15α-androstane-16-one | 1032-16-2

• 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: 15α-androstane-16-one
• 英文别名: 5α-androstan-16-one；16-androstanone；5α-Androstanon-(16)；5α-Androstan-16-on；5alpha-Androstan-16-one；(5R,8S,9S,10S,13R,14S)-10,13-dimethyl-1,2,3,4,5,6,7,8,9,11,12,14,15,17-tetradecahydrocyclopenta[a]phenanthren-16-one
• CAS: 1032-16-2
• 化学式: C₁₉H₃₀O
• 分子量: 274.447
• InChiKey: UYNXNPZDSGEDON-XFMWHNAVSA-N

物化性质

• 保留指数：
  1930;1942

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.95
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  15α-androstane-16-one 在 溶剂黄146 、 三氯氧磷 作用下， 以 吡啶 、 乙醇 为溶剂， 反应 23.0h， 生成 16-acetyl-5α-androst-16-ene
  参考文献：
  名称：

  Synthesis of steroidal D-ring fused pyrazolines: Study of regiochemistry of addition

  摘要：

  The addition of diphenylnitrilimine and C-o-chlorodiphenylnitrilimine to 3 beta-hydroxyandrost-5,16-diene (3b) produced a 1/1 ratio of regioisomeric, 1,3-diaryl-2-pyrazolines (6a, 7a and 6b, 7b), whereas the addition of N-o-chlorodiphenylnitrilimine gave a 5/1 ratio in favor of the [17 alpha,16 alpha-d] regioisomer (7c). To further delineate the factors governing the regiochemistry of addition of diphenylnitrilimines to steroid 16-enes, additions were carried out on 16-acetyl-5 alpha-androst-16-ene (5b) and 1-acetylcyclopentene (10).

  DOI：

  10.1016/0039-128x(94)90061-2
• 作为产物：
  描述：

  17-iodo-androst-16-ene 在 4-硝基过氧化苯甲酸 、 乙醇 、 锌 作用下， 生成 15α-androstane-16-one
  参考文献：
  名称：

  羟基类固醇。第十八部分。17β-氯-16α，17α-环氧-5α-雄甾烷的反应及17β-碘-16α，17α-环氧-5α-雄甾烷的制备

  摘要：

  17β-氯-和17β-碘-16α，17α-环氧-5α-雄甾烷是反应性化合物，它们容易重新排列为16-卤素-17-酮。用氯化铝处理后，氯代环氧化合物发生甲基迁移，以82％的收率得到17-甲基-18-nor-5α-androst-13（17）-en-16-one。通过在苯中用过氧月桂酸氧化17-碘5α-雄甾16-烯可以最好地获得不稳定的碘化环氧化物（22％的收率）。

  DOI：

  10.1039/p19720000486

文献信息

• Studies in the steroid group. Part LXXX. Preparation of 2- and 16-oxo-, and 3,16- and 2,16-dioxo-5α-androstane, and 2-oxo-5α-cholestane
  作者：J. E. Bridgeman、C. E. Butchers、Ewart R. H. Jones、A. Kasal、G. D. Meakins、P. D. Woodgate

  DOI：10.1039/j39700000244

  日期：——

  16-Oxo-5α-androstanes are readily obtained from the 17-ketones in three stages, viz., condensation with benzaldehyde to 16-benzylidene-17-ketones, reduction with lithium aluminium hydride–aluminium chloride to 16-benzylidene-androstanes, and ozonolysis. This sequence is not suitable for the 3 → 2 transposition of oxo-groups in ring-A. Here the 2-arylidene-6-ketones are reduced with sodium borohydride

  从17个酮中分三个阶段即可轻松获得16-Oxo-5α-雄甾烷。，与苯甲醛缩合为16-亚苄基17-酮，氢化铝锂-氯化铝还原为16-亚苄基-雄烷二酮，并进行臭氧分解。此序列不适用于环A中3 → 2的氧代基团的转座。此处，将2-亚芳基-6-酮用硼氢化钠还原并在臭氧分解之前被乙酰化：通过用锌和乙酸还原除去3β-乙酰氧基-2-酮的乙酰氧基。
• REPLACEMENT OF A CARBONYL GROUP OF CYCLIC KETONES BY A SULFUR OR A NITROGEN ATOM. A NEW METHOD FOR TRANSFORMAT OF STEROIDAL KETONES INTO THIA- OR AZASTEROIDS
  作者：Hiroshi Suginome、Shinji Yamada

  DOI：10.1246/cl.1984.2079

  日期：1984.12.5

  We describe a new and versatile method for transforming cyclic ketones into cyclic sulfides or cyclic amines with the same ring size via five-step procedure. The transformation is stereospecific with regard to the chiral center adjacent to the carbonyl group of the ketones.

  我们描述了一种新的通用方法，通过五步程序将环酮转化为具有相同环大小的环硫化物或环胺。该转化对于与酮的羰基相邻的手性中心是立体有择的。
• Deoxygenation of Steroidal Ring-D 16,17-Ketols with Timethylsilyl Iodide.
  作者：Masao NAGAOKA、Etsuko NAGASAWA、Mitsuteru NUMAZAWA

  DOI：10.1248/cpb.46.1857

  日期：——

  Reaction of various steroidal 16, 17-ketols, 16α-hydroxy-17-ketones 1-3, and 15, 16β-hydroxy-17-ketone 4, and 17β-hydroxy-16-ketones 5-7, and 17, along with methyl ethers of 16α- and 17β-ketols, 1 and 5, with an excess of trimethylsilyl iodide (TMSI) or with HI in CHCl3, produced the deoxygenated products, a mixture of the corresponding 17-and 16-ketones, in low to quantitative yields, in which the 17-ketone was the major product in each case. When the 16β-deuterated 16α-ketol 3 and the 17α-deuterated 17β-ketol 7 were reached with TMSI for a brief period (15 min), the deuterium content at C-16β and C-17α of the recovered steroids 3 and 7 was reduced by 17 and 35%, respectively. The present results indicate that the deoxygenation proceeds not only through a direct iodination pathway producing α-iodoketone but also through other reaction pathways.

  各种类固醇16,17-酮醇、16α-羟基-17-酮1-3、15,16-羟基-17-酮4，以及17β-羟基-16-酮5-7和17的反应，以及16α-和17β-酮醇的甲醚1和5与过量的三甲基硅基碘(TMSI)或HI在氯仿中的反应，产生脱氧产物，即相应的17-和16-酮的混合物，产量从低到定量不等，其中17-酮是每种情况下的主要产物。当16β-氘化的16α-酮醇3和17α-氘化的17β-酮醇7与TMSI短暂接触（15分钟），恢复的类固醇3和7中的C-16β和C-17α位的氘含量分别减少了17%和35%。当前结果表明，脱氧过程不仅通过直接碘化途径生成α-碘酮，还通过其他反应途径。
• Microbiological hydroxylation of steroids. Part IV. The pattern of dihydroxylation of mono-oxygenated 5α-androstanes with cultures of the fungus Calonectria decora
  作者：A. M. Bell、P. C. Cherry、I. M. Clark、W. A. Denny、Ewart R. H. Jones、G. D. Meakins、P. D. Woodgate

  DOI：10.1039/p19720002081

  日期：——

  concerned with the relation between the pattern of the dihydroxylation by Calonectria decora of mono-oxygenated 5α-androstane derivatives (mainly ketones), and the position of the oxygen function in the substrate. Terminal ring ketones (3, 4, 16, and 17) are converted, in useful yields, into one or two dihydroxy-ketones. (Ring B and C ketones are much less satisfactory as substrates.) The structures of most

  该工作涉及单加氧的5α-雄烷衍生物（主要是酮）的Calonectria decora的二羟基化的图案与底物中的氧官能团的位置之间的关系。将末端环酮（3、4、16和17）以有用的产率转化为一个或两个二羟基酮。（环丁酮和丙环酮作为底物要令人满意的多。）大多数产品的结构是通过光谱研究得出的。必要时通过化学相关性对这种方法进行补充
• Mechanistic Studies of Deoxygenation of Steroidal Ring-D 16,17-Ketols with Trimethylsilyl Iodide.
  作者：Masao NAGAOKA、Etsuko NAGASAWA、Sadao SATO、Mitsuteru NUMAZAWA

  DOI：10.1248/cpb.47.548

  日期：——

  Deoxygenation reaction of steroidal 16, 17-ketols 1, 2 and 6 as well as their silyl ethers 3 and 7 and 16- and 17-iodoketone analogs 11, 12, and 14 with trimethylsilyl iodide (TMSI) or HI under various conditions was examined. The results indicate that the deoxygenation producing 16- and 17-ketones 9 and 8 proceeds through multiple reaction pathways; a direct iodination of a siloxy group of the ketol silyl ethers by iodide ion to give the iodoketones (path b), addition of TMSI to a carbonyl group of the ketol silyl ethers to yield diiodo derivatives 22 and 23 through iodo-bis-TMS compounds 20 and 21 (path a), and cleavage of ether bond of dimers 15-18 initially produced are, at least, involved. In these sequences, rearrangement of the 16-ketols 1 and 2 to the 17β-ketol 6 also plays a significant role. The yields of the ketones 9 and 8 and their relative amounts would be dependent on the relative importance of each pathway in the reaction.

  研究了甾族16、17-酮醇1、2和6及其甲硅烷基醚3和7以及16-和17-碘酮类似物11、12和14与三甲基碘硅烷(TMSI)或HI在各种条件下的脱氧反应。结果表明，脱氧生成16-和17-酮9和8是通过多种反应途径进行的；通过碘离子直接碘化酮醇甲硅烷基醚的甲硅烷氧基，得到碘酮（路径b），将TMSI加成到酮醇甲硅烷基醚的羰基上，通过碘-双-TMS化合物生成二碘代衍生物22和23 20和21(路径a)，并且至少涉及最初产生的二聚体15-18的醚键的断裂。在这些序列中，16-酮醇 1 和 2 重排为 17β-酮醇 6 也发挥着重要作用。酮9和8的产率及其相对量将取决于反应中每个途径的相对重要性。