O,S -Acetals in a New Modification of oxo -Friedel-Crafts-Bradsher Cyclization-Synthesis of Fluorescent (Hetero)acenes and Mechanistic Considerations.

This paper presents the use of O,S -acetals in a new modification of the oxo -Friedel-Crafts-Bradsher cyclization. In this reaction, under mild reaction conditions (25 °C), three- and four-ring fused RO -acenes (major) and/or HO(CH 2 ) 2 S -acenes (minor) are formed, the latter products having never been observed before in this type of cyclization. In this way, two electronically different fluorophores could be obtained in a single cyclization reaction, one of them having strong electron donor properties (+M effect of alkoxy groups) and the other having donor-acceptor properties (+M and -I effects of the HO(CH 2 ) 2 S -group, Hammett's constants). Further increasing the reaction temperature, HCl concentration or prolonging reaction time, surprisingly, yielded a 2:1 mixture of cis and trans dimeric isomers, as the only products of this cyclization. The DFT calculations confirmed a greater stability of the cis isomer compared to the trans isomer. The formation of unexpected dimeric products and HO(CH 2 ) 2 S -acenes sheds light on the mechanism of oxo -Friedel-Crafts-Bradsher cyclization, involving competitive O/S atom protonation in strained O,S -acetals and in strain-free side groups of intermediate species.