[(2R)-butan-2-yl] 4-[2,4,6-tri(propan-2-yl)benzoyl]benzoate | 205311-43-9

• 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: [(2R)-butan-2-yl] 4-[2,4,6-tri(propan-2-yl)benzoyl]benzoate
• CAS: 205311-43-9
• 化学式: C₂₇H₃₆O₃
• 分子量: 408.581
• InChiKey: DWTMQKYORKVGRV-LJQANCHMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.8
• 重原子数：
  30
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [(2R)-butan-2-yl] 4-[2,4,6-tri(propan-2-yl)benzoyl]benzoate 以 苯 为溶剂， 反应 4.0h， 生成 4-(7-Hydroxy-3,5-diisopropyl-8,8-dimethyl-bicyclo[4.2.0]octa-1(6),2,4-trien-7-yl)-benzoic acid (R)-sec-butyl ester
  参考文献：
  名称：

  Solid-State Photocyclization of 2,4,6-Triisopropyl-4‘-(methoxycarbonyl)benzophenone. Evidence for a Narrow Reaction Cavity and a Photoenol Diradical Intermediate

  摘要：

  The origin of the previously observed unusual photostability of 2,4,6-triisopropyl-4'-(methoxycarbonyl)benzophenone (1-p-CO2Me) in the solid state was investigated. 1-p-CO2Me was found to photocyclize normally to produce the corresponding benzocyclobutenol 2-p-CO2Me when its solid-state photolysis was carried out either (a) after thorough grinding, (b) after solid-solid mixing with 2,4,6-triisopropyl-4'-(ethoxycarbonyl)benzophenone (1-p-CO2Et), or (c) at elevated temperatures (an estimated energy barrier of 20 kcal/mol). Furthermore, when the photolysis was performed under more carefully deoxygenated conditions (closed argon atmosphere), formation of blue species that are persistent in the absence of oxygen was observed. On the basis of oxygen trapping and ESR experiments, the blue species are regarded as a mixture of a diradical intermediate DR and monoradicals derived thereof. The X-ray study of 1-p-CO2Me had revealed that the distances between the carbonyl oxygen and the o-i-Pr methine hydrogens are within the critical limit for hydrogen abstraction to occur, but a small reaction cavity or the compact crystal packing around both of the o-i-Pr groups is interfering with the photocyclization. The present results are consistent with this X-ray crystal structure; i.e., the photochemical hydrogen abstraction of 1-p-CO2Me to DR can take place, but DR reketonizes back to 1-p-CO2Me under the usual photolysis conditions because there is a high topochemical barrier to cyclization leading to 2-p-CO2Me.

  DOI：

  10.1021/jp973235e
• 作为产物：
  描述：

  (R)-(-)-2-丁醇 、 4'-chloroformyl-2,4,6-triisopropylbenzophenone 在 吡啶 作用下， 反应 24.0h， 以21%的产率得到[(2R)-butan-2-yl] 4-[2,4,6-tri(propan-2-yl)benzoyl]benzoate
  参考文献：
  名称：

  Diastereoselective Photocyclization of N-(p-(2,4,6-Triisopropylbenzoyl)benzoyl)-l- phenylalanine Methyl Ester in the Solid State

  摘要：

  DOI：

  10.1021/jo980139g

文献信息

• Diastereoselective Photocyclization of <i>N</i>-(<i>p</i>-(2,4,6-Triisopropylbenzoyl)benzoyl)-<scp>l</scp>- phenylalanine Methyl Ester in the Solid State
  作者：Yoshikatsu Ito、Gentaro Kano、Nobumasa Nakamura

  DOI：10.1021/jo980139g

  日期：1998.8.1
• Solid-State Photocyclization of 2,4,6-Triisopropyl-4‘-(methoxycarbonyl)benzophenone. Evidence for a Narrow Reaction Cavity and a Photoenol Diradical Intermediate
  作者：Yoshikatsu Ito、Satoshi Yasui、Jun Yamauchi、Shigeru Ohba、Gentaro Kano

  DOI：10.1021/jp973235e

  日期：1998.7.1

  The origin of the previously observed unusual photostability of 2,4,6-triisopropyl-4'-(methoxycarbonyl)benzophenone (1-p-CO2Me) in the solid state was investigated. 1-p-CO2Me was found to photocyclize normally to produce the corresponding benzocyclobutenol 2-p-CO2Me when its solid-state photolysis was carried out either (a) after thorough grinding, (b) after solid-solid mixing with 2,4,6-triisopropyl-4'-(ethoxycarbonyl)benzophenone (1-p-CO2Et), or (c) at elevated temperatures (an estimated energy barrier of 20 kcal/mol). Furthermore, when the photolysis was performed under more carefully deoxygenated conditions (closed argon atmosphere), formation of blue species that are persistent in the absence of oxygen was observed. On the basis of oxygen trapping and ESR experiments, the blue species are regarded as a mixture of a diradical intermediate DR and monoradicals derived thereof. The X-ray study of 1-p-CO2Me had revealed that the distances between the carbonyl oxygen and the o-i-Pr methine hydrogens are within the critical limit for hydrogen abstraction to occur, but a small reaction cavity or the compact crystal packing around both of the o-i-Pr groups is interfering with the photocyclization. The present results are consistent with this X-ray crystal structure; i.e., the photochemical hydrogen abstraction of 1-p-CO2Me to DR can take place, but DR reketonizes back to 1-p-CO2Me under the usual photolysis conditions because there is a high topochemical barrier to cyclization leading to 2-p-CO2Me.