(1RS,8bSR)-(hexahydro-1H,3H,6H,8bH-2a,5a,8a-triazaacenaphthylen-1-yl)acetonitrile

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 咪唑并嘧啶类
• 英文名称: (1RS,8bSR)-(hexahydro-1H,3H,6H,8bH-2a,5a,8a-triazaacenaphthylen-1-yl)acetonitrile
• 英文别名: 2-[(2S,12R)-1,4,8-triazatricyclo[6.3.1.04,12]dodecan-2-yl]acetonitrile
• 化学式: C₁₁H₁₈N₄
• 分子量: 206.291
• InChiKey: INLBWKQCDVUVSE-WDEREUQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  33.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1RS,8bSR)-(hexahydro-1H,3H,6H,8bH-2a,5a,8a-triazaacenaphthylen-1-yl)acetonitrile 在 lithium aluminium tetrahydride 作用下， 以 二氯甲烷 为溶剂， 反应 40.0h， 以100%的产率得到(1S,8bR)-2-(Hexahydro-2a,5a,8a-triaza-acenaphthylen-1-yl)-ethylamine
  参考文献：
  名称：

  Formal Transfers of Hydride from Carbon−Hydrogen Bonds. Generation of H₂ from Orthoformamides Designed To Undergo Intramolecular Protonolyses of Activated Carbon−Hydrogen Bonds

  摘要：

  Protonolysis of the central carbon-hydrogen bond of tricyclic orthoformamide 1 occurs readily to liberate H-2 and give the corresponding guanidinium ion 15 under mild conditions. To accelerate this process, we have attempted to make the reaction intramolecular by constructing molecules in which carbon-hydrogen bonds similarly activated as formal donors of hydride are held close to acidic sites. Spectroscopic and structural studies have indicated that orthoformamide 25 contains a central carbon-hydrogen bond activated as a formal donor of hydride by three antiperiplanar lone pairs on nitrogen, as well as an acidic ethylammonium group. As expected, pyrolysis of compound 25 produced the corresponding guanidinium ion 28 in high yield, anti H-2 was liberated and could be trapped in 39% yield. However, analogous bimolecular reactions of butylammonium chloride with simple orthoformamides 1 and 29, which do not contain intramolecular acidic sites, occurred at similar rates. This suggests that protonolyses of such structures may occur by collinear attack on the activated central carbon-hydrogen bond or that the observed liberation of Hz does not involve direct protonolysis.

  DOI：

  10.1021/jo951636p
• 作为产物：
  描述：

  1,5,7-三氮杂双环[4.4.0]癸-5-烯 在 sodium hydroxide 、 sodium tetrahydroborate 作用下， 以 乙醇 、 水 为溶剂， 反应 12.0h， 生成 (1RS,8bSR)-(hexahydro-1H,3H,6H,8bH-2a,5a,8a-triazaacenaphthylen-1-yl)acetonitrile
  参考文献：
  名称：

  Formal Transfers of Hydride from Carbon−Hydrogen Bonds. Generation of H₂ from Orthoformamides Designed To Undergo Intramolecular Protonolyses of Activated Carbon−Hydrogen Bonds

  摘要：

  Protonolysis of the central carbon-hydrogen bond of tricyclic orthoformamide 1 occurs readily to liberate H-2 and give the corresponding guanidinium ion 15 under mild conditions. To accelerate this process, we have attempted to make the reaction intramolecular by constructing molecules in which carbon-hydrogen bonds similarly activated as formal donors of hydride are held close to acidic sites. Spectroscopic and structural studies have indicated that orthoformamide 25 contains a central carbon-hydrogen bond activated as a formal donor of hydride by three antiperiplanar lone pairs on nitrogen, as well as an acidic ethylammonium group. As expected, pyrolysis of compound 25 produced the corresponding guanidinium ion 28 in high yield, anti H-2 was liberated and could be trapped in 39% yield. However, analogous bimolecular reactions of butylammonium chloride with simple orthoformamides 1 and 29, which do not contain intramolecular acidic sites, occurred at similar rates. This suggests that protonolyses of such structures may occur by collinear attack on the activated central carbon-hydrogen bond or that the observed liberation of Hz does not involve direct protonolysis.

  DOI：

  10.1021/jo951636p