1-methyl-cis-2,4-diphenyl-3-azabicyclo<3.3.1>nonan-9-one

• 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: 1-methyl-cis-2,4-diphenyl-3-azabicyclo<3.3.1>nonan-9-one
• 英文别名: 1-methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9-one；(1S,2R,4R,5R)-1-methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9-one
• 化学式: C₂₁H₂₃NO
• 分子量: 305.42
• InChiKey: DHDHFCNPYMPTKV-HDAAZOAOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-methyl-cis-2,4-diphenyl-3-azabicyclo<3.3.1>nonan-9-one 在 盐酸 、 双氧水 、 三氟乙酸酐 、 sodium nitrite 作用下， 以 二氯甲烷 、 氯仿 、 水 、 甲苯 为溶剂， 反应 1.0h， 生成 (1R)-N-nitro-1-methyl-2,4-diphenyl-3-azabicyclo[3.3.1]nonane
  参考文献：
  名称：

  Spontaneous generation of chirality and chiroptical spectra of N-nitroso-2,4-diaryl-3-azabicyclo[3.3.1]nonanes

  摘要：

  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.

  DOI：

  10.1016/j.tetasy.2012.02.012
• 作为产物：
  描述：

  苯甲醛 、 2-甲基环己酮 在 乙酸铵 作用下， 以 甲醇 为溶剂， 生成 1-methyl-cis-2,4-diphenyl-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

• 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。
• Stereospecific synthesis of oximes and oxime ethers of 3-azabicycles: A SAR study towards antimicrobial agents
  作者：Paramasivam Parthiban、Paramasivam Rathika、Venkatachalam Ramkumar、Se Mo Son、Yeon Tae Jeong

  DOI：10.1016/j.bmcl.2010.01.048

  日期：2010.3

  Libraries of 1-methyl-2,4-diaryl-3-azabicyclo[3.3.1]nonan-9-ones/oximes/O-methyloximes 1-14/15-28/29-42 and 7-methyl-2,4-diaryl-3-azabicyclo[3.3.1]nonan-9-ones/oximes/O-methyloximes 43-48/49-54/55-60 were synthesized and their stereochemistry was established by 1D/2D NMR spectral and single crystal XRD studies. All the synthesized oximes and oxime ethers were screened for their in vitro antimicrobial activity against a panel of pathogenic bacteria (Bacillus subtilis, Staphylococcus aureus, Klebsiella pneumoniae and Pseudomonas aeruginosa) and fungi (Candida albicans, Candida parapsilosis, Aspergillus niger and Cryptococcus neoformans) using Gentamicin and Fluconazole as standards, respectively. From the SAR profile, the lead molecules were identified. (C) 2010 Elsevier Ltd. All rights reserved.
• 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.