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A (6—4) photoproduct of 5-bromouracil

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Abstract

The photoreactions of 5-bromouracil (BrUra) induced by 254 nm radiation have received a significant amount of scrutiny over the years, both when induced in liquid aqueous solution and in the frozen state. The characterized photoproducts in the liquid state include uracil, 5,5′-diuracil (I) and a variety of products arising from ring opening, while the photoreactivity of BrUra in ice using 254 nm radiation is very low. During examination of the photoreactions induced in BrUra in frozen aqueous solution by exposure to predominately UVB irradiation, we found that several products are formed. One of these products has an ultraviolet absorption spectrum similar to those associated with (6–4) adducts of the pyrimidine bases (λmax = 326 nm). Studies with 1H and 13C nuclear magnetic resonance spectroscopy and with mass spectrometry yielded data consistent with this compound indeed being a (6–4) product, namely 6-4′-(5′-bromopyrimidin-2′-one)-5,5-dihydroxy-5,6-dihydrouracil (IIa). The product IIa probably arises from an unstable precursor, namely 5-bromo-6-4′-(5′-bromopyrimidin-2′-one)-5-hydroxy-5,6-dihydrouracil (IV); this compound is a bromohydrin and, as such, is likely unstable to debromination to 6-4′-(5′-bromopyrimidin-2′-one)-5-oxo-5,6-dihydrouracil (V). Rehydration at the 5-position to form a gem diol would lead to IIa, the isolated product.

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Abbreviations

BrUra:

5-Bromouracil

BrdUrd:

5-Bromo-2¢-deoxyuridine

BrUrd:

5-Bromouridine

DMSO:

Dimethylsulfoxide

ESI:

Electrospray ionization

HPLC:

High performance liquid chromatography

MeOH:

Methanol

OHUra:

5-Hydroxyuracil

Thy:

Thymine

TMS:

Tetramethylsilane

TSP:

3-(Trimethylsilyl)propionic-2,2,3,3-d4 acid, sodium salt

Ura:

Uracil

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Author information

Authors and Affiliations

  1. Caixa Postal 007, Extrema, Minas Gerais, Brazil, 37640-006

    Martin D. Shetlar

  2. Department of Pharmaceutical Chemistry, School of Pharmacy, S-926, University of California, San Francisco, CA, 94143-0446, USA

    Vladimir J. Basus

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  1. Martin D. Shetlar
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Correspondence to Martin D. Shetlar.

Additional information

† Electronic supplementary information (ESI) available: Results of quan¬tum chemical calculations for the BrUra (6–4) adduct (IIa) and its lactim tautomer (IIb). See DOI: 10.1039/c0pp00242a

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Shetlar, M.D., Basus, V.J. A (6—4) photoproduct of 5-bromouracil. Photochem Photobiol Sci 10, 76–83 (2011). https://doi.org/10.1039/c0pp00242a

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