Unique Reactivity of Triazolyl Diazoacetates under Photochemical Conditions

The difference in the HOMO–LUMO gap for phenyl and triazolyl diazoacetates is reflected in their reactivity under light irradiation. While photochemical reactions for phenyl diazoacetates can be performed in DCM, triazolyl diazoacetates react with the solvent and become chlorinated. All alkyl halides studied behave in the same way. With other commonly used solvents, C–H or X–H insertions occur. The solvent that allows reactions with other reagents is dimethyl decarbonate.

苯基重氮乙酸酯与三唑基重氮乙酸酯的最高占据分子轨道-最低未占据分子轨道能隙（HOMO–LUMO gap）差异，体现在二者在光照射条件下的反应活性差异上。尽管苯基重氮乙酸酯的光化学反应可在二氯甲烷（DCM）中进行，但三唑基重氮乙酸酯会与溶剂发生反应并被氯化。所有受试卤代烷烃均表现出一致的反应行为。在其他常用溶剂中，则会发生C-H键或X-H键插入反应。可适配其他试剂反应的溶剂为二甲基脱碳酸酯（dimethyl decarbonate）。