Wavelength-dependent photochemistry of Diazo Meldrum's acid and its spirocyclic isomer, Diazirino Meldrum's acid: Wolff rearrangement versus isomerization.

Abstract

Photoreaction of diazo Meldrum's acid (1) shows a unique wavelength selectivity. At 254 nm it results in efficient (phi(254) = 0.34) Wolff rearrangement, while irradiation with 355 nm light leads to a completely different process, isomerization into corresponding cyclic alpha,alpha"-dicarbonyl diazirine 2 (phi(350) = 0.024). UV photolysis of diazirine 2 is accompanied by two competing processes: loss of nitrogen followed by the Wolff rearrangement and isomerization into diazo compound 1. Thermal decomposition of 1 leads to clean Wolff rearrangement, while heating of 2 causes quantitative conversion into diazo isomer 1.