化学学报 ›› 1965, Vol. 31 ›› Issue (3): 211-217. 上一篇    下一篇

论文

多环氮芥化合物的研究——Ⅰ.1-羰基-2[N-双(β-取代乙基)-氨次甲基]-1, 2, 3, 4-四氢菲的合成

褚季瑜, 張錦   

  1. 北京大学化学系
  • 收稿日期:1964-06-22 出版日期:1965-06-15 发布日期:2013-06-03

STUDIES ON NITROGEN MUSTARDS OF POLYCYCLIC COMPOUNDS Ⅰ. PREPARATION OF 1-KETO-2-[N-BIS(β-SUBSTITUTED ETHYL)-AMINOMETHYLENE]-1, 2, 3, 4-TETRAHYDROPHENANTHRENE

CHU CHI-YU, CHANG CHIN   

  1. Department of Chemistry, Peking University
  • Received:1964-06-22 Online:1965-06-15 Published:2013-06-03

1-羰基-1,2,3,4-四氢菲(Ⅰ)与二乙醇胺盐酸盐及36%甲醛水溶液在95%乙醇中进行Mannich反应,除得到Mannich碱1-羰基-2-[N-双(β-羟乙基)-氨次甲基]-1,2,3,4-四氢菲盐酸盐(Ⅱ)外,还得到少量的1-羰基-2-次甲基-1,2,3,4-四氢菲(Ⅲ)及其二聚物(Ⅴ)。此反应若在无水乙醇中进行,三小时内主要生成Mannich碱(Ⅱ)。反应时间若延长至廿小时以上,剐所得主要产物为二聚物(Ⅴ)。反应若在异戊醇中进行,虽仅一小时左右,亦生成较大量的副产物(Ⅴ)。化合物(Ⅱ)极不稳定,在甲醇-水溶液中稍热即失去胺基而成Ⅲ。Ⅲ在苯溶液中,以5%鈀-炭为催化剂,很顺利地氢化成1-羰基-2-甲基-1,2,3,4-四氢菲(Ⅳ)。Ⅲ的二聚物(Ⅴ)与羟氨盐酸盐不形成肟。Ⅰ与多聚甲醛在乙醇钠催化作用下缩合,形成2,2'-次甲基-双(1-羰基-1,2,3,4-四氢菲)(Ⅵ),此物经证明与Ⅴ有区别。Ⅰ与氮芥盐酸盐及36%甲醛水溶液在乙醇中反应生成1-羰基-2-[N-双(β-氯乙基)-氨次甲基]-1,2,3,4-四氢菲盐酸盐,由此可得相应的游离胺(Ⅶ)。

When the Mannich reaction between 1-keto-1,2,3,4-tetrahydrophenanthrene (Ⅰ),diethanolamine hydrochloride and 36% aqueous solution of formaldehyde was carried out in 95% ethanol solution,three products were isolated.The main one is the hydrochloride of 1-keto-2-[N-bis (β-hydroxyethyl)-aminomethylene]-1,2,3,4-tetrahydrophenanthrene (Ⅱ),and two nitrogen-free by-products,namely 1-keto-2-methylene-1,2,3,4-tetrahydrophenan-threne (Ⅲ) and its dimer (Ⅴ).