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笔赠款支持罗格斯大学罗伯特·A·莫斯教授的持续工作。卡宾和相关的反应中间体将通过直接光谱方法进行研究，特别是通过激光闪光光解。该项目的要素是：（1）剖析光引发的卡宾反应，以揭示激发态前体（卡宾模拟反应）的污染； (2) 检查同位素对分子内重排的影响，以及隧道效应的证据； (3) 不对称环取代环丙基卤代卡宾竞争性1,2-碳迁移中的电子和空间效应研究； (4)酰氧基卡宾中1,2-酰基迁移的电子特征的测量以及酰氧基二氮烯的碱性裂解可能产生酰基阴离子； (5)卡宾-吡啶叶立德形成动力学的测定。 卡宾，二价碳物种，是有机化学中重要的反应中间体。将研究卡宾反应的各个方面，例如氢和碳原子迁移的模式以及卡宾前体光解产物的来源。这项研究可能会给我们对卡宾化学的理解带来新的见解。