Selectivity in the Photo-Fries
Rearrangement of Some
Aryl Benzoates in Green and Sustainable Media. Preparative and Mechanistic
Studies
GastoĢn Siano
Stefano Crespi
Mariella Mella
Sergio M. Bonesi
10.1021/acs.joc.9b00334.s001
https://acs.figshare.com/articles/journal_contribution/Selectivity_in_the_Photo-Fries_Rearrangement_of_Some_Aryl_Benzoates_in_Green_and_Sustainable_Media_Preparative_and_Mechanistic_Studies/7887440
Irradiation
of a series of <i>p</i>-substituted aryl
benzoates under N<sub>2</sub> 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, <i>p</i>-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 <i>p</i>-substituted phenoxy radical
and substituted 2-benzoylcyclohexadienone transients in homogeneous
and micellar environment.
2019-03-15 00:00:00
2- benzoylcyclohexadienone transients
N 2 atmosphere
2- hydroxybenzophenone derivatives
NOESY
micellar media
aryl benzoates
Mechanistic Studies Irradiation
laser flash photolysis experiments