N,N-二{羰基亚甲基[N,N-二(乙氧基羰基亚甲基)胺基]}胺的合成及表征

SYNTHESIS AND CHARACTERIZATION OF ETHYL[({[(DIETHOXYCARBONYLMETHYLCARBAMOYL)-METHYL]AMINO}ACETYL)ETHOXYCARBONYLMETHYLAMINO]ACETATE

以亚氨基二乙酸为原料,经氨基保护、缩合、脱保护三步反应制备了树枝状化合物N,N-二{羰基亚甲基[N,N-二(乙氧基羰基亚甲基)胺基]}胺(EDMAA)。氨基保护反应中,亚氨基二乙酸在V(1,4-二氧六环):V(水)=1:1的碱性溶剂系统中与(Boc)2O反应制得2,2-((叔丁氧羰基)亚氨基)二乙酸(BCIA),收率73.8%。在羧酸与氨的缩合反应中,以二环己基碳二亚胺(DCC)为缩合剂,4-二甲胺基吡啶(DMAP)为催化剂,投料比为:n(BCIA):n(DCC):n(亚氨基二乙酸二乙酯):n(DMAP)-1:3:4:0.1,收率为69.1%。缩合反应时,羧酸BCIA与DCC先于0℃缩合0.5~1h,再加入亚氨基二乙酸二乙酯,可减少副反应。探讨了Boc脱保护反应条件,发现PhzO体系收率较高,达95.00A,反应结束后,以石油醚洗涤溶液即可得到产物。以^(1)HNMR、^(13)CNMR和IR表征了产物结构。

Low-generation dendrimer{ethyl[({[(diethoxycarbonylmethylcarbamoyl)methyl]amino}acetyl)ethoxy-carbonylmethylamino]acetate,EDMAA}was prepared from iminodiacetic acid via the three steps of amino protection,condensation reaction and deprotection of the amino-protected groups.In the amino protection,iminodiacetic acid reacting with t-butyloxycarbonyl anhydride in the basic solvent system of dioxane-water(1:1,volume ratio)gave the yield of 73.8%.In the condensa-tion reaction,DCC and DMAP were used as the dehydrating agent and catalyst,respectively.Under the conditions ofn(BCIA):n(DCC):n(Diethyl iminodiacetate):n(DMAP)=1:3:4:0.1,the yield was 69.1%.Addition of diethyl iminodiacetate after the condensation of BCIA with DCC for about 0.5-1 h at 0℃could reduce the content of by-products.For the Boc deprotection,the system of Ph20 was an ideal,giving a higher yield of 95.0%and the separation being simple.The product was obtained by washing the solution after reaction using petroleum ether.The structure of the product had been characterized with IR,^(1)H NMR and^(13)C NMR.