3-methoxyestra-1,3,5(10)-triene-16,17-dione 16-oxime | 40822-17-1

• 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: 3-methoxyestra-1,3,5(10)-triene-16,17-dione 16-oxime
• 英文别名: (16-hydroxyiminoestrone-3-methyl ether)；(8R,9S,13S,14S)-16-(hydroxyimino)-3-methoxy-13-methyl-6,7,8,9,11,12,13,14,15,16-decahydro-17H-cyclopenta[a]phenanthren-17-one；NSC 60777；3-Methoxy-oestra-1,3,5(10)-trien-16,17-dion-16-oxim；(8R,9S,13S,14S)-16-hydroxyimino-3-methoxy-13-methyl-6,7,8,9,11,12,14,15-octahydrocyclopenta[a]phenanthren-17-one
• CAS: 40822-17-1
• 化学式: C₁₉H₂₃NO₃
• 分子量: 313.397
• InChiKey: CZHINTJOYWQKED-JEWRLFTDSA-N

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：
  0.58
• 拓扑面积：
  58.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-methoxyestra-1,3,5(10)-triene-16,17-dione 16-oxime 在 四氯化钛 作用下， 以 二氯甲烷 为溶剂， 反应 10.0h， 以73%的产率得到3-methoxy-16,170secoestra-1,3,5(10)-triene-16-nitrile-17-oic acid
  参考文献：
  名称：

  Synthesis of 16,17-seco-steroids with iminomethyl-2-pyridine and aminomethylene-2-pyridine structures as chiral ligands for copper ions and molecular oxygen activation

  摘要：

  Starting from 16-oximino-3-methoxy-estra-1,3,5(10)-trien-17-one, the 16,17-seco-13alpha-carbaldehyde with a 16-nitrile function and its corresponding carboxylic acid have been synthesized via a Beckmann fragmentation. The corresponding 13alpha-amine is available by Curtius degradation of the carboxylic acid. Condensation of the carboxaldehyde with 2(aminomethyl)pyridine and the primary amine with pyridine-2-carboxaldehyde gave the corresponding iminomethyl-2-pyridine and the aminomethylene-2-pyridine compounds. Copper-mediated ligand hydroxylations with molecular oxygen were not successful. Reasons for this are discussed. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(03)00539-1
• 作为产物：
  描述：

  3-甲氧基雌酮 在 potassium tert-butylate 、 亚硝酸异戊酯 作用下， 以 叔丁醇 为溶剂， 以63 %的产率得到3-methoxyestra-1,3,5(10)-triene-16,17-dione 16-oxime
  参考文献：
  名称：

  C-C 键断裂诱导的 C- 至 N-酰基转移用于酰胺的合成

  摘要：

  开发了一种制备酰胺的新方法，使用 C-C 键断裂引发 C- 到 N- 酰基转移，采用活化酮作为酰化试剂和胺亲核试剂。该反应在常用于肽键形成的偶联试剂系统下进行。该方法使得能够在温和条件下使用线性和环状酮底物实际制备酰胺。

  DOI：

  10.1021/acs.orglett.4c01154

文献信息

• Enolate-Based Regioselective Anti-Beckmann C–C Bond Cleavage of Ketones
  作者：Tomáš Mašek、Ullrich Jahn

  DOI：10.1021/acs.joc.1c01169

  日期：2021.9.3

  provides a direct and regioselective way of fragmenting ketones into esters and oximes or ω-hydroxyimino esters, respectively. A comprehensive study of the scope of this reaction with respect to ketone classes and alkyl nitrites is presented. Control over the site of cleavage is gained through regioselective enolate formation by various bases. Oxidation of kinetic enolates of unsymmetrical ketones leads to

  Baeyer-Villiger 或 Beckmann 重排是在酸性条件下裂解酮衍生物的成熟方法，在更多取代的位点选择性地处理不对称前体。然而，断裂区域选择性不能切换，并且在较少取代的末端断裂到目前为止是不可能的。我们在此报告，酮烯醇化物与商业亚硝酸烷基酯的反应提供了一种直接和区域选择性的方式，可将酮分别分解为酯和肟或 ω-羟基亚氨基酯。介绍了该反应在酮类和亚硝酸烷基酯方面的范围的综合研究。通过各种碱基的区域选择性烯醇化物形成获得对切割位点的控制。不对称酮的动力学烯醇化物的氧化导致在较少取代的侧链上无法获得的“反贝克曼”裂解，而相同酮的热力学烯醇化物的裂解代表了 Baeyer-Villiger 氧化或碱性条件下贝克曼重排的替代方法状况。该方法适用于天然产物的转化，并能够获得正交反应性二羰基化合物。
• Synthesis and investigation of the anticancer effects of estrone-16-oxime ethers in vitro
  作者：Ágnes Berényi、Renáta Minorics、Zoltán Iványi、Imre Ocsovszki、Eszter Ducza、Hubert Thole、Josef Messinger、János Wölfling、Gergő Mótyán、Erzsébet Mernyák、Éva Frank、Gyula Schneider、István Zupkó

  DOI：10.1016/j.steroids.2012.10.009

  日期：2013.1

  An expanding body of evidence indicates the possible role of estrane derivatives as useful anticancer agents. The aim of this study was to describe the cytotoxic effects of 63 newly synthetized estrone-16-oxime ethers on human cancer cell lines (cervix carcinoma HeLa, breast carcinoma MCF7 and skin epidermoid carcinoma A431), studied by means of the MTT assay. Four of the most promising compounds were selected for participation in additional experiments in order to characterize the mechanism of action, including cell cycle analysis, morphological study and the 5-bromo-2'-deoxyuridine incorporation assay. The cancer selectivity was tested on a noncancerous fibroblast cell line (MRC-5). Since apoptosis and cell cycle disturbance were observed, caspase-3 activities were further assayed for the two most effective agents. These estrone-16-oxime analogs activated caspase-3 and changed the mRNA level expression of endogenous factors regulating the G1-S phase transition (retinoblastoma protein, CDK4 and p16). The repression of retinoblastoma protein was reinforced at a protein level too. These experimental data lead to the conclusion that estrone-16-oxime ethers may be regarded as potential starting structures for the design of novel anticancer agents. (c) 2012 Elsevier Inc. All rights reserved.
• 377. Experiments on the synthesis of substances related to the sterols. Part XXIII. Formation of oestrone from a dicarboxylic acid obtained by degradation of oestrone methyl ether
  作者：F. Litvan、Robert Robinson

  DOI：10.1039/jr9380001997

  日期：——
• Butenandt; Schaeffler, Zeitschrift fur Naturforschung, 1946, vol. 1, p. 82,85
  作者：Butenandt、Schaeffler

  DOI：——

  日期：——
• DE875656
  申请人：——

  公开号：——

  公开（公告）日：——