六 - 2 -（β - 羧基乙烯基苯氧基）环三磷腈：合成、性质、结构建模

Hexakis-2-(β-carboxyethenylphenoxy)cyclotriphosphazene: Synthesis, Properties, Modeling Structure.

作者信息

Yudaev Pavel, Konstantinova Anastasia, Volkov Vladimir, Chistyakov Evgeniy

机构信息

Mendeleev University of Chemical Technology of Russia, Miusskaya sq., 9, 125047 Moscow, Russia.

Shubnikov Institute of Crystallography, Federal Scientific Research Centre "Crystallography and Photonics", Russian Academy of Sciences, Leninsky Prospect, 59, 119333 Moscow, Russia.

出版信息

Molecules. 2023 Sep 11;28(18):6571. doi: 10.3390/molecules28186571.

DOI:10.3390/molecules28186571

PMID:37764347

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10534807/

Abstract

Condensation of hexakis-2-(formylphenoxy)cyclotriphosphazene with malonic acid yielded hexakis-2-(β-carboxyethenylphenoxy)cyclotriphosphazene (2-CEPP), whose structure was confirmed by P, H, C NMR spectroscopy and MALDI-TOF mass spectrometry. A quantum-chemical calculation for the 2-CEPP molecule using the ab initio methods in the 6-311G basis set and the DFT-PBE0/6-311g** method was performed with geometry optimization of all parameters by the standard gradient method. The acid strength of 2-CEPP was theoretically estimated. Using the small-angle X-ray scattering method, it was found that 2-CEPP is an amorphous substance, which, when heated, can transform into a crystalline state. However, when heated at 370 °C, 2-CEPP undergoes decarboxylation and polymerization to form an insoluble heat-resistant product. The occurrence of decarboxylation and polymerization reactions in the formed styrene fragments was confirmed by thermal (differential-scanning calorimetry) and spectral (solid-state C NMR spectroscopy) analysis.

摘要

六 - 2 -（甲酰基苯氧基）环三磷腈与丙二酸缩合得到六 - 2 -（β - 羧基乙烯基苯氧基）环三磷腈（2 - CEPP），其结构通过磷、氢、碳核磁共振光谱和基质辅助激光解吸电离飞行时间质谱得以确认。使用6 - 311G基组中的从头算方法和DFT - PBE0/6 - 311g**方法对2 - CEPP分子进行了量子化学计算，并通过标准梯度法对所有参数进行了几何优化。从理论上估算了2 - CEPP的酸强度。使用小角X射线散射法发现，2 - CEPP是一种无定形物质，加热时可转变为结晶态。然而，在370℃加热时，2 - CEPP会发生脱羧和聚合反应，形成一种不溶性耐热产物。通过热分析（差示扫描量热法）和光谱分析（固态碳核磁共振光谱）证实了所形成的苯乙烯片段中发生了脱羧和聚合反应。