diethyl (3a1s,4a1s)-7,8-dimethoxy-4,11-dioxo-5,10-dihydro-1H,3H,4H,11H-2-oxa-3a,4a,10a,11a-tetraazabenzo[f]indeno[2,1,7-ija]azulene-3a1,4a1-dicarboxylate | 444929-66-2

• 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: diethyl (3a1s,4a1s)-7,8-dimethoxy-4,11-dioxo-5,10-dihydro-1H,3H,4H,11H-2-oxa-3a,4a,10a,11a-tetraazabenzo[f]indeno[2,1,7-ija]azulene-3a1,4a1-dicarboxylate
• CAS: 444929-66-2
• 化学式: C₂₂H₂₆N₄O₉
• 分子量: 490.47
• InChiKey: GITHGYGWDMRTFK-SZPZYZBQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.66
• 重原子数：
  35.0
• 可旋转键数：
  6.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  127.39
• 氢给体数：
  0.0
• 氢受体数：
  9.0

反应信息

• 作为反应物：
  描述：

  diethyl (3a1s,4a1s)-7,8-dimethoxy-4,11-dioxo-5,10-dihydro-1H,3H,4H,11H-2-oxa-3a,4a,10a,11a-tetraazabenzo[f]indeno[2,1,7-ija]azulene-3a1,4a1-dicarboxylate 在 聚合甲醛 、 对甲苯磺酸 、 三氟乙酸 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 78.0h， 生成
  参考文献：
  名称：

  Cucurbit[n]uril Analogues:  Synthetic and Mechanistic Studies

  摘要：

  The synthesis of cucurbit[n]uril analogues (18, 19, (+/-)-20, 33, 34, 35, 36, and 37) is presented. These CB[5], CB[6], and CB[7] analogues all contain bis(phthalhydrazide) walls that are incorporated into the macrocycle. The tailor-made synthesis of these CB[n] analogues proceeds by the condensation of the appropriate bis(electrophile) (4, 7, or 9) with bis(phthalhydrazide) (17), which delivers the CB[6] and CB[7] analogues in good yield, whereas the CB[5] analogue is formed in low yield. To improve the solubility characteristics of the CB[n] analogues for recognition studies in water or organic solution, the CO2Et groups were transformed to CO2H and CO2(CH2)(9)CH3 groups. On the basis of the results of product resubmission experiments, we conclude that these macrocycles are kinetic products. To help rationalize the good yields obtained in the CB [6] and CB [7] analogue macrocyclization reactions, we performed mechanistic studies of model methylene bridged glycoluril dimers, which suggest an intramolecular isomerization during CB[n] analogue formation.

  DOI：

  10.1021/jo051655r
• 作为产物：
  描述：

  聚合甲醛 、 7,8-Dimethoxy-1,4-dioxo-1,2,3,4,5,10-hexahydro-2,3,4a,10a-tetraaza-benzo[g]cyclopenta[cd]azulene-2a,10b-dicarboxylic acid diethyl ester 在 三氟乙酸 作用下， 以52%的产率得到diethyl (3a1s,4a1s)-7,8-dimethoxy-4,11-dioxo-5,10-dihydro-1H,3H,4H,11H-2-oxa-3a,4a,10a,11a-tetraazabenzo[f]indeno[2,1,7-ija]azulene-3a1,4a1-dicarboxylate
  参考文献：
  名称：

  亚甲基桥甘脲二聚体：合成方法。

  摘要：

  亚甲基桥甘脲二聚体是葫芦素（CB [6]），其同系物（CB [n]）及其衍生物的基本组成部分。本文介绍了三种互补的合成C型和S型亚甲基桥甘脲二聚体的方法（29-34和37-44）。为此，我们制备了在其凸面上具有多种功能的甘脲衍生物（1a-d）。这些甘脲衍生物在碱性条件下（DMSO，t-BuOK）用1,2-双（卤甲基）芳烃6-15烷基化，得到4a-d和16-24，其中含有一个芳族邻二甲苯基环并可能具有亲核性脲基NH基团。带有潜在亲电环醚基团（5a-f）和25-28的甘脲衍生物是通过各种方法制备的，包括在回流的含多聚甲醛的TFA中进行缩合反应。在大多数情况下，在无水酸性条件下（PTSA，ClCH（2）CH（2）Cl，回流），4a-d和16-24与低聚甲醛的缩合反应可得到C形和S形亚甲基桥接的甘脲高产到高产。在许多情况下，优选以高非对映选择性形成C形化合物。环醚5a，df和25-26经历高度非对

  DOI：

  10.1021/jo0258958

文献信息

• Synthesis of novel unsymmetrical molecular clips derived from glycoluril
  作者：Hu Sheng-Li、Wu Yan-Dong、Cao Li-Ping、Wu An-Xin

  DOI：10.3184/030823409x465349

  日期：2009.7

  Four novel unsymmetrical molecular clips derived from glycoluril have been designed and synthesised and the structure and conformation of one was also confirmed by single crystal X-ray diffraction.

  已经设计并合成了四种源自甘脲的新型不对称分子夹，其中一种的结构和构象也通过单晶 X 射线衍射证实。
• Diastereoselective Formation of Glycoluril Dimers:  Isomerization Mechanism and Implications for Cucurbit[<i>n</i>]uril Synthesis
  作者：Arindam Chakraborty、Anxin Wu、Dariusz Witt、Jason Lagona、James C. Fettinger、Lyle Isaacs

  DOI：10.1021/ja025876f

  日期：2002.7.1

  possible previously. For example, we present strong evidence that the mechanism of CB[n] synthesis proceeds via the intermediacy of both S-shaped and C-shaped dimers. The first experimental determination of the relative free energies of the S-shaped and C-shaped dimers indicates a thermodynamic preference (1.55-3.25 kcal mol(-)(1)) for the C-shaped diastereomer. This thermodynamic preference is not because

  Cucurbit[6]uril (CB[6]) 是一种大环化合物，由甘脲和甲醛在一锅中制备，其分子识别特性使其成为深入研究的对象。CB[n] 形成机制的研究可能为 CB[n] 同系物和衍生物的定制合成提供见解，但由于 CB[n] 的复杂结构而受到阻碍。通过降低形成 S 形 (12S-18S) 和 C 形 (12C-18C) 亚甲基桥联甘脲二聚体的反应复杂性，我们已经能够探索 CB[n] 机制的基本步骤合成到以前不可能达到的水平。例如，我们提出了强有力的证据，证明 CB[n] 合成的机制是通过 S 形和 C 形二聚体的中介进行的。S 形和 C 形二聚体的相对自由能的第一次实验测定表明 C 形非对映异构体的热力学偏好 (1.55-3.25 kcal mol(-)(1))。这种热力学偏好不是因为自缔合、溶剂化或模板效应。此外，标记实验使我们能够阐明 S 形和 C 形非对映异构体之间这种酸催化平衡
• Diastereoselective Formation of Methylene-Bridged Glycoluril Dimers
  作者：Dariusz Witt、Jason Lagona、Fehmi Damkaci、James C. Fettinger、Lyle Isaacs

  DOI：10.1021/ol991382k

  日期：2000.3.1

  The acid-catalyzed formation of methylene-bridged glycoluril dimers yields the C-2v-diastereomer selectively. Product resubmission experiments establish that the selectivity is the result of thermodynamic control. A modified synthetic route is presented that allows for the preparation of unsymmetrically substituted dimers, We present the X-ray crystal structures of both diastereomers, This class of compounds is useful for studies of self-assembly in aqueous solution.
• Introverted CB[N] Compounds
  申请人：Isaacs Lyle David

  公开号：US20100010215A1

  公开（公告）日：2010-01-14

  Inverted cucurbituril compounds having at least one pair of hydrogen atoms protruding into an internal molecular cavity thereof.
• US8513409B2
  申请人：——

  公开号：US8513409B2

  公开（公告）日：2013-08-20