Reactivities of stable rotamers. XXII. Lewis acid-catalyzed reactions of 3-(1,4-disubstituted 9-triptycyl)-3-methylbutanoyl chloride. Isolation of rotameric ketones and competition between cyclizations to substituted and to unsubstituted benzene rings.
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概要
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Rotational isomers of 3-(1,4-disubstituted 9-triptycyl)-3-methylbutanoic acid, where the substituent is either a methoxyl or a methyl, have been prepared, starting from 1,4-disubstituted 9-(1,1-dimethyl-3-butenyl)triptycene. Lewis acid-catalyzed reactions of the <I>ap</I>-acid chloride afforded corresponding ketones expected from the intramolecular Friedel–Crafts reaction. The <I>sc</I> form of the 1,4-dimethoxy compound gave a ketone that was formed by the reaction of the unsubstituted benzene ring and a lactone which was derived by the attack of the acylium ion on the methoxy-oxygen followed by demethylation. The <I>sc</I> form of the 1,4-dimethyl compound afforded a ketone which was expected from cyclization to the unsubstituted benzene ring and another ketone that was derived from the ipso attack of the acylium ion followed by 1,2-methide migration. In both cases, the ketone derived from the <I>ap</I> form of the acid chloride was different from that obtained from the <I>sc</I>. The barriers to isomerization of the <I>ap</I>-ketone to the <I>sc</I>-ketone was 29.6 kcal mol<SUP>−1</SUP> at 100.5 °C and 25.6 kcal mol<SUP>−1</SUP> at 56.0 °C for the methoxy and the methyl compounds, respectively. In both cases, the ketone derived from the <I>sc</I>-form was more stable than that from the <I>ap</I>, the <I>sc</I>/<I>ap</I> ratio at the equilibrium being 20.0 (56.0 °C) and 5.9 (100.5 °C), respectively, for the methyl and the methoxy compounds. In the reaction of the <I>sc</I> form, the competitive results between the cyclization toward the unsubstituted benzene ring and that toward the substituted vary according to the solvent and the Lewis acid used.
- 公益社団法人 日本化学会の論文
著者
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Yamamoto Gaku
Department Of Chemistry Faculty Of Science The University Of Tokyo
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Tanaka Toshimasa
Department Of Applied Chemistry Faculty Of Engineering Gifu University
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Yonemoto Katsumi
Department Of Chemistry Faculty Of Science The University Of Tokyo
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Oki Michinori
Department Of Chemistry Faculty Of Science Okawama University Of Science
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Nakai Yasufumi
Department of Chemistry, Faculty of Science, The University of Tokyo
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