Electron-Withdrawing β-Substituent, Ring-Strain, and Ortho Effects on Reactivity, Selectivity, and Stability of o-Alkoxybenzyl Carbocations

Meng Yun Tseng, Hsin Yi Hung, Kuangsen Sung

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4 Citations (Scopus)

Abstract

o-Alkoxybenzyl carbocations 1 and 2 were generated by laser flash photolysis of the corresponding o-alkoxybenzyl alcohols 3 and 4 to understand how the electron-withdrawing β-substituent, the ring-strain, and the ortho effects affect the reactivity (electrophilicity), selectivity, and stability of 1 and 2, and to fit the electrophilicity of 1 and 2 into the current carbocation electrophilicity scale (E). Our finding is that both the electron-withdrawing β-substituent and the ring-strain effects make 1 less stable than 2 by 3.0 kcal/mol. These effects plus the ortho effect of 2 make 1 more reactive than 2, but the selectivity of 1 and 2 toward amine nucleophiles is almost the same within experimental errors. The electrophilicity of 1 and 2 has been fit into the current carbocation electrophilicity scale (E) quite well. (Chemical Equation Presented).

Original languageEnglish
Pages (from-to)3905-3912
Number of pages8
JournalJournal of Physical Chemistry A
Volume119
Issue number17
DOIs
Publication statusPublished - 2015 Apr 30

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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