Thermochemical properties of dibenzyloxy disulfides

The in situ thermal behavior of dialkoxy disulfides (OSSO) has been previously explored, however their neat thermal stability has yet to be examined. We synthesized a library of ten dibenzyloxy disulfide derivatives with various para-substituents. Each derivative was analyzed by TGA and DSC to discern molecular fragmentation. A correlation of the pattern of fragmentation to Swain and Lupton's R-value was observed. Also, DSC analysis revealed that when the para-substituent was a phenyl (i.e. bis(p-phenylbenzyloxy) disulfide), and successive runs were performed, the thermogram showed the presence of the fragmentation, and upon 1H NMR analysis its corresponding alcohol and aldehyde were observed.

Figure optionsDownload as PowerPoint slideHighlights
► Synthesis of ten dibenzyloxy disulfide derivatives with various para-substituents.
► Derivatives were analyzed by TGA and DSC to discern molecular fragmentation.
► A correlation of fragmentation to Swain and Lupton's R-value was observed.
► DSC thermogram of bis(p-phenylbenzyloxy) disulfide revealed fragmentation.