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

Hiromu Kawakubo, Tomoko Suzuki, Kazutaka Nishino, Futaba Hara, Tomoyoshi Takano, Yoshito Takebayashi, Masato Onodera, Aya Mitsui, Haruka Yahagi, Hiroyuki Takayama, Manabu Kuroboshi, Hideo Tanaka

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

(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.

Original languageEnglish
Pages (from-to)1068-1072
Number of pages5
JournalSynthetic Communications
Volume45
Issue number9
DOIs
Publication statusPublished - 2015

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ethyl allophanate

Keywords

  • 1,8-Diazabicyclo[5.4.0]-7-undecene; diethylazodicarboxylate; diethylhydrazo-dicarboxylate; Hofmann-typerearrangement

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Facile Synthesis of Diethyl Azodicarboxylate and Diethylhydrazodicarboxylate via the Sequential Bromination and Hofmann-Type Rearrangement of Ethyl Allophanate. / Kawakubo, Hiromu; Suzuki, Tomoko; Nishino, Kazutaka; Hara, Futaba; Takano, Tomoyoshi; Takebayashi, Yoshito; Onodera, Masato; Mitsui, Aya; Yahagi, Haruka; Takayama, Hiroyuki; Kuroboshi, Manabu; Tanaka, Hideo.

In: Synthetic Communications, Vol. 45, No. 9, 2015, p. 1068-1072.

Research output: Contribution to journalArticle

Kawakubo, H, Suzuki, T, Nishino, K, Hara, F, Takano, T, Takebayashi, Y, Onodera, M, Mitsui, A, Yahagi, H, Takayama, H, Kuroboshi, M & Tanaka, H 2015, 'Facile Synthesis of Diethyl Azodicarboxylate and Diethylhydrazodicarboxylate via the Sequential Bromination and Hofmann-Type Rearrangement of Ethyl Allophanate', Synthetic Communications, vol. 45, no. 9, pp. 1068-1072. https://doi.org/10.1080/00397911.2014.1002137
Kawakubo, Hiromu ; Suzuki, Tomoko ; Nishino, Kazutaka ; Hara, Futaba ; Takano, Tomoyoshi ; Takebayashi, Yoshito ; Onodera, Masato ; Mitsui, Aya ; Yahagi, Haruka ; Takayama, Hiroyuki ; Kuroboshi, Manabu ; Tanaka, Hideo. / Facile Synthesis of Diethyl Azodicarboxylate and Diethylhydrazodicarboxylate via the Sequential Bromination and Hofmann-Type Rearrangement of Ethyl Allophanate. In: Synthetic Communications. 2015 ; Vol. 45, No. 9. pp. 1068-1072.
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AU - Tanaka, Hideo

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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.

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