THE THEORETICAL-STUDY ON THE ACID-CATALYZ ED DECOMPOSITION DYNAMICS OF PRIMARY NITRAMINES

The geometries and electronic structures of the primary nitramines (RN HNO(2), R=Me, Et, Pr-i, Bu(t) and CH2CO2H) have been fully optimized b y SCF-MO AM1 method. The transition states and activation energies of the following fifteen acid-catalysed decomposition reactions of the pr imary nitramines have been calculated: RNHNO(2)+H+ --> [RNH(2)NO(2)]() (A) RNHNO(2)+H3O+ --> [RNH(2)NO(2) ... H2O](+) (A)' [RNH(2)NO(2)](+) +H2O --> [ROH(2)](+)+NH2NO2 (B)' Based on the analysis of static struc tures and dynamic characters, it was found that electron-donation by R favours the acid-catalysed decomposition, the relative rates are: R=B u(t)>Pr-i>Et>Me>CH2CO2H; the solvation effect reduces the activation e nergies of protonation processes of title compounds, and favours the a cid-catalysed decomposition.