cyclopenta-1,3-dienyl-(1R,2S,5R)-4-methyl-1-(prop-2-yl)-cyclohexane | 891826-22-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: cyclopenta-1,3-dienyl-(1R,2S,5R)-4-methyl-1-(prop-2-yl)-cyclohexane
• 英文别名: cyclopenta-1,3-dienyl-(1S,2S,5R)-4-methyl-1-(prop-2-yl)-cyclohexane；C5H5-4-(1R,2S,5R-menthyl)；[(-)-menthylCpH]；(1S,2R,4R)-2-cyclopenta-1,4-dien-1-yl-4-methyl-1-propan-2-ylcyclohexane
• CAS: 891826-22-5
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: SJKXVWMRLOIOJI-SNPRPXQTSA-N

物化性质

• 沸点：
  273.8±7.0 °C(Predicted)
• 密度：
  0.906±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 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：

  氯化锆(IV) 、 cyclopenta-1,3-dienyl-(1R,2S,5R)-4-methyl-1-(prop-2-yl)-cyclohexane 在 n-BuLi 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 以30%的产率得到bis(η5((1R,2S,5R)-5-methyl-2-[prop-2-yl]-cyclohex-1-yl)cyclopentadienyl)-zirconium dichloride
  参考文献：
  名称：

  Kagan的薄荷基取代的二茂钛和二茂锆锆的合成方法改进，晶体结构比较和初步催化剂评估

  摘要：

  描述了1和2的改进的合成，其允许以催化应用所需的多克量获得这些络合物。比较了1和2的晶体结构，并讨论了对催化应用很重要的配体的构象偏好。评价复合物2作为碳镁反应的催化剂。

  DOI：

  10.1016/j.jorganchem.2005.10.026
• 作为产物：
  描述：

  (1Alpha,2Alpha,5β)-(+-)-5-甲基 在 sodium hydride 作用下， 以 四氢呋喃 、 吡啶 为溶剂， 反应 39.0h， 生成 cyclopenta-1,3-dienyl-(1R,2S,5R)-4-methyl-1-(prop-2-yl)-cyclohexane
  参考文献：
  名称：

  Kagan的薄荷基取代的二茂钛和二茂锆锆的合成方法改进，晶体结构比较和初步催化剂评估

  摘要：

  描述了1和2的改进的合成，其允许以催化应用所需的多克量获得这些络合物。比较了1和2的晶体结构，并讨论了对催化应用很重要的配体的构象偏好。评价复合物2作为碳镁反应的催化剂。

  DOI：

  10.1016/j.jorganchem.2005.10.026

文献信息

• A chiral menthyl cyclopentadienyl molybdenum tricarbonyl chloro complex: Synthesis, heterogenization on MCM-41/MCM-48 and application in olefin epoxidation catalysis
  作者：Marta Abrantes、Ayyamperumal Sakthivel、Carlos C. Romão、Fritz E. Kühn

  DOI：10.1016/j.jorganchem.2006.03.037

  日期：2006.7

  55 °C using chloroform as solvent. Results under homogeneous conditions prompted the authors to immobilize complex 1 on mesoporous MCM-41 and MCM-48 surfaces leading to the grafted materials AM-41CpMoChi and AM-48CpMoChi. The presence of the organometallic complexes in the materials was confirmed by powder X-ray diffraction, N2 adsorption/desorption isotherms, TEM, EA, FT-IR, 1H MAS NMR and TG-MS. AM-41CpMoChi

  络合物[（ - ） - menthylCp]的Mo（CO）3 Cl（上1）由钼（CO）的反应合成的3（EtCN）3与[（ - ） - menthylCpH]以产生氢化物[（ - ） - menthylCp]的Mo（CO）3 H.后一种化合物，然后用四氯化碳反应4，以形成[（ - ） - menthylCp]的Mo（CO）3 Cl（上1）。在叔丁基氢过氧化物（TBHP）的存在下，使用氯仿作为溶剂，在55°C的条件下，测试了化合物1作为顺式-环辛烯，苯乙烯和反式-β-甲基苯乙烯的环氧化催化剂。在均质条件下的结果促使作者固定了复杂的化合物1介孔MCM-41和MCM-48的表面导致接枝材料AM-41CpMoChi和AM-48CpMoChi。通过粉末X射线衍射，N 2吸附/解吸等温线，TEM，EA，FT-IR，1 H MAS NMR和TG-MS证实了材料中有机金属配合物的存在。还测试了AM-41Cp
• Mechanisms of Stereocontrol for Doubly Silylene-Bridged <i>C</i><i>_s</i>- and <i>C</i>₁-Symmetric Zirconocene Catalysts for Propylene Polymerization. Synthesis and Molecular Structure of Li₂[(1,2-Me₂Si)₂{C₅H₂-4-(1<i>R</i>,2<i>S</i>,5<i>R</i>-menthyl)}{C₅H-3,5-(CHMe₂)₂)}]·3THF and [(1,2-Me₂Si)₂{η⁵-C₅H₂-4-(1<i>R</i>,2<i>S</i>,5<i>R</i>-menthyl)}{η⁵-C₅H-3,5-(CHMe₂)₂}]ZrCl₂
  作者：Dario Veghini、Lawrence M. Henling、Terry J. Burkhardt、John E. Bercaw

  DOI：10.1021/ja982868j

  日期：1999.1.1

  Doubly [SiMe2]-bridged metallocenes (1,2-SiMe2)(2)eta(5)-C5H2-4-R}eta(5)-C5H-3,5-(CHMe2)(2)}ZrCl2 (R = H (1a), CHMe2 (1b), SiMe3 (1c), CHMe(CMe3) (1d), (+)-menthyl (1e)), when activated by methylaluminoxane (MAO), catalyze propylene polymerization with high activities. The preparations and X-ray structures of the dilithio salt of an enantiopure, doubly silylene-bridged bis(cyclopentadienyl) ligand, Li-2[(1,2-Me2Si)(2)-C5H2-4-(1R,2S,5R-menthyl)}(C5H-3,5-(CH as well as the corresponding zirconocene dichloride, [(1,2-Me2Si)(2)eta(5)-C5H2-4-( 1R,2S,5R-menthyl)}eta(5)-C5H-3,5-(CHMe2)(2)}]ZrCl2 (1e), are reported. The C-s,symmetric systems la-e are highly regiospecific and syndiospecific (>99.5%) in neat propylene. At lower propylene concentrations, polymers with lower molecular weights and tacticity (mostly m-type stereoerrors) are obtained. The microstructures of polymers produced under differing reaction conditions are consistent with stereocontrol dominated by a site epimerization process, an inversion of configuration at zirconium resulting from the polymer chain swinging from one side of the metallocene wedge to the other without monomer insertion. The relative importance of chain epimerization (at the beta carbon) has been established by parallel polymerization of 2-d(1)-propylene and d(0)-propylene with 1b/MAO at low propylene concentrations. The C-1-symmetric systems 1d,e/MAO display an unusual dependence of stereospecificity on propylene concentration, switching from isospecific to syndiospecific with increasing propylene pressure, consistent with a competitive unimolecular site epimerization process and a bimolecular chain propagation. The microstructures of the polypropylenes produced by 1d/MAO and 1e/MAO with [r] approximate to 50% resemble the hemiisotactic microstructure produced by Me2C(eta(5)-C5H3-3-Me)(eta(5)-C13H8)ZrCl2 (2b)/MAO. Contrastingly, the hemiisotactic polypropylene microstructure obtained with 2b/MAO is found to be maintained at all propylene concentrations examined.
• An improved synthesis of Kagan’s menthyl substituted titanocene and zirconocene dichloride, comparison of their crystal structures, and preliminary catalyst evaluation
  作者：Andreas Gansäuer、Sanjay Narayan、Noëllie Schiffer-Ndene、Harald Bluhm、J. Enrique Oltra、Juan Manuel Cuerva、Antonio Rosales、Martin Nieger

  DOI：10.1016/j.jorganchem.2005.10.026

  日期：2006.5

  An improved synthesis of 1 and 2 is described that allows access to these complexes in multigram quantities necessary for catalytic applications. The crystal structures of 1 and 2 are compared and the conformational preferences of the ligands, that are important for catalytic applications, are discussed. Complex 2 was evaluated as a catalyst for carbomagnesation reactions.

  描述了1和2的改进的合成，其允许以催化应用所需的多克量获得这些络合物。比较了1和2的晶体结构，并讨论了对催化应用很重要的配体的构象偏好。评价复合物2作为碳镁反应的催化剂。