(1R,2S,5R)-1-cyclopentadienyl-cis-5-methyl-trans-2-(2-propyl)cyclohexane | 139756-61-9

• 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: (1R,2S,5R)-1-cyclopentadienyl-cis-5-methyl-trans-2-(2-propyl)cyclohexane
• 英文别名: (+)-neomenthylcyclopentadiene；(1S,2R,4R)-2-cyclopenta-2,4-dien-1-yl-4-methyl-1-propan-2-ylcyclohexane
• CAS: 139756-61-9
• 化学式: C₁₅H₂₄
• 分子量: 204.356
• InChiKey: VSCSJIGNZYNECE-SNPRPXQTSA-N

物化性质

• 沸点：
  271.8±7.0 °C(Predicted)
• 密度：
  0.898±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 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：

  (1R,2S,5R)-1-cyclopentadienyl-cis-5-methyl-trans-2-(2-propyl)cyclohexane 在 ion-exchange resin 、 sodium hydride 作用下， 以 乙酸乙酯 为溶剂， 反应 17.5h， 生成 cis-2-neomenthyl-6-(5-undecyl-1,3-dioxan-2-yl)azulene
  参考文献：
  名称：

  The azulene ring as a structural element in liquid crystals

  摘要：

  介绍了一种合成苊系液晶的新方法，基于Hafner的程序，涉及吡啶盐与环戊二烯阴离子的反应。本文描述了利用这种方法制备多种液晶材料的过程。报道了在苊环的6位单取代和在2,6位双取代的变体。探讨了苊环作为核心或偶极末端结构元素的影响。6-(5-烷基-1,3-二恶烷-2-基)苊被证明具有近晶A相，而2-环己基-6-(5-十三烷基-1,3-二恶烷-2-基)苊显示了近晶A和B相。记录了这些材料的相态特性，并对其中一个代表性化合物的近晶A相进行了X射线测量。还简要回顾了苊类介晶的二向色性研究结果。

  DOI：

  10.1039/a606139g
• 作为产物：
  描述：

  (1Alpha,2Alpha,5β)-(+-)-5-甲基 、 alkaline earth salt of/the/ methylsulfuric acid 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 25.5h， 生成 (1R,2S,5R)-1-cyclopentadienyl-cis-5-methyl-trans-2-(2-propyl)cyclohexane
  参考文献：
  名称：

  Chiral Organolanthanides Designed for Asymmetric Catalysis. Synthesis, Characterization, and Configurational Interconversions of Chiral, C1-Symmetric Organolanthanide Halides, Amides, and Hydrocarbyls

  摘要：

  This contribution describes the synthesis, structural systematics, absolute configurations, and structural interconversions of a series of C-1-symmetric lanthanide chloro, hydrocarbyl, and amide complexes/precatalysts based on chiral chelating Me(2)Si(eta(5)-Me(4)C(5)) (eta(5)-C(5)H(3)R*)(2-) ligands [Me(2)SiCp''(R*Cp)](2-), where R* = (+)-neomenthyl, (-)-menthyl, and (-)-phenylmenthyl. The ligands are prepared in three steps from known chiral cyclopentadienes. Metalation of the chiral dienes followed by condensation with Me(4)C(5)Si(CH3)(2)Cl and in situ lithiation provides the dianions in nearly quantitative yield. Transmetalation of the lithiated ligands with anhydrous lanthanide trichlorides followed by ambient temperature ether workup provides Me(2)SiCp''(R*Cp)LnCl(2)Li(OEt(2))(2) complexes in high yield. For (R)-Me(2)SiCp'' [(+)-neomenthylCp]Lu(mu-Cl)(2)Li(OEt(2))(2): space group P2(1)2(1)2(1); a = 12.240(2), b = 12.876(2), and c = 24.387(5) Angstrom, (24 degrees C); Z = 4; R(F) = 0.0509. As established by NMR and circular dichroism, the diastereomerically pure chloro complexes can be epimerized in appropriate donor solvents to afford mixtures of (R)- and (S)-configurational isomers with the isomer ratio dependent on solvent, R*, and lanthanide ion. Selective epimerization allows enrichment in either antipode with diastereomerically pure complexes obtained in a single recrystallization. Li+ sequestering crown ethers inhibit epimerization. The temperature dependence of the (R) reversible arrow (S) equilibrium constant in THF yields Delta H = 1.7 +/- 0.3 kcal/mol and Delta S 3.6 +/- 0.8 eu for Me(2)SiCp''[(+)-neomenthylCp)Lu(mu-Cl)(2)Li(OEt(2))(2) and Delta H = 4.8 +/- 0.5 kcal/mol and Delta S = 13.4 +/- 0.5 eu for Me(2)SiCp''[(-)-menthylCp]Sm(mu-Cl)(2)Li(OEt(2))(2). The mechanism is proposed to involve reversible ring detachment to an intermediate LiCpR* complex. Alkylation or amidation with ME(SiMe(3))(2) (M = Li or K, E = CH; M = Na or K, E = N) yields the corresponding chiral hydrocarbyls and amides in high yield. For (R/S)-Me(2)SiCp''[(+)-neomenthylCp]YCH(SiMe(3))(2): space group P2(1); a 19.178(4), b = 8.736(1), and c = 21.391(5) Angstrom; beta = 97.62(;); Z = 4; R(F) = 0.071. For (R)-Me(2)SiCp''[(-)-menthylCp]SmCH(SiMe(3))(2) space group P1; a = 8.993(3), b = 12.738(2), and c 16.549(4) Angstrom; alpha = 86.04(2)degrees; beta = 82.81(2)degrees, gamma = 72.91(2)degrees; Z = 2; R(F) = 0.026.For (R)-Me(2)SiCp''[(-)-menthylCp]YCH(SiMe(3))(2); space group P2(1); a = 12.319(3), b = 15.707(4), and c = 18.693(5) Angstrom; beta 91.59)(2)degrees; Z = 4; R(F) = 0.054. For (S)-Me(2)SiCp''[(+)-neomenthylCp]SmN(SiMe(3))(2): space group P2(1); a = 9.122(2), b = 10.112(3), and c = 18.478(3) Angstrom; beta = 90.58(2)degrees; Z = 2; R(F) = 0.029, For (S)-Me(2)SiCp''[(-)-menthylCp]SmN(SiMe(3))(2): space group P2(1)2(1)2(1); a = 10.217(3), b = 19.103(6), and c = 19.456(7) Angstrom; Z = 4; R(F) = 0.044. For (R)-Me(2)SiCp''[(-)-menthylCp]YN(SiMe(3))(2); space group P1; a = 8.937(3), b = 12,397(6), and c = 16.673(7) Angstrom; alpha = 85.53(2)degrees, beta = 82.17(2)degrees, gamma = 74.78(2)degrees Z = 2; R(F) = 0.065. The preferred planar chiral configurations of these complexes can be largely understood on the basis of significant, crystallographically identifiable, nonbonded interactions between R* and the remainder of the molecule. The hydrocarbyl and amide complexes are configurationally stable in toluene at 60 degrees C for many hours but undergo facile epimerization in the presence of primary alkyl amines, presumably via reversible Cp protonation/detachment. The hydrocarbyl complexes undergo rapid hydrogenolysis at ambient temperature, with retention of configuration, to yield the corresponding hydrides.

  DOI：

  10.1021/ja00101a047