氯化亚锡还原法合成4′-氨基黄体酮类苯亚甲基衍生物

doi:10.3724/SP.J.1095.2014.30351

摘要/Abstract

摘要： 以黄体酮为原料，合成了4′-硝基苯亚甲基衍生物3,将其在SnCl2·2H2O/HCl体系中还原后得4′-氨基苯亚甲基衍生物4。还原时以乙酸乙酯为溶剂，还原剂SnCl2为底物5倍化学计量时产率达74%，为甾类氨基衍生物的合成提供了一种便利方法。

关键词: 黄体酮, 苯亚甲基甾体衍生物, 氯化亚锡

Abstract: The 4′-nitrobenzylidene derivative 3 prepared from progesterone was reduced by SnCl2·2H2O/HCl to obtain 4′-aminobenzylidene derivative 4. When ethyl acetate was used as the solvent and five equivalents of SnCl2 was used as the reducing agent, the yield was up to 74%, which provides a convenient route to synthesize amino-modified steroidal derivatives.

Key words: progesterone, benzylidene steroidal derivatives, tin(Ⅱ) chloride

中图分类号:

O625

范宁娟, 王长如, 汤江江, 高锦明. 氯化亚锡还原法合成4′-氨基黄体酮类苯亚甲基衍生物[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30351.

FAN Ningjuan, WANG Changru, TANG Jiangjiang*, GAO Jinming. Synthesis of 4′-Aminobenzylidene Derivative of Progesterone with Tin(II) Chloride as Reducing Agent[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30351.

参考文献

[1] Poirier D,Chang H J,Azzi A,et al. Estrone and Estradiol C-16 Derivatives as Inhibitors of Type 1 17β-Hydroxysteroid Dehydrogenase[J]. Mol Cell Endocrinol,2006,248(1/2):236-238.

[2] Banday A H,Zargar M I,Ganaie B A. Synthesis and Antimicrobial Studies of Chalconyl Pregnenolones[J]. Steroids,2011,76(12):1358-1362.

[3] Kakati D,Sarma R K,Saikia R,et al. Rapid Microwave Assisted Synthesis and Antimicrobial Bioevaluation of Novel Steroidal Chalcones[J]. Steroids,2013,78(3):321-326.

[4] Chattopadhaya R,Jindal D P,Minu M,et al. Synthesis and Cytotoxic Studies of Hydroximino Derivatives of Some 16-E-Arylidenosteroids[J]. Arzneim-Forsch/Drug Res,2004,54(9):456-466.

[5] Dubey S,Piplani P,Jindal D P. Synthesis and In Vitro Antineoplastic Evaluation of Certain 16-(4-Substituted Benzylidene) Derivatives of Androst-5-ene[J]. Chem Biodivers,2004,1(10):1529-1536.

[6] Shan L H,Liu H M,Huang K X,et al. Synthesis of 3β,7α,11α-Trihydroxy-pregn-21-benzylidene-5-en-20-one Derivatives and Their Cytotoxic Activities[J]. Bioorg Med Chem Lett,2009,19(23):6637-6639.

[7] Khuri N,Usubillaga A,Vaz S C,et al. Synthesis, Stereochemical Analysis, and Neuromuscular Blocking Activity of Oximino Ether Derivatives of Progesterone[J]. J Pharm Sci,1991,80(7):661-664.

[8] Abdelhamid A O,Mervat M A,Gamal A E. New Routes to Steroidal Heterocyclic Derivatives: Synthesis of Biologically Active Pyrazolyl- and Isoxazolylpregnene Derivatives[J]. J Heterocycl Chem,2007,44(1):7-11.

[9] MacNevin C J,Atif F,Sayeed I,et al. Development and Screening of Water-soluble Analogues of Progesterone and Allopregnanolone in Models of Brain Injury[J]. J Med Chem,2009,52(19):6012-6023.

[10] Mohareb R M,Elmegeed G A,Baiuomy A R,et al. Evaluation of Anti-inflammatory, Anti-nociceptive, and Anti-ulcerogenic Activities of Novel Synthesized Thiazolyl and Pyrrolyl Steroids[J]. Arch Pharm Chem Life Sci,2011,344(10):595-604.

[11] Jin C S,Roh J S,Sun W S,et al. N-Benzylbenzamides:A New Class of Potent Tyrosinase Inhibitors[J]. Bioorg Med Chem Lett,2006,16(10):2682-2684.

[12] Ren J,Wang Y C,Wang J L,et al. Synthesis and Antitumor Activity of N-Sulfonyl-3,7-dioxo-5β-cholan-24-amides, Ursodeoxycholic Acid Derivatives[J]. Steroids,2013,78(1):53-58.

[13] Khan K M,Saeed S,Ali M,et al. Unsymmetrically Disubstituted Urea Derivatives:a Potent Class of Antiglycating Agents[J]. Bioorg Med Chem,2009,17(15):2447-2451.

[14] Fan N J,Bai Y B,Zhang F Y,et al. Synthesis and Cytotoxicity Of Some Novel 21E-Benzylidene Steroidal Derivatives[J]. Steroids,2013,78(9):874-879.

[15] Ono M,Haratake M,Mori H,et al. Novel Chalcones as Probes for In Vivo Imaging of β-Amyloidplaques in Alzheimer′s Brains[J]. Bioorg Med Chem,2007,15(21):6802-6809.

[16] Sonmez F,Sevmezler S,Atahan A,et al. Evaluation of New Chalcone Derivatives as Polyphenol Oxidase Inhibitors[J]. Bioorg Med Chem Lett,2011,21(24):7479-7482.

[17] VanVliet D S,Gillespie P,Scicinski J J. Rapid One-pot Preparation of 2-Substituted Benzimidazoles from 2-Nitroanilines Using Microwave Conditions[J]. Tetrahedron Lett,2005,46(39):6741-6743.