4-{[3-(三甲氧基硅烷基)丙氧基]甲基}-1H-1,2,3-三氮唑的合成

Synthesis of 4-{[3-(Trimethoxysilyl)propoxy]methyl}-1H-1,2,3-triazole

以特戊酸氯甲酯为原料,经过叠氮取代、环加成和威廉森合成反应,制得一种新型可传导质子的单体4-{[3-(三甲氧基硅烷基)丙氧基]甲基}-1H-1,2,3-三氮唑(Ⅲ)。采用正交实验设计和单因素实验考察了反应温度、反应时间、反应物料摩尔比和催化剂用量等因素对收率的影响,合成特戊酸叠氮甲酯(Ⅰ)的最佳工艺条件:n(叠氮钠)∶n(特戊酸氯甲酯)=1.5∶1,反应时间20 h,反应温度78℃;合成[4-(羟甲基)-1H-1,2,3-三唑-1-基]-特戊酸甲酯(Ⅱ)的最佳工艺条件:n(丙炔醇)∶n(Ⅰ)=1.3∶1,反应温度50℃,反应时间24 h,n(CuSO4.5H2O)∶n(抗坏血酸)∶n(Ⅰ)=0.02∶0.1∶1,在该条件下目标产物收率为63.9%。用FTIR、1HNMR和13CNMR对产物的结构进行了表征。

With chloromethyl pivalate as the main raw material, a novel proton-conducting monomer 4- { [3-（trimethoxysilyl）propoxy] methyl }-1H-1,2,3-triazole （Ⅲ） was synthesized through a series of reactions of azide substitution, cycloaddition and Williamsen synthesis. The effects of reaction temperature ,reaction time, molar ratio of raw materials and amount of catalysts on the yield were investigated by orthogonal test and single factor experiments. The optimum reaction conditions for preparing azidomethyl pivalate （ Ⅰ ） were as follows ： n （ sodium azide ） ： n （ chloromethyl pivalate） = 1.5：1, reaction time 20 h, reaction temperature 78 ℃. Those for preparing 2,2-dimethyl propionic acid- （4-hydroxymethyl-l,2,3-triazol-1-yl） methyl ester （ Ⅱ ） were ： n （ propargyl alcohol） ： n （ Ⅰ ） = 1.3：1, reaction temperature 50 ℃ ,reaction time 24 h and n（CuSO4·5H2O）：n（ ascorbic acid）：n（ Ⅰ ） = 0. 02：0. 1：1. The yield of the product m was 63.9%. The structures of the synthesized compounds were characterized by means of FTIR,1HNMR and 13CNMR.