1,1',3,3',4,5,6,6',8,8',9,10-dodecadeuterio-1,2,3,6,7,8-hexahydropyrene | 174809-23-5

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 1,1',3,3',4,5,6,6',8,8',9,10-dodecadeuterio-1,2,3,6,7,8-hexahydropyrene
• 英文别名: 1,1,3,3,4,5,6,6,8,8,9,10-dodecadeuterio-1,2,3,6,7,8-hexahydropyrene
• CAS: 174809-23-5
• 化学式: C₁₆H₁₆
• 分子量: 220.208
• InChiKey: MBAIEZXRGAOPKH-XOUIOAOESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.82
• 重原子数：
  16.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  1,1',3,3',4,5,6,6',8,8',9,10-dodecadeuterio-1,2,3,6,7,8-hexahydropyrene 在 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 甲苯 为溶剂， 反应 2.0h， 以83%的产率得到1,3,4,5,6,8,9,10-octadeuteriopyrene
  参考文献：
  名称：

  Relative Solution Electron Affinities of Selectively Deuteriated Pyrenes:  Correlations between Voltammetric, Electron Paramagnetic Resonance, and Semiempirical PM3 Data

  摘要：

  The equilibrium isotope effects (EIE) for the one-electron transfer between pyrene and seven regioselectively deuteriated pyrene isotopic isomers in dimethylformamide with 0.1 M tetrabutylammonium hexafluorophosphate were measured electrochemically. These data correlate linearly with the free energies (Delta G(o)) obtained in tetrahydrofuran using electron paramagnetic resonance (EPR) techniques. However, the slope of the resulting line is not unity, and it indicates that the EIE in the DMF system is only two-thirds of that in the THF system. PM3 calculated Delta G(o,)s, which would correspond to the gas phase electron transfers, also correlate linearly with both sets of experimental data, but the predicted magnitudes of the EIE's are smaller than those observed experimentally by either technique. The nonunity slopes probably reflect slight differences in ion solvation and/or ion association parameters between the anion radicals of the isotopic isomers. No general relationship between the EIE and the charge on the hydrogen/deuterium substituted carbon atom was found.

  DOI：

  10.1021/jp952098n
• 作为产物：
  描述：

  1,2,3,6,7,8-六氢芘 在 氘代二甲亚砜 、 sodium hydride 作用下， 反应 23.0h， 生成 1,1',3,3',4,5,6,6',8,8',9,10-dodecadeuterio-1,2,3,6,7,8-hexahydropyrene
  参考文献：
  名称：

  Relative Solution Electron Affinities of Selectively Deuteriated Pyrenes:  Correlations between Voltammetric, Electron Paramagnetic Resonance, and Semiempirical PM3 Data

  摘要：

  The equilibrium isotope effects (EIE) for the one-electron transfer between pyrene and seven regioselectively deuteriated pyrene isotopic isomers in dimethylformamide with 0.1 M tetrabutylammonium hexafluorophosphate were measured electrochemically. These data correlate linearly with the free energies (Delta G(o)) obtained in tetrahydrofuran using electron paramagnetic resonance (EPR) techniques. However, the slope of the resulting line is not unity, and it indicates that the EIE in the DMF system is only two-thirds of that in the THF system. PM3 calculated Delta G(o,)s, which would correspond to the gas phase electron transfers, also correlate linearly with both sets of experimental data, but the predicted magnitudes of the EIE's are smaller than those observed experimentally by either technique. The nonunity slopes probably reflect slight differences in ion solvation and/or ion association parameters between the anion radicals of the isotopic isomers. No general relationship between the EIE and the charge on the hydrogen/deuterium substituted carbon atom was found.

  DOI：

  10.1021/jp952098n

文献信息

• Perturbation of Spin Density Distribution Due to Deuterium Substitution
  作者：Han Zuilhof、Gerrit Lodder、Robert P. van Mill、Patrick P. J. Mulder、David E. Kage、Richard C. Reiter、Cheryl D. Stevenson

  DOI：10.1021/j100011a010

  日期：1995.3

  The EPR analysis of the anion radicals of 1,3,6,8-tetradeuteriopyrene and 1,3,4,5,6,8,9,10-octadeuteriopyrene in THF with K+ at 173 K shows that the observed coupling constant for the protons in the 2,7 positions is decreased in both anion radicals by 25 mG (Delta a(H) = -25 mG) from its value in the anion radical of pyrene itself. This implies that there is only a very small, if any, contribution to this reduction in the spin density at the 2,7 positions resulting from deuterium substitution in the 4,5,9,10 positions. Ab initio calculations (6-31G(**) and 6-311G(**) basis sets) carried out considering the C-D bond to be shorter than the C-H bond by 0.01 Angstrom predict the effects of octadeuteriation to be 21 and 18 mG, respectively, in good agreement with experiment. The calculations do, however, predict an approximately equal contribution from the two tetradeuterio substitution patterns, with the effect of 1,3,6,8-deuteriation being slightly larger than that of 4,5,9,10-tetradeuteriation.