DE1073130B - Process for the manufacture of vat dyes - Google Patents

Description

Process for the preparation of vat dyes It has been found that new vat dyes with good coloring properties are obtained if triazines of general structure I. reacts with linkable amines in such a way that the remainder of A and the remainder of the linkable amine to be reacted with I are different. In the formulas, Ha denotes chlorine or bromine, A denotes the remainder of an amine which can be vetted, R denotes a phenyl group, which in turn also carries or can be fused by benzene nuclei.

Examples of amines that can be linked are: 1- and 2-aminoanthraquinone, 1,4- and 1,5-diaminoanthraquinone, l-amino4- or -5-aroylaminoanthraquinone, 1-amino-4- - (or 5-, 6- and 7-) halogenanthraquinone, l-aminoanthraquinone sulfonic acid amide, l-Aminoanthraquinonylmethylsulfone, 1, 4-Diamino - 2 - acetylanthraquinone, l-Amino-4-alkoxyanthraquinone, 4-Amino-1 (N), 2-anthraquinone benzene acridone and its alkyl, alkylsulfonyl, Amidosulfonyl, alkoxy or trifluoromethyl groups or halogen-containing derivatives, 1, 4-diaminoanthraquinone, which in the 2-position is the residue of a benzoxazole or benzothiazole, which can be further substituted by the Phthaloyirest, carries, 1, 4Diaminoanthraquinone, which carries the residue of a 1,3,4-oxdiazole in the 2-position, l-aminoanthraquinone, the in the 2-position the residue of a 1,3,4-oxdiazoles (2) containing an aminophenyl residue in the 5'-position wearing.

It is known that vat dyes are obtained when using triazines of the general type with interchangeable amines. Each halogen atom is replaced by the remainder of a linkable amine, it also being possible for the two halogen atoms of the triazine to be replaced by various residues of linkable amines. However, it has never been possible to obtain uniform dyes with two different linkable radicals, since mixtures of XX, XX and X'X 'were always obtained under the conditions previously observed, where XX, etc. should mean that two on the triazine nucleus identical or two different residues of connectable amines are bound. Such mixtures are of little practical importance because they are z. B. unevenly dye mixed fabrics made of cotton and regenerated cellulose and also the dyebath prematurely depleted because of the different drawing speed and affinity of the components to one of the components, so that z. B. The beginning and end of a long length of fabric that is passed through the bathroom is colored in different tones.

In addition, the mixtures are usually unsightly in color and difficult to reproduce. All these disadvantages are avoided if, as is possible for the first time according to the present invention, uniform compounds with two different residues of connectable amines are prepared and used. The hitherto unknown halogen compounds of type 1 are obtained by adding 1 mol of the dihalogen compound of type II where R has the meaning given above, treated in suitable solvents with 1 mol of an amine AN Nah ,, where A has the meaning given above, at ordinary or elevated temperature. Suitable solvents are, for example, lactams, such as caprolactam or N-methylpyrrolidone, and glycols, such as ethylene glycol and pyridine or quinoline. The compounds of type I separate out in uniform crystalline form under these circumstances, while with the usual solvents such as xylene, chlorobenzene, nitrobenzene, etc., only mixtures of unreacted starting material with its mono- and di-derivatives are obtainable.

The new dyes produce on cotton, regenerated cellulose, Polyamides and polyurethanes strong, real colors or prints in so far for Part of inaccessible tones.

The parts in the following examples are parts by weight.

Example 1 To a 90 "C solution of 200 parts of 1-aminoanthraquinone 200 parts of 2-phenyl-4,6-dichlorotriazine-1,3,5 are added to 900 parts of N-methylpyrrolidone with stirring, heats the mixture to 1000 C and keeps it at this temperature for 1 hour. Divorce it yellow crystals form, the number of which increases as the product cools down.

They are washed with methanol and dried at 60 ° C.

Yield: 283 parts. constitution 42 parts of this half chloride, 34 parts of 4-aminoanthraquinone-I (N), 2-benzolacridone and 840 parts of nitrobenzene are stirred at 1950 ° C. for 4 hours. The temperature is then allowed to drop to 100 ° C. The dye which has separated out is placed on a filter and washed first with nitrobenzene at 1000 ° C. and then with cold methanol. After drying, 64 parts of blue-green crystals are obtained, and the cotton from a red-violet vat is olive-green stain, constitution likely With 2-aminoanthraquinone instead of l-aminoanthraquinone, a dye is obtained that dyes cotton from a red-violet vat clear green.

Example 2 80 parts of 1,4-diamino-2-acetylanthraquinone are dissolved in 640 parts of N-methylpyrrolidone. At an internal temperature of 600 ° C., 66 parts of 2-phenyl-4,6-dichlorotriazine-1,3.5 are added to the solution with stirring; the reaction mixture is then kept at 70 ° C. for 30 minutes. It is then allowed to cool. The crystals which have separated out are filtered off with suction, washed with methanol and dried at 60 ° C. Yield: 126 parts of the semi-chloride which is obtained in the form of blue-violet crystals.

47 parts of the half chloride are stirred together with 34 parts of 4-aminoanthraquinone-1 (N), 2-benzolacridone and 840 parts of nitrobenzene at 195 ° C. for 3 hours. Work according to the example, paragraph 2, and win 70 parts of a reddish blue powder that dyes cotton in neutral blue tones from a reddish-purple vat. Constitution likely Example 3 23.5 parts of the half-chloride already used in Example 9 from 2-phenyl-4,6-dichlorotriazine-1,3,5 and 1,4-diamino-2-acetylanthraquinone are mixed with 19 parts of 6'-amino-3 ' -chloranthraquinone-1 (N), 2-benzolacridone and 300 parts of nitrobenzene for 3 hours at 170 ° C. The procedure is continued according to Example 1, paragraph 2, and 38 parts of a violet powder are obtained, which from red-violet cotton vat in blue-violet Tones colors.

The constitution of the dye is likely Example 4 If one proceeds as described in Example 10, but instead of 19 parts of 6'-amino-3'-chloranthraquinone-l (N), 2-benzolacridone, 22 parts of 6'-amino-3'-phenoxyanthraquinone l (N), 2-benzolacridone, 40 parts of a dark blue powder are obtained. The dye dyes cotton from a red-violet vat in reddish-tinged blue tones. His constitution is likely EXAMPLE 5 47 parts of the half-chloride obtained according to Example 2 from 2-phenyl-4,6-dichlorotriazine-1,3,5 and 1,4-diamino-2-acetylanthraquinone are 39 parts of a 1,3,4-oxdiazole derivative of the formula and 1200 parts of nitrobenzene for 3 hours at 1800 C. The procedure is as described in Example 2, and 72 parts of a blue crystalline powder are obtained which, from a bluish-tinged vat, dyes cotton in brilliant red-tinged blue shades. The fastness to chlorine, soda boiling and the light fastness of the dyeings are very good.

If, instead of the oxdiazole substituted in the 5'-position by phenyl, the corresponding compound of the formula substituted by methyl is used in this way a dye is obtained which dyes cotton from a red vat in blue-tinged red shades with similarly good fastness properties.

Example 6 223 parts of l-aminoanthraquinone are dissolved in 1000 parts of N-methylpyrrolidone and 306 parts of 6- [l'-methoxynaphthy1- (4 ')] -2,4-dichlorotriazine are added to the solution at 900 ° C. with stirring. The reaction mixture is then stirred at 100 ° C. for 1 hour. After cooling, the precipitated reaction mixture is filtered off with suction, washed with methanol and dried at 60 ° C. 330 parts of the semi-chloride of the formula are obtained in the form of golden yellow leaves.

147 parts of this half chloride are combined with 102 parts of 1-amino-5-benzoylaminoanthraquinone Stirred in 2000 parts of nitrobenzene at 195 ° C. for 3 hours.

The reaction mixture is worked up in the manner indicated in Example 1, paragraph 2, and 195 parts of the dye of the formula are obtained as an orange-brown powder. The dye dyes cotton from a dark red vat in real golden-orange tones. Example 7 256 parts of 6- (4'-methoxyphenyl) -2,4-dichlorotriazine are introduced into a solution of 223 parts of l-aminoanthraquinone in 1000 parts of N-methylpyrrolidone at 900.degree. The reaction mixture is then stirred for 1 hour at 100 ° C., and after cooling, the material which has crystallized out is filtered off with suction, washed with methanol and dried at 600 ° C. There are 310 parts of the semi-chloride of the formula obtained as golden yellow crystal powder.

221 parts of this half chloride are combined with 171 parts of 1-amino-5-benzoylaminoanthraquinone Stirred in 2500 parts of nitrobenzene at 195 ° C. for 3 hours.

The reaction mixture is worked up in the manner indicated in Example 1, paragraph 2, and 310 parts of the dye of the formula are obtained as an orange powder. The dye dyes cotton from a red-brown vat in real golden-orange tones.

Example 8 223 parts of 1-aminoanthraquinone are dissolved in 1000 parts N-methylpyrrolidone and carries 260 parts of 6- (4'-chlorophenyl) -2,4-dichlorotriazine into the solution heated to 900 ° C. a.

The reaction mixture is then stirred for 1 hour at 100 ° C. After cooling, the material which has crystallized out is filtered off with suction, washed with methanol and dried at 60 ° C. 235 parts of the semi-chloride of the formula are obtained as yellow crystal powder.

223 parts of this half chloride are stirred together with 171 parts of l-amino-5-benzoylaminoanthraquinone in 3000 parts of nitrobenzene for 3 hours at 195 ° C. The reaction mixture is worked up as indicated in Example 1, paragraph 2, and 185 parts are obtained of the dye of the formula as an orange powder. The dye dyes cotton from a dark red vat in real golden yellow tones.

Example 9 223 parts of 1-aminoanthraquinone are used in 1000 parts of N-methylpyrrolidone solved. In the 900 C warm solution 240 parts of 6- (4'-methylphenyl) -2,4-dichlorotriazine are carried with stirring. The reaction mixture is then stirred at 1000 ° C. for 1 hour lets it cool down afterwards.

The precipitated reaction material is filtered off with suction, washed with methanol and dried at 60 ° C. There are 264 parts of the semi-chloride of the formula obtained as yellow crystal powder.

213 parts of this Halbohlorids are kept together with 170 parts of 4-ammoanthraquinone-1 (N}, 2-benzolacridone in 3 parts of nitrobenzene for 3 hours at 1950 ° C. The mixture is worked up as in Example 1, paragraph 2, and thus obtains 304 parts of the dye of the formula as a dark green powder. The dye dyes cotton from a wine-red vat in real olive-green tones.

If 2-aminoanthraquinone is used instead of 1-aminoanthraquinone with otherwise the same procedure, 358 parts of the corresponding semi-chloride and 379 parts of the dye of the formula are obtained as a blue-green powder. The dye dyes cotton from a wine-red vat in real green tones.

Claims (1)

PATENT CLAIM: Process for the production of vat dyes, characterized in that triazines of the general my formula R. MMM NN ML MM. A-HN N Hal where Hal is chlorine or bromine, A is the radical of a vettable amine and R is a phenyl nucleus which can also carry alkyl, hydroxy, alkoxy, trifluoromethyl, amidosulfonyl or alkylsulfonyl radicals or chlorine or bromine atoms or which can be fused by benzene nuclei Reacts with connectable amines that the remainder A and the remainder of the connectable amine to be converted are different. Documents considered: German Patent No. 1 026 456. When the registration is announced, there is 1 coloring table with an explanation has been laid out.