2H-1,2-噁嗪,2-(4-氯苯基)-3,6-二氢-4,5-二甲基- | 105207-76-9

• 分子结构分类: 有机化合物 - 苯类化合物 - N-苯基羟胺
• 中文名称: 2H-1,2-噁嗪,2-(4-氯苯基)-3,6-二氢-4,5-二甲基-
• 英文名称: 2-(4-chlorophenyl)-4,5-dimethyl-3,6-dihydro-2H-[1,2]-oxazine
• 英文别名: 2H-1,2-Oxazine, 2-(4-chlorophenyl)-3,6-dihydro-4,5-dimethyl-；2-(4-chlorophenyl)-4,5-dimethyl-3,6-dihydrooxazine
• CAS: 105207-76-9
• 化学式: C₁₂H₁₄ClNO
• 分子量: 223.702
• InChiKey: RVHRFPNLPAZJIL-UHFFFAOYSA-N

物化性质

• 熔点：
  74-75 °C
• 沸点：
  304.2±52.0 °C(Predicted)
• 密度：
  1.153±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2H-1,2-噁嗪,2-(4-氯苯基)-3,6-二氢-4,5-二甲基- 在 copper(l) chloride 作用下， 以 乙腈 为溶剂， 以72 %的产率得到1-(4-chlorophenyl)-3,4-dimethyl-1H-pyrrole
  参考文献：
  名称：

  使用甲酸作为 CO 替代物在二烯存在下还原硝基芳烃：通过 1,2-恶嗪两步合成 N-芳基吡咯

  摘要：

  使用甲酸作为 CO 替代物，将硝基芳烃脱氧为亚硝基芳烃，该反应由钯/菲咯啉络合物催化。亚硝基芳烃被共轭二烯捕获，得到 3,6-二氢-2H- [ 1,2]-恶嗪。然后使用 CuCl 作为催化剂将后者转化为N-芳基吡咯。该反应可以制备在 2 和 5 位上缺乏任何取代基的吡咯，而使用大多数吡咯合成方法很难生产这种吡咯。

  DOI：

  10.1002/ejoc.202300809
• 作为产物：
  描述：

  对氯苯胺 、 2,3-二甲基-1,3-丁二烯 在 MoO(O₂)(2,6-pyridinedicarboxylato-O,N,O')(HMPA) 双氧水 作用下， 反应 18.0h， 以51%的产率得到2H-1,2-噁嗪,2-(4-氯苯基)-3,6-二氢-4,5-二甲基-
  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

• Synthesis of 3,6-Dihydro-2<i>H</i>-[1, 2]-Oxazines from Nitroarenes and Conjugated Dienes, Catalyzed by Palladium/Phenanthroline Complexes and Employing Phenyl Formate as a CO Surrogate
  作者：Mohamed A. EL-Atawy、Dario Formenti、Francesco Ferretti、Fabio Ragaini

  DOI：10.1002/cctc.201801223

  日期：2018.10.23

  Palladium/phenanthroline catalyzed reduction of nitroarenes by in situ‐generated carbon monoxide, from the decomposition of phenyl formate, affords the corresponding nitrosoarenes. The latter are trapped by conjugated dienes to give the corresponding 3,6‐dihydro‐2H‐[1, 2]‐oxazines (hetero Diels‐Alder adducts). Many functional groups are well tolerated. Yields are higher than those obtainable by any

  钯/菲咯啉通过原位生成的一氧化碳，从甲酸苯基酯的分解中催化还原硝基芳烃，得到相应的亚硝基芳烃。后者被共轭二烯捕获，得到相应的3,6-dihydro-2 H- [1,2]-恶嗪（杂Diels-Alder加合物）。许多功能组的耐受性良好。产率高于通过任何先前报道的方法可获得的产率，包括二烯与纯亚硝基芳烃的直接反应。该反应可在单个标准玻璃压力管中进行，而无需高压釜或高压CO管线。
• Synthesis of Oxazines and <i>N</i>-Arylpyrroles by Reaction of Unfunctionalized Dienes with Nitroarenes and Carbon Monoxide, Catalyzed by Palladium−Phenanthroline Complexes
  作者：Fabio Ragaini、Sergio Cenini、Daniela Brignoli、Michela Gasperini、Emma Gallo

  DOI：10.1021/jo0260589

  日期：2003.1.1

  The reaction between an unfunctionalized conjugated diene and a nitroarene under CO pressure and at 100 degrees C, catalyzed by [Pd(Phen)2][BF4]2 (Phen = 1,10-phenanthroline), affords the corresponding hetero-Diels-Alder adduct (oxazine) in up to 91% yields in one pot. If the reaction mixture is then heated to 200 degrees C, the oxazines are converted into the corresponding N-arylpyrroles in good yields

  [Pd（Phen）2] [BF4] 2（Phen = 1,10-phenothroline）催化，在CO压力和100°C下，未官能化的共轭二烯与硝基芳烃之间的反应，得到相应的杂Diels-Alder一罐中的加合物（恶嗪）收率高达91％。如果然后将反应混合物加热至200℃，则恶嗪以良好的产率转化为相应的N-芳基吡咯。可以使用低至5 bar的压力，0.08％的催化剂足以完成转化。通过使用硝基芳烃或二烯作为限制剂，该反应可以同样地进行，并且对于带有吸电子或温和供电子的取代基的硝基芳烃很好地起作用。硝基芳烃（邻甲基）的中等位阻是可以很好耐受的，但是1,4-二取代-1,3-二烯不是合适的底物。
• 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.
• Use of Formic Acid as a CO Surrogate for the Reduction of Nitroarenes in the Presence of Dienes: A Two‐Step Synthesis of <i>N</i>‐Arylpyrroles via 1,2‐Oxazines
  作者：Manar Ahmed Fouad、Francesco Ferretti、Simone Galiè、Fabio Ragaini

  DOI：10.1002/ejoc.202300809

  日期：2023.10.9

  Formic acid was employed as a CO surrogate to deoxygenate nitroarenes to nitrosoarenes, a reaction catalyzed by a palladium/phenanthroline complex. Nitrosoarenes, trapped by conjugated dienes, afforded 3,6-dihydro-2H-[1,2]-oxazines. The latter were then transformed into N-arylpyrroles employing CuCl as the catalyst. The reaction allows to prepare pyrroles lacking any substituent in the 2 and 5 positions

  使用甲酸作为 CO 替代物，将硝基芳烃脱氧为亚硝基芳烃，该反应由钯/菲咯啉络合物催化。亚硝基芳烃被共轭二烯捕获，得到 3,6-二氢-2H- [ 1,2]-恶嗪。然后使用 CuCl 作为催化剂将后者转化为N-芳基吡咯。该反应可以制备在 2 和 5 位上缺乏任何取代基的吡咯，而使用大多数吡咯合成方法很难生产这种吡咯。