Studies in vacuum ultraviolet photochemistry. Part III. 2-Methyl-2-nitropropane, 2-methyl-2-nitrosopropane, and t-butyl nitrite

Abstract

2-Methyl-2-nitropropane, t-butyl nitrite and 2-methyl-2-nitrosopropane have been photolysed in the gas phase at 147 and 123·6 nm to conversions of <1%. The main primary processes are (i)–(iii). For the nitrite there is, Bu^t–NO₂+hν→ Bu^t+ NO₂(i), Bu^t–ONO +hν→ Bu^t+ NO₂(ii), Bu^t–NO +hν→ Bu^t+ NO (iii) another important process (iv), the nitric oxide being produced in an electronically excited state which fluoresces. Bu^t–ONO +hν→ Bu^tO + NO(A²Σ⁺)(iv) The overall photochemistry is interpreted on the basis of these primary processes, and subsequent reaction of the fragments produced in these processes.