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CN106632007B - 吡啶-3-基芳氧基苯氧基烷酸酯化合物及其应用 - Google Patents

吡啶-3-基芳氧基苯氧基烷酸酯化合物及其应用 Download PDF

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CN106632007B
CN106632007B CN201611160733.7A CN201611160733A CN106632007B CN 106632007 B CN106632007 B CN 106632007B CN 201611160733 A CN201611160733 A CN 201611160733A CN 106632007 B CN106632007 B CN 106632007B
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刘祈星
周海峰
朱瑞
陈蕾
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Yichang Xinnada Biotechnology Co ltd
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China Three Gorges University CTGU
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Abstract

本发明公开了吡啶‑3‑基芳氧基苯氧基烷酸酯化合物及其除草活性，其化学结构式如式I或Ⅱ所示：式中，X为氮或碳；Y为‑N＝CH‑或氧；X1、X2、X3为氢或氟或氯或溴或碘或三氟甲基或氰基或硝基中的任意一种；X4、X5、X6为氢或氟或氯或溴或碘或三氟甲基或氰基或硝基或C1～C2烷基或C1～C2烷氧基中的任意一种；R1为氢或C1～C3烷基或C1～C3卤代烷基中的任意一种；本发明还涉及含有上述化合物的组合物及吡啶‑3‑基芳氧基苯氧基烷酸酯化合物在农用除草剂方面的应用，部分化合物具有很高的除草活性，在5克/亩用量下可以获得很好的防治效果。

Description

吡啶-3-基芳氧基苯氧基烷酸酯化合物及其应用
技术领域
本发明涉及一种化合物，具体涉及一种吡啶-3-基芳氧基苯氧基烷酸酯化合物及其应用。
背景技术
芳氧苯氧丙酸(APP)类衍生物作为禾本科杂草类除草剂，因具有高效、低毒、高选择性和对环境友好等特点，自上市以来，其研究备受关注。此类除草剂经抑制禾本科杂草内乙酰辅酶A羧化酶(ACCase)，阻断植株体内酯肪酸的合成，从而有效的选择性地防除禾本科杂草，从而对阔叶作物无影响。
通常，此类化合物的R构型体为除草剂的活性成分。在1991年，诺华公司开发了第一个用于小麦田的APP类除草剂——炔草酯，此后，道化学和韩国化工技术研究院陆续开发出了两种用于水稻田的APP类除草剂——氰氟草酯(P1)和噁唑酰草胺(P2)。研究发现，当苯氧基被吡啶氧基替代后，选择性和活性将大幅提高。在此类APP类除草剂中，氟吡乙禾灵(P3)为代表性除草剂。
为获得活性更高的化合物，发明人将3-羟基吡啶引入芳氧苯氧烷酸结构中，设计并合成一系列未见文献报道的吡啶-3-基芳氧基苯氧基烷酸酯化合物，发现其具有显著的除草活性。
发明内容
本发明提供了一种吡啶-3-基芳氧基苯氧基烷酸酯化合物及其异构体，其特征在于，其化学结构式如式I或Ⅱ所示：
式中，X为氮或碳；Y为-N＝CH-或氧；X1、X2、X3为氢或氟或氯或溴或碘或三氟甲基或氰基或硝基中的任意一种；X4、X5、X6为氢或氟或氯或溴或碘或三氟甲基或氰基或硝基或C1～C2烷基或C1～C2烷氧基中的任意一种；R1为氢或C1～C3烷基或C1～C3卤代烷基中的任意一种。
上面给出的化合物(I、II)的定义中，所用术语不论单独使用还是用在复合词中，代表如下取代基:
烷基：指直链或支链烷基；
卤代烷基：指直链或支链烷基，在这些烷基上的氢原子部分或全部被卤原子取代；
本发明的化合物可以一种或多种异构体的形式存在。异构体包括对映异构体、非对映异构体、几何异构体。如本发明的式(I、II)所示的化合物，由于一个碳原子上连接四个不同的取代基而形成立体异构体(分别以R和S来表示不同的构型)，本发明包括R型异构体和S型异构体以及它们任何比例的混合物。
优选的方案中，所述的吡啶-3-基芳氧基苯氧基烷酸酯化合物的具体结构式为：
本发明还涉及所述的吡啶-3-基芳氧基苯氧基烷酸酯化合物的除草活性，在5克/亩用量下具有显著的除草活性。
本发明提供的式(I、II)化合物具有很好的杂草防治作用，在很低的剂量下就可以获得很好的效果。
本发明提供的式(I、II)化合物，具有生物活性且有的化合物具有很好的生物活性。特别是在农业、园艺、花卉和卫生杂草的防治方面表现出活性。这里所述的杂草包括，但不仅限于此：
禾本科杂草：马唐、稗草、狗尾草、硬草、菵草、雀麦、看麦娘、节节麦、碱茅、星星草、野燕麦、黑麦草；
阔叶杂草：苘麻、繁缕、龙葵、藜、凹头苋、反枝苋等。
单独使用本发明的式(I、II)化合物时，对控制杂草是有效的，它们也可以与其他生物化学物质一起使用，这些生物化学物质包括其他除草剂。
本发明还涉及所述的吡啶-3-基芳氧基苯氧基烷酸酯化合物农用除草剂中的应用。
本发明涉及的吡啶-3-基芳氧基苯氧基烷酸酯化合物的合成原料易得，制备方法简单，易于工业化生产。
具体实施方式
下面结合具体实施，进一步阐明本发明。这些实施例应理解为仅用于说明本发明而不是用于限制本发明的保护范围。在阅读了本发明记载的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等效变化和修饰同样落入本发明权利要求书所限定的范围。
实施例1:吡啶-3-基-(R)-2-[4-(3-氟-5-氯吡啶-2-氧基)苯氧基]丙酸酯(1)的制备
N,N-二甲基甲酰胺(40mL)、(R)-(+)-2-(4-羟基苯氧)丙酸(0.02mol，3.64g)，碳酸钾(0.02mol，2.76g)，75℃下搅拌0.5h后，再加入等量的碳酸钾，继续搅拌0.5h。缓慢滴加2,3-二氟-5-氯吡啶(0.02mol，3.00g)，滴加完毕后，反应温度维持75℃，过夜。停止加热，冷却至室温，将反应液倒入200mL冰水中，稀盐酸调节pH 4-5，过滤，用少量冰水洗涤三次，真空干燥，得(R)-2-[4-(3-氟-5-氯吡啶-2-氧基)苯氧基]丙酸白色固体3.86g，产率62.0％。
甲苯40mL，(R)-2-[4-(3-氟-5-氯吡啶-2-氧基)苯氧基]丙酸(3.3mmol，1.04g)，加入到100mL的单口烧瓶中，搅拌溶解后，加入氯化亚砜(20mmol，2.24g)，回流反应4h，减压蒸馏，得到(R)-2-[4-(3-氟-5-氯吡啶-2-氧基)苯氧基]丙酰氯黄色油状液体，无需分离纯化，直接用于下一步反应。
向上一步制得的(R)-(+)-2-[4-(3-氟-5-氯吡啶-2-氧基)苯氧基]丙酰氯中加入二氯甲烷(40mL)，3-羟基吡啶(0.31g,3.3mmol)，4-二甲氨基吡啶(DMAP,0.02g,0.17mmol)，冰浴下搅拌15min，逐滴加入三乙胺(1.37mL,10mmol)，滴加完毕后，继续搅拌10min，撤去冰浴，自然升温至室温，搅拌4h，停止反应，将反应液倒入150mL冰水中，二氯甲烷萃取(40mL*3)，有机相先后用50mL饱和碳酸氢钠溶液和100mL水洗，无水硫酸钠干燥，过滤，减压蒸除二氯甲烷，硅胶柱层析分离纯化产品，洗脱剂(V石油醚：V乙酸乙酯＝3:1)，得吡啶-3-基-(R)-2-[4-(3-氟-5-氯吡啶-2-氧基)苯氧基]丙酸酯(1)黄色油状液体0.23g，产率18.0％；1H NMR(CDCl3,400MHz)δ:1.81(d,J＝6.8Hz,3H,CHCH3 ),5.00(q,J＝6.8Hz,1H,CHCH3),7.02(d,J＝9.2Hz,2H,PhH),7.11(d,J＝9.2Hz,2H,PhH),7.35(dd,J＝8.4Hz,4.4Hz,1H,Py-H),7.44～7.47(m,1H,Py-H),7.50(dd,J＝9.2Hz,2.0Hz,1H,Py-H),7.88(d,J＝2.0Hz,1H,Py-H),8.39(d,J＝2.8Hz,1H,Py-H),8.50(dd,J＝4.4Hz,1.6Hz,1H,Py-H)；13C NMR(CDCl3,100MHz)δ:18.57,73.19,116.28,122.47,124.02,124.90,125.08,129.06,140.17,142.94,145.63,147.00,147.24,147.40,148.28,154.67,170.22.
实施例2:吡啶-3-基-(R)-2-[4-(3-氯-5-三氟甲基吡啶-2-氧基)苯氧基]丙酸酯(2)的制备
(R)-2-(4-羟基苯氧基)丙酸(3g)，DMF(35ml)，缓慢加入K2CO3(4.55g)，升温至70～80℃，搅拌1h，逐滴加入2,3-二氯-5-三氟甲基吡啶(3.56g)，保持70～80℃搅拌8h，停止反应，自然冷却至室温，将混合物倒入冰水(200mL)中，使用稀盐酸调节pH 4～5，用乙酸乙酯萃取，有机相水洗，干燥，脱溶得(R)-2-[4-(5-三氟甲基-3-氯吡啶-2-氧基)苯氧基]丙酸棕色液体5.03g，产率84.4％。
(R)-2-[4-(5-三氟甲基-3-氯吡啶-2-氧基)苯氧基]丙酸(3.3mmol，1.08g)，溶于甲苯(35mL)中，滴加SOCl2(20mmol，2.24g)，加热回流，反应4h，脱溶得(R)-2-[4-(5-三氟甲基-3-氯吡啶-2-氧基)苯氧基]丙酰氯直接用于下一步。
所得酰氯溶于二氯甲烷(35mL)中，加入中间体3-羟基吡啶(0.26g)及催化量的DMAP，于搅拌下缓慢滴入三乙胺(0.85g)，搅拌反应5h。反应完成，将混合物到到倒入冰水(100mL)中，用二氯甲烷(80mL*2)萃取，有机相水洗，干燥，脱溶。经柱层析纯化得吡啶-3-基-(R)-2-[4-(3-氯-5-三氟甲基吡啶-2-氧基)苯氧基]丙酸酯(2)淡黄色透明液体0.06g，产率5.20％。1H NMR:δ1.83(d,J＝6.8Hz,3H,CHCH3 ),5.02(q,J＝6.8Hz,1H,CHCH3),7.05(d,J＝8.8Hz,2H,Ph-H),7.12(d,J＝8.8Hz,2H,Ph-H),7.35(dd,J＝8.4Hz,4.8Hz,1H,Py-H),7.44-7.48(m,1H,Py-H),7.97(d,J＝2.4Hz,1H,Py-H),8.27-8.28(m,1H,Py-H),8.39(d,J＝2.4Hz,1H,Py-H),8.50(d,J＝4.0Hz,1H,Py-H)；13C NMR:δ18.56,73.20,116.10,116.30,119.18,122.61,122.86,124.00,129.03,136.30,142.61,142.95,147.19,147.27,155.03,161.29,170.18,172.27.
实施例3:吡啶-3-基-(R)-2-[4-(4-氰基-2-氟苯氧基)苯氧基]丙酸酯(3)的制备
在N,N-二甲基甲酰胺(DMF,40mL)中，加入(R)-2-(4-羟基苯氧)丙酸(3.03g,0.02mol)，分批加入碳酸钾(5.52g,0.04mol)，升温到70℃～80℃下，持续搅拌1h，逐量加入3,4-二氟苯腈的(2.38g,0.02mol)，继续搅拌反应6～7h。冷却至室温，倒入冰水(250mL)中，缓慢加入稀盐酸，调节至pH 4～5，抽滤，水洗，经真空干燥箱干燥得(R)-2-[4-(4-氰基-2-氟苯氧基)苯氧基]丙酸灰色固体的(R)-2-[4-(4-氰基-2-氟苯氧基)苯氧基]丙酸3.26g，产率65.7％。
(R)-2-[4-(4-氰基-2-氟苯氧基)苯氧基]丙酸(1g,3.3mmol)溶解于甲苯(40ml)中，缓慢加入SOCl2(1.18g,10mmol)，回流反应5h，用旋转蒸发仪脱去溶剂后，得(R)-2-[4-(4-氰基-2-氟苯氧基)苯氧基]丙酰氯，直接进行下一步反应。
将所得酰氯溶于二氯甲烷(40ml)中，加入3-羟基吡啶(0.31g,3.3mmol)与催化量的4-二甲基氨基吡啶(DMAP)，冰浴下搅拌10min，逐滴滴加三乙胺(1g,10mmol)。继续搅拌10h。反应完成后，倒入100ml冰水中，二氯甲烷萃取，收集有机相，并用水洗(100ml×2)，所得粗产物用无水硫酸钠干燥，脱溶后经硅胶色谱柱提纯得黄色黏液状的吡啶-3-基-(R)-2-[4-(4-氰基-2-氟苯氧基)苯氧基]丙酸酯(3)0.15g，产率11.6％。1H NMR:δ1.85(d,J＝6.4Hz,3H,CHCH 3),5.03(q,J＝6.4Hz,1H,CHCH3),6.91～7.09(m,4H,PhH),7.30～7.51(m,5H,PhH,Py-H),8.43(s,1H,Py-H),8.55(s,1H,Py-H)；13C NMR:δ18.56,73.13,116.52,116.65,116.83,118.81,120.57,120.78,121.12,124.13,129.11,129.40,135.26,142.82,147.03,147.25,149.11,154.69,170.07.
实施例4:吡啶-3-基-(R)-2-[4-(6-氯喹喔啉-2-氧基)苯氧基]丙酸酯(4)的制备
在100mL反应瓶中加入N，N-二甲基甲酰胺(DMF)(40mL)，将(R)-2-(4-羟基苯氧)丙酸(3.00g,0.02mol)加入到反应瓶中，搅拌溶解。在室温下，分批缓慢加入碳酸钾(4.46g,0.03mol)，继续搅拌15～30min，升温至75℃搅拌2h，缓慢加入2,6-二氯喹喔啉(3.28g,0.02mol)，升温至145℃反应6h。反应结束后，冷却至室温，将反应液倒入冰水(250mL)中，滴加稀盐酸至pH＝4～5，过滤，水洗，干燥得到黄色的固体(R)-2-(4-((6-氯喹喔啉-2-基)氧)苯氧)丙酸5.55g，产率97％。
在100mL反应瓶中加入甲苯(40mL)，(R)-2-(4-((6-氯喹喔啉-2-基)氧)苯氧)丙酸(1.0g,3.3mmol)，搅拌下加入二氯亚砜(1.19g,10mmol)，升温至125℃，回流反应4h，冷却脱溶得(R)-2-(4-((6-氯喹喔啉-2-基)氧)苯氧)丙酸酰氯，直接用于下一步。
在装有酰氯的反应瓶中加入二氯甲烷(40mL)，3-羟基吡啶(0.32g,3.3mmol)和DMAP(催化量)，冰浴搅拌下滴入三乙胺(1.0g,10mmol)。将反应混合物搅拌8h后倒入200mL冰水中，用二氯甲烷萃取。将有机相水洗，加入无水硫酸钠干燥，脱去溶剂得到粗产物。柱层析(V石油醚/乙酸乙脂＝4:1)得到0.30g淡黄色固体产物吡啶-3-基-(R)-2-[4-(6-氯喹喔啉-2-氧基)苯氧基]丙酸酯(4)，产率21.89％，m.p.81-82℃，1HNMR:δ1.85(d,J＝6.8Hz,3H,CHCH 3),5.05(d,J＝6.8Hz,1H,CHCH3),7.07(d,J＝9.2Hz,2H,PhH),7.23(d,J＝9.2Hz,2H,PhH),7.35(dd,J＝8.4Hz,4.8Hz,1H,Py-H),7.47-7.50(m,1H,Py-H),7.62(dd,J＝8.8Hz,2.4Hz,1H,quinoxaline-H),7.70(d,J＝8.8Hz,1H,quinoxaline-H),8.05(d,J＝2.4Hz,1H,quinoxaline-H),8.41(d,J＝2.8Hz,1H,Py-H),8.52(dd,J＝4.8Hz,1.2Hz,1H,Py-H),8.69(s,1H,quinoxaline-H)；13C NMR:δ18.59,73.14,116.21,122.68,123.99,127.93,128.82,129.01,131.18,132.91,138.48,139.78,140.10,142.96,146.93,146.99,147.30,154.82,157.15,170.23.
实施例5:吡啶-3-基-(R)-2-[4-(6-氯苯并噁唑-2-氧基)苯氧基]丙酸酯(5)的制备
称取2-(4-羟基苯氧)丙酸3.64g(0.02mol)加入到置于冰水浴的20mL10％的NaOH溶液中，搅拌0.5h制得2-(4-羟基苯氧)丙酸钠。将其滴加到30mL的2,6-二氯苯并噁唑(3.67g,0.02mol)的甲苯溶液中，加入0.2g四丁基溴化铵，将温度升到50℃，任其反应3h后，升温至115℃回流1h。将反应液冷却后，分液取水层用稀盐酸调节PH为3～4使产物完全析出，然后过滤并用水洗涤产物，将产物用真空干燥箱干燥即得(R)-2-[4-(6-苯并噁唑-2-氧基)苯氧基)丙酸2.53g，产率36.83％。
(R)-2-[4-(6-苯并噁唑-2-氧基)苯氧基)丙酸(3.3mmol，1.13g)，甲苯40mL，氯化亚砜(10mmol，1.18g)，115℃回流反应4h，旋蒸脱去甲苯溶得到(R)-2-[4-(6-苯并噁唑-2-氧基)苯氧基)丙酰氯，直接用于下一步。
将(R)-2-[4-(6-苯并噁唑-2-氧基)苯氧基)丙酰氯溶于二氯甲烷(40mL)，加入3-羟基吡啶(0.31g,3.3mmol)和4-二甲氨基吡啶(DMAP,0.02g)，于冰水浴中搅拌10分钟后滴入三乙胺1.00g，继续在冰水浴中搅拌3h。然后将反应液倒入100mL冰水中，二氯甲烷萃取，有机相用100mL的冰水洗涤两次，无水硫酸钠干燥，过滤，旋蒸脱去溶剂得到粗产物。通过柱层析(石油醚：乙酸乙酯＝4：1)得到吡啶-3-基-(R)-2-[4-(6-氯苯并噁唑-2-氧基)苯氧基]丙酸酯(5)棕黄色固体0.17g，产率15.6％，熔点105.2℃～107.4℃；1H NMR:δ1.82(d,J＝6.8Hz,3H,CHCH3 ),5.02(q,J＝6.8Hz,1H,CHCH3),7.05(d,J＝9.2Hz,2H,PhH),7.24(dd,J1＝8.4Hz,J2＝2.0Hz,1H,benzoxazole-H),7.34(dd,J1＝8.4Hz,J2＝4.4Hz,1H,Py-H),7.38(d,J＝9.2Hz,2H,PhH),7.41(d,J＝8.4Hz,1H,benzoxazole-H),7.45(d,J＝2.0Hz,1H,benzoxazole-H),7.46～7.49(m,1H,Py-H),8.41(d,J＝2.8Hz,1H,Py-H),8.50(dd,J1＝4.4Hz,J2＝1.6Hz,1H,Py-H).13C NMR:δ18.54,73.19,110.69,116.48,119.21,121.45,123.99,124.37,125.09,128.95,140.28,142.98,146.79,146.95,147.39,151.73,153.17,153.85,169.72.
实施例6:除草活性评价
方法如下：(1)在截面积64cm2的塑料盆钵中定量装土压平，置于不锈钢盆中，选取籽粒饱满、大小一致的种子，分单子叶杂草(马唐Digitaria sanguinalis、稗草Echinochloa crus-galli、狗尾草Setaria viridis)和双子叶杂草(苘麻Abutilontheophrasti(或繁缕Stelleria media或龙葵Solanum nigrum)、藜Chenopodium album、凹头苋Amaranthus ascedense或反枝苋Amaranthus retroflexus)分钵播种，各占钵面积的1/3，覆1cm厚细土，从塑料盆钵底部加水至上层土壤浸润，置于温室培养，待试材长至所需叶龄进行试验处理；(2)称取适量本发明提供的吡啶-3-基芳氧基苯氧基烷酸酯化合物，以N，N-二甲基甲酰胺溶解，再加入少量吐温80乳化剂，搅拌均匀，加入定量清水，配制成所需浓度，设相应溶剂和清水为对照；(3)处理方式：试材播种次日进行苗前土壤处理，单子叶试材长至1叶1心期、双子叶试材长至2片真叶期进行苗后茎叶处理；(4)按设置剂量定量移取药液进行茎叶喷雾和土壤喷雾处理，分别以喷雾溶剂和清水为对照；(5)处理试材置于温室培养；(6)处理15-25天后目测地上部生长情况，根据调查结果，按以下公式计算各化合物对杂草的防效：防效(％)＝100*(对照株高-处理株高)/对照株高；(7)根据防效进行除草活性分级：A级防效＞90％，B级防效75～90％，C级防效50～75％，D级防效25～50％，E级防效＜25％。结果表明本发明化合物在5g/亩剂量下，化合物对单子叶杂草具有选择性的除草活性，其中化合物1、2、4对单子叶杂草茎叶处理和土壤处理均具有A级除草活性，化合物3对单子叶杂草茎叶处理具有C级除草活性，部分结果如下。

Claims (4)

1.一种吡啶-3-基芳氧基苯氧基烷酸酯化合物，其特征在于，所述的吡啶-3-基芳氧基苯氧基烷酸酯化合物为R型异构体，具体结构式为：
2.根据权利要求1所述的吡啶-3-基芳氧基苯氧基烷酸酯化合物在制备除草剂上的应用。
3.根据权利要求2所述的应用，其特征在于，所述的除草剂作用的杂草包括禾本科杂草，具体包括马唐，稗草，狗尾草。
4.根据权利要求2所述的应用，其特征在于，所述的除草剂的用量为5克/亩。
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