Department of Chemistry, Kanagawa University, Tsuchiya, Hiratsuka, Kanagawa, 259-1293, Japan.
Luminescence. 2013 Sep-Oct;28(5):696-704. doi: 10.1002/bio.2419. Epub 2012 Sep 21.
Bicyclic dioxetanes 2a-c bearing a 2'-alkoxy-2-hydroxy-1,1'-binaphthyl-7-yl moiety were effectively synthesized and their base-induced chemiluminescent decomposition was investigated by the use of alkaline metal (Na(+) and K(+) ) or Mg(2+) alkoxide in MeOH. When 2a-c were treated with tetrabutylammonium fluoride (TBAF) in dimethyl sulfoxide (DMSO) as a reference system, they showed chemiluminescence as a flash of orange light (maximum wavelength λmax (CL) = 573-577 nm) with efficiency Φ(CL) = 6-8 × 10(-2) . On the other hand, for an alkaline metal (Na(+) or K(+) ) alkoxide/MeOH system, 2a-c decomposed slowly to emit a glow of chemiluminescence, the spectra of which were shifted slightly toward red from the TBAF/DMSO system, and Φ(CL) (= 1.4-2.3 × 10(-3) ) was considerably decreased. In addition, Mg(OMe)2 was found to play a characteristic role as a base for the chemiluminescent decomposition of 2a-c through coordination to the intermediary oxidoaryl-substituted dioxetanes 13. Thus, Mg(2+) increased Φ(CL) to more than twice those with Na(+) or K(+) , while it shifted λmax (CL) considerably toward blue (λmax (CL) = 550-566 nm).
双环二氧杂环丁烷 2a-c 带有 2'-烷氧基-2-羟基-1,1'-联萘-7-基部分，通过在 MeOH 中使用碱金属（Na(+) 和 K(+)）或 Mg(2+)烷氧化物有效地合成，并研究了它们的碱诱导化学发光分解。当 2a-c 用四丁基氟化铵（TBAF）在二甲亚砜（DMSO）中作为参考体系处理时，它们表现出橙色光的化学发光（最大波长 λmax（CL）= 573-577nm），效率 Φ(CL) = 6-8×10(-2)。另一方面，对于碱金属（Na(+)或 K(+)）烷氧化物/MeOH 体系，2a-c 缓慢分解以发射化学发光辉光，其光谱相对于 TBAF/DMSO 体系略微向红色移动，并且 Φ(CL)（= 1.4-2.3×10(-3)）显著降低。此外，发现 Mg(OMe)2 通过与中间氧代芳基取代的二氧杂环丁烷 13 配位，对 2a-c 的化学发光分解起到了特征性的碱的作用。因此，Mg(2+)将 Φ(CL)提高到两倍以上，而 Na(+)或 K(+)的 Φ(CL)，同时将 λmax（CL）明显移向蓝色（λmax（CL）= 550-566nm）。
