Oxidative transformations of 1-nitropyrene under simulated environmental conditions.
Oxidative transformations of 1-nitropyrene under simulated environmental conditions.
复制标题
1-硝基芘在模拟环境条件下的氧化转化。
DOI：
10.1021/tx970162h
复制
发表时间：
1998
影响因子：
4.1
通讯作者：
Singh,M
中科院分区：
文献类型：
--
作者：
Murray,RW;Singh,M
吸附在硅胶上的 1-硝基芘 (1-NP) 用二甲基二氧杂环己烷 (DMD) 氧化，形成 1-硝基芘 4,5-氧化物和 1-硝基芘 9,10-氧化物，比例为 74/26（4,5-氧化物/9,10-氧化物）。当吸附的 1-NP 暴露于四甲基乙烯 (TME) 与臭氧在 -40 °C 的气相反应产物中时，会以 72/28 的比例生成相同的氧化物。在这两种不同类型的实验中，氧化物的比例基本相同，这一事实非常重要。我们推测 TME 的气相臭氧分解会产生富含能量的羰基氧化物，即丙酮氧化物。一些羰基氧化物可能环化成异构 DMD，我们认为，DMD 是 TME/臭氧实验中氧化物形成的原因。这一提议得到了以下观察结果的支持：单独使用臭氧氧化 1-NP 不会导致氧化物形成。因此，在 TME/臭氧实验中负责氧化物形成的氧化剂必须在臭氧分解中产生。我们建议这种氧化剂是DMD。
The oxidation of 1-nitropyrene (1-NP), adsorbed on silica gel, with dimethyldioxirane (DMD) leads to the formation of 1-nitropyrene 4,5-oxide and 1-nitropyrene 9,10-oxide in a ratio of 74/26 (4,5-oxide/9,10-oxide). When the adsorbed 1-NP is exposed to the products of the gas-phase reaction of tetramethylethylene (TME) with ozone at −40 °C, the same oxides are produced in a ratio of 72/28. The fact that the ratio of the oxides is essentially the same in these two different types of experiments is highly significant. We have speculated that the gas-phase ozonolysis of TME produces an energy-rich form of the carbonyl oxide, acetone oxide. Some of this carbonyl oxide may cyclize to the isomeric DMD which, we propose, is responsible for oxide formation in the TME/ozone experiment. This proposal is supported by the observation that using ozone alone to oxidize 1-NP does not lead to oxide formation. Thus the oxidant responsible for oxide formation in the TME/ozone experiment must be produced in the ozonolysis. We suggest that this oxidant is DMD.