1-methylenespiro[3.3]heptane | 675877-39-1

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1-methylenespiro[3.3]heptane
• 英文别名: 3-Methylidenespiro[3.3]heptane
• CAS: 675877-39-1
• 化学式: C₈H₁₂
• 分子量: 108.183
• InChiKey: PWGLDWBGMCUAFP-UHFFFAOYSA-N

物化性质

• 沸点：
  139.6±7.0 °C(Predicted)
• 密度：
  0.91±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  1-methylenespiro[3.3]heptane 在 2,4,6-三甲基吡啶 、 三氟甲磺酸酐 、 (-)-diisopinocamphenylborane chloride 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 26.75h， 生成 (5S,10S)-(+)-trispiro[3.0.0.3.2.2]tridecan-10-ol
  参考文献：
  名称：

  A new approach to helical primary structures of four-membered rings: (P)- and (M)-tetraspiro[3.0.0.0.3.2.2.2]hexadecane

  摘要：

  A new approach to helical primary structures of four-membered rings uses a cycloaddition of a trimethylenketeniminium salt to suitable tailored methylenecyclobutanes to assemble the desired carbon framework. The results are short and effective syntheses of (M)-trispiro[3.0.0.3.2.2]tridecane [(M-5], and (P)- and (M)-tetraspiro[3.0.0.0.3.2.2.2]hexadecane [(P)- and (M)-24]. Unlike helices of three-membered rings, the specific rotation decreases, as the length of the helix increases. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.11.081
• 作为产物：
  描述：

  螺[3.3]庚烷-1-酮 、 甲基三苯基溴化膦 在 potassium tert-butylate 作用下， 以 乙醚 为溶剂， 反应 0.5h， 生成 1-methylenespiro[3.3]heptane
  参考文献：
  名称：

  A new approach to helical primary structures of four-membered rings: (P)- and (M)-tetraspiro[3.0.0.0.3.2.2.2]hexadecane

  摘要：

  A new approach to helical primary structures of four-membered rings uses a cycloaddition of a trimethylenketeniminium salt to suitable tailored methylenecyclobutanes to assemble the desired carbon framework. The results are short and effective syntheses of (M)-trispiro[3.0.0.3.2.2]tridecane [(M-5], and (P)- and (M)-tetraspiro[3.0.0.0.3.2.2.2]hexadecane [(P)- and (M)-24]. Unlike helices of three-membered rings, the specific rotation decreases, as the length of the helix increases. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.11.081

文献信息

• Pseudohelical and Helical Primary Structures of 1,2-Spiroannelated Four- and Five-Membered Rings:  Syntheses and Chiroptical Properties
  作者：Tien Widjaja、Lutz Fitjer、Aritra Pal、Hans-Georg Schmidt、Mathias Noltemeyer、Christian Diedrich、Stefan Grimme

  DOI：10.1021/jo7017558

  日期：2007.11.1

  The pseudohelical hydrocarbons (R)-6, (S)-7, and (R)-8 and the helical hydrocarbon (P)-9, formally derived from the helical hydrocarbon (P)-4 by stepwise replacement of each of the four-membered rings by a five-membered ring, have been prepared. Their optical rotations vary systematically, both in magnitude and sign. Of the extremes, (P)-4 represents the usual case of a right-handed dextrorotatory

  伪螺旋烃（R）-6，（S）-7和（R）-8和螺旋烃（P）-9是通过逐步置换四种烃的形式正式衍生自螺旋烃（P）-4的五元环的五元环已经准备好了。它们的旋光度在大小和符号上都有系统的变化。在极端情况下，（P）-4代表右旋右旋螺旋的通常情况，而（P）-9代表代表右旋左旋螺旋的异常情况。为了使这些事实合理化，DFT计算了（P的旋转功率）已完成三元，四元和五元环的螺旋。结果表明，三元环的刚性螺旋与实验数据非常吻合，并且始终显示四元和五元环的柔性螺旋的正确符号和量级，Boltzmann平均旋光度为最多必须使用六个conformer。在后者的共形体中，内球键的一组大二面角对应于高的比旋度，而一组小二面角对应于低的比旋度。结果，玻尔兹曼平均值明显取决于所涉及的构象异构体的几何形状和重量。
• A new approach to helical primary structures of four-membered rings: (P)- and (M)-tetraspiro[3.0.0.0.3.2.2.2]hexadecane
  作者：Lutz Fitjer、Andreas Kanschik、Ralf Gerke

  DOI：10.1016/j.tet.2003.11.081

  日期：2004.1

  A new approach to helical primary structures of four-membered rings uses a cycloaddition of a trimethylenketeniminium salt to suitable tailored methylenecyclobutanes to assemble the desired carbon framework. The results are short and effective syntheses of (M)-trispiro[3.0.0.3.2.2]tridecane [(M-5], and (P)- and (M)-tetraspiro[3.0.0.0.3.2.2.2]hexadecane [(P)- and (M)-24]. Unlike helices of three-membered rings, the specific rotation decreases, as the length of the helix increases. (C) 2003 Elsevier Ltd. All rights reserved.