氟菌唑代谢物FM-6-1的合成与表征
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摘要
氟菌唑代谢物4-氯-α,α,α-三氟-N-(1-氨基-2-丙氧基亚乙基)-氧-甲苯胺(FM-6-1)的合成方法目前尚无文献报道,以2-氨基-5-氯三氟甲苯为原料,经氯化、缩合、氯化、胺化4步反应合成目标产物,4步反应总收率达60%。目标产物经~1HNMR、~(19)FNMR、~(13)CNMR、HRMS表征确认。该路线具有原料廉价易得、操作简单、后处理方便、收率较高等优点,通过高效液相色谱确认化学纯度达到99%以上,可以作为农残检测标准品用于食品安全检测和环境监测领域。
The synthesis of triflumizole metabolite 4-chloro-α,α,α-trifluoro-N-( 1-amino-2-propoxyethylidene)-o-toluidine( FM-6-1) hasn' t been reported in the literature up to date. Disclosed its synthesis using 4-chloro-2-( trifluoromethyl) aniline as raw material in four steps,acid chlorination,amine acylation,amide chlorination,and amination,in 60% overall yield. The target product was confirmed by~1HNMR,~(19) FNMR,~(13)CNMR and HRMS.The synthetic route has the advantages of economic raw materials,simple operation,easy post-processing and high yield.In addition,the chemical purity was higher than 99% based on HPLC,which can be used as reference material for pesticide residue screening and testing for food safety and environmental monitoring industries.
The synthesis of triflumizole metabolite 4-chloro-α,α,α-trifluoro-N-( 1-amino-2-propoxyethylidene)-o-toluidine( FM-6-1) hasn' t been reported in the literature up to date. Disclosed its synthesis using 4-chloro-2-( trifluoromethyl) aniline as raw material in four steps,acid chlorination,amine acylation,amide chlorination,and amination,in 60% overall yield. The target product was confirmed by~1HNMR,~(19) FNMR,~(13)CNMR and HRMS.The synthetic route has the advantages of economic raw materials,simple operation,easy post-processing and high yield.In addition,the chemical purity was higher than 99% based on HPLC,which can be used as reference material for pesticide residue screening and testing for food safety and environmental monitoring industries.
引文
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[8]NIU J H,HU J Y.Dissipation behaviour and dietary risk assessment of boscalid,triflumizole and its metabolite(FM-6-1)in open-field cucumber based on Quechers using HPLC-MS/MS technique[J]. J. SCI. Food Agric.,2018,98(12):4 501-4 508.
[9]国家卫生和计划生育委员会,国家食品药品监督管理总局,农业部.食品中农药最大残留限量标准:GB2763—2016[S].2016-12-18.
[10]庞国芳,张磊,张紫娟,等.世界常用农药核磁谱图集[M].北京:化学工业出版,2018:1 151-1 152.
[2]KAWAHARA N,NOMURA M,DAIDO H. Compositions containing amides and other pesticides for controlling pests and plant diseases:WO,2 007 013 150[P]. 2007-02-01.
[3]KOZUE J,KAWAHARA A,TANIGAWA H,et al. Paste formulations of pesticides:JP,2 007 246 496[P]. 2007-09-27.
[4]谭成侠,徐瑶,曾仲武,等.杀菌剂氟菌唑的合成及表征[J].农药,2008,47(7):497-499.
[5]TAKESHI G,YASUSHI M,SHOGO Y,et al. Analytical method for the residues of triflumizole fungicide and its main metabolite in crops by high performance liquid and gas chromatography[J].Anal.Sci.,1991,7:749-756.
[6]TORRES CM,PICOY,REDONDO M J,et al.Matrix solid-phase dispersion extraction procedure for multiresidue pesticide analysis in oranges[J]. J. Chromatogr. A,1996,719(1):95-103.
[7]INAM R,GULERMAN EZ,SARIGUL T.Determination of triflumizole by differential pulse polarography in formulation,soil and natural water samples[J].Anal.Chim. Acta,2006,579(1):117-123.
[8]NIU J H,HU J Y.Dissipation behaviour and dietary risk assessment of boscalid,triflumizole and its metabolite(FM-6-1)in open-field cucumber based on Quechers using HPLC-MS/MS technique[J]. J. SCI. Food Agric.,2018,98(12):4 501-4 508.
[9]国家卫生和计划生育委员会,国家食品药品监督管理总局,农业部.食品中农药最大残留限量标准:GB2763—2016[S].2016-12-18.
[10]庞国芳,张磊,张紫娟,等.世界常用农药核磁谱图集[M].北京:化学工业出版,2018:1 151-1 152.