cis-5,6-diphenylbicyclo<3.1.0>hexan-2-one | 21414-81-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: cis-5,6-diphenylbicyclo<3.1.0>hexan-2-one
• 英文别名: cis-5,6-diphenylbicyclo[3.1.0]hexan-2-one；rac.-trans-5,6-Diphenyl-bicyclo<3.1.0>hexanon-(2)；(+/-)-1r,6c-Diphenyl-bicyclo<3.1.0>hexanon-(4)；cis-5,6-Diphenylbicyclo<3.1.0>hexan-2-on；rac.-trans-5,6-Diphenyl-bicyclo[3.1.0]hexanon-(2)；(1S,5S,6R)-5,6-diphenylbicyclo[3.1.0]hexan-2-one
• CAS: 21414-81-3；25129-49-1；95272-24-5；123050-46-4
• 化学式: C₁₈H₁₆O
• 分子量: 248.324
• InChiKey: IJXHRYRHSFUZEX-BZSNNMDCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.28
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  cis-5,6-diphenylbicyclo<3.1.0>hexan-2-one 在 sodium iodide 作用下， 生成 hex-2-oxo-3-yl)-propyl>-triphenylphosphonium-iodid
  参考文献：
  名称：

  Multiplicity and molecular flexibility in controlling molecular reactivity. Mechanistic and exploratory organic photochemistry

  摘要：

  DOI：

  10.1021/ja00846a029
• 作为产物：
  描述：

  3-氧代环戊烷甲腈 在 copper(l) iodide 、 水 、 草酸 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 、 甲苯 、 苯 为溶剂， 反应 63.5h， 生成 cis-5,6-diphenylbicyclo<3.1.0>hexan-2-one
  参考文献：
  名称：

  General Theoretical Treatments of Solid-State Photochemical Rearrangements and a Variety of Contrasting Crystal versus Solution Photochemistry

  摘要：

  In continuing our investigations of control of excited state reactivity by inclusion in crystal lattices, we have encountered a variety of new examples of differing reactivity resulting from lattice restraints. Different theoretical treatments were tested and several proved applicable. Not only could the course of reactions imposed by the crystal lattice be predicted but also the ability to react versus lack of reactivity. For cyclohexenones with C-2 and C-5 substitution, either of two aryl groups at C-4 are available for migration; which one migrates depends on the lattice. One C-2 substituted and seven C-5 substituted cyclohexenones were investigated. Additionally some cyclopentenone photochemistry was investigated. Throughout, programming was developed to generate a ''mini crystal lattice'' having the appropriate space group symmetry and X-ray coordinates and with a central molecule surrounded by reactant molecules. Replacement of the central molecule with a transition state molecule provided a new ''mini-lattice''. Generally, the first diradical intermediate was used to simulate the reaction transition state. The mini-lattice was then subject to study. Overlap of the central, partially reacted species with the surrounding molecules provided one criterion. Molecular motion of the reactant excited state in forming the partially reacted species provided a test of least motion as a second criterion. A third test utilizing MM3 geometry optimization of the reacting species imbedded in the rigid mini-lattice, provided a measure of the increase in intra- and intermolecular energy of this molecule. A final approach determined the points of nearest molecule-lattice approach and mapped these in the form of a ''lock and key''; this has the advantage of indicating which interactions result in inhibition or lack thereof of a particular reaction route. Predicting ability to react proved important since reactivity falls into three categories: (I) no reaction in the lattice, (2) differing reactivity compared to solution, (3) the same behavior in solution. Perturbing an intermediate geometry toward that of the reactant and then determining the deformation energy provided a reactivity measure.

  DOI：

  10.1021/ja00124a008

文献信息

• Quantitative Cavities and Reactivity in Stages of Crystal Lattices:  Mechanistic and Exploratory Organic Photochemistry¹^,²
  作者：Howard E. Zimmerman、Evgueni E. Nesterov

  DOI：10.1021/ja0124562

  日期：2002.3.1

  solution. The stage behavior was investigated using X-ray analysis and Quantum Mechanics/Molecular Mechanics computations. This permitted us to determine the sources and details of the stage phenomenon. The analysis revealed how a product molecule as a neighbor affects reactivity. The computations were employed to follow the course of a solid-state reaction from reactant through the succeeding stages.

  在继续我们对固态有机光化学的研究中，我们一直在分阶段研究反应性现象。在这项研究中，我们展示了新的例子，其中光化学反应性在转化过程中的某个时间点发生不连续变化。在这些情况下，固体的反应过程不同于溶液中的反应过程。一个例子是2-甲基-4,4-二苯基环己烯酮的反应，在固态时遇到了一个不寻常的反应过程；并且，在两种可能的机制中，一种是通过同位素标记建立的。第二种情况是 4,5,5-三苯基环己烯酮。发现这种烯酮的固态反应产生了一种新的光化学转化，即 C 型重排，这是一个涉及 delta 到 alpha 芳基迁移的过程。在3-叔丁基-5的情况下，5-二苯基环己烯酮即使在溶液中也会发生C型重排。使用 X 射线分析和量子力学/分子力学计算来研究平台行为。这使我们能够确定舞台现象的来源和细节。分析揭示了作为邻居的产物分子如何影响反应性。计算用于跟踪从反应物到后续阶段的固态反应过程。此外，利用 Delta 密
• Mechanistic and exploratory organic photochemistry. XLV. Di-.pi.-methane rearrangement of 1-methylene-4,4-diphenyl-2-cyclohexene and related photochemical processes
  作者：Howard Elliot Zimmerman、Gary E. Samuelson

  DOI：10.1021/ja01047a020

  日期：1969.9
• Molecular control of excited cross-conjugated triene rearrangements. Exploratory and mechanistic organic photochemistry
  作者：Howard E. Zimmerman、Donald R. Diehl

  DOI：10.1021/ja00501a035

  日期：1979.3
• Multiplicity and molecular flexibility in controlling molecular reactivity. Mechanistic and exploratory organic photochemistry
  作者：Howard E. Zimmerman、Frederick X. Albrecht、Michael J. Haire

  DOI：10.1021/ja00846a029

  日期：1975.6
• General Theoretical Treatments of Solid-State Photochemical Rearrangements and a Variety of Contrasting Crystal versus Solution Photochemistry
  作者：Howard E. Zimmerman、Zhaoning Zhu

  DOI：10.1021/ja00124a008

  日期：1995.5

  In continuing our investigations of control of excited state reactivity by inclusion in crystal lattices, we have encountered a variety of new examples of differing reactivity resulting from lattice restraints. Different theoretical treatments were tested and several proved applicable. Not only could the course of reactions imposed by the crystal lattice be predicted but also the ability to react versus lack of reactivity. For cyclohexenones with C-2 and C-5 substitution, either of two aryl groups at C-4 are available for migration; which one migrates depends on the lattice. One C-2 substituted and seven C-5 substituted cyclohexenones were investigated. Additionally some cyclopentenone photochemistry was investigated. Throughout, programming was developed to generate a ''mini crystal lattice'' having the appropriate space group symmetry and X-ray coordinates and with a central molecule surrounded by reactant molecules. Replacement of the central molecule with a transition state molecule provided a new ''mini-lattice''. Generally, the first diradical intermediate was used to simulate the reaction transition state. The mini-lattice was then subject to study. Overlap of the central, partially reacted species with the surrounding molecules provided one criterion. Molecular motion of the reactant excited state in forming the partially reacted species provided a test of least motion as a second criterion. A third test utilizing MM3 geometry optimization of the reacting species imbedded in the rigid mini-lattice, provided a measure of the increase in intra- and intermolecular energy of this molecule. A final approach determined the points of nearest molecule-lattice approach and mapped these in the form of a ''lock and key''; this has the advantage of indicating which interactions result in inhibition or lack thereof of a particular reaction route. Predicting ability to react proved important since reactivity falls into three categories: (I) no reaction in the lattice, (2) differing reactivity compared to solution, (3) the same behavior in solution. Perturbing an intermediate geometry toward that of the reactant and then determining the deformation energy provided a reactivity measure.