TETRAHEDRON, vol.56, no.33, pp.6115-6120, 2000 (SCI-Expanded)
The electrophilic addition of bromine to 7-oxabenzonorbornadiene (8) at 0 degrees C led in high yield to the formation of dibromoaldehyde 10. However, high-temperature bromination of 8 in carbontetrachloride at 77 degrees C gave non-rearranged products 17 and 18. From the elimination of non-rearranged products, 2-bromo-7-oxabenzonorbornadiene (12) was obtained. Similarly, bromination of monobromide 12 at 77 degrees C yielded the non-rearranged tribromides 19 and 20 while bromination of 12 at 0 degrees C gave the rearranged product 11. The dehydrobromination of tribromides (19, 20) provided the 2,3-dibromo-7-oxabenzonorbornadiene (21), which is a synthon for the trimerization, in high yield (C) 2000 Elsevier Science Ltd. All rights reserved.