6-vinylspiro<2.4>hept-4-ene | 133673-56-0

• 分子结构分类: 有机化合物 - 碳氢化合物 - 多环烃
• 英文名称: 6-vinylspiro<2.4>hept-4-ene
• 英文别名: 5-ethenylspiro[2.4]hept-6-ene
• CAS: 133673-56-0
• 化学式: C₉H₁₂
• 分子量: 120.194
• InChiKey: CAFHCNLJAOMSCR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.53
• 重原子数：
  9.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  spiro(cyclopropane-1,3'-tricyclo<3,2,0,0^2,7>heptane) 以 正戊烷 为溶剂， 反应 1.5h， 以12%的产率得到Spirohept-5-ene-2,1'-cyclopropane>
  参考文献：
  名称：

  The 185-nm photolysis and pyrolysis of the spirocyclopropane-substituted azoalkanes of 2,3-diazatricyclo[4.3.0.04,9]non-2-ene and their denitrogenated hydrocarbon products, the tricyclo[3.2.0.02,7]heptanes

  摘要：

  The 185-nm photolysis and pyrolysis of the spirocyclopropane derivatives of the azoalkanes 2,3-diazatricyclo[4.3.0.0(4,9)]non-2-ene (1a), 4',5'-diazaspiro(cyclopropane-1,8'-tricyclo[4.3.0.0(3,7)]non-4'-ene) (1b), and 4'5'-diazadispiro(cyclopropane-1,2'-tricyclo[4.3.0.0(3,7)]non-4'-ene-8',1"-cyclopropane) (1c) and their denitrogenated hydrocarbon derivatives tricyclo[3.2.0.0(2,7)]heptane (2a), spiro(cyclopropane-1,3'-tricyclo[3.2.0.0(2,7)]heptane) (2b), and dispiro(cyclopropane-1,3'-tricyclo[3.2.0.0(2,7)]heptane-6'1"-cyclopropane) (2c) were investigated. It was shown that the 185-nm photochemical behavior of these substrates does not depend on the degree of spirocyclopropane substitution. As common products in the 185-nm photolysis of the azoalkanes 1a-c were obtained the tricycloalkanes 2a-c (major products), the norbornenes 3a-c, the vinylcyclopentenes 5a-c (minor products), and the exo-methylenecyclohexenes 6a-c (traces). In the case of the parent azoalkane 1a additionally bicyclo[3.2.0]hept-2-ene (4) and bicyclo[4.1.0]hept-2-ene (7a) were detected. The major products in the photolysis of the tricycloheptanes 2a-c were the vinylcyclopentenes 5a-c, but also the norbornenes 3a-c and the methylenecyclohexenes 6a-c were formed in considerable amounts. Although the norbornenes 3a-c and the bicyclo[3.2.0]heptene 4a are logical Wagner-Meerwein rearrangement products, attempts to trap the suspected radical-cationic and zwitterionic intermediates with CF3CH2OH failed. Efforts to generate the authentic radical-cationic species by means of photosensitized electron transfer (PET) by using sensitizers such as cyanoarenes, quinones, and pyrylium salts were unproductive. Vibrationally excited bicyclo[2.2.1]hepta-2,7-diyls, generated by the pyrolyses of 2a-c, are not precursors to the norbornenes 3a-c because, instead of such rearrangement products, cyclobutane cleavage of the bicyclo[2.1.0]pentane moiety takes place to afford the isomeric vinylcyclopentenes 5'a-c. Carbene intermediates, produced either from the 1,3-diyl-type species through fragmentation or from the photodenitrogenation of diazoalkanes, which are generated by retro-cleavage of n,pi* excited azoalkanes 1a-c, in turn obtained through internal conversion of higher excited states such as 1-pi,pi*, 1n,sigma*, and R(y), are proposed as the most likely precursors to either the vinylcyclopentenes 5a-c or methylenecyclohexenes 6a-c, respectively. In violation of Kasha's rule, photochemistry directly from the higher excited states of the azoalkanes 1a-c competes with internal conversion to the lowest excited state, namely the n,pi* state, as it was shown by the formation of norbornenes 3a-c.

  DOI：

  10.1021/jo00010a026

文献信息

• Adam, Waldemar; Oppenlaender, Thomas, Angewandte Chemie, 1986, vol. 98, # 8, p. 659 - 670
  作者：Adam, Waldemar、Oppenlaender, Thomas

  DOI：——

  日期：——
• The 185-nm photolysis and pyrolysis of the spirocyclopropane-substituted azoalkanes of 2,3-diazatricyclo[4.3.0.04,9]non-2-ene and their denitrogenated hydrocarbon products, the tricyclo[3.2.0.02,7]heptanes
  作者：Waldemar Adam、Gerald Zang

  DOI：10.1021/jo00010a026

  日期：1991.5

  The 185-nm photolysis and pyrolysis of the spirocyclopropane derivatives of the azoalkanes 2,3-diazatricyclo[4.3.0.0(4,9)]non-2-ene (1a), 4',5'-diazaspiro(cyclopropane-1,8'-tricyclo[4.3.0.0(3,7)]non-4'-ene) (1b), and 4'5'-diazadispiro(cyclopropane-1,2'-tricyclo[4.3.0.0(3,7)]non-4'-ene-8',1"-cyclopropane) (1c) and their denitrogenated hydrocarbon derivatives tricyclo[3.2.0.0(2,7)]heptane (2a), spiro(cyclopropane-1,3'-tricyclo[3.2.0.0(2,7)]heptane) (2b), and dispiro(cyclopropane-1,3'-tricyclo[3.2.0.0(2,7)]heptane-6'1"-cyclopropane) (2c) were investigated. It was shown that the 185-nm photochemical behavior of these substrates does not depend on the degree of spirocyclopropane substitution. As common products in the 185-nm photolysis of the azoalkanes 1a-c were obtained the tricycloalkanes 2a-c (major products), the norbornenes 3a-c, the vinylcyclopentenes 5a-c (minor products), and the exo-methylenecyclohexenes 6a-c (traces). In the case of the parent azoalkane 1a additionally bicyclo[3.2.0]hept-2-ene (4) and bicyclo[4.1.0]hept-2-ene (7a) were detected. The major products in the photolysis of the tricycloheptanes 2a-c were the vinylcyclopentenes 5a-c, but also the norbornenes 3a-c and the methylenecyclohexenes 6a-c were formed in considerable amounts. Although the norbornenes 3a-c and the bicyclo[3.2.0]heptene 4a are logical Wagner-Meerwein rearrangement products, attempts to trap the suspected radical-cationic and zwitterionic intermediates with CF3CH2OH failed. Efforts to generate the authentic radical-cationic species by means of photosensitized electron transfer (PET) by using sensitizers such as cyanoarenes, quinones, and pyrylium salts were unproductive. Vibrationally excited bicyclo[2.2.1]hepta-2,7-diyls, generated by the pyrolyses of 2a-c, are not precursors to the norbornenes 3a-c because, instead of such rearrangement products, cyclobutane cleavage of the bicyclo[2.1.0]pentane moiety takes place to afford the isomeric vinylcyclopentenes 5'a-c. Carbene intermediates, produced either from the 1,3-diyl-type species through fragmentation or from the photodenitrogenation of diazoalkanes, which are generated by retro-cleavage of n,pi* excited azoalkanes 1a-c, in turn obtained through internal conversion of higher excited states such as 1-pi,pi*, 1n,sigma*, and R(y), are proposed as the most likely precursors to either the vinylcyclopentenes 5a-c or methylenecyclohexenes 6a-c, respectively. In violation of Kasha's rule, photochemistry directly from the higher excited states of the azoalkanes 1a-c competes with internal conversion to the lowest excited state, namely the n,pi* state, as it was shown by the formation of norbornenes 3a-c.