CN113831246B - 一种含芳香环的烯酸酯类化合物及其制备与应用 - Google Patents

一种含芳香环的烯酸酯类化合物及其制备与应用 Download PDF

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CN113831246B
CN113831246B CN202111273217.6A CN202111273217A CN113831246B CN 113831246 B CN113831246 B CN 113831246B CN 202111273217 A CN202111273217 A CN 202111273217A CN 113831246 B CN113831246 B CN 113831246B
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杨新玲
潘世香
杨朝凯
刘彦
秦耀果
凌云
石卓
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China Agricultural University
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Abstract

本发明公开了一种含芳香环的烯酸酯类化合物及其制备与应用。本发明的化合物结构简单，易于合成，合成原料源于天然产物，对环境无公害，生态友好。本发明提供的化合物对蚜虫具有较好的驱避和杀死作用，同时对植物病原菌有很好的抑制活性，可作为蚜虫控制剂及杀菌剂，在害虫及植物病害的绿色防控方面具有良好的应用前景。

Description

一种含芳香环的烯酸酯类化合物及其制备与应用
技术领域
本发明属于农用化学品领域，具体涉及一种含芳香环的烯酸酯类化合物及其制备方法，以及该类化合物在蚜虫防治及植物病害防治方面的应用。
背景技术
农药是保证粮食稳产丰产的有力工具，每年可挽回因病虫草害造成的损失达20-50％。但是随着传统农药的不断使用，带来了诸多问题：抗药性、环境污染以及对非靶标生物安全等，引起人们广泛关注。因此，进行生态友好的新农药的创制迫在眉睫。
蚜虫属于同翅目蚜总科(Aphidoidea)，具有种类多、繁殖快、寄主广、易产生抗药性等特点，是一类非常重要的农业害虫(Wang,G.-P et al.J.Integr.Plant.Biol.2015,57,770.)。目前用于蚜虫防治的化学药剂大多存在着抗性问题或对非靶标生物的安全问题等，尤其是因对蜜蜂的毒性而被禁用(Butler D.Nature,2018.)。因此如何以生态安全为前提，寻找新的安全有效的蚜虫控制剂具有深远的意义。
天然产物一直是科研工作者进行药物开发的宝库，在自然界中也存在着许多对蚜虫具有拮抗作用的物质。研究发现，丁香酚(式1)和香芹酚(式2)具有良好的杀蚜活性，此外香芹酚、百里香酚(式3)和水杨酸甲酯(式4)具有良好的驱避蚜虫活性；反-(β)-法尼烯(式5)、香叶醇(式6)及法尼醇(式7)对蚜虫也具有良好的驱避活性且在高浓度下有杀蚜活性，其结构分别如式1-7所示。(Pettersson J,et al.Journal of Chemical Ecology,1994,20(10)，2565-2574；Isman,et al.Crop protection,2000,19(8-10):603-608；Webster B,etal.Animal Behaviour,2010,79(2):451-457.)我们关注到两类对蚜虫有生物活性的天然物质，一类为对蚜虫有生物活性的天然酚类物质，另一类为含有2-甲基-2丁烯结构单元的萜烯类物质。有趣的是这两类物质在植物病害的防治中也发挥着重要的作用：香芹酚及百里香酚抑菌谱广且活性强，具有作为植物源杀菌剂的开发应用的潜力；法尼醇对病原真菌具有抑制作用且可作为增效剂在植物病害防治中应用。(侯辉宇等,植物保护学报,2020,47(06):1362-1369；中国发明专利:ZL201810279381.X,ZL201810279382.4,ZL201810759419.3，ZL201810279387.7)
Figure BDA0003328532010000011
发明内容
本发明的目的是提供一种含芳香环的烯酸酯类化合物及其制备与应用，本发明以天然产物为原料合成得到含芳香环的烯酸酯类化合物，该化合物对蚜虫具有驱避及毒杀作用且对植物病原菌具有抑制作用，可以作为生态友好的药剂用于农业害虫及病害的防治。
本发明所提供的含芳香环的烯酸酯类化合物，其结构式如式I-a、式I-b或式I-c所示：
Figure BDA0003328532010000021
式I-a、式I-b、式I-c中：
m为0～2的整数，具体可为0、1或2；
R1表示苯环上的取代基，可为单取代或多取代，R1可独立地选自由氢、卤素、硝基、氰基、烯基(如烯丙基-CH2CHCH2)，C1～C8烷氧基、酰基(具体可为甲酰基-CHO、乙酰基-COCH3)、芳杂基、杂环基、羧基、酯基(具体可为COOCH3)、C1～C8直链或支链烷基、卤素取代的C1～C8直链或支链烷基、卤素取代的C1～C8烷氧基组成的组中的至少一种；
当R1为环结构时，R1与苯环以单键或者并苯环连接；
具体地，R1为单取代或多取代，R1独立地为甲基、异丙基、甲酰基(-CHO)、酯基(-COOCH3)、甲氧基、烯丙基-CH2CHCH2、3,4-亚甲二氧基、3,4-吡咯基、乙酰基-COCH3、Cl、F、-NO2、-CF3、-OCF3、乙氧基、Br、H、羰基三氟甲基中的至少一种。
式I-a所示化合物具体可为如下任意一种：
Figure BDA0003328532010000022
Figure BDA0003328532010000031
式I-b所示化合物具体可为如下任意一种：
Figure BDA0003328532010000032
Figure BDA0003328532010000041
式I-c所示化合物具体可为如下任意一种：
Figure BDA0003328532010000051
本发明还提供了上述式I-a、式I-b、式I-c所示化合物的制备方法。
本发明所提供的式I-a、式I-b、式I-c所示化合物的制备方法，包括如下步骤：在有机溶剂中，将式Ⅱ-a、式Ⅱ-b、式Ⅱ-c所示化合物分别与式Ⅲ所示化合物进行酯化缩合反应，得到式I-a、式I-b、式I-c所示化合物；
Figure BDA0003328532010000052
式III中的m和R1与式I-a中的m和R1相同；
上述的制备方法中，所述有机溶剂可选自环己烷、己烷、四氢呋喃、二氯甲烷、1,4-二氧六环、乙酸乙酯、石油醚、甲醇、乙醇、正丙醇、四氯化碳、DMF、氯仿、二乙醚、乙腈中的至少一种或两种及以上的任意组合；
所述酯化缩合反应中还加入缩合试剂活化所述式Ⅱ所示化合物中的羧基；
所述缩合试剂可为DIC、DIEA、DCC、DMAP、EDCI和HOBt中的至少一种。
上述的制备方法中，所述酯化缩合反应的温度可为-10～80℃，优选反应温度可为10～40℃，时间可为2～24小时，优选反应时间可为8小时、4～8小时、8～12小时或10～20小时；
所述式II-a、II-b或II-c所示化合物和所述式III所示化合物的摩尔比可为1:1～10，具体可为1:1.5、1:1.5～10、1:1～1.5、1:1～5或1:1～7.5。
上述的制备方法中，通过柱层析纯化得到反应产物。
上述式I-a、I-b或I-c所示化合物在蚜虫防治、蚜虫行为控制及植物病害防治中的应用也属于本发明的保护范围，
所述蚜虫行为控制指蚜虫的驱避行为控制；
所述蚜虫具体可为桃蚜或苹果黄蚜；
所述植物病害具体可为瓜果腐霉病菌、水稻纹枯病菌、油菜菌核病菌和水稻稻瘟病菌引起的病害。
以式I-a、I-b或I-c所示含芳香环的烯酸酯类化合物为活性成分的药物也在本发明的保护范围之内。
所述药物具体可为蚜虫防治剂、蚜虫行为控制剂或植物病害防治剂。
本发明含芳香环的烯酸酯类化合物，经试验证实有明显的杀蚜活性、驱避活性和杀菌活性，即对蚜虫有直接的化学防治效果，还具有调控蚜虫行为的活性，可作为蚜虫控制剂，用于防治农作物、果树、中草药及花卉蚜虫；还可以应用于植物的病害防治中。
本发明原料来源于天然物质，制备方法简便易行，产物纯化容易，成本较低，对环境无公害，生态友好，部分化合物具有优异的杀虫活性、驱避活性及杀菌活性，在害虫和植物病害的绿色防控方面具有良好的应用前景。
经生物活性研究证明，本发明提供了具有防虫抗菌双重功能的绿色安全植物保护产品。
具体实施方式
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
下述实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1、5-异丙基-2-甲基苯基-3-甲基丁-2-烯酸酯的制备(I-a-01)
方法1：取100ml单口烧瓶，加入0.60g(6mmol)3-甲基-2-丁烯酸及25mL四氢呋喃，然后加入1.03g(9mmol)DIC和0.07g(0.6mmol)DMAP，室温搅拌反应1h。随后将含有0.90g(6mmol)5-异丙基-2-甲基苯酚的15mL的四氢呋喃溶液滴加至上述反应液中，室温反应8h。抽滤后，用饱和氯化钠水溶液洗涤滤液，干燥后减压脱去溶剂，硅胶柱层析分离(洗脱液为石油醚：乙酸乙酯V:V＝50：1)，得5-异丙基-2-甲基苯基3-甲基丁-2-烯酸酯(I-a-01)，收率50.4％。
方法2：取100ml单口烧瓶，加入0.60g(6mmol)3-甲基-2-丁烯酸及25mL二氯甲烷，然后加入1.49g(7.2mmol)DCC和0.07g(0.6mmol)DMAP，室温搅拌反应0.5h。随后将含有0.90g(6mmol)5-异丙基-2-甲基苯酚的15mL的二氯甲烷溶液滴加至上述反应液中，室温反应6h。抽滤后，用饱和氯化钠水溶液洗涤滤液，干燥后减压脱去溶剂，硅胶柱层析分离(洗脱液为石油醚：乙酸乙酯V:V＝50：1)，得5-异丙基-2-甲基苯基3-甲基丁-2-烯酸酯(I-a-01)，收率55.6％
方法3：取100ml单口烧瓶，加入0.60g(6mmol)3-甲基-2-丁烯酸及25mL二氯甲烷，然后加入1.38g(7.2mmol)EDCI和0.41g(3mmol)HOBt，室温搅拌反应1h。随后将含有0.90g(6mmol)5-异丙基-2-甲基苯酚的15mL的二氯甲烷溶液滴加至上述反应液中，室温反应6h。抽滤后，用饱和氯化钠水溶液洗涤滤液，干燥后减压脱去溶剂，硅胶柱层析分离(洗脱液为石油醚：乙酸乙酯V:V＝50：1)，得5-异丙基-2-甲基苯基3-甲基丁-2-烯酸酯(I-a-01)，收率48.4％。
核磁氢谱数据如下：1H NMR(500MHz,Chloroform-d)δ7.17–7.11(m,1H),7.00(dd,J＝7.8,1.8Hz,1H),6.87(d,J＝1.8Hz,1H),5.95(p,J＝1.4Hz,1H),2.93–2.81(m,1H),2.23(d,J＝1.3Hz,3H),2.13(s,3H),1.99(d,J＝1.4Hz,3H),1.23(d,J＝7.0Hz,6H)。
参考上述I-a-01的制备方法，可以制备得到式I-a系列化合物。
实施例2、5-异丙基-2-甲基苯基-(E)-3,7-二甲基辛基-2,6-二烯酸酯的制备(I-b-27)
步骤1：(E)-3,7-二甲基辛基-2,6-二烯醛的制备
Figure BDA0003328532010000071
取300ml单口瓶，向其中加入4.62g(30mmol)(E)-3,7-二甲基辛基-2,6-二烯醇及100ml的二氯甲烷，冰浴下分批加入26.08g(300mmol)活性二氧化锰，室温反应12h。将反应液滴于砂芯漏斗中抽滤，用二氯甲烷和乙酸乙酯洗涤，减压脱去溶剂，得(E)-3,7-二甲基辛基-2,6-二烯醛，产率95％。
步骤2：(E)-3,7-二甲基辛基-2,6-二烯酸的制备
向500ml单口瓶中加入2.57g(16.9mmol)(E)-3,7-二甲基辛基-2,6-二烯醛及27.5ml二甲基二丁烯和50ml丙酮，然后缓慢滴加由13.09g(144.7mmol)亚氯酸钠和22.4g(125.8mmol)二水磷酸二氢钠配成的100ml水溶液，滴加时间约0.5h，滴加完毕后室温继续反应1h。用50ml乙酸乙酯萃取三次，干燥脱溶后得(E)-3,7-二甲基辛基-2,6-二烯酸，产率92％。
步骤3：5-异丙基-2-甲基苯基-(E)-3,7-二甲基辛基-2,6-二烯酸酯(I-b-27)的制备
取100ml单口烧瓶，加入1.01g(6mmol)(E)-3,7-二甲基辛基-2,6-二烯酸及25mL的二氯甲烷中，随后将1.49g(7.2mmol)DCC和0.07g(0.6mmol)DMAP添加至单口烧瓶中，室温搅拌反应0.5h，随后将含有0.90g(6mmol)5-异丙基-2-甲基苯酚的15mL二氯甲烷溶液滴加至上述反应液中，室温反应8h。抽滤后，用饱和氯化钠水溶液洗涤滤液，干燥、减压脱去溶剂，硅胶柱层析分离(洗脱液为石油醚：乙酸乙酯V:V＝100：1)，得5-异丙基-2-甲基苯基-(E)-3,7-二甲基辛基-2,6-二烯酸酯(I-b-27)，收率60.1％。1HNMR(500MHz,Chloroform-d)δ7.14(d,J＝7.8Hz,1H),7.00(dd,J＝7.8,1.9Hz,1H),6.88(d,J＝1.9Hz,1H),5.94(d,J＝1.3Hz,1H),5.12(dddd,J＝6.9,5.5,2.9,1.5Hz,1H),2.87(hept,J＝6.9Hz,1H),2.29–2.19(m,7H),2.14(s,3H),1.71(d,J＝1.4Hz,3H),1.64(d,J＝1.4Hz,3H),1.24(s,3H),1.22(s,3H)。
参考上述制备方法，可以制备得到式I-b及I-c的系列化合物。
部分具体式I-a、I-b、I-c化合物的外观、熔点及收率列于表1中，1H NMR谱的数据列于表2中。
表1式I-a、I-b、I-c部分化合物的熔点、外观和收率
Figure BDA0003328532010000081
Figure BDA0003328532010000091
Figure BDA0003328532010000101
Figure BDA0003328532010000111
表2式I-a、I-b、I-c部分化合物的核磁氢谱数据
Figure BDA0003328532010000112
Figure BDA0003328532010000121
Figure BDA0003328532010000131
Figure BDA0003328532010000141
Figure BDA0003328532010000151
实施例3、本发明化合物对蚜虫的杀虫活性
用本发明部分化合物作为实施例的代表(如表3、4所示)测试对蚜虫的杀虫活性。使用万分之一天平称取6mg样品，用0.6mL DMSO溶解，用移液枪吸取0.3mL药液注入20mL小烧杯中，并加入9.7mL曲拉通Triton X-100(5‰)水溶液配制成300mg/L溶液。将市场购买来的甘蓝叶用清水清洗干净并擦干后，并且用直径为15mm的打孔器打出合适大小的叶子，并浸入稀释的含有化学品溶液中20s后，将叶子自然干燥，待溶剂挥发后置于35mm的生测培养皿中，将叶子的背面向上翻转，并接入20头桃蚜，每个处理重复3次试验。置于温度为(25±1)℃的人工气候室中，48h后检查蚜虫死亡数。用加入0.3mL的DMSO和9.7mL曲拉通水溶液作溶剂空白对照。
对于苹果黄蚜的杀虫活性测试除将甘蓝叶换为海棠叶外，其余与桃蚜杀虫活性测试一致。
死亡判断标准为：轻触虫体，以完全不动者为死亡。
校正死亡率(％)＝(处理组死亡率-空白组死亡率)/(1-空白组死亡率)*100％
杀桃蚜活性测试结果见表3；杀苹果黄蚜活性测试结果见表4。
表3部分式I-a、I-b、I-c化合物对桃蚜的杀虫活性(浓度300mg/L)
Figure BDA0003328532010000152
Figure BDA0003328532010000161
表4部分式I-b化合物对苹果黄蚜的杀虫活性(浓度300mg/L)
Figure BDA0003328532010000162
表3结果表明，本发明的化合物在高浓度下对蚜虫具有杀死活性，其中化合物I-b-30、I-b-33和I-b-38在300mg/L的剂量下对桃蚜的抑制死亡率均在70％以上；表4结果表明，化合物I-b-27、I-b-28和I-b-34在300mg/L的剂量下对苹果黄蚜的抑制死亡率均在90％以上，具有作为蚜虫防治剂进一步开发的价值。
实施例4、本发明化合物对蚜虫的驱避活性
用本发明部分化合物作为实施例的代表(如表5所示)测试对蚜虫的驱避活性。测试设备为本实验室自制T型嗅觉仪，由释放口释放20头以上无翅成蚜，每臂经抽气泵以0.2L/min通入经活性炭及蒸馏水的潮湿空气。测试臂导入的潮湿空气先经过5μg样品味源物，另一臂作为对照臂，导入的潮湿空气先经过溶剂。记录导入样品15min时蚜虫在各臂的数目。每重复一次均用无水乙醇清洗嗅觉仪及皮管、更换滤纸片、且对调两臂使用，每个样品实验至少重复三次。以越过嗅觉仪中心为准计入处理组或对照组，未越过的蚜虫记为未反应组。
计算驱避率，公式如下所示
驱避率＝(对照组虫数-处理组虫数)/(对照组虫数+处理组虫数)*100％
蚜虫驱避活性测试结果见表5
表5部分式I-a、I-b、I-c化合物对桃蚜的驱避活性
Figure BDA0003328532010000171
Figure BDA0003328532010000181
表5结果表明，本发明的化合物在低浓度下对桃蚜具有驱避活性，其中化合物I-b-05、I-b-17、I-b-33、I-b-37、I-b-38、I-c-03和I-c-10在5μg的剂量下对桃蚜的驱避率均在60％以上，且上述化合物合成简便可行，原料来源绿色安全，生态友好，具有作为蚜虫行为控制剂进一步开发的价值，具有良好应用前景。
实施例5、本发明化合物对植物病原菌的抑制活性
用本发明部分化合物作为实施例的代表(如表6所示)对植物多种病原菌进行了离体抑菌活性测试。供试菌种为瓜果腐霉病菌、水稻纹枯病菌、油菜菌核病菌和水稻稻瘟病菌。本发明对农药领域多种病原菌表现出很好的活性，可以作为杀菌剂用于上述植物病原菌的防治。
将本发明化合物溶于二甲基亚砜，配制成10000μg/ml的药液备用。取1ml备用药液与199ml PDA培养基混匀，制备成浓度为50μg/ml的含毒培养基。将其倒入直径为90cm的培养皿中，每皿大约15ml，待其固化后，接入活化好的病原真菌菌饼，置于25℃培养箱中培养，二甲基亚砜为溶剂对照，无菌水为空白对照，每个样品重复3次，以上操作为严格的无菌操作，待空白对照菌落充分生长后，以十字交叉法量取每个处理的菌落直径，取其平均值。按照以下公式计算菌丝生长抑制率：
Figure BDA0003328532010000182
本发明部分代表化合物对瓜果腐霉病菌、水稻纹枯病菌、油菜菌核病菌和水稻稻瘟病菌的离体杀菌活性数据见表6。
表6式I-a部分化合物的离体杀菌活性数据(50μg/mL)
Figure BDA0003328532010000183
从表6可以看出，本发明提供的部分式I-a化合物对所测试的4种植物病原菌均具有一定的抑制活性。在50μg/mL浓度下，3个化合物对水稻纹枯病菌的抑制率超过85％。化合物I-a-03杀菌活性优异，对水稻纹枯病菌和油菜菌核病菌的抑制率均为100％。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。

Claims (3)

1.如下化合物：
Figure FDA0003752986450000011
。
2.权利要求1中化合物I-a-01、I-a-03在对水稻纹枯病菌防治中的应用；
化合物I-a-12在对水稻纹枯病菌防治中的应用
Figure FDA0003752986450000012
3.权利要求1中化合物I-a-03在对油菜菌核病菌防治中的应用。
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