d,l-Isoequilenin-methylaether | 1229-32-9

• 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
• 英文名称: d,l-Isoequilenin-methylaether
• 英文别名: (+/-)-Isoequilenin-methylether；(13S,14R)-3-methoxy-13-methyl-12,14,15,16-tetrahydro-11H-cyclopenta[a]phenanthren-17-one
• CAS: 1229-32-9；3907-67-3；4820-49-9；4820-56-8
• 化学式: C₁₉H₂₀O₂
• 分子量: 280.367
• InChiKey: LAFFTPKGTZPBMG-MJGOQNOKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  d,l-Isoequilenin-methylaether 在 氢氧化钾 、 水 、 碘 作用下， 以 甲醇 为溶剂， 以55%的产率得到Bis-dehydro-isomarrianolic acid methylether
  参考文献：
  名称：

  Photophysical and Structural Features of Inclusion Complexes with Fluorescent Dyes

  摘要：

  The synthesis of a new water-soluble beta-cyclodextrin CD-St with seven steroidic naphthalene chromophores linked to the primary rim, is reported together with the photophysical and structural features of its inclusion complexes with merocyanine and oxazine fluorescent dyes. These complexes were formed in a buffer at pH 10. At this pH the cyclodextrin is 14 times negatively charged since each chromophore bears two carboxylic groups. No excimer emission was detected, as expected from the design principles. Two complexes can be formed with stoichiometries 1:1 and 2:1 (CD:dye) for both dyes. The respective association constants were determined. In the 2:1 complexes, the cyclodextrin secondary rims are facing each other. Such complexes are outstanding artificial antennae with 14 chromophores surrounding an energy acceptor. Comparison was made with another (previously reported) water-soluble beta-cyclodextrin CD-NA with seven naphthalene chromophores-also linked to the primary rim-but bearing only one carboxylic group each. In fact, CD-NA only forms 1:1 complexes with the same dyes. The difference in complexing abilty of CD-NA and CD-St is discussed.

  DOI：

  10.1002/(sici)1521-3765(19991203)5:12<3666::aid-chem3666>3.0.co;2-2
• 作为产物：
  描述：

  racem.-14-Dehydroequileninmethylaether 在 氢氧化钾 、 palladium on activated charcoal 、 乙醇 作用下， 生成 d,l-Isoequilenin-methylaether
  参考文献：
  名称：

  与类固醇有关的稠合环结构的新合成；17-equilenones；马鞭草素的总合成。

  摘要：

  DOI：

  10.1021/ja01204a007

文献信息

• An Improved Synthesis of Estrogens.
  作者：Takuichi Miki、Kentaro Hiraga、Tsunehiko Asako

  DOI：10.1248/cpb.13.1285

  日期：——

  A short step synthesis of estradiol was presented. 1-Vinyl-6-methoxy-1-tetralol (I) was condensed with 2-methyl-1, 3-cyclopentanedione (II)in the presence of Triton B to give dl-3-methoxy-8, 14-secoestra-1, 3, 5(10), 9-tetraene-14, 17-dione (III) which was converted by phosphorus pentoxide into the known dl-3-methoxyestra-1, 3, 5(10), 8, 14-pentaen-17-one(IV). The ketone (IV) was treated with sodium borohydride in methanol, yielding dl-3-methoxyestra-1, 3, 5(10), 8, 14-pentaen-17β-ol(V). Catalytic hydrogenation of this compound over Raney nickel was found to be stereospecific, yielding dl-3-methoxyestra-1, 3, 5, (10), 8-tetraen-17β-ol(VI). This compound was subjected to K-NH3reduction to give dl-estradiol 3-methyl ether (VII).Racemic V was resolved through its 17 l-menthoxyacetate and d-estradiol 3-methyl ether obtained by the above series of reactions was identical with the material of natural origin. dl-Equilenin 3-methyl ether was prepared from dl-3-methoxyestra-1, 3, 5(10), 8-tetraen-17β-ol (VI) by oxidation with Jones' reagent at one step.

  介绍了一种雌二醇的短步合成方法。1-Vinyl-6-methoxy-1-tetralol (I) 与 2-甲基-1，3-环戊二酮 (II) 在 Triton B 的存在下缩合，得到 dl-3-甲氧基-8，14-secoestra-1，3，5(10)，9-tetraene-14，17-dione (III)，用五氧化二磷将其转化为已知的 dl-3-甲氧基雌甾-1，3，5(10)，8，14-戊烯-17-酮 (IV)。在甲醇中用硼氢化钠处理酮（IV），得到 dl-3-甲氧基雌甾-1，3，5(10)，8，14-戊烯-17β-醇（V）。在 Raney 镍上对该化合物进行催化氢化反应，发现其具有立体特异性，生成了 dl-3-甲氧基雌甾-1，3，5，(10)，8-四烯-17β-醇（VI）。外消旋体 V 通过其 17 l-甲氧基乙酸酯被分解，通过上述系列反应得到的 dl-estradiol 3-甲基醚与天然来源的物质相同。dl-Equilenin 3-甲基醚是由 dl-3-甲氧基雌甾-1，3，5(10)，8-四烯-17β-醇（VI）一步用琼斯试剂氧化制得的。
• Über Steroide. 79. Mitteilung. Totalsynthesen in der Oestronreihe II
  作者：J. Heer、K. Miescher

  DOI：10.1002/hlca.19480310514

  日期：——

  Auf totalsynthetischem Wege gewannen wir aus α-Monodehydro-marrianolsäure das Δ8,9-Monodehydro-iso-oestron mit cis-Stellung der Rdnge C und D.

  使用完全合成路线中，我们得到的Δ 8，9与长度C和d的顺位-monodehydro异雌酮从α-monodehydro-marrianolic酸。
• Practical semisynthesis of equilenin and its derivatives
  作者：Tao Yue、Hong-Ping Li、Kai Ding

  DOI：10.1016/j.tetlet.2016.09.062

  日期：2016.10

  are important intermediates in the synthesis of steroidal drugs. Until now, these estrogens were produced by extraction from pregnant mare’s urine due to the lack of efficient synthetic methods. Most reported semisyntheses of equilenin involve expensive raw materials or toxic reagents to suppress undesired epimerization at C/D ring juncture. Herein, we reported a practical synthesis of highly pure

  Equilenin 2及其衍生物是甾体药物合成中的重要中间体。到目前为止，由于缺乏有效的合成方法，这些雌激素是通过从怀孕母马的尿液中提取而产生的。大多数报道的马来烯半合成涉及昂贵的原料或有毒试剂，以抑制C / D环连接处不希望的差向异构。在此，我们报道了使用常规试剂从容易获得的原料6中实际合成高纯度马鞭草蛋白及其衍生物的方法。
• Introduction of the Angular Methyl Group. III. The Alkoxymethylene Blocking Group¹
  作者：William S. Johnson、Harvey Posvic

  DOI：10.1021/ja01198a036

  日期：1947.6
• Configuration of the Estrones. Total Synthesis of the Remaining Stereoisomers
  作者：William S. Johnson、Israel A. David、Henry C. Dehm、Robert J. Highet、E. W. Warnhoff、W. David Wood、E. T. Jones

  DOI：10.1021/ja01536a040

  日期：1958.2