Department of Colloid Chemistry, Max Planck Institute of Colloids and Interfaces Max Planck Institute for Colloids and Interfaces , Am Mühlenberg 1 OT-Golm, 14476 Potsdam, Germany.
J Org Chem. 2018 Jan 19;83(2):684-689. doi: 10.1021/acs.joc.7b02631. Epub 2018 Jan 2.
Alkylating ionic liquids based on the thioimidazolium structure combine the conventional properties of ionic liquids, including low melting point and nonvolatility, with the alkylating function. Alkyl transfer occurs exclusively from the S-alkyl position, thus allowing for easy derivatization of the structure without compromising specificity. We apply this feature to tune the electrophilicty of the cation to profoundly affect the reactivity of these alkylating ionic liquids, with a caffeine-derived compound possessing the highest reactivity. Anion choice was found to affect reaction rates, with iodide anions assisting in the alkylation reaction through a "shuttling" process. The ability to tune the properties of the alkylating agent using the toolbox of ionic liquid chemistry highlights the modular nature of these compounds as a platform for alkylating agent design and integration in to future systems.
基于硫代咪唑啉结构的烷基化离子液体结合了离子液体的常规性质，包括低熔点和非挥发性，以及烷基化功能。烷基转移仅从 S-烷基位置发生，从而可以在不影响特异性的情况下轻松对结构进行衍生化。我们应用此功能来调节阳离子的亲电性，以极大地影响这些烷基化离子液体的反应性，其中一种咖啡因衍生的化合物具有最高的反应性。发现阴离子的选择会影响反应速率，碘阴离子通过“穿梭”过程协助烷基化反应。使用离子液体化学工具箱来调节烷基化试剂的性质的能力突出了这些化合物作为烷基化试剂设计和集成到未来系统的平台的模块性质。
