1,4,5,5-Tetramethyl-cyclopentadien | 4249-11-0

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: 1,4,5,5-Tetramethyl-cyclopentadien
• 英文别名: 1,4,5,5-Tetramethylcyclopentadiene；1,4,5,5-tetramethylcyclopenta-1,3-diene
• CAS: 4249-11-0
• 化学式: C₉H₁₄
• 分子量: 122.21
• InChiKey: LSFQBLLDQCVIGF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  1,4,5,5-Tetramethyl-cyclopentadien 在 氢气 作用下， 生成 cis-1,2,2,3-Tetramethyl-cyclopentan
  参考文献：
  名称：

  Descotes,G. et al., Bulletin de la Societe Chimique de France, 1968, p. 382 - 384

  摘要：

  DOI：
• 作为产物：
  描述：

  5,6-二甲基庚-5-烯-2-酮 在 aluminum oxide 作用下， 生成 1,4,5,5-Tetramethyl-cyclopentadien
  参考文献：
  名称：

  Descotes,G. et al., Bulletin de la Societe Chimique de France, 1968, p. 382 - 384

  摘要：

  DOI：

文献信息

• Rhodium catalysed decarbonylation of optically active campholenal analogues
  作者：C. Chapuis、B. Winter、K.H. Schulte-Elte

  DOI：10.1016/s0040-4039(00)60025-4

  日期：1992.10

  (+)-1a–d were decarbonylated with a catalytic amount of Rh/Al2O3 with only slight racemization. Experiment with other catalysts showed that racemization increases with the ability of the metal to form a π-allyl complex and to catalyse the hydrogenation of the β-elimination side product. (Ph3P)3RhCl gave the best results.

  用催化量的Rh / Al 2 O 3进行去羰基化的喜树碱类似物（+）- 1a–d，仅出现少量外消旋作用。用其他催化剂进行的实验表明，外消旋作用随金属形成π-烯丙基络合物和催化β-消除副产物氢化的能力而增加。（Ph 3 P）3 RhCl效果最佳。
• Substitution in the cyclopentadienide anion series
  作者：S. McLean、P. Haynes

  DOI：10.1016/s0040-4020(01)93888-8

  日期：1965.1
• Cyclic unsaturated compounds
  作者：V. A. Mironov、A. P. Ivanov、A. A. Akhrem

  DOI：10.1007/bf00850989

  日期：1973.2
• Photosensitized electron transfer from azoalkanes: generation, fragmentation, and rearrangement of radical cations structurally related to dicyclopentadiene
  作者：Waldemar Adam、Juergen Sendelbach

  DOI：10.1021/jo00072a008

  日期：1993.9

  The azoalkanes 1a-c extrude nitrogen upon photosensitized electron transfer (PET) to yield 1,3-radical cation intermediates 2.+, which undergo interesting transformations. Electron back transfer (BET) affords the unrearranged housanes 2, but significant rearrangement to dicyclopentadiene derivatives 3 occurs prior to BET. In some cases, fragmentation to cyclopentadienes 4 is observed, a cycloreversion that occurs at the 1,3-radial cation stage rather than through the corresponding 1,3-biradical intermediates. The diphenyl-substituted azoalkane la affords high yields of the symmetric cyclopentadiene 4a, while the alkyl-substituted lb produces only small amounts of a rearranged cyclopentadiene 4'b. The housanes 2a,b are also oxidized by PET, but are more reluctant to rearrange. Strong electron acceptors such as triphenylpyrylium tetrafluoroborate (TPT) or cosensitization with biphenyl (Ph2) must be utilized to induce rearrangement to 3a,b and fragmentation to 4 and 4'.