Application of Crowned Spirobenzopyran Derivatives as Colorimetric Reagents

合成了含单氮杂冠醚或双氮杂冠醚单元的螺苯并吡喃类化合物，并在液-液萃取过程中，用分光光度法测定了它们在黑暗和光照条件下对碱金属离子的萃取行为。在黑暗条件下，含有单氮杂-12-冠-4、-15-冠-5和-18-冠-6单元的冠醚并苯并吡喃衍生物分别选择性地萃取锂、锂和钠离子。在紫外光照射条件下，冠醚螺偶氮衍生物对金属离子的萃取能力较暗条件下有所提高，而在可见光照射条件下，则相反。含有两个螺苯并吡喃单元的二氮杂-12-冠-4衍生物分别在碱金属离子和碱土金属离子的液-液萃取中选择性地萃取锂和钙离子。经紫外光照射后，其对锂离子的萃取能力显著提高。研究了含螺苯并吡喃单元的单氮杂-12-冠-4和二氮杂-12-冠-4衍生物(S)在黑暗和紫外光照射条件下对锂离子的萃取比色。二氮杂-12-冠-4衍生物对锂离子具有较高的选择性，在紫外光照射下对锂离子有较强的萃取能力。

Spirobenzopyrane derivatives bearing monoazacrown ether or diazacrown ether units were synthesized, and in the liquid - liquid extraction their extraction behavior of alkali metal ions was determined by spectrophotometry under the dark and the photo-irradiation conditions. Under the dark conditions, crowned spirobenzopyran derivatives bearing monoaza -12-crown-4, -15-crown-5, and -18-crown-6 units extracted selectively lithium, lithium, and sodium ions, respectively. The metal ion extraction abilities of the crowned spirobenzopyan derivatives were increased under UV-irradiation conditions compared with those of under the dark conditions, and vice versa under the visible light irradiation conditions. Diaza-12-crown-4 derivative bearing two spirobenzopyran units extracted lithium and calcium ions selectively in the liquid - liquid extraction of alkali and alkaline earth metal ions, respectively. The extraction ability for lithium ion was increased remarkably by UV-irradiation. The extraction colorimetry of lithium ion was studied by the flow injection analysis (FIA) using monoaza-12-crown-4 and diaza-12-crown-4 derivatives bearing spirobenzopyran unit(s) under the dark and UV-irradiation conditions. Diaza-12-crown-4 derivative showed the higher selectivity for lithium ion, and the enhancement of the extraction ability was observed by UV-irradiation.