N-Nitroso-r-2,t-3,t-5,c-6-tetraphenylpiperidin-4-one | 134848-30-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: N-Nitroso-r-2,t-3,t-5,c-6-tetraphenylpiperidin-4-one
• 英文别名: 1-Nitroso-2,3,5,6-tetraphenylpiperidin-4-one
• CAS: 134848-30-9
• 化学式: C₂₉H₂₄N₂O₂
• 分子量: 432.522
• InChiKey: YOSWCGUILOMJQV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  33
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  49.7
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2,3,5,6-tetraphenylpiperidin-4-one 在 盐酸 、 sodium nitrite 作用下， 以 乙醇 为溶剂， 以72.3%的产率得到N-Nitroso-r-2,t-3,t-5,c-6-tetraphenylpiperidin-4-one
  参考文献：
  名称：

  Chemistry of N-nitroso compounds. 1. Synthesis and stereodynamics of N-nitrosopiperidines and N-nitrosopiperidin-4-ones

  摘要：

  The stereochemistry of a series of N-nitroso-r-2,c-6-diphenylpiperidin-4-ones (10-15) and N-nitroso-r-2,c-6-diphenylpiperidines (16-18) in solution has been investigated by H-1 NMR, C-13 NMR, and dynamic H-1 NMR spectroscopic studies. Unlike the r-2,c-6-dialkyl-N-nitrosopiperidines, which have diaxial alkyl groups, these N-nitroso-r-2,c-6-diphenylpiperidines (16-18) and N-nitroso-r-2,c-6-diphenylpiperidin-4-ones (10-15) have diequatorial phenyl groups even though the nitroso group is coplanar to the dynamically averaged plane of the piperidine ring. The rotamer populations of the N-NO orientations in the nitrosamines were derived from continuous wave H-1 NMR spectral data and are correlated with the steric bulk of the substituents present at the C-3 and C-5 positions. N-Nitroso-r-2,c-6-diphenylpiperidine-4-one (10) was found to have a higher rotational barrier than N-nitroso-r-2,c-6-diphenylpiperidine (16). We attribute this difference to a greater degree of coplanarity (C3-C2-N1-C6-C5) in 10 than in 16. The rotational barriers in 10 were found to decrease as the bulk of the substituents at C3 and C5 increased. The rotational barrier in N-nitroso-r-2,c-6-diphenylpiperidine (16) was found to be lower than the reported rotational barriers of N-nitroso-r-2,c-6-dimethylpiperidine and N-nitroso-2,2,6,6-tetramethylpiperidine.

  DOI：

  10.1021/jo00016a007

文献信息

• Chemistry of N-nitroso compounds. 1. Synthesis and stereodynamics of N-nitrosopiperidines and N-nitrosopiperidin-4-ones
  作者：Thiruvenkadam Ravindran、Ramasubbu Jeyaraman、Robert W. Murray、Megh Singh

  DOI：10.1021/jo00016a007

  日期：1991.8

  The stereochemistry of a series of N-nitroso-r-2,c-6-diphenylpiperidin-4-ones (10-15) and N-nitroso-r-2,c-6-diphenylpiperidines (16-18) in solution has been investigated by H-1 NMR, C-13 NMR, and dynamic H-1 NMR spectroscopic studies. Unlike the r-2,c-6-dialkyl-N-nitrosopiperidines, which have diaxial alkyl groups, these N-nitroso-r-2,c-6-diphenylpiperidines (16-18) and N-nitroso-r-2,c-6-diphenylpiperidin-4-ones (10-15) have diequatorial phenyl groups even though the nitroso group is coplanar to the dynamically averaged plane of the piperidine ring. The rotamer populations of the N-NO orientations in the nitrosamines were derived from continuous wave H-1 NMR spectral data and are correlated with the steric bulk of the substituents present at the C-3 and C-5 positions. N-Nitroso-r-2,c-6-diphenylpiperidine-4-one (10) was found to have a higher rotational barrier than N-nitroso-r-2,c-6-diphenylpiperidine (16). We attribute this difference to a greater degree of coplanarity (C3-C2-N1-C6-C5) in 10 than in 16. The rotational barriers in 10 were found to decrease as the bulk of the substituents at C3 and C5 increased. The rotational barrier in N-nitroso-r-2,c-6-diphenylpiperidine (16) was found to be lower than the reported rotational barriers of N-nitroso-r-2,c-6-dimethylpiperidine and N-nitroso-2,2,6,6-tetramethylpiperidine.