DE693061C - Process for the production of Kuepen dyes - Google Patents

Description

Process for the production of vat dyes It has been found that one arrives at valuable vat dyes, if one carboxylic acid halides of Ring compounds in which benzene nuclei are linked to one another by azo or azoxy groups are, with primary amines of küpenden ring systems, which are in the o-position to the amino group contain an amino group, a hydroxyl group or a mercapto group ,. under Condensed conditions in which the formation of an imidazole ring or an oxazole or thiazole ring, i.e. azole ring key.

The starting compounds can also contain further substituents. The preparation of the new vat dyes is expedient in an organic solvent performed. The implementation of the acid chlorides of the azo or azoxy compounds mentioned above with the amines occurs sometimes even at room temperature. She will then at increased temperature to the end, at the same time the formation of the azole ring he follows.

The same vat dyes can also be obtained by using starts from such amines küpender ring systems which are in the o-position to the amino group one which can be replaced by an amino, oxy or mercapto group or into such a group Group convertible substituents, such as halogen, contains and. this after Condensation of the amine with the carboxylic acid halide by an amino, hydroxyl or mercapto 'group replaced or converted into such a group. Afterward then the formation of the azole ring takes place.

The new dyes obtained in this way have good fastness properties, in particular, they outperform analogous dyes that - in same Way using polynuclear acid chlorides which do not contain any azo or azoxy groups or containing the azo group in a ring-shaped manner, in the lightfastness. The azo or azoxy bridges are not split when dyeing from the vat.

Example i 28 kg of the sodium salt of 2-amino-imercaptoanthraquinone are finely dispersed in 2oö kg of nitrobenzene stirred. After adding 16 kg Azobenzene-4; q .'-. dicarboxylic acid dichloride, the temperature is slowly increased. in the Over the course of about two hours, the mixture is heated to the boil and then another boiled under reflux for several hours. The visually soluble dye will sucked off, washed and, if necessary, by post-treatment with diluted soda-alkaline Chlorine solution cleaned. It dissolves in concentrated sulfuric acid with a red color and dyes cotton from purple-tinged red I #, '- iipe in very real; yellow tones.

The dye also prepared from 3, 3 @ -Dimethoxyazobenzol-4, q .'- dicarboxylic acid dichloride and the sodium salt of 2-Aminoi-inercaptoanthraquinone also dyes cotton in very real, yellow tones.

Use the same amount of sodium salt as described above of 2-amino-iinercaptoanthraquinone with 16 kg of azoxybenzene-4, 4 '-, dicarboxylic acid, dichloride condensed, in this way a dye is obtained, which is the same as cotton from a purple-tinged red vat Shades colors like the dye obtainable in accordance with paragraph i. Examples of a suspension of 28 kg of the sodium salt of 2-amino-i-mercaptoanthraquinone in 300 kg of nitrobenzene 16 kg of azobenzo1-3, 3'- @ dicarboxylic acid dichloride are added. After about three hours The mixture is stirred at room temperature and refluxed for about 8 hours boil and sucks off while still warm, the dye dissolves in concentrated sulfuric acid with a weak yellow-brown color and dyes cotton from .violettstichigroter vat in strong greenish yellow tones. The dyeings have good fastness properties. The dye can be purified by treating it with sodium chloride solution.

A dye of almost the same properties is obtained when one in the above example instead of azobenzene-3, 3'-dicarboxylic acid dichloride corresponding amount of 4, q .'-dichloroazobenzene-3, 3 '- @ dicarboxylic acid dichloride used.

Example 3 28 kg of the sodium salt of 2-amino-i-mercaptoanthraquinone become with 23 kg of diphenylazodiphenyl-4, 4 '-, dicarboxylic acid dichloride in nitrobenzene as in Example: 2 condensed. The resulting dye dissolves in concentrated sulfuric acid with purple-tinged red color and dyes cotton from purple-red vat in a very high color real, yellow tones.

When using the equimolecular amount of the acid dichloride of the composition: ' Instead of the acid dichloride used above, a yellow vat dye is also obtained.

Example 4 To a solution of 241.9 i-amino-2-oxyanthraquinone kept at 160.degree 16 kg of azobenzene-4,4'-dicarboxylic acid dichloride are added to 300 kg of nitrobenzene and the mixture is boiled then refluxed for about 8 hours: the one already in the heat almost completely excreted dye is suctioned off and washed: it dissolves in concentrated sulfuric acid with orange-red color and 'dyes cotton from dark red Küpe in very real, slightly greenish yellow tones: the dye can be treated with can be easily cleaned with a dilute, soda-alkaline chlorine solution.

The same way using diphenylazodiphenyl-4, Dye produced by 4'-dicarboxylic acid dyes cotton from a purple-tinged dark reddish color Küpe in very real, slightly greenish yellow tones. Example S To a solution 24 kg of i, 2-diaminoanthraquinone in 30o kg of trichlorobenzene are added with stirring at about - 160 ° C. 16 kg of azobenzene-4, 4'-dicarboxylic acid dichloride and left for about 8 hours boil under reflux. The dye, which has already precipitated in the heat, becomes vacuumed and washed. It dissolves in concentrated sulfuric acid with orange-red Color and dyes cotton from a red-brown vat in very real, yellow-orange tones.

A similar dye is obtained when using azoebenzene-3,3'-dicarboxylic acid dichloride instead of azobenzene-4,4'-dicarboxylic acid dichloride. Example 6 14 kg of the sodium salt .des i-Amino-2-mercaptoanthraquinone are .mit. - 8 kg of azobenzene q., 4'-dicarboxylic acid dichloride condensed by heating in nitrobenzene at 2200 ° C. for several hours with stirring. The dye is separated off as usual. It dissolves in concentrated sulfuric acid with an orange-red color and colors tree walls from a dark red vat in very genuine, greenish-yellow tones. EXAMPLE 7 16 kg of azobenzene-4,4'-dicarboxylic acid dichloride are added to a solution of 26 kg of 2-aminochloranthraquinone in about 30o kg of i, 2-dichlorobenzene at about 160 ° C. and the mixture is refluxed for 2 to 3 hours. After cooling, the condensation compound obtained becomes of the composition vacuumed and washed. It only dyes cotton slightly yellow.

6 kg of it are finely divided with a solution of 5.2 kg of concentrated sodium sulphide and q. kg of sulfur in about 35 liters of water and about 1 alcohol kept in the autoclave at about 160 ° C. for 12 hours. If necessary, the thiazole formed can be cleaned with sodium chloride solution; it corresponds to the dye obtainable according to paragraph i of example i.

Example 8 6 kg of the condensation compound described in Example 7, paragraph i, of 2-amino-chloroanthraquinone with azobenzene-4,4-dicarboxylic acid dichloride are mixed in the presence of nitrobenzene with 3.5 kg of benzenesulfonic acid amide with the addition of 3 kg of soda and 0.03 kg of copper chloride condensed by boiling for several hours. The condensation compound is after. sucked off after cooling ,. washed, dried and then dissolved in about 60 kg of concentrated sulfuric acid and some. Stirred time at room temperature. It is then poured onto ice, the free amino compound is filtered off with suction, washed and dried. If this compound is now heated to boiling under reflux cooling in nitrobenzene for some time, the dye known from paragraph i of Example 5 is obtained.

Example 9 5, q. kg of i-amino-2-nitroanthraquinone are through several hours Cooking in the presence of i, 2-dichlorobenzene with 3 kg of azobenzene-q., Q .'-dicarboxylic acid dichloride condensed. After cooling, the condensation product is filtered off with suction and washed; dried and then in the presence of about 60 kg of naphthalene and 10 kg of anhydrous Sodium carbonate condenses to the oxazole by boiling for several hours. It corresponds according to paragraph 1 of example q. available dye.

Claims (2)

PATENT CLAIMS: i. Process for the production of vat dyes, characterized in that one carboxylic acid halides of ring compounds in which Benzene nuclei are linked together by azo or azoxy groups, with primary Amines of coupling ring systems which have an amino group in the o-position to the amino group, contain a hydroxyl group or a mercapto group, condensed under conditions in which azole ring closure occurs. 2. Modification of the method according to the patent claim i, characterized in that one primary amines linking ring systems which are in the o-position to the amino group an exchangeable by an amino, hydroxyl or mercapto group or substituents which can be converted into such a group, with Eden carboxylic acid halides implements; then the substituent in the o-position to the amino group of the coupling ring system replaced by an amino, oxy or mercapto group or into one of these groups converts and then brings about azole ring closure.