(9R,10R)-1-Nitrimino-9-chloro-10-methyldecalin | 171233-63-9

• 分子结构分类: 有机化合物 - 有机1,3-偶极化合物 - 烯丙基型1,3-偶极有机化合物
• 英文名称: (9R,10R)-1-Nitrimino-9-chloro-10-methyldecalin
• CAS: 171233-63-9
• 化学式: C₁₁H₁₇ClN₂O₂
• 分子量: 244.721
• InChiKey: MTDDPFHQPGYFST-AGOHDZRISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.36
• 重原子数：
  16.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  55.5
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (9R,10R)-1-Nitrimino-9-chloro-10-methyldecalin 在 1,4-二氧六环 、 sodium tetrahydroborate 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 25.0h， 生成 (1R,9R,10R)-10-Methyl-1,9-(N-nitroaziridino)decalin
  参考文献：
  名称：

  N-Nitro-Substituted Azetidines and Aziridines. The Inherently Nonplanar Nitroamines: Conformational and Chiroptical Properties

  摘要：

  Optically active inherently nonplanar nitroamines, i.e., (2R)-1-nitro-2-methylazetidine (2b), (4S)-1-nitro-2,2-dibutyl-4-methylazetidine (2d), and (1R,SR,10R)-10-methyl-1,9-(N-nitroaziridino)decalin (3d), are synthesized and their CD, UV, and NMR spectra are studied. Experimental data are interpreted on the basis of nonempirical quantum chemical calculations of model compounds-the parent N-nitro-substituted azetidine 2a and aziridine 3a and their mono- and trimethyl derivatives 2a,b and 3b,c. It is shown that owing to the stereochemical lability of the pyramidal nitroamine chromophore, the closest asymmetrical environment causes torsional deformation of the chromophore and thus induces its intrinsic chirality. The latter determines the Cotton effect sign of the n(0)(-)-pi* transition in accordance with a spiral rule, which was formulated for the non-planar amide and nitrosoamine chromophores. The wavelength of the Cotton effect depends mainly on the pyramidality of the ring nitrogen atom and the intensity on the amount of twisting around the NN bond.

  DOI：

  10.1021/jo00123a027
• 作为产物：
  描述：

  10-methyl-Δ^1,9-octalin 在 吡啶 、 亚硝酰氯 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 (9R,10R)-1-Nitrimino-9-chloro-10-methyldecalin
  参考文献：
  名称：

  N-Nitro-Substituted Azetidines and Aziridines. The Inherently Nonplanar Nitroamines: Conformational and Chiroptical Properties

  摘要：

  Optically active inherently nonplanar nitroamines, i.e., (2R)-1-nitro-2-methylazetidine (2b), (4S)-1-nitro-2,2-dibutyl-4-methylazetidine (2d), and (1R,SR,10R)-10-methyl-1,9-(N-nitroaziridino)decalin (3d), are synthesized and their CD, UV, and NMR spectra are studied. Experimental data are interpreted on the basis of nonempirical quantum chemical calculations of model compounds-the parent N-nitro-substituted azetidine 2a and aziridine 3a and their mono- and trimethyl derivatives 2a,b and 3b,c. It is shown that owing to the stereochemical lability of the pyramidal nitroamine chromophore, the closest asymmetrical environment causes torsional deformation of the chromophore and thus induces its intrinsic chirality. The latter determines the Cotton effect sign of the n(0)(-)-pi* transition in accordance with a spiral rule, which was formulated for the non-planar amide and nitrosoamine chromophores. The wavelength of the Cotton effect depends mainly on the pyramidality of the ring nitrogen atom and the intensity on the amount of twisting around the NN bond.

  DOI：

  10.1021/jo00123a027