Reaction of bicyclo[2.2.1]hept‐5‐ene‐endo‐2‐ylmethylamine and nitrophenyl glycidyl ethers

Abstract

Reactions of 2‐nitro‐, 4‐nitro‐ and 2,4‐dinitrophenylglycidyl ethers with bicyclo[2.2.1]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.

Nucleophilic Aliphatic Substitution

“…53 A small amount of disubstituted product and some aromatic substitution product were formed in the reactions. Theoretical calculations at the B3LYP/6-311+G(d,p) level in the gas phase and using the IEFPCM model to account for the solvent supported the experimental results.…”

“…107 The analysis of the reactions of many ambident nucleophiles with a variety of substrates indicates that Marcus theory, which derives Discussed earlier have been substituent effects: on the Grignard reagent and on the nitrogen of the chiral N-hetereocyclic carbene ligand−Cu(I) catalyst in the S N 2 reaction between an aryl Grignard reagent and γ -alkyl allyl bromide; 19 on the (salen)Coee and amine-co-catalysed enantioselective ring opening of para-substituted styrene oxides by fluoride ion; 48 on the bonding, electron density at the reacting atoms, atomic ee charges on the atoms, the source function, and the intermolecular interactions in epoxides; 51 on the regiospecific S N 2 ring-opening reaction of ortho-and para-nitro-or 2,4-dinitrophenylglycidyl ethers by bicyclo[2.2.1]hept-5-ene-endo-2-ylmethylamine in 2-propanol; 53 on the secondary αand perdeutero-deuterium KIEs, E2/S N 2 ratios, reaction efficiencies, transition-state looseness parameters, and the relative basicities of the nucleophiles in the gas-phase reactions between methyl, ethyl, i-propyl, and t-butyl iodides and SH − , Cl − , and CN − ; 77 on the S N reactions between m-and p-X-substituted benzyl amines and N-methyl-α-bromo-p-Y-substituted acetanilides in DMSO; 78 on the α-effect for the gas-phase S N 2 reactions between HOO − versus MeO − , OH − , or EtO − and methyl fluoride, anisole, and 4-fluoroanisole; 82 on the gas-phase S N 2 reactions between dimethylmethylphosphonate and methylformate and HOO − versus HO − , MeO − , or EtO − in an attempt to discover the origin of the α-effect; 83 on the S N 2 reaction of carbanions with 4-substituted benzyl chlorides in liquid ammonia; 84 on the solvolysis reaction 85,86 and the S N 2 reaction between phenoxide ions, and both neutral and negatively charged amines and 4-substituted benzyl chlorides in liquid ammonia; 85 on the ionization rates (the k 1 step) of the S N 1 reactions of many substituted trityl halides and carboxylates in aqueous acetone and in aqueous and pure acetonitrile in the presence of piperidine; 90 on the ionization rates (k 1 ) of the S N 1 reactions of various diarylmethyl chlorides in the presence of piperidine, pyridine, or PPh 3 in several dipolar aprotic solvents; 91 on the solvolyses of X,Y-substituted benzhydryl acetates in various aqueous MeOH and EtOH solutions; 92 and on the dispersions observed in Grunwald-Winstein correlations of S N 1 solvolyses of substrates with substituents containing adjacent π -electrons. 96…”

Probability of reaction pathways of amine with epoxides in the reagent ratio of 1:1 and 1:2

“…Experimental studies [14,15] have shown that the interaction of amine ((1S,2S,4S)-bicyclo[2.2.1]hept-5en-2-ylmethanamine (1) with epoxides (2-((cyclohexyloxy)methyl)oxirane (2), 2-(phenoxymethyl)oxirane…”

Nucleophile-electrophile interactions in the reaction of oxiranes with carboxylic acids in the presence of tertiary amines

“…Oxiranes reactions with OH‐acids are widely used for synthesis of the epoxy resin monomers, pharmaceutical substances and are a convenient model for studying detoxification of oxirane compounds in biological systems:…”