2,3-diazabicyclo<2.2.1>hept-2-ene-exo,exo-5,6-d2 | 60400-43-3

• 分子结构分类: 有机化合物
• 英文名称: 2,3-diazabicyclo<2.2.1>hept-2-ene-exo,exo-5,6-d2
• 英文别名: (1S,4R,5S,6R)-5,6-dideuterio-2,3-diazabicyclo[2.2.1]hept-2-ene
• CAS: 60400-43-3
• 化学式: C₅H₈N₂
• 分子量: 98.116
• InChiKey: IJDUBDHNOXAHCQ-JLWOFXPXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  7
• 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：

  2,3-diazabicyclo<2.2.1>hept-2-ene-exo,exo-5,6-d2 在 potassium permanganate 、 甲基三辛基氯化铵 、 乙酰氯 作用下， 以 水 、 苯 为溶剂， 350.0 ℃ 、101.33 kPa 条件下， 反应 1.0h， 生成 cis-3,4-dideuterioglutaric anhydride
  参考文献：
  名称：

  双环[2.1.0]戊烷和环戊烯的185-nm光化学

  摘要：

  La photolyse du bicyclo [2.1.0] 戊烷管道 au pentadiene-1,4 et au cyclopentene comme produits primaires et au 亚甲基环丁烷comme produit secondaire。La photolyse du 环戊烯管道 au 亚甲基环丁烷和双环 [2.1.0] 戊烷通过 l'intermediaire cyclobutylmethylene comme produits Majoritaires

  DOI：

  10.1021/ja00299a029

文献信息

• UV laser photochemistry: triplet biradical trapping efficiencies and lifetimes
  作者：Waldemar. Adam、Klaus. Hannemann、R. Marshall. Wilson

  DOI：10.1021/ja00265a015

  日期：1986.3

  been studied quantitatively. The lifetime of 1 has been found to range between 720 and 900 ns and that of 2 between 53 and 94 ns depending on the solvent. The biradical 1 was found to be trapped in essentially quantitative yield with no indication of oxygen-catalyzed intersystem crossing. In contrast, 2 was found to be trapped in 54-79% yield with the residual biradical quenching being due to oxygen-catalyzed

  三线态 1,3-环戊二基 (1) 和三线态 1,4-双基 2-(2-乙基) 环戊-2-烯基 (2) 与分子氧的捕获已进行了定量研究。已发现 1 的寿命在 720 到 900 ns 之间，而 2 的寿命在 53 到 94 ns 之间，具体取决于溶剂。发现双自由基 1 以基本上定量的产率被捕获，没有氧催化系统间交叉的迹象。相比之下，发现 2 以 54-79% 的产率被捕获，残留的双自由基猝灭是由于氧催化的系统间交叉。这些和其他双自由基捕获数据已与 1,3-双自由基几何相关联，并且发现符合塞勒姆关于三重双自由基中自旋轨道耦合的规则。28 篇参考文献、7 幅图、2 张表格。
• Solvent effects in the photodenitrogenation of the azoalkane diazabicyclo[2.2.1]hept-2-ene: viscosity- and polarity-controlled stereoselectivity in housane formation from the diazenyl diradical
  作者：Waldemar Adam、Manfred Diedering、Alexei V. Trofimov

  DOI：10.1039/b110562k

  日期：2002.3.4

  manifest the same free-volume requirements and thereby reflect similar frictional impositions on the stereoselective inversion for the DBH photolysis in these solvents. The Onsager bulk-polarity parameter (e − 1)/(2e + 1) accounts adequately for the observed solvent influence. This fact implies that stabilization of the dipole moment in the diazenyl diradical 1DZ retards the inversion process during the

  二氮杂双环[2.2.1]hept-2-ene (DBH) 液相光解中的立体选择性，以形成倒置 [2(inv)] 与保留 [ 2(ret)] housanes，取决于介质的粘度和体积极性，而氢键对立体分化几乎没有影响。醇和异辛烷/nujol 混合物中 kinv/kret 比的相似粘度曲线表现出相同的自由体积要求，从而反映了对这些溶剂中 DBH 光解的立体选择性反转的相似摩擦力。Onsager 体积极性参数 (e - 1)/(2e + 1) 充分说明了观察到的溶剂影响。
• Pressure dependence of the stereoselectivity in the photodenitrogenation of diazabicyclo[2.2.1]hept-2-ene in supercritical fluids: evidence for the diazenyl diradical
  作者：Waldemar Adam、Manfred Diedering、Alexei V. Trofimov

  DOI：10.1016/s0009-2614(01)01326-4

  日期：2001.12

  The present study shows that the preference for the stereoselective inversion upon the photolytic nitrogen extrusion from the stereolabeled DBH derivative exo-d2-diazabicyclo[2.2.1]heptene (1) in supercritical media (sc-CO2, sc-C2H6) depends on pressure. The increase of pressure up to 200 bar leads to ca. 2.3-fold decrease of the stereoselectivity (kinv/kret ratio) in sc-CO2 and sc-C2H6. Analysis of

  本研究表明，用于在所述立体选择性反转偏好光解氮挤出从stereolabeled DBH衍生物外-d 2二氮杂双环[2.2.1]庚烯（1在超临界介质）（SC-CO 2，SC-C 2 ħ 6）取决于压力。压力增加到200 bar导致大约 sc-CO 2和sc-C 2 H 6中的立体选择性（k inv / k ret比）降低2.3倍。根据碰撞（自扩散系数）和摩擦（粘度）效应对观察到的压力依赖性的分析表明，流体介质施加的摩擦力最能说明本文报道的实验结果。这种与压力有关的粘度效应与DBH在超临界相中进行光解的逐步脱氮机理相一致，该过程通过不对称的含氮瞬态，即单重氮基二氮烯基双自由基进行。
• Structural dependence on the stereoselective formation of inverted housane in the viscosity-controlled photodenitrogenation of DBH-type azoalkanes
  作者：Waldemar Adam、Manfred Diedering、Meledathu C. Sajimon、Alexei V. Trofimov

  DOI：10.1039/b209182h

  日期：2003.1.2

  The influence of structural changes on the α parameter, which represents the effective volume involved in molecular reorganizations, has been determined through the viscosity dependence of the stereoselectivity in the photodenitrogenation of the DBH-type azoalkanes 1a–c. The structural variation reveals that the stereoselective formation of housane is not only subject to the frictional impositions exerted by the solvent molecules on the flap motion of the methylene bridge, but also on the displacement of the bridgehead substituents during the inversion process.

  通过DBH型偶氮烷1a-c的光脱氮反应中立体选择性的粘度依赖性，确定了结构变化对α参数的影响，该参数表示分子重组中涉及的有效体积。结构变化表明，胡桑的立体选择性形成不仅受溶剂分子对亚甲基桥的瓣状运动施加的摩擦力影响，还受反式过程中桥头取代基位移的影响。
• Dynamic models for the thermal deazetization of 2,3-diazabicyclo[2.2.1]hept-2-ene
  作者：Barbara A. Lyons、Jorg Pfeifer、Thomas H. Peterson、Barry K. Carpenter

  DOI：10.1021/ja00059a043

  日期：1993.3

  Kinetic studies on the thermal nitrogen extrusion from 2,3-diazabicyclo[2.2.1]hept-2-ene-exo,exo-5,6-d2 are reported. The ratio of rate constants for formation of the label-isomeric products (bicyclo[2.1.0]pentane-exo,exo-2,3-d2 and -endo,endo-2,3-d2) is found to exhibit no statistically significant temperature dependence. A comparison of gas-phase and solution-phase results is presented. The results are interpreted in terms of two complementary dynamic models. In the first,classical trajectory calculations are run on a three-dimensional projection (two geometric coordinates) of the potential energy hypersurface. These calculations correctly identify the major product, and reproduce the near temperature-independence of the rate-constant ratio, but do not match the ratio quantitatively. Modification of the trajectory calculations to simulate the effect of collisions with solvent molecules also qualitatively matches the observed difference between gas-phase and solution-phase behavior. In the second model, the vector of atomic displacements corresponding to the reaction coordinate at the transition state for nitrogen loss is identified by both semiempirical and ab initio calculations. The components of this vector pointing along the paths to the post-transition-state minima are computed and are shown to lead to a prediction of the product ratio that is in good (if partly fortuitous) agreement with the experimental result. The vector model is used to predict isotope effects on the product ratio, which are then investigated experimentally with 2,3-diazabicyclo[2.2.1]hept-2-ene-endo,endo-1,4,5,6,7,7-d6 and -endo-7-d.