1,1'-{2-[4-methyl-1,3-pentadien-1-yl]-1,1-cyclopropanediyl}dibenzene | 1133909-74-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1,1'-{2-[4-methyl-1,3-pentadien-1-yl]-1,1-cyclopropanediyl}dibenzene
• 英文别名: 1,1-diphenyl-2-(4-methylpenta-1,3-dienyl)cyclopropane
• CAS: 1133909-74-6
• 化学式: C₂₁H₂₂
• 分子量: 274.406
• InChiKey: TYRFDKBXZMHAKH-UHFFFAOYSA-N

物化性质

• 沸点：
  385.7±42.0 °C(Predicted)
• 密度：
  1.060±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.52
• 重原子数：
  21.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  1,1'-{2-[4-methyl-1,3-pentadien-1-yl]-1,1-cyclopropanediyl}dibenzene 在 氧气 、 tetraphenylporphyrin 作用下， 以 四氯化碳 、 二氯甲烷 为溶剂， 反应 0.5h， 生成 二苯甲酮
  参考文献：
  名称：

  On the mechanism of the [4+2] cycloaddition of 1Ο2 with 1,3-dienes: Identifying the putative biradical/dipolar intermediate by employing the gem-diphenylcyclopropyl group as a mechanistic probe

  摘要：

  The mechanism of the [4+2] cycloaddition reaction of singlet oxygen (O-1(2)) with simple acyclic dienes, i.e. (E)/(Z)-1 and (E,E)/(Z,E)-2, was investigated by employing the gem-diphenylcyclo-propylcarbinyl radical clock as a hypersensitive mechanistic probe. In both cases, benzophenone, a decomposition product of the rearranged endoperoxide intermediates 11 and 12, was identified as the major product. The formation of this product is consistent with the intervention of an open biradical or dipolar intermediate having a lifetime greater than 2 psec. Our attempts to further trap any endoperoxide intermediate revealed a new mode of reactivity of these dienic systems with O-3(2), that mainly affords the corresponding 1,2-dioxolane derivatives (E)-13 and (E,E)-14, respectively, through a photoinduced electron transfer mechanism, co-sensitized by methylene blue (MB) and thiourea. The structures of (E)-13 and (E,E)-14 were supported by experimental and theoretical NMR studies.

  DOI：

  10.3998/ark.5550190.0016.307

文献信息

• Concerning the Reactivity of PTAD with Isomeric Dienes: The Mechanism of the Diels−Alder Cycloaddition
  作者：Mariza N. Alberti、Michael Orfanopoulos

  DOI：10.1021/ol900363n

  日期：2009.4.2

  Cyclopropyl substituted dienes are employed as mechanistic probes in the triazolinedione Diels−Alder (DA) reaction. In aprotic and protic solvents, apart from the DA adducts that bear an intact cyclopropyl group, complicated and rearranged products are also obtained. These results provide solid evidence for the involvement of an open intermediate with a lifetime greater than 2 × 10−12 s.

  环丙基取代的二烯用作三唑啉二酮Diels-Alder（DA）反应中的机理探针。在质子惰性和质子溶剂中，除了带有完整环丙基的DA加合物以外，还可以获得复杂且重排的产物。这些结果为寿命大于2×10 -12 s的开放式中间体的介入提供了有力的证据。