cis-3,8-Dicarbomethoxy-3,8-dihydroheptalene | 160426-42-6

• 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: cis-3,8-Dicarbomethoxy-3,8-dihydroheptalene
• 英文别名: dimethyl cis-3,8-dihydroheptalene-3,8-dicarboxylate；cis-3,8-dihydroheptalene-3,8-dicarboxylate
• CAS: 160426-42-6
• 化学式: C₁₆H₁₆O₄
• 分子量: 272.301
• InChiKey: JROUHYKASYTRAA-OKILXGFUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.11
• 重原子数：
  20.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  cis-3,8-Dicarbomethoxy-3,8-dihydroheptalene 在 氧气 、 tetraphenylporphyrin 作用下， 以 四氯化碳 为溶剂， 反应 2.0h， 以27%的产率得到dimethyl 13,14-dioxatetracyclo[7.3.2.0^2,8.0^10,12]tetradeca-2(8),3,6-triene-5,11-dicarboxylate
  参考文献：
  名称：

  Pyramidalized Double Bonds Containing Endoperoxide Linkages:  Photooxygenation of Dimethyl cis-3,8-Dihydroheptalene-3,8-dicarboxylate

  摘要：

  Diels-Alder cyclo;addition utilizing singlet oxygen as the dienophile with dimethyl cis-3,8-dihydraheptalene-3,8-dicarboxylate (5) has been investigated, and monoaddition product 7 has been isolated. The addition of a second singlet oxygen to the cycloheptatriene unit in 7 gave syn-bis(norcaradiene) bis(endoperoxide) 4. H-1 NMR spectral studies and theoretical calculations indicate the increased pyramidalization in syn-4 compared with carbon analogue. The increased pyramidalization results from hyperconjugation between the central pi-bond and the four adjacent C-O bonds and by rehybridization at C3, C4, C5, and C6. Furthermore, the increased reactivity for syn-4, which is probably arising from further folding of the central double band, is also in agreement with theoretical calculations.

  DOI：

  10.1021/jo990393o
• 作为产物：
  描述：

  3,8-Dihydro-heptalene-3,8-dicarboxylic acid dimethyl ester 在 silica gel (741-Kieselgel 60 HF_254-366) 作用下， 以 氯仿 为溶剂， 反应 96.0h， 以61%的产率得到cis-3,8-Dicarbomethoxy-3,8-dihydroheptalene
  参考文献：
  名称：

  Synthesis of a New System Containing a Pyramidalized Double Bond: cis-Dicarbomethoxydihydroheptalene and Its Reaction with Benzyne

  摘要：

  The strained system syn-1 was the object of synthetic and structural studies because of its double bond pyramidalization. The starting material, cis-3, 8-dicarbomethoxy-3,8-dihydroheptalene, was synthesized by two different approaches. Addition of ethyl diazoacetate then gave syn-addition product 2. Transesterification and NBS-bromination followed by Zn-AcOH elimination resulted in the formation of cis-dihydroheptalene 5, which was also synthesized by silica gel catalyzed isomerization of the trans-5 isomer. Addition of benzyne to cis-5 gave the target compound syn-1, whose structure was investigated by X-ray diffraction. These data show its pyramidalization angle to be 16.8 degrees.

  DOI：

  10.1021/jo00109a012

文献信息

• Synthesis of new substituted dihydroheptalene derivatives: SiO<sub>2</sub>- and base-catalyzed rearrangement of dimethyl <i>trans</i>-3,8-dihydroheptalene-3,8-dicarbo×ylate
  作者：Nurullah Saraçoglu、Abdullah Menzek、Armagan Kinal、Metin Balci

  DOI：10.1139/cjc-79-1-35

  日期：——

  Dimethyl trans-3,8-dihydroheptalene-3,8-dicarboxylate (trans-3) isomerizes to dimethyl cis-3,8-dihydroheptalene-3,8-dicarboxylate (cis-3) upon treatment with SiO2. On the other hand, base-catalyzed reaction of trans-3 undergoes a direct 1,3-intramolecular proton shift to give 6 at room temperature in 5 min. Prolonged reaction time formed isomers 7 and 8 in a ratio of 4:1. AM1 calculations indicate that the isomer 8, which is formed as minor product, has a lower heat of formation (-99.34 kcal mol(1)) than that of the major isomer 7 (-92.05 kcal mol(1)). However, when a similar reaction was performed at 100 degreesC, the thermodynamically more stable isomer 8 was formed as the major product. Furthermore, cycloaddition reactions of these new dihydroheptalene derivatives 6 and 7 with different dienophiles have been studied. The mechanism has been discussed.