合成精胺盐酸盐的新方法

A new method to prepare spermine

以糖精为原料合成精胺。用1,4-二氯丁烷将糖精烃基化,然后将所碍烃基化产物1,6-二(邻酰基苯磺酰基)-1,6-二氮杂已烷(Ⅰ)在碱性条件下水解得到1,6-二(邻-羟基甲酰基苯磺酰基)-1,6-二氮杂己烷(Ⅱ),(Ⅱ)再与丙烯腈进行Michael加成反应,生成4,9-二(邻-羟基甲酰基苯磺酰基)-4,9-二氮杂十二二腈(Ⅲ),在双催化剂(Raney Ni-Pd／C)存在下使用催化加氢生成5,10-二(邻-羟基甲酰基苯磺酰基)-1,5,10,14-四氮杂十四烷(Ⅳ),后者在盐酸中水解生成精胺盐酸盐(Ⅴ),总收率达到26％。

A new method for preparing spermine from saccharin is presented. Saccharin was alkylated by 1,4-dichlorobu-tane obtaining 1,6-bis(o-acyl-benzenesulfonyl)-l,6-diazahexane (I) which is hydrolyzed in alkaline aqueous solution and 1,6-bis((o-hydroxylformyl)-benzenesulfonyl)-l,6-diazahexane (II) was obtained. Compound (II) reacted with acrylonitrile in the presence of sodium hydroxide resulting in 4,9-bis(o-hydroxylformyl)-benzenesulfonyl)-4,9-diazalaurodinitrile (III), by which 5,10-bis((o-hydroxylformyl) -benzenesulfonyl)-l,5,10,14-tetraazatetradecane (IV) was obtained by hydrogenating with Raney Ni and Pd-charcoal as catalyst. Spermine tetrahydrochloride(V) was produced by hydrolysis of compound (IV) in hydrochloric acid. The yield of spermine tetrahydrochloride is higher than 26%.