Synthesis of sulfanyl-, sulfinyl-, and sulfonyl-substituted bicyclic dioxetanes and their base-induced chemiluminescence

Article abstract of DOI:10.1021/jo902477n

(Chemical Equation Presented) The singlet oxygenation of 4-tert-butyl-3,3-dimethyl-5-(3-oxyphenyl)-2,3-dihydrothiophenes 5c-e bearing an acetoxy or methoxy group at the 2-position exclusively gave the corresponding sulfanylsubstituted bicyclic dioxetanes 2c-e, while that of 5a without 2-substituent mainly gave sulfoxide 11 alongwith a small amount of dioxetane 2a. These dioxetanes were sufficiently stable thermally to permit handling at room temperature. Sulfanyl-substituted dioxetanes, 2c and 2e, were further oxidized with m-chloroperbenzoic acid to afford the corresponding sulfinyl-substituted dioxetanes 3c, 3e and sulfonylsubstituted dioxetanes 4c, 4e. X-ray single crystallographic analysis was performed for 2c and 4e. Baseinduced decomposition of the dioxetanes in DMSO gave light with a maximum wavelength λ_max^CL at 554 nmfor 2a and 565 nmfor 2e in moderate light yields,while sulfinyl-derivative 3e gaveweak light with λ_max^CL = 795 nm and sulfonyl-derivative 4e gave very weak light with λ_max^CL = 848 nm. 2010 American Chemical Society.