Ionic Organic Reactions and Their Intermediates

离子有机反应及其中间体

• 批准号: 0445574
• 负责人: George Olah
• 金额: $ 30万
• 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: 2005
• 资助国家: 美国
• 起止时间: 2005-09-01 至 2008-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0445574&HistoricalAwards=false
• 关键词: Ionic; Organic; Reactions; Their; Intermediates

This project addresses the synthesis and study of novel carbocations and onium ions. Protonated highly-substituted benzenium dications such as m-xylene, mesitylene and hexamethylbenzene will be generated in superacids under stable ion conditions. The elusive bis-, tris- and tetradiazomethane di, tri- and tetracation, respectively, will be modeled with ab initio/GIAO-MP2 calculations and prepared and spectrally characterized in superacid solution. A number of interesting trifluoromethylsubstituted allyl cations and polyallyl cations and several silylated onium ions, including silylated urea, guanidinium ion, formamide and acetamide ions, will also be examined. Superelectrophilic activation of N,N-dimethylmethyleniminium ion, CH2=N(CH3)2+ and the isomeric isopropyleniminium ion, (CH3)2C=NH2+ will be investigated by hydrogen/deuterium exchange experiments. Sulfur and phosphorous analogs of dialkyl ether/poly(hydrogen fluoride) i.e dialkyl thioether/poly(hydrogen fluoride) and trialkyl phosphine/poly(hydrogen fluoride) complexes will be prepared and studied as new ionic liquids.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Dr. George A. Olah of the Department of Chemistry at the University of Southern California. Combining experimental structural and mechanistic studies with theoretical analyses, Professor Olah and his students are elucidating fundamental steps in chemical processes. Their studies are focused on the generation, structure, and reaction chemistry of reactive intermediates bearing one or more positive charges. Such novel intermediates have been implicated in numerous processes of laboratory and commercial significance. These studies are providing important insights into the design of selective organic reactions and into the phenomena at play in large-scale petrochemical processes such as catalytic cracking and alkylation reactions.

本计画主要研究新颖碳正离子与鎓离子之合成与研究。质子化的高度取代的苯阳离子，如间二甲苯，均三甲苯和六甲基苯，将在稳定的离子条件下在超强酸中产生。难以捉摸的双，三-和四重氮甲烷的二，三-和四，分别，将建模与从头算/GIAO-MP2计算和制备，并在超强酸溶液中的光谱特征。一些有趣的三氟甲基取代的烯丙基阳离子和多烯丙基阳离子和几个硅烷基化鎓离子，包括硅烷基化脲，胍离子，甲酰胺和乙酰胺离子，也将被检查。通过氢/氘交换实验研究了N，N-二甲基亚甲基亚胺离子CH 2 =N（CH 3）2+和异构体异丙基亚甲基亚胺离子（CH 3）2C= NH 2+的超亲电活化。二烷基醚/聚氟化氢的硫和磷类似物，即二烷基硫醚/聚氟化氢和三烷基膦/聚氟化氢复合物将被制备和研究作为新的离子液体。有了这个奖项，有机和大分子化学计划支持博士乔治A。南加州大学化学系的Olah说。将实验结构和机理研究与理论分析相结合，Olah教授和他的学生正在阐明化学过程中的基本步骤。他们的研究重点是产生，结构和反应化学的反应中间体轴承一个或多个正电荷。这些新的中间体已经涉及许多具有实验室和商业意义的方法。这些研究为选择性有机反应的设计以及催化裂化和烷基化反应等大规模石化过程中的现象提供了重要的见解。