三甲基硅基肼的合成
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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 rawmaterials,1,2-bis( trimethylsilyl) hydrazine was synthesized with the yield of 83%. T hen 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 showthat 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 ℃.
Using anhydrous hydrazine and trimethyl chlorosilane as rawmaterials,1,2-bis( trimethylsilyl) hydrazine was synthesized with the yield of 83%. T hen 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 showthat 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 ℃.
引文
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[2]ZHOU Cheng,WANG Bo-zhou,HUO Huan,et al.A novel energetic material hydrazinium 3,5-dinitroamino-1,2,4-triazole:synthesis and properties[J].C hinese Journal of Energetic Materials(H anneng C ailiao),2014,22(4):576-578.
[3]许诚,毕福强,张敏,等.3,3'-二硝胺基-4,4'-偶氮呋咱二肼盐的合成、表征及性能研究[J].固体火箭技术,2015,38(1):98-101.XU Cheng,BI Fu-qiang,Z HAN G M in,et al.Synthesis,characterization and properties of dihydrazinun salt of 3,3'-bis(nitramino)-4,4'-azofurazan[J].Journal of Solid Rocket T echnology,2015,38(1):98-101.
[4]Hammerl A,Klap9tke T M,N9th H.[N2H5]+2[N4C-NN-CN4]2-:Anew high-nitrogen high-energetic material[J].Inorganic Chemistry,2001,40(14):3570-3575.
[5]乔小晶,郝志坚,樊帆,等.高氯酸碳酰肼类配合物的比热容研究[J].含能材料,2009,17(1):103-106.Q IAO X iao-jin,HAO Z hi-jian,FAN Fan,et al.Specific heat capacities of carbohydrazide perchloric acid coordination compounds[J].C hinese Journal of Energetic Materials(H anneng C ailiao),2009,17(1):103-106.
[6]王为强,薛云娜,梅苏宁,等.双肼基均四嗪十氢十硼酸盐的合成[J].含能材料,2014,22(3):428-429.W AN G W ei-qiang,X U E Yun-na,M El Su-ning,et al.Synthesis of dihydrazine-1,2,4,5-tetrazine decahydrodecaborate[J].C hinese Journal of Energetic Materials(H anneng C ailiao),2014,22(3):428-429.
[7]Furst A,Berlo R C,Hooton S,et al.Hydrazine as a reducing agent for organic compounds(catalytic hydrazine reductions)[J].C hemical R eviews,1965,65(1):51-68.
[8]Tian M,He Y,Zhang X,et al.Synthesis of pyrazolo[5,1-a]isoindoles and pyrazolo[5,1-a]isoindole-3-carboxamides through one-pot cascade reactions of 1-(2-bromophenyl)buta-2,3-dien-1-ones w ith isocyanide and hydrazine or acetohydrazide[J].T he Journal of O rganic C hemistry,2015,80(15):7447-7455.
[9]Buscemi S,Pace A,Piccionello A P,et al.Fluorinated heterocyclic compounds.An effective strategy for the synthesis of fluorinated Z-oximes of 3-perfluoroalkyl-6-phenyl-2H-1,2,4-triazin-5-ones via a ringenlargement reaction of 3-benzoyl-5-perfluoroalkyl-1,2,4-oxadiazoles and hydrazine[J].T he Journal of O rganic C hemistry,2005,70(8):3288-3291.
[10]禹天福,吴志坚.空间环境下无水肼和甲基肼的爆炸危险性[J].火箭推进,2001(6):1-5.YU T ian-fu,W U Z hi-jian.Explosive potential of hydrazine and M M H in the space environment[J].Journal of Rocket Propulsion,2001(6):1-5.
[11]Eaborn,C.Organosilicon compounds[M].London:Butterworths,1960.
[12]Ebsworth,E A V.Volatile silicon compounds[M].New York:Pergamon,1963.
[13]Kataria J,Vasisht S K,Sharma A,et al.Silyl stabilized azanes:reactions of lithiumbis(trimethylsilyl)hydrazine w ith trialkyltin halides[J].Journal of O rganometallic C hemistry,2005,690:1507-1510.
[14]Zdilla M J,Verma A K,Lee S C.Iron-mediated hydrazine reduction and the formation of iron-arylimide heterocubanes[J].Inorganic C hemistry,2011,50(4):1551-1562.
[15]胡长诚.国外水合肼无水肼制备及提纯方法研发进展[J].化学推进剂与高分子材料,2005,3(4):1-5.HU C hang-cheng.Foreign research and development progress of preparation and purification methods for hydrazine hydrate and anhydrous hydrazine[J].C hemical Propellants&Polymeric Materials,2005,3(4):1-5.
[16]Welsh T W B,Broderson H J.Anhydrous hydrazine.Ⅳ.Chemical reactions in anhydrous hydrazine[J].Journal of the A merican C hemical Society,1915,37(4):825-832.
[17]Wannagat U,Liehr W.Hydrazin-silicium-verbindungen[J].Angewandte C hemie,1957,69(24):783-783.
[18]West R.1,2-Anionic rearrangements of organosilicon and germanium compounds[J].A dvances in O rganometallic C hemistry,1977,16:1-31.
[19]Wannagat U,Niederprum H.Darstellung mehrfach silyl-substituierter stickstoff-verbindungen mit hilfe von lithiumphenyl[J].A ngewandte C hemie.1959,71(18):574-574.
[20]Mitzel N W,Bissinger P,Schrnidbaur H.Synthesis and structure of(hydridosilyl)hydrazines[J].Chemische Berichte,1993,126(2):345-350.
[21]Aylett B J.The silyl group as an electron acceptor[J].Journal of Inorganic and N uclear C hemistry,1956,2(5-6):325-329.
[22]Wannagat U.The chemistry of silicon-nitrogen compounds[J].Advances in Inorganic C hemistry and R adiochemistry,1964,6:225-278.
[23]Wannagat U,Liehr W.Hydrazin-silicium-verbindungen.Ⅰ.Monound bis-(triorganosilyl)-hydrazine[J].Zeitschrift für A norganische und A llgemeine C hemie,1958,297:129-136.
[24]West R,Ishikawa M,Bailey R E.New anionic rearrangements.Ⅳ.Kinetics of catalyzed anionic rearrangement of bis(organosilyl)methylhydrazines[J].Journal of the A merican C hemical Society,1967,89(16):4072-4076.