(Z)-2-(6-chloro-4H-benzo[1,4]oxazin-3-ylidene)-N,N-diethylacetamide

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并恶嗪类
• 英文名称: (Z)-2-(6-chloro-4H-benzo[1,4]oxazin-3-ylidene)-N,N-diethylacetamide
• 英文别名: (2Z)-2-(6-chloro-4H-1,4-benzoxazin-3-ylidene)-N,N-diethylacetamide
• 化学式: C₁₄H₁₇ClN₂O₂
• 分子量: 280.754
• InChiKey: KIZLFCMQNUYUDO-FLIBITNWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  41.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  4-氯-2-硝基苯酚 在 air 、 三氯化铁 、 铁粉 、 potassium carbonate 、 溶剂黄146 、 potassium iodide 、 palladium(II) iodide 作用下， 以 乙醇 、 N,N-二甲基乙酰胺 、 丙酮 、 甲苯 为溶剂， 100.0 ℃ 、2.03 MPa 条件下， 反应 29.0h， 生成 (Z)-2-(6-chloro-4H-benzo[1,4]oxazin-3-ylidene)-N,N-diethylacetamide
  参考文献：
  名称：

  A New Synthesis of 2,3-Dihydrobenzo[1,4]dioxine and 3,4-Dihydro-2H-benzo[1,4]oxazine Derivatives by Tandem Palladium-Catalyzed Oxidative Aminocarbonylation−Cyclization of 2-Prop-2-ynyloxyphenols and 2-Prop-2-ynyloxyanilines

  摘要：

  2-[(Dialkylcarbamoyl)methylene]-2,3-dihydrobenzo[1,4]dioxine and 3-[(dialkylcarbamoyl)methylene]-3,4-dihydro-2H-benzo[1,4]oxazine derivatives (3 and 5, respectively) were synthesized for the first time starting from readily available 2-prop-2-ynyloxyphenols 1 and 2-prop-2-ynyloxyanilines 4, respectively, through tandem oxidative aminocarbonylation of the triple bond-intramolecular conjugate addition. Reactions were carried out in the presence of catalytic amounts of PdI2 in conjunction with an excess of KI in N,N-dimethylacetamide (DMA) as the solvent at 80-100 degrees C and under 20 atm (at 25 degrees C) of a 4:1 mixture of CO-air. The reaction showed a significant degree of stereoselectivity, the Z isomers being formed preferentially or exclusively. The configuration around the double bond of the major stereoisomers was unequivocally established by X-ray diffraction analysis.

  DOI：

  10.1021/jo061229l

文献信息

• A New Synthesis of 2,3-Dihydrobenzo[1,4]dioxine and 3,4-Dihydro-2<i>H</i>-benzo[1,4]oxazine Derivatives by Tandem Palladium-Catalyzed Oxidative Aminocarbonylation−Cyclization of 2-Prop-2-ynyloxyphenols and 2-Prop-2-ynyloxyanilines
  作者：Bartolo Gabriele、Giuseppe Salerno、Lucia Veltri、Raffaella Mancuso、Zhiyu Li、Alessandra Crispini、Anna Bellusci

  DOI：10.1021/jo061229l

  日期：2006.9.1

  2-[(Dialkylcarbamoyl)methylene]-2,3-dihydrobenzo[1,4]dioxine and 3-[(dialkylcarbamoyl)methylene]-3,4-dihydro-2H-benzo[1,4]oxazine derivatives (3 and 5, respectively) were synthesized for the first time starting from readily available 2-prop-2-ynyloxyphenols 1 and 2-prop-2-ynyloxyanilines 4, respectively, through tandem oxidative aminocarbonylation of the triple bond-intramolecular conjugate addition. Reactions were carried out in the presence of catalytic amounts of PdI2 in conjunction with an excess of KI in N,N-dimethylacetamide (DMA) as the solvent at 80-100 degrees C and under 20 atm (at 25 degrees C) of a 4:1 mixture of CO-air. The reaction showed a significant degree of stereoselectivity, the Z isomers being formed preferentially or exclusively. The configuration around the double bond of the major stereoisomers was unequivocally established by X-ray diffraction analysis.