DE367344C - Process for the preparation of sulfur and nitrogen-containing condensation products of the aromatic series - Google Patents

Description

Process for the preparation of sulfur- and nitrogen-containing condensation products of the aromatic series. The patent 36o69o describes new substances containing nitrogen, sulfur and halogen, which are formed by the action of chlorosulfur (S, C12) on the dry salts of aromatic bases. It has now been found that the same bodies are formed if the free bases or their N-acidyl (most suitably their acetyl) compounds are used instead of the salts. The deviating results of earlier authors (see in particular Claus and Krall, Ber.3 fi87o], p. 527, and Ber. 4 [1871], p. 99, S mit, Ber. 8 [1875], p. 1445, E . B. Schmidt, Ber 11 [1878] S. 1169, ii7o, 1171, and Edeleanu, Ber 24 [i.:. 89ij, Papers pp 192, 193) therein find their explanation that even unsuitable solvents or. Diluents such as carbon disulfide (Claus and Krall and Edeleanu op. Cit.), Which take part in the reaction itself, were used, and further that these authors, because they worked towards the preparation of thioaniline and dithioaniline, aniline or acetanilide and chlorosulfur in a ratio of 1 molecule of chlorosulfur Allow 2 to 4 molecules of base or acetyl compound to act. ..

But if you work with an excess of chlorosulphur and use not less than 3 molecules of chlorosulphur per one molecule of base or, if the acetyl compounds are used, an even larger excess of chlorosulphur, the bodies described in detail in the main patent are produced in good yield.

When working with the free bases, the reaction is advantageous Use of an anhydrous diluent that is indifferent to chlorosulfur moderate. Suitable diluents are fatty and aromatic hydrocarbons Series, carbon tetrachloride, glacial acetic acid, formic acid, etc. When using acetyl compounds a diluent is unnecessary. The reaction is likely to be that initially the hydrochloric acid salt decomposes with some of the chlorosulphur the base is formed and this reacts further with excess chlorosulfur.

The sulfur precipitated in the first phase of the reaction no longer takes part in the further course of the reaction, but remains in the mixture in an inert manner. It is this out for sure from the fact that During d throughout the duration of the reaction only hydrochloric acid, hydrogen sulfide is not removed even in traces, from the Journal of the Chemical Society Vol. Ioi [igi2], p 1695, and Vol 105 [19141, p. 954, described reaction, the action of sulfur on aniline and o-toluidine in the presence of the hydrochloric acid salts of these bases, the present process is therefore sharply differentiated. Here the carrier of the reaction is sulfur, because the reaction takes place with strong evolution of hydrogen sulfide, the addition of hydrochloric acid salts of the bases used only serves as a contact substance and can be replaced with small amounts of iodine with the same success (see the publications cited), also finite the resulting end products, the trithioaniline or trithio-otoluidin, from. the reaction products of the present process are completely different.

Example 1.

--o kg of aniline -%, ground with the same volume of naphtha or ligroin and added to a ratio of 120 kg of chlorosulfur and 600 kg of naphtha; Under exposure, hydrochloric aniline and sulfur are soon separated out; the whole is then heated to 70 to 100 ° C. with stirring until no unchanged base can be detected any longer; it is allowed to cool, the yellow-brown-colored body which has separated out is filtered off, washed with toluene or benzene until it is free of adhering chlorosulfur and dried at low temperature. It is identical to the action product of chlorosulphur on hydrochloric acid aniline obtained according to example -i of the patent 36o15go, gives in particular, like this one, the blue-violet color reaction with aniline and gives the same condensation product with a melting point of 2o6'C condensed with monochloroacetic acid . Exactly in the same - O-toluidine, a- and p-naphthylamine, p-phenylenedianxine, benzidine, etc. react and give p-toluidine and m-xylidine the yellow sulfur dyes described in example ii of the main patent.

Example q-9.3 kg of aniline are dissolved in approximately the same weight of glacial acetic acid and gradually allowed to run into 80 kg of chlorosulfur with good external cooling. The mixture turns yellow-brown to orange when heated. The mixture is then heated slowly in ascending order for about 4 hours to 50 to 65 ' and finally increases the temperature for a short time to 70 to 80 ° C. After cooling, it is diluted with benzene or other suitable hydrocarbon and the crystalline, yellow- colored reaction product is filtered off with suction , washed and dried.

It is identical to the body produced according to Example i. In a similar way, the corresponding action products of the chlorosulfur on these bases can be obtained from o- and m-toluidine and from the chloroanilines. Example 3.

10 kg of 9-naphthylamine are dissolved in approximately 12 kg of ice-cream acetic acid and the cooled, comminuted mass is added to 85 kg of chlorinated sulfur, with thorough stirring. The reaction initially takes place without external supply of heat with vigorous evolution of hydrochloric acid. As soon as the latter subsides, the reaction mass is heated to 50 to -7 ° C for a few hours; the reaction product separates out at the end almost completely as an orange-colored, crystalline body, it is diluted with benzene or naphtha, filtered off with suction, the reaction product is washed free of adhering excess chlorosulfur and dried. It is identical to the body obtained according to Example 7 of the main patent.

Example 4.

1: 8.4 kg of benzidine are stirred into a mixture of 100 kg of glacial acetic acid and 100 g of chlorosulfur with thorough stirring, the mixture is first heated to 40 to 50 ° for a few hours and then gradually increased to 100 to 10 ° C; this is held until no more benzidine that can be diazotized or coupled can be detected. It is allowed to cool, the almost completely separated reaction product is filtered off with suction, washed with benzene or another suitable inert diluent and dried. The same is identical to the body obtained from benzidine pure hydrochloric acid according to example 10 of the main patent.

In a completely analogous manner, m-phenylenediamine oxamine acids can be obtained obtain the corresponding action product of chlorosulfur.

Example 5.

20 kg of acetanilide are heated with 5 to 10 times the amount of chlorosulphur with constant stirring for a long time (1 to 20 hours) to 70 to 20 ° C. When the reaction has ended, an anhydrous solvent, such as. B. benzene, gasoline or naphtha diluted, the precipitate sucked off and dried.

The body obtained is identical to in terms of its properties the product of action contained in example i of patent 36o69o, of chlorosulfur on hydrochloric aniline.

In the same way, acet-o- and mtoluidin, Acet-a- and P-naphthylamine the same exposure products as the mineral acid salts thereof Bases.

Claims (1)

PATENT ANSPRUCII: Modification of the process protected by patent 36o6co for the preparation of sulfur and nitrogen-containing condensation products of the aromatic series, consisting in the fact that instead of the dry salts of aromatic amino compounds or their derivatives, the free bases or their N-acidyl compounds with excess chlorosulfur , S, Cl, optionally with the addition of an anhydrous solvent or diluent which is indifferent to chlorosulfur.