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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)。
Mannich reaction of 1-carbonyl-1,2,3,4-tetrahydrophenanthrene (I) with diethanolamine hydrochloride and 36% aqueous formaldehyde in 95% ethanol gave the Mannich base 1-carbonyl-2- [N -bis (β-hydroxyethyl) -aminomethylene] -1,2,3,4-tetrahydrophenanthrene (II), a small amount of 1-carbonyl-2-methyne-1 , 2,3,4-tetrahydrophenanthrene (III) and its dimer (V). If this reaction is carried out in absolute ethanol, Mannich base (II) is predominantly formed within three hours. If the reaction time is extended to more than 20 hours, 主 the main product obtained dimer (Ⅴ). The reaction, if carried out in isoamyl alcohol, also produces a larger amount of by-product (V) in about an hour or so. Compound (II) is very unstable, slightly lost in the methanol - aqueous solution of the amine group was formed Ⅲ. Ⅲ in benzene was hydrogenated to 1-carbonyl-2-methyl-1,2,3,4-tetrahydrophenanthrene (IV) with 5% palladium on carbon as catalyst. The dimer (V) of III and hydroxylamine hydrochloride do not form an oxime. Ⅰ and paraformaldehyde are condensed under the action of sodium ethoxide to form 2,2’-methine-bis (1-carbonyl-1,2,3,4-tetrahydrophenanthrene) (VI) Ⅴ different. Ⅰ with nitrogen mustard hydrochloride and 36% aqueous formaldehyde in ethanol to produce 1-carbonyl-2- [N-bis (β-chloroethyl) -aminomethylene] -1,2,3,4-tetrakis Hydropic acid hydrochloride, whereby the corresponding free amine (VII) is obtained.