- Jun 11, 2018 -
The simplest synthetic method for tosyl azide is the reaction of p-Toluenesulfonyl Chloride with Sodium Azide. Tosyl azide prepared in ethanol may contain 7-20% of ethyl p-toluenesulfonate;the formation of this byproduct can be avoided by working in aqueous acetone instead of ethanol. The 1H NMR spectrum of tosyl azide prepared (99% yield) according to Curphey exhibits signals for traces of dichloromethane (<1%);the compound is pure by TLC, while HPLC reveals traces (>1.5%) of an impurity. Polymer-bound tosyl chloride can be transformed to polymer-bound tosyl azide. A polymer-bound phase-transfer catalyst may also be employed (94% yield).Further methods for the preparation of tosyl azide are the oxidation of p-Toluenesulfonylhydrazide by Iron(III) Nitrate-K10 Montmorillonite Clay (83% yield),by Nitrogen Dioxide in CCl4 (95% yield),or by Nitrosonium Tetrafluoroborate (85% yield).
Handling, Storage, and Precautions: crystallizes to a white solid at -20 °C and can be stored indefinitely at this temperature. Particular care is required for all reactions in which tosyl azide is heated at or above 100 °C. The initial temperature of the explosive decomposition is about 120 °C.Severe explosions during the attempted distillation of tosyl azide have been reported.Polymer-bound tosyl azide can be stored indefinitely at room temperature and, in contrast to tosyl azide itself, is not sensitive to mechanical shock. Use in a fume hood.