第2卷第6期現(xiàn)代農(nóng)藥Vol.2 No.62003年12月Modern AgrochemicalsDec. 2003甲基嘧啶磷的合成仇是勝牛安忠 李祥志張世海(江蘇神農(nóng)化工集團(tuán)江蘇徐州21112)2摘要介紹了由2-二乙氨基6-甲基4羥基嘧啶和0,0-二甲基硫代磷酰氯反應(yīng)合成甲基嘧啶磷原油的方法，得到了優(yōu)惠工藝條件.關(guān)鍵詞甲基嘧啶磷 合成 .甲基嘧啶磷是-種速效殺蟲劑和殺螨劑，具有觸殺和熏蒸作用。本品低毒，能滲透到葉子組織中，4 實(shí)驗(yàn)結(jié)果和討論有傳導(dǎo)作用，使用范圍廣，持效期長(zhǎng)，對(duì)許多谷物影響反應(yīng)的主要因素有溶劑類型、反應(yīng)溫度、害蟲、倉(cāng)庫(kù)害蟲、家庭及公共衛(wèi)生害蟲效果好，藥效持久，對(duì)谷物種子安全，是替代高毒有機(jī)磷農(nóng)藥反應(yīng)配比和反應(yīng)時(shí)間， 筆者對(duì)以上因素進(jìn)行了探的理想藥劑之一。1理化性質(zhì)4.1溶劑類型選擇本品為黃色液體，相對(duì)密度(d0) 1.157， 折分別在A、B、C 3種溶劑下進(jìn)行反應(yīng)，反應(yīng)光率(np320) 1.527. 30C蒸氣壓約13 mPa,熔點(diǎn)15~溫度為30'C~40C，反應(yīng)配比為羥基嘧啶:甲基氯17C。水中溶解度約5 mg/L. (30C)，在大多數(shù)有化物=1 : 1.08，反應(yīng)時(shí)間3 ha比較3種溶劑下所機(jī)溶劑中互溶或易溶，在強(qiáng)酸和堿性介質(zhì)中水解。得產(chǎn)物含量和收率，以A溶劑為最好。2合成路線4.2反應(yīng)溫度的影響由2-二乙氨基-6-甲基-4羥基嘧啶和0,0-二甲分別在3種溫度下進(jìn)行反應(yīng)，選用溶劑A，配基硫代磷酸氯反應(yīng)合成甲基嘧啶磷，反應(yīng)式如下:比為羥基嘧啶:甲基氯化物=1 : 1.08， 反應(yīng)時(shí)間3OH。結(jié)果表明反應(yīng)溫度以30C~40C為宜(見表1)。表1反應(yīng)溫度的影響OCH號(hào)溫度(C)原油含量(%)收率(%)N(CH)220-3091.690.730~4090.288.3H,Ci,OCH,40~-50CH，+H2O+NCI4.3反 應(yīng)時(shí)間的影響反應(yīng)溫度30~40C，溶劑A,配比為羥基嘧啶:甲基氯化物=1 : 1.08，反應(yīng)時(shí)間結(jié)果見表2。3實(shí)驗(yàn)表2反應(yīng)時(shí)間的影響在裝有攪拌器、溫度計(jì)、恒壓滴液漏斗、冷凝序號(hào)時(shí)間(h)收率(%72.385.10.9器(下接分水器)的反應(yīng)瓶中加入羥基嘧啶38 g(含90.392.6量96%)，固體氫氧化鈉和適量溶劑，攪拌0.5 h91791.8后，加熱脫出生成水約3.5 ml.再在一-定溫度 下，由表2可知，反應(yīng)3 h后,反應(yīng)結(jié)果差異不大。滴加入0,0-二甲基硫代磷酰氯36 g (含量98%),滴畢，保溫反應(yīng)，反應(yīng)畢，水洗分層，油層濃縮得甲基嘧啶磷原油61 g,含量92% ( 氣譜分析)。收稿日期: 2003-08-25作者簡(jiǎn)介:仇是勝(1968- - ),男,高級(jí)工程師。從事農(nóng)藥合成與生產(chǎn)工作。中國(guó)煤化工轉(zhuǎn)第27頁)MHCNMH G.2003年12月.譚輝華，等:硝蟲硫磷在柑桔和土壤中的殘留分析研究2:3 Simpli cio A L, Vilas Boas L validation of solid- phase micro extraction1method for the determination of organophosphorus pesticides in fruits三and fruit juice [D]. Journal of Chromatography A.199.833(1):35-424 Carolyn M M, Bernadette M M, et al. Pesticide Analytical Manual [M].母94,0l..rd ed)5樊德方. 農(nóng)藥殘留分析與檢測(cè)[M].上海: 上?？茖W(xué)技術(shù)出版社.時(shí)間Im n)1982圖4桔皮對(duì)照色譜圖圖5桔皮添加樣品色譜圖Determination of Xiaochongliulin Residue in Soiland Orange by Chromatography宣Tan Huihua' Li Xuesheng Lin Mingzhen2 Lu Zhixin2(1. College of Agronomy, Guangxi University, Nanning 530005China; 2. Appied pesticide research center, Guangxi Academyof Agriculture SoSciences,, Nanning 530007 China)時(shí)間Imin45Abstract: A method was developed to determine residue of圖6土壤對(duì)照色譜圖圖7土壤添加樣品色譜圖Xiaochongliulin, a new insecticide, in soil and orangerespectively by capillary gas chromatography with a NPD.. The3結(jié)論samples were extracted with acetone by blending and the本試驗(yàn)建立硝蟲硫磷在柑桔和土壤中殘留分析extracts were partitioned with dichloromethane. Afer方法可靠，操作簡(jiǎn)便，成本低，方法精密度、靈敏cleanup on a mixture column of aluminum oxide (neutral) and度高，添加回收試驗(yàn)結(jié)果達(dá)到農(nóng)藥殘留分析要求。activated charcoal, the residues were analyzed by gachromatograph with DB-17 capillary column and NPD for參考文獻(xiàn)quantitative analysis. Limit of detection for Xiaochongliulin1萬積秋, 李健強(qiáng)，張雄等.硝蟲硫磷的合成及對(duì)矢尖蚧的藥效試驗(yàn)was 1.4X 10'lg Recoveries of Xiaochongliulin in orange, rindD.現(xiàn)代農(nóng)藥. 2002, 1():14-15and soil were 81.93% ~ 83.96%，81.40% ~ 87.21% and2 Stan H J. Pesticide residue analysis in foodstufs applying cpillaly as-81.37%- -89.23%, respectively.chromatography with mass spectrometric detection 0. Journal of Key words:Xiaochongliulin; orange; soil; residue;Chromatography A.200.892(1~2 ):347~377gas chromatograph.(上接第20頁)4.4物料配比對(duì) 反應(yīng)的影響化工部農(nóng)藥信息總站. 國(guó)外農(nóng)藥品種手冊(cè)[M]. 85-86反應(yīng)溫度30~40C，溶劑A，反應(yīng)時(shí)間3 h; .2沈德隆等.嘧啶磷的合成研究[]. 農(nóng)藥2001, 40(1)8利用黃金分割法采用不同物料配比，結(jié)果見表3。周玉昆等.甲基嘧啶磷的合成研究[J]. 農(nóng)藥. 2002, 41(1):14~ - 15表3物料配比對(duì)反應(yīng)的影響潘力勇等.乙氧嘧啶磷的合成研究[J]. 農(nóng)藥2002, 41(5):11-12比原油含量(%收率(%)Synthesis of Pirimiphos methyl:1.0590.31:1.08 .92.192.3Qiu Shisheng Niu Anzhong Li Xiangzhi et al.1:1.1390.091.11:1.2089.8(Jiangsu Shennong Chemical Industry Group, Xuzhou 221112由表3可知，選擇配比羥基嘧啶:甲基氯化物China)=1:1.08時(shí)反應(yīng)結(jié)果最好。Abstract: This paper introduced the synthetic method of根據(jù)以.上實(shí)驗(yàn)結(jié)果，最后得出最佳工藝條件pirimiphos- methyl by reaction with 2- diethylamino-6-methyl- 4-為:反應(yīng)溶劑A，反應(yīng)溫度30C~40"C，反應(yīng)時(shí)間hydroxypyrimidine and O,O-dimethyl-hiophosphoryl chloride.3h,物料配比1 : 1.08 ( 摩爾比)。Via a series of study. We aobtained the ontimal process conditions.中國(guó)煤化工Key words:MYHCNMH G.