ELECTROCHEMICAL REDUCTION OF PYRIMIDINE, CYTOSINE AND RELATED COMPOUNDS: POLAROGRAPHY AND MACROSCALE ELECTROLYSIS
The electrochemical reduction of pyrimidine and certain derivatives was investigated over the normal pH range by polarography, coulometry, and macroscale electrolysis. Reduction products were examined chemically, polarographically, and spectrophotometrically. Pyrimidine was first reduced at the 3,4-position in a 1e process to a free radical, which may dimerize or be reduced (1e process) to 3,4-dihydropyrimidine; the latter can be further reduced (2e process) to tetrahydropyrimidine. The 2-amino- and 2-amino-4-methylpyrimidines was reduced in two 1e steps, first to a free radical and then to the 3,4-dihydro derivative. 4-Amino-2,6-dimethylpyrimidine gave a single 4e wave, which likely involved 2e reduction to the 3,4-dihydro compound followed by deamination to 2,6- dimethylpyrimi-dine, which was reduced (2e process) to 2,6-dimethyl-3, 4- dihydropyrimidine. Cytosine (4-amino-2-hydroxypyrimidine) underwent a 3e reduction, which probably involved 2e reduction of the 3,4-N =C bond, deamination to form 2hydroxypyrimidine and 1e reduction of the latter to a free radical which dimerized. 2-Hydroxypyrimidine itself showed only 1e reduction. The dihydro and tetrshydro products were unstable in aqueous solution; pseudo-first-order rate of disappearance is shown by the two compounds examined. In general, 4- aminopyrimidines having the 3,4Position hydrogenated deaminated readily to generate the reducible 3,4-N = C bond. (auth)
- Research Organization:
- Univ. of Michigan, Ann Arbor
- Sponsoring Organization:
- USDOE
- NSA Number:
- NSA-16-027000
- OSTI ID:
- 4803656
- Journal Information:
- Journal of the American Chemical Society (U.S.), Journal Name: Journal of the American Chemical Society (U.S.) Vol. Vol: 84; ISSN JACSA
- Country of Publication:
- Country unknown/Code not available
- Language:
- English
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