有机化学 ›› 1989, Vol. 9 ›› Issue (2): 166-170. 上一篇    下一篇

研究论文

连氨基头孢菌素72位引入烷氧基的温和方法

孙快麟;李润荪   

  1. 国家医药管理局上海医药工业研究院
  • 发布日期:1989-04-25

A mild method of introducing 7α-alkoxy in cephalosporins

SUN KUAILIN;LI RUNSUN   

  • Published:1989-04-25

笔者曾在合成青霉素的过程开发了在连氯基青霉素上引入6α烷氧基的方法. 本文运用这一方法于头孢菌素系列在7α位引入烷氧基, 连氮基头孢菌素, 由于硝基的强吸电子性, 使共轭链的电子云向其偏移, 在C7位形成缺电子中心, 这样低级烷氧基可以相应的醇在温和条件下在质子酸存在下立体选择性地引入C-7α位, 叔丁醇和C74的高级醇不起反应. 运用这一方法合成了12个7α-烷氧基-7β-腙头孢菌素二苯甲酯衍生物, 并用UV, IR, 质子磁共振和质谱鉴定了它们的结构.

关键词: 紫外分光光度法, 烷氧基, 红外分光光度法, 质谱法, 质子磁共振谱法, 一元醇, 头孢霉素, 烷氧化反应

A mild method of introducing 7a-alkoxy in cephalosporins was developed. An electrophilic center was formed at the C-7 position of 7-substituted-azino-cephalosporins with the help of a nitro group via the conjugated system. The lower alkoxy groups (including C1-C3 alkyl and Bu) were stereoselectively introduced into the C-7a position under mild conditions from the corresponding alcs., in the presence of protic acids. tert-Bu alcohol and its higher homologs do not react. Twelve new benzyhydryl esters of 7a-alkoxy-7b-hydrazonocephalosporins I (R = H, OAc, methyltetrazolylthio; R1 = nitrophenyl, nitrothienyl, nitrofuryl; R2 = Me, Et, Pr, Me2CH, Bu) were synthesized, the structures of which were identified with UV, IR, 1H NMR and mass spectra.

Key words: ULTRAVIOLET SPECTROPHOTOMETRY, ALKOXYL GROUP, INFRARED SPECTROPHOTOMETRY, MASS SPECTROGRAPHY, PROTON MAGNETIC RESONANCE SPECTROMETRY, MONOHYDRIC ALCOHOL, CEPHALOSPORINS

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