0000000001152984
AUTHOR
Zofia Talik
Specificity of 15N NMR chemical shifts to the nature of substituents and tautomerism in substituted pyridine N-oxides
1H, 13C, and 15N NMR chemical shifts have been measured for 2-aminopyridine N-oxide (1), its eleven derivatives (2–10, 13, 14), and 3-Cl and 3-Br substituted 4-nitropyridine N-oxides (11, 12). δ(15N) of pyridine ring nitrogen in 2-acetylaminopyridine N-oxides are 5.9–11.5 ppm deshielded from those in 2-aminopyridine N-oxides. When amino and acetylamino substituents are in 4-position, δ(15N) of ring nitrogen is 21.3 ppm deshielded in the acetylated derivative. The strong resonance interaction between 2-amino and 5-nitro groups reflects in the decrease of amino nitrogen shielding about 5.3–17.9 ppm. Also, 1H and 13C NMR spectral data are in agreement with 15N NMR results reflected as deshield…
1H,13C and15N NMR spectroscopic, x-ray structural andab initio/HF studies on nitramino andN-alkylamino-4-nitro derivatives of pyridineN-oxides and pyridines
The 1H, 13C and 15N NMR spectra in DMSO-d6 were measured for eight nitraminopyridine N-oxides, ten 4-nitropyridine N-oxides, four 2-nitraminopyridines and five 4-nitropyridines. Their chemical shift assignments are based on PFG 1H,X (X = 13C and 15N) HMQC and HMBC experiments. The relative energies for the tautomers of two nitraminopyridine N-oxides were determined by ab initio HF/6–311G** calculations. A single-crystal x-ray structural analysis was made for 4-methyl-2-nitraminopyridine: C6H7O2N3, M = 153.15, triclinic, space group P-1 (No. 2), a = 7.0275(4), b = 6.8034(3), c = 8.6086(5) A, α = 103.620(2), β = 90.309(2), γ = 122.215(3)°, V = 334.11(3) A3, Z = 2. Copyright © 2003 John Wiley …