Five Membered Heterocyclic Nitrenium Ions: Generation, Structure, Reactivity

五元杂环氮离子：产生、结构、反应性

• 批准号: 9015972
• 负责人: Rudolph Abramovitch
• 金额: $ 13.07万
• 依托单位: Clemson University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 1991
• 资助国家: 美国
• 起止时间: 1991-03-01 至 1994-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9015972&HistoricalAwards=false
• 关键词: Five; Membered; Heterocyclic; Nitrenium; Ions; Five; Membered; Heterocyclic; Nitrenium; Ions

With support from the Organic Dynamics Program, Dr. Rudolph A. Abramovitch will study the synthesis and chemistry of five-membered heterocyclic nitrenium ions. These species are highly reactive intermediates whose chemical reactivity is of interest to physical organic chemists and to theoretical chemists. In addition to their inherent theoretical interest, these species are of potential importance as a new class of electrophilic primary aminating agents that are of interest to synthetic organic chemists as well. Of particular interest is the potential ability of these species to undergo isomerization to other cationic systems. The generation and trapping of these heterocyclic sigma-cations by nucleophiles will be studied via ion cyclotron resonance mass spectrometry in an effort to obtain information concerning the operation of pi-to-sigma "electronic isomerizations" in the nitrenium ions. Trapping experiments will also be performed in solution with the same objective in mind. Detailed analysis of the various reaction products thereby obtained is expected to afford insight into the nature of the reactive intermediate(s) present in each case.

在有机动力学计划的支持下，Rudolph A. Abramovitch博士将研究五元杂环氮离子的合成和化学。这些物种是高反应性的中间体，其化学反应性对物理有机化学家和理论化学家感兴趣。除了它们固有的理论兴趣外，这些物种还具有潜在的重要性，这是一种新型的亲电代理剂，它们也对合成有机化学家感兴趣。 特别令人感兴趣的是这些物种的潜在能力将异构化与其他阳离子系统进行。 将通过离子回旋共振质量谱法研究这些杂环sigma-cations的产生和捕获，以获取有关硝酸离子中PI到Sigma“电子异构化”操作的信息。陷阱实验也将在解决方案中进行，并考虑到相同的目标。因此，预期对所获得的各种反应产物的详细分析可以洞悉每种情况下存在的反应性中间体的性质。