The hydrolysis of acyl derivatives of malonaldehyde dianil was examined. Alkaline hydrolysis of 1-(N-acetyl-p-methylphenylamino)-3-(p-methylphenylimino)-1-propene (V) in aqueous ethanol gave simply 1-(p-methylphenylamino)-3-(p-methylphenylimino)-1-propene (malonaldehyde dianil of p-toluidine) (VI) and acetic acid. Hydrolysis of 1-(N-benzoyl-p-methylphenylamino)-3-(p-methylphenylimino)-1-propene (VII) in aqueous dioxane in the presence of equimolar amounts of acetic acid and sodium acetate gave β-(p-toluidino) acrolein (VIII), β-(N-benzoyl-p-toluidino) acrolein (XIII) and N-benzoyl-p-toluidine. A small amount of β-(p-toluidino) crotonaldehyde (II) was obtained by hydrolysis of 1-(N-benzoyl-p-methylphenylamino)-3-(p-methylphenylimino)-1-butene (IX). The buffer-catalyzed hydrolysis reaction of VII was followed by measuring the PMR spectrum of the reaction solution to elucidate the sequence of the reaction process.
对马隆醛
二苯胺酰衍
生物的
水解进行了研究。在
水结合
乙醇中,对1-(N-乙酰-p-甲基苯基
氨基)-3-(p-甲基苯基
亚胺)-
1-丙烯(V)的碱性
水解简单生成了1-(p-甲基苯基
氨基)-3-(p-甲基苯基
亚胺)-
1-丙烯(p-甲
苯胺的马隆醛
二苯胺)(VI)和
乙酸。在
水合
二氧六环中,在等摩尔的
乙酸和
醋酸钠存在下,
水解1-(N-苯甲酰-p-甲基苯基
氨基)-3-(p-甲基苯基
亚胺)-
1-丙烯(VII)生成了β-(p-
甲苯氨基)
丙烯醛(VIII)、β-(N-苯甲酰-p-
甲苯氨基)
丙烯醛(XIII)和N-苯甲酰-p-甲
苯胺。通过
水解1-(N-苯甲酰-p-甲基苯基
氨基)-3-(p-甲基苯基
亚胺)-1-
丁烯(IX)获得少量β-(p-
甲苯氨基)克罗顿醛(II)。通过测量反应溶液的PMR光谱,跟踪VII的缓冲催化
水解反应,以阐明反应过程的顺序。