O-(α-氰基-间-苯氧基苄基)硫代磷酸酯和磷酰胺的NMR研究

本文合成了20个题示的化合物,研究了它们的¹H和³¹P谱,找出了δ_P与取代基关系的一些规律,观察到了手性中心对δ_H的影响、及一个手性中心对另一个手性中心R、S体不等价的诱导位移,并观察了产物中R、S体的不同含量比例。     

手性硫代磷酸及其衍生物的研究(Ⅸ)——O-乙基O-苯基硫代磷酰胺水解反应的立体化学

旋光活性O-乙基O-苯基硫代磷酰氯在碱存在下与伯胺、仲胺或氨反应,得到构型翻转的O-乙基O-苯基硫代磷酰胺.其酸性水解在6mol/L或9mol/L盐酸/二氧六环中进行,得P-N键断裂的构型翻转产物;碱性水解在1mol/L或3mol/LNaOH/二氧六环中进行,得到以OPh为离去基团的构型翻转产物.水解反应机理用三角双锥(TBP)中间体概念得到合理解释.     

Bis(tetraethylthiophosphoramidoyl)methylamine as an electrochemical ligand for the simultaneous detection of iron and copper bivalent cations

A new thiophosphoramide-based electrochemical ligand was synthesized and used as a bivalent metallic cation sensor. Electrochemical studies reveal a sensitive detection process toward various cations such as Fe²⁺, Co²⁺, Ni²⁺, Cd²⁺, Cu²⁺ and Ca²⁺. The chelation process was accompanied by dramatic changes in the redox properties of the free ligand. Interestingly, the ligand shows a simultaneous sensing behavior towards iron and copper cations. The oxidation peak potentials of the two complexes can be well separated, allowing sensitive detection. Furthermore, UV–Visible spectra showed redshifts of absorbance bands of the free ligand in the presence of cations due to the coordination of the thiophosphoryl groups. Electrochemical and UV–Visible studies confirmed that the metal-ligand complexes have 1:2 stoichiometry.