CN118164880A - 联苯三氟乙硫醚化合物及其应用 - Google Patents
联苯三氟乙硫醚化合物及其应用 Download PDFInfo
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Abstract
本发明提供一种对植物病虫害具有优异防治效力的化合物,具体涉及一种式I所示的联苯三氟乙硫醚化合物及其应用。式I化合物具有优异的杀螨和杀菌活性,可用于防治各种害螨和病菌。
Description
技术领域
本发明属农用杀螨剂和杀菌剂领域,具体涉及一种联苯三氟乙硫醚化合物及其应用。
背景技术
联苯硫醚类衍生物具有良好的杀螨活性。专利WO9955668记载了3-芳基苯基硫化物衍生物具有杀虫和杀螨活性,其中式Ⅱ化合物(列表化合物I-575)在500ppm浓度下对二斑叶螨的致死活性大于90%;专利WO2017067500公开了作为杀螨剂的式Ⅲ化合物(列表化合物1)。相关的专利文献还有WO2007034755、JP2009023910A、WO2012176856、WO2013027660、WO2022012483和CN114957062A等。
现有技术中,如本发明式I所示的化合物及其杀螨和杀菌活性未见公开。同时,本发明化合物对植物病虫害具有更加优异的防治效果。
发明内容
本发明为了发现对植物病虫害具有优异的防治效力的化合物进行研究,结果发现,下述式I所示的联苯三氟乙硫醚化合物具有优异的杀螨和杀菌活性,可应用于农业、林业及卫生领域中害螨和病菌的防治。
本发明的技术方案如下:
一种联苯三氟乙硫醚化合物,由式I所示:
所述的式I化合物在农业、林业及卫生领域中作为杀螨剂的应用。
所述的式I化合物在农业、林业及卫生领域中作为杀菌剂的应用。
一种杀螨组合物,组合物中含有所述的式I化合物和农业上可接受的载体;以所述式I化合物为活性组分,所述组合物中活性组分的重量百分含量为0.1-99%。
一种杀菌组合物,组合物中含有所述的式I化合物和农业上可接受的载体;以所述式I化合物为活性组分,所述组合物中活性组分的重量百分含量为0.1-99%。
本发明所述式I化合物具有优异的病虫害防治效力,可应用于农业、林业及卫生领域中螨害和菌害的防治。
下面提及的病虫害的例子仅用来说明本发明,但绝不限定本发明。
螨目(螨):瘿螨属,如柑橘锈瘿螨,苹果刺锈螨;细螨属,如侧多食跗线螨;细须螨属,如紫红短须螨;叶螨属,如朱砂叶螨、神泽叶螨、太平洋叶螨、棉叶螨和二斑叶螨,苹果叶螨、柑橘叶螨等。
本发明式I所示的化合物在低浓度使用时,对于各种害螨也显示出优良的防除作用,在害螨生命周期的每一阶段均具有杀螨活性,对于那些对传统杀螨剂产生了抗药性的害螨,本发明的式I化合物也显示出优良的防除活性。同时,式I化合物对许多有益的昆虫和螨虫、哺乳动物、鱼、鸟,具有低毒性,而且没有植物毒性。
植物病害:卵菌纲病害,如霜霉病(黄瓜霜霉病、油菜霜霉病、大豆霜霉病、甜菜霜霉病、甘蔗霜霉病、烟草霜霉病、豌豆霜霉病、丝瓜霜霉病、冬瓜霜霉病、甜瓜霜霉病、白菜类霜霉病、菠菜霜霉病、萝卜霜霉病、葡萄霜霉病、葱霜霉病),白锈病(油菜白锈病、白菜类白锈病),猝倒病(油菜猝倒病、烟草猝倒病、番茄猝倒病、辣椒猝倒病、茄子猝倒病、黄瓜猝倒病、棉苗猝倒病),绵腐病(辣椒绵腐病、丝瓜绵腐病、冬瓜绵腐病),疫病(蚕豆疫病、黄瓜疫病、南瓜疫病、冬瓜疫病、西瓜疫病、甜瓜疫病、辣椒疫病、韭菜疫病、大蒜疫病、棉花疫病),晚疫病(马铃薯晚疫病、番茄晚疫病)等;半知菌病害,如枯萎病(甘薯枯萎病、棉花枯萎病、芝麻枯萎病、蓖麻枯萎病、番茄枯萎病、菜豆枯萎病、黄瓜枯萎病、丝瓜枯萎病、南瓜枯萎病、冬瓜枯萎病、西瓜枯萎病、甜瓜枯萎病、辣椒枯萎病、蚕豆枯萎病、油菜枯萎病、大豆枯萎病),根腐病(辣椒根腐病、茄子根腐病、菜豆根腐病、黄瓜根腐病、苦瓜根腐病、棉黑根腐病、蚕豆根腐病),立枯病(棉苗立枯病、芝麻立枯病、辣椒立枯病、黄瓜立枯病、白菜立枯病),炭疽病(高粱炭疽病、棉花炭疽病、红麻炭疽病、黄麻炭疽病、亚麻炭疽病、烟草炭疽病、桑炭疽病、辣椒炭疽病、茄子炭疽病、菜豆炭疽病、黄瓜炭疽病、苦瓜炭疽病、西葫芦炭疽病、冬瓜炭疽病、西瓜炭疽病、甜瓜炭疽病、荔枝炭疽病),黄萎病(棉花黄萎病、向日葵黄萎病、番茄黄萎病、辣椒黄萎病、茄子黄萎病),黑星病(西葫芦黑星病、冬瓜黑星病、甜瓜黑星病),灰霉病(棉铃灰霉病、红麻灰霉病、番茄灰霉病、辣椒灰霉病、菜豆灰霉病、芹菜灰霉病、菠菜灰霉病、猕猴桃灰霉病),褐斑病(棉花褐斑病、黄麻褐斑病、甜菜褐斑病、花生褐斑病、辣椒褐斑病、冬瓜褐斑病、大豆褐斑病、向日葵褐斑病、豌豆褐斑病、蚕豆褐斑病),黑斑病(亚麻假黑斑病、油菜黑斑病、芝麻黑斑病、向日葵黑斑病、蓖麻黑斑病、番茄黑斑病、辣椒黑斑病、茄子黑斑病、菜豆黑斑病、黄瓜黑斑病、芹菜黑斑病、胡萝卜黑腐病、胡萝卜黑斑病、苹果黑斑病、花生黑斑病),斑枯病(番茄斑枯病、辣椒斑枯病、芹菜斑枯病),早疫病(番茄早疫病、辣椒早疫病、茄子早疫病、马铃薯早疫病、芹菜早疫病),轮纹病(大豆轮纹病、芝麻轮纹病、菜豆轮纹病),叶枯病(芝麻叶枯病、向日葵叶枯病、西瓜叶枯病、甜瓜叶枯病),茎基腐病(番茄茎基腐病、菜豆茎基腐病),及其他(玉米圆斑病、红麻腰折病、稻瘟病、栗黑鞘病、甘蔗眼斑病、棉铃曲霉病、花生冠腐病、大豆茎枯病、大豆黑点病、甜瓜大斑病、花生网斑病、茶赤叶斑病、辣椒白星病、冬瓜叶斑病、芹菜黑腐病、菠菜心腐病、红麻叶霉病、红麻斑点病、黄麻茎斑病、大豆紫斑病、芝麻叶斑病、蓖麻灰斑病、茶褐色叶斑病、茄子褐色圆星病、菜豆红斑病、苦瓜白斑病、西瓜斑点病、黄麻枯腐病、向日葵根茎腐病、菜豆炭腐病、大豆靶点病、茄子棒孢叶斑病、黄瓜靶斑病、番茄叶霉病、茄子叶霉病、蚕豆赤斑病等)等;担子菌病害,如锈病(小麦条锈病、小麦杆锈病、小麦叶锈病、花生锈病、向日葵锈病、甘蔗锈病、韭菜锈病、葱锈病、栗锈病、大豆锈病),黑穗病(玉米丝黑穗病、玉米黑粉病、高粱丝黑穗病、高粱散黑穗病、高粱坚黑穗病、高梁柱黑粉病、栗粒黑穗病、甘蔗黑穗病、菜豆锈病)及其他(如小麦纹枯病、水稻纹枯病等)等;子囊菌病害,如白粉病(小麦白粉病、油菜白粉病、芝麻白粉病、向日葵白粉病、甜菜白粉病、茄子白粉病、豌豆白粉病、丝瓜白粉病、南瓜白粉病、西葫芦白粉病、冬瓜白粉病、甜瓜白粉病、葡萄白粉病、蚕豆白粉病),菌核病(亚麻菌核病、油菜菌核病、大豆菌核病、花生菌核病、烟草菌核病、辣椒菌核病、茄子菌核病、菜豆菌核病、豌豆菌核病、黄瓜菌核病、苦瓜菌核病、冬瓜菌核病、西瓜菌核病、芹菜菌核病),黑星病(苹果黑星病、梨黑星病)等。
由于其积极的特性,本发明化合物可有利地用于保护农业和园艺业重要的作物、家畜和种畜,以及人类常去的环境免于害螨或病菌的伤害。
为获得理想效果,化合物的用量因各种因素而改变,例如施用的作物、有害生物的类型、感染程度、气候条件、施药方法、采用的剂型。
根据通常的生物学和/或化学的物理参数,可以用多种方式配制式I化合物。适合的制剂选择实例为:可湿性粉剂(WP)、可湿性液剂(SL)、可溶性粉剂(SP)、可分散液剂(DC)、水剂(AS)、微乳剂(ME)、乳油(EC)、水乳剂(EW)、可喷洒溶液、悬浮剂(SC)、可分散油悬浮剂(OD)、粉剂(DP)、微囊悬浮剂(CS)、水分散粒剂(WG)、水溶性粒剂(SG)、大粒剂(GG)、用于撒播和土壤施药的颗粒剂(GR)、气雾剂(AE)、超低容量剂(ULV)和蜡制品。必要的制剂助剂,例如惰性物质、表面活性剂、溶剂及其它添加剂。
为了实际应用于农业,使用含有本发明式I化合物的组合物通常是有益的。
因此,本发明的另外一种技术方案还包括一种杀螨或杀菌组合物,其特征在于:组合物中含式I化合物和农业上可接受的载体;以所述式I化合物为活性组分,所述组合物中活性组分的重量百分含量为0.1-99%。
本发明的组合物可以制剂的形式施用。式I所示化合物作为活性组分溶解或分散于载体中或配制成制剂以便作为杀菌使用时更易于分散。例如:这些化学制剂可被制成可湿性粉剂、油悬剂、水悬剂、水乳剂、水剂或乳油等。在这些组合物中,至少加入一种液体或固体载体,并且当需要时可以加入适当的表面活性剂。
可用的固体稀释剂或载体可以是二氧化硅、高岭土、膨润土、滑石、硅藻土、白云石、碳酸钙、氧化镁、白垩、粘土、合成硅酸盐、硅镁土、海泡石等。
除水以外,可用的液体稀释剂是芳族有机溶剂(二甲苯或烷基苯的混合物、氯苯等)、石蜡(石油馏分)、醇类(甲醇、丙醇、丁醇、辛醇、甘油)、酯类(乙酸乙酯、乙酸异丁酯等)、酮类(环己酮、丙酮、苯乙酮、异佛尔酮、乙基戊基酮等)、酰胺类(N,N-二甲基甲酰胺、N-甲基吡咯烷酮等)。
可用的表面活性剂是烷基磺酸盐、烷基芳基磺酸盐、聚氧乙烯烷基酚、山梨醇的聚氧乙烯酯、木质素磺酸盐等的钠、钙、三乙基胺或三乙醇胺盐。
组合物还可含特殊的添加剂用于特定的目的,例如粘合剂如阿拉伯胶、聚乙烯醇、聚乙烯吡咯烷酮等。
上述组合物中活性成分的浓度可根据活性成分、其使用目的、环境条件和采用的制剂类型而在宽范围内改变。通常,活性成分的浓度范围是1-90%,优选5-50%。
对于某些应用,例如在农业上可在本发明的杀螨或杀菌组合物中加入一种或多种其它的杀菌剂、杀虫杀螨剂、除草剂、植物生长调节剂或肥料等,由此可产生附加的优点和效果。
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
以下具体实施例用来进一步说明本发明,但本发明绝非限于这些例子(除另有注明外,所用原料均有市售)。
合成实施例
实施例1:式I所示化合物的制备
室温下,将15.4g(0.1mol)2-氟-4-甲基苯硼酸、30.3g(0.1mol)2-氟-4-甲基-5-三氟乙硫基溴苯(参见专利WO2014202505中化合物VIIa-1的合成)、0.58g四三苯基膦钯和20.7g(0.15mol)碳酸钾,放入1000ml三口瓶中,加入乙二醇二甲醚(200ml)和水(200ml),通氮气保护搅拌回流反应4小时,TLC监测反应完毕后冷却,加入乙酸乙酯,萃取分层,得有机层,再用水、饱和食盐水依次洗涤,无水硫酸镁干燥、过滤,减压脱溶,残余物经柱层析纯化,得26.7g白色固体。1H NMR(600MHz,CDCl3)δ(ppm):7.56(d,1H),7.23(t,1H),7.05(d,1H),7.02(d,1H),6.98(d,1H),3.33(q,2H),2.52(s,3H),2.40(s,3H)。
生物活性测定实施例
实施例2:杀朱砂叶螨成螨的活性测定
根据待测化合物的溶解性,用丙酮或二甲亚砜溶解,然后用含有0.1%吐温80溶液配制成所需浓度的待测液50毫升,丙酮或二甲亚砜在溶液中的含量不超过10%,待用。取两片真叶菜豆苗,接种朱砂叶螨成螨并调查基数后,用手持喷雾器进行整株喷雾处理,每处理3次重复,处理后置于标准观察室,72小时后调查存活成螨数,计算死亡率。
本发明化合物在浓度为600mg/L时对朱砂叶螨成螨的致死率为100%;在更低的浓度100mg/L时对朱砂叶螨成螨的防治效果仍然很好,死亡率100%。
按照上述方法,对本发明化合物与如下比较化合物KC1(WO9955668列表化合物Ⅰ-636)、KC2(CN114957062A列表化合物5)和KC3(参考本发明实施例1的方法合成)进行杀螨活性的平行测试,具体化合物结构如下:
杀朱砂叶螨成螨活性平行测试的试验结果见下表:
实施例3:黄瓜白粉病的活体保护活性测定
采用活体盆栽测定方法,将待测化合物样品用少量溶剂(溶剂的种类如丙酮、甲醇、DMF等,并且依据其对样品的溶解能力而选择,溶剂量与喷液量的体积比等于或小于0.05)溶解,用含有0.1%吐温80的水稀释,配制成浓度为400mg/L待测液。在作物喷雾机上,将待测液喷施于病害寄主植物上(寄主植物为在温室内培养的标准盆栽苗),24小时后进行病害接种。依据病害特点,将需要控温保湿培养的病害植物接种后放在人工气候室中培养,待病害完成侵染后,移入温室培养,将不需要保湿培养的病害植物直接在温室内接种并培养。待对照充分发病后(通常为一周时间)进行化合物防病效果评估。
本发明化合物对黄瓜白粉病的防效为100%。
按照上述方法,测试背景技术中记载的式Ⅱ化合物和式Ⅲ化合物对黄瓜白粉病的活体保护活性,其结果是防效为0%。
综上所述本发明式I化合物对杀菌、杀螨具有突出的效果,进而可见不同取代基的位置,以及不同选择会直接影响其效果特点,其是需要通过进一步。
Claims (5)
1.一种联苯三氟乙硫醚化合物,其特征在于:化合物为式I所示:
2.一种按照权利要求1所述的式I化合物在农业、林业及卫生领域中作为杀螨剂的应用。
3.一种按照权利要求1所述的式I化合物在农业、林业及卫生领域中作为杀菌剂的应用。
4.一种杀螨组合物,其特征在于:组合物中含有权利要求1所述的式I化合物和农业上可接受的载体;以所述式I化合物为活性组分,所述组合物中活性组分的重量百分含量为0.1-99%。
5.一种杀菌组合物,其特征在于:组合物中含有权利要求1所述的式I化合物和农业上可接受的载体;以所述式I化合物为活性组分,所述组合物中活性组分的重量百分含量为0.1-99%。
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