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Experimental investigation of chiral melting phase diagrams in high-pressure CO2 containing organic modifiers
The Journal of Supercritical Fluids ( IF 3.9 ) Pub Date : 2021-07-15 , DOI: 10.1016/j.supflu.2021.105352
Márton Kőrösi 1 , János Béri 1 , Dóra Arany 1 , Csaba Varga 1 , Edit Székely 1
Affiliation  

A measurement method suitable to investigate the melting behavior of solid mixtures in a high-pressure, co-solvent–modified CO2 atmosphere was developed, using a variable volume, high-pressure view-cell. The solid sample is added after loading the organic solvents and pressurizing the cell with CO2. Investigation of the melting behavior was done by a first-and-last melting point method at 16 MPa pressure. The melting point depression depended on the organic modifier (being acetonitrile or the 7:3 mixture of cyclohexane and isopropyl acetate). Adding acetonitrile in 2% to the carbon dioxide atmosphere shifted the chiral melting phase diagram of 3-chloromandelic acid by approx. 8–10 °C compared to the values measured earlier in pure carbon dioxide at the same pressure. The eutectic composition of the racemic compound remained unchanged (around 70–75% ee), which is comparable to the limiting composition observed in our earlier antisolvent recrystallization results aiming the enantiomeric purification of the model molecule.



中文翻译:

高压含CO2有机改性剂手性熔融相图的实验研究

开发了一种适合研究固体混合物在高压、共溶剂改性 CO 2气氛中的熔化行为的测量方法,使用可变体积的高压观察室。在加载有机溶剂并用 CO 2对池加压后加入固体样品. 在 16 MPa 压力下通过首末熔点法对熔化行为进行研究。熔点降低取决于有机改性剂(乙腈或环己烷和乙酸异丙酯的 7:3 混合物)。在二氧化碳气氛中加入 2% 的乙腈使 3-氯扁桃酸的手性熔融相图移动了大约 8–10 °C 与之前在相同压力下在纯二氧化碳中测得的值相比。外消旋化合物的共晶成分保持不变(约 70-75% ee),这与我们早期的抗溶剂重结晶结果中观察到的限制成分相当,旨在对模型分子的对映体纯化。

更新日期:2021-08-27
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