Spegazzini Nicolás, Ruisánchez Itziar, Larrechi M Soledad, Cádiz Virginia, Canadell Judit
Chemometrics, Qualimetrics and Nanosensors group, Rovira i Virgili University. Marcel.li Domingo s/n, 43007, Tarragona, Spain.
Analyst. 2008 Aug;133(8):1028-35. doi: 10.1039/b802161a. Epub 2008 May 27.
The spiroorthoester synthesis includes several competitives reactions. A way of determining the reactions that are taking place and their sequential order, is presented. The reaction between the phenylglycidylether and gamma-butyrolactone to obtain a spiroorthoester has been monitored by near-infrared spectroscopy (NIR). In addition to the formation of the corresponding spiroorthoester, some parallel processes can occur. By means of two-dimensional correlation analysis, only one reaction is postulated, the one corresponding to the spiroorthoester formation. This was confirmed by recording the NMR spectra of the final product. Applying multivariate curve resolution-alternating least squares (MCR-ALS) to the NIR spectra obtained during the reaction, it has been possible to obtain the concentration values of the species involved in the reaction. The recovered spectra were compared with the experimentally recorded spectra for the reagents (phenylglycidylether, gamma-butyrolactone) and the final product (spiroorthoester) and the correlation coefficients were, in all cases, higher than 0.990. The maximum and minimum limits associated with the ALS solutions were calculated, making it possible to limit to a considerable extent the ambiguity that is characteristic of these curve resolution methods.
螺原酸酯的合成包括几个竞争反应。本文提出了一种确定正在发生的反应及其顺序的方法。通过近红外光谱（NIR）监测了苯基缩水甘油醚与γ-丁内酯反应生成螺原酸酯的过程。除了生成相应的螺原酸酯外，还可能发生一些平行过程。通过二维相关分析，仅假设了一个反应，即与螺原酸酯形成对应的反应。这通过记录最终产物的核磁共振光谱得到了证实。将多元曲线分辨交替最小二乘法（MCR-ALS）应用于反应过程中获得的近红外光谱，得以获得反应中涉及的物种的浓度值。将恢复的光谱与试剂（苯基缩水甘油醚、γ-丁内酯）和最终产物（螺原酸酯）的实验记录光谱进行比较，在所有情况下，相关系数均高于0.990。计算了与交替最小二乘法解相关的最大和最小限值，从而在很大程度上限制了这些曲线分辨方法所特有的模糊性。
