亚氨基芪的合成及氯甲酰基保护基脱除新工艺

对在基因工程，材料学等方面有应用的重要合成原料亚氨基芪的合成工艺进行了新的探索。以亚氨基二苄为原料，在甲苯中和三光气回流反应10h，得到酰氯亚氨基二苄，然后经溴化，脱溴化氢得到亚氨基芪甲酰氯，最后在异丙醇的氢氧化钠溶液中脱保护，高收率得到亚氨基芪，各步反应的最佳反应条件和收率(反应温度，反应时间，摩尔收率)分别为，酰氯化： 110℃, 10 h, 93.0%; 溴化、脱溴化氢：100℃, 2h而后130℃, 5h, 88.0%; 脱保护： 40℃, 3h, 98.2%，三步总收率达到80.4%。标题化合物通过¹H NMR确证结构，同时研究了酰氯作为保护基团脱去的较佳工艺条件和酰氯作为保护基保护胺基的应用。

Novel synthesis process of 5H-dibenz[b,f]azepine and removal of chloroformyl protection group

A novel synthesis process of 5H-dibenz［b,f］azepine was studied.It is an important intermediate of 5H-dibenz［b,f］azepine-5-carboxamide, used in genetic engineering, materials science and so on.With 10,11-dihydro-5H-dibenz［b,f］azepine as raw material, 5-chloroformyl-5H-dibenz［b,f］azepine was prepared by reflux with triphosgene in toluene, brominated with bromine in chlorobenzene, and dehydrobrominated at 130℃, finally, the title compound was obtained by removing chloroformyl group with NaOH in isopropanol with 80.4% overall yield.The optimal reaction conditions and yields (temperature, time, molar yield) were as follows: acyl chlorination, 110℃, 10 h, 93.0%;bromination, dehydrobromination, 100℃, 2 h, 130℃, 5 h, 88.0%;removal of chloroformyl group, 40℃, 3 h, 98.2%. The melting point of the title compound was the same as literature reported, and its structure was confirmed by ¹H NMR.The optimal technology condition to remove chloroformyl group as protection group and its application of protection for some amine compounds were also studied.