CN108640871B - 一种含氟吡啶哌嗪脲类化合物及其应用 - Google Patents

一种含氟吡啶哌嗪脲类化合物及其应用 Download PDF

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CN108640871B
CN108640871B CN201810587098.3A CN201810587098A CN108640871B CN 108640871 B CN108640871 B CN 108640871B CN 201810587098 A CN201810587098 A CN 201810587098A CN 108640871 B CN108640871 B CN 108640871B
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王明慧
彭壮
许良忠
崔建强
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Qingdao University of Science and Technology
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    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract

本发明公开了一种含氟吡啶哌嗪脲类化合物，结构如式Ⅰ所示：

Description

一种含氟吡啶哌嗪脲类化合物及其应用
技术领域
本发明属于农药中杀螨剂领域，具体涉及一种含氟吡啶哌嗪脲类化合物及其应用。
背景技术
由于现有杀螨剂的长期频繁使用，使得螨虫对其产生了不同程度的抗药性，因此开发新型杀螨剂是治理螨类抗药性的有效途径。CN102378754A公开了3-氨基乙二酰基氨基苯甲酰胺衍生物在杀虫、杀螨的活性研究，部分化合物表现出了高的杀螨活性。CN104285968A公开了以吡螨胺为活性组分的杀螨剂的杀螨活性，并表现出在低浓度下具有优良的杀螨活性。现有杀螨剂大部分都是羧酸酯类、苯甲酰胺类化合物，本发明是以哌嗪为桥链，将含氟吡啶和含有酰胺化合物连接生成一种新化合物，在现有技术中，如本发明所述式I化合物及其用作杀螨剂未见公开。
发明内容
本发明的目的在于提供一种含氟吡啶哌嗪脲类化合物，用作杀螨剂防治农业或林业害螨。
本发明的技术方案如下：
本发明提供了一种含氟吡啶哌嗪脲类化合物，如式I所示：
Figure BDA0001686357010000011
式I化合物可由下列反应制得：
Figure BDA0001686357010000012
Ⅲ和Ⅱ在乙酸乙酯或二氯甲烷中以三乙胺为缚酸剂反应制得Ⅰ。中间体Ⅲ的制备见本发明实例。
本发明的优点及积极效果：
现有杀螨剂螺螨酯、吡螨胺、哒螨灵等的长期频繁使用，使得螨虫对杀螨剂的抗药性不断增强，本发明是以哌嗪为桥链，将含氟吡啶和含有酰胺化合物拼连接生成一种脲类化合物，是一种结构新颖的杀螨剂，由于在化合物中同时存在含氟吡啶基、哌嗪、脲键结构，显著提高了其内吸传导作用，显著提高了其药效(见表1)，使其具有意想不到的杀螨活性，避免了螨虫高抗药性问题。同时，本发明设计合成的式I化合物原料来源广泛，合成工艺简单，生产成本低，毒性低、用药量小，符合现代农业对低公害、超高效、长持效的要求，具有商品化潜力。
本发明化合物在防治螨虫时，可根据实际需要，可单独使用，也可与其他活性物质组合使用，以提高产品的综合性能。
本发明还包括式I化合物作为活性组分的杀螨组合物，该杀螨组合物中活性组合的重量百分含量在1-99％之间。该杀螨组合物中还包括林业、农业上可接受的载体。
本发明的组合物可以以制剂的形式使用：式I化合物作为活性组分溶于或分散于载体或溶剂中，添加适量的表面活性剂制成乳油、悬浮剂、微乳剂等。
应明确的是，在本发明的权利要求所限定的范围内，可进行各种变换和改动。
具体实施方式
下列合成实施例及生测试验结果可用来进一步说明本发明，但不意味着限制本发明。
合成实例：
实例1、中间体Ⅲ的制备：
Figure BDA0001686357010000021
称取17.2g(0.2mol)无水哌嗪加入250mL反应瓶中，加入60mL甲醇，搅拌溶解并升温至40℃，然后用50mL甲醇溶解21.6g(0.1mol)2,3-二氯-5-(三氟甲基)吡啶，缓慢滴加入反应瓶中，滴毕，于40℃恒温反应6h，TLC跟踪至原料反应完全，降至室温，抽滤，将滤液旋蒸除去甲醇，析出白色固体，加水搅拌溶解剩余的无水哌嗪，抽滤、水洗滤饼2次，得白色固体22.6g，熔点65.8～67.3℃，收率为85％。
1H NMR(500MHz,DMSO-d6),δ(ppm)8.53(s,1H),8.15(s,1H),3.37–3.35(t,4H),2.82–2.80(t,4H).
实例2、化合物I的制备：
Figure BDA0001686357010000022
取5.3g(0.02mol)中间体Ⅲ加入250mL反应瓶中，然后加入30g乙酸乙酯，再加2.22g三乙胺，搅拌下滴加异氰酸正丁酯1.98g(0.02mol)，滴毕后于60℃反应40min，TLC跟踪中间体Ⅲ反应完全，加入100mL水搅拌后分液，有机相用无水硫酸钠干燥，旋蒸除去乙酸乙酯，冷却得白色固体6.8g，熔点121.1～122.7℃，收率93％。
1H NMR(500MHz,DMSO-d6)，δ(ppm)：8.56(s,1H),8.20(s,1H),6.54～6.52(t,1H),3.45～3.39(m,8H),3.06～3.01(m,2H),1.42～1.36(m,2H),1.30～1.25(m,2H),0.89～0.85(t,3H).
生物活性测定
实例3、杀螨活性测定
实例3、杀螨活性测定
采用浸渍法和统计校正害虫死亡率的方法测定杀螨卵活性。具体过程是：将供试药剂按有效成分分别稀释至所需浓度，在无菌条件下各吸取50mL药液注入培养皿内，再分别浸入有朱砂螨卵(螨卵按室内标准化方法正常饲养的群体)的叶片，以添加50mL灭菌水的平板做空白对照。以螺螨酯作为对比药物。将培养皿放在24±1℃恒温培养箱内。48h后调查统计死亡率。每次实验重复3次，取平均值。
表1化合物I的杀螨活性测试结果
Figure BDA0001686357010000031
根据表1中的测试结果，可以得知，在相同剂量下，本发明所得的系列化合物I的杀螨活性显著高于螺螨酯。在1ppm的低浓度时对螨卵杀灭率仍达90％以上。

Claims (2)

1.一种式I化合物在防治农林业螨害中的用途，所述式I化合物的结构式为：
Figure FDA0002297880710000011
2.一种杀螨组合物，含有式Ⅰ化合物为活性组分和农业或林业上可接受的载体，所述式I化合物的结构式为：
Figure FDA0002297880710000012
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