Pteridine hydroxy

The molecular features of covalent hydration are also present in the dihydroxy series, i.e., in pteridine-2,6-dione (30) and in pteridine-4,6-dione. The latter compound is hydrated only at the C(7)—N(8) double bond, whereas (30) forms two hydrated species, 7-hydroxy-7,8-dihydro- (29) and 4-hydroxy-3,4-dihydro-pteridin-2,6-dione (31) (equation 8). Structure (29) is thermodynamically the more stable substance (31) is formed more rapidly in solution but disappears slowly with time (63JCS5151). Insertion of a 4-methyl group greatly reduces the extent of 3,4- in favour of 7,8-hydration by a blocking effect . 

AT-Oxidation is very sensitive to steric effects, since 1-substituted lumazines and pterins give only 5-oxides and the presence of bulky substituents at position 7 also directs oxidation to N-5. The pteridine 5-oxide (52) and 8-oxide (53) and the 5,8-dioxide (55) contain the AT-oxide groups as such, even when the possibility of AT-hydroxy tautomers exists, as in (53) i(54). 

The reaction of 6-amino-5-(l,2-diethoxycarbonylhydrazino)pyrimidines with enamines represents another convenient method for the preparation of pteridines. Fusion of 5-(l,2-diethoxycarbonylhydrazino)-2,4,6-triaminopyrimidine (281) with an excess of mor-pholinocyclohexene leads to 2,4-diaminotetrahydrobenzo[g]pteridine, and with the morpholinoenamine (282) from 17/3-hydroxy-5a-androstan-3-one regioselective condensation to the fused pteridine (283) takes place in almost quantitative yield (equation 101) (71CC83). 6-Amino-5-nitroso- and 6-amino-5-phenylazo-pyrimidines react similarly, imitating the Timmis-type reaction (72CPB1428). 

Isopterin — see Pteridin-2-one, 4-atnino-Isopyrazole, 4-hydroxy-rearrangement, 5, 250 Isopyrazole, tetramethyl-thermal isomerization, 5, 249 Isopyrazole, 3,4,4,5-tetramethyl-mass spectrometry, 5, 204 Isopyr azoles H NMR, 5, 185, 188 Af-oxide... 

Pteridine, 4-hydroxy-3,4-dihydro-reactions, 3, 265 Pteridine, 6-hydroxymethyl-synthesis, 3, 311... 

Pteridine-4-carboxylic acid, 2-hydroxy-ethyl ester, 3, 276... 

Pteridine-6-carboxylic acid, 2-amino-7-hydroxy-properties, 3, 277... 

Pteridine-7-carboxylic acid, 6-oxo-synthesis, 3, 310 Pteridinecarboxylic acids structure, 3, 276-277 Pteridine-4-carboxylic acids ethyl ester hydrolysis, 3, 276 Pteridine-6-carboxylic acids properties, 3, 277 reactions, 3, 304 Pteridine-7-carboxylic acids properties, 3, 277 reactions, 3, 304 Pteridine-6,7-dicarboxylic acid properties, 3, 277 Pteridine-2,4-dione, 7-hydroxy-tautomerism, 3, 271... 

Pteridine-6,7-dione, 4-amino-2-chloro-chlorination, 3, 296 Pteridine-6,7-dione, 2,4-dichloro-synthesis, 3, 291 Pteridine-6,7-dione, 5-hydroxy-synthesis, 3, 316 Pteridine-6,7-dione, 8-methyl-reduction, 3, 298 Pteridine-2,6-diones structure, 3, 272 Pteridine-4,6-diones structure, 3, 272 synthesis, 3, 310 Pteridine-6,7-diones reduction, 3, 298 synthesis, 3, 316... 

Pteridin-4-one, 7-chloro-2-methylthio-synthesis, 3, 296 Pteridin-4-one, 5,6-dihydro-structure, 3, 279 Pteridin-4-one, 7,8-dihydro-structure, 3, 279 Pteridin-4-one, 3-hydroxy-structure, 3, 282 synthesis, 3, 318... 

Pteridin-7-one, 2,4-diamino-8-hydroxy-structure, 3, 282 Pteridin-7-one, 5,6-dihydro-oxidation, 3, 307 structure, 3, 279 Pteridin-7-one, 8-hydroxy-synthesis, 3, 319 Pteridin-7-one, 8-methyl-synthesis, 3, 297... 

Thieno[3,4-d]oxazole-3a(4H)-carboxylic acid, dihydro-2-methyl-synthesis, 6, 1020 Thieno[2,3-d Joxazoles synthesis, 6, 990 Thieno[3,2-g]pteridine structure, 3, 284 lH-Thieno[3,4-c]pyran-2-ones synthesis, 4, 1032 Thienopyrazines synthesis, 4, 1022-1024 Thieno[2,3-6]pyrazines, 4, 1023 electrophilic substitution, 4, 1024 Thieno[3,4-6]pyrazines, 4, 1024 Thieno[3,4-c]pyrazole, 4,6-dihydro-3-hydroxy-carbamates... 

Ultraviolet spectral comparisons also indicate that structure 174 represents the predominant form of pteridin-4-one (a similar conclusion was reached for 2-amino-6,7-dimethylpteridin-4-one ), and a value of 1.72 has been calculated for log K p between forms 174 and 175 from pKa data. " It is possible, however, that the hydroxy... 

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. 

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