Facile Synthesis of Diethyl Azodicarboxylate and Diethylhydrazodicarboxylate via the Sequential Bromination and Hofmann-Type Rearrangement of Ethyl Allophanate

(Chemical Equation Presented). Diethyl azodicarboxylate (DEAD) is a well-known coupling reagent that can be readily synthesized from diethylhydrazodicarboxylate (DEHD). The bromination of commercially available ethyl allophanate (1) in CHCl followed by the Hofmann-type rearrangement reaction of the resulting N-brominated species 2 and 3 in CH in the presence of 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), gave DEHD in good yield from a one-pot process. Interestingly, however, the bromination and Hofmann-type rearrangement reactions did not occur in the presence of N(C These results therefore suggest that this reaction is reliant upon a high level of reactivity during the bromination reaction to give 2 and 3, and that these N-brominated species require the presence of a strong and nonnucleophilic base to undergo the Hofmann-type rearrangement to give DEHD.