Preparative and Kinetic Aspects of Radiation Chemistry

• Publisher: John Wiley and Sons
• Year: 1966
• Tongue: English
• Weight: 461 KB
• Volume: 5
• Category: Article
• ISSN: 0044-8249
• DOI: 10.1002/anie.196607372

✦ Synopsis

Extension of the reaction whereby "nucleoside dialdehydes" are cyclized by nitromethane [1,21 to nitromethane homologues [31 would be expected to produce branched nucleosides of pharmacological interest. 2-U-[(R)-Formyl-(1uracilyl)methyl] -( R )glyceraldehyde ("uridine dialdehyde") ( I ) , obtained by oxidation of uridine with periodate, is converted by nitromethane/sodium methoxide in methanol into a crystalline mixture of isomers (yield 79.7 % based on uridine), from which 1-(3'-deoxy-3'-C-methy~-3'-nitro-~-~-g~ucopyranosyl)uracil ( I ) , m.p. 226 to 240 "C (decomp.), [a]?:: = +25.5 O (HzO), can be separated as main product by fractional crystallization. Acetylation of this product in acidic solution gives the tri-U-acetate ( 3 ) , m.p. 228 "C, [a]'," = -8 " (CHC13); hydrogenation in presence of Raney nickel gives 1-(3'-amino-3'-deoxy-3'-C-methyl-~-oglucopyranosyl)uraci1(4) as monohydrate, m.p. 146-148 "C, [m]'," = +39" (HzO). With acetic anhydride/methanol the amine affords the acetamido compound (5), m.p. 248-250 "C (decomp.), [a]'," = +72 (HzO), which is converted by further acetylation into the tetraacetate (6), m.p. 133'C, [a]'," = +21 ' (CHC13).