孕甾-5-烯-3,20-二酮 | 1236-09-5

• 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
• 中文名称: 孕甾-5-烯-3,20-二酮
• 英文名称: pregn-5-ene-3,20-dione
• 英文别名: 5-Pregnene-3,20-dione；3-oxo-4-pregnen-20-one；5-pregnen-3,20-dione；isoprogesterone；progesterone；Pregn-5-en-3,20-dion；(8S,9S,10R,13S,14S,17S)-17-acetyl-10,13-dimethyl-1,2,4,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-3-one
• CAS: 1236-09-5
• 化学式: C₂₁H₃₀O₂
• 分子量: 314.468
• InChiKey: MNRHZPCIEGLWGK-LEKSSAKUSA-N

物化性质

• 熔点：
  181 °C
• 沸点：
  440.1±45.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  孕甾-5-烯-3,20-二酮 生成 黄体酮
  参考文献：
  名称：

  人皮肤中3β-羟基类固醇脱氢酶/δ5δ4异构酶的表征，表达和免疫组化定位。

  摘要：

  三种β-羟基类固醇脱氢酶/δ5-δ4异构酶（3β-HSD）催化了所有种类激素类固醇的生物合成中的强制性步骤，即3β-羟基-5-烯类固醇的氧化/异构化。性腺和周围组织中相应的3-酮-4-烯类固醇。由于人类在某些灵长类动物中具有独特之处，因为它们的肾上腺分泌大量的类固醇前体脱氢表雄甾酮（DHEA）及其硫酸盐（DHEA-S），其异常大的体积使皮肤成为类固醇生物合成的重要部位，因此我们进行了分离和鉴定来自人皮肤λgt11文库的编码3个β-羟类固醇脱氢酶/δ5-δ4异构酶的cDNA克隆。获得的最长的克隆包含I 3β-HSD类型的完整编码序列（372个氨基酸）以及5'-非翻译区的其他131个核苷酸。包含整个编码区的1647 bp插入片段已插入pCMV表达载体中，并转染到人宫颈癌细胞（HeLa）中。表达的酶有效地催化孕烯醇酮，DHEA和二氢睾丸酮分别转化为孕酮，4-雄烯二酮和5α-雄烷-3β，17β-二

  DOI：

  10.1111/1523-1747.ep12616131
• 作为产物：
  描述：

  黄体酮 在 氢氧化钾 、 碳酸氢钠 、 溶剂黄146 作用下， 以 乙二醇二甲醚 为溶剂， 反应 15.0h， 以77%的产率得到孕甾-5-烯-3,20-二酮
  参考文献：
  名称：

  Double bond migration over solid KOH suspended in aprotic solvents

  摘要：

  DOI：

  10.1016/s0040-4020(01)91490-5

文献信息

• Expedient Method for Oxidation of Alcohol by Hydrogen Peroxide in the Presence of Amberlite IRA 400 Resin (Basic) as Phase‐Transfer Catalyst
  作者：Nishi Bhati、Kuladip Sarma、Amrit Goswami

  DOI：10.1080/00397910801916090

  日期：2008.4

  IRA 400 (strongly basic), a classical polymer imparts phase‐transfer catalysis in the oxidation of primary and secondary alcohols by hydrogen peroxide to give excellent yields of the corresponding carbonyl compounds or carboxylic acids in acetonitrile solvent at reflux temperature in 4–6 h. The catalytic system is inert to other susceptible oxidation sites such as carbon–carbon double bonds

  摘要 Amberlite IRA 400（强碱性）是一种经典聚合物，在过氧化氢氧化伯醇和仲醇过程中具有相转移催化作用，在回流温度为 4-6 H。催化系统对其他敏感的氧化位点（如碳-碳双键）是惰性的
• Studies on Steroidal Compounds. XI. Reaction of 5-Ene Steroids with Sulfuryl Chloride in Pyridine.
  作者：Hiromu Mori、Joji Yamada

  DOI：10.1248/cpb.11.1418

  日期：——

  Some 3β-acetoxy-5-ene steroids were reacted with sulfuryl chloride in pyridine and the corresponding 3β-acetoxy-5α, 6β-dichloro steroids were obtained. Dehydroepiandrosterone acetate (VII) was transformed into 5α, 6β, 16, 16-tetrachloro compound (VI) on treatment with sulfuryl chloride in chloroform. The reaction of androst-5-ene-3, 17-dione (IX) with sulfuryl chloride in pyridine gave 6α-chloroandrost-4-ene-3, 17-dione (X), whereas the same reaction on pregn-5-ene-3, 20-dione (V) afforded the corresponding 5α, 6β-dichloro compound (IIIa). Some transformations of compounds above-mentioned were also written.

  一些3β-乙酰氧基-5-烯类类固醇与氯化亚砜在吡啶中反应，获得了相应的3β-乙酰氧基-5α, 6β-二氯类固醇。脱氢表雄酮醋酸酯（VII）在氯仿中与氯化亚砜反应后转化为5α, 6β, 16, 16-四氯化合物（VI）。而甾-5-烯-3, 17-二酮（IX）与氯化亚砜在吡啶中的反应则生成了6α-氯甾-4-烯-3, 17-二酮（X），而同样的反应在孕-5-烯-3, 20-二酮（V）中则获得了相应的5α, 6β-二氯化合物（IIIa）。上述化合物的一些转化反应也有所描述。
• Δ⁵-3β-Hydroxysteroid Dehydrogenase (3βHSD) from <i>Digitalis lanata</i>. Heterologous Expression and Characterisation of the Recombinant Enzyme
  作者：Vanessa Herl、Jördis Frankenstein、Nadine Meitinger、Frieder Müller-Uri、Wolfgang Kreis

  DOI：10.1055/s-2007-981537

  日期：2007.6

  During the biosynthesis of cardiac glycosides, Δ5-3β-hydroxysteroid dehydrogenase (3βHSD, EC 1.1.1.51) converts pregnenolone (5-pregnen-3β-ol-20-one) to isoprogesterone (5-pregnene-3,20-dione). A 3βHSD gene was isolated from leaves of Digitalis lanata. It consisted of 870 nucleotides containing a 90 nucleotide long intron. A full-length cDNA clone that encodes 3βHSD was isolated by RT-PCR from the same source. A Sph I/Kpn I 3βHSD cDNA was cloned into the pQE30 vector and then transferred into E. coli strain M15[pREP4]. 3βHSD cDNA was functionally expressed as a His-tagged fusion protein (pQ3βHSD) composed of 273 amino acids (calculated molecular mass 28,561 Da). pQ3βHSD was purified by metal chelate affinity chromatography on Ni-NTA. Pregnenolone and other 3β-hydroxypregnanes but not cholesterol were 3β-oxidised by pQ3βHSD when NAD was used as the co-substrate. Testosterone (4-androsten-17β-ol-3-one) was converted to 4-androstene-3,17-dione indicating that the pQ3βHSD has also 17β-dehydrogenase activity. pQ3βHSD was able to reduce 3-keto steroids to their corresponding 3β-hydroxy derivatives when NADH was used as the co-substrate. For comparison, 3βHSD genes were isolated and sequenced from another 6 species of the genus Digitalis. Gene structure and the deduced 3βHSD proteins share a high degree of similarity.

  在毛地黄属植物心脏苷的生物合成过程中，Δ5-3β-羟类固醇脱氢酶(3βHSD，EC 1.1.1.51)将孕烯醇酮转化为异孕酮。从毛地黄叶片中分离出了一个3βHSD基因，该基因由870个核苷酸组成，包含90个核苷酸长度的内含子。通过RT-PCR从同一来源分离出编码3βHSD的全长cDNA克隆。将SphI/KpnI 3βHSD cDNA克隆到pQE30载体中，然后转移到大肠杆菌M15[pREP4]菌株中。3βHSD cDNA被功能性表达为由273个氨基酸组成的His标签融合蛋白(pQ3βHSD，计算分子量28,561 Da)。通过Ni-NTA金属螯合亲和层析纯化pQ3βHSD。当使用NAD作为辅底物时，pQ3βHSD可以将孕烯醇酮和其他3β-羟基孕烷类物质进行3β-氧化，但不能氧化胆固醇。睾酮被转化为雄甾烯二酮，表明pQ3βHSD也具有17β-脱氢酶活性。当使用NADH作为辅底物时，pQ3βHSD能够将3-酮类固醇还原为相应的3β-羟基衍生物。为了比较，从毛地黄属另外6个物种中分离并测序了3βHSD基因。基因结构和推导出的3βHSD蛋白具有高度相似性。
• Palladium-Catalyzed Reaction of Enol Triflates with 1-Alkynes. A New Route to Conjugated Enynes
  作者：Sandro Cacchi、Enrico Morera、Giorgio Ortar

  DOI：10.1055/s-1986-31599

  日期：——

  Cross coupling of enol triflates with 1-alkynes in the presence of a base and bis[triphenylphosphine]-palladium(II) diacetate as catalyst at 60°C affords conjugated enynes in good yields. The addition of copper(I) iodide as co-catalyst allows the reactions to proceed at room temperature.

  在碱和双[三苯基膦]-二乙酸钯（II）作为催化剂的存在下，在 60°C 的温度下，三羟基烯醇与 1-炔的交叉偶联能以良好的收率生成共轭炔。加入碘化铜（I）作为辅助催化剂，可使反应在室温下进行。
• Steroids and Steroidases. XVI. An Evaluation of Synthetic Routes to Variously C-17-Substituted Δ⁵-3-Ketosteroids
  作者：J. Bryan Jones、Keith D. Gordon

  DOI：10.1139/v72-435

  日期：1972.8.15

  Several routes to variously C-17-substituted Δ5-3-ketosteroids have been surveyed. The most convenient method was found to be oxidation of Δ5-3β-alcohol precursors with the Collins reagent, dipyridine chromium trioxide in methylene chloride. The purities of the desired acid- and base-labile compounds obtained were ≥ 99% in each case.

  已经研究了几种不同的 C-17 取代的 Δ5-3-酮类固醇的途径。发现最方便的方法是用柯林斯试剂氧化 Δ5-3β-醇前体，二吡啶三氧化铬在二氯甲烷中。在每种情况下，所获得的所需酸和碱不稳定化合物的纯度均≥ 99%。