7-methylenedispiro<2.0.2.1>heptane | 50874-25-4

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 7-methylenedispiro<2.0.2.1>heptane
• 英文别名: 7-Methylendispiro<2.0.2.1>heptan；7-methylenedispiro[2.0.2.1]heptane；Methylene<4>UT；7-Methylendispiro[2.0.2.1]heptan；7-Methylidenedispiro[2.0.2~4~.1~3~]heptane；7-methylidenedispiro[2.0.24.13]heptane
• CAS: 50874-25-4
• 化学式: C₈H₁₀
• 分子量: 106.167
• InChiKey: PQFGODFYRQJZOI-UHFFFAOYSA-N

物化性质

• 沸点：
  120-122 °C
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  8
• 可旋转键数：
  0
• 环数：
  3.0
• 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：

  7-methylenedispiro<2.0.2.1>heptane 以 邻二氯苯 、 苯 为溶剂， 反应 9.0h， 生成 5-(2,4,6-trimethylphenyl)-4-azadispiro[2.0.2.4]dec-5-en-7-one
  参考文献：
  名称：

  Studies on the Synthesis of Aza Analogues of Illudins by Cycloadditions to Highly Strained Methylenecyclopropanes

  摘要：

  A series of 3-spirocyclopropane-tetrahydropyrid-4-ones has been synthesized by the method consisting of nitrone cycloaddition to bicyclopropylidene and thermal rearrangement of the adducts. Regioisomeric 5-spirocyclopropanetetrahydropyrid-4-ones and 5-spirocyclopropanedihydropyrid-4 ones were instead obtained by cycloaddition of nitrones and nitrile oxides, respectively, to methylenespiropentane, followed by thermal rearrangement. Methylenedispiro[2.0.2.1]heptane gave, in turn, 5,6-bis(spirocyclopropane)dihydropyrid-4 The new compounds were prepared as simple aza analogues of the cytotoxic natural products illudins and ptaquiloside in order to study their activity in cleaving a DNA plasmid. The activities shown by several of the compounds are moderate, but from a comparative qualitative analysis of the results a useful structure-activity relationship for this new class of compounds could be derived.

  DOI：

  10.1021/jo990873f
• 作为产物：
  描述：

  7-chloro-7-methyldispiro<2.0.2.1>heptane 在 potassium tert-butylate 作用下， 以 二甲基亚砜 为溶剂， 生成 7-methylenedispiro<2.0.2.1>heptane
  参考文献：
  名称：

  Yufit, D.S.; Lukin, K.A.; Kozhushkov, S.I., Doklady Chemistry, 1991, vol. 320, # 1-3, p. 288 - 292

  摘要：

  DOI：

文献信息

• Relative Stabilities of Spirocyclopropanated Cyclopropyl Cations
  作者：Sergei I. Kozhushkov、Thomas Späth、Monica Kosa、Yitzhak Apeloig、Dmitrii S. Yufit、Armin de Meijere

  DOI：10.1002/ejoc.200300440

  日期：2003.11

  the ring-retained product 25 (66%) along with the ring-opened product 26 (33%). Apparently, an increasing number of spiro-annelated three-membered rings stabilizes a cyclopropyl cation against ring opening under solvolysis conditions. The rate of solvolysis, however, is only slightly affected by this spiroannelation, as the rate coefficient for the triflate 3 in sodium acetate-buffered methanol was determined

  二螺[2.0.2.1]庚-1-基三氟甲磺酸酯(3)、7-溴-7-苯基二螺[2.0.2.1]庚烷(4)和7-氯-7-苯硫基二螺[2.0.2.1]庚烷(6)分别为分别以 50%、77% 和 90% 的总收率由双环亚丙基 (5) 制备。7-溴-7-环丙基二螺[2.0.2.1]庚烷(8)和7-溴-7-甲基二螺[2.0.2.1]庚烷(11)是通过7-环亚丙基-(7)和7-亚甲基二螺[2.0.2.1]庚烷的氢溴化得到的。 2.0.2.1]庚烷 (10)（分别为 78% 和 95%）。triangulane 衍生物 4、6 和 8 的甲醇分解以及 6 的乙酰化都在保留二螺[2.0.2.1]庚烷骨架的情况下进行，产生相应的 7-取代的 7-甲氧基二螺[2.0.2.1]庚烷 15、21 和23 以及 7-乙酰氧基-7-苯基硫基二螺[2.0.2.1]庚烷 22 的产率分别为 90、100、100 和 88%。1-溴-1-环丙基环丙烷
• Reactivities of Methylenetriangulanes and Spirocyclopropanated Bicyclopropylidenes toward Bromine. Relative Stabilities of Spirocyclopropanated versus Methyl-Substituted Bromonium Ions
  作者：Sergei Kozhushkov、Thomas Späth、Torsten Fiebig、Bernard Galland、Marie-Francoise Ruasse、Prince Xavier、Yitzhak Apeloig、Armin de Meijere

  DOI：10.1021/jo0162686

  日期：2002.6.1

  rings enhances the rate of bromination and stabilizes the intermediate cyclopropyl bromonium cations against ring opening in the course of bromine addition. Calculations at the B3LYP/6-311G(d,p) level show that unsymmetrical bromonium ions are the intermediates, and that they are stabilized by the spiroannelation with cyclopropane rings. The bromonium ion derived from 1 is less stable by 6.3 kcal mol-1

  在25℃下在甲醇中向亚甲基环丙烷（1），双环亚丙基（2）和螺环丙烷化的亚甲基环丙烷和双环亚丙基3-6中的溴加成基本上以与相应的低聚甲基取代的乙烯相同的速率进行。越来越多的螺环氮化三元环提高了溴化速率，并稳定了中间体环丙基溴阳离子对溴的添加过程中的开环。在B3LYP / 6-311G（d，p）水平进行的计算表明，不对称的溴离子是中间体，并且它们通过与环丙烷环的螺线环化反应得以稳定。与异丁烯相比，衍生自1的溴离子的稳定性差6.3 kcal mol-1。3和4中的一个或两个螺环丙烷环分别以9.6和16.4 kcal mol-1稳定相应的溴离子，而乙烯基环丙烷（7）和1,1-二环丙基乙烯（8）中的一个或两个α-环丙基取代基稳定相应的溴离子分别为13和29 kcal mol-1。所有研究的烯烃的实验溴化速率与相应的溴离子的相对能量计算得很好相关（r2 = 0.93）。在亚甲基环丙烷1、3和4（r2 =
• Fitjer, Lutz, Chemische Berichte, 1982, vol. 115, # 3, p. 1047 - 1060
  作者：Fitjer, Lutz

  DOI：——

  日期：——
• Zefirov, N. S.; Lukin, K. A.; Kozhushkov, S. I., Journal of Organic Chemistry USSR (English Translation), 1989, vol. 25, # 2.1, p. 278 - 284
  作者：Zefirov, N. S.、Lukin, K. A.、Kozhushkov, S. I.、Kuznetsova, T. S.、Domarev, A. M.、Sosonkin, I. M.

  DOI：——

  日期：——
• Branched triangulanes: general strategy of synthesis
  作者：N. S. Zefirov、S. I. Kozhushkov、B. I. Ugrak、K. A. Lukin、O. V. Kokoreva、D. S. Yufit、Y. T. Struchkov、Stephan Zoellner、Roland Boese、Armin De Meijere

  DOI：10.1021/jo00028a054

  日期：1992.1

  A general synthetic strategy for the construction of branched triangulanes (BTs) (spirocondensed polycyclopropanes) has been elaborated. The synthetic utility of the method is illustrated by the synthesis of some members of the [5]- and [6]BT families, especially 13a,b and 14. An independent synthesis of the perspirocyclopropanated spiropentane 14 is also presented.