GB435708A - Manufacture of phenylated, aromatic and hydroaromatic hydrocarbons and derivatives thereof - Google Patents

Abstract

Aromatic and hydroaromatic compounds substituted by phenyl groups are obtained by reacting phenyl-substituted cyclopentadienones with unsaturated compounds of the ethylene or acetylene series. The reaction may be effected by heating the reagents in the presence or absence of a solvent. The probable course of the reaction is illustrated by reference to the reaction of tetraphenylcyclopentadienone with maleic anhydride; the initial product of this reaction is probably 3 : 4 : 5 : 6-tetraphenyl-3 : 6-endocarbonyl-1 : 2-dihydrophthalic anhydride which loses carbon monoxide when heated to 125--150 DEG C. and yields 3 : 4 : 5 : 6-tetraphenyl-1 : 2-dihydrophthalic anhydride; further heating to about 200 DEG C. causes dehydrogenation, and tetraphenylphthalic anhydride is then obtained. Other examples are given in which (1) tetraphenylcyclopentadienone and phenyl acetylene yield pentaphenylbenzene; (2) tetraphenylcyclopentadienone and diphenylacetylene yield hexaphenylbenzene; (3) tetraphenylcyclopentadienone and stilbene yield hexaphenyldihydrobenzene, which yields hexaphenylbenzene when heated with zinc dust or selenium; (4) a diphenyldiphenylenecyclopentadienone (formula given) and maleic anhydride yield a 3 : 6 - diphenyl - 4 : 5 - diphenylenephthalic anhydride (formula given); (5) a phenylated cyclopentadienone derivative (formula given) obtained from acenaphthenequinone and dibenzyl ketone is treated with diphenylacetylene to yield a tetraphenylfluoranthene; (6) tetraphenylcyclopentadienone and phenylpropiolic ethyl ester yield pentaphenylbenzoic ethyl ester; (7) tetraphenylcyclopentadienone and the acetal of phenylpriolaldehyde yield pentaphenylbenzaldehyde acetal, which yields pentaphenylbenzaldehyde when boiled with glacial acetic acid. A sample has been furnished under Sect. 2 (5) of tetraphenylbenzene, obtained from tetraphenylcyclopentadienone and acetylene. Phenyl - substituted cyclopentadienones are obtainable, as described in German Specification 575,857, by condensing an aromatic o-diketone or a derivative or reduction product thereof with a ketone containing a reactive methylene group. Thus, tetraphenylcyclopentadienone is obtained from benzil and dibenzyl ketone.