RESEARCH ON HIGH EFFICIENT PROCESS UTILIZING HYPERVALENT IODINE COMPOUNDS

本研究旨在开发利用高价碘化合物，特别是（对苯）铋盐合成有机化合物的高效新工艺。（对苯）比西碘鎓盐的合成以碘基苯和三氟甲烷磺酸为原料制备了一种新型比西碘（III）试剂，并与芳香族底物和乙基化合物反应制备了（对苯）比西碘鎓盐。以二乙酸碘苯和邻碘基苯甲酸为原料，制备了新型高价碘试剂。（对苯）铋酸盐与亲核反应炔基（对苯）铋酸盐与硫氰酸盐离子反应得到炔基硫氰酸盐，与苯二酮烯酸酯和苯氧化合物离子反应得到戊烯和苯并呋喃衍生物。虽然（对苯）铋盐对亲核试剂表现出较高的反应活性，但反应是通过迈克尔加成-重排过程进行的。与炔基铜试剂反应得到二乙炔衍生物，并应用于液晶二乙炔的合成。芳基（对苯基）铋盐与吡啶、三苯基膦和二苯基硫化物反应。用类似的方法制备了l-芳基苯并噻吩盐。

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.