The photochemical reactions of nitrogen-rich mesoionic 1,3-diphenyltetrazolium heterocycles and related compounds

Abstract

Photochemical reactions of azo and triazo derivatives of mesoionic 1,3-diphenyltetrazolium heterocycles and related compounds were studied. The reaction paths were found to depend markedly on the types of substrate, substituent and reaction solvent giving diverse products. Upon irradiation of the 1,1′3,3′-tetraphenylazoditetrazolium salt 1, the addition of hydrogen and acetone to the NN bond was observed in methanol and acetone, respectively, whereas the bond was cleaved in diethyl ketone to give the 5-aminotetrazolium salt 10. The corresponding radical cation 11 also gave the reduction product in methanol. On the other hand, the 1,3-diphenyl-5-(phenylazo)tetrazolium salt 12 underwent nitrogen evolution giving the 1,3-diphenyltetrazolium salt 13via the corresponding tetrazolium radical. Triazene derivatives 14 and 17 underwent an N–N bond cleavage to give tetrazolio-5-amide 4. The mesoionic triazene compounds bearing a tosyl 18 or cyano group 19 gave products 20 and 23. Triphenylphosphinotriazene 24 liberated nitrogen to give phosphinoimide 25 and its hydrolysis product 10. Tetrazolylamide 26 lost a phenyldiazonium group from the 1,3-diphenyltetrazolium ring to give the guanidine derivative 27.