3-methyl-2,5-dihydrobenzo[b]oxepine | 72085-92-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噁庚英
• 英文名称: 3-methyl-2,5-dihydrobenzo[b]oxepine
• 英文别名: 3-Methyl-2,5-dihydro-1-benzoxepine；3-methyl-2,5-dihydro-1-benzoxepine
• CAS: 72085-92-8
• 化学式: C₁₁H₁₂O
• 分子量: 160.216
• InChiKey: FWZCNUGJGBFSFP-UHFFFAOYSA-N

物化性质

• 沸点：
  246.8±25.0 °C(Predicted)
• 密度：
  1.024±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• 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

• 作为产物：
  描述：

  2-(tert-butyldimethylsilyloxy)toluene 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 N-溴代丁二酰亚胺(NBS) 、 三苯胂 、 四丁基氟化铵 、 4-甲基苯磺酸吡啶 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 乙二醇二甲醚 为溶剂， 反应 1.0h， 生成 3-methyl-2,5-dihydrobenzo[b]oxepine
  参考文献：
  名称：

  A new preparation of 2,5-dihydro-1-benzoxepins using Mitsunobu cyclization, and the synthesis of natural radulanins

  摘要：

  Mitsunobu cyclization of o-[4-hydroxy-3-methyl-2(Z)-butenyl]pheno 2a effected selective seven-membered cyclization to give 3-methyl-2,5-dihydro-1-benoxepin la. Using this procedure, natural radulanin A and radulanin A methyl ether were synthesized effectively. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(00)00676-6

文献信息

• A Scalable Membrane Pervaporation Approach for Continuous Flow Olefin Metathesis
  作者：Christopher P. Breen、Christine Parrish、Ning Shangguan、Sudip Majumdar、Hannah Murnen、Timothy F. Jamison、Matthew M. Bio

  DOI：10.1021/acs.oprd.0c00061

  日期：2020.10.16

  The translation of olefin metathesis reactions from the laboratory to process scale has been challenging with traditional batch techniques. In this contribution, we describe a continuous membrane reactor design that selectively permeates the ethylene byproduct from metathetical processes, thereby overcoming the mass-transport limitations that have negatively influenced the efficiency of this transformation

  使用传统的批处理技术，将烯烃复分解反应从实验室转换为工艺规模一直具有挑战性。在这一贡献中，我们描述了一种连续膜反应器设计，该设计可选择性地渗透易位过程中的乙烯副产物，从而克服了对分批容器中这种转化效率产生负面影响的传质限制。在二烯丙基丙二酸二乙酯闭环复分解的情况下，膜框式透膜蒸发模块的转换数> 7500。更具挑战性，低效率的底物，环辛烯和14元大环内酯的制备也是有效的。
• A Unique Ruthenium Carbyne Complex: A Highly Thermo-endurable Catalyst for Olefin Metathesis
  作者：Mingbo Shao、Lu Zheng、Weixia Qiao、Jingjing Wang、Jianhui Wang

  DOI：10.1002/adsc.201200119

  日期：2012.10.8

  A cationic ruthenium carbyne complex was prepared and was found to initiate olefin metathesis reactions with good activities, which throws a new light on the design of a new type of ruthenium catalyst for RCM reactions. More importantly, no double bond isomerized by-product was observed even at elevated temperatures in reactions catalyzed by the new carbyne complex. A mechanism involving the in situ

  制备了一种阳离子钌卡宾络合物，发现该催化剂能引发烯烃复分解反应，并具有良好的活性，这为新型的用于RCM反应的钌催化剂的设计提供了新的思路。更重要的是，即使在新的卡宾络合物催化的反应中，即使在升高的温度下，也没有观察到双键异构化的副产物。还提出了一种机制，该机制涉及通过将碘化物添加到卡宾碳上而将卡宾碳烯原位转化为钌卡宾络合物。
• Synthesis and reactivity of oxygen chelated ruthenium carbene metathesis catalysts
  作者：Yiran Zhang、Mingbo Shao、Huizhu Zhang、Yuqing Li、Dongyu Liu、Yu Cheng、Guiyan Liu、Jianhui Wang

  DOI：10.1016/j.jorganchem.2014.01.017

  日期：2014.4

  and the terminal oxygen of the benzylidene ether are both coordinated to the metal to give an octahedral structure. However, the carbonyl oxygen of complexes (H2IMes)(Cl)2RuC(H)[(C6H3X)OCH(CH2C(O)OCH2)(X = H, OMe)] does not coordinate to the metal due to the steric effect of the lactone. All these complexes were used as catalysts for olefin metathesis reactions and all exhibited excellent performances

  Hoveyda催化剂的引发速率受作用于Ru O配位的电子和空间效应的影响。为了提高Hoveyda催化剂的活性，已经开发了一系列新型的含有N-杂环卡宾（NHC）和羰基的氧螯合钌卡宾复分解催化剂，并研究了它们对烯烃复分解反应的催化活性。配合物的脂肪族端基（H 2 IMes）（Cl）2 Ru C（H）[（C 6 H 3 X）OCH（Me）（C（O）OEt）（X = H，OMe，Me，NO 2）]通过连接直链酯进行官能化。复杂（H 2 IMes）（Cl）2的X射线结构Ru C（H）[（C 6 H 4）OCH（Me）（C（O）NMe 2）]显示酰胺的羰基氧和亚苄基醚的末端氧均与金属配位，得到八面体结构。但是，配合物（H 2 IMes）（Cl）2 Ru C（H）[（C 6 H 3 X）OCH（CH 2 C（O）OCH 2）（X = H，OMe）]由于内酯的空间效应不与金属配位。所有这些络合物均用作烯烃
• Efficient ruthenium metathesis catalysts containing carborane ligands
  作者：Guiyan Liu、Huizhu Zhang、Xia Zhao、Jianhui Wang

  DOI：10.1016/j.jorganchem.2013.09.005

  日期：2014.1

  A first generation Hoveyda–Grubbs ruthenium complex with a closo-1,2-C2B10H11 tag has been prepared. This new catalyst was tested in ring-closing metathesis (RCM) reactions and proved to be quite efficient. In addition, the recovery and reuse of a previously reported second generation Hoveyda–Grubbs ruthenium carbene complex bearing an ionic [nido-7,8-C2B9H10]− tag was further studied. When used in

  制备了带有closo-1,2-C 2 B 10 H 11标签的第一代Hoveyda-Grubbs钌络合物。该新型催化剂已在闭环复分解（RCM）反应中进行了测试，并被证明非常有效。另外，还对先前报道的带有离子[nido-7,8-C 2 B 9 H 10 ] -标记的第二代Hoveyda-Grubbs钌卡宾络合物的回收和再利用进行了研究。当用于离子液体中时，该催化剂可以方便地回收和再利用，而对含二或三取代双键的含氧和N保护的底物的RCM活性仅有非常轻微的损失。
• Synthesis and Catalytic Activity of a Grubbs-Hoveyda Pre-catalyst Having a Trimeric Resting State
  作者：Guiyan Liu、Bin Wu、Jianhui Wang

  DOI：10.1002/cjoc.201400765

  日期：2015.4

  A Grubbs‐Hoveyda pre‐catalyst having a trimeric resting state based on 2,4,6‐trichloro‐1,3,5‐triazine was synthesized and the complex was characterized by NMR, HRMS and elemental analysis. The activity of this complex for ring‐closing metathesis (RCM) was investigated. The catalytic system possesses high catalytic activity for many different olefin substrates.

  合成了基于2,4,6-三氯-1,3,5-三嗪的三聚体静止状态的Grubbs-Hoveyda预催化剂，并通过NMR，HRMS和元素分析对其进行了表征。研究了该复合物在闭环复分解（RCM）中的活性。该催化体系对许多不同的烯烃底物具有高催化活性。