1-(cyanomethyl)hexanydro-1H,3H,6H-5a,8a-diaza-2a-azoniaacenaphthylene bromide

• 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: 1-(cyanomethyl)hexanydro-1H,3H,6H-5a,8a-diaza-2a-azoniaacenaphthylene bromide
• 英文别名: 2-(1,8-Diaza-4-azoniatricyclo[6.3.1.04,12]dodec-4(12)-en-2-yl)acetonitrile;bromide
• 化学式: Br*C₁₁H₁₇N₄
• 分子量: 285.187
• InChiKey: JQABFAANJQBTJG-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  -2.93
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  33.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-(cyanomethyl)hexanydro-1H,3H,6H-5a,8a-diaza-2a-azoniaacenaphthylene bromide 在 sodium tetrahydroborate 作用下， 以 乙醇 、 水 为溶剂， 以67%的产率得到(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
• 作为产物：
  描述：

  4-bromobut-2-enenitrile 、 1,5,7-三氮杂双环[4.4.0]癸-5-烯 在 sodium hydroxide 作用下， 生成 1-(cyanomethyl)hexanydro-1H,3H,6H-5a,8a-diaza-2a-azoniaacenaphthylene bromide
  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

文献信息

• Formal Transfers of Hydride from Carbon−Hydrogen Bonds. Generation of H₂ from Orthoformamides Designed To Undergo Intramolecular Protonolyses of Activated Carbon−Hydrogen Bonds
  作者：Philippe Brunet、James D. Wuest

  DOI：10.1021/jo951636p

  日期：1996.1.1

  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.