3,6-dicyano-4,5-benzotricyclo<4.2.1.0.^3,8>-4-nonene | 102359-62-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 3,6-dicyano-4,5-benzotricyclo<4.2.1.0.^3,8>-4-nonene
• 英文别名: Tetracyclo[8.2.1.02,7.08,11]trideca-2,4,6-triene-1,8-dicarbonitrile
• CAS: 102359-62-6
• 化学式: C₁₅H₁₂N₂
• 分子量: 220.274
• InChiKey: DVNMHQZKSRGSLU-UHFFFAOYSA-N

物化性质

• 熔点：
  152-153 °C
• 沸点：
  446.0±45.0 °C(Predicted)
• 密度：
  1.29±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  1-(2-丙烯基)-1,2-二氢萘-1,4-二腈 以 乙腈 为溶剂， 生成 3,6-dicyano-4,5-benzotricyclo<4.2.1.0.^3,8>-4-nonene
  参考文献：
  名称：

  用烯丙基三甲基硅烷的单-和dicyanonaphthalenes光诱导电子转移反应：benzotricyclo [4.2.1.0合成3,8 ]通过还原photoallylation和分子内（2壬烯π 2 π）光环

  摘要：

  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。

  DOI：

  10.1016/0040-4020(95)00326-4

文献信息

• Photochemical reactions of 1,4-dicyanonaphthalene with allylic silanes: control of reaction modes by use of solvent and additive effects
  作者：Kazuhiko Mizuno、Toshinori Nishiyama、Kiyotaro Terasaka、Masahide Yasuda、Kensuke Shima、Yoshio Otsuji

  DOI：10.1016/s0040-4020(01)81184-4

  日期：——

  Solvent and additive effects on the photoreaction of 1,4-dicyanonaphthalene, (1,4-DCN) with allylic silanes (1a–c) have been investigated. Irradiation of acetonitrile solutions containing 1,4-DCN and 1a–c in the presence of NaOMe selectively afforded the substitution products 1-(2′-alkenyl)-4-cyanonaphthalenes (2a–c) in high yields. The photoreaction of1,4-DCN with 1a–c in the presence of pyrene in

  研究了溶剂和添加剂对1,4-二氰基萘（1,4-DCN）与烯丙基硅烷（1a–c）的光反应的影响。在NaOMe的存在下，辐照含有1,4-DCN和1a-c的乙腈溶液，可以高收率选择性地提供取代产物1-（2'-烯基）-4-氰基萘（2a-c）。在CH 3 CN-MeOH（4：1）中，在of存在下1,4-DCN与1a–c的光反应选择性地提供了加成产物1-（2'-烯基）-1,4-二氰基-1,2 -二氢萘（3a–c，3c'）高产。CH 3中菲存在下1,4-DCN与1a-c的光反应CN-MeOH（4：1）提供三环化合物3,6-dicyano-4,5-苯并三环-[4.2.1.0 3,8 ] -4-壬烯（4a–c，4c'）和5b（4b），这是通过3a–c和2c'的分子内（3π+2π）光环加成反应产生的。讨论了这些光反应的机理。
• Regioselective photoallylations of dicyanopolycyclic aromatic compounds via electron transfer
  作者：Kazuhiko Mizuno、Kiyotaro Terasaka、Munehiro Ikeda、Yoshio Otsuji

  DOI：10.1016/s0040-4039(00)98935-4

  日期：——

  Upon irradiation with allyltrimethylsilane, dicyanopolycyclic aromatic compounds undergo two modes of photoallylations, depending on the compounds and the reaction conditions. Both the photoreactions occur in a highly regioselective manner via electron transfer.

  在用烯丙基三甲基硅烷辐照时，取决于化合物和反应条件，二氰基多环芳族化合物经历两种光烯丙基化方式。两种光反应都通过电子转移以高度区域选择性的方式发生。
• 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.
• NAKANISHI, KAZUHISA;MIZUNO, KAZUHIKO;OTSUJI, YOSHIO, J. CHEM. SOC. CHEM. COMMUN.,(1991) N, C. 90-92
  作者：NAKANISHI, KAZUHISA、MIZUNO, KAZUHIKO、OTSUJI, YOSHIO

  DOI：——

  日期：——
• MIZUNO, KAZUHIKO;TERASAKA, KIYOTARO;IKEDA, MUNEHIRO;OTSUJI, YOSHIO, TETRAHEDRON LETT., 1985, 26, N 47, 5819-5822
  作者：MIZUNO, KAZUHIKO、TERASAKA, KIYOTARO、IKEDA, MUNEHIRO、OTSUJI, YOSHIO

  DOI：——

  日期：——