2-氯-4-氟-5-硝基苯基碳酸乙酯的合成

化工进展

2-氯-4-氟-5-硝基苯基碳酸乙酯的合成

赵德明1，竺三奇1，张建庭1，金宁人1，徐新华2，汪大翚2

1浙江工业大学化学工程与材料学院，浙江杭州 310032；2浙江大学环境与资源学院

出版日期:2010-07-05 发布日期:2010-07-05

Synthesis of 2-chloro-4-fluoro-5-nitrophenyl ethyl carbonate

ZHAO Deming1，ZHU Sanqi1，ZHANG Jianting1，JIN Ningren1，XU Xinhua2，WANG Dahui2

1College of Chemical Engineering and Materials，Zhejiang University of Technology；
2College of Environmental and Resource Scinences，Zhejiang University

Online:2010-07-05 Published:2010-07-05

摘要/Abstract

摘要： 采用2-氯-4-氟苯酚为原料，水为溶剂，经氯甲酸乙酯酰化，得到2-氯-4-氟苯基碳酸乙酯，后经混酸硝化，最终得到2-氯-4-氟-5-硝基苯基碳酸乙酯。研究了合成2-氯-4-氟苯基碳酸乙酯和2-氯-4-氟-5-硝基苯基碳酸乙酯的生产工艺条件，并对其反应机理和硝化反应动力学进行了分析。实验结果表明酰化反应较佳条件为：n(2-氯-4-氟苯酚)∶n(氯甲酸乙酯)=1∶1.06，pH值为6.8～7.0，反应温度25 ℃，反应时间2 h；硝化反应的较佳条件为：n(硝酸)∶n(2-氯-4-氟苯基碳酸乙酯)=1∶1.25，温度为15 ℃下滴加发烟硝酸，混酸中浓硫酸的质量分数为80%，反应时间2 h，反应温度20 ℃。以2-氯-4-氟苯酚计两步总收率为92.95%，2-氯-4-氟-5-硝基苯基碳酸乙酯的HPLC纯度为99.21%。2-氯-4-氟苯基碳酸乙酯和2-氯-4-氟-5-硝基苯基碳酸乙酯产品结构经1H-NMR、FT-IR和元素分析表征确认。

Abstract: Through acylation and nitration reactions，2-chloro-4-fluoro-5-nitrophenyl ethyl carbonate was synthesized from 2-choro-4-fluorophenol，ethyl chloroformate and fuming nitric acid. Influencing factors，reaction mechanism and kinetics of acylation and nitration reactions were investigated. Proper experimental conditions for acylation reaction were found as：n(2-choro-4-fluorophenol)∶n(ethyl chloroformate)=1∶1.06，pH 6.8—7.0，reaction temperature 25 ℃ and reaction time 2 h. The optimal nitration reaction conditions were found as：n(HNO3)∶n(2-chloro-4-fluorophenyl ethyl carbonate)=1∶1.25，reaction time 2 h，reaction temperature 20 ℃. The purity of 2-choro-4- fluoro-5-nitrophenyl ethyl ester was 99.21% as determined by HPLC，and the total yield of 2- choro-4-fluoro-5-nitrophenyl ethyl ester based on 2-choro-4-fluorophenol was 92.95%. The molecular structure of 2-chloro-4-fluorophenyl ethyl carbonate and 2-choro-4-fluoro-5-nitrophenyl ethyl ester were exactly identified by 1H-NMR，FT-IR and elementary analysis.

赵德明1，竺三奇1，张建庭1，金宁人1，徐新华2，汪大翚2. 2-氯-4-氟-5-硝基苯基碳酸乙酯的合成 [J]. 化工进展.

ZHAO Deming1，ZHU Sanqi1，ZHANG Jianting1，JIN Ningren1，XU Xinhua2，WANG Dahui2. Synthesis of 2-chloro-4-fluoro-5-nitrophenyl ethyl carbonate[J]. Chemical Industry and Engineering Progree.