ethyl 2,3,6-triphenyl-2H-1,4-oxazine-5-carboxylate | 1198359-05-5

• 英文名称: ethyl 2,3,6-triphenyl-2H-1,4-oxazine-5-carboxylate
• CAS: 1198359-05-5
• 化学式: C₂₅H₂₁NO₃
• 分子量: 383.447
• InChiKey: XDZUWUYWEYDHAV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  47.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl 2,3,6-triphenyl-2H-1,4-oxazine-5-carboxylate 以 氘代氯仿 为溶剂， 反应 1.5h， 以61%的产率得到
  参考文献：
  名称：

  Rh(II)-carbenoid mediated 2H-azirine ring-expansion as a convenient route to non-fused photo- and thermochromic 2H-1,4-oxazines

  摘要：

  The Rh2(OAc)(4)-catalyzed domino reaction of 2H-azirines with 2-acyl-2-diazoacetates provides a unique synthetic approach to non-fused 2H-1,4-oxazines. The reaction proceeds via sequential formation of a rhodium carbenoid, an azirinium ylide, and a 1-acyl-1-(alkoxycarbonyl)-2-azabuta-1,3-diene to give, after 1,6-pi-electrocyclization, a 2H-1,4-oxazine derivative in good yield. The observed stereoselectivity of 2-azadiene formation is consistent with DFT calculations of the azirinium ylide-2-azadiene isomerization, providing evidence for the ylide mechanism of the reaction. The substitution pattern and configuration of the carbon carbon double bond in 2-azadienes has a dramatic influence on their cyclization to oxazines: the CO2R group on C-4 stabilizes an open-chain form and, as the result of this, a new class of stable 2-azadienes, 1-acyl-2-azadiene-1,4-dicarboxylates, could be isolated. The 1,4-oxazines obtained by this method are the first representatives of monocyclic 2H-1,4-oxazine derivatives, which exhibit photo- and thermochromic activity. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.03.106
• 作为产物：
  描述：

  C₂₅H₂₁NO₃ 以 氘代苯 为溶剂， 生成 ethyl 2,3,6-triphenyl-2H-1,4-oxazine-5-carboxylate
  参考文献：
  名称：

  Rh(II)-carbenoid mediated 2H-azirine ring-expansion as a convenient route to non-fused photo- and thermochromic 2H-1,4-oxazines

  摘要：

  The Rh2(OAc)(4)-catalyzed domino reaction of 2H-azirines with 2-acyl-2-diazoacetates provides a unique synthetic approach to non-fused 2H-1,4-oxazines. The reaction proceeds via sequential formation of a rhodium carbenoid, an azirinium ylide, and a 1-acyl-1-(alkoxycarbonyl)-2-azabuta-1,3-diene to give, after 1,6-pi-electrocyclization, a 2H-1,4-oxazine derivative in good yield. The observed stereoselectivity of 2-azadiene formation is consistent with DFT calculations of the azirinium ylide-2-azadiene isomerization, providing evidence for the ylide mechanism of the reaction. The substitution pattern and configuration of the carbon carbon double bond in 2-azadienes has a dramatic influence on their cyclization to oxazines: the CO2R group on C-4 stabilizes an open-chain form and, as the result of this, a new class of stable 2-azadienes, 1-acyl-2-azadiene-1,4-dicarboxylates, could be isolated. The 1,4-oxazines obtained by this method are the first representatives of monocyclic 2H-1,4-oxazine derivatives, which exhibit photo- and thermochromic activity. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2013.03.106

文献信息

• Rh(II)-Catalysed reactions of 2H-azirines with ethyl 2-acyl-2-diazoacetates. Synthesis of novel photochromic oxazines
  作者：Vsevolod A. Khlebnikov、Mikhail S. Novikov、Alexander F. Khlebnikov、Nikolai V. Rostovskii

  DOI：10.1016/j.tetlet.2009.09.033

  日期：2009.11

  Photochromic non-fused 2H-1,4-oxazines are synthesised by a Rh-2(OAc)(4)-catalysed reaction of 2H-azirines with ethyl 2-acyl-2-diazoacetates. The reaction proceeds via the formation of an azirinium ylide which undergoes ring-opening to a 2-azadiene followed by 1,6-electrocyclisation (C) 2009 Elsevier Ltd All lights reserved