Please use this identifier to cite or link to this item: http://hdl.handle.net/10995/27205
Title: Long-range 1H-15N J couplings providing a method for direct studies of the structure and azide-tetrazole equilibrium in a series of azido-1,2,4-triazines and azidopyrimidines
Authors: Shestakova, T. S.
Shenkarev, Z. O.
Deev, S. L.
Chupakhin, O. N.
Khalymbadzha, I. A.
Rusinov, V. L.
Arseniev, A. S.
Issue Date: 2013
Citation: Long-range 1H-15N J couplings providing a method for direct studies of the structure and azide-tetrazole equilibrium in a series of azido-1,2,4-triazines and azidopyrimidines / T. S. Shestakova, Z. O. Shenkarev, S. L. Deev [et al.] // Journal of Organic Chemistry. — 2013. — Vol. 78. — № 14. — P. 6975-6982.
Abstract: The selectively 15N labeled azido-1,2,4-triazine 2*A and azidopyrimidine 4*A were synthesized by treating hydrazinoazines with 15N-labeled nitrous acid. The synthesized compounds were studied by 1H, 13C, and 15N NMR spectroscopy in DMSO, TFA, and DMSO/TFA solutions, where the azide-tetrazole equilibrium could lead to the formation of two tetrazoles (T, T′) and one azide (A) isomer for each compound. The incorporation of the 15N label led to the appearance of long-range 1H-15N coupling constants (JHN), which can be measured easily by using amplitude-modulated 1D 1H spin-echo experiments with selective inversion of the 15N nuclei. The observed JHN patterns enable the unambiguous determination of the mode of fusion between the azole and azine rings in the two groups of tetrazole isomers (2*T′, 4*T′ and 2*T, 4*T), even for minor isoforms with a low concentration in solution. However, the azide isomers (2*A and 4*A) are characterized by the absence of detectable J HN coupling. The analysis of the JHN couplings in 15N-labeled compounds provides a simple and efficient method for direct NMR studies of the azide-tetrazole equilibrium in solution. © 2013 American Chemical Society.
Keywords: AMPLITUDE-MODULATED
COUPLING CONSTANTS
J COUPLING
LOW CONCENTRATIONS
NITROUS ACID
NMR STUDIES
SPIN ECHO
TETRAZOLES
NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY
ISOMERS
1,2,4 TRIAZINE DERIVATIVE
AZIDE
DIMETHYL SULFOXIDE
HYDROGEN
NITROGEN 15
PYRIMIDINE DERIVATIVE
PYRROLE
TETRAZOLE DERIVATIVE
1,2,4 TRIAZINE
1,2,4-TRIAZINE
1H TETRAZOLE
1H-TETRAZOLE
AZIDE
NITROGEN
PROTON
TRIAZINE DERIVATIVE
AMPLITUDE MODULATION
ARTICLE
CARBON NUCLEAR MAGNETIC RESONANCE
CHEMICAL STRUCTURE
ELECTROSPRAY
ISOMER
ISOMERIZATION
NITROGEN NUCLEAR MAGNETIC RESONANCE
NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY
PROTON NUCLEAR MAGNETIC RESONANCE
SIGNAL TRANSDUCTION
STRUCTURE ANALYSIS
SYNTHESIS
X RAY CRYSTALLOGRAPHY
CHEMISTRY
STANDARD
AZIDES
MAGNETIC RESONANCE SPECTROSCOPY
MOLECULAR STRUCTURE
NITROGEN ISOTOPES
PROTONS
PYRIMIDINES
REFERENCE STANDARDS
TETRAZOLES
TRIAZINES
URI: http://hdl.handle.net/10995/27205
SCOPUS ID: 84880541437
WOS ID: WOS:000322210700013
PURE ID: 896243
ISSN: 0022-3263
DOI: 10.1021/jo4008207
Appears in Collections:Научные публикации, проиндексированные в SCOPUS и WoS CC

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