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

无溶剂的有机合成是一个非常不可取的环境方面。在过去几年中，室内温度麦芽盐，命名为离子液体，已经提出了一个新的类别的承诺，因为它们的良好电作用、非挥发性、热稳定性、非挥发性和可重用性。因此，当离子液体被用作电介质、有机电反应或部分电有机合成物时，在没有任何有机溶剂的情况下都是有可能的。然而，在离子液体中，仍有有限数量的纸张交易与有机电合成。在这个项目中，我们已经完成了以下的主题。1）3-苯基硫醚、4-苯基硫醚-1、3-二氧烷-2 - 1和1-苯基硫醚-2、3，4，6-四-O-乙酰-β-D-葡萄糖苷在离子液体中如Et_3N·nHF （n = 4，5）和Et_4NF·nHF（n = 4，5）的任何溶剂都能提供相应的单氟醚产品，至少能达到好的产量。In（In） ... More sharp对比，在Et_3N·3 HF中的异源荧光，并且没有在α-荧光下的协同荧光，排除或最好地进行非饱和荧光。它也被证明是在溶剂无条件条件下使用3-苯三氟醚的电化学氟醚的电化学氟醚（Et_4NF·4 HF）实现并重复了四次。因此，我们展示了荧光还原法的第一个例子，即离子液体荧光盐的利用。（n=4，5）。2）Co（II）盐介质对环氯二溴胺的减少的催化效应通过环氯伏安法进行了研究。宏观尺度控制的潜在电解质给了相应的拆卸产品在中等水平到良好的年份。在一个离子液体中产生的电中毒后的工作要比有机溶液中的有机溶液更简单。离子液体的可能性可能性被证明是在某些范围内。3）有机污染物的光降解，如萘酚蓝黑色、Amarance和2-氯酚（2CP）被携带在离子液体中的TiO_2。“前两个氮染料的物理分解率在与水中的离子液体相比时得到了极大的增强。”在清晰的对比下，2CP的光降解在离子液体、高通量下是增强的，如1，3-氧硫氰胺-21在离子液体中成功地携带了类似Et_4NF·4 HF的环硫代化合物的异黄酮。Less（低）

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