原位磷酰化衍生-核磁共振法鉴定非磷化学毒剂前体

In Situ Phosphitylation for Nuclear Magnetic Resonance Identification of Precursors of Chemical Warfare Agents

~1H谱鉴定复杂基质中禁止化学武器公约附表2的非磷化学毒剂前体化合物存在困难,一种替代方法是采用2-氯-4,4,5,5-四甲基-1,3,2-二噁磷杂戊环(CTMP)为衍生试剂,在核磁管中原位衍生含羟基的前体化合物并进行磷31-核磁共振谱测定。采用频哪醇及3个同分异构体氨基醇类化合物;2-(N,N-二丙氨基)乙醇、2-(N-异丙基-N-丙基氨基)乙醇和2-(N-正丁基-N-乙基氨基)乙醇,考察了方法的专一性、稳定性、灵敏度和选择性。结果表明,本方法的衍生反应产物单一,稳定性好,能清楚分辨同分异构体的氨基醇。本方法成功应用于禁止化学武器公约组织(OPCW)指定核查实验室第32次官方水平考试,实现了有机液样品中3个氨基醇同分异构体混合物(原始浓度10μg/mL)的检测及鉴定。

There is a trouble for ~1H NMR identification of non-phosphorus precursors of chemical warfare agents listed in Schedule 2,part B of Chemical Weapons Convention（CWC） in complex matrix.An alternative method was proposed for identification by in situ derivatization of the precursors containing hydroxyl functions with 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane（CTMP） in a NMR tube followed by phosphorus-31 NMR detection.The specificity,stability,sensitivity and selectivity of the method were evaluated with pinacol and three aminoalcohols isomers,2-（N,N-dipropylamino） ethanol,2-（N-butyl-Nethylamino） ethanol and 2-（N-isopropyl-N-propylamino） ethanol.The results showed that the phosphorylation products were single,stable and allowing clear distinction between aminoalcohols isomers.The method was used for the detection and identification of three mixed aminoalcohols isomers present（at original concentration of 10 μg/mL） in an organic sample from 32^（th） OPCW Official Proficiency Tests.