2-isopropoxy-4-nitrostyrene | 753031-08-2

• 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: 2-isopropoxy-4-nitrostyrene
• 英文别名: 1-Ethenyl-4-nitro-2-propan-2-yloxybenzene
• CAS: 753031-08-2
• 化学式: C₁₁H₁₃NO₃
• 分子量: 207.229
• InChiKey: NEGIRWXKQSHFDC-UHFFFAOYSA-N

物化性质

• 沸点：
  296.4±20.0 °C(Predicted)
• 密度：
  1.122±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  55
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Umicore M31 、 2-isopropoxy-4-nitrostyrene 以 甲苯 为溶剂， 反应 2.0h， 以85%的产率得到Grela's catalyst
  参考文献：
  名称：

  METHOD FOR PREPARATION OF RUTHENIUM-BASED METATHESIS CATALYSTS WITH CHELATING ALKYLIDENE LIGANDS

  摘要：

  本发明涉及一种制备基于钌的螯合烷基配体（“Hoveyda型催化剂”）的方法，通过将一种五配位钌（II）-烷基烯配合物（L）（Py）X1X2Ru（烷基烯）与适当的烯烃衍生物在交叉重排反应中反应。该方法提供高产率，并且最好在芳香烃溶剂中进行。可以避免使用含膦基钌烷基配合物作为起始材料。可以获得高纯度的催化剂产品，特别是低铜含量的催化剂产品。

  公开号：

  US20120101279A1
• 作为产物：
  描述：

  2-溴-5-硝基苯酚 在 四(三苯基膦)钯 、 potassium carbonate 、 caesium carbonate 作用下， 以 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 6.17h， 生成 2-isopropoxy-4-nitrostyrene
  参考文献：
  名称：

  Nitro-Substituted Hoveyda−Grubbs Ruthenium Carbenes:  Enhancement of Catalyst Activity through Electronic Activation

  摘要：

  The design, synthesis, stability, and catalytic activity of nitro-substituted Hoveyda-Grubbs metathesis catalysts are described. The highly active and stable meta- and para-substituted complexes are attractive from a practical point of view. These catalysts operate in very mild conditions and can be successfully applied in various types of metathesis [ring-closing metathesis, cross-metathesis (CM), and enyne metathesis]. Although the presence of a NO2 group leads to catalysts that are dramatically more active than both the second-generation Grubbs's catalyst and the phosphine-free Hoveyda's carbene, enhancement of reactivity is somewhat lower than that observed for a sterically activated Hoveyda-Grubbs catalyst. Attempts to combine two modes of activation, steric and electronic, result in severely decreasing a catalyst's stability. The present findings illustrate that different Ru catalysts turned out to be optimal for different applications. Whereas phosphine-free carbenes are catalysts of choice for CM of various electron-deficient substrates, they exhibit lower reactivity in the formation of tetrasubstituted double bonds. This demonstrates that no single catalyst outperforms all others in all possible applications.

  DOI：

  10.1021/ja048794v

文献信息

• Easily removable olefin metathesis catalysts
  作者：Krzysztof Skowerski、Celina Wierzbicka、Grzegorz Szczepaniak、Łukasz Gułajski、Michał Bieniek、Karol Grela

  DOI：10.1039/c2gc36015b

  日期：——

  A small family of olefin metathesis catalysts bearing a polar quaternary ammonium group is described. The presence of this group allows for efficient separation of ruthenium impurities after the reaction. Application of catalysts 9 and 11 leads to organic products of high purity, which exhibit surprisingly low ruthenium contamination levels (usually below 5 ppm) after a simple and inexpensive purification step.

  描述了一类带有极性季铵盐官能团的小型烯烃复分解催化剂家族。该官能团的存在使得反应后能够高效分离铑杂质。应用催化剂9和11，能够得到高纯度的有机产物，在简单廉价的后处理后，显示出了令人惊讶的低铑污染水平（通常低于5ppm）。
• Remarkable Ability of the Benzylidene Ligand To Control Initiation of Hoveyda–Grubbs Metathesis Catalysts
  作者：Tymoteusz Basak、Krzysztof Grudzień、Michał Barbasiewicz

  DOI：10.1002/ejic.201600435

  日期：2016.7

  chelating benzylidene ligand offers the unique ability to control the initiation of Hoveyda–Grubbs metathesis catalysts. Apart from steric and electronic effects acting on the step involving opening of the chelate ring, changes related to the following ligand-exchange process may also play a critical role. Our mechanistic model reveals that ligands substituted at the 6-position of the benzylidene ring enter

  螯合亚苄基配体的结构提供了控制 Hoveyda-Grubbs 复分解催化剂引发的独特能力。除了空间和电子效应作用于螯合环打开的步骤之外，与随后的配体交换过程相关的变化也可能起到关键作用。我们的机理模型表明，在亚苄基环的 6 位取代的配体以非最佳螯合构象进入复分解循环，因此钌中心的配位数暂时增加到 6（缔合机制）。实际上，催化剂的合成和引发变得困难，配体交换过程的能垒受配位 OR 基团的结构控制。而且，
• Routes to High-Performing Ruthenium–Iodide Catalysts for Olefin Metathesis: Ligand Lability Is Key to Efficient Halide Exchange
  作者：Christian O. Blanco、Daniel L. Nascimento、Deryn E. Fogg

  DOI：10.1021/acs.organomet.1c00253

  日期：2021.6.28

  shown to enable high productivity in olefin metathesis. For the second-generation Grubbs and Hoveyda catalysts (GII: RuCl2(H2IMes)(PCy3)(═CHPh); HII: RuCl2(H2IMes)(═CHAr), Ar = C6H4-2-OiPr), slow salt metathesis is shown to arise from the low lability of the ancillary PCy3 or ether ligands, which retards access to the four-coordinate intermediate required for efficient halide exchange. To exploit the lability

  描述了二碘化钌催化剂的清洁、高产路线，该催化剂最近被证明可以实现烯烃复分解的高生产率。对于第二代Grubbs和Hoveyda催化剂（ GII : RuCl 2 (H 2 IMes)(PCy 3 )(=CHPh); HII : RuCl 2 (H 2 IMes)(=CHAr), Ar = C 6 H 4 -2 -O i Pr)，缓慢的盐复分解作用被证明是由辅助 PCy 3或醚配体的低不稳定性引起的，这阻碍了有效卤化物交换所需的四配位中间体的获得。为了利用第一代催化剂的稳定性，通过处理“Grubbs I”(RuCl 2 (PCy 3 ) 2 (=CHPh)， GI制备二碘化物配合物RuI 2 (PCy 3 )(=CHARr) HI-I 2 ) 与 NaI、H 2 C=CHARr ( 1a ) 和磷化氢清除 Merrifield 碘化物 ( MF-I ) 树脂。随后安装 H 2 IMes 或环状
• Process for Preparation of Ruthenium-Based Carbene Catalysts with Chelating Alkylidene Ligands
  申请人：Monsaert Stijn Frans

  公开号：US20130035494A1

  公开（公告）日：2013-02-07

  The invention relates to a method for preparation of ruthenium-based carbene catalysts with chelating alkylidene ligands (so-called “Hoveyda-type catalysts”) in a cross metathesis reaction by reacting a ruthenium-alkylidene complex with an olefin derivate in the presence of a polymer-supported cation-exchange resin (PSR) acting as a ligand (i.e. phosphine or amine) scavenger. Preferably, penta-coordinated ruthenium benzylidene or indenylidene carbene complexes are employed. The polymer-supported cation-exchange resin (PSR) may be an acidic resin (comprising sulfonic acid or carboxylic groups) or a resin containing carboxylic acid chloride (—COCl) groups or sulfonyl chloride (—SO 2 Cl) groups. The process is versatile and environmentally friendly; high yields are obtained.

  本发明涉及一种制备带有螯合烷基亚烯配体（称为“Hoveyda型催化剂”）的基于钌的卡宾催化剂的方法，通过在聚合物支持的阳离子交换树脂（PSR）的存在下，将钌-烷基亚烯配合物与烯烃衍生物反应，作为配体（即膦或胺）清除剂的交换树脂。优选地，采用五配位钌苄基亚烯或茚基亚烯卡宾配合物。聚合物支持的阳离子交换树脂（PSR）可以是酸性树脂（包含磺酸或羧基团）或含有羧酸氯（-COCl）基团或磺酰氯（-SO2Cl）基团的树脂。该过程具有多功能性和环保性，可获得高收率。
• Process for preparation of ruthenium-based carbene catalysts with chelating alkylidene ligands
  申请人：Umicore AG & Co. KG

  公开号：EP2361683A1

  公开（公告）日：2011-08-31

  The invention relates to a method for preparation of ruthenium-based carbene catalysts with chelating alkylidene ligands (so-called "Hoveyda-type catalysts") in a cross metathesis reaction by reacting a ruthenium-alkylidene complex with an olefin derivate in the presence of a polymer-supported cation-exchange resin (PSR) acting as a ligand (i.e. phosphine or amine) scavenger. Preferably, penta-coordinated ruthenium benzylidene or indenylidene carbene complexes are employed. The polymer-supported cation-exchange resin (PSR) may be an acidic resin (comprising sulfonic acid or carboxylic groups) or a resin containing carboxylic acid chloride (-COC1) groups or sulfonyl chloride (-SO2C1) groups. The process is versatile and environmentally friendly; high yields are obtained.

  本发明涉及一种在交叉复分解反应中制备具有螯合亚烷基配体的钌基碳烯催化剂（即所谓的 "Hoveyda 型催化剂"）的方法，该方法是在聚合物支撑阳离子交换树脂（PSR）作为配体（即膦或胺）清除剂的存在下，使钌-亚烷基络合物与烯烃衍生物反应。最好是使用五配位钌苄叉碳化物或茚叉碳化物络合物。聚合物支持的阳离子交换树脂（PSR）可以是酸性树脂（包含磺酸或羧基）或含有羧酰氯（-COC1）基团或磺酰氯（-SO2C1）基团的树脂。该工艺用途广泛，对环境友好，产量高。