Kseniia Yutilova, Anastasiia Tkach, Vladislav Tarasenko, Elena Shved
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Finding the right balance between tertiary amine steric effect and solvent polarity for the regioselectivity and kinetics of epichlorohydrin acetolysis
The asymmetric oxirane ring-opening reaction leading to the formation of regioisomeric chlorohydrin esters was studied in the reaction series “acetic acid–epichlorohydrin–tetrahydrofuran (nitrobenzene)–trialkylamine” by kinetic methods and FT-IR spectroscopy. The effect of solvent polarity and the structure of tertiary amines on the regioselectivity and reaction rate were studied. Tertiary amines with comparable basicity but different nucleophilicity and spatial structure were chosen as catalysts. It was shown that in solvents of different polarity, the components of the initial reaction system are present both as hydrogen-bonded complexes and as individual substances. The reaction orders with respect to acid and amine in solvents of different polarity were established. Correlations between the reaction rate and the parameters of nucleophilicity and structure of amines as well as the polarity of the solvent were established. The regioselectivity of the reaction was studied by 1H NMR spectroscopy using the ratio of regioisomeric reaction products. It was shown that the regioselectivity and rate of catalytic acetolysis of epichlorohydrin are effectively controlled by the structure of tertiary amines and the polarity of the solvent. The scheme of reaction regio-flows was detailed.
期刊介绍:
The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.