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

Autor:	Hideo Tanaka, Aya Mitsui, Kazutaka Nishino, Futaba Hara, Haruka Yahagi, Tomoko Suzuki, Manabu Kuroboshi, Hiromu Kawakubo, Masato Onodera, Hiroyuki Takayama, Tomoyoshi Takano, Yoshito Takebayashi
Rok vydání:	2015
Předmět:	chemistry.chemical_classification Ethyl allophanate Base (chemistry) Organic Chemistry Halogenation Coupling reagent Medicinal chemistry Diethyl azodicarboxylate chemistry.chemical_compound chemistry Yield (chemistry) Organic chemistry Reactivity (chemistry) Rearrangement reaction
Zdroj:	Synthetic Communications. 45:1068-1072
ISSN:	1532-2432 0039-7911
DOI:	10.1080/00397911.2014.1002137
Popis:	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 CHCl3, followed by the Hofmann-type rearrangement reaction of the resulting N-brominated species 2 and 3 in C2H5OH 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(C2H5)3. 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.
Databáze:	OpenAIRE
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