Conformational study of acyclic alcohols by NMR spectroscopic analysis, molecular force field and ab initio calculations.

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概要

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• Conformations of a series of acyclic alcohols (CH<SUB>3</SUB>CH(R)CH(OH)CH<SUB>3</SUB>, CH<SUB>3</SUB>CH(R)CH(OH)CH(R′)CH<SUB>3</SUB>, and CH<SUB>3</SUB>CH(R)CH(OH)Bu<I><SUP>t</SUP></I>) were studied (1) by measuring vicinal H–H coupling constants (<SUP>3</SUP><I>J</I><SUB>H–H</SUB>), (2) by lanthanoid-induced shift (LIS) analysis, (3) by molecular mechanics calculations (MM2), and (4) by ab initio (STO-3G, 4-31G geometry optimization) calculations. In the case of conformationally flexible alcohol as exemplified by 2-butanol and 3-pentanol, population of conformers determined by the LIS method do not agree with those determined by the <SUP>3</SUP><I>J</I><SUB>H–H</SUB>, MM2, and ab initio methods. The discrepancy comes from the fact that the LIS measurement gives the most stable conformation of the alcohol in the LSR-alcohol complex and not of the free alcohol. In some flexible molecules, the most stable conformer in the complex can be different from that of the free molecule. In general, the conformational equilibrium is shifted by coordination of the shift reagent to the conformer whose alkyl chain stretches opposite to the direction of the coordination site of the shift reagent.

• 公益社団法人 日本化学会の論文

著者

• Ito Kohichi

  Department Of Biotechnology Graduate School Of Engineering Osaka University

• Hirota Minoru

  Department Of Animal Science Obihiro University Of Agriculture And Veterinary Medicine

• HIROTA Minoru

  Department of Synthetic Chemistry, Division of Materials Science and Chemical Engineering, Faculty of Engineering, Yokohama National University

• Suezawa Hiroko

  Department of Synthetic Chemistry, Division of Materials Science and Chemical Engineering, Faculty of Engineering, Yokohama National University

• Suezawa Hiroko

  Deparment of Synthetic Chemistry, Division of Materials Science and Chemical Engineering, Faculty of Engineering, Yokohama National University

• Abe Kazuhisa

  Department of Applied Chemistry, Faculty of Engineering, Yokohama National University

• Nishio Motohiro

  Central Research Laboratotries, Meiji Seika Kaisha, Ltd.

• Nishio Motohiro

  Central Research Laboratories, Meiji Seika Kaisha Ltd.

• Hirota Minoru

  Deparment of Synthetic Chemistry, Division of Materials Science and Chemical Engineering, Faculty of Engineering, Yokohama National University

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