CN108794462A - 一种含氟氰亚胺噻唑烷取代的噁二唑类杀虫杀菌剂 - Google Patents
一种含氟氰亚胺噻唑烷取代的噁二唑类杀虫杀菌剂 Download PDFInfo
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Abstract
本发明提供一种含氟氰亚胺噻唑烷取代的噁二唑类杀虫杀菌剂，结构如式I所示：
Description
技术领域 本发明属于农药杀虫剂和杀菌剂领域，具体涉及一种含氟氰亚胺噻唑烷取代的噁二唑类杀虫杀菌剂。
背景技术 2013年孟山都开发了新型高效杀线虫剂噻吩和苯基取代的噁二唑类化合物Tioxazafen(化合物II)，其具有全新的作用机理，通过干扰线虫核糖体的活性而发挥药效(Slomczynska U,South M S,Bunkers G J,et al.Tioxazafen:A New Broad-Spectrum Seed Treatment Nematicide[M]，Discovery and Synthesis of CropProtection Products，2015。)。噻虫啉(Thiacloprid)(化合物III)是由德国拜耳农化公司和日本拜耳农化公司合作开发的新型氯代烟碱类杀虫剂。本发明通过活性基团拼接技术，将活性基团氰亚胺噻唑烷引入1,2,4-噁二唑5-位上，将二氟乙氧基苯基引入1,2,4-噁二唑3-位上，得到结构如式Ⅰ所示化合物，在现有技术中，如本发明所示的式I化合物用作农林业杀虫杀菌剂未见公开。
发明内容 本发明的目的在于提供一种结构新颖、高效、安全、防治成本低的一种含氟氰亚胺噻唑烷取代的噁二唑类杀虫杀菌剂。
本发明的技术方案如下：
一种含氟氰亚胺噻唑烷取代的噁二唑化合物，结构如I所示：
式I化合物可通过如下反应制备：
中间体式IV化合物与式V化合物在DMF中以碳酸钾为缚酸剂升温至80℃，反应4h制得式I化合物。具体制备方法见本说明书合成实例。
本发明式I化合物经杀虫试验，对甜菜夜蛾和小菜蛾有优异的杀虫效果，对水稻纹枯病菌、辣椒炭疽病菌、小麦赤霉病菌和月季霜霉病菌有良好抑制作用，因此本发明还包括式Ⅰ化合物用于农林业虫害菌害防治的用途。
本发明的优点及积极效果：
本发明化合物是一种全新结构的吡唑取代1,2,4-噁二唑化合物，在其结构中含有噁二唑、氰亚胺噻唑烷、二氟乙氧苯基结构，由于分子中同时含有噁二唑和氰亚胺噻唑烷结构，使得该化合物同时具有杀虫和杀菌作用，起到一药两用的功效，同时引入噁二唑和氰亚胺噻唑烷等杂环药效基团，增加了作用位点，有益于增加药效和广谱性，受害虫抗性影响小，对甜菜夜蛾和小菜蛾抗性强的害虫表现出意想不到的超高杀灭活性；由于本发明化合物中含有-OCH2CHF2基团，增加了脂溶性和渗透性，显著提高了其内吸传导作用，从而提高了其药效。本发明化合物合成原料易得，合成工艺简单，无需高温高压和特殊设备，生产中产生“三废”少，收率较高，生产成本低。本发明化合物为氮杂环类化合物，具有对人、畜及有益生物低毒性、易降解、环境相容性好的特点，具有作为创制性杀虫剂新品种产业化的前景和商品化的潜力。
本发明还包括式I化合物作为活性组分的杀虫杀菌组合物，该组合物中还包括农业上可接受的载体。
本发明化合物在防治虫害菌害时，可单独使用，也可与其它活性化合物组合使用，以利于提高本产品的综合防治性能。
本发明化合物的组合物可以制成试剂施用，本发明化合物作为活性组分分散于或溶于载体或溶剂中，加合适的表面活性剂制成悬浮剂、微乳剂、乳油及水乳剂等。
应明确的是，在本发明的权利要求所限定范围内，可进行各种改动与变换。
具体实施方式：
以下合成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
(1)2-(2,2-二氟乙氧基)苄腈的合成
向250mL的三口烧瓶中加入0.1mol(11.9g)水杨腈，0.105mol(14.49g)碳酸钾，100mL DMF做溶剂。搅拌，升温至80℃，用50mL的滴液漏斗将0.12mol(19.2g)2,2-二氟乙醇甲基磺酸酯缓慢分批滴入反应瓶中，搅拌反应4h。将反应液倒入500mL烧瓶中，加入1％的氢氧化钠溶液100mL洗涤，洗去未反应完的少量水杨腈，并加入100mL乙酸乙酯萃取产物，分液保留有机相，然后再用3×100mL饱和食盐水洗涤，分液，将有机相用无水硫酸钠干燥，减压蒸除溶剂，得到浅黄色油状液体2-(2,2-二氟乙氧基)苄腈17.1g，收率93.4％(以水杨腈计)。
(2)中间体2-(2,2-二氟乙氧基)-N'-羟基苯甲脒的合成
向250mL的三口烧瓶中加入0.19mol(13.21g)的盐酸羟胺，0.2mol(20.2g)三乙胺，100mL乙醇做溶剂，加热回流半小时，再加入0.1mol(18.3g)2-(2,2-二氟乙氧基)苄腈，搅拌回流四小时，TLC检测到2-(2,2-二氟乙氧基)苄腈点消失，将乙醇蒸干，加入200mL乙酸乙酯，将产物提取到有机相中，抽滤去除三乙胺，滤液减压旋蒸掉乙酸乙酯，得到油状产物，用石油醚:乙酸乙酯10:1重结晶，得到灰白色晶体2-(2,2-二氟乙氧基)-N'-羟基苯甲脒18.59g，收率85.6％，熔点89～92℃。
(3)N'-(2-氯乙酰氧基)-2-(2,2-二氟乙氧基)苯甲脒的合成
向250mL的三口烧瓶中加入0.02mol(4.32g)2-(2,2-二氟乙氧基)-N'-羟基苯甲脒，50mL乙酸乙酯做溶剂，0.022mol(2.2g)三乙胺做缚酸剂，将反应瓶置于冰水浴中，搅拌，将0.02mol(2.24g)乙酰氯用50mL乙酸乙酯稀释，用100mL的滴液漏斗缓慢将其滴入，滴完后反应2h。TLC跟踪至2-乙氧基-N-羟基-苯甲脒的点消失，抽滤，收集滤液旋蒸干，得到油状产物，重结晶得到N'-(2-氯乙酰氧基)-2-(2,2-二氟乙氧基)苯甲脒5.5g，收率94.1％，熔点81～84℃。
(4)5-(氯甲基)-3-(2-(2,2-二氟乙氧基)苯基)-1,2,4-噁二唑的合成
向250mL的三口烧瓶中加入0.02mol(5.85g)N'-(2-氯乙酰氧基)-2-(2,2-二氟乙氧基)苯甲脒，100mL甲苯做溶剂，加热至回流，反应2h，TLC跟踪至原料点消失，减压旋蒸干甲苯溶剂，得到棕黄色油状物6.4g，加入少量甲醇重结晶，得到白色固体5-(氯甲基)-3-(2-(2,2-二氟乙氧基)苯基)-1,2,4-噁二唑5.03g，收率91.6％，熔点80～83℃。
(5)式I化合物的合成
向250mL的三口瓶中加入0.01mol(1.28g)2-氰基亚胺基-1,3-噻唑烷，100mL DMF做溶剂，0.011mol(1.52g)碳酸钾做缚酸剂，升温到80℃，搅拌半小时，再加入0.01mol(2.73g)5-(氯甲基)-3-(2-(2,2-二氟乙氧基)苯基)-1,2,4-噁二唑，保温反应4h，TLC跟踪至原料点消失，冷却至室温，加入100mL水继续搅拌，有固体析出，抽滤，得粗产品，用甲醇重结晶，得式I化合物[5-((2-氰基亚胺基-1,3-噻唑基)甲基)-3-(2-(2,2-二氟乙氧基)苯基-1,2,4-噁二唑]3.0g，收率82.1％，熔点168～171℃。1H NMR(500MHz，DMSO-d6)，δ(ppm)：3.42～3.45(t，2H)，4.16～4.18(t，2H)，4.21～4.27(m，2H)，5.06(s，2H)，6.20～6.41(m，1H)，7.21～7.23(t，1H)，7.34～7.37(d，1H)，7.50～7.53(m，1H)，7.87～7.89(d，1H).
生物活性测定
(1)药剂配制：
将式I化合物用二甲基亚砜溶解，然后用1‰的吐温80水溶液稀释，配置成所需浓度的待测液50毫升，二甲基亚砜在总溶液中的含量不超过10％。
(2)杀虫活性测定
采用侵叶法测定本文合成化合物的生物活性。以小菜蛾(Plutella xylostellaLinnaeus)、甜菜夜蛾(Beet armyworm)为测试对象，分成两组，并设置空白对照。选取长势一致的甘蓝叶片在配好的药剂中浸渍10s，用镊子取出甩干药液，按照顺序依次在干净的平板上铺开。晾干后将叶片转入到已经排序好含有保湿滤纸的培养皿中，每个培养皿中植入生长状况相似的2龄甜菜夜蛾30头，并放置在恒温培养箱(25±1℃)中饲养，光周期L:D＝16:8，相对湿度60％，48h后检查甜菜夜蛾的死亡情况，并记录死亡个数。重复3次实验，取平均值，计算校正死亡率，计算公式(1)如下：
式中：P1——死亡率，单位为百分率(％)；K——表示死亡虫数；N——表示处理总虫数。
对小菜蛾的药效试验植入的同是2龄虫，实验方法与上述步骤相同。以化合物III作为对照，试验结果列于表1。
表1式I化合物对甜菜夜蛾和小菜蛾的生物活性数据
由表1数据可见，式I化合物对甜菜夜蛾和小菜蛾表现出超高杀灭活性，优于对照药噻虫啉。
(3)杀菌活性测定
采用平皿法测定化合物的杀菌效果。以水稻纹枯病菌(Rhizoctonia solani)、辣椒炭疽病菌(Colletotrichum capsici)、小麦赤霉病菌(Gibberella zeae)、月季霜霉病菌四种菌丝为测试对象，分成四组，并设置空白对照。吸取1mL药液，注入预先融化了灭菌培养基的无菌锥形瓶中，充分摇匀，然后等量倒入3个直径为9cm的培养皿中，制成浓度为50μg/L的含药平板，设置3次重复实验，并用无药剂的做相同处理作为空白对照。将以上培养好的病原菌，在无菌条件下用直径5mm的灭菌打孔器，自菌落边缘切取菌饼，用接种器接种于含药平板中央，菌丝面朝上，盖上培养皿盖，将培养皿放于(24±1)℃的恒温培养箱中进行培养。72h后用卡尺测量菌落直径，采用十字交叉法直径各测量一次，测其平均直径。根据实验结果，按公式(1)、(2)计算不同药剂对供试靶标菌的菌丝生长抑制率。
D＝D1-D2…………………………………………………(1)
式中：D—菌落增长直径；D1——菌落直径；D2——菌饼直径。
式中：I——菌丝生长抑制率；D0——空白对照菌落增长直径；Dt——药剂处理菌落增长直径。
结果列于表2。
表2化合物对四种病菌的生物活性数据
由表2数据可见，式I化合物有杀菌作用。
Claims (4)
1.一种含氟氰亚胺噻唑烷取代的噁二唑类化合物，结构如式I所示：
2.根据权利要求1所述的一种含氟氰亚胺噻唑烷取代的噁二唑类化合物的用途，其特征在于式I化合物用作农业或林业杀虫剂。
3.根据权利要求1所述的一种含氟氰亚胺噻唑烷取代的噁二唑类化合物的用途，其特征在于式I化合物用作农业或林业杀菌剂。
4.一种杀虫杀菌组合物，含有权利要求1所述的式I化合物为活性组分和农业或林业上可接受的载体。
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