Decomposition rates, synthesis, and spectral properties of a series of alkyl hyponitrites

A number of trans-alkyl hyponitrites (RON=NOR) weee synthesized and characterized. At 66.1 - 0.1 °C in isooctane and with millimolar to micromolar concentrations first-order kinetics were observed with half-lives (min) of 12.8 - 0.2 (CH3), 32.3 - 1.1 (2-C3H7), 15.0 - 0.3 (cyclohexyl), 25.2 - 1.2 (tert-butyl), 18.3 - 0.3 (tert-pentyl), 3.0 - 0.1 (benzyl), 11.2 - 0.5 (2-phenylethyl), and 5.5 - 0.3 (1-phenylethyl). The rate constants were concentration independent and showed little change with changes in solvent polarity or viscosity. Ultraviolet, magnetic resonance, infrared, and mass spectra for the new hyponitrites are reported. Most of the hyponitrites were highly crystalline solids that could be stored for long periods without change below 0 °C.