Labile aminomethyl and hydroxymethyl derivatives of 6‐mercaptopurine (I) (6‐MP) and S6‐acyloxymethyl‐6‐MP have been converted to stable acetyloxymethyl derivatives by their reaction with acetic anhydride. Analysis of the reaction products and comparison of their 'H nmr spectra and hplc chromatograms with those of acetyloxymethyl derivatives of known structures suggested 1) that the aminomethyl derivatives of 6‐MP were 7‐substituted derivatives, 2) that the aminomethyl derivative of S6‐acetyloxylmethyl‐6‐MP was a 9‐derivative, 3) that the hydroxymethyl derivative of 6‐MP was a mixture of 7‐substituted and S6,3‐disubstitu‐ted derivatives, and 4) that the hydroxymethyl derivative of S6‐pivaloyloxymethyl‐6‐MP was a 9‐substituted derivative. In addition, a previously unreported dialkyl derivative of 6‐MP VI was isolated from its reaction with aminomethylating agent and characterized. Analyses of the 'H nmr spectra and hplc chromatograms of the reaction of VI with acetic anhydride suggested that VI was a 1,7‐disubstituted derivative.
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