Reaction of oxide radical ion (O.–) with substituted pyrimidines

Reaction of oxide radical ion (O.–) with substituted pyrimidines Pulse radiolysis technique has been used to investigate the reaction of oxide radical ion (O.–) with 4,6-dihydroxy-2-methyl pyrimidine (DHMP), 2,4-dimethyl-6-hydroxy pyrimidine (DMHP), 5,6-dimethyl uracil (DMU) and 6-methyl uracil (MU) in strongly alkaline medium. The second-order rate constants for the reaction of O.– with these compounds are in the range 2-5 × 108 dm3 mol–1 s–1. The transient absorption spectra obtained with DHMP have two maxima at 290 and 370 nm and with DMHP have maxima at 310 and 470 nm. The transient spectrum from DMU is characterized by its absorption maxima at 310 and 520 nm and that of MU by its single maximum at 425 nm. The intermediate species were found to react with N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD) with high G(TMPD.+) values ranged between 3.9 × 10–7 molJ–1 and 4.8 × 10–7 molJ–1. These radicals undergo decay by second-order kinetics (2k/∈ = 1.0-1.7 × 106 s–1). The reaction of O.– with the selected pyrimidines is proposed to proceed through a hydrogen abstraction from the methyl group forming allyl type radicals. These are mainly oxidizing radicals and hence readily undergo electron transfer reactions with TMPD. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

Reaction of oxide radical ion (O.–) with substituted pyrimidines

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Publisher
Springer Journals
Copyright
Copyright © 2002 by VSP 2002
Subject
Chemistry; Inorganic Chemistry; Physical Chemistry; Catalysis
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1163/15685670260188610
Publisher site
See Article on Publisher Site

Abstract

Pulse radiolysis technique has been used to investigate the reaction of oxide radical ion (O.–) with 4,6-dihydroxy-2-methyl pyrimidine (DHMP), 2,4-dimethyl-6-hydroxy pyrimidine (DMHP), 5,6-dimethyl uracil (DMU) and 6-methyl uracil (MU) in strongly alkaline medium. The second-order rate constants for the reaction of O.– with these compounds are in the range 2-5 × 108 dm3 mol–1 s–1. The transient absorption spectra obtained with DHMP have two maxima at 290 and 370 nm and with DMHP have maxima at 310 and 470 nm. The transient spectrum from DMU is characterized by its absorption maxima at 310 and 520 nm and that of MU by its single maximum at 425 nm. The intermediate species were found to react with N,N,N′,N′-tetramethyl-p-phenylenediamine (TMPD) with high G(TMPD.+) values ranged between 3.9 × 10–7 molJ–1 and 4.8 × 10–7 molJ–1. These radicals undergo decay by second-order kinetics (2k/∈ = 1.0-1.7 × 106 s–1). The reaction of O.– with the selected pyrimidines is proposed to proceed through a hydrogen abstraction from the methyl group forming allyl type radicals. These are mainly oxidizing radicals and hence readily undergo electron transfer reactions with TMPD.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Oct 13, 2004

References

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