DE2245093A1 - Sol azo dyes of the pyrimido-bis-benzimidazole series - for colouring polyamides in yellow to orange shades - Google Patents

Abstract

The dyes are of formula: (in which D is the gp. of a diazo component, M is H, Na, K or opt. substd. ammonium and n is 2, 3 or 4). D is pref. a 2-nitro phenyl gp., opt. substd. in 4-position, and n is 2. They are suitable for dyeing natural and synthetic polyamides, e.g. wool, silk, leather, and esp. nylon-6 and -6, 6.

Description

Water-soluble azo dyes of the pyrimido-bis-benzimidazole series The invention relates to new azo-pyrimido-bis-benzimidazole dyes of the formula I in which D is the remainder of a diazo component and M is hydrogen, sodium, potassium or optionally substituted ammonium and n is 2, 3 or 4.

The radicals D of the diazo component are preferably those which differ from anilines, aminoazobenzenes, aminophthalimides and aminoanthraquinones derive, which are preferred as substituents halogen, alkyl, alkoxy, cyano, alkylsulfonyl, Nitro, carboxyl, carbalkoxy, carbamoyi, N-substituted carbamoyl, sulfonamide, N-substituted sulfonamide and also the sulfonate group SO, carry know, where M has the meaning defined above. In particular, preferred substituents are: Chlorine, Bron, Methyl, - ^ thyl, Mthoxy, Xthoxy, Methylsulfonyl, Äthylsulfonyl, Nitro, Carbomethoxy, carboethoxy,% carbo-ß-ethoxyethoxy, carbo-ß-methoxyethoxy, Carbobutoxy, Carbo-ß-butoxyethoxy, carbamoyl, N-methylcarbamoyl, N- <thylcarbamoyl, N-propylcarbamoyl, N-butylcarbamoyl, N-hexylcarbamoyl, N-ß-ethylhexylcarbamoyl, N-ß-hydroxyethylcarbamoly, N-ß-Methoxyäthylcarbamoly, N-ß-Methoxypropylcarbamoyl, N-Cyclohexylcarbamoyl, N-Phenylcarbamoyl, N, N-dimethylcarbamoyl, N, N-diethylcarbamoyl, N-methyl-N-ß-hydroxyethylcarbamoyl, N-ethyl-N-ß-hydroxyethylcarbamoyl, N-butyl-N-ß-hydroxyethylcarbamoyl, N-methyl-N-phenylcarbamoyl, Carboxylic acid piperidide, carboxylic acid morpholide, carboxylic acid pyrrolidide, optionally phenylazo substituted by methyl, methyl, methoxy, thoxy, sulfonate and nitro, Sulphonamide, N-methylsulphonamide, N-thylsulronamide, N-propylsulphonamide, N-butylsulphonamide, N-hexylsulfonamide, N-ß-ethylhexylsulfonamide, N-ß-hydroxyethylsulfonamide, N-ß-methoxyethylsulfonamide, M-Y-Methoxypropylsulfonamid, N-Cyclohexylsulfonamid, N-Phenylsulfonamid, N, N-Dimethylsulfonamid, N, N-diethyl sulfonamide, N-methyl-N-ß-hydroxyethylsulfonamide, N-ethyl-N-ß-hydroxyethylsulfonymide, N-butyl-N-ß-hydroxyethylsulfonamide, N-methyl-N-phenylsulfonamide, sulfonic acid piperidide, Sulfonic acid morpholide and sulfonic acid pyrrolidide. In the case of the aniline derivatives the number of substituents in the diazo radical D is generally up to 5, preferably but are 2 or 3 substituents, the nature of which can be identical or different. Positionally the 2- and 4-positions relative to the diazo group i are preferred for the substituents aromatic core.

As substituted ammonium cations in the SO »M group are for example Trimethylammonium, triisopropylammonium, monoethanolammonium, diethanolammonium, Triethanolammonium, methoxyethylammonium, Ethylhexoxypropylammonium and dimethylphenylbenzylammonium.

According to the invention, the number of SO3M groups in the total dye molecule is 2, 5 or 4, whereby compounds with a number of 2 SO3M groups as substituents in the pyrimido-bis-benzimidazole component are preferred.

Dyes of the formula I a are of particular industrial importance in which -A is hydrogen, chlorine, bromine, methyl, ethyl, methoxy, thoxy, nitro, carboxyl, carbalkoxy optionally substituted by hydroxy or alkoxy and having 2 to 9 carbon atoms, carbamoyl, N-mono- or N, N-disubstituted carbamoyl, sulfonamide , N-mono- or N, N-disubstituted sulfonamide, optionally substituted phenylazo or the sulfonate group SO3M and M has the meaning given.

To prepare the dyestuffs of the formula I, diazo compounds of amines of the formula II D-NH2 with coupling components of the formula III where m stands for an integer from 1 to 3, implement in a manner known per se.

The dyes of the formula I can also be prepared by using compounds of the formula IV sulfated in a manner known per se. A particularly suitable sulfonation agent is oleum.

Examples of compounds of the formula II are: aniline, 2-, 3- and 4-chloro-aniline, 2-, 3- and 4-bromoaniline, 2-, 3- and 4-nitroaniline, 2-, 3- and 4-toluidine, 2-, 3- and 4-cyananiline, 2,4-dicyanoaniline, 3,4- or 2,5-dichloroaniline, 2,4,5-trichloroaniline, 2,4,6-trichloroaniline, 2 -Chlor-4-nitroaniline, 2-bromo-4-nitroaniline, 2-cyano-4-nitroaniline, 2-methylsulfonyl-4-nitroaniline, 2-methoxy-4-nitroaniline, 1-amino-2-trifluoromethyl-4-chlorobenzene , 2-chloro-5-aminobenzonitrile, 2-amino-5-chlorobenzonitrile, 1-amino-benzene-4-methylsulfone, 4-methyl-2-nitroaniline, 4-methoxy-2-nitroaniline, 4-ethoxy-2-nitroaniline, 4-chloro-2-nitroaniline, 2-jitroazdline-4-sulfonic acid, 4-nitroaniline-2-sulfonic acid, 2-nitroaniline-4-sulfonic acid amide, 2-nitroaniline-sulfonic acid methylamide, 2-nitroaniline-4-sulfonic acid dimethylamide, 2-nitroaniline 4-sulfonic acid ethylamide, 2-nitroaniline-4-sulfonic acid-ß-hydroxyethylamide, 2-nitroaniline-4-sulfonic acid-di-ß-hydroxyethylamide, 2-nitroaniline-4-sulfonic acid-n-butylamide, 2-nitroaniline-4-sul Acid-cyclohexylamide, 2-nitroaniline-4-sulfonic acid anilide, 2-nitroaniline-4-sulfonic acid-N-methylanilide, 2-nitroaniline-4-sulfonic acid pyrrolidide, 2-nitroaniline-4-sulfonic acid piperidide, 2-nitro-aniline-4-sulfonic acid, 2-nitroaniline-carboxylic acid-2-nitroaniline-4-carboxylic acid-n-butylamide, 2-nitroaniline-4-carboxylic acid ethyl ester, 2-nitroaniline-4-carboxylic acid i-butyl ester, 3,5-dichloroanthranilic acid methyl ester, propyl ester, - ß-methoxyethyl ester, 3,5-dibromo-anthranilic acid methyl ester, -ethyl ester, - (n) -butyl ester, -ß-methoxy-ethyl ester, N-acetyl-p-phenylenediamine, N-acetyl-m-phenylenediamine, 4-aminobenzophenone , 4-Amino-diphenylsulfone, 2-, 3- and 4-aminobenzoic acid methyl ester, ethyl ester, propyl ester, butyl ester, β-methoxyethyl ester, methyl diglycol ester, ethyl glycol ester, methyl triglycol ester, 3- and 4-aminophthalic acid, llinoterephthalic acid dimethyl ester, diethyl ester, dipropyl ester, dibutyleate.r, 4-aminobenzoic acid amide, methyl amide, propyl amide, butylaoid, β-ethyl-hexyl amide, 2-, 3- u nd 4-aminobenzoic acid-dimethylamide, 3- and 4-amino-phthalic acid-imide, -B-hydroxyethylinide, -methylinide, -ethylimide, -tolylimide, 4-aminobenzenesulfonic acid-dimethylamide, -diethylamide, -pyrrolidide, -morpholide, 4-amino-naphthalic acid-ethylimide, 1- and 2-amino-anthraquinone, 1-aminoanthraquinone-2-sulfonic acid, 4-amino-azobenzene, 2 ', 3-dimethyl-4-amino-azobenzene, 3', 2-dimethyl -4-amino-azobenzene, 3,5-dibromo-4-amino-azobenzene, 3-methoxy-4-aminoazobenzene, and the diazo components of the formulas Particularly preferred diazo components are: 2-nitroaniline, 4-methyl-2-nitroaniline, 4-methoxy-2-nitroaniline, 4-nthoxy-2-nitroaniline, 4-chloro-2-nitroaniline, 2-nitroaniline-4-sulfonic acid, 2 -Nitroaniline-4-sulfonic acid-n-butylamide, 2-nitroaniline-4-carboxylic acid, 2-nitroaniline-4-carboxylic acid-ß-ethoxyethyl ester, 2,4-dinitroaniline, 4-aminoazobenzene, 5-nitro-4-aminoazobenzene-4 '-sulfonic acid, 2-chloro-4-amino-5-nitrobenzonitrile, 2-chloro-4-nitroaniline, 1- and 2-aminoanthraquinone.

The new dyes are yellow to orange and are suitable for dyeing of natural and synthetic polyamides such as wool, silk, and leather in particular Nylon 6 and nylon 6,6.

The following examples illustrate those according to the invention Substances, their manufacture and their dyeing application in detail. The listed Parts and percentages are based on weight. The parts of the room behave to parts of weight like the liter to the kilogram.

example 1 8.6 parts of 4-chloro-2-nitroaniline are poured over with 20 parts by volume of concentrated hydrochloric acid, stirred with 50 parts of ice and 16 parts by volume of 23% sodium nitrite solution are added at 0 to 5 ° C. over the course of one hour. The mixture is stirred for two hours, the excess nitrous acid is destroyed in the usual way and filtered.

24 parts of 6H, 13H-pyrimido- [1,6-a: 3,4-a '] bis-benzimidazol-13-one disulfonic acid are in 500 parts by volume of water and 10 parts of 50% sodium hydroxide solution at 60 to 70 0C dissolved and given with the addition of 400 parts of ice in the above diazo solution. Then the reaction mixture is made by dropwise addition of concentrated sodium acetate solution adjusted to pH 4 to 5 and stirred overnight. By adding 100 parts The dissolved dye is precipitated from table salt; then it is sucked off, with 10 pointer Washed saline and dried. A brown powder is obtained, its aqueous Solution Teztilmaterial made of synthetic polyamide in golden yellow tones with very good Color fastness to light and excellent wet fastness properties.

The coupling component used in Example 1 was prepared in the following way: 400 parts of di-benzimidazolyl- (2) -methane are stirred into 4000 parts of nitrobenzene. Phosgene is passed into this suspension at 120 ° C. for 6 hours. The phosgene is then expelled with a stream of nitrogen, and the product formed is filtered off with suction at room temperature, washed with nitrobenzene, benzene, methanol and finally with water until the washing water reacts neutral. After drying, 357 parts of a compound of the formula are obtained whose melting point is above 360 ° C.

Analysis: calc. C 70.1 ffi H 3.7% N 20.4% 0 5.8% found. 69.8 4.2 20.0 7.2 200 parts of this product are introduced into 2000 parts of 10% strength oleum at 10 to 15 ° C. After stirring for two hours at room temperature, the mixture is poured into 6000 parts of ice water and the somewhat cloudy solution is filtered. Then 2000 parts by volume of saturated saline solution are added and the mixture is stirred overnight. The deposited precipitate is filtered off with suction, washed free of sulfate with saturated sodium chloride solution and dried. 406 parts of a product of the formula are obtained which still contains 25% table salt.

Example 2 11 parts of 2-nitroaniline-4-sulfonic acid are dissolved in 200 parts of hot water and filtered. 15 parts by volume of concentrated hydrochloric acid are added and, after cooling, 50 parts of ice. Then you pour 16 rough parts 23 goat sodium nitrite solution under the surface; After stirring for one hour at 0 to 5 ° C, the excess nitrous acid is destroyed in the usual way.

The mixture, which has been cooled to 30.degree. C., is added to the diazotization mixture obtained in this way Solution of 24 parts of the coupling component used in Example 1 in 500 parts by volume Water and 10 parts of 50% strength sodium hydroxide solution. By adding sodium acetate solution dropwise is adjusted to pH 4 to 5 and stirred overnight. Then you place 200 room parts saturated saline solution, sucks off the precipitated dye and washes with it 10% saline solution. After drying, 36 parts of a brown powder are obtained, which dissolves in water with a reddish yellow color and polycaprolaotane fabric in dyes golden-yellow shades with very good lightfastness and excellent jass fastness properties.

Example 3 12.7 parts of 3-nitro-4-aminobenzoic acid-ß-ethoxyethyl ester are finely pulverized and introduced into 50 parts by volume of concentrated Balssäare. At 4 to 8 ° C, while stirring, 15 roughness parts of 23% sodium nitrite solution are added dropwise to this suspension, the mixture is stirred for one hour at 0 to 5 ° C, poured into 200 parts by volume of ice water and stirred again for half an hour at 0 to 5 ° C. Then the excess nitrite is destroyed in the usual way and the diazo solution filtered. 100 parts by volume of saturated sodium chloride solution are added to the filtrate and then 24 parts of the coupling component used in Example 1, dissolved in 500 parts by volume of water and 10 parts of 50% strength sodium hydroxide solution. It is buffered with about 250 parts by volume of saturated sodium acetate solution, another 400 parts of potassium chloride are added and the mixture is stirred overnight. It is then filtered off with suction, washed with saturated sodium chloride solution and dried. An orange powder is obtained which dissolves in water with a reddish-yellow color and dyes textile polyamide material in yellow shades with very good light fastness and excellent wet fastness properties.

Example 4 9.1 parts of 3-nitro-4-aminobenzoesäute are dissolved in 100 parts by volume of water and 3 parts by volume of 50 sodium hydroxide solution at 30 ° to 35 ° C. and filtered. 15 parts by volume of a 23% sodium nitrite solution are added to this. The resulting mixture is then added at 1-5 to 20 ° C within 30 minutes in a mixture of 75 parts by volume of water, 2.5 parts by volume of a 10% solution of an adduct of approximately 22 moles of ethylene oxide with sperm oil alcohol, 4 parts by volume of 23 subsequent sodium nitrite solution , 25 parts of ice and 20 parts by volume of concentrated hydrochloric acid. After two hours of stirring, the excess nitrate is destroyed and the almost clear solution is filtered. The coupling solution described in Example 2 is then added and the coupling is carried out as there. 26 parts of a redbrand powder are obtained, the orange-colored aqueous solution of which on Gevebe made of polycaprolactam give yellow dyeings with excellent fastness properties.

The following dyes are obtained in an analogous manner using the same coupling component: Example | Diazo Colonents | hue NO2 5 Qk'H2 yellow NO2 6 H3CO-OC 4 NH2 yellow J0 7 H03S e N, N> gold yellow 8 2 02-BH2 yellow Cl 9 2 4 2 yellow COOH 10 2 4 2 lgH3 yellow 5031 1 bra, yellow 11 2 4 2 yellow 12 H5C200MH2 yellow CO-OC2E5 3> JH2 yellow CO-OC2H5 Cl 14 NO 4 KE2 yellow For example diazo component color 15 N = NNH2 golden yellow 16 HO38N - N orange 17 H03S tX X <N 2 orange so H 3 18 9 S yellow COOH 19 N02 yellow 19 H30 NH2 yellow NO 2 20 E3C0 4 NH2 yellow NO2 21 H2N-O2S NH2 yellow NO2 22 LN-8O2 NK2 2 yellow NO 2 23 to NR-CO to E2 yellow NO2 24 9 NR-SO2 NR2 yellow I. Example diazo component color shade NO 2 25 t NH-S02 to NR2 yellow NO 2 26 <° 2 yellow - Cl 27 ClONR2 yellow SO H 3 Example 28 11.2 parts of 1-aminoanthraquinone are dissolved in 28.5 parts by volume of 96% strength sulfuric acid at 15 ° C. and 17.5 parts of nitrosylsulfuric acid are introduced.

After stirring for four hours at 15 oC and 15 minutes at 35 oC has, poured onto 500 parts of ice and 100 parts of water, stirred for half an hour and destroys the excess nitrous acid in the usual way. The diazo suspension becomes with 700 room parts Sodium acetate solution adjusted to pH 4 to 5. The coupling solution described in Example 2 is then added at 0 to 5 ° C and stir overnight. After suctioning off, it is washed with 10% sodium chloride solution and then it is dried. 41 parts of a brown powder are obtained aqueous solution dyes polycaprolactam fabric in red-brown shades with good fastness properties. Dyes of good lightfastness are also achieved on leather.

Example 29 13.7 parts of 2-nitroaniline-4-sulfonic acid-n-butylamide are dissolved in 50 parts of 96% strength sulfuric acid at 0 to 5 ° C. For this purpose, a mixture of 43 parts by volume of glacial acetic acid and 7 parts by volume of propionic acid and then 16 parts of nitrosylsulfuric acid is added dropwise at the same temperature and the mixture is stirred for two hours at 0-5.00. The mixture is then poured onto 200 parts of ice and 100 parts of water and, after the destruction of the Excess nitrite is filtered. The coupling solution described in Example 2 is then added and the coupling is carried out in the manner indicated there. 37 parts of an orange powder are obtained which dissolves in water with a reddish-yellow color and dyes polycaprolactam fabric and wool in yellow shades with excellent fastness properties.

The following dyes are obtained in an analogous manner using the same coupling component: Example diazo component color shade 0 30 X NE2 orange 0 N ° 2 31 NO 1H2 - yellow Cl O 'NH2 1, 2 32 3 e X yellow 0 NO 33 2 4 2 yellow 34 021 NH2 - yellow-brown C1 NO 35 02m to NH2 yellow-brown 102 36 Cl 4 WITHOUT2 yellow Br Example diazo component color shade Cl 37 02N <% Cc1NR2 yellow ON 38 N ye NR2 yellow-brown Br CN 39 2 NH2 yellow COOCH, 40 o, ar - t SO2CH3 41 ~ C302C 3 yellow brown Example 42 10 parts of the dye prepared by coupling 2-nitro-4-chloroaniline to 6H, 13H-pyrimido- [1,6-a: 3,4-a '] bis-benzimidazol-13-one (see Example 1) entered at 15 ° C. in 100 parts of 10% strength oleum and heated to 50 ° C. for 5 hours. Then it falls into 600 parts of ice water, sucks the precipitated dye off and washes it with it.

10% saline solution and dries. A brown powder is obtained, dyes the polyamide fabric in golden yellow tones.

Claims (5)

Claims 1. Water-soluble azo dyes of the pyrimido-bis-benzimidazole series of the formula in which D is the remainder of a diazo component and M is hydrogen, sodium, potassium or optionally substituted ammonium and n is 2, 3 or 4. 2. Water-soluble azo dyes of the formula in which A is hydrogen, chlorine, bromine, methyl, ethyl, methoxy, thoxy, nitro, carboxyl, carbalkoxy optionally substituted by hydroxyl or alkoxy and having 2 to 9 carbon atoms, carbamoyl, N-mono- or N, N-disstituted carbamoyl, sulfonamide, N-mono- or N, N-disubstituted sulfonamide, optionally substituted phenylazo or the sulfonate group SO 5M and M has the meaning given. 3. Process for the preparation of dyes according to Claim 1, characterized in that diazo compounds of amines of the formula D-NH2 with coupling components of the formula are used where M has the meaning given and m can be 1, 2 or 3, is reacted in a manner known per se. 4. Process for the preparation of dyes according to Claim 1, characterized in that compounds of the formula sulfated in a manner known per se. 5. Use of dyes according to claim 1 for dyeing natural and synthetic polyamides.