CN104920408A - 一种硫脲类杀虫杀螨剂 - Google Patents
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Abstract
本发明公开了一种硫脲类杀虫杀螨剂，结构如式I所示：
Description
技术领域 本发明属于农药中杀虫杀螨剂领域，涉及一种硫脲类杀虫杀螨剂。
背景技术 丁醚脲(式Ⅱ化合物)是汽巴-嘉基公司开发的硫脲类杀虫杀螨剂，对农业主要害虫如小菜蛾、粘虫及粉虱及多种螨类有良好的防治效果，与现有的杀虫杀螨剂无交互抗性，对抗药性害虫害螨有较好的防治效果，已成为目前害虫、害螨防治的常规农药品种。但是由于该化合物不溶于水，难以配制成水剂制剂，其主要剂型为乳油、可湿性粉剂及悬浮剂。在生产、加工成本及安全性方面有待进一步提高，且由于其制剂剂型的局限性，在花生、黄瓜及十字花科蔬菜等方面受药剂浓度和温度的影响易产生药害，使用安全性问题严重影响了该产品的应用推广。本发明人针对丁醚脲及其制剂存在的上述问题，在丁醚脲母体结构中引入成盐基团，设计合成了式Ⅰ化合物，将其与无机酸或有机酸成盐后，很容易制备成水剂制剂或微乳剂制剂，不仅降低了制剂生产及使用成本，提高了生产及贮运安全性，也出乎意料地增加了产品的防治效果及使用安全性。在现有技术中，如本发明所示的式Ⅰ化合物及其盐用作杀虫杀螨剂未见公开。
发明内容 本发明的目的是提供一种结构新颖、生产及使用安全、杀虫杀螨效果好、防治成本低的硫脲类式Ⅰ化合物及其盐，可用于农业或林业有害虫、螨的防治。
本发明的技术方案如下：
一种硫脲类杀虫杀螨剂，结构如式I所示：
式I化合物与无机酸或有机酸反应生成相应的式I化合物无机酸盐或有机酸盐；无机酸选自盐酸、硫酸或磷酸，有机酸选自柠檬酸、十二烷基苯磺酸、乙酸或乳酸。
式I化合物与无机酸或有机酸以水为溶剂，经搅拌溶解并添加适量的表面活性剂可制成式I化合物盐的水剂或微乳剂。
配制式I化合物盐的水剂或微乳剂时，表面活性剂选自绿色环保型非离子表面活性剂，如烷基糖苷、吐温-80及BY-125(蓖麻油聚氧乙烯醚)等。
根据需要，式I化合物本身也可作为杀虫杀螨组分用于杀虫杀螨单剂或复合制剂的生产，其适宜剂型为乳油、悬浮剂及可湿性粉剂等。
式I化合物及其盐的制备见本发明合成实例。
本发明的优点和积极效果：
本发明首次将叔胺类成盐基团引入丁醚脲母体结构中，制得的式I化合物与无机酸或有机酸成盐后具有优良的水溶性，可制备式I化合物的无机酸盐或有机酸盐杀虫杀螨水剂，克服了乳油制剂需用有毒、易燃非环保溶剂的弊端，对降低生产及使用成本、提高生产及贮运安全性具有积极意义；也解决了悬浮剂及可湿性粉剂有效利用率低、加工成本高工艺复杂等问题；更出人意料的是，本发明式I化合物成盐制备的水剂杀虫杀螨剂，不仅防效高，对作物的安全性也大幅度提高。因此，本发明式I化合物无机酸盐或有机酸盐水剂作为环保剂型，与现有技术相比，具有生产及使用安全、成本低、防效高、低毒环保等显著优点。
本发明式I化合物及其盐在防治有害虫、螨时，可单独使用，也可与其它活性物质组合使用，以提高产品的综合性能。
应该明确的是，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
下列合成实例、制剂实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、式Ⅰ化合物的制备：
式Ⅰ化合物的制备反应式：
向250mL三口烧瓶中加入31.16g(0.1mol)2,6-二异丙基-4-苯氧基异硫氰酸苯酯，90mL乙酸乙酯，10.71g(0.105mol)N,N-二甲基-1,3-丙二胺，搅拌升温至50℃，搅拌反应3h。薄层色谱跟踪反应，待原料点消失后，停止反应。减压蒸馏除去溶剂得粗品35.57g，产率86％。用石油醚重结晶制得精品。式Ⅰ化合物熔点：146.5-150.0℃。
1H NMR(500MHz,DMSO)，δ/ppm：1.051-1.115(m,12H,CH3),1.495-1.505(t,2H,CH2),1.851(s,6H,CH3),2.114-2.135(t,2H,CH2),2.951-3.005(m,2H,CH),3.450-3.480(m,2H,CH2),6.802(s,2H,ArH),7.051-7.150(m,3H,ArH),7.350-7.360(t,1H,NH),7.400-7.450(m,2H,ArH),9.110(s,1H,NH)。
实例2、式Ⅰ化合物盐的制备：
在制备水剂时，称取等摩尔的式Ⅰ化合物和相应的无机酸或有机酸，加入适量水，搅拌溶解，即可得相应的式Ⅰ化合物的无机酸盐或有机酸盐。也可以按此方法成盐后，蒸馏脱去水，得到固体式Ⅰ化合物的无机酸盐或有机酸盐。
无机酸选自盐酸、硫酸或磷酸，有机酸选自柠檬酸、十二烷基苯磺酸、乙酸或乳酸。
制剂实施例
实例3、25％式I化合物乳油的制备：
称取25g式I化合物，用65g二甲苯溶解，加入4g农乳500#和6g农乳602#，搅拌至澄清透明，得25％式I化合物乳油。
实例4、22.5％式I化合物盐酸盐水剂的制备：
分别称取20.1g式I化合物、70g水和5g浓盐酸，搅拌溶解至澄清透明，然后加入4.3g吐温-80，搅拌均匀即得22.5％式I化合物盐酸盐水剂。
实例5、35％式I化合物柠檬酸盐水剂的制备：
分别称取23.9g式I化合物、11.1g柠檬酸和60g水，搅拌溶解至澄清透明，然后加入5g吐温-80，搅拌均匀即得35％式I化合物柠檬酸盐水剂。
实例6、18％式I化合物十二烷基苯磺酸盐水剂的制备：
分别称取10.3g式I化合物、8.6g十二烷基苯磺酸(96％)、15.1g BY-125和66g水，搅拌溶解至澄清透明，得18％式I化合物十二烷基苯磺酸盐水剂。
用上述相同方法可分别制得式I化合物的硫酸盐、磷酸盐、乙酸盐或乳酸盐水剂。
生物活性测定实施例
实例7、杀虫活性测定
本发明部分化合物杀小菜蛾活性测定：
采用浸叶法。采用国际抗性行动委员会(IRAC)提出的浸叶法。用配制好的待测药液，用直头眼科镊子浸渍甘蓝叶片，时间3-5秒，甩掉余液，每次1片，每个样品共3片，按样品标记顺序依次放在处理纸上。待药液干后，放入具有标记的10cm长的直型管内，接入2龄小菜蛾幼虫30头，用纱布盖好管口。将试验处理置于标准处理室内，72h检查结果以拨针轻触虫体，不动者为死亡。计算死亡率。(试验做3次重复，取平均值)。
选取本发明部分化合物，将式I化合物制备成乳油，将式I化合物盐制备成水剂，选取丁醚脲(CK)制备成乳油作平行试验对照，对小菜蛾的防效试验结果列于表1。
表1 杀小菜蛾活性测定数据
| 化合物编号 | 浓度(ppm) | 72h死亡率(％) |
| 式I化合物 | 100 | 90.2 |
| 式I化合物盐酸盐 | 100 | 94.0 |
| 式I化合物柠檬酸盐 | 100 | 93.8 |
| 丁醚脲(CK) | 100 | 80.1 |
由表1结果说明，本发明化合物对小菜蛾与已知化合物丁醚脲相比有较高的生物活性。
实例8、杀螨活性测定
本发明部分化合物杀山楂叶螨活性测定：
采用玻片法进行触杀活性测定。玻片法为FAO推荐使用的方法，具体方法为：将1cm宽的双面胶带纸贴在载玻片一端，选取大小一致的健康雌成螨，用零号毛笔将其背面向下成两行固定在胶带纸上，于解剖镜下剔除死螨及不活泼螨后，保证每一载玻片上有成螨30头。在处理液中浸5s后取出，用滤纸轻轻吸掉多余的处理液，12h后观察叶螨的死亡情况。以毛笔尖轻触后，足不动者即视为死亡。计算死亡率。(试验做3次重复，取平均值)。
选取本发明部分化合物，将式I化合物制备成乳油，将式I化合物盐制备成水剂，选取丁醚脲(CK)制备成乳油作平行试验对照，对山楂叶螨的防效试验结果列于表2。
表2 杀山楂叶螨活性测定数据
| 化合物编号 | 浓度(ppm) | 12h死亡率(％) |
| 式I化合物 | 100 | 97.0 |
| 式I化合物盐酸盐 | 100 | 95.1 |
| 式I化合物柠檬酸盐 | 100 | 95.6 |
| 丁醚脲(CK) | 100 | 85.0 |
由表2结果说明，本发明化合物对山楂叶螨与已知化合物丁醚脲相比有较高的生物活性。
Claims (3)
1.一种硫脲类杀虫杀螨剂，结构如式I所示：
2.根据权利要求1所述的一种硫脲类杀虫杀螨剂，其特征在于：式I化合物与无机酸或有机酸结合形成相应的无机酸盐或有机酸盐；无机酸选自盐酸、硫酸或磷酸，有机酸选自柠檬酸、十二烷基苯磺酸、乙酸或乳酸。
3.一种杀虫杀螨组合物，含有权利要求1所述的式I化合物或权利要求2所述的式I化合物盐作为活性组分和农业或林业上可接受的载体。
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