The Retentive Solvolysis. VII. Structural Effect of the Leaving Group on the Steric Course of the SN1 Phenolysis of 1-Phenylethyl Systems

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概要

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• A series of optically active 1-phenylethyl systems with various leaving groups has been phenolyzed in the phenolic solvents. The 1-phenylethyl systems with a negative leaving group (<I>i.e</I>., 1-phenylethyl chloride, bromide, 3,5-dinitrobenzoate, and tosylate) afforded 1-phenylethyl phenyl ether with a net retained configuration. In contrast, the 1-phenylethyl systems with a positively-charged leaving group (<I>i.e</I>., the 1-phenylethyldiazonium ion, the diethyl-(1-phenylethyl)-oxonium ion, and the protonated 2,6-di-<I>t</I>-butyl-4-methyl-4-(l-phenylethyl)-cyclohexadien-l-one) .gave the 1-phenylethyl phenyl ether with a net inverted configuration. These results provide further support for the view that the retentive S<SUB>N</SUB>1 phenolysis proceeds <I>via</I> a four-center transition state between the phenol molecule and the ion-pair intermediate. Besides the phenolic ether, the <I>o</I>- and <I>p</I>-(1-phenylethyl)-phenols with net inverted configurations were obtained from all optically active substrates except 1-phenylethyl 3,5-dinitrobenzoate and the 1-phenylethyldiazonium ion. The 3,5-dinitrobenzoate gave the completely racemic <I>o</I>-alkylated phenol, along with the inverted <I>p</I>-alkylated phenol, whereas the diazonium ion afforded the <I>o</I>-alkylated phenol with a net retained configuration, together with the inverted <I>p</I>-alkylated phenol. The stereochemical and mechanistic implications of the <I>C</I>-alkylation are also discussed on the basis of the results of the acidic rearrangement of the phenolic ether under the S<SUB>N</SUB>1 phenolysis conditions.

• 公益社団法人 日本化学会の論文

著者

• KINOSHITA Tomomi

  Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University

• Shingu Haruo

  Department of Fuel Chemistry Faculty of Engineering Kyoto University

• Okamoto Kunio

  Department of Fuel Chemistry Faculty of Engineering Kyoto University

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