Solvolysis of 1-[trans-2-(m- or p-Substituted Phenyl)cyclopropyl]-1-methylethyl p-Nitrobenzoates^<1)>

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Abstract

The solvolyses of 1-[<i>trans</i>-2-(<i>m</i>- or <i>p</i>-substituted phenyl)cyclopropyl]-1-methylethyl <i>p</i>-nitrobenzoates in 80% aqueous acetone have been studied with regard to both reactivity and product composition. For the less reactive substituents such as <i>m</i>-Br, <i>m</i>-Cl, and <i>m</i>-CF<sub>3</sub>, the solvolysis products were the corresponding 2-(2-arylcyclopropyl)-2-propanol, indicating the cyclopropylmethyl cation intermediate. The ring-opened products increased as the electron-donating ability of the substituents increased. The application of the Yukawa–Tsuno equation to the reactivity afforded a <i>ρ</i> value of −1.43 and <i>r</i> value of 0.59 with a correlation coefficient of 0.997. A large value of <i>r</i> indicates the presence of the allylic cation intermediate where much more charge develops at the benzylic carbon for the derivatives with electron-donating substituents than is the case for the cyclopropylmethyl cation intermediate. Thus the solvolysis reaction proceeds via two independent pathways: one has a cyclopropyl cation intermediate and the other has a homoallylic cation intermediate.

Journal

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 71(3), 685-691, 1998-03-15

    The Chemical Society of Japan

References:  32

  • <no title>

    the 7th International Conference on Correlation Analysis in Chemistry (CAIC-VII), 1996

    Cited by (1)

  • <no title>

    COULSON C. A.

    J. Chem. Phys. 15, 151, 1947

    Cited by (1)

  • <no title>

    WALSH A. D.

    Nature 159, 165 and 712, 1947

    Cited by (1)

  • <no title>

    CHARTON M.

    The Chemistry of Alkenes 2, Cha 10, 1970

    Cited by (1)

  • <no title>

    RICHEY H. G. Jr.

    Carbonium Ions 3, Cha 25, 1972

    Cited by (1)

  • <no title>

    WIBERG K. B.

    Carbonium Ions 3, Cha 26

    Cited by (1)

  • <no title>

    TIDWELL T. T.

    The Chemistry of the Cyclopropyl Group Cha 10, 1987

    Cited by (1)

  • <no title>

    FRIEDRICH E. C.

    The Chemistry of the Cyclopropyl Group Cha 11, 1987

    Cited by (1)

  • <no title>

    SCHLEYER P. V.

    J. Am. Chem. Soc. 88, 2321, 1966

    Cited by (1)

  • <no title>

    SHONO T.

    J. Org. Chem. 35, 42, 1970

    Cited by (1)

  • <no title>

    KUSUYAMA Y.

    Bull. Chem. Soc. Jpn. 46, 204, 1973

    Cited by (2)

  • <no title>

    KUSUYAMA Y.

    Bull. Chem. Soc. Jpn. 64, 2954, 1991

    Cited by (1)

  • <no title>

    YUKAWA Y.

    Bull. Chem. Soc. Jpn. 68, 3199, 1995

    Cited by (1)

  • <no title>

    LEFFLER J. E.

    Rates and Equilibria of Organic Reactions 204, 1963

    Cited by (1)

  • <no title>

    BROWN H. C.

    J. Am. Chem. Soc. 80, 4979, 1958

    Cited by (14)

  • <no title>

    STOCK L. M.

    Adv. Phys. Org. Chem. 1, 35, 1963

    Cited by (7)

  • <no title>

    KUSUYAMA Y.

    Bull. Chem. Soc. Jpn. 46, 204, 1973

    Cited by (2)

  • <no title>

    TSUNO Y.

    Bull. Chem. Soc. Jpn. 48, 3337, 1975

    Cited by (6)

  • <no title>

    TSUNO Y.

    Bull. Chem. Soc. Jpn. 51, 596, 1978

    Cited by (2)

  • <no title>

    TSUNO Y.

    Bull. Chem. Soc. Jpn. 51, 601, 1978

    Cited by (1)

  • <no title>

    YUKAWA Y.

    Nippon Kagaku Zasshi 86, 783, 1965

    Cited by (1)

  • <no title>

    SHORTER J.

    Correlation Analysis in Chemistry Cha 4, 141, 1978

    Cited by (1)

  • <no title>

    FUJIO M.

    Bull. Chem. Soc. Jpn. 70, 929, 1997

    Cited by (4)

  • <no title>

    INUKAI T.

    Bull. Chem. Soc. Jpn. 35, 400, 1962

    Cited by (1)

  • <no title>

    KUSUYAMA Y.

    Bull. Chem. Soc. Jpn. 49, 724, 1976

    Cited by (1)

  • <no title>

    KISPERT L. D.

    J. Am. Chem. Soc. 93, 6948, 1971

    Cited by (1)

  • <no title>

    WILCOX C. F.

    J. Am. Chem. Soc. 95, 8192, 1973

    Cited by (3)

  • <no title>

    CHILDS R.

    The Chemistry of the Cyclopropyl Group 2, 411, 1995

    Cited by (1)

  • <no title>

    SUBBOTIN O. A.

    Org. Magn. Reson. 4, 53, 1972

    Cited by (1)

  • <no title>

    WALSH A. D.

    Trans. Faraday Soc. 45, 179, 1949

    DOI  Cited by (3)

  • <no title>

    KUSUYAMA Y.

    Magn. Reson. Chem. 30, 361, 1992

    DOI  Cited by (1)

  • <no title>

    KUSUYAMA Y.

    Org. Magn. Reson. 20, 159, 1982

    DOI  Cited by (1)

Codes

  • NII Article ID (NAID)
    10008929907
  • NII NACSIS-CAT ID (NCID)
    AA00580132
  • Text Lang
    ENG
  • Article Type
    ART
  • ISSN
    00092673
  • NDL Article ID
    4440384
  • NDL Source Classification
    ZP1(科学技術--化学・化学工業)
  • NDL Call No.
    Z53-B35
  • Data Source
    CJP  NDL  J-STAGE 
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