2,10-Di-tert-butyl-12,12,14,14-tetramethyl-5,7,12,14-tetrahydro-5,7-diaza-pentacene | 858779-79-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹啉及其衍生物
• 英文名称: 2,10-Di-tert-butyl-12,12,14,14-tetramethyl-5,7,12,14-tetrahydro-5,7-diaza-pentacene
• 英文别名: 2,10-Ditert-butyl-12,12,14,14-tetramethyl-5,7-dihydroquinolino[3,2-b]acridine
• CAS: 858779-79-0
• 化学式: C₃₂H₄₀N₂
• 分子量: 452.683
• InChiKey: YOYKIOLJOBHROK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.1
• 重原子数：
  34
• 可旋转键数：
  2
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  24.1
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,10-Di-tert-butyl-12,12,14,14-tetramethyl-5,7,12,14-tetrahydro-5,7-diaza-pentacene 在 二甲基二环氧乙烷 作用下， 以 丙酮 为溶剂， 以59%的产率得到2,10-Ditert-butyl-13a-hydroxy-12,12,14,14-tetramethylquinolino[3,2-b]acridin-6-one
  参考文献：
  名称：

  Oxidation of Annelated Diarylamines: Analysis of Reaction Pathways to Nitroxide Diradical and Spirocyclic Products

  摘要：

  Oxidation of diaryldiamine 2, a tetrahydrodiazapentacene derivative, provides diarylnitroxide diradical 1 accompanied by an intermediate nitroxide monoradical and a multitude of isolable diamagnetic products. DFT-computed tensors for EPR spectra and paramagnetic H-1 NMR isotropic shifts for nitroxide diradical 1 show good agreement with the experimental EPR spectra in rigid matrices and paramagnetic H-1 NMR spectra in solution, respectively. Examination of the diamagnetic products elucidates their formation via distinct pathways involving C-O bond-forming reactions, including Baeyer-Villiger-type oxidations. An unusual diiminoketone structure and two spirocyclic structures of the predominant diamagnetic products are confirmed by either X-ray crystallography or correlations between DFT-computed and experimental spectroscopic data such as H-1, C-13, and N-15 NMR chemical shifts and electronic absorption spectra.

  DOI：

  10.1021/jo2017923
• 作为产物：
  描述：

  苯,1,5-二溴-2,4-二(1-甲基乙烯基)- 在 palladium diacetate 、 三叔丁基膦 、 磷酸 、 sodium t-butanolate 作用下， 以 甲苯 为溶剂， 反应 12.0h， 生成 2,10-Di-tert-butyl-12,12,14,14-tetramethyl-5,7,12,14-tetrahydro-5,7-diaza-pentacene
  参考文献：
  名称：

  π-Conjugated Conjoined Double Helicene via a Sequence of Three Oxidative CC- and NN-Homocouplings

  摘要：

  Dimerization of planarized diamine 2 using benzoyl peroxide gave dihydrazine 1 in about 70% yield; that is, three dehydrogenations (one CC- and two NN-homocouplings) and two ring closures were attained in one synthetic step. Dihydrazine 1 may be viewed as a chiral pi-conjugated conjoined double helicene, with two homochiral [5]helicene-like fragments, annelated in their mid-sections. A relatively high barrier of approximately 35 kcal mol-1 for inversion of configuration for one of the [5]helicene-like helices in 1 was found.

  DOI：

  10.1021/ja051521v

文献信息

• Isolation of the Triplet Ground State Aminyl Diradical
  作者：Przemysław J. Boratyński、Maren Pink、Suchada Rajca、Andrzej Rajca

  DOI：10.1002/anie.201002811

  日期：——

  cycle: A high‐spin nitrogen‐centered (aminyl) diradical with a triplet (S=1) ground state (see picture) has a large singlet‐triplet energy gap (ΔEST). Effective shielding of the reactive aminyl radical centers provides stability at room temperature and maintains the planarity of the π system required for the triplet ground state and large ΔEST value. The diradical assembles in solution to form a π‐dimer‐like

  自旋循环：具有三重态（S = 1）基态的高自旋氮中心（氨基）双自由基（见图）具有较大的单重态-三重态能隙（ΔE ST）。有效地屏蔽反应性胺基自由基中心可在室温下提供稳定性，并保持三重态基态和大ΔE ST值所需的π系统的平面度。双自由基在溶液中组装形成具有弱交换耦合的π二聚体结构。
• High-Spin Diradical Dication of Chiral π-Conjugated Double Helical Molecule
  作者：Chan Shu、Hui Zhang、Arnon Olankitwanit、Suchada Rajca、Andrzej Rajca

  DOI：10.1021/jacs.9b08711

  日期：2019.10.30

  configurationally stable for 48 h at room temperature, thus providing the lower limit for inversion barrier of configuration of 27 kcal mol-1. The enantiomers of conjoined bis[5]diazahelicene and its diradical dication show strong chirooptical properties that are comparable to [6]helicene or carbon-sulfur [7]helicene, as determined by the anisotropy factors, |g| = |Δε|/ε = 0.007 at 348 nm (neutral) and |g| = 0.005

  我们报告了手性 D2 对称连体双 [5] 二氮杂黑烯的空气稳定双自由基指示，具有前所未有的高自旋（三重态）基态，单重态三重态能隙，EST = 0.3 kcal mol-1。双自由基指示具有闭壳 (Kekulé) 共振形式，具有 16 个 π 电子周长。双自由基双自由基在低温下在邻苯二甲酸二丁酯 (DBP) 基质中是单体，在环境条件下，在过量氧化剂存在下，它的半衰期超过两周。已经通过实验确定了约 35 kcal mol-1 的势垒用于中性连体双 [5] 二氮杂黑烯中的构型反转，而其自由基阳离子和双自由基双自由基中的反转势垒通过 DFT 计算预测在几 kcal 以内mol-1 在中性物种中。手性 HPLC 拆分提供了富含 (P,P)- 或 (M,M)- 对映异构体的手性 D2 对称连体双 [5] 二氮杂黑烯。对映异构体富集的三线态双自由基在室温下构型稳定 48 小时，从而为 27 kcal mol-1
• Stable diarylnitroxide diradical with triplet ground state
  作者：Andrzej Rajca、Kouichi Shiraishi、Suchada Rajca

  DOI：10.1039/b909741d

  日期：——

  Nitroxide diradical , the first isolated diarylnitroxide diradical, is stable in the solid state at room temperature and it possesses triplet ground state with strong ferromagnetic coupling.

  一氧化二氮自由基，第一个分离出的二芳基硝基氧自由基，在室温下处于稳定状态，并具有三重态基态和强铁磁耦合。
• Triplet (<i>S</i> = 1) Ground State Aminyl Diradical
  作者：Andrzej Rajca、Kouichi Shiraishi、Maren Pink、Suchada Rajca

  DOI：10.1021/ja071881d

  日期：2007.6.13

  Aminyl diradical, which is stable in solution at low temperatures, is prepared. EPR spectra and SQUID magnetometry indicate that the diradical is planar and it possesses triplet ground state, with strong ferromagnetic coupling.

  制备了在低温下在溶液中稳定的氨基双自由基。EPR 谱和 SQUID 磁力计表明双自由基是平面的，它具有三重基态，具有强铁磁耦合。