(1α,4α,4aα,5aα)-4,4a,5,5a-Tetrahydro-1,4,6,6-tetramethyl-1,4-methano-1H-cyclopropapyridazin | 109746-11-4

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: (1α,4α,4aα,5aα)-4,4a,5,5a-Tetrahydro-1,4,6,6-tetramethyl-1,4-methano-1H-cyclopropapyridazin
• 英文别名: (1α,4α,4aα,5aα)-4,4a,5,5a-tetrahydro-1,4,6,6-tetramethyl-1,4-methano-1H-cyclopropa[d]pyridazine；(1α,4α,4aα,5aα)-4,4a,5,5a-Tetrahydro-1,4,6,6-tetramethyl-1,4-methano-1H-cyclopropa[d]pyridazin；(1S,2S,4R,5R)-1,5,8,8-tetramethyl-6,7-diazatricyclo[3.2.1.02,4]oct-6-ene
• CAS: 109746-11-4
• 化学式: C₁₀H₁₆N₂
• 分子量: 164.25
• InChiKey: HGLGAIGSQWTBOG-OXMRFTEPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  24.7
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1α,4α,4aα,5aα)-4,4a,5,5a-Tetrahydro-1,4,6,6-tetramethyl-1,4-methano-1H-cyclopropapyridazin 以 氘代氯仿 为溶剂， 生成 1,5,6,6-tetramethylcyclohexa-1,4-diene
  参考文献：
  名称：

  Influence of Ring Annelation on the Mode Selectivity of the Ionized Diazabicycloheptenes and Corresponding Housanes: An ESR and ENDOR Study

  摘要：

  The tricyclic azoalkanes, (1 alpha ,4 alpha ,4a alpha ,7a alpha)-4,4a,5,6,7,7a-hexahydro-1,4,8,8-tetramethyl-1,4-methano-1H-cyclopenta[d]pyridazine (1c), (1 alpha ,4 alpha ,4a alpha ,6a alpha)-4,4a,5,6,6a-pentahydro-1,4,7,7-tetramethyl-1,4-methano-1H-cyclobuta[d]pyridazine (1d), (1 alpha ,4 alpha ,4a alpha ,6a alpha)-4,4a,6a-trihydro-1,4,7,7-tetramethyl-1,4-methano-1H-cyclobuta[d]pyridazine (1e). and (1 alpha ,4 alpha ,4a alpha ,5a alpha)-4,4a,5,5a-tetrahydro-1,4,6,6-tetramethyl-1,4-methano-1H-cyclopropa[d]pyridazine (1f), as well as the corresponding housanes, the 2,3,3,4-tetramethyl-substituted tricyclo[3.3.0.0(2,4)]octane (2c). tricyclo[3.2.0.0(2,4)]heptane (2d), and tricyclo[ 3.2.0.0(2,4) ]hept-6-ene (2e), were subjected to gamma -irradiation in Freon matrices. The reaction products were identified with the use of ESR and. in part, ENDOR spectroscopy. As expected, the strain on the C-framework increases on going from the cyclopentane-annelated azoalkanes and housanes (1c and 2c) to those annelated by cyclobutane (1d and 2d), by cyclobutene (1e and 2e), and by cyclopropane (1f). Accordingly, the products obtained from Ic and 2c in all three Freons used, CFCl3, CF3CCl3, and CF2ClCFCl2, were the radical cations 3c(.+) and 2c(.+) of 2,3,4,4-tetramethylbicyclo[3.3.0]oct-2-ene and 2,3,3,4-tetramethylbicyclo[3,3,0]octane-2,4-diyl, respectively. In CFCl3, and CF3CCl3, matrices, Id and 2d yielded analogous products, namely the radical cations 3d(.+) and 2d(.+) of 2,3,4,4-tetramethylbicyclo[3.2.0]hept-2-ene and 2,3,3,4-tetramethylbicyclo[3.2.0]heptane-2,4-diyl. The radical cations 3c(.+) and 3d(.+) and 2c(.+) and 2d(.+) correspond to their non-annelated counterparts 3a(.+) and 3b(.+) and 2a(.+) and 2b(.+) generated previously under the same conditions from 2,3-diazabicyclo[2.2.1]hept-2-ene (1a) and bicyclo[2.1.0]pentane (2a), as well as from their 1,4-dimethyl derivatives (lb and 2b). However, in a CF2ClCFCl2 matrix, both ld and 2d gave the radical cation 4d(.+) of 2,3,3,4-tetramethylcyclohepta-1,4-diene. Starting from le and 2e, the radical cations 4e(.+) and 4e ' (.+) of the isomeric 1,2,7,7- and 1,6,7,7-tetramethylcyclohepta-1,3,5-trienes appeared as the corresponding products, while 1f was converted into the radical cation 4f(.+) of 1,5,6,6-tetramethylcyclohexa-1,4-diene which readily lost a proton to yield the corresponding cyclohexadienyl radical 4f(.). Reaction mechanisms leading to the pertinent radical cations are discussed.

  DOI：

  10.1002/1522-2675(20010613)84:6<1470::aid-hlca1470>3.0.co;2-w
• 作为产物：
  描述：

  3,4,4,5-四甲基-4H-吡唑 、 cyclopropene 以 氯仿 为溶剂， 反应 6.0h， 以7%的产率得到(1α,4α,4aα,5aα)-4,4a,5,5a-Tetrahydro-1,4,6,6-tetramethyl-1,4-methano-1H-cyclopropapyridazin
  参考文献：
  名称：

  Beck, Karin; Huenig, Siegfried; Klaerner, Frank-Gerrit, Chemische Berichte, 1987, vol. 120, p. 2041 - 2052

  摘要：

  DOI：

文献信息

• BECK, KARIN;HUNIG, SIEGFRIED;KLARNER, FRANK-GERRIT;KRAFT, PETRA;ARTSCHWAG+, CHEM. BER., 120,(1987) N 12, 2041-2051
  作者：BECK, KARIN、HUNIG, SIEGFRIED、KLARNER, FRANK-GERRIT、KRAFT, PETRA、ARTSCHWAG+

  DOI：——

  日期：——
• Beck, Karin; Huenig, Siegfried; Klaerner, Frank-Gerrit, Chemische Berichte, 1987, vol. 120, p. 2041 - 2052
  作者：Beck, Karin、Huenig, Siegfried、Klaerner, Frank-Gerrit、Kraft, Petra、Artschwager-Perl, Uwe

  DOI：——

  日期：——
• Influence of Ring Annelation on the Mode Selectivity of the Ionized Diazabicycloheptenes and Corresponding Housanes: An ESR and ENDOR Study
  作者：Fabian Gerson、Coşkun Şahin

  DOI：10.1002/1522-2675(20010613)84:6<1470::aid-hlca1470>3.0.co;2-w

  日期：2001.6.13

  The tricyclic azoalkanes, (1 alpha ,4 alpha ,4a alpha ,7a alpha)-4,4a,5,6,7,7a-hexahydro-1,4,8,8-tetramethyl-1,4-methano-1H-cyclopenta[d]pyridazine (1c), (1 alpha ,4 alpha ,4a alpha ,6a alpha)-4,4a,5,6,6a-pentahydro-1,4,7,7-tetramethyl-1,4-methano-1H-cyclobuta[d]pyridazine (1d), (1 alpha ,4 alpha ,4a alpha ,6a alpha)-4,4a,6a-trihydro-1,4,7,7-tetramethyl-1,4-methano-1H-cyclobuta[d]pyridazine (1e). and (1 alpha ,4 alpha ,4a alpha ,5a alpha)-4,4a,5,5a-tetrahydro-1,4,6,6-tetramethyl-1,4-methano-1H-cyclopropa[d]pyridazine (1f), as well as the corresponding housanes, the 2,3,3,4-tetramethyl-substituted tricyclo[3.3.0.0(2,4)]octane (2c). tricyclo[3.2.0.0(2,4)]heptane (2d), and tricyclo[ 3.2.0.0(2,4) ]hept-6-ene (2e), were subjected to gamma -irradiation in Freon matrices. The reaction products were identified with the use of ESR and. in part, ENDOR spectroscopy. As expected, the strain on the C-framework increases on going from the cyclopentane-annelated azoalkanes and housanes (1c and 2c) to those annelated by cyclobutane (1d and 2d), by cyclobutene (1e and 2e), and by cyclopropane (1f). Accordingly, the products obtained from Ic and 2c in all three Freons used, CFCl3, CF3CCl3, and CF2ClCFCl2, were the radical cations 3c(.+) and 2c(.+) of 2,3,4,4-tetramethylbicyclo[3.3.0]oct-2-ene and 2,3,3,4-tetramethylbicyclo[3,3,0]octane-2,4-diyl, respectively. In CFCl3, and CF3CCl3, matrices, Id and 2d yielded analogous products, namely the radical cations 3d(.+) and 2d(.+) of 2,3,4,4-tetramethylbicyclo[3.2.0]hept-2-ene and 2,3,3,4-tetramethylbicyclo[3.2.0]heptane-2,4-diyl. The radical cations 3c(.+) and 3d(.+) and 2c(.+) and 2d(.+) correspond to their non-annelated counterparts 3a(.+) and 3b(.+) and 2a(.+) and 2b(.+) generated previously under the same conditions from 2,3-diazabicyclo[2.2.1]hept-2-ene (1a) and bicyclo[2.1.0]pentane (2a), as well as from their 1,4-dimethyl derivatives (lb and 2b). However, in a CF2ClCFCl2 matrix, both ld and 2d gave the radical cation 4d(.+) of 2,3,3,4-tetramethylcyclohepta-1,4-diene. Starting from le and 2e, the radical cations 4e(.+) and 4e ' (.+) of the isomeric 1,2,7,7- and 1,6,7,7-tetramethylcyclohepta-1,3,5-trienes appeared as the corresponding products, while 1f was converted into the radical cation 4f(.+) of 1,5,6,6-tetramethylcyclohexa-1,4-diene which readily lost a proton to yield the corresponding cyclohexadienyl radical 4f(.). Reaction mechanisms leading to the pertinent radical cations are discussed.