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                您當前位置:網站首頁 >> 化工新聞 >> 綜合新聞 >> 腈吡螨酯(cyenopyrafen)的合成與殺螨活性
               
               
              腈吡螨酯(cyenopyrafen)的合成與殺螨活性
              2019-07-30 11:56:51 來源:農藥快訊信息網 瀏覽:1013

              摘要:腈吡螨酯是由日產化學公司開發的丙烯腈類殺螨劑。以丙酮、草酸二乙酯和對叔丁基苯乙腈等為起始原料經7步反應合成了腈吡螨酯,目標化合物的結構經1H NMR確證。初步生物活性測試結果表明,腈吡螨酯對朱砂葉螨具有優異的活性。

               

              螨類,尤其是以植食性為主的農業螨類,在世界各地的農作物上都有發現。其具有個體小、繁殖快、發育歷期短、行動范圍小、適應性強、突變率高和易產生抗藥性等特點,是公認的難防有害生物群落。因此,結構新穎,作用機制獨特的新型高效殺螨劑的不斷發現是農業生產的需要

               

              2000年之后,日產化學、曹達、石原產業等農藥公司在大約5年的時間里先后公開了幾十篇丙烯腈類化合物的專利。2009年在日本、韓國上市的新型殺螨劑腈吡螨酯(cyenopyrafen),不僅結構新穎,而且作用機制獨特。結構中叔丁酯水解后對線粒體呼吸鏈復合體Ⅱ表現出優異的抑制作用,與現有殺螨劑無交互抗性,并對非靶標生物安全,是較為理想的殺螨劑。

               

              腈吡螨酯(商品名Starmite)由日產化學工業株式會社開發,主要用于水果和蔬菜。2013年,腈吡螨酯進入哥倫比亞和厄瓜多爾市場,主要用于觀賞植物。2016年,腈吡螨酯銷售額接近0.2億美元。腈吡螨酯IUPAC名(E)-2-(4-tert-butylphenyl)-2-cyano-1-(1,3,4-trimethyl-1H-pyrazol-5-yl)vinyl 2,2-dimethylpropanoate,分子式C24H31N3O2,相對分子質量393.24,CAS登錄號560121-52-0。純品為白色晶體,熔點為93℃94℃(圖1)。

               

              1  腈吡螨酯的化學結構式

               

              本文以丙酮、草酸二乙酯和對叔丁基苯乙腈等為起始原料,經7步反應合成腈唑螨酯(圖2)。

               

               

              注:a:草酸二乙酯、甲醇鈉、甲醇、濃鹽酸;b:水合肼、二氯甲烷;c:硫酸二甲酯、二氯甲烷;d:多聚甲醛、濃硫酸、鹽酸氣、1,4-二氧六環;e:鈀碳、氫氣、甲苯、氮氣;f:甲醇鈉、甲苯、甲醇、對叔丁基苯乙腈;g:特戊酰氯、三乙胺、四氫呋喃

              2  腈吡螨酯的合成路線

               

              1  實驗部分

              1.1  儀器與試劑

              所用試劑為市售化學純或分析純。

              Mercury 300(Varian)核磁共振儀(氘代氯仿為溶劑,TMS為內標);天津分析儀器廠生產的RY-1型熔點儀;Agilent 1100系列高效液相色譜。

               

              1.2  關鍵中間體的合成步驟

              1.2.1  2,4-二酮戊酸甲酯(中間體M-1)的合成

              冰鹽浴下,將20%甲醇鈉溶液300.00 g(1.10 mol)加入到三口瓶中,加入甲醇500 mL,機械攪拌均勻,慢慢滴加丙酮(58.00 g,1.00 mol)和草酸二乙酯(146.50 g,1.00 mol)的混合液,90 min滴完。滴加過程中溶液變渾濁,有大量固體生成,滴加結束升溫至35℃反應10 h。反應液過濾,所得固體溶于500 mL冰水混合物,用濃鹽酸調節pH值為3~4。用乙酸乙酯(2×500 mL)萃取,有機相用飽和食鹽水(2×200 mL)洗滌,無水硫酸鎂干燥,減壓蒸除溶劑,得100.10 g紅色油狀物(中間體M-1),收率為69%。

               

              1.2.2  3-甲基-1H-吡唑-5-羧酸甲酯(中間體M-2)的合成

              反應瓶內加入2,4-二酮戊酸甲酯100.00 g(0.70 mol)和500 mL二氯甲烷,冰水浴中攪拌,將85%水合肼水溶液45.00 g(0.80 mol)滴加到反應瓶中,滴加結束,冰浴保溫反應1 h。反應液脫溶后加入500 mL乙酸乙酯溶解,用水(2×200 mL)洗滌,無水硫酸鎂干燥,減壓蒸除溶劑,得72.03 g紅色固體(中間體M-2),收率為74%。

               

              1.2.3  1,3-二甲基-1H-吡唑-5-羧酸甲酯(中間體M-3)的合成

              3-甲基-1H-氫吡唑-5-羧酸甲酯3.00 g(0.02 mol)溶于30 mL二氯甲烷中,將硫酸二甲酯4.20 g(0.03 mol)滴入反應液內,升溫至回流,反應8 h。反應液脫溶,加入50 mL水,用100 mL乙酸乙酯萃取,有機相分別用50 mL飽和碳酸氫鈉水溶液洗滌,50 mL飽和食鹽水洗滌,無水硫酸鎂干燥,脫溶得黃色油狀物3.54 g,采用色譜柱提純得黃色油狀物(中間體M-3)2.33 g,收率71%。

               

              1.2.4  4-氯甲基-1,3-二甲基-1H-吡唑-5-羧酸甲酯(中間體M-4)的合成

              1,3-二甲基-1H-吡唑-5-羧酸甲酯5.00 g(0.03 mol)溶于50 mL 1,4-二氧六環,攪拌,將多聚甲醛5.80 g(0.20 mol)投入反應液,緩慢滴加濃硫酸5.00 g(0.03 mol),滴畢升溫至90 ℃,通鹽酸氣攪拌反應8 h。降溫至室溫,向反應液加入100 mL水,用150 mL乙酸乙酯萃取,有機相分別用飽和碳酸氫鈉水溶液(2×100 mL)、飽和食鹽水(2×100 mL)洗滌,無水硫酸鎂干燥,脫溶得黃色油狀物(中間體M-4)3.29 g,收率51%。

               

              1.2.5  1,3,4-三甲基-1H-吡唑-5-羧酸甲酯(中間體M-5)的合成

              4-氯甲基-1,3-二甲基-1H-吡唑-5-羧酸甲酯2.00 g(0.01 mol)溶于20 mL甲苯,將三乙胺1.00 g(0.01 mol)滴入反應液內,加入5%鈀碳0.30 g(0.0002 mol),用氮氣置換反應體系內氣體,常溫常壓通氮氣,攪拌反應5 h。反應液過濾,用50 mL乙酸乙酯洗滌濾餅,濾液中加入50 mL乙酸乙酯萃取,有機相分別用50 mL飽和食鹽水洗滌,無水硫酸鎂干燥,脫溶得黃色油狀物,經色譜柱提純得黃色油狀物(中間體M-5)1.53 g,收率92%。

               

              1.2.6  3-(1,3,4-三甲基-1H-吡唑-5-基)-2-(4-叔丁基苯基)-3-羥基丙烯腈(中間體M-6)的合成

              向反應瓶中加入正庚烷20 mL、1,3,4-三甲基-1H-吡唑-5-甲酸甲酯0.85 g(0.005 mol)、對叔丁基苯乙腈0.99 g(0.006 mol),脫水1 h。回流條件下,緩慢滴加甲醇鈉甲醇溶液,脫甲醇反應,溶液逐漸變為棕黃色,并有黃色固體生成。5 h后,將反應液加入冰水(50 mL)中,用乙酸乙酯(10 mL)萃取2次,水相用鹽酸酸化至pH值為1~2,再用乙酸乙酯(50 mL×3)萃取,合并有機相,分別用少量碳酸氫鈉水溶液和水洗滌,無水硫酸鎂干燥,減壓脫溶得黃色固體(中間體M-6)1.27 g,收率81%。

               

              1.2.7  腈吡螨酯的合成

              3-(1,3,4-三甲基-1H-吡唑-5-基)-2-(4-叔丁基苯基)-3-羥基丙烯腈2.02 g(0.006 mol)溶于20 mL無水二氯甲烷中,冰浴降溫,加入2,2-二甲基丙酸0.76 g(0.006 mol)、4-二甲氨基吡啶1.52 g(0.007 mol),將二環己基碳二亞胺0.85 g(0.007 mol)溶于10 mL無水二氯甲烷,滴加到反應容器內,滴畢升溫至室溫反應30 min。反應液過濾,所得濾液脫溶,加入100 mL乙酸乙酯、50 mL水,有機相分別用飽和碳酸氫鈉水溶液、飽和氯化鈉水溶液洗滌,無水硫酸鎂干燥,濃縮得黃色油狀物,經柱色譜提純得目標物腈吡螨酯白色固體0.73 g。HPLC歸一質量分數99%,收率28%,熔點93~94 ℃。

               

              1H NMR(300 MHz,CDCl3δ1.17(s,9H,C(CH3)3)、1.34(s,9H,C(CH3)3)、2.10(s,3H,CH3)、2.21(s,3H,CH3)、3.91(s,3H,NCH3)、7.47(q,4H,Ph-H)。

               

              2  殺螨活性的測定

              2.1  對朱砂葉螨成螨活性的測定

              根據待測化合物的溶解性,腈吡螨酯原藥用丙酮或二甲亞砜溶解,然后用1‰吐溫80溶液配制成所需濃度的待測液50 mL,丙酮或二甲亞砜在溶液中的含量不超過10%。

               

              2片真葉菜豆苗,接種朱砂葉螨成螨并調查基數后,用手持噴霧器進行整株噴霧處理,每處理3次重復,處理后置于標準觀察室,72 h后調查存活螨數,計算死亡率(表1)。

               

              1  腈吡螨酯的殺螨活性

               

              2.2  殺卵活性的測定

              稱取一定量腈吡螨酯,用丙酮制成母液,按試驗設計用含有0.1%吐溫80的靜置自來水稀釋成系列濃度。取2片真葉盆栽菜豆苗,去除1片真葉,然后將健康朱砂葉螨雌成螨10頭接種到葉片上,24 h后去除成螨,調查卵數并進行噴霧處理。5 d后待空白對照卵全部孵化,調查各處理未孵化卵數,計算孵化抑制率(表2)。

               

              2 腈吡螨酯的殺螨卵

               

              3  結果與討論

              本文以丙酮、草酸二乙酯和對叔丁基苯乙腈等為起始原料經7步反應合成目標化合物腈吡螨酯,目標化合物的結構經1H NMR確證。初步生物活性測試結果表明,腈吡螨酯對朱砂葉螨具有優異的活性。本文對腈吡螨酯類似化合物的研究具有重要意義。


              來源:程巖, 吳鴻飛, 羅艷梅, 李斌. 現代農藥, 2019, (3): 9-11

              作者單位介紹:沈陽中化農藥化工研發有限公司,新農藥創制與開發國家重點實驗室

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