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Kinetics of isotopic hydrogen exchange in 3-hydroxypyridine N-oxide

Journal Article · · Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.); (United States)
OSTI ID:6576190
This study investigated the isotopic exchange of H/D in 3-hydroxypyridine N-oxide (3-HPO), working at 160/sup 0/C over the pD range from 1.0 to 9.5. The effect of temperature on the protonation (K/sub C/) and ionization (K/sub N) constants of the compound and the pH of aqueous solutions of the compound at 24-90/sup 0/C were also examined. The experimental data were used to develop the expressions which could be used to estimate ..delta..pH(24-t/sup 0/C) values over the 24-t/sup 0/C temperature interval and the 1.0-9.5 pH range. The protonation and ionization constants, pK/sub C/ and pK/sub N/, and their dependence on the pH of the medium, were determined from the measured chemical shifts of the 3-HPO ring protons, using a previously described method. The value of the pH of each solution was measured at 24/sup 0/C, and the value of the additive ..delta..pH(24-t /sup 0/C) term was calculated. The variation of pK/sub C/ and pK/sub N/ over the 24-90/sup 0/C interval could be described satisfactorily by equations of the pK = C/T + D + ET form. Analysis of the kinetics of H/D exchange in 3-hydroxypyridine N-oxide at 160/sup 0/C and pD 1.9-9.5 showed electrophilic substitution at high pD to involve the D/sub 3/O/sup +/ ion and the anion form of 3-hydroxypyridine N-oxide; at pD <6H/D exchange involves the OD/sup -/ ion and the cation and neutral forms of the compound.
Research Organization:
Academy of Sciences of the USSR, Moscow
OSTI ID:
6576190
Journal Information:
Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.); (United States), Journal Name: Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.); (United States) Vol. 30:9; ISSN BACCA
Country of Publication:
United States
Language:
English