DE641675C - Process for the preparation of oxyarylaminophenanthrene compounds - Google Patents

Description

Process for the preparation of oxyarylaminophenanthrene compounds It has been found that n i valuable, previously unknown condensation products The phenanthrene series is obtained if oxy or amino compounds of the phenanthrene series are used with aminophenols. This conversion is carried out according to the known reaction B u c h e r e r in water in the presence of acidic salts of sulphurous acid higher temperature in an open or closed vessel.

This implementation has not yet been carried out in the phenanthrene series runs very smoothly and leads in good yield to new products, which are used as intermediates to be used for the production of dyes and medicinal products.

The success of the present process could not be foreseen, since the conversion of aromatic amines and oxy compounds according to the well-known Bucherer reaction is by no means a generally applicable procedure; rather, its smooth feasibility has so far been demonstrated primarily on the naphthalene series, while it remarkably fails completely in the benzene series . In addition, the reaction with aminooxy compounds in the general Bucherer reaction is still particularly difficult (cf. patent 530 825). On the basis of these facts, it was not possible to make any assumptions about the course of the present conversion in the phenanthrene series. Example 1 kg of 3-oxyphenanthrene and 25 kg of p-aminophenol are heated in a stirred autoclave in zoo kg of sodium bisulfite solution (27 ° Be) to about 16 ° for a few hours. After cooling, the practically completely separated reaction product is filtered off with suction and suitably purified by dissolving it in dilute sodium hydroxide solution with the addition of a little hydrosulfite, filtering the solution thus obtained and reprecipitating it with sodium biscuit solution. Maxi receives p'-oxyphenyl-3-phenanthrylamine in good yield. In its pure state it is an almost colorless powder which, in an alkaline solution, rapidly oxidizes in the air.

You can work at a slightly lower temperature with the same success, if you heat it for longer.

If the corresponding amount of 3-oxyphenanthrene-2-carboxylic acid is used instead of 3-oxyphenanthrene, in this way the same compound is obtained with the elimination of carbon dioxide.

If you take the place of 3-oxyphenanthrene from the equivalent Amount of '3-phenanthrylamine and leads the 1 - #, ondensation otherwise as above indicated by, da-s-, p'-oxyphenyl-3-phenanthrylamine is also obtained in a smooth reaction.

In the same way, the isomers; Convert phenanthrols into the corresponding condensation products. Example a The solution of 10 kg of 9-oxyphenanthrene with a melting point of 150 to 151 ° in 6o l of dilute sodium hydroxide solution containing 40 g of caustic soda per liter is stirred into 1 ¢ o kg of bisulfite solution (38 ° B6) and the suspensions: -sion after adding 20 kg of p-aminophenol in a stirred autoclave heated to between 20 and 125 hours for about 25 to 30 hours. After cooling, the reaction product is filtered off with suction, freed from the admixed p-aminophenol by extraction with cold dilute hydrochloric acid and, for further purification, appropriately dissolved in dilute sodium hydroxide solution with the addition of hydrosulfite, filtered and reprecipitated with bisulfite. The p-oxyphenyl-9-phenanthrylamine obtained in this way forms an almost colorless powder in its pure form, which rapidly oxidizes with a red-brown color in alkaline solution in the air. Example 3 -io kg 3-oxyphenanthrene and 25 kg p-amino- ', -Phenol are heated with the addition of a solution of 53 kg of potassium bisulfite in a stirred autoclave for a few hours at 150 to 170 °. After cooling, the reaction product separates out practically completely and is separated off in the manner described in Example i. It is identical to the p'-oxyphenyl-3-phenanthrylamine obtained according to Example s.

With the same result one can get a solution of 46 kg calcium bisulfite use.

Claims (1)

PATENT CLAIM: Process for the production of oxyarylaminophenanthrene compounds, consisting in that one phenanthrols or phenanthrylamines or nuclear substitution pr products of the same with amiophenols or substitution products of the same in water heated with the addition of acid salts of sulphurous acid.