Abstract
The oxygenation of the potassium salts of alkylnitronates in absolute DMSO leads to potassium nitrite (nitrate) and the corresponding aldehydes or ketones at 40°C. Kinetic measurements for potassium 1-propylnitronate (K-1-PN) resulted in the rate law -d[K-1-PN]/dt = k2[K-1-PN][O2]. The rate constant, activation enthalpy, and entropy at 313.16 K are as follows: k/M-1 s-1 = (1.43±0.04), DH‡/kJ mol-1 = 57±10 DS‡/J mol-1 K-1 = -60±32. The presence of superoxide ion as a result of a SET from the nitronate to dioxygen was proved by NBT test.
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