Quinol-4-ones, methylation

Recently, many investigators have extended the early observations that the ultraviolet spectra of - and y-hydroxypyridines resemble those of their A -methyl (not the 0-methyl) derivatives. This spectral resemblance is found both in aqueous solutions and in solutions of solvents with low dielectric constants, e.g., quinol-4-one in benzene, indicating that these compounds exist predominantly in the oxo form under all conditions. These data are summarized in Table I. In contrast, 4-hydroxyquinoline-3-carboxylic acid has been tentatively concluded to exist in the hydroxy form %- pjTid-2-one-4-carboxylic acid has also been formulated as a hydroxy compound, but this has been disputed. ... 

Reports of [ 2 + 2] cycloaddition of nitrogen containing heterocycles to alkenes are so numerous that attention can be drawn here to only a few. Recent examples include the acetone-sensitized photoaddition of 4-oxazolin-2-one (248) to ethylene to give the cis-adduct 249,203 the photocycloadditions of N-substituted imidazoles to acrylonitrile204 and of N-methyl-4-hydroxy-quinol-2-one to cyclohexene,205 and the photoaddition of pentafluoro-pyridine to ethylene to give the 1 1- and 1 2-adducts 250 and 251,... 

Another example of crystals containing more than one component is provided by the clathrates. In clathrates of, 3-quinol, three quinol molecules are hydrogen bonded together to form an approximately spherical cavity of radius 4 A (Figure 15.13). Any molecule of appropriate size such as oxygen, nitrogen, krypton, xenon, methane, sulfur dioxide, or methyl alcohol can be trapped, and if it is not disordered within the clathrate, its location and orientation can be determined in the crystalline state by X-ray diffraction methods. In most cases, when a clathrate is... 

A derivative of a hitherto unknown nucleus was produced when 4-amino-5-aminomethyl-3-methyltriazole was refluxed with carbon disulfide and triethylamine in pyridine, which yielded 3-methyl-3,7-dihydro-l,2,3-triazolo-[4,5-d][l,3]thiazine-5-thione (98) (3 hr, 53%) the 3-benzyl analog was made similarly (63%) [80JCS(P1)2009]. Cyclization of 4-anilino-5-ethoxycarbonyltriazole with polyphosphoric acid produced 1 f/-triazolo-[4,5-h]quinol-4-one (99) [80EUP(A)2562]. Similarly, ring closure of 4-(2-pyridylamino)triazole-5-carboxylic acid (or its esters) gave l//-pyrido-[l,2-a]-l,2,3-triazolo[4,5-d]pyrimidin-4-one (100) (77GEP2757929). 4-Amino-5-formyl-3-methyltriazole and pentane-2,4-dione, set aside in 20% sulfuric acid, yielded 3,5-dimethyl-3//-l,2,3-triazolo [4,5-6] pyridin-6-yl... 

The aromatic nucleus and one of the methyl groups are derived from homo-gentisic acid, a product of L-tyrosine degradation (D 22). Homogentisic acid reacts with prenylpyrophosphates of different chain length (D 6). The quinols formed are reversibly dehydrogenated to the corresponding quinones, e.g.,... 

---