Ionic Organic Reactions and Their Intermediates

离子有机反应及其中间体

• 批准号: 0102258
• 负责人: George Olah
• 金额: $ 47.7万
• 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: 2001
• 资助国家: 美国
• 起止时间: 2001-07-01 至 2004-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0102258&HistoricalAwards=false
• 关键词: Ionic; Organic; Reactions; Their; Intermediates

With the support of the Organic and Macromolecular Chemistry Program, Professor George A. Olah, of the Department of Chemistry at the University of Southern California, is studying protolytically activated superelectrophiles and their chemistry. This includes the investigation of superacid catalyzed carbonylation of alkanes and cycloalkanes with protolytically activated formyl cation [HCO+...HA or, in the limiting case, HCOH(2+)] as the de facto formylating agent in both liquid and solid superacid systems. Superelectrophilic nitrations with activated nitronium ion reagents [NO2H(2+)], nitrosations with NOH(2+) equivalents, and acylations with protioacyl dications [RCOH(2+)] will be investigated. The chemistry of fluorine-substituted allyl cations and polyallyl cations, several elusive azo onium dications, including bisdiazonium dication [N4(2+)] and diazo acyl cation [N2CO(2+)], and a number of silylated onium ions, including silylated CO, CO2, COS, CS2, N2O, O2, and O3, will also be explored.Numerous chemical transformations are effected by acids. Extremely potent acids have been discovered which can react with compounds which are only very weakly basic, and through such reactions of "superacids", extremely reactive species may be generated. Through the preparation and study of such species, one may gain insight into the mechanisms by which organic molecules react and develop the ability to effect chemical transformations of otherwise unreactive molecules, including petrochemical feedstocks. Professor George A. Olah, of the Department of Chemistry at the University of Southern California, is carrying out fundamental studies of superacid-activated molecules and their reactions with the support of the Organic and Macromolecular Chemistry Program.

在有机和高分子化学项目的支持下，乔治A.南加州大学化学系的Olah正在研究质子活化的超亲电体及其化学。这包括研究超强酸催化的羰基化烷烃和环烷烃与质子活化的甲酰基阳离子[HCO+... HA或在限制情况下HCOH（2+）]作为液体和固体超强酸体系中的事实上的甲酰化剂。将研究用活化的硝离子试剂[NO2H（2+）]进行的超亲电硝化、用NOH（2+）当量进行的亚硝化和用质子酰基二价阳离子[RCOH（2+）]进行的酰化。氟取代的烯丙基阳离子和多烯丙基阳离子、几种难以捉摸的偶氮阳离子（包括双重氮阳离子[N4（2+）]和重氮酰基阳离子[N2 CO（2+）]）以及许多甲硅烷基化的阳离子（包括甲硅烷基化的CO、CO2、COS、CS2、N2 O、O2和O3）的化学也将被探索。许多化学转化受到酸的影响。已经发现了极强的酸，其可以与仅是非常弱碱性的化合物反应，并且通过这种“超强酸”的反应，可以产生极强的反应性物质。通过制备和研究这些物种，人们可以深入了解有机分子反应的机制，并发展影响其他非反应性分子（包括石化原料）化学转化的能力。乔治教授A. Olah是南加州大学化学系的教授，在有机和大分子化学项目的支持下，正在进行超强酸活化分子及其反应的基础研究。