2-(4-chlorophenyl)-4,6,6-trimethyl-3,6-dihydro-2H-[1,2]oxazine

• 分子结构分类: 有机化合物 - 苯类化合物 - N-苯基羟胺
• 英文名称: 2-(4-chlorophenyl)-4,6,6-trimethyl-3,6-dihydro-2H-[1,2]oxazine
• 英文别名: 2-(4-chlorophenyl)-4,6,6-trimethyl-3H-oxazine
• 化学式: C₁₃H₁₆ClNO
• 分子量: 237.729
• InChiKey: NLXZPSDZCCUZLP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  16
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2,4-二甲基-1,3-戊二烯 、 对氯苯胺 在 MoO(O₂)(2,6-pyridinedicarboxylato-O,N,O')(HMPA) 双氧水 作用下， 反应 18.0h， 生成 2-(4-chlorophenyl)-3,3,5-trimethyl-3,6-dihydro-2H-[1,2]oxazine 、 2-(4-chlorophenyl)-4,6,6-trimethyl-3,6-dihydro-2H-[1,2]oxazine
  参考文献：
  名称：

  A Molybdenum-Catalyzed Oxidative System Forming Oxazines (Hetero-Diels−Alder Adducts) from Primary Aromatic Amines, Hydrogen Peroxide, and Conjugated Dienes

  摘要：

  The development of a new molybdenum-catalyzed procedure for the formation of oxazines-hetero-Diels-Alder adducts-from primary aromatic amines, hydrogen peroxide, and conjugated dienes is presented, The method is based on a molybdenum-peroxo complex, which in the presence of hydrogen peroxide as the terminal oxidant selectively catalyzes the oxidation of primary aromatic amines to the corresponding dienophilic nitroso compounds. The molybdenum-peroxo catalyst is under the present reaction conditions not reactive toward conjugated dienes and substituents attached to the aromatic nuclei of the primary aromatic amines. Several oxazines are synthezised following this new procedure using primary aromatic amines having either electron-withdrawing or electron-donating substituents and 1,3-cyclohexadiene as the standard diene. The scope of the new procedure is also demonstrated by the preparation of several oxazines using different alkyl- and phenyl-substituted conjugated dienes and 4-chloroaniline as precursor for the dienophile. Moderate diastereomeric excesses are found when the reaction is carried out with 1-(2-aminophenyl)-ethanol and 1,3-cyclohexadiene or (E)-1-phenyl-1,3-butadiene. The stereochemical and electronic factors governing the reaction course are briefly discussed.

  DOI：

  10.1021/jo9608127

文献信息

• A Molybdenum-Catalyzed Oxidative System Forming Oxazines (Hetero-Diels−Alder Adducts) from Primary Aromatic Amines, Hydrogen Peroxide, and Conjugated Dienes
  作者：Eval Rud Møller、Karl Anker Jørgensen

  DOI：10.1021/jo9608127

  日期：1996.1.1

  The development of a new molybdenum-catalyzed procedure for the formation of oxazines-hetero-Diels-Alder adducts-from primary aromatic amines, hydrogen peroxide, and conjugated dienes is presented, The method is based on a molybdenum-peroxo complex, which in the presence of hydrogen peroxide as the terminal oxidant selectively catalyzes the oxidation of primary aromatic amines to the corresponding dienophilic nitroso compounds. The molybdenum-peroxo catalyst is under the present reaction conditions not reactive toward conjugated dienes and substituents attached to the aromatic nuclei of the primary aromatic amines. Several oxazines are synthezised following this new procedure using primary aromatic amines having either electron-withdrawing or electron-donating substituents and 1,3-cyclohexadiene as the standard diene. The scope of the new procedure is also demonstrated by the preparation of several oxazines using different alkyl- and phenyl-substituted conjugated dienes and 4-chloroaniline as precursor for the dienophile. Moderate diastereomeric excesses are found when the reaction is carried out with 1-(2-aminophenyl)-ethanol and 1,3-cyclohexadiene or (E)-1-phenyl-1,3-butadiene. The stereochemical and electronic factors governing the reaction course are briefly discussed.