Scheme 125. Cationic Azapyrenoids.

Reagents and conditions: (a)²⁵⁴ (1) KOH, EtOH, 0 °C, rt, 26 h, (2) NH₂OH·HCl, reflux, 2 h; (b) 5% HCl, hν (300 nm), air, rt, 24 h; (c) (1) MeI or RBr, DMF, 100 °C, 48 h, (2) KPF₄, H₂O, rt; (d)²⁵⁵ I₂, pyridine/1,4-dioxane, rt, 12 h; (e) TCNQ, MeCN, reflux, 20 h; (f) 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane, MeCN, reflux, overnight; (g)²⁵⁶ (1) DMF, argon, 60 °C, 2 h, (2) toluene, Dean–Stark apparatus, 140 °C, 6 h; (h) (1) MeCN, O₂, hν (300–400 nm), 14 h, (2) NH₄PF₆; (i)²⁵⁷ Fe(acac)₃, AcOH, 90 °C, 12 h; (j) MeOTf, 1,2-DCE, 50 °C, 16 h; (k) Et₃N, MeCN/DCM, argon, rt, 2 h.