trans-11,12-dihydroxy-anti-13,14-epoxy-11,12,13,14-tetrahydrodibenzo[def,p]chrysene | 191151-57-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 芘
• 英文名称: trans-11,12-dihydroxy-anti-13,14-epoxy-11,12,13,14-tetrahydrodibenzo[def,p]chrysene
• 英文别名: (+/-)-r11,t12-dihydrodiol-t13,14-epoxide-11,12,13,14-tetrahydrodibenzo[a,l]pyrene；(11R,12S)-dihydroxy-(13S,14R)-epoxy-11,12,13,14-tetrahydrodibenzo[a,l]pyrene；(+/-)-anti-dibenzo[a,l]pyrene 11,12-dihydrodiol 13,14-epoxide；(+)-anti-Dbpde；(3S,5R,6R,7S)-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: 191151-57-2
• 化学式: C₂₄H₁₆O₃
• 分子量: 352.389
• InChiKey: CJAMAUFDXDSQLU-UARRHKHWSA-N

物化性质

• 沸点：
  669.7±55.0 °C(Predicted)
• 密度：
  1.554±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(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：

  2'-脱氧腺苷-5'-单磷酸 、 trans-11,12-dihydroxy-anti-13,14-epoxy-11,12,13,14-tetrahydrodibenzo[def,p]chrysene 以 四氢呋喃 、 三乙胺 为溶剂， 反应 48.0h， 生成 (-)-cis-anti-DB[a,l]PDE-N6-dAMP
  参考文献：
  名称：

  合成和表征的站点特定和立体异构的峡湾二苯并[a，l] py二醇环氧-N（6）-腺嘌呤加合物：修饰的DNA双链体的异常热稳定。

  摘要：

  在动物模型系统中，峡湾多环芳烃化合物二苯并[a，l] py（DB [a，l] P）的致瘤性明显高于海湾地区的苯并[a] py。DB [a，l] P及其峡湾区二醇环氧化物代谢产物异常强大的遗传毒性特性的分子起源引起人们极大的兴趣，并被认为与所形成的DNA加合物的结构特征有关。通过将5'-d（CTCTCACTTCC）（I）中的单个腺嘌呤残基与外消旋的峡湾二醇环氧化物r11，t12-二氢二醇-t13,14-环氧化物-11,12,13,14-反应，制得位点特异性修饰的寡核苷酸水溶液中的四氢二苯并[a，l] py（抗-DB [a，l] PDE）。四个不同的寡核苷酸I，其单个腺苷残基涉及DB [a，鉴定并纯化了1PDE和N（6）-dA。单核苷酸加合物的CD光谱类似于Li等人的那些。[李等人。（1999）Chem。Res。毒药。[12,758]描述了通过CD和NMR方法的组合来表征DB [a，l] PDE-N（6）-dA加合物。四种DB

  DOI：

  10.1021/tx010157k
• 作为产物：
  描述：

  trans-11,12-dihydroxy-11,12-dihydrodibenzo[def,p]chrysene 在 间氯过氧苯甲酸 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以86%的产率得到trans-11,12-dihydroxy-anti-13,14-epoxy-11,12,13,14-tetrahydrodibenzo[def,p]chrysene
  参考文献：
  名称：

  氧化代谢物的合成牵连作为高度有效的致癌烃二苯并活性形式[ DEF，p ]屈（chrysene）

  摘要：

  多环芳香烃（PAH）是环境致癌物的一类重要的，和二苯并[ DEF，p ]屈（chrysene）是目前已知的最有效的致癌PAH。报道了二苯并[ def，p ] ch的各种氧化代谢产物的合成，涉及与DNA直接或间接相互作用以诱导导致肿瘤诱导的突变的生物活性形式。这些包括8,9-和11,12-二氢二醇（2和3），8,9,11,12-双-二氢二醇（5）和3的峡湾区抗二醇环氧衍生物（4）。

  DOI：

  10.1016/s0040-4020(98)01082-5

文献信息

• Spectral and Conformational Analysis of Deoxyadenosine Adducts Derived from <i>syn- </i>and <i>anti</i>-Dibenzo[<i>a</i>,<i>l</i>]pyrene Diol Epoxides: Fluorescence Studies
  作者：Ryszard Jankowiak、Cheng-Huang Lin、Dan Zamzow、Kenneth P. Roberts、Kai-Ming Li、Gerald J. Small

  DOI：10.1021/tx980233s

  日期：1999.9.1

  a half-chair structure in the cyclohexenyl ring, but a deviation from planarity in the fjord region different from that of conformer II of cis-anti-DB[a, l]PDE-N(6)dA. This new structure is labeled as conformer II'. Its (0, 0) fluorescence band is at 388.1 and 388.3 nm in ethanol and glycerol/water glasses, respectively, consistent with the folded-type configuration revealed by the calculations. The

  反式-顺式，顺式-顺式，反式-反式和顺式-二苯并[a，l] py二醇环氧（DB [a，l] PDE）-的低温荧光光谱和构象研究结果给出了衍生的脱氧腺苷（dA）加合物，并将其与先前获得的立体异构DB [a，l] P四醇[Jankowiak，R.等人。（1997）Chem。Res。毒药。10，677-686]。与仅反式异构体表现出两个构象的DB [a，l] P四元醇相反，所有立体异构体dA加合物采用两种不同的构象，环己烯基环具有半椅或半船结构，并且带有一个“开放”- dA和DB [a，1] P部分之间的“折叠”型构型。反式-顺式，顺式-顺式和反式-DB [a，可根据先前对DB [a，l] P四元醇的计算分配l] PDE-14-N（6）dA。反式-顺式-顺式-DB-DB [a，l] PDE-14-N（6）dA加合物的主要构象物存在于构象I和II中，其荧光起源带在大约382和大约389 nm处，分
• 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.
• 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.
• Syntheses of oxidized metabolites implicated as active forms of the highly potent carcinogenic hydrocarbon dibenzo[def,p]chrysene
  作者：Jin-Tao Zhang、Ronald G Harvey

  DOI：10.1016/s0040-4020(98)01082-5

  日期：1999.1

  Polycyclic aromatic hydrocarbons (PAHs) are an important class of environmental carcinogens, and dibenzo[def,p]chrysene is the most potent carcinogenic PAH currently known. Syntheses of various oxidized metabolites of dibenzo[def,p]chrysene implicated as the biologically active forms that interact directly or indirectly with DNA to induce mutations that lead to tumor induction are reported. These include

  多环芳香烃（PAH）是环境致癌物的一类重要的，和二苯并[ DEF，p ]屈（chrysene）是目前已知的最有效的致癌PAH。报道了二苯并[ def，p ] ch的各种氧化代谢产物的合成，涉及与DNA直接或间接相互作用以诱导导致肿瘤诱导的突变的生物活性形式。这些包括8,9-和11,12-二氢二醇（2和3），8,9,11,12-双-二氢二醇（5）和3的峡湾区抗二醇环氧衍生物（4）。
• Synthesis and Characterization of Site-Specific and Stereoisomeric Fjord Dibenzo[<i>a,l</i>]pyrene Diol Epoxide−<i>N</i>⁶-Adenine Adducts:  Unusual Thermal Stabilization of Modified DNA Duplexes
  作者：Qian Ruan、Alexander Kolbanovskiy、Ping Zhuang、Junxin Chen、Jacek Krzeminski、Shantu Amin、Nicholas E. Geacintov

  DOI：10.1021/tx010157k

  日期：2002.2.1

  complementary strand (IC), T(m) = 43.8 +/- 0.5 degrees C, were compared with the same duplexes containing stereoisomeric anti-DB[a,l]PDE-N(6)-dA lesions. The T(m) of duplexes I.IC containing lesions with R absolute configurations at C14 of the DB[a,l]PDE residues are greater by 6-8 degrees C, while those with S configuration are lower by 6-10 degrees C. Similar effects are observed with adducts in the same

  在动物模型系统中，峡湾多环芳烃化合物二苯并[a，l] py（DB [a，l] P）的致瘤性明显高于海湾地区的苯并[a] py。DB [a，l] P及其峡湾区二醇环氧化物代谢产物异常强大的遗传毒性特性的分子起源引起人们极大的兴趣，并被认为与所形成的DNA加合物的结构特征有关。通过将5'-d（CTCTCACTTCC）（I）中的单个腺嘌呤残基与外消旋的峡湾二醇环氧化物r11，t12-二氢二醇-t13,14-环氧化物-11,12,13,14-反应，制得位点特异性修饰的寡核苷酸水溶液中的四氢二苯并[a，l] py（抗-DB [a，l] PDE）。四个不同的寡核苷酸I，其单个腺苷残基涉及DB [a，鉴定并纯化了1PDE和N（6）-dA。单核苷酸加合物的CD光谱类似于Li等人的那些。[李等人。（1999）Chem。Res。毒药。[12,758]描述了通过CD和NMR方法的组合来表征DB [a，l] PDE-N（6）-dA加合物。四种DB