endo-10,10-ethylenedioxy-1,7-diphenyl-8,9-diazatricyclo[5.2.1.0^2,6]dec-8-ene | 660437-52-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: endo-10,10-ethylenedioxy-1,7-diphenyl-8,9-diazatricyclo[5.2.1.0^2,6]dec-8-ene
• 英文别名: (1'R,2'S,6'R,7'S)-1',7'-diphenylspiro[1,3-dioxolane-2,10'-8,9-diazatricyclo[5.2.1.02,6]dec-8-ene]
• CAS: 660437-52-5
• 化学式: C₂₂H₂₂N₂O₂
• 分子量: 346.429
• InChiKey: NBLOUCRDDGCXNR-FXELSEDVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  26
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  43.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  endo-10,10-ethylenedioxy-1,7-diphenyl-8,9-diazatricyclo[5.2.1.0^2,6]dec-8-ene 以 氘代甲苯 为溶剂， 反应 3.0h， 生成 3,3-ethylenedioxy-2,4-diphenyltricyclo[3.3.0.0^2,4]octane
  参考文献：
  名称：

  Effects of Spiroconjugation on the Calculated Singlet−Triplet Energy Gap in 2,2-Dialkoxycyclopentane-1,3-diyls and on the Experimental Electronic Absorption Spectra of Singlet 1,3-Diphenyl Derivatives. Assignment of the Lowest-Energy Electronic Transition of Singlet Cyclopentane-1,3-diyls

  摘要：

  The effect of a 2,2-ethylene-ketal functionality on the singlet-triplet energy gap (DeltaE(ST)) and on the first electronic transition in singlet cyclopentane-1,3-diyls (1) has been investigated. UDFT calculations predict a significant increase in the preference for a singlet ground state in the diradical with the cyclic ketal at C2 (11 g; DeltaE(ST) = -6.6 kcal/mol in C symmetry and -7.6 kcal/mol in C, symmetry), compared to the 2,2-dihydroxy- and 2,2-dimethoxy-disubstituted diradicals (1d, DeltaE(ST) = -3.6 kcal/mol in C2 symmetry, and le, DeltaE(ST) = -3.4 kcal/mol in C-2 symmetry). Spiroconjugation is shown to be responsible for the larger calculated value of \DeltaE(ST)\ in 1g, relative to 1d and le. A strong correlation between the calculated values of DeltaE(ST) and the computed electronic excitation energies of the singlet diradicals is found for diradicals 1d, le, and 1g and for 2,2-difluorocyclopentane-1,3-diyl (1c). A similar correlation between DeltaE(ST) and lambda(calcd) is predicted for the corresponding 1,3-diphenylcyclopentane-1,3-diyls 3, and the predicted blue shift in the spectrum of 3g, relative to 3e, has been confirmed by experimental comparisons of the electronic absorption spectra of the annelated derivatives 2c, 2e, and 2g in a glass at 77 K. The wavelength of the first absorption band in the singlet diradicals decreases in the order 2e (lambda(onset) = 650 nm) > 2g (lambda(onsel) = 590 nm) > 2c (lambda(onset) = 580 nm). The combination of these computational and experimental results provides a sound basis for reassignment of the first electronic absorption band in singlet diradicals 2c, 2e, and 2g to the excitation of anelectron from the HOMO to the LUMO of these 2,2-disubstituted derivatives of cyclopentane1,3-diyl.

  DOI：

  10.1021/ja038305b
• 作为产物：
  描述：

  1,3-二苯基丙烷三酮 在 potassium carbonate 、 一水合肼 作用下， 以 四氢呋喃 、 氯仿 、 二甲基亚砜 为溶剂， 反应 48.0h， 生成 endo-10,10-ethylenedioxy-1,7-diphenyl-8,9-diazatricyclo[5.2.1.0^2,6]dec-8-ene
  参考文献：
  名称：

  Effects of Spiroconjugation on the Calculated Singlet−Triplet Energy Gap in 2,2-Dialkoxycyclopentane-1,3-diyls and on the Experimental Electronic Absorption Spectra of Singlet 1,3-Diphenyl Derivatives. Assignment of the Lowest-Energy Electronic Transition of Singlet Cyclopentane-1,3-diyls

  摘要：

  The effect of a 2,2-ethylene-ketal functionality on the singlet-triplet energy gap (DeltaE(ST)) and on the first electronic transition in singlet cyclopentane-1,3-diyls (1) has been investigated. UDFT calculations predict a significant increase in the preference for a singlet ground state in the diradical with the cyclic ketal at C2 (11 g; DeltaE(ST) = -6.6 kcal/mol in C symmetry and -7.6 kcal/mol in C, symmetry), compared to the 2,2-dihydroxy- and 2,2-dimethoxy-disubstituted diradicals (1d, DeltaE(ST) = -3.6 kcal/mol in C2 symmetry, and le, DeltaE(ST) = -3.4 kcal/mol in C-2 symmetry). Spiroconjugation is shown to be responsible for the larger calculated value of \DeltaE(ST)\ in 1g, relative to 1d and le. A strong correlation between the calculated values of DeltaE(ST) and the computed electronic excitation energies of the singlet diradicals is found for diradicals 1d, le, and 1g and for 2,2-difluorocyclopentane-1,3-diyl (1c). A similar correlation between DeltaE(ST) and lambda(calcd) is predicted for the corresponding 1,3-diphenylcyclopentane-1,3-diyls 3, and the predicted blue shift in the spectrum of 3g, relative to 3e, has been confirmed by experimental comparisons of the electronic absorption spectra of the annelated derivatives 2c, 2e, and 2g in a glass at 77 K. The wavelength of the first absorption band in the singlet diradicals decreases in the order 2e (lambda(onset) = 650 nm) > 2g (lambda(onsel) = 590 nm) > 2c (lambda(onset) = 580 nm). The combination of these computational and experimental results provides a sound basis for reassignment of the first electronic absorption band in singlet diradicals 2c, 2e, and 2g to the excitation of anelectron from the HOMO to the LUMO of these 2,2-disubstituted derivatives of cyclopentane1,3-diyl.

  DOI：

  10.1021/ja038305b

文献信息

• Effects of Spiroconjugation on the Calculated Singlet−Triplet Energy Gap in 2,2-Dialkoxycyclopentane-1,3-diyls and on the Experimental Electronic Absorption Spectra of Singlet 1,3-Diphenyl Derivatives. Assignment of the Lowest-Energy Electronic Transition of Singlet Cyclopentane-1,3-diyls
  作者：Manabu Abe、Waldemar Adam、Weston Thatcher Borden、Masanori Hattori、David A. Hrovat、Masatomo Nojima、Koichi Nozaki、Jakob Wirz

  DOI：10.1021/ja038305b

  日期：2004.1.1

  The effect of a 2,2-ethylene-ketal functionality on the singlet-triplet energy gap (DeltaE(ST)) and on the first electronic transition in singlet cyclopentane-1,3-diyls (1) has been investigated. UDFT calculations predict a significant increase in the preference for a singlet ground state in the diradical with the cyclic ketal at C2 (11 g; DeltaE(ST) = -6.6 kcal/mol in C symmetry and -7.6 kcal/mol in C, symmetry), compared to the 2,2-dihydroxy- and 2,2-dimethoxy-disubstituted diradicals (1d, DeltaE(ST) = -3.6 kcal/mol in C2 symmetry, and le, DeltaE(ST) = -3.4 kcal/mol in C-2 symmetry). Spiroconjugation is shown to be responsible for the larger calculated value of \DeltaE(ST)\ in 1g, relative to 1d and le. A strong correlation between the calculated values of DeltaE(ST) and the computed electronic excitation energies of the singlet diradicals is found for diradicals 1d, le, and 1g and for 2,2-difluorocyclopentane-1,3-diyl (1c). A similar correlation between DeltaE(ST) and lambda(calcd) is predicted for the corresponding 1,3-diphenylcyclopentane-1,3-diyls 3, and the predicted blue shift in the spectrum of 3g, relative to 3e, has been confirmed by experimental comparisons of the electronic absorption spectra of the annelated derivatives 2c, 2e, and 2g in a glass at 77 K. The wavelength of the first absorption band in the singlet diradicals decreases in the order 2e (lambda(onset) = 650 nm) > 2g (lambda(onsel) = 590 nm) > 2c (lambda(onset) = 580 nm). The combination of these computational and experimental results provides a sound basis for reassignment of the first electronic absorption band in singlet diradicals 2c, 2e, and 2g to the excitation of anelectron from the HOMO to the LUMO of these 2,2-disubstituted derivatives of cyclopentane1,3-diyl.