Reactivities of stable rotamers. XXIV. Formation of isomeric ketones by cyclization of rotameric 3-methyl-3-(1,2,3,4-tetrahalo-9-triptycyl)butanoyl chloride and barriers to isomerization of the ketones.

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• Rotational isomers of 3-methyl-3-(1,2,3,4-tetrahalo-9-triptycyl)butanoic acid, where the halo is either fluoro or chloro have been prepared. Cyclization of their acid chlorides afforded <I>ap</I>- and <I>sc</I>-ketones from <I>ap</I>- and <I>sc</I>-isomers, respectively. The barriers to isomerization were 29.9 and 26.8 kcal mol<SUP>−1</SUP> at 363 K, for the fluoro and the chloro ketones, respectively, for the <I>ap</I>→±<I>sc</I> process. The equilibrium constants (<I>sc</I>/<I>ap</I>) at 363 K were 2.34 and 18.5 for the fluoro and the chloro compounds respectively. The barriers to isomerization and the relative stabilities of the isomeric ketones were discussed based on the MMP2(NONPLANAR) calculation results and the steric congestion in the ground state.

• 公益社団法人 日本化学会の論文

著者

• Yamamoto Gaku

  Department Of Chemistry Faculty Of Science The University Of Tokyo

• Oki Michinori

  Department Of Chemistry Faculty Of Science Okawama University Of Science

• Tanaka Yasuhiro

  Department Of Advance Materials Science Faculty Of Engineering Kagawa University

• Tanuma Toshihiro

  Asahi Glass Research Center

• Tanaka Yasuhiro

  Department of Chemistry, Faculty of Science, The University of Tokyo

• Tanuma Toshihiro

  Department of Chemistry, Faculty of Science, The University of Tokyo

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