3-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)benzonitrile

• 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: 3-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)benzonitrile
• 英文别名: 3-(4,4-dimethyl-5H-1,3-oxazol-2-yl)benzonitrile
• 化学式: C₁₂H₁₂N₂O
• 分子量: 200.24
• InChiKey: ZYTPIXFRXSSQTM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  45.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)benzonitrile 在 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex 、 碘 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以77%的产率得到3-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)-4-iodobenzonitrile
  参考文献：
  名称：

  Selective functionalization of cyano-phenyl-2-oxazolines using TMPMgCl·LiCl

  摘要：

  Metalated phenyl-2-oxazolines bearing cyano groups can be selectively obtained through the reaction of TMPMgCl center dot LiCl with the appropriate substrate. Subsequent reaction with different electrophiles furnished the functionalized derivatives in good yields. Density functional theory (DFT) calculations were performed to evaluate the influence of the ring substituents on the acidity of the aromatic hydrogens. Application to the synthesis of novel functionalized phthalides illustrates the great potential of the methodology to the synthesis of bioactive compounds. (C) 2017 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2017.09.051
• 作为产物：
  描述：

  3-氰基苯甲醛 、 2-氨基-2-甲基-1-丙醇 在 N-溴代丁二酰亚胺(NBS) 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以81%的产率得到3-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)benzonitrile
  参考文献：
  名称：

  腈取代的2-（恶唑啉基）-酚类化合物：基于简约激发态的分子内质子转移（ESIPT）的荧光团

  摘要：

  在本文中，我们提出了简约的单苯，激发态分子内质子转移（ESIPT）基荧光团作为强大的固态发射器。非常简单的合成，得到访问腈取代的2-（恶唑啉基）-phenols的所有四个区域异构体（中号w ^ = 216.1）。就其发射特性而言，它们可分为聚集诱发发射增强（AIEE）发光体（1-CN和2-CN），双态发射（DSE）发射体（3-CN）和聚集引起的猝灭（ACQ）荧光团（4-CN）。值得注意的是，使用化合物1-CN，我们发现了一种基于ESIPT的简约荧光团，在固态Φ中具有极高的量子产率˚F =在87.3％ λ EM = 491纳米。此外，在溶液中量子产率的测定高达Φ ˚F = 63.0％，结合斯托克斯向上移动直到11.310厘米-1。与温度有关的发射图，晶体结构分析和与时间有关的密度泛函理论（TDDFT）计算对发射特性的起源提供了深刻的了解。

  DOI：

  10.1039/d0tc00776e

文献信息

• 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.
• Selective functionalization of cyano-phenyl-2-oxazolines using TMPMgCl·LiCl
  作者：Leandro A. Bozzini、João H.C. Batista、Murilo B.M. de Mello、Ricardo Vessecchi、Giuliano C. Clososki

  DOI：10.1016/j.tetlet.2017.09.051

  日期：2017.11

  Metalated phenyl-2-oxazolines bearing cyano groups can be selectively obtained through the reaction of TMPMgCl center dot LiCl with the appropriate substrate. Subsequent reaction with different electrophiles furnished the functionalized derivatives in good yields. Density functional theory (DFT) calculations were performed to evaluate the influence of the ring substituents on the acidity of the aromatic hydrogens. Application to the synthesis of novel functionalized phthalides illustrates the great potential of the methodology to the synthesis of bioactive compounds. (C) 2017 Elsevier Ltd. All rights reserved.
• Nitrile-substituted 2-(oxazolinyl)-phenols: minimalistic excited-state intramolecular proton transfer (ESIPT)-based fluorophores
  作者：Dominik Göbel、Daniel Duvinage、Tim Stauch、Boris J. Nachtsheim

  DOI：10.1039/d0tc00776e

  日期：——

  intramolecular proton transfer (ESIPT)-based fluorophores as powerful solid-state emitters. The very simple synthesis gave access to all four regioisomers of nitrile-substituted 2-(oxazolinyl)-phenols (MW = 216.1). In respect of their emission properties they can be divided into aggregation-induced emission enhancement (AIEE) luminophores (1-CN and 2-CN), dual state emission (DSE) emitters (3-CN) and aggregation-caused

  在本文中，我们提出了简约的单苯，激发态分子内质子转移（ESIPT）基荧光团作为强大的固态发射器。非常简单的合成，得到访问腈取代的2-（恶唑啉基）-phenols的所有四个区域异构体（中号w ^ = 216.1）。就其发射特性而言，它们可分为聚集诱发发射增强（AIEE）发光体（1-CN和2-CN），双态发射（DSE）发射体（3-CN）和聚集引起的猝灭（ACQ）荧光团（4-CN）。值得注意的是，使用化合物1-CN，我们发现了一种基于ESIPT的简约荧光团，在固态Φ中具有极高的量子产率˚F =在87.3％ λ EM = 491纳米。此外，在溶液中量子产率的测定高达Φ ˚F = 63.0％，结合斯托克斯向上移动直到11.310厘米-1。与温度有关的发射图，晶体结构分析和与时间有关的密度泛函理论（TDDFT）计算对发射特性的起源提供了深刻的了解。