(11R,12S)-dihydroxy-(13S,14R)-epoxy-11,12,13,14-tetrahydrodibenzo[a,l]pyrene | 153926-04-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 英文名称: (11R,12S)-dihydroxy-(13S,14R)-epoxy-11,12,13,14-tetrahydrodibenzo[a,l]pyrene
• 英文别名: (-)-anti-dibenzo[a,l]pyrene-(11R,12S)-dihydrodiol (13S,14R)-epoxide；(-)-anti-dibenzo[a,l]pyrene 11,12-dihydrodiol 13,14-epoxide；anti-11,12,12a,13a-Tetrahydrodibenzo(5,6:10,11)chryseno(3,4-b)oxirene-11,12-diol；(3R,5S,6S,7R)-4-oxaheptacyclo[11.10.2.02,8.03,5.010,24.017,25.018,23]pentacosa-1(24),2(8),9,11,13(25),14,16,18,20,22-decaene-6,7-diol
• CAS: 153926-04-6
• 化学式: C₂₄H₁₆O₃
• 分子量: 352.389
• InChiKey: CJAMAUFDXDSQLU-QPXUXIHVSA-N

物化性质

• 沸点：
  669.7±55.0 °C(Predicted)
• 密度：
  1.554±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  27
• 可旋转键数：
  0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.17
• 拓扑面积：
  53
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (11R,12S)-dihydroxy-(13S,14R)-epoxy-11,12,13,14-tetrahydrodibenzo[a,l]pyrene 、 2'-脱氧腺苷 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 以60%的产率得到(11R,12S,13R)-trihydroxy-(14S)-N⁶deoxyadenosine-11,12,13,14-tetrahydro-dibenzo[a,l]pyrene
  参考文献：
  名称：

  Structure Elucidation of the Adducts Formed by Fjord-Region Dibenzo[a,l]pyrene 11,12-Dihydrodiol 13,14-Epoxides and Deoxyadenosine

  摘要：

  Model adducts to be used in the identification of biologically formed adducts were synthesized by reaction of fjord-region dibenzo[a,l]pyrene 11,12-dihydrodiol 13,14-epoxides (DB[a,l]PDE) and deoxyadenosine (dA). The (+/-)-anti-DB[a,l]PDE was reacted with dA in dimethylformamide at 100 degrees C for 30 min to give four DB[a, l]PDE-14-N(6)dA adducts: (-)-anti-trans (26%), (+)-anti-trans (26%), (-)-anti-cis (17%), and (+)-anti-cis (17%). The (+/-)-syn-DB[a,l]PDE was reacted with dA under the same conditions to yield four DB[a, l]PDE-14-N(6)dA adducts and one N7Ade adduct: (+)-syn-cis (19%), (+)-syn-trans (13%), (-)-syn-cis (19%), (-)-syn-trans (13%), and (+/-)-syn-DB[a,l]PDE-14-N7Ade (22%). The structures of the eight stereoisomers of DB[a,l]PDE-14-N(6)dA were unequivocally assigned by reacting optically pure (-)-anti-DB[a,l]PDE and (+)-syn-DB[a,l]PDE with dA and by a combination of NMR, circular dichroism, and fast atom bombardment mass spectrometry. Reactions at 100 degrees C yielded mainly the trans-opened adducts at the benzylic C-14 position for both (+/-)-anti-DB[a,l]PDE and (-)-anti-DB[a,l]PDE, whereas (+/-)-syn-DB[a,l]PDE and (+)-syn-DB[a,l]PDE afforded mainly cis-opened adducts. At room temperature, however, only trans-opened adducts were obtained from (+/-)-anti-DB[a,l]PDE and only cis-opened adducts from (+/-)-syn-DB[a,l]PDE. Steric hindrance created by the fjord region may be an important factor for the stereoselectivity observed at room temperature.

  DOI：

  10.1021/tx980197x

文献信息

• Structure Elucidation of the Adducts Formed by Fjord Region Dibenzo[<i>a</i>,<i>l</i>]pyrene-11,12-dihydrodiol 13,14-Epoxides with Deoxyguanosine
  作者：Kai-Ming Li、Mathai George、Michael L. Gross、Cheng-Huang Lin、Ryszard Jankowiak、Gerald J. Small、Albrecht Seidel、Heiko Kroth、Eleanor G. Rogan、Ercole L. Cavalieri

  DOI：10.1021/tx980234k

  日期：1999.9.1

  (+/-)-anti-Dibenzo[a,l]pyrene-11,12-dihydrodiol 13,14-epoxide (+/-)-anti-DB[a,l]PDE} was reacted with deoxyguanosine (dG) in dimethylformamide at 100 degrees C for 30 min, and two sets of adducts were isolated: a mixture of (+/-)-anti-cis- & -trans-N(2)dG (43%) and a mixture of (+/-)-anti-cis- & -trans-N7Gua (45%). Both are mixtures of four stereoisomers that cannot be separated by HPLC. Similarly, (+/-)-syn-DB[a,l]PDE was reacted with dG under the same conditions, and (+/-)-syn-cis- & -trans-N(2)dG (38%) and (+/-)-syn-cis- & -trans-N7Gua (59%) were obtained. The structures of the adducts were determined by a combination of NMR and fast atom bombardment mass spectrometry. By reacting (-)-anti-DB[a,l]PDE or (+)-syn-DB[a,l]PDE with dG under the same conditions, however, optically pure N(2)dG and N7Gua isomers were obtained: (-)-anti-cis-N(2)dG (12%), (-)-anti-trans-N(2)dG (17%), (-)-anti-trans-N7Gua (43%), (+)-syn-cis-N(2)dG (7%), (+)-syn-trans-N(2)dG (3%), (+)-syn-cis-N7Gua (36%), and (+)-syn-trans-N7Gua (22%). The structures of the optically pure adducts were assigned by NMR. syn- and anti-DB[a,l]PDE-N(2)dG adducts can be distinguished by fluorescence line-narrowing spectroscopy (FLNS). Moreover, distinction between cis- and trans-stereochemistry of the adducts is also straightforward by FLNS, because the FLN spectra for the four DB[a,l]PDE-N(2)dG adducts, anti-cis, anti-trans, syn-cis, and syn-trans, are spectroscopically unique.
• Structure Elucidation of the Adducts Formed by Fjord-Region Dibenzo[<i>a</i>,<i>l</i>]pyrene 11,12-Dihydrodiol 13,14-Epoxides and Deoxyadenosine
  作者：Kai-Ming Li、Mathai George、Michael L. Gross、Albrecht Seidel、Andreas Luch、Eleanor G. Rogan、Ercole L. Cavalieri

  DOI：10.1021/tx980197x

  日期：1999.9.1

  Model adducts to be used in the identification of biologically formed adducts were synthesized by reaction of fjord-region dibenzo[a,l]pyrene 11,12-dihydrodiol 13,14-epoxides (DB[a,l]PDE) and deoxyadenosine (dA). The (+/-)-anti-DB[a,l]PDE was reacted with dA in dimethylformamide at 100 degrees C for 30 min to give four DB[a, l]PDE-14-N(6)dA adducts: (-)-anti-trans (26%), (+)-anti-trans (26%), (-)-anti-cis (17%), and (+)-anti-cis (17%). The (+/-)-syn-DB[a,l]PDE was reacted with dA under the same conditions to yield four DB[a, l]PDE-14-N(6)dA adducts and one N7Ade adduct: (+)-syn-cis (19%), (+)-syn-trans (13%), (-)-syn-cis (19%), (-)-syn-trans (13%), and (+/-)-syn-DB[a,l]PDE-14-N7Ade (22%). The structures of the eight stereoisomers of DB[a,l]PDE-14-N(6)dA were unequivocally assigned by reacting optically pure (-)-anti-DB[a,l]PDE and (+)-syn-DB[a,l]PDE with dA and by a combination of NMR, circular dichroism, and fast atom bombardment mass spectrometry. Reactions at 100 degrees C yielded mainly the trans-opened adducts at the benzylic C-14 position for both (+/-)-anti-DB[a,l]PDE and (-)-anti-DB[a,l]PDE, whereas (+/-)-syn-DB[a,l]PDE and (+)-syn-DB[a,l]PDE afforded mainly cis-opened adducts. At room temperature, however, only trans-opened adducts were obtained from (+/-)-anti-DB[a,l]PDE and only cis-opened adducts from (+/-)-syn-DB[a,l]PDE. Steric hindrance created by the fjord region may be an important factor for the stereoselectivity observed at room temperature.