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Environmentally Friendly Electroorganic Synthesis in Ionic Liquids Toward a Solvent-Free Process

离子液体中的环保有机电合成迈向无溶剂工艺

基本信息

批准号：
16550090
负责人：
FUCHIGAMI Toshio
金额：
$ 2.37万
依托单位：
Tokyo Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

项目摘要

Solvent free electroorganic synthesis is highly desirable from an environmental aspect. In recent years, room-temperature molten salts, namely ionic liquids, have proved to be a new class of promising solvents because of their good electroconductivity, nonflammability, thermal stability, nonvolatality, and reusability. Therefore, when ionic liquids are used as electrolytic media, organic electrolytic reactions, particularly electroorganic synthesis should be possible without any organic solvents. However, there have been still a limited number of papers dealing with organic electrosynthesis in ionic liquids. In this project, we have achieved the following subjects.1) Anodic fluorodesulfurization of 3-phenylthiophthalide, 4-phenylthio-1,3-dioxolan-2-one, and 1-arylthio-2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside in ionic liquids like Et_3N・nHF (n=4,5) and Et_4NF・nHF (n=4,5) without any solvents provided the corresponding monofluorinated products exclusively in moderate to good yields. In … More sharp contrast, the anodic fluorination in Et_3N・3HF with and without co-solvent resulted in α-fluorination without desulfurization exclusively or preferentially. It was also demonstrated that the electrochemical fluorodesulfurization of 3-phenylthiophthalide under solvent free conditions was achieved repeatedly four times by the reuse of a fluoride salt, Et_4NF・4HF. Thus, we have shown the first example of fluorodesulfurization by the reuse of an ionic liquid fluoride salt. (n=4,5).2) The catalytic effect of a Co(II)salen mediator on the reduction of cyclic vio-dibromide was investigated in ionic liquids by cyclic volteammetry. Macro-scale controlled potential electrolysis gave the corresponding debrominated product in moderate to good yields. The workup after electrolysis in an ionic liquid proved to be much simpler than that in organic solvents. The possibility of reruse of the ionic liquid was demonstrated to some extent.3) Photocatalytic degradation of organic pollutants such as naphthol blue black, Amarance, and 2-chlorophenol (2CP) was carried out using TiO_2 in ionic liquids. The phtocatalytic degradation rate of the former two azo dyes were greatly enhanced in ionic liquids compared with those in water. In sharp contrast, the photodegradation of 2CP was not efficient in an ionic liquid, however, the degradation was enhanced under simultaneous ultrasonication.4) Anodic fluorination of cyclic thiocarbonates like 1,3-oxathiolane-2one was successfully carried out in ionic liquids like Et_4NF・4HF. Less

从环境的角度来看，无溶剂电有机合成是非常可取的。近年来，室温熔盐，即离子液体，由于具有良好的导电性、不可燃性、热稳定性、非挥发性和可重复使用等优点，被证明是一类很有前途的新型溶剂。因此，当使用离子液体作为电解介质时，有机电解反应，特别是电有机合成应该可以在没有任何有机溶剂的情况下进行。然而，关于离子液体中的有机电合成的论文仍然很少。1)在离子液体Et_3N·nHF(n=4，5)和Et_4nF·nHF(n=4，5)中，3-苯硫基-2-酮、4-苯硫基-1，3-二氧戊环-2-酮和1-arylthio-2，3，4，6-tetra-O-acetyl-β-D-glucopyranoside在无任何溶剂的情况下进行了阳极氟化反应，得到了相应的单氟化产物。在…中与之形成鲜明对比的是，Et_3N·3Hf溶液在有无共溶剂的情况下进行的阳极氟化反应导致了α-氟化反应，而没有进行排他性或优先脱硫剂。通过重复使用氟化盐Et_4nF·4HF，实现了3-苯基硫杂菲在无溶剂条件下的四次电化学氟化。因此，我们展示了第一个通过重复使用离子液体氟化物盐进行氟化的例子。(n=4，5)2)用循环伏安法研究了Co(II)Salen介体对离子液体中环状VIO-二溴还原的催化作用。宏观控制电位电解法以中高产率得到相应的脱溴产物。在离子液体中电解后的处理比在有机溶剂中简单得多。3)研究了离子液体中的二氧化钛光催化降解有机污染物如萘酚蓝黑、紫红色和邻氯苯酚(2CP)。前两种偶氮染料在离子液体中的光催化降解速率比在水中的光催化降解速率有很大提高。与之形成鲜明对比的是，在离子液体中，2CP的光降解效率不高，但在同时超声的作用下，2CP的降解被增强。4)在Et_4Nf·4HF等离子液体中，成功地实现了1，3-氧硫杂环己酮等环状硫代碳酸酯的阳极氟化。较少