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

从环境方面，非常需要溶剂的无溶性电机合成。近年来，由于其良好的电导率，不易受性，热稳定性，非挥发性和可重用性，因此事实证明，室温熔融盐，即离子液体，被证明是一类新的承诺溶液。因此，当将离子液体用作电解介质时，没有任何有机溶液的有机电解反应，尤其是电机合成。但是，在离子液体中处理有机电气合成的论文数量仍然有限。在这个项目中，我们已经实现了以下主题。1）阳极荧光硫化物的3-苯基噻吩，4-苯基噻吩，4-苯基噻吩-1,3-二氧糖 - 二氧和1-芳基硫代硫化物和1-芳族-2,3,4,6--tetra-o-o-o-o-o-o-o-o-o-o-o-β-β-β-β-β-β-β-β-β-d-d-丙型固醇等液体液体中的ies_3n = 4 H.5） ET_4NF ・NHF（n = 4,5）没有任何解决方案，提供了相应的单氟化产品，专门以现代为到良好的产量。在…更尖锐的对比度中，ET_3N ・3HF中有和没有共溶剂的阳极氟化导致α-荧光，而无需脱硫，而无限制地或优先脱硫。还证明，在溶剂的自由条件下，3-苯基噻吩二苯二甲酸酯的电化学荧光硫化是通过重复使用氟盐的重复使用，ET_4NF ・4HF的四次。这就是我们通过重复使用离子液氟盐来展示了氟化物溃疡的第一个例子。（n = 4,5）.2）CO（II）沙龙介质对通过环状电效应中的离子液体中的循环vio-Dibromide的还原的催化作用。宏观受控电势电解以中等至良好的收率使相应的脱溴产物。事实证明，在离子液体中电解后的检查比有机溶液中要简单得多。在一定程度上证明了重新恢复离子液体的可能性。3）有机污染物的光催化降解，例如萘酚蓝色黑色，敏感性和2氯苯酚（2CP），在离子液体中使用TIO_2进行。与水中的液体相比，离子液体中前两个偶氮染料的phtocatalytic降解速率大大提高。相比之下，在离子液体中，2CP的光降解效率不高，但是在同时超声处理下，降解得到了增强。4）在像ET_4NF诸如ET_4NF之类的离子液体中成功地进行了环环硫代碳酸酯（如1,3-氧磷酸）2酮（如1,3-氧硫代苯甲酸酯）的阳极荧光。较少的