Formation of a methide derivative upon photolysis of thymidine bromohydrins.
Reaction of bromine with thymidine in aqueous solution produces, in high yield, the corresponding 5-bromo-6-hydroxy-5,6-dihydroderivative (thymidine bromohydrins). UVC photolysis of thymidine bromohydrins gives rise to a reactive intermediate that is converted into 5-(hydroxymethyl)-2'-deoxyuridine upon incubation in water. When the former compound is left in methanol, ethanol, or propanol, the corresponding 5-alkoxymethyl derivatives are produced. The proposed structure for the primary photolysis product of thymidine bromohydrins is a methide derivative of the thymine ring. This compound could be an interesting intermediate in the synthesis of methyl-substituted thymidine.
Douki
Thierry
T
Laboratoire Lésions des Acides Nucléiques, Service de Chimie Inorganique et Biologique, UMR 5046, CEA/DSM/Département de Recherche Fondamentale sur la Matière Condensée, CEA-Grenoble, France. tdouki@cea.fr
Vadesne-Bauer
Guillaume
G
Cadet
Jean
J
D000438:Alcohols / Q000737:chemistry; D002851:Chromatography, High Pressure Liquid; D006842:Hydrocarbons, Brominated / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008697:Methane / Q000138:chemical synthesis; D015394:Molecular Structure; D010782:Photolysis; D013237:Stereoisomerism; D013936:Thymidine / Q000031:analogs & derivatives* / Q000737:chemistry*; D014867:Water
D000438:Alcohols; D006842:Hydrocarbons, Brominated; D014867:Water; C054175:thymidine bromohydrin; D008697:Methane; D013936:Thymidine