title: Synthesis of sulfanyl-, sulfinyl-, and sulfonyl-substituted bicyclic dioxetanes and their base-induced chemiluminescence.
abstract: 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 sulfanyl-substituted bicyclic dioxetanes 2c-e, while that of 5a without 2-substituent mainly gave sulfoxide 11 along with 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 sulfonyl-substituted dioxetanes 4c, 4e. X-ray single crystallographic analysis was performed for 2c and 4e. Base-induced decomposition of the dioxetanes in DMSO gave light with a maximum wavelength lambda(max)(CL) at 554 nm for 2a and 565 nm for 2e in moderate light yields, while sulfinyl-derivative 3e gave weak light with lambda(max)(CL) = 795 nm and sulfonyl-derivative 4e gave very weak light with lambda(max)(CL) = 848 nm.
authors.affiliation: Department of Chemistry, Kanagawa University, Tsuchiya, Hiratsuka, Kanagawa 259-1293, Japan.
authors.forename: Nobuko
authors.initials: N
authors.lastname: Watanabe
authors.forename: Masato
authors.initials: M
authors.lastname: Kikuchi
authors.forename: Yuusuke
authors.initials: Y
authors.lastname: Maniwa
authors.forename: Hisako K
authors.initials: HK
authors.lastname: Ijuin
authors.forename: Masakatsu
authors.initials: M
authors.lastname: Matsumoto