Experimental and theoretical analysis of the photochemistry and thermal reactivity of ethyl diazomalonate and its diazirino isomer. The role of molecular geometry in …

A Bogdanova, VV Popik

Index: Bogdanova, Aneta; Popik, Vladimir V. Journal of the American Chemical Society, 2004 , vol. 126, # 36 p. 11293 - 11302

Full Text: HTML

Citation Number: 28

Abstract

The photochemical or thermal decomposition of ethyl diazomalonate (1) or ethyl 3, 3- diazirinedicarboxylate in methanol solutions yields the OH insertion product 6, while products of the Wolff rearrangement were not detected in both cases. The analysis of temperature-dependent 13C NMR spectra and the results of DFT B3LYP/6-311+ G (3df, 2p) and MP2/aug-cc-pVTZ//B3LYP/6-311+ G (3df, 2p) calculations allow us to conclude that ...