Unexpected regioselectivity observed in the bromination and epoxidation reactions of p-benzoquinone-fused norbornadiene: An experimental and computational study

Essiz S., Dalkilic E., Sari O., DAŞTAN A., BALCI M.

TETRAHEDRON, vol.73, no.12, pp.1640-1649, 2017 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 73 Issue: 12
  • Publication Date: 2017
  • Doi Number: 10.1016/j.tet.2017.02.017
  • Journal Name: TETRAHEDRON
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus
  • Page Numbers: pp.1640-1649
  • Keywords: Bromination, Epoxidation, Norbornadiene, 1,4-Benzoquinone, Electrophilic addition, HIGH-TEMPERATURE BROMINATION, DENSITY FUNCTIONALS, MOLECULAR-ENERGIES, DERIVATIVES, BENZONORBORNADIENE, BROMOBENZONORBORNENES, THERMOCHEMISTRY, 1ST
  • Middle East Technical University Affiliated: Yes

Abstract

The bromination reaction of p-benzoquinone-fused norbornadiene was studied at various temperatures (-78, 50, 0, 25, and 77 degrees C). At room temperature, the double bonds of the p-benzoquinone units were mainly brominated. The double bond of the norbornene unit also underwent a bromination reaction in a yield of only 2%. However, the reaction at -78 degrees C resulted in the formation of products derived from the attack of bromine on the norbornene double bond with higher charge density. In contrast to the bromination reaction, the epoxidation reaction of the same compound with m-chloroperbenzoic acid and dimethyldioxirane exclusively resulted in the formation of products derived from the addition to the double bond of norbornadiene. The regioselectivity observed was investigated and the results were supported by theoretical calculations. (C) 2017 Elsevier Ltd. All rights reserved.