氨基甲酸乙酯与3,4,6-三苄氧基-D-葡萄烯糖的反应及其分析应用

Research and application on the reaction of ethyl carbamate and 3,4,6-Tri-O-benzyl-D-glucal

以氨基甲酸乙酯(EC)为亲核试剂,在Lewis酸三氟甲烷磺酸钐(Sm(OTf)_3)的催化作用下,与3,4,6-三苄氧基-D-葡萄烯糖进行Ferrier(Ⅰ)重排反应制得2,3-不饱和糖苷。通过荧光分光光度法测定反应产物2,3-不饱和糖苷的荧光强度来间接测定EC的含量。实验发现,2,3-不饱和糖苷的荧光强度与EC的浓度在5.0×10^(-8)~1.0×10^(-5)mol/L范围呈良好的线性关系,检出限为1.07×10^(-8)mol/L(S/N=3)。EC的衍生化也使采用HPLC来测定EC浓度成为可能。2,3-不饱和糖苷HPLC的峰面积值与EC的浓度在2.0×10^(-5)~2.0×10^(-4)mol/L(1.7~17μg/m L)范围内呈良好的线性关系,检出限达到1.6×10^(-6)mol/L(0.59μg/m L)(S/N=3)。

2,3-Unsaturated glycoside was synthesized by Ferrier（ I） rearrangement. Ethyl carbamate（ EC） was used as nucleophile,catalyzed by samarium trifluoromethanesulfonate（ Sm（ OTf）3）,and acted with 3,4,6-TriO-benzyl-D-glucal. Fluorometric spectrophotometry was employed to detect the fluorescent intensity of 2,3-unsaturated glycoside to indirectly determine the concentration of EC. It was found that there is a good linear relationship between the concentration of EC and the fluorescent intensity of 2,3-unsaturated glycoside in the range from5. 0 × 10^-8to 1. 0 × 10^-5 mol / L. The limit of detection（ LOD） was 1. 07 × 10^-8mol / L（ S / N = 3）. Under the optimized conditions,high performance liquid chromatography（ HPLC） was also employed to detect 2,3- unsaturated glycoside,which would indirectly to detect EC. The HPLC peak area of 2,3-unsaturated glycoside linearly increased with the increase of EC concentration in the range from 2. 0 × 10^-5to 2. 0 × 10^-4mol / L（ 1. 7 ～ 17μg /m L） with the LOD of 1. 6 × 10～（-6）mol / L（ 0. 59 μg / m L）（ S / N = 3）. Indirectly determination of EC by HPLC method has the advantages of more reliable and has less interference. It could provide certain technical and theoretical supports for rapid detection of EC in alcoholic beverages and fermented food.