4,4-dimethyl-2-(2-(trifluoromethyl)phenyl)-4,5-dihydrooxazole

• 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: 4,4-dimethyl-2-(2-(trifluoromethyl)phenyl)-4,5-dihydrooxazole
• 英文别名: 4,4-Dimethyl-2-(2-(trifluoromethyl) phenyl)-4,5-dihydrooxazole；4,4-dimethyl-2-[2-(trifluoromethyl)phenyl]-5H-1,3-oxazole
• 化学式: C₁₂H₁₂F₃NO
• 分子量: 243.229
• InChiKey: HWQOBOHXBPWAAV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  17
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  4,4-dimethyl-2-(2-(trifluoromethyl)phenyl)-4,5-dihydrooxazole 在 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex 、 氧气 作用下， 以 四氢呋喃 为溶剂， 反应 26.0h， 以56%的产率得到2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)-3-(trifluoromethyl)phenol
  参考文献：
  名称：

  对 2-(恶唑啉基)-苯酚和 1,2,5-硫属二唑环化衍生物的取代效应：发射颜色可调、极简激发态分子内质子转移 (ESIPT) 基发光体

  摘要：

  合成了被不同给电子和吸电子基团取代的简约 2-(恶唑啉基)-苯酚及其 1,2,5-硫属二唑环化衍生物，并研究了它们在溶液和固体中的发射行为状态。根据引入的取代基的性质及其位置，发射效率会增加或减少，从而产生 AIE 或 ACQ 特性。单晶分析揭示了 J 型和 H 型包装基序以及迄今为止未描述的以酮形式分离的基于 ESIPT 的荧光团。

  DOI：

  10.1021/acs.joc.1c00846
• 作为产物：
  描述：

  邻三氟甲基苯甲醛 、 2-氨基-2-甲基-1-丙醇 在 potassium phosphate 、 N-溴代丁二酰亚胺(NBS) 作用下， 以 二氯甲烷 为溶剂， 反应 21.0h， 以58%的产率得到4,4-dimethyl-2-(2-(trifluoromethyl)phenyl)-4,5-dihydrooxazole
  参考文献：
  名称：

  对 2-(恶唑啉基)-苯酚和 1,2,5-硫属二唑环化衍生物的取代效应：发射颜色可调、极简激发态分子内质子转移 (ESIPT) 基发光体

  摘要：

  合成了被不同给电子和吸电子基团取代的简约 2-(恶唑啉基)-苯酚及其 1,2,5-硫属二唑环化衍生物，并研究了它们在溶液和固体中的发射行为状态。根据引入的取代基的性质及其位置，发射效率会增加或减少，从而产生 AIE 或 ACQ 特性。单晶分析揭示了 J 型和 H 型包装基序以及迄今为止未描述的以酮形式分离的基于 ESIPT 的荧光团。

  DOI：

  10.1021/acs.joc.1c00846

文献信息

• Ruthenium-Catalyzed Dehydrogenative Silylation of Aryloxazolines with Hydrosilanes via C–H Bond Cleavage
  作者：Fumitoshi Kakiuchi、Kimitaka Igi、Mitsutaka Matsumoto、Naoto Chatani、Shinji Murai

  DOI：10.1246/cl.2001.422

  日期：2001.5

  The reaction of aryloxazolines with trialkylhydrosilanes using Ru3(CO)12 or Ru(H)2(CO)(PPh3)3 complex as a catalyst resulted in dehydrogenative silylation to form ortho silylated aryloxazolines in good to excellent yields. This reaction can be applied to aryloxazolines having either electron-donating (Nme2, Ome, and CH3) or -withdrawing (CF3 and F) groups.

  芳基恶唑啉与三烷基氢硅烷使用 Ru3(CO)12 或 Ru(H)2(CO)(PPh3)3 配合物作为催化剂的反应导致脱氢甲硅烷基化，以良好到极好的产率形成邻甲硅烷基化芳基恶唑啉。该反应可应用于具有给电子（Nme2、Ome 和 CH3）或吸电子（CF3 和 F）基团的芳基恶唑啉。
• The ruthenium-catalyzed silylation of aromatic CH bonds with triethylsilane
  作者：Fumitoshi Kakiuchi、Mitsutaka Matsumoto、Kazuyuki Tsuchiya、Kimitaka Igi、Tomoo Hayamizu、Naoto Chatani、Shinji Murai

  DOI：10.1016/s0022-328x(03)00448-0

  日期：2003.11

  experiment using phenyloxazoline-d5 was carried out in the absence of olefin, partial H/D scrambling occurred between the ortho positions of the phenyloxazoline and the SiH of triethylsilane. This labeling experiment indicates that CH bond cleavage is not the rate-determining step and that a rapid equilibrium prior to CSi bond formation (i.e. the reductive elimination step) occurs in this catalytic reaction

  Ru 3（CO）12催化的芳族化合物（如芳唑，芳胺和芳基吡啶）与三乙基硅烷（2）的反应可产生甲硅烷基化产物，收率良好或优异。酰胺基和酯基也可以用作导向基团。在几乎所有情况下，CSi键的形成都在邻位发生给指导小组。该偶联反应对给电子基团和吸电子基团例如甲氧基，氟和三氟甲基均是耐受的。我们预期使用2-萘基-3-甲基吡啶不会导致偶联产物的形成，因为甲基和8位的氢原子之间的强烈空间排斥会强烈地抑制a的获得。共面几何。然而，有趣的是，2-萘基-3-甲基吡啶的反应以定量收率得到了相应的甲硅烷基化产物。该观察表明，金属环中间体的形成对于进行催化反应不是必需的。使用苯恶唑啉进行氘标记实验时-d 5由于在没有烯烃的条件下进行，在苯基恶唑啉的邻位和三乙基硅烷的Si 3 H之间发生了部分H / D加扰。该标记实验表明，CH键断裂不是决定速率的步骤，并且在该催化反应中发生了CSi键形成之前的快速平衡（即还原消除步骤）。
• Aerobic C(sp²)–H Hydroxylations of 2-Aryloxazolines: Fast Access to Excited-State Intramolecular Proton Transfer (ESIPT)-Based Luminophores
  作者：Dominik Göbel、Nils Clamor、Enno Lork、Boris J. Nachtsheim

  DOI：10.1021/acs.orglett.9b01350

  日期：2019.7.19

  The direct hydroxylation of 2-aryloxazolines via a deprotonative magnesiation using TMPMgCl center dot LiCl and subsequent oxidation with molecular oxygen or air as a green oxidant is reported. This method proceeds under mild conditions at room temperature with high regioselectivity and chemoselectivity. The obtained phenols exhibit tunable luminescence properties, induced by excited-state intramolecular proton transfer. This method opens a new opportunity for the sustainable synthesis of luminescent organic molecules.
• Direct Carbonylation at a C−H Bond in the Benzene Ring of 2-Phenyloxazolines Catalyzed by Ru₃(CO)₁₂. Scope, Limitations, and Mechanistic Aspects
  作者：Yutaka Ie、Naoto Chatani、Takashi Ogo、Daniel R. Marshall、Takahide Fukuyama、Fumitoshi Kakiuchi、Shinji Murai

  DOI：10.1021/jo991660t

  日期：2000.3.1

  The ruthenium-catalyzed carbonylation at a C-H bond in the benzene ring of a 2-phenyloxazoline is described. The reaction of 2-phenyloxazolines with CO and ethylene in toluene in the presence of a catalytic amount of Ru-3(CO)(12) resulted in propionylation at an ortho C-H bond in the benzene ring. The presence of the oxazoline ring on the benzene ring is essential for the carbonylation to proceed. Other heterocycles, such as oxazine, oxazole, and thiazoline rings, also served as acceptable directing groups as did the oxazoline ring. A wide functional group compatibility was observed. The site selectivity of the carbonylation was examined using meta-substituted phenyloxazolines. It was found that the carbonylation took place exclusively at the less-hindered C-H bond, irrespective of the nature of substituents, indicating that the site selectivity was determined by steric factors. The reaction was also applicable, not only to a benzene ring, but also to naphthyl and thiophenyl rings. Olefins such as propene and trimethylvinylsilane in place of ethylene could also be used in the carbonylation reaction, while other olefins, such as l-hexene, tert-butylethylene, vinylcyclohexane, isoprene, 1,5-hexadiene, cyclohexene, 1,5-cyclooctadiene, styrene, methyl acrylate, vinyl acetate, allyltrimethylsilane, and triethoxyvinylsilane did not afford the coupling products. An equilibrium between 2-phenyloxazolines, carbon monoxide, and olefins exists on one hand and the corresponding ketones on the other hand, and product composition is governed by the equilibrium thermodynamics of the system. The results of deuterium labeling experiments suggest that the catalysis involves a reversible C-H bond cleavage and that the rate-determining step is not the cleavage of a C-H bond. The results of kinetic study of the effects of CO pressure show that the reaction rate accelerates with decreasing CO pressure.
• Substitution Effect on 2-(Oxazolinyl)-phenols and 1,2,5-Chalcogenadiazole<i>-</i>Annulated Derivatives: Emission-Color-Tunable, Minimalistic Excited-State Intramolecular Proton Transfer (ESIPT)-Based Luminophores
  作者：Dominik Göbel、Pascal Rusch、Daniel Duvinage、Tim Stauch、Nadja-C. Bigall、Boris J. Nachtsheim

  DOI：10.1021/acs.joc.1c00846

  日期：2021.11.5

  Minimalistic 2-(oxazolinyl)-phenols substituted with different electron-donating and -withdrawing groups as well as 1,2,5-chalcogenadiazole-annulated derivatives thereof were synthesized and investigated in regard to their emission behavior in solution as well as in the solid state. Depending on the nature of the incorporated substituent and its position, emission efficiencies were increased or diminished

  合成了被不同给电子和吸电子基团取代的简约 2-(恶唑啉基)-苯酚及其 1,2,5-硫属二唑环化衍生物，并研究了它们在溶液和固体中的发射行为状态。根据引入的取代基的性质及其位置，发射效率会增加或减少，从而产生 AIE 或 ACQ 特性。单晶分析揭示了 J 型和 H 型包装基序以及迄今为止未描述的以酮形式分离的基于 ESIPT 的荧光团。