Studies on the Synthesis of Compounds related to Adenosine 3', 5'-Cyclic Phosphate. IV. The Synthesis of 2-Sulfo- and 2-Carboxy-adenosine 3', 5'-Cyclic Phosphate

Abstract

The reactions of 2-mercapto-1, N⁶-etheno c-AMP (c-AMP : adenosine 3', 5'-cyclic phosphate) (V) and 2-mercapto c-AMP (III) with hydrogen peroxide afforded 2-sulfo-1, N⁶-etheno c-AMP (VIII) and 2-sulfo c-AMP (IX), respectively. Deblocking of the etheno residue of VIII afforded IX. Potassium cyanide reacted with 2-bromo-1, N⁶-etheno c-AMP (VI) in dimethylformamide (DMF) at room temperature to yield 2-cyano-1, N⁶-etheno c-AMP (X), which was isolated by Dowex 50-X8 (H⁺) column chromatography. Compound (X) was hydrolyzed to 2-carbamoyl-1, N⁶-etheno c-AMP (XI), then to 2-carboxy-1, N⁶-etheno c-AMP (XII) by aqueous sodium hydroxide. Compound XII was converted to 1, N⁶-etheno c-AMP (IV) by heating in dimethylsulfoxide (DMSO). Deblocking of the etheno residue of XI and XII afforded 2-carbamoyl c-AMP (XIII) and 2-carboxy c-AMP (XIV), respectively. Compound XIII was hydrolyzed by aqueous sodium hydroxide to yield XIV.