Selectivity in the photo-fries rearrangement of some aryl benzoates in green and sustainable media. Preparative and mechanistic studies

CRESPI, STEFANO; MELLA, MARIELLA; SIANO, GASTÓN; BONESI, SERGIO M.

JOURNAL OF ORGANIC CHEMISTRY

AMER CHEMICAL SOC

Año: 2019 vol. 84 p. 4338 - 4352

0022-3263

Irradiation of a series of p-substituted aryl benzoates under N2 atmosphere in homogeneous and micellar media was investigated by means of steady-state condition and of time-resolved spectroscopy. A notable selectivity in favor of the 2-hydroxybenzophenone derivatives was observed in micellar media. The benzophenone derivatives were the main photoproduct. On the other hand, in homogeneous media (cyclohexane, acetonitrile, and methanol) the observed product distribution was entirely different, viz. substituted 2-hydroxybenzophenones, p-substituted phenols, benzyl and benzoic acid were found. The binding constants in the surfactant were also measured and NOESY experiments showed that the aryl benzoates were located in the hydrophobic core of the micelle. Laser flash photolysis experiments led to the characterization of both p-substituted phenoxy radical and substituted 2-benzoylcyclohexadienone transients in homogeneous and micellar environment.