RESEARCH ON HIGH EFFICIENT PROCESS UTILIZING HYPERVALENT IODINE COMPOUNDS

本研究的目的是开发利用高价碘化合物，特别是（对苯撑）双碘鎓盐合成有机化合物的高效新工艺.（对苯撑）双碘鎓盐的合成以碘代苯和三氟甲磺酸为原料合成了一种新的双碘（III）试剂，并将其与芳香底物和炔类化合物反应合成了（对苯撑）双碘鎓盐，进而以二乙酸碘苯和邻碘代苯甲酸为原料合成了新型高价碘试剂.炔基（对亚苯基）双碘鎓盐与硫氰酸根离子反应生成炔基硫氰酸酯，而与苯基茚二酮烯醇盐和苯氧根离子反应分别生成戊烯和苯并呋喃衍生物。虽然（对亚苯基）bisiodonium盐显示出高的反应性亲核试剂，反应进行通过迈克尔加成重排过程。芳基（对苯撑）双碘鎓盐与吡啶、三苯基膦、二苯硫醚反应，得到了具有液晶性的二乙炔类化合物。以类似的方式制备1-芳基苯并噻吩鎓盐。

The aim of this research was devoted to develop new high efficient process for synthesis of organic compounds by utilizing hypervalent iodine compounds, especially (p-phenylene) bisiodonium salts.1. Synthesis of (p-phenylene) bisiodonium saltsA new bisiodine (III) reagent was prepared from iodosylbenzene and trifluoromethanesulfonic acid and used to prepare the (p-phenylene) bisiodonium salts by reaction with aromatic substrates and acetylenic compounds.Furthermore, new types of hypervalent iodine reagents were obtained from iodobenzene diacetate and o-iodosylbenzoic acid.2. Reaction of (p-phenylene) bisiodonium salts with nucleophilesReaction of alkynyl (p-phenylene) bisiodonium salts with thiocyanate ion gave alkynylthiocyanates but the reaction with the enolate of phenylindanedione and phenoxide ion provided pentene and benzofuran derivatives, respectively. Although the (p-phenylene) bisiodonium salts showed a high reactivity to nucleophiles, the reaction proceeded via a Michael addition-rearrangement process. Reaction with alkynylcopper reagents gave diacetylene derivatives and was applied to synthesis of liquid-crystalline diacetylenes.Aryl (p-phenylene) bisiodonium salts reacted with pyridine, triphenylphosphine, and diphenyl sulfide. l-Arylbenzothiophenium salts were prepared in a similar manner.