Structure/Reactivity Relationships in the Benzo[c]phenanthrene Skeleton: Stable Ion and Electrophilic Substitution (Nitration, Bromination) Study of Substituted Analogues, Novel Carbocations and Substituted Derivatives

摘要

A series of novel carbocations were generated by low-temperature protonation of substituted benzo[c]-phenanthrenes, B[c]Phs, and their charge delocalization pathways were elucidated by NMR on the basis of the magnitude of Δδ~(13)C values. It has been shown that the protonation regioselectivity is strongly controlled by methoxy and hydroxyl substituents, whose directive effects override methyl substitution effects. Regiocontrol by -OMe and -OH substituents, and its stronger influence relative to methyl groups, was also observed in the nitration and bromination reactions. Charge distribution modes in the regioisomeric protonated carbocations formed via parent B[c]Ph as well as in the benzylic carbocation formed via fjord-region epoxide ring opening were deduced by gauge-invariant atomic orbital density functional theory (GIAO-DFT) and from the natural population analysis (NPA)-derived changes in charges over CHs. These patterns were compared with those derived from NMR experiments in the substituted derivatives. NMR-based charge delocalization mapping provided insight into structure/activity relationships in the methylated and fluorinated B[c]Phs. Regioselectivities observed in the nitration and bromination reactions in representative cases are the same as those via protonations. Among a group of novel nitro and bromo derivatives synthesized in this study are examples, where the nitro group is introduced into the fjord region, for which the X-ray structure could be obtained in one case.