CN117567285A - 一种含酯基的β-紫罗兰酮类似物及其制备与应用 - Google Patents

一种含酯基的β-紫罗兰酮类似物及其制备与应用 Download PDF

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CN117567285A
CN117567285A CN202311494194.0A CN202311494194A CN117567285A CN 117567285 A CN117567285 A CN 117567285A CN 202311494194 A CN202311494194 A CN 202311494194A CN 117567285 A CN117567285 A CN 117567285A
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杨新玲
潘世香
刘彦
石卓
秦耀果
杨朝凯
凌云
周钲欣
杨菁
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China Agricultural University
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Abstract

本发明公开了一种含酯基的β‑紫罗兰酮类似物及其制备与应用。其结构式如式I‑a、式I‑b所示。本发明通过对植物挥发物β‑紫罗兰酮进行酯化修饰，得到一类含酯基的β‑紫罗兰酮类似物，经生物活性研究，发现此类化合物具有驱避蚜虫和引诱蚜虫天敌双重功能，在蚜虫的绿色防控方面具有良好的应用前景。

Description

一种含酯基的β-紫罗兰酮类似物及其制备与应用
技术领域
本发明属于农用化学品领域，具体涉及一种含酯基的β-紫罗兰酮类似物及其制备方法，以及该类化合物在驱避蚜虫及引诱瓢虫方面的应用。
背景技术
蚜虫是一类非常重要的农业害虫，具有种类多、繁殖快、易产生抗药性等特点(Wang,G.-P et al.J.Integr.Plant.Biol.2015,57,770.)。目前主要使用化学药剂进行防治，但由于长期的不合理使用导致了抗药性增长或对非靶标生物的毒性等问题，尤其是蜂毒问题使得主流的防治药剂使用受到限制(Butler D.Nature,2018.)。而近年来，利用蚜虫天敌来对蚜虫进行生物防治因其环境友好、对非靶标生物安全的优点受到人们的青睐。
异色瓢虫(Harmonia axyridis)是瓢甲科、瓢虫属完全变态昆虫，对蚜虫、叶螨、介壳虫等重要害虫具有很强的捕食能力，作为一种重要的生防天敌，在全世界农业生产中广泛应用(Koch,JInsect Sci.2003,1-16)，对控制蚜虫的种群数量起到非常重要的作用。
虫害诱导的植物挥发物(HIPVs)是由当植物被害虫危害时释放出的化学信息物质，可以通过作用于蚜虫及其天敌的化学通讯系统中气味结合蛋白及嗅觉受体从而对蚜虫及其天敌的行为产生调控，在“植物-蚜虫-天敌”的三级营养关系中扮演着重要的角色。β-紫罗兰酮(式I)是一种重要的植物挥发物，不仅对于桃蚜具有良好的驱避作用(Gabrys B,et al.2005)，还可以由多种植物释放并对取食昆虫具有驱避或摄食震慑作用(Cáceres L,et al.JChem Ecol.2016,42,107-117；Wang S,et al.Phytochemistry,1999,52,601-605.)。除此之外，β-紫罗兰酮能与多种蚜虫天敌的气味结合蛋白结合，如异色瓢虫(Qu C,et al.FrontPhysiol,2022,13:829766.)、食蚜蝇(Wang B,et al.Curr Biol,2022,32,951-962.)及草蛉(Li Z.Q,et al.Molecular&Integrative Physiology.2015,185:51-57.)等，但缺乏对活体行为研究，因此其对上述蚜虫天敌的行为活性值得进一步研究，以期开发兼具蚜虫驱避和天敌引诱双重活性的蚜虫控制剂。
虽然天然植物挥发物具有专属性强、微量及生态友好的优点，但同时具有易挥发、结构不稳定及在田间应用难的缺点。因此以植物挥发物为活性先导，开发活性与稳定性兼备的蚜虫控制剂，对蚜虫的绿色防控具有重要意义。
发明内容
本发明的目的之一是提供一种含酯基的β-紫罗兰酮类似物。
本发明所提供的含酯基的β-紫罗兰酮类似物，其结构式如式I-a、式I-b所示：
式I-a、式I-b中，R1各自独立地选自：C1-C12直链或支链烷基(具体可为C1-C6直链或支链烷基，如甲基、乙基、丙基、丁基、戊基、己基、庚基)、卤代C1-C12直链或支链烷基、C3-C12环烷基(具体可为C4-C6环烷基，如环丙基、环丁基、环戊基、环己基)、C2-C10烯基(具体可为单烯基(乙烯基、异丁烯基)、二烯基(如))、芳杂环(如噻吩、呋喃)、C3-C12环烷基取代的C1-C6直链或支链烷基(如/>)、芳基取代的C1-C6直链或支链烷基(具体可为苯基取代的C2-C4烷基如/>)中的任意一种；
式I-a所示化合物具体可为如下化合物中的任意一种：
式I-b所示化合物具体可为如下任意一种：
本发明的目的之二是提供上述式I-a、式I-b所示化合物的制备方法。
本发明所提供的式I-a、式I-b所示化合物的制备方法，包括如下两种方法：
方法一：在缚酸剂存在下，在有机溶剂中由式IV所示取代酰氯与式II或式III所示化合物进行缩合反应，得到式I-a或式I-b所示化合物：
式IV中R1与式I-a或式I-b的R1相同；
或，
方法二：在脱水剂、催化剂存在下，在有机溶剂中由式V所示取代酸与式II或式III所示化合物进行酯化缩合反应，得到式I-a或式I-b所示化合物：
式V中R1与式I-a或式I-b的R1相同。
上述两种方法中，式II所示化合物通过如下步骤制备得到：在还原剂存在下，在有机溶剂中对β-紫罗兰酮进行还原，得到式II所示化合物；
式III所示化合物通过如下步骤制备得到：在缚酸剂的存在下，在溶剂中β-紫罗兰酮与盐酸羟胺反应，得到式III所示化合物。
上述方法中，式II或式III所示化合物与取代酰氯、缚酸剂的摩尔比依次可为1:1-2:1-2；具体可为1:1:1；1:1:1.5；1:1:2；1:1.5:2；1:2:2；
所述缚酸剂可选自氢氧化钠、氢氧化钾、醋酸钠、乙醇钠、碳酸钠、碳酸铯、碳酸钾、三乙胺、N,N`-二异丙基乙胺、吡啶中的至少一种；
式II或式III所示化合物与取代酸、脱水剂、催化剂的摩尔比依次可为1:1:1-3:0.1-0.5，具体可为1:1:1:0.1；1:1:1.2:0.2；1:1:1.5:0.3；1:1:2:0.4；1:1:3:0.5；
所述脱水剂可选自二环己基碳二亚胺、N,N-二异丙基碳二亚胺、1-(3-二甲氨基丙基)-3-乙基碳二亚胺一种或几种任意混合；
所述催化剂可选自4-二甲氨基吡啶，1-羟基苯并三氮唑中的一种；
上述反应的温度可为-20℃～100℃，优选为0℃～40℃；反应时间可为0.5-24小时；优选反应时间可为2～12小时；
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；
上述的制备方法中，通过柱层析纯化得到纯的反应产物。
本发明的目的之三是提供上述含酯基的β-紫罗兰酮类似物在蚜虫防治中的应用。
所述应用为：将上述含酯基的β-紫罗兰酮类似物作为蚜虫控制剂或在制备蚜虫控制剂中的应用，
所述蚜虫控制剂兼具驱避蚜虫和引诱蚜虫天敌双重活性；
所述蚜虫具体可为豌豆蚜、大豆蚜；
所述蚜虫天敌具体可为瓢虫。
含式I-a、I-b所示含酯基的β-紫罗兰酮类似物为活性成分的蚜虫控制剂也在本发明的保护范围之内。
所述蚜虫控制剂兼具驱避蚜虫和引诱蚜虫天敌双重活性；
所述蚜虫具体可为豌豆蚜、大豆蚜；
所述蚜虫天敌具体可为瓢虫。
本发明含酯基的β-紫罗兰酮类似物，经试验证实不仅对蚜虫有明显的驱避活性而且对蚜虫天敌有明显的引诱活性，具有双重活性，可用于农作物、果树、中草药及花卉蚜虫的防治中。
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，生态友好，部分化合物具有优异的驱避蚜虫活性及引诱蚜虫天敌活性，在蚜虫的绿色防控方面具有良好的应用前景。
本发明通过对植物挥发物β-紫罗兰酮(式I)进行酯化修饰，得到一类含酯基的β-紫罗兰酮类似物，经生物活性研究，发明了一种具有驱避蚜虫和引诱蚜虫天敌双重功能的绿色农用化学品。
具体实施方式
下面结合具体实施方式对本发明进行进一步的详细描述，给出的实施例仅为了阐明本发明，而不是为了限制本发明的范围。以下提供的实施例可作为本技术领域普通技术人员进行进一步改进的指南，并不以任何方式构成对本发明的限制。
下述实施例中的实验方法，如无特殊说明，均为常规方法，按照本领域内的文献所描述的技术或条件或者按照产品说明书进行。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、(E)-4-(2,6,6-三甲基环己-1-烯-1-基)丁-3-烯-2-醇的制备(式II)
将β-紫罗兰酮(19.23g，100mmol)于500mL烧瓶中，加入甲醇(150mL)，在冰浴条件下慢慢加入硼氢化钠(7.57g，200mmol)。加完后升至室温，搅拌2h，然后减压除去甲醇，加入二氯甲烷溶解，用水洗涤，分液，再用饱和氯化钠溶液洗涤，分液，有机相用无水Na2SO4干燥，得产物β-紫罗兰醇，产率96.7％。核磁氢谱数据如下：1H NMR(500MHz,Chloroform-d)δ6.05(ddt,J＝16.0,2.1,1.0Hz,1H),5.49(dd,J＝15.9,6.8Hz,1H),4.40–4.33(m,1H),1.99–1.96(m,2H),1.67(d,J＝1.1Hz,3H),1.60(ddt,J＝9.8,6.3,3.4Hz,2H),1.53(s,1H),1.46–1.43(m,2H),1.32(d,J＝6.3Hz,3H),0.99(d,J＝1.7Hz,6H)。
实施例2、(E)-4-(2,6,6-三甲基环己基-1-烯-1-基)丁-3-烯-2-乙酸酯的制备(I-a-01)
将β-紫罗兰醇(0.97g，5mmol)于100mL烧瓶中，加入二氯甲烷(20mL)溶解，加入吡啶(0.59g，7.5mmol)，将乙酰氯(0.59g，7.5mmol)溶于20mL二氯甲烷后，在冰浴条件下滴加至烧瓶中，滴加完毕后室温反应4h，TLC监测反应完毕后，使用饱和碳酸氢钠溶液洗涤，分液，收集有机相，浓缩后进行柱层析，得产物I-a-01，产率72.3％。
实施例3、(E)-4-(2,6,6-三甲基环己基-1-烯-1-基)丁-3-烯-2-乙酸酯的制备(I-a-01)
将β-紫罗兰醇(0.97g，5mmol)于100mL烧瓶中，加入二氯甲烷(20mL)溶解，加入三乙胺(0.76g，7.5mmol)，将乙酰氯(0.59g，7.5mmol)溶于20mL二氯甲烷后，在冰浴条件下滴加至烧瓶中，滴加完毕后室温反应3h，TLC监测反应完毕后，使用饱和碳酸氢钠溶液洗涤，分液，收集有机相，浓缩后进行柱层析，得产物I-a-01，产率70.5％。
实施例4、(E)-4-(2,6,6-三甲基环己-1-烯-1-基)丁-3-烯-2-基3-甲基丁烯酸酯的制备(I-a-05)
在100mL三口瓶中，加入3,3-二甲基丙烯酸(0.50g，5mmol)、二环己基碳二亚胺(1.24g，6mmol)及4-二甲氨基吡啶(0.12g，1mmol)使用30mL的二氯甲烷溶解，滴加β-紫罗兰醇(0.97g，5mmol)，室温反应8h，TLC监测反应完毕后。使用饱和碳酸氢钠溶液洗涤，分液，收集有机相，浓缩后进行柱层析，得产物I-a-05，产率73.2％。
实施例5、(E)-4-(2,6,6-三甲基环己-1-烯-1-基)丁-3-烯-2-基3-甲基丁烯酸酯的制备(I-a-05)
在100mL三口瓶中，加入3,3-二甲基丙烯酸(0.50g，5mmol)、N,N-二异丙基碳二亚胺(0.76g，6mmol)及4-二甲氨基吡啶(0.12g，1mmol)使用30mL的二氯甲烷溶解，滴加β-紫罗兰醇(0.97g，5mmol)，室温反应8h，TLC监测反应完毕后。使用饱和碳酸氢钠溶液洗涤，分液，收集有机相，浓缩后进行柱层析，得产物I-a-05，产率72.3％。
参考上述I-a-01或I-a-05的制备方法，可以制备得到式I-a系列化合物。
实施例6、(2E,3E)-4-(2,6,6-三甲基环己-1-烯-1-基)丁-3-烯-2-酮肟(式III)
在500mL的烧瓶中，加入β-紫罗兰酮(19.23g，100mmol)、盐酸羟胺(10.42g，150mmol)及醋酸钠(20.51g，250mmol)，溶于乙醇的水溶液中，加热回流搅拌2h，TLC监测反应完毕后，用乙酸乙酯萃取3次，合并有机相后用饱和碳酸氢钠溶液洗涤，经干燥、浓缩得产物β-紫罗兰酮肟，产率98.9％。核磁氢谱数据如下：1H NMR(500MHz,Chloroform-d)δ9.09(s,1H),6.50(dd,J＝16.7,2.1Hz,1H),6.10(d,J＝16.5Hz,1H),2.06(s,3H),2.04–1.98(m,2H),1.70(d,J＝1.3Hz,3H),1.64–1.59(m,2H),1.50–1.44(m,2H),1.02(s,6H).
实施例7、(2E,3E)-4-(2,6,6-三甲基环己-1-烯-1-基)丁-3-烯-2-酮-O-乙酰肟(I-b-01)
将β-紫罗兰酮肟(1.04g，5mmol)于100mL烧瓶中，加入二氯甲烷(20mL)溶解，加入碳酸钾(1.04g，7.5mmol)，将乙酰氯(0.59g，7.5mmol)溶于20mL二氯甲烷后，在冰浴条件下滴加至烧瓶中，滴加完毕后室温反应4h，TLC监测反应完毕后，使用饱和碳酸氢钠溶液(100mL)洗涤，分液，收集有机相，浓缩后进行柱层析，得产物I-b-01，产率74.4％。
实施例8、(2E,3E)-4-(2,6,6-三甲基环己-1-烯基)丁-3-烯-2-酮-O-(3-甲基丁-2-烯酰基)肟的制备(I-b-05)
在100mL三口瓶中，加入3,3-二甲基丙烯酸(0.50g，5mmol)、1-(3-二甲氨基丙基)-3-乙基碳二亚胺(0.93g，6mmol)及4-二甲氨基吡啶(1.20g，1mmol)使用30mL的二氯甲烷溶解，滴加β-紫罗兰酮肟(1.04g，5mmol)，室温反应6h，TLC监测反应完毕后。使用饱和碳酸氢钠溶液洗涤，分液，收集有机相，浓缩后进行柱层析，得产物I-b-05，产率70.2％。
参考上述I-b-01或I-b-05的制备方法，可以制备得到式I-b系列化合物。
下面表1列出了式I-a、式I-b化合物的结构及基本的理化数据，表2为式I-a、式I-b化合物的核磁共振氢谱数据，它们均是按照类似于前述实施例1-8中所示的方法制备的。
表1式I-a、I-b化合物的性状及收率
表2式I-a、I-b化合物的核磁氢谱数据
实施例9、本发明化合物对蚜虫的驱避活性
参考文献(Yang,Z.-K.et al.PestManag.Sci.2023,79:760–770)中报道的方法，用本发明的化合物作为实施例的代表(如表3所示)测试对蚜虫的驱避活性。测试设备为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通入空气。测试臂导入的空气先经过5μg样品味源物，另一臂作为溶剂对照臂。记录导入样品15min时蚜虫在各臂的数目。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3
表3式I-a、I-b化合物对豌豆蚜的驱避活性
表4式I-a、I-b部分化合物对大豆蚜的驱避活性
表3结果表明，本发明的化合物在低浓度下对豌豆蚜均具有驱避活性，其中化合物I-a-07、I-a-13、I-b-06、I-b-07、I-b-09、I-b-12和I-b-13在5μg的剂量下对豌豆蚜的驱避率均在50％以上。进一步研究发现I-a-07、I-a-13、I-b-07、I-b-13在5μg的剂量下对大豆蚜的驱避率在50％以上(表4)，显著优于天然化合物β-紫罗兰酮。上述化合物合成简便可行，原料来源绿色安全，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10、本发明化合物对瓢虫的引诱活性
用本发明部分化合物作为实施例的代表对异色瓢虫的生物活性。测试设备为Y形嗅觉仪，在Y形嗅觉仪中放入一根Y形铁丝，便于瓢虫爬行。将Y形嗅觉仪两侧分别与味源物和空白连接，以0.6L/min的风速，从Y形嗅觉仪两侧通入空白和100μg味源物。在Y形管底部放入一头瓢虫，5min后观察瓢虫的选择。需越过Y形嗅觉仪分叉处7cm后为有效。每5个瓢虫为一组，每组结束后，使用清水和无水乙醇清洗Y形嗅觉仪，对调Y形嗅觉仪的两端朝向，进行下一组实验。测试分雌雄虫进行，并分别统计结果，有效雌雄异色瓢虫各需统计60头。
选择率(％)＝处理有效瓢虫数/(处理有效瓢虫数+空白有效瓢虫数)*100％
异色瓢虫引诱活性测试结果见表5。
表5部分式I-a、I-b化合物对异色瓢虫的引诱活性
从表5可以看出，本发明提供的先导β-紫罗兰酮及部分式I-a、I-b化合物及对异色瓢虫雄虫和雌虫均有较好的引诱活性。I-a-07、I-a-12、I-b-08、I-b-13化合物的引诱活性均优于天然物质β-紫罗兰酮，对雄虫的引诱活性优于对雌虫的引诱活性。其中化合物I-b-08活性表现最为突出，对雄虫和雌虫的引诱率均在70％以上，可作为瓢虫引诱剂用于蚜虫的绿色防控。
以上对本发明进行了详述。对于本领域技术人员来说，在不脱离本发明的宗旨和范围，以及无需进行不必要的实验情况下，可在等同参数、浓度和条件下，在较宽范围内实施本发明。虽然本发明给出了特殊的实施例，应该理解为，可以对本发明作进一步的改进。总之，按本发明的原理，本申请欲包括任何变更、用途或对本发明的改进，包括脱离了本申请中已公开范围，而用本领域已知的常规技术进行的改变。

Claims (10)

1.一种含酯基的β-紫罗兰酮类似物，其结构式如式I-a、式I-b所示：
式I-a、式I-b中，R1各自独立地选自：C1-C12直链或支链烷基、卤代C1-C12直链或支链烷基、C3-C12环烷基、C2-C10烯基、芳杂环、C3-C12环烷基取代的C1-C6直链或支链烷基、芳基取代的C1-C6直链或支链烷基中的任意一种。
2.根据权利要求1所述的含酯基的β-紫罗兰酮类似物，其特征在于：R1各自独立地选自：C1-C6直链或支链烷基、C4-C6环烷基、C2-C10单烯基、C2-C10二烯基、苯基取代的C2-C4烷基中的任意一种。
3.根据权利要求1或2所述的含酯基的β-紫罗兰酮类似物，其特征在于：R1各自独立地选自：C4-C6直链烷基、C5-C6环烷基、C7-C9二烯基中的任意一种。
4.根据权利要求1所述的含酯基的β-紫罗兰酮类似物，其特征在于：式I-a所示化合物为如下化合物中的任意一种：
5.根据权利要求1所述的含酯基的β-紫罗兰酮类似物，其特征在于：式I-b所示化合物为如下任意一种：
6.权利要求1-5中任一项所述的含酯基的β-紫罗兰酮类似物在蚜虫防治中的应用。
7.根据权利要求6所述的应用，其特征在于：所述应用为：含酯基的β-紫罗兰酮类似物作为蚜虫控制剂或在制备蚜虫控制剂中的应用。
8.根据权利要求7所述的应用，其特征在于：所述蚜虫控制剂兼具驱避蚜虫和引诱蚜虫天敌双重活性。
9.一种蚜虫控制剂，含有权利要求1-5中任一项所述的含酯基的β-紫罗兰酮类似物。
10.根据权利要求9所述的蚜虫控制剂，其特征在于：所述蚜虫控制剂兼具驱避蚜虫和引诱蚜虫天敌双重活性。
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