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Synthesis of 1-(3-tert-butyldimethylsiloxy)phenyl-5,5-dimethyl-2,7,8-trioxabicyclo[4.2.0]octanes: new dioxetanes giving high chemiexcitation yields in thermolysis and in fluoride-induced CIEEL-decay

✍ Scribed by Masakatsu Matsumoto; Junko Murayama; Masao Nishiyama; Yasuko Mizoguchi; Toshimitsu Sakuma; Nobuko Watanabe

Publisher: Elsevier Science
Year: 2002
Tongue: French
Weight: 105 KB
Volume: 43
Category: Article
ISSN: 0040-4039
DOI: 10.1016/s0040-4039(02)00052-7

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✦ Synopsis

Dioxetanes with annelated six-membered ring, 1-(3-tert-butyldimethylsiloxy)phenyl-5,5-dimethyl-2,7,8-trioxabicyclo[4.2.0]octanes (2a-2c) were synthesized by singlet oxygenation of the corresponding aryl-substituted dihydropyrans (3). Thermolysis of 2a-2c gave the corresponding ketoesters (5a-5c) as a normal decomposition product together with a considerable amount (23-26%) of ester (6) derived from Norrish type I reaction of the triplet-excited ester (5). On the other hand, treatment with tetrabutylammonium fluoride (TBAF) in DMSO induced rapid decomposition of 2 to emit blue light in high chemiexcitation yield (72-75%) of the oxyanion of a ketoester (10). These results show that the chemiexcitation efficiency of dioxetanes (2) was higher than that of their five-membered ring analog (1) not only for thermolysis and but also for the base-induced CIEEL.

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