化学学报 ›› 1957, Vol. 23 ›› Issue (5): 391-404. 上一篇    下一篇

论文

喹唑啉类杂环化合物的化学Ⅱ.喹唑酮-4的氧化反应

蔣明謙, 李鈞   

  1. 北京医学院药学系
  • 投稿日期:1957-05-28 发布日期:2013-06-03

CHEMISTRY OF THE QUINAZOUNE SERIES Ⅱ. OXIDATION OF QUINAZOLONE-4

Chiang Ming-Chien(M. C. Chiang), Li Chun   

  1. Department of Pharmacy, Peking Medical College
  • Received:1957-05-28 Published:2013-06-03

喹唑酮在冰醋酸中与三氧化铬作用,形成喹唑酮铬酸盐(Ⅰ);在中性或硷性溶液中与高锰酸钾作用,形成喹唑酮草酸盐(Ⅲ),但在酸性溶液中与高锰酸钾作用,则形成2,4-二羟基喹唑啉(Ⅱ)。以过氧化氢在冰醋酸或醋酸酐中与喹唑酮作用,分离出N1,N3-二氧化喹唑酮(Ⅳ),2,4,6-三羟基喹唑啉(Ⅴ),N-甲酰隣硝基苯甲酰胺(Ⅵ),隣硝基苯甲酰胺(Ⅶ)及苯甲酸(Ⅷ)等化合物。这些氧化产物的相对产量,随反应条件不同而有很大的差别。在较强烈的条件下,主要产物为氧化程度较高的衍化物(Ⅵ-Ⅷ);而在较温和的条件下,则主要产物为氧化程度较浅的化合物(Ⅳ-Ⅵ)。以过氧化苯甲酸在氯仿中与喹唑酮作用,则只分离出IV。N1,N3-二氧化喹唑酮在醋酸中以碘化钾脱氧得到喹唑酮;在醋酸中重排为2,4,6-三羟基喹唑啉;在冰醋酸中与过氧化氢进一步反应,则得隣硝基苯甲酰胺。2,4,6-三羟基喹唑啉与醋酸酐作用,可得2,4二羟基-6-乙酰氧基喹唑啉,后者水解又得到三羟基喹唑啉。2,4,6-三羟基喹唑啉与五氯化磷在三氯氧磷中作用,即氯化为2,4,6-三氯喹唑啉,后者水解则得到2,4-二羟基6-氯喹唑啉。N-甲酰隣硝基苯甲酰胺与沸水,冷碳酸氢钠水溶液或湿吡啶作用,则水解为隣硝基苯甲酰胺及甲酸。

In this work the oxidation reactions of quinazolone-4 with chromic acid, potassium permanganate, peracetic acid, and perbenzoic acid have been studied.When quinazolone was heated with chromic anhydride in glacial acetic acid, quinazolone chromate(Ⅰ) was isolated as previously reported in literature.Oxidation of quinazolone with potassium permanganate in neutral or alkaline solutions gave quinazolone oxalate (Ⅲ) and with the same reagent in acidic solutions produced benzoylene urea (2,4-dihydroxyquinazoline, Ⅱ).Carbon dioxide and ammonia were always liberated in these experiments, but no other oxidation product was isolated.