(3alpha,14Xi)-17-乙炔基-7-甲基雌甾-5(10)-烯-3,17-二醇 | 100239-44-9

• 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: (3alpha,14Xi)-17-乙炔基-7-甲基雌甾-5(10)-烯-3,17-二醇
• 英文名称: 3alpha-Hydroxytibolone
• 英文别名: [3α,7α,17α]-3,17-dihydroxy-7-methyl-19-norpregn-5(10)-en-20-yne；17α-ethynyl-7α-methyl-estr-5(10)-ene-3α,17β-diol；17α-ethynyl-7α-methyl-5(10)-estren-3α,17β-diol；7α-methyl-19-norpregn-5(10)-en-20-yn-3α,17β-diol；3α-hydroxytibolone；3α-OH-tibolone；(3R,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: 100239-44-9
• 化学式: C₂₁H₃₀O₂
• 分子量: 314.468
• InChiKey: YLEUWNOTNJZCBN-CZTKNSHGSA-N

物化性质

• 熔点：
  72-74°C
• 溶解度：
  易溶于可溶于氯仿、甲醇

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：

  (3alpha,14Xi)-17-乙炔基-7-甲基雌甾-5(10)-烯-3,17-二醇 在 偶氮二甲酸二异丙酯 、 sodium carbonate 、 三苯基膦 作用下， 以 甲醇 、 乙醚 、 水 为溶剂， 反应 4.0h， 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
• 作为产物：
  描述：

  替勃龙 在 吡啶 、 辛醇 、 Candida antarctica lipase B Novozym 435 、 二异丁基氢化铝 作用下， 以 甲苯 为溶剂， 反应 30.0h， 生成 (3alpha,14Xi)-17-乙炔基-7-甲基雌甾-5(10)-烯-3,17-二醇
  参考文献：
  名称：

  A practical chemoenzymatic approach to the synthesis of 3-hydroxy metabolites of tibolone

  摘要：

  Stereoselective preparation of the 3-hydroxy metabolites of tibolone is easily accomplished by diastereoselective Candida antarctica lipase B-catalyzed transformations of 3alpha- and 3beta-alcohols or acetates Mixtures in organic solvents, in suitable amounts for biological studies. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00712-7

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。
• Gas chromatography/chemical ionization triple quadrupole mass spectrometry analysis of anabolic steroids: ionization and collision-induced dissociation behavior
  作者：Michael Polet、Wim Van Gansbeke、Peter Van Eenoo、Koen Deventer

  DOI：10.1002/rcm.7472

  日期：2016.2.28

  detection of new anabolic steroid metabolites and new designer steroids is a challenging task in doping analysis. Switching from electron ionization gas chromatography triple quadrupole mass spectrometry (GC/EI‐MS/MS) to chemical ionization (CI) has proven to be an efficient way to increase the sensitivity of GC/MS/MS analyses and facilitate the detection of anabolic steroids. CI also extends the possibilities

  新的合成代谢类固醇代谢物和新设计的类固醇的检测在掺杂分析中是一项艰巨的任务。从电子电离气相色谱三重四极杆质谱（GC / EI-MS / MS）切换到化学电离（CI）是提高GC / MS / MS分析灵敏度并促进合成代谢类固醇检测的有效方法。CI还扩展了GC / MS / MS分析的可能性，因为分子离子由于较软的电离而保留为其质子化形式。在EI中，由于分子离子的丰度低或不存在以及广泛的（很大程度上是不可预测的）碎片，很难找到以前未知但预期的代谢物。这项工作的主要目的是研究大量合成代谢雄激素类固醇（AAS）作为其三甲基甲硅烷基衍生物的CI和碰撞诱导解离（CID）行为，以确定结构与CID片段化之间的相关性。需要澄清这些相关性，以阐明未知类固醇和新代谢产物的结构。
• 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）。
• 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.