9,12-dioxa-1,6,14,19-eicosatetraene | 42954-38-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 9,12-dioxa-1,6,14,19-eicosatetraene
• 英文别名: ethyl-1,2-di(octa-2,7-dienyl)ether；1,2-bis(2,7-octadien-1-yloxy)-ethane；8-(2-Octa-2,7-dienoxyethoxy)octa-1,6-diene；8-(2-octa-2,7-dienoxyethoxy)octa-1,6-diene
• CAS: 42954-38-1
• 化学式: C₁₈H₃₀O₂
• 分子量: 278.435
• InChiKey: CGHNQABZZONXFF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  20
• 可旋转键数：
  15
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  乙二醇 、 1,3-丁二烯 在 palladium catalyst 作用下， 反应 20.0h， 以80%的产率得到9,12-dioxa-1,6,14,19-eicosatetraene
  参考文献：
  名称：

  Dzhemilev, U. M.; Kunakova, R. V.; Baibulatova, N. Z., Journal of Organic Chemistry USSR (English Translation), 1980, vol. 16, p. 999 - 1002

  摘要：

  DOI：

文献信息

• Synthesis of octyl-ethers of biomass-based glycols through two competitive catalytic routes: Telomerization and etherification
  作者：Andrei N. Parvulescu、Peter J.C. Hausoul、Pieter C.A. Bruijnincx、Robertus J.M. Klein Gebbink、Bert M. Weckhuysen

  DOI：10.1016/j.cattod.2010.05.021

  日期：2010.12

  pathway can be followed for the synthesis of the desired end products. One such example is the synthesis of octyl-ethers from biomass-based glycols, which can be made either via the telomerization of 1,3-butadiene or the direct etherification of long linear alkenes. For both processes active and selective catalysts have been developed in our groups and their activity and selectivity have been investigated

  人们对生物质增值的兴趣日益浓厚，引发了全球范围内寻找新的催化路线来转变交通燃料和有价值的化学物质中基于生物质的衍生物的探索。预期在大多数情况下，可以遵循一个以上的催化途径来合成所需的最终产物。一个这样的例子是由基于生物质的二醇合成辛基醚，其可以通过1，3-丁二烯的端粒化或长直链烯烃的直接醚化来进行。对于这两种方法，我们小组都开发了活性催化剂和选择性催化剂，并在无溶剂条件下研究了它们的活性和选择性。1,3-丁二烯的端粒化提供线性均相的Pd / TOMPP（TOMPP = Tris-（o-甲氧基苯基）膦）催化剂可高产率（最高80％）合成辛基醚。对于乙二醇与1-辛烯的直接醚化反应，H-Beta沸石是非常有前途的非均相催化剂，可生产支链辛基醚，收率高达80％。在这项工作中，详细说明了催化剂性能和乙二醇结构的影响，并讨论了两种催化途径的优缺点。
• Telomerization of 1,3-butadiene with various alcohols by Pd/TOMPP catalysts: new opportunities for catalytic biomass valorization
  作者：Regina Palkovits、Andrei N. Parvulescu、Peter J. C. Hausoul、Cornelis A. Kruithof、Robertus J. M. Klein Gebbink、Bert M. Weckhuysen

  DOI：10.1039/b904274a

  日期：——

  The telomerization of 1,3-butadiene with various alcohols has been investigated using a catalyst based on a Pd(acac)2 precursor and a phosphine ligand, TOMPP (TOMPP = tris-(o-methoxyphenyl)phosphine). We were able to demonstrate the capability of the catalyst to telomerize 1,3-butadiene with various multifunctional nucleophiles having primary and secondary alcohol functions. High yields of telomer products (>98%) were obtained in very short reaction times (<2 h). The telomerization activity and selectivity of the Pd/TOMPP complex was strongly influenced by the type of alcohol used as substrate. When diols were used, telomerization of 1,3-butadiene with 1,2-propanediol and 1,2-butanediol afforded the highest yield of mono-telomer (over 70%) and for 1,2-butanediol a turnover frequency (TOF) of 300 000 h−1 was reached, combined with a turnover number (TON) of 7800.

  使用基于Pd(acac)2前体和磷配体TOMPP（TOMPP = 三(邻甲氧基苯基)膦）的催化剂，研究了1,3-丁二烯与各种醇的调聚反应。我们证明了该催化剂具有将1,3-丁二烯与具有伯醇和仲醇功能的多功能亲核试剂进行调聚的能力。在非常短的反应时间内（<2小时），获得了高产率的调聚产物（>98%）。Pd/TOMPP络合物的调聚活性和选择性受到所用醇类型的强烈影响。当使用二醇时，1,3-丁二烯与1,2-丙二醇和1,2-丁二醇的调聚反应获得了最高的一调聚物产率（超过70%），而对于1,2-丁二醇，达到了300,000 h−1的转化频率（TOF）和7800的转化数（TON）。
• Application of the solvent water in two-phase telomerisation reactions and recycling of the homogeneous palladium catalysts
  作者：Arno Behr、Julia Leschinski

  DOI：10.1039/b820305a

  日期：——

  In the chemical industry organic solvents should be avoided wherever possible. They are often toxic to marine organisms and plants as well as to higher organisms and humans. Moreover, volatile organic compounds (VOC) cause air pollution which leads to the necessity of expensive separation technologies like waste water or exhaust gas treatments. Solutions for these problems are either the development of processes without the use of any solvent or the use of environmentally benign solvents such as water. In this contribution it is shown how versatile water can be, used as a solvent in homogeneously catalysed processes, for example, telomerisation reactions with methanol, diethylamine, ethylene glycol and glycerol. In this context another positive effect of the solvent water is the ecologically and economically required retention of the transition metal catalyst inside the process. Furthermore, different reactor types, a loop reactor and a mixer-settler reactor, are presented to cope with the challenges of mass transport limitations and selectivity control in aqueous biphasic systems.

  在化学工业中，应尽可能避免使用有机溶剂。它们通常对海洋生物和植物以及高等生物和人类有毒。此外，挥发性有机化合物（VOC）会造成空气污染，因此必须采用昂贵的分离技术，如废水或废气处理。解决这些问题的办法要么是开发不使用任何溶剂的工艺，要么是使用对环境无害的溶剂，如水。本论文展示了水在均相催化过程中作为溶剂的多功能性，例如与甲醇、二乙胺、乙二醇和甘油的端聚反应。在这种情况下，溶剂水的另一个积极作用是在工艺中保留过渡金属催化剂，这既符合生态学要求，也符合经济学要求。此外，还介绍了不同类型的反应器（循环反应器和混合器-沉降器反应器），以应对水基双相系统中质量传输限制和选择性控制的挑战。