| 136202-22-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 136202-22-7
• 化学式: C₂₇H₂₆O₄S₂
• 分子量: 478.633
• InChiKey: MYFHOKWEXWNDAW-DHAHQMQGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.29
• 重原子数：
  33.0
• 可旋转键数：
  4.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  68.28
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  生成
  参考文献：
  名称：

  Mechanistic Analysis of Double Hydrogen Dyotropy in syn-Sesquinorbornene Disulfones. A Combined Kinetic and Theoretical Evaluation of Primary Deuterium Isotope Effects

  摘要：

  Two sets of syn-sesquinorbornene disulfones have been prepared that carry either one or two deuterium atoms ct to the sulfonyl substituents. The rates of dyotropic rearrangement were measured in these systems in order to assess the deuterium isotope effects associated with single and double H/D transfer. The temperature dependence of the deuterium isotope effects in the biscyclopropane series 3b-5b [k(HH)/k(HD) = 5.4 (0 degrees C) and 2.9 (100 degrees C); k(HH)/k(DD) = 33 (0 degrees C) and 8.5 (100 degrees C)] is not as steep as that when only one cyclopropane ring is present as in 3a-5a [k(HH)/k(HD) = 3.8 (0 degrees C) and 2.1 (100 degrees C); k(HH)/k(DD) = 200 (0 degrees C) and 11.2 (100 degrees C)]. Only in the b series is the Rule of Geometric Mean obeyed. In an effort to gain detailed insight into the relationship between strain energy changes and rates of these reactions, the isomerization rates for a significant number of syn-sesquinorbornene disulfones were first modeled by means of the empirical MM3 force field. Good agreement was found based upon a concerted model. Transition structures for seven concerted dyotropic hydrogen transfers of syn-sesquinorbornene analogs were located with ab initio 3-21G calculations. The potential energy paths for concerted and stepwise hydrogen transfer were also evaluated at the CASSCF level of theory using minimum STO-3G and 3-21G basis sets. The concerted path is predicted to be favored in the absence of tunneling as in the b series. To take the tunneling effect into consideration, a more detailed dynamic treatment of the one- or two-dimensional barrier issue was next implemented, This model supports-tunneling by a stepwise mechanism for both 3a-5a and 3b-5b, but the empirical energy parameters do not agree well with the best CASSCF calculations. Elaborate direct dynamics calculations on model compounds identical with 3a-5a except for the phenylsulfonyl groups were Carried out. Although they yielded results consistent with the two-oscillator calculations, the resulting activation energies are too low and leave room for some uncertainty about the mechanism, especially for compounds 3b-5b.

  DOI：

  10.1021/ja00103a005
• 作为产物：
  描述：

  4,7-二氢-4,7-甲桥-2H-茚 在 potassium hydride 作用下， 以 四氢呋喃 为溶剂， -45.0~25.0 ℃ 、1103.16 MPa 条件下， 反应 121.25h， 生成
  参考文献：
  名称：

  Consequences of Modulated Precompression along Reaction Coordinates. Synthesis, Crystallographic Structural Studies, and Rate of Intramolecular Dyotropy in an Extended Series of syn-Sesquinorbornene Disulfones

  摘要：

  In order to produce a broad range of syn-sesquinorbornene disulfones, (Z)-1,2-bis(phenylsulfonyI)ethylene was added in Diels-Alder fashion (high-pressure conditions) to tricyclo[5.2.1.0(2.6)]deca-2,5,8-trienes carrying isopropylidene or spirocyclopropane subunits at one or two sites. The central double bond in these adducts was then regiospecifically reduced with diimide, epoxidized with MCPBA, or cyclopropanated by [3 + 2] cycloaddition with diazomethane and subsequent photoinduced nitrogen extrusion. Each product in ah-three series was subjected to X-ray crystallographic analysis in order to quantify in the solid state the distance which each endo alpha-sulfonyl proton is required to traverse during dyotropic migration to the proximal norbornene double bond. The kinetics of these isomerizations were also determined, a relative reactivity scale was realized, and the values of k(ref) at 160 degrees C were found not to correlate well with the average distance across the intracavity gap. Although proximity of the reaction centers is clearly a prerequisite for smooth operation of the dyotropic shifts, modulation of this distance is not the sole contributor to reaction rate. Rather, the data are in agreement with the working hypothesis that various levels of steric compression within these disulfones facilitate passage over the relevant transition state to a greater or lesser degree depending on the magnitude of these nonbonded interactions.

  DOI：

  10.1021/ja00103a004

文献信息

• Paquette, Leo A.; O'Doherty, George A.; Rogers, Robin D., Journal of the American Chemical Society, 1991, vol. 113, # 20, p. 7761 - 7762
  作者：Paquette, Leo A.、O'Doherty, George A.、Rogers, Robin D.

  DOI：——

  日期：——