4a,8a-diaza-2,6-dioxa-3,4,7,8-tetrahydro-4,4,8,8-tetramethylanthracene-1,5-dione | 135005-65-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 4a,8a-diaza-2,6-dioxa-3,4,7,8-tetrahydro-4,4,8,8-tetramethylanthracene-1,5-dione
• 英文别名: 7,7,14,14-Tetramethyl-5,12-dioxa-1,8-diazatricyclo[8.4.0.03,8]tetradeca-2,9-diene-4,11-dione
• CAS: 135005-65-1
• 化学式: C₁₄H₁₈N₂O₄
• 分子量: 278.308
• InChiKey: OUJDVDMRNOBYII-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  59.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4a,8a-diaza-2,6-dioxa-3,4,7,8-tetrahydro-4,4,8,8-tetramethylanthracene-1,5-dione 在 palladium on activated charcoal 氢气 作用下， 以 溶剂黄146 为溶剂， 生成 4a,8a-diaza-2,6-dioxa-3,4,7,8,9,9a-hexahydro-4,4,8,8-tetramethylanthracene-1,5,-dione
  参考文献：
  名称：

  来自反芳香族电子供体的新型电荷转移复合物。可能通过俘获效应稳定自由基

  摘要：

  我们报告了基于 1,4-二氢吡嗪环系统的 CT 盐的新型电子供体的合成和表征，4a,8a-diaza-2,6-dioxa-3,4,7,8-tetahydro-4,4 ,8,8-四甲基蒽-1,5-二酮 (DDTTA)，并将其氧化为异常持久、俘获稳定的自由基阳离子

  DOI：

  10.1021/ja00015a082
• 作为产物：
  描述：

  3-(chloromethyl)-5,6-dihydro-5,5-dimethyl-1,4-oxazin-2-one 在 次氯酸叔丁酯 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以22%的产率得到4a,8a-diaza-2,6-dioxa-3,4,7,8-tetrahydro-4,4,8,8-tetramethylanthracene-1,5-dione
  参考文献：
  名称：

  来自反芳香族电子供体的新型电荷转移复合物。可能通过俘获效应稳定自由基

  摘要：

  我们报告了基于 1,4-二氢吡嗪环系统的 CT 盐的新型电子供体的合成和表征，4a,8a-diaza-2,6-dioxa-3,4,7,8-tetahydro-4,4 ,8,8-四甲基蒽-1,5-二酮 (DDTTA)，并将其氧化为异常持久、俘获稳定的自由基阳离子

  DOI：

  10.1021/ja00015a082

文献信息

• Carbonyl and thiocarbonyl stabilized 1,4-dihydropyrazines: synthesis and characterization
  作者：David J. R. Brook、Bruce C. Noll、Tad H. Koch

  DOI：10.1039/a705391f

  日期：——

  8-Hexamethyl-3,4,7,8-tetrahydro-2,4a,6,8a-tetraazaanthracene-1(2H),5(6H)-dione (HTTA) is synthesized by chlorination of the previously reported 5,6-dihydro-1,3,5,5-tetramethylpyrazin-2(1H)-one with tert-butyl hypochlorite and self condensation of the resulting α-chloromethylimine in the presence of diisopropylethylamine in dimethylformamide (DMF). Thioxo derivatives 3,4,7,8-tetrahydro-4,4,8,8-tetramethyl-5-thioxo-2

  1,4-二氢吡嗪，3,4,7,8-四氢-4,4,8,8-四甲基-2,6-二氧杂-4a，8a-二氮杂蒽-1,5-二酮（DDTTA）的三个类似物，已经合成。2,4,4,6,8,8-六甲基-3,4,7,8-四氢-2,4a，6,8a-四氮杂蒽-1（2 H），5（6 H）-二酮（HTTA）通过用先前的次氯酸叔丁酯氯化先前报道的5,6-二氢-1,3,5,5-四甲基吡嗪-2（1 H）-一并在二异丙基乙胺存在下使生成的α-氯甲基亚胺自缩合来合成在二甲基甲酰胺（DMF ）中。硫代氧衍生物3,4,7,8-四氢-4,4,8,8-四甲基-5-硫代氧-2,6-二氧杂-4a，8a-二氮杂蒽-1-酮（DDTTA-S）和3,4 ，7,8-四氢-4,4,8,8-四甲基-2,6-二氧杂-4a，8a-二氮杂蒽-1,5-二硫酮（DDTTA–S2）是通过在吡啶中用五硫化二磷直接硫代DDTTA合成的。所有三个分子均已通过光谱表征。另
• Synthesis, structure, and reactivity of an antiaromatic, 2,5-dicarboxy-stabilized 1,4-dihydropyrazine
  作者：David J. R. Brook、R. Curtis Haltiwanger、Tad H. Koch

  DOI：10.1021/ja00041a018

  日期：1992.7

  3-(Chloromethyl)-5,6-dihydro-5,5-dimethyl-1,4-oxazin-2-one (4) undergoes self-condensation in the presence of diisopropylethylamine to yield 4a,8a-diaza-2,6-dioxa-3,4,7,8-tetrahydro-4,4,8,8-tetramethylanthracene-1,5-dione (DDTTA). DDTTA is an example of a modestly stable, almost flat 1,4-dihydropyrazine. It is green in color, and the long-wavelength visible absorption band shows significant solvatochromism. DDTTA gives reversible one-electron-oxidation waves in methylene chloride at -0.33 and 0.61 V vs ferrocene/ferrocenium (0.07 and 1.01 V vs NHE, respectively) and reacts with Fe(1,10-phenanthroline)3(3+) to yield DDT7A+ (5) characterized by ESR spectroscopy. The radical cation is also produced in purple-black crystals by cocrystallization with tetracyanoquinodimethane (TCNQ). The black material has the composition DDTTA+-TCNQ)2-, and in solution it is unstable to molecular oxygen. Air-stable radical cation 5 is produced by air oxidation of DDTTA in trifluoroacetic acid. The resulting trifluoroacetate crystallizes as pale blue parallelepipeds with the composition DDTTA+CF3CO2-(CF3CO2H)2; the radical cations are arranged in sheets with short C-H...O intermolecular contacts as established by X-ray analysis. DDTTA reacts with molecular oxygen in acetic acid to yield the unstable dioxetane 7, 4a,8a-diaza-2,6-dioxa-9,9a-epidioxy-3,4,7,8,9,9a-hexahydro-4,4,8,8-tetramethylanthracene-1,5-dione, and in acetonitrile to yield the aldehyde 9, 5,6-dihydro-2-oxo-5,5-dimethyl-1,4-oxazine-3-carboxaldehyde. Mechanisms for the air oxidations are proposed in Scheme I. [2 + 21-Cycloaddition of DDTTA occurs with 1-phenyl-1,3,4-triazoline-2,5-dione (PTAD) to give the diazetidine 17. Catalytic hydrogenation of DDTTA gives 4a,8a-diaza-2,6-dioxa-3,4,7,8,9,9a-hexahydro-4,4,8,8-tetramethylanthracene-1,5-dione (13), which air oxidizes to a mixture of DDTTA and 4a,8a-diaza-2,6-dioxa-3,4,7,8,9,9a-hexahydro-9a-hydroxy-4,4,8,8-tetramethylanthracene-1,5-dione (14) via the relatively persistent, purple radical cation 16. DDTTA represents a new electron donor with three stable redox states and, consequently, has potential as a component in formation of organic electrically conducting materials.
• Dioxygen Oxidation of a Stable 1,4-Dihydropyrazine
  作者：David J. R. Brook、Bruce C. Noll、Tad H. Koch

  DOI：10.1021/jo970222o

  日期：1997.10.1

  The stable 1,4-dihydropyrazine 4a,8a-diaza-2,6-dioxa-3,4,7,8-tetrahydro-4,4,8,8-tetramethylanthracene-1,5-dione (DDTTA) is oxidized by dioxygen in various organic solvents to give mixtures of 5,6-dihydro-5,5-dimethyl-3-formyl-1,4-oxazine-2-one (1) and a second product that was previously ascribed a dioxetane structure. The latter is now fully characterized by X-ray crystallography and found to be the diol 4a,8a-diaza-9,9a-dihydroxy-2,6-dioxa-3,4,7,8,9,9a-hexahydro-4,4,8,8-tetramethylanthracene-1,5-dione (4). The oxidation rate and product ratio are highly solvent dependent, Trapping experiments, reaction stoichiometry, and kinetic measurements are all consistent with a hydroperoxide intermediate that reacts with DDTTA to give the diol 4 or undergoes intramolecular fragmentation to give aldehyde 1. Both DDTTA and the intermediate hydroperoxide are significantly less reactive than their biologically active 1,4-dihydropyrazine counterparts.
• New type of charge-transfer complex from an antiaromatic electron donor. Possible radical cation stabilization by the captodative effect
  作者：David J. R. Brook、R. Curtis Haltiwanger、Tad H. Koch

  DOI：10.1021/ja00015a082

  日期：1991.7

  CT salts based on the 1,4-dihydropyrazine ring system, 4a,8a-diaza-2,6-dioxa-3,4,7,8-tetahydro-4,4,8,8-tetramethylanthracene-1,5-dione (DDTTA), and its oxidation to an exceptionally persistent, captodatively stabilized radical cation

  我们报告了基于 1,4-二氢吡嗪环系统的 CT 盐的新型电子供体的合成和表征，4a,8a-diaza-2,6-dioxa-3,4,7,8-tetahydro-4,4 ,8,8-四甲基蒽-1,5-二酮 (DDTTA)，并将其氧化为异常持久、俘获稳定的自由基阳离子