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第17讲-炔烃;烯丙基中间体和二烯烃中的共轭

Lecture 17 - Alkynes; Conjugation in Allylic Intermediates and Dienes
课程网址: http://videolectures.net/yalespan125bs2011_mcbride_lec17/  
主讲教师: J. Michael McBride
开课单位: 耶鲁大学
开课时间: 2014-08-19
课程语种: 英语
中文简介:
由于其不寻常的酸性,非常强的碱使内部乙炔异构化为较不稳定的末端异构体成为可能。许多化学反应可以用局域键来理解,但共轭体系的特殊稳定性要求考虑离域轨道或“共振”。涉及烯丙基阳离子、阴离子、过渡态的体系中的平衡常数、速率和区域化学,自由基证明烯丙基共轭值约为13千卡/摩尔。DCl与1,3-戊二烯加成的区域选择显示烯丙基离子对的快速崩塌。通过使用NBS控制Br2浓度,溴的烯丙基取代比Br2加成更有利。二烯共轭的价值远低于烯丙基共轭。
课程简介: Because of their unusual acidity very strong base makes it possible to isomerize an internal acetylene to the less stable terminal isomer. Many chemical reactions may be understood in terms of localized bonds, but the special stability of conjugated systems requires considering delocalized orbitals or "resonance." Equilibrium constants, rates, and regiochemistry in systems involving allylic cations, anions, transition states, and free radicals demonstrate that allylic conjugation is worth about 13 kcal/mole. Regioselection in addition of DCl to 1,3-pentadiene reveals rapid collapse of an allylic ion pair. Allylic substitution of bromine can be favored over Br2 addition by using NBS to control Br2 concentration. Diene conjugation is worth much less than allylic conjugation.
关 键 词: 乙炔; 末端异构体; 共轭体系
课程来源: 视频讲座网
数据采集: 2021-11-19:zkj
最后编审: 2021-11-19:zkj
阅读次数: 81