(1α,4α,4aα,5β,8β,8aα)-1,4,4a,5,8,8a-Hexahydro-1,4,10,10-tetramethyl-1,4;5,8-dimethanophthalazin | 89703-45-7

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: (1α,4α,4aα,5β,8β,8aα)-1,4,4a,5,8,8a-Hexahydro-1,4,10,10-tetramethyl-1,4;5,8-dimethanophthalazin
• CAS: 89703-45-7
• 化学式: C₁₄H₂₀N₂
• 分子量: 216.326
• InChiKey: JUDKFCHTGMLLBJ-AWHURUNMSA-N

物化性质

• 熔点：
  109-110 °C
• 沸点：
  258.0±40.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.45
• 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：
  0.86
• 拓扑面积：
  24.72
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (1α,4α,4aα,5β,8β,8aα)-1,4,4a,5,8,8a-Hexahydro-1,4,10,10-tetramethyl-1,4;5,8-dimethanophthalazin 以 乙腈 为溶剂， 反应 1.67h， 以88%的产率得到3,4,4,5-Tetramethyl-(1rC¹⁰,2tH,3cH)-tetracyclo[5,2,1,0^2,6,0^3,5]-dec-8-en
  参考文献：
  名称：

  Huenig, Siegfried; Kraft, Petra, Journal fur praktische Chemie (Leipzig 1954), 1990, vol. 332, # 2, p. 133 - 142

  摘要：

  DOI：
• 作为产物：
  描述：

  3,4,4,5-四甲基-4H-吡唑 、 2,5-降冰片二烯 在 三氟乙酸 作用下， 以 氯仿 为溶剂， 反应 96.0h， 以2%的产率得到(c-4a,c-8a)-1,4,4a,5,8,8a-Hexahydro-1,4,10,10-tetramethyl-r-1,c-4:c-5,c-8-dimethanophthalazin
  参考文献：
  名称：

  Beck, Karin; Hoehn, Arthur; Huenig, Siegfried, Chemische Berichte, 1984, vol. 117, # 2, p. 517 - 533

  摘要：

  DOI：

文献信息

• Charge-Transfer-Induced Photoreduction of Azoalkanes by Amines
  作者：Waldemar Adam、Jarugu N. Moorthy、Werner M. Nau、J. C. Scaiano

  DOI：10.1021/ja9706460

  日期：1997.7.1

  aziranes 3. In contrast, the azoalkane 1c undergoes appreciable photoreduction only in neat amines, while the azoalkane 1d (φISC ca. 0.10) is not reduced even under such conditions. Except for N,N-dimethylbenzylamine, the amine oxidation products of the azoalkane photoreduction are analogous to those obtained from the reactions of amines with triplet benzophenone. In marked contrast, the absolute quan

  独特的 DBH 型偶氮烷 1 表现出高系统间交叉量子产率，使探索 n,π* 三线态激发的偶氮发色团的双分子光还原成为可能。在激光闪光光解中，发现胺以高速率常数 (kq ca. 108 M-1 s-1) 淬灭三重偶氮烷烃 1a。在脂肪族伯胺、仲胺和叔胺存在下，偶氮烷烃 1a 和 1b（φISC 约 0.5）的稳态光解得到了相应的肼 4a 和 4b 的高化学产率，与单分子产物（即 housanes 2）竞争和氮杂环烷 3。相比之下，偶氮烷 1c 仅在纯胺中发生明显的光还原反应，而偶氮烷 1d（φISC 约 0.10）即使在这种条件下也不会被还原。除 N,N-二甲基苄胺外，偶氮烷光还原的胺氧化产物类似于从胺与三线态二苯甲酮反应获得的那些。与此形成鲜明对比的是，绝对质量...
• Beck, Karin; Huenig, Siegfried; Klaerner, Frank-Gerrit, Chemische Berichte, 1987, vol. 120, p. 2041 - 2052
  作者：Beck, Karin、Huenig, Siegfried、Klaerner, Frank-Gerrit、Kraft, Petra、Artschwager-Perl, Uwe

  DOI：——

  日期：——
• Huenig, Siegfried; Kraft, Petra; Klaerner, Frank-Gerrit, Liebigs Annalen, 1995, # 2, p. 351 - 356
  作者：Huenig, Siegfried、Kraft, Petra、Klaerner, Frank-Gerrit、Artschwanger-Perl, Uwe、Peters, Karl、Schnering, Hans-Georg von

  DOI：——

  日期：——
• Solvent Effect on Product Distribution in Photochemical Pathways of α C−N versus β C−C Cleavage of n,π* Triplet-Excited Azoalkanes
  作者：Waldemar Adam、Jarugu N. Moorthy、Werner M. Nau、J. C. Scaiano

  DOI：10.1021/ja963948v

  日期：1997.6.1

  The product distribution in;the photolysis of the triplet-excited azoalkanes 1a,b depends markedly on the type of solvent used; in contrast, the azoalkanes 1c,d, which undergo efficient deazatization from the singlet-excited state, display solvent-independent photobehavior. Thus, the aziranes 3 are produced essentially exclusively in polar protic solvents, while the housanes 2 predominate in nonpolar ones. The excellent correlation (r(2) = 0.963, seven solvents) of the azirane 3b yield with Gutmann's AN solvent parameter reveals that a combination of solvent properties such as the polarity and polarizability of the medium and the hydrogen-bonding ability is decisive for the photoproduct distribution. That the observed solvent dependence derives from bulk medium effects is borne out by the similar product distribution for the hydroxy-substituted derivative 1f to that for the azoalkane 1b in benzene, i.e., the intramolecular hydroxy functionality in the azoalkane If is ineffective in influencing the photochemistry of the triplet azo chromophore. Selective formation of the aziranes 3 from the triplet-excited azoalkanes 1 in the polar protic solvents is rationalized in terms of solvent stabilization of the more polar transition state for beta cleavage (azirane 3) over that for the alpha scission (housane 2). In marked contrast to the appreciable deuterium isotope effect for quenching of the singlet-excited azoalkanes by protic solvents, the lifetimes (laser-flash photolysis) and reactivity (product analysis) of the triplet azoalkanes are not affected by deuterium substitution.
• Phosphorescence and Transient Absorption of Azoalkane Triplet States
  作者：Waldemar Adam、Gianfranco Fragale、Dieter Klapstein、Werner M. Nau、Jakob Wirz

  DOI：10.1021/ja00155a022

  日期：1995.12

  Fused derivatives of 2,3-diazabicyclo[2,2.1]hept-2-ene (DBH) were studied by transient absorption, optical emission, and photoelectron spectroscopy, and their reaction quantum yields were measured. For the first time, long-lived azoalkane triplet states were observed by phosphorescence and transient absorption spectroscopy. The assignment of the transient absorptions to the triplet states of the azoalkanes was proven by quenching and energy transfer experiments in solution. Quantitative agreement was found between the real-time kinetic data of triplet quenching determined by flash photolysis and Stem-Volmer analyses of the effect of quenchers on the product distributions and quantum yields. Triplet energies of 62.5 +/- 1 kcal mol(-1) were determined from the 0-0 bands of the phosphorescence spectra. The triplet energies of azoalkanes that have been previously evaluated by techniques other than phosphorescence are critically evaluated. The radiative rate constant of azoalkane phosphorescence was determined as ca. 3 s(-1). The transient absorption spectra had maxima at ca. 315 and 500 nm, and the triplet lifetimes were as long as 0.63 mu s. Intersystem crossing (ISC) was found to be an efficient process for most of the azoalkanes examined; for azoalkane la, the triplet quantum yield was estimated to be 0.5 +/- 0.2 at ambient temperature. No internal or external heavy-atom effects were observed on phosphorescence and ISC. In some cases, formation of 1,3-cyclopentanediyl biradicals from the azoalkane triplet states was observed by transient absorption spectroscopy. The yield of triplet biradicals, generated by direct photolysis of azoalkanes in solution, served as a qualitative probe for the involvement of ISC and azoalkane triplet states. Possible factors which govern the triplet lifetimes and ISC of azoalkanes are discussed; molecular rigidity appears to favor both high triplet yields and long triplet lifetimes. Assignments of the two T-T absorption bands are proposed. All experimental results are consistent with the expected n,pi* configuration for the lowest excited singlet and triplet states of aliphatic azoalkanes.