ethyl 2-azido-2-methyl-3-oxobutanoate | 76062-29-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl 2-azido-2-methyl-3-oxobutanoate
• 英文别名: ethyl 2-azido-2-methylacetoacetate；2-azido-2-methyl-acetoacetic acid ethyl ester；2-Azido-2-methyl-acetessigsaeure-aethylester；Butanoic acid, 2-azido-2-methyl-3-oxo-, ethyl ester
• CAS: 76062-29-8
• 化学式: C₇H₁₁N₃O₃
• 分子量: 185.183
• InChiKey: IMVXDNBTRHPTCI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  57.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl 2-azido-2-methyl-3-oxobutanoate 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 苯 为溶剂， 以80%的产率得到2-乙酰氨基丙酸乙酯
  参考文献：
  名称：

  Radical Chain Reactions of α-Azido-β-keto Esters with Tributyltin Hydride. A Novel Entry to Amides and Lactams through Regiospecific Nitrogen Insertion

  摘要：

  A variety of acyclic and carbocyclic alpha-azido-beta-keto esters have been readily prepared from the parent dicarbonyl compounds, and their radical chain reactions with tributyltin hydride have been investigated. These reactions normally result in efficient production of alkoxycarbonyl-substituted amides and lactams and thence provide a new, useful method for regiospecific nitrogen insertion of keto ester compounds. The likely mechanism entails initial addition of tributylstannyl radical to the azido moiety to give a stannylaminyl radical, which readily undergoes intramolecular three-membered cyclization onto the ketone group to form an alkoxyl radical. The alkoxyl radical then undergoes regiospecific beta-scissian to form a stable ring-opened radical that is eventually reduced by tributyltin hydride to propagate the chain. With certain substrates, concomitant deazidation occurs to an important extent. This process, which is unusually observed in radical reactions of alkyl azides, is ascribed to addition of the stannyl radical to the terminal azido nitrogen; subsequent fragmentation of the ensuing 1,3-triazenyl adduct gives stannyl azide and a deazidated alkyl radical, resonance-stabilized by the adjacent carbonyl groups. The radical reactions of 2-azido-2-(ethoxy-carbonyl)-1-tetralone with allyltributylstannane and allyltriphenylstannane have also been investigated with the (missed) aim to achieve nitrogen insertion and concomitant allylation.

  DOI：

  10.1021/jo990837g
• 作为产物：
  描述：

  2-甲基乙酰乙酸乙酯 在 sodium azide 、 manganese triacetate 作用下， 以 甲醇 为溶剂， 反应 3.0h， 以56%的产率得到ethyl 2-azido-2-methyl-3-oxobutanoate
  参考文献：
  名称：

  通过叠氮化物的捕获终止基于Mn（III）的氧化环化反应。

  摘要：

  β-酮基酯和丙二酸酯的基于Mn（III）的氧化自由基环化反应中形成的自由基可以用叠氮化钠和Mn（III）捕集，以30-80％的收率得到环状和双环叠氮化物。叠氮化物的还原得到双环和三环内酰胺。[反应：看文字]

  DOI：

  10.1021/ol049805s

文献信息

• Termination of Mn(III)-Based Oxidative Cyclizations by Trapping with Azide
  作者：Barry B. Snider、Jeremy R. Duvall

  DOI：10.1021/ol049805s

  日期：2004.4.1

  The radicals formed in Mn(III)-based oxidative free-radical cyclizations of beta-keto esters and malonate esters can be trapped with sodium azide and Mn(III) to give cyclic and bicyclic azides in 30-80% yield. Reduction of the azide gives bi- and tricyclic lactams. [reaction: see text]

  β-酮基酯和丙二酸酯的基于Mn（III）的氧化自由基环化反应中形成的自由基可以用叠氮化钠和Mn（III）捕集，以30-80％的收率得到环状和双环叠氮化物。叠氮化物的还原得到双环和三环内酰胺。[反应：看文字]
• Reactions of Benzocyclic β-Keto Esters with Sulfonyl Azides. 2.¹ Further Insight into the Influence of Azide Structure and Solvent on the Reaction Course
  作者：Luisa Benati、Daniele Nanni、Piero Spagnolo

  DOI：10.1021/jo9901541

  日期：1999.7.1

  The reactions of 2-ethoxycarbonyl-1-benzosuberone, with 4-methoxybenzenesulfonyl, 2,4,6-triiso-propylbenzenesulfonyl, methanesulfonyl, and trifluoromethanesulfonyl azide, in the presence of triethylamine, have been investigated in N,N-dimethylformamide, acetonitrile, or tetrahydrofuran with the intent of clarifying the influence of both the azide electrophile and solvent on the reaction course. The present findings, in addition to those previously obtained with tosyl and 4-nitrobenzenesulfonyl azide, indicate that both the electronic features of the sulfonyl azide and the solvent polarity greatly affect the possible occurrence of azidation and/or Favorskii-type ring contraction at the expense of deacylating diazo transfer. Azidation is promoted by the less electrophilic azides, while it is virtually avoided by the more electrophilic ones. Ring contraction occurs to a limited extent with the less electrophilic azides, but it becomes the main process with those more electrophilic. Moreover, azidation is virtually unaffected by the solvent polarity, while ring contraction can markedly be enhanced by a highly polar solvent. Firm evidence has additionally been obtained that, in contrast to a previous claim, trifluoromethanesulfonyl azide can normally perform diazotization of acyclic beta-keto esters in preference to azidation.
• Forster; Newman, Journal of the Chemical Society, 1910, vol. 97, p. 1367
  作者：Forster、Newman

  DOI：——

  日期：——
• Hakimelahi, Gholam Hosein; Just, George, Synthetic Communications, 1980, vol. 10, # 6, p. 429 - 436
  作者：Hakimelahi, Gholam Hosein、Just, George

  DOI：——

  日期：——
• HAKIMELAHI G. H.; JUST G., SYNTH. COMMUN., 1980, 10, NO 6, 429-435
  作者：HAKIMELAHI G. H.、 JUST G.

  DOI：——

  日期：——