Photoinduced reaction of diethyl 2-bromo-1-phenylethylidenemalonate with 1-benzyl-1,4-dihydronicotinamide and the effect of magnesium (II) ion on the reaction

Document Type

Article

Publication Date

2-12-1997

Abstract

2-Bromo-1-phenylethylidenemalonic ester reacts with 1-benzyl-1,4-dihydronicotinamide (BNAH) in acetonitrile under illumination at λ > 320 nm to give three debrominated products: an α,β-unsaturated ester, a β,γ-unsaturated ester and a dimer. In the presence of magnesium ion, the β,γ-unsaturated ester is formed exclusively. Using deuterated BNAH-4,4-d2 as reagent and spin-trapping technique for monitoring reactive intermediate, it has been shown that the reaction proceeds via two different mechanistic pathways: e- transfer-debromination-H abstraction or dimerization for the formation of the α,β-unsaturated ester and the dimer, and e- transfer-debromination-e- transfer-H+ transfer for the formation of the β,γ-unsaturated ester. © 1997 Elsevier Science S.A. All rights reserved.

Publication Source (Journal or Book title)

Journal of Photochemistry and Photobiology A: Chemistry

First Page

101

Last Page

104

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