162284-62-0Relevant articles and documents
Development of reactions of 6- and 5-substituted 1,3-dimethyluracils with dimethylsulfoxonium methylide
Norris, Peter,Shechter, Harold
, p. 7290 - 7298 (2007/10/03)
6-Chloro-1,3-dimethyluracil (1) reacts with dimethylsulfoxonium methylide (3, 2 equiv) to give sulfoxonium ylide 8 (51%). The structure of 8 is established spectroscopically and by its reactions with various electrophiles and electron-deficient olefins. Thus, 8 is converted by HCl to sulfoxonium chloride 7, which then yields the 6-(chloromethyl)uracil 17 by heating in acetonitrile. Ylide 8 undergoes deuterium exchange at the 5- position, at its methine carbon, and into its methyl groups attached to sulfur. Reaction of 8 with benzoyl chloride gives the highly substituted ylide 19 or the nucleophilic substitution products 17 and 18 depending on reaction conditions. Treatment of 8 with electron-deficient olefins yields 6- cyclopropyluracils 20-31. Many of the cyclopropyluracils have been converted to trans-1-(1,3-dimethyluracilyl)-2-vinylcyclopropanes and cycloheptenyluracils. Reactions of 5-substituted uracils 2 (Z = SOPh and SeOPh) with ylide 3 have been developed. 5-(Phenylsulfinyl)uracil 48 yields cyclothymine derivative 49; 5-phenylseleninyluracil 52 gives methylide 8 as the major product.
