N-methyl-2-bromo-2-phenethylamine hydrobromide

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: N-methyl-2-bromo-2-phenethylamine hydrobromide
• 英文别名: 1-Phenyl-2-methylamino-aethylbromid-hydrobromid；2-bromo-N-methyl-2-phenylethanamine;hydron;bromide
• 化学式: BrH*C₉H₁₂BrN
• 分子量: 295.017
• InChiKey: GYMGYXUALHDDLE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.92
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  12
• 氢给体数：
  2
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-methyl-2-bromo-2-phenethylamine hydrobromide 在 甲基锂 作用下， 以45%的产率得到1-methyl-2-phenylaziridine
  参考文献：
  名称：

  Interproton coupling constant variations in 3-membered ring heterocycles. Separation of lone pair and inductive effects

  摘要：

  AbstractIn order to separate inductive and lone pair effects on geminal and vicinal coupling constants in a stereochemically well‐defined system, the 1H NMR spectra of phenylcyclopropane (1), N‐methyl‐2‐phenylaziridine (2), styrene oxide (3) and 1,1‐dimethyl‐2‐phenylaziridinium fluorosulfonate (4) were compared. In D2O the heterocyclic ring protons of 4 were split into an ABX pattern which gave J(cis) = 8.5, J(trans) = 7.4 and J(gem) = −4.8 Hz (signs consistent with INDOR results). From the small solvent effects on J(vic) determined from 4‐d1, it was concluded that J(gem) is −5.0 ± 1.0 Hz in methylene chloride. The absolute values for the coupling constants for 1 and 4 provide a measure of the inductive effect of the ring hetero group on J. Values of J(gem) for 2 and 3 deviated from those predicted on the basis of the above inductive effect, suggesting lone pair contributions to J(gem) of c. +5.5 Hz per lone pair. With this estimate it was possible to predict accurately the J(gem) values for 2‐t‐butyloxaziridine and 1‐t‐butyldiaziridine. The values of J(cis) and J(trans) for 2 and 3 likewise suggested a contribution of −2.5 Hz to J(cis) and −2.7 Hz to J(trans) per lone pair. The present results suggest that the major factors causing positive J(gem) values in epoxides and aziridines are increased s character to the CH bonds and lone pair effects, while the so‐called electronegativity effect actually operates in the opposite direction to decrease J(gem). Also, the unusually low J(vic) values of epoxides relative to cyclopropanes are now seen to be due more to negative lone pair contributions than to the electron withdrawing ability of oxygen.

  DOI：

  10.1002/mrc.1270130110

文献信息

• Interproton coupling constant variations in 3-membered ring heterocycles. Separation of lone pair and inductive effects
  作者：Delanson R. Crist、Arnold P. Borsetti、Guy J. Jordan、Charles F. Hammer

  DOI：10.1002/mrc.1270130110

  日期：1980.1

  AbstractIn order to separate inductive and lone pair effects on geminal and vicinal coupling constants in a stereochemically well‐defined system, the 1H NMR spectra of phenylcyclopropane (1), N‐methyl‐2‐phenylaziridine (2), styrene oxide (3) and 1,1‐dimethyl‐2‐phenylaziridinium fluorosulfonate (4) were compared. In D2O the heterocyclic ring protons of 4 were split into an ABX pattern which gave J(cis) = 8.5, J(trans) = 7.4 and J(gem) = −4.8 Hz (signs consistent with INDOR results). From the small solvent effects on J(vic) determined from 4‐d1, it was concluded that J(gem) is −5.0 ± 1.0 Hz in methylene chloride. The absolute values for the coupling constants for 1 and 4 provide a measure of the inductive effect of the ring hetero group on J. Values of J(gem) for 2 and 3 deviated from those predicted on the basis of the above inductive effect, suggesting lone pair contributions to J(gem) of c. +5.5 Hz per lone pair. With this estimate it was possible to predict accurately the J(gem) values for 2‐t‐butyloxaziridine and 1‐t‐butyldiaziridine. The values of J(cis) and J(trans) for 2 and 3 likewise suggested a contribution of −2.5 Hz to J(cis) and −2.7 Hz to J(trans) per lone pair. The present results suggest that the major factors causing positive J(gem) values in epoxides and aziridines are increased s character to the CH bonds and lone pair effects, while the so‐called electronegativity effect actually operates in the opposite direction to decrease J(gem). Also, the unusually low J(vic) values of epoxides relative to cyclopropanes are now seen to be due more to negative lone pair contributions than to the electron withdrawing ability of oxygen.