlorophenyl, methoxyphenyl, benzyl, phenylethyl, cyclohexyl, 2-pyridyl, 2-thiazolyl, 1-piperidyl, 2-morpholinyl, methoxycarbonyl, ethoxycarbonyl, Carbamoyl, N, N-dimethylcarbamyl, N, N'-diethylcarbonamido, chloro, cyano, nitro, Amino, hydroxy, bromo, methoxy, ethoxy, diethylamino, N -methylbenzylamino, N-methylanilino, Anilino, methoxycarbonylmethyl, methylsulfonylmethyl, anilinocarbonylmethyl, cyanomethyl, N, N-dimethylaminocarbonylmethyl, N-nonylcarbamyl, nonyloxycarbonyl, N-phenylcarbamyl, N-benzylcarbamyl, N, N-dibenzylcarbamyl, 2-furyl, 2-thienyl, 2-pyrryl and phenoxymethyl.

R is preferably methyl.

Specific examples of R1, R4 and R5 are hydrogen, CN, methyl, Ethyl, n-propyl, n-butyl, sec-butyl, ß-Hydroxyethyl, B-methoxy- ode ethoxy-ethyl, Cyanomethyl, carbamoylmethyl, carbethoxymethyl, acetylmethyl, cyclohexyl, cyclopentyl, Benzyl, ß-phenyl- Phenyl, tolyl, chlorophenyl, methoxyphenyl, 2-pyridyl, 2-thiazolyl, 1-piperidinyl and 1-morphilinyl. Examples of nitrogen-containing heterocyclic Rings that are formed by R4 and R5 together with the nitrogen are piperidine, Morpholine, piperazine and pyrrolidine.

Specific examples for R2 and R3 are methyl ethyl, propyl, butyl, 2-chloroethyl, 2-bromoethyl, 2-ethoxyethyl, allyl, benzyl, cyclohexyl, 2-phenylethyl, 2-carbamoylethyl, 2-carbamoyl-2-methylethyl, methoxyethyl, methylcarbonylethyl, 2-Hydroxyethyl, 2-Cyanoethyl, 2-Carbamylethyl and Phenyl.

R2 is preferably methyl, ethyl or phenyl.

Examples of bridge members Z are those which form the ring formed by Z together with the 2 N atoms and one C atom to form a 4-, 5-, 6- or 7-membered, preferably 5- or 6-membered ring <T add to. The following are mentioned here: where Y stands for hydrogen, methyl, ethyl, methoxy, ethoxy, chlorine, bromine, β-hydroxyethyl, C1-C4-alkoxycarbonyl, carbamoyl, aminosulfonyl, nitro, cyano, C1-C6-alkylsulfonyl, phenylsulfonyl and n 1, 2 or 3 means, and preferably the bridge members -CH2-CH2-, -CH2-CH2-CH2 - and where Y and n have the meaning given.

The following should be mentioned as anions A (): Anions of inorganic acids, e.g. chloride, bromide, tetrachlorozincate, bisulfate, sulfate, Tetrafluoroborate, sulfamate, nitrate, phosphate and fluoride, and anions of organic Acids, e.g. methosulphate, ethosulphate, methylsulphonate, p-tolylsulphonate, acetate, oxalate, Hydrogen oxalate and formate. In those cases where the anion is polyvalent, will the water-soluble dye has a corresponding molecular proportion of the cationic Part of the dye included.

Of the dyes of the formula I, mention should be made in particular of those in which D is a radical of the formulas (R6 8 R 0 NX R7 is where m 0, 1, 2 or 3 R6 C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine, nitro, optionally by nitro, C1-C4-alkyl, tri- (C1-C4-alkyl) -ammonium, tri - (C1 -C4-alkyl) -ammonium-acetyl substituted phenylazo, acetylamino, acetoxy, acetyl, C1-C4-alkoxycarbonyl, phenoxy, cyano, C1-C4-alkylsulfonyl, benzthiazolyl-2, tri- (C1-C4-alkyl) -ammonium, tri- (C1-C4-alkyl) -ammonium-acetyl, 1,3-dimethyl-1,3,4-triazolyl (2) -azo, N-methyl-benzthiazolium (2), R7 hydrogen, C1- C4-alkyl or benzyl, R8 denotes C1-C4-alkyl or benzyl, Rg denotes hydrogen, C1-C4-alkyl or C1-C4-alkoxy, or in which D is a radical of the formula where R10 is p-phenylene, p, p'-diphenylene or the radicals or means, R for C1-C4-alkyl, which can be substituted by hydroxy, C1-C4-alkoxycarbonyl, C1-C4-alkoxy, C1-C4-alkylsulfonyl, cyano, phenoxy or NR4R5, for cyclohexyl, 3-methyl-1, 2-thiazolyl (5), C1-C4-alkoxycarbonyl, pyridyl (2), - (3) or - (4), cyano or CONR4R51 R1 for cyano, CONR4R5 or benzthiazolyl (2), R2 and R3 for C1-C4- Alkyl, which can be substituted by C1-C4-alkoxy, hydroxy, cyano or NR4R5, and R3 also stands for hydrogen, R4 and R5 for C-C4-alkyl, which can be substituted by C1-C4-alkoxy, hydroxy or cyano R5 also stands for hydrogen or NR4R5 for morpholino or piperidino, Z for ethylene, I, 3-propylene, 1,2-propylene, o-phenylene, 1,8- or 1,2-naphthylene, represented by C1-C4-alkyl or chlorine can be substituted, or for the remainder and stand for an anion.

Particularly preferred dyes are those of the formula I in which D is m for 1, 2 or 3 R6 for C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine, nitro, cyano or C1-C4-alkylsulfonyl, Z for ethylene, 1,2-propylene, 1,3-propylene or o-phenyl <n and the other symbols have the preferred meanings mentioned above.

The subject of the invention is also the preparation of dyes of the general formula I by reacting compounds of the general formula in any order with compounds of the general formulas R2 ~ R and / or R3-A (III) (IV) or with alkylene oxides of the formula in the presence of an acid that provides the anion A (-), or with a compound of the formula CH2 = CH-R13 (VI) in the presence of an acid that provides the anion A (), and with amines of the formula D-NH2 ( VII) after their diazotization.

Depending on the reaction sequence, the intermediate stages arise respectively.

In formulas II-IX, D, R-R3, A) and Z have those given in formula I. Meaning. A stands for a residue which is split off as anion A) during quaternization, R11 and R12 stand for hydrogen or an alkyl group two carbons less as R2 or R3 and R2 and R3 can be substituted accordingly, R13 is for CN, CONR4R5 or COO-C1-C4-alkyl.

Examples of quaternizing agents III and IV are alkyl halides! such as methyl, ethyl, propyl and butyl chloride and the corresponding bromides, alkenyl halides, such as allyl chloride or bromide, aralkyl halides such as benzyl chloride or bromide, Dialkyl sulfates, such as D methyl sulfate, diethyl sulfate, dipropyl sulfate and dibutyl sulfate, Alkyl esters of aryl sulfonates such as methyl and ethyl p-toluenesulfonate and others Lower alkyl esters of strong mineral acids or organic sulfonates.

The reaction between the quaternizing agents III and

IV and the compounds II and VIII can be used without the addition of other solvents are executed. But you can also in an inert organic solvent Aie benzene, toluene, xylene, chlorobenzene, nitrobenzene, acetone, Carbon tetrachloride, tetrachloroethane, perchlorethylene, chloroform, dimethylformamide, Acetonitrile, acetic acid, formic acid or 2-ethoxyethanol.

The quaternization can also be carried out in an aqueous phase optionally in the presence of an organic solvent. The quaternizing agent can be used in substantial excess, for example up to 6 moles each Moles of dye.

Suitable temperatures are 20 to 1500C and in particular 20 to 900C. The use of an acid binder is often useful. Suitable means are for example magnesium oxide, sodium and potassium carbonate, sodium and potassium bicarbonate, Magnesium and calcium carbonate, potassium acetate and mixtures of such agents.

The quaternization with compounds RrI is preferably in a organic or mineral acid, such as acetic, formic or hydrochloric acid or a Mixture of these, can be carried out at 50 to 1000C.

The quaternization with alkylene oxides V is preferably carried out in a solvent carried out in the presence of a mineral or organic acid which has the anion At ), at temperatures of 10 to 1000C and preferably 40 to 900C. Suitable acids are sulfur, hydrochloric, hydrogen bromide, phosphorus, benzene: ilfon-, Toluenesulfonic, formic, acetic or proponic acid. These acids can also be used as solvents serve or can be mixed with each other or with other organic solvents, such as dimethylformamide, acetonitrile, dioxane, tetrahydrofuran, chlorobenzene, toluene, Xylene, nitrobenzene, acetone or methyl ethyl ketone can be used.

When the reaction of the dye VIII in hydrophobic organic solvents then the quaternized dye is usually insoluble and can be isolated by filtration. Optionally, the quaternized dye isolated from aqueous solution by precipitation in the form of a salt, for example as tetrachlorozincate obtained by adding zinc chloride to the aqueous solution will.

As a result of quaternization, the dye can, for example in the form of chloride, bromide or methosulphate, depending on the one used Alkylating agents. If the dye is desired as a salt of another anion, then an anion can be replaced by methods known per se, such as by metathesis will.

Examples of clutch components II are given, for example, in the German Laid-open documents 1 964 690, 2 023 295, 2 510 373, 2 532 540, 2 631 164 and 2 701 659.

Examples of diazo components VII are given, for example, in the British patent application 2 021 616 A.

The dyes according to the invention are particularly suitable for dyeing of paper and for dyeing synthetic polymeric materials such as polyacrylonitrile, acid-modified polyester and polyamide fibers, by applying from an aqueous Bath. Give the dyes exquisite luminous shades, first of all Line yellow shades, with very high color intensity.

The dyes according to the invention are particularly suitable for dyeing of polyacrylonitrile materials to which they are acidic, neutral: or weak alkaline dye baths (i.e. pH 3 to 8) at temperatures between, for example 40 and 1200C, preferably 80 and 1200C, or by printing techniques using thickened printing pastes can be applied. Thereby the colorations with excellent Retained fastness properties to washing, sweating, steam ironing and light. They have a good affinity for fibers.

The dyes can also be used for dyeing synthetic polymers Materials, especially polyacrylonitrile materials, by the wet transfer printing process can be used in which a T: beam, e.g.

Paper, printed with a printing ink that contains the dye the printed carrier is brought into contact with a textile material, and the whole thing is then exposed to heat and pressure under damp / wet conditions, to transfer the dye to the textile material.

Example 1 6.9 g of p-nitroaniline are diazotized and 11 g of the pyridine Formula CH30 ru HO 't -CH3 HO N coupled, the dye of the formula is obtained.

7.5 g of this dye, 8 g of magnesium oxide and 25 g of dimethyl sulfate are heated to boiling with 25 g of glacial acetic acid for 5 hours. The mixture is cooled to room temperature and poured into 50 g of water. The dye is precipitated by adding KJ and has the following tonality: It dyes acrylic fibers in a brilliant yellow shade with excellent fastness properties. Further dyes of the formula I with likewise good fastness properties can be obtained by similar processes and are listed in the following table: Example R R1 R2 R3 DZA (-) color shade on acrylic fibers ft 1; fl; S; 9 2 CH3 ba ¢ Q C 6 3 CH3 -C0NH2 C2H C2H5 CH2CH2 Cl greenish yellow 4 CH3 NHC2H5 CH3 CH3 + I cH2CH2- J greenish yellow H 5 CB3 to $ CH3 CH3 CH3 Cl 3 rrf CH3 6 CH3 CH3 cH3 (VM Cl greenish yellow 7 CH3 -NHC2H4 - $ X OCH3 n = nnmm e mtr t G bN y Ç W n NX sr ms> a, X fi H ft -t ft; f ru cN22 ru cl r) 3 rl rf FI UU m IIIII CM (N Cq Cq N 12 tqq cH3 Q qN C2H5 II ~ Pr Ye YB 8 YY E 8 zg 8 N cq o7 ç 8 6 Y 1 <m «) IN I LO P .; Y, wy y YSUN æ ON Max - - E.g. R R1 R2 R3 DZ shade on acrylic fibers 13 CH3 a C2H5 CH3 a'222 greenish yellow N (CH3) 3 14 -flsoC4H9 CONH2 CH CH3 CH3O%) \ / cH2CH22 reddish yellow 15 c} {) »3 N CH2CH2CH3 CH3 cH2CH2CH2- greenish yellow gyvyy Y (YN, N 3: m P g CH3 H2 ç g Q 17 CH3 H3 CH3 N = N CH2 22 reddish yellow F7 n E. BS tn 6 N ç yN n ys f Z n g ye E.g. R R1 R2 R3 DZ shade on acrylic fibers 18 oC2H5 -CN ß CH3 CH3 \ / CH2I2CH2 medium yellow 19 I - a, 3 NH- CH3 CH3 C - \ / 2 2 2 greenish yellow C6H5 tr rl - 20 -cH3 I C2H5 C2H5 CH37NCH2OO \ / CH2CH22 greenish yellow CH3 YY gs 21 Cfl3 NH2 3 (N < YYYW mm rn 6 mm mn 3 In YYYY N Ln f YY c0 OO E.g. R R1 R2 R3 DZ shade on acrylic fibers 22 -OOOC2H5 NHC4H9 CH3 CH3 ß N - 23 Ct3, f 3 CH3 Cl \ / red CH X CH3 S. E. 6 tm3 6 S. U 8 mN m YYV g mX QQ m 8 §3 g N mtn (N C9 N (N E.g. R R1 R2 R3 DZ shade on acrylic fibers cl u N (CH3) 3 CH3 27 H3 2 H3 CH3 N = N red 28 H3 3 CH3 N = N ½ {\ red 29 -CH3 1 OOCH 30 C2i5 CN -CH3 CH3 N = N <L \ rot V n V 'z tS W C Ezm ffl m on mmn E. g) yX m) rtql Cf (N. G N «) rr W> O o CS (N (N CN re E.g. R R1 R2 R3 DZ shade on acrylic fibers a, 1T a, c ½ »O - 4 <$ E o: cj 51 l 0113 I -CH3 CH3 C2H5O2 0H20H- reddish yellow NN I CI> 0 in the 2nd 8-fL m A YY 33 ffiH25OOO mgg N n Z> = Z AC) CJ O q w V Yn Vm n C) r U) SL) tY) tw 0t1 C1 v mnmn E.g. R R1 R2 R3 DZ shade on acrylic fibers HH 35! CONHOH% $} T3 CH3 Cl)) / OH2OH2 greenish yellow 2 I. CH3 Cl h-rv cu cu Y OOOC2H5 C (H2 YY I. Ln 0 38 OH3 OONH2 0H3 -CIb 1 "0H2OH2- reddish yellow f § | s YYY g r) m E. YYU tn v)> co E.g. R R1 R2 R3 DZ shade on acrylic fibers 39 OH3 CN 0H2CI2OONH2 0H2OH2OOGN2 CH22- medium yellow OCH3 40 O2H4OC2H5 CN OH3 OH3 CN2 OH2OH2- greenish yellow CH 3 g < 7th ? NY Yn Yç N NN S. YYY f Ct O r N E.g. R R1 R2 R3 DZ shade on acrylic fibers 43 OH3 OON2 OH3 OH3 a, H CH3O 44 -CFI2SO2CH3 00NH2 OH3 OH3 NLI OH20H2 medium yellow H 45 -CH2CN 00NH2 OH2CH2CN OH2CH2 yN »wis red NO2 ER2 46 oo2 00NH2 OH3 cI3 Cl # ff medium yellow PS E. YYYY dN E. YYYY eN 0 gN eN m c3 SUN YYU! nv t etz E.g. R R1 R2 R3 DZ shade on acrylic fibers ft fl <, b m = above 47 CH3 OONHOH2OH2OH OH3 0H3 C2H5OOc OH20H2 middle yellow : 1 1JI NN OONHOH2OH2OH O2H5 O2H5 f N N c N cu 7 N OONHCH2OH2OCH3 OH3 OH3 N = N ½; 1/3 2-cH2- orange 3 Ln g YYY m YY ff N eN O rg 8 ç 10 r V Ç rs 03 m O vt X Ln E.g. R R1 R2 R3 DZ shade on acrylic fibers 51 OH2CH2CH3 ON OH2CH2OH CH3 O2N%) l OHOH2OH2- greenish yellow Cl 52 OH3 OOOHOH2CH2CH3 OH3 CH3 $ ffi3 0H22 OH2 middle yellow x 13; Cl 53 OH2OON (CH3) 2 OONHOH2CH2CH3 OH3 CH3 H OH20H2OH2- greenish yellow 3 O C) E Cç YY Y m 6 HN CE yN U N Cf Cm E Cg YYY E.g. R R1 R2 R3 DZ shade on acrylic fibers O a m U ti to bro 54 -CH3 -CONHC4U9 -CH3 CH3 orange mc, cr oo RR t -CH2 OC2H5 t CONH2 -CH3 CH3> ½) orange Cl 56 -CU3 -CN -CH3 CH3 CH3 south red-orange az 3 t E CH3 mm C) CJ C) V nmnn UVUV O m v U tN ZZ S m N tN UU oo m N m N lV C) lV y t UN kS) t ~ E.g. R R1 R2 R3 DZ shade on acrylic fibers c> ooo kkk ooo tri t tr a ZZ 58 -CH3 -CO-NH2 -C2H5 -C2H5 c $) 73 U orange red 1 ru U cu cu v -CONH -CN N NHC 2H4 OH oOCI3 S. = mn (N: C m UC) U VZ CM m Ln U U <N cm 5 lll CS m Z o ZZ VUC) III m O v X N mm ZZ mmo UUC) X m O S Lr kD E.g. R R1 R2 R3 DZ shade on acrylic fibers Q u1 C. r U u -rl -IJ I c, : 0 0 0 0 II k ll pOH3 62 -9H3 -CONH-CH2-CH3 -CH3 -CH3 S) red OCH 9 -CONHC2H4OH -CONH-CH2-CH2- rz -CH3 Q) I% $ O3i¼ -CH t tZ red CH3 m c1 mm mmx uuuu C) C) UU CH3 n X mm mm = S UUC? C) ! s I w n N c9 N mm N mmm oZ oZ on Z C) C) C) EU llll must oo mr = eq c9 = C) U X rz n, z tN C) CD UU llll N mv k E.g. R R1 R2 R3 DZ shade on acrylic fibers a O < rc u rI cl r ( oc, k: 0 k Ur U UX 66 -CH2COOC2H5 -CONH2 -CH2CH2OH -CH2-CH2 -OH CH3OO lt -CH3 -CONH2 E -CH3 CN Z 3 68 -CH3 -CONH-CH2-CH2 - -CH3 -CH3 N = N -CH2-CH2 reddish yellow OC25 m Xf y m O N X CJm Ú U = N $ m cq - yZ ° l ° lm In Z 04 mu, u õ CS U O O m C 7 n c $) V m V S tD rs CO S k E.g. R R1 R2 R3 DZ shade on acrylic fibers a u a, ol m 6 u u pl -c (rs fll :OK rI I. N cq m UU N cq e X Ct) C) Zot om U nn mm lU iU nn mm U Ct) n r 1N U Z Oq mh, oo UC) ll nm mm UC) 55 0 s> Dyes of the formula X can be prepared by tetrazotizing a diamine and coupling it with two molecular equivalents of the pyridone coupling components described in Examples 1-66 and then in a similar manner. Performs a quaternization as described in Example 1; they are described in the following table: E.g. R R1 R2 R3 DZ color on paper @ approx k 0 IA c rl C, 0 O a, o zi rJI k I. 54 sk rk 71 CH3 -CONH2 -CH3 -CH3 ¼ -CH2-CH2- red v muw ú UUU I e II cu <u N ll -CONH2 l -C2H5 -CH2-Cfl2- red-orange 73 -COOC2H5 -CN -CH3 -CH3 NH $ "- NH -CH2-CH2- yellow 74 OH3 -CONH-CH3 -C2H5. -C2H5 oT red m In n: S nx 2 N m N cJ c) c) U mxnx x N Ac N cD U uu l ß ll n x u NN zzz oo Sz o uuu U Ln x N O m re O n :: xux uc) lc) v b rs

Claims (5)

Claims 1. Azo dyes of the general formula wherein D is the radical of an aromatic-isocyclic or heterocyclic diazo or tetrazo component, R is hydrogen, alkyl, aralkyl, cycloalkyl, aryl, a heterocyclic radical or a group of the formula -CN, -OH, -COOR4, -CONR4R5, -CORr or -CONH2, R1 hydrogen, halogen, nitro, alkyl, cycloalkyl, aralkyl, aryl a heterocyclic radical or a group of the formula -CN, -OH, -COOR4, -CONR4R5, -COR5 or -CONH2, R2 and R @ alkyl7 cycloalkyl, Aralkyl, aryl or alkenyl, R3 is also hydrogen, R4 and R5 are alkyl, cycloalkyl, aralkyl, aryl or a heterocyclic radical and R5 is also hydrogen or R4 and R5 are alkylene optionally interrupted by heteroatoms, Z is a bridge member and an anion, and wherein the cyclic and acyclic substituents can be further substituted by nonionic radicals. 2. Azo dyes of the formula of claim 1, wherein D is a radical of the formulas R8 .6 N 1 "r, t,; 8 1 R. N 7 8 9 5 y½i s S ' stands where 0 m 0, 1 or 3 R6 C1-C4-alkyl) C1-C4-alkoxy, chlorine, bromine, nitro 'optionally by nitro, C1-C4-alkyl, tri- (C1-C4-alkyl) ammonium, tri- (C1 -C4-alkyl) -ammonium-acetyl-substituted phenylazo, acetylamino, acetoxy, acetyl, C1-C4-alkoxycarbonyl, phenoxy, cyano, C1-C4-alkylsulfonyl, benzothiazolyl-2, tri- (C1-C4-alkyl) -ammonium, Tri- (C1-C4-alkyl) -ammonium-acetyl, 1,3-dimethyl-1,3,4-triazolyl (2) -azo, N-methylbenzthiazolium (2), R7 hydrogen, C1-C4-alkyl or benzyl , R8 is C1-C4-alkyl or benzyl, R9 is hydrogen, C1-C4-alkyl or C1-C4-alkoxy, or in which D is a radical of the formula where R10 is p-phenylene, p, p'-diphenylene or the radicals or means, R for C1-C4-alkyl, which can be substituted by hydroxy, C1-C4-alkoxycarbonyl, C1-C4-alkoxy, C1-C4-alkylsulfonyl, cyano, phenoxy or NR4R5, for cyclohexyl, 3-methyl-1, 2-thiazolyl (5), C1-C4-alkoxycarbonyl, pyridyl (2), - (3) or - (4), cyano or CONR4R5, R1 for cyano, CONR4R5 or benzthiazolyl (2), R2 and R3 for C1-C4 -Alkyl, which can be substituted by C1-C4-alkoxy, hydroxy, cyano or IJR4R5, and R3 also represents hydrogen, R4 and R5 represents C1-C4-alkyl, which can be substituted by C1-C4-alkoxy, hydroxy or cyano , and R5 also stands for hydrogen, or NR4R5 for morpholino or piperidino, Z for ethylene, 173-propylene, 1,2-propylene, o-pnenylene, 1,8- or 1,2-naphthylene, represented by C1-C4-alkyl or chlorine can be substituted, or for the remainder and stand for an anion. 3. Azo dyes according to Claims 1 and 2 wherein D is m for 1, 2 or 3 R6 for C1-C4-alkyl, C1-C4-alkoxy, chlorine, bromine, nitro, cyano or C1-C4-alkylsulfonyl, Z for ethylene, 1,2-propylene, 1,3-propylene or o-phenylene, and the other symbols have the meaning of claim 2. 4. Process for the preparation of azo dyes of claim 1, characterized in that compounds of the general formula in any order with compounds of the general formulas R2-A and / or R3-A or with alkylene oxides of the formula in the presence of an acid which supplies the anion A (), or with a compound of the formula CH2 = CE-R13 in the presence of an acid which supplies the anion A (), and reacts with amines of the formula D-NH2 after their diazotization. 5. Use of azo dyes of claim 1 for dyeing paper and synthetic polymeric materials.