Study on the Production and the Reaction Mechanism of Unstable Molecules produced by the Pyrolysis and Photolysis

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Infrared spectra of the N-Cl containing molecules and their pyrolytic products have been observed. The Spectra were analyzed guided by the results of ab initio MO calculations. The pyrolytic mechanism were considered experiment-ally and also theoretically using the information of the structures and energ-ies of the transition states.(1) High resolution spectra of NH_2Cl were measured in the mid-infrared region. The amino scissorring level has the inversion splitting of about 0.2cm^<-1>. This is the first of observation of the inversion splitting except the wagging band. The amino twisting band was observed, and nu_0 was determined to be 1169cm^<-1>.(2) There have been observed two branchings of the pyrolysis reaction of dialkylamines, R_1(R_2)NCl (R_1, R_2 : C_2H_5, C_3H_7), one is the dehydrochlorination, and the other is C-N cession. The branching is temperature-dependent. and at lower temperature proceeds the dehydrochlorination to give imines.(3) MOPAC-PM3 method was applied to calculate the relative stabilities of the molecules and transition states related to the pyrolysis of amines. The results were used to identify and predict the reaction products. The pyrotitic mechanism including the intramolecular hydrogen transfer, ring cession, and dehydrogen has been invesigated in detail.