A (6-4) photoproduct of 5-bromouracil.
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 (λ(max) = 326 nm). Studies with (1)H and (13)C 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.
Department of Pharmaceutical Chemistry, School of Pharmacy, S-926, University of California, San Francisco, CA 94143-0446, USA. shetlar@cgl.ucsf.edu
Martin D
MD
Shetlar
Vladimir J
VJ
Basus
D001976:Bromouracil / Q000737:chemistry* / Q000528:radiation effects; D018736:DNA Adducts / Q000737:chemistry*; D007053:Ice; D013058:Mass Spectrometry; D011744:Pyrimidinones / Q000737:chemistry*; D012996:Solutions / Q000737:chemistry; D014466:Ultraviolet Rays; D014498:Uracil / Q000031:analogs & derivatives* / Q000737:chemistry
D018736:DNA Adducts; D007053:Ice; D011744:Pyrimidinones; D012996:Solutions; D001976:Bromouracil; D014498:Uracil