N,N′,N″,N'''-四对甲苯磺酰1,4,7,10-四氮杂环十二烷的微波常压快速水解

A Rapid Detosylation of N,N′,N″,■-Tetra(p-tosyl)-1,4,7,10-tetraaza- cyclododecane under Microwave Irradiation and Normal Pressure

N ,N′ ,N″ ,N 四对甲苯磺酰 1,4,7,10 四氮杂环十二烷是Atkins法合成 1,4,7,10 四氮杂环十二烷的关键中间体 ,但其水解脱磺酰基比较困难 ,常规水解一般需要采用 96%～ 98%硫酸在 14 0℃左右加热 2～ 3d .报道了一种微波促进快速水解法 ,即在稍加改装或未改装的家用微波炉中 ,采用 95 %～ 98%硫酸 ,控制火力 2～ 5档 ,全对甲苯磺酰化全氮冠醚仅需5 0～ 12 0s即可完成水解 ,比常规加热水解所需时间缩短约 3 0 0 0～ 80 0 0倍 ,浓硫酸用量也比常规加热水解少 ,收率较常规水解高 .

An efficient and rapid detosylation of N,N′,N″,N-tetra(p-tosyl)-1,4,7,10-tetraazacyclododecane, the key intermediates in Atikins' route for preparing 1,4,7,10-tetraazacyclododecane, has been investigated by hydrolysis in concentrated sulfuric acid under microwave irradiation condition in a simply refitted domestic microwave oven equipped with an electromagnetic stirrer and a refluxing condenser. The results indicated that the hydrolysis and detosylation of poly(p-tosyl) compounds were completed within 50 ～120 s in 95%～98% sulfuric acid under the irradiation power of 75～375 W. In comparison with the common hydrolysis which was completed for 2～3 d at 140 ℃ in 96%～98% sulfuric acid, the microwave irradiation accelerated (MIA) hydrolysis is rather rapid.