5-(p-Methoxyphenyl)-1-phenyl-2,4,4-trimethyl-1,2-cyclopentanediol | 161260-26-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 5-(p-Methoxyphenyl)-1-phenyl-2,4,4-trimethyl-1,2-cyclopentanediol
• 英文别名: 3-(4-Methoxyphenyl)-1,4,4-trimethyl-2-phenylcyclopentane-1,2-diol
• CAS: 161260-26-0
• 化学式: C₂₁H₂₆O₃
• 分子量: 326.436
• InChiKey: GGTWTOJDEFQPMA-UHFFFAOYSA-N

物化性质

• 沸点：
  440.3±45.0 °C(predicted)
• 密度：
  1.124±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  24
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  49.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5-(p-Methoxyphenyl)-1-phenyl-2,4,4-trimethyl-1,2-cyclopentanediol 在 吡啶 、 三氯氧磷 作用下， 反应 2.0h， 生成 4,4-Dimethyl-3-(p-methoxyphenyl)-1-methylene-2-phenylcyclopent-2-ene 、 1-(p-Methoxyphenyl)-2-phenyl-3,5,5-trimethylcyclopentadiene
  参考文献：
  名称：

  Singlet Photochemistry of Vinyl Cyclopropenes: Regioselectivity and Mechanism; Mechanistic and Exploratory Organic Photochemistry

  摘要：

  A study of the direct photochemistry of 1-anisyl-2-phenyl-3-methyl-3-isobutenylcyclopropene (5) was pursued with the objective of elucidating the reaction regioselectivity and casting light on alternative reaction mechanisms for this reaction known to afford cyclopentadienes. Two mechanisms had previously been advanced-one proceeding by an initial three-ring bond fission to afford an intermediate vinyl carbene and the other by vinyl-vinyl bonding to afford a housane diradical intermediate. The two reaction mechanisms predict different reaction regiochemistry. The experimental observation in the case of vinylcyclopropene 5 was a preference for formation of that product in which the C1-C3 three-ring single bond is severed to give an anisyl-substituted carbene. Then bonding occurs between the isobutenyl moiety and the carbene center. CASSCF computations mere run on S-1 of the reactant cyclopropene as well as S-0 and S-1 of the two regioisomeric carbenes. The preferred carbene, both in the ground state and the first excited singlet, was that having the anisyl group on the carbene center. The S-1 carbenes were Linear at the carbene center while the S-0 carbenes were bent. The aryl group at the carbene center of S-1 preferred to overlap with a pentadienyl pi-system. The lower energy of the excited singlet carbenes with anisyl at the carbene center accounts for the regioselectivity of opening with internal conversion occurring during or subsequent to bond stretching.

  DOI：

  10.1021/jo00108a036
• 作为产物：
  描述：

  3,3-Dimethyl-2-(p-methoxyphenyl)-1-phenyl-1,5-hexanedione 在 magnesium iodide 作用下， 以 乙醚 为溶剂， 反应 20.0h， 生成 5-(p-Methoxyphenyl)-1-phenyl-2,4,4-trimethyl-1,2-cyclopentanediol
  参考文献：
  名称：

  Singlet Photochemistry of Vinyl Cyclopropenes: Regioselectivity and Mechanism; Mechanistic and Exploratory Organic Photochemistry

  摘要：

  A study of the direct photochemistry of 1-anisyl-2-phenyl-3-methyl-3-isobutenylcyclopropene (5) was pursued with the objective of elucidating the reaction regioselectivity and casting light on alternative reaction mechanisms for this reaction known to afford cyclopentadienes. Two mechanisms had previously been advanced-one proceeding by an initial three-ring bond fission to afford an intermediate vinyl carbene and the other by vinyl-vinyl bonding to afford a housane diradical intermediate. The two reaction mechanisms predict different reaction regiochemistry. The experimental observation in the case of vinylcyclopropene 5 was a preference for formation of that product in which the C1-C3 three-ring single bond is severed to give an anisyl-substituted carbene. Then bonding occurs between the isobutenyl moiety and the carbene center. CASSCF computations mere run on S-1 of the reactant cyclopropene as well as S-0 and S-1 of the two regioisomeric carbenes. The preferred carbene, both in the ground state and the first excited singlet, was that having the anisyl group on the carbene center. The S-1 carbenes were Linear at the carbene center while the S-0 carbenes were bent. The aryl group at the carbene center of S-1 preferred to overlap with a pentadienyl pi-system. The lower energy of the excited singlet carbenes with anisyl at the carbene center accounts for the regioselectivity of opening with internal conversion occurring during or subsequent to bond stretching.

  DOI：

  10.1021/jo00108a036