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Article

Synthesis, Characterization, and Computational Modeling of N-(1-Ethoxyvinyl)pyridinium Triflates, an Unusual Class of Pyridinium Salts

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Chemistry Department, Hamilton College, 198 College Hill Road, Clinton, NY 13323, USA
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Rigaku Oxford Diffraction, 9009 New Trails Drive, The Woodlands, TX 77381, USA
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Department of Chemistry, Grove City College, 100 Campus Drive, Grove City, PA 16127, USA
*
Author to whom correspondence should be addressed.
Molecules 2018, 23(2), 413; https://doi.org/10.3390/molecules23020413
Received: 18 January 2018 / Revised: 9 February 2018 / Accepted: 11 February 2018 / Published: 14 February 2018
(This article belongs to the Section Organic Chemistry)
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. View Full-Text
Keywords: pyridinium salt; N-(1-alkoxyvinyl); N,O-ketene acetal; ethoxyacetylene; triflic acid; quaternary ammonium compound; hydrogen bonding; X-ray diffractions; crystal structure pyridinium salt; N-(1-alkoxyvinyl); N,O-ketene acetal; ethoxyacetylene; triflic acid; quaternary ammonium compound; hydrogen bonding; X-ray diffractions; crystal structure
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MDPI and ACS Style

Shapiro, J.D.; Sonberg, J.C.; Schafer, B.C.; Williams, C.C.; Ferris, H.R.; Reinheimer, E.W.; Van Wynsberghe, A.W.; Kriley, C.E.; Majireck, M.M. Synthesis, Characterization, and Computational Modeling of N-(1-Ethoxyvinyl)pyridinium Triflates, an Unusual Class of Pyridinium Salts. Molecules 2018, 23, 413. https://doi.org/10.3390/molecules23020413

AMA Style

Shapiro JD, Sonberg JC, Schafer BC, Williams CC, Ferris HR, Reinheimer EW, Van Wynsberghe AW, Kriley CE, Majireck MM. Synthesis, Characterization, and Computational Modeling of N-(1-Ethoxyvinyl)pyridinium Triflates, an Unusual Class of Pyridinium Salts. Molecules. 2018; 23(2):413. https://doi.org/10.3390/molecules23020413

Chicago/Turabian Style

Shapiro, Jonathan D., Justin C. Sonberg, Benjamin C. Schafer, Christopher C. Williams, Hannah R. Ferris, Eric W. Reinheimer, Adam W. Van Wynsberghe, Charles E. Kriley, and Max M. Majireck 2018. "Synthesis, Characterization, and Computational Modeling of N-(1-Ethoxyvinyl)pyridinium Triflates, an Unusual Class of Pyridinium Salts" Molecules 23, no. 2: 413. https://doi.org/10.3390/molecules23020413

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