Liu Michael T H, Choe Yoong-Kee, Kimura Masahiro, Kobayashi Kaoru, Nagase Shigeru, Wakahara Takatsugu, Niino Yasuyuki, Ishitsuka Midori O, Maeda Yutaka, Akasaka Takeshi
Department of Chemistry, University of Prince Edward Island, Charlottetown, Prince Edward Island C1A4P3, Canada.
J Org Chem. 2003 Sep 19;68(19):7471-8. doi: 10.1021/jo034949q.
The thermal decomposition of phenylchlorodiazirine (1), phenyl-n-butyldiazirine (2), and 2-adamantane-2,3'-[3H]diazirine (3) has been studied in solution in the presence of C(60). The C(60) probe technique indicates that in the decomposition diazirine 1 yielded exclusively phenylchlorocarbene, diazirine 2 yielded mainly a diazo intermediate, and diazirine 3 yielded a mixture of carbene and diazo compound. In the case of diazirine 2, 13% of (E)-1-phenyl-1-pentene resulted from the direct thermal rearrangement of diazirine without the participation of a carbene. As well, the thermal decomposition of these diazirines has been studied theoretically with ab initio and density functional methods. The experimental results are broadly in agreement with the theoretical predictions. The calculations further indicate that the rebound reaction between carbene and molecular nitrogen leading to the formation of a diazo intermediate is an important reaction in the gas-phase decomposition of diazirine.
在富勒烯（C(60)）存在的情况下，对苯基氯代二氮烯（1）、苯基正丁基二氮烯（2）和2-金刚烷-2,3'-[3H]二氮烯（3）在溶液中的热分解进行了研究。C(60)探针技术表明，在分解过程中，二氮烯1仅生成苯基氯卡宾，二氮烯2主要生成重氮中间体，二氮烯3生成卡宾和重氮化合物的混合物。在二氮烯2的情况下，13%的（E）-1-苯基-1-戊烯是由二氮烯直接热重排产生的，没有卡宾的参与。此外，还采用从头算和密度泛函方法对这些二氮烯的热分解进行了理论研究。实验结果与理论预测大致相符。计算进一步表明，卡宾与分子氮之间导致重氮中间体形成的反弹反应是二氮烯气相分解中的一个重要反应。
