N_2O_5/HNO_3硝解乌洛托品制备RDX的机理
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摘要
利用13 C NMR谱监测了乌洛托品(HA)在N2O5/HNO3和N2O5/HNO3/CH2Cl2硝化体系中硝解反应的历程,根据实验13 C NMR谱和计算13 C NMR谱的解析结果,并结合HA硝解反应过程中可能存在中间体和副产物的13 CNMR理论计算结果,提出了硝解历程中可能存在的中间体与副产物的结构,推测了HA在N2O5/HNO3体系中的硝解历程为:HA首先与两分子HNO3结合生成乌洛托品二硝酸盐(HADN);HADN再经环三亚甲基硝胺母体逐步降解为黑索今(RDX)。
The reaction mechanism for the nitrolysis of hexamethylenetetramine(HA)in the nitrating system of N2O5/HNO3 and N2O5/HNO3/CH2Cl2 was monitored by using 13 C NMR spectroscopy.Based on the analytical result of the 13 C NMR spectrum,and combined the result of calculated 13 C NMR of the possible intermediates and by-products in the nitrolysis reaction process of HA,the structures of the possible intermediates and by-products in the nitrolysis reaction process of HA were presented.A possible mechanism for the nitrolysis of HA in the nitrating system of N2O5/HNO3 was speculated.In the first step,hexamethylenetetramine dinitrate(HADN)was formed via one molecular HA and two molecular HNO3.And then,HADN gradually degrades to RDX via cyclotrimethylen enitramine matrix.
The reaction mechanism for the nitrolysis of hexamethylenetetramine(HA)in the nitrating system of N2O5/HNO3 and N2O5/HNO3/CH2Cl2 was monitored by using 13 C NMR spectroscopy.Based on the analytical result of the 13 C NMR spectrum,and combined the result of calculated 13 C NMR of the possible intermediates and by-products in the nitrolysis reaction process of HA,the structures of the possible intermediates and by-products in the nitrolysis reaction process of HA were presented.A possible mechanism for the nitrolysis of HA in the nitrating system of N2O5/HNO3 was speculated.In the first step,hexamethylenetetramine dinitrate(HADN)was formed via one molecular HA and two molecular HNO3.And then,HADN gradually degrades to RDX via cyclotrimethylen enitramine matrix.
引文
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[19]WU Qiong,ZHU Wei-hua,XIAO He-ming.Molecular design of tetrazole-and tetrazine-based high-density energy compounds with oxygen balance equal to zero[J].Journal of Chemical and Engineering Data,2013,58(10):2748-2762.
[20]Goddard D R,Hughes E D,Ingold C K.Chemistry of nitronium salts.Part I:isolation of some nitronium salts[J].Journal of the Chemical Society,1950,4:2559-2575.
[2]周敬,杨丽侠,陈晓明,等.RDX基高能发射药的抗撞击损伤性能[J].火炸药学报,2013,36(6):86-90.ZHOU Jing,YANG Li-xia,CHEN Xiao-ming,et al.Anti-impact fracture property of RDX-based high-energy gun propellants[J].Chinese Journal of Explosives and Propellants,2013,36(6):86-90.
[3]曹端林,曹明保,李永祥.绿色硝解技术合成RDX酮[J].火炸药学报,2004,27(1):12-15.CAO Duan-lin,CAO Ming-bao,LI Yong-xiang.Synthesis of keto-RDX using dinitrogen pentoxide as the nitrating agent[J].Chinese Journal of Explosives and Propellants,2004,27(1):12-15.
[4]George H C.The nitration of hexamethylenetetramine[J].Journal of the American Chemical Society,1925,47(11):2754-2763.
[5]Bachmann W E,John S C.A new method of preparing the high explosive RDX[J].Journal of the American Chemical Society,1949,71(5):1842-1845.
[6]Dunning W J,Millard B,Nutt C W.The heat of nitrolysis of hexamie in nitric acid[J].Journal of the Chemical Society,1952:1264-1269.
[7]FANG Zhi-jie,LI Chen,WANG Shao-fang,et al.Study on the nitrolysis of hexamethylenetetramine by NMR spectrometry[J].Propellants,Explosives,Pyrotechnics,1995,20(2):83-86.
[8]FANG Zhi-jie,LI Chen,WANG Shao-fang,et al.Study on the nitrolysis of hexamethylenetetramine by NMR spectrometry II.some new evidences of the intermediate of HOCH2NHNO2 as a possible precursor to RDX[J].Propellants,Explosives,Pyrotechnics,1997,22(2):78-80.
[9]FANG Zhi-jie,JU Chen,LI Fu-ping.Study on the nitrolysis of hexamethylenetetramine by NMR spectrometry.Part III:the NMR spectral data of some products and intermediates from the nitrolysis of HA[J].Propellants,Explosives,Pyrotechnics,1997,22(6):314-316.
[10]FANG Zhi-jie,WANG Shao-fang,LI Fu-ping.Study on the nitrolysis of hexamethylenetetramine by NMRspectrometry.Part IV:a novel mechanism of the formation of RDX from HA[J].Propellants,Explosives,Pyrotechnics,1998,23(6):317-319.
[11]何志勇.离子液体催化N2O5硝解反应制备HMX及硝解机理研究[D].南京:南京理工大学,2012.HE Zhi-yong.Synthesis of HMX by nitrolysis with dinitrogen pentoxide catalyzed by acidic ionic liquid and study on the nitrolysis mechanism[D].Nanjing:Nanjing University of Science and Technology,2012.
[12]钱华,叶志文,吕春绪.N2O5/HNO3硝化硝解TAIW制备CL-20[J].应用化学,2008(3):378-380.QIAN Hua,YE Zhi-wen,LüChun-xu.Nitration and nitrolysis of TAIW with N2O5/HNO3 to synthesize CL-20[J].Chinese Journal of Applied Chemistry,2008(3):378-380.
[13]John F W,Ronald A L.Direct preparation of 1,3,5-triaza-1,3,5-trinitrocyclohexane from hexamethylenetetramine[J].Organic Preparations and Procedures International,1986,18(4):281-283.
[14]覃光明,葛忠学.含能化合物合成反应与过程[M].北京:化学工业出版社,2011.
[15]石煜.黑索今的合成工艺研究[D].南京:南京理工大学,2010.SHI Yu.Study on synthetic process of RDX[D].Nanjing:Nanjing University of Science and Technology,2010.
[16]张颖.密度泛函方法在NMR理论计算中的系统研究[D].厦门:厦门大学,2008.ZHANG Ying.Systematic study on DFT prediction of NMR properties[D].Xiamen:Xiamen University,2008.
[17]Frisch M J,Trucks G W,Schlegel H B,et al.Gaussian09[CP/CD].Wallingford CT:Gaussian,Inc.,2009.
[18]John P A,Stephen B J,Rolf S.Theoretical models incorporating electron correlation[J].International Journal of Quantum Chemistry,1976,10(S10):1-19.
[19]WU Qiong,ZHU Wei-hua,XIAO He-ming.Molecular design of tetrazole-and tetrazine-based high-density energy compounds with oxygen balance equal to zero[J].Journal of Chemical and Engineering Data,2013,58(10):2748-2762.
[20]Goddard D R,Hughes E D,Ingold C K.Chemistry of nitronium salts.Part I:isolation of some nitronium salts[J].Journal of the Chemical Society,1950,4:2559-2575.