16-亚甲基-17-羟基孕甾-1,4,9(11)-三烯-3,20-二酮 | 19683-23-9

• 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: 16-亚甲基-17-羟基孕甾-1,4,9(11)-三烯-3,20-二酮
• 英文名称: 16-methylene-17α-hydroxypregna-1,4,9(11)-triene-3,20-dione
• 英文别名: 16-Methylene-17-hydroxypregna-1,4,9(11)-triene-3,20-dione；(8S,10S,13S,14S,17R)-17-acetyl-17-hydroxy-10,13-dimethyl-16-methylidene-6,7,8,12,14,15-hexahydrocyclopenta[a]phenanthren-3-one
• CAS: 19683-23-9
• 化学式: C₂₂H₂₆O₃
• 分子量: 338.447
• InChiKey: DYQRAHCJWPSDRS-AMGKQAFBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  25
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  16α,17-epoxy-16β-methyl-5α-pregn-1,4,9(11)-triene-3,20-dione 在 三氟乙酸 作用下， 以 苯 为溶剂， 反应 18.0h， 以132 mg的产率得到16-亚甲基-17-羟基孕甾-1,4,9(11)-三烯-3,20-二酮
  参考文献：
  名称：

  Synthesis and 1H and 13C nuclear magnetic resonance of 16-methylene-17α-hydroxypregna-1,4,9(11)-triene-3,20-dione

  摘要：

  A three-step synthesis of 16-methylene-17alpha-hydroxypregna-1,4,9(11)-triene-3,20-dione, which has been previously obtained by microbial transformation, was achieved from 3beta-hydroxy-16alpha, 17-epoxy-16beta-methyl-5alpha-pregn-9(11)-en-20-one in an overall yield of 35%. All compounds involved in the process were characterized spectroscopically and their C-13 NMR shielding effects are briefly discussed.

  DOI：

  10.1016/0039-128x(93)90077-z

文献信息

• 16-Methylene-17.alpha.-hydroxy-progesterones
  申请人：The Upjohn Company

  公开号：US04567001A1

  公开（公告）日：1986-01-28

  16-Methylene-17-keto steroids (III) are transformed to the corresponding 16-methylene-17.alpha.-hydroxyprogesterones (VII) which are intermediates useful in the production of betamethasone, diflorasone diacetate and melengesterol acetate.

  16-亚甲基-17-酮类固醇（III）被转化为相应的16-亚甲基-17α-羟基孕酮（VII），这些中间体在贝塔甲酸、二氟松醋酸盐和美林松醋酸盐的生产中很有用。
• Novel 19-nor-pregnahexaenes, process for the preparation thereof, and pharmaceutical compositions containing them
  申请人：Technobiotic Ltd.

  公开号：EP0000609A1

  公开（公告）日：1979-02-07

  19-Nor-pregnahexaenes of formula wherein A is hydrogen, lower alkyl, fluoro or fluoro- substituted methyl; R1 is hydrogen, lower alkyl, or an acyl radical of a carboxylic acid; W is (H,H); (H, lower alkyl); (H, α-OR2), with R2 being hydrogen or an acyl radical of a carboxylic acid; or - CHT, with T being hydrogen, lower alkyl, fluorine, or chlorine; Q is OR4, with R4 being hydrogen or an acyl radical of a carboxylic acid; hydrogen, provided W is (H,H) or (H, lower alkyl); or together with W represents a 16α, 17α-lower alkylidenedioxy grouping; Y is (H,H), (H,OH), or oxygen; Z is hydrogen, chlorine or bromine; R, is hydrogen or an acyl radical of a carboxylic acid; or OR3 together with Q represents an alkylidenedioxy or alkylorthoalkanoate grouping; and when Q is hydroxy and R3 is hydrogen, the 17a, 20; 20, 21-bismethylanedioxy derivatives thereof; These compounds are novel, with the exception of the 21-acetate and 3,21-diacetate of 19-nor-pregna- 1,3,5 (10), 6,8,14- hexanene-3,17a,21- triol-20-one, while pharmaceutical compositions containing the latter two compounds are also novel. The preparation of the novel compounds by three methods is described, in particular dehydrogenation in position 14 of appropriate 19-nor-pregna- 1,3,5(10), 6,8-pentaenes by DDq. Representative compounds of the inventions have been shown to exhibit antimitotic activity and, in particular, are useful in treating psoriasis.

  式中的 19-正regnahexaenes 其中 A 是氢、低级烷基、氟或氟取代的甲基； R1 是氢、低级烷基或羧酸酰基； W 是（H，H）；（H，低级烷基）；（H，α-OR2），其中 R2 是氢或羧酸酰基；或 - CHT，其中 T 是氢、低级烷基、氟或氯；Q 是 OR4，其中 R4 是氢或羧酸酰基；氢，条件是 W 是（H，H）或（H，低级烷基）；或与 W 一起代表 16α、17α-低级亚烷基二氧基基团； Y 是（H,H）、（H,OH）或氧； Z 是氢、氯或溴； R，是氢或羧酸酰基；或 OR3 与 Q 一起代表亚烷基二氧基或烷基正烷酸酯基团； 以及当 Q 为羟基且 R3 为氢时，其 17a、20；20、21-二烷基二氧基衍生物； 除了 19-去甲-1,3,5(10),6,8,14-己烯-3,17a,21-三醇-20-酮的 21-乙酸酯和 3,21-二乙酸酯之外，这些化合物都是新颖的，而含有后两种化合物的药物组合物也是新颖的。本发明介绍了通过三种方法制备新型化合物，特别是通过 DDq 在适当的 19-去氢-1,3,5(10),6,8-戊烯的第 14 位进行脱氢。本发明中具有代表性的化合物已被证明具有抗变态反应活性，特别是可用于治疗牛皮癣。
• 16-methylene-steroids and their preparation
  申请人：THE UPJOHN COMPANY

  公开号：EP0104054A2

  公开（公告）日：1984-03-28

  16-Methylene-17-keto-steroids are transformed to the corresponding 16-methylene-17a-hydroxyprogesterones which are intermediates useful in the production of betamethasone, diflorasone diacetate and melengesterol acetate. 17a-Hydroxy-6, 16-dimethylene-pregn-4-ene-3, 20-dione is simultaneously isomerized and acylated to 17a-hydroxy-6-methyl-16-methylenepregna-4, 6-diene-3, 20-dione 17-acetate.

  16-亚甲基-17-酮类类固醇可转化为相应的 16-亚甲基-17a-羟基黄体酮，这些黄体酮是生产倍他米松、双醋酸地氟松和醋酸美伦孕酮的中间体。17a-羟基-6，16-二亚甲基孕甾-4-烯-3，20-二酮同时异构化和酰化为 17a-羟基-6-甲基-16-亚甲基孕甾-4，6-二烯-3，20-二酮 17-乙酸酯。
• 16-Sulfinylmethyl-steroids, their preparation and use
  申请人：THE UPJOHN COMPANY

  公开号：EP0179496A1

  公开（公告）日：1986-04-30

  Novel 16-sulfinylmethyl-steroids are prepared by reaction of the corresponding 16-methylene-17β-hydroxy-steroid with a sulfenylating agent, and are converted to corresponding 16-methylene-17a-hydroxy-progesterones by reaction with a thiophile. 17a-Hydroxy-6,16-dimethylene-pregn-4- ene-3,20-dione is simultaneously isomerised and acylated to give melengestrol acetate.

  通过相应的 16-亚甲基-17β-羟基类固醇与亚磺酰化剂反应，制备新型 16-亚磺酰甲基类固醇，并通过与亲硫剂反应转化为相应的 16-亚甲基-17a-羟基孕酮。
• US4526720A
  申请人：——

  公开号：US4526720A

  公开（公告）日：1985-07-02