2,3-bis<3-(1-methylethylidene)cyclopenta-1,4-diene>-2,3-dimethylbutane | 123533-48-2

• 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: 2,3-bis<3-(1-methylethylidene)cyclopenta-1,4-diene>-2,3-dimethylbutane
• 英文别名: 2,3-Dimethyl-2,3-bis[3-(methylethyliden)cyclopenta-1,4-dienyl]butan；2,3-dimethyl-2,3-bis(6,6-dimethylpentafulven-2-yl)butane；2,3-bis[3-(1-methylethylidene)cyclopenta-1,4-diene]-2,3-dimethylbutane；2-[2,3-Dimethyl-3-(3-propan-2-ylidenecyclopenta-1,4-dien-1-yl)butan-2-yl]-5-propan-2-ylidenecyclopenta-1,3-diene
• CAS: 123533-48-2
• 化学式: C₂₂H₃₀
• 分子量: 294.48
• InChiKey: VMIGFLQZBVEJBL-UHFFFAOYSA-N

物化性质

• 沸点：
  395.5±12.0 °C(Predicted)
• 密度：
  0.977±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.8
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  2,3-bis<3-(1-methylethylidene)cyclopenta-1,4-diene>-2,3-dimethylbutane 、 甲基锂 以34%的产率得到
  参考文献：
  名称：

  You Shaochun, Gubler Matthias, Neuenschwander Markus, Helv. chim. acta, 77 (1994) N 5, S 1346-1362

  摘要：

  DOI：
• 作为产物：
  描述：

  6,6-二甲基-5-亚甲基-1,3-环戊二烯 在 sodium ethanolate 、 sodium 作用下， 以 乙醚 、 乙醇 为溶剂， 反应 18.0h， 生成 2,3-bis<3-(1-methylethylidene)cyclopenta-1,4-diene>-2,3-dimethylbutane
  参考文献：
  名称：

  αω，-二（环戊二烯基）烷烃-二胺的氧化偶联†

  摘要：

  Cu II诱导的αω，-二（环戊二烯基）烷烃-二叠氮化物6（n = 2-5）的氧化偶合主要通过分子间途径进行，从而生成聚合物8，而分子内偶合6的产率很强。随着烷基链的碳原子数n的增加而降低（方案3）。对于n = 2，通过用Me基团取代6a（n = 2）的CH 2 CH 2桥的H原子，可以大大增强分子内偶联。在这种情况下，分子内偶联11 20（方案7）和22 23 + 24（方案8）的总收率分别达到59％和54％。迄今为止，所有研究的分子内偶联都立体选择性地进行，以得到具有固定椅子构象的C 2对称环己烷7a，20和23。这些结果很容易解释的，如果构象平衡ê⇄˚F可操作其中大取代基R假定增强笨拙-conformation ˚F其是用于分子内连接件的有利的构象。桥联的二氢五富瓦烯20和23在碱或酸催化下，将它们分别定量地重排至热力学上优选的桥连的五烯丙基戊烯27和28（方案9）。

  DOI：

  10.1002/hlca.19940770515

文献信息

• Oxidative Coupling of ??,-Di(cyclopentadienyl)alkane-diides
  作者：Shaochun You、Matthias Gubler、Markus Neuenschwander

  DOI：10.1002/hlca.19940770515

  日期：1994.8.10

  intramolecular couplings 11 20 (Scheme 7) and 22 23 + 24 (Scheme 8) are accomplished with a total yield of 59% and 54%, respectively. All the intramolecular couplings investigated so far proceed stereoselectively to give the C2-symmetrical cyclohexanes 7a, 20 and 23 with a fixed chair conformation. These results are easily explained, if a conformational equilibrium E ⇄ F is operative in which large

  Cu II诱导的αω，-二（环戊二烯基）烷烃-二叠氮化物6（n = 2-5）的氧化偶合主要通过分子间途径进行，从而生成聚合物8，而分子内偶合6的产率很强。随着烷基链的碳原子数n的增加而降低（方案3）。对于n = 2，通过用Me基团取代6a（n = 2）的CH 2 CH 2桥的H原子，可以大大增强分子内偶联。在这种情况下，分子内偶联11 20（方案7）和22 23 + 24（方案8）的总收率分别达到59％和54％。迄今为止，所有研究的分子内偶联都立体选择性地进行，以得到具有固定椅子构象的C 2对称环己烷7a，20和23。这些结果很容易解释的，如果构象平衡ê⇄˚F可操作其中大取代基R假定增强笨拙-conformation ˚F其是用于分子内连接件的有利的构象。桥联的二氢五富瓦烯20和23在碱或酸催化下，将它们分别定量地重排至热力学上优选的桥连的五烯丙基戊烯27和28（方案9）。
• Stereoselectivity in the synthesis of tetramethylethano-bridged 3,3′-di-tert-butyltitanocene dichloride
  作者：Mark S. Erickson、Frank R. Fronczek、Mark L. McLaughlin

  DOI：10.1016/0022-328x(91)83282-9

  日期：1991.9

  Racemic and meso ansa-(2,3-dimethyl-2,3-butano)-3,3'-bis(1,1'-dimethylethyl)cyclopenta-1,3-dien-5-yl)titanium dichloride (5 and 4) were prepared in a 1:4 to 1:2 ratio by the addition of TiCl3.3THF to 2,3-bis[3-(1,1-dimethylethyl)-1,3-cyclopentadien-5-yl]-2,3-dimethylbutanedilithium (3) in THF with subsequent oxidation by HCl in a 44% yield. A 30% yield of the 1:1 racemic:meso ratio resulted when 3 was treated with titanocene dichloride in THF followed by carbon tetrachloride oxidation. In the attempts to synthesize the desired anti isomer, 3 was treated with in-situ generated racemic dichloro-1,1'-bi-2-naphtholatetitanium(IV) to give ansa-(2,3-dimethyl-2,3-butano)-anti-3,3'-bis(1,1-dimethylethyl)cyclopenta-1,3-dien-5-yl)titanium 1,1'-bi-2-naphtholate (6) in a 10-15% yield. 6 crystallized in a monoclinic space group P2(1)/c with a = 10.084(2) angstrom, b = 29.312(7) angstrom, c = 12.190(2) angstrom, beta = 99.37(2)degrees, V = 3555(2) angstrom3, and Z = 4. Refinement of 425 least squares variables converged to R = 0.044 and R(w) = 0.046 for 4153 observed reflections with I > 2-sigma(I). The molecule contains an approximate C2 axis of symmetry with the t-butyl groups anti to each other. The C(Cp)-C(t-butyl) bonds are displaced from the plane defined by the cyclopentadienyls by about 10-degrees.
• You Shaochun, Gubler Matthias, Neuenschwander Markus, Helv. chim. acta, 77 (1994) N 5, S 1346-1362
  作者：You Shaochun, Gubler Matthias, Neuenschwander Markus

  DOI：——

  日期：——
• Versuche zur Synthese von [2.2]- und [2.3]Cyclopentadienophanen
  作者：Marcel Fischer、Peter Bönzli、Brigitte Stofer、Markus Neuenschwander

  DOI：10.1002/(sici)1522-2675(19990908)82:9<1509::aid-hlca1509>3.0.co;2-e

  日期：1999.9.8

  The first [2.2]Cyclopentadienophane (= 2,2,3,3.8,8,9,9-octamethyltricyclo[8.2.1.1(4.7)]tetradecatetraene; 1b) has been synthesized (Scheme 5) by reductive coupling of 6,6-dimethylfulvens 3 --> 5 (50%) followed by base-induced twofold condensation of 1,2-di(cyclopentadienyl)-1,2-dimethylbutane 5 with acetone to give difulvene 15 (95%). Reductive coupling of 15 gives a complex mixture of tautomers of 16, 17, and 1b, which contains ca. 50% of thr target molecule 1b. Other synthetic attempts towards [2.2]cyclopentadienophanes 1a and 1b and [2.3]cyclopentadienophane 18 are discussed.