Ionic Organic Reactions and Their Intermediates

离子有机反应及其中间体

• 批准号: 9122356
• 负责人: George Olah
• 金额: $ 44.02万
• 依托单位: University of Southern California
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1992
• 资助国家: 美国
• 起止时间: 1992-04-01 至 1995-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9122356&HistoricalAwards=false
• 关键词: Ionic; Organic; Reactions; Their; Intermediates

Research will continue on ionic organic reactions and their intermediates with emphasis on the role of electrophilic (proto) solvation in activating onium ions, carboxonium ions and certain carbocationic systems by interaction with the available non-bonded electron pairs of the heteroatoms. Some potential oxonium and carboxonium dications will be studied such as diprotonated alcohols, diprotonated CO, diprotonated HCN and diprotonated CO2 as well as diprotonated esters. Included will be experimental superacidic investigations based on isotopic exchange studies, as well as low temperature spectroscopic investigations and theoretical studies. The protolytic (alkylative) chemistry will also be studied. The protolytic (coordinative) activation of the Friedel-Crafts reaction will be explored in reactions of alkanes, as well as highly deactivated aromatics. Halooxonium ions and mixed halo-alkyl derivatives will be also prepared and studied in chlorination reactions. Polyhalonium dications will be explored, as will be bora-cations. The search for persistent silicenium ions will be continued, including solid state 29Si NMR studies. The recently discovered derivatization of C60 and C70 fullerenes will be followed up including halogenation, alkylation, acyclation and other reactions. %%% With this award, the Organic Synthesis Program will support the research of Dr. George A. Olah at the Univeristy of Southern California. The research will explore the generation of diprotonated species formed by the interaction of a proton with the unshared electron pairs on oxygen and nitrogen atoms in stable molecular species. The chemistry of these reactive species will be studied. This will result in the development of some new unique synthetic methodology that should benefit research in biochemistry and medicine as well as in the chemical industry.

将继续研究离子有机反应及其中间体，重点是亲电(原)溶剂化作用在通过与杂原子的可用非键电子对相互作用而激活洋葱离子、碳正离子和某些碳阳离子体系中的作用。一些潜在的氧和碳正离子将被研究，如二质子化的醇、二质子化的CO、二质子化的HCN和二质子化的二氧化碳以及二质子化的酯。将包括基于同位素交换研究的实验性超酸调查，以及低温光谱调查和理论研究。还将研究质子化(烷基化)化学。在烷烃和高度失活的芳烃的反应中，将探索Friedel-Craft反应的质子分解(配位)活化。还将制备卤代氧离子和混合卤代烷基衍生物，并研究其在氯化反应中的应用。本课程将探讨多卤素离子，以及波拉阳离子。对持久硅离子的搜索将继续进行，包括固态29Si核磁共振研究。最近发现的C60和C70富勒烯的衍生化将包括卤化、烷基化、环化等反应。有了这个奖项，有机合成计划将支持南加州大学乔治·A·奥拉博士的研究。这项研究将探索稳定分子物种中由质子与氧和氮原子上未共享的电子对相互作用形成的二质子化物种的产生。将对这些活性物种的化学进行研究。这将导致一些新的独特的合成方法的发展，这将有利于生物化学和医学以及化学工业的研究。