Low and high temperature bromination of 2,3-dicarbomethoxy and 2,3-dicyano benzobarrelene: unexpected substituent effect on bromination

TASKESENLIOGLU S., DAŞTAN A., DALKILIC E., GUNEY M., Abbasoglu R.

NEW JOURNAL OF CHEMISTRY, cilt.34, sa.1, ss.141-150, 2010 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 34 Sayı: 1
  • Basım Tarihi: 2010
  • Doi Numarası: 10.1039/b9nj00372j
  • Dergi Adı: NEW JOURNAL OF CHEMISTRY
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.141-150
  • Atatürk Üniversitesi Adresli: Evet

Özet

The bromination of 2,3-dicarbomethoxy benzobarrelene yielded the dibromide regio- and stereospecifically arising from the aryl shift where the bromine exclusively attacks the double bond from the exo face of the double bond. High temperature bromination of this compound yielded aryl-shift products. From the low temperature bromination of 2,3-dicyano benzobarrelene, non-rearranged products were obtained along with the rearranged products. Surprisingly, we observed that the yield of non-rearranged products decreased on increasing the temperature. A possible role of the substituent was discussed using DFT calculations on model compounds.