Studies on chemical alterations of nucleic acids and their components. VI. N-amination of some nucleic acid bases containing basic nitrogen with hydroxylamine-o-esters

Synthesis and Reaction of Pyrimidine Nucleosides

“…(103) A study on the rate and mode of the reaction of m-chloroperbenzoic acid with nucleic acid components as a function of pH has been presented. ( H ydroxylamine-O-esters or -O-aryl ethers are regarded as ammo cation sources for aromatic electrophilic substitution, and with the appropriate purine nucleosides, N 1-aminoguanosine ( 109) and N 1-aminoadenosine ( 110) have been prepared. Treatment of the sodium salt of uridine, 2',3'-O-isopropylideneuridine, or 5-bromouridine with 2,4-dinitrophenoxyamine in dimethylformamide at 37°C for 4 days gave the corresponding N 3 -aminouridines (36) in moderate to high yield.…”

“…Cytidine was converted to 3-aminocytidine (37) with dinitrophenoxy amine, which was isolated in the form of a hydrochloride. (110) Cyclization of this nucleoside with triethyl orthoformate afforded the triazolopyrimidine (38). (111) It is of interest that ami nation of 1,3-dimethyluracil with hydroxylamine-O-sulfonic acid in aqueous solution at pH 2 gave the 5-aminouracil deriva tive.…”

“…They epimerize at pH 5 and 30°C, probably by the cleavage and recyclization of the N I -C 6 linkage. An The reaction of dimethyloxosulfonium methyl ide with uridine derivatives afforded the S,6-dihydro-S,6-methylene derivatives (110). These derivatives were photoisomerized to the corresponding diazepinone derivatives (111).…”

Synthesis and biological properties of some cyclic phosphotriesters derived from 2'-deoxy-5-fluorouridine

“…In order to obtain a compound that could be more easily hydrolyzed, 2,2-difluoropropane-l,3-diol was condensed with phosphoryl chloride to give 2-chloro-5,5-difluoro-1,3,2-dioxaphosphacyclohexane 2-oxide (10). This was condensed with thymidine and with 2'-deoxy-5-fluorouridine to give compounds 11 and 12, respectively.…”

“…1981, 19, 321. (10) be deficient for thymidine kinase (TK).10 *This is reflected by the differences in the IDS0 values of the compounds for L1210/0 and L1210/BdUrd cells. The ID50 values recorded for the L1210/BdUrd cells were many hundreds of times higher than those for the parent L1210/0 cells.…”