Reaction of bicyclo[2.2.1]hept‐5‐ene‐endo‐2‐ylmethylamine and nitrophenyl glycidyl ethers |
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| Authors: | Liliya I Kasyan Stanislav A Prid'ma Vitaliy A Palchikov Leonid D Karat Alexandr V Turov Olexandr Isayev |
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| Institution: | 1. Department of Organic Chemistry, Oles Gonchar Dnipropetrovsk National University, Dnipropetrovsk 49010, Ukraine;2. Ukrainian Research Institutes of Plastics, Donetsk 83059, Ukraine;3. Department of Organic Chemistry, Taras Shevchenko Kiev National University, Kiev 01601, Ukraine;4. Department of Chemistry, Jackson State University, Jackson, MS 39217, USA |
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| Abstract: | Reactions of 2‐nitro‐, 4‐nitro‐ and 2,4‐dinitrophenylglycidyl ethers with bicyclo2.2.1]hept‐5‐ene‐endo‐2‐ylmethylamine in isopropanol have been studied. The mixtures of products were chromatographed on silica gel and eluted with ether or ether/2‐propanol (1:1), the structures of individual products have been confirmed by IR spectra, NMR 1H, 13C spectra, using experiments that involve homonuclear and heteronuclear scalar coupling interactions (COSY, TOCSY, HMQC, HMBC), and mass spectrometry. Amino alcohols as the major products of regioselective aminolysis of epoxides (according to the Krasusky rule) have been obtained. The minor products were the compounds with two hydroxyalkyl fragments at the nitrogen atom. In case of dinitrophenylglycidyl ether, it was the minor product of aryl nucleophilic substitution (SNAr). The abnormal course of aminolysis has been confirmed by the results of quantum‐chemical calculations of activation barries and Free Gibbs energies of the competitive reactions of epoxides (at the B3LYP/6‐311 + G(d,p) level of theory). Copyright © 2010 John Wiley & Sons, Ltd. |
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| Keywords: | β ‐amino alcohol synthesis aryl nucleophilic substitution DFT glycidyl ethers theoretical calculations |
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