Benzotriazole-Mediated Conversions of para-H-Substituted Pyrylium, Benzo[b]pyrylium, and Xanthylium Salts into para-Position Functionalized Derivatives (An Indirect Electrophilic Substitution of Electron-Deficient Heteroaromatics)

Alan R. Katritzky; Peter Czerney; Julian R. Levell

doi:10.1021/jo971174a

Benzotriazole-Mediated Conversions of para-H-Substituted Pyrylium, Benzo[b]pyrylium, and Xanthylium Salts into para-Position Functionalized Derivatives (An Indirect Electrophilic Substitution of Electron-Deficient Heteroaromatics)

J Org Chem. 1997 Nov 14;62(23):8198-8200. doi: 10.1021/jo971174a.

Authors

Alan R. Katritzky¹, Peter Czerney, Julian R. Levell

Affiliation

¹ Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, Gainesville, Florida 32611-7200, and Institut für Physikalische Chemie, Friedrich Schiller-Universität Jena, Lessingstrasse 10, D 07743 Jena, Germany.

PMID: 11671932
DOI: 10.1021/jo971174a

Abstract

4H-Substituted pyrylium 9, benzo[b]pyrylium 15, and xanthylium salts 22 react with benzotriazole to give the corresponding 4H-(benzotriazol-1-yl)pyrans 10, benzo[b]pyrans 16, or xanthenes 23. Novel anion precursors 10, 16, and 23 undergo smooth lithiations at the positions alpha to the benzotriazol-1-yl function, i.e., at the para-position of the O-heterocycle. Subsequent trapping with different alkyl halides gives intermediates 14, 21, and 25, which are converted by mineral acid into para-functionalized pyrylium 11-13, benzo[b]pyrylium 17-20, and the xanthylium 24 salts in good to excellent yields.