17,17-Aethylendioxy-5-androsten-1α,3β-diol | 50556-47-3

• 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: 17,17-Aethylendioxy-5-androsten-1α,3β-diol
• 英文别名: 17,17-ethylenedioxyandrost-5-ene-1α,3β-diol；17,17-Ethylenedioxy-1alpha,3beta-dihydroxy-androst-5-ene；(1S,3R,8R,9S,10R,13S,14S)-10,13-dimethylspiro[1,2,3,4,7,8,9,11,12,14,15,16-dodecahydrocyclopenta[a]phenanthrene-17,2'-1,3-dioxolane]-1,3-diol
• CAS: 50556-47-3
• 化学式: C₂₁H₃₂O₄
• 分子量: 348.483
• InChiKey: IAHQWTSXBJZXED-WDCLZLQXSA-N

物化性质

• 沸点：
  501.3±50.0 °C(Predicted)
• 密度：
  1.22±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  25
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  17,17-Aethylendioxy-5-androsten-1α,3β-diol 在 盐酸 、 4-二甲氨基吡啶 作用下， 以 吡啶 、 甲醇 为溶剂， 反应 49.0h， 生成 1α,3α-diacetoxyandrost-5-ene-17-one
  参考文献：
  名称：

  EINE ergiebige Herstellung冯1α，3β二羟基Δ 5 -steroiden第三人以Reduktion冯1α，2α环氧-4,6-二烯-3- onen MIT锂在Ammoniak †

  摘要：

  用于制备1α，3β二羟基Δ的有效程序5个由1α还原，-steroids2α环氧-4,6-二烯-3-酮与锂在氨

  DOI：

  10.1002/hlca.19810640621
• 作为产物：
  描述：

  17,17-Aethylendioxy-1α,2α-epoxy-4,6-androstadien-3-on 在 lithium 、 氯化铵 作用下， 生成 17,17-Aethylendioxy-5-androsten-1α,3β-diol
  参考文献：
  名称：

  EINE ergiebige Herstellung冯1α，3β二羟基Δ 5 -steroiden第三人以Reduktion冯1α，2α环氧-4,6-二烯-3- onen MIT锂在Ammoniak †

  摘要：

  用于制备1α，3β二羟基Δ的有效程序5个由1α还原，-steroids2α环氧-4,6-二烯-3-酮与锂在氨

  DOI：

  10.1002/hlca.19810640621

文献信息

• Synthesis of the Core Structure of the Cyclocitrinols via SmI₂-Mediated Fragmentation of a Cyclopropane Precursor
  作者：Hans-Günther Schmalz、Sherif El Sheikh、Aike Meier zu Greffen、Johann Lex、Jörg-Martin Neudörfl

  DOI：10.1055/s-2007-984521

  日期：2007.7

  cyclocitrinols, a new class of natural products possessing a steroid-analogue structure with a characteristic bicyclo[4.4.1]undecane AB ring system, was elaborated. In the key step, a cyclopropanated intermediate (prepared from dehydroepiandrosterone) was subjected to reductive fragmentation (using SmI 2 in THF).

  详细阐述了环柠檬醇的第一个合成条目，这是一类新的天然产物，具有类固醇类似物结构和特征性双环 [4.4.1] 十一烷 AB 环系统。在关键步骤中，对环丙烷化中间体（由脱氢表雄酮制备）进行还原裂解（在 THF 中使用 SmI 2）。
• Hydroboration of steroidal-1,5-dien-3.BETA.-ols: A general procedure for the introduction of a hydroxyl group at 1.ALPHA.-position of the 3-oxygenated steroids.
  作者：CHIKARA KANEKO、AKIKO SUGIMOTO、SACHIKO YAMADA、MASAYUKI ISHIKAWA、SATOSHI SASAKI、TATSUO SUDA

  DOI：10.1248/cpb.22.2101

  日期：——

  The procedure used for the preparation of 1α-hydroxycholesterol from cholesta-1, 4-dien-3-one was applied to 17, 17-ethylenedioxyandrosta-1, 4-dien-3-one and 20, 20-ethylenedioxypregna-1, 4-dien-3-one. The successful results described in this paper serve to provide a basis for evaluation of wide scope of this procedure for the introduction of a hydroxyl group at 1α-position of 3-oxygenated steroid derivatives. The procedure consists of three steps starting from 3-keto-△1, 4-steroids available readily from 3-oxygenated steroids : 1) deconjugation to 3-keto-△1, 5-steroids, 2) reduction with metalhydride to 3β-hydroxy-△1, 5-steroids, and 3) hydroboration to 1α, 3β-dihydroxy-△5-steroids. This paper also includes definite identification of the final and intermediate compounds in the procedure and interpretation of their mass and nuclear magnetic resonance spectroscopic behaviors.

  从胆甾-1，4-二烯-3-酮制备 1α-羟基胆固醇的程序被应用于 17，17-亚乙二氧基雄甾-1，4-二烯-3-酮和 20，20-亚乙二氧基孕甾-1，4-二烯-3-酮。本文所描述的成功结果为评估该程序在 3 氧甾体衍生物 1α 位引入羟基的广泛应用范围提供了依据。该过程包括三个步骤，从 3-酮-△1，4-类固醇开始：1）脱共轭为 3-酮-△1，5-类固醇；2）用金属酸酐还原为 3β-羟基-△1，5-类固醇；3）氢硼化为 1α，3β-二羟基-△5-类固醇。本文还包括在该过程中最终和中间化合物的明确鉴定，以及对其质量和核磁共振光谱行为的解释。
• Process for 1.alpha.,3.beta.-dihydroxy-.DELTA..sup.5 -steroids
  申请人：Hoffmann-La Roche Inc.

  公开号：US04305881A1

  公开（公告）日：1981-12-15

  A process for the synthesis of 1.alpha.,3.beta.-dihydroxy-.DELTA..sup.5 -steroids from steroids such as 1.alpha.,2.alpha.-epoxy-cholesta-4,6-dien-3-one, which is reacted with lithium in liquid ammonia in the absence of a proton donator and subsequently reduced by repeated alternative additions of a proton donator, said additions being followed in each case by an equivalent amount of lithium. The final product, a 1.alpha.,3.beta.-dihydorxy-.DELTA..sup.5 -steroid, is useful in the synthesis of derivatives of cholecalciferol.

  一种从类固醇合成1α,3β-二羟基-Δ^5-类固醇的方法，其中类固醇如1α,2α-环氧胆甾-4,6-二烯-3-酮与液氨中的锂在无质子给体的情况下反应，并通过重复交替添加质子给体的方式进行还原，每次添加后紧接着相等量的锂。最终产物为1α,3β-二羟基-Δ^5-类固醇，可用于合成胆钙醇衍生物。
• Recoverable Pd/C catalyst mediated dehydrogenation of sterols and an improved synthesis of 1α-hydroxydehydroepiandrosterone
  作者：Yi-Zhen Yin、Chao Liu、Long-Qian Tang、Zhao-Peng Liu

  DOI：10.1016/j.steroids.2012.08.018

  日期：2012.11

  A novel recyclable Pd/C catalyst mediated dehydrogenation of sterols is developed. The conversion of sterols to 1,4,6-trien-3-ones is best achieved with Pd/C as a catalyst (10%) in the presence of six equivalents of allyl diethyl phosphate (ADP) and excess amount of sodium carbonate in DMF under vigorous reflux conditions. This transformation gives 17,17-ethylenedioxyandrost-1,4,6-trien-3-one in better yield than that of DDQ oxidation and thus provides an improved synthesis of 1 alpha-hydroxydehydroepiandrosterone from DHEA. (C) 2012 Elsevier Inc. All rights reserved.
• US4305881A
  申请人：——

  公开号：US4305881A

  公开（公告）日：1981-12-15