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Reactions of singlet oxygen and singlet oxygen mimics with dicyclopropylethylenes: comparison of reactivity and mechanisms

By Gina Elizabeth Alume

Abstract

An extensive study of the reaction pathways of 1,1- dicyclopropyl ethylene, cis- and trans- 1,2-dicyclopropylethylenes has been undertaken with different electrophiles 4-methyl-1,2,4- triazoline-3,5-dione (MTAD), tetracyanoethylene (TCNE), and singlet oxygen (102). Comparison of reactivity and reaction mechanisms among the electrophiles is investigated. Singlet oxygen exhibits significantly lower reactivity compared to the other electrophiles. MTAD and TCNE react with dicyclopropylethylenes to produce predominantly \u222+2\u22 adducts and a small amount of the \u22ene\u22 adducts. The \u222+2\u22 is the major product presumably because of the high activation energy leading to the highly strained \u22ene\u22 products. Solvent trapping studies provide strong evidence of a \u22stepwise\u22 mechanism, involving a zwitterionic or aziridinium imide as an intermediate from the study of the reactions products of dicyclopropylethylenes and MTAD

Topics: Chemistry
Publisher: FIU Digital Commons
Year: 1996
OAI identifier: oai:digitalcommons.fiu.edu:etd-2386

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