2-(Z)-triisopropylsilylmethylidene-4-phenyl-6-trifluoromethyl-2H-1,4-benzoxazin-3(4H)-one

• 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: 2-(Z)-triisopropylsilylmethylidene-4-phenyl-6-trifluoromethyl-2H-1,4-benzoxazin-3(4H)-one
• 英文别名: (2Z)-4-phenyl-6-(trifluoromethyl)-2-[tri(propan-2-yl)silylmethylidene]-1,4-benzoxazin-3-one
• 化学式: C₂₅H₃₀F₃NO₂Si
• 分子量: 461.599
• InChiKey: OBVXIMXNSFLELD-HAHDFKILSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.86
• 重原子数：
  32
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  4-trifluoromethylphenyl triisopropylsilylethynyl ether 、 异氰酸苯酯 在 zinc diacetate 、 palladium diacetate 、 三环己基膦 作用下， 以 甲苯 为溶剂， 反应 6.0h， 以58%的产率得到2-(Z)-triisopropylsilylmethylidene-4-phenyl-6-trifluoromethyl-2H-1,4-benzoxazin-3(4H)-one
  参考文献：
  名称：

  Palladium-catalyzed Cycloaddition of Aryl Silylethynyl Ethers with Isocyanates viao-C–H Cleavage

  摘要：

  钯催化的炔基芳醚与异氰酸酯的环加成反应通过邻位C–H活化进行，生成2-甲基亚烯-2H-1,4-苯并噁嗪-3(4H)-酮衍生物。氘标记实验表明，邻位氢选择性断裂并迁移到产物中的2-甲基亚烯部分。多种底物被应用于该转化，生成不同取代的环加成产物。1,4-双(炔氧基)苯可用于合成多缩合环，生成苯并[1,2-b:4,5-b′]双[1,4]噁嗪-3,8-二酮衍生物。

  DOI：

  10.1246/cl.140452

文献信息

• Palladium-catalyzed Cycloaddition of Aryl Silylethynyl Ethers with Isocyanates via<i>o</i>-C–H Cleavage
  作者：Yasunori Minami、Mayuko Kanda、Tamejiro Hiyama

  DOI：10.1246/cl.140452

  日期：2014.9.5

  Palladium-catalyzed cycloaddition of alkynyl aryl ethers with isocyanates proceeds through o-C–H activation to afford 2-methylidene-2H-1,4-benzoxazin-3(4H)-one derivatives. Deuterium-labeling experiment shows that o-hydrogen is cleaved selectively and migrated to 2-methylidene moiety in the product. Various substrates are applied to this transformation to afford various substituted cycloadducts. 1,4-Bis(alkynoxy)benzenes can be used for the synthesis of multicondensed cycles to afford benzo[1,2-b:4,5-b′]bis[1,4]oxazine-3,8-dione derivatives.

  钯催化的炔基芳醚与异氰酸酯的环加成反应通过邻位C–H活化进行，生成2-甲基亚烯-2H-1,4-苯并噁嗪-3(4H)-酮衍生物。氘标记实验表明，邻位氢选择性断裂并迁移到产物中的2-甲基亚烯部分。多种底物被应用于该转化，生成不同取代的环加成产物。1,4-双(炔氧基)苯可用于合成多缩合环，生成苯并[1,2-b:4,5-b′]双[1,4]噁嗪-3,8-二酮衍生物。
• Palladium-catalyzed annulation of alkynyl aryl ethers with isocyanates through o-C–H cleavage. Synthesis of solid-state emissive 2-methylidene-2H-1,4-benzoxazin-3(4H)-ones
  作者：Yasunori Minami、Mayuko Kanda、Megumi Sakai、Tamejiro Hiyama

  DOI：10.1016/j.tet.2015.02.062

  日期：2015.7

  The title transformation can be achieved by the o-C-H cleavage of allcynyl aryl ethers, which is easily derived from phenols, followed by the insertion/annulation with isocyanates in the presence of a palladium catalyst. Various alkynyl aryl ethers and arylisocyanates are applied to this transformation to give the corresponding cyclic products. Mechanistic study indicates that the C-H cleavage is effected reversibly by the concerted metalation-deprotonation pathway. The products exhibit solid-state luminescence upon irradiation of UV light. Fluorescent maxima and quantum yields can be controlled by the substituents at appropriate sites in the products. (C) 2015 Elsevier Ltd. All rights reserved.