The Origins of the Benzotriazole Project, Its Versatility Illustrated by a New -C=CHCH+OEt Synthon, and Novel Syntheses of α,β-Unsaturated Aldehydes and Ketones, Furans, Pyrroles and Allyl Ethers

Alan R. Katritzky; Hong Wu; Linghong Xie; Stanislaw Rachwal; Bogumila Rachwal; Jinlong Jiang; Guifen Zhang; Hengyuan Lang

doi:10.1055/s-1995-4102

Synthesis 1995; 1995(10): 1315-1323
DOI: 10.1055/s-1995-4102

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The Origins of the Benzotriazole Project, Its Versatility Illustrated by a New ^-C=CHCH⁺OEt Synthon, and Novel Syntheses of α,β-Unsaturated Aldehydes and Ketones, Furans, Pyrroles and Allyl Ethers

Alan R. Katritzky^* , Hong Wu, Linghong Xie, Stanislaw Rachwal, Bogumila Rachwal, Jinlong Jiang, Guifen Zhang, Hengyuan Lang

^*Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, Gainesville, Florida 32611-7200, USA, Fax +1(904)3929199; E-mail KATRITZK@PINE.CIRCA.UFL.EDU

Abstract

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A historical introduction describes the discovery and progress of benzotriazole synthetic methodology. 3-(Benzotriazol-1-yl)-1-ethoxyprop-1-ene (6), readily prepared from 3-(benzotriazo-1-yl)-3-ethoxyprop-1-ene (4) via zinc bromide promoted allylic rearrangement, undergoes lithiation and regiospecific single or double 3-alkylation to give products which undergo (i) hydrolysis to afford α,β-unsaturated aldehydes, (ii) silica gel promoted reverse allylic rearrangement of the benzotriazolyl group, followed by further alkylation and subsequent hydrolysis to furnish α,β-unsaturated ketones, (iii) intramolecular cyclizations to construct pyrroles and furans, and (iv) intermolecular nucleophilic substitution with Grignard reagents to provide allyl ethers.

β-formylvinyl anion equivalents - allylic rearrangement of benzotriazolyl group

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