
Magnesium nitride has been recommended as a reagent for converting esters to amides as well as in the preparation of heterocyclics sich as dihydropyridines and pyrroles (Org Lett 2008,10, 3623 and 3627; SynLett 2008, 2597). However a recent letter in C&E News (April 13, 2009, p2) reported an explosion when preparing amides with magnesium nitride, using a slightly modified procedure on 3 times the reported scale. Now Steven Ley (Univ of Cambridge), the senior author on the original publications has replied (C&E News, June 8, 2009, p4) indicating that in their hands over 200 experiments have been carried out without incident but recently they have also observed explosions when using heterocyclic (furan and indole) esters, and that extreme caution is recommended on small scale work - a maximum of 0.25 mmol is suggested
Although it is possible that the nitride may be, on occasions contaminated with the azide, Prof Ley suggests that the explosion may be caused by an initial exothermic ammonia-generating reaction followed by a runaway in the ammonia reaction with esters. It is suggested that if the initial exotherm can be controlled by an ice-bath for about an hour, it may be then possible to slowly heat the reaction to 80 to complete the process safely; this is currently being investigated. Meanwhile all workers trying this procedure should do so with extreme caution, on small scale and with appropriate precautions
Although it is possible that the nitride may be, on occasions contaminated with the azide, Prof Ley suggests that the explosion may be caused by an initial exothermic ammonia-generating reaction followed by a runaway in the ammonia reaction with esters. It is suggested that if the initial exotherm can be controlled by an ice-bath for about an hour, it may be then possible to slowly heat the reaction to 80 to complete the process safely; this is currently being investigated. Meanwhile all workers trying this procedure should do so with extreme caution, on small scale and with appropriate precautions















