REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-516 Caparica, Portugal.
J Phys Chem A. 2012 Feb 23;116(7):1765-73. doi: 10.1021/jp2107796. Epub 2012 Feb 9.
Fundamental data on 1,4-dioxaspiro[4.5]decane-2-methanol are scarce. This work presents the foremost systematic data on the solubility of 1,4-dioxaspiro[4.5]decane-2-methanol in sustainable solvents such as water and ionic liquids accompanied by the interpretation of interactions occurring in such binary systems. 1,4-Dioxaspiro[4.5]decane-2-methanol, here called protected glycerol, has been synthesized in order to protect the two hydroxyl groups of glycerol, thus avoiding the formation of side products in a specific process. A series of imidazolium salts accompanied by pyridinium, phosphonium, and ammonium ones with various types of counterions were used in this study. The liquid-liquid and solid-liquid equilibrium measurements in binary systems were carried out by using a dynamic method at atmospheric pressure over the temperature range from 273.00 to 378.30 K or below the boiling point of the solvent. Among all tested sustainable solvents, protected glycerol exhibited limited solubility, with only a few of them in the temperature range studied. The majority of the examined ionic liquids, either hydrophilic or hydrophobic, showed complete miscibility with this monohydroxyol. The Fourier-transform infrared (FTIR) spectroscopy studies of solute and solvents showing a miscibility gap and of their mixtures were performed to obtain insight into major inter- and intramolecular interactions in the investigated systems. Furthermore, the differential scanning calorimetry was used for the first time to determine the melting point, the enthalpy of melting, and the temperature and enthalpy of the solid-solid phase transition of 1-allyl-3-methylimidazolium chloride [Amim][Cl]. The results for the solubility of protected glycerol in sustainable solvents can be used to design future alternative reactions, such as telomerization with protected glycerol in ionic liquids for more specific building blocks and extraction/or separation that involves these mixtures.
关于 1,4-二氧杂螺[4.5]癸烷-2-甲醇的基础数据很少。本工作首次提供了在水和离子液体等可持续溶剂中 1,4-二氧杂螺[4.5]癸烷-2-甲醇的溶解度的系统数据，并对这些二元体系中发生的相互作用进行了解释。1,4-二氧杂螺[4.5]癸烷-2-甲醇，这里称为保护甘油，是为了保护甘油的两个羟基，从而避免在特定过程中形成副产物而合成的。本研究使用了一系列带有不同类型反离子的咪唑鎓盐，以及吡啶鎓、磷鎓和铵盐。在大气压下，通过动态法在 273.00 到 378.30 K 或溶剂沸点以下的温度范围内进行了二元体系的液-液相和固-液相平衡测量。在所测试的所有可持续溶剂中，保护甘油的溶解度有限，在所研究的温度范围内只有少数几种溶剂。大多数亲水或疏水的离子液体与这种单羟基醇完全混溶。对溶质和溶剂（显示混合间隙）及其混合物进行傅里叶变换红外（FTIR）光谱研究，以深入了解所研究体系中的主要分子间和分子内相互作用。此外，首次使用差示扫描量热法测定了 1-烯丙基-3-甲基咪唑氯化物[Amim][Cl]的熔点、熔化焓以及固-固相变的温度和焓。保护甘油在可持续溶剂中的溶解度数据可用于设计未来的替代反应，例如与离子液体中的保护甘油进行齐聚反应，以获得更特定的构建块，以及涉及这些混合物的萃取/分离。
