4,4-dimethyl-2-(3-(trifluoromethyl)phenyl)-4,5-dihydrooxazole | 263382-61-2

• 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-(3-(trifluoromethyl)phenyl)-4,5-dihydrooxazole
• 英文别名: 4,4-dimethyl-2-[3-(trifluoromethyl)phenyl]-5H-1,3-oxazole
• CAS: 263382-61-2
• 化学式: C₁₂H₁₂F₃NO
• 分子量: 243.229
• InChiKey: HDCONLXTZSWJTD-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-(3-(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89%的产率得到2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)-4-(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：

  间三氟甲基苯腈 、 2-氨基-2-甲基-1-丙醇 在 calcium chloride 作用下， 以 5,5-dimethyl-1,3-cyclohexadiene 为溶剂， 生成 4,4-dimethyl-2-(3-(trifluoromethyl)phenyl)-4,5-dihydrooxazole
  参考文献：
  名称：

  Practical reduction of oxazolines to alcohols

  摘要：

  A two-step, one-pot procedure using methyl chloroformate and lithium borohydride was developed to transform 2-substituted-oxazolines into alcohols. This methodology is compatible with a wide range of Substrates including heterocyclic, aromatic, and aliphatic functionalized 2-oxazolines. Best results are obtained with electron-rich and ortho substituted 2-aryl-oxazolines. (c) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2008.09.061

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。
• Secondary Phosphine Oxide Preligands for Palladium-Catalyzed C-H (Hetero)Arylations: Efficient Access to Pybox Ligands
  作者：Debasish Ghorai、Valentin Müller、Helena Keil、Dietmar Stalke、Giuseppe Zanoni、Boryslav A. Tkachenko、Peter R. Schreiner、Lutz Ackermann

  DOI：10.1002/adsc.201700663

  日期：2017.9.18

  C–H arylations of oxazolines were accomplished with a well‐defined palladium catalyst derived from a secondary bisdiamantyl phosphine oxide. The single‐component secondary phosphine oxide (SPO)‐palladium complex enabled C–H activations with aryl bromides and challenging aryl chlorides in the absence of directing groups, setting the stage for the step‐economical synthesis of pybox ligands under racemization‐free

  恶唑啉的C–H芳基化反应是使用衍生自仲双双金刚烷基氧化膦的明确定义的钯催化剂完成的。单组分仲氧化膦（SPO）-钯配合物可在没有引导基团的情况下用芳基溴化物和具有挑战性的芳基氯化物进行C-H活化，为在无消旋反应条件下逐步经济地合成pybox配体奠定了基础。
• 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.
• C–H Bond Arylations and Benzylations on Oxazol(in)es with a Palladium Catalyst of a Secondary Phosphine Oxide
  作者：Lutz Ackermann、Sebastian Barfüsser、Christoph Kornhaass、Anant R. Kapdi

  DOI：10.1021/ol200986x

  日期：2011.6.17

  An air-stable, well-defined palladium complex derived from secondary phosphine oxide (SPO) (1-Ad)(2)P(O)H enabled efficient C-H bond functionalizations with ample scope, which set the stage for direct arylations and benzylations of (benz)oxazoles, as well as unprecedented palladium-catalyzed C-H bond arylations on nonaromatic oxazolines.
• 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.