端氨基己二胺支化物的合成及质谱结构指认

Synthesis of Amino-terminal Hexamethylenediamine Branched Compound and Structure Identification of It Using ESI-MS

以己二胺、丙烯酸甲酯为原料,甲醇钠为催化剂,吩噻嗪为阻聚剂,在甲醇介质中通过Michael加成反应室内合成了己二胺四丙酸甲酯(0.5G支化物),考察了阻聚剂种类对产物收率的影响。再以0.5G支化物为原料与乙二胺通过酰胺化缩合反应合成了己二胺四丙酰胺二胺(1.0G支化物),并对其合成条件进行了研究。结果表明:1.0G支化物的最佳合成条件为n(己二胺)∶n(0.5G)=4.5∶1,反应温度为40℃,反应时间为24 h,收率为92.87%。同时借助IR光谱及ESI-MS对1.0G产物进行了官能团验证和结构表征,研究并归属了该化合物主要特征碎片离子的裂解途径。

Taking hexamethylenediamine and methyl acrylate as raw materials,sodium methoxide as catalyst,phenothiazine as polymerization inhibitor,methanol solution as reaction medium,tetramethyl 3,3 ＇,3 ＇,3 ＇＇-（ hexane-1,6-diylbis（ azanetriyl）） tetrapr- opanoate（ 0.5G branched compound） was synthesized by Michael addition reaction in laboratory. The effect of the type of the polymerization inhibitor on the yield of the product was studied. Then taking 0. 5G compound and ethylenedamine as raw materials,3,3＇,3＇,3＇＇-（ hexane-1,6-diylbis（ azanetriyl）） tetrakis（ N-（ 2-aminoethyl） prop-anemide）（ 1. 0G branched compound） was synthesized by amidation condensation reaction,and its synthetic conditions were optimized. The results show that the optimal reaction conditions for 1. 0G branched compound are n（ hexamethylenediamine） ∶ n（ 0. 5G） = 4. 5 ∶ 1,the reaction temperature 40 ℃,the reaction time 24 h. Under the optimal conditions,the yield of 1. 0G branched compound is 92. 87%. At the same time,the functional groups and the structure of 1. 0G branched compound were characterized by IR spectrum and ESI-MS,and the fragmentation pathways of its main fragment ions were researched.