Synthesis, Characterization, and Computational Modeling of N-(1-Ethoxyvinyl)pyridinium Triflates, an Unusual Class of Pyridinium Salts
| Autor: | Justin C. Sonberg, Christopher C. Williams, Benjamin C. Schafer, Hannah R Ferris, Jonathan D. Shapiro, Adam W. Van Wynsberghe, Charles E. Kriley, Eric W. Reinheimer, Max M. Majireck |
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| Rok vydání: | 2018 |
| Předmět: |
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Molecular crystal structure Pyridines Pharmaceutical Science Pyridinium Compounds Sulfonic acid 010402 general chemistry Ring (chemistry) 01 natural sciences N O-ketene acetal Article Analytical Chemistry lcsh:QD241-441 chemistry.chemical_compound lcsh:Organic chemistry Drug Discovery Polymer chemistry pyridinium salt Physical and Theoretical Chemistry N-(1-alkoxyvinyl) chemistry.chemical_classification Mesylates triflic acid Molecular Structure 010405 organic chemistry Hydrogen bond Organic Chemistry ethoxyacetylene quaternary ammonium compound hydrogen bonding X-ray diffractions Hydrogen Bonding 0104 chemical sciences Oxygen chemistry Chemistry (miscellaneous) Reagent Molecular Medicine Organic synthesis Salts Pyridinium Triflic acid Trifluoromethanesulfonate |
| Zdroj: | Molecules : A Journal of Synthetic Chemistry and Natural Product Chemistry Molecules; Volume 23; Issue 2; Pages: 413 Molecules, Vol 23, Iss 2, p 413 (2018) |
| ISSN: | 1420-3049 |
| Popis: | N-Substituted pyridinium salts constitute one of the most valuable reagent classes in organic synthesis, due to their versatility and ease of use. Herein we report a preliminary synthesis and detailed structural analysis of several N-(1-ethoxyvinyl)pyridinium triflates, an unusual class of pyridinium salts with potentially broad use as a reagent in organic synthesis. Treatment of pyridines with trifluoromethane sulfonic acid and ethoxyacetylene generates stable, isolable adducts which have been extensively characterized, due to their novelty. Three-dimensional structural stability is perpetuated by an array of C–H•••O hydrogen bonds involving oxygen atoms from the –SO3 groups of the triflate anion, and hydrogen atoms from the aromatic ring and vinyl group of the pyridinium cation. Predictions from density functional theory calculations of the energy landscape for rotation about the exocyclic C–N bond of 2-chloro-1-(1-ethoxyvinyl)pyridine-1-ium trifluoromethanesulfonate (7) and 1-(1-ethoxyvinyl)pyridine-1-ium trifluoromethanesulfonate (16) are also reported. Notably, the predicted global energy minimum of 7 was nearly identical to that found within the crystal structure. |
| Databáze: | OpenAIRE |
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