First examples of stable arenium ions from large methylene-bridged polycyclic aromatic hydrocarbons (PAHs). Directive effects and charge delocalization mode.
In connection to a growing interest in developing structure/activity trends in nonalternant polyarenes, we report on the generation and NMR studies of the first series of persistent arenium ions from large methylene-bridged PAHs (mostly 22pi six-fused ring systems). Low-temperature protonation (FSO(3)H/SO(2)ClF) and model nitration (with HNO(3)/HOAc or NO(2)(+) BF(4)(-)) were used as mimic reactions for generation of biological electrophiles. The site(s) of protonation (and nitration) were determined as a function of PAH structure. Charge delocalization mode in the resulting arenium ions of protonation are assessed based on detailed low-temperature NMR studies at 500 MHz. Systems studied were 1-methylcyclopenta[def]phenanthrene 2, 11H-benz[bc]aceanthrylene 8, 5H-benzo[b]cyclopenta[def]chrysene 9, 13H-dibenzo-[bc,l]aceanthrylene 10, 13H-cyclopenta[rst]pentaphene 11, 4H-benzo[b]cyclopenta[mno]chrysene 12, 6H-cyclopenta[ghi]picene 13, 4H-cyclopenta[pqr]picene 14, 4H-cyclopenta[def]dibenz[a,c]anthracene 15. For comparison, dibenzo[a,c]anthracene 16 and dibenzo[a,h]anthracene 17 were also included (Figures 1 and 2). It is shown that the methano-bridge exerts a strong directive effect which diminishes as the bridge moves from the more central "inner" positions to more peripheral "outer" positions. Charge delocalization mode in the resulting carbocations are discussed based on the magnitude of Deltadelta (13)C values. Possible relationships with biological electrophiles formed by epoxide ring opening in the putative metabolites are also considered.
Laali
K K
KK
Department of Chemistry, Kent State University, Kent, Ohio 44242, USA. klaali@kent.edu
Okazaki
T
T
Harvey
R G
RG
D006838:Hydrocarbons; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008968:Molecular Conformation; D011084:Polycyclic Aromatic Hydrocarbons / Q000138:chemical synthesis* / Q000737:chemistry
D006838:Hydrocarbons; D011084:Polycyclic Aromatic Hydrocarbons; C030011:carbene; D008697:Methane