(2-羟基-4-甲基苯基)(对甲苯基)甲酮 | 81652-53-1

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: (2-羟基-4-甲基苯基)(对甲苯基)甲酮
• 英文名称: (2-hydroxy-4-methylphenyl)(p-tolyl)methanone
• 英文别名: 2-hydroxy-4,4'-dimethylbenzophenone；Benzophenone, 2-hydroxy-4,4'-dimethyl-；(2-hydroxy-4-methylphenyl)-(4-methylphenyl)methanone
• CAS: 81652-53-1
• 化学式: C₁₅H₁₄O₂
• 分子量: 226.275
• InChiKey: DSWBOAWBBNCUDO-UHFFFAOYSA-N

物化性质

• 熔点：
  73–74°C
• 沸点：
  376.1±27.0 °C(Predicted)
• 密度：
  1.139±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2-羟基-4-甲基苯基)(对甲苯基)甲酮 在 甲酸 、 氯磺酰异氰酸酯 、 sodium hydride 作用下， 以 N,N-二甲基乙酰胺 、 mineral oil 为溶剂， 以40%的产率得到4-(4-methylphenyl)-7-methyl-1,2,3-benzoxathiazine 2,2-dioxide
  参考文献：
  名称：

  Enantioselective Synthesis of Cyclic Sulfamidates via Pd-Catalyzed Hydrogenation

  摘要：

  Using Pd(CF3CO2)(2)/(SS)-f-binaphane as the catalyst, an efficient enantioselective synthesis of cyclic sulfamidates was developed via asymmetric hydrogenation of the corresponding cyclic imines in 2,2,2-trifluoroethanol at room temperature with high enantioselectivities (up to 99% ee).

  DOI：

  10.1021/ol800591u
• 作为产物：
  描述：

  4,4'-二甲基二苯甲酮 在 palladium diacetate 、 [双(三氟乙酰氧基)碘]苯 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 2.0h， 以86%的产率得到(2-羟基-4-甲基苯基)(对甲苯基)甲酮
  参考文献：
  名称：

  Palladium-Catalyzed ortho-CH-Bond Oxygenation of Aromatic Ketones

  摘要：

  A palladium-catalyzed C-(sp2)-H bond oxygenation reaction is described. This protocol represents the first example of a C-H bond cleavage/C-O bond formation sequence, by employing a ketone moiety as the directing group. With this new catalytic method, a variety of ortho-acylphenols can be easily accessed from arylketones.

  DOI：

  10.1021/ol303088z

文献信息

• Sandmeyer reactions. Part 5. Estimation of the rates of 1,5-aryl/aryl radical translocation and cyclisation during Pschorr fluorenone synthesis with a comparative analysis of reaction energetics
  作者：Stephen A. Chandler、Peter Hanson、Alec B. Taylor、Paul H. Walton、Allan W. Timms

  DOI：10.1039/b006184k

  日期：——

  During the Pschorr cyclisation of 2-aroylphenyl radicals, a rearrangement occurs reversibly by 1,5-hydrogen transfer to give 2-benzoylaryl radicals. Rate constants of (1.2 ± 0.2) × 106 s−1 at 293 K are estimated for both the forward and back reactions in the equilibrium between 2-(4-methylbenzoyl)phenyl and 2-benzoyl-5-methylphenyl radicals. Assuming an empirical estimate of 1.6 × 10−2 dm3 mol−1 s−1 for the hypothetical rate of abstraction of hydrogen from benzene by phenyl radicals, the radical translocation is calculated to occur with a statistically corrected effective molarity of 2.2 × 108 mol dm−3. By contrast, the competing cyclisation, though occurring at a rate of (8.0 ± 0.9) × 105 s−1, exhibits an effective molarity of only 5.3 mol dm−3. The causes of these differences are analysed in terms of reaction mechanism.

  在2-芳酰基苯基自由基的Pschorr环化过程中，通过1,5-氢转移发生可逆的重排，生成2-苯甲酰基芳基自由基。在2-(4-甲基苯甲酰基)苯基和2-苯甲酰基-5-甲基苯基自由基之间的平衡中，正向和反向反应的速率常数估计为(1.2 ± 0.2) × 106 s−1（293 K）。假设苯基自由基从苯中夺取氢的假设速率为1.6 × 10−2 dm3 mol−1 s−1，自由基转移的统计校正有效摩尔浓度为2.2 × 108 mol dm−3。相比之下，竞争性的环化反应尽管发生速率为(8.0 ± 0.9) × 105 s−1，但其有效摩尔浓度仅为5.3 mol dm−3。这些差异的原因通过反应机理进行了分析。
• Iridium- and rhodium-catalyzed C–H activation and formyl arylation of benzaldehydes under chelation-assistance
  作者：Xifa Yang、He Wang、Xukai Zhou、Xingwei Li

  DOI：10.1039/c6ob00825a

  日期：——

  Mild and efficient synthesis of benzophenones via Ir(iii)- and Rh(iii)-catalyzed, directing group-assisted formyl C–H arylation of benzaldehydes has been achieved using diaryliodonium salts, in which Rh(iii) and Ir(iii) catalysts exhibited a complementary substrate scope.

  通过使用二芳基碘鎓盐，已经实现了对苯甲醛进行Rh(iii)和Ir(iii)催化、取向基辅助的甲酰C-H芳基化的温和高效合成苯甲酮，其中Rh(iii)和Ir(iii)催化剂展示出互补的底物范围。
• One-pot synthesis of ortho -acylphenols by palladium-catalyzed phenol C–H addition to nitriles
  作者：Tao-Shan Jiang、Bei Gan、Xi Wang、Xiuli Zhang

  DOI：10.1016/j.tetlet.2017.09.062

  日期：2017.11

  The regioselective one-pot synthesis of ortho-acylphenols via the palladium-catalyzed addition of phenols to nitriles and subsequent hydrolysis is reported. The acylation reaction proceeded smoothly using the Pd(OAc)2/DMSO system and TFA as the additive. This method also provides a direct strategy for the synthesis of a salicylketoxime scaffold.

  据报道，通过钯催化的苯酚向腈的加成反应和随后的水解反应，可以进行邻位酰基苯酚的区域选择性一锅合成。使用Pd（OAc）2 / DMSO系统和TFA作为添加剂，酰化反应可顺利进行。该方法还提供了合成水杨基酮肟支架的直接策略。
• Direct Acylation of Phenol and Naphthol Derivatives in a Mixture of Graphite and Methanesulfonic Acid
  作者：Hashem Sharghi、Mona Hosseini-Sarvari、Razieh Eskandari

  DOI：10.1055/s-2006-942384

  日期：2006.6

  Graphite in methanesulfonic acid is used to prepare o-hydroxyketones by direct acylation of phenol and naphthol derivatives with carboxylic acids.

  甲磺酸中的石墨用于通过苯酚和萘酚衍生物与羧酸的直接酰化来制备邻羟基酮。
• Directed Hydroxylation of sp² and sp³ C–H Bonds Using Stoichiometric Amounts of Cu and H₂O₂
  作者：Rachel Trammell、Lorenzo D’Amore、Alexandra Cordova、Pavel Polunin、Nan Xie、Maxime A. Siegler、Paola Belanzoni、Marcel Swart、Isaac Garcia-Bosch

  DOI：10.1021/acs.inorgchem.9b00901

  日期：2019.6.3

  protocol for the regioselective hydroxylation of sp2 and sp3 C–H bonds using a directing group, stoichiometric amounts of Cu and H2O2. A wide array of aromatic ketones and aldehydes are oxidized in the carbonyl γ-position with remarkable yields. We also expanded this methodology to hydroxylate the β-position of alkylic ketones. Spectroscopic characterization, kinetics, and density functional theory calculations

  与其他金属相比，将铜用于C–H键功能化的研究相对较少。在本文中，我们报告了使用导向基团，化学计量的Cu和H 2 O 2对sp 2和sp 3 C–H键的区域选择性羟基化的合成方案。各种各样的芳族酮和醛在羰基γ位被氧化，收率很高。我们还扩展了该方法以羟基化烷基酮的β-位。光谱表征，动力学和密度泛函理论计算都指向单核LCu II（OOH）物种的参与，该物种会氧化芳香族sp 2 通过协调的杂合O-O键裂解C-H键，并伴随对芳烃系统的亲电子攻击。