Temperature Dependence of Enantioselectivity in Complexations of Optically Active Phenolic Crown Ethers with Chiral Amines in Solution

この論文にアクセスする

この論文をさがす

著者

抄録

The association constants (K) of complexes of chiral neutral amines with optically active crown ethers ((S,S)-1, (S,S)-2, (S,S)-4 and (S,S)-5) which contain the phenyl chiral barriers and the phenol moiety bearing an additional para-substituent were determined at various temperatures by the 1H n.m.r. spectroscopic method in CDCl3. The thermodynamic parameters for complexation, which were determined from the van't Hoff plots of the K values, suggested that the acidity of the phenolic crown ethers markedly affected the enthalpy and entropy changes upon complexation with neutral amines. The crown ethers ((S,S)-2, (S,S)-4 and (S,S)-5) having higher acidity showed more negative ΔH and ΔS values and a larger slope in the enthalpy-entropy compensation plot than crown ether (S,S)-1 having a lower acidity. The temperature-dependent enantioselectivity in complexation of chiral neutral amines with (S,S,S,S)-6 containing phenyl substituents and the cyclohexane moieties as chiral barriers together with the p-(2,4-dinitrophenylazo)phenol moiety was also examined, demonstrating that steric interactions between the bulky steric barriers and the amine induced larger conformational changes of the host and guest molecules upon complexation. The data of the temperature-dependent enantioselectivity demonstrate a reversal of the relative merits of the enantioselectivity depending upon the temperature. A linear relatioship between the TΔR,SΔS values and the ΔR,SΔH values (TΔR,SΔS=0.812ΔR,SΔH-0.342, R=0.983) shows that the ΔR,SΔH and ΔR,SΔS values compensate each other. Therefore, complexation having a larger ΔR,SΔH value does not always show a higher degree of the enantioselectivity at any temperature than that having a smaller ΔR,SΔH value.

収録刊行物

  • Analytical sciences : the international journal of the Japan Society for Analytical Chemistry

    Analytical sciences : the international journal of the Japan Society for Analytical Chemistry 14(1), 175-182, 1998-02-10

    社団法人 日本分析化学会

参考文献:  34件中 1-34件 を表示

  • <no title>

    MORRISON J. D.

    Asymmetric Organic Reactions Tables 5-6 and 5-7, 1971

    被引用文献3件

  • <no title>

    RETEY J.

    A Stereospecificity in Organic Chemistry and Enzymology, 1982

    被引用文献1件

  • <no title>

    MORISON J. D.

    Asymmetric Synthesis, 1-5, 1983

    被引用文献1件

  • <no title>

    COPPOLA G. M.

    Asymmetric Synthesis, 1987

    被引用文献2件

  • <no title>

    WATABE K.

    Angew. Chem., Int. Ed. Engl. 28, 192, 1989

    被引用文献2件

  • <no title>

    SCHURIG V.

    Angew. Chem., Int. Ed. Engl. 28, 194, 1989

    被引用文献3件

  • <no title>

    van PHAM T.

    J. Am. Chem. Soc. 111, 1935, 1989

    被引用文献2件

  • <no title>

    INOUE Y.

    Nature[London] 341, 225, 1989

    被引用文献2件

  • <no title>

    NAEMURA K.

    J. Chem. Soc., Chem. Commun. 1996, 2749

    被引用文献1件

  • <no title>

    NAEMURA K.

    Asymm. 8, 2585, 1997

    被引用文献1件

  • <no title>

    CRAM D. J.

    Pure Appl. Chem. 43, 327, 1975

    被引用文献2件

  • <no title>

    STODDART J. F.

    Progress in Macrocyclic Chemistry, 1981

    被引用文献1件

  • <no title>

    STODDART J. F.

    Topics in Stereochemistry 17, 1987

    被引用文献1件

  • <no title>

    CRAM D. J.

    Angew. Chem., Int. Ed. Engl. 27, 1009, 1988

    被引用文献18件

  • <no title>

    IZATT R. M.

    Crown Compounds : Toward Future Applications, 1992

    被引用文献1件

  • <no title>

    BRADSHAW J. S.

    J. Coord. Chem. 27, 105, 1992

    被引用文献1件

  • <no title>

    KANEDA T.

    Crown Ethers and Analogous Compounds, 1992

    被引用文献1件

  • <no title>

    STILL W. C.

    Acc. Chem. Res. 29, 155, 1996

    被引用文献5件

  • <no title>

    WEBB T. H.

    Chem. Soc. Rev. 22, 38, 1993

    被引用文献1件

  • <no title>

    SHIBUKAWA A.

    Chiral Separations by HPLC, 1989

    被引用文献1件

  • <no title>

    ARMSTRONG D. W.

    Anal. Chem. 66, 1473, 1994

    被引用文献5件

  • <no title>

    NAEMURA K.

    Tetrahedron : Asymm. 8, 873, 1997

    被引用文献1件

  • <no title>

    NAEMURA K.

    J. Chem. Soc., Perkin Trans. 1 1996, 383

    被引用文献1件

  • <no title>

    SMITHURD D. B.

    J. Am. Chem. Soc. 113, 5420, 1991

    被引用文献1件

  • <no title>

    INOUE Y.

    J. Chem. Soc., Perkin Trans. 2 1985, 935

    被引用文献1件

  • <no title>

    INOUE Y.

    J. Chem. Soc., Perkin Trans. 2 1990, 1239

    被引用文献2件

  • <no title>

    INOUE Y.

    J. Am. Chem. Soc. 115, 475, 1993

    被引用文献12件

  • <no title>

    KANEDA T.

    J. Am. Chem. Soc. 110, 2970, 1988

    被引用文献1件

  • <no title>

    KANEDA T.

    J. Am. Chem. Soc. 111, 742, 1989

    被引用文献6件

  • <no title>

    HIROSE K.

    J. Chem. Soc. Perkin Trans. 2 1997, 1649

    被引用文献1件

  • <no title>

    NAEMURA K.

    J. Am. Chem. Soc. 115, 8475, 1993

    被引用文献3件

  • <no title>

    NAEMURA K.

    Coordination Chemistry Reviews 148, 199, 1996

    DOI 被引用文献3件

  • <no title>

    DOTSEVI G.

    J. Am. Chem. Soc. 98, 3038, 1976

    DOI 被引用文献1件

  • <no title>

    SHINBO T.

    J. Chromatogr. 405, 145, 1987

    DOI 被引用文献8件

各種コード

  • NII論文ID(NAID)
    10002414573
  • NII書誌ID(NCID)
    AA10500785
  • 本文言語コード
    ENG
  • 資料種別
    ART
  • ISSN
    09106340
  • NDL 記事登録ID
    4406441
  • NDL 雑誌分類
    ZP4(科学技術--化学・化学工業--分析化学)
  • NDL 請求記号
    Z54-F482
  • データ提供元
    CJP書誌  NDL  J-STAGE 
ページトップへ