A computational study of the Wallach rearrangement

ÖZEN A. S., ERDEM S., AVİYENTE V.

STRUCTURAL CHEMISTRY, cilt.9, sa.1, ss.15-25, 1998 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 9 Sayı: 1
  • Basım Tarihi: 1998
  • Doi Numarası: 10.1023/a:1022479430316
  • Dergi Adı: STRUCTURAL CHEMISTRY
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.15-25
  • Anahtar Kelimeler: Wallach rearrangement, quinonoid intermediate, N,N-oxide intermediate, dicationic intermediate, molecular orbital theory
  • Marmara Üniversitesi Adresli: Hayır

Özet

Treatment of azoxybenzene and its derivatives with acids is known to result in the Wallach rearrangement, which leads to 2- or 4-hydroxyazobenzenes. Starting in the 1960s, experimental findings have lead to the proposal of several mechanisms for this rearrangement. In this work, molecular orbital theory employing the semiempirical AM1 method is used to locate and discuss the energetics of the intermediates and the transition states for this rearrangement. Based on the results of AM1 calculations in vacuum and in solution, the most plausible mechanistic pathways are proposed and discussed.