17α-ethynyl-17β-hydroxy-5-androsten-3-one ethylene ketal | 50407-76-6

• 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: 17α-ethynyl-17β-hydroxy-5-androsten-3-one ethylene ketal
• 英文别名: 3,3-ethylenedioxy-17α-ethynylandrost-5-en-17β-ol；3,3-ethanediyldioxy-17βH-pregn-5-en-20-yn-17-ol；3,3-Aethandiyldioxy-17βH-pregn-5-en-20-in-17-ol；17α-ethynyl-3,3-ethylenedioxy-5-androsten-17β-ol；3,3-ethylenedioxy-17β-hydroxy-17α-ethinylandrost-5-ene；3,3-Ethylenedioxy-17beta-hydroxy-17alpha-ethinylandrost-5-ene；(8'R,9'S,10'R,13'S,14'S,17'R)-17'-ethynyl-10',13'-dimethylspiro[1,3-dioxolane-2,3'-2,4,7,8,9,11,12,14,15,16-decahydro-1H-cyclopenta[a]phenanthrene]-17'-ol
• CAS: 50407-76-6
• 化学式: C₂₃H₃₂O₃
• 分子量: 356.505
• InChiKey: BWEWWHQUVVQNTN-GUCLMQHLSA-N

物化性质

• 熔点：
  258-259 °C
• 沸点：
  471.2±45.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Predicted)
• LogP：
  3.8 at 25℃ and pH5

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  26
• 可旋转键数：
  1
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

上下游信息

• 上游原料

  中文名称	英文名称	CAS号	化学式	分子量
  雄甾-5-烯-17-酮-3-乙烯缩酮	3,3-ethylenedioxy-5-androsten-17-one	3754-63-0	C21H30O3	330.467
  炔孕酮	levonorgestrel	434-03-7	C21H28O2	312.452

• 下游产品

  中文名称	英文名称	CAS号	化学式	分子量
  ——	3,3-ethanediyldioxy-17-tetrahydropyran-2-yloxy-pregn-5-en-20-yne	115916-54-6	C28H40O4	440.623
  螺内酯EP杂质C	3-oxopregn-4-ene-21,17α-carbolactone	976-70-5	C22H30O3	342.478

反应信息

• 作为反应物：
  描述：

  17α-ethynyl-17β-hydroxy-5-androsten-3-one ethylene ketal 在 盐酸 、 dirhodium tetraacetate 、 tris(triphenylphosphine)ruthenium(II) chloride 、 三氟甲磺酸三甲基硅酯 、 氢气 、 四氯苯醌 、 N-甲基吗啉氧化物 、 三苯基膦 作用下， 以 四氢呋喃 、 乙酸乙酯 、 N,N-二甲基甲酰胺 、 叔丁醇 为溶剂， 25.0~80.0 ℃ 、1.2 MPa 条件下， 反应 21.67h， 生成 螺内酯
  参考文献：
  名称：

  A novel synthesis of spironolactone. An application of the hydroformylation reaction

  摘要：

  DOI：

  10.1021/jo00282a041
• 作为产物：
  描述：

  炔孕酮 在 对甲苯磺酸 、 乙二醇 、 苯 作用下， 生成 17α-ethynyl-17β-hydroxy-5-androsten-3-one ethylene ketal
  参考文献：
  名称：

  Barton et al., Journal of the Chemical Society, 1959, p. 1957,1959

  摘要：

  DOI：

文献信息

• Process for the preparation of (Z)-17.alpha.-halovinyl steroids
  申请人：Schering Aktiengesellschaft

  公开号：US04885117A1

  公开（公告）日：1989-12-05

  (Z)-17.alpha.-halovinyl steroids of general Formula I ##STR1## wherein . . . . is a single bond or a double bond, V is a carbon-to-carbon bond or a methylene group, R.sub.1 is a hydrogen atom or a methyl group, X is a chlorine atom, a bromine atom or an iodine atom, and A symbolizes the remainder of the steroid molecule, are prepared by hydrogenating a 17.alpha.-haloethynyl steroid of formula II with diimide. ##STR2## wherein . . . , V, R.sub.1, X and A have the meanings given above. The compounds of Formula I include both known and novel compounds, all of which are pharmacologically active.

  通式I中的(Z)-17.alpha.-卤乙烯类固醇 ##STR1## 其中...是单键或双键，V是碳与碳之间的键或亚甲基基团，R.sub.1是氢原子或甲基基团，X是氯原子、溴原子或碘原子，而A代表类固醇分子的其余部分。这些化合物通过用双亚胺氢化17.alpha.-卤乙炔基固醇II而制备得到。 ##STR2## 其中...，V，R.sub.1，X和A具有上述给定的含义。通式I的化合物包括已知的和新颖的化合物，所有这些化合物都具有药理活性。
• Process and intermediates to prepare17beta-hydroxy-7alpha-methyl-19-nor-17alpha-pregn -5(10)-en-20-yn-3-one
  申请人：Martynow Jacek

  公开号：US20060111332A1

  公开（公告）日：2006-05-25

  The present invention is a process for the preparation of 17β-hydroxy-7α-methyl-19-nor-17α-pregn-5(10)-en-20-yn-3-one (17α-ethynyl-17β-hydroxy-7α-methyl-5(10)-estren-3-one, tibolone) of formula 1, which comprises hydrolysis of 17α-ethynyl-17β-hydroxy-7α-methyl-5(10)-estrene 3,3 -cyclic ketals of formula 2, where groups R 1 , R 2 , R 3 and R 4 are hydrogen atoms or alkyl groups, or R 1 and R 3 , taken together with the carbon atoms within the dioxolane ring to which they are attached, form an alicyclic ring fused to the dioxolane ring, with R 2 and R 4 being hydrogen atoms, or R 1 and R 3 together with the carbon atoms to which they are attached form an aromatic ring fused to the dioxolane ring, where R 2 and R 4 , taken together, form a chemical bond within said aromatic ring. In addition, the present invention includes an intermediate, compound of formula 2 and two processes to prepare 17α-ethynyl-17β-hydroxy-7α-methyl-5(10)-estrene 3,3 -cyclic ketals of formula 2: (a) by contacting 17α-ethynyl-17β-hydroxy-7α-methyl-4-estren-3-one with vicinal diols in the presence of a protic acid, and (b) by contacting 7α-methyl-5(10)-estrene-17-one 3,3-cyclic ketals of formula 4, where R 1 -R 4 are defined as above, with metal acetylides, in inert solvents.

  本发明涉及一种制备17β-羟基-7α-甲基-19-去氢-17α-孕-5（10）-烯-20-炔-3-酮（17α-乙炔基-17β-羟基-7α-甲基-5（10）-雌甾-3-酮，替泼酮）的方法，其包括对式2的17α-乙炔基-17β-羟基-7α-甲基-5（10）-雌甾-3,3-环糊精酮进行水解，其中基团R1、R2、R3和R4是氢原子或烷基，或者R1和R3与它们所附着的二氧兰环内的碳原子一起形成螺环并与二氧兰环融合，其中R2和R4是氢原子，或者R1和R3与它们所附着的碳原子一起形成与二氧兰环融合的芳香环，其中R2和R4一起在该芳香环内形成化学键。此外，本发明还包括一个中间体，化合物的式子为2，并且还包括两种制备式2的17α-乙炔基-17β-羟基-7α-甲基-5（10）-雌甾-3,3-环糊精酮的方法：（a）通过在质子酸存在下与邻二醇接触17α-乙炔基-17β-羟基-7α-甲基-4-雌甾-3-酮，和（b）通过在惰性溶剂中与金属乙炔基化合物接触式4的7α-甲基-5（10）-雌甾-17-酮3,3-环糊精酮，其中R1-R4的定义如上。
• Spironolactone process
  申请人：The Upjohn Company

  公开号：US04211701A1

  公开（公告）日：1980-07-08

  Spironolactone (VIII) is produced from ethisterone (I) by formation of the lactone (IV), a halo lactone (VI) and a .DELTA.4,6-lactone (VII).

  Spironolactone（VIII）是通过形成内酯（IV），卤代内酯（VI）和.DELTA.4,6-内酯（VII）从乙烯雌酮（I）生产的。
• Preparation of 17α-iodoethynylandrosta- and 17α-(2-iodoethenyl) androsta-4,6-dien-17β-ol-3-ones as active site-directed photoaffinity ligands for androgen-binding proteins
  作者：Pablo J. Diaz Cruz、N.Scott Mason、Benjamin J. Danzo、Howard E. Smith

  DOI：10.1016/0039-128x(92)90027-7

  日期：1992.11

  Unsaturated analogues of androst-4-en-17 beta-ol-3-one, each with a 17 alpha-iodoethynyl or 17 alpha-(2-iodoethenyl) substituent, were prepared, and their relative binding affinities (RBAs) for androgen-binding protein (ABP) were compared with those of 5 alpha-androstan-17 beta-ol-3-one, androst-4-en-17 beta-ol-3-one, androsta-4,6-dien-17 beta-ol-3-one, and androsta-1,4,6-trien-17 beta-ol-3-one. These binding studies indicate that the iodine[125I] analogues of 17 alpha-iodoethynyl and 17 alpha-[(E)-2-iodoethenyl] derivatives of androsta-4,6-dien-17 beta-ol-3-one and androsta-1,4,6-trien-17 beta-ol-3-one will have RBAs at least twice as great as that of 5 alpha-androstan-17 beta-ol-3-one. They can be prepared from 17 alpha-ethynylandrosta-4-en-17 beta-ol-3-one, the final synthetic step using N-[125I]iodosuccinimide, and are potential radioiodinated, active site-directed photoaffinity ligands for ABP and testosterone-binding globulin.
• Cyclic ketals of 3-keto-17-hydroxy-17-ethynyl-cyclopentanoperhydrophenanthrenes, andmethod of preparing them
  申请人：SQUIBB &

  公开号：US02288854A1

  公开（公告）日：1942-07-07