Elimination reactions of (E)-2,4,6-trinitrobenzaldehyde O-aryloximes promoted by R3N/R3NH+ in 70 mol% MeCN(aq). Effect of β-aryl group the nitrile-forming transition-state

Sang Yong Pyun, Woong Sub Byun, Bong Rae Cho

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Nitrile-forming eliminations from (E)-2,4,6-(NO2) 3C6H2CH=NOC6H4-2-X-4- NO2 (1) promoted by R3NH/R3NH+ in 70 mol % MeCN(aq) have been studied kinetically. When X = NO2, the reactions exhibited secondorder kinetics as well as Brönsted β = 0.63 and |βlg| = 0.34-0.46, and an E2 mechanism is evident. As the leaving group was made poorer (X = H, Cl, and CF3), Brönsted β value increased from 0.63 to 0.85-0.89 without much change in the |βlg| value E2, indicating that structure of the transition state changed to an E1cb-like with extensive Cβ-H bond cleavage, significant negative charge development at the β-carbon, and limited Cα-Oar bond cleavage.

Original languageEnglish
Pages (from-to)1921-1924
Number of pages4
JournalBulletin of the Korean Chemical Society
Volume32
Issue number6
DOIs
Publication statusPublished - 2011 Jun 20

Keywords

  • E2 and Elcb-like
  • Elimination
  • β-aryl group effect

ASJC Scopus subject areas

  • Chemistry(all)

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