Regioselective oxidations of benzocarbaporphyrins with ferric chloride: a facile synthesis of bridged [18]annulene ketals with strong absorptions in the far red and an unexpected halogenation reaction at the interior carbon atom

Benzocarbaporphyrins 4 were found to undergo regioselective oxidations with ferric chloride in methanol, ethanol, isopropyl alcohol, or ethylene glycol to give bridged benzo18]annulene ketal derivatives 5 in excellent yields. These polar derivatives were generally isolated in a monoprotonated form and the corresponding free bases appeared to be relatively unstable. Addition of TFA resulted in the formation of spectroscopically distinct dications. The ketals 5 were highly diatropic in nature, showing the internal alkoxy substituents upfield beyond -1 ppm in their proton NMR spectra. The external meso-protons resonated near 10 ppm, confirming the presence of a strong aromatic ring current. The UV-vis spectra for 5 showed a Soret band at 422 nm, and two strong absorptions in the far red at 751 and 832 nm. A carbaporphyrin with a fused acenaphthylene ring was also oxidized with ferric chloride and this produced a ketal derivative with still further bathochromically shifted absorptions particularly for the Soret band. Also, the use of different alcohols in these reactions allows the overall polarity of these ketal products to be controlled and this could have merit in biomedical applications. Reaction of carbaporphyrin 4a with aqueous ferric chloride afforded the corresponding 21-chloro derivative 20 in good yields, and at longer reaction times a nonaromatic dione was isolated. Aqueous ferric bromide gave a 21-bromocarbaporphyrin product but in this case very poor yields (<10%) were noted. Mechanisms are proposed to explain the formation of these unusual oxidation products. The structure of 21-chlorocarbaporphyrin 20 was further demonstrated by X-ray crystallography. The presence of the interior chlorine atom was found to tilt the indene moiety by 29.59(4) degrees relative to the 18]annulene macrocyclic ring. The crystal packing for 20 shows offset face-to-face pi-stacking interactions that link the porphyrinoid molecules as closely paired dimers.