4-pentenoate | 20224-66-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 4-pentenoate
• 英文别名: Pent-4-enoate
• CAS: 20224-66-2
• 化学式: C₅H₇O₂
• 分子量: 99.1094
• InChiKey: HVAMZGADVCBITI-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  40.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  一氧化碳 、 4-pentenoate 在 acetylacetonatodicarbonylrhodium(l) 、 4-diphenylphosphanyl-N-[2-[1-[7-[(4-diphenylphosphanylbenzoyl)amino]-3-methyl-1H-indol-2-yl]propyl]-3-methyl-1H-indol-7-yl]benzamide 、 氢气 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 40.0 ℃ 、2.0 MPa 条件下， 反应 24.0h， 生成 adipate semialdehyde
  参考文献：
  名称：

  Rh催化末端和内部烯烃加氢甲酰化反应选择性的精确超分子控制

  摘要：

  在这项研究中，我们报告了一系列 DIMPhos 配体 L1-L3，双齿磷配体，配有完整的阴离子结合位点（DIM 口袋）。配位研究表明，这些配体以双齿方式与铑中心结合。在加氢甲酰化条件下的实验证实了单核氢化双羰基铑配合物的形成，这些配合物通常被认为在加氢甲酰化中具有活性。形成的金属配合物仍然与配体结合位点的阴离子物质强结合，而不影响金属配位球。DIMPhos 的这些双功能特性通过铑络合物的晶体结构进一步证明，其中醋酸根阴离子结合在配体的结合位点。催化研究表明，通过结合在配体的 DIM 口袋中进行的底物预组织导致末端和内部烯烃的加氢甲酰化具有前所未有的选择性。值得注意的是，选择性控制阴离子基团甚至可以与反应性双键相距 10 个键，这证明了这种超分子方法的潜力。对照实验证实了阴离子结合对选择性的关键作用。对决定性中间体的 DFT 研究表明，DIM 口袋中的阴离子结合限制了反应双键的旋转自由度。结

  DOI：

  10.1021/ja4046235

文献信息

• Regioselective Hydroformylation of Internal and Terminal Alkenes via Remote Supramolecular Control
  作者：Pim R. Linnebank、Stephan Falcão Ferreira、Alexander M. Kluwer、Joost N. H. Reek

  DOI：10.1002/chem.202000620

  日期：2020.7.2

  Regioselective catalytic transformations using supramolecular directing groups are increasingly popular as it allows for control over challenging reactions that may otherwise be impossible. In most examples the reactive group and the directing group are close to each other and/or the linker between the directing group is very rigid. Achieving control over the regioselectivity using a remote directing

  使用超分子指导基团的区域选择性催化转化正变得越来越普遍，因为它可以控制原本不可能的挑战性反应。在大多数实例中，反应性基团和导向基团彼此靠近和/或导向基团之间的连接基非常刚性。由于这种底物的构象自由度大，使用具有柔性接头的远程指导基团来实现对区域选择性的控制明显更具挑战性。在本文中，我们报告了含有中性羧酸盐受体（DIM袋）且亚磷酸酯金属结合部分与DIM袋之间的距离较大的超分子Rh-双亚磷酸酯加氢甲酰化催化剂的重新设计。首次证明了含有远端羧酸酯导向基团的内部和末端烯烃的区域选择性转化。对于在Δ-9位具有内部双键的羧酸酯底物，可以观察到区域选择性。因此，该催化剂用于以区域选择性方式加氢甲酰化天然单不饱和脂肪酸（MUFA），形成过量的10-甲酰基产物（10-甲酰基/ 9-甲酰基产物比率为2.51），这是首次报道这种底物的区域选择性加氢甲酰化反应的研究。
• Method for polymerizing cycloolefin polymer containing polar functional groups and electronic devices employing the polymerized cycloolefins
  申请人：Yoon Sung-Cheol

  公开号：US20050085606A1

  公开（公告）日：2005-04-21

  Disclosed is a method for preparing a cycloolefin polymer containing polar functional groups, comprising: preparing a catalyst mixture including i) a precatalyst, containing a Group 10 transition metal having a ligand containing oxygen ions bonded to the metal; ii) a first cocatalyst which is an organic compound containing a Group 15 element; and iii) a second cocatalyst which is capable of providing an anion and weakly coordinating to the metal of the precatalyst; and subjecting a monomer solution comprising a norbornene-based compound containing a polar functional group to an addition polymerization reaction in the presence of an organic solvent and the catalyst mixture, at a temperature of 80-200° C., the total amount of the organic solvent being 50-800% by weight based on the total weight of the monomer contained in the monomer solution, and the product yield of the polymer being 50% by weight or more based on the total weight of the monomer.

  本发明公开了一种制备含极性官能团的环氧烷基聚合物的方法，包括：制备催化剂混合物，其中包括i）一种前催化剂，其含有一个含氧离子与金属配位的第10族过渡金属；ii）一种第一辅助催化剂，其是一种含有第15族元素的有机化合物；和iii）一种能够提供阴离子并弱配位于前催化剂金属的第二辅助催化剂；并在有机溶剂和催化剂混合物的存在下，将含有极性官能团的诺博烯基化合物的单体溶液在80-200℃的温度下进行加成聚合反应，所述有机溶剂的总量基于单体溶液中的单体总重量为50-800重量％，聚合物的产率基于单体的总重量为50重量％或更高。
• Method for preparing norbornene based addition polymer containing ester or acetyl functional group
  申请人：——

  公开号：US20040254318A1

  公开（公告）日：2004-12-16

  The present invention relates to a method for preparing a cyclic olefin polymer by addition polymerization, and more particularly to a method for preparing a norbornene-based addition polymer, which comprises a step of contacting a norbornene-based monomer having an ester or acctyl group with a catalyst system comprising: a Group X transition metal compound; a compound comprising a neutral Group XV electron donor ligand having a cone angle of at least 160°; and a salt capable of offering an anion that can be weakly coordinated to the transition metal, in solvent. The norbornene-based addition polymer having an ester or acetyl group according to the present invention is transparent, has superior adhesivity and a low dielectric constant, and it generates no byproducts when attached to metal. Therefore, it can be used as an optical film, a retardation film, a protection film for a polarizer POFs (plastic optical fiber), PCBs (printed circuit board), or insulators of electronic devices.

  本发明涉及一种通过加成聚合制备环烯基聚合物的方法，更具体地涉及一种制备基于诺伯烯的加成聚合物的方法，其中包括以下步骤：将具有酯基或乙酰基的诺伯烯基单体与催化剂体系接触，该催化剂体系包括：X族过渡金属化合物；包含一个具有至少160°锥角的中性XV族电子给体配体的化合物；以及一种能够提供能够弱配位于过渡金属的阴离子的盐，在溶剂中进行反应。本发明提供的具有酯基或乙酰基的诺伯烯基加成聚合物具有透明性，具有优异的粘附性和低介电常数，当附着于金属时不会产生副产物。因此，它可以用作光学膜、减速膜、偏振器POFs（塑料光纤）的保护膜、PCBs（印刷电路板）或电子器件的绝缘体。
• Nobonene-ester based addition polymer and method for preparing the same
  申请人：Chun Sung-Ho

  公开号：US20050010006A1

  公开（公告）日：2005-01-13

  The present invention relates to a norbornene based addition polymer, and more particularly to an addition polymer of norbornene based monomers containing an ester group. The present invention provides a norbornene-ester based addition polymer having a molecular weight (Mn) larger than 20,000 and comprising a norbornene-ester based monomer comprising more than 50 mol % of exo norbornene-ester monomer as a repeating unit, a method for preparing the same, and an optically anisotropic film comprising the same. The norbornene-ester based addition polymer of the present invention is transparent, has a low dielectric constant, has good thermal stability and strength, leaves no unwanted materials when attached to metals or other polymers, and has good adhesivity, so that it can be used for optical films, retardation films, plastic substrate materials, transparent polymers such as POF or PCB, insulating materials, or insulating electronic devices such as PCB or insulating materials.

  本发明涉及一种基于诺博烯的加成聚合物，更具体地涉及一种含有酯基的诺博烯单体的加成聚合物。本发明提供了一种分子量（Mn）大于20,000的诺博烯酯基加成聚合物，其包含超过50摩尔％的exo诺博烯酯单体作为重复单元的诺博烯酯基单体，以及其制备方法和包含该聚合物的光学各向异性膜。本发明的诺博烯酯基加成聚合物是透明的，具有低介电常数，具有良好的热稳定性和强度，当附着于金属或其他聚合物时不留下不需要的物质，并具有良好的粘着性，因此可用于光学膜、减速膜、塑料基材料、如POF或PCB的透明聚合物、绝缘材料或绝缘电子器件，如PCB或绝缘材料。
• Catalyst system for polymerizing cyclic olefin having polar functional group, polymerizing method using the catalyst system, olefin polymer produced by the method and optical anisotropic film comprising the olefin polymer
  申请人：Yoon Cheol Sung

  公开号：US20060058477A1

  公开（公告）日：2006-03-16

  A catalyst system capable of producing a cyclic olefin polymer having a polar functional group and a high molecular weight with a high yield in which a catalyst is not deactivated due to polar functional groups of monomers, and a method of producing polymers using the same are provided. The catalyst system for polymerization of olefin according to the present invention has good thermal and chemical stability, and thus, in the method of preparing polyolefin using the catalyst system, the deactivation of a catalyst due to a polar functional group of the monomer can be prevented, and thus a high yield of the cyclic olefin polymer with a high molecular weight can be obtained when a ratio of the catalyst to the monomer is 1:5000, and the removal of a catalyst residue is not required.

  提供了一种催化剂体系，能够产生具有极性功能基和高分子量的环状烯烃聚合物，并具有高产率，其中催化剂不会因单体的极性功能基而失活，以及使用相同的聚合物生产方法。根据本发明的烯烃聚合催化剂体系具有良好的热稳定性和化学稳定性，因此，在使用该催化剂体系制备聚烯烃的方法中，可以防止由于单体的极性功能基而导致催化剂失活，因此当催化剂与单体的比例为1:5000时，可以获得高产率的具有高分子量的环状烯烃聚合物，并且不需要去除催化剂残留物。