Photolytic decomposition of dibenzylic sulfites

Chemical shift and coupling constant analysis of dibenzyloxy disulfides

“…However, when graphing with Swain and Lupton's F-value [35], we observed a parabolic relationship (Figure 6and 7). This was unsurprising; we have observed this parabolic phenomenon with Swain and Lupton's Fvalue in previous studies, particularly with the analogous dibenzylicdialkoxy disulfides which underwent both photolytic [16] and thermolytic [17] decomposition at rates that parabolically correlated to F-values, in addition to a bis(benzyl) sulfites photolytic decomposition study [36].It can be rationalized that a substituent with a high F-value, such as nitro, withdraws the electron cloud towards it and away from the benzylic protons, hence allowing for the proton, that is participating with intramolecular H-bonding, to do so at a greater extent. As the magnitude of the F-value decreases, this polarization difference decreases, "bottoming-out" with methoxy [37] at an F-value of 0.29.…”

Ionic Pathways in the Photochemistry of Cyclic Sulfite Esters

“…An early report on the photochemistry of aryl sulfones (e.g., 7 ) showed the initial generation of radicals , while a report on the photochemistry of benzyl sulfite postulated radical and/or ionic intermediates. Another report on the photolytic decomposition of dibenzylic sulfites showed radical intermediates . Because the range of products of the photolysis of cyclic sulfite esters was not the same as in the photoreactions of cyclic carbonate esters, we surmised that because the products were ketone 6 , the photochemical reaction of cyclic sulfite esters may involve ionic rather than radical intermediates (Scheme ).…”