(+/-)-8H,16H-7,15-methanodinaphtho<2,1-bis><2',1'-f>-diazocine | 652-82-4

• 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: (+/-)-8H,16H-7,15-methanodinaphtho<2,1-bis><2',1'-f>-diazocine
• 英文别名: 8H,16H-7,15-methanodinaphtho[2,1-b][2',1'-f][1,5]diazocine；1,13-Diazahexacyclo[11.11.1.02,11.05,10.014,23.017,22]pentacosa-2(11),3,5,7,9,14(23),15,17,19,21-decaene
• CAS: 652-82-4；160453-90-7；160453-91-8
• 化学式: C₂₃H₁₈N₂
• 分子量: 322.409
• InChiKey: DQSKXSNSJBSJLS-UHFFFAOYSA-N

物化性质

• 沸点：
  586.9±50.0 °C(Predicted)
• 密度：
  1.33±0.1 g/cm3(Predicted)
• 熔点：
  213-215 °C

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  25
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+/-)-8H,16H-7,15-methanodinaphtho<2,1-bis><2',1'-f>-diazocine 生成 (-)-8H,16H-7,15-methanodinaphtho<2,1-bis><2',1'-f>-diazocine
  参考文献：
  名称：

  Synthesis and resolution of naphthyl-Tröger's base

  摘要：

  A naphthyl analogue of Troger's base {8H, 16H-7,15-methanodinaphtho[2,1-b][2',1'-f] [1,5]-diazocine (NTB)} was prepared and successfully resolved using (-)- and (+)-di-p-toluoyl-tartaric acid. Enantiomers obtained show extremely high specific rotations related to (i) the rigid [1,5]-diazocine skeleton with molecular asymmetry and (ii) the presence of condensed aromatic rings, similar to helicenes. (C) 1998 Elsevier Science Ltd. AII rights reserved.

  DOI：

  10.1016/s0957-4166(98)00439-x
• 作为产物：
  描述：

  2-萘胺 生成 (+/-)-8H,16H-7,15-methanodinaphtho<2,1-bis><2',1'-f>-diazocine
  参考文献：
  名称：

  KANAO SEIZO, YAKUGAKU DZASSI, YAKUGAKU ZASSNI, Z.

  摘要：

  DOI：

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。
• Spiro Tröger’s Base Derivatives: Another Structural Phoenix?
  作者：Ameneh Tatar、Jan Čejka、Vladimír Král、Bohumil Dolenský

  DOI：10.1021/ol1004774

  日期：2010.4.16

  Recently, naphthalenoide derivatives of Tröger’s base (TB) have become important as structural compartments of molecular tweezers and compounds with high specific rotation. The formation of TB derivatives and byproducts from naphthalen-2-amine, methyl 6-aminonaphthalene-2-carboxylate, and anthracen-2-amine was studied. It was discovered that the formation of a naphthalenoide TB derivative is followed by the

  最近，作为分子镊子和具有高比旋光度的化合物的结构部分，特洛格碱（TB）的萘二甲酸酯衍生物已变得很重要。研究了由萘-2-胺，6-氨基萘-2-羧酸甲酯和蒽-2-胺形成的结核菌衍生物和副产物。已经发现，形成萘甲醚TB衍生物之后，形成TB的独特结构异构体：spiroTB。
• Selective formation of either Tröger’s base or spiro Tröger’s base derivatives from [2-aminoporphyrinato(2-)]nickel by choice of reaction conditions
  作者：Ameneh Tatar、Bohumil Dolenský、Hana Dvořáková、Vladimír Král

  DOI：10.1016/j.tetlet.2012.08.097

  日期：2012.11

  formaldehyde to form selectively either the symmetric Tröger’s base or the asymmetric spiro Tröger’s base bis(metalloporphyrin) derivative. The reaction is driven by the choice of acid catalyst, formaldehyde source, and particularly, solvent, to give a mixture of both derivatives in preparative yields of about 90%, or to give selectively one of the derivatives in a yield of about 60%.

  该文章报道了[2-氨基卟啉（2-）]镍与甲醛的酸催化反应的独特操作，该反应选择性地形成了对称的Tröger碱或不对称的螺环Tröger的碱双（金属卟啉）衍生物。通过选择酸催化剂，甲醛源，特别是溶剂来驱动反应，以制备产率约90％得到两种衍生物的混合物，或以产率约60％选择性地得到一种衍生物。
• Convenient Syntheses of Tröger’s Base Derivatives in Ionic Liquids
  作者：Hui Wu、Pu Zhang、Yang Shen、Fu-ren Zhang、Yu Wan、Da-qing Shi

  DOI：10.1055/s-2007-968001

  日期：2007.2

  Derivatives based on Troger's base's skeleton bearing fused pyrazole or isoxazole rings were prepared in good yields by reacting amino-substituted pyrazole or isoxazole with formaldehyde or acetaldehyde in ionic liquid [bpy][BF 4 ].

  通过氨基取代的吡唑或异恶唑与甲醛或乙醛在离子液体[bpy][BF 4 ]中反应，以良好的收率制备了基于具有稠合吡唑或异恶唑环的Troger碱骨架的衍生物。
• Synthesis and characterisation of a new naphthalene tris-Tröger’s base derivative—a chiral molecular clip
  作者：Bohumil Dolenský、Jiří Kessler、Milan Jakubek、Martin Havlík、Jan Čejka、Jana Novotná、Vladimír Král

  DOI：10.1016/j.tetlet.2012.11.035

  日期：2013.1

  Serial tris-Tröger’s base derivatives (trisTBs) are members of a recently introduced family of chiral molecular clips. Naphthalene tris-Tröger’s base is prepared via both stepwise and one-pot approaches. All three diastereoisomers are isolated and unambiguously identified, and their NMR spectra, enantioseparation and binding ability are studied. The syn,syn-trisTB diastereoisomer, a molecular clip

  tris-Tröger系列的基础衍生物（trisTBs）是最近推出的手性分子片段家族的成员。萘tris-Tröger的碱是通过逐步法和一锅法制备的。分离并明确鉴定了所有三种非对映异构体，并研究了它们的NMR谱，对映体分离和结合能力。发现syn，syn -trisTB非对映异构体是一种分子夹子，是缺电子的氰基苯的潜在分子受体。外消旋体syn，syn-trisTB通过制备型HPLC（手性色谱柱）拆分，并通过比较实验值和计算出的ECD光谱确定绝对构型。建议对酸性介质中的oligoTB稳定性和潜在的阴离子结合具有一般依赖性。