CN115724729A - 一类1-芳基-α,β-不饱和酮类化合物及其合成方法和在制备杀根结线虫药物中的应用 - Google Patents
一类1-芳基-α,β-不饱和酮类化合物及其合成方法和在制备杀根结线虫药物中的应用 Download PDFInfo
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Abstract
本发明涉及一类1‑芳基‑α,β‑不饱和酮类化合物的制备方法及该类化合物作为杀根结线虫药物的应用。一类1‑芳基‑α,β‑不饱和酮类化合物的合成方法，具有以下反应特征：
其中：R1是邻位、对位或间位的甲基，甲氧基，硝基，氟，氯，溴，碘等；R2是H或者烷基、链烯基、芳基,该类化合物作为有效成分在制备杀植物根结线虫药物中的应用。本发明所涉及的不饱和酮类化合物具有结构简单、合成容易、杀虫活性强、对动植物毒性小及成本低廉的优点，在开发新型高效杀线虫药物方面具有巨大潜力。
Description
技术领域
本发明涉及新农药研发及时领域，具体涉及一类1-芳基-α,β-不饱和酮类化合物及其合成方法和在制备杀根结线虫药物中的应用。
背景技术
化学杀虫剂是目前预防和治疗植物线虫病的主要手段。现有的杀线虫药物主要存在产品种类少、防治效果不理想、易产生抗药性和环境残留等问题。因此，研发新型高效、低毒的杀线虫剂是目前农业生产的迫切需求。
不饱和酮类化合物广泛存在于多种天然化合物中，如查尔酮、黄酮、香豆素、肉桂醛和肉桂酸衍生物等。该类化合物不仅普遍具有抗炎、抗菌、抗病毒、杀虫、抗肿瘤等多种药理活性，而且具有结构简单、易于化学合成和对人畜毒性小的优点，因此，不饱和酮类化合物在新药创制中占有重要地位。
一些结构简单的芳基酮已被证明具有杀线虫活性。例如，4-硝基苯乙酮、2,4-二氯苯乙酮和2-甲氧基-α-溴苯乙酮对南方根结线虫的EC50值分别为12、4和1mg/L。1-芳基-α,β-不饱和酮类化合物已被发现具有杀动物螨虫活性(周搏航，等。ZL 201610047752.2，2019.3.1)和杀蚜活性(侯太平，等。有机化学，2002，22(1)：67-70)。到目前为止，尚未见任何关于1-芳基-α,β-不饱和酮类化合物杀根结线虫的活性报道。
文献所报道的1-芳基-α,β-不饱和酮类化合物的合成方法主要有Witting反应和傅-克酰基化反应两种。传统的Witting方法通常由2-3步反应组成，首先是α-溴代芳基乙酮与三苯膦形成鏻盐，然后再用强碱如氢氧化钠处理鏻盐，形成膦烷。最后膦烷再与醛反应，形成1-芳基-α,β-不饱和酮。该方法步骤多、产率低且反应的立体选择低。
发明内容
本发明提供一类1-芳基-α,β-不饱和酮类化合物及其合成方法和在制备杀根结线虫药物中的应用，此类化合物可作为有效成分，用于开发新型杀线虫药物。
为实现上述目的，本发明采用的技术方案为：一类1-芳基-α,β-不饱和酮类化合物的合成方法，合成反应为：
其中：
R1是邻位、对位或间位的甲基，甲氧基，硝基，氟，氯，溴，碘等；R2是H或者烷基、链烯基、芳基。
一类1-芳基-α,β-不饱和酮类化合物的合成反应方法为：
α-溴代酮:醛:三苯基膦:N,N-二甲基丙烯酰胺的摩尔比为1.0:1.0～1.5:2.0:1.0，优选为1.0:1.2:2.0:1.0；
溶剂为：氯仿、乙醇或氯仿-乙醇混合液，优选氯仿-乙醇混合液，氯仿-乙醇的体积比为1:1；
反应温度为：50～100℃，优选80℃；
反应时间：4～12h，优选8h。
上述合成过程中去除三苯氧膦的方法为：
将反应液减压蒸除溶剂，在搅拌下，向残留物中依次加入四氢呋喃和正己烷混合溶液，静置半小时后，抽滤，除去固体三苯氧膦。
上述四氢呋喃和正己烷加入量的体积比为1:2。
上述合成方法合成所得的一类不饱和酮类化合物
一类不饱和酮类化合物作为有效成分在制备杀植物根结线虫药物中的应用。
该类化合物作为单一有效成分或与其他杀根结线虫药物一起作为混合有效成分在制备植物根结线虫药物中的应用。
该药物对植物根结线虫尤其是南方根结线虫具有显著的杀灭活性。
与现有技术相比，本发明具有以下优点：
1)本发明采用三步合一的“一锅煮”法合成一类1-芳基-α,β-不饱和酮类化合物，具有操作简单、收率高、纯度高、成本低和适宜于规模化生产的优点。
2)本发明所涉及的一类1-芳基-α,β-不饱和酮类化合物对南方根结线虫有高效灭杀活性，且具有对动植物毒性低和环境相容性好的优点，可作为有效成分用于新型杀植物根结线虫药物的开发。
具体实施方式
下面结合具体实施方式对本发明进行详细的说明。
本发明涉及的一类不饱和酮类化合物，具有如下分子结构特征：
R1是甲基，甲氧基，硝基，氟，氯，溴，碘等分布的位置是苯环上邻位、对位或间位；R2是H或者烷基、烯基或苯基。
本发明涉及的一类1-芳基-α,β-不饱和酮类化合物的合成方法，具有如下反应特征：
其中：
R1是甲基，甲氧基，硝基，氟，氯，溴，碘等分布的位置是苯环上邻位、对位或间位。
R2是H或者烷基、链烯基、芳基；
一类1-芳基-α,β-不饱和酮类化合物作为有效成分在制备杀植物根结线虫药物中的应用。
一类1-芳基-α,β-不饱和酮类化合物作为单一有效成分或与其他杀根结线虫药物一起作为混合有效成分在制备植物根结线虫药物中的应用。
一类1-芳基-α,β-不饱和酮类化合物的药物对植物根结线虫尤其是南方根结线虫具有显著的杀灭活性。
对于上述不饱和酮类化合物的合成，本发明提供了如下的具体方法和工艺：
一、不饱和酮类化合物的制备
通用制备方法：向500mL烧瓶中，依次加入100mL氯仿、50mL乙醇、三苯基膦(52.5g,0.2mol)、α-溴代苯乙酮或苯环取代的α-溴代苯乙酮(0.1mol)和N,N-二甲基丙烯酰胺(9.91g,0.1mol)。室温搅拌约10分钟后，向反应液中加入醛(0.075mol)，在搅拌下，向反应液中再加入第二批醛(0.075mol)，将反应液在80℃加热回流4-12h优选8h，直至反应体系变成清亮的黄色溶液。
将反应液在25-40℃进行减压浓缩，向所得残留物中加入4～8倍质量的正己烷和四氢呋喃的混合液(2:1，v/v)，搅拌20-30分钟，静置半小时有大量沉淀生成，减压抽滤，将所得固体用正己烷-四氢呋喃混合溶液(1:1,v/v)洗涤三次，合并滤液和洗涤液。将所得溶液减压浓缩至干，将所得残留物中溶于80mL乙醇中，然后加入10％氯化锌的乙醇溶液(20mL)，搅拌均匀后，室温静置30分钟。减压抽滤，将所得滤液减压蒸除溶剂。
将所得残留物进行硅胶柱层析分离，乙酸乙酯和石油醚的混合液为洗脱剂，得无色或淡黄色α,β-不饱和酮类化合物，产率80-91％。
二、α,β-不饱和酮化合物的物理性质和结构分析：
(E)-1-苯基-2-丙烯酮(1)，淡黄色油状液体；1H NMR(500MHz,CDCl3,TMS)δ7.94(dd,J＝8.2,1.5Hz,2H),7.57(t-like,J＝7.7Hz,1H),7.47(t,J＝8.0Hz,2H),7.15(dd,J＝17.0,10.5Hz,1H),6.43(dd,J＝17.0,1.5Hz,1H),5.93(dd,J＝10.5,1.5Hz,1H)；13C NMR(125MHz,CDCl3)δ191.1,137.3,133.0,132.4,130.1,128.7,128.6；EI-MS m/z:132[M]+.
(E)-1-苯基-2-丁烯酮(2)，淡黄色油状液体；1H NMR(500MHz,CDCl3,TMS)δ7.92(dd,J＝8.3,1.4Hz,2H),7.55(t-like,J＝7.6Hz,1H),7.47(t,J＝8.0Hz,2H),7.07(dq,J＝15.5,6.9Hz,1H),6.90(dq,J＝15.5,1.6Hz,1H),2.00(dd,J＝6.9,1.6Hz,3H)；13C NMR(125MHz,CDCl3)δ190.8,145.0,138.0,132.6,128.5,128.5,127.6,18.8；EI-MS m/z:146[M]+.
(E)-1-苯基-2-戊烯酮(3)，淡黄色油状液体；1H NMR(500MHz,CDCl3,TMS)δ7.92(dd,J＝8.5,1.3Hz,2H),7.55(t-like,J＝7.6Hz,1H,H-4′),7.46(t,J＝8.0Hz,2H),7.11(dt,J＝15.5,6.4Hz,1H、),6.87(dt,J＝15.5,1.6Hz,1H),2.34(m,2H),1.14(t,J＝7.4Hz,3H)；13C NMR(125MHz,CDCl3)δ191.2(C-1),151.4,138.1,132.6,128.6,128.5,125.1,25.9,12.4.
(E)-1-苯基-2-己烯酮(4)，淡黄色油状液体；1H NMR(500MHz,CDCl3,TMS)δ7.93(dd,J＝8.4,1.4Hz,2H),7.57(t-like,J＝7.6Hz,1H),7.48(t,J＝7.9Hz,2H),7.06(dt,J＝15.4,7.0Hz,1H),6.88(dt,J＝15.4,1.6Hz,1H),2.30(m,2H),1.56(m,2H),0.98(t,J＝7.6Hz,3H)；13C NMR(125MHz,CDCl3)δ191.0,149.9,138.1,132.6,128.5,128.5,126.1,34.9,21.5,13.8；EI-MS m/z:174[M]+.
(E)-1-苯基-2-庚烯酮(5)，淡黄色油状液体；1H NMR(500MHz,CDCl3,TMS)δ7.92(dd,J＝8.5,1.1Hz,2H),7.55(t-like,J＝7.6Hz,1H),7.46(t,J＝7.9Hz,2H),7.06(dt,J＝15.4,7.3Hz,1H),6.87(dt,J＝15.4,1.5Hz,1H),2.32(m,2H),1.52(m,2H),1.39(m,2H),0.94(t,J＝7.3Hz,3H)；13CNMR(125MHz,CDCl3)δ191.0,150.1,138.1,132.6,128.5,128.5,126.0,32.6,31.3,22.3,13.9；EI-MS m/z:188[M]+.
(E)-1-苯基-2-辛烯酮(6)，淡黄色油状液体；1H NMR(500MHz,CDCl3,TMS)δ7.92(dd,J＝8.5,1.4Hz,2H),7.55(t-like,J＝7.7Hz,1H),7.46(t,J＝8.1Hz,2H),7.07(dt,J＝15.4,7.0Hz,1H),6.87(dt,J＝15.4,1.5Hz,1H),2.31(m,2H),1.53(m,2H),1.36–1.32(m,4H),0.91(t,J＝6.9Hz,3H)；13C NMR(125MHz,CDCl3)δ191.0,150.2,138.1,132.6,128.6,128.51,125.9,32.9,31.5,27.9,22.5,14.0；EI-MS m/z:202[M]+.
(E)-1-苯基-2-壬烯酮(7)，淡黄色油状液体；1H NMR(500MHz,CDCl3,TMS)δ7.92(d,J＝8.3Hz,2H),7.55(t,J＝7.4Hz,1H),7.46(t,J＝7.9Hz,2H),7.06(dt,J＝15.4,6.8Hz,1H),6.87(d,J＝15.4Hz,1H),2.31(m,2H),1.52(m,2H),1.39–1.30(m,6H,H-6),0.90(t,J＝6.6Hz,3H)；13C NMR(125MHz,CDCl3)δ191.0,150.2,138.1,132.6,128.5,128.5,126.0,32.9,31.6,28.9,28.2,22.6,14.1；EI-MS m/z:216[M]+.
(E)-1-苯基-2-十一烯酮(8)，淡黄色油状液体，产率68％，1H NMR(500MHz,CDCl3,TMS)δ7.92(dd,J＝8.5,1.4Hz,2H),7.55(t-like,J＝8.0Hz,1H),7.46(m,2H),7.06(dt,J＝15.4,7.1Hz,1H),6.87(dt,J＝15.4,1.5Hz,1H),2.31(m,2H),1.52(m,2H),1.37–1.26(m,10H),0.88(t,J＝7.3Hz,3H)；13C NMR(125MHz,CDCl3)δ191.0,150.2,138.1,132.6,128.5,128.5,126.0,32.9,31.9,29.4,29.3,29.2,28.2,22.7,14.1；EI-MS m/z:244[M]+.
(E)-1,3-二苯基丙烯酮(9)，淡黄色固体；1H NMR(500MHz,CDCl3):δ8.03(dd,J＝7.2,1.3Hz,2H),7.83(d,J＝15.8Hz,1H),7.65(dd,J＝7.3,3.6Hz,2H),7.60(t-like,J＝7.3Hz,1H),7.55–7.49(m,3H),7.42–7.40(m,3H)；13C NMR(125MHz,CDCl3):δ190.60,144.88,138.26,134.93,132.82,130.58,129.00,128.67,128.54,128.49,122.15.Positive ESI-MS m/z:209[M+H]+.
(E)-1-苯基-2,4-戊二烯酮(10)，淡黄色油状液体；1H NMR(500MHz,CDCl3,TMS)δ7.94(dd,J＝8.5,1.4Hz,2H),7.55(t-like,J＝7.6Hz,1H),7.47(t,J＝7.9Hz,2H),7.40(dd,J＝15.0,10.5Hz,1H),6.87(d,J＝15.0Hz,1H),6.37–6.24(m,2H),1.91(d,J＝6.6Hz,3H)；13C NMR(125MHz,CDCl3)δ191.0,1453,141.1,138.3,132.5,130.6,128.5,128.4,123.4,18.9；
(E)-4-甲基-1-苯基-2-戊烯酮(11)，淡黄色油状液体；1H NMR(500MHz,CDCl3,TMS)δ7.92(dd,J＝8.4,1.6Hz,2H),7.55(t-like,J＝7.6Hz,1H),7.46(t,J＝7.9Hz,2H),7.03(dd,J＝15.5,6.7Hz,1H),6.82(dd,J＝15.5,1.2Hz,1H,),2.57(m,1H),1.13(d,J＝6.9Hz,6H)；13C NMR(125MHz,CDCl3)δ191.4,156.1,138.2,132.6,128.6,128.5,123.2,31.6,21.4；EI-MS m/z:174[M]+.
(E)-5-甲基-1-苯基-2-己烯酮(12)，淡黄色油状液体；1H NMR(500MHz,CDCl3,TMS)δ7.93(dd,J＝8.0,1.3Hz,2H),7.54(t-like,J＝8.0Hz,1H),7.46(t,J＝8.0Hz,2H),7.04(dt,J＝15.4,7.5Hz,1H),6.86(d-like,J＝15.4Hz,1H),2.21(m,2H),1.83(m,1H),0.96(d,J＝6.6Hz,6H)；13C NMR(125MHz,CDCl3)δ190.9,148.9,138.1,132.6,128.5,128.5,127.0,42.1,28.0,22.5；EI-MS m/z:188[M]+.
(E)-4-甲基-1-苯基-2-己烯酮(13)，淡黄色油状液体；1H NMR(500MHz,DMSO-d6,TMS)δ7.96(dd,J＝8.5,1.1Hz,2H),7.65(t-like,J＝8.0Hz,1H),7.53(m,2H),7.03(dd,J＝15.4,0.9Hz,1H),6.85(dd,J＝15.4,7.9Hz,1H),2.36(m,1H),1.43(m,2H),1.07(d,J＝6.6Hz,3H),0.87(t,J＝7.3Hz,3H)；13C NMR(125MHz,CDCl3)δ191.2,155.1,138.2,132.6,128.6,128.5,124.4,38.8,29.0,19.1,11.7.
(E)-1-苯基-2-庚烯-1-酮(14)，淡黄色油状液体；1H NMR(500MHz,CDCl3)δ7.92(dd,J＝8.5,1.1Hz,2H),7.55(t-like,J＝7.6Hz,1H),7.46(t,J＝7.9Hz,2H),7.06(dt,J＝15.4,7.3Hz,1H),6.87(dt,J＝15.4,1.5Hz,1H),2.32(m,2H),1.52(m,2H),1.39(m,2H),0.94(t,J＝7.3Hz,3H),13C NMR(125MHz,CDCl3)δ191.0,150.1,138.1,132.6,128.5,128.5,126.0,32.6,31.3,22.3,13.9.
(E)-1-(2-羟基苯基)-2-庚烯-1-酮(15):淡黄色油状液体；1H NMR(500MHz,CDCl3)δ12.73(s,1H),7.84–7.78(m,1H),7.50–7.43(m,1H),7.21(dt,J＝15.2,7.0Hz,1H),7.05–6.98(m,2H),6.90(ddd,J＝8.2,7.1,1.2Hz,1H),2.40–2.31(m,2H),1.56–1.51(m,2H),1.43–1.37(m,2H),0.95(t,J＝7.3Hz,3H)；13C NMR(125MHz,CDCl3)δ194.2,163.6,151.0,136.2,129.9,123.9,119.6,118.7,118.5,32.7,30.3,22.4,13.9.
(E)-1-(2-甲基苯基)-2-庚烯-1-酮(16)：淡黄色油状液体；1H NMR(500MHz,CDCl3)δ7.39–7.14(m,4H),6.71(dt,J＝15.8,6.9Hz,1H),6.47(dt,J＝15.8,1.5Hz,1H),2.38(s,3H),2.31–2.22(m,2H),1.49–1.42(m,2H),1.38–1.32(m,2H),0.91(t,J＝7.3Hz,3H)；13CNMR(125MHz，CDCl3)δ197.1,151.7,139.1,136.6,131.1,130.8,130.1,128.0,125.3,32.4,30.2,22.3,20.1,13.8.
(E)-1-(3-甲基苯基)-2-庚烯-1-酮(17)：淡黄色油状液体；1H NMR(500MHz,CDCl3)δ7.74–7.69(m,2H),7.36–7.33(m,2H),7.05(dt,J＝15.4,7.0Hz,1H),6.86(dt,J＝15.4,1.6Hz,1H),2.41(s,3H),2.32(qd,J＝7.0,1.5Hz,2H),1.54–1.48(m,2H),1.41–1.36(m,2H),0.94(t,J＝7.3Hz,3H)；13CNMR(125MHz,CDCl3)δ191.2,149.8,138.3,138.1,133.3,129.1,128.3,126.1,125.7,32.5,30.3,22.3,21.4,13.9.
(E)-1-(4-甲基苯基)-2-庚烯-1-酮(18)：淡黄色油状液体；1H NMR(500MHz,CDCl3)δ7.85–7.82(m,2H),7.27–7.24(m,2H),7.05(dt,J＝15.4,6.9Hz,1H),6.87(dt,J＝15.4,1.5Hz,1H),2.41(s,3H),2.31(qd,J＝7.1,1.5Hz,2H),1.54–1.47(m,2H),1.41–1.35(m,2H),0.93(t,J＝7.3Hz,3H)；13CNMR(125MHz,CDCl3)δ190.4,149.5,143.3,135.5,129.2,129.2,128.7,125.9,32.5,30.4,22.3,21.6,13.9.
(E)-1-(2-甲氧基苯基)-2-庚烯-1-酮(19):淡黄色油状液体；1H NMR(500MHz,CDCl3)δ7.50-7.48(m,1H),7.45–7.40(m,1H),7.02–6.93(m,2H),6.84(dt,J＝15.7Hz,6.97Hz,1H),6.65(dt,J＝15.6Hz,1H),3.85(s,3H),2.26(qd,J＝7.1,1.5Hz,2H),1.49–1.44(m,2H),1.36(m,2H),0.92(t,J＝7.3Hz,1H)；13C NMR(125MHz,CDCl3)δ193.8,157.8,149.1,132.4,130.7,130.0,120.6,111.5,55.6,32.3,30.2,22.3,13.9.
(E)-1-(3-甲氧基苯基)-2-庚烯-1-酮(20):淡黄色油状液体；1H NMR(500MHz,CDCl3)δ7.52–7.48(m,1H),7.47–7.45(m,1H),7.39–7.34(m,1H),7.13–7.08(m,1H),7.07(dt,J＝16.0Hz,6.90Hz,1H),6.85(d,J＝15.4Hz,1H),3.86(s,3H),2.32(qd,J＝7.1,1.6Hz,2H),1.55–1.47(m,2H),1.39(q,J＝7.5Hz,2H),0.94(t,J＝7.3Hz,3H)；13C NMR(125MHz,CDCl3)δ190.7,159.8,150.1,139.5,129.5,125.9,121.1,119.1,112.9,55.5,32.6,30.3,22.4,13.9.
(E)-1-(4-甲氧基苯基)-2-庚烯-1-酮(21):淡黄色油状液体；1H NMR(500MHz,CDCl3)δ7.96–7.79(m,2H),6.97(dt,J＝15.3,6.9Hz,1H),6.89–6.84(m,2H),6.81(dt,J＝15.3,1.6Hz,1H),3.79(s,3H),2.24(td,J＝8.4,7.7,6.3Hz,2H),1.47–1.38(m,2H),1.31(h,J＝7.3Hz,2H),0.86(t,J＝7.3Hz,3H)；13C NMR(125MHz,CDCl3)δ189.2,163.3,149.0,130.9,130.8,125.5,113.7,55.5,32.5,30.4,22.4,13.9.
(E)-1-(2-硝基苯基)-2-庚烯-1-酮(22):金黄色油状液体；1H NMR(500MHz,CDCl3)δ8.13(dd,J＝8.2,1.2Hz,1H),7.72(td,J＝7.5,1.2Hz,1H),7.62(td,J＝7.9,1.5Hz,1H),7.43(dd,J＝7.6,1.5Hz,1H),6.48(dt,J＝16.0,6.7Hz,1H),6.39(dt,J＝16.1,1.3Hz,1H),2.24(td,J＝7.9,7.4,6.1Hz,2H),1.44–1.38(m,2H),1.35–1.27(m,2H),0.89(t,J＝7.3Hz,3H)；13C NMR(125MHz,CDCl3)δ193.2,152.1,146.8,136.3,133.9,130.6,130.4,128.8,124.4,32.4,30.0,22.2,13.8.
(E)-1-(3-硝基苯基)-2-庚烯-1-酮(23):淡黄色油状液体，产率46.5％；1H NMR(500MHz,CDCl3)δ8.75–8.71(m,1H),8.41(dq,J＝8.3,1.6Hz,1H),8.27(dq,J＝7.7,1.5Hz,1H),7.70(td,J＝8.0,1.4Hz,1H),7.21-7.12(m,1H),6.92(dq,J＝15.3,1.6Hz,1H),2.42–2.33(m,2H),1.57–1.51(m,2H),1.43–1.37(m,2H),0.95(t,J＝7.3,3H)；13C NMR(125MHz,CDCl3)δ:183.6,147.7,134.5,129.4,125.1,122.1,120.1,118.5,27.9,25.4,17.6,9.1.
(E)-1-(4-硝基苯基)-2-庚烯-1-酮(24):金黄色油状液体；1H NMR(500MHz,CDCl3)δ8.27–8.22(m,2H),8.00–7.95(m,2H),7.05(dt,J＝15.5,7.0Hz,1H),6.77(dt,J＝15.4,1.6Hz,1H),2.29(qd,J＝7.1,1.5Hz,2H),1.50–1.41(m,2H),1.37–1.28(m,2H),0.87(t,J＝7.3Hz,3H)；13C NMR(125MHz,CDCl3)δ188.4,151.6,148.9,141.9,128.4,124.5,122.7,31.7,29.1,21.3,12.8.
(E)-1-(2-氟苯基)-2-庚烯-1-酮(25):淡黄色油状液体，产率47.6％；1H NMR(500MHz,CDCl3)δ7.62(td,J＝7.5,1.9Hz,1H),7.44–7.36(m,1H),7.14(td,J＝7.5,1.1Hz,1H),7.04(ddd,J＝10.7,8.4,1.1Hz,1H),6.91(dtd,J＝15.6,7.0,1.8Hz,1H),6.70–6.56(m,1H),2.22(qd,J＝7.1,1.5Hz,2H),1.46–1.37(m,2H),1.30(dq,J＝14.4,7.2Hz,2H),0.85(t,J＝7.3Hz,3H)；13C NMR(125MHz,CDCl3)δ189.8(d,J＝2.4Hz),162.0,160.0,150.7,133.5(d,J＝8.7Hz),130.8(d,J＝3.0Hz),129.6(d,J＝5.5Hz),124.4(d,J＝3.6Hz),116.5,116.3,32.4,30.2,22.3,13.8；19F NMR(471MHz,CDCl3)δ-111.1.
(E)-1-(3-氟苯基)-2-庚烯-1-酮(26):淡黄色油状液体；1H NMR(500MHz,CDCl3)δ7.64–7.61(m,1H),7.55–7.51(m,1H),7.38–7.35(m,1H),7.18–7.15(m,1H),7.02(dt,J＝15.5,7.0Hz,1H),6.75(dt,J＝15.4,1.6Hz,1H),2.25(qd,J＝7.1,1.5Hz,2H),1.46–1.40(m,2H),1.34–1.29(m,2H),0.86(t,J＝7.3Hz,3H)；13C NMR(125MHz,CDCl3)δ189.5(d,J＝2.2Hz),163.8,161.8,151.0,130.1(d,J＝7.7Hz),125.5,124.2(d,J＝3.1Hz),119.6(d,J＝21.5Hz),115.3(d,J＝22.2Hz),32.6,30.3,22.3,13.9；19F NMR(471MHz,CDCl3)δ-112.0.
(E)-1-(4-氟苯基)-2-庚烯-1-酮(27):淡黄色油状液体；1H NMR(500MHz,CDCl3)δ7.90–7.87(m,2H),7.08–7.04(m,2H),7.00(dt,J＝15.4,6.9Hz,1H),6.78(dt,J＝15.3,1.5Hz,1H),2.29–2.19(m,2H),1.47–1.39(m,2H),1.31(qd,J＝7.4,2.9Hz,2H),0.86(t,J＝7.3Hz,3H)；13C NMR(125MHz,CDCl3)δ189.2,166.5,164.5,150.3,131.1(d,J＝9.1Hz),125.5,115.6(d,J＝21.8Hz),32.6,30.3,22.3,13.9；19F NMR(471MHz,CDCl3)δ(ppm):-106.0.
(E)-1-(2-氯苯基)-2-庚烯-1-酮(28)：淡黄色油状液体；1H NMR(500MHz,CDCl3)δ7.42–7.31(m,4H),6.71(dt,J＝15.9,6.9Hz,1H),6.46(dt,J＝15.8,1.5Hz,1H),2.28(td,J＝8.3,7.7,6.2Hz,2H),1.49–1.44(m,2H),1.38–1.32(m,2H),0.91(t,J＝7.3Hz,3H)；13CNMR(125MHz,CDCl3)δ194.4,152.7,139.1,131.1,131.0,130.4,130.1,129.1,126.7,32.5,30.0,22.3,13.8.
(E)-1-(3-氯苯基)-2-庚烯-1-酮(29)：淡黄色油状液体；1H NMR(500MHz,CDCl3)δ7.89(t,J＝1.9Hz,1H),7.79(dt,J＝7.7,1.4Hz,1H),7.53–7.49(m,1H),7.40(t,J＝7.9Hz,1H),7.09(dt,J＝15.4,7.0Hz,1H),6.82(dt,J＝15.4,1.6Hz,1H),2.33(qd,J＝7.1,1.5Hz,2H),1.55–1.48(m,2H),1.42–1.36(m,2H),0.94(t,J＝7.3Hz,3H)；13C NMR(125MHz,CDCl3)δ189.5,151.1,139.7,134.8,132.5,129.8,128.6,126.6,125.5,32.6,30.3,22.3,13.8.
(E)-1-(4-氯苯基)-2-庚烯-1-酮(30)：淡黄色油状液体；1H NMR(500MHz,CDCl3)δ7.88–7.85(m,2H),7.45–7.42(m,2H),7.08(dt,J＝15.4,7.0Hz,1H),6.84(dt,J＝15.4,1.5Hz,1H),2.36–2.29(m,2H),1.54–1.48(m,2H),1.41–1.36(m,2H),0.94(t,J＝7.3Hz,3H)；13CNMR(125MHz,CDCl3)δ189.6,150.7,139.0,136.3,129.9,129.8,128.9,128.8,125.4,32.6,30.3,22.3,13.9.
(E)-1-(2-溴苯基)-2-庚烯-1-酮(31)：淡黄色油状液体；1H NMR(500MHz,CDCl3)δ7.62–7.58(m,1H),7.38–7.35(m,1H),7.32–7.27(m,2H),6.68(dt,J＝15.9,6.9Hz,1H),6.43(dt,J＝15.9,1.5Hz,1H),2.34–2.23(m,2H),1.50–1.42(m,2H),1.37–1.32(m,2H),0.91(t,J＝7.3Hz,3H)；13C NMR(125MHz,CDCl3)δ195.3,153.3,141.1,133.3,131.0,130.2,128.9,127.1,119.3,32.5,29.9,22.3,13.8.
(E)-1-(3-溴苯基)-2-庚烯-1-酮(32):淡黄色油状液体；1H NMR(500MHz,CDCl3)δ8.04(t,J＝1.8Hz,1H),7.84(dt,J＝7.8,1.3Hz,1H),7.71–7.63(m,1H),7.35(t,J＝7.9Hz,1H),7.09(dt,J＝15.3,7.0Hz,1H),6.82(dt,J＝15.4,1.6Hz,1H),2.33(qd,J＝7.1,1.5Hz,2H),1.55–1.48(m,2H),1.42–1.35(m,2H),0.94(t,J＝7.3Hz,3H)；13C NMR(125MHz,CDCl3)δ189.4,151.2,139.8,135.4,131.5,130.1,127.0,125.4,122.8,32.6,30.2,22.3,13.9.
(E)-1-(4-溴苯基)-2-庚烯-1-酮(33):淡黄色油状液体；1H NMR(500MHz,CDCl3)δ7.75–7.64(m,2H),7.55–7.47(m,2H),6.99(dt,J＝15.5,7.0Hz,1H),6.74(dt,J＝15.3,1.6Hz,1H),2.24(qd,J＝6.9,1.3Hz,2H),1.42(p,J＝7.3Hz,2H),1.30(q,J＝7.5Hz,2H),0.85(t,J＝7.3Hz,1H)；13C NMR(125MHz,CDCl3)δ189.7,150.8,136.7,131.8,131.8,130.1,127.7,125.4,32.6,30.3,22.4,13.9.
三、杀根结线虫活性的测定
1、供试虫和供试虫卵选择南方根结线虫(M.incognita)的虫卵和第二阶段的幼虫J2s为供试对象。供试虫卵分离于感染南方根结线虫的番茄或南瓜的根部。供试虫由孵化所获的虫卵得到。
2、杀虫活性的测定采用96孔组织培养板进行。每孔加入约50条幼虫J2s或150枚虫卵，然后，向各孔中加入1-10μL的供试液。孔内试验化合物的终浓度为30μg/ml。将培养板在22℃下黑暗条件下孵育24小时，在体视显微镜下，对幼虫的存活和死亡情况进行观察和计数。每个试验设三个平行和三个重复，无菌水做空白对照。以虫体对物理刺激无任何反应作为虫子死亡的标准。取三个重复的平均值，按照如下公式计算校正致死率(M)。
其中，Mt和Mc分别为处理组和对照组的百分死亡率。
试验结果显示，在30μg/mL时，本发明涉及的不饱和酮化合物对南方根结线虫均有显著的杀灭活性。其中部分化合的活性优于或接近一线杀线虫阳性药物——噻唑膦。
由此可见，本发明涉及的不饱和酮化合物普遍具有较强的杀南方根结线虫活性，具有作为有效成分，用于制备新型杀线虫药物的潜在用途。
本发明的内容不限于实施例所列举，本领域普通技术人员通过阅读本发明说明书而对本发明技术方案采取的任何等效的变换，均为本发明的权利要求所涵盖。
Claims (8)
1.一类1-芳基-α,β-不饱和酮类化合物的合成方法，其特征在于：合成反应为：
其中：
R1是邻位、对位或间位的甲基，甲氧基，硝基，氟，氯，溴，碘等；R2是H或者烷基、链烯基、芳基。
2.如权利要求1所述的一类1-芳基-α,β-不饱和酮类化合物的合成反应方法，其特征在于：方法为：
α-溴代酮:醛:三苯基膦:N,N-二甲基丙烯酰胺的摩尔比为1.0:1.0～1.5:2.0:1.0，优选为1.0:1.2:2.0:1.0；
溶剂为：氯仿、乙醇或氯仿-乙醇混合液，优选氯仿-乙醇混合液，氯仿-乙醇的体积比为1:1；
反应温度为：50～100℃，优选80℃；
反应时间：4～12h，优选8h。
3.如权利要求1或2所述的一类1-芳基-α,β-不饱和酮类化合物的合成方法，其特征在于：
合成过程中去除三苯氧膦的方法为：
将反应液减压蒸除溶剂，在搅拌下，向残留物中依次加入四氢呋喃和正己烷混合溶液，静置半小时后，抽滤，除去固体三苯氧膦。
4.如权利要求3所述的一类1-芳基-α,β-不饱和酮类化合物的合成方法，其特征在于：所述四氢呋喃和正己烷加入量的体积比为1:2。
5.如权利要求1所述的合成方法合成所得的一类不饱和酮类化合物。
6.如权利要求5所述的一类不饱和酮类化合物作为有效成分在制备杀植物根结线虫药物中的应用。
7.如权利要求5所述的一类不饱和酮类化合物作为有效成分在制备杀植物根结线虫药物中的应用，其特征在于：该类化合物作为单一有效成分或与其他杀根结线虫药物一起作为混合有效成分在制备植物根结线虫药物中的应用。
8.如权利要求6或7所述的一类不饱和酮类化合物作为有效成分在制备杀植物根结线虫药物中的应用，其特征在于：该药物对植物根结线虫尤其是南方根结线虫具有显著的杀灭活性。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833631A (zh) * | 2014-02-27 | 2014-06-04 | 内蒙古华天制药有限公司 | 四氢异喹啉类化合物作为制备动物杀螨药物的应用 |
| CN105669418A (zh) * | 2016-01-25 | 2016-06-15 | 西北农林科技大学 | α,β-不饱和酮化合物及其合成方法、以及含有该化合物的药物及应用 |
| CN110283078A (zh) * | 2019-07-10 | 2019-09-27 | 南京工业大学 | 一种多取代的1，4二烯烃类化合物及其制备方法 |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833631A (zh) * | 2014-02-27 | 2014-06-04 | 内蒙古华天制药有限公司 | 四氢异喹啉类化合物作为制备动物杀螨药物的应用 |
| CN105669418A (zh) * | 2016-01-25 | 2016-06-15 | 西北农林科技大学 | α,β-不饱和酮化合物及其合成方法、以及含有该化合物的药物及应用 |
| CN110283078A (zh) * | 2019-07-10 | 2019-09-27 | 南京工业大学 | 一种多取代的1，4二烯烃类化合物及其制备方法 |
Non-Patent Citations (3)
| Title |
|---|
| CHARLES D. PAPAGEORGIOU，等: "Enantioselective Organocatalytic Cyclopropanation via Ammonium Ylides", ANGEW. CHEM. INT. ED., vol. 43, pages 2 * |
| PANKAJ，等: "Bioefficacy evaluation of chalcone derivatives against Meloidogyne graminicola infecting rice, Oryza sativa L.", JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART B, vol. 56, pages 1 - 2 * |
| SUMONA KUMARI，等: "Synthesis and Bioevaluation of 3-(substitutedphenyl)-1-(4-hydroxyphenyl)-2-propen-1-ones and their Carbamate Derivatives against Root - Knot Nematode (Meloidogyne javanica)", ORIENTAL JOURNAL OF CHEMISTRY, vol. 30, no. 3 * |
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