RADICAL CYCLIZATION AND 1,5-HYDROGEN TRANSFER IN SELECTED AROMATIC DIAZONIUM SALTS

2-(Methyl(3-methyl-1-phenyl-1H-pyrazol-5-yl)carbamoyl)thiophene-3-diazonium hydrogen sulfate 20, 2-(methyl(3-methyl-isoxazol-5yl)carbamoyl)-benzenediazonium hydrogen sulfate 21 and 2-(methyl(phenyl)carbamoyl)-benzenediazonium hydrogen sulphate 22 were synthesized and reacted with a CuSO4/NaCl/ascorbic acid combination to give complex mixtures. The structuresof the reaction products were elucidated, depending upon the pathways followed.Compound 20 almost exclusively afforded an Ar-5 cyclization product and traceamounts of the product derived from a competing Ar-6 Pschorr closure. In thecase of compound 21, the Ar-6 cyclization was not observed, while the Ar-5cyclization and 1,5-hydrogen radical transfer processes equally occurred. Finally,the Ar-6 cyclization was observed as the main process for compound 22,accompanied by the Ar-5 cyclization and, in a much lesser extent, by an1,5-hydrogen radical transfer process.