Alpha-Azido Alcohols and Other Short Lived Azides

最近，我们首次证明了-叠氮醇与醛和水合苯甲酸建立了快速平衡。这使得获得标题化合物特别简单，但在有机合成中处理和利用这些化合物时必须考虑到这一点。对α -叠氮醇的两个双官能团可能发生的各种反应进行机理研究，以找出可行的合成新产物的方法。由于标题化合物可以在非常温和的反应条件下氧化为酰基叠氮化物，因此我们首次能够使用这种氧化还原过程生成相当短寿命的叠氮化物甲酰基。对相应的Curtius重排进行了动力学分析，并将得到的活化参数与高质量量子化学计算的结论进行了比较。叠氮化物是在惰性气体基质中光化学合成甲酰亚硝基的优良前驱体。叠氮乙炔作为第一种1-叠氮-1-炔和另一种寿命较短的叠氮化合物，将被制备并通过光谱数据和二次反应进行表征，结果表明它是一种富电子炔和氰碳烯的前体。最初的实验已经成功了。最后还将合成1,1,4,4-四叠氮-2,3-二氮-1,3-丁二烯，以研究导致四唑的异常慢环化。

Recently, we showed for the first time that alpha-azido alcohols establish a rapid equilibration with aldehydes and hydrazoic acid. This allows a particularly simple access to the title compounds but has to be taken into account when these compounds are handled and utilized in organic synthesis. The variety of possible reactions, which both geminal functional groups of alpha-azido alcohols offer, should be mechanistically investigated in order to work out practicable synthetic methods for new products. Because the title compounds can be oxidized to acyl azides under very mild reaction conditions, we were able to use this redox process to generate the quite short-lived formyl azide for the first time. The corresponding Curtius rearrangement has been kinetically analyzed, and the resulting activation parameters have been compared with the conclusions of high-quality quantum chemical calculations. Formyl azide is an excellent precursor to photochemically generate formylnitrene in noble-gas matrix. Azidoacetylene, as the first 1-azido-1-alkyne and another short-lived azide, will be prepared and characterized by spectroscopic data and by secondary reactions, which present it as an electron-rich alkyne and a precursor of cyanocarbene. First experiments already were successful. Finally 1,1,4,4-tetraazido-2,3-diaza-1,3-butadiene will also be synthesized to investigate the abnormally slow cyclization that lead to a tetrazole.