methyl 3-(7-hydroxy-3,5-diisopropyl-8,8-dimethylbicyclo<4.2.0>octa-1,3,5-trien-7-yl)benzoate | 96825-60-4

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: methyl 3-(7-hydroxy-3,5-diisopropyl-8,8-dimethylbicyclo<4.2.0>octa-1,3,5-trien-7-yl)benzoate
• 英文别名: Methyl 3-[7-hydroxy-8,8-dimethyl-3,5-di(propan-2-yl)-7-bicyclo[4.2.0]octa-1,3,5-trienyl]benzoate
• CAS: 96825-60-4
• 化学式: C₂₄H₃₀O₃
• 分子量: 366.5
• InChiKey: VBHUEUPQIWKYPO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  27
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  3-(氯羰基)苯甲酸甲酯 在 三氯化铝 作用下， 以 二硫化碳 、 苯 为溶剂， 反应 13.0h， 生成 methyl 3-(7-hydroxy-3,5-diisopropyl-8,8-dimethylbicyclo<4.2.0>octa-1,3,5-trien-7-yl)benzoate
  参考文献：
  名称：

  Photochemistry of meta-substituted and para-substituted aromatic polycarbonyl compounds

  摘要：

  DOI：

  10.1021/jo00216a018

文献信息

• Structures and Photoreactivities of 2,4,6-Triisopropylbenzophenones
  作者：S. Fukushima、Y. Ito、H. Hosomi、S. Ohba

  DOI：10.1107/s0108768198005515

  日期：1998.12.1

  Crystal structures of 2,4,6-triisopropylbenzophenone (I) and its ten derivatives have been determined: (II) 2,4,6-triisopropyl-3′-methoxybenzophenone, (III) 3′-chloroformyl-2,4,6-triisopropylbenzophenone, (IV) methyl 3-(2,4,6-triisopropylbenzoyl)benzoate, (V) 2,4,6-triisopropyl-4′-methylbenzophenone, (VI) 4′-tert-butyl-2,4,6-triisopropylbenzophenone, (VII) 2,4,6-triisopropyl-4′-methoxybenzophenone, (VIII) 4-(2,4,6-triisopropylbenzoyl)benzoic acid, (IX) 4′-chloroformyl-2,4,6-triisopropylbenzophenone, (X) methyl 4-(2,4,6-triisopropylbenzoyl)benzoate and (XI) ethyl 4-(2,4,6-triisopropylbenzoyl)benzoate. The conformations of these molecules are essentially the same. The central carbonyl moiety is approximately coplanar with the 3′- or 4′-substituted phenyl group and perpendicular to the triisopropylphenyl ring. The photostability of (IX) and (X) in the solid state is attributed to the narrow reaction cavity of the triisopropylphenylcarbonyl moiety, i.e. the intramolecular movements of isopropyl groups in the triisopropylphenyl plane toward the carbonyl C atom are suppressed by intermolecular close contacts. One of the barriers for the photocyclization of (IX) and (X) is caused by a dimeric structure in crystals through the π–π interaction, which is the result of having a polar methoxycarbonyl or chloroformyl group at position 4′ of the phenyl ring.

  测定了 2,4,6-三异丙基二苯甲酮（I）及其十种衍生物的晶体结构：(II) 2,4,6-三异丙基-3′-甲氧基二苯甲酮，(III) 3′-氯甲酰-2,4,6-三异丙基二苯甲酮，(IV) 3-（2,4、(V) 2,4,6-三异丙基-4′-甲基二苯甲酮， (VI) 4′-叔丁基-2,4,6-三异丙基二苯甲酮、(VII) 2,4,6-三异丙基-4′-甲氧基二苯甲酮， (VIII) 4-(2,4,6-三异丙基苯甲酰基)苯甲酸， (IX) 4′-氯甲酰-2,4、(X) 4-(2,4,6-三异丙基苯甲酰基)苯甲酸甲酯和 (XI) 4-(2,4,6-三异丙基苯甲酰基)苯甲酸乙酯。这些分子的构象基本相同。中心羰基与 3′-或 4′-取代的苯基近似共面，与三异丙基苯环垂直。(IX)和(X)在固态下的光稳定性归因于三异丙基苯基羰基的狭窄反应腔，即三异丙基苯基平面上的异丙基向羰基 C 原子的分子内运动受到分子间紧密接触的抑制。(IX)和(X)的光环化障碍之一是晶体中的π-π相互作用造成的二聚体结构，这是在苯环的 4′位上有极性甲氧基羰基或氯甲酰基团的结果。
• 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.