Absolute Kinetic Studies of Intramolecular and Intermolecular Carbenic Reactions

分子内和分子间卡宾反应的绝对动力学研究

• 批准号: 9411637
• 负责人: Robert Moss
• 金额: $ 38.9万
• 依托单位: Rutgers University New Brunswick
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 1995
• 资助国家: 美国
• 起止时间: 1995-01-01 至 1998-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9411637&HistoricalAwards=false
• 关键词: Absolute; Kinetic; Studies; Intramolecular; Intermolecular

This grant from the Organic Dynamics Program supports the continuing work of Professor Robert A. Moss at Rutgers University. Carbenes and related reactive intermediates will be studied by direct spectroscopic methods, particularly by laser flash photolysis. Elements of the project are: (1) dissection of the photoinitiated carbenic reactions to reveal contamination by excited state precursors (carbene mimetic reactions); (2) examination of isotope effects on intramolecular rearrangements, and evidence for tunneling; (3) the study of electronic and steric effects in competitive 1,2-carbon migrations of unsymmetrically ring-substituted cyclopropylhalocarbenes; (4) the measurement of the electronic character of 1,2-acyl migrations in acyloxycarbenes and the possible generation of acyl anions by the basic cleavage of acyloxydiazirenes; and (5) determination of the kinetics of carbene-pyridine ylide formation. Carbenes, divalent carbon species, are important reactive intermediates in organic chemistry. Aspects of the reactions of carbenes will be studied such as the mode of hydrogen and carbon atom migrations and the origin of the products of photolysis of carbene precursors. This research could lead to new insights in our understanding of carbene chemistry.

有机动力学计划的这一资助支持了罗伯特·A.罗格斯大学的莫斯。卡宾和相关的活性中间体将通过直接光谱方法，特别是激光闪光光解进行研究。该项目的内容包括：（1）剖析光引发的卡宾反应，以揭示激发态前体的污染（2）同位素效应对分子内重排的影响，以及隧道效应的证据;（3）不对称环取代的环丙基卤代卡宾竞争性1，2-碳迁移中的电子效应和空间效应的研究;（4）酰氧基卡宾中1，2-酰基迁移的电子性质的测定和酰氧基二氮杂环烯碱裂解可能产生的酰基阴离子的测定;（5）卡宾-吡啶叶立德形成动力学的测定。 卡宾是二价碳物种，是有机化学中重要的反应中间体。本文将研究卡宾反应的各个方面，如氢原子和碳原子的迁移方式以及卡宾前体光解产物的来源。这项研究可能会为我们对卡宾化学的理解带来新的见解。