While a great variety of straight-chain aliphatic compounds of large molecular weight are known, the information in regard to many groups of branched aliphatic compounds is relatively meager. For example, of the 38 tertiary alcohols listed in the new edition of Beilstein's "Handbuch" (which covers the literature to 1910), 32 contain only primary alkyl groups. Of the remaining 6, four contain one secondary group and two primary groups, while only two contain a tertiary group; none contains more than one secondary or tertiary group. Although a great deal of work in aliphatic chemistry has been published in the last eighteen years, our information concerning branched compounds has not materially increased. Purely aliphatic carbinols of the type4 (R3)3COH, (RS)2R3-COH and (R2)3COH appear to be still unknown.6 In regard to the hydrocarbons our information is even more restricted. The only hexaalkylethanes, (R3C-CR3), that have been prepared are hexamethyl-ethane6 and tetramethyldiethylethane.
The Fries reaction consists in the conversion of an ester of a phenol to an ortho‐ or para‐hydroxyketone, or a mixture of both, by treatment with aluminum chloride. Three different mechanisms for the fries rearrangement have received serious consideration.: the ester is assumed to react with aluminum chloride to give an acid chloride and a phenoxyaluminum chloride which combine to form a derivative of the hydroxyketone; one molecule of the phenyl ester is acylated by another molecule; the Fries reaction is considered ti be a true intramolecular rearrangement in which the acyl group shifts directly from the oxygen atom to the carbon atom of the ring.
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