title: 15N NMR spectra and reactivity of 2,4,6-triazidopyridines, 2,4,6-triazidopyrimidine and 2,4,6-triazido-s-triazine.
abstract: 2,4,6-Triazido-s-triazine, 2,4,6-triazidopyrimidine and six different 2,4,6-triazidopyridines were studied by (15)N NMR spectroscopy. The assignment of signals in the spectra was performed using the gauge-independent atomic orbital (GIAO)-Tao-Perdew-Staroverov-Scuseria exchange-correlation functional (TPSS)h/6-311+G(d,p) calculations on the M06-2X/6-311+G(d,p) optimized molecular geometries. The Truhlar and coworkers' continuum solvation model called SMD was applied to treat solvent effects. With this approach, the root mean square error in estimations of the (15)N chemical shifts for the azido groups was just 1.9 ppm. It was shown that the different reactivity of the α- and γ-azido groups in pyridines correlates well with the chemical shifts of the Nα signals of these groups. Of two nonequivalent azido groups of azines, the azido group with the most shielded Nα signal is the most electron-deficient and reactive toward electron-rich reagents. By contrast, the azido group of azines with the most deshielded Nα signal is the most reactive toward electron-poor reagents.
authors.affiliation: Institute of Problems of Chemical Physics, Russian Academy of Sciences, 142432, Chernogolovka, Moscow Region, Russian Federation. chap@icp.ac.ru
authors.forename: Sergei V
authors.initials: SV
authors.lastname: Chapyshev
authors.forename: Evgeny N
authors.initials: EN
authors.lastname: Ushakov
authors.forename: Alexander V
authors.initials: AV
authors.lastname: Chernyak
mesh_terms: D001386:Azides / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000592:standards; D015394:Molecular Structure; D009587:Nitrogen Isotopes; D011743:Pyrimidines / Q000737:chemistry*; D012015:Reference Standards; D014227:Triazines / Q000737:chemistry*
chemical_list: D001386:Azides; D009587:Nitrogen Isotopes; D011743:Pyrimidines; D014227:Triazines
keywords: 15N NMR; DFT calculations; azido-s-triazines; azidopyridines; azidopyrimidines; cross-linking reagents; energy materials