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项赠款支持罗格斯大学罗伯特·A·莫斯教授的持续工作。碳烯和相关的反应性中间体将通过直接光谱方法研究，特别是通过激光闪光光解。该项目的要素是：（1）剖析光启动的卡宾反应，以揭示激发态前体的污染（卡宾模拟反应）； （2）检查同位素对分子内重排和隧穿的证据； （3）研究在竞争性的1,2碳迁移中，对无环基丙丙基丙烯的1,2-碳迁移的研究； （4）通过基本的腺苷二氮嗪的基本裂解，测量1,2-酰基迁移的电子特征和可能产生的酰基阴离子； （5）确定卡宾 - 吡啶ylide形成的动力学。 卡宾斯（二价碳种类）是有机化学中重要的反应性中间体。将研究碳烯反应的各个方面，例如氢和碳原子迁移的模式以及碳前体光解的产物。这项研究可能会导致我们对卡宾化学的理解的新见解。