tetracyclo<6.3.2.0^2,7.0^10,13>trideca-2,4,6-triene-8-carbonitrile | 144001-72-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: tetracyclo<6.3.2.0^2,7.0^10,13>trideca-2,4,6-triene-8-carbonitrile
• 英文别名: 3-cyano-4,5-benzotricyclo<4.2.1.0.^3,8>-4-nonene；Tetracyclo[8.2.1.02,7.08,11]trideca-2,4,6-triene-8-carbonitrile
• CAS: 144001-72-9
• 化学式: C₁₄H₁₃N
• 分子量: 195.264
• InChiKey: UCQRGMSJQRBHJW-UHFFFAOYSA-N

物化性质

• 沸点：
  360.4±21.0 °C(Predicted)
• 密度：
  1.21±0.1 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：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  3,4-dihydro-4-(2-propenyl)naphthalene-1-carbonitrile 以 乙腈 为溶剂， 反应 1.5h， 生成 tetracyclo<6.3.2.0^2,7.0^10,13>trideca-2,4,6-triene-8-carbonitrile
  参考文献：
  名称：

  The photochemical reaction between aromatic nitriles and allylsilane

  摘要：

  The results obtained from the irradiation of aromatic nitriles and allyltrimethylsilane (ATMS) depend on the redox parameters of these molecules and their singlet energies. The reaction between 1-naphthalenecarbonitrile (NN) and ATMS in apolar solvents leads to [2 + 2] cycloaddition at positions 1 and 2 (via the exciplex); in polar solvents, electron transfer becomes a possibility, and loss of the trimethylsilyl cation followed by allylation of NN at positions 2 and 4 is also observed. When naphthalene-1,4-dicarbonitrile (NDN) is used, electron-transfer-initiated allylation (both addition and cyano group substitution) is the main pathway, but in apolar solvents cycloaddition at positions 4a and 5 occurs as a minor pathway. The reaction with benzene-1,2,4,5-tetracarbonitrile (BTN) gives substitution of an allyl for a cyano group as the only process. Finally, with both NDN and BTN and a high ATMS concentration in apolar solvents, the reaction pathway changes to photosensitized [2 + 2] dimerization of ATMS, proposed to occur via a terplex. Rationalizations for the observed reactions (including regiochemistry of addition and cycloaddition and nature of the intermediates) are offered.

  DOI：

  10.1021/jo00049a031

文献信息

• Photoinduced electron transfer reaction of mono- and dicyanonaphthalenes with allyltrimethylsilane: Synthesis of benzotricyclo[4.2.1.03,8]nonenes by reductive photoallylation and intramolecular (2π+2π) photocycloaddition
  作者：Toshinori Nishiyama、Kazuhiko Mizuno、Yoshio Otsuji、Hiroo Inoue

  DOI：10.1016/0040-4020(95)00326-4

  日期：1995.6

  photoinduced electron transfer from 1 to the excited singlet states of mono- and dicyanonaphthalenes. The reductive allylation products from the former cyanonaphthalenes afforded the benzotricyclic compounds by an intramolecular (2π+2π) photocycloaddition in good yields. The regioselectivity in the allylation reaction is discussed on the basis of the results of MO calculations of the radical anions of mono-

  通过派热克斯滤光片（> 280 nm）辐照含有1-氰基萘和烯丙基三甲基硅烷（1）的乙腈-甲醇（4：1）溶液，区域选择性地产生3-氰基-4,5-苯并三环[4.2.1.0 3,8] -4-壬烯。2-氰基萘，1-氰基-2-甲基萘，1-氰基-4-甲基萘，1，5-和2，3-二氰基萘与1的光反应也以区域选择性的方式得到了相应的苯并三环化合物。然而，2，3-二取代的1，4-二氰基萘与1的光反应没有得到苯并三环化合物，而只得到了烯丙基取代和还原性烯丙基化产物。这些光反应是通过从1到单氰基和双氰基萘的激发单重态的光诱导电子转移引发的。从得到benzotricyclic化合物前者cyanonaphthalenes还原烯丙基化产物通过分子内（2 π 2 π）进行光环加成，收率良好。基于对单氰基和双氰基萘的自由基阴离子的MO计算结果，讨论了烯丙基化反应中的区域选择性。
• The photochemical reaction between aromatic nitriles and allylsilane
  作者：M. Mella、E. Fasani、A. Albini

  DOI：10.1021/jo00049a031

  日期：1992.11

  The results obtained from the irradiation of aromatic nitriles and allyltrimethylsilane (ATMS) depend on the redox parameters of these molecules and their singlet energies. The reaction between 1-naphthalenecarbonitrile (NN) and ATMS in apolar solvents leads to [2 + 2] cycloaddition at positions 1 and 2 (via the exciplex); in polar solvents, electron transfer becomes a possibility, and loss of the trimethylsilyl cation followed by allylation of NN at positions 2 and 4 is also observed. When naphthalene-1,4-dicarbonitrile (NDN) is used, electron-transfer-initiated allylation (both addition and cyano group substitution) is the main pathway, but in apolar solvents cycloaddition at positions 4a and 5 occurs as a minor pathway. The reaction with benzene-1,2,4,5-tetracarbonitrile (BTN) gives substitution of an allyl for a cyano group as the only process. Finally, with both NDN and BTN and a high ATMS concentration in apolar solvents, the reaction pathway changes to photosensitized [2 + 2] dimerization of ATMS, proposed to occur via a terplex. Rationalizations for the observed reactions (including regiochemistry of addition and cycloaddition and nature of the intermediates) are offered.