CN112094181B - 4-氧代-反-2-己烯醛类似物的合成方法及其应用 - Google Patents

4-氧代-反-2-己烯醛类似物的合成方法及其应用 Download PDF

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CN112094181B
CN112094181B CN201910523340.5A CN201910523340A CN112094181B CN 112094181 B CN112094181 B CN 112094181B CN 201910523340 A CN201910523340 A CN 201910523340A CN 112094181 B CN112094181 B CN 112094181B
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宁君
梅向东
王留洋
马好运
吴孔明
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Abstract

本发明公开了属于生物防治技术领域的4‑氧代‑反‑2‑己烯醛类似物的合成方法及其应用。所述类似物包括5‑甲基‑4‑氧代反‑2‑己烯醛、5，5‑二氟‑4‑氧代反‑2‑己烯醛、4‑氧代‑反‑2‑己烯酸、4‑氧代‑反‑2‑己烯醇、4‑羟基‑反‑2‑己烯醛。上述5种化合物中的一种或几种对绿盲蝽、牧草盲蝽、中黑盲蝽性信息素组分中的4‑氧代‑反‑2‑己烯醛完全取代。本发明的5‑甲基‑4‑氧代反‑2‑己烯醛、5，5‑二氟‑4‑氧代反‑2‑己烯醛合成方法均为首次发现，其应用组合物可以显著减缓诱芯释放速率，延长诱捕时间，节约成本，且能避免4‑氧代‑反‑2‑己烯醛在田间不稳定问题，更有效的诱杀绿盲蝽、牧草盲蝽、中黑盲蝽等雄虫。

Description

4-氧代-反-2-己烯醛类似物的合成方法及其应用
技术领域
本发明属于有机合成、生物防治技术领域，具体涉及一种用于防治绿盲蝽、中黑盲蝽、牧草盲蝽的性信息素类似物的合成方法及其应用。
背景技术
绿盲蝽(Apolygus lucorμm)、牧草盲蝽(Lygus pratensis Linnaeus)、中黑盲蝽(Adelphocoris suturalis Jakovlev)，均属半翅目，盲蝽科，是我国棉区重要的害虫，给我国棉花产业造成重大损失。
昆虫性信息素的研究为高效防治三种盲蝽科害虫开辟了一条新型绿色途径，但随着对三种盲蝽科害虫性信息素的研究发现，其共有的组分4-氧代-反-2-己烯醛具有自身易缩合，田间释放快、持效期短、长期使用4-氧代-反-2-己烯醛可能导致昆虫抗性的产生等缺点。因此，制备释放缓慢、持效期长且具较强的引诱能力的性信息素类似物，为绿色防控绿盲蝽、牧草盲蝽、中黑盲蝽提供新的思路。
发明内容
本发明的目的在于提供一种4-氧代-反-2-己烯醛类似物的合成方法及其应用。
本发明公开了五种4-氧代-反-2-己烯醛类似物。
五种分别为5-甲基-4-氧代反-2-己烯醛、5，5-二氟-4-氧代反-2-己烯醛、4-氧代-反-2-己烯酸、4-氧代-反-2-己烯醇、4-羟基-反-2-己烯醛，其中的一种或几种可以替代绿盲蝽、牧草盲蝽、中黑盲蝽性信息素组分中的4-氧代-反-2-己烯醛，用于防治绿盲蝽、牧草盲蝽、中黑盲蝽。
5-甲基-4-氧代反-2-己烯醛的结构式为
Figure BDA0002097396170000021
5，5-二氟-4-氧代反-2-己烯醛的结构式为
Figure BDA0002097396170000022
4-氧代-反-2-己烯酸的结构式为
Figure BDA0002097396170000023
4-氧代-反-2-己烯醇的结构式为
Figure BDA0002097396170000024
4-羟基-反-2-己烯醛的结构式为
Figure BDA0002097396170000025
本发明还公开了5-甲基-4-氧代反-2-己烯醛与5，5-二氟-4-氧代反-2-己烯醛的合成方法。
所述5-甲基-4-氧代反-2-己烯醛的合成方法为：以甲基异丙基甲酮和乙二醛为原料，以稀NaOH溶液为催化剂，在4-5℃环境下进行羟醛缩合，反应过程如图1。
所述5，5-二氟-4-氧代反-2-己烯醛的合成方法为：以2,2-二氟丙酸为起始原料，与氨反应成盐、生成的盐用无氧化二磷脱水成腈，与碘化甲基镁反应后水解生成3,3-二氟-2-丁酮，3,3-二氟-2-丁酮与乙二醛以稀NaOH溶液为催化剂，在4-5℃环境下进行羟醛缩合，反应过程如图2。
上述两种类似物的合成方法为首次发现，并没有现有技术公开过。
本发明还公开了包含4-氧代-反-2-己烯醛类似物的性引诱剂。
所述绿盲蝽原本性信息素组分为4-氧代-反-2-己烯醛，反-2-丁酸己烯酯；所述中黑盲蝽原本性信息素组分为4-氧代-反-2-己烯醛、丁酸己酯；所述牧草盲蝽性原本信息素组分为4-氧代-反-2-己烯醛、丁酸己酯、丁酸-反-2-己烯酯、乙酸-反-2-己烯酯、肉豆蔻酸甲酯、4-甲基戊基丁酸、(Z)-3-己烯醇丁酸。
本发明提出的五种类似物中的一种或几种替代绿盲蝽、牧草盲蝽、中黑盲蝽原本性信息素中成分4-氧代-反-2-己烯醛，替代后的性引诱剂比原本性信息素诱捕活性更高，稳定性好，持效期长。
本发明还公开了包含4-氧代-反-2-己烯醛类似物的性引诱剂的应用。
一种用于绿盲蝽、牧草盲蝽、中黑盲蝽性的4-氧代-反-2-己烯醛类似物的性引诱剂诱芯的制备，将性引诱剂中除含4-氧代-反-2-己烯醛类似物以外成分的正己烷溶液按相应比例滴加到诱芯上，再将含有4-氧代-反-2-己烯醛类似物的正己烷溶液滴加该诱芯上，待正己烷挥发后再将一定量的正己烷滴加到该诱芯上，待正己烷完全挥发后，即制的含有绿盲蝽、牧草盲蝽、中黑盲蝽性信息素组合物的诱芯，每个诱芯中置入100-2000μg组合物，将诱芯保存在-20℃的冰箱中备用。将诱芯置于船型诱捕器中，放置于绿盲蝽、牧草盲蝽、中黑盲蝽发生或者可能发生地域。
与现有技术相比，本发明具有如下有益效果：本发明4-氧代-反-2-己烯醛类似物的合成所需的原料易得，本发明含有4-氧代-反-2-己烯醛类似物的性引诱剂比原本性信息素诱捕活性更高，稳定性好，持效期长，防治效果可维持30天以上；专一性强，不会使三种盲蝽科害虫产生抗性；对人畜无害，环境友好；抗逆性强，使用方便。本发明可准确应用于三种盲蝽科害虫虫情测报、干扰交配、降低繁殖速率，大量诱捕，从而达到防治害虫的目的。
附图说明
图1为5-甲基-4-氧代反-2-己烯醛设计合成示意图。
图2为5,5-二氟-4-氧代反-2-己烯醛设计合成示意图。
图3为不同诱芯配方的平均雄虫诱捕数量图，其中不同字母表示在0.05水平上雄虫诱捕数量。
图4为诱捕绿盲蝽数量与诱捕天数的关系图。
具体实施方式
下面结合附图和实施例对本发明作详细描述，但本发明的实施不仅限于此。
实施例1 5-甲基-4-氧代反-2-己烯醛的制备方法
本发明中的化合物5-甲基-4-氧代反-2-己烯醛的合成路线如图2所示。
在100mL的烧瓶中，将1g(11.61mmol)甲基异丙基甲酮溶于30mL的浓度为0.08mol·L-1氢氧化钠溶液中，并逐渐滴加乙二醛溶液0.85g(14.5mmol)，反应过程TLC监测，原料不再减少后，反应完全，反应温度维持在4-5℃，反应时间5h。将粗产物倒入25mL饱和食盐水溶液中洗涤3次，无水硫酸镁干燥30min，过滤进行减压旋蒸。硅胶色谱柱分离(乙酸乙酯：石油醚＝1：50)得到目标化合物。
5-甲基-4-氧代反-2-己烯醛的物理性状、收率、核磁共振数据及质谱数据如下：
无色油状液体，收率89.2％；1H NMR(300MHz,CDCl3)δ:9.52(s,1H),7.22～7.30(m,2H),1.93(m,3H)；13C NMR(75MHz,CDCl3)δ:197.6,193.3,145.9(C2),129.3,19.8；HR-MS(ESI)m/z:Calcd for C6H6F2NaO2{[M+Na]+}171.0336,found 171.1208。
实施例2 5,5-二氟-4-氧代-反-2-己烯醛的制备
本发明中的化合物5,5-二氟-4-氧代-反-2-己烯醛的合成路线如图3所示。
在100mL的三口烧瓶中，加入2g(18.18mmol)2,2-二氟丙酸、30mL的干燥甲醇溶液，用氮气置换三口烧瓶中的空气，通入氨气，氨化反应2～4h，控制反应温度为室温。生成2,2-二氟丙酰胺1.6g，收率80.8％。1.6g(14.68mmol)2,2-二氟丙酰胺溶于25mL甲苯溶液，在P2O5存在下脱水成2,2-二氟丙腈。将生成的2,2-二氟丙腈与甲基碘化镁反应后水解即可合成3,3-二氟-2-丁酮，收率73.6％。
将1g(9.25mmol)3,3-二氟-2-丁酮溶于30mL的浓度为0.08mol·L-1氢氧化钠溶液中，并逐渐滴加乙二醛溶液0.68g(11.63mmol)，反应过程TLC监测，原料不再减少后，反应完全。反应温度维持在4-5℃，反应时间5h。将粗产物倒入25mL饱和食盐水溶液中洗涤3次，无水硫酸镁干燥30min，过滤进行减压旋蒸。硅胶色谱柱分离(乙酸乙酯：石油醚＝1：40)得到目标化合物。
5,5-二氟-4-氧代-反-2-己烯醛的物理性状、收率、核磁共振数据及质谱数据如下：
无色油状液体，收率70.2％。
1H NMR(300MHz,CDCl3)δ:9.68(s,1H),7.18～7.26(m,2H),3.16(m,H),1.06(m,6H)；13C NMR(75MHz,CDCl3)δ:203.9,192.3,146.7(C2),39.1,18.9(C2)；HR-MS(ESI)m/z:Calcd for C7H10NaO2{[M+Na]+}149.0681,found 149.0329。
实施例3田间引诱绿盲蝽试验
将制得绿盲蝽性引诱剂组合物的诱芯置于船型诱捕器中，将诱捕器放置于可能发生较多绿盲蝽危害的地块。为保证释放效果，每1mL的橡胶诱芯中置入100–2000μg绿盲蝽性引诱剂组合物。为了进一步说明本实施例的可行性，表1中给出10个具体配方。
表1
Figure BDA0002097396170000061
选择可能发生较多绿盲蝽危害的地块，每种配方设置诱捕器离地面高度120cm左右，诱捕器之间的距离10m，随机放置上述含绿盲蝽性信息素组合物的诱捕器，每个处理设立5个重复。放置后隔天调查一次诱捕到的绿盲蝽的数量，并随机更换诱捕位置，持续调查20天。调查结果如表2：
表2
Figure BDA0002097396170000071
Figure BDA0002097396170000081
由图3结果可知，绿盲蝽性引诱剂组合物对绿盲蝽有较好的诱捕效果，5-甲基-4-氧代反-2-己烯醛、5,5-二氟-4-氧代-反-2-己烯醛完全取代4-氧代-反-2-己烯醛的处理的诱捕量与绿盲蝽性信息素处理SP的诱捕量相比差异显著(P＜0.05)，说明5-甲基-4-氧代反-2-己烯醛、5,5-二氟-4-氧代-反-2-己烯醛的引诱活性强于4-氧代-反-2-己烯醛。同时，配方L8、L9、L10的诱捕量与SP的诱捕量相当，说明4-氧代-反-2-己烯酸、4-氧代-反-2-己烯醇、4-羟基-反-2-己烯醛可以替代4-氧代-反-2-己烯醛的引诱绿盲蝽雄虫，并且稳定性较好。
实施例4性引诱剂组合物持效期试验
为了进一步说明本实施例的可行性，表3中给出6个具体配方
表3
Figure BDA0002097396170000091
选择绿盲蝽为害较为严重的地块，设置诱芯离地面高度120cm左右，诱捕器之间的距离10m，随机放置上述含绿盲蝽性信息素组合物的诱捕器，每个处理设立5个重复。放置后隔天调查一次诱捕到的绿盲蝽的数量，并随机更换诱捕位置，持续调查一个月。
由图4结果可知，随着诱捕天数的增加，引诱绿盲蝽数量逐渐减少，其中第一周诱芯活性最强。当5-甲基-4-氧代反-2-己烯醛、5,5-二氟-4-氧代-反-2-己烯醛完全取代4-氧代-反-2-己烯醛时，31天后依然能引诱到绿盲蝽雄虫，平均每天为2头，其他的类似物完全替代4-氧代-反-2-己烯醛后，在第31天引诱少量的雄虫，每天平均引诱0.33头，对比绿盲蝽性信息素组分发现，在第23后完全引诱不到绿盲蝽雄虫，说明合成的4-氧代-反-2-己烯醛类似物能延长诱芯的活性，具有明显增效的化合物为5-甲基-4-氧代反-2-己烯醛、5,5-二氟-4-氧代-反-2-己烯醛。
以上公开的仅为本发明的具体实施例，但是，本发明并非局限于此，任何本领域的技术人员能思之的变化都应落入本发明的保护范围。

Claims (3)

1.一种用于防治绿盲蝽的性引诱剂，其特征在于，所述性引诱剂的组分为反-2-丁酸己烯酯600μg，5-甲基-4-氧代反-2-己烯醛900μg；
或所述性引诱剂的组分为反-2-丁酸己烯酯600μg，5,5-二氟-4-氧代-反-2-己烯醛900μg。
2.权利要求1所述的5,5-二氟-4-氧代-反-2-己烯醛的合成方法，其特征在于，以2,2-二氟丙酸为起始原料，与氨反应成盐、生成的盐用无氧化二磷脱水成腈，与碘化甲基镁反应后水解生成3,3-二氟-2-丁酮，3,3-二氟-2-丁酮与乙二醛以稀NaOH溶液为催化剂，在4-5℃环境下进行羟醛缩合。
3.权利要求1所述的性引诱剂在防治绿盲蝽中的应用，其特征在于，制备含有所述性引诱剂的诱芯，将诱芯置于船型诱捕器中，放置于绿盲蝽发生或者可能发生地域。
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