DE639168C - Process for the preparation of compounds of the coeranthrene and coerbianthrene series - Google Patents

Description

Process for the preparation of compounds of the coeranthrene and coerbianthrene series Compounds of the coeranthrene and coerbianthrene series have so far been made by reduction the corresponding coeroxonol or coeroxenol compounds with hydrogen iodide in Presence of phosphorus produced. This way of working comes because of the usage of hydrogen iodide practically out of the question; all the more so than the resulting Products are obtained in impure form. It has also been suggested to use coeroxonole to reduce in alcoholic-alkaline solution, but the reduction leads here only up to the coeroxenol stage.

It has now been found that compounds of the coeranthrene and coerbianthrene series can be used can be produced very smoothly and in pure form if one uses the corresponding coeroxonols or coeroxenols treated with hydrogen in the presence of catalysts or they subjected to a vigorous reduction in alkaline liquid until the resulting compounds have become practically insoluble in alkali. The procedure can at normal or higher temperatures, e.g. 6o to r2o °, possibly below Pressure carried out.

You can z. B. proceed in such a way that the above-mentioned starting material -e in the presence of solvents or thinners (e.g. cyclohexane, tetrahydronaphthalene, Decahydronaphthalene, hexane, etc.) with hydrogen in the presence of hydrogenation catalysts, such as finely divided nickel, copper, cobalt, palladium; Platinum, etc., by itself or in a mixture with each other or with other substances, e.g. B. Activators, at increased Temperature, optionally under pressure, treated. One can also use the coeroxonols or developing coeroxenols in an alkaline medium with nascent hydrogen treat vigorous reducing agents, for example with aluminum, zinc, tin, Lead and the like, in the presence of alkaline solutions or ammonia. In some cases it turns out it is advantageous to add the reducing agent evolving to the nascent hydrogen organic solvents such as alcohol, acetone, etc. to be added. Electrolytic too Reduction in an alkaline medium leads to the goal.

The reaction products are from the reaction mixture in any Separated way and are characterized by great purity. They are for coloring of materials, e.g. B. gasoline, fats and oils, suitable and can also be used as a starting material serve to produce new dyes.

Example z 5 parts of dimethylcoeroxonol, which was prepared according to Annalen der Chemie, Vol. 356, p. 323, are suspended with stirring in 5o parts of about 20% sodium hydroxide solution, whereupon the mixture, after the addition of Z.5 parts, zinc dust and optionally 2o- parts of ethyl alcohol is heated to boiling for 5 hours. The end of the reaction is noticeable by a strong lightening of the solution, which was initially red in color. The mixture of excess zinc dust and the reduction product formed is removed The procedure is similar if one uses coeroxenol instead of dimethylcoeroxonol.

The coeroxenes obtained show contrast in organic solvents strong fluorescence in relation to the coeroxonols and coeroxenols.

Example 2 5 parts of purified .Coeroxonol are in 100 parts of cyclohexane suspended and after the addition of i part of very finely divided nickel powder with hydrogen under ioo atm. Pressure heated to 100 ° for 4 hours. The deeply colored reduction product is worked up in the usual way.

Example 3 2 parts 14.20 - Dimethylcoerbioxendiol- (9, io), which by Condensation of 1, 5-di-p-cresoxyanthraquinone with concentrated sulfuric acid and Obtained phosphoric acid and treating the condensation product with water and alkalis is, and 15 parts of zinc dust is suspended in 100 parts of water and left in the Slowly add dropwise 25 parts of a 35% sodium hydroxide solution at the boiling point. One heats up for several hours and then works on in the usual way. The received Dimethylcoerbioxen is a red-brown product that. in organic solvents dissolves with strong fluorescence. .

Example 4 'A slurry of 25 parts of 4,14-dibutylcoeroxonol of makeup [Obtainable by reacting phthalic anhydride with i-oxy-4- (trimethyl) methylbenzene in the presence of concentrated sulfuric acid and treating the resulting 2,7-dibutylfluorane with 23 percent fuming sulfuric acid] and 61 parts of zinc dust in zoo parts of water are heated to about ioo °, leaves with good stirring .es powder that dissolves very easily in organic solvents with a light yellow color and strong yellow-green fluorescence.

Example A slurry heated to between 70 and 80 is electrolyzed of 25 parts of 4,14-Dimethylcoeroxonol in 2ooo parts of iop% alcoholic Caustic soda on a mercury cathode at 3 amps. After about. has io hours the Dimethylcoeroxen deposited in the form of yellow flakes. You suck it off, wash them off and dry them. The behavior of the connection corresponds to that of described in example i.

Example 6 3o parts of 4, 14-dichloroeroxonol (available from 2, 7-dichlorofluorane by ring closure using 23 percent fuming sulfuric acid) in the manner described in example i. After working up you get one Dye that is in organic solvents with a light yellow color and more intense green-yellow fluorescence. -Used in place of the 4, 14-Dichlorcoeroxonols 3,13-Dichlorcoeroxonol (can be prepared from 3,6-dichlorofluorane by treating with fuming sulfuric acid), a slightly greenish fluorescent one is obtained Dye.

Example 7 A slurry of 25 parts of 3, 13- or 3, 15-dimethylcoeroxonol and 75 parts of zinc dust in zoo parts of water is heated to about 1000. 90 parts of 35% sodium hydroxide solution are added dropwise with constant stirring and the mixture is worked up after 5 hours. The 3, 13- or 3, 15-dimethylcoeroxene obtained in this way is yellow-red in color and dissolves in organic solvents with a light yellow color and strong yellow-green fluorescence.

If instead of 3, 13-Dimethylcoeroxonol a from technical m-Kre-'sol obtainable mixture of 3, 13- and 4, 14-Dimethylcoeroxonol, so obtained a mixture of the corresponding coeroxenes that fluoresces a little more yellow and has a better solubility than the pure compounds.

Example 8 To a slurry heated to about 100 ° of 100% Parts 3, 4, 13, 14-tetramethylcoeroxonol and ioo parts of zinc dust 36o parts of 35 percent sodium hydroxide solution are left in 800 parts of water with constant stirring drop in and work up the mixture in a known manner after about 8 hours. Man. thus obtains a connection that works very well with Irish solvents with a yellow color and strong green-yellow fluorescence.

Example g 100 parts of 3,13-dimethyl-2, 16-dichloroeroxonol are reduced in the manner described in the previous example. After working up you get a compound that is slightly greener in organic solvents Fluorescence dissolves as the compound obtainable according to Example i. '-Used one instead of the pure 3, 13-dimethyl-z, 16-dichloroeroxonols, a mixture of dimethyldichloroeroxoriols, how it is done with the chlorination of raw cresol, reaction with - phthalic anhydride and ring closure is obtained by means of fuming sulfuric acid, a mixture is obtained of the corresponding coeroxene, which has a better solubility with a similar fluorescent color in organic solvents possesses than the pure compounds.

Claims (1)

PATENT CLAIM: Decorative processes for the production of compounds of the coeranthrene and coerbianthrene series, characterized in that the corresponding coeroxonols or coeroxenols are treated with hydrogen in the presence of catalysts or they are subjected to a vigorous reduction in an alkaline liquid until the compounds formed have become practically insoluble in alkali are.