Formation of triphenylmethyl radicals upon alkaline hydrolysis of diphenyl sulfophthalide

Triphenylmethyl radicals (TPMR) with ano-positioned sulfonate group are generated by alkaline hydrolysis of diphenyl sulfophthalide in DMSO. Electronic and ESR spectra of these radicals are characterized. It is suggested that the radicals result from one-electron transfer reactions. Triarylmethyl radicals are also formed in alkaline hydrolysis of polyarylenesulfophthalides. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2015–2017, October, 1999.     

Formation of color centers and paramagnetic species by alkaline hydrolysis of polydiphenylenesulfophthalide

Blue color centers (CC) (an intense absorption band (AB) at 566 nm and a weaker AB at 350 nm) and paramagnetic species (PMS) that give an ESR singlet withg=2.0028 and δH=10 Oe are formed by the treatment of a DMSO solution of polydiphenylenesulfophthalide with an excess of LiOH. The formation of blue CC is accompanied by a decrease in the intensity of the absorption band of the phenyl groups of the polymer at 270 nm. The blue CC were attributed to quinoid structures like the Chichibabin hydrocarbon. The long-wave absorption at 650–800 nm was assigned to the regions of quinoid-benzoid conjugation. The color centers and PMS were also observed when the polymer was hydrolyzed in cyclohexanone; however, in this case, the reaction was accompanied by polymer aggregation. The electronic spectrum of the Chichibabin hydrocarbon was calculated by the PM3 method. The identity of CC formed by alkaline hydrolysis and appearing in the polymer—aniline—cyclohexanone system was shown. The absence of “quinoid” CC for polyterphenyl sulfophthalide was explained by the energetically unfavorable singlet state for structures similar to the Müller hydrocarbon. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya No. 2, pp. 295–300, February, 2000.