Kinetics and mechanism of the oxygenation of potassium nitronates. Evidence for a single electron transfer (SET) mechanism ?? |
| |
| Authors: | József Kaizer Norbert Durkó Miklós Czaun Gábor Speier |
| |
| Affiliation: | (1) Research Group for Petrochemistry, Hungarian Academy of Sciences, 8201 Veszprém, Hungary;(2) Department of Organic Chemistry, University of Veszprém, 8201 Veszprém, Hungary;(3) Department of Organic Chemistry, University of Veszprém, 8201 Veszprém, Hungary;(4) Research Group for Petrochemistry, Hungarian Academy of Sciences Department of Organic Chemistry, University of Veszprém, 8201 Veszprém, Hungary 8201 Veszprém, Hungary |
| |
| Abstract: | Summary 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. |
| |
| Keywords: | nitroalkanes oxygenation SET 2-Nitropropane dioxygenase kinetics |
| 本文献已被 SpringerLink 等数据库收录！ |
|
