Kk. Laali et al., Novel annulene dications from methylated [2.2]metacyclophane monoenes and [e]-ring benzannelated dimethyldihydropyrene, J ORG CHEM, 66(16), 2001, pp. 5329-5332
Tetramethyl- and hexamethyl-substituted [2.2]metacyclophane monoenes (10 an
d 11) are transformed into their corresponding trans-dimethyldihydroethanop
henanthrenium dications (14(2+) and 15(2+)) in FSO3H . SbF5 (4:1) and FSO3H
. SbF5 (1:1) with SO2ClF or SO2 as the solvent; these 10 pi -dications are
equivalent to the C-4/C-5 diprotonated dications of the 2,7-dimethyl deriv
ative of trans-DMDHP, 3a. The trans-12c,12d-dimethyl-12c,12d-dihydrobenzo[e
]pyrene (6) reacts with FSO3H/SO2ClF under surprisingly mild conditions to
give initially a persistent diprotonated dication (6H(2)(2+)) and, subseque
ntly, the oxidation dication (6(2+)); the 6(2+):6H(2)(2+) ratio reaches 4:1
after 1 week at low temperature. Protonation of the anti-metacyclophane (1
3) was also examined. Charge delocalization mode and tropicity in the resul
ting dications are gauged via detailed NMR studies at 500 MHz.