DIRECTIVE EFFECTS IN ATTACK OF PHENYL RADICALS ON CARBON-HYDROGEN BONDS
DIRECTIVE EFFECTS IN ATTACK OF PHENYL RADICALS ON CARBON-HYDROGEN BONDS
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DOI：
10.1021/ja00906a009
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发表时间：
1963-01-01
影响因子：
15
通讯作者：
RUSSELL, GA
中科院分区：
文献类型：
--
作者：
BRIDGER, RF;RUSSELL, GA
测定了各种脂肪族碳-氢键与苯基的反应活性。除了烷烃和功能取代烷烃外，烯丙基型和苄基型氢原子的反应性也已被研究。还测量了与碳以外的原子相连的氢原子的反应性。在反应条件下，苯基自由基与芳烷基烃反应，几乎只发生苄基进攻。对于末端烯烃，相当一部分苯基自由基被加成过程消耗掉.目前的结果代表了最广泛的反应性系列可用于氢提取过程。苯基在与饱和碳氢键的反应中似乎相当不受极性效应的影响。因此，与苯基自由基观察到的反应性规模应该是一个重要的标准在评估极性效应的重要性，在其他自由基processs.Although芳香族取代反应涉及苯基自由基已被广泛研究，苯基自由基的攻击饱和碳-氢键很少受到关注。我们研究了苯基自由基与各种碳氢键的反应，通过测量苯和氯苯形成的竞争反应的产物。
The reactivities of a wide variety of aliphatic carbon-hydrogen bonds toward the phenyl radical have been de-termined. In addition to alkanes and functionally substituted alkanes, thereactivities of allylic and benzylietype hydrogen atoms have been studied. The reactivities of hydrogen atoms attached to atoms other than carbon have also been measured. Under the reaction conditions phenyl radicals reacted with aralkyl hydro-carbons to give almost exclusive benzylic attack. For terminal olefins an appreciable fraction of the phenyl radicals was consumed byaddition processes. The present results represent themost extensive reactivity series available for a hydrogen abstraction process. The phenyl radical appears to be fairly free of polar effects in its reactions with saturated carbon-hydrogen bonds. Therefore the reactivity scale observed with a phenyl radical should be an important standardin assessing the importance of polar effects in other free radical processes.Although aromatic substitution reactions involving phenyl radicals have been extensively investigated, the attack of phenyl radicals on saturated carbon-hydrogen bonds has received little attention. We have studied the reactions of phenyl radicals with a wide variety of carbon-hydrogen bonds by measuring the benzene and chlorobenzene formed as products of the competing reactions.