1,5,8,8b-tetrahydro-4H,4bH-cyclobuta[1,2-b;3,4-b']dipyridine-3,4a,7,8a-tetracarboxylic acid tetraethyl ester | 26439-33-8

• 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: 1,5,8,8b-tetrahydro-4H,4bH-cyclobuta[1,2-b;3,4-b']dipyridine-3,4a,7,8a-tetracarboxylic acid tetraethyl ester
• 英文别名: 1,5,8,8b-tetrahydro-4H,4bH-cyclobuta[1,2-b;3,4-b']dipyridine-3,4a,7,8a-tetracarboxylic acid tetraethyl ester
• CAS: 26439-33-8；26439-34-9
• 化学式: C₂₂H₃₀N₂O₈
• 分子量: 450.489
• InChiKey: VKHMCWWQFBJAOH-MSGZKTSVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.72
• 重原子数：
  32.0
• 可旋转键数：
  8.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  129.26
• 氢给体数：
  2.0
• 氢受体数：
  10.0

反应信息

• 作为产物：
  描述：

  3,5-diethyl 1,4-dihydropyridine-3,5-dicarboxylate 在 1-methyl-3-phenacylimidazolium bromide 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以41%的产率得到tetraethyl 3,9-diazahexacyclo[6.4.0.0^2,7.0^4,11.0^5,10]dodecane-1,5,7,11-tetracarboxylate
  参考文献：
  名称：

  Triplet phenacylimidazoliums-catalyzed photocycloaddition of 1,4-dihydropyridines: An experimental and theoretical study

  摘要：

  The photocycloadditions of 1,4-dihydropyridines (DHPs) were achieved by using phenacylimidazoliums (Plms) as photosensitizers. Irradiation of DHPs 3a-g in the presence of Plms 1a-e and 2 performed an efficient formation of 3,9-diazatetraasteranes in shorter times under a lower power lamp. The mechanism of photocycloaddition catalyzed by Plm was studied by laser flash photolysis and theoretical OFT computation. These time-resolved results showed that the triplet excited states of Plms were generated with high efficiency and detected by their characteristic ultraviolet absorptions, which were quenched by DHP at almost diffusion controlled rate. Theoretical studies suggest that Plm is involved in the photocycloaddition process through the (3)(DHP center dot center dot center dot Plm)* triplet complexes and assists the stabilization of intermediates. All subsequent steps are predicted to be favorable and exothermic, leading to the cage dimers. (C) 2012 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jphotochem.2012.05.013

文献信息

• Manipulating [2 + 2] photodimerization of 1,4-dihydropyridines within γ -cyclodextrin
  作者：Wuji Sun、Qiangwen Fan、Hong Yan

  DOI：10.1016/j.jphotochem.2018.03.046

  日期：2018.5

  volume in γ-CD is responsible for the observed selectivity. The formation of 1:2 host-guest inclusion complex plays an important role in this reaction, and manipulates DHPs to perform [2 + 2] photodimerization as expected. In order to investigate the inclusion process, the spectral characteristics were investigated and the theoretical study was performed using density functional theory (DFT).

  在γ-环糊精（γ -CD）存在下照射1,4-二氢吡啶（DHP）可以在中压汞灯下有效形成笼状二聚体。γ -CD中复合的DHP的笼二聚体产率可达到约80％，远高于非复合状态的DHP 。假设可用的腔体体积为γ-CD负责观察到的选择性。1：2宿主-客体包含复合物的形成在此反应中起重要作用，并按预期操作DHP进行[2 + 2]光二聚。为了研究包含过程，研究了光谱特征，并使用密度泛函理论（DFT）进行了理论研究。