Conclusions
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1.
The gas-phase dimerization reactions of ethyleneimine and the reactions of protonated ethylenimine with dimethylamine and diethylamine, which simulate the formation of a branched chain of polyethylenimine, have been investigated by the semiempirical quantum-chemical MINDO/3 method. Two channels have been established for the dimerization reaction, viz., the cis (toward a C-N bond) and the trans (toward the C-C bond) approaches of the nucleophile toward the protonated ring, the activation energy in the trans channel being significantly lower. The results obtained are consistent with the experimental data.
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2.
The high values obtained for the activation energies of the reactions of protonated ethylenimine with disubstituted amines may be attributed, as the calculations of the proton affinity of dimethyl- and diethylamine show, to the errors of the MINDO/3 method.
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2259–2264, October, 1985.
We thank V. I. Faustov for providing the MINDO/3 program.
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Timofeeva, L.M., Zhuk, D.S. Quantum-chemical investigation of the nucleophilic opening of the ethylenimine ring 1. Chain-growth reactions in the synthesis of polyethylenimine. Russ Chem Bull 34, 2090–2094 (1985). https://doi.org/10.1007/BF00963240
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DOI: https://doi.org/10.1007/BF00963240