ロジウム触媒による立体規則性ポリ(N-プロパルギルアミド)の合成と構造 : 水素結合によるらせん構造の安定化  [in Japanese] Synthesis and Structure of Rh-Based Stereoregular Poly (N-propargylamide)s : Stabilization of Helical Structure by Means of Hydrogen Bond  [in Japanese]

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Abstract

置換アセチレンの1つであるN-プロパルギルアミドがRh触媒によって速やかに重合し, 選択的にシス-トランソイドの立体規則性をもつポリマーを収率よく与えることを見いだした. 生成ポリマー, ポリ (<I>N</I>-プロパルギルアミド), の側鎖間には分子内水素結合が形成され, これによって主鎖にらせん構造が誘起・安定化されることを明らかにした. また, らせん構造は熱や極性溶媒の添加といった外部環境の変化に応答して容易にランダムコイルへと変化し, その際吸収挙動が大きく変化することを見いだした. さらに, ポリ (<I>N</I>-プロパルギルアミド) のらせん構造は大きな負のエントロピーとエンタルピーのバランスの上に成り立っていることをスペクトル的に証明した.

<I>N</I>-Propargylamides have proven to polymerize in the presence of Rh catalysts to give stereoregular (<I>cis</I>-transoidal) polymers in good yields. Intramolecular hydrogen bonds are constructed between the pendant amide groups, which induces and stabilizes the helical conformation of the main chain. The helical structure is readily deformed into the randomly coiled state, which is promoted by the external stimuli such as heating or adding polar solvents. The transition from the disordered to helical conformations was spectroscopically evidenced to involve negatively large entropy and enthalpy changes.

Journal

  • KOBUNSHI RONBUNSHU

    KOBUNSHI RONBUNSHU 59(4), 190-198, 2002-04-25

    The Society of Polymer Science, Japan

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Codes

  • NII Article ID (NAID)
    10008223883
  • NII NACSIS-CAT ID (NCID)
    AN00085011
  • Text Lang
    JPN
  • Article Type
    REV
  • ISSN
    03862186
  • NDL Article ID
    6154255
  • NDL Source Classification
    ZP16(科学技術--化学・化学工業--高分子化学・高分子化学工業)
  • NDL Call No.
    Z17-92
  • Data Source
    CJP  NDL  J-STAGE 
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