9α-hydroxy-3-methoxy-3,5-androstenedione-17-one | 116256-30-5

• 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: 9α-hydroxy-3-methoxy-3,5-androstenedione-17-one
• 英文别名: 9α-Hydroxy-3-methoxyandrosta-3,5-diene-17-one；9α-hydroxy-3-methoxyandrosta-3,5-dien-17-one；3-methoxy-9α-hydroxyandrosta-3,5-dien-17-one；9-alpha-hydroxy-3-methoxyandrosta-3,5-dien-17-one；3-Methoxy-9alpha-hydroxyandrosta-3,5-dien-17-one；(8S,9R,10S,13S,14S)-9-hydroxy-3-methoxy-10,13-dimethyl-2,7,8,11,12,14,15,16-octahydro-1H-cyclopenta[a]phenanthren-17-one
• CAS: 116256-30-5
• 化学式: C₂₀H₂₈O₃
• 分子量: 316.441
• InChiKey: PWDABEQXFVHNIT-CZKCSJLSSA-N

物化性质

• 熔点：
  196-201 °C
• 沸点：
  484.0±45.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  9α-hydroxy-3-methoxy-3,5-androstenedione-17-one 在 盐酸 、 异丙苯 、 溴 、 吡啶盐酸盐 、 potassium hydrogencarbonate 、 溶剂黄146 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 为溶剂， 反应 43.0h， 生成 21-Bromo-9α,17α-dihydroxy-16β-methylpregn-4-ene-3,20-dione
  参考文献：
  名称：

  Synthesis of corticoids from 9.alpha.-hydroxyandrost-4-ene-3,17-dione

  摘要：

  The synthesis of 17-alpha,21-bis(acetyloxy)-16-beta-methylpregna-4,9(11)-diene-3,20-dione (24) from the sterol-derived 9-alpha-hydroxyandrost-4-ene-3,17-dione (1) has been completed. The key steps in the synthesis are 16-beta-methylation and conversion of the 17-ketone to 17-beta-cyanohydrin 11. Elaboration of 11 to 9-alpha-hydroxy-16-beta-methylpregn-4-ene-3,20-dione (15) followed by 21-acetoxylation and simultaneous introduction of 9,11-unsaturation and 17-alpha-acetoxylation gave 24.

  DOI：

  10.1021/jo00029a032
• 作为产物：
  描述：

  9α-羟基-4-雄甾烯-3,17-二酮 在 硫酸 、 三乙胺 、 原甲酸三甲酯 作用下， 以 甲醇 、 水 为溶剂， 生成 9α-hydroxy-3-methoxy-3,5-androstenedione-17-one
  参考文献：
  名称：

  9-alpha-hydroxy steroids, process for their preparation, process for the

  摘要：

  新的9-α-羟基类固醇是通过在9-α-羟基雄烯二酮-3,17-二烯的D环上引入取代基而制备的。所得化合物是合成皮质类固醇中有用的中间体。

  公开号：

  US05352809A1

文献信息

• The chemistry of 9α-hydroxy steroids. 2. Epimerization and functionalization of 17α-ethylnylated 9α-hydroxy steroids
  作者：Jacobus N.M. Batist、Adrianus F.M. Slobbe、Arthur F. Marx

  DOI：10.1016/0039-128x(89)90006-8

  日期：1989.9

  Practical routes to 9α-hydroxypregnenes were developed by epimerization and hydration of 17α-ethynyl-9α,17β-dihydroxyandrost-4-en-3-one. In the three different methods of epimerization which were used, the C-9α hydroxy group was not susceptible to rearrangement or other side reactions. C-21 functionalized 9α-hydroxypregnenes were obtained by introducing a 17α-halogenated ethynyl group into 9α-hydroxyandrost-4-ene-3

  通过 17α-乙炔基-9α,17β-dihydroxyandrost-4-en-3-one 的差向异构化和水合开发了 9α-羟基孕烯的实用途径。在使用的三种不同的差向异构化方法中，C-9α 羟基不易发生重排或其他副反应。C-21 官能化 9α-羟基孕烯是通过将 17α-卤代乙炔基引入 9α-羟基雄酮-4-烯-3,17-二酮中获得的。17β-硝基氧法的差向异构化和水合产生21-卤代9α-羟基孕烯，其进一步转化为21-乙酰氧基-9α-羟基孕-4-烯-3,20-二酮。
• 一种16ɑ-甲基甾族化合物的制备方法
  申请人：江西赣亮医药原料有限公司

  公开号：CN104327142B

  公开（公告）日：2016-07-20

  本发明公开了一种16ɑ?甲基甾族化合物的制备方法，以化合物I为起始原料，经保护反应，亲核取代反应，水解反应，对3位和16位进行改造，制得终产物VI。本发明使用新的起始原料，反应步骤短，上16ɑ甲基步骤放在整个产品靠前的位置，极大的方便了各具备16ɑ甲基甾族药品新线路设计，使后续各步反应相对容易实现，收率较高，使生产更加经济、安全，更适合工业生产；本发明改变了现行业内使用的格式反应上16ɑ甲基的方式，改变了构型选择性较差的、副反应较多、并需要多个位置保护的现状，极大地促进了行业的技术进步；本发明采用亲核取代的方式基本避免了构型异构体的产生，几乎没有副反应，极大的提高了该步收率，降低了成本。
• 9.alpha.-hydroxy-17-methylene steroids, process for their preparation
  申请人：Gist-Brocades N.V.

  公开号：US05194602A1

  公开（公告）日：1993-03-16

  New 9.alpha.-hydroxy-17-methylene steroids are prepared by the introduction of a substituted 17-methylene group in 9.alpha.-hydroxyandrost-4-ene-3, 17-dione. The resulting compounds are useful starting compounds in the synthesis of corticosteroids.

  新的9.alpha.-羟基-17-亚甲基类固醇是通过在9.alpha.-羟基雄烯酮-4-烯-3,17-二酮中引入一个取代的17-亚甲基基团来制备的。所得的化合物是合成皮质类固醇中有用的起始化合物。
• The chemistry of 9α-hydroxysteroids. 1. preparation of 9α,17β-dihydroxy-17α-ethynylandrost-4-en-3-one
  作者：Jagdish C. Kapur、Arthur F. Marx、Jan Verweij

  DOI：10.1016/0039-128x(88)90002-5

  日期：1988.9

  9 alpha-Hydroxyandrost-4-ene-3,17-dione 1, when allowed to react with dipotassium acetylide in tetrahydrofuran, resulted, after chromatographic separation, in 4-methyl-19-norandrosta-4,9-diene-1,17-dione 2, 4 xi-methyl-19-norandrosta-5(10),9(11)-diene-1,17-dione 3, 4-methyl-17 alpha-ethynyl-17 beta-hydroxy-19-norandrosta-4,9-dien-1-one 4, 4 xi-methyl-17 alpha-ethynyl-17 beta-hydroxy-19-norandrosta-5(10),9(11)-dien- 1-one 5, and 17 alpha-ethynyl-17 beta-hydroxy-9,10-secoandrost-4-ene-3,9-dione 6. Selective protection of delta 4-3-ketone of 9 alpha-hydroxyandrost-4-ene-3,17-dione 1 as its dienol methyl ether 7, and subsequent reaction with lithium acetylide-ethylenediamine followed by acidic hydrolysis, afforded 9 alpha,17 beta-dihydroxy-17 alpha- ethynylandrost-4-en-3-one 8.
• The chemistry of 9α-hydroxysteroids. 3. Methods for selective formation and dehydrations of 17β-cyano-9α,17α-dihydroxyandrost-4-en-3-one
  作者：Jacobus N.M. Batist、Nicolaas C.M.E. Barendse、Arthur F. Marx

  DOI：10.1016/0039-128x(90)90005-v

  日期：1990.3

  Two methods to produce the 17-cyanohydrin, using potassium cyanide in acetic acid/methanol or acetone cyanohydrin with aqueous sodium hydroxide, were followed with 9 alpha-hydroxyandrost-4-ene-3,17-dione, both providing 17 beta-cyano-9 alpha,17 alpha-dihydroxyandrost-4-en-3-one. The selectivity of one of these methods, that which uses acetone cyanohydrin, is not in agreement with a comparable reaction with the 9 alpha-unsubstituted androst-4-ene-13,17-dione to give the 17 alpha-cyano-17 beta-hydroxy product, as reported in the literature and confirmed by us. The 9 alpha-hydroxy and 17 alpha-hydroxy groups were used for the regioselective introduction of 9(11)- and 16(17)-double bonds by dehydrating 17 beta-cyano-9 alpha,17 alpha-dihydroxyandrost-4-en-3-one under different conditions.