Pteridine-triones, methylation

Pteridine-2,4,7-trione, 8-benzyl-6-methyl-hydrolysis, 3, 294 Pteridine-2,4,7-trione, 1-methyl-reactions, 3, 296 Pteridine-2,4,7-trione, 3-methyl-reactions, 3, 296 Pteridine-2,6,7-trione, 4-amino-chlorination, 3, 296 Pteridinetriones structure, 3, 272... 

Trihydroxypteridine exists predominantly in the dioxo-mono-hydroxy form 191(R = H), its ultraviolet spectrum closely resembling those of both the 1- and the 3-methyl derivatives and that of l,3-dimethyl-7-methoxypteridine-2,4-dione (191, R = Me). These spectra are quite different from those of 8-methyl- (192, R = H) and l,3,8-trimethyl-pteridine-2,4,7-trione (192, R = Me), which are similar to each other and to those of other 8-substituted pteridine-2,4,7-triones. However, the ultraviolet spectrum of 2,4,7-trihydroxypteri-dine does, indeed, show that a small proportion of the trioxo form is present at equilibrium. A somewhat larger proportion of the 6-methyl derivative exists in the trioxo form, although structure 193 predominates. The trioxo form (194) of 2,4,7 trihydroxy-l,3,6-trimethyl-pteridine is the most important tautomer, but the corresponding 6-carboxylic acid exists entirely in the monohydroxy-dioxo form 195. 

An acid-catalyzed substitution of a 6-oxo group on 2-aminopteridine-4,6-dione with hydrogen chloride in alcohols (65-100°, 3 hr, 80% yield) represents a convenient synthesis of the 6-alkoxy analogs. The reaction proceeds also with pteridine-2,4,6-trione and its 1-methyl and 1,3-dimethyl derivatives. While methoxylation of 2,4,7-trichloro-quinoline gives about equal amounts of 2- and 4-substitution, acid-catalyzed hydrolysis gives specific reaction at the 2-position only. ... 

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