4,4-Dimethyl-3,5-diphenyl-endo-tetracyclo[5.2.1.0^2,6.0^3,5]dec-8-en | 105817-85-4

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 环丁烷木脂素
• 英文名称: 4,4-Dimethyl-3,5-diphenyl-endo-tetracyclo[5.2.1.0^2,6.0^3,5]dec-8-en
• 英文别名: (1R,2R,3S,5R,6S,7S)-4,4-dimethyl-3,5-diphenyltetracyclo[5.2.1.02,6.03,5]dec-8-ene
• CAS: 105817-85-4
• 化学式: C₂₄H₂₄
• 分子量: 312.455
• InChiKey: RXNPJOYFXOAOFK-DBRTVHEWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.42
• 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：

  4,4-Dimethyl-3,5-diphenyl-endo-tetracyclo[5.2.1.0^2,6.0^3,5]dec-8-en 在 联苯 、 9,10-二氰基蒽 作用下， 以 乙腈 为溶剂， 反应 0.05h， 生成 5,5-Dimethyl-1,4-diphenylcyclopenta-1,3-diene 、 (3aα,3α,4β,7β,7aα)-1,3-Diphenyl-2,3-dimethyl-3a,4,7,7a-tetrhydro-4,7-methanoindene
  参考文献：
  名称：

  Photosensitized electron transfer from azoalkanes: generation, fragmentation, and rearrangement of radical cations structurally related to dicyclopentadiene

  摘要：

  The azoalkanes 1a-c extrude nitrogen upon photosensitized electron transfer (PET) to yield 1,3-radical cation intermediates 2.+, which undergo interesting transformations. Electron back transfer (BET) affords the unrearranged housanes 2, but significant rearrangement to dicyclopentadiene derivatives 3 occurs prior to BET. In some cases, fragmentation to cyclopentadienes 4 is observed, a cycloreversion that occurs at the 1,3-radial cation stage rather than through the corresponding 1,3-biradical intermediates. The diphenyl-substituted azoalkane la affords high yields of the symmetric cyclopentadiene 4a, while the alkyl-substituted lb produces only small amounts of a rearranged cyclopentadiene 4'b. The housanes 2a,b are also oxidized by PET, but are more reluctant to rearrange. Strong electron acceptors such as triphenylpyrylium tetrafluoroborate (TPT) or cosensitization with biphenyl (Ph2) must be utilized to induce rearrangement to 3a,b and fragmentation to 4 and 4'.

  DOI：

  10.1021/jo00072a008
• 作为产物：
  描述：

  (1α,4α,4aα,5β,8β,8aα)-1,4,4a,5,8,8a-Hexahydro-9,9-dimethyl-1,4-diphenyl-1,4;5,8-dimethanophthalazin 以 氘代氯仿 为溶剂， 反应 0.5h， 以98%的产率得到4,4-Dimethyl-3,5-diphenyl-endo-tetracyclo[5.2.1.0^2,6.0^3,5]dec-8-en
  参考文献：
  名称：

  Beck, Karin; Huenig, Siegfried, Chemische Berichte, 1987, vol. 120, p. 477 - 484

  摘要：

  DOI：

文献信息

• Charge-Transfer-Induced Photoreduction of Azoalkanes by Amines
  作者：Waldemar Adam、Jarugu N. Moorthy、Werner M. Nau、J. C. Scaiano

  DOI：10.1021/ja9706460

  日期：1997.7.1

  aziranes 3. In contrast, the azoalkane 1c undergoes appreciable photoreduction only in neat amines, while the azoalkane 1d (φISC ca. 0.10) is not reduced even under such conditions. Except for N,N-dimethylbenzylamine, the amine oxidation products of the azoalkane photoreduction are analogous to those obtained from the reactions of amines with triplet benzophenone. In marked contrast, the absolute quan

  独特的 DBH 型偶氮烷 1 表现出高系统间交叉量子产率，使探索 n,π* 三线态激发的偶氮发色团的双分子光还原成为可能。在激光闪光光解中，发现胺以高速率常数 (kq ca. 108 M-1 s-1) 淬灭三重偶氮烷烃 1a。在脂肪族伯胺、仲胺和叔胺存在下，偶氮烷烃 1a 和 1b（φISC 约 0.5）的稳态光解得到了相应的肼 4a 和 4b 的高化学产率，与单分子产物（即 housanes 2）竞争和氮杂环烷 3。相比之下，偶氮烷 1c 仅在纯胺中发生明显的光还原反应，而偶氮烷 1d（φISC 约 0.10）即使在这种条件下也不会被还原。除 N,N-二甲基苄胺外，偶氮烷光还原的胺氧化产物类似于从胺与三线态二苯甲酮反应获得的那些。与此形成鲜明对比的是，绝对质量...
• Beck, Karin; Huenig, Siegfried, Chemische Berichte, 1987, vol. 120, p. 477 - 484
  作者：Beck, Karin、Huenig, Siegfried

  DOI：——

  日期：——
• Adam, Waldemar; Nau, Werner M.; Sendelbach, Jürgen, Journal of the American Chemical Society, 1994, vol. 116, # 16, p. 7049 - 7054
  作者：Adam, Waldemar、Nau, Werner M.、Sendelbach, Jürgen

  DOI：——

  日期：——
• Solvent Effect on Product Distribution in Photochemical Pathways of α C−N versus β C−C Cleavage of n,π* Triplet-Excited Azoalkanes
  作者：Waldemar Adam、Jarugu N. Moorthy、Werner M. Nau、J. C. Scaiano

  DOI：10.1021/ja963948v

  日期：1997.6.1

  The product distribution in;the photolysis of the triplet-excited azoalkanes 1a,b depends markedly on the type of solvent used; in contrast, the azoalkanes 1c,d, which undergo efficient deazatization from the singlet-excited state, display solvent-independent photobehavior. Thus, the aziranes 3 are produced essentially exclusively in polar protic solvents, while the housanes 2 predominate in nonpolar ones. The excellent correlation (r(2) = 0.963, seven solvents) of the azirane 3b yield with Gutmann's AN solvent parameter reveals that a combination of solvent properties such as the polarity and polarizability of the medium and the hydrogen-bonding ability is decisive for the photoproduct distribution. That the observed solvent dependence derives from bulk medium effects is borne out by the similar product distribution for the hydroxy-substituted derivative 1f to that for the azoalkane 1b in benzene, i.e., the intramolecular hydroxy functionality in the azoalkane If is ineffective in influencing the photochemistry of the triplet azo chromophore. Selective formation of the aziranes 3 from the triplet-excited azoalkanes 1 in the polar protic solvents is rationalized in terms of solvent stabilization of the more polar transition state for beta cleavage (azirane 3) over that for the alpha scission (housane 2). In marked contrast to the appreciable deuterium isotope effect for quenching of the singlet-excited azoalkanes by protic solvents, the lifetimes (laser-flash photolysis) and reactivity (product analysis) of the triplet azoalkanes are not affected by deuterium substitution.
• Photosensitized electron transfer from azoalkanes: generation, fragmentation, and rearrangement of radical cations structurally related to dicyclopentadiene
  作者：Waldemar Adam、Juergen Sendelbach

  DOI：10.1021/jo00072a008

  日期：1993.9

  The azoalkanes 1a-c extrude nitrogen upon photosensitized electron transfer (PET) to yield 1,3-radical cation intermediates 2.+, which undergo interesting transformations. Electron back transfer (BET) affords the unrearranged housanes 2, but significant rearrangement to dicyclopentadiene derivatives 3 occurs prior to BET. In some cases, fragmentation to cyclopentadienes 4 is observed, a cycloreversion that occurs at the 1,3-radial cation stage rather than through the corresponding 1,3-biradical intermediates. The diphenyl-substituted azoalkane la affords high yields of the symmetric cyclopentadiene 4a, while the alkyl-substituted lb produces only small amounts of a rearranged cyclopentadiene 4'b. The housanes 2a,b are also oxidized by PET, but are more reluctant to rearrange. Strong electron acceptors such as triphenylpyrylium tetrafluoroborate (TPT) or cosensitization with biphenyl (Ph2) must be utilized to induce rearrangement to 3a,b and fragmentation to 4 and 4'.