雌二醇-2,3-邻苯醌 | 42261-16-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 中文名称: 雌二醇-2,3-邻苯醌
• 英文名称: 17β-estradiol-2,3-quinone
• 英文别名: 17b-Estradiol-2,3-quinone；oestradiol-2,3-quinone；(8R,9S,13S,14S,17S)-17-hydroxy-13-methyl-6,7,8,9,11,12,14,15,16,17-decahydrocyclopenta[a]phenanthrene-2,3-dione
• CAS: 42261-16-5
• 化学式: C₁₈H₂₂O₃
• 分子量: 286.371
• InChiKey: LBSRSXWOMYPVBY-XSSYPUMDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  21
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-乙酰-L-半胱氨酸 、 雌二醇-2,3-邻苯醌 以 水 、 溶剂黄146 、 乙腈 为溶剂， 反应 0.5h， 生成 、
  参考文献：
  名称：

  Synthesis and Structure Elucidation of Estrogen Quinones Conjugated with Cysteine, N-Acetylcysteine, and Glutathione

  摘要：

  Catechol estrogen quinones (CE-Q) have been implicated as ultimate carcinogenic metabolites in estrogen-induced carcinogenesis. CE-Q may covalently bind to DNA to initiate cancer. These quinones can also be conjugated with glutathione, a reaction that prevents damage to DNA by CE-Q. The glutathione conjugates are then catabolized through mercapturic acid biosynthesis to cysteine and N-acetylcysteine conjugates. This may be the most important detoxification pathway of CE-Q. The chemical synthesis and characterization of these conjugates are the first essential steps to better understand their function in biological systems. Eighteen conjugates were synthesized by reaction of estrone-3,4-quinone (E-1-3,4-Q), estradiol-3,4-quinone (E-2-3,4-Q), estrone-2,3-quinone (E-1-2,3-Q), or estradiol-2,3-quinone (E-2-2,3-Q) with various sulfur: nucleophiles, RSH, in which R is the cysteine, N-acetylcysteine, or glutathione moiety. Reactions of E-1-3,4-Q and E-2-3,4-Q produce regiospecifically 4-OHE1-2-SR and 4-OHE2-2-SR, respectively, in almost quantitative yield. E-1-2,3-Q and E-2-2,3-Q react regioselectively and quantitatively to form S-OHE1(E-2)-1-SR and 8-OHE1(E-2)-4-SR, in which the l-isomers are always the major products. The ratio between 1 and 4 isomers is 3.5 for cysteine, 2.7 for N-acetylcysteine, and 2.5 for glutathione. The synthesized conjugates will be used as standards in the identification of these compounds formed in biological systems.

  DOI：

  10.1021/tx9702291
• 作为产物：
  描述：

  雌甾-1,3,5(10)-三烯2,3,17-三醇 在 sodium periodate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 雌二醇-2,3-邻苯醌
  参考文献：
  名称：

  Assay of labile estrogen o-quinones, potent carcinogenic molecular species, by high performance liquid chromatography–electrospray ionization tandem mass spectrometry with phenazine derivatization

  摘要：

  A sensitive and selective assay method for labile estrogen o-quinones, estrone (E-1)-2,3-quinone (Q), E-1-3,4-Q, estrachol (E-2)-2,3-Q and E-2-3,4-Q based on the use of phenazine (Phz) derivatization with o-phenylenediamine and high performance liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS) was described The Phz derivatives of four estrogen o-quinones were purified by solid phase extraction and analyzed by HPLC-ESI-MS/MS The protonated molecule was observed as a base peak for all Phz derivatives in their ESI-mass spectra (positive mode) In multiple reaction monitoring, the transition from [M+H](+) to m/z 231 was chosen for quantification Calibration curves for the o-quinones were obtained using standard catechol estrogens after sodium metaperiodate treatment and Phz derivatization Using this method, these four estrogen o-quinones were analyzed with the limit of quantification of 5 ng/ml in acetonitrile (MeCN)-blank matrix (1 4, v/v), respectively, on a basis of the weight of catechol estrogens Assay accuracy and precision for four estrogen o-quinones were 896-113 0% and 3 1-12.6% (5, 125 and 2000 ng/ml in MeCN-blank matrix) Applications of this method enabled to determine the catalytic activities on hydroxylation and subsequent oxidation of E-1 and E2 of Mushroom tyrosinase and rat liver microsomal fraction It was confirmed by this method that tyrosinase exhibited 2- and 4-hydroxylation and further oxidation activities for catechols in the ring-A of estrogens. Whereas rat liver microsomal fraction possessed only 2- and 4-hydroxylation activities, and further oxidation activity for catechol estrogens was low (C) 2010 Elsevier Ltd All rights reserved.

  DOI：

  10.1016/j.jsbmb.2010.02.016

文献信息

• Preparation of unstable quinones in aqueous solution via pulse radiolytic one-electron oxidation of dihydroxybenzenes
  作者：Edward J. Land

  DOI：10.1039/ft9938900803

  日期：——

  The stoichiometry of the reactions of semiquinones resulting from the one-electron oxidation of various dihydroxybenzenes is examined. It is verified that the semiquinones of hydroquinone and catechol disproportionate completely to give p-benzoquinone and o-benzoquinone, respectively. With resorcinol, however, the corresponding semioxidised radical reaction is different, giving unstable dimers which

  检查了由各种二羟基苯的单电子氧化引起的半醌反应的化学计量。证实对苯二酚和邻苯二酚的半醌完全不成比例，分别得到对-苯醌和邻-苯醌。然而，对于间苯二酚，相应的半氧化自由基反应是不同的，产生不稳定的二聚体，其随后重排成四羟基联苯。
• Reactions of Estradiol-2,3-quinone with Deoxyribonucleosides:  Possible Insights in the Reactivity of Estrogen Quinones with DNA
  作者：Odile Convert、Christel Van Aerden、Laurent Debrauwer、Estelle Rathahao、Huguette Molines、Françoise Fournier、Jean-Claude Tabet、Alain Paris

  DOI：10.1021/tx015561y

  日期：2002.5.1

  by NMR and LC-MS(n)() in order to determine the structure and the stereochemistry of the resulting covalent adducts. Although estradiol- and estrone-2,3-quinones were previously thought to give mainly stable adducts, identification of depurinating adducts with both nucleosides, i.e., 2-OHE(2)-6(alpha,beta)-N7Gua and 2-OHE(2)-6(alpha,beta)-N7Ade, was unambiguously obtained. This is of particular interest

  雌激素2，3-和3，4-醌是对亲核试剂和迈克尔受体的反应性物质。因此，它们可以与DNA结合并诱导细胞损伤。作为烷基化模型，以前已经通过质谱研究了雌二醇-2，3-醌与脱氧核糖核苷的反应。在这项工作中，雌激素-脱氧核糖核苷加合物是通过17β-雌二醇-2,3-醌与脱氧鸟苷或脱氧腺苷反应合成的，并通过NMR和LC-MS（n）（）分析，以确定其结构和立体化学。产生共价加合物。尽管以前认为雌二醇和雌酮-2,3-醌主要产生稳定的加合物，但鉴定了具有两个核苷（即2-OHE（2）-6（alpha，beta）-N7Gua和2-OHE（）的去嘌呤加合物。清楚地获得2）-6α-β-N7Ade。这是特别令人感兴趣的，因为脱嘌呤加合物是从DNA生成的，因此，其数量应与嘌呤位点的平行形成相关，而嘌呤位点可能在癌症的起始过程中起重要作用。此外，已经明确鉴定了对应于2-羟基雌二醇的不稳定烷基化产物的副产物2-羟基-11-氧
• Assay of labile estrogen o-quinones, potent carcinogenic molecular species, by high performance liquid chromatography–electrospray ionization tandem mass spectrometry with phenazine derivatization
  作者：Kouwa Yamashita、Akina Masuda、Yuka Hoshino、Sachiko Komatsu、Mitsuteru Numazawa

  DOI：10.1016/j.jsbmb.2010.02.016

  日期：2010.4

  A sensitive and selective assay method for labile estrogen o-quinones, estrone (E-1)-2,3-quinone (Q), E-1-3,4-Q, estrachol (E-2)-2,3-Q and E-2-3,4-Q based on the use of phenazine (Phz) derivatization with o-phenylenediamine and high performance liquid chromatography-electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS) was described The Phz derivatives of four estrogen o-quinones were purified by solid phase extraction and analyzed by HPLC-ESI-MS/MS The protonated molecule was observed as a base peak for all Phz derivatives in their ESI-mass spectra (positive mode) In multiple reaction monitoring, the transition from [M+H](+) to m/z 231 was chosen for quantification Calibration curves for the o-quinones were obtained using standard catechol estrogens after sodium metaperiodate treatment and Phz derivatization Using this method, these four estrogen o-quinones were analyzed with the limit of quantification of 5 ng/ml in acetonitrile (MeCN)-blank matrix (1 4, v/v), respectively, on a basis of the weight of catechol estrogens Assay accuracy and precision for four estrogen o-quinones were 896-113 0% and 3 1-12.6% (5, 125 and 2000 ng/ml in MeCN-blank matrix) Applications of this method enabled to determine the catalytic activities on hydroxylation and subsequent oxidation of E-1 and E2 of Mushroom tyrosinase and rat liver microsomal fraction It was confirmed by this method that tyrosinase exhibited 2- and 4-hydroxylation and further oxidation activities for catechols in the ring-A of estrogens. Whereas rat liver microsomal fraction possessed only 2- and 4-hydroxylation activities, and further oxidation activity for catechol estrogens was low (C) 2010 Elsevier Ltd All rights reserved.
• Synthesis and Structure Elucidation of Estrogen Quinones Conjugated with Cysteine, <i>N</i>-Acetylcysteine, and Glutathione
  作者：Kai Cao、Douglas E. Stack、Ragulan Ramanathan、Michael L. Gross、Eleanor G. Rogan、Ercole L. Cavalieri

  DOI：10.1021/tx9702291

  日期：1998.8.1

  Catechol estrogen quinones (CE-Q) have been implicated as ultimate carcinogenic metabolites in estrogen-induced carcinogenesis. CE-Q may covalently bind to DNA to initiate cancer. These quinones can also be conjugated with glutathione, a reaction that prevents damage to DNA by CE-Q. The glutathione conjugates are then catabolized through mercapturic acid biosynthesis to cysteine and N-acetylcysteine conjugates. This may be the most important detoxification pathway of CE-Q. The chemical synthesis and characterization of these conjugates are the first essential steps to better understand their function in biological systems. Eighteen conjugates were synthesized by reaction of estrone-3,4-quinone (E-1-3,4-Q), estradiol-3,4-quinone (E-2-3,4-Q), estrone-2,3-quinone (E-1-2,3-Q), or estradiol-2,3-quinone (E-2-2,3-Q) with various sulfur: nucleophiles, RSH, in which R is the cysteine, N-acetylcysteine, or glutathione moiety. Reactions of E-1-3,4-Q and E-2-3,4-Q produce regiospecifically 4-OHE1-2-SR and 4-OHE2-2-SR, respectively, in almost quantitative yield. E-1-2,3-Q and E-2-2,3-Q react regioselectively and quantitatively to form S-OHE1(E-2)-1-SR and 8-OHE1(E-2)-4-SR, in which the l-isomers are always the major products. The ratio between 1 and 4 isomers is 3.5 for cysteine, 2.7 for N-acetylcysteine, and 2.5 for glutathione. The synthesized conjugates will be used as standards in the identification of these compounds formed in biological systems.