11-ethoxycarbonylmethyl-2,5,8-trioxa-1-oxocycloundecane | 188915-93-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 11-ethoxycarbonylmethyl-2,5,8-trioxa-1-oxocycloundecane
• 英文别名: Ethyl (8-oxo-1,4,7-trioxacycloundecan-9-yl)acetate；ethyl 2-(8-oxo-1,4,7-trioxacycloundec-9-yl)acetate
• CAS: 188915-93-7
• 化学式: C₁₂H₂₀O₆
• 分子量: 260.287
• InChiKey: YTVQYBUJOVRVNX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为产物：
  描述：

  富马酸单乙酯 在 吡啶 、 草酰氯 、 偶氮二异丁腈 、 三正丁基氢锡 、 sodium iodide 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 丙酮 、 苯 为溶剂， 反应 38.0h， 生成 11-ethoxycarbonylmethyl-2,5,8-trioxa-1-oxocycloundecane
  参考文献：
  名称：

  Macrocyclic Ethers by Free Radical Cyclizations

  摘要：

  Tin hydride reduction of omega-iodo-polyoxaalkyl acrylates 1 using syringe pump addition of both reactants to a solution of AIBN in benzene at 80 degrees C afforded the corresponding cyclic polyethers in excellent yields.

  DOI：

  10.1080/00397919708004135

文献信息

• Formation of Macrocyclic Ethers by Free Radical Cyclization:  Effects of Chain Length, Substituents, and Solvents
  作者：Annie Philippon、Marie Degueil-Castaing、Athelstan L. J. Beckwith、Bernard Maillard

  DOI：10.1021/jo980259o

  日期：1998.10.1

  Free radical reduction by tributylstannane of omega-iodopolyoxaalkyl acrylates derived from tri-, tetra-, penta-, hexa-, and heptaethylene glycols gives mixtures of uncyclized reduction products and macrocyclic ethers formed by endo cyclization. The rate constants for cyclization of the intermediate radicals at 80 degrees C in benzene were determined under carefully defined conditions to be 15 x 10(4)

  通过三丁基锡烷自由基还原衍生自三，四，五，五，六和七乙二醇的ω-碘多聚氧杂烷基丙烯酸酯，得到未环化还原产物和通过内环化形成的大环醚的混合物。在精心定义的条件下，确定80℃下苯中的中间体自由基环化的速率常数为15 x 10（4），13 x 10（4），5.1 x 10（4），10 x 10（4）和3.6 x 10（4）s（-）（1），分别用于形成12、15、18、21和24元环。这些值表明，与先前报道的烯基物质的环化相比，链中氧原子的存在使速率增加了10-30倍。苯在80摄氏度时的速率常数和甲基丙烯酸酯，巴豆酸酯，已经确定了8-碘-3,6-二氧杂辛醇的肉桂酸酯，马来酸酯和富马酸酯。在极性不同的溶剂中丙烯酸8-碘-3,6-二氧杂辛酯的还原表明环化速率具有相对较低的溶剂依赖性。
• Formation of substituted macrocyclic ethers by radical cyclisation
  作者：Athelstan L. J. Beckwith、Kitty Drok、Bernard Maillard、Marie Degueil-Castaing、Annie Philippon

  DOI：10.1039/a608494j

  日期：——

  ω-Iodopolyoxaalkyl acrylates and related compoundsundergo radical cyclisation when treated with tributylstannane to afford substituted macrocylic polyethers.

  ω-碘聚氧乙烯醚丙烯酸酯及相关化合物经三丁基锡烷处理后会发生自由基环化反应，生成取代的大环聚醚。
• Structural and conformational study of macrocyclic polyethers by NMR spectroscopy and molecular modeling
  作者：A. Philippon、M. Laguerre、M. Petraud、I. Pianet

  DOI：10.1002/(sici)1097-458x(199711)35:10<691::aid-omr155>3.0.co;2-6

  日期：1997.11

  Two macrocyclic polyether isomers were obtained by radical cyclization of (E)-8-iodo-3,6-dioxaoctyl-3-ethoxycarbonylpropenoate and separated by liquid-solid chromatography over silica gel. They were characterized, for the first time, by two-dimensional NMR; notably, the HMBC experiment gave access to the assignment of the two isomers through coupling via the carbonyl oxygen belonging to the macroheterocycle. The determination of the (3)J(HH) coupling, associated with Monte Carlo simulation, gave information on the conformational space of these two isomers and showed that 85 conformers for one isomer and 29 conformers for the other were in equilibrium in the solution mixture. These results are discussed with regard to the complexing properties of these macrocyclic polyethers. (C) 1997 John Wiley & Sons, Ltd.