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Detailing the elementary stages in the oxirane ring opening reactions with carboxylic acids catalyzed by tertiary amines
Author(s) -
Bakhtin Stanislav,
Shved Elena,
Bespalko Yuliia,
Tyurina Tatyana,
Palchykov Vitalii
Publication year - 2020
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.4071
Subject(s) - chemistry , electrophile , epichlorohydrin , reagent , catalysis , ring (chemistry) , proton , medicinal chemistry , organic chemistry , polymer chemistry , photochemistry , physics , quantum mechanics
The study of the reaction systems “R 3 N – proton‐donor reagent ( Nu H) – epichlorohydrin” using a complex of various kinetic methods of investigation allowed the reaction pathway and the catalysis mechanism of the oxirane ring opening by proton‐donor reagents in the presence of R 3 N to be detailed. It was confirmed that the catalytic activity of R 3 N consists in their quaternization by oxirane under the obligatory condition of its electrophilic assistance with the Nu H reagent. The quaternization process of tertiary amines was studied using 1 H NMR and UV spectroscopy, quantum chemical modeling, and correlation analysis. It was shown that the transition states of the quaternization stage are dissociative, and their degree of looseness depends on the electrophilic activation of the oxirane ring.