Photolytic, autocatalyzed decomposition of benzylic dialkoxy disulfides

The dialkoxy disulfide moiety has been shown to go through an intramolecular fragmentation to liberate trappable S2, and can yield an alkoxy radical under photolytic conditions. We have examined a family of benzylic dialkoxy disulfides (X–Ph–CH2–O–S–S–O–CH2–Ph–X) under photolytic conditions and observed a correlation of decomposition based upon the substituent. We have been able to show that the decomposition is autocatalyzed and has a parabolic correlation with Swain and Lupton’s field constant, F .