Ortho-quinone Monoxime Inner Complexes

Abstract

for fifteen minutes, giving a clear solution Most of the alcohol was distilled off and the residual solution, on cooling, deposi ed white plates of the oxime XIX (500 mg.) melting at 195-196' Rec~ystallimtion from alcohol gave : a product melting at 196-197'. Anal Calcd. for Cp2HleO~P.l: C, 80.20; €5, 5.82.Found: C , 80.09; H, 621Oxidation.--The tetralone XVIII (1 g.) and potassiuni dichroniate (3 g . ) were rrfluxed in acetic acid (30 cc.) for SIX hours. The green solution was poured into water (100 t c.) and most of the acetic acid was neutralized with sodium carbonate. Some sticky, orange material rose to the top of the solution, thia was removed with a spatula. The aqueous solution was extracted with benzene, and the benzene solution then extracted with sodium hydroxide solution (10%). The alkaline extraction was acidified and steam distilled. From the distillate, benzoic acid (200 mg.), m. p. and mixed m. p. 121°, was isolated. The residue in the distilling flask was extracted with ether; from the ether extract, o-benzoylbenzoic acid (hydrate) (520 mg.), m. p. and mixed m. p. 88-90', was isolated. From the sticky orange solid originally found in the oxidation, a very sniall amount of the red quinone VI, m. p. and mixed m. p. 245 ' , was isolated by repeated crystallization from alcohol Naphthol 1V.-The tetralone XVIII (500 mg.), acetic acid (15 cc.) and sulfuric acid (5 drops) were boiled for thirty minutes and then poured into water. The pinkish solid was removed, dissolved in alcohol and the solution decolorized with charcoal. The alcohol was boiled off and replaced by petroleum ether (b. p. 9O-10Oo). On cooling white needles of 3,4-diphenyl-cY-naphthol IV (430 mg ) were deposited. These had a melting point and mixed melting point of 142-143 ' and showed the phenomenon of solidification after melting with remelting a t 153-154" (see above under properties of IV). This is the same wbstance reported by Fmnssen as having structure S V I I Acetate 1X.-The tetralone XVIII (1 g.), acetic anhydride (7.5 cc.) and sulfuric acid (1 drop) were boiled for fifteen minutes. The cooled solution was poured onto ice and the pinkish solid (m. p. 16@-162") was removed.The solid was dissolved in chloroform and the solution was decolorized with charcoal. Most of the chloroform was removed, alcohol was added and the solution was cooled. White cubes of the acetate I X (950 mg.), m. p. and mixed m. p. 162-162.5', were obtained. This is the same subqtance reported by Franssen as having structure XVI Summary I . lliphenylketene and phenylacetylene react by addition to form, in good yield, 3,4-diphenyl-a-naphthol, IV.The structure of the naphthol was proved by degradation and by an independent synthesis from 1,4-naphthoquinone and phenylmagnesium bromide.The work of Franssen on the addition of phenylmagnesium bromide to 1,4-naphthoquinone has been repeated and his structures for the products have been shown to be incorrect. These have been supplanted by the correct structures.The reaction between diphenylketene and acetylenes ap...