o-Nitroaryl-bis(5-methylfur-2-yl)methanes as Versatile Synthons for the Synthesis of Nitrogen-Containing Heterocycles 英文参考文献.docVIP

Molecules 1997, 2, 62–68 molecules ISSN 1420-3049 o-Nitroaryl-bis(5-methylfur-2-yl)methanes as Versatile Synthons for the Synthesis of Nitrogen-Containing Heterocycles Alexander V. Butin1,*, Vladimir T. Abaev2, Tat’yana A. Stroganova1, and Andrey V. Gutnov2 1 Research Laboratory of Furan Chemistry, Kuban State Technological University, Moskovskaya 2, Krasnodar, 350072, Russia. Fax +7 8612 576592 2 Department of Organic Chemistry, North Ossetian State University,Vatutina 46, Vladikavkaz, 362025, Russia. (nosu@nosu. vladikavkaz.su) Received: 25 October 1996 / Accepted: 17 January 1996 / Published: 10 April 1997 Abstract: 2-Nitroaryldifurylmethanes 1a and 1b, readily available by condensation of 2-nitrobenzaldehyde and 6-nitroveratraldehyde with 2-methylfuran, were transformed into indole, cinnoline and benzothiazine-3,1 derivatives. The reduction of 2-nitroaryldifurylmethanes gave the corresponding anilines 2a,b or indole 3 depending on the reaction conditions. A plausible mechanism for the last reaction involving intramolecular heterocyclic addition between a nitroso-group and a furan ring is proposed. Diazotisation of the amine 2b gave a cinnoline derivative - a product of intramolecular oxidative furan ring opening. Treatment of isothiocyanates 7a,b with perchloric acid resulted in a new rearrangement with furan ring migration leading to the 4-H- benzothiazine-3,1 derivatives. Keywords: 2-Nitroaryldifurylmethanes, reduction, cycloaddition, N-containing heterocycles Introduction In developing methods for the synthesis of 2- hydroxyaryldifurylmethanes, we have established that these compounds, under acidic conditions, undergo recyclisation to the benzofuran carbonyl derivatives [6], which in their turn can be cyclised with the formation of tetracyclic derivatives (Scheme 1). Difurylarylmethanes are of interest to the flavour manufacturring [1], the food industry [2