1-methylenespiro[2.3]hexane | 20036-34-4

• 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[2.3]hexane
• 英文别名: 1-Methylen<2.3>spirohexan；1-Methylen[2.3]spirohexan；Methylenespiro[2,3]hexane；2-methylidenespiro[2.3]hexane
• CAS: 20036-34-4
• 化学式: C₇H₁₀
• 分子量: 94.1564
• InChiKey: JKOBTKLXDUBEEF-UHFFFAOYSA-N

物化性质

• 沸点：
  111.7±7.0 °C(Predicted)
• 密度：
  0.92±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 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[2.3]hexane 在 2,2'-双(二苯基磷)联苯 作用下， 以 1,4-二氧六环 为溶剂， 反应 48.0h， 生成 2-vinyl-1,3-butadien
  参考文献：
  名称：

  Ruthenium-Catalyzed Hydroarylations of Methylenecyclopropanes: Mild C−H Bond Functionalizations with Conservation of Cyclopropane Rings

  摘要：

  Ring conservation was observed in the first catalytic intermolecular hydroarylation of methylenecyclopropanes via C-H bond functionalization, a remarkable reactivity mode for a transformation proceeding through (cyclopropylcarbinyl)metal intermediates.

  DOI：

  10.1021/ol8011875
• 作为产物：
  描述：

  环丙亚基环丁烷 生成 1-methylenespiro[2.3]hexane
  参考文献：
  名称：

  Thermal reorganizations of C6H8 hydrocarbons

  摘要：

  DOI：

  10.1021/ja00745a020

文献信息

• Competitive 1,2-C Atom Shifts in the Strained Carbene Spiro[3.3]hept-1-ylidene Explained by Distinct Ring-Puckered Conformers
  作者：Murray G. Rosenberg、Theodor Schrievers、Udo H. Brinker

  DOI：10.1021/acs.joc.6b02445

  日期：2016.12.16

  Spiro[3.3]hept-1-ylidene is a markedly strained carbene reaction intermediate that was generated by high-vacuum flash pyrolysis (HVFP) of the corresponding p-tosylhydrazone sodium salt. Five hydrocarbons were produced from the Bamford–Stevens reactant in 82% overall yield. The carbene undergoes two [1,2]-sigmatropic rearrangements via competing 1,2-C atom shifts. Ring-contraction yields cyclopropylidenecyclobutane

  螺[3.3]庚-1-亚基是一种显着拉紧的卡宾反应中间体，由相应的对甲苯磺酰hydr钠盐的高真空闪速热解（HVFP）产生。班福德-史蒂文斯反应物生产了五种烃，总产率为82％。卡宾通过竞争性的1,2-C原子位移经历了两个[1,2]-σ重排。环收缩产生环亚丙基环丁烷，而环扩展产生双环[3.2.0]庚-1（5）-烯。尽管形成了一些1-亚甲基螺[2.3]己烷，但是环的收缩是区域特异性的。它不在HVFP条件下源自卡宾。相反，它来自化学活化的环亚丙基环丁烷的亚甲基环丙烷型重排。类似地，一些化学活化的双环[3.2.0]庚-1（5）-烯经由环的开环重排为1，2-二亚甲基环戊烷。考虑到初级产物向次级产物的转化，相对产率表明，卡宾内的环收缩比环扩展占优势6.7：1。计算化学被用来评估这些重排的结构，构象，能量，应变能，过渡态和活化能，目的是解释产物的选择性。预计双环卡宾将采用与过渡态选择有关的四个不同的几何构象
• Reduction of 1-Nitrospiro[2.2]pentanecarboxylates: Convenient Synthesis of Novel Polyspirocyclic Cyclopropane Amino Acids
  作者：Tamara S. Kuznetsova、Nikolai V. Yashin、Elena B. Averina、Yuri K. Grishin、Nikolai S. Zefirov

  DOI：10.1055/s-2005-918514

  日期：——

  A facile method for the preparation of a series ofracemic spiropentane amino acids is described. An approach involving sequential catalytic cyclopropanation of polycyclic methylenecyclopropanes with nitrodiazoesters and reduction of the nitro group is described.

  描述了一种制备一系列外消旋螺戊烷氨基酸的简便方法。描述了一种涉及多环亚甲基环丙烷与硝基重氮酯的顺序催化环丙烷化和硝基还原的方法。
• Unusual methylation reaction of gem-bromofluorospiropentanes with methyllithium
  作者：Elena B. Averina、Kseniya N. Sedenkova、Ilya S. Borisov、Yuri K. Grishin、Tamara S. Kuznetsova、Nikolai S. Zefirov

  DOI：10.1016/j.tet.2009.05.032

  日期：2009.7

  A series of novel gem-bromofluorospiropentanes were synthesized and investigated in the reaction with methyllithium. Either substitution of the fluorine atom for a methyl group or rearrangement into methylated cyclobutene derivatives occurred under these conditions.

  合成了一系列新型的宝石-溴氟螺戊烷，并与甲基锂反应进行了研究。在这些条件下，要么发生氟原子被甲基取代，要么发生重排成甲基化的环丁烯衍生物。
• Carbenoid rearrangement of gem-dihalogenospiropentanes
  作者：Elena B. Averina、Rashad R. Karimov、Kseniya N. Sedenkova、Yurii K. Grishin、Tamara S. Kuznetzova、Nikolai S. Zefirov

  DOI：10.1016/j.tet.2006.06.086

  日期：2006.9

  A skeletal rearrangement of dihalogenospiropentanes in the presence of alkyllithium reagents has been systematically studied using a number of gem-dibromospiropentanes. The scope and limitations of this carbenoid rearrangement are outlined and its mechanism is discussed. (c) 2006 Elsevier Ltd. All rights reserved.
• gem-Bromochlorospiropentane reactivity toward methyllithium: an unusual carbenoid rearrangement
  作者：Kseniya N. Sedenkova、Elena B. Averina、Yuri K. Grishin、Tamara S. Kuznetzova、Nikolai S. Zefirov

  DOI：10.1016/j.tet.2010.07.054

  日期：2010.10

  A skeletal carbenoid rearrangement of the gem-bromochlorospiropentanes in the presence of methyllithium has been studied. The synthetic and mechanistic aspects of this rearrangement as well as the influence of the halogen atom nature on the reaction pathway are discussed. (C) 2010 Elsevier Ltd. All rights reserved.