期刊文献+

甾体-17-酮肟的Beckmann裂解反应研究

Study on Beckmann Fragmentation of Steroid-17-One Oximes
下载PDF
导出
摘要 研究了甾体-17-酮肟(1a^1i)在PCl5/2,6-二甲基吡啶/CH2Cl2体系中的Beckmann裂解反应。反应得到的烯-腈化合物(2a^2i)是18-去甲基甾体的重要中间体,其结构经1HNMR,IR,MS和元素分析表征。实验结果表明,1的取代基和构型对反应结果没有明显影响。 Beckmann Fragmentation of Steroid-17-One Oximes were studied in CH2Cl2 homogeneous solution of the reagent PCl5/2,6-lutidine to give the corresponding alkylene-nitrile compounds(2a^2i).2 were key intermediates of preparation 18-norsteroids.The structures of 2 were characterized by 1H NMR,IR,MS and elemental analysis.The experimental results showed that effect of substituents and stereochemistry on the Beckmann fragmentation was not observed.
出处 《合成化学》 CAS CSCD 北大核心 2010年第5期626-628,632,共4页 Chinese Journal of Synthetic Chemistry
基金 江苏省高校自然科学基金资助项目(05KJB-150039)
关键词 甾体-17-酮肟 Beckmann裂解反应 18-去甲基甾体 合成 steroid-17-one oxime Beckmann fragmentation 18-norsteroid synthesis
  • 相关文献

参考文献14

  • 1Fieser L, Fieser M. Steroids [ M ]. Reinhold Publication Corporation, New York, 1959.
  • 2Jiang X, Wang J, Hu J, et al. Synthesis of (5α)-17- azaandrostan-3-ols and ( 5α )-17-aza-D-homoandrostan-3-ols and their N-acylated derivatives [ J ]. Steroids, 2001, 66: 655 - 662.
  • 3Covey D, Han M, Kumar A S, et al. Neurosteroid analogues. 8. Structure-activity studies of N-acylated 17a- aza-D-homosteroid analogues of the anesthetic steroids (3α, 5α ) - and ( 3α, 5α ) -3-hydroxypregnan-20-one [ J]. J Med Chem ,2000 ,43 (17) :3201 - 3204.
  • 4Verma A K, Lee C Y, Habtemariam S, et al. Synthesis and biological activity of 17-azasteroidal neuromuscular-blocking agents [ J ]. Eur J Med Chem, 1994,29 (5) :331 -338.
  • 5Singh H, Paul D J. Steroids and related studies. Part XXV. Chandonium iodide ( 17a-methyl-3β-pyrrolidino- 17a-aza-D-homoandrost-5-ene dimethiodide) and other quaternary ammonimn steroid analogues [ J ]. Chem Soc, Perkin Trans 1,1974 : 1475 - 1479.
  • 6Abraham J, Jindal D P, Singh H, et at. Steroids and related studies:Part 90 -- certain new azasteroidal bisquatemary neuromuscular blockers [ J ]. Eur J Med Chem,1993,28(3) :231 -234.
  • 7Gandiha A, Marshall I. G. , Paul D, et al. Neuromuscular and other blocking actions of a new series of mono and bisquaternary aza steroids [ J ]. J Pharm Pharmacol, 1974,26 ( 11 ) : 871 - 877.
  • 8Schoneeker A X, Lange C, Kotteritzsch, M, et al. Conformational design for 13α-steroids [ J ]. J Org Chem ,2000 ,65 (18) :5487 - 5497.
  • 9Anderson A, Boyd A C, Clark J K, et al. Conformationally constrained anesthetic steroids that modulate GABAA receptors [ J ]. J Med Chem, 2000,43 (22) : 4118 -4125.
  • 10Andre A F St, Macphillary H B, Nelson J A, et al. Direct introduction of oxygen into the steroid nucleus [ J ]. J Am Chem Soc, 1952,74 : 5506 - 5511.

二级参考文献24

  • 1Miescher W. Uber cyclopentan-1,3-dione und isomere enol-lactone. 3. Mitteilung. Butanoliden-y-essigstiure ( 5- oxo-tetrahydrofuryliden-(2) -essigsaure [ J ]. Helv Chim Acta, 1950,33( 1 ) :20 -23.
  • 2Acldin W, Prelog V. Reaktionen mit mikroorganismen. 9. Mitteilung. Die bestimmung der absoluten konfigura-don von 8-methyl-hydrindan-derivaten durch asymmetrische synthese. Fine intramolekulare 1,5-hydrid-verschiebung in der cis-hydrindan-reihe [ J ]. Helv Chim Acta, 1959,42(4) : 1239 - 1247.
  • 3Boyce C B C, Whitehurst J S. Some preliminary synthetical studies with 5,6,7,8-tetrahydro-8-methylin- dane-1,5-dione[ J ]. J Chem Soc, 1960:4547 -4553.
  • 4Hajos Z G, Parrish D G. ( + )-(7aS)-7a-methyl-2, 3,7,7a-tetrahydro-1H-indene-1, 5-(6H) -dione [ J ]. Org Synth, 1985,63:363 - 368.
  • 5Harrison C A, Leineweber R, Moody C J, et al. Synthesis of cyclopent-bindoles by formal [3 + 2]-addition of indolylmethyl cations to alkenes [ J ]. Tetrahedron Lett, 1993,34(52) :8527 - 8530.
  • 6Hagiwara H, Sakai H, Uchiyama T, et al. The first enantioselective total synthesis of eyelomyhaylane-5-ol and determination of its absolute stereochemistry [ J ]. J Chem Soe Perkin Trans 1,2002, (5) :583 - 591.
  • 7Yang Z, Shannon D, Truong V L, et al. Studies directed toward asymmetric synthesis of eardioactive steroids via anionic polycyclization[J]. Org Lett,2002,4 : 4693 - 4696.
  • 8Lepage O, Stone C, Deslongehamps P. Nazarov reagents for convergent and expedient synthesis of new steroids[J]. Org Lett,2002,4:1091 - 1094.
  • 9Lajunen M, Koskinen A. Hajos-parrish ketone: approaches toward C-ring precursors of 7-deoxytaxol[ J]. J Chem Soc Perkins Trans 1,2000, (9) :1439 -1443.
  • 10Daniewski A R, Liu W. A novel silylcopper catalyst for the reductive bromination of Hajos dione. Improved preparation of a CD synthon for the synthesis of vitamin D[ J]. J Org Chem,2001,66:626 - 628.

共引文献1

相关作者

内容加载中请稍等...

相关机构

内容加载中请稍等...

相关主题

内容加载中请稍等...

浏览历史

内容加载中请稍等...
;
使用帮助 返回顶部