1H-3,4-dihydro-3,3,4,4-tetramethyl-6,7-dicyanobenzopyran-1-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: 1H-3,4-dihydro-3,3,4,4-tetramethyl-6,7-dicyanobenzopyran-1-one
• 英文别名: 3,3,4,4-Tetramethyl-1-oxoisochromene-6,7-dicarbonitrile；3,3,4,4-tetramethyl-1-oxoisochromene-6,7-dicarbonitrile
• 化学式: C₁₅H₁₄N₂O₂
• 分子量: 254.288
• InChiKey: LIGAKIZCEGCLCX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  19
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  73.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2,3-二甲基-2-丁烯 、 1,2,4,5-四氰基苯 在 水 作用下， 以 乙腈 为溶剂， 反应 1.0h， 以4%的产率得到1H-3,4-dihydro-3,3,4,4-tetramethyl-6,7-dicyanobenzopyran-1-one
  参考文献：
  名称：

  2 + 2 + 2 Cycloaddition vs Radical Ion Chemistry in the Photoreactions of 1,2,4,5-Benzenetetracarbonitrile with Alkenes in Acetonitrile

  摘要：

  Irradiation of 1,2,4,5-benzenetetracarbonitrile (TCB) in acetonitrile in the presence of 1-hexene leads to two isomeric tetrahydroisoquinolines through a 2 + 2 + 2 cycloaddition between TCB, the alkene, and MeCN. The process occurs with moderate quantum yield via a strongly polarized exciplex. With di- and polysubstituted alkenes no cycloaddition takes place, the only reaction observed being substitution of a cyano group by an allyl radical. This is a low quantum yield process occurring via deprotonation of the alkene radical cation and TCB*(-)-allyl radical coupling. The selectivity in the attack on the allyl radical depends on steric hindering. Alternatively, the alkene radical cation can be trapped by methanol, yielding a (beta-methoxyethyl)benzenetricarbonitrile. In the presence of water, the corresponding alcohols are not isolated, since they rapidly fragment to yield alkylbenzenetricarbonitriles. The mechanism is discussed on the basis of the competition of chemical reactions and back electron transfer.

  DOI：

  10.1021/ja00101a027

文献信息

• 2 + 2 + 2 Cycloaddition vs Radical Ion Chemistry in the Photoreactions of 1,2,4,5-Benzenetetracarbonitrile with Alkenes in Acetonitrile
  作者：Matteo Vanossi、Mariella Mella、Angelo Albini

  DOI：10.1021/ja00101a027

  日期：1994.11

  Irradiation of 1,2,4,5-benzenetetracarbonitrile (TCB) in acetonitrile in the presence of 1-hexene leads to two isomeric tetrahydroisoquinolines through a 2 + 2 + 2 cycloaddition between TCB, the alkene, and MeCN. The process occurs with moderate quantum yield via a strongly polarized exciplex. With di- and polysubstituted alkenes no cycloaddition takes place, the only reaction observed being substitution of a cyano group by an allyl radical. This is a low quantum yield process occurring via deprotonation of the alkene radical cation and TCB*(-)-allyl radical coupling. The selectivity in the attack on the allyl radical depends on steric hindering. Alternatively, the alkene radical cation can be trapped by methanol, yielding a (beta-methoxyethyl)benzenetricarbonitrile. In the presence of water, the corresponding alcohols are not isolated, since they rapidly fragment to yield alkylbenzenetricarbonitriles. The mechanism is discussed on the basis of the competition of chemical reactions and back electron transfer.