4-(2,4,6-triisopropylbenzoyl)benzoic acid | 76893-82-8

• 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: 4-(2,4,6-triisopropylbenzoyl)benzoic acid
• 英文别名: 4'-Carboxyl-2,4,6-triisopropylbenzophenone；4-[2,4,6-tri(propan-2-yl)benzoyl]benzoic acid
• CAS: 76893-82-8
• 化学式: C₂₃H₂₈O₃
• 分子量: 352.474
• InChiKey: OXAFDQSFACYGSS-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：

  4-(2,4,6-triisopropylbenzoyl)benzoic acid 以 乙醇 为溶剂， 生成
  参考文献：
  名称：

  晶体中Norrish-Yang反应动力学不同的原因。结构与光谱研究

  摘要：

  以X，通过1,3,5,7-四氮杂三环[3.3.1.13,7]癸烷4-（2,4,6-三异丙基苯甲酰基）苯甲酸酯为例研究了单晶中光化学诺里斯·杨反应的动力学。射线衍射和拉曼光谱。所研究化合物中的反应按Johnson-Mehl-Avrami-Kolmogorov模型描述的两个阶段进行。在第一阶段中，反应以恒定的速率均匀地进行，但是对于第二种模式，该反应从大约1分钟开始。50％的转化率，反应随着自身抑制而进行。这种自动抑制的原因是：（i）在第二阶段反应中心的几何结构发生了变化，而这在第一阶段没有观察到；（ii）C–H··π相互作用随着作用的增强而增强。反应进度 （iii）羧酸根基团向羧基样基团的特性变化。如在晶胞参数随紫外线辐射的特性变化的基础上所述，诺里什·杨反应也以0.2 GPa的晶体进行。

  DOI：

  10.1021/acs.cgd.0c00245
• 作为产物：
  描述：

  4'-chloroformyl-2,4,6-triisopropylbenzophenone 在 sodium hydroxide 作用下， 以 水 为溶剂， 反应 1.0h， 以82%的产率得到4-(2,4,6-triisopropylbenzoyl)benzoic acid
  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

• 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。
• Photocyclization reaction and triplet lifetime of hindered o-alkyl benzophenones
  作者：Yoshikatsu Ito、Yasutoshi Umehara、Yutaka Yamada、Teruo Matsuura

  DOI：10.1039/c39800001160

  日期：——

  The triplet lifetimes of hindered 4′-substituted-2,4,6-tri-isopropylbenzophenones decrease (increase) with the increasing electron-donating (withdrawing) ability of the ring substituents; this is the opposite effect to that expected from the rate of the intermolecular hydrogen-abstraction reaction of unhindered benzophenones.

  受阻的4'-取代的2,4,6-三异丙基二苯甲酮的三重态寿命随着环取代基的供电子（抽出）能力的增加而降低（增加）；这与不受阻碍的二苯甲酮的分子间吸氢反应速率所预期的相反。
• 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。
• Steering photochemical reactivity of 2,4,6-triisopropylbenzophenonate anion in a crystalline state
  作者：Julia Bąkowicz、Joanna Olejarz、Ilona Turowska-Tyrk

  DOI：10.1016/j.jphotochem.2013.09.003

  日期：2014.1

  hybrid mechanism for 1. The rate constant was much higher for 3 than for 1. The differences in the reactivity were explained by the intramolecular geometrical parameters and intermolecular interactions mapped onto the Hirshfeld surfaces. The results showed that it is possible to largely change reactivity of the one organic species, even several hundred times, by modifying the crystal lattice in which

  Norrish-Yang反应是在苄基铵，吡咯烷鎓和4-（2,4,6-三异丙基苯甲酰基）苯甲酸铵（1-3）的晶体中进行的。确定了1-3的晶体结构，这些化合物的部分反应的晶体的六个结构以及用于1的纯产物晶体的结构。部分反应的晶体中产物的含量允许通过JMAK模型计算速率常数的值以及1和3的反应阶数。结果表明，Norrish-Yang反应对3均匀进行，并根据1的混合机理进行。3的速率常数比1对速率常数高得多。反应性的差异由分子内几何参数和分子间相互作用绘制到Hirshfeld表面上。
• 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.