DE631655C - Process for the production of asymmetrical indigoid dyes - Google Patents

Description

Process for the production of asymmetrical indigoid vat dyes It has been found that industrially valuable unsymmetrical indigoid vat dyes can be obtained obtained when alkoxydichloroxythionaphthenes, which the alkoxy group in 5-, 6- or 7-position and in which one o-position to the alkoxy group is unsubstituted is, or their reactive a-derivatives, z. B. Anile, Oxime and the like Build-up of indigoid dyes condenses suitable components.

The dyes are characterized by beautiful nuances and very good fastness properties of dyeings and prints.

In some cases, post-halogenation can cause their coloring Properties can still be improved depending on the selection of the components.

The Alkoxydichloroxythionaphthene are obtained z. B. from the corresponding Dichloralkoxybenzenesulfonic acids by converting into the sulfochlorides, mercaptans, Thioglycolic acids and ring closure or from the corresponding dichloroalkoxyaminobenzenes according to one of the known methods by introducing a sulfur-containing residue in o-position to the amino group. These oxythionaphthenes can continue in their reactive a-derivatives are converted.

Example 1 12.5 kg of 5-methoxy-6,7-dichlorooxythionaphthen are added ii, 6 kg of 8-chloro-i, 2-naphthisatin and 150 kg of glacial acetic acid were stirred at 100 ° C. for 2 hours. The dye formed is filtered off with suction after cooling. He dyes from a yellow vat Cotton in gray tones with excellent fastness properties. Dissolves in sulfuric acid he himself with yellow-brown color: The 5-methoxy-6, 7-dichloroxythionaphthen can z. B. can be obtained in the following manner.

2,3-Dichloroanisole-q.-Sodium sulphate, which is obtained by sulphonation and subsequent alkylation of 2,3-dichlorophenol is readily available by heating with phosphorus pentachloride converted into the corresponding sulfochloride. That obtained therefrom by reduction Mercaptan is converted into thioglycolic acid in alkaline solution with monochloroacetic acid convicted. The i-methoxy-2,3-dichlorobenzene-4.-thioglycolic acid shows from 50% Acetic acid recrystallized, melting point 159'C. From thioglycolic acid can then with the help of phosphorus trichloride and aluminum chloride the 5-methoxy-6, 7-dichloroxythionaphthene can be represented. .

Example 2 11.3 kg of 5-brornisatin are used in zoo kg of chlorobenzene 10.5 kg of phosphorus pentachloride heated to 100 ° C. for about 1 hour. The solution of the educated 5-Bromisatin chloride runs at 5o to 6o ° C in a suspension of 12.5 kg of 5-methoxy-q., 7-dichloroxythionaphthene in 100 kg of chlorobenzene. After stirring for 3 hours at 80 ° C the dye has deposited and is filtered after cooling. He forms a blauvio- Jettes powder and dyes cotton from yellow Vat in navy blue tones. Its solution color in sulfuric acid is green-blue.

The production of 5-methoxy-q., 7-dichloro-oxythionaphthens takes place from the 2, 5-dichlizanisole-4-sulfonic acid sodium in an analogous manner. as indicated in example i. = -Methoxy-2,5-dichlorobenzene- [thioglycolic acid, the melting point of which is 116 ° C., can be converted smoothly into 5-methoxy q.7-dichlorooxythionaphthene by means of chlorosulfonic acid. Example 3 13.2 kg of 6-ethoxy-q., 7-dichlorooxythionaphthen AMnd z5.6, kg of 6-methoxy-3-oxythionaphthen -, #: p-dimethylaminoanil) are treated with zoo kg of ice, e Mg for 2 to 3 hours Heats to 130 ° C with stirring. After cooling, the dye formed is filtered off with suction. It forms an orange colored powder, dissolves in sulfuric acid with a violet color and dyes cotton from a yellow vat in bright orange shades with good fastness properties. 5-methoxy-6,7-dichloroxythionaphthen solution color in the color of the dye on sulfuric acid vat cotton with 5, 7-dichloroisatin chloride .... green-blue 'yellow violet 5, 7-dibromoisatin chloride .... green-blue yellow blue-violet 2, i-naphthoxythionaphthene - dark blue orange brown anil 5-methoxy-4, 7-dichloroxythionaphthene results with 5, 7-dichloroisatin chloride ..... blue orange blue 4-methyl-5-chloro-7-methoxy steel blue yellow blue isatin chloride 8-chloro-i , 2-naphthisatin- - green yellow violet chloride 6-ethoxy-4, 7-dichlofoxythionaphthen e gives with 4-methyl-6-chloroxythionaph- green yellow scarlet thenanil 6-ethoxyoxythiönaphthenanil violet yellow orange oxythionaphthenanil ....... olive yellow blue-red 7-methoxy-q., 5-dichloroxythionaphthene results in 4-methyl-5-chloro-7-methoxy blue yellow blue isatin chloride 5-bromoisatin chloride ........ blue yellow violet 6 ethoxyoxythionaphthenanil olive green yellow - ruby For the production of 6 = ethoxy-q., 7-dichloroxythionaphthens, the chlorohydrate of 2; 5-dichloro-4-ethoxyaniline is converted into i-amino-2, 5-dichloro-ethoxybenzene-6-thioglycolic acid via the chlorosulfur compound and this is further converted into 6-ethoxy = q., 7 by cyanation, conversion into aminothionaphthenecarboxylic acid -dichloroxythionaphthene. It can be purified by recrystallization from glacial acetic acid and then melts at igi to 192, C. Example ¢ xo, 8 kg of 5,7-dichloroisatin are converted into the chloride by heating with 16.5 kg of phosphorus pentachloride in 150 kg of chlorobenzene for x hours. At 50 ° C, this solution runs into a slurry of 12.5 kg of 7-methoxy-4,5-dichlorooxythionaphthene in zoo kg of chlorobenzene. After stirring for 3 hours at 80 ° C., the finished dye is filtered off with suction. It dissolves in sulfuric acid with a blue color and dyes cotton in blue tones. The preparation of 7-methoxy-4, 5-dichloroxythionaphthens can be carried out in a manner analogous to that given in Example x, from FIG. 3, q. Dichloroanisole-6-sulfonic acid take place. The 3,4-dichloroanisole-6-thioglycolic acid obtained from this melts at r22 ° C. It can be converted into 7-methoxy-4,5-dichlorooxythionaphthene with the aid of chlorosulfonic acid. .

From the thionaphthenes described, by varying the Components produce additional dyes, as shown in the table on the right.

Claims (1)

PATENT CLAIM: Process for the production of asymmetrical indigoid Vat dyes, characterized in that alkoxydichloroxythionaphthenes, which contain the alkoxy group in the 5-, 6- or 7-position and where an o-position is unsubstituted to the alkoxy group, or their reactive a-derivatives with the Build-up of indigoid dyes condenses suitable components.