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
作者:Masakatsu Matsumoto、Junko Murayama、Masao Nishiyama、Yasuko Mizoguchi、Toshimitsu Sakuma、Nobuko Watanabe
DOI:10.1016/s0040-4039(02)00052-7
日期:2002.2
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
通过单原子氧化合成带有二环六元环的二氧杂环丁烷1-(3-叔丁基二甲基甲硅烷氧基)苯基5,5-二甲基-2,7,8-三氧杂双环[4.2.0]辛烷(2a - 2c)。相应的芳基取代的二氢吡喃(3)。热分解图2a - 2c中得到相应的酮酯(5A - 5C)与酯(有相当数量的(23-26%),为正常分解产物一起6来自三重激发酯的Norrish I型反应得到的)(5) 。另一方面,在DMSO中用四丁基氟化铵(TBAF)处理可导致2的快速分解。以高化学激发率(72-75%)的酮酸酯的氧阴离子发出蓝光(10)。这些结果表明,不仅对于热分解,而且对于碱诱导的CIEEL ,二氧环乙烷(2)的化学激发效率均高于其五元环类似物(1)的化学激发效率。