MECHANISM OF ENDOPEROXIDE FORMATION .3. UTILIZATION OF THE YOUNG AND CARLSSON KINETIC TECHNIQUES
MECHANISM OF ENDOPEROXIDE FORMATION .3. UTILIZATION OF THE YOUNG AND CARLSSON KINETIC TECHNIQUES
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DOI：
10.1021/ja00335a040
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发表时间：
1984-01-01
影响因子：
15
通讯作者：
MEHRSHEIKHMOHAMMADI, ME
中科院分区：
文献类型：
--
作者：
CLENNAN, EL;MEHRSHEIKHMOHAMMADI, ME
测定了单氧与39呋喃和环戊二烯加成的反应速率常数。取代基对观察到的速率常数的影响被解释为单线态氧加成的几何形状受电子密度分布的影响。内过氧化物的形成也与Diels-Alder反应进行了比较。这些反应的不同性质有力地证明了在反应表面上有异构体形成内过氧化物。
Therate constants for the additions of singletoxygen to 39 furans and cyclopentadienes have been determined. The effect of substituents on the observed rate constants was interpreted to suggest that the geometry of singlet oxygen addition is influenced by electron density distributions. The formation of endoperoxides was also compared tothe Diels-Alder reaction. The different character of these reactions is compelling evidence for the presence of exciplexes on the reaction surfaces for the formationof endoperoxides.