DE2500064A1 - Cationic azo dyes from 2,6-dihydroxy pyridine - coupling components contg benzimidazolyl, benzoxazolyl or benzthiazolyl substits - Google Patents

Abstract

Basiz azo dyes of formula (I): (where D is the gp. of a diazo component; n is 0 or 1; R is methyl, ethyl, beta-hydroxy ethyl or beta-hydroxypropyl; R2 is H, Cl or methyl; R1 is as R2, Br, methoxy or ethoxy; X is NH, NR O or S; A- is an anion) are used for the dyeing of synthetic polyamides or esp. polyesters (dyes with n=O), or anionic modified fibres, e.g. polyesters and acrylonitrile, (dyes with n=1), in yellow to violet shades. The dyes have good to very good fastness, esp. to light.

Description

Azo dyes The invention relates to dyes of the formula in which D is the remainder of a Diaaokoponente, n 0 or 1, R is methyl, ethyl, ß-hydroxyethyl or ß-hydroxypropyl, R¹ is hydrogen, chlorine, bromine, methyl, methoxy or ethoxy, R2 is hydrogen, chlorine or methyl, X NH, NR , 0 or S and A- represent an anion.

The radicals D are derived in particular from amines of benzene, benzothiazole, Benzisothiazole, thiazole, thiadiazole, thiophene, azobenzene or inthraquinone series away.

Substituents for the radicals D of the diazo components are, for example to be mentioned: In the benzene series: chlorine, bromine, nitro, cyano, trifluoromethyl, methylsulfonyl, Ethylsulfonyl, phenylsulfonyl, carbomethoxy, carbobutoxy, carbo-ß-methoxyethoxy, Carbo-ß-hydroxyethoxy, optionally N-mono- or N-disubstituted carbon- or Sulfonamide, methyl, ethyl, butyl, octyl, hexyl, methoxy or ethoxy.

N-substituents of the carbon or sulfonamides are z. B. methyl, Ethyl, propyl, butyl, β-hydroxyethyl, γ-hydroxypropyl, ß-methoxyethyl, γ-methoxypropyl or y-ethoxypropyl and the pyrrolidide, piperidide or morpholide.

In the izobenzene series: chlorine, bromine, nitro, cyano, methyl, ethyl, methoxy or ethoxy.

In the heterocyclic series: chlorine, bromine, nitro, cyano, methyl, ethyl, Phenyl, methoxy, ethoxy, methyl mercapto, ß-carbomethoxyethyl mercapto, ß-carboethoxyethyl mercapto, Carbomethoxy, carboethoxy, acetyl, methylsulfonyl or ethylsulfonyl.

Diazo components with at least one substituent are preferred such as ethyl sulfonyl, phenylsulfonyl, ethylsulfonyl, carbalkoxy, optionally N-substituted Carbamoyl and especially nitro or cyano.

The remainder of B is derived in detail z. B. from the following amines: o-, m- or p-nitroaniline, o-, m- or p-cyananiline, 2,4-dicyananiline, 2,4,6-tribromaniline, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline, 2-cyano-4-nitroaniline, 2-methylsulfonyl-4-nitroaniline, 2-methyl-4-nitroaniline, 2-methoxy-4-nitroaniline, 4-chloro-2-nitroaniline, 4-methyl-2-nitroaniline, 2-hexyl-4-nitroaniline, 4-methoxy-2-nitroaniline, 1-amino-2-trifluoromethyl-4-chlorobenzene, 2-chloro-5-aiinobenzonitrile, 2-amino-5-chlorobenzonitrile, 1-amino-2-nitrobenzene-4-sulfonic acid-n-butylamide or -ß-methoxyethylamide, 2,4-dinitroaniline, 2,4-dinitro-6-chloroaniline, 2,4-dinitro-6-bromaniline, 2,4-dinitro-6-cyananiline, 1-amino-2,4-dinitrobenzene-6-methylsulfone, 2,6-dichloro-4-nitroaniline, 2,6-dibromo-4-nitroaniline, 2-chloro-6-broa-4-nitroaniline, 2,6-dicyan-4-nitroaniline, 2-cyano-4-nitro-6-chloroaniline, 2-cyano-4-nitro-6-bronaniline, 1-aminobenzene-4-methylsulfone, 1-amino-2,6-dibromobenzene-4-methylsulfone, 1-amino-2,6-dichlorobenzene-4-methylsulfone, 1-Amino-2,4-dinitrobenzene-6-carboxylic acid methyl ester or -ß-methoxyethyl ester, 3,5-dichloroanthranilic acid propyl ester, 3,5-dibromanthranilic acid-ß-methoxyethyl ester, N-acetyl-p-phenylenediamine, 4-alinoacetophenone, 4- or 2-aminobenzophenone, 2- and 4-liinodiphenylsulfone, 5-xitroanthranilic acid methyl ester, -isobutyl ester, methyl diglycol ester, -S-methoxyethyl ester, -ß-butoxyethyl ester, -ß-acetoxyethyl ester, 3- or 4-aminophthalic acid, 3-amino-6-nitrophthalic acid-ß-hydroxyethylamide, Methylsulfonic acid 2'-, -3'- or -4'-aminophenyl ester, ethylsulfonic acid 2'-, -3'- or -4'-aminophenyl ester, butylsulfonic acid 2'-, -3'- or -4'-aminophenyl ester, Benzenesulfonic acid 2'-, -3'- or -4'-aminophenyl ester, 2-aminoanthraquinone, 1-amino-4-chloroanthraquinone, 2-aminobenzothiazole, 2-amino-6-carboxylic acid methyl ester benzothiazole, 2-amino-6-methylsulfonylbenzthiazole, 2-amino-6-cyanobenzothiazole, 2-amino-6-nitrobenzthiazole, 5,6- or 6,7-dichloro-2-aminobenzthiazole, 4-amino-5-bromo-7-nitro-1,2-benzisothiazole, 3-amino-5-nitro-2,1-benzisothiazole, 3-amino-5-nitro-7-bromo-2,1-benzisothiazole, 2-aminothiazole, 2-amino-5-nitrothiazole, 2-amino-4-methylthiazole-5-carboxylic acid ethyl ester, 2-amino-4-methyl-5-acetylthiazole, 2-amino-3-cyano-4-methylthiophene-5-carboxylic acid ester, 2-phenyl-5-amino-1,3,4-thiadiazole, 3-methylmercapto-5-amino-1,2,4-thiadiazole, 3-ß-carbomethoxyethylmercapto-5-amino-1,2,4-thiadiazole, 2,4-dicyano-3,5-dimethylaniline.

Suitable diazo components of the aminoazobenzene series are, for example: 4-aminoazobenzene, 2 ', 3-dimethyl-4-aminoazobenzene, 3', 2-dimethyl-4-aminoazobenzene, 2,5-dimethyl-4-aminoazobenzene, 2-methyl-5-methoxy-4-aminobenzene, 2-methyl-4 ', 5-dimethoxy-4-aminoazobenzene, 4'-chloro-2-methyl-5-methoxy-4-aminoazobenzene, 4'-nitro-2-methyl-5-methoxy-4-aminoazobenzene, 4'-chloro-2-methyl-4-aminoazobenzene, 2,5-dimethoxy-4-aminoazobenzene, 4'-chloro-2,5-dimethoxy-4-aminoazobenzene, 4'-nitro-2,5-dimethoxy-4-aminobenzene, 4'-chloro-2,5-dimethyl-4-aminobenzene, 4'-methoxy-2,5-dimethyl-4-aminoazobenzene, 4'-nitro-4-aminoazobenzene, 3,5-dibromo-4-aminoazobenzene, 2,3'-dichloro-4-aminoazobenzene, 3-methoxy-4-aminoazobenzene, 4'-hydroxy-2'-ethyl-4-sninossobensol.

The anions A- are derived from simple or complex inorganic ones or organic acids. Examples include: chloride, Bromide, jitrate, sulfate, methosulfate, ethosulfate, phosphate, formate, acetate, toluenesulfonate or tetrachlorozincate.

for the preparation of the dyestuffs of the formula 1, a diaso compound of amines of the formula II D-NH2 II can be used with a coupling component of the formula III implement by methods known per se and quaternize the reaction products if necessary.

Compounds of the formula III are from the patent (patent application P24 36420.3) known.

Diazotization and coupling and, if appropriate, the quaternization take place As usual, details can be found in the examples.

Dyes of the formula I a are of particular importance and I b where D1 is a diazo component of the aniline or aminoazobenzene series, R4 is hydrogen or methyl and Y is hydrogen, chlorine, bromine, methyl, methoxy or nitro and R, X and A- have the meaning given.

The dyes of the formula I are yellow to purple and are suitable for dyeing synthetic fibers on polpiids and especially polyesters (dyes lit n = O) and of anionically modified fibers such as polyesters and acrylonitrile polymers (Dyes with n = 1) Dyeings of good to very good fastness properties are obtained especially light fastness.

In the following examples, parts and percentages relate to unless otherwise noted, by weight.

Example 1 6.9 parts of o-nitroaniline are dissolved in 13 parts of solid sulfuric acid and 15 parts of water at 70 ° C. and dissolved in a mixture of 30 parts of water and stirred in 30 parts of ice. Add another 25 parts of ice to the mixture itt 16 parts by volume of a 23% sodium trite solution are added in portions. It will then stirred for a further 1 hour at 0.50C, filtered and the excess sodium drained destroyed by standard methods.

The solution of 18 parts of 2,6-dihydroxy-4- (benzimidazoyl-2 -) - pyridine in 115 parts of 6.5% sodium hydroxide solution is added dropwise at 0 ° -5 ° C. to the resulting diazonium salt solution. The acidic dye suspension is brought to a pH between 4 and 5 with saturated sodium acetate solution, stirred overnight, filtered off with suction, washed with water and dried. 17.5 parts of a yellow powder of the formula are obtained the polyethylene terephthalate fabric dyes in yellow shades with very good fastness properties.

The following dyes characterized by diazo and tupping components are also obtained analogously to the procedure described: Table 1 E.g. D- a color tone 1 os yellow Cl 1 1 3 Cl 1 1 4 l 1 1 Cl CI 5 d 6 O2J 1 1 7 1 1 7th C1 8 1 1 Ex. D- R | hue 10 2 9 Cl 4 ° 2 H yellow CI 10 02N u 102 11 0219-dc nn 10 12 ° 2J 4 1 a Br Cl 13 ° 2J ß Cl 14 4 102 15 34 nn COIH 16 2 1 1 COOClE3 17 1 1 18 115C200C 1 1 No. § D- R shade N02 19 CH, Od H orange 20 H5C 60CHN 1 1 21 H3COCHII 1 n 22 1 1 23 tJ45 w. CH CH = S> 8 24 1 1 25 (H5C2) 2B ew purple 26 (HoEsC2) 2Je 27 S CH3 yellow 28 1 1 No. D- R shade 29 Cl CK3 yellow Cl 30th C1 CI 31 6 nn 32 02N NO 33 6 n 102 34 nnn Cl 35 02 per n 102 36 Cl 1 CI 37 02Nb n COOCE 38 6 n 39 tX6 n orange Example 2 17.4 parts of the dye described in Example 1 are suspended in 150 parts by volume of o-dichlorobeniol, then 6 parts of magnesium oxide and 12.6 parts of dimethyl sulfate are added. The reaction mixture is then stirred at 120 ° C. for 5 hours. When cooling, the yellow precipitate is filtered off with suction, washed with ligroin and dissolved with 400 parts of acetic acid. By adding 1000 parts of aqueous 10% zinc chloride solution, the quaternized dye precipitates in the form of the zinc chloride double salt, which is filtered off with suction, washed bit of saturated sodium chloride solution and dried will.

20 parts of dye of the formula are obtained The dye dyes polyacrylonitrile fibers yellow with good lightfastness.

Analogously to the procedure described, the following cationic dyes are also obtained by quaternizing the corresponding azo dyes: Table 2 Jr. B-R shade 1 H Ae E yellow cl 2 ° A4 1 3 2 1 1 Cl 1 1 5 Cl 1 w 0 6 1 1 1 1 Cl No. D- R {shade CI 8 6 H yellow 9 H3COCHN e orange 10 H5C6CHff en 11 ttnw 102 12 6 CH3 yellow Cl 13 1 14th Cl 15 ° 2§ 4 1 16 0219n 17 t yy t orange Example 3 11.2 parts of 2,6-dihydroxy-4- [benzoxazolyl-2] pyridine are dissolved with 300 parts by volume of 10% sodium hydroxide solution and 150 parts by volume of N-methylpyrrolidone, filtered and converted into a diazotized solution (Example 1) of 6 , 9 parts of o-nitroaniline dripped. The pH value is maintained between 4 and 5 by simultaneously adding 30% of an acetic acid. After stirring overnight, the yellow precipitate is filtered off with suction, washed with water and dried. 18 parts of the dye of the formula are obtained The yellow dyeings that can be achieved on polyethylene terephthalate fabric with this dye base are very lightfast.

The following azo dyes are also obtained analogously to the procedure described: Table 3 Jr. D shade 1 & yellow 2 o2J 1 2 3 C1 4 102 4 ° / < Br 102 5 54 10 6 ZOOC 4 10 7 aX300: 4 No. D shade JO2 8 v OC 4 yellow 102 9 CH3O 4 orange 10 o Nt n Example 4 17.5 parts of 2,6-dihydroxy-4- (bensthiazolyl-2) pyridine are dissolved in 250 parts by volume of N-methylpyrrolidone and 5 parts of 50% sodium hydroxide solution and poured into a 6.9 parts diazotized solution as in Example 1 -Nitraniline dripped. The reaction mixture is then brought to a pH between 4 and 5 by adding 80 parts by volume of saturated sodium acetate solution and stirred overnight at room temperature. The yellow precipitate is then filtered off with suction, washed with water and dried.

25 parts of the dye of the formula are obtained the polyethylene terephthalate fabric turns yellow.

The following dyes, characterized by diazo and coupling components, are also obtained analogously to the procedure described: Table 4 No. t D shade yellow 2 02Ne n 3 N02 n 3n Cl 4 02Nb n 102 5. Clbo2 n 102 6 CH34o2 n 7th Cl 8 t§ oranBe

Claims (4)

Claims 1. Azo dyes of the formula in which D is the remainder of a diazo component, n is 0 or 1, R is methyl, ethyl, ß-hydroxyethyl or ß-hydroxypropyl, R1 is hydrogen, chlorine, broa, methyl, methoxy or ethoxy, R2 is hydrogen, chlorine or methyl, X is NH, NR , O or S and A- represent an anion. 2. Dyestuffs according to Claim 1 of the formula in which Y is hydrogen, chlorine, bromine, methyl, methoxy or nitro and R is hydrogen or methyl, and X has the meaning given. 3. A process for the preparation of dyes according to claim 1, characterized in that a diazo compound of amines of the formula II D-NH2 II with a coupling component of the formula III is reacted by methods known per se and the reaction products are optionally quaternized. 4. Dye preparations for dyeing synthetic fibers, containing In addition to the usual constituents, dyestuffs according to Claim 1.