石凯威, 王琴, 黄伟, 吴进龙. 三甲苯草酮溶液稳定性研究[J]. 农药学学报, 2020, 22(6): 1047-1053. DOI: 10.16801/j.issn.1008-7303.2020.0119
    引用本文: 石凯威, 王琴, 黄伟, 吴进龙. 三甲苯草酮溶液稳定性研究[J]. 农药学学报, 2020, 22(6): 1047-1053. DOI: 10.16801/j.issn.1008-7303.2020.0119
    SHI Kaiwei, WANG Qin, HUANG Wei, WU Jinlong. Study on the stability of traloxydim solution[J]. Chinese Journal of Pesticide Science, 2020, 22(6): 1047-1053. DOI: 10.16801/j.issn.1008-7303.2020.0119
    Citation: SHI Kaiwei, WANG Qin, HUANG Wei, WU Jinlong. Study on the stability of traloxydim solution[J]. Chinese Journal of Pesticide Science, 2020, 22(6): 1047-1053. DOI: 10.16801/j.issn.1008-7303.2020.0119

    三甲苯草酮溶液稳定性研究

    Study on the stability of traloxydim solution

    • 摘要: 初步研究了三甲苯草酮在不同溶剂和不同温度下的溶液稳定性。三甲苯草酮标样经乙腈、甲醇和V (乙腈) : V (2%乙酸水溶液) = 80 : 20的混合溶剂溶解后,分别在25 ℃、40 ℃和60 ℃条件下恒温水浴,24 h内多点取样,样品经超高效液相色谱-串联质谱仪 (UPLC-MS/MS) 定性分析,高效液相色谱-二极管阵列检测器 (HPLC-DAD) 定量分析,通过分析三甲苯草酮异构体比例和噁唑重排产物转化率,对溶液的稳定性进行了评估。结果表明:烯醇式E-三甲苯草酮和Z-三甲苯草酮存在异构化现象,其中前者为优势构象;三甲苯草酮在溶液中的稳定性与溶剂种类和温度密切相关。本研究中,在极性较低的乙腈溶剂中三甲苯草酮稳定性较好;在极性较高的甲醇和V (乙腈) : V (2%乙酸水溶液) = 80 : 20混合溶剂中,存在E-三甲苯草酮向Z-三甲苯草酮转化现象,并很快达到平衡,同时可经贝克曼重排生成1,3-噁唑重排产物,且高温和高极性溶剂都有利于噁唑重排产物的生成。研究表明,极性较低的乙腈适宜作为三甲苯草酮的储备液溶剂和流动相,且低温环境有利于提高三甲苯草酮溶液的稳定性。

       

      Abstract: The stability of traloxydim in acetonitrile, methanol and acetonitrile-2% acetic acid (80 : 20, V/V) was investigated under different conditions. The traloxydim standard solution was stored at 25 ℃, 40 ℃, 60 ℃, and sampled at intervals in 24 h. Qualitative and quantitative analysis were established through ultra-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) and high-performance liquid chromatography coupled with diode array detection (HPLC-DAD), respectively. The stability of traloxydim was evaluated by analyzing the isomer ratio and inversion rate of the oxazole product. The results showed that tralkoxydim existed as planar enol forms of E-isomer and Z-isomer, and predominated by the former isomer. The stability of traloxydim was closely related to the solvent and the storage temperature. Traloxydim was stable in acetonitrile and no degradation was observed. In methanol and acetonitrile-2% acetic acid (80 : 20, V/V), the isomerization fromE-isomer to Z-isomer was detected in rapid equilibrium. Furthermore, tralkoxydim underwent Beckmann rearrangement by the loss of ethanol to give more oxazole products at high temperature and polar solvents. Therefore, acetonitrile was suitable to be the solvent and mobile phase of tralkoxydim, and low temperature contributed to the improvement of its stability in the solution.

       

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