1,4-dimethyl-2,3-diaza-bicyclo[2.2.1]hept-2-ene | 71312-54-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 1,4-dimethyl-2,3-diaza-bicyclo[2.2.1]hept-2-ene
• 英文别名: 1,4-Dimethyl-2,3-diazabicyclo[2.2.1]hept-2-ene
• CAS: 71312-54-4
• 化学式: C₇H₁₂N₂
• 分子量: 124.186
• InChiKey: ORMQPBKHZKMZAA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  1,4-dimethyl-2,3-diaza-bicyclo[2.2.1]hept-2-ene 270.0 ℃ 、101.32 kPa 条件下， 以55%的产率得到1,4-dimethylbicyclo<2.1.0>pentane
  参考文献：
  名称：

  烷基取代双环偶氮烷烃的热解、光致电子转移 (PET)、激光喷射和 185 nm 光化学的比较研究

  摘要：

  2,3-二氮杂双环[2.2.1]庚-2-烯(1a)、syn-7-methyl-2的气相热解、光致电子转移(PET)、激光喷射和185-nm光化学， 3-二氮杂双环[2.2.1]hept-2-ene (syn-1b), anti-7-methyl-2,3-diazabicyclo[2.2.1]hept-2-ene (anti-1b), 1,4-二甲基-2,3-二氮杂双环[2.2.1]庚-2-烯(1c)、7,7-二甲基-2,3-二氮杂双环[2.2.1]庚-2-烯(1d)和syn-7 -(1-甲基乙基)-2,3-二氮杂双环[2.2.1]庚-2-烯(syn-1e)进行了研究，并将它们的产品研究结果相互比较。偶氮烷烃 1 的热解和常规直接和二苯甲酮敏化的 350 nm 光解产生双环 [2.1.0] 戊烷 2 和数量可忽略不计的环戊烯 3

  DOI：

  10.1021/ja00039a012
• 作为产物：
  描述：

  5-methylhex-5-en-2-on p-tosylhydrazone 在 三氟化硼乙醚 作用下， 以 苯 为溶剂， 反应 6.0h， 以39%的产率得到5,8,8-trimethyl-3-(3'-methyl-3'-butenyl)-1,2-diazabicyclo<3.3.0>oct-2-ene
  参考文献：
  名称：

  Intra- and intermolecular cyclization of olefinic tosylhydrazones under acidic conditions. A facile synthesis of bicyclic azoalkanes

  摘要：

  DOI：

  10.1021/ja00525a029

文献信息

• Regioselective Rearrangement of Bridgehead-Methyl-Substituted Radical Cations Derived from Bicyclo[2.1.0]pentanes and 2,3-Diazabicyclo[2.2.1]hept-2-enes through Photoinduced Electron Transfer and Radiolytic Oxidation: Product Distribution and Matrix ESR Studies
  作者：Waldemar Adam、Coskun Sahin、Juergen Sendelbach、Herbert Walter、Guo-Fei Chen、Ffrancon Williams

  DOI：10.1021/ja00085a043

  日期：1994.3

  essential localization of positive charge at the tertiary center as the reaction proceeds in the 1,3-diyl radical cation 1b[sup [sm bullet]+]. The symmetrical dimethyl derivative 1c rearranged much more reluctantly than 1b despite its lower oxidation potential, and this is attributed to the greater persistence of radical cation 1c[sup [sm bullet]+] through its reluctance to undergo a 1,2-H shift. The oxidation

  环戊烷-1,3-二基自由基阳离子由 1-甲基-和 1,4-二甲基取代的双环-[2.1.0] 戊烷 1b,c 通过光致电子转移 (PET) 和辐射分解氧化产生。不对称桥头取代的双环戊烷 1b 在 PET 条件下自发且排他性地重排为 3-甲基环戊烯 3b。ESR 研究同样表明 3b[sup [sm bullet]+] 是 1b 的唯一最终氧化产物；未检测到初始自由基阳离子 1b[sup [sm bullet]+]，因为它通过 1,2-氢转变为 3b[sup [sm bullet]+] 快速且立体选择性地重排，即使在 80 K 下，也没有痕迹观察到更稳定的 1-甲基环戊烯自由基阳离子 3a[sup [sm bullet]+]。当反应在 1,3-二基自由基阳离子 1b[sup [sm bullet]+] 中进行时，这种逆热力学区域选择性被合理化为正电荷在三级中心的基本定位。尽管氧化电位较低，但对称二甲基衍生物
• UV-laser photochemistry: diffusion-controlled trapping of cyclic 1,3-diradicals by molecular oxygen - conformational effects on triplet lifetimes
  作者：Waldemar Adam、Peter Hoessel、Walter Huemmer、Herbert Platsch、R. Marshall Wilson

  DOI：10.1021/ja00258a074

  日期：1987.11

  and hence it should have a relatively long triplet lifetime. In contrast, the rigid puckered bicyclo(2.2.1)hepta-2,7-diyl should be the most short-lived species of the three. The flexible twist-boat conformation of the cyclohexa-1,3-diyl possesses intermediate lifetime. Other than such conformational effects, it is difficult to rationalize the lifetimes of these rather similar 1,3-diradicals.

  为了探索甲基取代在自由基位点和环大小的影响，从各自的偶氮烷烃中生成 1,3-双自由基并定量测定氧捕获。分子力学计算表明，在最低能量构象中，轨道间角约为。1,3-双基分别为 0/sup 0/、45/sup 0/ 和 60/sup 0/。因此，对于平面 cyclopenta-1,3-diyl（平面性证实为 ESR）系统间交叉自旋轨道耦合应该是最困难的，因此它应该具有相对较长的三重态寿命。相比之下，刚性褶皱双环（2.2.1）hepta-2,7-diyl 应该是三者中寿命最短的物种。cyclohexa-1,3-diyl 的灵活扭船构象具有中等寿命。除了这种构象效应，
• Denitrogenation of bicyclic azoalkanes through photosensitized electron transfer: generation and intramolecular trapping of radical cations
  作者：Waldemar Adam、Juergen Sendelbach

  DOI：10.1021/jo00072a009

  日期：1993.9

  To elucidate the intermediates that intervene in the denitrogenation of bicyclic azoalkanes by photosensitized electron transfer (PET), the 2,3-diazabicyclo[2.2.1]hept-2-ene (DBH) derivative 1b was synthesized, and its PET reactions were examined. With triphenylpyrylium tetrafluoroborate (TPT) or 9,10-dicyanoanthracene (DCA) as sensitizers and biphenyl as cosensitizer, the azoalkane lb gave through intramolecular cyclization the spiro ethers 5 and 6 as trapping products, in addition to the bicyclopentane 2b and the cyclopentenes 3b,b', the latter as rearrangement products. Comparison with 1,4-dimethyl-DBH (1c) revealed that trapping of a 1,3-diyl radical cation as the major pathway is unlikely. PET experiments with the regioisomeric cyclopentenes 3b,b', which both led to the spiro ether 5, imply the involvement of the allyl cation 3b(-H)+ as the decisive intermediate in the nucleophilic trapping reactions. Comparison of the PET chemistry of the azoalkane lb and the corresponding bicyclopentane 2b gave further insight into the mechanism of denitrogenation of azoalkanes through single electron transfer. The latter results lend additional support for the involvement of the diazenyl radical cation 1.+, which to date has escaped direct detection.
• WILSON R. M.; REKERS J. W., J. AMER. CHEM. SOC., 1979, 101, NO 14, 4005-4007
  作者：WILSON R. M.、 REKERS J. W.

  DOI：——

  日期：——
• Adam Waldemar, Sahin Coskun, Sendelbach Juergen, Walter Herbert, ChenGuo-+, J. Amer. Chem. Soc, 116 (1994) N 6, S 2576-2584
  作者：Adam Waldemar, Sahin Coskun, Sendelbach Juergen, Walter Herbert, ChenGuo-+

  DOI：——

  日期：——