1α,3β-bis<(tert-butyldimethylsilyl)oxy>androst-5-en-17-one | 111594-61-7

• 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: 1α,3β-bis<(tert-butyldimethylsilyl)oxy>androst-5-en-17-one
• 英文别名: (1S,3R)-1,3-bis(tert-butyldimethylsilyloxy)androst-5-en-17-one；[1α,3β]-1,3-bis(t-butyldimethylsilyloxy)-androst-5-en-17-one；1α,3β-bis[(tert-butyldimethylsilyl)oxy]androst-5-en-17-one；(1I+/-,3I(2))-1,3-Bis[[(1,1-dimethylethyl)dimethylsilyl]oxy]androst-5-en-17-one；(1S,3R,8R,9S,10R,13S,14S)-1,3-bis[[tert-butyl(dimethyl)silyl]oxy]-10,13-dimethyl-1,2,3,4,7,8,9,11,12,14,15,16-dodecahydrocyclopenta[a]phenanthren-17-one
• CAS: 111594-61-7
• 化学式: C₃₁H₅₆O₃Si₂
• 分子量: 532.955
• InChiKey: HKAIWAAWDDYIHL-SFUFRWFUSA-N

物化性质

• 熔点：
  153 °C
• 沸点：
  526.4±50.0 °C(Predicted)
• 密度：
  0.99±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.91
• 重原子数：
  36
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1α,3β-bis<(tert-butyldimethylsilyl)oxy>androst-5-en-17-one 在 2,4,6-三甲基吡啶 、 N-溴代丁二酰亚胺(NBS) 、 cerium(III) chloride 、 15-冠醚-5 、 偶氮二异丁腈 、 potassium tert-butylate 、 四丁基氟化铵 、 双氧水 、 sodium hydride 、 sodium hydroxide 作用下， 以 四氢呋喃 、 正庚烷 、 甲苯 、 mineral oil 为溶剂， 反应 120.75h， 生成 马沙骨化醇
  参考文献：
  名称：

  Industrial Synthesis of Maxacalcitol, the Antihyperparathyroidism and Antipsoriatic Vitamin D₃ Analogue Exhibiting Low Calcemic Activity

  摘要：

  Maxacalcitol, the 22-oxa-derivative of 1 alpha,25-dihydroxyvitamin D-3 and used currently as an antihyperparathyroidism and antipsoriatic drug, has been synthesized in seven chemical steps from 1 alpha-hydroxydehydroepiandrosterone on the basis of our previously developed route. The present synthesis allows the production of the protected form of the penultimate intermediate in 26% overall yield in a kilogram scale reaction employing neither difficult reaction conditions nor chromatographic purification, having overcome all the difficulties involved in the previous route.

  DOI：

  10.1021/op049822x
• 作为产物：
  描述：

  1-羟基去氢表雄酮 在 咪唑 、 2,6-二甲基吡啶 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 1.0h， 生成 1α,3β-bis<(tert-butyldimethylsilyl)oxy>androst-5-en-17-one
  参考文献：
  名称：

  An Alternative and Efficient Synthesis of 24,24-Difluoro-1.ALPHA.,25-dihydroxyvitamin D3.

  摘要：

  本文介绍了标题化合物 2 的另一种合成方法，它是 1α，25-二羟基维生素 D3 (1) 的强效类似物。从 1α，3β-双[(叔丁基二甲基硅烷基)氧基]雄甾-5-烯 (8)开始，经过 10 个步骤，以 3.8% 的总收率获得了 2。这种方法得到的化合物 2 的收率远远高于之前报道的方法。

  DOI：

  10.1248/cpb.40.1120

文献信息

• Process for the preparation of 24,24-difluoro-1.alpha.,25-dihydroxy
  申请人：Hoffmann-La Roche Inc.

  公开号：US04421690A1

  公开（公告）日：1983-12-20

  The present invention relates to a process and intermediates for the preparation of 24,24-difluoro-1.alpha.,25-dihydroxycholecalciferol from the readily-available 1.alpha.,3.beta.-dihydroxyandrost-5-en-17-one which is made by a known microbiological process from 3.beta.-hydroxyandrost-5-en-17-one [R. M. Dodson, A. H. Goldkamp and R. D. Muir, J. Amer. Chem. Soc. 82 4026 (1960)].

  本发明涉及一种从易得的1α，3β-二羟基雄烯酮制备24,24-二氟-1α，25-二羟基胆钙化醇的过程和中间体，该1α，3β-二羟基雄烯酮是通过已知的微生物学过程从3β-羟基雄烯酮制备的【R. M. Dodson，A. H. Goldkamp和R. D. Muir，J. Amer. Chem. Soc. 82 4026（1960）】。
• Synthetic studies of vitamin D3 analogues. VIII Synthesis of 22-oxavitamin D3 analogues.
  作者：Eigoro Murayama、Katsuhito Miyamoto、Noboru Kubodera、Takashi Mori、Isao Matsunaga

  DOI：10.1248/cpb.34.4410

  日期：——

  The synthesis of two vitamin D3 analogues, 1α-hydroxy-22-oxavitamin D3 (3a) and 1α, 25-dihydroxy-22-oxavitamin D3 (3b)from dehydroepiandrosterone (4__-) is described.

  描述了从脱氢表雄酮（4__-）合成 1α-羟基-22-氧维生素 D3（3a）和 1α，25-二羟基-22-氧维生素 D3（3b）这两种维生素 D3 类似物的过程。
• Novel vitamin D derivatives and process for producing the same
  申请人：Chugai Seiyaku Kabushiki Kaisha

  公开号：EP0184112A2

  公开（公告）日：1986-06-11

  Vitamin D derivatives of the formula where R1, R2 and R3 which may be the same or different each represents a hydrogen atom or a hydroxyl group; X is an oxygen atom, the group of the formula OR4 (where R4 is either a hydrogen atom or a lower alkyl having 4 to 6 carbon atoms that may or may not be substituted by a hydroxyl group), or the group of the formula=N-OR5 (where R5 is either a hydrogen atom or a lower alkyl group having 1 to 5 carbon atoms that may or may not be substituted by a hydroxyl group, an amino group or a lower alkylamino group having 1 to 3 carbon atoms), provided that the carbon atom at 20-position is linked to X by a single bond when X is the group of the formula OR4, and by a double bond in other cases, and a process for preparing the derivatives are disclosed. The derivatives have both the immunoregulating action and the ability to induce differentiation in tumor cells and hence are useful as medicines such as antiallergic agents, antirheumatic agents and antitumor agents.

  本发明涉及一种维生素D衍生物，其化学式为：其中R1、R2和R3可能相同或不同，分别代表氢原子或羟基；X代表氧原子、化学式为OR4的基团（其中R4可以是氢原子或具有4至6个碳原子的低级烷基，可以或不可以被羟基取代），或化学式为N-OR5的基团（其中R5可以是氢原子或具有1至5个碳原子的低级烷基，可以或不可以被羟基、氨基或具有1至3个碳原子的低级烷基氨基取代），但当X为化学式为OR4的基团时，20位碳原子与X之间是通过单键连接的，其他情况下是通过双键连接的。本发明还涉及一种制备该衍生物的方法。该衍生物具有免疫调节作用和诱导肿瘤细胞分化的能力，因此可用作药物，如抗过敏药、抗风湿药和抗肿瘤药。
• PROCESS FOR PRODUCING VITAMIN D DERIVATIVE USING PHOTOREACTION
  申请人：Kawase Akira

  公开号：US20100261917A1

  公开（公告）日：2010-10-14

  There are provided a novel process for producing [(5Z,7E)-(1S,3R,20S)-1,3-dihydroxy-9,10-secopregna-5,7,10(19),16-tetraen-20-yl}oxy]-N-(2,2,3,3,3-pentafluoropropyl)acetamide, which process is characterized by irradiating a compound represented by the formula: with UV to ring-open the compound, and then isomerizing the resulting compound; an intermediate useful for carrying out the process; and a process for producing the intermediate.

  提供了一种新的生产[(5Z,7E)-(1S,3R,20S)-1,3-二羟基-9,10-分裂孕酮-5,7,10(19),16-四烯-20-基}氧]-N-(2,2,3,3,3-五氟丙基)乙酰胺的方法，其特征在于用紫外线照射代表以下公式的化合物使其环开裂，然后异构化所得化合物；用于执行该过程的中间体；以及生产该中间体的方法。
• Synthesis of 21-nor-22-oxa-1α,25-dihydroxyvitamin D3 derivatives in quest of a drug with low calcemic activity
  作者：Hitoshi Shimizu、Kazuki Shimizu、Yasushi Uchiyama、Atsuko Sugita、Tetsuhiro Mikami、Tsuyoshi Yamauchi、Masahiro Kato、Kazumi Morikawa

  DOI：10.1016/j.tetlet.2004.08.160

  日期：2004.10

  Two 21-nor-22-oxa- 1alpha,25-dihydroxyvitamin D-3 derivatives have been synthesized in quest of a drug with lower calcemic activity than Maxacalcitol, 22-oxa-1alpha,25-dihydroxyvitamin D-3, being used as antihyperparathyroidism and antipsoriatic drug. Of two 21-nor products obtained, the product carrying one carbon elongated side chain with diethylcarbinol moiety has been found to exhibit comparable differentiation-inducing activity to Maxacalcitol with much lower exhibition of calcemic activity. (C) 2004 Elsevier Ltd. All rights reserved.