Coexistence of Two 1:1 Complexes of Oxyphenonium Bromide and α-Cyclodextrin

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The complexation of 2-(2-cyclohexyl-2-hydroxy-2-phenylacetoxy)-<I>N</I>,<I>N</I>-diethyl-<I>N</I>-methylethanaminium bromide (oxyphenonium bromide, OB) and α-cyclodextrin (α-CD) in deuterium oxide was investigated by 500 MHz proton NMR spectroscopy, molecular mechanics, and molecular surface-area calculations. The ROESY spectrum revealed that two 1:1 complexes of OB and α-CD, the phenyl-in complex and the cyclohexyl-in complex, coexist simultaneously. The ROE intensities of intermolecular cross-peaks and molecular-mechanics calculations provided the structures of these complexes. The ROE intensities were well-correlated with the effective inter-proton distances for the estimated structures. The observed binding constant (70 dm<SUP>3</SUP> mol<SUP>−1</SUP>) was close to the sum of the binding constants of α-CD with phenol and cyclohexanol. This agreement supported the coexistence of the two complexes, and allowed us to estimate the mole fraction of the phenyl-in complex of 0.3. The chemical shift variations (Δδ<SUB>OB–CD</SUB>) at full binding for aromatic protons of OB are smaller than those of the benzenesulfonate–α-CD complex. Their ratio gave another estimate of the phenyl-in complex mole fraction (0.38). The averaged structure of OB in the two complexes was estimated from a comparison between the observed and theoretical shifts for four pairs of cyclohexyl protons; the phenyl and cyclohexyl groups in the complexes are slightly more distant than those in the free state. The structures of the phenyl-in complex and the cyclohexyl-in complex, estimated by hydrophobic molecular surface-area calculations, predicted binding constants closer to the observed ones than those by molecular-mechanics calculations.

収録刊行物

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 76(5), 903-911, 2003-05-15

    公益社団法人 日本化学会

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各種コード

  • NII論文ID(NAID)
    10012811904
  • NII書誌ID(NCID)
    AA00580132
  • 本文言語コード
    ENG
  • 資料種別
    ART
  • ISSN
    00092673
  • NDL 記事登録ID
    6532792
  • NDL 雑誌分類
    ZP1(科学技術--化学・化学工業)
  • NDL 請求記号
    Z53-B35
  • データ提供元
    CJP書誌  CJP引用  NDL  J-STAGE 
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