(c-4a,c-8a)-1,4,4a,5,8,8a-Hexahydro-10,10-dimethyl-r-1,c-4:t-5,t-8-dimethanophthalazin | 89703-41-3

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (c-4a,c-8a)-1,4,4a,5,8,8a-Hexahydro-10,10-dimethyl-r-1,c-4:t-5,t-8-dimethanophthalazin
• 英文别名: (1R,2R,3R,6S,7S,8S)-12,12-dimethyl-4,5-diazatetracyclo[6.2.1.13,6.02,7]dodeca-4,9-diene
• CAS: 89703-41-3
• 化学式: C₁₂H₁₆N₂
• 分子量: 188.272
• InChiKey: DOVAPCUYIHVHJZ-MXULBQIISA-N

物化性质

• 熔点：
  102-103 °C
• 沸点：
  248.8±40.0 °C(Predicted)
• 密度：
  1.50±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.67
• 重原子数：
  14.0
• 可旋转键数：
  0.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  (c-4a,c-8a)-1,4,4a,5,8,8a-Hexahydro-10,10-dimethyl-r-1,c-4:t-5,t-8-dimethanophthalazin 在 反-1,3-戊二烯 作用下， 以 苯 为溶剂， 生成 (1α,2β,5α,7α,8β,9α)-6,6-dimethyl-4,5-diazatetracyclo[7.2.1.0^2,8,0^5,7]dodeca-3,10-diene
  参考文献：
  名称：

  Phosphorescence and Transient Absorption of Azoalkane Triplet States

  摘要：

  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.

  DOI：

  10.1021/ja00155a022
• 作为产物：
  描述：

  2,5-降冰片二烯 、 alkaline earth salt of/the/ methylsulfuric acid 在 三氟乙酸 作用下， 以 氯仿 为溶剂， 反应 0.67h， 生成 (1α,4α,4aα,5α,8α,8aα)-1,4,4a,5,8,8a-Hexahydro-10,10-dimethyl-1,4:5,8-dimethanophthalazin 、 (c-4a,c-8a)-1,4,4a,5,8,8a-Hexahydro-10,10-dimethyl-r-1,c-4:t-5,t-8-dimethanophthalazin
  参考文献：
  名称：

  Beck, Karin; Huenig, Siegfried; Klaerner, Frank-Gerrit, Chemische Berichte, 1987, vol. 120, p. 2041 - 2052

  摘要：

  DOI：

文献信息

• Photoreduction of Azoalkanes by Direct Hydrogen Abstraction from 1,4-Cyclohexadiene, Alcohols, Stannanes, and Silanes
  作者：Waldemar Adam、Jarugu N. Moorthy、Werner M. Nau、J. C. Scaiano

  DOI：10.1021/jo971105w

  日期：1997.11.1

  silane. In contrast, the hydrazine yields derived for the azoalkanes 1c and 1d are significantly lower even at high hydrogen donor concentrations due to their lower triplet yields and shorter triplet lifetimes. A clear dependence of the hydrazine yields on the bond dissociation energies of the hydrogen donors has been observed, which is reflected in the quenching rate constants obtained from time-resolved

  已对偶氮烷1进行了n，pi三重态激发偶氮发色团光还原的机理研究，偶氮烷1表现出有效的跨体系量子产率（约0.5）。在多种氢供体的存在下，偶氮烷1a和1b容易地光还原为相应的肼，所述氢供体包括2-丙醇，苯甲醇，1,4-环己二烯，三丁基锡烷和三（三甲基甲硅烷基）硅烷。相反，偶氮烷1c和1d的肼产率甚至在高氢供体浓度下也显着较低，这是由于它们的三重态产率较低和三重态寿命较短。已经观察到肼收率对氢供体的键解离能有明显的依赖性，它反映在时间分辨瞬态吸收光谱法获得的猝灭速率常数上。三联偶氮烷1a与氢供体相互作用的绝对速率常数通常比二苯甲酮低（约10-100倍），这与不利的反应热力学一致。三重激发偶氮烷1a猝灭速率常数和2,3-二氮杂双环[2.2.2] oct-2-ene（DBO）单重激发态的猝灭速率常数的比较表明，激发的偶氮烷对氢的反应性相似捐助者；可以根据激发态的能量变化来解释差异。激发的偶氮烷与三丁
• 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; Hoehn, Arthur; Huenig, Siegfried, Chemische Berichte, 1984, vol. 117, # 2, p. 517 - 533
  作者：Beck, Karin、Hoehn, Arthur、Huenig, Siegfried、Prokschy, Frank

  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.
• Adam; Nau; Sendelbach, Journal of the American Chemical Society, 1993, vol. 115, # 26, p. 12571 - 12572
  作者：Adam、Nau、Sendelbach

  DOI：——

  日期：——