CN114630821A - 3-(二氟甲基)-1-甲基-n-(1,1,3-三甲基-2,3-二氢-1h-茚-4-基)-1h-吡唑-4-甲酰胺的晶体 - Google Patents
3-(二氟甲基)-1-甲基-n-(1,1,3-三甲基-2,3-二氢-1h-茚-4-基)-1h-吡唑-4-甲酰胺的晶体 Download PDFInfo
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Abstract
本发明提供一种晶体,其为3‑(二氟甲基)‑1‑甲基‑N‑(1,1,3‑三甲基‑2,3‑二氢‑1H‑茚‑4‑基)‑1H‑吡唑‑4‑甲酰胺的选自如下晶体中的至少1种晶体,即,在基于Cu‑Kα射线的粉末X射线衍射中,分别具有说明书中记载的衍射峰的Ra1型晶体、Ra2型晶体以及Ra3型晶体。
Description
技术领域
本发明涉及一种具有植物病害防除效力的3-(二氟甲基)-1-甲基-N- (1,1,3-三甲基-2,3-二氢-1H-茚-4-基)-1H-吡唑-4-甲酰胺的新型晶体。
背景技术
3-(二氟甲基)-1-甲基-N-(1,1,3-三甲基-2,3-二氢-1H-茚-4-基) -1H-吡唑-4-甲酰胺(以下记作化合物A)是熔点131~134℃的晶体,报告过对植物病害显示出防除效力(专利文献1)。
现有技术文献
专利文献
专利文献1:WO 92/12970
发明内容
发明所要解决的课题
本发明的目的在于,提供一种新型的晶体,其具有与专利文献1中记载的公知的晶体(以下记作Ra4型晶体)不同的物理学性质,另外,植物病害防除效力更加优异。
用于解决课题的手段
本发明人等发现了对植物病害具有优异的防除效力的化合物A的3 种新型的晶体(Ra1型晶体、Ra2型晶体以及Ra3型晶体)。
即,本发明如下所示。
[1]一种晶体,其为3-(二氟甲基)-1-甲基-N-(1,1,3-三甲基-2, 3-二氢-1H-茚-4-基)-1H-吡唑-4-甲酰胺的选自如下晶体中的至少1种晶体:
在基于Cu-Kα射线的粉末X射线衍射中的2θ=7.1±0.2°、8.6±0.2°、8.9±0.2°、9.1±0.2°、13.3±0.2°、14.0±0.2°、14.3±0.2°、14.8±0.2°、16.0±0.2°、 16.4±0.2°、20.3±0.2°以及20.6±0.2°具有衍射峰的Ra1型晶体、
在基于Cu-Kα射线的粉末X射线衍射中的2θ=4.3±0.2°、8.5±0.2°、 10.8±0.2°、11.4±0.2°、12.4±0.2°、12.8±0.2°、15.1±0.2°、16.1±0.2°、16.8±0.2°以及19.1±0.2°具有衍射峰的Ra2型晶体、以及
在基于Cu-Kα射线的粉末X射线衍射中的2θ=3.6±0.2°、7.1±0.2°、 7.4±0.2°、9.6±0.2°、11.9±0.2°、12.5±0.2°、12.9±0.2°、14.3±0.2°、15.7±0.2°以及17.9±0.2°具有衍射峰的Ra3型晶体。
[2]根据[1]中记载的晶体,其中,在3-(二氟甲基)-1-甲基-N- (1,1,3-三甲基-2,3-二氢-1H-茚-4-基)-1H-吡唑-4-甲酰胺中,是在基于Cu-Kα射线的粉末X射线衍射中的2θ=7.1±0.2°、8.6±0.2°、8.9±0.2°、 9.1±0.2°、13.3±0.2°、14.0±0.2°、14.3±0.2°、14.8±0.2°、16.0±0.2°、16.4±0.2°、 20.3±0.2°以及20.6±0.2°具有衍射峰的Ra1型晶体。
[3]根据[1]中记载的晶体,其中,在3-(二氟甲基)-1-甲基-N- (1,1,3-三甲基-2,3-二氢-1H-茚-4-基)-1H-吡唑-4-甲酰胺中,是在基于Cu-Kα射线的粉末X射线衍射中的2θ=4.3±0.2°、8.5±0.2°、10.8±0.2°、 11.4±0.2°、12.4±0.2°、12.8±0.2°、15.1±0.2°、16.1±0.2°、16.8±0.2°以及19.1±0.2°具有衍射峰的Ra2型晶体。
[4]根据[1]中记载的晶体,其中,在3-(二氟甲基)-1-甲基-N- (1,1,3-三甲基-2,3-二氢-1H-茚-4-基)-1H-吡唑-4-甲酰胺中,是在基于Cu-Kα射线的粉末X射线衍射中的2θ=3.6±0.2°、7.1±0.2°、7.4±0.2°、 9.6±0.2°、11.9±0.2°、12.5±0.2°、12.9±0.2°、14.3±0.2°、15.7±0.2°以及 17.9±0.2°具有衍射峰的Ra3型晶体。
[5]一种植物病害防除组合物,其包含[1]~[4]中任一项记载的1种以上的晶体。
[6]一种植物病害的防除方法,其包括用[1]~[4]中任一项记载的1种以上的晶体的有效量对植物或植物生长的土壤进行处理。
[7]一种[1]~[4]中任一项记载的1种以上的晶体的用途,其用于防除植物病害。
[8]一种组合物,其含有选自组(a)、组(b)、组(c)及组(d) 中的1种以上的成分、和[1]~[4]中任一项记载中记载的1种以上的晶体:
组(a):包含杀虫活性成分、杀螨活性成分及杀线虫活性成分的组;
组(b):杀菌活性成分;
组(c):植物生长调节成分;
组(d):驱避成分。
[9]一种种子或营养繁殖器官,其保持有[1]~[4]中任一项记载的1种以上的晶体或[7]中记载的组合物的有效量。
发明效果
本发明提供对植物的病害显示出防除效力的化合物A的3种新型的晶体(Ra1型晶体、Ra2型晶体以及Ra3型晶体)。这些晶体与公知的Ra4 型晶体相比对植物病害显示出更加优异的防除效力。
附图说明
图1是表示Ra1型晶体的粉末X射线衍射图的图。纵轴为衍射强度 (单位:cps),横轴表示衍射角度2θ(单位:°)。
图2是表示Ra2型晶体的粉末X射线衍射图的图面。纵轴为衍射强度(单位:cps),横轴表示衍射角度2θ(单位:°)。
图3是表示Ra3型晶体的粉末X射线衍射图的图。纵轴为衍射强度 (单位:cps),横轴表示衍射角度2θ(单位:°)。
图4是表示Ra4型晶体的粉末X射线衍射图的图。纵轴为衍射强度 (单位:cps),横轴表示衍射角度2θ(单位:°)。
图5是表示Ra1型晶体的晶格中的分子堆积的图。
图6是表示Ra2型晶体的晶格中的分子堆积的图。
图7是表示Ra3型晶体的晶格中的分子堆积的图。
图8是表示Ra1型晶体的差示扫描量热测定(DSC)曲线的图。纵轴表示热流量(单位:W/g),横轴表示温度(单位:℃)。
图9是表示Ra2型晶体的差示扫描量热测定(DSC)曲线的图。
图10是表示Ra3型晶体的差示扫描量热测定(DSC)曲线的图。
图11是表示Ra4型晶体的差示扫描量热测定(DSC)曲线的图。
图12是表示Ra1型晶体的红外光谱的光谱图的图。纵轴为透射率,横轴表示所照射的红外线的波数。
图13是表示Ra2型晶体的红外光谱的光谱图的图。纵轴为透射率,横轴表示所照射的红外线的波数。
图14是表示Ra3型晶体的红外光谱的光谱图的图。纵轴为透射率,横轴表示所照射的红外线的波数。
图15是表示Ra4型晶体的红外光谱的光谱图的图。纵轴为透射率,横轴表示所照射的红外线的波数。
图16是表示Ra1型晶体的拉曼光谱的光谱图的图。纵轴为强度,横轴表示拉曼位移数。
图17是表示Ra2型晶体的拉曼光谱的光谱图的图。纵轴为强度,横轴表示拉曼位移数。
图18是表示Ra3型晶体的拉曼光谱的光谱图的图。纵轴为强度,横轴表示拉曼位移数。
图19是表示Ra4型晶体的拉曼光谱的光谱图的图。纵轴为强度,横轴表示拉曼位移数。
图20是表示Ra1型晶体的光学显微镜的照片的图。
图21是表示Ra2型晶体的光学显微镜的照片的图。
图22是表示Ra3型晶体的光学显微镜的照片的图。
图23是表示Ra4型晶体的光学显微镜的照片的图。
具体实施方式
本发明涉及化合物A的新型的晶体(Ra1型晶体、Ra2型晶体以及 Ra3型晶体)。3-(二氟甲基)-1-甲基-N-(1,1,3-三甲基-2,3-二氢-1H- 茚-4-基)-1H-吡唑-4-甲酰胺是具有R体及S体的2种对映体的化合物,化合物A是它们的等量混合物,即外消旋体。另外,将该R体与S体各自等量地具有规则性地在晶格中排列而得的晶体是本发明的晶体,根据制造条件,各自成为Ra1型晶体、Ra2型晶体、或Ra3型晶体。
Ra4型晶体的熔点约为131~134℃,在使用Cu-Kα射线的粉末X射线衍射图中,作为2θ值(°)的衍射峰,可以举出5.8±0.2、7.2±0.2、8.6±0.2、 13.8±0.2、16.3±0.2、16.7±0.2、17.4±0.2、17.7±0.2、19.4±0.2、19.8±0.2 以及20.7±0.2。
Ra1型晶体、Ra2型晶体以及Ra3型晶体各自具有下述的物理学性质。
Ra1型晶体是熔点约为134~136℃、且在使用Cu-Kα射线的粉末X 射线衍射图中作为2θ值(°)的衍射峰具有7.1±0.2、8.6±0.2、8.9±0.2、 9.1±0.2、13.3±0.2、14.0±0.2、14.3±0.2、14.8±0.2、16.0±0.2、16.4±0.2、 20.3±0.2以及20.6±0.2的晶体。
Ra1型晶体可以依照以下的制法制造。
将必需量(例如约200mg)的Ra2型晶体在适当的容器(例如20mL 样品瓶)中在约130℃加热一定的时间(约2小时),得到Ra1型晶体。
Ra2型晶体是熔点约为124~126℃、且在使用Cu-Kα射线的粉末X 射线衍射图中作为2θ值(°)的衍射峰具有4.3±0.2、8.5±0.2、10.8±0.2、 11.4±0.2、12.4±0.2、12.8±0.2、15.1±0.2、16.1±0.2、16.8±0.2以及19.1±0.2 的晶体。
Ra2型晶体可以依照以下的制法制造。
将必需量(例如约30mg)的化合物A在约60℃溶解于适量(约80μL) 的有机溶剂(例如甲醇)中,制备成一定量的溶解浓度(约375mg/mL)。将该溶液冷却至室温后,在一定的条件下照射激光,将溶液在约20℃静置,得到Ra2型晶体。
激光照射条件如下所示,然而并不限定于此。
<飞秒激光器>
波长:800nm
脉冲宽度:181fs
脉冲数:125脉冲/10秒
作为该有机溶剂,例如可以举出醇系溶剂,优选举出碳数为1~3的烷基系溶剂。具体而言,为甲醇、乙醇、丙醇以及异丙醇,优选甲醇。
作为有机溶剂的量,对于将化合物A溶解时使用的有机溶剂,可以举出达成约200mg/mL~约1000mg/mL的溶解浓度的量,溶解浓度优选举出约300mg/L~约500mg/mL,例如可以举出约375mg/mL。
Ra3型晶体是熔点约为129~131℃、且在使用Cu-Kα射线的粉末X 射线衍射图中作为2θ值(°)的衍射峰具有3.6±0.2、7.1±0.2、7.4±0.2、 9.6±0.2、11.9±0.2、12.5±0.2、12.9±0.2、14.3±0.2、15.7±0.2以及17.9±0.2 的晶体。
Ra3型晶体可以依照以下的制法制造。
向上文中制造的Ra1型晶体的必需量(例如约100mg)中添加适量 (例如约1mL)的有机溶剂,将该悬浮液加热至约60℃,在一定的条件下(约1000rpm)搅拌一定的时间(约2天)后,除去溶剂,得到Ra3 型晶体。
作为该有机溶剂,例如可以举出醚系溶剂,优选举出包含碳数为1~ 3的烷基的二烷基醚系溶剂。具体而言,可以举出二甲醚、二乙醚、二丙醚以及二异丙醚等,优选二异丙醚。
对于有机溶剂的量,相对于所使用的Ra1型晶体的1重量份为5~10 重量份,优选为6~8重量份的范围内。
选自Ra1型晶体、Ra2型晶体以及Ra3型晶体中的1种以上的晶体可以与选自下述组(a)、组(b)、组(c)以及组(d)中的1种以上的成分(以下记作本成分)混用或并用。
所述所谓混用或并用,是指将选自Ra1型晶体、Ra2型晶体以及Ra3 型晶体中的1种以上的晶体和本成分同时地各自使用,或者拉开时间间隔地使用。
在同时地使用选自Ra1型晶体、Ra2型晶体以及Ra3型晶体中的1 种以上的晶体和本成分的情况下,选自Ra1型晶体、Ra2型晶体以及Ra3 型晶体中的1种以上的晶体及本成分可以分别包含于不同的制剂中,也可以包含于1个制剂中。
本发明的1个方面是含有选自组(a)、组(b)、组(c)及组(d)中的1种以上的成分以及选自Ra1型晶体、Ra2型晶体及Ra3型晶体中的1 种以上的晶体的组合物(以下记作本发明组合物)。
组(a)是包含乙酰胆碱酯酶抑制剂(例如氨基甲酸酯系杀虫剂、有机磷系杀虫剂)、GABA-激动性氯离子通道拮抗剂(例如苯基吡唑系杀虫剂)、钠通道调节剂(例如拟除虫菊酯系杀虫剂)、烟碱型乙酰胆碱受体拮抗调节剂(例如新烟碱系杀虫剂)、烟碱型乙酰胆碱受体变构调节剂、谷氨酸激动性氯离子通道变构调节剂(例如大环内酯系杀虫剂)、保幼激素类似物、多位点抑制剂、弦音器官TRPV通道调节剂、螨类生长抑制剂、线粒体ATP生物合成酶抑制剂、氧化磷酸化解偶联剂、烟碱型乙酰胆碱受体通道阻断剂(例如沙蚕毒素系杀虫剂)、壳多糖合成抑制剂、脱皮抑制剂、蜕皮激素受体激动剂、章胺受体激动剂、线粒体电子传递系统复合体I、II、III和IV抑制剂、电位依赖性钠通道阻滞剂、乙酰基辅酶A羧化酶抑制剂、鱼尼丁受体调节剂(例如二酰胺系杀虫剂)、弦音器官调节剂、微生物杀虫剂的各活性成分以及其他杀虫活性成分、杀螨活性成分、杀线虫活性成分的组。它们记载于基于IRAC的作用机理的分类中。
组(b)为包含核酸合成抑制剂(例如苯基酰胺系杀菌剂、酰基氨基酸系杀菌剂)、细胞分裂和细胞骨架抑制剂(例如MBC杀菌剂)、呼吸抑制剂(例如QoI杀菌剂、QiI杀菌剂)、氨基酸合成及蛋白质合成抑制剂 (例如苯胺基吡啶系杀菌剂)、信号传递抑制剂、脂质合成及膜合成抑制剂、甾醇生物合成抑制剂(例如三唑系等DMI杀菌剂)、细胞壁合成抑制剂、黑色素合成抑制剂、植物防御诱导剂、多作用位点接触活性杀菌剂、微生物杀菌剂以及其他杀菌活性成分的组。它们记载于基于FRAC的作用机理的分类中。
组(c)为植物生长调节成分(包含菌根菌及根瘤菌)的组。
组(d)为包含鸟驱避成分及昆虫驱避成分的驱避成分的组。
以下,记载选自Ra1型晶体、Ra2型晶体以及Ra3型晶体中的1种以上的晶体与本成分的组合的例子。例如,棉铃威(alanycarb)+SX是指棉铃威(alanycarb)与SX的组合。
需要说明的是,SX的简写符号是指Ra1型晶体、Ra2型晶体、或Ra3 型晶体(以下记作本发明晶体)。另外,以下记载的本成分均为公知的成分,可以由市售的制剂得到,或者可以利用公知的方法制造。在本成分为微生物的情况下,也可以从菌种保藏机构获得。需要说明的是,括号内的数字表示CAS RN(注册商标)。
上述组(a)的本成分与本发明晶体的组合:
阿维菌素(abamectin)+SX、乙酰甲胺磷(acephate)+SX、灭螨醌 (acequinocyl)+SX、啶虫脒(acetamiprid)+SX、乙酰虫腈(acetoprole) +SX、氟丙菊酯(acrinathrin)+SX、3-内-[2-丙氧基-4-(三氟甲基)苯氧基]-9-[5-(三氟甲基)-2-吡啶氧基]-9-氮杂双环[3.3.1]壬烷(acynonapyr) +SX、双丙环虫酯(afidopyropen)+SX、阿福拉纳(afoxolaner)+SX、棉铃威(alanycarb)+SX、涕灭威(aldicarb)+SX、丙烯菊酯(allethrin) +SX、α-氯氰菊酯(alpha-cypermethrin)+SX、α-硫丹(alpha-endosulfan) +SX、磷化铝(aluminiumphosphide)+SX、双甲脒(amitraz)+SX、印楝素(azadirachtin)+SX、甲基吡磷(azamethiphos)+SX、乙基谷硫磷 (azinphos-ethyl)+SX、甲基谷硫磷(azinphos-methyl)+SX、三唑锡 (azocyclotin)+SX、苦皮藤树皮(bark of Celastrus angulatus)+SX、虫威(bendiocarb)+SX、四氟苯菊酯(benfluthrin)+SX、丙硫克百威 (benfuracarb)+SX、杀虫磺(bensultap)+SX、苯螨特(benzoximate) +SX、5-(1,3-二烷-2-基)-4-[4-(三氟甲基)苄氧基]嘧啶(benzpyrimoxan) +SX、β-氟氯氰菊酯(beta-cyfluthrin)+SX、β-氯氰菊酯(beta-cypermethrin) +SX、联苯肼酯(bifenazate)+SX、联苯菊酯(bifenthrin)+SX、生物丙烯菊酯(bioallethrin)+SX、生物苄呋菊酯(bioresmethrin)+SX、双三氟虫脲(bistrifluron)+SX、硼砂(borax)+SX、硼酸(boric acid)+SX、溴虫氟苯双酰胺(broflanilide)+SX、溴螨酯(bromopropylate)+SX、噻螨酮(buprofezin)+SX、丁叉威(butocarboxim)+SX、氧丁叉威(butoxycarboxim)+SX、硫线磷(cadusafos)+SX、磷化钙(calcium phosphide)+SX、甲萘威(carbaryl)+SX、克百威(carbofuran)+SX、丁硫克百威(carbosulfan)+SX、杀螟丹盐酸盐(cartap hydrochloride)+SX、杀螟丹(cartap)+SX、灭螨猛(chinomethionat)+SX、氯虫酰胺 (chlorantraniliprole)+SX、氯丹(chlordane)+SX、氯氧磷(chlorethoxyfos) +SX、溴虫腈(chlorfenapyr)+SX、毒虫畏(chlorfenvinphos)+SX、氟啶脲(chlorfluazuron)+SX、氯甲磷(chlormephos)+SX、氯化苦 (chloropicrin)+SX、氯吡硫磷(chlorpyrifos)+SX、甲基毒死蜱 (chlorpyrifos-methyl)+SX、环虫酰肼(chromafenozide)+SX、四螨嗪(clofentezine)+SX、噻虫胺(clothianidin)+SX、刀豆素A(concanamycinA) +SX、蝇毒磷(coumaphos)+SX、冰晶石(cryolite)+SX、杀螟腈(cyanophos) +SX、溴氰虫酰胺(cyantraniliprole)+SX、环溴虫酰胺(cycloniliprole) +SX、乙氰菊酯(cycloprothrin)+SX、环氧虫啶(cycloxaprid)+SX、腈吡螨酯(cyenopyrafen)+SX、丁氟螨酯(cyflumetofen)+SX、氟氯氰菊酯(cyfluthrin)+SX、氯氟氰虫酰胺(cyhalodiamide)+SX、氯氟氰菊酯(cyhalothrin)+SX、三环锡(cyhexatin)+SX、氯氰菊酯(cypermethrin) +SX、苯醚氰菊酯(cyphenothrin)+SX、灭蝇胺(cyromazine)+SX、二甲噻嗪(dazomet)+SX、溴氰菊酯(deltamethrin)+SX、甲基内吸磷 (demeton-S-methyl)+SX、丁醚脲(diafenthiuron)+SX、二嗪农(diazinon) +SX、敌敌畏(dichlorvos)+SX、敌克美施(dicloromezotiaz)+SX、三氯杀螨醇(dicofol)+SX、百治磷(dicrotophos)+SX、氟螨嗪(diflovidazin) +SX、除虫脲(diflubenzuron)+SX、四氟甲醚菊酯(dimefluthrin)+SX、乐果(dimethoate)+SX、甲基毒虫畏(dimethylvinphos)+SX、嗪虫唑酰胺(dimpropyridaz)+SX、呋虫胺(dinotefuran)+SX、八硼酸二钠(disodium octaborate)+SX、乙拌磷(disulfoton)+SX、DNOC(2-甲基-4,6-二硝基苯酚)+SX、多拉克丁(doramectin)+SX、欧洲鳞毛蕨干叶(dried leaves of Dryopterisfilix-mas)+SX、甲氨基阿维菌素苯甲酸盐 (emamectin-benzoate)+SX、烯炔菊酯(empenthrin)+SX、硫丹(endosulfan) +SX、EPN(O-乙基O-(4-硝基苯基)苯基硫代磷酸酯)+SX、ε-甲氧苄氟菊酯(epsilon-metofluthrin)+SX、ε-氟氯氰菊酯(epsilon-momfluorothrin) +SX、S-氰戊菊酯(esfenvalerate)+SX、乙硫苯威(ethiofencarb)+SX、乙硫磷(ethion)+SX、乙虫腈(ethiprole)+SX、灭线磷(ethoprophos) +SX、醚菊酯(etofenprox)+SX、乙螨唑(etoxazole)+SX、苦艾提取物 (extract of Artemisiaabsinthium)+SX、决明提取物(extract of Cassia nigricans)+SX、蝶豆提取物(extractof clitoria ternatea)+SX、聚合草提取物(extract of Symphytum officinale)+SX、土荆芥提取物(extracts or simulated blend of Chenopodium ambrosioides)+SX、菊蒿提取物(extract of Tanacetum vulgare)+SX、异株荨麻提取物(extract of Urticadioica)+SX、白果槲寄生提取物(extract of Viscum album)+SX、氨磺磷(famphur) +SX、苯线磷(fenamiphos)+SX、喹螨醚(fenazaquin)+SX、苯丁锡(fenbutatin oxide)+SX、杀螟松(fenitrothion)+SX、仲丁威(fenobucarb) +SX、苯氧威(fenoxycarb)+SX、甲氰菊酯(fenpropathrin)+SX、唑螨酯(fenpyroximate)+SX、倍硫磷(fenthion)+SX、氰戊菊酯(fenvalerate) +SX、氟虫腈(fipronil)+SX、2-乙基-3,7-二甲基-6-[4-(三氟甲氧基) 苯氧基]喹啉-4-基甲基碳酸酯(flometoquin)+SX、氟啶虫酰胺(flonicamid) +SX、嘧螨酯(fluacrypyrim)+SX、三氟嘧啶酰胺(fluazaindolizine)+SX、氟啶脲(fluazuron)+SX、氟虫双酰胺(flubendiamide)+SX、氟环脲 (flucycloxuron)+SX、氟氰戊菊酯(flucythrinate)+SX、氟噻虫砜 (fluensulfone)+SX、三氟醚菊酯(flufenoprox)+SX、氟虫脲(flufenoxuron)+SX、丁虫腈(flufiprole)+SX、氟氯苯菊酯(flumethrin)+SX、氟吡呋喃酮(flupyradifurone)+SX、N-[(2E)-1-[(6-氯吡啶-3-基)甲基]吡啶 -2(1H)-亚基]-2,2,2-三氟乙酰胺(flupyrimin)+SX、氟雷拉纳(fluralaner) +SX、氟胺氰菊酯(fluvalinate)+SX、氟唑酰胺(fluxametamide)+SX、伐虫脒(formetanate)+SX、噻唑磷(fosthiazate)+SX、炔呋菊酯 (furamethrin)+SX、呋线威(furathiocarb)+SX、γ-氯氟氰菊酯 (gamma-cyhalothrin)+SX、谷氨酰胺合成酶-Ω/κHXTX-Hv1a肽 (GS-omega/kappa HXTX-Hv1apeptide)+SX、苄螨醚(halfenprox)+SX、氯虫酰肼(halofenozide)+SX、右旋七氟甲醚菊酯(heptafluthrin)+SX、庚虫磷(heptenophos)+SX、氟铃脲(hexaflumuron)+SX、噻螨酮(hexythiazox)+SX、啤酒花β-酸的钾盐(potassium salt of hop beta acid) +SX、氟蚁腙(hydramethylnon)+SX、烯虫乙酯(hydroprene)+SX、新烟磷(imicyafos)+SX、吡虫啉(imidacloprid)+SX、氯噻啉(imidaclothiz) +SX、炔咪菊酯(imiprothrin)+SX、茚虫威(indoxacarb)+SX、异噁唑虫酰胺(isocycloseram)+SX、异柳磷(isofenphos)+SX、灭扑威(isoprocarb) +SX、异丙基-O-(甲氧基氨基硫代磷酰基)水杨酸酯(isopropyl-O-(methoxyaminothiophosphoryl)salicylate)+SX、异唑磷(isoxathion)+SX、双氢除虫菌素(ivermectin)+SX、噻嗯菊酯(kadethrin)+SX、κ-七氟菊酯(kappa-tefluthrin)+SX、κ-联苯菊酯(kappa-bifenthrin)+SX、丙诺保幼素(kinoprene)+SX、λ-氯氟氰菊酯(lambda-cyhalothrin)+SX、雷诺霉素(lenoremycin)+SX、雷皮菌素(lepimectin)+SX、石硫合剂(lime sulfur)+SX、洛替拉纳(lotilaner)+SX、虱螨脲(lufenuron)+SX、机油(machineoil)+SX、马拉硫磷(malathion)+SX、灭蚜磷(mecarbam) +SX、氯氟醚菊酯(meperfluthrin)+SX、氰氟虫腙(metaflumizone)+SX、威百亩(metam)+SX、甲胺磷(methamidophos)+SX、杀扑磷(methidathion) +SX、灭虫威(methiocarb)+SX、灭多威(methomyl)+SX、烯虫酯(methoprene)+SX、甲氧氯(methoxychlor)+SX、甲氧虫酰肼 (methoxyfenozide)+SX、甲基溴(methyl bromide)+SX、甲氧苄氟菊酯 (metofluthrin)+SX、速灭威(metolcarb)+SX、虫酮(metoxadiazone) +SX、速灭磷(mevinphos)+SX、密灭汀(milbemectin)+SX、米尔贝肟(milbemycin oxime)+SX、莫氟杀林(momfluorothrin)+SX、久效磷 (monocrotophos)+SX、莫昔克丁(moxidectin)+SX、二溴磷(naled) +SX、苦楝油(neem oil)+SX、烟碱(nicotine)+SX、硫酸烟碱 (nicotine-sulfate)+SX、烯啶虫胺(nitenpyram)+SX、氟酰脲(novaluron) +SX、多氟脲(noviflumuron)+SX、驱虫藜籽油(oil of the seeds of Chenopodiumanthelminticum)+SX、氧乐果(omethoate)+SX、杀线威 (oxamyl)+SX、2-[3-(乙基磺酰基)-2-吡啶基]-5-[(三氟甲基)磺酰基] 苯并噁唑(oxazosulfyl)+SX、砜吸磷(oxydemeton-methyl)+SX、对硫磷(parathion)+SX、甲基对硫磷(parathion-methyl)+SX、氯菊酯(permethrin)+SX、苯醚菊酯(phenothrin)+SX、稻丰散(phenthoate) +SX、甲拌磷(phorate)+SX、伏杀磷(phosalone)+SX、亚胺硫磷(phosmet) +SX、磷胺(phosphamidon)+SX、磷化氢(phosphine)+SX、肟硫磷(phoxim) +SX、抗蚜威(pirimicarb)+SX、甲嘧硫磷(pirimiphos-methyl)+SX、炔丙菊酯(prallethrin)+SX、丙溴磷(profenofos)+SX、丙氟菊酯 (profluthrin)+SX、炔螨特(propargite)+SX、胺丙畏(propetamphos) +SX、残杀威(propoxur)+SX、藻酸丙二醇酯(propylene glycol alginate) +SX、丙硫磷(prothiofos)+SX、3′-异丁基-N-异丁酰基-1,3,5-三甲基 -4′-[2,2,2-三氟-1-甲氧基-1-(三氟甲基)乙基]吡唑-4-甲酰苯胺 (pyflubumide)+SX、吡蚜酮(pymetrozine)+SX、吡唑硫磷(pyraclofos) +SX、除虫菊酯(pyrethrins)+SX、哒螨灵(pyridaben)+SX、三氟甲吡醚(pyridalyl)+SX、打杀磷(pyridaphenthion)+SX、氟虫吡喹(pyrifluquinazone)+SX、嘧螨醚(pyrimidifen)+SX、嘧螨胺 (pyriminostrobin)+SX、吡啶氟虫腈(pyriprole)+SX、蚊蝇醚 (pyriproxyfen)+SX、喹硫磷(quinalphos)+SX、苄呋菊酯(resmethrin) +SX、鱼藤酮(rotenone)+SX、兰尼碱(ryanodine)+SX、沙罗拉纳(sarolaner) +SX、司拉克丁(selamectin)+SX、σ-氯氰菊酯(sigma-cypermethrin)+SX、氟硅菊酯(silafluofen)+SX、硼酸钠(sodium borate)+SX、偏硼酸钠(sodium metaborate)+SX、乙基多杀菌素(spinetoram)+SX、多杀霉(spinosad) +SX、螺螨酯(spirodiclofen)+SX、螺甲螨酯(spiromesifen)+SX、甲氧哌啶乙酯(spiropidion)+SX、螺虫乙酯(spirotetramat)+SX、氟虫胺 (sulfluramid)+SX、治螟磷(sulfotep)+SX、氟啶虫胺(sulfoxaflor)+SX、硫(sulfur)+SX、硫酰氟(sulfuryl fluoride)+SX、吐酒石(tartaremetic) +SX、τ-氟胺氰菊酯(tau-fluvalinate)+SX、虫酰肼(tebufenozide)+SX、吡螨胺(tebufenpyrad)+SX、丁基嘧啶磷(tebupirimfos)+SX、氟苯脲 (teflubenzuron)+SX、七氟菊酯(tefluthrin)+SX、双硫磷(temephos) +SX、特丁硫磷(terbufos)+SX、由土荆芥提取的萜烯成分(terpeneconstituents of the extract of chenopodium ambrosioides nearambrosioides) +SX、四氯虫酰胺(tetrachlorantraniliprole)+SX、杀虫畏(tetrachlorvinphos) +SX、四氯杀螨砜(tetradifon)+SX、胺菊酯(tetramethrin)+SX、四氟醚菊酯(tetramethylfluthrin)+SX、氟氰虫酰胺(tetraniliprole)+SX、θ- 氯氰菊酯(theta-cypermethrin)+SX、噻虫啉(thiacloprid)+SX、噻虫嗪 (thiamethoxam)+SX、杀虫环(thiocyclam)+SX、硫双威(thiodicarb) +SX、久效威(thiofanox)+SX、甲基乙拌磷(thiometon)+SX、杀虫双(thiosultap-disodium)+SX、杀虫单(thiosultap-monosodium)+SX、3- 苯基-5-(2-噻吩基)-1,2,4-噁二唑(tioxazafen)+SX、唑虫酰胺(tolfenpyrad) +SX、四溴菊酯(tralomethrin)+SX、四氟苯菊酯(transfluthrin)+SX、唑蚜威(triazamate)+SX、三唑磷(triazophos)+SX、敌百虫(trichlorfon) +SX、三氟苯嘧啶(triflumezopyrim)+SX、杀铃脲(triflumuron)+SX、混杀威(trimethacarb)+SX、N-[3-氯-1-(3-吡啶基)吡唑-4-基]-N-乙基-3-[(3, 3,3-三氟丙基)硫代]丙酰胺(tyclopyrazoflor)+SX、蚜灭多(vamidothion) +SX、苏里南苦木提取物(wood extract of Quassia amara)+SX、XMC(3,5-二甲基苯基N-甲基氨基甲酸酯、3,5-dimethylphenyl N-methylcarbamate) +SX、灭杀威(xylylcarb)+SX、ζ-氯氰菊酯(zeta-cypermethrin)+SX、磷化锌(zinc phosphide)+SX、4-[5-(3,5-二氯苯基)-5-(三氟甲基) -4,5-二氢-1,2-噁唑-3-基]-2-甲基-N-(1-氧代噻丁环-3-基)苯甲酰胺 (1241050-20-3)+SX、3-甲氧基-N-(5-{5-(三氟甲基)-5-[3-(三氟甲基)苯基]-4,5-二氢-1,2-噁唑-3-基}茚满-1-基)丙酰胺(1118626-57-5) +SX、2-氯-4-氟-5-{[5-(三氟甲硫基)戊基]氧基}苯基2,2,2-三氟乙基亚砜(1472050-04-6)+SX、4-氯-5-[2,2-二氟-2-(3,4,5-三氟苯基) 乙氧基]-2-甲基苯基2,2,2-三氟乙基亚砜(1632218-00-8)+SX、4-氟-5-[2,2-二氟-2-(3,4,5-三氟苯基)乙氧基]-2-甲基苯基2,2,2-三氟乙基亚砜(1632217-98-1)+SX、2-({2-氟-4-甲基-5-[(2,2,2-三氟乙基)亚磺酰基]苯基}亚氨基)-3-(2,2,2-三氟乙基)-1,3-噻唑烷-4-酮 (1445683-71-5)+SX、(1Z)-2-(4-叔丁基苯基)-2-氰基-1-(1-乙基-3- 甲基-1H-吡唑-5-基)乙烯基2,2-二甲基丙酸酯(1253429-01-4)+SX、 N-[(1S,2S)-2-(2,4-二氯苯基)环丁基]-2-(三氟甲基)吡啶-3-甲酰胺(1644251-74-0)+SX、(3R)-3-(2-氯噻唑-5-基)-8-甲基-7-氧代-6- 苯基-2,3-二氢噻唑并[3,2-a]嘧啶-4-鎓-5-氧化物(2249718-27-0)+SX、 BT作物的蛋白质Cry1Ab(BT crop proteinCry1Ab)+SX、BT作物的蛋白质Cry1Ac(BT crop protein Cry1Ac)+SX、BT作物的蛋白质Cry1Fa(BT crop proteinCry1Fa)+SX、BT作物的蛋白质Cry1A.105(BT crop proteinCry1A.105)+SX、BT作物的蛋白质Cry2Ab(BT crop protein Cry2Ab)+SX、BT作物的蛋白质Vip3A(BT crop proteinVip3A)+SX、 BT作物的蛋白质Cry3A(BT crop protein Cry3A)+SX、BT作物的蛋白质Cry3Ab(BT crop protein Cry3Ab)+SX、BT作物的蛋白质Cry3Bb(BT crop protein Cry3Bb)+SX、BT作物的蛋白质Cry34Ab1/Cry35Ab1(BT crop protein Cry34Ab1/Cry35Ab1)+SX、茶小卷叶蛾颗粒体病毒BV-0001株 (Adoxophyes oranagranulosis virus BV-0001)+SX、黎豆夜蛾核型多角体病毒(Anticarsia gemmatalis mNPV)+SX、苜蓿银纹夜蛾核型多角体病毒(Autographa californica mNPV)+SX、苹果小卷蛾颗粒体病毒V15(Cydia pomonella GVstrain V15)+SX、苹果小卷蛾颗粒体病毒V22(Cydia pomonella GV strain V22)+SX、苹果异形小卷蛾颗粒体病毒(Cryptophlebia leucotreta GV)+SX、马尾松毛虫细胞质多角体病毒(Dendrolimus punctatus cypovirus)+SX、棉铃虫核型多角体病毒BV-0003株(Helicoverpa armigera NPV strain BV-0003)+SX、谷实夜蛾核型多角体病毒(Helicoverpa zea NPV)+SX、舞毒蛾核型多角体病毒(Lymantria dispar NPV)+SX、甘蓝夜蛾核型多角体病毒(Mamestra brassicae NPV)+SX、蓓带夜蛾核型多角体病毒(Mamestraconfigurata NPV)+SX、黑头松叶蜂核型多角体病毒 (Neodiprion abietis NPV)+SX、红头松叶蜂核型多角体病毒(Neodiprion lecontei NPV)+SX、欧洲松叶蜂核型多角体病毒(Neodiprion sertifer NPV) +SX、蝗虫微孢子虫(Nosema locustae)+SX、枞树毒蛾核型多角体病毒 (Orgyia pseudotsugata NPV)+SX、菜粉蝶颗粒体病毒(Pieris rapae GV) +SX、印度谷螟颗粒体病毒(Plodia interpunctella GV)+SX、甜菜夜蛾核型多角体病毒(Spodoptera exigua mNPV)+SX、海灰翅夜蛾核型多角体病毒(Spodoptera littoralismNPV)+SX、斜纹夜蛾核型多角体病毒 (Spodoptera litura NPV)+SX、指状节丛孢(Arthrobotrys dactyloides) +SX、坚强芽孢杆菌GB-126株(Bacillus firmus strainGB-126)+SX、坚强芽孢杆菌I-1582株(Bacillus firmus strain I-1582)+SX、巨大芽孢杆菌 (Bacillus megaterium)+SX、圆形芽胞杆菌AQ175株(Bacillus sp.strain AQ175)+SX、圆形芽胞杆菌AQ177株(Bacillus sp.strain AQ177)+SX、圆形芽胞杆菌AQ178株(Bacillussp.strain AQ178)+SX、球形芽孢杆菌 2362(Bacillus sphaericus strain 2362)+SX、球形芽孢杆菌ABTS1743株 (Bacillus sphaericus strain ABTS1743)+SX、球形芽孢杆菌血清型H5a5b 株(Bacillus sphaericus Serotype strain H5a5b)+SX、苏云金芽孢杆菌AQ52株(Bacillus thuringiensis strain AQ52)+SX、苏云金芽孢杆菌BD#32株 (Bacillusthuringiensis strain BD#32)+SX、苏云金芽孢杆菌CR-371株 (Bacillus thuringiensisstrain CR-371)+SX、苏云金芽孢杆菌鲇泽亚种 ABTS-1857株(Bacillus thuringiensissubsp.Aizawai strain ABTS-1857) +SX、苏云金芽孢杆菌鲇泽亚种AM65-52株(Bacillusthuringiensis subsp. Aizawai strain AM65-52)+SX、苏云金芽孢杆菌鲇泽亚种GC-91株(Bacillus thuringiensis subsp.Aizawai strain GC-91)+SX、苏云金芽孢杆菌鲇泽亚种血清型H-7株(Bacillus thuringiensis subsp.Aizawai Serotype strain H-7)+SX、苏云金芽孢杆菌库尔斯塔克亚种ABTS351株(Bacillus thuringiensis subsp.Kurstakistrain ABTS351)+SX、苏云金芽孢杆菌库尔斯塔克亚种BMP123株(Bacillusthuringiensis subsp.Kurstaki strain BMP123)+SX、苏云金芽孢杆菌库尔斯塔克亚种EG234株(Bacillus thuringiensis subsp.Kurstaki strain EG234)+SX、苏云金芽孢杆菌库尔斯塔克亚种EG7841株(Bacillus thuringiensis subsp.Kurstaki strain EG7841) +SX、苏云金芽孢杆菌库尔斯塔克亚种EVB113-19株(Bacillus thuringiensissubsp.Kurstaki strain EVB113-19)+SX、苏云金芽孢杆菌库尔斯塔克亚种F810株(Bacillus thuringiensis subsp.Kurstaki strain F810) +SX、苏云金芽孢杆菌库尔斯塔克亚种HD-1株(Bacillus thuringiensis subsp.Kurstaki strain HD-1)+SX、苏云金芽孢杆菌库尔斯塔克亚种PB54 株(Bacillus thuringiensis subsp.Kurstaki strainPB54)+SX、苏云金芽孢杆菌库尔斯塔克亚种SA-11株(Bacillus thuringiensissubsp.Kurstaki strain SA-11)+SX、苏云金芽孢杆菌库尔斯塔克亚种SA-12株(Bacillusthuringiensis subsp.Kurstaki strain SA-12)+SX、苏云金芽孢杆菌拟步行甲亚种NB176株(Bacillus thuringiensis subsp.Tenebriosis strain NB176)+SX、苏云金芽孢杆菌苏云金亚种MPPL002株(Bacillus thuringiensis subsp. Thuringiensis strain MPPL002)+SX、苏云金芽孢杆菌莫里逊亚种(Bacillus thuringiensis subsp.morrisoni)+SX、苏云金芽孢杆菌科尔默变种(Bacillus thuringiensis var.colmeri)+SX、苏云金芽孢杆菌达姆斯塔特变种24-91株 (Bacillus thuringiensis var.darmstadiensis strain 24-91)+SX、苏云金芽孢杆菌松蠋变种(Bacillus thuringiensis var.dendrolimus)+SX、苏云金芽孢杆菌蜡螟变种(Bacillus thuringiensis var.galleriae)+SX、苏云金芽孢杆菌以色列变种BMP144株(Bacillus thuringiensis var.israelensis strain BMP144)+SX、苏云金芽孢杆菌以色列变种血清型H-14株(Bacillus thuringiensis var.israelensisserotype strain H-14)+SX、苏云金芽孢杆菌日本变种buibui株(Bacillusthuringiensis var.japonensis strain buibui)+SX、苏云金芽孢杆菌圣地亚哥变种M-7株(Bacillus thuringiensis var.san diego strain M-7)+SX、苏云金芽孢杆菌7216变种株(Bacillus thuringiensis var.7216)+SX、苏云金芽孢杆菌埃及变种株(Bacillusthuringiensis var. aegypti)+SX、苏云金芽孢杆菌T36变种株(Bacillus thuringiensisvar.T36) +SX、球孢白僵菌ANT-03株(Beauveria bassiana strain ANT-03)+SX、球孢白僵菌ATCC74040株(Beauveria bassiana strain ATCC74040)+SX、球孢白僵菌GHA株(Beauveria bassiana strain GHA)+SX、布氏白僵菌 (Beauveria brongniartii)+SX、新型伯克氏菌A396株(Burkholderia rinojensis strain A396)+SX、活性紫色细菌PRAA4-1T株(Chromobacterium subtsugae strain PRAA4-1T)+SX、梭形小指孢霉(Dactyllelaellipsospora) +SX、Dectylaria thaumasia+SX、明尼苏达被毛孢(Hirsutellaminnesotensis) +SX、洛斯里被毛孢(Hirsutella rhossiliensis)+SX、汤氏多毛菌(Hirsutella thompsonii)+SX、大链壶菌(Lagenidium giganteum)+SX、蜡蚧轮枝菌 KV01株(Lecanicillium lecanii strain KV01)+SX、蜡蚧轮枝菌 DAOM198499株的分生孢子(Lecanicillium lecanii conidia of strain DAOM198499)+SX、蜡蚧轮枝菌DAOM216596株的分生孢子 (Lecanicillium lecanii conidia of strain DAOM216596)+SX、Lecanicillium muscarium strain Ve6+SX、绿僵菌F52株(Metarhizium anisopliaestrain F52)+SX、金龟子绿僵菌变种株(Metarhizium anisopliae var.acridum) +SX、绿僵菌BIPESCO 5/F52株(Metarhizium anisopliae var.anisopliae BIPESCO 5/F52)+SX、黄绿绿僵菌(Metarhizium flavoviride)+SX、瘤捕单顶孢菌(Monacrosporiumphymatopagum)+SX、玫烟色拟青霉 Apopka97株(Paecilomyces fumosoroseus Apopkastrain 97)+SX、淡紫色拟青霉251株(Paecilomyces lilacinus strain 251)+SX、细脚拟青霉T1株 (Paecilomyces tenuipes strain T1)+SX、日本甲虫类芽孢杆菌(Paenibacillus popilliae)+SX、巴斯德杆菌Pn1株(Pasteuria nishizawae strain Pn1)+SX、侵入巴斯德氏芽菌(Pasteuria penetrans)+SX、巴氏杆菌(Pasteuria usgae)+SX、Pesteuria thoynei+SX、嗜虫沙雷菌(Serratia entomophila)+SX、厚垣轮枝孢菌(Verticillium chlamydosporium)+SX、蜡蚧轮枝菌NCIM1312株(Verticillium lecanistrain NCIM1312)+SX、2- 氯-N-环丙基-5-{1-[2,6-二氯-4-(1,1,1,2,3,3,3-七氟丙烷-2-基) 苯基]-1H-吡唑-4-基}-N-甲基吡啶-3-甲酰胺(1771741-86-6)+SX、N-{4- 氯-3-[(1-氰基环丙基)氨基甲酰基]苯基}-1-甲基-4-(甲磺酰基)-3-(1, 1,2,2,2-五氟乙基)-1H-吡唑-3-甲酰胺(1400768-21-9)+SX、11-(4- 氯-2,6-二甲基苯基)-12-羟基-1,4-二氧杂-9-氮杂二螺[4.2.4.2]十四碳-11- 烯-10-酮(907187-07-9)+SX、3-(4'-氟-2,4-二甲基[1,1'-联苯基]-3-基) -4-羟基-8-氧杂-1-氮杂螺[4.5]癸-3-烯-2-酮(1031385-91-7)+SX、N-[3-氯 -1-(吡啶-3-基)-1H-吡唑-4-基]-2-(甲磺酰基)丙酰胺(2396747-83-2) +SX、2-异丙基-5-[(3,4,4-三氟-3-丁烯-1-基)磺酰基]-1,3,4-噻二唑 (2058052-95-0)+SX、1,4-二甲基-2-[2-(3-吡啶基)-2H-吲唑-5-基]-1, 2,4-三唑烷-3,5-二酮(2171099-09-3)+SX、环丙氟虫胺(cyproflanilide) +SX。
上述组(b)的本成分与本发明晶体的组合:
阿拉酸式苯-S-甲基(acibenzolar-S-methyl)+SX、4-十二烷基-2,6- 二甲基吗啉(aldimorph)+SX、唑嘧菌胺(ametoctradin)+SX、4-苯氧基苄基2-氨基-6-甲基烟酸酯(aminopyrifen)+SX、吲唑磺菌胺(amisulbrom) +SX、敌菌灵(anilazine)+SX、阿扎康唑(azaconazole)+SX、嘧菌酯 (azoxystrobin)+SX、碱式硫酸铜(basic copper sulfate)+SX、苯霜灵 (benalaxyl)+SX、精苯霜灵(benalaxyl-M)+SX、麦锈灵(benodanil) +SX、苯菌灵(benomyl)+SX、苯噻菌胺(benthiavalicarb)+SX、苯噻菌胺异丙酯(benthivalicarb-isopropyl)+SX、苯丙烯氟菌唑 (benzovindiflupyr)+SX、乐杀螨(binapacryl)+SX、联苯(biphenyl) +SX、联苯三唑醇(bitertanol)+SX、联苯吡菌胺(bixafen)+SX、杀稻瘟素S(blasticidin-S)+SX、波尔多液(Bordeaux mixture)+SX、啶酰菌胺(boscalid)+SX、溴菌腈(bromothalonil)+SX、糠菌唑(bromuconazole) +SX、乙嘧酚磺酸酯(bupirimate)+SX、敌菌丹(captafol)+SX、克菌丹(captan)+SX、多菌灵(carbendazim)+SX、萎锈灵(carboxin)+SX、环丙酰菌胺(carpropamid)+SX、灭螨猛(chinomethionat)+SX、壳多糖 (chitin)+SX、氯甲氧苯(chloroneb)+SX、百菌清(chlorothalonil)+SX、乙菌利(chlozolinate)+SX、colletochlorin B+SX、乙酸铜(II)(copper (II)acetate)+SX、氢氧化铜(II)(copper(II)hydroxide)+SX、碱式氯化铜(copper oxychloride)+SX、硫酸铜(II)(copper(II)sulfate)+SX、丁香菌酯(coumoxystrobin)+SX、氰霜唑(cyazofamid)+SX、环氟菌胺 (cyflufenamid)+SX、霜脲氰(cymoxanil)+SX、环丙唑醇(cyproconazole) +SX、嘧菌环胺(cyprodinil)+SX、dichlobentiazox+SX、抑菌灵 (dichlofluanid)+SX、双氯氰菌胺(diclocymet)+SX、哒菌酮(diclomezine) +SX、氯硝胺(dicloran)+SX、乙霉威(diethofencarb)+SX、苯醚甲环唑(difenoconazole)+SX、氟嘧菌胺(diflumetorim)+SX、菌核净 (dimethachlone)+SX、二甲嘧酚(dimethirimol)+SX、烯酰吗啉 (dimethomorph)+SX、醚菌胺(dimoxystrobin)+SX、烯唑醇(diniconazole) +SX、烯唑醇M(diniconazole-M)+SX、敌螨普(dinocap)+SX、亚磷酸氢二钾(dipotassium hydrogenphosphite)+SX、dipymetitrone+SX、二噻农(dithianon)+SX、十二烷基苯磺酸双乙二胺铜(II)络盐 (dodecylbenzenesulphonic acidbisethylenediaminecopper(II)salt)+SX、吗菌灵(dodemorph)+SX、多果定(dodine)+SX、敌瘟磷(edifenphos) +SX、烯肟菌酯(enoxastrobin)+SX、氟环唑(epoxiconazole)+SX、乙环唑(etaconazole)+SX、噻唑菌胺(ethaboxam)+SX、乙菌定(ethirimol) +SX、土菌灵(etridiazole)+SX、互叶白千层提取物(extract from Melaleuca alternifolia)+SX、大虎杖提取物(extract from Reynoutria sachalinensis) +SX、羽扇豆子叶提取物(extract from the cotyledons oflupine plantlets (“BLAD”))+SX、大蒜提取物(extract of Allium sativum)+SX、问荆提取物(extract of Equisetum arvense)+SX、旱金莲提取物(extract of Tropaeolum majus)+SX、噁唑菌酮(famoxadone)+SX、咪唑菌酮(fenamidone)+SX、烯肟菌胺(fenaminstrobin)+SX、氯苯嘧啶醇 (fenarimol)+SX、腈苯唑(fenbuconazole)+SX、甲呋酰胺(fenfuram) +SX、环酰菌胺(fenhexamid)+SX、氰菌胺(fenoxanil)+SX、拌种咯 (fenpiclonil)+SX、fenpicoxamid+SX、苯锈啶(fenpropidin)+SX、丁苯吗啉(fenpropimorph)+SX、胺苯吡菌酮(fenpyrazamine)+SX、三苯基乙酸锡(fentin acetate)+SX、三苯基氯化锡(fentin chloride)+SX、三苯基氢氧化锡(fentinhydroxide)+SX、福美铁(ferbam)+SX、嘧菌腙 (ferimzone)+SX、(1S)-2,2-双(4-氟苯基)-1-甲基乙基-N-[[3-(乙酰氧基)-4-甲氧基-2-吡啶基]羰基]-L-丙氨酸(florylpicoxamid)+SX、氟啶胺(fluazinam)+SX、咯菌腈(fludioxonil)+SX、氟菌螨酯 (flufenoxystrobin)+SX、fluindapyr+SX、氟吗啉(flumorph)+SX、氟吡菌胺(fluopicolide)+SX、氟吡菌酰胺(fluopyram)+SX、氟醚菌酰胺 (fluopimomide)+SX、唑呋草(fluoroimide)+SX、fluoxapiprolin+SX、氟嘧菌酯(fluoxastrobin)+SX、氟喹唑(fluquinconazole)+SX、氟硅唑 (flusilazole)+SX、磺菌胺(flusulfamide)+SX、氟噻唑菌腈(flutianil) +SX、氟酰胺(flutolanil)+SX、粉唑醇(flutriafol)+SX、氟唑菌酰胺 (fluxapyroxad)+SX、灭菌丹(folpet)+SX、三乙膦酸(fosetyl)+SX、乙膦铝(fosetyl-aluminium)+SX、麦穗宁(fuberidazole)+SX、呋霜灵 (furalaxyl)+SX、呋吡菌胺(furametpyr)+SX、双胍盐(guazatine)+SX、己唑醇(hexaconazole)+SX、噁霉灵(hymexazole)+SX、抑霉唑(imazalil)+SX、亚胺唑(imibenconazole)+SX、双胍辛胺(iminoctadine)+SX、双胍辛胺三乙酸盐(iminoctadine triacetate)+SX、inpyrfluxam+SX、碘代丙炔基丁基甲胺酸酯(iodocarb)+SX、种菌唑(ipconazole)+SX、艾分氟康挫(ipfentrifluconazole)+SX、ipflufenoquin+SX、异稻瘟净(iprobenfos) +SX、异菌脲(iprodione)+SX、异丙菌胺(iprovalicarb)+SX、异丙噻菌胺(isofetamid)+SX、isoflucypram+SX、稻瘟灵(isoprothiolane)+SX、吡唑萘菌胺(isopyrazam)+SX、异噻菌胺(isotianil)+SX、春雷霉素 (kasugamycin)+SX、醚菌酯(kresoxim-methyl)+SX、海带多糖(laminarin) +SX、栎树叶和树皮(leaves and bark ofQuercus)+SX、代森锰锌 (mancozeb)+SX、曼德斯宾(mandestrobin)+SX、双炔酰菌胺(mandipropamid)+SX、代森锰(maneb)+SX、氯氟醚菌唑 (mefentrifluconazole)+SX、嘧菌胺(mepanipyrim)+SX、灭锈胺(mepronil) +SX、消螨多(meptyldinocap)+SX、甲霜灵(metalaxyl)+SX、精甲霜灵(metalaxyl-M)+SX、叶菌唑(metconazole)+SX、磺菌威(methasulfocarb) +SX、代森联(metiram)+SX、苯氧菌胺(metominostrobin)+SX、苯菌酮(metrafenone)+SX、metyltetraprole+SX、矿物油(mineral oils)+SX、腈菌唑(myclobutanil)+SX、奈替芬(naftifine)+SX、氟苯嘧啶醇(nuarimol) +SX、辛噻酮(octhilinone)+SX、呋酰胺(ofurace)+SX、肟醚菌胺 (orysastrobin)+SX、噁霜灵(oxadixyl)+SX、氟噻唑吡乙酮(oxathiapiprolin)+SX、8-羟基喹啉铜(oxine-copper)+SX、噁喹酸(oxolinic acid)+SX、噁咪唑(oxpoconazole)+SX、噁咪唑富马酸盐(oxpoconazolefumarate)+SX、氧化萎锈灵(oxycarboxin)+SX、土霉素(oxytetracycline) +SX、稻瘟酯(pefurazoate)+SX、戊菌唑(penconazole)+SX、戊菌隆 (pencycuron)+SX、氟唑菌苯胺(penflufen)+SX、吡噻菌胺(penthiopyrad) +SX、氰烯菌酯(phenamacril)+SX、亚磷酸(phosphorous acid)+SX、四氯苯酞(phthalide)+SX、四唑吡氨酯(picarbutrazox)+SX、啶氧菌酯 (picoxystrobin)+SX、粉病灵(piperalin)+SX、多氧菌素(polyoxins) +SX、碳酸氢钾(potassium hydrogencarbonate)+SX、亚磷酸二氢钾 (potassiumdihydrogenphosphite)+SX、噻菌灵(probenazole)+SX、咪鲜胺(prochloraz)+SX、腐霉利(procymidone)+SX、丙烷脒(propamidine) +SX、霜霉威(propamocarb)+SX、丙环唑(propiconazole)+SX、丙森锌(propineb)+SX、丙氧喹啉(proquinazid)+SX、胺丙威(prothiocarb) +SX、丙硫菌唑(prothioconazole)+SX、氟唑菌酰羟胺(pydiflumetofen) +SX、吡唑醚菌酯(pyraclostrobin)+SX、唑胺菌酯(pyrametostrobin) +SX、唑菌酯(pyraoxystrobin)+SX、pyrapropoyne+SX、pyraziflumid+SX、吡菌磷(pyrazophos)+SX、吡菌苯威(pyribencarb)+SX、稗草畏 (pyributicarb)+SX、pyridachlometyl+SX、啶斑肟(pyrifenox)+SX、嘧霉胺(pyrimethanil)+SX、丁吡吗啉(pyrimorph)+SX、甲氧苯唳菌(pyriofenone)+SX、氯啶菌酯(pyrisoxazole)+SX、咯喹酮(pyroquilon) +SX、皂树科植物提取物(Quillaja extract)+SX、唑喹菌酮(quinconazole) +SX、quinofumelin+SX、苯氧喹啉(quinoxyfen)+SX、五氯硝基苯 (quintozene)+SX、藜麦皂甙(Saponins of Chenopodiumquinoa)+SX、氟唑环菌胺(sedaxane)+SX、硅噻菌胺(silthiofam)+SX、硅氟唑(simeconazole)+SX、碳酸氢钠(sodium hydrogencarbonate)+SX、螺环菌胺(spiroxamine)+SX、链霉素(streptomycin)+SX、硫(sulfur)+SX、戊唑醇(tebuconazole)+SX、特弗喹啉(tebufloquin)+SX、叶枯酞 (teclofthalam)+SX、四氯硝基苯(tecnazene)+SX、特比萘芬(terbinafine) +SX、四氟醚唑(tetraconazole)+SX、噻菌灵(thiabendazole)+SX、噻呋酰胺(thifluzamide)+SX、硫菌灵(thiophanate)+SX、甲基硫菌灵(thiophanate-methyl)+SX、福美双(thiram)+SX、百里香酚(thymol) +SX、噻酰菌胺(tiadinil)+SX、甲基立枯磷(tolclofos-methyl)+SX、唑虫酰胺(tolfenpyrad)+SX、托普威(tolprocarb)+SX、对甲抑菌灵 (tolylfluanid)+SX、三唑酮(triadimefon)+SX、三唑醇(triadimenol) +SX、咪唑嗪(triazoxide)+SX、氯啶菌酯(triclopyricarb)+SX、三环唑 (tricyclazole)+SX、十三吗啉(tridemorph)+SX、肟菌酯(trifloxystrobin) +SX、氟菌唑(triflumizole)+SX、嗪胺灵(triforine)+SX、灭菌唑 (triticonazole)+SX、有效霉素(validamycin)+SX、缬菌胺(valifenalate) +SX、乙烯菌核利(vinclozolin)+SX、黄芥末粉(yellow mustard powder)+SX、噻唑锌(zinc thiazole)+SX、代森锌(zineb)+SX、福美(ziram) +SX、苯酰菌胺(zoxamide)+SX、N′-[4-({3-[(4-氯苯基)甲基]-1,2, 4-噻二唑-5-基}氧基)-2,5-二甲基苯基]-N-乙基-N-甲基甲脒 (1202781-91-6)+SX、N′-{4-[(4,5-二氯噻唑-2-基)氧基]-2,5-二甲基苯基}-N-乙基-N-甲基甲脒(929908-57-6)+SX、N′-(2,5-二甲基-4-苯氧基苯基)-N-乙基-N-甲基甲脒(1052688-31-9)+SX、N′-[5-氯-4-(2-氟苯氧基)-2-甲基苯基)-N-乙基-N-甲基甲脒(2055589-28-9)+SX、N′-[2- 氯-4-(2-氟苯氧基)-5-甲基苯基)-N-乙基-N-甲基甲脒(2055756-21-1) +SX、N′-[4-(1-羟基-1-苯基-2,2,2-三氟乙基)-2-甲基-5-甲氧基苯基) -N-异丙基-N-甲基甲脒(2101814-55-3)+SX、N′-[5-溴-6-(1-甲基-2-丙氧基乙氧基)-2-甲基吡啶-3-基)-N-乙基-N-甲基甲脒(1817828-69-5)+SX、 4-(2-溴-4-氟苯基)-N-(2-氯-6-氟苯基)-1,3-二甲基-1H-吡唑-5-胺 (1362477-26-6)+SX、2-[6-(3-氟-4-甲氧基苯基)-5-甲基吡啶-2-基]喹唑啉(1257056-97-5)+SX、5-氟-4-亚氨基-3-甲基-1-甲苯磺酰基-3,4-二氢嘧啶-2(1H)-酮(1616664-98-2)+SX、乙基(2Z)-3-氨基-2-氰基-3- 苯基丙烯酸酯(39491-78-6)+SX、N-[(2-氯噻唑-5-基)甲基]-N-乙基-6- 甲氧基-3-硝基吡啶-2-胺(1446247-98-8)+SX、5-(4-氯苄基)-2-(氯甲基)-2-甲基-1-(1H-1,2,4-三唑-1-基甲基)环戊烷-1-醇(1394057-11-4) +SX、(1R,2S,5S)-5-(4-氯苄基)-2-(氯甲基)-2-甲基-1-(1H-1,2, 4-三唑-1-基甲基)环戊烷-1-醇(1801930-06-2)+SX、(1S,2R,5R)-5- (4-氯苄基)-2-(氯甲基)-2-甲基-1-(1H-1,2,4-三唑-1-基甲基)环戊烷-1-醇(1801930-07-3)+SX、2-(氯甲基)-5-(4-氟苄基)-2-甲基-1- (1H-1,2,4-三唑-1-基甲基)环戊烷-1-醇(1394057-13-6)+SX、(1R, 2S,5S)-2-(氯甲基)-5-(4-氟苄基)-2-甲基-1-(1H-1,2,4-三唑-1- 基甲基)环戊烷-1-醇(1801930-08-4)+SX、(1S,2R,5R)-2-(氯甲基) -5-(4-氟苄基)-2-甲基-1-(1H-1,2,4-三唑-1-基甲基)环戊烷-1-醇 (1801930-09-5)+SX、甲基3-[(4-氯苯基)甲基]-2-羟基-1-甲基-2-(1H-1, 2,4-三唑-1-基甲基)环戊烷-1-甲酸酯(1791398-02-1)+SX、1-(2,4- 二氟苯基)-2-(1H-1,2,4-三唑-1-基)-1-[1-(4-溴-2,6-二氟苯氧基) 环丙基]乙醇(2019215-86-0)+SX、1-(2,4-二氟苯基)-2-(1H-1,2, 4-三唑-1-基)-1-[1-(4-氯-2,6-二氟苯氧基)环丙基]乙醇(2019215-84-8) +SX、1-[2-(1-氯环丙基)-3-(2-氟苯基)-2-羟基丙基]-1H-咪唑-5-甲腈 (2018316-13-5)+SX、1-[2-(1-氯环丙基)-3-(2,3-二氟苯基)-2-羟基丙基]-1H-咪唑-5-甲腈(2018317-25-2)+SX、4-({6-[2-(2,4-二氟苯基)-1,1-二氟-2-羟基-3-(1H-1,2,4-三唑-1-基)丙基]吡啶-3-基}氧基) 苄腈(2046300-61-0)+SX、2-[6-(4-溴苯氧基)-2-(三氟甲基)吡啶-3- 基]-1-(1H-1,2,4-三唑-1-基)丙烷-2-醇(2082661-43-4)+SX、2-[6- (4-氯苯氧基)-2-(三氟甲基)吡啶-3-基]-1-(1H-1,2,4-三唑-1-基) 丙烷-2-醇(2082660-27-1)+SX、甲基({2-甲基-5-[1-(4-甲氧基-2-甲基苯基)-1H-吡唑-3-基]苯基}甲基)氨基甲酸酯(1605879-98-8)+SX、2- (二氟甲基)-N-[1,1,3-三甲基-2,3-二氢-1H-茚-4-基]吡啶-3-甲酰胺 (1616239-21-4)+SX、2-(二氟甲基)-N-[3-乙基-1,1-二甲基-2,3-二氢-1H-茚-4-基]吡啶-3-甲酰胺(1847460-02-9)+SX、2-(二氟甲基)-N-[3- 丙基-1,1-二甲基-2,3-二氢-1H-茚-4-基]吡啶-3-甲酰胺(1847460-05-2) +SX、(2E,3Z)-5-{[1-(4-氯苯基)-1H-吡唑-3-基]氧基}-2-(甲氧基亚氨基)-N,3-二甲基戊-3-烯酰胺(1445331-27-0)+SX、(2E,3Z)-5-{[1- (2,4-二氯苯基)-1H-吡唑-3-基]氧基}-2-(甲氧基亚氨基)-N,3-二甲基戊-3-烯酰胺(1445331-54-3)+SX、5-氯-4-({2-[6-(4-氯苯氧基)吡啶-3-基]乙基}氨基)-6-甲基嘧啶(1605340-92-8)+SX、N-(1-苄基-1,3- 二甲基丁基)-8-氟喹啉-3-甲酰胺(2132414-04-9)+SX、N-(1-苄基-3, 3,3-三氟-1-甲基丙基)-8-氟喹啉-3-甲酰胺(2132414-00-5)+SX、4,4- 二甲基-2-({4-[5-(三氟甲基)-1,2,4-噁二唑-3-基]苯基}甲基)异噁唑烷-3-酮(2098918-25-1)+SX、5,5-二甲基-2-({4-[5-(三氟甲基)-1,2, 4-噁二唑-3-基]苯基}甲基)异噁唑烷-3-酮(2098918-26-2)+SX、放射性农杆菌K1026株(Agrobacterium radiobactor strain K1026)+SX、放射性农杆菌K84株(Agrobacteriumradiobactor strain K84)+SX、解淀粉芽孢杆菌(Aveo(商标)EZ Nematicide)+SX、解淀粉芽孢杆菌AT332株 (Bacillus amyloliquefaciens strain AT332)+SX、解淀粉芽孢杆菌B3株 (Bacillus amyloliquefaciens strain B3)+SX、解淀粉芽孢杆菌D747株 (Bacillusamyloliquefaciens strain D747)+SX、解淀粉芽孢杆菌DB101 株(Bacillusamyloliquefaciens strain DB101)+SX、解淀粉芽孢杆菌DB102 株(Bacillusamyloliquefaciens strain DB102)+SX、解淀粉芽孢杆菌GB03 株(Bacillusamyloliquefaciens strain GB03)+SX、解淀粉芽孢杆菌FZB24 株(Bacillusamyloliquefaciens strain FZB24)+SX、解淀粉芽孢杆菌FZB42 株(Bacillusamyloliquefaciens strain FZB42)+SX、解淀粉芽孢杆菌IN937a 株(Bacillusamyloliquefaciens strain IN937a)+SX、解淀粉芽孢杆菌MBI600 株(Bacillusamyloliquefaciens strain MBI600)+SX、解淀粉芽孢杆菌 QST713株(Bacillusamyloliquefaciens strain QST713)+SX、解淀粉芽孢杆菌分离株B246株(Bacillusamyloliquefaciens isolate strain B246)+SX、解淀粉芽孢杆菌F727株(Bacillusamyloliquefaciens strain F727)+SX、解淀粉芽孢杆菌植物亚种D747株(Bacillusamyloliquefaciens subsp. plantarum strain D747)+SX、地衣芽孢杆菌HB-2株(Bacillus licheniformis strain HB-2)+SX、地衣芽孢杆菌SB3086株(Bacilluslicheniformis strain SB3086)+SX、短小芽孢杆菌AQ717株(Bacillus pumilus strainAQ717) +SX、短小芽孢杆菌BUF-33株(Bacillus pumilus strain BUF-33)+SX、短小芽孢杆菌GB34株(Bacillus pumilus strain GB34)+SX、短小芽孢杆菌QST2808株(Bacilluspumilus strain QST2808)+SX、单纯杆菌CGF2856 株(Bacillus simplexstrain CGF2856)+SX、枯草芽孢杆菌AQ153株 (Bacillus subtilis strain AQ153)+SX、枯草芽孢杆菌AQ743株(Bacillus subtilis strain AQ743)+SX、枯草芽孢杆菌BU1814株(Bacillus subtilis strain BU1814)+SX、枯草芽孢杆菌D747株(Bacillus subtilisstrain D747)+SX、枯草芽孢杆菌DB101株(Bacillus subtilis strain DB101)+SX、枯草芽孢杆菌FZB24株(Bacillus subtilis strain FZB24)+SX、枯草芽孢杆菌GB03 株(Bacillussubtilis strain GB03)+SX、枯草芽孢杆菌HAI0404株(Bacillus subtilis strainHAI0404)+SX、枯草芽孢杆菌IAB/BS03株(Bacillus subtilis strain IAB/BS03)+SX、枯草芽孢杆菌MBI600株(Bacillus subtilis strain MBI600)+SX、枯草芽孢杆菌QST30002/AQ30002株(Bacillus subtilis strain QST30002/AQ30002)+SX、枯草芽孢杆菌QST30004/AQ30004株(Bacillus subtilis strain QST30004/AQ30004)+SX、枯草芽孢杆菌QST713株(Bacillus subtilis strain QST713)+SX、枯草芽孢杆菌QST714株(Bacillus subtilisstrain QST714)+SX、解淀粉枯草芽孢杆菌变种FZB24株(Bacillus subtilisvar.Amyloliquefaciens strain FZB24)+SX、枯草芽孢杆菌Y1336株(Bacillus subtilisstrain Y1336)+SX、洋葱伯克霍尔德菌(Burkholderia cepacia)+SX、洋葱伯克霍尔德菌威斯康星州型J82株(Burkholderia cepacia type Wisconsin strain J82)+SX、洋葱伯克霍尔德菌威斯康星州型M54株 (Burkholderia cepacia type Wisconsin strain M54)+SX、橄榄假丝酵母O 株(Candida oleophila strain O)+SX、水解假丝酵母(Candidasaitoana) +SX、角毛壳菌(Chaetomium cupreum)+SX、粉红螺旋聚孢霉(Clonostachysrosea)+SX、盾壳霉CGMCC8325株(Coniothyrium minitans strain CGMCC8325)+SX、盾壳霉CON/M/91-8株(Coniothyrium minitans strain CON/M/91-8)+SX、浅白隐球菌(cryptococcus albidus)+SX、胡萝卜软腐欧文氏菌CGE234M403株(Erwinia carotovorasubsp.carotovora strain CGE234M403)+SX、尖孢镰刀菌Fo47株(Fusarium oxysporumstrain Fo47) +SX、链孢粘帚霉J1446株(Gliocladium catenulatum strain J1446)+SX、多粘类芽孢杆菌AC-1株(Paenibacillus polymyxa strain AC-1)+SX、多粘类芽孢杆菌BS-0105株(Paenibacillus polymyxa strain BS-0105)+SX、成团泛菌E325株(Pantoeaagglomerans strain E325)+SX、大伏革菌 VRA1992株(Phlebiopsis gigantea strainVRA1992)+SX、致金色假单胞菌TX-1株(Pseudomonas aureofaciens strain TX-1)+SX、绿针假单胞菌 63-28株(Pseudomonas chlororaphis strain 63-28)+SX、绿针假单胞菌AFS009株(Pseudomonas chlororaphis strain AFS009)+SX、绿针假单胞菌MA342株(Pseudomonas chlororaphis strain MA342)+SX、荧光假单胞菌1629RS株(Pseudomonasfluorescens strain 1629RS)+SX、荧光假单胞菌A506株(Pseudomonas fluorescensstrain A506)+SX、荧光假单胞菌 CL145A株(Pseudomonas fluorescens strain CL145A)+SX、荧光假单胞菌G7090株(Pseudomonas fluorescens strain G7090)+SX、假单胞菌 CAB-02株(Pseudomonas sp.strain CAB-02)+SX、丁香假单胞菌742RS 株(Pseudomonassyringae strain 742RS)+SX、丁香假单胞菌MA-4株 (Pseudomonas syringae strain MA-4)+SX、Pseudozyma flocculosa PF-A22UL株(Pseudozyma flocculosa strain PF-A22UL)+SX、罗氏假单胞菌HAI-0804株(Pseudomonas rhodesiae strain HAI-0804)+SX、寡雄腐霉DV74株(Pythium oligandrum strain DV74)+SX、寡雄腐霉M1株 (Pythium oligandrumstrain M1)+SX、灰绿链霉菌K61株(Streptomyces griseoviridis strain K61)+SX、利迪链霉菌WYCD108US株(Streptomyces lydicus strain WYCD108US)+SX、利迪链霉菌WYEC108株(Streptomyces lydicus strain WYEC108)+SX、黄蓝状菌SAY-Y-94-01株(Talaromycesflavus strain SAY-Y-94-01)+SX、黄蓝状菌V117b株(Talaromyces flavus strainV117b)+SX、棘孢木霉ICC012株(Trichoderma asperellum ICC012) +SX、棘孢木霉SKT-1株(Trichoderma asperellum SKT-1)+SX、棘孢木霉T25株(Trichoderma asperellum strainT25)+SX、棘孢木霉T34株 (Trichoderma asperellum strain T34)+SX、棘孢木霉TV1株(Trichoderma asperellum strain TV1)+SX、深绿木霉CNCM1-1237株(Trichodermaatroviride strain CNCM1-1237)+SX、深绿木霉LC52株(Trichoderma atroviride strainLC52)+SX、深绿木霉IMI 206040株(Trichoderma atroviride strain IMI 206040)+SX、深绿木霉SC1株(Trichoderma atroviride strain SC1)+SX、深绿木霉SKT-1株(Trichodermaatroviride strain SKT-1) +SX、深绿木霉T11株(Trichoderma atroviride strain T11)+SX、盖姆斯木霉菌ICC080株(Trichoderma gamsiiI strain CC080)+SX、哈茨木霉21 株(Trichoderma harzianum strain 21)+SX、哈茨木霉DB104株(Trichoderma harzianumstrain DB104)+SX、哈茨木霉DSM14944株(Trichoderma harzianum strain DSM 14944)+SX、哈茨木霉ESALQ-1303株(Trichoderma harzianum strain ESALQ-1303)+SX、哈茨木霉ESALQ-1306株 (Trichoderma harzianum strain ESALQ-1306)+SX、哈茨木霉IIHR-Th-2株(Trichoderma harzianum strain IIHR-Th-2)+SX、哈茨木霉ITEM908 株(Trichodermaharzianum strain ITEM908)+SX、哈茨木霉kd株 (Trichoderma harzianum strain kd)+SX、哈茨木霉MO1株(Trichoderma harzianum strain MO1)+SX、哈茨木霉SF株(Trichoderma harzianum strain SF)+SX、哈茨木霉T22株(Trichoderma harzianumstrain T22)+SX、哈茨木霉T39株(Trichoderma harzianum strain T39)+SX、哈茨木霉T78株(Trichoderma harzianum strain T78)+SX、哈茨木霉TH35株(Trichoderma harzianumstrain TH35)+SX、多孢木霉IMI206039株(Trichoderma polysporum strain IMI 206039)+SX、子座木霉(trichoderma stromaticum) +SX、绿色木霉G-41株(Trichoderma virensstrain G-41)+SX、绿色木霉 GL-21株(Trichoderma virens strain GL-21)+SX、绿色木霉菌(Trichoderma viride)+SX、争论贪噬菌CGF4526株(Variovorax paradoxus strainCGF4526)+SX、超敏蛋白(Harpin protein)+SX、氟苯醚酰胺(flubeneteram) +SX、N-乙酰基-2-(乙磺酰基)-N-[2-(甲氧基羰基)-4-(三氟甲氧基) 苯基]-4-(三氟甲基)苯甲酰胺(2043675-28-9)+SX、(2S,3S)-3-(2- 甲基苯基)丁烷-2-基N-[(3-乙酰氧基-4-甲氧基吡啶-2-基)羰基]-L-丙氨酸酯(2376210-00-1)+SX、(2S,3S)-3-(4-氟-2-甲基苯基)丁烷-2-基 N-[(3-乙酰氧基-4-甲氧基吡啶-2-基)羰基]-L-丙氨酸酯+SX、(2S,3S) -3-(4-甲氧基-2-甲基苯基)丁烷-2-基N-[(3-乙酰氧基-4-甲氧基吡啶-2- 基)羰基]-L-丙氨酸酯+SX、(2S,3S)-3-(2,4-二甲基苯基)丁烷-2- 基N-[(3-乙酰氧基-4-甲氧基吡啶-2-基)羰基]-L-丙氨酸酯(2376209-13-9) +SX、(2S,3S)-3-(2-甲基苯基)丁烷-2-基N-({3-[(2-甲基丙酰基) 氧基]-4-甲氧基吡啶-2-基}羰基)-L-丙氨酸酯(2376210-02-3)+SX、(2S, 3S)-3-(4-氟-2-甲基苯基)丁烷-2-基N-({3-[(2-甲基丙酰基)氧基]-4- 甲氧基吡啶-2-基}羰基)-L-丙氨酸酯+SX、(2S,3S)-3-(4-甲氧基-2-甲基苯基)丁烷-2-基N-({3-[(2-甲基丙酰基)氧基]-4-甲氧基吡啶-2-基} 羰基)-L-丙氨酸酯(2376209-40-2)+SX、(2S,3S)-3-(2,4-二甲基苯基)丁烷-2-基N-({3-[(2-甲基丙酰基)氧基]-4-甲氧基吡啶-2-基}羰基) -L-丙氨酸酯(2376209-15-1)+SX、N′-(2-氯-4-苯氧基-5-甲基苯基)-N- 乙基-N-甲基甲脒(2062599-39-5)+SX、(2S,3S)-3-(2-甲基苯基)丁烷-2-基N-[(3-羟基-4-甲氧基吡啶-2-基)羰基]-L-丙氨酸酯+SX、(2S,3S) -3-(4-氟-2-甲基苯基)丁烷-2-基N-[(3-羟基-4-甲氧基吡啶-2-基)羰基]-L- 丙氨酸酯+SX、(2S,3S)-3-(4-甲氧基-2-甲基苯基)丁烷-2-基N-[(3- 羟基-4-甲氧基吡啶-2-基)羰基]-L-丙氨酸酯+SX、(2S,3S)-3-(2,4- 二甲基苯基)丁烷-2-基N-[(3-羟基-4-甲氧基吡啶-2-基)羰基]-L-丙氨酸酯+SX、(2S,3S)-3-(4-氟-2-甲基苯基)-4-甲基戊烷-2-基N-[(3-乙酰氧基-4-甲氧基吡啶-2-基)羰基]-L-丙氨酸酯+SX、(2S,3S)-3-(2-氟-4- 甲基苯基)-4-甲基戊烷-2-基N-[(3-乙酰氧基-4-甲氧基吡啶-2-基)羰基]-L-丙氨酸酯+SX、(2S,3S)-3-(2,4-二氟苯基)-4-甲基戊烷-2-基N-[(3- 乙酰氧基-4-甲氧基吡啶-2-基)羰基]-L-丙氨酸酯+SX、(2S,3S)-3-(2, 4-二甲基苯基)-4-甲基戊烷-2-基N-[(3-乙酰氧基-4-甲氧基吡啶-2-基)羰基]-L-丙氨酸酯+SX、(2S,3S)-3-(4-氟-2-甲氧基苯基)-4-甲基戊烷-2- 基N-[(3-乙酰氧基-4-甲氧基吡啶-2-基)羰基]-L-丙氨酸酯+SX、(2S,3S) -3-(4-氟-2-甲基苯基)-4-甲基戊烷-2-基N-{[3-(乙酰氧基甲氧基)-4-甲氧基吡啶-2-基]羰基}-L-丙氨酸酯+SX、(2S,3S)-3-(2-氟-4-甲基苯基) -4-甲基戊烷-2-基N-{[3-(乙酰氧基甲氧基)-4-甲氧基吡啶-2-基]羰基}-L- 丙氨酸酯+SX、(2S,3S)-3-(2,4-二氟苯基)-4-甲基戊烷-2-基N-{[3- (乙酰氧基甲氧基)-4-甲氧基吡啶-2-基]羰基}-L-丙氨酸酯+SX、(2S,3S) -3-(2,4-二甲基苯基)-4-甲基戊烷-2-基N-{[3-(乙酰氧基甲氧基)-4- 甲氧基吡啶-2-基]羰基}-L-丙氨酸酯+SX、(2S,3S)-3-(4-氟-2-甲氧基苯基)-4-甲基戊烷-2-基N-{[3-(乙酰氧基甲氧基)-4-甲氧基吡啶-2-基]羰基}-L-丙氨酸酯+SX、(2S,3S)-3-(4-氟-2-甲基苯基)-4-甲基戊烷-2- 基N-({3-[(异丁酰氧基)甲氧基]-4-甲氧基吡啶-2-基}羰基)-L-丙氨酸酯+SX、(2S,3S)-3-(2-氟-4-甲基苯基)-4-甲基戊烷-2-基N-({3-[(异丁酰氧基)甲氧基]-4-甲氧基吡啶-2-基}羰基)-L-丙氨酸酯+SX、(2S,3S) -3-(2,4-二氟苯基)-4-甲基戊烷-2-基N-({3-[(异丁酰氧基)甲氧基]-4- 甲氧基吡啶-2-基}羰基)-L-丙氨酸酯+SX、(2S,3S)-3-(2,4-二甲基苯基)-4-甲基戊烷-2-基N-({3-[(异丁酰氧基)甲氧基]-4-甲氧基吡啶-2- 基}羰基)-L-丙氨酸酯+SX、(2S,3S)-3-(4-氟-2-甲氧基苯基)-4-甲基戊烷-2-基N-({3-[(异丁酰氧基)甲氧基]-4-甲氧基吡啶-2-基}羰基)-L- 丙氨酸酯+SX、(2S,3S)-3-(4-氟-2-甲基苯基)-4-甲基戊烷-2-基N-[(3- 羟基-4-甲氧基吡啶-2-基)羰基]-L-丙氨酸酯+SX、(2S,3S)-3-(2-氟-4- 甲基苯基)-4-甲基戊烷-2-基N-[(3-羟基-4-甲氧基吡啶-2-基)羰基]-L- 丙氨酸酯+SX、(2S,3S)-3-(2,4-二氟苯基)-4-甲基戊烷-2-基N-[(3-羟基-4-甲氧基吡啶-2-基)羰基]-L-丙氨酸酯+SX、(2S,3S)-3-(2,4- 二甲基苯基)-4-甲基戊烷-2-基N-[(3-羟基-4-甲氧基吡啶-2-基)羰基]-L- 丙氨酸酯+SX、(2S,3S)-3-(4-氟-2-甲氧基苯基)-4-甲基戊烷-2-基N-[(3- 羟基-4-甲氧基吡啶-2-基)羰基]-L-丙氨酸酯+SX。
上述组(c)的本成分与本发明晶体的组合:
1-甲基环丙烯(1-methylcyclopropene)+SX、1,3-二苯基脲(1,3-diphenylurea)+SX、2,3,5-三碘苯甲酸(2,3,5-triiodobenzoic acid) +SX、IAA((1H-吲哚-3-基)乙酸((1H-indol-3-yl)acetic acid))+SX、 IBA(4-(1H-吲哚-3-基)丁酸((4-(1H-indol-3-yl)butyric acid))+SX、 MCPA(2-(4-氯-2-甲基苯氧基)乙酸(2-(4-chloro-2-methylphenoxy) acetic acid))+SX、MCPB(4-(4-氯-2-甲基苯氧基)丁酸(4- (4-chloro-2-methylphenoxy)butyric acid))+SX、4-CPA(4-氯苯氧基乙酸(4-(4-chlorophenoxyacetic acid))+SX、5-氨基乙酰丙酸盐酸盐 (5-aminolevulinic acidhydrochloride)+SX、6-苄基氨基嘌呤 (6-benzylaminopurine)+SX、脱落酸(abscisicacid)+SX、AVG(氨基乙氧基乙烯基甘氨酸(aminoethoxyvinylglycine))+SX、嘧啶醇(ancymidol) +SX、地乐胺(butralin)+SX、碳酸钙(calcium carbonate)+SX、氯化钙(calcium chloride)+SX、甲酸钙(calcium formate)+SX、过氧化钙(calcium peroxide)+SX、石硫合剂(calcium polysulfide)+SX、硫酸钙(calcium sulfate)+SX、矮壮素(chlormequat-chloride)+SX、氯苯胺灵(chlorpropham) +SX、氯化胆碱(cholinechloride)+SX、调果酸(cloprop)+SX、氨基氰(cyanamide)+SX、环丙酸酰胺(cyclanilide)+SX、丁酰肼(daminozide) +SX、癸烷-1-醇(decan-1-ol)+SX、2,4-滴丙酸(dichlorprop)+SX、呋状素(dikegulac)+SX、噻节因(dimethipin)+SX、敌草快(diquat)+SX、乙烯利(ethephon)+SX、吲熟酯(ethychlozate)+SX、氟节胺(flumetralin) +SX、调嘧醇(flurprimidol)+SX、吡效隆(forchlorfenuron)+SX、芒柄花黄素(formononetin)+SX、赤霉素A(Gibberellin A)+SX、赤霉素 A3(Gibberellin A3)+SX、抗倒胺(inabenfide)+SX、玻璃酸酶(Kinetin) +SX、脂质几丁寡糖SP104(lipochitooligosaccharide SP104)+SX、马来酸酰肼(maleic hydrazide)+SX、氟磺酰草胺(mefluidide)+SX、缩节胺 (mepiquat-chloride)+SX、氧化型谷胱甘肽(oxidized glutathione)+SX、多效唑(pacrobutrazol)+SX、二甲戊灵(pendimethalin)+SX、调环酸钙 (prohexandione-calcium)+SX、茉莉酸丙酯(prohydrojasmon)+SX、吡草醚(pyraflufen-ethyl)+SX、杀雄啉(sintofen)+SX、1-萘乙酸钠 (sodium1-naphthaleneacetate)+SX、氰酸钠(sodium cyanate)+SX、链霉素(streptmycin)+SX、噻苯隆(thidiazuron)+SX、抑芽唑(triapenthenol) +SX、脱叶磷(Tribufos)+SX、抗倒酯(trinexapac-ethyl)+SX、烯效唑 -P(uniconazole-P)+SX、2-(萘-1-基)乙酰胺(2-(naphthalene-1-yl) acetamide)+SX、[4-氧代-4-(2-苯基乙基)氨基]丁酸+SX、5-(三氟甲基)苯并[b]噻吩-2-甲酸甲酯+SX、3-[(6-氯-4-苯基喹唑啉-2-基)氨基]-1- 丙醇+SX、幼套近明球囊霉(Claroideoglomus etunicatum)+SX、近明球囊霉(Claroideoglomus claroideum)+SX、接种摩西管柄囊霉(Funneliformis mosseae)+SX、珍珠巨孢囊霉(Gigaspora margarita)+SX、玫瑰红巨孢囊霉(Gigaspora rosea)+SX、聚丛球囊霉(Glomus aggregatum)+SX、沙漠球囊霉(Glomus deserticola)+SX、单孢球囊霉(Glomus monosporum) +SX、巴西类球囊霉(Paraglomus brasillianum)+SX、明球囊霉(Rhizophagus clarus)+SX、根内根孢囊霉RTI-801(Rhizophagus intraradices RTI-801)+SX、丛枝菌根真菌DAOM 197198(Rhizophagus irregularis DAOM 197198)+SX、茎瘤固氮根瘤菌(Azorhizobium caulinodans)+SX、亚马孙固氮螺菌(Azospirillum amazonense)+SX、巴西固氮螺菌XOH (Azospirillum brasilense XOH)+SX、巴西固氮螺菌Ab-V5(Azospirillum brasilense Ab-V5)+SX、巴西固氮螺菌Ab-V6(Azospirillum brasilenseAb-V6)+SX、Azospirillum caulinodans+SX、卤虫固氮螺菌(Azospirillumhalopraeferens)+SX、伊拉克固氮螺菌(Azospirillum irakense)+SX、产脂固氮螺菌(Azospirillum lipoferum)+SX、埃氏慢生根瘤菌SEMIA 587 (Bradyrhizobium elkaniiSEMIA 587)+SX、埃氏慢生根瘤菌SEMIA 5019 (Bradyrhizobium elkanii SEMIA5019)+SX、大豆慢生根瘤菌TA-11 (Bradyrhizobium japonicum TA-11)+SX、大豆慢生根瘤菌USDA110(Bradyrhizobium japonicum USDA110)+SX、辽宁慢生根瘤菌 (Bradyrhizobiumliaoningense)+SX、羽扇豆根瘤菌(Bradyrhizobium lupini)+SX、食酸戴尔福特菌RAY209(Delftia acidovorans RAY209)+SX、鹰嘴豆中慢生根瘤菌(Mesorhizobium ciceri)+SX、中慢生华癸根瘤菌 (Mesorhizobium huakii)+SX、百脉根根瘤菌(Rhizobium loti)+SX、菜豆根瘤菌(Rhizobium etli)+SX、山羊豆根瘤菌(Rhizobium galegae)+SX、豌豆根瘤菌菜豆生物变种(Rhizobium leguminosarum bv.phaseoli)+SX、豌豆根瘤菌三叶草生物变种(Rhizobium leguminosarum bv.trifolii)+SX、豌豆根瘤菌蚕豆生物变种(Rhizobiumleguminosarum bv.viciae)+SX、三叶草根瘤菌(Rhizobium trifolii)+SX、热带根瘤菌(Rhizobium tropici) +SX、费氏中华根瘤菌(Sinorhizobium fredii)+SX、苜蓿中华根瘤菌 (Sinorhizobium meliloti)+SX、西葫芦黄花叶病毒弱毒株(Zucchini Yellow MosaikVirus weak strain)+SX。
上述组(d)的本成分与本发明晶体的组合:
蒽醌(anthraquinone)+SX、避蚊胺(deet)+SX、埃卡瑞丁(icaridin) +SX。
本发明晶体与本成分的比没有特别限定,然而以重量比(本发明晶体:本成分)计可以举出1000:1~1:1000、500:1~1:500、100:1~1: 100、50:1、20:1、10:1、9:1、8:1、7:1、6:1、5:1、4:1、3: 1、2:1、1:1、1:2、1:3、1:4、1:5、1:6、1:7、1:8、1:9、1: 10、1:20、1:50等。
本发明晶体可以与化学肥料(硫酸铵、磷酸铵、硝酸胺、尿素、氯化铵等)混用或并用。
本发明晶体或本发明组合物能够防除真菌(fungi)、卵菌(Oomycete)、植物黏菌(Phytomyxea)、细菌(bacteria)等植物病原性微生物所引起的植物病害。作为真菌(fungi),例如可以举出子嚢菌门(Ascomycota)、担子菌门(Basidiomycota)、芽枝霉门(Blasto cladiomycota)、壶菌门 (Chytridiomycota)、毛霉亚门(Mucoromycota)及油壶菌门 (Olpidiomycota)。作为植物病害,可以举出以下的例子。括号内表示引起该病害的植物病原性微生物的学名。
稻子的病害:瘟病(稻瘟病菌(Pyricularia oryzae))、胡麻叶枯病(宫部旋孢腔菌(Cochliobolus miyabeanus))、纹枯病(纹枯病菌(Rhizoctonia solani))、恶苗病(藤仓赤霉(Gibberella fujikuroi))、黄化萎缩病(大孢指疫霉(Sclerophthora macrospora))、拟稻瘟病及穗枯病(黑附球菌 (Epicoccum nigrum))、苗立枯病(绿色木霉(Trichodermaviride)、米根霉(Rhizopus oryzae));
小麦的病害:白粉病(布氏白粉菌(Blumeria graminis))、赤霉病(禾谷镰刀菌(Fusarium graminearum)、燕麦镰刀菌(Fusarium avenaceum)、黄色镰刀菌(Fusariumculmorum)、雪霉微座孢(Microdochium nivale))、黄锈病(条锈菌(Pucciniastriiformis))、黑锈病(杆锈菌(Puccinia graminis))、赤锈病(隐匿柄锈菌(Pucciniarecondita))、红色雪腐病(雪霉微座孢(Microdochium nivale)、雪霉镰孢菌(Microdochium majus))、雪腐小粒菌核病(肉孢核瑚菌(Typhula incarnata)、雪腐病核瑚菌(Typhula ishikariensis))、散黑穗病(小麦散黑粉病菌(Ustilago tritici))、腥黑穗病 (网腥黑穗病菌(Tilletia caries)、矮腥黑粉菌(Tilletia controversa))、眼斑病(小麦基腐病菌(Pseudocercosporella herpotrichoides))、叶枯病(小麦壳针孢(Septoriatritici))、颖枯病(颖枯壳多孢(Stagonospora nodorum))、黄斑病(偃麦草核腔菌(Pyrenophora tritici-repentis))、由丝核菌属菌引起的苗立枯病(立枯丝核菌(Rhizoctonia solani))、立枯病(全蚀病菌(Gaeumannomyces graminis))、瘟病(Pyricularia graminis-tritici);
大麦的病害:白粉病(布氏白粉菌(Blumeria graminis))、赤霉病(禾谷镰刀菌(Fusarium graminearum)、燕麦镰刀菌(Fusarium avenaceum)、黄色镰刀菌(Fusariumculmorum)、雪霉微座孢(Fusarium culmorum))、黄锈病(条锈菌(Pucciniastriiformis))、黑锈病(杆锈菌(Puccinia graminis))、条锈病(大麦柄锈菌(Pucciniahordei))、散黑粉病(散黑粉菌(Ustilago nuda))、云纹病(大麦云纹病菌(Rhynchosporiumsecalis))、网斑病(圆核腔菌(Pyrenophora teres))、斑枯病(平脐蠕孢菌(Cochliobolussativus))、叶条纹病(麦类核腔菌(Pyrenophora graminea))、柱隔孢叶斑病(柱隔孢叶斑病菌(Ramularia collo-cygni))、由丝核菌属菌引起的苗立枯病(立枯丝核菌(Rhizoctonia solani));
玉米的病害:锈病(高粱柄锈菌(Puccinia sorghi))、南方锈病(多堆柄锈菌(Puccinia polysora))、大斑病(杂虫子囊菌(Setosphaeria turcica))、热带型锈病(玉米壳锈菌(Physopella zeae))、胡麻叶枯病(异旋孢腔菌(Cochliobolus heterostrophus))、炭疽病(禾生毛盘孢 (Colletotrichum graminicola))、灰色叶斑病(玉米灰斑病菌(Cercospora zeae-maydis))、褐斑病(玉蜀黍球梗孢(Kabatiella zeae))、暗球腔菌叶斑病(Phaeosphaeria maydis)、二孢腐病(玉米狭壳柱孢(Stenocarpella maydis)、大孢狭壳柱孢(Stenocarpella macrospora))、茎腐病(禾谷镰刀菌(Fusarium graminearum)、轮枝镰孢菌(Fusarium verticilioides)、禾生毛盘孢(Colletotrichum graminicola))、黑穗病(玉米黑穗菌(Ustilago maydis))、茎腐病(玉蜀黍节壶菌(Physoderma maydis));
棉花的病害:炭疽病(棉花炭疽病菌(Colletotrichum gossypii))、白霉病(白斑柱隔孢(Ramularia areola))、黑斑病(大孢链格孢(Alternaria macrospora)、棉链格孢(Alternaria gossypii))、根黑腐病(根黑腐病菌 (Thielaviopsis basicola));
咖啡的病害:锈病(咖啡锈菌(Hemileia vastatrix))、叶斑病(咖啡尾孢(Cercospora coffeicola));
油菜的病害:菌核病(核盘菌(Sclerotinia sclerotiorum))、黑斑病(甘蓝黑斑病链格孢(Alternaria brassicae))、根腐病(黑胫病菌(Phoma lingam))、淡叶斑病(油菜叶斑病菌(Pyrenopeziza brassicae));
甘蔗的病害:锈病(黑顶柄锈菌(Puccinia melanocephela)、黄锈病菌(Pucciniakuehnii))、黑穗病(甘蔗黑穗病菌(Ustilago scitaminea));
向日葵的病害:锈病(向日葵柄锈菌(Puccinia helianthi))、霜霉病 (向日葵霜霉病菌(Plasmopara halstedii));
柑橘类的病害:黑变病(柑橘间座壳菌(Diaporthe citri))、疮痂病(柑橘疮痂病菌(Elsinoe fawcetti))、青霉腐烂病(指状青霉(Penicillium digitatum))、青霉病(柑橘青霉菌(Penicillium italicum))、疫病(寄生疫霉(Phytophthora parasitica)、柑橘褐腐疫霉(Phytophthora citrophthora))、曲霉病(黑曲霉(Aspergillus niger));
苹果的病害:花腐病(苹果链核盘菌(Monilinia mali))、溃疡病(苹果黑腐皮壳菌(Valsa ceratosperma))、白粉病(白叉丝单囊壳(Podosphaera leucotricha))、链格孢叶斑病(苹果病变型链格孢(Alternaria alternata apple pathotype))、黑星病(苹果黑星菌(Venturia inaequalis))、炭疽病(苹果炭疽病菌(Glomerella cingulata)、多犯性植物炭疽病菌(Colletotrichum acutatum))、褐斑病(苹果褐斑病菌(Diplocarpon mali))、环腐病(贝伦格葡萄座腔菌(Botryosphaeria berengeriana))、疫病(仙人掌疫霉(Phytophtora cactorum))、赤星病(桧胶锈菌(Gymnosporangium juniperi-virginianae)、垂丝海棠锈病菌(Gymnosporangium yamadae));
梨的病害:黑星病(日本梨黑星菌(Venturia nashicola)、梨黑星菌 (Venturiapirina))、黑斑病(日本梨病变型链格孢(Alternaria alternata Japanese pearpathotype))、赤星病梨胶锈菌(Gymnosporangium haraeanum));
桃的病害:灰星病((桃褐腐菌(Monilinia fructicola))、黑星病(嗜果枝孢菌(Cladosporium carpophilum))、褐纹病(Phomopsis rot)(拟茎点霉(Phomopsis sp.))、缩叶病(桃缩叶病菌(Taphrina deformans));
葡萄的病害:黑痘病(痂囊腔菌(Elsinoe ampelina))、晚腐病(苹果炭疽病菌(Glomerella cingulata)、多犯性植物炭疽病菌(Colletotrichum acutatum))、白粉病(葡萄白粉病菌(Uncinula necator))、锈病(葡萄层锈菌(Phakopsora ampelopsidis))、黑腐病(葡萄球座菌(Guignardia bidwellii))、霜霉病(葡萄生轴霜霉(Plasmoparaviticola));
柿的病害:炭疽病(柿盘孢子菌(Gloeosporium kaki)、多犯性植物炭疽病菌(Colletotrichum acutatum))、落叶病(柿角斑病菌(Cercospora kaki)、柿叶球腔菌(Mycosphaerella nawae));
无花果的病害:锈病(西田层锈菌(Phakopsora nishidana));
葫芦类的病害:炭疽病(黄瓜炭疽病菌(Colletotrichum lagenarium))、白粉病(黄瓜白粉病菌(Sphaerotheca fuliginea))、蔓枯病(蔓枯病菌(Didymella bryoniae))、褐斑病(多主棒孢霉(Corynespora cassiicola))、枯萎病((尖孢镰刀菌(Fusariumoxysporum))、霜霉病(黄瓜霜霉病菌 (Pseudoperonospora cubensis))、疫病(辣椒疫霉(Phytophthora capsici))、苗立枯病(腐霉菌(Pythium sp.));
番茄的病害:环腐病(索兰氏链格孢(Alternaria solani))、叶霉病(黄枝孢霉(Cladosporium fulvum))、煤霉病(Pseudocercospora fuligena))、疫病(致病疫霉(Phytophthora infestans))、白粉病(鞑靼内丝白粉菌 (Leveillula taurica));
茄子的病害:褐纹病(褐纹拟茎点霉(Phomopsis vexans))、白粉病 (二孢白粉菌(Erysiphe cichoracearum));
十字花科蔬菜的病害:黑斑病(日本链格孢(Alternaria japonica))、白斑病(白菜白斑菌(Cercosporella brassicae))、根肿病(甘蓝根肿菌 (Plasmodiophorabrassicae))、霜霉病(寄生霜霉(Peronospora parasitica))、白锈病(白锈菌(Albugocandida));
葱的病害:锈病(葱柄锈菌(Puccinia allii));
大豆的病害:紫斑病(菊池尾孢(Cercospora kikuchii))、黑痘病(大豆黑痘病菌(Elsinoe glycines))、黑点病(菜豆间座壳大豆变种(Diaporthe phaseolorumvar.sojae))、锈病(豆薯层锈菌(Phakopsora pachyrhizi))、褐色环腐病(多主棒孢霉(Corynespora cassiicola))、炭疽病(大豆炭疽菌(Colletotrichum glycines)、平头炭疽菌(Colletotrichum truncatum))、腐叶病(立枯丝核菌(Rhizoctonia solani))、褐纹病(大豆壳针孢(Septoria glycines))、斑点病((大豆灰斑病菌(Cercospora sojina))、菌核病(核盘菌(Sclerotinia sclerotiorum))、白粉病(扩散叉丝壳(Microsphaeradiffusa))、茎疫病(大豆疫霉(Phytophthora sojae))、霜霉病(东北霜霉 (Peronosporamanshurica))、猝死综合症(大豆猝死综合症病原菌 (Fusarium virguliforme))、红冠腐病(冬青丽赤壳菌(Calonectria ilicicola))、间座壳属和拟茎点霉属病原菌复合体(Diaporthe/Phomopsis complex)(Diaporthe longicolla);
菜豆的病害:菌核病(核盘菌(Sclerotinia sclerotiorum))、锈病(疣顶单孢锈菌(Uromyces appendiculatus))、角斑病(Phaeoisariopsis griseola)、炭疽病(菜豆炭疽菌(Colletotrichum lindemuthianum))、根腐病(茄腐皮镰刀菌(Fusarium solani));
花生的病害:黑斑病(球座尾孢菌(Cercospora personata))、褐斑病 (花生尾孢菌(Cercospora arachidicola))、白绢病(齐整小核菌(Sclerotium rolfsii))、红冠腐病(冬青丽赤壳菌(Calonectria ilicicola));
豌豆的病害:白粉病(豌豆白粉菌(Erysiphe pisi))、根腐病(茄腐皮镰刀菌(Fusarium solani));
马铃薯的病害:早疫病(索兰氏链格孢(Alternaria solani))、疫病(致病疫霉(Phytophthora infestans))、绯腐病(马铃薯绯腐病菌(Phytophthoraerythroseptica))、粉痂病(马铃薯粉痂菌(Spongospora subterranea f.sp.subterranea))、黄萎病(黑白轮枝菌(Verticillium albo-atrum)、大丽轮枝菌(Verticillium dahliae)、变黑轮枝菌(Verticillium nigrescens))、干腐病 (茄腐皮镰刀菌(Fusarium solani))、癌肿病(马铃薯癌肿病菌 (Synchytrium endobioticum));
草莓的病害:白粉病(律草单囊壳菌(Sphaerotheca humuli));
茶的病害:网饼病(网状外担菌(Exobasidium reticulatum))、白星病(茶白星病菌(Elsinoe leucospila))、轮斑病(拟盘多毛孢(Pestalotiopsis sp.))、炭疽病(茶炭疽病菌(Colletotrichum theae-sinensis));
烟草的病害:赤星病(长柄交链孢(Alternaria longipes))、炭疽病(烟草炭疽病菌(Colletotrichum tabacum))、霜霉病(烟草霜霉(Peronospora tabacina))、疫病(烟草疫霉(Phytophthora nicotianae));
甜菜的病害:褐斑病(甜菜尾孢(Cercospora beticola))、叶枯病(瓜亡革菌(Thanatephorus cucumeris))、根腐病(烟草靶斑病菌(Thanatephorus cucumeris))、黑根病(aphanomyces root rot)(黑腐丝囊霉(Aphanomyces cochlioides))、锈病(甜菜单孢锈菌(Uromyces betae));
蔷薇的病害:黑星病(蔷薇双壳菌(Diplocarpon rosae))、白粉病(蔷薇单囊壳菌(Sphaerotheca pannosa));
菊的病害:褐斑病(野菊壳针孢(Septoria chrysanthemi-indici))、白锈病((堀柄镑菌(Puccinia horiana));
洋葱的病害:白斑叶枯病(botrytis leaf blight)(贵腐霉菌(Botrytiscinerea)、葱细丝葡萄孢(Botrytis byssoidea)、葱鳞葡萄孢(Botrytis squamosa))、灰腐病(葱腐葡萄孢(Botrytis allii))、小菌核颈腐病(葱鳞葡萄孢(Botrytis squamosa));
各种作物的病害:灰霉病(灰色葡萄孢(Botrytis cinerea))、菌核病 (核盘菌(Sclerotinia sclerotiorum))、苗立枯病(瓜果腐霉(Pythium aphanidermatum)、畸雌腐霉(Pythium irregulare)、终极腐霉(Pythium ultimum));
萝卜的病害:黑斑病(芸薹生链格孢(Alternaria brassicicola));
草坪草的病害:币斑病(Sclerotinia homoeocarpa)、褐斑病(brown patch)、大斑病(large patch)(立枯丝核菌(Rhizoctonia solani))、腐霉枯萎病(瓜果腐霉(Pythiumaphanidermatum));
香蕉的病害:香蕉叶斑病(Sigatoka disease)(斐济球腔菌(M Mycosphaerellafijiensis)、香蕉生球腔菌(Mycosphaerella musicola));
兵豆的病害:Ascochyta病(Ascochyta lentis);
鹰嘴豆的病害:壳二孢疫病(鹰嘴豆壳二孢(Ascochyta rabiei));
青椒的病害:炭疽病(Colletotrichum scovillei);
芒果的病害:炭疽病(Colletotrichum acutatum);
果树的病害:白纹羽病(Rosellinia necatrix)、紫纹羽病(桑卷担子菌(Helicobasidium mompa));
收获后的苹果、梨等果实的病害:毛霉病(Mucor rot diseases)(梨形毛霉(Mucorpiriformis));
由霉菌属(Aspergillus)、青霉菌属(Penicillium)、镰刀菌属(Fusarium)、赤霉菌属(Gibberella)、木霉菌属(tricoderma)、根串珠霉菌属 (Thielaviopsis)、根霉菌属(Rhizopus)、毛霉菌属(Mucor)、伏革菌属 (Corticium)、茎点霉属(Phoma)、丝核菌属(Rhizoctonia)、色二孢属 (Diplodia)等引起的种子病害或生长早期的病害;
病毒病:由甘蓝油壶菌(Olpidium brassicae)介导的生菜的巨脉病、由多粘菌属(Polymyxa)(例如甜菜多粘菌(Polymyxa betae)及禾谷多粘菌(Polymyxa graminis))介导的各种作物的病毒病;
细菌(bacteria)所引起的病害:稻的细菌性苗立枯病(伯克霍尔德菌(Burkholderia plantarii))、黄瓜的细菌性角斑病(Pseudomonas syringaepv.Lachrymans)、茄子的青枯病(青枯雷尔氏菌(Ralstonia solanacearum))、柑橘的溃疡病(柑橘溃疡病菌(Xanthomonas citri))、白菜的软腐病(胡萝卜软腐欧文氏菌(Erwiniacarotovora))、马铃薯的疮痂病(疥疮链霉菌 (Streptomyces scabiei))、玉米的内州萎蔫病(Clavibacter michiganensis)、葡萄、橄榄、桃等的冠瘿病(木质部难养菌(Xylellafastidiosa))、苹果、桃、樱桃等蔷薇科植物的根瘤病(农杆菌(Agrobacteriumtumefaciens))。
作为本发明的植物病害防除方法,可以通过用本发明晶体或本发明组合物的有效量对植物或土壤进行处理来进行。作为处理方法,例如可以举出茎叶处理、土壤处理及种子处理。
本发明晶体或本发明组合物通常与固体载体及液体载体等非活性载体混合,根据需要添加表面活性剂、其他的制剂用辅助剂,制剂化成固体制剂、水性悬浮制剂等后使用。在这些制剂中以重量比计通常含有 0.0001~99%的本发明晶体或本发明组合物。
作为固体载体,例如可以举出粘土类(高岭粘土、硅藻土、膨润土、酸性白土等)、干式二氧化硅、湿式二氧化硅、滑石、陶瓷、其他无机矿物(绢云母、石英、硫黄、活性炭、碳酸钙等的微粉末及粒状物等)以及合成树脂(聚丙烯、聚丙烯腈、聚甲基丙烯酸甲酯、聚对苯二甲酸乙二醇酯等聚酯树脂、尼龙-6、尼龙-11、尼龙-66等尼龙树脂、聚酰胺树脂、聚氯乙烯、聚偏二氯乙烯、氯乙烯-丙烯共聚物等)。
作为液体载体,例如可以举出水、醇类(甲醇、乙醇、异丙醇、丁醇、己醇、苯甲醇、乙二醇、丙二醇、苯氧基乙醇等)、酮类(丙酮、甲乙酮、环己酮等)、芳香族烃类(甲苯、二甲苯、乙苯、十二烷基苯、苯基二甲苯基乙烷、甲基萘等)、脂肪族烃类(己烷、环己烷、煤油、轻油等)、酯类(乙酸乙酯、乙酸丁酯、肉豆蔻酸异丙酯、油酸乙酯、己二酸二异丙酯、己二酸二异丁酯、丙二醇单甲醚乙酸酯等)、腈类(乙腈、异丁腈等)、醚类(二异丙醚、1,4-二氧杂环己烷、1,2-二甲氧基乙烷、二乙二醇二甲醚、二乙二醇单甲醚、丙二醇单甲醚、二丙二醇单甲醚、3-甲氧基-3-甲基-1- 丁醇等)、酰胺类(N,N-二甲基甲酰胺、N,N-二甲基乙酰胺等)、亚砜类 (二甲亚砜等)、碳酸亚丙酯及植物油(大豆油、棉籽油等)。
作为表面活性剂,例如可以举出聚氧乙烯烷基醚、聚氧乙烯烷基芳基醚、聚乙二醇脂肪酸酯等非离子表面活性剂、以及烷基磺酸盐、烷基苯磺酸盐、烷基硫酸盐等阴离子表面活性剂。具体而言,可以举出Nimbus(注册商标)、Assist(注册商标)、Aureo(注册商标)、Iharol(注册商标)、 Silwet L-77(注册商标)、BreakThru(注册商标)、SundanceII(注册商标)、 Induce(注册商标)、Penetrator(注册商标)、AgriDex(注册商标)、Lutensol A8(注册商标)、NP-7(注册商标)、Triton(注册商标)、Nufilm(注册商标)、Emulgator NP7(注册商标)、Emulad(注册商标)、TRITON X 45 (注册商标)、AGRAL 90(注册商标)、AGROTIN(注册商标)、ARPON (注册商标)、EnSpray N(注册商标)以及BANOLE(注册商标)等。
作为其他的制剂用辅助剂,可以举出增稠剂、消泡剂、防腐剂以及防冻剂等。
作为增稠剂,例如可以举出黄原胶、鼠李糖胶、刺槐豆胶、瓜尔胶、角叉菜胶、韦兰胶、藻酸、藻酸盐、黄芪胶等天然多糖类;硅酸铝、硅酸铝镁、绿土(smectite)、膨润土、锂蒙脱石、合成水合硅酸、干式二氧化硅等矿物质粉末;以及铝溶胶。
在本发明组合物含有增稠剂的情况下,其合计含量相对于本发明组合物100重量%通常为0.1~5重量%。
作为消泡剂,例如可以举出ANTIFOAM C乳液(Toray Dowcorning 株式会社商品名)、ANTIFOAM CE(Toray Dowcorning株式会社商品名)、ANTIFOAM A COMPOUND(TorayDowcorning株式会社商品名)、FS ANTIFOAM 1266(Toray Dowcorning株式会社商品名)、KM-98(信越化学工业株式会社商品名)、KS-530(信越化学工业株式会社商品名)、 KS-538(信越化学工业株式会社商品名)、BREAKTHRU AF5503(Evonik Industries AG公司商品名)、ANTIFOAM E-20(花王株式会社商品名)、 TSA730(Momentive Performance MaterialsJapan合同会社商品名)、 TSA731(Momentive Performance Materials Japan合同会社商品名)、 TSA732(Momentive Performance Materials Japan合同会社商品名)、 YMA6509(Momentive Performance Materials Japan合同会社商品名)等硅酮系消泡剂;以及FLUOWET PL80(Clariant公司商品名)等氟系消泡剂;FoamStar 220(Cognis Japan株式会社商品名)。
在本发明组合物含有消泡剂的情况下,其合计含量相对于本发明组合物100重量%通常为0.05~0.5重量%。
作为防腐剂,例如可以举出对羟基苯甲酸酯、水杨酸衍生物、1,2- 苯并异噻唑啉-3-酮(例如Proxel GXL(Lonza公司商品名))及异噻唑啉 -3-酮衍生物(例如Biohope L(日文:バイオホープL)(KI化成公司商品名))。
在本发明组合物含有防腐剂的情况下,其合计含量相对于本发明组合物100重量%通常为0.01~3重量%。
作为防冻剂,例如可以举出乙二醇、丙二醇等水溶性二醇类。
在本发明组合物含有防冻剂的情况下,其合计含量相对于本发明组合物100重量%通常为1~20重量%。
本发明中,在植物中包含植物整体及植物的特定的部分。作为植物的特定的部分,例如可以举出茎叶、花、穗、果实、树干、枝、树冠、种子、营养繁殖器官及苗。
所谓营养繁殖器官是指:植物的根、茎、叶等当中的、将该部位从主体切离而设置在土壤中时具有进行生长的能力的部位。作为营养繁殖器官,例如可以举出块根(tuberousroot)、匍匐根(creeping root)、鳞茎(bulb)、球茎(corm或solid bulb)、块茎(tuber)、根茎(rhizome)、匍匐枝(stolon)、根托(rhizophore)、茎插条(cane cuttings)、繁殖芽(propagule)及蔓插条(vine cutting)。需要说明的是,匍匐枝有时也被称为匍匐茎(runner),繁殖芽也被称为珠芽,分为肉芽(broad bud)及鳞芽(bulbil)。所谓蔓插条是指番薯、日本薯蓣等的苗条(叶及茎的总称,无根苗(shoot))。也将鳞茎、球茎、块茎、根茎、茎插条、根托或块根总称为球根。薯类的栽培是通过将块茎植入土壤中开始的,但所使用的块茎通常被称为种薯。
本发明晶体或本发明组合物的施用量也根据气象条件、制剂形态、施用时期、施用方法、施用场所、对象病害、对象作物等而不同,在茎叶处理或土壤处理的情况下,每1000m2中通常为1~500g。在种子处理的情况下,相对于种子1Kg,本发明晶体或本发明组合物的量通常为0.001~100g。在本发明晶体或本发明组合物被制剂化为乳剂、可湿性粉剂(日文:水和剤)、悬浮剂等时,通常以使有效成分浓度为0.01~10000ppm的方式用水稀释后施用,粉剂、粒剂等通常直接施用。
作为种子处理,例如可以举出本发明晶体或本发明组合物对种子或营养繁殖器官进行的处理,具体而言,例如可以举出使本发明晶体或本发明组合物的悬浮液成为雾状而喷洒至种子表面或营养繁殖器官表面的喷洒处理、将本发明晶体或本发明组合物涂布于种子或营养繁殖器官的涂沫处理、将种子在本发明晶体或本发明组合物的药液中浸渍一定时间的浸渍处理、利用含有本发明晶体或本发明组合物的载体包被种子或营养繁殖器官的方法(包膜处理、粒料包覆处理等)。作为上述的营养繁殖器官,特别可以举出种薯。
在用本发明组合物对种子或营养繁殖器官进行处理的情况下,可以将本发明组合物制成1种制剂对种子或营养繁殖器官进行处理,也可以将本发明组合物制成不同的多种制剂分为多次地对种子或营养繁殖器官进行处理。作为将本发明组合物制成不同的多种制剂而分为多次地进行处理的方法,例如可以举出用仅包含本发明晶体作为有效成分的制剂进行处理、在使种子或营养繁殖器官风干后、用包含本成分的制剂进行处理的方法;以及用包含本发明晶体及本成分作为有效成分的制剂进行处理、在使种子或营养繁殖器官风干后、用包含处理完的本成分以外的本成分的制剂进行处理的方法。
本发明中的所谓保持有本发明晶体或本发明组合物的种子或营养繁殖器官是指,在种子或营养繁殖器官的表面附着有本发明晶体或本发明组合物的状态的物质。上述的保持有本发明晶体或本发明组合物的种子或营养繁殖器官也可以在本发明晶体或本发明组合物向种子或营养繁殖器官附着的前后,附着有本发明晶体或本发明组合物以外的材料。
另外,在本发明组合物成为层地附着于种子或营养繁殖器官的表面的情况下,该层由1层或多层形成。另外,在由多层形成的情况下,各个层是包含有1种以上的有效成分的层,或者由包含有1种以上的有效成分的层和不含有有效成分的层形成。
保持有本发明晶体或本发明组合物的种子或营养繁殖器官例如可以通过将包含本发明晶体或本发明组合物的制剂利用所述的种子处理的方法对种子或营养繁殖器官施用而得到。
本发明晶体或本发明组合物可以作为旱田、水田、草坪、果树园等农耕地中的植物病害的防除剂使用。作为植物,例如可以举出以下的植物:
玉米、稻、小麦、大麦、黑麦、燕麦、高粱、棉、大豆、花生、荞麦、甜菜、油菜、向日葵、甘蔗、烟草、茄科蔬菜(茄子、番茄、青椒、辣椒、马铃薯等)、葫芦科蔬菜(黄瓜、南瓜、西葫芦、西瓜、甜瓜等)、十字花科蔬菜(萝卜、芜菁、辣根、苤蓝、白菜、卷心菜、芥菜、西兰花、花椰菜等)、菊科蔬菜(牛蒡、春菊、洋蓟、生菜等)、百合科蔬菜(葱、洋葱、蒜、芦笋等)、伞形科蔬菜(胡萝卜、欧芹、芹菜、欧防风等)、藜科蔬菜 (菠菜、厚皮菜等)、唇形科蔬菜(紫苏、薄荷、罗勒等)、草莓、番薯、日本薯蓣、芋头、梨果类(苹果、西洋梨、日本梨、木瓜海棠、榅桲等)、核果类(桃、李、油桃、青梅、樱桃、杏、西梅等)、柑橘类(温州蜜柑、橙、柠檬、青柠、葡萄柚等)、坚果类(栗、核桃、榛子、杏仁、开心果、腰果、澳洲坚果等)、浆果类(蓝莓、小红莓、黑莓、覆盆子等)、葡萄、柿、橄榄、枇杷、香蕉、咖啡、椰枣、椰子、茶、桑葚、观赏植物、森林植物、草坪草类、牧草类。
在上述植物中也包括转基因作物。
实施例
以下,给出制造例、参考制造例、制剂例以及试验例,对本发明进行更具体的说明,然而本发明并不限定于这些例子。需要说明的是,实施例中的“%”及“份”只要没有特别指出,就是指“重量%”及“重量份”。
另外,对所制造的本发明晶体,如下所示地使用装置(附带测定条件) 测定各种物性。
粉末XRD
粉末X射线衍射装置:SmartLab(株式会社Rigaku制)
X射线输出:Cu-Kα、45kV、200mA
取样宽度:0.02°
扫描范围:2°~50°
测定温度:室温
单晶XRD
(Ra1型晶体)
装置:R-AXIS RAPID(株式会社Rigaku制)
X射线源:Mo-Kα
测定温度:室温
Solve:SHELXT
Refinement:SHELXL
(Ra2型晶体)
装置:R-AXIS RAPID(株式会社Rigaku制)
X射线源:Mo-Kα
测定温度:室温
Solve:SIR2014
Refinement:SHELXL
(Ra3型晶体)
装置:XtaLAB Synergy(株式会社Rigaku制)
X射线源:Cu-Kα
测定温度:100K
Solve:SHELXT
Refinement:SHELXL
DSC
装置:DSC Q2000(TA Instruments制)
升温速度:2℃/min
试样量:0.5~5mg
测定气氛:氮气
傅里叶变换红外分光法(FT-IR)
装置:Nicolet iS50(Thermo Fisher Scientific Inc.制)
测定法:金刚石ATR法
显微拉曼分光法
装置:NRS-5100(日本分光制)
激光波长:532nm
光学显微镜
光学显微镜:Leica Z16 APO(Leica Microsystems制)
相机:Leica MC170 HD(Leica Microsystems制)
倍率:115倍
记载本发明晶体的制造例。
制造例1
(Ra2型晶体的制造)
将30mg的化合物A在60℃溶解于甲醇中,制备为375mg/mL。将该溶液冷却至室温后,在下述条件下照射激光,其后在20℃静置,得到Ra2 型晶体。
激光照射条件设为以下条件。
<飞秒激光器>
波长:800nm
脉冲宽度:181fs
脉冲数:125脉冲/10秒
制造例2
(Ra1型晶体的制造)
在20mL容积样品瓶中量取制造例1中得到的Ra2型晶体200mg,在130℃加热2小时,得到Ra1型晶体。
制造例3
(Ra3型晶体的制造)
在制造例2中得到的Ra1型晶体100mg中添加二异丙醚1mL,将该悬浮液加热至60℃,以1000rpm搅拌2天,其后除去溶剂,得到Ra3型晶体。
参考制造例1
(Ra4型晶体的制造)
Ra4型晶体的制造法依照WO 92/12970(专利文献1)中记载的方法,使化合物A溶解于甲苯中后进行重结晶,由此制造。
将本发明的晶体的物性数据表示如下。
Ra1型晶体
IR特性峰:2933.0、1648.4、1632.0、1606.6、1554.6、1338.8、1082.9 以及1036.5cm-1。
拉曼特性峰:2946、2927、2858、1649、1631以及1397cm-1附近的峰。
XRD特性峰:
对图1所示的粉末X射线衍射图中的特征性衍射峰,将设为衍射角度(2θ±0.2°)形式的衍射峰值表示于表1,然而并不限定于它们。
表1
【表1】
作为典型的衍射峰值,例如可以举出表1所示的7.1±0.2、8.6±0.2、 8.9±0.2、9.1±0.2、13.3±0.2、14.0±0.2、14.3±0.2、14.8±0.2、16.0±0.2以及16.4±0.2。
Ra2型晶体
IR特性峰:3292.4、2957.1、2927.5、1659.1、1642.0、1544.1、1133.5 以及1123.2cm-1。
拉曼特性峰:3118、2924、2876、1658以及1641cm-1附近的峰。
XRD特性峰:
对于图2所示的粉末X射线衍射图中的特征性衍射峰,将设为衍射角度(2θ±0.2°)形式的衍射峰值表示于表2中,然而并不限定于它们。
表2
【表2】
作为典型的衍射峰值,例如可以举出上述表2所示的4.3±0.2、8.5±0.2、 10.8±0.2、11.4±0.2、12.4±0.2、12.8±0.2、15.1±0.2、16.1±0.2、16.8±0.2 以及19.1±0.2。
Ra3型晶体
IR特性峰:3301.7、2959.1、2858.1、1654.4、1644.3、1545.6、1518.3、 1133.9、1123.3以及1032.8cm-1。
拉曼特性峰:3046、2928、1652、1588以及1545cm-1附近的峰。
XRD特性峰:
对于图3所示的粉末X射线衍射图中的特征性衍射峰,将设为衍射角度(2θ±0.2°)形式的衍射峰值表示于表3中,然而并不限定于它们。
表3
【表3】
作为典型的衍射峰值,例如可以举出表3所示的3.6±0.2、7.1±0.2、 7.4±0.2、9.6±0.2、11.9±0.2、12.5±0.2、12.9±0.2、14.3±0.2、15.7±0.2以及17.9±0.2。
为了与本申请发明的Ra1型晶体、Ra2型晶体以及Ra3型晶体进行比较,将Ra4型晶体的各种光谱值表示如下。
Ra4型晶体
IR特性峰:2953.8、1635.5、1608.7、1553.2、1138.7、1066.8、1034.2 以及1012.3cm-1。
拉曼特性峰:2928、2859、1491、1398以及1311cm-1附近的峰。
XRD特性峰
对于图4所示的粉末X射线衍射图中的特征性衍射峰,将设为衍射角度(2θ±0.2°)形式的衍射峰值表示于表4中,然而并不限定于它们。
表4
【表4】
作为典型的衍射峰值,例如可以举出表4所示的5.8±0.2、7.2±0.2、 8.6±0.2、13.8±0.2、16.3±0.2、16.7±0.2、17.4±0.2、17.7±0.2、19.5±0.2、 19.8±0.2及20.7±0.2。
对于本发明晶体,将单晶的晶体学的数据表示于下述表5中。
表5
【表5】
利用以下的试验例测定出本发明晶体对植物病害的防除效力。
试验例1
将Ra1型晶体、或作为比较对象的Ra4型晶体5份、白炭黑与聚氧乙烯烷基醚硫酸铵盐的混合物(重量比例1∶1)35份及水60份混合,利用湿式粉碎法进行微粉碎,由此得到制剂。在该制剂中加入水而使得 Ra1型晶体或Ra4型晶体的浓度为2ppm,得到稀释液。
向塑料盆中填入土壤,在其中播种大豆(品种:黑千石),在温室内生长15天。其后喷雾接种大豆锈病菌(Phakopsora pachyrhizi)孢子的水悬浮液。接种后在23℃、多湿条件下放置1夜,再在温室下栽培3天后,将上述稀释液以充分附着在上述大豆的叶面的方式进行茎叶喷洒。喷洒后将植物风干,仅在夜间放置于多湿条件下,喷洒7天后调查病斑面积(处理区的病斑面积)。
另一方面,在未处理区中,除了没有用Ra1型晶体或Ra4型晶体进行处理以外进行与处理区同样的操作,调查未处理区中的大豆锈病的病斑面积(未处理区的病斑面积)。
根据处理区及未处理区各自的病斑面积,利用下述“式1”求出处理区的效力。
将其结果表示于表6中。
「式1」
效力(%)=〔1-(处理区的病斑面积/未处理区的病斑面积)〕×100
表6
【表6】
供试晶体 | 效力(%) |
Ra1型晶体 | 72 |
Ra4型晶体 | 54 |
可知Ra1型晶体显示出比Ra4型晶体高的效力。
试验例2
将Ra2型晶体、Ra3型晶体、或作为比较对象的Ra4型晶体5份、白炭黑与聚氧乙烯烷基醚硫酸铵盐的混合物(重量比例1∶1)35份及水 60份混合,利用湿式粉碎法进行微粉碎,由此得到制剂。在该制剂中加入水,使得Ra2型晶体、Ra3型晶体、或Ra4型晶体为50ppm,得到稀释液。
向塑料盆中填入土壤,在其中播种稻子(品种:Hinohikari(日文:ヒフヒカリ)),在温室内生长17天。将上述稀释液以充分地附着于上述稻子的叶面的方式进行茎叶喷洒。喷洒后将植物风干,在室外栽培8天。其后在温室下在白天24℃、夜间20℃多湿条件下,在使进行了所述喷洒处理的稻子与罹患水稻稻瘟病菌(Pyricularia oryzae)的稻苗接触的同时放置11天后,调查病斑面积(处理区的病斑面积)。
另一方面,在未处理区中,除了未用Ra2型晶体、Ra3型晶体或Ra4 型晶体进行处理以外进行与处理区同样的操作,调查未处理区中的水稻稻瘟病的病斑面积(未处理区的病斑面积)。
根据处理区及未处理区各自的病斑面积,利用上述“式1”求出处理区的效力。
将其结果表示于表7中。
表7
【表7】
供试晶体 | 效力(%) |
Ra2型晶体 | 85 |
Ra3型晶体 | 75 |
Ra4型晶体 | 50 |
可知Ra2型晶体及Ra3型晶体显示出比Ra4型晶体高的效力。
产业上的可利用性
本发明晶体(Ra1型晶体、Ra2型晶体以及Ra3型晶体)对植物病害显示出优异的防除效果。
Claims (9)
1.一种晶体,其为3-(二氟甲基)-1-甲基-N-(1,1,3-三甲基-2,3-二氢-1H-茚-4-基)-1H-吡唑-4-甲酰胺的选自如下晶体中的至少1种晶体:
在基于Cu-Kα射线的粉末X射线衍射中的2θ=7.1±0.2°、8.6±0.2°、8.9±0.2°、9.1±0.2°、13.3±0.2°、14.0±0.2°、14.3±0.2°、14.8±0.2°、16.0±0.2°、16.4±0.2°、20.3±0.2°以及20.6±0.2°具有衍射峰的Ra1型晶体、
在基于Cu-Kα射线的粉末X射线衍射中的2θ=4.3±0.2°、8.5±0.2°、10.8±0.2°、11.4±0.2°、12.4±0.2°、12.8±0.2°、15.1±0.2°、16.1±0.2°、16.8±0.2°以及19.1±0.2°具有衍射峰的Ra2型晶体、以及
在基于Cu-Kα射线的粉末X射线衍射中的2θ=3.6±0.2°、7.1±0.2°、7.4±0.2°、9.6±0.2°、11.9±0.2°、12.5±0.2°、12.9±0.2°、14.3±0.2°、15.7±0.2°以及17.9±0.2°具有衍射峰的Ra3型晶体。
2.根据权利要求1所述的晶体,其中,在3-(二氟甲基)-1-甲基-N-(1,1,3-三甲基-2,3-二氢-1H-茚-4-基)-1H-吡唑-4-甲酰胺中,是在基于Cu-Kα射线的粉末X射线衍射中的2θ=7.1±0.2°、8.6±0.2°、8.9±0.2°、9.1±0.2°、13.3±0.2°、14.0±0.2°、14.3±0.2°、14.8±0.2°、16.0±0.2°、16.4±0.2°、20.3±0.2°以及20.6±0.2°具有衍射峰的Ra1型晶体。
3.根据权利要求1所述的晶体,其中,在3-(二氟甲基)-1-甲基-N-(1,1,3-三甲基-2,3-二氢-1H-茚-4-基)-1H-吡唑-4-甲酰胺中,是在基于Cu-Kα射线的粉末X射线衍射中的2θ=4.3±0.2°、8.5±0.2°、10.8±0.2°、11.4±0.2°、12.4±0.2°、12.8±0.2°、15.1±0.2°、16.1±0.2°、16.8±0.2°以及19.1±0.2°具有衍射峰的Ra2型晶体。
4.根据权利要求1所述的晶体,其中,在3-(二氟甲基)-1-甲基-N-(1,1,3-三甲基-2,3-二氢-1H-茚-4-基)-1H-吡唑-4-甲酰胺中,是在基于Cu-Kα射线的粉末X射线衍射中的2θ=3.6±0.2°、7.1±0.2°、7.4±0.2°、9.6±0.2°、11.9±0.2°、12.5±0.2°、12.9±0.2°、14.3±0.2°、15.7±0.2°以及17.9±0.2°具有衍射峰的Ra3型晶体。
5.一种植物病害防除组合物,其包含权利要求1~4中任一项所述的1种以上的晶体。
6.一种植物病害的防除方法,其包括用权利要求1~4中任一项所述的1种以上的晶体的有效量对植物或植物生长的土壤进行处理。
7.一种权利要求1~4中任一项所述的1种以上的晶体的用途,其用于防除植物病害。
8.一种组合物,其含有选自组(a)、组(b)、组(c)及组(d)中的1种以上的成分、和权利要求1~4中任一项所述的1种以上的晶体,
组(a):包含杀虫活性成分、杀螨活性成分及杀线虫活性成分的组;
组(b):杀菌活性成分;
组(c):植物生长调节成分;
组(d):驱避成分。
9.一种种子或营养繁殖器官,其保持有权利要求1~4中任一项所述的1种以上的晶体或权利要求7所述的组合物的有效量。
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US5093347A (en) * | 1991-01-28 | 1992-03-03 | Monsanto Company | 3-difluoromethylpyrazolecarboxamide fungicides, compositions and use |
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