Ionic Organic Reactions and Their Intermediates

离子有机反应及其中间体的研究将继续进行，重点是亲电（原）溶剂化作用，通过与杂原子的可用非键电子对相互作用，激活离子、碳离子和某些碳阳离子系统。将研究一些潜在的氧鎓和碳鎓指示物，如双质子化醇、双质子化CO、双质子化HCN和双质子化CO2以及双质子化酯。包括基于同位素交换研究的超酸性实验研究，以及低温光谱研究和理论研究。原解（烷基化）化学也将被研究。在烷烃和高度失活的芳烃的反应中，将探讨Friedel-Crafts反应的原解（配位）活化。在氯化反应中还将制备卤代氙离子和混合卤代烷基衍生物。多卤元素指示将被探索，同时也将被探索。对持久性硅离子的研究将继续进行，包括固态29Si核磁共振研究。最近发现的C60和C70富勒烯的衍生化反应将继续进行，包括卤化、烷基化、环化等反应。有了这笔奖金，有机合成项目将支持南加州大学乔治·a·奥拉博士的研究。本研究将探索在稳定的分子物质中，由质子与氧和氮原子上的未共享电子对相互作用形成双质子化物质的产生。这些反应性物质的化学性质将被研究。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。

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.