DE2118536A1 - Basic azo dyes - Google Patents

Abstract

Basic azo dyes have formula: (where D is opt. substd. aromatic-carbocyclic or aromatic-heterocyclic; R1 is CN, acyl ro carboxylic acid; R2 is unsubstd. alkyl or opt. subst. aryl or opt. substd. heterocyclic radical, or -NR3R4; R3 and Rj are H or opt. substd. alkyl or aryl, or together with the N atom form a ring; Y1 is a divalent gp.; K+ is opt. substd., etherified hydroxylammonium gp.; and A-1 is anion. Dyes can be used for dyeing or printing acrylonitrile textile material.

Description

Basic azo dyes free of sulfonic acid groups, their preparation and Use.

The invention relates to new, sulfonic acid group-free basic azo dyes of the formula where D is an optionally substituted aromatic carbocyclic or aromatic heterocyclic radical, R1 is the cyano group, an acyl radical or a carboxylic acid ester radical, 2 is an unsubstituted alkyl radical or an optionally substituted aryl radical or an optionally substituted heterocyclic radical or a group of the formula R3 and R4 each represent a hydrogen atom or an optionally substituted alkyl or aryl radical, or can form a ring together with -N-, Y1 is a divalent bridge member, an optionally substituted, etherified hydroxylammonium group and As is an anion.

Interesting dyes conform to the formula where R1 and R2 each represent an optionally substituted alkyl or cycloalkyl radical and R3 an optionally substituted hydrocarbon radical + and R1 'and R2' can form a heterocycle together with the N atom and D, R1, R2, Y1 and As are as indicated above Have meanings. or the formula where R2 "denotes an optionally substituted alkyl or cycloalkyl radical and D, R1, R2, Y1, R1 ', R3' and A- have the meanings given above.

The new basic azo dyes of the formula (I) can be prepared by converting the diazo compound from an amine of the formula D — NH2 (IV) with a compound of the formula clutch.

The azo dyes of the formula (I) can also be prepared using a compound of the formula in which A is a radical which can be converted into an anion, is reacted with an optionally substituted etherified hydroxylamine.

The azo dyes of the formula (II) can also be obtained by combining a compound of the formula (VI) with a compound of the formula implements.

The azo dyes of the formula (III) can be obtained by using a compound of the formula quaternized, e.g. with a connection R211 - A.

The new compounds are used for dyeing or printing fibers, Threads or textiles made therefrom, which are made from acrylonitrile polymers or -mischpolmerisaten exist or contain such.

You can also use synthetic polyamides or synthetic polyesters, which are modified by acidic groups, dye or print. Such polyamides are known for example from the Belgian patent specification 706 104. The corresponding Polyesters are known from US Pat. No. 3,379,723.

The compounds are also used to color plastic masses and leather and paper. It is particularly advantageous to dye in aqueous, neutral or acidic Medium at temperatures from 600C to boiling point or at temperatures above ) O 00C under pressure. Level dyeings with good and good lightfastness are obtained Wet fastness properties.

Those compounds which have good solubility in organic Own solvents are also used for coloring natural plastic masses or dissolved or undissolved plastic, synthetic or natural resin compounds. Some of the new connections can be used, for example, for dyeing taned cotton, Wool, silk, regenerated cellulose and synthetic polyamides are used will. It has been shown that mixtures of two or more can also be advantageous of the new compounds or mixtures with other cationic dyes can.

In the compounds of the formula (1), the anion can be replaced by others Exchange anions, e.g. with the help of an ion exchanger or by reaction with salts or acids, (, possibly in several stages, e.g. via the hydroxide.

Anion k is understood to mean both organic and inorganic ions, for example halogen such as chlorine, bromine, iodine or hydroxide, carbonate, bicarbonate, methyl sulphate, sulphate, disulphate, perchlorate, phosphate, phosphorus tungsten molybdate -, benzenesulfonate or naphthalenesulfonate, 4-chlorobenzenesulfonate, amidosulfonate, oxalate, acetate, maleate, lactate, propionate, citrate, methanesulfonate, chloroacetate or benzoate ions or complex anions, such as e.g. of zinc chloride double salts It is to be assumed that the compounds of the formula (I) are in a tautomeric state of the formulas is marked.

Particularly good connections are obtained when R1 is the cyano group and R2 denotes the methyl or ethyl radical or an aryl radical, e.g. a phenyl radical.

The compounds of the formula (I) are preferably free from water-soluble making groups, especially sulfonic acid groups.

Halogen is in any case bromine, fluorine or iodine, in particular however chlorine 7.u understand.

The radicals R3 and R4 and Ri to R3 can be an optionally substituted, preferably low molecular weight straight-chain or branched alkyl radical with, for example 1 to 6 and advantageously 1 to 4 carbon atoms. If these radicals are substituted are, they contain in particular a hydroxyl group, a halogen atom, the cyano or an acyl group; Alkyl can for such cases for an aralkyl, E.g. a benzyl shower.

R2 is advantageously f; Qr is an unsubstituted alkyl radical with, for example 1 to 6 carbon atoms or for an optionally substituted aryl radical. The alkyl radicals can be straight-chain or branched.

Cycloalkyl radicals are advantageous for cyclohexyl radicals, which through Alkyl or alkoxy groups or halogen can be substituted.

Aryl radicals mainly represent optionally substituted phenyl radicals; but they can also stand for naphthyl radicals.

The radicals R 'and R' can be used together with the neighboring + N atom form a heterocycle, for example a pyrrolidine, piperidine, morpholine, Aziridine or piperazine ring.

Heterocyclic radicals, such as, for example, the radicals D and / or R2, can be used for 5- or 6-membered ring systems, which may be cycloaliphatic, heterocyclic or aromatic rings can be fused; they can e.g. a pyridine, Quinoline, piperidine, isoquinoline, tetrahydroquinoline, thiazole, benzthiazole, Thiadiazole, indazole, imidazole, Pyrrole, indole, oxazc, l-, isoxazole- or pyrazoline ring, etc. mean.

Aromatic radicals D advantageously belong to the benzene or naphthalene series at.

Divalent bridge members Y1 can denote optionally substituted alkylene radicals having, for example, 1 to 6 carbon atoms, it being possible for the alkylene radicals to be straight-chain or branched or interrupted by heteroatoms or heteroatom groups, for example by wherein R6 denotes a hydrogen atom or an optionally substituted hydrocarbon radical.

As residues A, e.g. acid residues of esters, there are preferably those the hydrohalic acids into consideration; A preferably represents chlorine or bromine. Further acid residues A are, for example, those of sulfuric acid, a sulfonic acid or of hydrogen sulphide.

Preferred acyl radicals, preferably non-water-soluble acyl radicals, correspond to the formula R7-X1 or R8-X2 where R7 is an optionally substituted hydrocarbon radical which may contain heteroatoms, R8 is a hydrogen atom or an optionally substituted hydrocarbon radical optionally containing teroatoms, X1 -O-CO- or -S02-, mean.

Hydrocarbon radicals are in particular optionally substituted Alkyl, cyclohexyl, phenyl or naphthyl radicals.

Preferred etherified hydroxylamines are, for example, those mentioned below or The coupling of diazotized compounds of the formula (IV) with a compound of the formula (V) can be carried out by the customary methods, for example in a neutral to acidic medium, if appropriate in the presence of a buffer and at temperatures around 0.degree.

The reaction of a compound of the formula (VI) with an optionally substituted, etherified hydroxylamine, is preferably carried out in an organic Solvent and at temperatures from -500C to + 2500C, advantageously at -10 ° to + 1200C.

The reaction can be carried out in an aqueous medium, if appropriate with addition an organic solvent or completely without solvents in the case of the above Perform temperatures.

The quaternization can also be carried out according to the usual methods e.g. in an inert solvent or optionally in aqueous suspension or without solvent in an excess of the quaternizing agent, if necessary, at elevated temperatures and, if necessary, in a buffered medium. Advantageous is the use of organic acids, possibly in conjunction with an additive a basic compound.

Quaternizing agents are, for example, alkyl halides, e.g.

Methyl or ethyl chloride, bromide or iodide, alkyl sulfates, such as Dimethyl sulfate, benzyl chloride, acrylic acid amide / hydrochloride, e.g. CH2 = CH-CO-NH2 / HCl, Alkyl chloroacetate, ß-chloropropionamide, epoxy such as ethylene oxide, porpylene oxide, Epichlorohydrin.

In the following examples the parts mean parts by weight which Percentages by weight, the temperatures are given in degrees Celsius.

For example, 13.5 parts of 1-amino-4-acetylbenzene are mixed with 6.9 parts Sodium nitrite diazotized in the usual way. The present, ice-cold diazo solution you add it up, always at 00, gradually over the course of an hour with 38 Parts of dimethyl-N'-methoxy-amino)] - ethyl-2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridinemethylsul fat. The pH of the reaction solution is then adjusted with sodium acetate 4.5 and stir at 00 until the coupling reaction is complete.

The reaction mixture is heated to 350, the resulting dye precipitated from solution with sodium chloride, collected on a filter, washed with aqueous Washed, dried and ground sodium chloride solution. The new dye lies as a water-soluble powder, with the polyacrylonitrile materials in lively yellow shades can be dyed with excellent fastness properties.

The one in this example. applied coupling component is obtained by condensation of cyanoacetic acid-2 '- (N'-methyl-N'-methoxy) -amino-ethylamide (produced by reacting cyanoacetic acid ester with N-methyl-N-methoxyamine) with acetoacetic ester by heating in absolute alcohol in the presence of piperidine and subsequent reaction with dimethyl sulfate.

Similar dyes with just as good fastness properties are found if you replace the 13.5 parts of 1-amino-4-acetylbenzene by the equivalent amount of the following Components replaced: l-amino-2- or -3-chlorobenzene, 1-amino-2-, -3- or -4-methylbenzene, 1-pminobenzene, l-amino-2- -3- or -4-methoxybenzene, 4-amino-1,1'-diphenyl ether, 4-amino-4'-chloro-1,1'-diphenyl ether, 1-amino-2,5-dichlorobenzene, 1-amino-2-hydroxy-4-chlorobenzene, 1-amino-4-chloro-2,5-dimethoxybenzene, 1-amino-2-methyl-5-chlorobenzene, 1-amino-2-chloro-4-nitrobenzene, 4-amino-4'-cyclohexyl-1,1'-diphenyl ether, l-amino-2- or -4-nitrobenzene, l-amino-4-methyl-3-nitrobenzene, 1-amino-4-methyl-2-nitrobenzene, 1-amino-2,4-dimethylbenzene, 1-amino-3,4-dichlorobenzene, 2-acetylamino-4-amino-1-methylbenzene, 3-aminoacetanilide.

Dyeing instruction 20 parts of the dye from Example 1 are with 80 parts of dextrin mixed in a ball mill for 48 hours; 1 part of the so The preparation obtained is made into a paste with 1 part of 40% acetic acid, the pulp with Pour 200 parts of demineralized water and briefly boil it. One dilutes with 7000 parts of demineralized water, add 2 parts of glacial acetic acid and add 600 with 100 parts of polyacrylonitrile fabric into the bath. You can do the material beforehand 10 to 15 minutes at 60 ° in a bath consisting of 8000 parts of water and Pre-treat 2 parts of glacial acetic acid.

The mixture is heated to 98-100 ° within 30 minutes and cooked for 1 1/2 hours long and rinse. A yellow dyeing with good lightfastness and good fastness is obtained Wet fastness properties.

Example 2 16.2 parts of 1-amino-2,5-dichlorobenzene are known Kind of diazotized. The hydrochloric acid diazo solution is left at 0 ° in the course of one hour 21.3 parts of 1- (2'-hydroxy) -ethyl-2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine, dissolved in 50 parts of glacial acetic acid are added dropwise. At the same time, 200 parts of a 7 will show aqueous solution of crystallized sodium acetate was added dropwise. After the clutch the isolated and dried dye is in a mixture of 70 parts of dimethylformamide and 700 parts of toluene dissolved. This solution is mixed with 13.2 parts in one hour Thionyl chloride and heats the reaction mass to 1050 for some time the resulting 5- (2,5-dichloro) -phenylazo-1- (2-chloro) -ethyl-2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine isolated and purified by primary crystallization. 19 parts of this purified substance are in an aqueous 1 containing 4 parts hydroxylamine and 10 parts sodium acetate, Solution finely suspended and stirred at 800 for a long time. After completion of the implementation The dye is isolated (control by means of thin-layer chromatogram), salt-free washed, dried and for peralkylation (quaternization) in the presence of magnesium oxide and dimethylformamide in 300 parts of chlorobenzene with 13 parts of dimethyl sulfate several Treated at 1200 hours. After cooling, the quaternary dye is isolated and purified by recrystallization.

The new, water-soluble dye is used to color polyacrylonitrile in very real greenish yellow nuances.

Example 3 A solution consisting of 10 parts of 2-amino-thiazole in 100 parts of sulfuric acid from 530 Baume is within one hour at 0 ° with 13.7 Parts of nitrosylsulfuric acid are added. The diazo solution thus obtained is increased to 150 Pour parts of ice and destroy the excess acid with aminosulfonic acid. To the Diazo solution is left with a solution consisting of 27.5 parts of 1- (3'-methoxy-3'-methylamino) propyl-2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydroxypyridine and 50 parts of water are added dropwise over the course of an hour, then 60 parts of table salt are added and isolate the dye in the usual way.

Dried and ground, it is a water-soluble powder, which is suitable for dyeing polyacrylonitrile in real neutral yellow tones.

Reached similar dyes with equally good properties if in Example 3 the 27.5 parts of 1- (3'-methoxy-3'-methylamino) propyl-2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine by the equivalent amount of 1- (3'-methoxy-3'-methylamino) -propyl-2-keto-3-cyano-4-phenyl-6-hydroxy-1,2-dihydropyridine or 1- [4 '- (# "- Methoxy - #" - methylamino) - acetamino -ph enyl- 2-keto- 3-cyano- 3-methyl- 6-hydroxy-1,2-dihydropyridine or 1- (2'-ethoxy-2 1-aethylamino) -ethyl- -2-keto-2-cyano-4-methyl-6-hydro = .y-1,2-dihydropitria n or 1- (2'-butoxy-2'-butylamino) -ethyl-2-keto-3-cyano-4-phenyl-6-hydroxy-1,2-dihydropyridine replaced or by the amount of the diazo component used by an equivalent Amount of 3-amino-1,2,4-triazolone or 3-methyl-5-amino-1,2,4-triazole or 3-aminoindazole or 4-methyl-3-amino-indazole or 2-amino-1,3,4-thiadiazole or 2-amino-4-methyl-1,3,4-thiadiazole or 2-amino-4-methyl-1,3,4-thiadiazole or # -dimethylamino-4-amino-acetophenone or 2'-dimethylamino-4-aminopropipphenone or 1 - (# - dimethylamino) acetamino-4-aminobenzene or l-tw-diethylamino) -acetamino-4-aminobenzene.

Example 4 34.6 parts of the dye of the formula obtained according to Example 3 are dissolved in 750 parts of chlorobenzene and quaternized with 50 parts of dimethyl sulfate in the presence of 4 parts of magnesium oxide. The dye salt is filtered off, purified by washing with acetone and by recrystallization. The new dye is water-soluble and is suitable for dyeing polyacrylonitrile in neutral yellow real tones.

Likewise, large dyes are obtained if those mentioned in Example 3 are used Compounds used and quaternized as indicated above.

Example 5 17.25 parts of 1-amino-2-nitro-4-chlorobenzene are known Kind of diazotized. The hydrochloric acid diazo solution is left at 0 ° over the course of one hour 21.3 parts of 1- (2'-hydroxy) ethyl-2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine, dissolved in 50 parts of glacial acetic acid, add dropwise. At the same time, 200 parts of a 7 will show aqueous solution of crystallized sodium acetate was added dropwise. The dried one Dye is then added in a mixture consisting of 700 parts of toluene and 70 Parts of dimethylformamide, dissolved. This solution is added over the course of an hour with 13.2 parts of thionyl chloride and the reaction mass is heated to 1,050 it is cooled to 400 and the solution is mixed with 13.7 parts of N-methoxy-N-methyl-2-hydroxy-ethylamine and heated to 1050 for 5 hours. The precipitated dye is on a Filters collected, dried, and purified by recrystallization.

The new dye is readily soluble in water and can be used to dye polyacrylonitrile can be used in real greenish yellow nuances.

Very similar, equally good dyes are obtained if one im Example 5 the 17.25 parts of 1-amino-2-nitro-4-chlorobenzene by the equivalent amount l-amino-4-nitro-2-chlorobenzene or l-amino-2-nitro-4-methylbenzene or l-aminobenzene-4-sulfodimethylamide or 1-aminobenzene-4-acetylbenzene or 4-aminobenzoic acid ethyl ester or l-amino-2,5-dichlorobenzene or l-amino-2,4-dinitrobenzene or by adding 13.7 parts of N-methoxy-N-methyl-2-hydroxy-ethylamine by the equivalent amount of N-methoxy-N-methylbenzylamine, triethylhydroxylamine, N-Aethoxy-N-äthal-2-hydroxy-äthalamin, N-Metoxydibutylamin replaced.

All of these amines can be present in any of their cationic structure other dyes occur.

Example 6 39.0 parts of the compound of the formula are dissolved in 500 parts of chlorobenzene and treated with 50 parts of dimethyl sulfate at 1200 and quaternized at 1300. The solution is then cooled to room temperature, the precipitated dye is filtered off, washed with acetone and dried. The yellow powder obtained is readily soluble in water and is particularly suitable for coloring polyacrylonitrile.

Dyes that are just as good can be obtained by following the example above the quaternization is carried out with diethyl sulfate.

The compound used can be obtained by coupling diazotized 1-amino-4-chlorobenzene to 1- (3'-methoxy-3'-methylamino) propyl-2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine can be obtained.

Example 7 13.5 parts of 1-amino-4-acetylbenzene are in 200 parts 6% ice-cold hydrochloric acid diazotized as usual. This solution is added dropwise 0 ° a solution consisting of trimethylhydroxylammonium) propyl-2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine methyl sulfate and 150 parts of water in one hour. At the same time you bet. 200 parts of a 14% aqueous solution of crystallized sodium acetate too. After the clutch the dye is converted into the chloride with sodium chloride and sintered out. The new dye is filtered off, washed out, dried and milled a yellow powder. It dissolves in water and can be used to color polyacrylonitrile can be used in real green-tinged yellow tones. If you replace in this example the 40 parts of 1- (3'-N'-N ', N'-trimethylhydroxylammonium) propyl-2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine by the equivalent amounts of 1- (2'- N '-Methoxy-N' -methyl-N'-benzyl ammonium) -ethyl-2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine methyl sulfate or 1- [2 '- (N'-methoxy-N'-methyl-2 "-hydroxyethylammonium chloride)] - ethyl-2-keto-3-cyano-4'-methyl-6-hydroxy-1,2-dihydropyridine, thus, dyes having excellent properties are obtained as well.

Example 8 12.32 parts of 1-amino-2-methoxy-benzene are known Kind of diazotized. A solution is added to the ice-cold mineral acid diazo solution from 25 parts of 1- (3'-methoxy-30-methylaminopropyl) -2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine in 80 parts of water. Then the stirring is continued at 0 °. The new dye is then salted out by means of sodium chloride at 80 °, filtered off and dried. 38.5 parts of the dye are dissolved in 500 parts of chlorobenzene at 1000. at 26 parts of dimemethyl sulfate are added at the same temperature and the mixture is stirred for a further 5 hours at 2000.

After cooling, collect the precipitated salt from the qu; erern Dye on a filter and wash it off with chloroform and petroleum ether.

When taken in an aqueous bath, this salt gives polyacrylonitrile fibers a high color lightfast and wetfast in reddish-yellow clear shades of yellow.

An analogous dye is obtained if, instead of dimethyl sulfate, 35 parts of benzyl chloride are used.

Instead of the 25 parts of 1- (3'-methoxy-3'-methylaminopropyl) -2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine, an equivalent amount of a compound of the formula used and moves ie. If, moreover, quaternizing is carried out according to the information in Example 8, quaternary dyes with equally good Z properties are obtained, where X10 stands for the following radicals -CH2-CH-CH3 and where F stands for the radicals listed in Table A. These groupings can easily be exchanged for another of the groupings indicated in each individual dye.

Example 9 In a suspension of 17.25 parts of 1-amino-2-nitro-4-chlorobenzene In 200 parts of 6-point hydrochloric acid, 30 parts of 23-point sodium nitrite solution are left at 0-5 ° come in. The resulting diazo solution is diluted with 200 parts of ice water and then adds 24 parts of 1- (3'-N'-methoxy-N'-methylaminopropyl) -2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine, as a hydrochloric aqueous solution. After coupling, the dye formed is precipitated in the usual way as a hydrate of chlorine by means of sodium chloride, on a Filters collected and dried.

It can be purified by recrystallization, e.g. from acetic acid. When ground, the dye is a yellow powder that dissolves in water and is polyacrylonitrile colors in pure yellow, lightfast and wetfast tones.

For the preparation of 1- (3'-N'-methoxy-N'-methylaminopropyl) -2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine is cyanoacetic acid ester using a known method with 3-N'-methoxy-N'-methylaminopropylamine converted to cyanoacetic acid 3-N'-methoxy-N'-methyleminopropylamide and this in known methods to I- (3'-N'-methoxy-N'-methylaminopropyl) - 2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine condensed. The so obtained Dyes are quaternized with dimethyl sulfate as described in Example 8.

The following table shows the structure of other dyes indicated - as obtained according to the information in Example 8, ie. be quaternized can.

They correspond to the formula in which R1, R3, X1 and F have the meanings given in the table.

The symbol F can represent any of those listed in Table A. Remnants F are. These groupings can easily be found in any single dye be replaced by another of the specified groupings.

Table A F can stand for the symbols Fl-Fll, where F1 to F11 are the means below groupings.

T able A Nuance of Ex. R1 xl FR staining No. II polyacrylic nitrile NO 10 S -C2H4- F1 -CH3 yellow 11 do do P F9 c? S do 12 do -C3H6- F9 do do 13 6-Methylsulfo do F -CH3 do 1 9 lyl-2 NO 2 14 C1 -C2H4- 1 do do 15 do do F2 do do 16 do da F3 do 1 do 17 da do F4 do thu 18 do do F5 do do 19 do do F6 do do 20 do do F7 do do 21 do do F8 do do 22 do do F9 do do 23 do do flo do do 24 do da F11 do do 25 do CH2-CH2-CH2- F1 do do 26 do do F2 do do 27 do do F3 do do 28 do do - F4 do do 1 9844/1652 w Nuance of E.g. RXF staining No. 1 1 3 R3 polyacrylic nitrile N02 2 29 C1 9 -CH2-CH2-CH2- F5 -CH3 yellow 30 do do F6 do do 31 do do F7 do do 32 do do F8 do do 33 do do F9 do dc 34 do - do flo do do 35 do do F11 do do 36 do -C2H4- F1 e do 37 do do F2 do do 38 do do F3 do do 39 do do F4 do do 40 do do F5 do do 41 do do F6 * do do 42 do do F7 do do 43 do do F8 do do 44 do do F9 do do 45 do do F10 do do 46 do do F11 do do 47 do -CH2-CH2-CH2- F1 do do 48 do do F2 do do 49 do do F3 do do Nuance of E.g. PR, polyacrylic No, s J 50 Cl 2 -CH2-CH2-CH2- F4 e yellow 51 da da F5 do da 52 da do F6 do thu 53 do do F7 there do 54 do do F8 do do 55 do do F9 do do 56 do do flo do do 57 do do F11 do do 58 do 2 <F1 -CH3 do 59 do do F9 do do 60 do do F2 do do 61 do -NH-CO-CH2- F4 do do 62 do do F4 do do 63 there do F3 do there 64 do -NH-CO- 9 CH2- F4 do do 65 do do F9 do do 66 do do P F5 i there there 67 da -H2C o N-CO-CH2 F4 do do 68 do do F9 do do 69 do do F6 do do 6th 70 do 2 do r 70 da - NH-O0-OH F4 dc dc Nuance of Ex. RXFR staining No. 1 1 3 polyacrylic nitrile nitrile 71 C1 H2ONH-O0-OH2 F9 OH3 yellow 2 72 do do F1 do there NH- CO- OH2- 73 do -H2C 4 SH-CO-CH2- 2 F4 do do 74 do do F9 do do 75 do do F2 do do 76 do -CH2cH-CH3 F4 t do 77 dc do F9 do do 78 do dc F11 do do 79 do -NH-CO-CH2-F4 do; do 80 do do F9 do do 81 do do flo do do 82 do -NH-CO o CH2- F4 do do 83 do do F9 do r 84 do do F5 do 'ao 85 doH2C-Q F4 do do 86 do do F9 do do 87 do do F7 do do If the 17.25 parts of l-amino-2-nitro-4-chlorobenzene in Examples 5 and 9 are replaced by an equivalent amount of the amines1 mentioned below, quaternary dyes with equally good properties are obtained. The dyes obtained give yellow to reddish yellow colorations on polyacrylonitrile.

1-amino-2-nitro-4-methylbenzene l-amino-4-benzoylaminobenzene l-amino-4'-chlorodiphenyl ether l-amino-4-sulfonic acid dimethylamide l-amino-2-chlorobenzene l-amino-4-chlorobenzene l-amino-3-chlorobenzene 1-amino-2,5-dichlorobenzene l-amino-3,4-dichlorobenzene 1-amino-2-bromobenzene l-amino-3-bromobenzene 1-amino-2,4,6-tribromobenzene 1-amino-2,4,6-trichlorobenzene 1-amino-2-methoxybenzene 1-amino-2-methylbenzene 1-amino-3-methylbenzene 1-amino-4-methylbenzene 1-amino-2,5-dimethylbenzene 1-Amino-2-methoxybenzene-5-sulfonic acid amide 1-amino-4-nitrobenzene 1-amino-3-nitrobenzene 1-aminobenzene 1-amino-2-methoxy-4-nitrobenzene 1-Amino-2-methoxy-5-nitrobenzene 1-amino-3-chloro-4-methoxybenzene 1-amino-4-acetylaminobenzene l-amino-4-methoxybenzene l-amino-4-ethoxybenzene l-amino-2,6-dichloro-4-nitrobenzene 1-amino-2,4,5-trichlorobenzene 4-amino-4'-chloro-1,1'-diphenyl ether.

B e i 5 p i e 1 88 300 parts of 4-pointer hydrochloric acid are 9.3 parts Aminobenzene diazotized in the usual way. A solution is then added dropwise at 0 ° of 29 parts of 1- (4'-N'-methoxy-N'-methylaminomethylphenyl) -2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine (produced by reacting ethyl cyanoacetate with 4-amino-N'-methoxy-N'-methylbenzylamine to 4-cyanoacetamino-N'-methoxy-N'-methylbenzylamine and subsequent condensation the product obtained with ethyl acetoacetate in the presence of ammonium acetate, dissolved in 50 parts Glacial acetic acid, and at the same time added 100 parts of 12.5 ° / ager aqueous sodium acetate solution. After the coupling, the Reaction mass heated to 600, made mineral acid with hydrochloric acid and then the New dye present as a hydrochloric acid salt by salting out and filtering off isolated. It can be purified by recrystallization. Dried and ground you get a water-soluble powder, with which polyacrylonitrile in real yellow Tones can be colored.

The dye obtained is quaternized according to the information in the example 8 with dimethyl sulfate, an excellent quaternary dye is obtained, which colors polyacrylonitrile in ec ten yellow tones.

Example 89 17 parts of 1-amino-2-nitro-4-methylbenzene are diazotized according to the customary method and with 30.6 parts of a compound of the formula dissolved in an aqueous solution of hydrochloric acid, coupled. After coupling, the dyestuff formed is precipitated in the usual way as a hydrate of chlorine using sodium chloride and then quaternized with dimethyl sulfate as described in Example 8. When ground, the dye is a yellow powder, which gives polyacrylonitrile an excellent color in pure yellow, lightfast and wetfast shades.

If the coupling component of the formula (a) given above is replaced by an equivalent amount of the coupling component of the formula and quaternized with dimethyl sulfate in the same way, a yellow dye is also obtained with the same good properties.

For example 1 90 10.7 parts of 1-amino-4-methylbenzene are used in 200 Parts of 6% hydrochloric acid are diazotized at O with 6.9 parts of sodium nitrite. To the ice cold Diazo solution is given a solution consisting of 23 parts in the course of one hour 1-2 '- (N'-Methoxy-N'-methylaminoethyl) -2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine, 30 parts of dimethylformamide and 70 parts of methyl alcohol. This is where the pH value is set dss reaction medium to 4.0 by adding sodium acetate and stir until the end the clutch.

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

10 parts of the dye are in 100 parts of dimethyl sulfate for 1 hour heated to 100e for a long time. The mass is diluted with 300 parts of ethyl alcohol and finally the quaternary dye precipitated by the addition of ether.

Filtered off, dried and ground, lies a yellow water-soluble one Powder before which polyacrylonitrile fibers are colored in very real yellow tones can be. A similar, equally valuable, dye can be obtained if in this example, the 10.7 parts of 1-amino-4-methylbenzene are replaced by 13.5 parts of 1-amino-4-acetylbenzene replaced and otherwise proceed as described.

The coupling component used is obtained by condensation of the Reaction product of ethyl cyanoacetate with 2; -Methoxy-2'-methylethylenediamine with ethyl acetoacetate in the presence of a secondary amine1 such as morpholine.

B e i 5 p i e 1 91 19.7 parts of 4-amino-1,1'-azobenzene, which are based on known Art were diazotized in 200 parts of 6% hydrochloric acid with 6.9 parts of sodium nitrite, wer.den at 200 with a solution consisting of 21.5 parts of 1- (2'-hydroxyethyl) -2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine and 120 parts of methyl alcohol are added. The pH of the reaction mass is adjusted with sodium carbonate set to 4.0 and stirred further until the coupling reaction is complete.

20.1 parts of the dye obtained are dissolved in 180 parts of dimethylformamide, the solution is treated with 5.6 parts of thionyl chloride at room temperature, and the mixture is stirred for 45 minutes at 600 and the chlorine-containing dye precipitates by dilution with water, collects put it on a filter, wash it with water and dry it.

21 parts of this dye are mixed with 200 ') parts of dimethylformamide added and heated to 700 for 1 hour with 8.4 parts of N, N-dimethylhydroxylamine. The dye solution obtained is then made mineral acid by adding hydrochloric acid placed and the dye precipitated as hydrochloride by adding sodium chloride. According to the information in example 8 wfrd the dye with dimethyl sulfate quaternized, an orange-brown powder is obtained, the polyacrylonitrile in real reddish yellow tones.

Used the chlorine-containing dye instead of N, O-dimethylhydroxylamine with the equivalent amount of N-ethoxy-2t-hydroxyethylamine or N, O-di-benzylhydroxylamine added, the corresponding quaternary salts of the dye are obtained. she also color polyacrylonitrile in real rusty yellow tones.

The coupling component can be obtained by condensation of 2-hydroxyethyl amide cyanoacetic acid with acetoacetic acid ter, for example in the presence of a secondary amine, such as e.g. N, O-dimethylhydroxylamine, N-ethoxy-2'-hydroxyethylamine, N, O-dibenzylhydroxylamine, N, O- (di-2'-hydroxyethyl) -hydroxylamine are produced.

For example 92 9.3 parts of 1-aminobenzene are added at 0 ° in 200 parts 6 pointer hydrochloric acid dissolved with 6.9 parts of sodium nitrate: it is diazotized. The ice cold one Diazo solution is added to a neutral aqueous solution over the course of one hour from 24 parts of 1- (2'-N ', N'-dimethylhydroxylamino) -alkyl- (4) -2-keto-3-cyano-4-methyl-6-hydroxy-1,2-dihydropyridine and 200 parts of water. The pH of the reaction medium is then increased Dropping of 10 of the above sodium carbonate solution to 5.5 and stir at 00 until the clutch is terminated. The mass is then mineralized with hydrochloric acid and the dye at 45 "by adding sodium chloride as the chlorohydrate failed. Filtered off, washed with hydrochloric acid brine, dried and ground, is a yellow water-soluble powder with which polyacrylonitrile fibers in real tones can be colored.

To convert into a quaternary compound, 10 parts of the Dyestuff dissolved in 200 parts of chlorobenzene with 15 parts of dimethyl sulfate and 1.2 Parts of magnesium oxide heated to 1300 for several hours. Cooled to room temperature, the quaternary dye is precipitated with acetone, filtered off and washed with acetone washed. The dye can be mixed with sodium chloride from a hydrochloric, aqueous solution precipitated as chloride. This dye is also suitable for dyeing Polyacrylonitrile fibers in very real yellow tones.

The coupling component used in this example is obtained through Condensation of the reaction product of methyl cyanoacetate and N-methoxy-N-methyl-N- (2'-amino) ethylamine with methyl acetoacetate.

EXAMPLE 93 99 parts of methyl cyanoacetate become 102 Parts of 3- (N-methoxy-N-methyl) propylamine are added dropwise so that the reaction temperature; Ir does not rise above 400. Then you boil the G-mix under reflux, leave it Temperature drop somewhat, sets 116 parts of methyl acetoacetate and 7.1 parts Diethylamine is added and then refluxed for a further 3 hours. The educated Methyl alcohol and the water formed are removed from the reaction mass under reduced pressure distilled off.

After the temperature has dropped to 950, the piston residue becomes diluted with 100 parts of water. A 52.5% aqueous solution of 1- (3'-N'-methoxy-N'-methylamino) -propyl-2-keto-3-cyano-4-methyl-6-hydroxy-1,2- dihydropyridine.

50 parts of this solution are now allowed to form an ice-cold aqueous solution Diazo suspension, which by a known method from 24.8 parts of 1-aminobenzene-4-sulfonic acid phenylamide has been made, add dropwise. The dye is isolated as the hydrochloride. When dried and ground, it is a water-soluble yellow powder made from fibers Polyacrylonitrile and polyvinylidene. cyanide in very real greenish yellow tones colors.

16 parts of the dye obtained are in 100 parts of dimethyl sulfate 1 hour at 10c? heated. The reaction mass is made with 300 parts of methyl alcohol diluted and the quaternary dye precipitated by adding ether. Dried then lies a dye salt before, which is in water with yellow Color dissolves and polyacrylonitrile and polyvinylidenecyanide fibers in greenish yellow, colors very real tones.

Similar dyes that are so excellent can be obtained if in the above example the 102 parts of 3-amino-N'-methoxy-N '-methylpropylamine replaced by an equivalent amount of the following amines N'-methoxy-N'-methylamino-ethylainn, N'-ethoxy-N'-ethylamino-ethylamine, N'-methoxy-N'-methylaminopropylamine, N'-ethoxy-N'-ethylaminopropylamine, N '-Methoxy-N' - (2 '' -hydroxyethyl) -aminoethylamine, 2 '- [N'-methyl-O' - (2 "-hydroxyethyl)] - aminmoäthylamino, N'-ethoxy-N '- (2'-hydroxyethyl) aminopropylamine, and then with dimethyl sulfate quaternized.

Similar, equally valuable dyes can be produced if in the above example, the 24.8 parts of 1-aminobenzene-4-sulfonic acid phenylamide are carried out the equivalent amount of 4-aminobenzoic acid ethyl ester, 4-aminobenzoic acid phenylamide, 2-aminobenzoic acid methyl ester, 1-amino-2-nitro-4-methylbenzene, l-amino-l, 5-dichlorobenzene, 4-aminodiphenyl, 2-aminodiphenyl, 2-amino-4-chlorodiphenyl ether, 4-amino-4'-chlorodiphenyl ether, l-amino-4-methylbenzene-3-sulfonic acid phenylamide, 2-aminobenzene-l-sulfonic acid-N-ethyl-N-phenylamide, l-amino-3-benzoylaminobenzene, l-amino-3-chloro-4-methoxybenzene, l-amino-3-chloro-4-methylbenzene, 4-amino-2 ', 4'-dinitrodiphenylamine, l-amino-4-methylbenzene, l-amino-2-methyl-4-chlerbenzene, l-amino-2-chlorobenzene, l-amino-2-cyano-5-chlorobenzene, l-amino-2-chloro-4-nitrobenzene, l-amine-2-methoxy-4-nitrobenzene, l-amino-4-benzoylaminobenzene, 4-aminobenzenesulfonic acid dimethylamide, l-amino-2-methyl-5-nitrobenzene, 1-amino-4-carbethoxybenzene, 4-amine-azebenzene, 4i-amino-4'-methylbenzophenone, 4-amino-2 ', 4'-dinitro-diphenylamine, replaced.

B e i 5 p i e 1 94 25.6 parts of 4-amino-4'-chloro-1,1'-diphenyl ether chlorohydrate are dissolved in 300 parts of water and, after the addition of 18 parts, 30 pointers hydrochloric acid diazotized with 6.9 parts of sodium nitrite in the usual way. This diazo solution gives one then in a 100% solution consisting of 24.9 parts of 1- (3'-N'-methoxy-N'-methylamino-ethyl) -2-keto-3-cyano-4-methyl-6-hydroxy-1 , 2-dihydropyridine and 200 parts of 2 point aqueous hydrochloric acid, and stirred until the coupling has ended. The dye produced in this way is precipitated at 600 with sodium chloride and filtered off and dried. The new dye is an orange-colored powder that contains polyacrylonitrile fibers colors in reddish yellow, pure lightfast and wetfast tones.

15 parts of the dye obtained are in 150 parts of isopropyl alcohol stirred, mixed with 15 parts of dimethyl sulfate and the mixture heated for one hour. After cooling, the quaternized dye with ether or dioxane or Acetone will be precipitated. Filtered off and dried, a dye is obtained which from aqueous solution polyacrylonitrile and polyvinylidenecyanide fibers in reddish tint yellow, lightfast and wetfast tones.

The coupling component is produced by condensation of cyanoacetic acid 3-N-methoxy-N-methylamino-n-propylamide made with ethyl acetoacetate.

B e i s i e l 95 12.75 parts of 1-amino-2-chlorobenzene are in a Mixture consisting of 250 parts of water and 40 parts of 30-point hydrochloric acid 1 dissolved and diazotized in the usual way with 6.9 parts of sodium nitrite at 0 °. To the diazo solution a solution is now allowed to exist in the course of an hour, with stirring and cooling from 1- (4-ethyl) -phenyl-2-keto-3-cyano-4-methyl-2 ", 6-dihydroxy-1,2-dihydropyridine add dropwise in 150 parts of glacial acetic acid and stir until the coupling is complete. Of the The dyestuff precipitated in crystallized form is filtered off and recrystallized cleaned.

40.8 parts of this dye are dissolved in 300 parts of pyridine and added this solution at 100 with 22 parts of 4-methylbenzenesulfonic acid chloride. After 7 hours Stirring at 100 is the esterified dye by diluting with 1500 parts of water precipitated, filtered off and dried. 11.3 parts of dimethylaminobenzene and 6.5 parts Trimethylhydroxylamine boiled under reflux for 8 hours. The one while cooling down precipitated quaternary dye is collected on a filter and washed with chloroform washed out.

It dyes fibers made of polyacrylonitrile and pelyvinylidenecyanide in in greenish yellow nuances with excellent fastness properties.

Similar dyes, also yellow, are obtained if one places of trimethylhydroxylamine, triethylhydroxylamine, N-methoxy-N-methyl- (2'-hydroxy) -ethylamine, N-methoxy-N- (2 "-hydroxy) -ethyl- (2" -hydroxy) -ethylamine is used.

The coupling component used in this example can be produced by condensation of cyanoacetic acid 4- (2'-hydroxy) ethylphenylamide with ethyl acetoacetate in In the presence of a secondary amine such as piperidine.

Claims (13)

P atent claims 1. Basic azo dyes of the formula where D is an optionally substituted aromatic carbocyclic or aromatic heterocyclic radical, Rj is the cyano group, an acyl radical or a carboxylic acid ester radical, R2 is an unsubstituted alkyl radical or an optionally substituted aryl radical or an optionally substituted heterocyclic radical or a group of the formula R3 and R4 each represent a hydrogen atom or an optionally substituted alkyl or aryl radical, or together with -N- can form a ring, yl is a divalent bridge member, an optionally substituted, etherified hydroxylammonium group and A- is an anion. 2. Basic azo dyes according to claim 1 of the formula where R'1 and R @ 'each represent an optionally substituted alkyl or cycloalkyl radical and R3' an optionally substituted hydrocarbon radical and R'1 and R'2 together with the N atom can form a heterocycle and D, R1, R2, Y1 and AS have the meanings given in the claim. 3. Basic azo dyes according to patent claims of the formula where R2 "denotes an optionally substituted alkyl or cycloalkyl radical and D, R1, R2, Y1, R1 ', R3' and A- have the meanings given in claim 2. 4. Process for the preparation of basic azo dyes of the formula (I) according to claim 1, characterized in that the diazo compound is coupled from an amine of the formula D-NH2 (IV) with a compound of the formula. 5. A process for the preparation of basic azo dyes of the formula (I) according to claim 1, characterized in that a compound of the formula is used where A denotes a radical which can be converted into an anion, is reacted with an optionally substituted, etherified hydroxylamine. 6. Process for the preparation of basic azo dyes of the formula (11) according to claim 2, characterized in that a compound of the formula (VI) according to claim 5 with a compound of the formula implements. 7. Process for the preparation of basic azo dyes of the formula (III) according to claim), characterized in that a compound of the formula quaternized. 8. Use of the dyes according to claim 1 for dyeing or Printing of fibers, threads or textiles made from them made from acrylonitrile polymers or -mischpolmerisaten exist or contain such. 9. Use of the dyes according to claim 1 for dyeing or Printing of fibers, threads or textiles made therefrom made from synthetic Polyamides or synthetic polyesters modified by acidic groups are, exist or contain such. 10. Use of the dyestuffs according to claim 1 for dyeing from Plastics and leather. 11. Use of the dyes according to claim 1 for dyeing Paper. 12. The materials colored according to claims 8 to 11. 13. The method according to claim 1, characterized in that; that the anion As is replaced by another anion.