10.1016/j.tetlet.2010.03.094
The research focuses on the synthesis and characterization of azidochloromethane and azidobromomethane. These compounds were prepared by treating tris(azidomethyl)amine with dry hydrogen halide. The study explores their role as intermediates in the nucleophilic substitution of dihalomethanes to generate diazidomethane. However, diazidomethane could not be detected in this transformation. The researchers also investigated the reactions of these azides with various reagents, such as cyclooctyne and phenylsulfenyl chloride, leading to the formation of different triazole compounds. The synthesized compounds were characterized using spectroscopic data, and some structures were confirmed by single crystal X-ray diffraction analysis. The research highlights the challenges in handling these hazardous compounds and their potential applications in the chemistry of organic azides.
10.1021/jo00190a015
Chen-Chih Cheng, Frederick D. Greene, and John F. Blount investigates the reaction products and kinetics of 4-phenyl-1,2,4-triazolinedione (PhTAD) with various acetylenes, including 3-hexyne, cyclooctyne, and diarylacetylenes. The study reveals that the major product from reactions of PhTAD with diarylacetylenes is a 2:1 adduct, identified as a bis(azomethine imine) and confirmed by X-ray analysis. The kinetics show that the reaction is first order in both acetylene and PhTAD, suggesting a pathway involving an initial 1:1 adduct. The research also compares the reactivity of PhTAD with bromine, noting significant differences in the sensitivity to substituents on the unsaturated substrates, particularly for aryl-substituted systems. The findings provide insights into the mechanism of electrophilic addition reactions involving triazolinediones and acetylenes.
