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RESEARCH PRODUCT

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

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Abstract Nine new and three earlier known 4-halogen (Cl and Br) substituted pyridine N-oxides have been prepared and their 1 H, 13 C and 15 N NMR chemical shifts assigned based on PFG 1 H, X (X= 13 C and 15 N) HMQC and HMBC experiments as well as the comparison with our earlier results for substituted pyridine N-oxide derivatives. The 15 N 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 13 C and 15 N 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 15 N NMR and DFT calculations suggest the prevailing of the dimeric amino form for one congener, which is further supported by ESI-TOF MS data.