isopropyl methyl 9,10-dihydro-9,10-ethenoanthracene-11,12-dicarboxylate | 118673-49-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 蒽
• 英文名称: isopropyl methyl 9,10-dihydro-9,10-ethenoanthracene-11,12-dicarboxylate
• CAS: 118673-49-7
• 化学式: C₂₂H₂₀O₄
• 分子量: 348.398
• InChiKey: IRDJIDNSIPFCRJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  26.0
• 可旋转键数：
  3.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  isopropyl methyl 9,10-dihydro-9,10-ethenoanthracene-11,12-dicarboxylate 以 苯 为溶剂， 生成 8c-methyl 8b-(2-propyl) 4b,8b,8c,8d-tetrahydrodibenzocyclopropapentalene-8c,8b-dicarboxylate 、 8b-methyl 8c-(2-propyl) 4b,8b,8c,8d-tetrahydrodibenzocyclopropapentalene-8c,8b-dicarboxylate
  参考文献：
  名称：

  Prototropic control of organic photochemistry. Hydrogen bonding effects on the di-.pi.-methane photorearrangement

  摘要：

  The IR and UV spectra as well as the photochemistry of the isopropyl monoester of dibenzobarrelene dicarboxylic acid 2 were analyzed in detail in several media. A correlation was found between the photochemical results and the spectroscopically detected hydrogen-bonded structures of 2. An equilibrium between dimeric (2-HD) and intramolecularly hydrogen bonded (2-HI) structures was detected by IR spectroscopy in nonpolar solvents having weak hydrogen-bond-accepting capabilities. The ratio of the two regioisomeric dibenzosemibullvalene products 3 and 4 formed in the di-pi-methane photorearrangement of 2 was found to correlate with such an equilibrium, and it was concluded that intramolecular (2-HI) and dimeric (2-HD) hydrogen-bonded structures display significantly different photochemical reactivity. The infrared spectra and the photoproduct ratio in polar solvents possessing hydrogen-bond-accepting capabilities (e.g., acetonitrile), on the other hand, turned out to be concentration independent. High regioselectivity was found in the solid state where the dimer 2-HD is the only species, leading to 4 as the major product. In contrast, 3 was obtained preferentially in aqueous sodium bicarbonate solutions where 2 exists as the carboxylate anion. Supporting evidence regarding the different hydrogen bonding arrangements in 2 was found in the solvent effects on its UV spectra.

  DOI：

  10.1021/jo00027a043

文献信息

• Crystal structures and solid-state photochemistry of an unsymmetrically substituted dibenzobarrelene and its two photoproducts (dibenzosemibullvalenes)
  作者：M. Garcia-Garibay、J. R. Scheffer、J. Trotter、F. C. Wireko

  DOI：10.1107/s0108768189010499

  日期：1990.2.1