稳定同位素氘标记苯脲类除草剂的合成研究
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摘要
为制备HPLC-MS/MS农药残留分析中使用的苯脲类除草剂同位素内标物,以取代苯胺为原料,与三光气反应制得取代的苯基异氰酸酯,再与二甲胺-D_6盐酸盐亲核加成,合成了9种苯脲类除草剂的氘取代物,分别是敌草隆-D_6、灭草隆-D_6、2,3-敌草隆-D_6、绿麦隆-D_6、甲氧隆-D_6、秀草隆-D_6、非草隆-D_6、伏草隆-D_6和异丙隆-D_6。通过NMR、MS、UV对其进行结构确证,化学纯度均大于98%,同位素丰度大于99.5%,完全满足质谱分析对内标物的要求,可作为HPLC-MS/MS分析的同位素内标物。
In order to prepare isotope internal standards of phenylurea hebicides for pesticide residue HPLC-MS/MS analysis,the N,N-dimethyl-deuterated forms of nine ingredients were synthesized form substituted phenylamine in two simple steps via the reaction with triphosgene,and nucleophilic addition with dimethyl-D_6-amine hydrochloride,the deuterium substituted compounds include Diuron-D_6,Monuron-D_6,2,3-Diuron-D_6,Chlorotoluron-D_6,Metoxuron-D_6,Bromuron-D_6,Fenuron-D_6,Fluometuron-D_6 and Isoproturon-D_6. The structures were confirmed by NMR,MS and UV. The purities of all chemicals are more than 98%,meanwhile,all the isotope purities are more than 99. 5%. These deuterium substituted compounds could be used an isotope internal standards by HPLC-MS/MS.
In order to prepare isotope internal standards of phenylurea hebicides for pesticide residue HPLC-MS/MS analysis,the N,N-dimethyl-deuterated forms of nine ingredients were synthesized form substituted phenylamine in two simple steps via the reaction with triphosgene,and nucleophilic addition with dimethyl-D_6-amine hydrochloride,the deuterium substituted compounds include Diuron-D_6,Monuron-D_6,2,3-Diuron-D_6,Chlorotoluron-D_6,Metoxuron-D_6,Bromuron-D_6,Fenuron-D_6,Fluometuron-D_6 and Isoproturon-D_6. The structures were confirmed by NMR,MS and UV. The purities of all chemicals are more than 98%,meanwhile,all the isotope purities are more than 99. 5%. These deuterium substituted compounds could be used an isotope internal standards by HPLC-MS/MS.
引文
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[21]张妮,王敏.气相色谱法检测农药残留过程中基质效应的研究[J].安徽农业科学,2014,21(21):7 073-7 075.
[22]苏萌,艾连峰.液相色谱-串联质谱基质效应及其消除方法[J].食品安全质量检测学报,2014,5(2):511-515.
[23]NGUYEN J V,OLSSON A O,BRAVO R,et al.Quantification of atrazine,phenylurea,and sulfonylurea herbicide metabolites in urine by high-performance liquid chromatography-tandem mass spectrometry[J].J.Anal.Toxicol.,2007,31(4):181-186.
[24]OMAILLE G,GO E P,HOANG L,et al.Metabolomics relative quantitation with mass spectrometry using chemical derivatization and isotope labeling[J].Spectroscopy,2008,22(5):327-343.
[25]胡伟,谢建伟,许建帼,等.取代脲类化合物合成研究进展[J].化工生产与技术,2010,17(3):33-36.
[26]郭佃顺,黄汝骐.非光气工艺合成除草剂异丙隆[J].农药,1994,33(5):13-13.
[27]许响生,杜晓华,胡智燕,等.二(三氯甲基)碳酸酯“一锅法”合成1-芳基-3,3-二甲基脲除草剂[J].农药,2005,44(5):210-211.
[28]马英高,膝德范,孙凤翥,等.水法合成取代脲类除草剂[J].农药,1981,133(5):30-31.
[29]陆阳,冯世龙,徐固华,等.二(三氯甲基)碳酸酯“一锅法”合成取代脲类除草剂[J].化工技术与开发,2006,35(4):6-8.
[30]刘东阳,江骥,胡蓓.LC-MS测定C13-尿素同位素丰度方法的建立[J].分析测试学报,2004,23(1):5-7.
[2]TIXIER C,MEUNIER L,BONNEMOY F,et al.Phototransformation of three herbicides:chlorbufam,isoproturon,and chlorotoluron.Influence of irradiation on toxicity[J].Int.J.Photoenergy,2000,2(1):1-8.
[3]支建梁,欧菊芳,陈铭学,等.多种水样和植物样品中苯脲类除草剂残留分析研究进展[J].中国环境监测,2007,23(5):10-14.
[4]SRIVASTAVA M K,RAIZADA R B.Developmental toxicity of the substituted phenylurea herbicide isoproturon in rats[J].Veterinary Human Toxicol.,1995,37(3):220-223.
[5]WANG S W,CHU C Y,HSU J D,et al.Haemotoxic effect of phenylurea herbicides in rats:role of haemoglobin-adduct formation in splenic toxicity[J].Food Chem.Toxico.,1993,31(4):285-295.
[6]CRISWELL J,SHELTON K,LUPEK C.Pesticide applicator certification series:toxicity of pesticides[J].Oklahoma Cooperative Extension Service,2014,7 457:1-8.
[7]RAGSDALE N N,MENZER R E.Carcinogenicity and pesticides:principles,issues and relationships[M].Washington DC:American Chemical Society,1989.
[8]佚名.欧盟禁用农药清单[J].农技服务,2009,26(3):97.
[9]FIELDING M,BARCELO D,HELWEG A,et al.Pesticides in ground and drinking water[C].Water Pollution Research Report27,Commission of the European Communities,Directorate2 General for Science,Research and Development,Brussels,1992.
[10]王霓霓.主要贸易国家和地区食品中农兽药残留限量标准[M].北京:中国标准出版社,2010.
[11]食品中农业化学品残留限量:日本肯定列表制度.食品卷[M].北京:中国标准出版社,2006.
[12]缪建洋,马军,曾建.衍生化气相色谱法定性分析污染事故样中的绿麦隆[J].环境保护科学,2003,29(3):33-34.
[13]ESCUDEROS-MORENAS M L,SANTOS-DELGADO M J,RUBIO-BARROSO S,et al.Direct determination of monolinuron,linuron and chlorbromuron residues in potato samples by gas chromatography with nitrogen-phosphorus detection[J].J.Chromatogr.A,2003,1 011(1/2):143-153.
[14]黄化成,慕卫,李军民,等.高效液相色谱法同时测定牛、羊肉中敌草隆、绿麦隆和阿特拉津的残留量[J].分析化学,1998,22(5):612.
[15]赵进英,辛暨华,郭英娜,等.固相萃取富集-高效液相色谱法分离检测水中3种苯脲除草剂[J].分析化学,2004,32(7):939-942.
[16]肖亮,王园朝,成美容.基质固相分散-反相高效液相色谱测定茶叶中苯脲类除草剂残留[J].茶叶科学,2010,30(1):52-56.
[17]李方实,DIETER M,ANTONIUS K.固相萃取-高效液相色谱法同时测定水中的16种苯脲除草剂[J].色谱,2001,19(6):534-537.
[18]CARABIAS-MARTINEZ R,GARCIA-HERMIDA C,RODRIGUEZ-GONZALO E,et al Determination of herbicides,including thermally labile phenylureas,by solidphase microextraction and gas chromatography-mass spectrometry[J].J.Chromatogr.A,2003,1 002(1/2):1-12.
[19]DI C A,COSTANTINO A,CRECENZI C,et al.Quantification of phenylurea herbicides and their free and humic acid-associated metabolites in natural waters[J].J.Chromatogr.A,1999,852(2):465-474.
[20]SILVA C L D,LIMA E C D,TAVARES M F M.Investigation of preconcentration strategies for the trace analysis of multi-residue pesticides in real samples by capillary electrophoresis[J].J.Chromatogr.A,2003,1 014(1/2):109-116.
[21]张妮,王敏.气相色谱法检测农药残留过程中基质效应的研究[J].安徽农业科学,2014,21(21):7 073-7 075.
[22]苏萌,艾连峰.液相色谱-串联质谱基质效应及其消除方法[J].食品安全质量检测学报,2014,5(2):511-515.
[23]NGUYEN J V,OLSSON A O,BRAVO R,et al.Quantification of atrazine,phenylurea,and sulfonylurea herbicide metabolites in urine by high-performance liquid chromatography-tandem mass spectrometry[J].J.Anal.Toxicol.,2007,31(4):181-186.
[24]OMAILLE G,GO E P,HOANG L,et al.Metabolomics relative quantitation with mass spectrometry using chemical derivatization and isotope labeling[J].Spectroscopy,2008,22(5):327-343.
[25]胡伟,谢建伟,许建帼,等.取代脲类化合物合成研究进展[J].化工生产与技术,2010,17(3):33-36.
[26]郭佃顺,黄汝骐.非光气工艺合成除草剂异丙隆[J].农药,1994,33(5):13-13.
[27]许响生,杜晓华,胡智燕,等.二(三氯甲基)碳酸酯“一锅法”合成1-芳基-3,3-二甲基脲除草剂[J].农药,2005,44(5):210-211.
[28]马英高,膝德范,孙凤翥,等.水法合成取代脲类除草剂[J].农药,1981,133(5):30-31.
[29]陆阳,冯世龙,徐固华,等.二(三氯甲基)碳酸酯“一锅法”合成取代脲类除草剂[J].化工技术与开发,2006,35(4):6-8.
[30]刘东阳,江骥,胡蓓.LC-MS测定C13-尿素同位素丰度方法的建立[J].分析测试学报,2004,23(1):5-7.