2-(2-chlorophenyl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione | 89955-57-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: 2-(2-chlorophenyl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione
• 英文别名: (1S,2R,6S,7R)-4-(2-chlorophenyl)-4-azatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione
• CAS: 89955-57-7
• 化学式: C₁₅H₁₂ClNO₂
• 分子量: 273.719
• InChiKey: IDGZIZWXZYTZJR-KGOITJQVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  19
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  37.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-(2-chlorophenyl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione 在 硫酸 、 双氧水 、 溶剂黄146 、 水 作用下， 以 水 为溶剂， 反应 3.0h， 以93%的产率得到(1S,2S,6R,7R,8S,9S)-4-(2-chlorophenyl)-8,9-dihydroxy-4-azatricyclo[5.2.1.02,6]decane-3,5-dione
  参考文献：
  名称：

  Stereochemistry of dihydroxylation of N-arylbicyclo[2.2.1]-hept-5-ene-endo- and -exo-2,3-dicarboximides

  摘要：

  Stereochemistry of the oxidation of N-arylbicyclo[2.2.1]hept-5-ene-endo-and-exo-2,3-dicarboximides at the double bond with peroxyacetic acid generated in situ in the presence of sulfuric acid and with an anhydrous dioxane solution of peroxyacetic acid was studied. In both cases, the reaction was stereospecific, regardless of the substituent in the N-aryl group and configuration of the imide ring, but the reaction direction depended on the presence of water in the system. In the first case, the corresponding trans-5,6-dihydroxy derivatives were formed, while in the second, exo-5,6-epoxy derivatives. The oxidation of N-arylbicyclo[2.2.1]-hept-5-ene-endo-and-exo-2,3-dicarboximides with a solution of potassium permanganate in aqueous acetone gave the corresponding N-aryl-cis-5,6-dihydroxybicyclo[2.2.1]heptane-endo-and-exo-2,3-dicarboximides. The exo,cis,exo and exo,cis,endo configurations of the synthesized compounds were determined by H-1 NMR spectroscopy.

  DOI：

  10.1134/s1070428007110097
• 作为产物：
  描述：

  邻氯苯胺 、 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride 在 sodium acetate 、 乙酸酐 作用下， 以 乙腈 为溶剂， 反应 1.5h， 以70%的产率得到2-(2-chlorophenyl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione
  参考文献：
  名称：

  来自分子扭转平衡的溶液中卤素-芳基π相互作用的直接实验证据

  摘要：

  我们使用基于双环N-芳基酰亚胺的分子扭转平衡系统实验性地分析了卤素-芳基π相互作用，该系统基于非键相互作用对折叠状态和未折叠状态之间的平衡的影响。通过比较高级卤素调节的平衡与氟平衡，我们确定了我们单分子体系中卤素-芳基π相互作用的幅度大于-5.0 kJ mol -1，这与生物分子体系中估计的幅度相当。我们的研究提供了溶液中卤素-芳基π相互作用的直接实验证据，到目前为止，该相互作用仅在固态下才得以揭示，并通过量子力学计算从理论上进行了评估。

  DOI：

  10.1002/anie.201700520

文献信息

• Direct Experimental Evidence for Halogen-Aryl π Interactions in Solution from Molecular Torsion Balances
  作者：Han Sun、André Horatscheck、Vera Martos、Max Bartetzko、Ulrike Uhrig、Dieter Lentz、Peter Schmieder、Marc Nazaré

  DOI：10.1002/anie.201700520

  日期：2017.6.1

  dissected halogen–aryl π interactions experimentally using a bicyclic N-arylimide based molecular torsion balances system, which is based on the influence of the non-bonded interaction on the equilibria between folded and unfolded states. Through comparison of balances modulated by higher halogens with fluorine balances, we determined the magnitude of the halogen–aryl π interactions in our unimolecular

  我们使用基于双环N-芳基酰亚胺的分子扭转平衡系统实验性地分析了卤素-芳基π相互作用，该系统基于非键相互作用对折叠状态和未折叠状态之间的平衡的影响。通过比较高级卤素调节的平衡与氟平衡，我们确定了我们单分子体系中卤素-芳基π相互作用的幅度大于-5.0 kJ mol -1，这与生物分子体系中估计的幅度相当。我们的研究提供了溶液中卤素-芳基π相互作用的直接实验证据，到目前为止，该相互作用仅在固态下才得以揭示，并通过量子力学计算从理论上进行了评估。
• Spatial arrangement of norbornanedicarboxylic acids N-arylimides
  作者：M. S. Salakhov、B. T. Bagmanov、N. S. Nabiev

  DOI：10.1134/s1070428010110023

  日期：2010.11

  The effect of substituents on the spatial arrangement of norbornane compounds was investigated. Norbornanedicarboxylic acids N-arylimides with OCH(3), Cl, NO(2) groups in the ortho-position of the aromatic ring form as conformational isomers with hindered rotation. The specific spatial isomerism is confirmed by the quantum-chemical calculations.
• SALAXOV M. S.; BAGMANOV B. T.; NAGIEV V. A., IN-T XLORORGAN. SINTEZA AN AZSSR, SUMGAIT,(1986) 12 S., IL., VINITI , 862+
  作者：SALAXOV M. S.、 BAGMANOV B. T.、 NAGIEV V. A.

  DOI：——

  日期：——
• Transition-State Stabilization by n→π* Interactions Measured Using Molecular Rotors
  作者：Erik C. Vik、Ping Li、Perry J. Pellechia、Ken D. Shimizu

  DOI：10.1021/jacs.9b08542

  日期：2019.10.23

  A series of 16 molecular rotors were synthesized to investigate the ability of n→π* interactions to stabilize transition states (TS) of bond rotation. Steric contributions to the rotational barrier were isolated using control rotors, which could not form n→π* interactions. Rotors with strong acceptor π* orbitals such as ketones, aldehydes, and nitriles had greatly increased rates of rotation. The TS

  合成了一系列 16 个分子转子以研究 n→π* 相互作用稳定键旋转过渡态 (TS) 的能力。使用无法形成 n→π* 相互作用的控制转子隔离对旋转屏障的空间贡献。具有强受体 π* 轨道（如酮、醛和腈）的转子的旋转速率大大提高。高达 ~10 kcal/mol 的 TS 稳定性与在平面 TS 中酰亚胺羰基氧和邻-R 基团之间形成强的 n→π* 稳定性是一致的。计算研究有效地模拟了 TS 的稳定性和几何形状，NBO 分析证实了 n→π* 相互作用在稳定 TS 中的作用。
• Stereochemistry of dihydroxylation of N-arylbicyclo[2.2.1]-hept-5-ene-endo- and -exo-2,3-dicarboximides
  作者：B. T. Bagmanov

  DOI：10.1134/s1070428007110097

  日期：2007.11

  Stereochemistry of the oxidation of N-arylbicyclo[2.2.1]hept-5-ene-endo-and-exo-2,3-dicarboximides at the double bond with peroxyacetic acid generated in situ in the presence of sulfuric acid and with an anhydrous dioxane solution of peroxyacetic acid was studied. In both cases, the reaction was stereospecific, regardless of the substituent in the N-aryl group and configuration of the imide ring, but the reaction direction depended on the presence of water in the system. In the first case, the corresponding trans-5,6-dihydroxy derivatives were formed, while in the second, exo-5,6-epoxy derivatives. The oxidation of N-arylbicyclo[2.2.1]-hept-5-ene-endo-and-exo-2,3-dicarboximides with a solution of potassium permanganate in aqueous acetone gave the corresponding N-aryl-cis-5,6-dihydroxybicyclo[2.2.1]heptane-endo-and-exo-2,3-dicarboximides. The exo,cis,exo and exo,cis,endo configurations of the synthesized compounds were determined by H-1 NMR spectroscopy.