DE400254C - Process for the preparation of highly chlorinated nitrogen-containing hydroaromatic products - Google Patents

Description

Process for the preparation of highly chlorinated nitrogenous hydroaromatic Products. It has been found that when the hydrochloric acid salts are chlorinated, they become more aromatic Amines in one. indifferent suspending agent that does not cause hydrolysis leaves, and with the exclusion of moisture leads to highly chlorinated products that derive from hydrogenated nuclei and, what is most important, still nitrogen contain. Neither this manufacturing method nor the bodies obtained are themselves known to this day.

Only one known compound belongs to this body class; it is this is that of Claus & J aecle, Journ. f. Prakt. Chem. 57, p. 1, described 1-chloro-2-acetnaphthylamine tetrachloride; but on the one hand, in contrast to the present proceedings, the protection of the Amino group achieved by acetylation, on the other hand the named body is an amino derivative, while the newly found compounds contain an imino group instead.

It is also known that the amino group during halogenation by Can protect salt formation. When brominating under these conditions one comes directly to brominated amines, d. H. there is only substitution here (Michaelis, Ber. d. D. no. Ges. 26, p. 2i96). At first, chlorine only has a substituting effect; so one gets chlorinated from aniline and its substitution products as the first phase Aniline. If all substitutable positions are occupied, the chlorine accumulates the double bonds. The latter reaction has been observed several times, but it has been carried out to this day under conditions under which the intermediately occurring nitrogenous chlorine addition products were not viable and immediately in the corresponding ketones passed over. Both Zincke, who uses this sequence of reactions in the Benzene series carried out (Ber. 27, p. 537), and more recently Fries (Ber. 53, p. 23 and Ber. 5q., P. 1g3), which has an exhaustive effect on u- and, ß-aminoanthraquinone with chlorine let, worked in glacial acetic acid, a solvent that works in the presence of the Hydrochloric acid occurring in the reaction is the result of the present process Imino derivatives hydrolyzed immediately.

According to the present process, not only the amine is now through Introducing dry hydrochloric acid into its hydrochloric acid converted to the amino group to protect. Excess dry hydrochloric acid is still added; during the Chlorination forms additional amounts of hydrochloric acid, all of which have this protective effect still increase. Only the total exclusion of water is of the greatest importance and the use of a completely inert solvent that does not hydrolyze allows.

Aniline absorbs 7 or 9 atoms of chlorine, depending on the conditions. If you work in chlorobenzene and heat for some time towards the end of the reaction while introducing chlorine, you arrive at the highly chlorinated product, octylilor-cblorketiniidoliexaliydrobenzol a beautiful crystalline body with a melting point of 151 '. Analysis: her. 78.39 percent, found 78.40 percent chlorine.

If benzene is used instead of chlorobenzene and the introduction of chlorine is discontinued soon after the solution has occurred, the main result is an ilexaclilorochloro-ketimidotetrahydrobenzene of the formula an equally beautifully crystalline body with a melting point of 25 °. Analysis: her. 73.85 percent, found 73.73 percent chlorine.

Contrary to expectations, both bodies are stable. Only when heated up about 70 ° decomposition occurs with the release of chlorine.

The two naphthylamines are converted into chlorinated tetrahydronaphthylamines with uptake of 6 chlorine atoms. The a-naphthylamine thus gives the pentachloro-x-chlorocetimidotetrahydronaphthalene in the form of prismatic crystals with a melting point of i22 °. Analysis: her. 60, q.8 percent, found. 6o, 53 percent chlorine. The ß-naphthylamine supplies the pentachloro-clilorketimidotetrahydronaphthalin in the form of prisms with a melting point of M8.5 °. Analysis: her. 6o, 48 percent, found 6o.6 percent chlorine.

While with, S-naphthylamine the reaction takes place at room temperature When the a-naphthylamine comes to an end, the temperature towards the end must be approximately ioo ° increase, which makes working in chlorobenzene necessary.

The aminoanthraquinones behave exactly like the napthylamines; here too there are 6 chlorine atoms. a-Aminoanthraquinone provides a pentachloro-x-clilorketimidotetrahy droanthraquinone in the form of light yellow prisms that melt with decomposition at igo °. Analysis: her. 49.23 percent, found 49.0 percent chlorine.

The 3-aminoanthraquinone provides the corresponding derivative in the form rhombic leaflets with a melting point of 2o @ '. Analysis: her. 49.23 percent, found 49.02 Percent chlorine.

Example x.

A solution of 100 g of aniline in 1.5 1 of chlorobenzene is with dry Hydrochloric acid gas saturated, creating a white gruel. In this one becomes without to cool, introduced chlorine, the temperature to about 100 ° towards the end increases and with further introduction of chlorine for about 2 to 3 hours on this Temperature leaves. The resulting solution is then evaporated in vacuo, the The residue to the nonachlor product solidified in crystalline form. For further cleaning can be recrystallized from gasoline.

Example 2.

100 g of a-naphthylamine are dissolved in 1.5 l of chlorobenzene and converted into the hydrochloric acid salt by introducing gaseous hydrochloric acid. Now it is cooled with a cold mixture and chlorine is introduced into the cold pulp, whereby everything dissolves. As soon as this has occurred, the temperature is gradually raised to 100 °. At first a paste forms again, which goes back into solution. The latter, distilled off in vacuo, yields a syrup that is absorbed in petroleum ether. When the petroleum ether solution evaporates, the hexachloro product is obtained in beautiful crystals.

Example 3.

In a solution of 100 g of ß-naphthylamine in 8oo cm3 of benzene is added Stir gaseous hydrochloric acid introduced until plentiful. Hydrochloric acid escapes. then is cooled and chlorine gas is introduced until it is saturated, then gradually increases heated in the water bath, whereby. Solution occurs. This solution is concentrated in vacuo, the benzene is driven off in vacuo by repeated addition of gasoline, with the chlorine addition product begins to separate, then it is cooled down and suctioned off. You get something like that Zoo g of a product that melts at 115 ° while the melting point of the pure Product is at iz8.5 °.

Example q ..

2o g finely powdered, dry α-aminoanthraquinone are in 600 cm " Benzene suspended and by passing gaseous hydrochloric acid into the hydrochloric acid Transforms salt. It is then cooled and passed in chlorine, whereby towards the end of the Reaction gradually increases the temperature to the boiling point of benzene. the The resulting solution is evaporated in vacuo and the residue with carbon tetrachloride offset. The reaction product separates out as a crystal slurry.

Example 5.

The representation of the hexachloro-ß-aminoanthraquinone is that of the α-aminoanthraquinone exactly the same, only that, instead of benzene, chlorobenzene is used here.

These compounds represent new valuable components for the dye industry represent.

Claims (1)

PATENT CLAIM: Process for the preparation of highly chlorinated nitrogenous hydroaromatic products, characterized in that aromatic amines in an inert solvent dissolves dry hydrochloric acid gas in this solution to saturation and then chlorinated with chlorine gas.