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.