4-methylenespirohexane | 137072-99-2

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 4-methylenespirohexane
• 英文别名: 4-methylenespiro<2.3>hexane；4-methylenespiro[2,3]hexane；Spiro[2.3]hexane, 4-methylene-；6-methylidenespiro[2.3]hexane
• CAS: 137072-99-2
• 化学式: C₇H₁₀
• 分子量: 94.1564
• InChiKey: PEUOGYZGFUSFQB-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：

  4-methylenespirohexane 在 rhenium(VII) oxide on aluminum oxide 、 四乙基铅 作用下， 反应 2.0h， 生成 4-(2-(1-(丙-1-烯-2-基)环丙基)亚乙基)螺[2.3]己烷
  参考文献：
  名称：

  Synthesis of energetic compounds via the metathesis reaction of 4-methylenespiro[2,3]hexane

  摘要：

  Transformations of methylenespiro[2,3]hexane (MSH) on a heterogeneous rhenium-alumina metathesis (disproportionation) catalyst were studied. It was found that, owing to a significant difference in the stability of carbenic complexes of methylene and disubstituted carbenes, MSH undergoes isomerization to 4-methylspiro[2,3]hex-4-ene followed by their cometathesis yielding bis(spiro[2,3]hexylidene-4). The feasibility of selective cometathesis of MSH and dicyclobutylidene on the rhenium-alumina catalyst resulting in the formation of 4-cyclobutylidenespiro[2,3]hexane was shown.

  DOI：

  10.1134/s0965544108040099
• 作为产物：
  描述：

  螺[2.3]己-4-酮 、 亚甲基三苯基膦烷 以 二甲基亚砜 为溶剂， 反应 0.5h， 以92%的产率得到4-methylenespirohexane
  参考文献：
  名称：

  Strain Energies in [n]Triangulanes and Spirocyclopropanated Cyclobutanes: An Experimental Study

  摘要：

  The enthalpies of formation for trispiro[2.0.0.2.1.1]nonane (3), [3]rotane (4), n-heptyl[3]rotane (6), spiro-[2.3]hexane (7), and the isomeric dispiro[2.0.2.2]octane (8) and dispiro[2.1.2.1]octane (9), as well as [4]rotane (10), have been determined by measuring their heats of combustion in a microcalorimeter; these values and the strain energies (SE) derived from them are compared with values from MM2/MM3 calculations. The results confirm previously reported theoretical and experimental values for spiropentane and establish an additivity scheme for strain energies in all sorts of [n]triangulanes, with an excessive strain energy increment of 8.6 kcal/mol per spiro carbon atom. Such an additional strain increment is virtually nonexistent for 7 (0.8 +/- 0.4 kcal/mol), 8 (0.6 +/- 0.2 kcal/mol), and 9 (0.3 +/- 0.3 kcal/mol) but is significant for 10, with Delta SE = 2.4 +/- 0.5 kcal/mol. Therefore, a simple additivity of strain energies without an excess increment can be employed for spirocyclopropanated cyclobutanes as well as larger rings including [n]rotanes (n > 4).

  DOI：

  10.1021/ja00153a006

文献信息

• Catalytic cyclopropanation of methylenecyclobutanes using ethyl nitrodiazoacetate. Synthesis of spirohexane amino acids
  作者：Nikolai V. Yashin、Elena B. Averina、Sergei M. Gerdov、Tamara S. Kuznetsova、Nikolai S. Zefirov

  DOI：10.1016/j.tetlet.2003.09.083

  日期：2003.11

  The reaction of ethyl nitrodiazoacetate with a series of methylenecyclobutanes was studied and both [1+2]- and [2+3]-cycloaddition pathways were observed depending on olefin structure. Amino acids of a spirohexane type were synthesized from methylenecyclobutanes by a three-step synthesis.

  研究了硝基重氮乙酸乙酯与一系列亚甲基环丁烷的反应，并根据烯烃的结构观察到了[1 + 2]-和[2 + 3]-环加成途径。通过三步合成，从亚甲基环丁烷合成螺己烷型氨基酸。
• Diethyl [Nitro(diazo)methyl]phosphonate: Synthesis and Reactivity towards Alkenes
  作者：Nikolai Yashin、Andrey Chemagin、Yuri Grishin、Tamara Kuznetsova、Nikolai Zefirov

  DOI：10.1055/s-0029-1217103

  日期：2010.1

  A novel and convenient synthesis of diethyl [nitro(di­azo)methyl]phosphonate and its reactions with various alkenes are described. The reactivity of diethyl [nitro(diazo)methyl]phosphonate is shown to be dependent on the structure of the alkene. A number of cyclopropyl α-nitrophosphonates were obtained. diazo compounds - phosphonates - alkenes - cyclopropanation - carbenes

  描述了[硝基（重氮）甲基]膦酸二乙酯的新颖和方便的合成及其与各种烯烃的反应。已显示[硝基（重氮）甲基]膦酸二乙酯的反应性取决于烯烃的结构。获得了许多环丙基α-硝基膦酸酯。 重氮化合物-膦酸酯-烯烃-环丙烷化-卡宾
• Synthesis of cyclopropylphosphonates on the basis of catalytic [1+2] cycloaddition of diazomethylphosphonic esters to alkenes
  作者：N. V. Yashin、A. V. Chemagin、Yu. K. Grishin、T. S. Kuznetsova、N. S. Zefirov

  DOI：10.1134/s0012500813060037

  日期：2013.6
• Magerramov, A. M.; Gyul'akhmedov, L. M.; Sadovaya, N. K., Journal of Organic Chemistry USSR (English Translation), 1990, vol. 26, # 11, p. 2014 - 2021
  作者：Magerramov, A. M.、Gyul'akhmedov, L. M.、Sadovaya, N. K.、Zhdankin, V. V.、Koz'min, A. S.

  DOI：——

  日期：——
• Three-component Reactions of Tetranitromethane with Olefins
  作者：E. B. Averina、E. M. Budynina、O. A. Ivanova、Yu. K. Grishin、S. M. Gerdov、T. S. Kuznetsova、N. S. Zefirov

  DOI：10.1023/b:rujo.0000034936.03355.d1

  日期：2004.2

  Three-component reactions of tetranitromethane with two different olefins taken in equimolar amounts are procedures fit for preparation of 3,3-dinitroisoxalidines of a mixed composition.