(1R,2R,4S,5S)-2,4-bis(2,6-difluorophenyl)-1,5-dimethyl-3-azabicyclo[3.3.1]nonan-9-one | 177492-42-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: (1R,2R,4S,5S)-2,4-bis(2,6-difluorophenyl)-1,5-dimethyl-3-azabicyclo[3.3.1]nonan-9-one
• CAS: 177492-42-1
• 化学式: C₂₂H₂₁F₄NO
• 分子量: 391.408
• InChiKey: NJCNDRYEMQHLOZ-KNGAYFSHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  28
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (1R,2R,4S,5S)-2,4-bis(2,6-difluorophenyl)-1,5-dimethyl-3-azabicyclo[3.3.1]nonan-9-one 在 盐酸 、 水 、 sodium nitrite 作用下， 以 氯仿 为溶剂， 生成 (1R,2R,4S,5S)-2,4-bis(2,6-difluorophenyl)-1,5-dimethyl-3-nitroso-3-azabicyclo[3.3.1]nonan-9-one
  参考文献：
  名称：

  N-Nitroso-2,4-二芳基-3-氮杂双环[3.3.1]壬烷和N-Nitroso-2,4-二芳基-3-氮杂双[3.3.1] nonan-9-ones的结构，构型和立体动力学（1）。

  摘要：

  测量了标题N-亚硝胺的可变温度（1）H，（13）C和（19）F NMR光谱。观察到的异常低的NN旋转势垒（12-15 kcal / mol）是亚硝胺系统与平面度的显着偏差造成的。两种化合物的X射线晶体结构以及UV光谱中n-pi吸收带的红移均证实了氨基氮的金字塔特征。亚硝氨基部分的非平面性是由于NNO基团与固定在双环骨架赤道位置的相邻芳基取代基之间的空间相互作用而引起的强拟假A（（1,3））应变所致。另外，在低于“冻结”所需的温度下检查了芳基CC旋转的障碍。

  DOI：

  10.1021/jo9600159
• 作为产物：
  描述：

  二甲基环已酮 、 2,6-二氟苯甲醛 在 乙酸铵 作用下， 以 甲醇 为溶剂， 生成 (1R,2R,4S,5S)-2,4-bis(2,6-difluorophenyl)-1,5-dimethyl-3-azabicyclo[3.3.1]nonan-9-one
  参考文献：
  名称：

  N-Nitroso-2,4-二芳基-3-氮杂双环[3.3.1]壬烷和N-Nitroso-2,4-二芳基-3-氮杂双[3.3.1] nonan-9-ones的结构，构型和立体动力学（1）。

  摘要：

  测量了标题N-亚硝胺的可变温度（1）H，（13）C和（19）F NMR光谱。观察到的异常低的NN旋转势垒（12-15 kcal / mol）是亚硝胺系统与平面度的显着偏差造成的。两种化合物的X射线晶体结构以及UV光谱中n-pi吸收带的红移均证实了氨基氮的金字塔特征。亚硝氨基部分的非平面性是由于NNO基团与固定在双环骨架赤道位置的相邻芳基取代基之间的空间相互作用而引起的强拟假A（（1,3））应变所致。另外，在低于“冻结”所需的温度下检查了芳基CC旋转的障碍。

  DOI：

  10.1021/jo9600159

文献信息

• Three-Center CF···HN Intramolecular Hydrogen Bonding in the 2,6-Bis(2,6-difluorophenyl)piperidine Systems¹
  作者：Marzena Pham、Maria Gdaniec、Tadeusz Połoński

  DOI：10.1021/jo9800457

  日期：1998.5.1

  H-1, C-13, and F-19 NMR spectroscopy provided evidence for an interaction between the NH proton and the neighboring fluorine atoms in 2,6-bis(2,6-difluorophenyl)piperidin-4-ones, which can be qualified as a three-center hydrogen bonding. This was confirmed by the X-ray crystal structures of two compounds revealing the axial orientation of the amino hydrogen and its short contacts to two fluorine atoms. Surprisingly, the IR. spectra exhibited shift of the NH stretching frequency to higher instead to lower wavenumbers in the 2,6-difluorophenyl derivatives. The variable temperature F-19 NMR spectra showed enhanced C-C rotation barriers of the aryl substituents in the 2,6-difluorophenyl derivatives, due to the intramolecular hydrogen bonding.
• Structure, Conformation, and Stereodynamics of <i>N</i>-Nitroso-2,4-diaryl-3-azabicyclo[3.3.1]nonanes and <i>N</i>-Nitroso-2,4-diaryl-3-azabicyclo[3.3.1]nonan-9-ones¹
  作者：Tadeusz Połoński、Marzena Pham、Maria J. Milewska、Maria Gdaniec

  DOI：10.1021/jo9600159

  日期：1996.1.1

  (1)H, (13)C, and (19)F NMR spectra were measured for the title N-nitrosamines. The observed unusually low N-N rotation barriers (12-15 kcal/mol) result from a significant deviation of the nitrosamino system from planarity. A pyramidal character of the amino nitrogen was confirmed by the X-ray crystal structures of two compounds and by bathochromic shifts of the n-pi absorption bands in the UV spectra

  测量了标题N-亚硝胺的可变温度（1）H，（13）C和（19）F NMR光谱。观察到的异常低的NN旋转势垒（12-15 kcal / mol）是亚硝胺系统与平面度的显着偏差造成的。两种化合物的X射线晶体结构以及UV光谱中n-pi吸收带的红移均证实了氨基氮的金字塔特征。亚硝氨基部分的非平面性是由于NNO基团与固定在双环骨架赤道位置的相邻芳基取代基之间的空间相互作用而引起的强拟假A（（1,3））应变所致。另外，在低于“冻结”所需的温度下检查了芳基CC旋转的障碍。
• Spontaneous generation of chirality and chiroptical spectra of N-nitroso-2,4-diaryl-3-azabicyclo[3.3.1]nonanes
  作者：Teresa Olszewska、Maria J. Milewska、Maria Gdaniec、Tadeusz Połoński

  DOI：10.1016/j.tetasy.2012.02.012

  日期：2012.2

  The crystal structures of several bicyclic N-nitrosamines indicate that they crystallize in the chiral (Sohncke) space group P2(1)2(1)2(1) as conglomerates. This allows the resolution of these compounds by manual picking of the enantiomorphous crystals. The optical activity of the single crystals was confirmed by their CD spectra taken in KBr disks. The absolute configurations of the title nitrosamines were assigned by crystallographic measurements and by a comparison of their CD spectra with those of a reference compound resolved by classical methods. The observed Cotton effect signs, corresponding to the n-pi* transition, were correlated with the helicity of the inherently chiral nitrosamine chromophore. (C) 2012 Elsevier Ltd. All rights reserved.