Photostimulated free radical chain reactions between alkoxide ions derived from primary alcohols and XCMe2NO2 (X= Cl, Br, NO2, PhSO2, N3, or p-ClC6H4S) occur to produce Me2C (OR) 2 by a reaction involving the trapping of Me2C (NO2)· by RO–, the decomposition of ROCMe2NO2·–to ROCMe2·, and the oxidation of ROCMe2· to Me2COR+ by XCMe2NO2·