γ-叠氮基苯丁酮中的分子内氢原子提取：1,5-酮基亚胺基自由基的形成
Intramolecular H-atom abstraction in gamma-azido-butyrophenones: formation of 1,5 ketyl iminyl radicals.
作者信息
Muthukrishnan Sivaramakrishnan, Sankaranarayanan Jagadis, Klima Rodney F, Pace Tamara C S, Bohne Cornelia, Gudmundsdottir Anna D
机构信息
Department of Chemistry, University of Cincinnati, PO Box 210172, Cincinnati, Ohio 45221, USA.
出版信息
Org Lett. 2009 Jun 4;11(11):2345-8. doi: 10.1021/ol900754a.
Photolysis of gamma-azidobutyrophenone derivatives yields 1,4 ketyl biradicals via intramolecular H-atom abstraction. The 1,4 ketyl biradicals expel a nitrogen molecule to form 1,5 ketyl iminyl biradicals, which decay by ring closure to form a new carbon-nitrogen bond. The 1,5 ketyl iminyl biradicals were characterized with transient spectroscopy. In argon/nitrogen-saturated solutions, the biradicals have lambda(max) approximately 300 nm and tau = 15 micros. DFT-TD calculations were used to support the proposed mechanism for formation of the 1,5 ketyl iminyl radicals.
γ-叠氮丁酰苯衍生物的光解通过分子内氢原子提取产生1,4-酮基双自由基。1,4-酮基双自由基排出一个氮分子形成1,5-酮基亚胺基双自由基，后者通过闭环衰变形成新的碳-氮键。用瞬态光谱对1,5-酮基亚胺基双自由基进行了表征。在氩气/氮气饱和溶液中，双自由基的λ(max)约为300nm，τ = 15微秒。采用密度泛函理论-含时密度泛函理论（DFT-TD）计算来支持所提出的1,5-酮基亚胺基自由基形成机理。
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