syn-1,4,7,8-Tetramethyl-8-(phenylmethyl)-2,4,6-triazatricyclo<5.1.0.02,6>octane-3,5-dione | 164321-96-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: syn-1,4,7,8-Tetramethyl-8-(phenylmethyl)-2,4,6-triazatricyclo<5.1.0.02,6>octane-3,5-dione
• 英文别名: syn-1,4,7,8-Tetramethyl-8-(phenylmethyl)-2,4,6-triazatricyclo<5.1.0.0^2,6>octane-3,5-dione
• CAS: 164321-96-4
• 化学式: C₁₆H₁₉N₃O₂
• 分子量: 285.346
• InChiKey: AGZLZDLELOPDOK-MUJYYYPQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.06
• 重原子数：
  21.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  48.93
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  syn-1,4,7,8-Tetramethyl-8-(phenylmethyl)-2,4,6-triazatricyclo<5.1.0.02,6>octane-3,5-dione 在 2,6-二叔丁基吡啶 、 tris-(4-bromophenyl)aminium hexachloroantimonate 作用下， 以 氘代氯仿 为溶剂， 以49%的产率得到6-Benzyl-2,6-dimethyl-5,7-dimethylene-dihydro-pyrazolo[1,2-a][1,2,4]triazole-1,3-dione
  参考文献：
  名称：

  尿嘧啶桥联的双环环戊烷（双环[2.1.0]戊烷）的化学电子转移（CET）氧化法生成4,5-二氮杂环戊烷-1,3-二烷基自由基阳离子及其化学转化。

  摘要：

  以三（4-溴苯基）ami六氯锑酸铵为氧化剂，通过脲醛桥连的双环环丁烷3的化学氧化反应生成4,5-二氮杂环戊烷-1,3-二基自由基阳离子3（*）（+）（）。烯烃产品4和5。产品研究表明，双烯烃5是双链烷烃3的双重氧化的结果，而单烯烃4是通过酸催化重排形成的，可以通过过量的碱（2,6-di -叔丁基吡啶）。在二苄基取代（3c）的情况下，两个单自由基物质5（H）c（*）的歧化可作为通往相应烯烃4和5的替代途径，因为在不存在碱的情况下，分离出的双氧化产物的数量比如果仅运行化学计量反应，则可以预期。半经验MO计算表明，电离发生在一个氮孤对上，而不是发生在显着较低（约0.5 eV）的电离势所暗示的应变的中央CC键上。此外，在最初起皱的自由基阳离子中，正电荷主要位于两个氮原子上，而在松弛到平面几何形状后，电荷基本上完全转移到自由基阳离子碳原子上。与甲醇的捕集反应导致产生了半缩醛型产物6和7，它们确定了阳

  DOI：

  10.1021/jo952022n
• 作为产物：
  描述：

  anti-1,4,7,8-Tetramethyl-8-(phenylmethyl)-2,4,6-triazatricyclo<5.1.0.02,6>octane-3,5-dione 以 氘代乙腈 为溶剂， 生成 syn-1,4,7,8-Tetramethyl-8-(phenylmethyl)-2,4,6-triazatricyclo<5.1.0.02,6>octane-3,5-dione
  参考文献：
  名称：

  Urazole-Bridged Bicyclic Azoalkanes: Generation, Nitroxyl Trapping, and ESR Spectra of the Heterosubstituted 4,5-Diaza-1,3-cyclopentanediyl Diradicals through Direct and Benzophenone-Sensitized Photochemical Deazetation

  摘要：

  The Diels-Alder reaction of isopyrazoles 3 with 4-methyl-1,2,4-triazoline-3,5-dione afforded the azoalkanes 4 in high yields. The stereochemistry of the syn- and anti-diastereomeric derivatives 4b was established on the basis of spectral data and an X-ray structure determination for syn-4b. Photochemical loss of dinitrogen through direct as well as benzophenone-sensitized photolysis led to the corresponding housanes 5. For the stereolabeled syn- and anti-4b azoalkanes, the respective housanes anti- and syn-5b were obtained as mixtures, the latter in preference (syn/anti > 90:10). Above -10 degrees C, the housanes 5b isomerized thermally to a 96:4 (at -30 degrees C) thermodynamic mixture of syn/anti, for which a van't Hoff treatment gave Delta G(243 K) = -4.4 kJ/mol in favor of syn-5b, Delta H = 4.2 kJ/mol, and Delta S = 36 J/mol K. AM1 calculations confirm that the syn-fib diastereomer is the preferred one. The triplet-sensitized photolysis at -30 degrees C of the separate syn- and anti-4b azoalkanes gave the same thermodynamically controlled mixture of housanes 5b (syn/anti = 96:4), which speaks for a planar triplet 1,3 diradical T-IIb as intermediate. The intervention of triplet diradicals T-IIa,d was confirmed by ESR spectroscopy under matrix isolation (T less than or equal to 77 K), and the triplet ground state was established by a Curie plot for the dimethyl derivative T-IIa. Since in the direct photolysis of the separate syn- and anti-4b azoalkanes also predominantly the syn-5b housane was obtained, fast intersystem crossing of the singlet 1,3 diradical S-IIb to the triplet species T-IIb is proposed. The small memory effect (retention) in the direct photolysis in solution implies a puckered conformation for the singlet 1,3 diradical S-IIb. Indeed, in the direct deazetation under matrix conditions at -78 degrees C, the memory effect (retention) is unequivocally established, i.e. syn/anti-5b = 24:76 for azoalkane syn-4b and syn/anti > 99:1 for anti-4b. In the presence of the nitroxyl radical scavenger 1,1,3,3-tetramethylisoindolin-2-yloxyl, the 1,3 diradicals were efficiently trapped in form of the isomeric bis-alkoxyamines 7 in the triplet-sensitized as well as direct photolyses of azoalkanes 4a,d. These unprecedented results imply that heteroatom substitution does not generally reduce the lifetime of triplet diradicals.

  DOI：

  10.1021/jo00107a007