(1R,2R,4S,5S)-2,3,3,4-Tetramethyl-tricyclo[3.2.0.0^2,4]hept-6-ene | 34801-23-5

• 分子结构分类: 有机化合物 - 碳氢化合物 - 多环烃
• 英文名称: (1R,2R,4S,5S)-2,3,3,4-Tetramethyl-tricyclo[3.2.0.0^2,4]hept-6-ene
• 英文别名: (1S,2S,4R,5R)-2,3,3,4-tetramethyltricyclo[3.2.0.02,4]hept-6-ene
• CAS: 34801-23-5
• 化学式: C₁₁H₁₆
• 分子量: 148.248
• InChiKey: DUFUNGUWSIDZTF-CBZSFBHOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (1R,2R,4S,5S)-2,3,3,4-Tetramethyl-tricyclo[3.2.0.0^2,4]hept-6-ene 以 various solvent(s) 为溶剂， 生成 1,6,7,7-tetramethylcyclohepta-1,3,5-triene radical cation
  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：

  (1α,4α,4aα,6aα)-4,4a,6a-trihydro-1,4,7,7-tetramethyl-1,4-methano-1H-cyclobuta[d]pyridazine 以 various solvent(s) 为溶剂， 生成 (1R,2R,4S,5S)-2,3,3,4-Tetramethyl-tricyclo[3.2.0.0^2,4]hept-6-ene
  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

文献信息

• Synthesis and thermal rearrangement of tricyclo[3.2.02,4]hept-6-enes. Analysis of structural requirements for effective intramolecular trapping of a 1,3-diradical by a remote cyclobutene ring
  作者：Leo A. Paquette、Louis M. Leichter

  DOI：10.1021/ja00749a029

  日期：1971.10
• Generation of Bicyclo[3.2.0]hept-6-ene-2,4-diyl Radical Cations by Chemical Electron Transfer (CET) with Trisarylaminium Salts and Intramolecular Cyclobutene Trapping as an Alternative Entry to the Quadricyclane-Norbornadiene Valence Isomers
  作者：Waldemar Adam、Thomas Heidenfelder、Coskun Sahin

  DOI：10.1021/ja00143a012

  日期：1995.9

  For the first time, chemical electron transfer (CET) studies have been conducted for the tricyclo[3.2.0.0(2,4)]-hept-6-enes 2 and the quadricyclanes 3 in solution. The 2,4-dimethyl-sustituted bicyclo[3.2.0]hept-6-ene-2,4-diyl radical cation 2a(.+), generated by trisarylaminium salt oxidation of 2a, is intramolecularly trapped by the juxtaposed cyclobutenyl double bond to afford the quadricyclane radical cation 3a(.+) in addition to the expected 1,2-methyl migration to the bicyclo[3.2.0]hepta-2,6-diene radical cation 6a(.+). Radical cation 3a(.+) leads to the norbornadiene 4a by valence isomerization and the bicyclo[3.2.0]hepta-2,6-diene 5a by skeletal rearrangement. For comparison, oxidation of quadricyclane 3a yields exclusively norbornadiene 4a. Whereas the 2,4-diphenyl-substituted bicycle[3.2.0]hept-6-ene-2,4-diyl radical cation 2b(.+) derived from 2b is intramolecularly trapped by the juxtaposed cyclobutenyl double bond to afford norbornadiene 4b and bicyclo[3.2.0]hepta-2,6-diene 5b through the quadricyclane radical cation 3b(.+), the quadricyclane 3b yields on oxidation also 5b besides 4b. These experimental facts are rationalized in terms of distinct radical cation structures, namely the pi complex (oxidation of the lateral cyclopropane bond) and trimethylene (oxidation of the internal cyclopropane bond). Their preferences are dictated by the substrate structure, i.e., tricycloheptene 2 versus quadricyclane 3 as well as by the substitution type (phenyl versus methyl) and is corroborated by AM1 calculations.