3-(cyclopentylmethyl)methylenecyclopentane

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 3-(cyclopentylmethyl)methylenecyclopentane
• 英文别名: 1-methylene-3-(cyclopentylmethyl)cyclopentane；1-(cyclopentylmethyl)-3-methylidenecyclopentane
• 化学式: C₁₂H₂₀
• 分子量: 164.291
• InChiKey: NSGUZPDYJLILQA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.92
• 重原子数：
  12.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  1,5-已二烯 在 二氯二茂锆 、 Bis(dimethylaluminium)oxid 作用下， 以 苯 为溶剂， 反应 24.0h， 生成 3-(cyclopentylmethyl)methylenecyclopentane
  参考文献：
  名称：

  调整活性茂金属齐格勒系统的特性，以潜在地用作有机合成中的碳-碳偶联催化剂

  摘要：

  多种弯曲的金属茂二氯化/甲基铝氧烷的催化剂，由二茂锆络合物衍生10，12-18，都在分子内烯烃的偶联反应，产生单体或二聚体的产品已采用。这是通过使用优化的反应条件实现的，该条件采用低底物浓度（1.0-1.8 M）和较长的反应时间。在这些特定条件下，将1，5-己二烯环二聚，得到1-亚甲基-3-（环戊基甲基）环戊烷（11）。1,6-庚二烯干净地转化为亚甲基环己烷，顺式-1,2-二乙烯基环戊烷（19）和顺式-1,2-二乙烯基环己烷（22））被环化以分别产生2-亚甲基双环[3.3.0]辛烷（20）和7-亚甲基双环[4.3.0]壬烷（23）。在许多情况下，环化产物伴随有源自双键变换反应的异构体，这些异构体通常在选择的特定反应条件下在这些催化剂体系中迅速发生，以使产物保持单体状态。

  DOI：

  10.1002/cber.19971300210

文献信息

• Salicylidene-imine-zirconium(IV) complexes in combination with methylalumoxane as catalysts for the conversion of hexa-1,5-diene: adjusting of the catalytic activity
  作者：Bernd Schweder、Dirk Walther、Thomas Döhler、Olaf Klobes、Helmar Görls

  DOI：10.1002/(sici)1521-3897(199911)341:8<736::aid-prac736>3.0.co;2-v

  日期：1999.11

  A variety of substituted Schiff base complexes of the composition ("salen")ZrCl2(thf)(1-21) were synthesized, with methylalumoxane ("MAO") activated and used for a systematic study of their catalytic activity towards hexa-1,5-diene ("salen": substituted salicylidene-ethylene-iminato ligands). Main product of the catalytic cycle is methylenecyclopentane. Dimers are only formed in minor amounts. The catalytic activity and selectivity of the Ziegler-Natta systems strongly depend on the nature and the position of the peripheric substituents in the Schiff base ligands. Electron-withdrawing substituents in para-position to the phenolate oxygen (5-position) decrease the catalytic activity. Improved activity and selectivity were obtained with electron-donating substituents in 5-position. Altering the ethylene bridge causes a lowering of the activity or inactivation. According to the X-ray analysis the metal center in the related complex (L)ZrCl2 (22) (L: N',N'-bis(ethylene)-N'-methyl-N,N"-bis(benzoylacetonatoimine) has a pentagonal-bipyramidal environment. The pentadentate Schiff base Ligand lies in the plane, and both chloro groups occupy the axial positions. In contrast to the catalytically active salene complexes 22 can not rearrange to form a species in which the both chlorides are cis to each other. Consequently 22 is catalytically inactive.