17-oxoestra-1,3,5(10),15-tetraen-3-yl acetate | 59169-10-7

• 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-oxoestra-1,3,5(10),15-tetraen-3-yl acetate
• 英文别名: 3-Acetoxyestra-1,3,5(10),15-tetraen-17-on；3-acetoxy-estra-1,3,5 (10),15-tetraen-17-one；[(8R,9S,13S,14S)-13-methyl-17-oxo-7,8,9,11,12,14-hexahydro-6H-cyclopenta[a]phenanthren-3-yl] acetate
• CAS: 59169-10-7
• 化学式: C₂₀H₂₂O₃
• 分子量: 310.393
• InChiKey: ABQWAHZTVOQNNH-XSYGEPLQSA-N

物化性质

• 熔点：
  246-248 °C(Solv: ethyl acetate (141-78-6); hexane (110-54-3))
• 沸点：
  462.8±45.0 °C(Predicted)
• 密度：
  1.172±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  23
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  17-oxoestra-1,3,5(10),15-tetraen-3-yl acetate 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 estra-1,3,5(10),15-tetraene-3,17β-diol
  参考文献：
  名称：

  Syntheses of 15α-Hydroxyestrone and 15α-Hydroxyestradiol

  摘要：

  通过新的合成路线，我们从雌酮中制备出了标题化合物（1、2）。用二硼烷对 14、15 或 15、16-双键进行氢硼化合，然后用碱性过氧化氢对有机硼烷进行氧化，很容易在 15α 位上引入羟基。在制备 1 的过程中，为了保护 3、17β-羟基，方便地使用了二甲基叔丁基硅烷官能团。

  DOI：

  10.1248/cpb.23.3141
• 作为产物：
  描述：

  雌酚酮 在 烯丙基甲基碳酸酯 、 三正丁基甲氧基锡 、 palladium diacetate 、 对甲苯磺酸 作用下， 以 乙腈 为溶剂， 生成 17-oxoestra-1,3,5(10),15-tetraen-3-yl acetate
  参考文献：
  名称：

  [EN] PROCESS FOR THE PRODUCTION OF ESTETROL INTERMEDIATES
  [FR] PROCÉDÉ POUR LA PRODUCTION D'INTERMÉDIAIRES D'ESTÉTROL

  摘要：

  本发明涉及一种制备化合物的方法，其化学式为(I)，所述方法包括以下步骤：a)将化合物的化学式为(II)与酰化剂或硅化剂反应，生成化合物的化学式为(III)，其中P1和P2分别独立地为选自R2-Si-R3R4或R1CO-的保护基，其中R1是选自C1-6烷基或C3-6环烷基的基团，每个基团可选择性地被一个或多个氟或C1-4烷基取代；R2、R3和R4分别独立地为选自C1-6烷基或苯基的基团，每个基团可选择性地被一个或多个氟或C1-4烷基取代；b)在钯醋酸或其衍生物存在下，将化合物的化学式为(III)反应，生成化合物的化学式为(IV)；c)将化合物的化学式为(IV)与还原剂反应，生成化合物的化学式为(I)。

  公开号：

  WO2012164096A1

文献信息

• PROCESS FOR THE PRODUCTION OF ESTETROL INTERMEDIATES
  申请人：ESTETRA S.A.

  公开号：US20140107358A1

  公开（公告）日：2014-04-17

  The present invention relates to a process for the preparation of a compound of formula (I) said process comprising the steps of: a) reacting a compound of formula (II), with an acylating or a silylating agent to produce a compound of formula (III), wherein P 1 and P 2 are each independently a protecting group selected from R 2− Si—R 3 R 4 , or R 1 CO—, wherein R 1 is a group selected from C 1-6 alkyl or C 3-6 cycloalkyl, each group being optionally substituted by one or more substituents independently selected from fluoro or C 1-4 alkyl; R 2 , R 3 and R 4 are each independently a group selected from C 1-6 alkyl or phenyl, each group being optionally substituted by one or more substituents independently selected from fluoro or C 1-4 alkyl; b) reacting the compound of formula (III) in the presence of palladium acetate or a derivative thereof to produce compound of formula (IV); and c) reacting the compound of formula (IV) with a reducing agent to produce compound of formula (I).

  本发明涉及一种制备式（I）化合物的方法，该方法包括以下步骤：a）将式（II）化合物与酰化剂或硅化剂反应，以产生式（III）化合物，其中P1和P2各自独立地选择自R2−Si—R3R4或R1CO—的保护基，其中R1为选择自C1-6烷基或C3-6环烷基的基团，每个基团可以选择地被一个或多个取代基独立地选择自氟或C1-4烷基取代；R2、R3和R4各自独立地选择自C1-6烷基或苯基的基团，每个基团可以选择地被一个或多个取代基独立地选择自氟或C1-4烷基取代；b）在钯醋酸或其衍生物的存在下，将式（III）化合物反应，以产生式（IV）化合物；c）将式（IV）化合物与还原剂反应，以产生式（I）化合物。
• Process for the production of estetrol intermediates
  申请人：Pascal Jean-Claude

  公开号：US11053274B2

  公开（公告）日：2021-07-06

  The present invention relates to a process for the preparation of a compound of formula (I) said process comprising the steps of: a) reacting a compound of formula (II), with an acylating or a silylating agent to produce a compound of formula (III), wherein P1 and P2 are each independently a protecting group selected from R2—Si—R3R4, or R1CO—, wherein R1 is a group selected from C1-6alkyl or C3-6cycloalkyl, each group being optionally substituted by one or more substituents independently selected from fluoro or C1-4alkyl; R2, R3 and R4 are each independently a group selected from C1-6alkyl or phenyl, each group being optionally substituted by one or more substituents independently selected from fluoro or C1-4alkyl; b) reacting the compound of formula (III) in the presence of palladium acetate or a derivative thereof to produce compound of formula (IV); and c) reacting the compound of formula (IV) with a reducing agent to produce compound of formula (I).

  本发明涉及一种制备式（I）化合物的工艺，所述工艺包括以下步骤：a) 式(II)化合物与酰化剂或硅烷化剂反应生成式(III)化合物，其中 P1 和 P2 各自独立地为选自 R2-Si-R3R4 或 R1CO- 的保护基团，其中 R1 为选自 C1-6 烷基或 C3-6 环烷基的基团，每个基团可任选被一个或多个独立选自氟或 C1-4 烷基的取代基取代；R2、R3 和 R4 各自独立地为选自 C1-6 烷基或苯基的基团，每个基团任选被一个或多个独立选自氟或 C1-4 烷基的取代基取代； b) 在乙酸钯或其衍生物存在下使式 (III) 化合物反应，生成式 (IV) 化合物；以及 c) 使式 (IV) 化合物与还原剂反应，生成式 (I) 化合物。
• Proton and carbon-13 nuclear magnetic resonance spectroscopy of diastereoisomeric 3- and 17β-tetrahydropyranyl ether derivatives of estrone and estradiol
  作者：Vincent Boucheau、Mélanie Renaud、Marc Rolland de Ravel、Elisabeth Mappus、Claude Y. Cuilleron

  DOI：10.1016/0039-128x(90)90018-7

  日期：1990.5

  Protection of 3- and 17 beta-hydroxyl groups of estrone and estradiol as tetrahydropyranyl ether derivatives led to mixtures of 2'(R)- and 2'(S)-diastereoisomers which were separated by crystallization (3-tetrahydropyranyl ethers), or by thin-layer chromatography (17-tetrahydropyranyl ethers), and characterized by 1H and 13C nuclear magnetic resonance (NMR). Assignments for NMR signals of estradiol 3,17 beta-ditetrahydropyranyl ether were facilitated by comparison with those of its 15 zeta, 16 zeta-dideuterio analog and by 2D 1H-13C heteroshift correlation experiments. Diastereoisomers of 3-tetrahydropyranyl ether derivatives could be identified through the 13C NMR doublet signals of the anomeric C-2' and the aromatic C-4 carbon atoms in CDCl3. Diastereoisomers of 17-tetrahydropyranyl ether derivatives were recognized from characteristic modifications of 1H NMR signals of H-2', H-6', H-1, H-17, and 18-CH3 protons as well as from the 13C NMR doublet signals corresponding to C-2', C-4', C-6', C-12, C-13, C-16, and C-17 carbon atoms. Low-temperature experiments showed a splitting of the C-2', C-6', and C-17 13C NMR signals of each of the two 17-tetrahydropyranyl ether isomers. The downfield signal (equatorial conformer) of the three resulting doublets was more intense for the 17-tetrahydropyranyl ether 2'(S)-isomer, whereas the upfield signal (axial conformer) was more intense for the 2'(R)-isomer.
• Syntheses of estetrol mqnoglucuronides
  作者：Toshio Nambara、Kenichl Sudo、Motoko Sudo(née Kurata)

  DOI：10.1016/0039-128x(76)90072-6

  日期：1976.1

  Four possible monoglucuronides of estetrol (estra-1,3,5(10)-triene-3,15 alpha, 16 alpha, 17 beta-tetraol) have been prepared from appropriately protected estetrol by the Koenigs-Knorr reaction employing cadmium carbonate as a catalyst. Condensation of methyl acetobromoglucuronate with estetrol 15,16,17-triacetate provided the 3-glucuronide acetate-methyl ester in a satisfactory yield. Introduction of the glucuronyl residue into C-17 was similarly attained by the use of estetrol 3-benzoate 15,16-acetonide. When estetrol 3,17-diacetate and acetobromosugar were stirred in anhydrous toluene in the presence of cadmium salt, the reaction occurred at C-16 and C-15 yielding two isomeric monoglucuronide derivatives in a ratio of ca. 5 to 2. Removal of the protecting groups in the four glucuronide acetate-methyl esters gave the desired estetrol glucuronides, respectively. These synthetic substrates underwent readily enzymatic hydrolysis with beef-liver beta-glucuronidase to afford estetrol.