1,4,7-Trimethyl-10,10-bis(phenylmethyl)-2,4,6,8,9-pentaazatricyclo<5.2.1.0^2,6>dec-8-ene-3,5-dione

• 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: 1,4,7-Trimethyl-10,10-bis(phenylmethyl)-2,4,6,8,9-pentaazatricyclo<5.2.1.0^2,6>dec-8-ene-3,5-dione
• 英文别名: (1R,7S)-10,10-dibenzyl-1,4,7-trimethyl-2,4,6,8,9-pentazatricyclo[5.2.1.02,6]dec-8-ene-3,5-dione
• 化学式: C₂₂H₂₃N₅O₂
• 分子量: 389.457
• InChiKey: SOIILXLRVCVPSA-OYRHEFFESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  29
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  68.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,4,7-Trimethyl-10,10-bis(phenylmethyl)-2,4,6,8,9-pentaazatricyclo<5.2.1.0^2,6>dec-8-ene-3,5-dione 以 二氯甲烷 为溶剂， 反应 1.17h， 以73%的产率得到1,4,7-Trimethyl-8,8-bis(phenylmethyl)-2,4,6-triazatricyclo<5.1.0.0^2,6>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
• 作为产物：
  描述：

  4-甲基-1,2,4-三吖啉-3,5-二酮 、 4,4-二苄基-3,5-二甲基-4H-吡唑 以 二氯甲烷 为溶剂， 以69%的产率得到1,4,7-Trimethyl-10,10-bis(phenylmethyl)-2,4,6,8,9-pentaazatricyclo<5.2.1.0^2,6>dec-8-ene-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

文献信息

• 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
  作者：Waldemar Adam、Karlheinz Goller、Thomas Kammel、Karl Peters

  DOI：10.1021/jo00107a007

  日期：1995.1

  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.