TY - JOUR
T1 - Facile Synthesis of Diethyl Azodicarboxylate and Diethylhydrazodicarboxylate via the Sequential Bromination and Hofmann-Type Rearrangement of Ethyl Allophanate
AU - Kawakubo, Hiromu
AU - Suzuki, Tomoko
AU - Nishino, Kazutaka
AU - Hara, Futaba
AU - Takano, Tomoyoshi
AU - Takebayashi, Yoshito
AU - Onodera, Masato
AU - Mitsui, Aya
AU - Yahagi, Haruka
AU - Takayama, Hiroyuki
AU - Kuroboshi, Manabu
AU - Tanaka, Hideo
N1 - Funding Information:
This work was supported by a Nihon Pharmaceutical University Research Grant.
Publisher Copyright:
© Taylor & Francis Group, LLC.
PY - 2015
Y1 - 2015
N2 - (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.
AB - (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.
KW - 1,8-Diazabicyclo[5.4.0]-7-undecene; diethylazodicarboxylate; diethylhydrazo-dicarboxylate; Hofmann-typerearrangement
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U2 - 10.1080/00397911.2014.1002137
DO - 10.1080/00397911.2014.1002137
M3 - Article
AN - SCOPUS:84925543654
SN - 0039-7911
VL - 45
SP - 1068
EP - 1072
JO - Synthetic Communications
JF - Synthetic Communications
IS - 9
ER -