ethyl 1-ethoxycarbonyl-2-oxocyclohex-3-en-1-ylacetate | 168334-05-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl 1-ethoxycarbonyl-2-oxocyclohex-3-en-1-ylacetate
• 英文别名: Ethyl 1-ethoxycarbonyl-2-oxocyclohex-3-enylacetate；<1-Carbethoxy-2-oxo-cyclohexen-(3)-yl>-essigsaeure-ethylester；Ethyl 1-(2-ethoxy-2-oxoethyl)-2-oxocyclohex-3-ene-1-carboxylate
• CAS: 168334-05-2
• 化学式: C₁₃H₁₈O₅
• 分子量: 254.283
• InChiKey: SRNBFRCWGHXSOK-UHFFFAOYSA-N

物化性质

• 沸点：
  346.3±42.0 °C(Predicted)
• 密度：
  1.140±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  18
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  ethyl 1-ethoxycarbonyl-2-oxocyclohex-3-en-1-ylacetate 在 盐酸 、 甲烷磺酸 、 三氟甲磺酸 、 potassium tert-butylate 作用下， 以 四氢呋喃 、 叔丁醇 、 苯 为溶剂， 反应 33.0h， 生成 ethyl 2-[(1R,4R,7R,8R,9S)-4-methyl-7-nitro-2,10-dioxo-3-oxatricyclo[6.2.2.04,9]dodecan-1-yl]acetate
  参考文献：
  名称：

  独脚金类似物前体的立体化学和合成

  摘要：

  8-甲基-5-硝基-1-氧代-Δ8(8a)-八氢萘异构体的相对构型和构象通过各种 1H 和 13C NMR 方法阐明。还确定了三环副产物的结构。

  DOI：

  10.1002/mrc.1260330306
• 作为产物：
  描述：

  diethyl 2-acetyl-2-(2-formylethyl)succinate 在 对甲苯磺酸 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以43%的产率得到ethyl 1-ethoxycarbonyl-2-oxocyclohex-3-en-1-ylacetate
  参考文献：
  名称：

  Syntheses of the terpenoid precursors cyclopent-2-enone and cyclohex-2-enone diesters

  摘要：

  Two reaction pathways were elaborated for the practical and convenient synthesis of the title compounds: The first route applies a bromination-dehydrobromination sequence to introduce the double bond into 1-alkoxycarbonyl-2-oxocycloalkylacetic and propionic esters (4a-c, 7a,b). The application of 2,6-lutidine for dehydrobromination of alpha-bromocycloalkanones diesters (5a-c, 8a, b) provides sufficient selectivity to carry out this step without affecting the sensitive ester group. Alternative pathways, involving Michael reaction of diethyl 2-acetylsuccinate or -glutarate with acrolein and subsequent intramolecular aldol condensation, are presented in the case of cyclohex-2-enone derivatives 2a, b.

  DOI：

  10.1007/bf00811764

文献信息

• Direct and indirect radical denitrations of intermediates in the synthesis of sorgolactone and its nuclear analogs+
  作者：Katalin Mikló、Joseph Cs. Jaszberenyi、István Kádas、Géza Árvai、László Tőke

  DOI：10.1016/0040-4039(96)00560-6

  日期：1996.5

  Denitration of various important intermediates in the synthesis of sorgolactone and its analogs using radical chemistry on nitroketones or on the derived isocyanides is described. The nitro group is needed for the first step of the annellation process, the Michael addition of substituted nitroalkanes to cyclopentenones. Then it can be removed directly or after reduction to the amine or via the ketone

  描述了使用自由基化学对硝基酮或衍生的异氰酸酯合成高粱内酯及其类似物时各种重要中间体的脱硝作用。硝基化过程的第一步需要硝基，即将取代的硝基烷烃迈克尔加成到环戊烯酮上。然后可以将其直接去除，或还原成胺后或通过Nef反应获得的酮去除。
• Baiocchi, Leandro; Giannangeli, Marilena; Bonanomi, Michele, Gazzetta Chimica Italiana, 1985, vol. 115, # 4, p. 199 - 216
  作者：Baiocchi, Leandro、Giannangeli, Marilena、Bonanomi, Michele、Picconi, Giuseppe、Ridolfi, Pietro

  DOI：——

  日期：——
• Syntheses of the terpenoid precursors cyclopent-2-enone and cyclohex-2-enone diesters
  作者：I. Kádas、V. Morvai、G. Árvai、L. Tőke、Á. Szöllősy、G. Tóth、M. Bihari

  DOI：10.1007/bf00811764

  日期：1995.1

  Two reaction pathways were elaborated for the practical and convenient synthesis of the title compounds: The first route applies a bromination-dehydrobromination sequence to introduce the double bond into 1-alkoxycarbonyl-2-oxocycloalkylacetic and propionic esters (4a-c, 7a,b). The application of 2,6-lutidine for dehydrobromination of alpha-bromocycloalkanones diesters (5a-c, 8a, b) provides sufficient selectivity to carry out this step without affecting the sensitive ester group. Alternative pathways, involving Michael reaction of diethyl 2-acetylsuccinate or -glutarate with acrolein and subsequent intramolecular aldol condensation, are presented in the case of cyclohex-2-enone derivatives 2a, b.
• Stereochemistry and synthesis of precursors to strigol analogues
  作者：Gábor Tóth、Judit Halász、István Kádas、Géza Árvai、Katalin Mikló、Rainer Haessner

  DOI：10.1002/mrc.1260330306

  日期：1995.3

  The relative configuration and conformation of the 8‐methyl‐5‐nitro‐1‐oxo‐Δ8(8a)‐octahydronaphthalene isomers were elucidated by various 1H and 13C NMR methods. The structure of the tricyclic by‐products was also determined.

  8-甲基-5-硝基-1-氧代-Δ8(8a)-八氢萘异构体的相对构型和构象通过各种 1H 和 13C NMR 方法阐明。还确定了三环副产物的结构。