Systems with Thirteen Conjugated Atoms

The triaryl compounds 290 (R = Ar) are prepared by condensation of 2-aminophenol with triarylpyrylium salts followed by treatment with alkali. The triphenyl betaine (290 R = Ph) is obtained as a purple solid, mp 165 C (decomp), which shows large thermo/solvatochromic effects. Oxidation of the betaine 290 (R = Ph) with hydrogen peroxide gives the triphenyl-pyridinium-3-olate 291 (R = Ph) (see Section III,A,2) and the pyrrole 292 (R = Ph). The mechanism of this unusual reaction has not yet been Established. 

Examples of these betaines (293) are the bridged heterocycles 295, which have been made by condensation of l,2,4-triazin-5-one derivatives 294 with aldehydes or ketones.2-2is yj g molecular structure of compound 295 (R = H, R2 = R = Me, R = SMe) has been determined by X-ray crystallography. Acetylation gives derivatives 295 (R = Ac) which with methyl iodide give the deep red salts 296 in high yield. 

Doleschall and K. Lempert, Acta Chim. Acad. Sci. Hung. 77, 345 (1973). 

The betaines 297 are easily prepared from a pyrylium salt and the appropriate 4-aminophenol followed by deprotonation. Typically, 2,4,6-triphenyl-pyridinium iodide and 4-aminophenol give the blue-black betaine (297 R = R = Ph, R = H) which also occurs as a red hexahydrate. With methyl iodide this compound gives 7V-(p-methoxyphenyl)-2,4,6-triphenyl-pyridinium iodide. 10,221 

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