(3beta,14Xi)-17-乙炔基-7-甲基雌甾-5(10)-烯-3,17-二醇 | 100239-45-0

• 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: (3beta,14Xi)-17-乙炔基-7-甲基雌甾-5(10)-烯-3,17-二醇
• 英文名称: (3β,7α,17α)-17-hydroxy-7-methyl-19-norpregn-5(10)-en-20-yn-3,17-diol
• 英文别名: (3β,7α,17α)-3,17-dihydroxy-7-methyl-19-norpregn-5(10)-en-20-yne；[3β,7α,17α]-3,17-dihydroxy-7-methyl-19-norpregn-5(10)-en-20-yne；(3β,7α,17α)-7-methyl-19-norpregn-5(10)-en-20-yne-3,17-diol；17α-ethynyl-7α-methyl-estr-5(10)-ene-3β,17β-diol；17α-ethynyl-7α-methyl-5(10)-estrene-3β,17β-diol；17α-ethynyl-7α-methyl-5(10)-estren-3β,17β-diol；3beta-Hydroxytibolone；(3S,7R,8R,9S,13S,14S,17R)-17-ethynyl-7,13-dimethyl-2,3,4,6,7,8,9,11,12,14,15,16-dodecahydro-1H-cyclopenta[a]phenanthrene-3,17-diol
• CAS: 100239-45-0
• 化学式: C₂₁H₃₀O₂
• 分子量: 314.468
• InChiKey: YLEUWNOTNJZCBN-XAAPQAIWSA-N

物化性质

• 熔点：
  165-169°C
• 沸点：
  449.1±45.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)
• 溶解度：
  溶于氯仿、乙酸乙酯

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3beta,14Xi)-17-乙炔基-7-甲基雌甾-5(10)-烯-3,17-二醇 在 三氧化硫吡啶 作用下， 以 1,4-二氧六环 、 N,N-二甲基甲酰胺 为溶剂， 生成 7α-methyl-19-norpregn-5(10)-en-20-yne-3β,17β-diol bis-sulfate
  参考文献：
  名称：

  恒定离子流失方法用于双硫酸盐代谢物的非目标检测

  摘要：

  II期代谢物的非靶向检测是研究生物系统中药物代谢的关键问题。灵敏且选择性的质谱（MS）技术与超高效液相色谱（UHPLC）系统相结合是最有效的方法。在这项研究中，我们使用三重四极杆仪器评估了针对双硫酸盐代谢物的非目标检测的不同质谱方法。合成了23种甾体代谢物的双硫酸盐，并对其MS行为进行了全面研究。双硫酸盐优先离子化为二价阴离子（[M – 2H] 2–），而单阴离子（[M – H] -）的贡献很小。从[M – 2H] 2 –前体离子产生的产物离子光谱主要由HSO的损失决定4 –生成两个产物离子，即m / z 97处的离子（HSO 4 –）和对应于其余单硫酸盐片段的离子。发现其他产物离子对某些结构具有特异性。例如，发现[CH 3 + SO 3 ] -的损失对于与硫酸盐相邻的几种不饱和化合物很重要。根据双硫酸盐代谢物的常见行为，对两种选择方案进行了非靶向检测双硫酸盐代谢物的评估（i）使用m /

  DOI：

  10.1021/acs.analchem.6b03671
• 作为产物：
  描述：

  替勃龙 在 lithium tri(t-butoxy)aluminum hydride 、 偶氮二甲酸二异丙酯 、 sodium carbonate 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 水 为溶剂， 反应 6.0h， 生成 (3beta,14Xi)-17-乙炔基-7-甲基雌甾-5(10)-烯-3,17-二醇
  参考文献：
  名称：

  通过核磁共振和量子化学研究对替勃龙的 3?-和 3?-羟基代谢物进行立体化学分析。GIAO 计算的实验测试

  摘要：

  通过广泛应用一维和二维 1H 和 13C NMR 光谱结合在 B3LYP/6-31G(d) 水平进行的分子建模，研究了替勃龙 3α-和 3β-羟基代谢物的 C-3 构型. 使用HF和DFT GIAO方法，计算了两种分子的屏蔽张量；计算的 NMR 化学位移与实验值的比较表明，密度泛函方法产生了分配质子和碳共振的最佳结果。尽管类固醇是相对较大的分子，但目前的方法似乎足够准确，可以通过使用计算的 13C 共振来确定相对构型；还可以通过使用计算的 1H 共振来确定成对的孪生 α/β 氢原子的化学位移。版权所有 © 2002 John Wiley & Sons，

  DOI：

  10.1002/mrc.1064
• 作为试剂：
  描述：

  替勃龙 、 硼氢化钠 在 ice 、 溶剂黄146 、 硼氢化钠 、 二氯甲烷 、 水 、 乙酸乙酯 、 碳酸氢钠 、 Brine 、 (3beta,14Xi)-17-乙炔基-7-甲基雌甾-5(10)-烯-3,17-二醇 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 生成 (3beta,14Xi)-17-乙炔基-7-甲基雌甾-5(10)-烯-3,17-二醇
  参考文献：
  名称：

  Method of producing tibolone metabolites by fermentation with Fusarium lini

  摘要：

  报道了一种通过将替布隆与亚麻镰刀菌（ATCC 9593）接触以生产Δ4-替布隆的方法。

  公开号：

  US20110124042A1

文献信息

• Diastereoselective Preparation of (<i>R</i>)- and (<i>S</i>)-2-Methoxy-2-phenylpent-3-ynoic Acids and Their Use as Reliable Chiral Derivatizing Agents
  作者：Salvador Pérez-Estrada、Pedro Joseph-Nathan、Hugo A. Jiménez-Vázquez、Manuel E. Medina-López、Francisco Ayala-Mata、L. Gerardo Zepeda

  DOI：10.1021/jo2016554

  日期：2012.2.17

  O-acetals 1a and 1b were used as chiral auxiliaries to achieve the diastereoselective preparation of both enantiomers of 2-methoxy-2-phenylpent-3-ynoic acids (MPPAs). The latter were condensed with several chiral secondary alcohols and some primary amines to evaluate their potential as chiral derivatizing agents (CDAs). The 1H NMR spectra of the corresponding esters and amides showed strong consistency with

  苯甲酰基-S，O-乙缩醛1a和1b用作手性助剂，以实现非对映选择性制备2-甲氧基-2-苯基戊-3-炔酸（MPPAs）的两种对映体。后者与几种手性仲醇和一些伯胺缩合，以评估其作为手性衍生剂（CDA）的潜力。的1个对应的酯和酰胺的1 H NMR光谱显示出很强的一致性与甲醇和胺部分，其观察到的ΔδL的绝对构型1和ΔδL 2个值分别为在0.1-0.4和0.02-0.12 ppm的范围。
• Method of producing tibolone metabolites by fermentation with Rhizopus stolonifer
  申请人：——

  公开号：US08148556B2

  公开（公告）日：2012-04-03

  A new method of producing metabolites of tibolone comprising fermenting tibolone with Rhizopus stolonifer (ATCC 12938) resulting in the formation of Δ4-Tibolone (C21H28O2), 6β-Hydroxytibolone, and 15β-Hydroxytibolone (C21H28O3) is reported.

  一种生产地泼龙代谢产物的新方法，包括将地泼龙与根霉菌（ATCC 12938）发酵，从而形成Δ4-地泼龙（C21H28O2）、6β-羟基地泼龙和15β-羟基地泼龙（C21H28O3）。
• Liquid chromatography–mass spectrometry (LC–MS) of steroid hormone metabolites and its applications
  作者：Trevor M. Penning、Seon-Hwa Lee、Yi Jin、Alejandro Gutierrez、Ian A. Blair

  DOI：10.1016/j.jsbmb.2010.01.005

  日期：2010.8

  Advances in liquid chromatography-mass spectrometry (LC-MS) can be used to measure steroid hormone metabolites in vitro and in vivo. We find that LC-electrospray ionization (ESI)-MS using a LCQ ion trap mass spectrometer in the negative ion mode can be used to monitor the product profile that results from 5 alpha-dihydrotestosterone (DHT)-17 beta-glucuronide, DHT-17 beta-sulfate, and tibolone-17 beta-sulfate reduction catalyzed by human members of the aldo-keto reductase (AKR) 1C subfamily and assign kinetic constants to these reactions. We also developed a stable isotope dilution LC-electron capture atmospheric pressure chemical ionization (ECAPCI)-MS method for the quantitative analysis of estrone (El)) and its metabolites as pentafluorobenzyl (PFB) derivatives in human plasma in the attomole range. The limit of detection for E1-PFB was 740 attomole on column. Separations can be performed using normal-phase LC because ionization takes place in the gas phase rather than in solution. This permits efficient separation of the regioisomeric 2- and 4-methoxy-E1. The method was validated for the simultaneous analysis of plasma E2 and its metabolites: 2-methoxy-E2, 4-methoxy-E2, 16 alpha-hydroxy-E2, estrone (E1), 2-methoxy-E1, 4-methoxy-E1, and 16 alpha-hydroxy-E1 from 5 pg/mL to 2000 pg/mL. Our LC-MS methods have sufficient sensitivity to detect steroid hormone levels in prostate and breast tumors and should aid their molecular diagnosis and treatment. (C) 2010 Elsevier Ltd. All rights reserved.
• Alpha-glucosidase and tyrosinase inhibitors from fungal hydroxylation of tibolone and hydroxytibolones
  作者：M. Iqbal Choudhary、S. Adnan Ali Shah、Atta-ur-Rahman、Shamsun-Nahar Khan、Mahmud Tareq Hassan Khan

  DOI：10.1016/j.steroids.2010.05.017

  日期：2010.12

  Sixteen new and one known metabolites 4-20 were obtained by incubation of tibolone (1) and hydroxytibolones (2 and 3) with various fungi. Their structures were elucidated by means of a homo and heteronuclear 2D NMR and by HREI-MS techniques. The relative stereochemistry was deduced by 2D NOESY experiment. Metabolites of tibolone (1) exhibited significant inhibitory activities against alpha-glucosidase and tyrosinase enzymes. Hydroxylations at C-6, C-10, C-11, C-15 positions and alpha,beta-unsaturation at C-1/C-2, C-4/C-5 showed potent inhibitory activities against these enzymes. (C) 2010 Elsevier Inc. All rights reserved.
• Enantioselective production of 3-hydroxy metabolites of tibolone by yeast reduction
  作者：Diego Romano、Valerio Ferrario、Diego Mora、Roberto Lenna、Francesco Molinari

  DOI：10.1016/j.steroids.2007.09.008

  日期：2008.1

  The enantioselective reduction of tibolone into the corresponding 3 alpha-hydroxy or 3 beta-hydroxy metabolite can be controlled by choosing suited strains of yeasts and biotransformation conditions. A restricted screening performed among 52 yeasts showed that the 3 alpha-epimer was preferentially obtained with high epimeric purity with various strains (i.e. with Kluyveromyces lactis CBS 2359), while only Saccharomyces cerevisiae CBS 3093 gave the 3 beta-epimer as major product. The reduction of tibolone with K. lactis CBS 2359 and S. cerevisiae CBS 3093 was optimised. S. cerevisiae CBS 3093 furnished a 96:4 ratio of 3 beta/3 alpha with complete molar conversion within 72 h when the initial concentration of substrate was below 2.5 g/L. K. lactis CBS 2359 gave a 99:1 ratio of 3 alpha/3 beta with complete conversion in 64 h. (C) 2007 Elsevier Inc. All rights reserved.