三甲基硅基肼的合成  

Synthesis of Trimethylsilylhydrazine

作　　者：丁可伟[1,2] 李陶琦 肖啸 刘庆[1,2] 朱勇 葛忠学[1,2] 

机构地区：[1]西安近代化学研究所,陕西西安710065 [2]氟氮化工资源高效开发与利用国家重点实验室,陕西西安710065

出　　处：《含能材料》2017年第6期498-502,共5页Chinese Journal of Energetic Materials

基　　金：国家自然科学基金资助(21502148)

摘　　要：以无水肼和三甲基氯硅烷为原料,合成了1,2-二(三甲基硅基)肼,收率83%;再经丁基锂活化合成了三(三甲基硅基)肼,总收率75%;进一步通过三(三甲基硅基)肼锂和三甲基氯硅烷的溶剂热反应合成了四(三甲基硅基)肼,总收率34%。通过核磁、红外、质谱和元素分析对上述产物进行了表征。分析了单(三甲基硅基)肼的自缩合反应和双(三甲基硅基)肼在热作用下的重排反应,结果表明,这些反应都是由三甲基硅基在肼基上的分子间和分子内迁移引起的,并且发现75℃以上双(三甲基硅基)就能发生异构体间的转化与平衡。Using anhydrous hydrazine and trimethyl chlorosilane as raw materials, 1,2-bis（trimethylsilyl）hydrazine was synthesized with the yield of 83%. Then through activation of butyllithium, tris（trimethylsilyl）hydrazine were synthesized with the total yield of 75%. Further through solvothermal reaction of lithium-tris（trimethylsilyl）hydrazine and trimethyl chlorosilane, tetra（trimethylsilyl）hydrazine were synthesized with the total yield of 34%. Their structures were characterized by means of NMR, IR, MS and elemental analysis. The self-condensation reaction of mono（trimethylsilyl）hydrazine and rearrangement reaction of bis（trimethylsilyl）hydrazine induced by heat action were analyzed. Results show that these reactions are caused by the inter- and intra-molecular migration of trimethylsilyl group on hydrazine, and isomerization of bis（trimethylsilyl）hydrazine could occur obove 75 ℃.

关 键 词：三甲基硅基肼 三甲基硅基肼锂 三甲基硅基迁移反应 合成 

分 类 号：TQ560.1[化学工程—炸药化工]