5-methyl-6-phenyl-2,3-dihydro-1,4-dioxine | 143164-78-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶英
• 英文名称: 5-methyl-6-phenyl-2,3-dihydro-1,4-dioxine
• 英文别名: 5-methyl-6-phenyl-2,3-dihydro-1,4-dioxin；1,4-Dioxin, 2,3-dihydro-5-methyl-6-phenyl-
• CAS: 143164-78-7
• 化学式: C₁₁H₁₂O₂
• 分子量: 176.215
• InChiKey: FOZNWJNEPDEAHE-UHFFFAOYSA-N

物化性质

• 沸点：
  272.1±40.0 °C(Predicted)
• 密度：
  1.087±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  α-Bromopropiophenone cyclic ethylene acetal 在 zinc(II) chloride 作用下， 以 氯苯 为溶剂， 反应 20.0h， 以15%的产率得到2-溴苯丙酮
  参考文献：
  名称：

  Soft and hard acidity in ion-exchanged Y zeolites: rearrangement of 2-bromopropiophenone ethylene acetal to 2-hydroxyethyl 2-phenylpropanoate

  摘要：

  锌交换Y沸石催化2-溴苯丙酮环状乙烯缩醛重排生成2-苯基丙酸2-羟乙酯，其活性比常规ZnCl2更高；由于布朗斯台德酸位点导致的缩醛部分的水解是主要副反应之一，而 5-甲基-6-苯基-2,3-二氢-1,4-二恶英的竞争性形成随着路易斯酸的柔软度而增加酸中心。

  DOI：

  10.1039/c39920000949

文献信息

• Probing the Lewis Acidity and Catalytic Activity of the Metal–Organic Framework [Cu3(btc)2] (BTC=Benzene-1,3,5-tricarboxylate)
  作者：Luc Alaerts、Etienne Séguin、Hilde Poelman、Frédéric Thibault-Starzyk、Pierre A. Jacobs、Dirk E. De Vos

  DOI：10.1002/chem.200600220

  日期：2006.9.25

  diffraction, optical microscopy, SEM, X-ray photoelectron spectroscopy, N2 sorption, thermogravimetry, and IR spectroscopy of adsorbed CO. CO adsorbs on a small number of Cu2O impurities, and particularly on the free CuII coordination sites in the framework. [Cu3(btc)2] is a highly selective Lewis acid catalyst for the isomerization of terpene derivatives, such as the rearrangement of alpha-pinene oxide to

  设计了一种优化程序，用于制备微孔金属有机骨架（MOF）[Cu3（btc）2]（BTC =苯-1,3,5-三羧酸酯）。通过X射线衍射，光学显微镜，SEM，X射线光电子能谱，N2吸附，热重分析和红外光谱对吸附的CO进行表征。CO吸附在少量Cu2O杂质上，尤其是在游离CuII上框架中的协调站点。[Cu3（btc）2]是用于萜烯衍生物异构化的高选择性路易斯酸催化剂，例如将α-pine烯氧化物重排为樟脑醛和将香茅醛环化为异胡薄荷醇。通过使用2-溴苯乙酮的乙烯缩酮作为测试底物，证明了[Cu3（btc）2]中的活性位是硬路易斯酸。催化剂稳定性，
• Soft and hard acidity in ion-exchanged Y zeolites: rearrangement of 2-bromopropiophenone ethylene acetal to 2-hydroxyethyl 2-phenylpropanoate
  作者：María V. Baldoví、Avelinc Corma、Vicente Fornés、Hermenegildo García、Agustín Martínez、Jaime Primo

  DOI：10.1039/c39920000949

  日期：——

  The rearrangement of the cyclic ethylene acetal of 2-bromopropiophenone to 2-hydroxyethyl 2-phenylpropanoate is catalysed by zinc exchanged Y zeolites with higher activity than the conventional ZnCl2; hydrolysis of the acetal moiety owing to the Brønsted acid sites is one of the major side reactions, while the competitive formation of 5-methyl-6-phenyl-2,3-dihydro-1,4-dioxine increases with the softness of the Lewis acid centres.

  锌交换Y沸石催化2-溴苯丙酮环状乙烯缩醛重排生成2-苯基丙酸2-羟乙酯，其活性比常规ZnCl2更高；由于布朗斯台德酸位点导致的缩醛部分的水解是主要副反应之一，而 5-甲基-6-苯基-2,3-二氢-1,4-二恶英的竞争性形成随着路易斯酸的柔软度而增加酸中心。
• CC bond formation strategy through ecocatalysis: Insights from structural studies and synthetic potential
  作者：Claire Garel、Brice-Loïc Renard、Vincent Escande、Anouk Galtayries、Peter Hesemann、Claude Grison

  DOI：10.1016/j.apcata.2015.01.021

  日期：2015.9

  We report the elaboration of novel bio-sourced ecocatalysts for Heck and Suzuki cross-coupling reactions. Ecocatalysis is based on the recycling of metals issued from phytoremediation or rehabilitation, and an innovative chemical valorization of the subsequent biomass in the field of catalysis. Here, we describe the efficient palladium accumulation by plants (Brassica juncea, Lolium multiflorum) via rhizofiltration. Taking advantage of the remarkable ability of the selected plants to accumulate Pd(II) species into their roots, these latter can be directly used for the preparation of ecocatalysts, called Eco-Pd (R). The formed Eco-Pd (R) catalysts are thoroughly characterized via ICP-MS, XRD, XPS, TEM, SEM in order to elucidate the chemical composition and morphology of the formed materials. Significant differences to conventional Pd-based catalysts such as palladium(II) chloride can principally be related to a particular Lewis acid behavior of the Eco-Pd (R) catalysts. Finally, the obtained Eco-Pd (R) appear as highly active catalysts in Heck and Suzuki cross-coupling reactions necessitating considerably lower Pd quantity compared to precedently reported bio-sourced palladium containing catalysts. (C) 2015 Elsevier B.V. All rights reserved.
• A test reaction to assess the presence of Brönsted and the softness/hardness of Lewis acid sites in palladium supported catalysts
  作者：Avelino Corma、Hermenegildo García、Ana Primo、Antonio Domenech

  DOI：10.1039/b311513e

  日期：——

  Cyclic ethylene acetal of α-bromopropiophenone gives rise to three distinctive products, each one being specific to Brönsted, hard Lewis and soft Lewis sites, respectively. In the presence of Brönsted sites, hydrolysis of cyclic acetal forms the corresponding α-bromophenone. Hard or soft Lewis sites promote selectively a rearrangement of the phenyl or ethylenedioxy group to form 2-phenylpropionate ester or dioxine, respectively. This test reaction has been used to assess the influence of the support on the catalytic activity of palladium in zeolites. Three series of supports including alkali-exchanged faujasite, Beta zeolites and sepiolites have been tested. It has been observed that the nature of the zeolite plays an important role on the palladium selectivity, basic supports increasing the softness of the palladium Lewis sites. The catalytic test correlates well with electrochemical data about the reduction potential of supported palladium, XPS characterization of the oxidation state of palladium supported on the surface and activity in the Suzuki reaction.

  α-溴苯丙酮的环状乙烯缩醛产生三种独特的产物，每种产物分别针对布朗斯台德、硬路易斯和软路易斯位点。在布朗斯台德位点存在下，环状缩醛水解形成相应的 α-溴苯酮。硬或软路易斯位点选择性地促进苯基或乙二氧基的重排，分别形成2-苯基丙酸酯或二恶英。该测试反应已用于评估载体对沸石中钯催化活性的影响。已经测试了三个系列的载体，包括碱交换八面沸石、β沸石和海泡石。据观察，沸石的性质对钯选择性起着重要作用，碱性载体增加了钯路易斯位点的柔软度。催化测试与负载钯还原电位的电化学数据、表面负载钯氧化态的 XPS 表征以及 Suzuki 反应的活性密切相关。