Alpha-Azido Alcohols and Other Short Lived Azides

• Applicant: Professor Dr. Klaus Banert (†)
• Subject Area: Organic Molecular Chemistry - Synthesis and Characterisation
• Term: from 2008 to 2017
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 81098143

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.

• DFG Programme: Research Grants
• Major Instrumentation: Online-IR-Spektrometer inkl. Transferoptik und ATR-Messsonde
• Instrumentation Group: 1830 Fourier-Transform-IR-Spektrometer