exo-3,4-diazotricyclo[4.2.1.0^2,5]nona-3,7-diene | 23979-29-5

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: exo-3,4-diazotricyclo[4.2.1.0^2,5]nona-3,7-diene
• 英文别名: (1S,2S,5R,6R)-3,4-diazatricyclo[4.2.1.02,5]nona-3,7-diene
• CAS: 23979-29-5
• 化学式: C₇H₈N₂
• 分子量: 120.154
• InChiKey: UNSPTTVDHBABCW-RNGGSSJXSA-N

物化性质

• 沸点：
  169.0±40.0 °C(Predicted)
• 密度：
  1.74±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  exo-3,4-diazotricyclo[4.2.1.0^2,5]nona-3,7-diene 在 三氟乙酸 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 14.0h， 生成 (1R,2R,5S,6S,7R,9S)-8-(4-chlorophenyl)-3,4,8-triazatetracyclo[4.3.1.02,5.07,9]dec-3-ene
  参考文献：
  名称：

  Rieber, N.; Boehm, H., Journal of Heterocyclic Chemistry, 1981, vol. 18, p. 1 - 7

  摘要：

  DOI：
• 作为产物：
  描述：

  (1S,2S,8R,9R)-5-methyl-3,5,7-triazatetracyclo[7.2.1.02,8.03,7]dodec-10-ene-4,6-dione 在 氢氧化钾 、 copper dichloride 作用下， 以 异丙醇 为溶剂， 生成 exo-3,4-diazotricyclo[4.2.1.0^2,5]nona-3,7-diene
  参考文献：
  名称：

  通过Diels-Alder环加成法合成Delta（1）-1,2-二氮杂环丁烷。

  摘要：

  [反应：见正文]提出了一种合成Delta（1）-1,2-二氮杂tine的新方法。亲二烯体4与五个二烯的狄尔斯-阿尔德环加成反应以良好至优异的产率提供了环加合物。将获得的四个环加合物转化为相应的地西汀。

  DOI：

  10.1021/ol0164942

文献信息

• Electron Transfer Induced Deazatization of Cyclic Azo Derivatives of Quadricyclane and Norbornadiene
  作者：Gregory W. Sluggett、Nicholas J. Turro、Heinz D. Roth

  DOI：10.1021/ja00145a007

  日期：1995.10

  flash photolysis techniques as well as chemically induced dynamic nuclear polarization (CIDNP). Irradiation of acetonitrile solutions of 9,lO-dicyanoan- thracene (DCA), 2,6,9,1O-tetracyanoanthracene (TCA), or chloranil (Chl) in the presence of Azo-Q results in rapid and efficient deazatization to afford N. Similar irradiation of DCA, TCA, and Chl in the presence of Azo-N yields N and Q. CIDNP experiments

  已经使用稳态和激光闪光光解技术以及化学诱导动态核极化 (CIDNP) 研究了四环烷 (Q) 和降冰片二烯 (N) 的两种环状偶氮烷衍生物 (Azo-Q、Azo-N) 的光敏氧化. 9,10-二氰基蒽 (DCA)、2,6,9,1O-四氰基蒽 (TCA) 或氯苯醌 (Chl) 的乙腈溶液在 Azo-Q 存在下的辐照导致快速有效的脱氮作用，得到 N . 在偶氮-N 存在下，DCA、TCA 和 Chl 的类似照射产生 N 和 Q。CIDNP 实验表明，极化的 N 在偶氮-Q 的 Chl 敏化光解中形成笼状产物，而极化的 N 和 Q 都是从 Azo-N 形成笼状产品。结果与 Azo-"+ 竞争性裂解为 N'+ 和 Q+ 一致，Azo-@+ 选择性脱氮为 N'+。在 Azo-Q 或 Azo-N 存在下辐照 1-氰基萘可产生 Q 和或 N，其化学产率与直接辐照和萘敏化辐照获得的化学产率相似，表明单线态能量转移淬灭。Azo-N
• Thermal Decomposition of a Series of 1,2-Diazetines
  作者：Gary W. Breton、John H. Shugart

  DOI：10.1021/jo0351926

  日期：2003.10.1

  A homologous series of tricyclic diazetines (6a-c), differing by the number of methylene groups in the saturated bridges of the fused carbon bicycles, was synthesized. The DeltaH(not equal) of decomposition for each of the diazetines to afford N-2 and the corresponding alkene was determined experimentally: 6a, 31.7; 6b, 39.3; 6c, 38.8 kcal/mol. The ground-state strain energy of each diazetine was estimated utilizing computationally obtained DeltaH(f)'s for each of the experimentally investigated diazetines as well as several other diazetines whose DeltaHs(not equal,) had been previously reported in the literature. The sum of the ground-state strain energies and DeltaHs(not equal,) of decomposition for all of the diazetines was nearly constant, with an average value of 59 kcal/mol, suggesting that all of the diazetines decompose via the same mechanism. Generally, the higher the ground-state strain energy of the diazetine, the less the DeltaH(not equal) for decomposition. The decomposition transition states for 6a-c and 7 were modeled computationally at the RB3LYP/6-311+G(3df,2p)//UB3LYP/6-31+G(d,p) level. The agreement of the experimentally determined DeltaH(not equal) values with transition-state energies obtained computationally supports the reaction mechanism originally proposed by Yamabe that the elimination process occurs by an unsymmetrical, yet concerted, transition state with strong biradical character.
• Hydrazinolysis of Urazoles: A Convenient and Mild Method for the Preparation of Azoalkanes
  作者：Waldemar Adam、Luis A. Arias、Ottorino De Lucchi

  DOI：10.1055/s-1981-29519

  日期：——
• Rh(III)-Photosensitized Interconversion of Norbornadiene and Quadricyclane
  作者：Gregory W. Sluggett、Nicholas J. Turro、Heinz D. Roth

  DOI：10.1021/jp972007h

  日期：1997.11.1

  The utility of two Rh(III) diimine complexes, Rh(phen)(3)(3+) and Rh(phi)(2)(phen)(3+) (phen = 1,10-phenanthroline, phi = 9,10-phenanthrenequinone diimine), as sensitizers for the interconversion of norbornadiene (N) and quadricyclane (Q) has been investigated using steady-state photochemical and laser flash photolysis (LFP) techniques. Irradiation of acetonitrile solutions of Rh(phen)(3)(3+) and N causes slow conversion to Q. The reaction is reversible; irradiation of Rh(phen)(3)(3+) in the presence of Q leads to N. Irradiation of acetonitrile solutions of Rh(phi)2(phen)3+ and Q yields N. However, this reaction is irreversible; irradiation of the Rh(In) complex in the presence of N fails to afford Q. Irradiation of methanol solutions of either Rh(III) complex in the presence of N or Q affords minor amounts of two methanol-C7 adducts but fails to quench the N-Q interconversion reaction. The results are consistent with N-Q interconversion via an exciplex intermediate. The Rh(III)-sensitized deazatization of two cyclic azoalkane derivatives (Azo-N, Azo-Q) of N and Q was also investigated. Deazatization was achieved by Rh(phen)(3)(3+) but not Rh(phi)(2)(phen)(3+) sensitization. The results are consistent with a mechanism involving triplet energy transfer, but the involvement of exciplex intermediates cannot be ruled out. Bimolecular rate constants for quenching of the Rh(III) excited states by N, Q, Azo-N, and Azo-Q were determined by LFP.