CN113831386B - 甾体哌啶酮衍生物及其合成方法与应用 - Google Patents

甾体哌啶酮衍生物及其合成方法与应用 Download PDF

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CN113831386B
CN113831386B CN202111114215.2A CN202111114215A CN113831386B CN 113831386 B CN113831386 B CN 113831386B CN 202111114215 A CN202111114215 A CN 202111114215A CN 113831386 B CN113831386 B CN 113831386B
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师宝君
蒋伟奇
马世闯
胡玉晓
王强平
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Abstract

本发明公开了甾体哌啶酮衍生物及其合成方法与应用，甾体哌啶酮衍生物具有通式(1)或通式(2)表示的化学结构，其中，R为烷基、苯基或取代苯基以及杂环中的任意一种；甾体哌啶酮衍生物的合成方法，以去氢表雄酮为基础原料，通过一系列反应得到本发明的甾体哌啶酮衍生物，该合成方法制备的产物产率高且产物易于分离，是制备本发明甾体哌啶酮衍生物的最优方法；本发明提供的甾体哌啶酮衍生物经生物测定证实对蚜虫、叶螨、稻飞虱以及粉虱等刺吸式昆虫表现出良好的毒杀活性，可应用于植物虫害防治。
Figure DDA0003274913400000011

Description

甾体哌啶酮衍生物及其合成方法与应用
技术领域
本发明属于药物合成技术领域，具体涉及甾体哌啶酮衍生物及其合成方法与应用。
背景技术
杂环化合物在自然界中普遍存在且用途广泛，在人们的现实生活中占有非常重要的地位。绝大多数药物和半数以上的有机化合物都为杂环化合物。杂环化合物的合成及其生物活性的探究是有机化学、药物化学及农药开发的重要研究领域之一，尤其是某些含有N、O杂原子的杂环化合物，表现出了良好的杀菌活性，在农药、医药等领域得到了广泛的应用。
含氮杂环中的哌啶酮类化合物由于具有广谱生物活性，是近年来研究开发较为活跃的领域之一，其应用领域主要是：在医药方面可用来做抗癌、消炎、退热等药物；在农药方面可用来做除草剂、抗菌剂、植物生长调节剂、杀虫剂等；同时，这类化合物还可作为重要的有机合成中间体。
刺吸式害虫害螨如蚜虫、粉虱、稻飞虱和叶螨等是农业上危害大多数农作物的主要害虫之一，但随着防治药剂的长期频繁使用，使其产生了特别严重的抗药性。根据杂环化合物和哌啶酮在农药方面的应用，合成出了一系列甾体哌啶酮衍生物，旨在可以得到更好的杀虫剂。
发明内容
本发明的目的在于克服现有技术的缺点，提供一系列结构新颖的甾体哌啶酮衍生物；
本发明的第二目的在于提供一种高收率的甾体哌啶酮衍生物的合成方法；
本发明的第三目的在于提供甾体哌啶酮衍生物在植物虫害防治中的应用。
本发明的目的通过以下技术方案来实现：甾体哌啶酮衍生物，具有通式(1)或通式(2)表示的至少一种化学结构，
Figure BDA0003274913380000011
其中，所述化学结构中R为烷基、苯基或取代苯基以及杂环中的任意一种，所述的烷基为脂肪链。
进一步地，所述的R为(1g)～(6g)中的任意一种：
Figure BDA0003274913380000021
其中，n＝1,2,3,4，……，n；
R1为邻位、间位或对位的取代基；
R2和R3为2,3取代、2,4取代、2,5取代，2,6取代、3,4取代、3,5取代、3,6取代、4,5取代、4,6取代或5,6取代中的任意一种；
R1、R2和R3的取代基为卤素、三氯甲基、甲基、硝基或甲氧基中的任意一种。卤素代表氟、氯、溴或碘；三氯甲基表示-CF3的基团；甲基表示-CH3的基团；硝基表示-NO2的基团；甲氧基表示-OCH3的基团。
进一步地，甾体哌啶酮衍生物具有以下化学结构：
Figure BDA0003274913380000022
Figure BDA0003274913380000031
Figure BDA0003274913380000041
甾体哌啶酮衍生物的合成方法，合成路线如下：
Figure BDA0003274913380000042
进一步地，步骤a的反应条件为：向溶有化合物(3)或(5)的二氯甲烷中，分别依次加入4-二甲氨基吡啶、三乙胺和含有各种取代基的酰氯，常温反应6h；步骤b的反应条件为：以甲醇为溶剂，加入碳酸钠，回流反应2h。
进一步地，所述化合物(3)和(5)的合成路线为：
Figure BDA0003274913380000043
进一步地，所述步骤c的反应条件为：化合物(7)的二氯甲烷溶液，加入乙酸酐，加入2,4-二甲氨基吡啶和三乙胺，25℃反应2h；
所述步骤d的反应条件为：以乙醇为溶剂，加入化合物(8)、盐酸羟胺和乙酸钠，常温反应0.5h；
所述步骤e的反应条件为：以四氢呋喃为溶剂，加入二氯亚砜，常温反应1h；
所述步骤f的反应条件为：以乙醇为溶剂，以Pb/C为催化剂，加入氢气，常温反应60h。
甾体哌啶酮衍生物在植物虫害防治中的应用。
进一步地，所述的植物虫害为刺吸式害虫害螨，具体可用于蚜虫、粉虱、稻飞虱和叶螨的防治。
所述的甾体哌啶酮衍生物制备的杀虫剂。
进一步地，所述杀虫剂中甾体哌啶酮衍生物的有效含量为0.01％～99.99％。
为了在农业和植保领域施用所述甾体哌啶酮衍生物，本领域普通技术人员可以将所述甾体哌啶酮衍生物中的一种或几种作为杀虫活性成分，与农药学上可接受的载体，或者是其他的农用活性成分组合使用，制备成便于施用的制剂，比如水分散粒剂、可湿性粉剂或可分散油悬浮剂等多种剂型。在配制上述不同剂型时，对本领域的普通技术人员来说，除需要使用含有供选的杀菌活性成分外，还需要选用多种助剂，可以根据需要选择使用不同的农药制剂辅助成分(助剂)。所述辅助成分可以为分散介质、分散剂、乳化剂、润湿剂、增稠剂、消泡剂、防冻剂、崩解剂、粘结剂、填料等中的一种或几种。
本发明具有以下优点：
(1)本发明首次提出了一系列全新的甾体哌啶酮衍生物。另外，本发明还提出了甾体哌啶酮衍生物的合成方法，以去氢表雄酮为基础原料，通过一系列反应得到本发明的甾体哌啶酮衍生物，该合成方法制备的产物产率高且产物易于分离，是制备本发明甾体哌啶酮衍生物的最优方法。
(2)本发明提供的甾体哌啶酮衍生物经生物测定证实对蚜虫、叶螨、稻飞虱以及粉虱等刺吸式昆虫表现出良好的毒杀活性，可应用于植物虫害防治。
附图说明
图1为本发明化合物(1)-6的单晶衍射示意图；
图2为本发明化合物(2)-9的单晶衍射示意图。
具体实施方式
下面结合附图及实施例对本发明做进一步的描述，本发明的保护范围不局限于以下所述：
甾体哌啶酮衍生物，具有通式(1)或通式(2)表示的化学结构，
Figure BDA0003274913380000061
其中，所述化学结构中R为烷基、苯基或取代苯基以及杂环中的任意一种，所述的烷基为脂肪链。
本发明所述甾体哌啶酮衍生物的合成路线为：
Figure BDA0003274913380000062
1.先将去氢表雄酮(7)与乙酸酐，2,4-二甲氨基吡啶、三乙胺反应保护(7)的三位羟基，然后以乙醇作溶剂，加入乙酸钠和盐酸羟胺得到化合物(9)，最后在亚硫酰氯的存在下得到化合物(3)，在用乙醇做溶剂，以Pb/C为催化剂得到化合物(5)；
2.以化合物(3)或(5)为反应原料，在二氯甲烷作溶剂的情况下加入三乙胺和2,4-二甲氨基吡啶得到化合物(4)或(6)，然后以甲醇作溶剂，在加入碳酸钠得到化合物(1)或(2)。
上述合成路线中各步骤的反应试剂与条件为：
步骤a：DMAP,Et3N,DCM,0℃；
步骤b：Na2CO3,MeOH,70℃；
步骤c：Ac2O,DMAP,Et3N,25℃；
步骤d：NH2OH·HCl,CH3COONa,EtOH,80℃；
步骤e：SOCl2,THF,0℃；
步骤f：Pb/C,H2,25℃。
实施例1：甾体哌啶酮衍生物的合成方法具体为：
(1)将4.33g去氢表雄酮15mmol溶解于含有40mL二氯甲烷的干燥圆底烧瓶中，搅拌待完全溶解，再依次加入2.24g乙酸酐(22mmol)、0.012g 4-二甲氨基吡啶(0.1mmol)和4.04g三乙胺(20mmol)，常温下反应2h。然后用水和二氯甲烷萃取，有机相用无水硫酸钠干燥，减压浓缩得到4.86g白色固体化合物(8)。之后将4.95g化合物(8)(15mmol)溶于50mL乙醇中，然后依次加入2.90g盐酸羟胺(45mmol)和3.69g乙酸钠(45mmol)，常温下反应0.5h。之后减压浓缩除去有机相，用冰水过滤得5.08g白色固体化合物(9)。在哌啶酮的合成中，将3.45g化合物(9)(10mmol)溶于15mL四氢呋喃中，加入2.38g亚硫酰氯(20mmol)，在常温下搅拌1h，用氢氧化胺调节pH至碱性，得到1.73g白色固体化合物(3)。
(2)将3.45g的化合物(3)(10mmol)溶于40mL乙醇溶液中，加入0.532g Pb/C(5％)做催化剂，在氢气保护下，常温反应60h，经过滤将滤液减压蒸馏得2.25g白色固体化合物(5)。
(3)将0.35g化合物(3)或者化合物(5)(1mmol)、0.06g 2,4-二甲氨基吡啶(0.5mmol)，0.30g三乙胺(3mmol)和相应的酰氯(2mmol)的混合物依次加入到10mL二氯甲烷中，0℃搅拌4h，反应完成后，用二氯甲烷和1mol/L的盐酸水溶液萃取，以石油醚和乙酸乙酯4:1(v/v)纯化得白色固体化合物(4)或(6)。再以甲醇为溶剂，加入0.11g碳酸钠(1mmol)水溶液，70℃反应3h。反应结束之后，之后减压浓缩除去有机相，用二氯甲烷和1mol/L的盐酸水溶液萃取，以石油醚和乙酸乙酯4:1(v/v)纯化得白色固体化合物(1)或(2)。
实施例2：
将通过上述方法制得的所述甾体哌啶酮衍生物通过1H-NMR、13C-NMR进行确认，其中化合物(1)-6和(2)-9的结构通过单晶衍射的方法予以确认，化合物(1)-6的单晶衍射示意图如图1所示，化合物(2)-9的单晶衍射示意图如图2所示，具体结果如下：
1.化合物(1)-1：
Figure BDA0003274913380000071
1H NMR(500MHz,CDCl3)δ＝7.74(t,J＝8.6Hz,1H),7.45–7.40(m,1H),7.19(t,J＝7.6Hz,1H),7.00(dd,J＝11.3,8.3Hz,1H),3.62–3.56(m,1H),2.60–2.44(m,3H),2.07–2.02(m,1H),1.98–1.93(m,1H),1.82–1.76(m,1H),1.74–1.67(m,2H),1.64(s,1H),1.62–1.57(m,2H),1.50(s,3H),1.41–1.25(m,9H),1.15–1.09(m,1H),1.01–0.93(m,2H),0.79(s,3H)。
13C NMR(125MHz,CDCl3)δ＝174.08,171.36,158.70,133.65(d,JCF＝9.0Hz),131.17,125.66(d,JCF＝10.0Hz),124.59,116.27(d,JCF＝23.3Hz),71.25,63.19,53.09,48.57,44.30,37.95,36.85,36.28,36.21,35.58,32.56,31.45,30.97,28.57,21.65,20.86,20.02,12.28。
2.化合物(1)-2：
Figure BDA0003274913380000081
1H NMR(500MHz,CDCl3)δ＝7.54(d,J＝7.9Hz,1H),7.43–7.35(m,2H),7.21–7.17(m,1H),3.60–3.53(m,1H),2.59–2.49(m,2H),2.21–1.94(m,3H),1.79–1.56(m,7H),1.51(s,3H),1.39–1.13(m,9H),0.99–0.90(m,2H),0.77(s,3H)。
13C NMR(125MHz,CDCl3)δ＝175.36,173.70,162.78(d,JCF＝247.2Hz),138.45(d,JCF＝6.7Hz),130.30(d,JCF＝7.9Hz),124.57(d,JCF＝2.8Hz),119.83(d,J JCF＝21.3Hz),115.70(d,JCF＝22.9Hz),71.11,62.29,53.09,48.26,44.29,37.87,36.81,36.39,36.32,35.56,32.01,31.36,30.90,28.48,21.34,21.03,20.18,12.25。
3.化合物(1)-3：
Figure BDA0003274913380000082
1H NMR(400MHz,CDCl3)δ＝7.79(dd,J＝8.7,5.5Hz,2H),7.07(t,J＝8.6Hz,2H),3.60–3.52(m,1H),2.57–2.53(m,2H),2.17–1.93(m,3H),1.78–1.55(m,7H),1.51(s,3H),1.42–1.09(m,9H),0.98–0.79(m,3H),0.77(s,3H)。
13C NMR(100MHz,CDCl3)δ＝175.21,173.40,165.70(d,JCF＝253Hz),132.37(d,JCF＝3.0Hz),131.72(d,JCF＝10.0Hz),115.86(d,JCF＝22.0Hz),71.11,62.02,53.12,48.25,44.29,37.86,36.80,36.47,36.34,35.56,31.83,31.35,30.90,28.48,21.29,21.15,20.18,12.25。
4.化合物(1)-4：
Figure BDA0003274913380000091
1H NMR(500MHz,CDCl3)δ＝7.51(d,J＝7.2Hz,1H),7.34–7.27(m,3H),3.63–3.57(m,1H),2.71–2.67(m,1H),2.57–2.49(m,2H),2.07–1.93(m,2H),1.83–1.71(m,3H),1.65–1.58(m,3H),1.52(s,3H),1.50–1.38(m,5H),1.27(d,J＝12.0Hz,3H),1.16–1.10(m,1H),1.01–0.84(m,3H),0.80(s,3H)。
13C NMR(125MHz,CDCl3)δ＝174.32,172.87,137.40,131.36,130.93,130.46,130.08,127.01,71.26,63.95,53.15,48.60,44.31,37.96,36.87,36.34,35.84,35.60,33.00,31.49,31.03,28.58,21.80,20.29,20.06,12.29。
5.化合物(1)-5：
Figure BDA0003274913380000092
1H NMR(400MHz,CDCl3)δ＝7.53(d,J＝7.9Hz,1H),7.45(d,J＝7.6Hz,1H),7.31(t,J＝7.8Hz,1H),7.21(t,J＝8.6Hz,1H),3.63–3.55(m,1H),2.74–2.69(m,1H),2.56–2.51(m,2H),2.07–1.92(m,2H),1.82–1.55(m,7H),1.52(s,3H),1.44–1.23(m,7H),1.16–1.08(m,1H),1.02–0.84(m,3H),0.79(s,3H)。
13C NMR(100MHz,CDCl3)δ174.44,173.50,139.33,133.79,131.34,129.82,127.45,119.60,71.21,64.06,53.11,48.50,44.26,37.89,36.83,36.30,35.68,35.57,33.09,31.43,31.01,28.54,21.77,20.15,20.06,12.27。
6.化合物(1)-6：
Figure BDA0003274913380000101
1H NMR(500MHz,CDCl3)δ＝7.85(t,J＝1.9Hz,1H),7.67–7.61(m,2H),7.29(d,J＝7.9Hz,1H),3.62–3.56(m,1H),2.58–2.54(m,2H),2.23–2.20(m,1H),2.11–2.06(m,1H),1.99–1.95(m,1H),1.82–1.78(m,1H),1.72–1.57(m,6H),1.52(s,3H),1.41–1.14(m,9H),1.02–0.92(m,2H),0.79(s,3H)。
13C NMR(125MHz,CDCl3)δ175.20,173.77,138.28,135.68,131.70,130.26,127.47,122.83,71.22,62.41,53.09,48.30,44.33,37.94,36.84,36.43,36.37,35.61,32.11,31.44,30.94,28.53,21.40,21.03,20.23,12.29。
7.化合物(1)-7：
Figure BDA0003274913380000102
1H NMR(400MHz,CDCl3)δ7.60(s,1H),7.54(d,J＝7.5Hz,1H),7.33–7.28(m,2H),3.60–3.52(m,1H),2.62–2.49(m,2H),2.38(s,3H),2.18–1.94(m,3H),1.79–1.55(m,7H),1.52(s,3H),1.42–1.13(m,8H),1.07–0.82(m,3H),0.78(s,3H)。
13C NMR(100MHz,CDCl3)δ176.65,173.34,138.50,136.06,133.88,129.55,128.54,126.32,71.13,61.87,53.09,48.17,44.30,37.88,36.80,36.39,36.33,35.56,31.87,31.37,30.90,28.51,21.48,21.31,21.17,20.24,12.25。
8.化合物(1)-8：
Figure BDA0003274913380000103
1H NMR(500MHz,CDCl3)δ＝7.61(s,1H),7.55(d,J＝7.5Hz,1H),7.33–7.28(m,2H),3.62–3.55(m,1H),2.60–2.50(m,2H),2.38(s,3H),2.19–1.96(m,3H),1.82–1.77(m,1H),1.63–1.59(m,4H),1.53(s,3H),1.45–1.36(m,4H),1.31–1.21(m,8H),0.98–0.90(m,2H),0.79(s,3H)。
13C NMR(125MHz,CDCl3)δ＝176.69,173.34,138.55,136.17,133.89,129.60,128.58,126.36,71.26,61.91,53.19,48.27,44.39,37.99,36.88,36.47,36.42,35.63,31.95,31.48,30.97,28.57,21.52,21.38,21.20,20.32,12.30。
9.化合物(1)-9：
Figure BDA0003274913380000111
1H NMR(500MHz,CDCl3)δ7.69(d,J＝7.9Hz,2H),7.20(d,J＝7.9Hz,2H),3.60–3.54(m,1H),2.57–2.53(m,2H),2.37(s,3H),2.15–2.04(m,2H),1.99–1.94(m,1H),1.79–1.64(m,3H),1.61–1.56(m,4H),1.52(s,3H),1.41–1.01(m,9H),0.96–0.86(m,2H),0.77(s,3H)。
13C NMR(125MHz,CDCl3)δ176.27,173.16,143.97,133.36,129.46,129.38,71.17,61.73,53.16,48.20,44.33,37.91,36.83,36.47,36.37,35.57,31.78,31.40,30.93,28.52,21.78,21.30,21.23,20.25,12.27。
10.化合物(1)-10：
Figure BDA0003274913380000112
1H NMR(500MHz,CDCl3)δ＝7.78(d,J＝8.4Hz,2H),6.90(d,J＝8.4Hz,2H),3.84(s,3H),3.62–3.55(m,1H),2.58–2.55(m,2H),2.11–2.04(m,2H),1.99–1.95(m,1H),1.79(d,J＝13.0Hz,1H),1.64–1.58(m,6H),1.52(s,3H),1.32–1.25(m,7H),0.99–0.84(m,4H),0.78(s,3H)。
13C NMR(125MHz,CDCl3)δ＝175.50,172.89,163.77,131.83,128.50,114.07,71.26,61.55,55.64,53.22,48.23,44.38,37.97,36.86,36.58,36.44,35.61,31.65,31.45,30.96,28.55,21.33,21.30,20.29,12.30。
11.化合物(1)-11：
Figure BDA0003274913380000121
1H NMR(500MHz,CDCl3)δ7.98(s,1H),7.89(d,J＝7.8Hz,1H),7.74(d,J＝7.7Hz,1H),7.53(t,J＝7.8Hz,1H),3.61–3.55(m,1H),2.58–2.53(m,2H),2.26–2.23(m,1H),2.12–2.07(m,1H),1.99–1.95(m,1H),1.71–1.58(m,6H),1.54(s,3H),1.42–1.37(m,3H),1.26(q,J＝11.2Hz,5H),1.12–0.83(m,4H),0.79(s,3H)。
13C NMR(125MHz,CDCl3)δ175.24,173.93,137.17,131.95,131.30(d,JCF＝32.9Hz),129.33,129.18,125.52(d,JCF＝4.0Hz),123.77(d,JCF＝272.5Hz),71.17,62.58,53.09,48.39,44.31,37.91,36.83,36.48,36.36,35.60,32.16,31.41,30.92,28.51,21.40,20.98,20.20,12.27。
12.化合物(1)-12：
Figure BDA0003274913380000122
1H NMR(400MHz,CDCl3)δ7.83(d,J＝8.1Hz,2H),7.65(d,J＝8.1Hz,2H),3.60–3.52(m,1H),2.57–2.53(m,2H),2.27–2.24(m,1H),2.12–2.05(m,1H),2.00–1.94(m,1H),1.77–1.56(m,7H),1.53(s,3H),1.42–1.22(m,8H),1.11–0.92(m,3H),0.78(s,3H)。
13C NMR(100MHz,CDCl3)δ175.39,173.96,133.91(q,JCF＝32.8Hz),128.95,125.75(q,JCF＝3.8Hz),125.05,122.34,71.08,62.56,53.10,48.37,44.27,37.83,36.79,36.41,36.29,35.55,32.14,31.33,30.91,28.46,21.37,20.93,20.11,12.23。
13.化合物(1)-13：
Figure BDA0003274913380000123
1H NMR(400MHz,CDCl3)δ8.24(d,J＝8.8Hz,2H),7.83(d,J＝8.8Hz,2H),3.63–3.55(m,1H),2.58–2.54(m,2H),2.36–2.32(m,1H),2.14–2.07(m,1H),2.01–1.95(m,1H),1.82–1.58(m,7H),1.54(s,3H),1.45–1.38(m,3H),1.28–1.24(m,4H),1.16–0.92(m,4H),0.80(s,3H)。
13C NMR(100MHz,CDCl3)δ174.74,174.26,149.87,141.95,129.30,123.96,71.18,63.00,53.13,48.53,44.31,37.90,36.85,36.46,36.34,35.60,32.40,31.41,30.97,28.49,21.48,20.79,20.12,12.29。
14.化合物(2)-1：
Figure BDA0003274913380000131
1H NMR(400MHz,CDCl3)δ＝7.74–7.70(m,1H),7.43–7.37(m,1H),7.17(t,J＝7.4Hz,1H),6.98(dd,J＝11.3,8.2Hz,1H),5.35–5.32(m,1H),3.50–3.42(m,1H),2.57–2.43(m,3H),2.31–2.14(m,4H),2.02–1.94(m,1H),1.83–1.55(m,6H),1.50(s,3H),1.47–1.23(m,4H),1.14–1.01(m,2H),0.96(s,3H)。
13C NMR(100MHz,CDCl3)δ＝174.00,171.22(d,JCF＝2.1Hz),159.83(d,JCF＝254.0Hz),140.80,133.60(d,JCF＝9.1Hz),131.01,125.46(d,JCF＝10.1Hz),124.48(d,JCF＝3.5Hz),120.60,116.17(d,JCF＝23.0Hz),71.37,62.82,48.79,48.77,41.82,36.90,36.59,35.52,32.78,32.59,31.44,31.39,21.31,20.77,20.06,19.21。
15.化合物(2)-2：
Figure BDA0003274913380000132
1H NMR(400MHz,CDCl3)δ＝7.53(dd,J＝7.8,1.4Hz,1H),7.44–7.34(m,2H),7.22–7.17(m,1H),5.38–5.35(m,1H),3.53–3.46(m,1H),2.60–2.55(m,2H),2.34–2.16(m,4H),2.06–2.00m,1H),1.83–1.79(m,3H),1.71–1.58(m,4H),1.54(s,3H),1.50–1.24(m,4H),1.15–1.01(m,2H),0.98(s,3H)。
13C NMR(100MHz,CDCl3)δ＝175.35(d,JCF＝2.9Hz),173.70,162.76(d,JCF＝247.2Hz),140.79,138.41(d,JCF＝6.9Hz),130.31(d,JCF＝7.7Hz),124.53(d,JCF＝2.9Hz),120.67,119.86(d,JCF＝21.4Hz),115.68(d,JCF＝22.9Hz),71.50,62.04,48.88,48.64,41.91,36.95,36.66,35.86,32.88,32.20,31.47,31.46,21.11,21.02,20.35,19.28。
16.化合物(2)-3：
Figure BDA0003274913380000141
1H NMR(500MHz,CDCl3)δ＝7.81–7.78(m,2H),7.07(t,J＝8.3Hz,2H),5.38–5.37(m,1H),3.54–3.48(m,1H),2.59–2.56(m,2H),2.34–2.17(m,4H),2.05–2.01(m,1H),1.84–1.80(m,2H),1.72–1.58(m,6H),1.55(s,3H),1.45–1.25(m,3H),1.14–1.02(m,2H),0.98(s,3H)。
13C NMR(125MHz,CDCl3)δ＝175.23,173.37,165.72(d,JCF＝254.6Hz),140.82,132.42,131.70(d,JCF＝9.4Hz),120.73,115.89(d,JCF＝22.2Hz),71.60,61.81,49.00,48.73,41.99,37.01,36.72,36.02,32.98,32.09,31.56,31.52,21.16,21.13,20.43,19.32。
17.化合物(2)-4：
Figure BDA0003274913380000142
1H NMR(500MHz,CDCl3)δ7.66(d,J＝8.6Hz,2H),7.34(d,J＝8.6Hz,2H),5.33–5.32(m,1H),3.46–3.40(m,1H),2.54(t,J＝8.0Hz,2H),2.28–2.13(m,5H),2.02–1.98(m,1H),1.79–1.55(m,6H),1.51(s,3H),1.48–1.22(m,5H),1.10–0.97(m,2H),0.94(s,3H)。
13C NMR(125MHz,CDCl3)δ175.38,173.42,140.74,139.22,134.55,130.26,128.96,120.62,71.50,61.84,48.89,48.65,41.88,36.91,36.61,35.89,32.87,32.07,31.46,31.41,21.05,20.99,20.30,19.21。
18.化合物(2)-5：
Figure BDA0003274913380000151
1H NMR(400MHz,CDCl3)δ＝7.53(d,J＝7.9Hz,1H),7.47–7.45(m,1H),7.31(t,J＝7.6Hz,1H),7.24–7.19(m,1H),5.37–5.35(m,1H),3.56–3.48(m,1H),2.77–2.72(m,1H),2.58–2.53(m,2H),2.35–2.18(m,3H),2.02–1.96(m 1H),1.89–1.58(m,8H),1.55(s,3H),1.49–1.38(m,2H),1.25(s,1H),1.18–1.05(m,2H),1.00(s,3H)。
13C NMR(100MHz,CDCl3)δ＝174.38,173.50,140.88,139.33,133.76,131.35,129.83,127.48,120.72,119.50,71.61,63.78,48.91,48.88,41.94,36.99,36.70,35.11,33.26,32.96,31.62,31.57,21.54,20.22,20.15,19.30。
19.化合物(2)-6：
Figure BDA0003274913380000152
1H NMR(500MHz,CDCl3)δ7.68(s,1H),7.47(t,J＝8.1Hz,2H),7.12(t,J＝7.8Hz,1H),5.19–5.18(m,1H),3.30–3.23(m,1H),2.46–2.32(m,2H),2.10–1.86(m,5H),1.65–1.59(m,2H),1.54–1.42(m,4H),1.35(s,3H),1.26–1.13(m,3H),1.06(s,2H),0.96–0.87(m,2H),0.80(s,3H)。
13C NMR(125MHz,CDCl3)δ174.88,174.18,140.63,137.53,135.66,131.44,130.05,127.26,122.48,120.23,70.77,62.03,48.63,48.18,41.23,36.71,36.40,35.66,32.68,31.53,31.08,30.74,20.81,20.59,19.86,18.80。
20.化合物(2)-7：
Figure BDA0003274913380000153
1H NMR(400MHz,CDCl3)δ＝7.39(d,J＝7.7Hz,1H),7.31–7.27(m,1H),7.21(d,J＝7.5Hz,1H),7.14(t,J＝7.6Hz,1H),5.36–5.34(m,1H),3.50–3.42(m,1H),2.54(s,3H),2.49–2.43(m,3H),2.31–2.15(m,4H),2.01–1.95(m,1H),1.85–1.76(m,2H),1.72–1.56(m,4H),1.54(s,3H),1.51–1.36(m,4H),1.17–1.01(m,2H),0.97(s,3H)。
13C NMR(100MHz,CDCl3)δ176.83,173.87,140.82,139.12,137.01,131.69,131.04,127.60,125.47,120.55,71.34,61.94,48.84,48.73,41.81,36.91,36.60,35.55,32.88,32.56,31.44,31.38,21.19,20.83,20.66,20.34,19.22。
21.化合物(2)-8：
Figure BDA0003274913380000161
1H NMR(400MHz,CDCl3)δ7.59(s,1H),7.53(d,J＝7.4Hz,1H),7.32–7.27(m,2H),5.35–5.34(m,1H),3.50–3.42(m,1H),2.63–2.52(m,2H),2.36(s,3H),2.31–2.16(m,5H),2.04–1.99(m,1H),1.82–1.57(m,6H),1.53(s,3H),1.47–1.24(m,4H),1.14–1.01(m,2H),0.96(s,3H)。
13C NMR(100MHz,CDCl3)δ176.58,173.30,140.81,138.44,135.95,133.84,129.46,128.49,126.24,120.57,71.37,61.56,48.84,48.48,41.83,36.90,36.60,35.83,32.84,31.95,31.38,29.72,21.42,21.11,21.03,20.33,19.22。
22.化合物(2)-9：
Figure BDA0003274913380000162
1HNMR(500MHz,CDCl3)δ7.68(d,J＝7.8Hz,2H),7.20(d,J＝7.8Hz,2H),5.37–5.36(m,1H),3.52–3.46(m,1H),2.61–2.52(m,2H),2.37(s,1H),2.33–2.15(m,4H),2.04–2.00(m,1H),1.84–1.58(m,8H),1.54(s,1H),1.38–1.25(m,3H),1.13–1.00(m,2H),0.97(s,2H)。
13C NMR(125MHz,CDCl3)δ176.24,173.12,143.96,140.81,133.31,129.44,129.33,120.69,71.52,61.46,48.96,48.59,41.94,36.97,36.67,35.96,32.92,31.94,31.50,31.47,21.77,21.21,21.08,20.41,19.29。
23.化合物(2)-10：
Figure BDA0003274913380000171
1HNMR(500MHz,CDCl3)δ＝7.78(d,J＝8.4Hz,2H),6.90(d,J＝8.4Hz,2H),3.84(s,3H),3.62–3.55(m,1H),2.58–2.55(m,2H),2.11–2.04(m,2H),1.99–1.95(m,1H),1.79(d,J＝13.0Hz,1H),1.64–1.58(m,6H),1.52(s,3H),1.32–1.25(m,7H),0.99–0.84(m,4H),0.78(s,3H)。
13C NMR(125MHz,CDCl3)δ＝175.50,172.89,163.77,131.83,128.50,114.07,71.26,61.55,55.64,53.22,48.23,44.38,37.97,36.86,36.58,36.44,35.61,31.65,31.45,30.96,28.55,21.33,21.30,20.29,12.30。
24.化合物(2)-11：
Figure BDA0003274913380000172
1H NMR(500MHz,CDCl3)δ7.98(s,1H),7.88(d,J＝7.9Hz,1H),7.74(d,J＝7.9Hz,1H),7.53(t,J＝7.9Hz,1H),5.38–5.37(m,1H),3.53–3.47(m,1H),2.60–2.53(m,2H),2.34–2.19(m,4H),2.07–2.03(m,1H),1.84–1.61(m,7H),1.56(s,3H),1.51–1.25(m,4H),1.16–1.03(m,2H),0.99(s,3H)。
13C NMR(125MHz,CDCl3)δ175.22,173.89,140.83,137.14,131.91,131.30(d,JCF＝32.7Hz),129.32,129.17,125.48(d,JCF＝4.0Hz),124.83,120.67,71.56,62.32,48.91,48.78,41.96,36.98,36.70,35.96,32.95,32.35,31.54,31.48,21.19,20.96,20.38,19.30。
25.化合物(2)-12：
Figure BDA0003274913380000181
1H NMR(500MHz,CDCl3)δ7.83(d,J＝8.0Hz,2H),7.65(d,J＝8.1Hz,2H),5.37–5.36(m,1H),3.52–3.46(m,1H),2.63–2.53(m,2H),2.33–2.18(m,4H),2.07–2.02(m,1H),1.85–1.80(m,3H),1.72–1.59(m,4H),1.55(s,3H),1.49–1.25(m,4H),1.15–1.01(m,2H),0.98(s,3H)。
13C NMR(125MHz,CDCl3)δ175.38,173.92,140.83,139.48,133.91(d,JCF＝32.7Hz),128.91,125.75(q,JCF＝3.7Hz),124.78,122.61,120.62,71.50,62.32,48.92,48.79,41.92,36.97,36.68,35.90,32.91,32.36,31.49,21.18,20.92,20.32,19.28。
26.化合物(2)-13：
Figure BDA0003274913380000182
1H NMR(500MHz,CDCl3)δ8.23(d,J＝8.2Hz,2H),7.83(d,J＝8.3Hz,2H),5.38–5.37(m,1H),3.55–3.48(m,1H),2.59–2.56(m,2H),2.38–2.19(m,4H),2.08–2.01(m,1H),1.85–1.82(m,2H),1.73–1.62(m,6H),1.56(s,3H),1.40–1.29(m,2H),1.14–1.04(m,2H),0.99(s,3H),0.92–0.84(m,1H)。
13C NMR(125MHz,CDCl3)δ174.71,174.23,149.85,141.94,140.84,129.25,123.95,120.64,71.55,62.74,48.93,48.91,41.94,37.00,36.71,35.90,32.94,32.58,31.53,29.81,21.26,20.76,20.30,19.31。
实施例3：甾体哌啶酮衍生物对蚜虫、粉虱、稻飞虱和螨的生物学活性研究
(1)甾体哌啶酮衍生物对蚜虫活性影响的实验
采用玻片浸渍法测定表1和表2所列的甾体哌啶酮衍生物对烟蚜、苹果黄蚜和甘蓝蚜虫、小麦蚜虫的抑制活性。具体方法：准确称量一定量待测化合物，以丙酮为溶剂，将化合物溶解，用0.1％Tween-80水溶液配制成浓度50和75μg/mL的溶液，室温下静置半小时待样品完全溶解后保存待用。将待测蚜虫粘贴到含有双面胶的载玻片上，然后将含有蚜虫的玻片在配置的药液中浸渍5s取出，用吸水纸吸干残余的药液，阳性对照为啶虫脒，阴性对照为0.1％Tween-80水溶液。在培养皿中保湿培养24h后观察其死亡率，结果见表1，对苹果黄蚜的抑制活性的LC50，结果见表2：
表1甾体哌啶酮衍生物对蚜虫活性的死亡率
Figure BDA0003274913380000191
表2甾体哌啶酮衍生物对苹果黄蚜的抑制活性的LC50
化合物 毒力方程 相关系数(r) LC<sub>50</sub>(μg/mL)
(1)-3 y＝2.4629x+1.8236 0.9813 24.6
(1)-4 y＝3.2757x+1.5982 0.9924 11.9
(2)-7 y＝3.1231x+1.8168 0.9877 10.3
(2)-9 y＝3.1644x+1.5771 0.9965 14.2
(2)-12 y＝2.9779x+1.5714 0.9992 21.9
啶虫脒 y＝3.1472x+1.8522 0.9846 9.95
表1和表2室内生物测定结果表明，测试化合物对烟蚜、苹果黄蚜和甘蓝蚜虫、小麦蚜虫具有较好的生物活性，部分化合物与啶虫脒具有相似的杀虫效果。
(2)甾体哌啶酮衍生物对螨活性影响的实验
采用玻片浸渍法测定表3所列的甾体哌啶酮衍生物对截形叶螨的抑制活性，具体方法与蚜虫相同，结果如表3所示：
表3甾体哌啶酮衍生物对截形叶螨的抑制活性
Figure BDA0003274913380000201
表3室内生物测定结果表明，测试化合物对截形叶螨具有较好的生物活性，部分化合物与哒螨灵具有相似的杀虫效果。
(4)甾体哌啶酮衍生物对粉虱活性影响的实验
采用叶面喷雾法测定表4所列的哌啶酮甾体衍生物对粉虱的毒杀活性。具体方法：准确称量一定量待测化合物，以丙酮溶解，用0.1％吐温80水溶液配制成浓度为50和75μg/mL的溶液保存待用。将药液喷施于黄瓜叶片的背面，待其自然晾干将待测粉虱放入植株叶片上。阳性对照为噻虫嗪，阴性对照为丙酮。观察其在7d后的死亡数并计算校正死亡率，结果见表3：
表4甾体哌啶酮衍生物对粉虱的抑制活性
Figure BDA0003274913380000202
表4室内生物测定结果表明，测试化合物对粉虱具有较好的生物活性，部分化合物与噻虫嗪具有相似的杀虫效果。
(4)甾体哌啶酮衍生物对稻飞虱活性影响的实验
采用叶面喷雾法测定表5所列的哌啶酮甾体衍生物对稻飞虱的毒杀活性。阳性对照为吡虫啉，阴性对照为丙酮。观察其在3d后的死亡数并计算校正死亡率，结果见表5：
表5甾体哌啶酮衍生物对稻飞虱的杀虫活性
Figure BDA0003274913380000211
表5室内生物测定结果表明，测试化合物对稻飞虱具有较好的生物活性，部分化合物与吡虫啉具有相似的杀虫效果。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都涵盖在本发明的保护范围之内。

Claims (7)

1.甾体哌啶酮衍生物，其特征在于，具有通式(1)或通式(2)表示的化学结构，
Figure FDA0003807247230000011
其中，所述的R为(5g)或(6g)：
Figure FDA0003807247230000012
R1为邻位、间位或对位的取代基；
R2和R3为2,3取代、2,4取代、2,5取代，2,6取代、3,4取代、3,5取代、3,6取代、4,5取代、4,6取代或5,6取代中的任意一种；
R1、R2和R3的取代基为卤素、三氟甲基、甲基、硝基或甲氧基中的任意一种。
2.根据权利要求1所述的甾体哌啶酮衍生物，其特征在于，具有以下化学结构：
Figure FDA0003807247230000013
Figure FDA0003807247230000021
Figure FDA0003807247230000031
3.根据权利要求1所述的甾体哌啶酮衍生物的合成方法，其特征在于，合成路线如下：
Figure FDA0003807247230000032
其中，步骤a的反应条件为：向溶有化合物(3)或(5)的二氯甲烷中，分别依次加入4-二甲氨基吡啶、三乙胺和含有各种取代基的酰氯，常温反应6h；步骤b的反应条件为：以甲醇为溶剂，加入碳酸钠，回流反应2h，其中，所述各种取代基为R，所述的R为(5g)或(6g)：
Figure FDA0003807247230000033
R1为邻位、间位或对位的取代基；
R2和R3为2,3取代、2,4取代、2,5取代，2,6取代、3,4取代、3,5取代、3,6取代、4,5取代、4,6取代或5,6取代中的任意一种；
R1、R2和R3的取代基为卤素、三氟甲基、甲基、硝基或甲氧基中的任意一种。
4.根据权利要求3所述的甾体哌啶酮衍生物的合成方法，其特征在于，所述化合物(3)和(5)的合成路线为：
Figure FDA0003807247230000041
其中，所述步骤c的反应条件为：化合物(7)的二氯甲烷溶液，加入乙酸酐，加入4-二甲氨基吡啶和三乙胺，25℃反应2h；
所述步骤d的反应条件为：以乙醇为溶剂，加入化合物(8)、盐酸羟胺和乙酸钠，常温反应0.5h；
所述步骤e的反应条件为：以四氢呋喃为溶剂，加入二氯亚砜，常温反应1h；
所述步骤f的反应条件为：以乙醇为溶剂，以Pb/C为催化剂，加入氢气，常温反应60h。
5.根据权利要求1或2所述的甾体哌啶酮衍生物在植物虫害防治中的应用。
6.根据权利要求5所述的应用，其特征在于，所述的植物虫害为刺吸式害虫害螨。
7.采用权利要求1或2所述的甾体哌啶酮衍生物制备的杀虫剂。
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