Experimental Study on the Reaction Pathway of α-Haloacetophenones with NaOMe: Examination of Bifurcation Mechanism

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Author(s)

    • Tagawa Kohei
    • Department of Chemistry and the Research Center for Smart Molecules, Rikkyo University
    • Sasagawa Keita
    • Department of Chemistry and the Research Center for Smart Molecules, Rikkyo University
    • Wakisaka Ken
    • Department of Chemistry and the Research Center for Smart Molecules, Rikkyo University
    • Monjiyama Shunsuke
    • Department of Chemistry and the Research Center for Smart Molecules, Rikkyo University
    • Katayama Mika
    • Department of Chemistry and the Research Center for Smart Molecules, Rikkyo University
    • Yamataka Hiroshi
    • Department of Chemistry and the Research Center for Smart Molecules, Rikkyo University

Abstract

The reaction of PhCOCH<sub>2</sub>Br and NaOMe in MeOH gave PhCOCH<sub>2</sub>OH as the major product and PhCOCH<sub>2</sub>OMe as the minor product. Substituent effects on the reactivity and product selectivity revealed that an electron-withdrawing substituent on the phenyl ring enhanced the overall reactivity and gave more alcohol than ether. It was indicated that the alcohol was formed via carbonyl addition-epoxidation, whereas the ether was formed by direct substitution. Substituent effects on the reaction rates, as well as the effects of NaOMe concentration on the rate and product ratio for both reactions of PhCOCH<sub>2</sub>Br and PhCOCH<sub>2</sub>Cl are in line with the mechanism that the alcohol and ether products were formed via two independent and concurrent routes, carbonyl addition and α-carbon attack, respectively, and thus the reaction mechanism could be different from the bifurcation mechanism previously predicted for the reaction of PhCOCH<sub>2</sub>Br by a simulation study in the gas phase.

Journal

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 87(1), 119-126, 2014

    The Chemical Society of Japan

Codes

  • NII Article ID (NAID)
    130004153260
  • Text Lang
    ENG
  • ISSN
    0009-2673
  • Data Source
    J-STAGE 
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