DE677967C - Process for the preparation of halogenated naphthindenones - Google Patents

Description

Process for the preparation of halogenated naphthindenones It has been found that valuable halogen compounds are obtained when one uses naphthindenones of the following structure: preferably those occupied 2-position, halogenating agents can act.

In addition to the halogens themselves, there are, for example, halogenating agents Chlorine iodine, phosphorus halides, sulfuryl chloride and phosgene in consideration. In general carries out the halogenation in the presence of a diluent, but is their Application is not a requirement. Sometimes it is also useful to add funds that facilitate halogenation, e.g. B. iodine, iron, sulfur, zinc halides or dimethylaniline. By suitable choice of the reaction conditions, i.e. the temperature, type and amount the halogenating agent, time of exposure, type of carrier and diluent, it is up to you to graduate the amount of halogen entering. After the Properties of the resulting compounds, the first halogen atom occurs in the reaction into the 6-position of the naphthindenone. So you get z. B. in the primary Effect of bromine on 2-chloronaphthindenone at about 50 ° in the calculated Yield the 2-chloro-6-bromonaphthindenone. If you use a large amount of bromine and works at a higher temperature, one obtains z. B. a connection that 2 to Contains 3 atoms of bromine in the molecule.

The end products of this process are generally very pure. If so desired you can clean them in the usual way, e.g. B. by recrystallization, sublimation, by gradual precipitation from strong mineral acids, by boiling or extraction with solvents or advantageously by gradual deposition on aluminum oxide, Barium sulfate or similar substances, which are different from naphthindenones have high intercepting power. The yields are generally very good.

The halogenated naphthindenones obtained in this way can be used for a wide variety of reactions. In particular, valuable dyes can be obtained from them, some of them can already be used as dyes themselves. Example i A solution of 1 part of 2-aminonaphthindenones in 20 parts of 80% sulfuric acid is mixed with 2 parts of bromine and the mixture is stirred for 1 hour 50 °, it is then poured onto ice, the resulting precipitate is stirred with dilute sodium hydroxide solution, filtered off with suction and washed neutral with water. The 2-amino-6-bromonaphtindenone thus obtained can be further purified if it is recrystallized from ethanol or butanol, for example. It forms red needles that dissolve in concentrated sulfuric acid with a yellow-red color and dye acetate silk in red-yellow tones. The yield is 1.5 parts, which is about 98 % of the calculated. EXAMPLE 2 A solution of 10 parts of 2-chloronaphthindenone in 100 parts of nitrobenzene is admixed with 0.5 parts of iodine and 10 parts of bromine are added dropwise at about 80 ° over the course of 5 hours. The mixture is then allowed to cool, the compound which has separated out is filtered off with suction and redissolved in ethanol, butanol or chlorobenzene. The 2-chloro-6-bromonaphthindenone thus obtained in a yield of 13.8 parts = 99% of the calculated yield forms yellow needles which melt at 25 ° to 252 ° and dissolve in concentrated sulfuric acid with a yellow-red color. Example 3 10 parts of finely powdered 2-chloronaphthindenone are slowly introduced into 50 parts of bromine. As soon as the mass has cooled down, water is poured over it, an excess of bromine is removed with dilute sodium hydroxide solution or bisulfite solution and the 2-chloro-6-bromonaphthindenone obtained in the calculated yield (1q. Part) is filtered off with suction. It is pure and agrees with the compound obtained according to Example 2.

Example q.

A mixture of 20 parts of naphthindenone, 1 part of iron powder, 2 parts Iodine and 100 parts of nitrobenzene are added while stirring at 6o to 70 ° with q.o. Share bromine. After working up, the 2-bromonaphthindenone is obtained, which is in concentrated sulfuric acid with a yellow color.

The 2-bromonaphthindenone thus prepared is stirred for 1 hour at room temperature again with qo parts of bromine, then pour the mixture into water and works it up in the manner described in Example 3. So you get in the calculated yield (37.5 parts) of pure 2,6-dibromonaphthindenone.

One can also proceed in such a way that a mixture of 10 parts of naphthindenone with 80 parts of bromine is stirred for 1 hour at ordinary temperature, the resulting mass is mixed with water and worked up. Here too, pure 2,6-dibromonaphthindenone is obtained in the calculated yield. EXAMPLE 5 235 parts of bromine are slowly added to a mixture of 100 parts of naphthindenone, 100 parts of nitrobenzene, 2 parts of iodine and 1 part of iron powder at 80 ° to 100 ° with stirring. When the reaction has ended, the mixture is allowed to cool and the tribromonaphthindenone formed in a yield of 208 parts = 90 % of the calculated amount is filtered off with suction. It contains i bromine atom in the 2-position and dissolves in concentrated sulfuric acid with a red color. Example 6 A mixture of 60 parts of bromine, 5 parts of naphthindenone and 0.5 parts of iodine is refluxed for 8 hours. It is then poured into water and worked up in the manner described in Example 3. A dibroma derivative of 2,6-dibromonaphthindenone is obtained in this way. The compound is obtained in a yield of 9 parts = 95% of the calculated yield and, after redissolving from dichlorobenzene, forms yellow needles which melt above 300 ° and dissolve in concentrated sulfuric acid with a red color.

If one uses 2-chloronaphthindenone in the manner described in the previous paragraph Treated with bromine, a uniform, multiply brominated 2-chloronaphthindenone is obtained. Example 7 By mixing 100 parts of chlorosulfonic acid with 5 parts of 2-chloronaphthindenone and 0.5 parts of iodine are passed in slowly for 1 hour at 80 ° with stirring Stream of gaseous chlorine. The mixture is then poured onto ice and the precipitated product is sucked off yellow precipitate and washes it off. The dichloro-2-chloronaphthindenone thus obtained Melts at 255 to 26o ° and contains 35.5% chlorine. It forms after recrystallization from chlorobenzene yellow needles, which are in concentrated sulfuric acid with yellow-red Dissolve paint. The yield is 7.2 parts. Example 8 Pass through a solution of 100 parts of naphthindenone and 5 parts of iodine in 50 parts of trichlorobenzene at 100 ° gaseous chlorine for several hours. Then let them cool and separate them received Tetrachloronaphthindenone, which has a chlorine atom in the 2-position is in the usual way. The yield is 170 parts.

Example 9 A mixture of 5 parts of 2-chloronaphthindenone, 30 parts Nitrobenzene, 0.5 parts of iodine and 10 parts of sulfur chloride are heated for about 10 hours long to 8o to 100 °. The nitrobenzene is then removed by means of steam and dissolves the yellow residue from butanol or chlorobenzene. You get so in one Yield of 6.5 parts = 94% of the calculated chlorinated one which crystallizes well 2-chloronaphthindenone, which melts up to 2o5 ° at Zoo and contains 32.6% chlorine.

Example 10 A mixture of 5 parts of naphthindenone-2-carboxylic acid, 0.5 parts of iodine and 40 parts of bromine is heated to the boil for 2 hours under reflux cooling. The mixture is then poured into water, an excess of bromine is removed using sodium bisulfite solution and the resulting bromine-containing naphthindenone-2-carboxylic acid, which is very likely brominated in the 6-position, is separated off in the usual way. They can be cleaned by dissolving them in alkalis and reprecipitating them. The yield is 6.5 parts = 97 % of the calculated. After recrystallization from trichlorobenzene, the compound melts at 330 ° with decomposition and dissolves in concentrated sulfuric acid with a yellow-red color. EXAMPLE II A mixture of 26 parts of 2-bromonaphthindenone, 60 parts of iodine and 260 parts of 5 percent fuming sulfuric acid is heated to 140 ° for 6 hours with stirring. The mixture is then allowed to cool, poured onto ice, the yellow precipitate is filtered off with suction, washed acid-free and dried. After recrystallization from chlorobenzene, it forms a yellow flour that melts at 253 to 254 ° and dissolves in strong sulfuric acid with a red color. The compound contains 2 atoms of iodine in the molecule.

In a similar way, a diiodine compound is obtained from 2-chloronaphthindenone. The naphthindenone itself also provides a diiodine derivative. z, 6-dibromonaphthindenone goes into a monoiodine in the treatment described - 2,6-dibromnaphthindenz) n above, which melts at 268 to 27o °.

Claims (1)

PATEN TA NS PR UCII: Process for the preparation of halogenated naphthindenones, characterized in that one uses naphthindenones of the following structure preferably those with occupied 2-position, halogenating agents can act.