2-cyanobenzotricyclo<3.3.0.0^2.8>octa-3,6-diene | 135074-84-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 四氢化萘
• 英文名称: 2-cyanobenzotricyclo<3.3.0.0^2.8>octa-3,6-diene
• 英文别名: Tetracyclo[6.4.0.02,4.03,7]dodeca-1(12),5,8,10-tetraene-2-carbonitrile
• CAS: 135074-84-9
• 化学式: C₁₃H₉N
• 分子量: 179.221
• InChiKey: PGDKSHLERHQMBP-UHFFFAOYSA-N

物化性质

• 沸点：
  322.0±41.0 °C(Predicted)
• 密度：
  1.30±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  23.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2-cyanobenzotricyclo<3.3.0.0^2.8>octa-3,6-diene 在 potassium diazodicarboxylate 、 溶剂黄146 作用下， 以 1,4-二氧六环 为溶剂， 反应 2.5h， 以76%的产率得到2-cyanobenzotricyclo<3.3.0.0^2.8>oct-3-ene
  参考文献：
  名称：

  Photochemistry of 4-cyano-2,3-benzobicyclo[4.2.0]octa-2,4,7-triene

  摘要：

  4-Cyano-2,3-benzobicyclo[4.2.0]octa-2,4,7-triene (11) was found to be thermally and photochemically reactive. Heating solutions of 11 at 150-degrees-C for 2 h gave 5-cyanobenzocyclooctatetraene (10) quantitatively. The direct irradiation of triene 11 gave 2-cyanobenzosemibullvalene (i.e., SB 12, 63%, PHI = 0.067), COT 10 (28%, PHI = 0.031), and 1-cyanonaphthalene (ca. 0.5%, PHI = 0.0005). Upon sensitization with p-(dimethylamino)benzophenone, 11 gave 12 (30%, PHI = 0.028), COT 10 (9%, PHI = 0.0093), and 1-cyanonaphthalene (2%, PHI = 0.0018). Studies with deuterium-labeled triene (11a) revealed that the semibullavene produced from direct irradiation possessed a different label distribution to that obtained from sensitized irradiation, and hence state-dependent pathways operate in the SB formation. The mechanism proposed for the SB formation from S1 of 11 involves a 1,2-shift with cleavage of the cyclobutene C1-C6 bond of the triene, while SB formation from T1 results from a Zimmerman di-pi-methane rearrangement.

  DOI：

  10.1021/jo00017a007
• 作为产物：
  描述：

  4-cyano-2,3-benzobicyclo<4.2.0>octa-2,4,7-triene 以 环己烷 为溶剂， 反应 2.0h， 以28%的产率得到5-cyanobenzocyclooctatetraene
  参考文献：
  名称：

  Photochemistry of 4-cyano-2,3-benzobicyclo[4.2.0]octa-2,4,7-triene

  摘要：

  4-Cyano-2,3-benzobicyclo[4.2.0]octa-2,4,7-triene (11) was found to be thermally and photochemically reactive. Heating solutions of 11 at 150-degrees-C for 2 h gave 5-cyanobenzocyclooctatetraene (10) quantitatively. The direct irradiation of triene 11 gave 2-cyanobenzosemibullvalene (i.e., SB 12, 63%, PHI = 0.067), COT 10 (28%, PHI = 0.031), and 1-cyanonaphthalene (ca. 0.5%, PHI = 0.0005). Upon sensitization with p-(dimethylamino)benzophenone, 11 gave 12 (30%, PHI = 0.028), COT 10 (9%, PHI = 0.0093), and 1-cyanonaphthalene (2%, PHI = 0.0018). Studies with deuterium-labeled triene (11a) revealed that the semibullavene produced from direct irradiation possessed a different label distribution to that obtained from sensitized irradiation, and hence state-dependent pathways operate in the SB formation. The mechanism proposed for the SB formation from S1 of 11 involves a 1,2-shift with cleavage of the cyclobutene C1-C6 bond of the triene, while SB formation from T1 results from a Zimmerman di-pi-methane rearrangement.

  DOI：

  10.1021/jo00017a007