CAN-Mediated Oxidative Cyclodehydrogenation of Hexapyrrolylbenzenes

Abstract

An efficient method for ceric ammonium nitrate mediated synthesis of annularly fused hexapyrrolohexaazacoronene by oxidative cyclodehydrogenation has been reported. The photophysical properties of the representative hexaazacoronene has also been described.

Key words

ceric ammonium nitrate - coronenes - azacoronene - hexapyrrolylbenzene - oxidative cyclodehydrogenation - MALDI-TOF

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• 16 1,2,3,4,5,6,7,8,9,10,11,12-Dodecakis[4-(trifluoromethyl)phenyl]-2a1,2b1,4b1,6b1,8b1,10b1-hexaazahexacyclopenta[bc,ef,hi,kl,no,qr]coronene (4b) Hexapyrrolylbenzene 3b (1.0 equiv) was dissolved in dry acetonitrile (2 mL) and cerium(IV) ammonium nitrate (12.0 equiv) was added under nitrogen. The reaction immediately turned to black, and the progress of the reaction was monitored by TLC. After completion of the reaction (5 min), the reaction was quenched with water (5 mL) and extracted with EtOAc (3 × 10 mL). After drying and filtration, the combined extracts were concentrated under reduced pressure. The residue was purified by column chromatography on silica gel using EtOAc and hexane as eluent to afford 4b as a brown solid; yield: 16%. MALDI-TOF-MS calcd for M⁺, C₁₁₄H₄₈N_6O6F₃₆: 2185.340; found: 2185.596. ¹H NMR (400 MHz, CDCl₃): δ = 7.66 (d, J = 7.4 Hz, 24 H), 7.58 (d, J = 7.8 Hz, 24 H). ¹³C NMR (300 MHz, CDCl₃): δ = 168.9, 137.1, 132.5, 131.9, 131.3, 130.3, 125.8,125.4. ¹³C NMR DEPT135 (101 MHz, CDCl₃): δ = 130.3, 126.1. ¹³C NMR DEPT90 (75 MHz, CDCl₃): δ = 130.3, 126.1. ¹⁹F NMR (282 MHz, CDCl₃): δ = –63.25. MALDI-TOF calcd for M⁺, C₁₁₄H₄₈F₃₆N₆: 2185.340; found: 2185.956.