1H, 13C and 15N NMR spectral and theoretical studies of some methyl and alkylamino derivatives of 4-halopyridine N-oxides

• Published in: Journal of molecular structure 2006-02, Vol.783 (1), p.73-78
• Main Authors: Laihia, K., Puszko, A., Linnanto, J., Kolehmainen, E.
• Format: Article
• Language: English
• Subjects: 1H, 13C, 15N NMR; 4-Halogen pyridine N-oxides; Chemical shifts; Density functional B3LYP/6-311G structure optimization and theoretical B3LYP/6-311G CSGT calculation; ESI-TOF mass spectrometry; Quantum chemical ab initio HF/6-311G
• ISSN: 0022-2860; 1872-8014
• DOI: 10.1016/j.molstruc.2005.01.065

Nine new and three earlier known 4-halogen (Cl and Br) substituted pyridine N-oxides have been prepared and their 1H, 13C and 15N NMR chemical shifts assigned based on PFG 1H, X (X= 13C and 15N) HMQC and HMBC experiments as well as the comparison with our earlier results for substituted pyridine N-oxide derivatives. The 15N resonances of the pyridine nitrogen are 27–40 ppm more shielded in 4-halo-2-alkylamino-6-methyl-5-nitropyridine N-oxide than in parent 4-halopyridine N-oxide. According to quantum chemical ab initio HF/6-311G** calculations the amino tautomer of 4-chloro-2-methylamino-6-methyl-5-nitropyridine N-oxide is more stable than its imino form. Using B3LYP/6-311G** optimized structures both 13C and 15N shifts were calculated by density functional B3LYP/6-311G** CSGT methods for the amino and imino tautomers as well as for the dimeric structure for 4-chloro-2-methylamino-6-methyl-5-nitropyridine N-oxide. The 15N NMR and DFT calculations suggest the prevailing of the dimeric amino form for one congener, which is further supported by ESI-TOF MS data.