PHENOLYSIS OF 2-(CHLOROMETHYL)OXIRANE IN THE PRESENCE OF TERTIARY AMINES: NUCLEOPHILIC-ELECTROPHILIC INTERACTIONS
DOI:
https://doi.org/10.15421/jchemtech.v34i1.352278Keywords:
epoxide ring opening, 2-(chloromethyl)oxirane (epichlorohydrin), phenolysis and acidolysis, N,N-dimethylaniline (tertiary amine), solvent polarity, regiospecificity and regioselectivity, NMR analysis, catalysis, nucleophilic-electrophilic interactions, reaction mechanismAbstract
The aim of this work is to study the reaction series “4-nitrophenol–2-(chloromethyl)oxirane (epichlorohydrin, ECH)–N,N-dimethylaniline,” nucleophilic-electrophilic interactions in the system to compile a kinetic model of oxiranes phenolysis. The catalytic phenolysis of epichlorohydrin was studied using kinetic methods, along with a similar acidolysis reaction for comparison. The reaction kinetics was studied in ECH excess, which acts simultaneously as substrate and solvent, as well as in its binary mixture with tetrahydrofuran. The kinetic scheme of the reaction was confirmed by studying the structure of the synthesized product using 1H NMR and gas chromatography–mass spectroscopy. The regiospecificity of ECH phenololysis was concluded. The zero order of the reaction with respect to the nucleophilic reagent and the first order of the reaction with respect to the amine were established. The effect of solvent polarity on the reaction kinetics was examined. The kinetic law of the reaction is the same as for the catalytic acidolysis of epichlorohydrin. The kinetic features of the phenolysis and acidolysis of epichlorohydrin with varying solvent polarity were analyzed. It was confirmed that the initial stage of the reaction – amine quaternization – has an SN2 character. Nucleophilic-electrophilic interactions in the system were analyzed. The mechanism of nucleophilic opening of the oxirane cycle was described in detail. Regiospecific phenolysis and regioselective acidolysis are described by a single kinetic model that corresponds to the mechanism of transfer of the anion of a nucleophilic reagent by an ion pair.
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