DE634987C - Process for the preparation of aza compounds - Google Patents

Description

Process for the preparation of aza compounds It has been found that new, technically very valuable aza compounds are obtained when ring-shaped Compounds that contain at least one nitrogen atom in a six-membered ring and an aromatic radical with two in a single bond via a carbon bridge Contain realizable o-positions, in the presence of condensing effects Agents of the anhydrous aluminum chloride type with aromatic o-dicarboxylic acids implements.

As nitrogenous starting materials of the type indicated are for example monopyridinodiphenyls, Bz-arylisoquinolines, Bz-arylacridines, mono- or polyaralkylpyridines, aralkylquinolines or isoquinolines and derivatives of mentioned compounds mentioned.

Phthalic acid, for example, can be used as aromatic o-dicarboxylic acids and their derivatives, naphthalene-o-dicarboxylic acids and anthracene-o-dicarboxylic acids into consideration. They are expediently used in the form of their chlorides or anhydrides.

Of condensing agents of the anhydrous aluminum chloride type besides this itself z. B. anhydrous aluminum bromide, iron chloride, iron bromide and called boron trifluoride. In general, the reaction is effected by heating of the starting mixture, to which it is then expedient to add substances that lower the melting point, z. B. salts of alkali or alkaline earth metals, such as potassium or sodium chloride, Sodium sulfate or calcium chloride. In some cases it is recommended to use it an organic diluent, e.g. B. of dimethylaniline or nitrobenzene. If you work in mild conditions - about below 12o ° - and the action Can only last a relatively short time, one can do the implementation initially take the resulting aroyl-o-carboxylic acids. At a higher temperature or for a long time The diketones corresponding to the aroyl-o-carboxylic acids are then formed.

Both types of compounds, especially the azaketones, are e.g. T. valuable dyes, z. T. They can be used with advantage for the production of dyes or drugs are used.

Example i 90 parts of 6-phenylquinoline are introduced into a 1,300 parts hot melt of 600 parts of anhydrous aluminum chloride and 120 parts of sodium chloride. 68 parts of phthalic anhydride are then gradually added with constant stirring. When the entire amount of anhydride has been added, the mixture is heated to 165 to 170 ° for a short time until the melt no longer foams and its color has turned pure red. -] Since they are poured onto ice, the 6 -. (2'-Anthracliinonyl) -i-azanaphthalene that has separated out is sucked off; - Washes neutral and dries. By sublimating, dissolving through its salts with strong acids, 'gis; clean yourself. It is olive-gray, dissolves in concentrated sulfuric acid with a yellow-brown color, produces a red vat and melts at 235 to 236 1 .

If you use 8-phenylquinoline instead of 6-phenylquinoline, you get a compound which melts at 243 to 244 'and is probably built up as follows: Other Bz-phenylquinolines and isoquinolines can also be reacted with phthalic anhydride. The melts are generally colored red. If you use 6- (p-chlorophenyl) -quinoline, the color of the melt is violet-blue.

Example 2 In a melt of. 100 parts of anhydrous aluminum chloride and 20 parts of sodium chloride are introduced in succession at 130 to 14o ° with 10 parts of 3,5-dibenzylpyridine and 12 parts of phthalic anhydride. The mixture is heated to 150 to 155 minutes for 1 to 2 hours and then the melt is poured onto ice. The diphthaloyl-3, 5-dibenzylpyridine which precipitates out forms almost colorless crystals when dissolved from dichlorobenzene; it dissolves. in sulfuric acid with a yellow color and delivers a red vat.

If the calculated amount of tribenzylpyridine is used instead of dibenzylpyridine; a triphthaloyltribenzylpyridine is thus obtained.

Example 3 In a melt of 1,000 parts of anhydrous aluminum chloride and zoo parts of sodium chloride one carries 70 parts of 6-phenylc-hinophthalone and 35 parts Phthalic anhydride. The melt is heated about. At 165 for 1/2 hour to 170 'and then pour it on ice. When releasing the precipitate that falls out from trichlorobenzene one obtains yellow crystals, which in sulfuric acid with red Dissolve color and vegetable fibers from the brown-red vat in strong yellow tones to dye. The connection obtained in this way is essentially identical to that which is obtained with Fusion of 6- (2'-anthraquinonyl) - -9 - methyl - i - azanaphthalene with '' Receives phthalic anhydride.

@ .: One can also proceed in such a way that one 6'P.henylchinaldin with a Treated excess of .I @ thalic anhydride.

Example In a melt of ioo parts of aluminum chloride and 2o of potassium chloride to wear at 140-1 50 '1o parts of 6-Benzylchinolin a, added 8 parts of phthalic anhydride and the mixture is stirred for i hour at i60 to i7oQ. It is then poured onto ice and worked up in the manner indicated in the previous examples. You get a connection that probably has the following structure: It crystallizes from monochlorobenzene in pale yellowish leaves that give a red vat. Similar built derivatives of anthraquinone are obtained if β-chlorophthalic anhydride is used instead of phthalic anhydride or the isomeric benzylquinolines are used instead of 6-benzylquinoline.

Example 5 A mixture of 10 parts of dihydrobenzyliderichinaldine, 7 parts of juthalic anhydride, 100 parts of aluminum chloride and 20 parts of sodium chloride is heated to 170 to 180 ° for 1/2 hour. After working up, a compound which crystallizes from monochlorobenzene in pale yellowish needles is obtained, which melts at 148 to 149 'and can be vat with a red color. According to the production and the analysis, it has the following structure: Instead of Dihydrobenzylidenquinaldins you can use other compounds constructed accordingly, z. B. those derived from halogen, Alkvl- or Naphthochinaldinen.

Claims (1)

Claim: A process for the preparation of Azav compounds, characterized in that ring-shaped compounds containing at least one nitrogen atom in a six-membered ring and an aromatic radical with two reactive o-positions in a single bond via a carbon bridge, in the presence of condensing agents of the type of anhydrous aluminum chloride with aromatic o-dicarboxylic acids.