Direct Observational Studies of Carbenes

卡宾的直接观察研究

• 批准号: 8812505
• 负责人: Robert Moss
• 金额: $ 33.3万
• 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: 1988
• 资助国家: 美国
• 起止时间: 1988-12-15 至 1992-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=8812505&HistoricalAwards=false
• 关键词: Direct; Observational; Studies; Carbenes

This grant in Organic and Macromolecular Chemistry provides support for the research of Dr. Robert Moss, Rutgers University. The work is focused on the direct observational studies of carbenes, which are a class of important reaction intermediates in organic chemistry. They are important because of their unusual reactivity which arises because carbenes are electron deficient and can exist in more than one accessible electronic state. Fundamental studies of carbenes and other highly reactive intermediates will be carried out by direct spectroscopic observation and absolute kinetic methods. The diazirine halide exchange reaction will be used to prepare novel diazirine precursors for dimethoxycarbene and fluoromethoxycarbene. For dimethoxycarbene, spectroscopic, absolute kinetic, activation parameter, and reactivity studies will define the behavior of this representative nucleophilic carbene. Parallel studies will be made with fluoromethoxycarbene. The free energies of activation of the carbene/alkene addition reactions will be determined and analyzed for enthalpy/entropy partition. Other carbenes to studied include methoxymethylcarbene, fluoromethylcarbene, and dimethylaminomethoxycarbene. Activation parameters will also be measured for additions of phenylhalocarbenes to hindered alkenes, where unusual behavior has already been observed. Finally, several methods of generating carbonium ion from diazirines and carbenes will be studied.

有机和高分子化学的这项资助提供了 支持罗格斯大学罗伯特·莫斯博士的研究 大学这项工作的重点是直接观察 卡宾反应是一类重要的反应， 有机化学中间体。它们很重要，因为 它们不寻常的反应性，这是因为卡宾是 电子缺陷，可以存在于一个以上的可访问 电子态 卡宾和其他高活性化合物的基础研究 中间体将通过直接光谱法进行 观察和绝对动力学方法。 二氮杂环丙烯卤化物 利用交换反应制备新型的二氮杂环丙烯 二甲氧基卡宾和氟甲氧基卡宾的前体。 为 二甲氧基卡宾，光谱，绝对动力学，活化 参数，反应性研究将定义的行为 这个代表性的亲核卡宾。平行研究将 用氟甲氧基卡宾制成。 的自由能 卡宾/烯烃加成反应的活化将是 确定并分析焓/熵分配。其他 研究的卡宾包括甲氧基甲基卡宾， 氟甲基卡宾和二甲基氨基甲氧基卡宾。 还将测量激活参数，以添加 苯基卤代卡宾受阻烯烃，其中异常行为 已经被观察到了。最后，几种方法 从二氮杂环丙烷和卡宾生成碳正离子将是 研究了