2,4,6-triisopropyl-3′-carboxybenzophenone | 205311-37-1

• 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: 2,4,6-triisopropyl-3′-carboxybenzophenone
• 英文别名: 3-[2,4,6-Tri(propan-2-yl)benzoyl]benzoic acid
• CAS: 205311-37-1
• 化学式: C₂₃H₂₈O₃
• 分子量: 352.474
• InChiKey: VVVKPSJLYFRWON-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.2
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2,4,6-triisopropyl-3′-carboxybenzophenone 以 苯 为溶剂， 反应 2.0h， 生成 3-(7-Hydroxy-3,5-diisopropyl-8,8-dimethyl-bicyclo[4.2.0]octa-1(6),2,4-trien-7-yl)-benzoic acid
  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：

  3'-chloroformyl-2,4,6-triisopropylbenzophenone 在 sodium hydroxide 作用下， 以 水 为溶剂， 反应 1.0h， 以69%的产率得到2,4,6-triisopropyl-3′-carboxybenzophenone
  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

• Absolute Asymmetric Photocyclization of Triisopropylbenzophenone Derivatives in Crystals and Their Morphological Changes
  作者：Hideko Koshima、Michitaro Fukano、Naoko Ojima、Kohei Johmoto、Hidehiro Uekusa、Motoo Shiro

  DOI：10.1021/jo5000913

  日期：2014.4.4

  caused highly enantioselective Norrish type II photocyclization to yield the (R)-cyclobutenol with 94% ee in 100% yield as the sole product, resulting in successful absolute asymmetric synthesis. In contrast, the (S)-cyclobutenol was obtained from the P crystal with 95% ee in 100% yield. The high enantiodifferentiation in the crystalline-state photocyclization is attributed to the shorter distance between

  尽管4-（2,4,6-三异丙基苯甲酰基）苄基苯甲酰胺是一种非手性分子，但手性晶体可以通过在甲醇溶液中自发结晶而形成。在M晶体中，沿α轴的分子之间沿逆时针方向形成两条螺旋状的氢键链，以产生晶体手性。作为Nujol的两个对映体晶体的固态圆二色性光谱显示出良好的镜像关系。M晶体在大于290 nm处的紫外线照射引起高度对映选择性的Norrish II型光环化反应，以100％的收率得到具有94％ee的（R）-环丁烯醇，是唯一的产物，从而成功地进行了绝对不对称合成。相反，（S从P晶体以100％的收率得到95％ee的β-环丁烯醇。结晶态光环化中的高对映异构反应归因于羰基氧原子与两个邻异丙基的次甲基γ-氢原子之一之间的距离更短，以及由于分子运动相似而具有最小分子运动的平稳转化反应物和产物分子的形状。板状晶体的紫外线照射导致在垂直于长轴（晶胞的轴）的方向上出现裂纹，这可能是因为在光环化过程中氢键链断裂了。
• 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.