Synthesis of 3-alkoxy-3-aryl-4,4-diisopropyl-1,2-dioxetanes and their base-induced chemiluminescence

• Published in: Tetrahedron Vol. 55; no. 14; pp. 4287 - 4298
• Main Authors: Watanabe, Nobuko, Suganuma, Hiroyuki, Kobayashi, Hisako, Mutoh, Hiroshi, Katao, Yuriko, Matsumoto, Masakatsu
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 01.04.1999; Elsevier
• Subjects: 2-dioxetane; chemiluminescence; Chemistry; Chemistry, Organic; Physical Sciences; Science & Technology; singlet oxygenation; temperature effect; 1; 2-dioxetane; singlet oxygenation; chemiluminescence; temperature effect; 1,2-dioxetane; THERMAL-STABILITY; LOW-VALENT TITANIUM; CHEMI-LUMINESCENCE; DIOXETANES; ELECTRON-EXCHANGE LUMINESCENCE
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/S0040-4020(99)00124-6

Low-temperature singlet oxygenation of 1-alkoxy-1-aryl-2,2-diisopropylethylenes ( 9) gives the corresponding 1,2-dioxetanes ( 10) in high selectivity. Dioxetanes ( 10) are thermally stable enough to permit handling at room temperature, though an alkoxy group affects significantly their thermal stability and the order of half-life is MeO < EtO < i-PrO ⪢ tert-BuO. On treatment with tetrabutylammonium fluoride in DMSO, dioxetanes ( 10e - 10h) bearing a m-siloxyphenyl decompose rapidly to emit intense blue light with Φ CL > 0.2. For the base-induced decomposition of 10e - 10h, the order of rate of decomposition is MeO < EtO < i-PrO < tert-BuO. Low-temperature singlet oxygenation of 1-alkoxy-1-(3- t-butyldimethylsiloxy)phenyl-2,2-diisopropylethylenes ( 1) gives the corresponding 1,2-dioxetanes ( 2). On treatment with tetrabutylammonium fluoride in DMSO, 2 decompose rapidly to afford intense blue light.