REACTIVITIES OF NITRENES GENERATED BY PHOTOLYSIS OF 2-(OMEGA-PHENYLALKYL)PHENYL AZIDES
REACTIVITIES OF NITRENES GENERATED BY PHOTOLYSIS OF 2-(OMEGA-PHENYLALKYL)PHENYL AZIDES
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DOI：
10.1021/jo00110a052
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发表时间：
1995-03-10
影响因子：
3.6
通讯作者：
TOMIOKA, H
中科院分区：
文献类型：
--
作者：
MURATA, S;YOSHIDOME, R;TOMIOKA, H
为了研究光解生成的芳基氮烯与分子内 CH 键的反应性，检查了 2-(omega-苯基烷基)苯基叠氮化物 (1a-d) 的光化学。溶液中的1的辐照表明，只有当反应性CH键（例如苄基）位于靠近氮烯中心时，氮烯才会插入相邻的CH键以得到环状化合物4和5。该过程可以与三线态氮烯衍生的产物的形成竞争，但不能与 DEA 捕获二脱氢吖庚因竞争。另一方面，在 12 K 下对 Ar 基质中的 1b 进行照射，得到 CH 插入产物 4b 和二脱氢吖庚因 15 的混合物。讨论了在溶液和基质中观察到的氮宾反应性差异的根源，以及参与 CH 插入反应的氮宾的自旋状态。
In order to investigate the reactivity of a photolytically generated arylnitrene with an intramolecular CH bond, the photochemistry of 2-(omega-phenylalkyl)phenyl azides (1a-d) was examined. Irradiation of 1 in solution revealed that the insertion of the nitrene into an adjacent CH bond to give cyclic compounds 4 and 5 occurs favorably only when a reactive CH bond, such as benzylic, is located close to the nitrenic center. This process can compete with the formation of products derived from triplet nitrene, but not with the capture of didehydroazepine by DEA. On the other hand, irradiation of 1b in an Ar matrix at 12 K gave a mixture of the CH insertion product 4b and the didehydroazepine 15. The origin of the difference in reactivity of the nitrene observed in solutions and in a matrix, and the spin state of the nitrene involved in the CH insertion reaction, are discussed.