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Pure Appl. Chem., 2007, Vol. 79, No. 6, pp. 993-1001

New mechanisms centered on reactive intermediates: Examples from diazirine and carbene chemistry

Robert A. Moss, Jingzhi Tian, Gaosheng Chu, Ronald R. Sauers and Karsten Krogh-Jespersen

Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, New Brunswick, NJ 08903, USA

Abstract: Laser flash photolysis (LFP) of appropriate diazirine precursors afforded the UV spectra of methylchlorocarbene, benzylchlorocarbene, cyclopropylchlorocarbene, and 1-adamantylchlorocarbene. The σ → p transitions of these carbenes were used to directly monitor their reaction kinetics. The unusual and highly reactive N2CO compound, diazirinone, was obtained from the reaction of fluoride ion with p-nitrophenoxychlorodiazirine. Diazirinone fragmented to CO and N2 in a reaction that was exothermic by >90 kcal/mol. Dichlorodiazirine (DCD) was generated by the reaction of chloride ion with p-nitrophenoxychlorodiazirine. Reactions of dichlorocarbene generated from DCD are discussed.