以甲酸为氢源的硝基苯转移加氢合成对氨基苯酚的高效液相色谱分析  

High performance liquid chromatography analysis of p-aminophenolsynthesized by nitrobenzene transfer hydrogenation using formic acid as hydrogen source

作　　者：张议升 车聪慧 王志苗[1,2] 薛伟 李芳[1,2] 王延吉 ZHANG Yisheng;CHE Conghui;WANG Zhimiao;XUE Wei;LI Fang;WANG Yanji(Hebei Provincial Key Laboratory of Green Chemical Technology and High Efficient Energy Saving,School of Chemical Engineering and Technology,Hehei University of Technology,Tianjin 300130,China;Tianjin Laboratory of Chemical Process Safety,Tianjin 300130,China;Hehei Industrial Technology Research Institute of Green Chemical Industry,Huanghua 061100,China)

机构地区：[1]河北工业大学化工学院河北省绿色化工与高效节能重点实验室,天津300130 [2]天津市本质安全化工技术重点试验室,天津300130 [3]河北省绿色化学工业产业研究院,黄骅061100

出　　处：《分析试验室》2022年第7期760-764,共5页Chinese Journal of Analysis Laboratory

基　　金：国家自然科学基金项目(21776057,U20A20152)资助。

摘　　要：采用电喷雾电离质谱对以甲酸为氢源、硝基苯转移加氢合成对氨基苯酚的反应体系中的主要副产物4-羟基苯甲酰胺进行定性分析。利用高效液相色谱对反应体系进行定量分析,色谱柱:Shim-pack VP-ODS(250 mm×4.6 mm,5μm),检测波长:254 nm,流动相:V(甲醇)∶V(缓冲盐水溶液)=1∶1(缓冲盐溶液中KH_(2)PO_(4)的浓度为4.8 mmol/L,Na_(2)HPO_(4)的浓度为1.9 mmol/L),流速:0.8 mL/min,柱温:35℃。以N-苯基香豆甲酯为内标物,采用内标法对反应体系中的硝基苯、对氨基苯酚、苯胺和甲酰苯胺进行定量分析,相关系数(R2)分别为0.9993,0.9995,0.9998和0.9992,相对标准偏差(RSD)分别小于1.0%,0.3%,0.2%和0.4%,回收率分别为95.5%~102.6%,101.2%~104.8%,95.1%~99.8%和95.7%~101.1%。此方法可用于以甲酸为氢源的硝基苯转移加氢反应中主副产物的同时测定。Qualitative analysis of the main by-product of 4-hydroxybenzamide in the synthesis of p-aminophenol bynitrobenzene transfer hydrogenation with formic acid as hydrogen source was carried out by electrospray ionization mass spectrometry.The reaction system was quantitatively analyzed by high performance liquid chromatography.The chromatographic conditions were shown as follows:Shim pack VP-ODS column(250 mm×4.6 mm,5μm),detection wavelength of 254 nm,V(methanol)∶V(buffer solution)=1∶1(4.8 mmol/L sodium dihydrogen phosphate solution,1.9 mmol/L dibasic sodium phosphate solution)as the mobile phase and the flow rate of 0.8 mL/min with a column temperature of 35℃.Nitrobenzene,p-aminophenol,aniline and formylaniline in the reaction system were quantitatively analyzed by standard curve method with methyl N-phenylcarbamate as internal standard.The correlation coefficients(R~2)were 0.9993,0.9995,0.9998 and 0.9992 for these analytes,respectively.The relative standard deviations(RSDs)were less than 1.0%,0.3%,0.2%and 0.4%,respectively.The recoveries were in the ranges of 95.5%-102.6%,101.2%-104.8%,95.1%-99.8%and 95.7%-101.1%,respectively.This method can be used for the simultaneous determination of main and by-products in the transfer hydrogenation of nitrobenzene with formic acid as hydrogen source.

关 键 词：高效液相色谱法 对氨基苯酚 硝基苯 苯胺 甲酰苯胺 4-羟基苯甲酰胺 

分 类 号：O657.7[理学—分析化学]