化学学报 ›› 1956, Vol. 22 ›› Issue (6): 513-523. 上一篇    下一篇

论文

氮大圜化合物的合成——Ⅱ.1-甲基氮七圜与1-甲基氮八圜的衍生物

陆启荣1,2, F. F. Blicke1,2   

  1. 1. 广州中山大学化学系;
    2. 密歇根大学药学系
  • 投稿日期:1956-08-06 发布日期:2013-06-03

SYNTHESIS OF LARGE-MEMBERED NITROGENOUS RING COMPOUNDS——Ⅱ.DERIVATIVES OF 1-METHYLHEXAMETHYLENIMINE AND 1-METHYLHEPTAMETHYLENIMINE

LU CHI-JUNG1,2, F. F. BLICKE1,2   

  1. 1. Department of Chemistry, Sun Yat-Sen University;
    2. College of Pharmacy, University of Michigan
  • Received:1956-08-06 Published:2013-06-03

1.环己酮与草酸二乙酯起缩合作用,生成物加热失去一氧化碳,生成2-乙氧羰基-环己酮。此酮与叠氮化钠起Schmidt反应,生成2-乙氧羰基-7-酮-氮七圜。此氮七圜用氢化铝锂还原,成2-羟甲基氮七圜。此化合物与三氯甲醛起反应,生成物再用氢化铝锂还原,成1-甲基-2-羟甲基氮七圜。2.1-甲基-2-羟甲基氮七圜的衍生物,皆用通常方法制备,其对氨基苯甲酸酯盐酸盐因刺激性强,未宜作局部麻醉药用。其他化合物药理试验结果未详。3.利用环庚酮为原料,用上述的反应程序,制备1-甲基-2-羟甲基氮八圜。此化合物的衍生物皆可用通常方法制备。其对氮基苯甲酸酯盐酸盐及其二苯基乙酸酯的溴甲烷季铵盐的药理试验结果亦未详。

1. Cyclohexanone was condensed with diethyloxalate to form ethyl 2-ketocyclohexylglyoxylate. This substance lost carbon monoxide, when heated with a mixture of powdered glass and powdered iron, to form 2-carbethoxycyclohexanone. The ester was treated with sodium azide and sulfuric acid (Schmidt reaction).in chloroform solution, and was thereby converted into 2-carbethoxy-7-ketohexamethylenimine. The lactam u}as hydrolyzed to alpha-aminopimelic acid, a known substance, which had been obtained previously by Shecter and Kirk, who hydrolyzed 7-cyano-2-ketohexamethylenimine.