18-hydroxypregn-4-ene-3,20-dione (18<*>20)hemiketal | 22618-71-9

• 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: 18-hydroxypregn-4-ene-3,20-dione (18<*>20)hemiketal
• 英文别名: 18-Hydroxyprogesterone hemiacetal；18-hydroxyprogesterone；20(α und β)-Hydroxy-18,20-epoxy-pregnen-4-on-3；Oxydo-18,20-hydroxy-20ζ-pregnen-4-on-3；3-Oxo-18,20-Oxido-20-hydroxy-pregnen-4；(1R,2S,5S,9R,12S,13R)-6-hydroxy-6,13-dimethyl-7-oxapentacyclo[10.8.0.02,9.05,9.013,18]icos-17-en-16-one
• CAS: 22618-71-9
• 化学式: C₂₁H₃₀O₃
• 分子量: 330.467
• InChiKey: QTYJGYMLVLIZGL-BSAOXSGVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  18-hydroxypregn-4-ene-3,20-dione (18<*>20)hemiketal 在 吡啶 、 双氧水 、 对甲苯磺酸 、 三甲胺 作用下， 以 1,4-二氧六环 为溶剂， 反应 19.5h， 生成 17β-Hydroxy-18-acetoxyandrost-4-ene-3-one
  参考文献：
  名称：

  An improved synthesis of 18-norandrost-4-ene-3,17-dione

  摘要：

  We describe the synthesis of 13beta- and 13alpha-H-18-nor-androst-4-ene-3,17-dione (1a and 1b) from 18-hydroxyprogesterone (18 --> 20) hemiketal, via the 18-acetoxy-17beta-hydroxyandrost-4-en-3-one formed by a modified Baeyer-Villiger reaction. Saponification of 18-acetoxyandrost-4-ene-3,17-dione with sonication, then retroaldolization in the presence of a formaldehyde trap, methone, afforded the mixture of 1a and 1b with 80% yield in a ''one-pot'' procedure and at room temperature. This yield was greatly improved, compared with the already published procedure.

  DOI：

  10.1016/0039-128x(93)90051-n
• 作为产物：
  描述：

  20α-hydroxyprogesterone 在 chromium(VI) oxide 、 碘苯二乙酸 、 硫酸 、 碘 、 silver(I) acetate 作用下， 以 四氯化碳 、 溶剂黄146 、 丙酮 为溶剂， 反应 2.42h， 生成 18-hydroxypregn-4-ene-3,20-dione (18<*>20)hemiketal
  参考文献：
  名称：

  Benedetti, M. O. Violeta; Burton, Gerardo, Organic Preparations and Procedures International, 1992, vol. 24, # 6, p. 701 - 704

  摘要：

  DOI：

文献信息

• Oxidative Cyclization of Iodo Ketones. Synthesis of 6-Oxa-5α-pregnane-3,20-dione
  作者：Daniel Nicoletti、Alberto A. Ghini、Gerardo Burton

  DOI：10.1021/jo960108q

  日期：1996.1.1

  The steroidal delta- and gamma-iodo ketones 1 and 9 were converted to the cyclic hemiketals 3 and 10, by oxidation to the iodoso derivatives with m-CPBA. Spontaneous cyclization of the latter intermediates to the corresponding oxocarbenium ions, followed by stereoselective addition of water, rendered the hemiketals. Depending on the reaction conditions, the five-membered oxocarbenium ion derived from

  通过用m-CPBA氧化成碘代衍生物，将甾族δ-和γ-碘酮1和9转化为环状半酮基3和10。后者中间体自发环化为相应的氧碳鎓离子，然后立体选择性地加水，得到半缩酮。取决于反应条件，由γ-碘酮9衍生的五元氧碳鎓离子可添加H（2）O或m-CPBA生成半酮状或BAeyer-Villiger型产物12，而由1只给出半数。当反应在干燥的甲醇中进行时，形成了甲基缩酮。使用这种方法可以使我们合成在C-19上有或没有功能的6-oxa-5alpha-孕烯。
• Reaktionen von Steroid-Hypojoditen II. Über die Herstellung 18-oxygenierter Pregnanverbindungen. Über Steroide, 187. Mitteilung
  作者：C. H. Meystre、K. Heusler、J. Kalvoda、P. Wieland、G. Anner、A. Wettstein

  DOI：10.1002/hlca.19620450431

  日期：——

  The reactions of 20-hydroxypregnanes with iodine and lead tetraacetate, mercuric or silver acetate yield the corresponding oxy radicals. With the latter two reagents, 20-hypoiodites are definitely intermediates. The primary reaction products, i.e. 18-iodo-20-hydroxy compounds, can be oxidized and hydrolized to 18-hydroxy-20-oxo-pregnanes. Under suitable conditions, especially with lead tetraacetate

  20-羟基孕烷与碘和四乙酸铅，汞或乙酸银的反应产生相应的氧自由基。对于后两种试剂，20次碘绝对是中间体。初级反应产物，即18-碘-20-羟基化合物，可被氧化并水解为18-羟基-20-氧-孕烯。在合适的条件下，特别是在四乙酸铅和碘的条件下，在18-碘-20-羟基-孕烷的碳18上发生第二次取代反应，生成（18 20）-半缩醛类型的化合物。这些可以被氧化为（18 20）-内酯。
• Choay,P. et al., Bulletin de la Societe Chimique de France, 1973, p. 1456 - 1459
  作者：Choay,P. et al.

  DOI：——

  日期：——
• Mineralocorticoid properties of potential metabolites of 18-hydroxydeoxycorticosterone and 18-hydroxyprogesterone
  作者：John F. Weet、George R. Lenz

  DOI：10.1021/jm00380a014

  日期：1985.2

  The high secretion rate of 18-hydroxydeoxycorticosterone in hypertensives and the steroids implication as a mineralocorticoid has led to the synthesis of potential di-, tetra-, and hexahydro metabolites of it and 18-hydroxy-progesterone. These potential metabolites have been synthesized by reduction of the double bond and the 3- and 20-ketones, singly or in combination. They have been evaluated for pro- and antimineralocorticoid activity and their affinity for the renal aldosterone receptor. All except one of the potential metabolites either lack or have reduced mineralocorticoid activity and aldosterone receptor binding affinity. The exception is the 3-ketopregn-4-ene-18,20-diol which has high receptor affinity but functions as an aldosterone antagonist.