<2.2>Paracyclophan-4,13-dicarbonsaeure-dimethylester | 53922-65-9

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: <2.2>Paracyclophan-4,13-dicarbonsaeure-dimethylester
• 英文别名: 4,13-bis(methoxycarbonyl)[2.2]paracyclophane；4,15-bis(methoxycarbonyl)[2.2]paracyclophane；4,15-dicarbomethoxy[2.2]paracyclophane；4,13-Bis(methoxycarbonyl)-<2.2>paracyclophan；4,15-Bis(methoxycarbonyl)-<2.2>paracyclophan；4,15-Bis(methoxycarbonyl)-[2.2]paracyclophan；dimethyl tricyclo[8.2.2.24,7]hexadeca-1(12),4,6,10,13,15-hexaene-5,12-dicarboxylate
• CAS: 53922-65-9；53990-90-2；189224-11-1
• 化学式: C₂₀H₂₀O₄
• 分子量: 324.376
• InChiKey: LOJQNBKPMSWUNW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  <2.2>Paracyclophan-4,13-dicarbonsaeure-dimethylester 在 铂 盐酸 、 manganese(IV) oxide 、 lithium aluminium tetrahydride 、 氢气 、 sodium methylate 、 对甲苯磺酰肼 作用下， 以 四氢呋喃 、 氯仿 、 溶剂黄146 为溶剂， 反应 108.5h， 生成 Octahydro<2.2.2>(1,2,4)cyclophan
  参考文献：
  名称：

  Murad, Abo El-Fetouh El-Sayed; Hopf, Henning, Chemische Berichte, 1980, vol. 113, # 7, p. 2358 - 2371

  摘要：

  DOI：
• 作为产物：
  描述：

  4,15-dibromo[2.2]paracyclophane 在 正丁基锂 、 氯化亚砜 作用下， 以 四氢呋喃 、 氯仿 为溶剂， 生成 <2.2>Paracyclophan-4,13-dicarbonsaeure-dimethylester
  参考文献：
  名称：

  The first regioselective double electrophilic substitution of the C2-symmetric pseudo-meta-disubstituted [2.2]paracyclophanes

  摘要：

  We report here the first examples of the regioselective double electrophilic substitution of chiral C-2-symmetric pseudometa-disubstituted [2.2]paracyclophanes. Thus, the double acylation of 4,15-dihydroxy[2.2]paracyclophane occurs ortho-regioseleclively, whereas the double acylation of its respective dimethyl ether is completely para-regioselective. Double bromination of ,15dicarbomethoxy[2.2] paracyclophane regioselectively generates the pseudo-gem-substitution pattern. The approaches elaborated allow the synthesis of all three possible types of chiral bis-bifunctional compounds, which have two independent, although chemically and stereochemically equal, functional fragments with pseudo-meta mutual orientation of both pairs of identical substituents. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.02.003

文献信息

• Symmetrically Tetrasubstituted [2.2]Paracyclophanes: Their Systematization and Regioselective Synthesis of Several Types of Bis-Bifunctional Derivatives by Double Electrophilic Substitution
  作者：Natalia V. Vorontsova、Valeria I. Rozenberg、Elena V. Sergeeva、Evgenii V. Vorontsov、Zoya A. Starikova、Konstantin A. Lyssenko、Henning Hopf

  DOI：10.1002/chem.200701683

  日期：2008.5.19

  the respective achiral diphenol 12 and bis(methoxycarbonyl) 40 derivatives of the pseudo-para-structure retain regioselectivities which are characteristic for their pseudo-meta-regioisomers. Imino ligands 26, 25, and 39, which were obtained from monoacyl- 22 and diacyldihydroxy[2.2]paracyclophanes 21, 38, are tested as chiral ligands in stereoselective Et(2)Zn addition to benzaldehyde producing 1-phenylpropanol

  具有不同类型的对称性（C（2），C（i），C（s），C（2v），C（2h））的手性和非手性四取代[2.2]对环环烷酮的可能数目，并进行评估，得出一个统一的，无关紧要的介绍了命名描述符系统。手性伪-元和非手性伪-对-二取代的[2.2]对环环亲电子的亲电取代的反应性和区域选择性以一种建议用于合成双-双官能[2.2]对环环烯的一般方法进行研究。手性伪-间-二羟基[2.2]对环环烷14与乙酰氯的单-和二酰化发生在邻位区域选择性生成三22、23和21个对称的四取代的酰基衍生物。与苯甲酰氯的相同反应既不具有区域选择性，也不具有化学选择性，并且会生成邻位/对位的混合物，单-/二酰化的化合物27-31。伪-间-二甲氧基[2.2]对环环烷18的双酰化是完全对位选择性的。伪元-双（甲氧羰基）[2.2]对环环烷20的亲电取代区域选择性地产生伪宝石取代模式。该底物的甲酰化仅产生单羰基衍生物35，而通过改变反应条件
• Ionization Energies of Methyl-substituted[2.2]Paracyclophanes
  作者：Yang Zhong-zhi、Branka Kova?、Edgar Heilbronner、Sayed Eltamany、Henning Hopf

  DOI：10.1002/hlca.19810640704

  日期：1981.11.4

  The photoelectron (PE.) spectra of thirteen methyl-substituted [2.2]paracyclophanes have been recorded and analyzed, to assess the influence of methyl-substitution on their ionization energies. It is shown that this influence is qualitatively and quantitatively the same as for benzenes and other π-systems. Comparison with the previous results obtained for the [2r]cyclophanes (r=2 to 6) strongly suggests

  记录并分析了13个甲基取代的[2.2]对环环烷的光电子（PE。）光谱，以评估甲基取代对其电离能的影响。结果表明，该影响在质量和数量上与苯和其他π系统相同。与先前对[2 r ]环烷（r = 2至6）获得的结果进行比较，强烈表明，烷基/π系统相互作用的超共轭模型比归纳模型更合适。
• Gilb,W. et al., Angewandte Chemie, 1977, vol. 89, p. 177 - 178
  作者：Gilb,W. et al.

  DOI：——

  日期：——
• Hopf,H.; Lenich,T., Chemische Berichte, 1974, vol. 107, p. 1891 - 1902
  作者：Hopf,H.、Lenich,T.

  DOI：——

  日期：——
• Three isomeric bis(methoxycarbonyl)[2.2]paracyclophanes
  作者：Peter G. Jones、Jörg Hillmer、Henning Hopf

  DOI：10.1107/s0108270102005140

  日期：2002.5.15

  The title isomers 4,16- (pseudo-ortho), 4,15- (pseudo-gem) and 4,12-bis(methoxycarbonyl)[2.2]paracyclophane (pseudopara), C20H20O4, all show the typical structural features of [2.2]paracyclophanes (flattened boat conformation of the rings, lengthened single bonds in the bridges and narrow ring angles at the bridgehead atoms). The 4,12-isomer displays crystallographic inversion symmetry. The carbonyl groups adopt a conformation in which they are directed away from the ring systems towards the nearest bridge; the corresponding angle at the ring substituent atom is widened. Crystal packing involves C-H...pi interactions for the 4,15-isomer and weak C-H...O hydrogen bonds for the other two isomers.