2-isopropoxy-5-chlorostyrene | 918870-78-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-isopropoxy-5-chlorostyrene
• 英文别名: 4-Chloro-2-ethenyl-1-[(propan-2-yl)oxy]benzene；4-chloro-2-ethenyl-1-propan-2-yloxybenzene
• CAS: 918870-78-7
• 化学式: C₁₁H₁₃ClO
• 分子量: 196.677
• InChiKey: VBAQGGGOUCMVEZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  13
• 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：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-isopropoxy-5-chlorostyrene 在 silver(I) chloride 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 生成 (1-(1-adamantyl)-3-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro((o-isopropoxy)m-chlorophenylmethylidene)ruthenium
  参考文献：
  名称：

  Carboxylate-Assisted C(sp³)–H Activation in Olefin Metathesis-Relevant Ruthenium Complexes

  摘要：

  The mechanism of C H activation at metathesis-relevant ruthenium(II) benzylidene complexes was studied both experimentally and computationally. Synthesis of a ruthenium dicarboxylate at a low temperature allowed for direct observation of the C H activation step, independent of the initial anionic ligand-exchange reactions. A first-order reaction supports an intramolecular concerted metalation-deprotonation mechanism with Delta G(298K)double dagger = 22.2 +/- 0.1 kcal.mol(-1) for the parent N-adamantyl-N'-mesityl complex. An experimentally determined Delta S double dagger = 5.2 +/- 2.6 eu supports a highly ordered transition state for carboxylate-assisted C(sp(3))-H activation. Experimental results, including measurement of a large primary kinetic isotope effect (k(H)/k(D) = 8.1 +/- 1.7), agree closely with a computed six-membered carboxylate-assisted C H activation mechanism where the deprotonating carboxylate adopts a pseudo-apical geometry, displacing the aryl ether chelate. The rate of cyclometalation was found to be influenced by both the electronics of the assisting carboxylate and the ruthenium ligand environment.

  DOI：

  10.1021/ja5021958

文献信息

• Recyclable ruthenium catalysts for metathesis reactions
  申请人：Zhan James Zheng-Yun

  公开号：US20070043180A1

  公开（公告）日：2007-02-22

  The invention relates to novel carbene ligands and their incorporated monomeric and resin/polymer linked ruthenium catalysts, which are recyclable and highly active for olefin metathesis reactions. It is disclosed that significant electronic effect of different substituted 2-alkoxybenzylidene ligands on the catalytic activity and stability of corresponding carbene ruthenium complexes, some of novel ruthenium complexes in the invention can be broadly used as catalysts highly efficient for olefin metathesis reactions, particularly in ring-closing (RCM), ring-opening (ROM), ring-opening metathesis polymerization (ROMP) and cross metathesis (CM) in high yield. The invention also relates to preparation of new ruthenium complexes and the use in metathesis.

  该发明涉及新型卡宾配体及其包含的单体和树脂/聚合物连接的钌催化剂，这些催化剂可回收利用，并且在烯烃转化反应中具有高活性。据披露，不同取代的2-烷氧基苯甲亚甲基配体对相应的卡宾钌配合物的催化活性和稳定性具有显著的电子效应，该发明中的一些新型钌配合物可广泛用作高效的烯烃转化反应催化剂，特别是在高产率下进行环内（RCM）、环开（ROM）、环开环聚合物化（ROMP）和交叉烯烃转化（CM）。该发明还涉及新型钌配合物的制备和在转化反应中的使用。
• RECYCLABLE RUTHENIUM CATALYSTS FOR METATHESIS REACTIONS
  申请人：ZHAN Zheng-Yun James

  公开号：US20100041844A1

  公开（公告）日：2010-02-18

  The invention relates to novel carbene ligands and their incorporated monomeric and resin/polymer linked ruthenium catalysts, which are recyclable and highly active for olefin metathesis reactions. It is disclosed that significant electronic effect of different substituted 2-alkoxybenzylidene ligands on the catalytic activity and stability of corresponding carbene ruthenium complexes, some of novel ruthenium complexes in the invention can be broadly used as catalysts highly efficient for olefin metathesis reactions, particularly in ring-closing (RCM), ring-opening (ROM), ring-opening metathesis polymerization (ROMP) and cross metathesis (CM) in high yield. The invention also relates to preparation of new ruthenium complexes and the use in metathesis.

  本发明涉及新型卡宾配体及其单体和树脂/聚合物连接的钌催化剂，该催化剂可回收利用且对烯烃重排反应具有高活性。本发明揭示了不同取代的2-烷氧基苯甲醛卡宾配体对相应卡宾钌配合物的催化活性和稳定性的显著电子效应。本发明中的一些新型钌配合物可广泛用作烯烃重排反应的高效催化剂，特别是在高收率下的环闭合反应（RCM）、环开放反应（ROM）、环开放重排聚合（ROMP）和交叉重排反应（CM）中。本发明还涉及新的钌配合物的制备和在重排反应中的应用。
• The utility of Hoveyda-type catalysts in ADMET chemistry: Sterics versus electronics
  作者：Florence C. Courchay、John C. Sworen、Armando Coronado、Kenneth B. Wagener

  DOI：10.1016/j.molcata.2006.02.073

  日期：2006.7

  remain constant regardless of the X substituent. Nevertheless, complexes bearing electron donating groups seem to be more stable and result in higher DPs than complexes bearing electron withdrawing groups. In any case, catalysts containing larger NHC ligands are more efficient in ADMET chemistry than any modified Hoveyda–Grubbs catalyst. At 60 °C, the electronic factor becomes evident and the substituted

  研究了在不同温度下（L）（Cl）2 Ru = CH（o - i PrOC 6 H 3 X）（L = H 2 IPr或H ）配合物的配体球形电子/空间对催化活性的影响。2 IMes，X ＝ NO 2，Cl，H，CH 3，OCH 3）。在ADMET聚合条件下评估了它们的动力学行为。在所有温度下，N-杂环卡宾H 2引起的位阻IPr主导任何电子效应，因为无论X取代基如何，初始速率均保持恒定。然而，带有电子给予基团的配合物似乎比带有吸电子基团的配合物更稳定并且导致更高的DP。无论如何，含有较大NHC配体的催化剂在ADMET化学中比任何改良的Hoveyda-Grubbs催化剂都更有效。在60°C时，电子因子变得明显，取代的催化剂表现出明显更高的反应性，从而导致ADMET反应中出现的最快初始速率。
• RUTHENIUM COMPLEX LIGAND, RUTHENIUM COMPLEX, CARRIED RUTHENIUM COMPLEX CATALYST AND THE PREPARING METHODS AND THE USE THEREOF
  申请人：Zannan Scitech Co., Ltd.

  公开号：EP1905777B2

  公开（公告）日：2018-06-27
• HERBIZID WIRKSAME 3-PHENYLISOXAZOLINDERIVATE
  申请人：Bayer CropScience AG

  公开号：EP2900645A1

  公开（公告）日：2015-08-05