2-Methoxy-8-nitro-6H,12H-5,11-methano-dibenzo[b,f][1,5]diazocine | 181813-15-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氮杂萘
• 英文名称: 2-Methoxy-8-nitro-6H,12H-5,11-methano-dibenzo[b,f][1,5]diazocine
• 英文别名: 5-Methoxy-13-nitro-1,9-diazatetracyclo[7.7.1.02,7.010,15]heptadeca-2(7),3,5,10(15),11,13-hexaene
• CAS: 181813-15-0
• 化学式: C₁₆H₁₅N₃O₃
• 分子量: 297.313
• InChiKey: ZPSLHKPFRVWWEW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  22
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  61.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2-Methoxy-8-nitro-6H,12H-5,11-methano-dibenzo[b,f][1,5]diazocine 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 、 氯仿 为溶剂， 反应 12.0h， 以100%的产率得到13-Methoxy-1,9-diazatetracyclo[7.7.1.02,7.010,15]heptadeca-2(7),3,5,10(15),11,13-hexaen-5-amine
  参考文献：
  名称：

  线性低聚-Troger碱基的合成路线。

  摘要：

  Troger碱基（TB）的衍生物因其刚性的V形而在受体的构建中发挥了重要作用。这些化合物中的一类是寡聚结核菌，可起空泡蛋白的作用。在这里，我们描述了适合制备线性低聚结核菌的逐步和一步法（低聚）方法。

  DOI：

  10.1021/ol047902f
• 作为产物：
  描述：

  聚合甲醛 、 N-(p-methoxyphenyl)-2-amino-5-nitrobenzylamine 在 盐酸 作用下， 以 乙醇 为溶剂， 反应 24.0h， 以46%的产率得到2-Methoxy-8-nitro-6H,12H-5,11-methano-dibenzo[b,f][1,5]diazocine
  参考文献：
  名称：

  Complete1H and13C NMR Analysis of an Asymmetric Tröger’s Base

  摘要：

  The H-1 and C-13 NMR spectra of an asymmetric Troger's base were recorded and the corresponding signals assigned on the basis of long-range coupling constants and H-1-C-13 correlations. III 1H NMR, ambiguities in the assignment of exo and endo hydrogen atoms and in the long-range couplings between the methylene hydrogens were resolved.

  DOI：

  10.1002/(sici)1097-458x(199609)34:9<708::aid-omr949>3.0.co;2-r

文献信息

• Polycyclic Indoline-Benzodiazepines through Electrophilic Additions of α-Imino Carbenes to Tröger Bases
  作者：Alessandro Bosmani、Alejandro Guarnieri-Ibáñez、Sébastien Goudedranche、Céline Besnard、Jérôme Lacour

  DOI：10.1002/anie.201803756

  日期：2018.6.11

  intermolecular reaction of Tröger bases with N‐sulfonyl‐1,2,3‐triazoles. Under RhII catalysis, α‐imino carbenes are generated and a subsequent cascade of [1,2]‐Stevens, Friedel–Crafts, Grob, and aminal formation reactions yield the polycyclic heterocycles as single isomers (d.r.>49:1, four stereocenters including two bridgehead N atoms). Further ring expansion by insertion of a second α‐imino carbene leads

  可通过Tröger碱与N-磺酰基-1,2,3-三唑的分子间反应获得多环吲哚啉-苯并二氮杂pine 。在Rh II催化下，生成α-亚氨基卡宾，随后的[1,2] -Stevens，Friedel-Crafts，Grob和氨基形成反应的级联反应生成多环杂环，为单个异构体（dr> 49：1，四个立体中心）包括两个桥头N原子）。通过插入第二个α-亚氨基卡宾进一步的环扩展导致精心设计的多环9元环三唑烷。
• One-Step Catalytic Asymmetric Synthesis of Configurationally Stable Tröger Bases
  作者：Ankit Sharma、Laure Guénée、Jean-Valère Naubron、Jérôme Lacour

  DOI：10.1002/anie.201100134

  日期：2011.4.11

  Bridging the gap: Configurationally stable ethano‐bridged Tröger bases have been prepared in a single step by the direct rhodium(II)‐catalyzed reaction of methano‐bridged Tröger bases and diazo esters (see scheme). The process is general, enantiospecific, diastereoselective (with introduction of a new quaternary carbon center), and regioselective.

  弥合差距：通过甲醇（II）桥连的Tröger碱与重氮酯的直接铑（II）催化反应，一步制备了结构稳定的乙醇桥连的Tröger碱（参见方案）。该过程是一般的，对映体特异性的，非对映选择性的（引入了新的季碳中心）和区域选择性的。
• Efficient Synthesis of Imino-methano Tröger Bases by Nitrene Insertions into C–N Bonds
  作者：Sandip A. Pujari、Laure Guénée、Jérôme Lacour

  DOI：10.1021/ol4016892

  日期：2013.8.2

  A direct nitrene insertion into C-N bonds is observed upon treatment of methano-Troger bases with arylsulfonyl iminophenyliodinanes under copper and dirhodium catalysis. Novel cyclic imino-methano Troger bases are obtained (55-88%). Enantiopure products (ee >= 99%) can be obtained with tailored substrates.
• Complete1H and13C NMR Analysis of an Asymmetric Tröger’s Base
  作者：Carmen Pardo、Mar Ramos、Alain Fruchier、José Elguero

  DOI：10.1002/(sici)1097-458x(199609)34:9<708::aid-omr949>3.0.co;2-r

  日期：1996.9

  The H-1 and C-13 NMR spectra of an asymmetric Troger's base were recorded and the corresponding signals assigned on the basis of long-range coupling constants and H-1-C-13 correlations. III 1H NMR, ambiguities in the assignment of exo and endo hydrogen atoms and in the long-range couplings between the methylene hydrogens were resolved.
• Synthetic Routes to Linear Oligo-Tröger's Bases
  作者：Bohumil Dolenský、Martin Valík、David Sýkora、Vladimír Král

  DOI：10.1021/ol047902f

  日期：2005.1.1

  Derivatives of Troger's base (TB) have played important roles in receptor construction due to their rigid V-shape. A new class of these compounds are the oligo-TBs, which can function as cavitands. Herein, we describe both stepwise and one-step (oligomerization) methods suitable for the preparation of linear oligo-TBs.

  Troger碱基（TB）的衍生物因其刚性的V形而在受体的构建中发挥了重要作用。这些化合物中的一类是寡聚结核菌，可起空泡蛋白的作用。在这里，我们描述了适合制备线性低聚结核菌的逐步和一步法（低聚）方法。