烯酰吗啉衍生物的合成  

Synthesis of Alkenylmorpholine Derivatives

作　　者：刘娟 张晨曦 李庆 万东升 王加辉 薛志勇 LIU Juan;ZHANG Chenxi;LI Qing;WAN Dongsheng;WANG Jiahui;XUE Zhiyong(College of Chemistry and Chemical Engineering,Wuhan Textile University,Wuhan 430073,China)

机构地区：[1]武汉纺织大学化学与化工学院,湖北武汉430073

出　　处：《合成化学》2023年第8期630-635,共6页Chinese Journal of Synthetic Chemistry

基　　金：国家自然科学基金资助项目(21602163);湖北省自然科学基金资助项目(2016CFB261);湖北省教育厅中青年人才资助项目(Q20161607);生物质纤维与生态染整湖北省重点实验室开放课题资助项目(STRZ201907)。

摘　　要：烯酰吗啉衍生物通过在烯酰吗啉原有的结构中引入羧基基团,能够与蛋白质分子发生酰化反应或重氮化反应,可以与大分子载体蛋白进行偶联,在杀菌方面具有更好的潜在价值。以烯酰吗啉和叔丁醇钾为原料,通过酯化水解、引入哌嗪-1-羧酸叔丁酯、三氟乙酸水解、引入4-溴丁酸叔丁酯和三氟乙酸水解五步反应,设计并合成了一种烯酰吗啉衍生物,其结构经^(1)H NMR,^(13)C NMR和MS(ESI)表征,并对关键合成工艺水解试剂种类以及最佳试剂用量、最佳投料比(物质的量之比,下同)和反应温度进行优化。结果表明:当水解试剂为叔丁醇钾时,烯酰吗啉酯化水解收率最佳,且烯酰吗啉与叔丁醇钾的最佳投料比为1∶6时,反应收率为87%。引入4-溴丁酸叔丁酯至反应中且温度为100℃时收率最高为85%。当水解试剂在脱酸酐基团反应中为三氟乙酸(2 mL)时,反应效果最好,产品收率为95%。By introducing carboxyl groups into the original structure of enoylmorpholine,enoylmorpholine derivatives can undergo acylation or diazotization reaction with protein molecules and can be coupled with macromolecular membrane transport protein,which has better potential value in sterilization.An enoylmorpholine derivative was designed and synthesized.It was synthesized by a five-step reaction,using enoylmorpholine and potassium tert-butoxide as raw materials through esterification hydrolysis,the introduction of tert-butyl piperazine-1-carboxylate,the hydrolysis of trifluoroacetic acid,the introduction of tert-buty 4-bromobutyrate,the hydrolysis by trifluoroacetic acid reaction.The structure of the final product was confirmed by^(1)H NMR,^(13)C NMR and MS(ESI).And optimize the types of hydrolysis reagents for key synthesis processes,as well as the optimal reagent dosage,optimal feed ratio(ratio of substance quantity,the same below),and reaction temperature.Results showed that when the hydrolysis reagent was potassium tert-butoxide,the hydrolysis yield of enoylmorpholine esterification was optimal,and the optimal feeding ratio of enoylmorpholine to potassium tert-butoxide was 1∶6.The reaction yield is 87%.In the introduction of tert-butyl 4-bromobutyrate reaction,the highest yield is 85%at a temperature of 100℃.When the hydrolysis reagent was trifluoroacetic acid(2 mL)in the deacidication anhydride group reaction,the reaction effect was the best.The product yield is 95%.

关 键 词：烯酰吗啉 衍生物 合成 酯水解 叔丁醇钾 三氟乙酸 烃基化 

分 类 号：O621.3[理学—有机化学]