Semiempirical calculations (AM1) have been carried out on the formation of 1,3-diazetidinediimines by dimerization of carbodiimides. The model cases of carbodiimide itself, HN=C=NH and N-amino-N′-methylcarbodiimide, H 2N-N=C=N-CH3, have been studied. For the second compound, eight isomeric diazetidines can be obtained by cyclodimerization. The two most stable isomers are the bis(hydrazono)-1,3-dimethyldiazetidines of Z,Z and E,E configuration which correspond to the kind of structures actually formed. For the study of the kinetic aspects of the dimerization, the complete two-dimensional surface has been determined for carbodiimide itself. It appears that the asynchronous reaction is favoured over the synchronous approach. In the case of N-amino-N′-methylcarbodiimide, twelve asynchronous transition states have been calculated. The lowest transition state corresponds to the formation of 1-amino-3-methyl-2,4-bis(hydrazono)diazetidine, analogous to the diazetidine isomer whose existence has been postulated to explain the mass spectra of bis(heteroarylimino)-1,3-diaryldiazetidines.
|Journal||Journal of the Chemical Society, Perkin Transactions 2|
|Publication status||Published - 1 Dec 1992|
Bertrán, J., Oliva, A., Jose, J., Duran, M., Molina, P., Alajarin, M., Leonardo, C. L., & Elguero, J. (1992). Theoretical study of the mechanism of dimerization of N,C-disubstituted carbodiimides. Journal of the Chemical Society, Perkin Transactions 2, (2), 299-304.