Structure of a ring enlarged product from the base induced rearrangement of dibromomethylenebenzonorbornene

BALCI M., Krawiec M., Taskesenligil Y., Watson W. H.

JOURNAL OF CHEMICAL CRYSTALLOGRAPHY, cilt.26, sa.6, ss.413-418, 1996 (SCI-Expanded) identifier identifier

  • Yayın Türü: Makale / Tam Makale
  • Cilt numarası: 26 Sayı: 6
  • Basım Tarihi: 1996
  • Doi Numarası: 10.1007/bf01665821
  • Dergi Adı: JOURNAL OF CHEMICAL CRYSTALLOGRAPHY
  • Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Sayfa Sayıları: ss.413-418
  • Atatürk Üniversitesi Adresli: Evet

Özet

The base-catalyzed rearrangement reactions of 2-bromomethylenebenzonorbornene 8 and 2,2-dibromomethylenebenzonorbornene 9 were studied. Reaction of 8 with potassium tert-butoxide in THF gave only the enol ether 11 whose formation is rationalized via a carbene-cycloalkyne mechanism. However, treatment of 9 with phenyllithium in THF at 40 degrees C gave the ring-enlarged dibromide 13 whose structure is reported herein. The ring-enlarged product 13 is rationalized in terms of carbanionic rearrangement. Quantum mechanical calculations are consistent with these observations.