cyclo-[3]-octyl malonate | 474781-10-7

• 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: cyclo-[3]-octyl malonate
• 英文别名: 1,5,14,18,27,31-Hexaoxacyclononatriacontane-2,4,15,17,28,30-hexone
• CAS: 474781-10-7
• 化学式: C₃₃H₅₄O₁₂
• 分子量: 642.785
• InChiKey: QTSBPGIRFXKCTP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.3
• 重原子数：
  45
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  158
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  足球烯 、 cyclo-[3]-octyl malonate 在 碘 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲苯 为溶剂， 反应 3.0h， 以55%的产率得到e,e,e-(cyclo-[3]-octylmalonyl)hexahydro[60]fullerene
  参考文献：
  名称：

  具有混合八面体加成模式的C60的新[3：2：1]六六六加合物的顺序束缚导向合成

  摘要：

  提出了富勒烯C 60的[3：2：1]六-加合物的区域选择性合成的新概念。基于顺序的束缚导向的远程官能化，通过逐步环丙烷化C 60合成具有不完全八面体加成模式的手性[3：2]五价加合物以及合适的大环三官能和双官能环丙二酸酯系链。使用手性HPLC分离得到的四种立体异构体。相应的对映异构体对在CD光谱中显示镜像行为。戊基加合物是空间控制的混合己基加合物合成的合适组成部分。带有官能团的单丙二酸酯的实施提供了八面体[3：2：1]六面体加合物，适用于以较高的收率构建较大的分子和超分子富勒烯结构。

  DOI：

  10.1002/chem.202100319
• 作为产物：
  描述：

  1,8-辛二醇 、 丙二酰氯 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 11.0h， 以8.1%的产率得到cyclo-[3]-octyl malonate
  参考文献：
  名称：

  Selective Syntheses of Novel Polyether Fullerene Multiple Adducts

  摘要：

  We have applied a modified macrocyclic tether approach to control multiple additions to C-60. The technique of He-3 NMR was used to confirm the selective formation of specific C-60 multiple adducts by the macrocyclic tether approach. An oligoglycol was used as a flexible linker to produce macrocyclic polyether-linked malonates 5, 6, 8, and 9 under solid-liquid PTC (phase-transfer-catalysis) conditions. The formation of a single C60 tris-adduct, 3, from macrocyclic malonate 1 and (HeC60)-He-3-C-@ was proven by He-3 NMR. Similarly, multiple additions to C-60 of macrocyclic polyether malonate 5 gave C-60 bis-adduct 10 selectively, while the reaction of C-60 with macrocyclic malonate 8 gave bis-adducts 11 and 12. A similar process with macrocyclic malonate 6 gave tris-adduct 13 with high selectivity as well. Saponification of these C-60 multiple adducts gives the corresponding polyacids that are potentially useful in biological applications. Macrocyclic polyether fullerenes are a new class of ionophores, which could be interesting for molecular recognition and for the development of biosensors.

  DOI：

  10.1021/jo034542l

文献信息

• Macrocyclic Cyclo[n]malonates – Synthetic Aspects and Observation of Columnar Arrangements by X-ray Crystallography
  作者：Nikos Chronakis、Torsten Brandmüller、Christian Kovacs、Uwe Reuther、Wolfgang Donaubauer、Frank Hampel、Felix Fischer、François Diederich、Andreas Hirsch

  DOI：10.1002/ejoc.200500921

  日期：2006.5

  interest are the macrocyclic bismalonates, as they show pronounced crystallisability and arrange into columnar motifs in the solid state. They feature distinctive dihedral angles: all ester moieties adopt anti conformations whereas the planes of the carboxy moieties of each malonate residue arrange in an approximately orthogonal fashion. The latter geometry is enforced by the macrocyclic structures, as

  通过丙二酰二氯与α,ω-二醇缩合，一步法合成了多种非手性和手性大环低聚丙二酸酯。我们通过改变二醇中间隔物的长度和类型研究了这种方法的适用性。产品分布分析表明，单体、二聚或三聚大环丙二酸酯的优先形成可以通过选择具有连接羟基的特定间隔基的二醇来控制。特别令人感兴趣的是大环双丙二酸酯，因为它们显示出明显的结晶性并在固态下排列成柱状图案。它们具有独特的二面角：所有酯部分都采用反构象，而每个丙二酸酯残基的羧基部分的平面以近似正交的方式排列。正如剑桥结构数据库中的构象搜索所揭示的那样，后一种几何结构由大环结构强制执行。X 射线衍射数据表明，C=O...H-C 和 C-O...H-C 氢键稳定了二聚环的柱状排列并形成管状组件。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
• A Highly Regioselective Approach to Multiple Adducts of C60 Governed by Strain Minimization of Macrocyclic Malonate Addends
  作者：Uwe Reuther、Torsten Brandmüller、Wolfgang Donaubauer、Frank Hampel、Andreas Hirsch

  DOI：10.1002/1521-3765(20020517)8:10<2261::aid-chem2261>3.0.co;2-c

  日期：2002.5.17

  the macrocyclic malonate. A variety of bis-, tris-, tetra-, and hexaadducts have been synthesized to show the scope of this approach. "Exotic" addition patterns such as trans-4,trans-4,trans-4, which has been synthesized and completely characterized for the first time, are also accessible by this method. The regioselectivity is ruled by the even distribution of the strain within the macrocyclic malonates

  通过使二氯丙二酰与链烷二醇反应制备了新的大环丙二酸酯2-5。这些环-[n]-烷基丙二酸酯与C60的反应具有很高的区域选择性。含有相同烷基间隔基的大环选择性地形成具有旋转对称性的C60的双和三加合物。区域选择性形成的低聚加合物的添加方式取决于大环丙二酸酯内烷基间隔基的大小。合成了多种双，三，四和六加合物，以显示该方法的范围。通过这种方法还可以访问“异国情调”添加模式，例如首次合成并完全表征的trans-4，trans-4，trans-4。区域选择性由应变在具有相同长度的间隔链烷烃链的大环丙二酸酯内的均匀分布决定：具有旋转对称性的加成图提供了丙二酸酯氧原子的完全相同的距离，因此仅通过这种方法形成。相反，当使用具有两个不同的烷基间隔长度的大环，例如9和10时，该反应仅产生C（s）-对称的双加合物。
• METHODS OF TREATING OXIDATIVE STRESS TO MODULATE REDOX BALANCE, PREVENTING OXIDATIVE STRESS INDUCED CELL DAMAGE AND DEATH
  申请人：Redox Balance LLC

  公开号：US20210145762A1

  公开（公告）日：2021-05-20

  Fullerene compounds and formulations are taught as useful in reducing oxidative stress in an organism because of their antioxidant properties and REDOX balance (homeostasis) properties.

  Fullerene化合物和配方被教授为有用的，因为它们具有抗氧化性质和氧化还原平衡（稳态）特性，可以减少生物体内的氧化应激。
• Spaenig, Fabian; Kovacs, Christian; Hauke, Frank, Journal of the American Chemical Society, 2009, vol. 131, p. 8180 - 8195
  作者：Spaenig, Fabian、Kovacs, Christian、Hauke, Frank、Ohkubo, Kei、Fukuzumi, Shunichi、et al.

  DOI：——

  日期：——
• Selective Syntheses of Novel Polyether Fullerene Multiple Adducts
  作者：Zhiguo Zhou、David I. Schuster、Stephen R. Wilson

  DOI：10.1021/jo034542l

  日期：2003.10.1

  We have applied a modified macrocyclic tether approach to control multiple additions to C-60. The technique of He-3 NMR was used to confirm the selective formation of specific C-60 multiple adducts by the macrocyclic tether approach. An oligoglycol was used as a flexible linker to produce macrocyclic polyether-linked malonates 5, 6, 8, and 9 under solid-liquid PTC (phase-transfer-catalysis) conditions. The formation of a single C60 tris-adduct, 3, from macrocyclic malonate 1 and (HeC60)-He-3-C-@ was proven by He-3 NMR. Similarly, multiple additions to C-60 of macrocyclic polyether malonate 5 gave C-60 bis-adduct 10 selectively, while the reaction of C-60 with macrocyclic malonate 8 gave bis-adducts 11 and 12. A similar process with macrocyclic malonate 6 gave tris-adduct 13 with high selectivity as well. Saponification of these C-60 multiple adducts gives the corresponding polyacids that are potentially useful in biological applications. Macrocyclic polyether fullerenes are a new class of ionophores, which could be interesting for molecular recognition and for the development of biosensors.