伯硝胺酸催化分解动力学的理论研究  

The Theoretical Study on the Acid-catalysed Decomposition Dynamics of Primary Nitra mines

作　　者：肖鹤鸣[1] 李宇敏[1] 李永富 

机构地区：[1]南京理工大学化学系,南京210094

出　　处：《化学学报》1995年第5期438-443,共6页Acta Chimica Sinica

摘　　要：用SCF-MO AM1方法全优化计算了伯硝胺化合物(RNHNO_2,R=Me,Et,Pr^i,Bu^t和CH_2CO_2H)的几何构型和电子结构,并求得以下15个反应的过渡态和活化能:RNHNO_2+H^+→[RNH_2NO_2]^+ (A)RNHNO_2+H_3O^+→[RNH_2NO_2…H_2O]^+ (A)’[RNH_2NO_2]^++H_2O→[ROH_2]^++NH+2NO_2 (B)’分析静态结构和动力学特征,发现取代基(R)供电性愈强,标题物的酸催化分解速率愈大,即相对速率为R=Bu^l>Pr^i>Et>Me>CH_2CO_2H;溶剂化效应将降低标题物质子化过程的活化能,有利于加速酸催化分解.The geometries and electronic structures of the primary nitramines (RNHNO2, R =Me, Et, Pr', Bu' and CH2CO2H) have been fully optimized by SCF-MO AM 1 method. The transition states and activation energies of the following fifteen acid-catalysed decomposition reactions of the primary nitramines have been calculated:RNHNO2+H+→[RNH2NO2]+ (A)RNHNO2+H3O+→[RNH2NO2…H2O]+ (A)'[RNH2NO2]++H2O→[ROH2]++NH2NO2 (B)'Based on the analysis of static structures and dynamic characters, it was found that electron-do-nation by R favours the acid-catalysed decomposition, the relative rates are: R = Bu'>Pr' >Et > Me>CH2CO2H; the solvation effect reduces the activation energies of protonation processes of title compounds, and favours the acid-catalysed decomposition.

关 键 词：硝胺 酸解反应 电子结构 AM1方法 分解动力学 

分 类 号：O623.737[理学—有机化学] O643.1[理学—化学]