采用高效液相色谱-紫外检测法测定了对羟基苯丙酮酸烯醇一酮式互变异构动力学.结果表明,在以甲醇与13mmol/LNaH2PO4-Na2HPO4缓冲液(pH为5.91)(体积比为10:90)为流动相,流速O.8mL/min时,对羟基苯丙酮酸烯醇式和酮式在10min内得以完全分离.根据酮式结构的含量测定工作曲线的线性范围为1.0×10^-5~1.0×10^-3mol/L,相关系数R2=0.9988,峰高和保留时间的相对标准偏差为3.4%和0.6%.对羟基苯丙酮酸互变异构符合一级反应动力学,测得其在20℃下的速率常数为k=0.005min^-1,半衰期为t1/2=138.6min.
The kinetics of keto-enol tautomerism of p-hydroxyphenylpyruvic acid (pHPP) in aqueous solution at room temperature (20 ℃ ) was first investigated by High Performance Liquid Chromatography with UV detection at 216 nm. The result showed that two tautomers could be separated and detected within 10 min by using a mobile phase of 13 mmol/L phosohate and methanol (90 : 10 v/v; pH5. 91) at a flow rate of 0. 8 mL/min . According to the ketonic form of pHPP, the linear range is between 1.0 × 10^-5-1. 0 × 10^-3 mol/L with correlation coefficient (R2) 0. 998 8. Relative standard deviation (RSD) for retention time and peak height is 3.4% and 0. 6%, respectively. The kinetics of keto-enol tautomerism of pHPP is first-order reaction. Under 20 ℃, the distribution fractions of enolic pHPP, kinetic rate constant and half-life were determined.