CN115136960A - 杀真菌组合物 - Google Patents
杀真菌组合物 Download PDFInfo
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- CN115136960A CN115136960A CN202210796156.XA CN202210796156A CN115136960A CN 115136960 A CN115136960 A CN 115136960A CN 202210796156 A CN202210796156 A CN 202210796156A CN 115136960 A CN115136960 A CN 115136960A
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Abstract
本发明涉及用于治疗有用植物的植物病原性疾病、尤其是植物病原性真菌的新颖的杀真菌组合物,并且涉及控制有用植物上的此类植物病原性疾病的方法。具体地,适合控制由植物病原菌引起的疾病的组合物包括具有化学式(I)的化合物
Description
本申请是发明名称为“杀真菌组合物”的中国发明专利申请No.202110862023.3的分案申请,其申请日是2014年9月26日,优先权日是2013年10月3日。
本发明涉及用于治疗有用植物的植物病原性疾病、尤其是植物病原性真菌的新颖的杀真菌组合物,并且涉及控制有用植物上的此类疾病、和/或真菌的方法。
从WO 2008/148570、WO 2010/063700、WO 2010/084078以及WO 2008/151828中已知某些吡唑基-甲酰胺衍生物具有针对植物病原性真菌的生物活性。另一方面,具有不同化学类别的不同的杀真菌化合物作为用于在栽培植物的不同作物上施用的植物杀真菌剂是众所周知的。然而,针对植物病原性植物真菌的作物忍受性和活性并不总是满足在许多事件和方面中的农业实践的需要。为了克服这个问题,在WO 2012/041874中提供了吡唑基-甲酰胺与某些杀真菌剂的一些二元混合物。
本发明提供了一种用于控制有用植物上或其繁殖材料上的植物病原性疾病的方法,该方法包括向这些有用植物、其所在地或其繁殖材料上施用以协同有效量的组分(A)和(B)的组合,其中组分(A)是具有化学式(I)的化合物
其中
R是氢或甲氧基;
Q是
其中
R1是氢、卤素或C1-C6烷基;
R2是氢、卤素、C1-C6烷基、C2-C6烯基、C3-C6炔基、C3-C6环烷基-C3-C6炔基、卤代苯氧基、卤代苯基-C3-C6炔基、C(C1-C4烷基)=NO-C1-C4烷基、C1-C6卤代烷基,C1-C6卤代烷氧基、C2-C6卤代烯基、或C2-C6卤代烯氧基;
R3是氢、卤素、C1-C6烷基;
R4、R5和R6彼此独立地是氢、卤素或-≡-R7;其条件是R4、R5和R6中的至少一个不同于氢;
R7是氢、C1-C6烷基、C1-C6卤代烷基或C1-C4烷氧基烷基;并且
R8是氢或甲氧基;
以及那些化合物的农业化学上可接受的盐、立体异构体、非对映异构体、对映异构体和互变异构体;
并且组分(B)是选自下组的化合物,该组由以下各项组成:
(B1)具有化学式(II)的化合物
其中两个R9是相同的并且代表甲基、乙基、正丙基或异丙基;
(B2)胺苯吡菌酮;
(B3)异丙噻菌胺(isofetamid);
(B4)欧塞匹林(oxathiapiprolin);
(B5)托普威(tolprocarb);
(B6)氟菌螨酯;
(B7)BLAD;
(B8)UK-2A普若赛德(UK-2A procide)即具有以下结构的(3S,6S,7R,8R)-8-苯甲基-3-(3-((异丁酰氧基)甲氧基)-4-甲氧基吡啶甲酰胺基)-6-甲基-4,9-二氧代-1,5-二氧戊环-7-基异丁酸酯
(B9)具有化学式(III)的化合物
(B10)丁香菌酯;
(B11)曼德斯宾(mandestrobin);
(B12)异丁乙氧喹啉(tebufloquin);
(B13)氯啶菌酯;
(B14)具有化学式IV的化合物
(B15)具有化学式V的化合物
(B16)双炔酰菌胺;或其农业化学上可接受的盐。
具有化学式(I)的化合物(其中R8是氢)可以按具有化学式(Ia)和(Ib)的两种对映异构体形式出现:
本发明包括具有化学式(I)的化合物的两种对映异构体形式。具有化学式(I)的化合物和它们的制备描述于WO 2010/063700、WO 2010/084078和WO 2008/151828中。
已经发现,与组分(A)组合使用组分(B)出人意料地并且大量地可以增强后者针对真菌的效果,反之亦然。此外,本发明的方法针对更宽的此种真菌谱是有效的,当单独使用时,这一方法的活性成分可以对抗这些真菌。
通常,组分(A)与组分(B)的重量比是从1000:1至1:1000,尤其是从50:1至1:50,更尤其是处于从40:1至1:40的比率,甚至更尤其是处于20:1至1:20的比率,甚至仍更尤其是从10:1至1:10,并且非常尤其是从5:1和1:5。给出特别优先至从2:1至1:2的比率,并且从4:1至2:1的比率是尤其优选的。优选的具体单个比率包括以下比率:1:1、5:1、5:2、5:3、5:4、4:1、4:2、4:3、3:1、3:2、2:1、1:5、2:5、3:5、4:5、1:4、2:4、3:4、1:3、2:3、1:2、1:600、1:300、1:150、1:100、1:50、1;40、1:35、1:20、2:35、4:35、1:10、1:75、2:75、4:75、1:6000、1:3000、1:1500、1:350、2:350、4:350、1:750、2:750、和4:750。
已经发现,出人意料地,组分(A)与组分(B)的特定重量比能够产生协同活性。因此,本发明的一个另外的方面是组合物,其中组分(A)和组分(B)以产生协同效应的量存在于该组合物中。该协同活性从以下事实中是明显的:包括组分(A)和组分(B)的组合物的杀真菌活性大于组分(A)和组分(B)的杀真菌活性之和。该协同活性以两种方式延伸了组分(A)和组分(B)的作用范围。第一,组分(A)和组分(B)的施用比率降低了,同时其作用保持同样地好,这意味着甚至在这样一种低施用比率范围中,这两种单独的组分已经变得总体无效的情况下,该活性成分混合物仍达到高度的植物病原菌控制。第二,存在可以被控制的植物病原菌谱的实质性扩展。
存在一种协同效应,无论何时,活性成分组合的作用大于单独组分的作用之和。对于给定的活性成分组合,预期的作用E服从所谓的科尔比(COLBY)公式并且可以按以下进行计算(科尔比(COLBY),S.R.,“计算除草剂组合的协同和拮抗反应(Calculatingsynergistic and antagonistic responses of herbicide combination)”.杂草(Weeds),第15期,第20-22页;1967):
ppm=每升喷洒混合物的活性成分(=a.i.)的毫克数
X=使用p ppm的活性成分按活性成分(A)计的%作用
Y=使用q ppm的活性成分按活性成分(B)计的%作用。
如果实际观察到的(O)作用大于预期的作用(E),那么该组合的作用是超级加性的,即存在一种协同效应。在数学方面,协同作用对应于(O-E)的差的正值。在纯互补性添加活性物(期待的活性)的情况下,所述差(O-E)为零。所述差(O-E)的负值标志着与期待的活性相比,活性的损失。
然而,除了相对于杀真菌活性的实际协同作用外,根据本发明的组合物还可以具有另外的出人意料的有利特性。可以提及的此类有利的特性的实例是:更有利的降解性;改善的毒理学和/或生态毒理学行为;或有用植物的改善的特征,包括:出苗、作物产量、根系统更发达、分蘖增加、株高增加、叶片更大、基部叶片死亡更少、分蘖更强、叶子颜色更绿、所需肥料更少、所需种子更少、分蘖更多产、开花更早、谷粒成熟更早、植物倒伏(伏到(lodging))更少、芽生长增强、改进的植物活力以及发芽早。
根据本发明的一些组合物具有一种内吸作用并且可以被用作叶上、土壤、以及种子处理的杀真菌剂。
使用根据本发明的组合物,有可能抑制或破坏植物病原性微生物,这些微生物发生于在多种不同的有用植物的植物或植物部分(果实、花、叶子、茎、块茎、根)上发生的疾病,同时还保护了稍后生长的植物部分免于被植物病原性微生物侵袭。
根据本发明的组合物可以被施用至植物病原性微生物、有用植物、其场所、其繁殖材料、储存货物或受微生物攻击威胁的技术材料。
可以在有用植物、其繁殖材料、储存货物或技术材料被微生物感染之前或之后施用根据本发明的组合物。
本发明的一个另外方面是控制在有用植物上或在其繁殖材料上由植物病原菌引起的疾病的方法,它包括将根据本发明的组合物施用至有用植物、其场所或其繁殖材料。优选的是以下方法,它包括将根据本发明的组合物施用至有用植物或至其场所,更优选地是施用至有用植物。另外优选的是以下方法,它包括将根据本发明的组合物施用至有用植物的繁殖材料。
组分(B)是已知的。胺苯吡菌酮是在C.A.注册号473798-59-3下注册的并且披露于EP 1072598 A1中。异丙噻菌胺(isofetamid)是在C.A.注册号875915-78-9下注册的并且披露于WO 2006/016708中。欧塞匹林是在C.A.注册号1003318-67-9下注册的并且披露于WO2008/013622中。tolprocarb是在C.A.注册号911499-62-2下注册的并且披露于EP 1681285A1中。氟菌螨酯是在C.A.注册号918162-02-4下注册的并且披露于WO 2007/000098中。BLAD(banda de Lupinus albus doce)是20kDa多肽。它在羽扇豆属植物的发育的短期内自然地出现于羽扇豆属植物中。它是β-羽扇豆球蛋白分解代谢的稳定分解产物,β-羽扇豆球蛋白是羽扇豆属植物的主要种子贮存蛋白。它由173个氨基酸残基组成,并且由编码来自羽扇豆属的β-羽扇豆球蛋的前体的基因(1791个核苷酸,在登录号AAS97865下公开基因银行(GenBank)中)的内部片段(519个核苷酸,在登录号ABB13526下保藏于基因银行中)编码。例如BLAD详细描述于WO 2012/049215中。例如,具有化学式II的化合物描述于WO 2012/123426和WO 2012/139889中。UK-2A普若赛德确切地披露为WO 03/035617中的化合物No.23并且披露为WO 2011/103240中的具有化学式II的化合物。具有化学式III的化合物描述于WO 2012/084812中。丁香菌酯是在C.A.注册号850881-70-8下注册的并且披露于WO 2005/044813中。曼德斯宾是在C.A.注册号173662-97-0下注册的并且披露于WO 95/27693中。异丁乙氧喹啉是在C.A.注册号376645-78-2下注册的并且在WO 01/92231中描述为表1中的化合物No.2。氯啶菌酯是在C.A.注册号902760-40-1下注册的并且描述于WO 2006/081759中。具有化学式IV的化合物是在C.A.注册号1202781-91-6下注册的,其化学命名是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,并且例如描述于WO 2009/156098中。例如,具有化学式V的化合物(氰烯菌酯)描述于以下中:作物保护(Crop Protection)27,(2008),90-95,化学与药学通报(Chemical&Pharmaceutical Bulletin)(1965),3(7),828-87和CN 1559210 A。双炔酰菌胺是在C.A.注册号298-04-4下注册的并且例如描述于EP1282595B1中。具有化学式I的化合物,具体地是化合物3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-甲基-2-(2,4,6-三氯苯基)乙基]吡唑-4-甲酰胺,对于控制树木疾病,例如葡萄中的支顶孢属、葡萄座腔菌属、葡萄座腔菌(Botryosphaeria obtuse)、葡萄溃疡病菌、头孢霉属、葡萄藤猝倒病菌、Formitiporiamediteranea、Phaemoniella chlamydospora、Phaeoacremonium aleophilum、瓶霉菌属和葡萄枝枯病菌,也是有用的。出于此目的,SDHI的用途也描述于WO 2013/124275中。
贯穿本文件,表述“组合物”是指组分(A)和(B)的不同混合物或组合,例如以一种单一的“掺水即用”的形式,以组合的喷洒混合物(该混合物由这些单一活性成分的单独配制品构成)(例如一种“桶混制剂”),并且当以一种顺序的方式(即,一个在另一个的适当短的时期之后,例如几小时或几天)施用时,以这些单独活性成分的组合使用。对于使本发明工作,施用组分(A)和(B)的顺序并不是必要的。
具有化学式(I)的化合物作为组分(A)是优选的,其中Q是Q1,其中R1、R2和R3优选地是卤素,特别是氯;R是甲氧基并且R8是氢。
优选的组分(A)列于下表1中:
表1:具有化学式Ic的化合物:
其中
Q是
另外优选的组分(A)列于下表2中:
表2:具有化学式Id的化合物:
其中
Q是
具体优选的组分(A)是化合物编号1.001(3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-甲基-2-(2,4,6-三氯苯基)乙基]吡唑-4-甲酰胺)。尤其优选的混合物包括组分(A)3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-甲基-2-(2,4,6-三氯苯基)乙基]吡唑-4-甲酰胺和一种组分(B)。
以下的组分(A)与组分(B)的二元混合物是优选的(缩写“TX”是指:“一种选自由具体地描述于表1和2中的本发明的化合物组成的组的化合物”):
一种具有化学式(II)的化合物
其中两个R9是相同的并且代表甲基+TX;
具有化学式(II)的化合物
其中两个R9是相同的并且代表乙基+TX;
具有化学式(II)的化合物
其中两个R9是相同的并且代表正丙基+TX;
具有化学式(II)的化合物
其中两个R9是相同的并且代表异丙基+TX;
胺苯吡菌酮+TX;
异丙噻菌胺(isofetamid)+TX;
欧塞匹林+TX;
托普威+TX;
氟菌螨酯+TX;
BLAD+TX;
UK-2A普若赛德+TX;
具有化学式(III)的化合物
丁香菌酯+TX;
曼德斯宾+TX;
异丁乙氧喹啉+TX;
(B13)氯啶菌酯+TX;
(B14)具有化学式(IV)的化合物
(B15)具有化学式(V)的化合物
(B16)双炔酰菌胺+TX。
组分(A)与组分(B)一起的特别优选的二元混合物是以下那些,其中组分B选自下组,该组由以下各项组成:具有化学式(II)的化合物(即B1)、胺苯吡菌酮(B2)、欧塞匹林(B4)、托普威(B5)、氟菌螨酯(B6)、具有化学式(III)的化合物(B9)、丁香菌酯(B10)、曼德斯宾(B11)、异丁乙氧喹啉(B12)、氯啶菌酯(B13)和具有化学式(V)的化合物(B14),并且每一种都与TX组合。具体地,其中组分B是化学式(II),其中R9是甲基的变体是优选的。
本发明的非常特别优选的组合包括:具有化学式(II)的化合物(即B1),具体地,其中R9是甲基,与作为组分A的3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-甲基-2-(2,4,6-三氯苯基)乙基]吡唑-4-甲酰胺一起;胺苯吡菌酮(B2)与作为组分A的3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-甲基-2-(2,4,6-三氯苯基)乙基]吡唑-4-甲酰胺一起;欧塞匹林(B4)与作为组分A的3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-甲基-2-(2,4,6-三氯苯基)乙基]吡唑-4-甲酰胺一起;托普威(B5)与作为组分A的3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-甲基-2-(2,4,6-三氯苯基)乙基]吡唑-4-甲酰胺一起;氟菌螨酯(B6)与作为组分A的3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-甲基-2-(2,4,6-三氯苯基)乙基]吡唑-4-甲酰胺一起;具有化学式(III)的化合物(B9)与作为组分A的3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-甲基-2-(2,4,6-三氯苯基)乙基]吡唑-4-甲酰胺一起;丁香菌酯(B10)与作为组分A的3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-甲基-2-(2,4,6-三氯苯基)乙基]吡唑-4-甲酰胺一起;曼德斯宾(B11)与作为组分A的3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-甲基-2-(2,4,6-三氯苯基)乙基]吡唑-4-甲酰胺一起;异丁乙氧喹啉(B12)与作为组分A的3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-甲基-2-(2,4,6-三氯苯基)乙基]吡唑-4-甲酰胺一起;氯啶菌酯(B13)与作为组分A的3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-甲基-2-(2,4,6-三氯苯基)乙基]吡唑-4-甲酰胺一起;以及具有化学式(V)的化合物(B14)与作为组分A的3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-甲基-2-(2,4,6-三氯苯基)乙基]吡唑-4-甲酰胺一起。
这些活性成分组合针对引起植物病原疾病的有害微生物(例如微生物),特别是针对植物病原真菌和细菌是有效的。
这些活性成分组合尤其针对属于以下类别的植物病原真菌是有效的:子囊菌纲(例如黑星菌、白粉病菌、白粉菌、链核盘菌、球腔菌、钩丝壳菌);担子菌纲(例如锈病菌属、丝核菌属、层锈菌属、柄锈菌属、黑粉菌属、腥黑粉菌属);不完全菌纲(也被称为半知菌纲;例如葡萄孢属、长蠕孢菌、黑麦喙孢、镰刀菌、壳针孢属、尾孢菌、链格孢菌、梨孢属以及假小尾孢属);卵菌纲(例如疫霉菌、霜霉菌、假霜霉菌、白锈属、盘梗霉菌、腐霉菌、假指梗霉属、单轴霉菌)。
根据本发明,“有用植物”典型地包括以下植物种类:葡萄藤;谷类(例如小麦、大麦、黑麦或燕麦);甜菜(比如甜菜或饲用甜菜);水果(比如梨果、核果或浆果,例如苹果、梨、李子、桃、扁桃、樱桃、草莓、覆盆子或黑莓);豆科植物(比如蚕豆、滨豆、豌豆或大豆);油料植物(比如油菜、芥菜、罂粟、橄榄、向日葵、椰子、蓖麻油植物、可可豆或落花生);瓜类植物(比如嫩葫芦、黄瓜或甜瓜);纤维植物(比如棉花、亚麻、大麻或黄麻);柑橘类水果(比如橙子、柠檬、葡萄柚或橘子);蔬菜(比如菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、番茄、马铃薯、葫芦或红辣椒);樟科(比如鳄梨、肉桂或樟脑);玉米;烟草;坚果;咖啡;甘蔗;茶;藤本植物;啤酒花;榴莲;香蕉;天然橡胶树;草皮或观赏植物(比如花卉、灌木、阔叶树或常绿植物例如针叶树)。该清单不代表任何限制。
术语“有用植物”应当理解为还包括由于常规育种方法或基因工程已经使之耐受除草剂如溴苯腈或多种除草剂类别(例如像HPPD抑制剂、ALS抑制剂,例如氟嘧磺隆、氟磺隆和三氟啶磺隆、EPSPS(5-烯醇-丙酮酰-莽草酸-3-磷酸-合酶)抑制剂、GS(谷氨酰胺合成酶)抑制剂)的有用植物。已经通过常规育种方法(诱变)变得对咪唑啉酮例如甲氧咪草烟具有耐受力的作物的一个实例是夏季油菜(卡诺拉(Canola))。通过遗传工程方法而被赋予了对多种除草剂或多种除草剂类别的耐受性的作物的实例包括草甘膦和草丁膦抗性玉米品种,它在和商标名下是可商购的。
术语“有用植物”应当理解为还包括已经通过使用重组DNA技术而被这样转化使其能够合成一种或多种选择性作用毒素的有用的植物,这些毒素如已知例如来自于产毒素细菌,尤其是芽孢杆菌属的那些细菌。
可通过所述转基因植物表达的毒素包括,例如杀虫蛋白质,例如来自于枯草芽孢杆菌或日本甲虫芽孢杆菌的杀昆虫蛋白质;或来自于苏云金芽孢杆菌的杀虫蛋白质,如δ-内毒素,例如CryIA(b)、CryIA(c)、CryIF、CryIF(a2)、CryIIA(b)、CryIIIA、CryIIIB(b1)或Cry9c,或营养期杀虫蛋白(VIP),例如VIP1、VIP2、VIP3或VIP3A;或线虫寄生性细菌的杀虫蛋白质,例如光杆状茵属或致病杆菌属,如发光光杆状茵、嗜线虫致病杆菌;由动物产生的毒素,如蝎毒素、蜘蛛毒素、黄蜂毒素和其他昆虫特异性神经毒素;由真菌产生的毒素,如链霉菌毒素;植物凝集素,如豌豆凝集素、大麦凝集素或雪花莲凝集素;凝集素类;蛋白酶抑制剂,如胰蛋白酶抑制剂、丝氨酸蛋白酶抑制剂、马铃薯贮存蛋白(patatin)、半胱氨酸蛋白酶抑制剂、木瓜蛋白酶抑制剂;核糖体失活蛋白(RIP),如蓖麻蛋白、玉米-RIP、相思豆毒蛋白、丝瓜籽毒蛋白、皂草毒素蛋白或异株泻根毒蛋白;类固醇代谢酶,如3-羟基类固醇氧化酶、蜕皮类固醇-UDP-糖基-转移酶、胆固醇氧化酶、蜕皮激素抑制剂、HMG-COA-还原酶,离子通道阻断剂,如钠通道或钙通道阻断剂,保幼激素酯酶,利尿激素受体、茋合酶、联苄合酶、几丁酶和葡聚糖酶。
在本发明的上下文中,δ-内毒素,例如CryIA(b)、CryIA(c)、CryIF、CryIF(a2)、CryIIA(b)、CryIIIA、CryIIIB(b1)或Cry9c,或营养期杀昆虫蛋白(VIP),例如VIP1、VIP2、VIP3或VIP3A应该明确地理解为也是混合型毒素、截短的毒素以及经修饰的毒素。混合型毒素是通过那些蛋白的不同区域的新组合重组产生的(参见,例如WO 02/15701)。截短的毒素的实例是截短的CryIA(b),它是以如下所述,来自Syngenta Seeds SAS(先正达种子公司)的Bt11玉米。在经修饰的毒素的情况下,天然存在的毒素的一个或多个氨基酸被置换。在这些氨基酸置换中,优选地将不是天然存在的蛋白酶识别序列插入到毒素中,例如像在CryIIIA055的情况下,将组织蛋白酶-D-识别序列插入到一个CryIIIA毒素中(参见WO 03/018810)
这样的毒素或能够合成这样的毒素的转基因植物的实例披露于例如EP-A-0 374753、WO 93/07278、WO 95/34656、EP-A-0 427 529、EP-A-451 878以及WO 03/052073中。
用于制备这样的转基因植物的方法对于本领域的普通技术人员是已知的并且描述在例如以上提及的公开案中。CryI-型脱氧核糖核酸及其制备例如从WO 95/34656、EP-A-0 367 474、EP-A-0 401 979以及WO 90/13651中已知。
包括在转基因植物中的毒素使得植物对有害昆虫有耐受性。这些昆虫可以存在于任何昆虫分类群,但尤其是通常在甲虫(鞘翅目)、双翅昆虫(双翅目)以及蝴蝶(鳞翅目)中发现。
包括一种或多种编码杀虫剂抗性并且表达一种或多种毒素的基因的转基因植物是已知的并且其中一些是可商购的。这样的植物的实例是:(玉米品种,表达一种CryIA(b)毒素);YieldGard (玉米品种,表达一种CryIIIB(b1)毒素);YieldGard (玉米品种,表达一种CryIA(b)以及一种CryIIIB(b1)毒素); (玉米品种,表达一种Cry9(c)毒素);Herculex(玉米品种,表达一种CryIF(a2)毒素以及实现对除草剂草丁膦铵的耐药性的酶草丁膦N-乙酰转移酶(PAT));NuCOTN(棉花品种,表达一种CryIA(c)毒素);Bollgard(棉花品种,表达一种CryIA(c)毒素);Bollgard(棉花品种,表达一种CryIA(c)和一种CryIIA(b)毒素);(棉花品种,表达一种VIP毒素);(马铃薯品种,表达一种CryIIIA毒素);和
这样的转基因作物的其他实例是:
1.Bt11玉米,来自先正达种子公司(Syngenta Seeds SAS),霍比特路(Chemin del’Hobit)27,F-31 790圣苏维尔(St.Sauveur),法国,注册号C/FR/96/05/10。遗传修饰的玉蜀黍,通过转基因表达截短的CryIA(b)毒素,使之能抵抗欧洲玉米螟(玉米螟和粉茎螟)的侵袭。Bt11玉米还转基因地表达PAT酶以达到对除草剂草丁膦铵盐的耐受性。
2.Bt176玉米,来自先正达种子公司,霍比特路27,F-31 790圣苏维尔,法国,注册号C/FR/96/05/10。遗传修饰的玉蜀黍,通过转基因表达CryIA(b)毒素,使之能抵抗欧洲玉米螟(玉米螟和粉茎螟)的侵袭。Bt176玉米还转基因地表达PAT酶以达到对除草剂草丁膦铵盐的耐受性。
3.MIR604玉米,来自先正达种子公司,霍比特路27,F-31 790圣苏维尔,法国,注册号C/FR/96/05/10。已经通过转基因表达经修饰的CryIIIA毒素变得抗昆虫的玉米。此毒素是通过插入一个组织蛋白酶-D-蛋白酶识别序列修饰的Cry3A055。这样的转基因玉米植物的制备描述于WO 03/018810中。
4.MON 863玉米,来自孟山都欧洲公司(Monsanto Europe S.A.)270-272特弗伦大道(Avenue de Tervuren),B-1150布鲁塞尔(Brussels),比利时,注册号C/DE/02/9。MON863表达CryIIIB(b1)毒素,并且对某些鞘翅目昆虫有抗性。
5.IPC 531棉花,来自孟山都欧洲公司270-272特弗伦大道,B-1150布鲁塞尔,比利时,注册号C/ES/96/02。
6.1507玉米,来自先锋海外公司(Pioneer Overseas Corporation),特德斯科大道(Avenue Tedesco),7B-1160布鲁塞尔,比利时,注册号C/NL/00/10。遗传修饰的玉米,表达蛋白质Cry1F以实现对某些鳞翅目昆虫的抗性和表达PAT蛋白质以实现对除草剂草丁膦铵盐的耐受性。
7.NK603×MON 810玉米,来自孟山都欧洲公司(Monsanto Europe S.A.),270-272特弗伦大道,B1150布鲁塞尔,比利时,登记号C/GB/02/M3/03。由通过使遗传修饰的品种NK603和MON 810杂交常规地培育的杂交玉米品种组成。NK603×MON 810玉米转基因表达由土壤杆菌属菌株CP4获得的CP4 EPSPS蛋白质,使之耐除草剂(含有草甘膦),以及由苏云金芽孢杆菌库尔斯塔克亚种获得的CryIA(b)毒素,使之耐某些鳞翅目昆虫,包括欧洲玉米螟。
抗昆虫的植物的转基因作物还描述于BATS(生物安全与可持续发展中心(Zentrumfür Biosicherheit und Nachhaltigkeit),BATS中心(Zentrum BATS),克拉斯崔舍(Clarastrasse)13,巴塞尔(Basel)4058,瑞士)报告2003中。
术语“有用植物”应当被理解为还包括已经通过使用重组DNA技术而被这样转化使其能够合成具有选择性作用的抗病原物质的有用的植物,这些抗病原物质例如所谓的“病程相关蛋白”(PRP,参见例如EP-A-0 392 225)。此类抗病原物质以及能够合成此类抗病原物质的转基因植物的实例例如从EP-A-0 392 225、WO 95/33818、和EP-A-0 353 191是已知的。生产此类转基因植物的方法对于本领域的技术人员通常是已知的并且描述于例如以上提及的公开物中。
可以由此类转基因植物表达的抗病原物质包括,例如,离子通道阻断剂(例如钠和钙通道阻断剂,像病毒的KP1、KP4或KP6毒素);茋合酶;联苄合酶;几丁质酶;葡聚糖酶;所谓的“病程相关蛋白”(PRPs,参见例如EP-A-0 392 225);由微生物产生的抗病原物质,例如涉及植物病原体防御的肽抗生素或杂环类抗生素(参见例如WO 95/33818)或蛋白质或多肽因子(所谓的“植物疾病抗性基因”,如描述于WO 03/000906中的)。
与本发明有关的更有兴趣的有用植物为谷物;大豆;水稻;油菜;梨果;核果;花生;咖啡;茶;草莓;草皮;藤本植物及蔬菜,例如番茄、马铃薯、葫芦及莴苣。
如在此使用的,术语有用植物的“场所”旨在包括这些有用植物在其上生长的地方,在这些地方这些有用植物的植物繁殖材料被播种或者在这些地方这些有用植物的植物繁殖材料将被置于土壤中。这样的场所的一个实例是作物植物在其上生长的大田。
术语“植物繁殖材料”应当被理解为表示该植物的生殖部分,例如种子,这些部分可以用于该植物的繁殖,以及营养性材料,例如插条或块茎(例如马铃薯)。可以提及,例如种子(在严格意义上)、根、果实、块茎、球茎、根茎以及植物的部分。还可以提及在发芽后或破土后将被移植的发芽植物和幼小植物。这些幼小植物可以通过浸渍进行完全或部分处理而在移植之前进行保护。优选地,“植物繁殖材料”应当理解为表示种子。
本发明的进一步方面是一种保护取自天然生命周期的植物和/或动物源的天然物质和/或其加工形式免受真菌攻击的方法,其包括将协同有效量的组分(A)与(B)的组合施用至所述植物和/或动物源的天然物质或其加工形式。
根据本发明,术语“取自天然生命周期的植物源的天然物质”是指从天然生命周期所收割并且处于新鲜收割形式的植物或其部分。这样的植物源的天然物质的实例为茎、叶、块茎、种子、果实或谷粒。根据本发明,术语“植物源的天然物质的加工形式”被理解为是指改进加工的结果的植物源的天然物质的形式。这样改进加工可以用于将植物源的天然物质转换成这样一种物质的更加可储存的形式(存储货物)。这样改进加工的实例为预干燥、湿润、压碎、粉碎、研磨、压缩或焙烧。也落在植物源的天然物质的加工形式定义下的是木材,无论为原木形式,例如建筑木材、输电塔和栅栏,或为制成品形式,例如从木材制造的家具或物体。
根据本发明,术语“取自天然生命周期的动物源的天然物质和/或其加工形式”被理解为是指动物源的材料例如皮、兽皮、革、毛皮、毛发及类似物。
根据本发明的组合可以预防不利的作用,例如腐败、褪色或发霉。
优选的实施例为一种保护取自天然生命周期的植物和源的天然物质和/或其加工形式免受真菌攻击的方法,它包括将协同有效量的组分(A)与(B)的组合施用至所述植物和/或动物源的天然物质或其加工形式。
另一优选实施例为一种保护取自天然生命周期的果实(优选为梨果、核果、浆果和柑橘类水果)和/或它们的加工形式的方法,该方法包括将协同有效量的组分(A)和(B)的组合施用至所述果实和/或它们的加工形式。
本发明的这些组合还可以在保护工业材料免受真菌攻击的领域中使用。根据本发明,术语“工业材料”表示为了在工业上使用而制备的非生命材料。例如,旨在保护其免受真菌攻击的工业材料可以是胶(glue)、浆料(size)、纸、木板、纺织品、地毯、皮革、木材、建筑、漆料、塑料物品、冷却润滑剂、水性液压液以及其他可以被微生物侵染或者分解的材料。可以被微生物的繁殖损害的冷却和加热系统、通风和空调系统以及生产设备的部分(例如冷却水线路)也可以在有待保护的材料之中提及。根据本发明的组合可以预防不利的作用,例如腐败、褪色或发霉。
本发明的这些组合还可以在保护技术材料免受真菌攻击的领域中使用。根据本发明,术语“技术材料”包括纸;地毯;建筑;冷却和加热系统;通风和空调系统等等。根据本发明的组合可以预防不利的作用,例如腐败、褪色或发霉。
根据本发明的组合针对以下项是特别有效的:白粉病;锈病;叶斑病种类;早疫病和发霉;尤其针对在谷类上的壳针孢属、柄锈菌属、白粉菌、核腔菌属以及Tapesia;在大豆上的层锈菌;在咖啡上的锈病菌;在玫瑰上的多胞锈菌属;在马铃薯、番茄和葫芦上的链格孢菌;在草皮、蔬菜、向日葵和油菜上的核盘菌;在藤本植物上的黑腐病、红火病(redfire)、白粉病、灰霉病以及枯藤病;在水果上的灰葡萄孢菌;在水果上的链核盘菌以及在水果上的青霉菌属。
此外,根据本发明的组合针对种子传播的和土壤传播的疾病是特别有效的,例如链格孢霉属、壳二孢属、灰葡萄孢菌、尾孢属、麦角菌、禾旋孢腔菌、炭疽菌属、附球菌属、禾谷镰刀菌、串珠镰刀菌、尖孢镰刀菌、层出镰刀菌、茄病镰刀菌、胶孢镰刀菌、graminis、长蠕孢菌、雪霉叶枯菌、茎点霉属、麦类核腔菌、稻梨孢、立枯丝核菌、禾谷丝核菌、核盘菌属、壳针孢属、丝黑穗病菌、腥黑粉菌、肉孢核瑚菌、条黑粉菌属(Urocystis occulta)、黑粉菌或轮枝孢属;特别是针对谷类,例如小麦、大麦、黑麦或燕麦;玉米;水稻;棉花;大豆;草皮;甜菜;油菜;马铃薯;豆类作物,例如豌豆、滨豆或鹰嘴豆;以及向日葵的病原菌。
此外,根据本发明的组合针对以下收获后疾病是特别有效的,例如灰葡萄孢菌、香蕉炭疽菌、新月弯孢霉、Fusarium semitecum、白地霉、褐腐病菌、对苹果褐腐菌、核果链核盘菌、梨形毛霉、意大利青霉、离生青霉、指状青霉或扩展青霉;特别是针对水果,例如梨果(例如苹果和梨)、核果(例如桃和李子)、柑橘、甜瓜、木瓜、猕猴桃、芒果、浆果(例如草莓)、鳄梨、石榴和香蕉,以及坚果的病原菌。
要施用的本发明的组合的量将取决于各种因素,例如所使用的化合物;处理的目标(例如像植物、土壤或种子);处理形式(例如像喷雾、洒粉或拌种);处理目的(例如像预防或治疗);要控制的真菌类型或施用时间。
包含选自表1和表2的具有化学式I的化合物以及一种或多种如上所述的活性成分的混合物可以例如以一种单一的“掺水即用”的形式施用,以组合的喷洒混合物(该混合物由这些单一活性成分的单独配制品构成)(例如一种“桶混制剂”)施用,并且当以一种顺序的方式(即,一个在另一个适度短的时期之后,例如几小时或几天)施用时组合使用这些单独活性成分来施用。施用选自表1的具有化学式I的化合物和如上所述活性成分的顺序对于实施本发明并不是至关重要的。
根据本发明的所述组合中的一些具有内吸作用并且可以被用作叶上、土壤和种子处理的杀真菌剂。
使用根据本发明的组合,有可能抑制或破坏植物病原性微生物,这些微生物发生于在多种不同的有用植物的植物或植物部分(水果、花、叶子、茎、块茎、根)上发生的疾病,同时还保护了稍后生长的植物部分免于被植物病原性微生物侵袭。
本发明的组合对于控制在不同的有用的植物或其种子中的真菌是特别有意义的,尤其是大田作物中,例如马铃薯、烟草和甜菜以及小麦、黑麦、大麦、燕麦、稻、玉米、菌苔、棉花、大豆、油菜、豆荚作物、向日葵、咖啡、甘蔗、在园艺和葡萄种植中的果实以及观赏的植物,在蔬菜(例如黄瓜、豆和葫芦)中的真菌。
根据本发明的组合是通过优选地以协同有效量的组分(A)与(B)的组合处理真菌、被真菌攻击威胁的有用植物、其所在地、其繁殖材料、取自天然生命周期的植物和/或动物源天然物质和/或其加工形式、或工业材料而施用。
根据本发明的组合可以在有用植物、其繁殖材料、取自天然生命周期的植物和/或动物源的天然物质和/或其加工形式,或工业材料被真菌侵染之前或之后施用。
根据本发明的组合用于控制以下植物疾病是特别有用的:
在水果和蔬菜上的链格孢霉属物种,
在豆类作物上的壳二孢属物种,
在草莓、番茄、向日葵、豆类作物、蔬菜以及葡萄上的灰葡萄孢菌,
在花生上的花生褐斑病菌,
在谷类上的禾旋孢腔菌,
在豆类作物上的炭疽菌属物种,
在谷类上的白粉菌物种,
在葫芦上的菊科白粉菌和黄瓜白粉病菌,
在谷类和玉米上的镰刀菌物种,
在玉米、水稻和马铃薯上的长蠕孢菌物种,
在咖啡上的咖啡驼孢锈菌,
在小麦和黑麦上的雪霉叶枯菌物种,
在大豆上的层锈菌属物种,
在谷类、阔叶作物和多年生植物上的柄锈菌属物种,
在谷类上的假小尾孢属物种,
在玫瑰上的病原为多胞锈菌,
在水果上的白粉病菌物种,
在大麦上的核腔菌属物种,
在水稻上的稻梨孢,
在大麦上的天鹅胶柱隔孢,
在棉花、大豆、谷类、玉米、马铃薯、水稻以及菌苔上的丝核菌属物种,
在大麦和黑麦上的黑麦喙孢,
在菌苔、莴苣、蔬菜以及油菜上的核盘菌物种,
在谷类、大豆以及蔬菜上的壳针孢属物种,
在玉米上的丝黑穗病菌,
在谷类上的腥黑粉菌属物种,
在藤本植物上的葡萄钩丝壳、葡萄球座菌以及葡萄生拟茎点霉属,
在黑麦上的条黑粉菌属,
在谷类和玉米上的黑粉菌属物种,
在水果里的黑星菌物种,
在水果上的链核盘菌物种,
在柑橘和苹果上的青霉菌物种。
根据本发明的组合在害虫防治领域中是有预防和/或治疗价值的活性成分,即使是以低的施用量施用,它们具有非常有利的杀生物谱并且是温血物种、鱼和植物良好耐受的。根据本发明的这些活性成分(它们由于其杀虫作用而被部分已知)作用于正常敏感的但是还抗药的动物害虫(例如昆虫或蜱螨目的代表)的所有的或个别的发育阶段。根据本发明的这些组合的杀昆虫的或杀螨的活性可以直接地表现自身,即:例如在蜕皮期间有害生物的破坏,其立即或者在一段时间之后发生;或间接地表现自身,例如减少的产卵和/或孵化率,良好的活性相应于至少50%至60%的破坏率(死亡率)。
上述动物有害生物的实例是:
来自蜱螨目,例如,
粗脚粉螨、柑桔瘤瘿螨、苹刺瘿螨、钝眼蜱属、锐缘蜱属、牛蜱属、短须螨属、苜蓿苔螨、上三节瘿螨属、皮螨属、鸡皮刺螨、鹅耳枥始叶螨、瘦螨属、璃眼蜱属、硬蜱属、草地小爪螨、钝缘蜱属、全爪螨属、柑桔锈螨、侧多食跗线螨、痒螨属、扇头蜱属、根嗜螨属、疥螨属、跗线螨属以及四爪螨属;
来自虱目,例如,
血虱属、长颚虱属、人虱属、天疱疮属以及木虱属;
来自鞘翅目,例如,
金针虫属、棉铃象甲属、甜菜隐食甲、甜菜胫跳甲、根颈象甲属、象虫属、皮蠹属、根萤叶甲属、食植瓢虫属、Eremnus spp.、马铃薯甲虫、稻水象甲属、金龟属、锯谷盗属、耳喙象属(Otiorhynchus spp.)、葡萄藤象鼻虫属、丽金龟属、油菜跳甲属、劫根蠹属、金龟子科、米象属、麦蛾属、拟步行虫属、拟谷盗属和斑皮蠹属;
来自双翅目,例如,
伊蚊属、高粱芒蝇、花园毛蚊、红头丽蝇、实蝇属、金蝇属、库蚊属、黄蝇属、寡毛实蝇属、黑腹果蝇、厕蝇属、胃蝇属、舌蝇属、皮蝇属、虱蝇属、斑潜蝇属、绿蝇属、黑潜蝇属、蝇属、狂蝇属、痿蚊属、瑞典麦秆蝇、甜菜潜叶蝇、草种蝇属、苹果实蝇、尖眼蕈蚊属、螫蝇属、虻属、螗蜩属以及大蚊属;
来自半翅目,例如,
臭虫属、可可瘤盲蜂、棉红蝽属、美洲蝽属、扁盾蝽属、稻缘蝽属、绿蝽属、拟网蝽属、红猎蝽属、可可褐盲蝽、黑蝽属以及锥蝽属;
来自同翅目,例如,
软毛粉虱、菜粉虱、肾圆盾蚧属、蚜科、蚜属、圆盾蚧属、烟粉虱、介壳虫属、褐圆蚧、网籽草叶圆蚧、褐软蚧、茶小绿叶蝉属、苹果绵蚜、叶蝉属、蜡蛤属、灰飞虱属、球坚蚧、牡蛎蚧属、长管蚜属、瘤蚜属、黑尾叶蝉属、褐飞虱属、片盾蚧属、棉蚜属、动性球菌属、白盾蚧属、粉蚧属、木虱属、棉蚧(Pulvinaria aethiopica)、笠圆盾蚧属、缢管蚜属、黑盔蚧属、带叶蝉属、二叉蚜属、麦蚜属(Sitobion spp.)、温室粉虱、非洲木虱和桔矢尖蚧;
来自膜翅目,例如,顶切叶蚁属、布切叶白蚁属、茎叶蜂属、松叶蜂属、锯角叶蜂科、松叶蜂(Gilpinia polytoma)、毛蚁属、小黄家蚁、厨蚁属、新松叶蜂属、水蚁属以及胡蜂属;
来自等翅目,例如,
散白蚁属;
来自鳞翅目,例如,
长翅卷蛾属、褐带卷蛾属、透翅蛾属、夜盗虫属、棉树叶虫、淀粉虫属、黎豆夜蛾、黄卷蛾属、带卷蛾属、丫纹夜蛾属、玉米茎蛀褐夜蛾、粉斑螟蛾、桃小食心虫、禾草螟属、色卷蛾属、葡萄果蠹蛾、纵卷叶野螟属、云卷蛾属、细卷蛾属、鞘蛾属、大菜螟、苹果异形小卷蛾、小卷蛾属、杆草螟属、苏丹棉铃虫、钻夜蛾属、粉斑螟属、花小卷蛾属、葡萄螟蛾、黄毒蛾属、切夜蛾属、小食心虫属、云雾广翅小卷蛾、实夜蛾属、菜螟、美国白蛾、番茄蠹蛾、旋纹潜叶蛾、潜叶细蛾属、葡萄浆果小卷蛾、毒蛾属、潜蛾属、天幕毛虫属、甘蓝夜蛾、烟草天蛾、秋尺蛾属、欧洲玉米螟、超小卷蛾属、褐卷蛾属、冬夜蛾、棉红铃虫、马铃薯块茎蛾、菜青虫、菜粉蝶属、小菜蛾、小白巢蛾属、白禾螟属、蛀茎夜蛾属、长须卷蛾属、夜蛾属、透翅蛾属、异舟蛾属、卷蛾属、粉纹夜蛾以及巢蛾属;
来自食毛目,例如,
畜虱属和啮毛虱属;
来自直翅目,例如,
蠊属、小蠊属、蝼蛄属、马德拉蜚蠊、飞蝗属、大蠊属以及沙漠蝗属;
来自啮虫目,例如,
虱啮属(Liposcelis spp);
来自蚤目,例如,
角叶蚤属、栉头蚤属和印鼠客蚤;
来自缨翅目,例如,
花蓟马属,褐带蓟马属,南非柑桔蓟马,带蓟马属,棕榈蓟马和烟蓟马;
来自缨尾目,例如,
衣鱼;
线虫,例如根结线虫、茎线虫以及叶面线虫;
尤其是异皮线虫属,例如甜菜异皮线虫、燕麦异皮线虫和三叶草异皮线虫;球异皮线虫属,例如马铃薯金线虫(Globodera rostochiensis);根结线虫属,例如西瓜根结瘤线虫(Meloidogyne incoginita)和爪哇根结线虫(Meloidogyne javanica);穿孔线虫属(Radopholus spp.),例如相似穿孔线虫(Radopholus similis);短体线虫属,例如落选短体线虫(Pratylenchus neglectans)和穿刺短体线虫(Pratylenchus penetrans);小垫刃线虫属,例如半穿刺线虫(Tylenchulus semipenetrans);长针线虫,毛刺线虫属,剑线虫属,双垫刃属,滑刃线虫属和鳗属;
十字花科植物跳甲(条跳甲属);
根蛆(地种蝇属)以及
卷心菜心皮象鼻虫(龟象属)。
根据本发明的组合可以用于控制,即限制或破坏,出现在农业、园艺和森林中的有用植物上,或在有用植物的器官例如果实、花、叶、茎、块茎或根上的上述类型的动物有害生物,并且在一些情况下,甚至在较晚的时间点形成的有用植物器官上保持针对这些动物有害生物的保护。
取决于用作组分(B)的化学品的类别,当与1至5000g a.i./ha,特别是2至2000ga.i./ha,例如100g a.i./ha、250g a.i./ha、500g a.i./ha、800g a.i./ha、1000g a.i./ha、1500g a.i./ha的组分(B)组合施用至有用植物时,组分(A)是以5至2000g a.i./ha,特别是10至1000g a.i./ha,例如50g a.i./ha、75g a.i./ha、100g a.i./ha或200g a.i./ha的比率施用的。
在农业实践中,根据本发明的组合的施用比率取决于所希望的作用的类型,并且典型地是在从20至4000g的总联合每公顷的范围内。
当本发明的组合用于处理种子时,比率为0.001至50g具有化学式I的化合物/每kg的种子、优选从0.01至10g/每kg的种子,以及0.001至50g的组分(B)的化合物/每kg的种子、优选从0.01至10g/每kg的种子,这一般是足够的。
本发明还提供杀真菌组合物,其如以上提及包括协同有效量的组分(A)与(B)的组合以及农业上可接受的载体以及任选地表面活性剂。在所述组合物中,(A)与(B)的重量比优选地是在1000:1与1:1000之间。
本发明的组合物能以任何常规形式使用,例如,具有双包装、干种子处理用的粉剂(DS)、种子处理用的乳液(ES)、种子处理用的可流动性浓缩剂(FS)、种子处理用的溶液(LS)、种子处理用的水分散性粉剂(WS)、种子处理用的胶囊悬浮剂(CF)、种子处理用的凝胶(GF)、乳液浓缩剂(EC)、悬浮浓缩剂(SC)、悬浮乳液(SE)、胶囊悬浮剂(CS)、水分散性粒剂(WG)、可乳化性粒剂(EG)、油包水型乳液(EO)、水包油型乳液(EW)、微乳液(ME)、分散性油悬剂(OD)、油悬剂(OF)、油溶性液剂(OL)、可溶性浓缩剂(SL)、超低容量悬浮剂(SU)、超低容量液剂(UL)、母药(TK)、可分散性浓缩剂(DC)、可湿性粉剂(WP)或与农业上可接受的佐剂组合的任何技术上可行的配制品形式。
能以常规方式生产这样的组合物,例如通过混合活性成分与适当的配制惰性剂(稀释剂、溶剂、填充剂及任选地其他配制成分,例如表面活性剂、杀生物剂、防冻剂、黏着剂、增稠剂及提供辅佐效果的化合物)。还可以使用意欲长期持续药效的常规缓释配制品。特别要以喷雾形式,如水可分散性浓缩物(例如EC、SC、DC、OD、SE、EW、EO和类似物)、可湿性粉剂及粒剂施用的配制品,可包含表面活性剂例如湿润剂和分散剂及提供辅佐效果的其他化合物,例如甲醛与萘磺酸盐、烷芳基磺酸盐、木质素磺酸盐、脂肪烷基硫酸盐及乙氧基化烷基酚和乙氧基化脂肪醇的缩合产物。
使用本发明的组合及稀释剂,以适合的拌种配制品形式,例如具有对种子的良好粘着性的水性悬浮液或干粉剂形式,用自身已知的方式将拌种配制品施用至种子。在本领域这样的拌种配制品是已知的。这样的拌种配制品可以包含封胶形式的单一活性成分或活性成分的组合,例如为缓释胶囊或微胶囊。
通常,配制品包括按重量计从0.01%至90%的活性成分,从0至20%的农业上可接受的表面活性剂及10%至99.99%的固体或液体配制惰性剂和一种或多种辅助剂,该活性剂是由至少具有化学式I的化合物与组分(B)和(C)一起,以及任选地其他活性剂(特别是杀微生物剂或防腐剂或类似物)组成的。按重量计,组合物的浓缩形式通常包含在约2%和80%之间,优选在约5%和70%之间的活性剂。配制品的施用形式可以例如包含按重量计从0.01%至20%,优选按重量计从0.01%至5%的活性剂。而商用的产品将优选地被配制为浓缩物,该最终使用者将通常使用稀释的配制品。
接下来的为说明本发明服务的实例中,“活性成分”表示处于特定混合比率的化合物I和组分(B)的化合物的混合物。
配制品实例
将该活性成分与这些辅助剂充分混合并且将混合物在一个适当的研磨机中充分研磨,从而获得了可以用水稀释而给出所希望的浓度的悬浮液的可湿性粉剂。
将活性成分与佐剂充分地混合并且在一个合适的研磨机中充分地研磨该混合物,得到可以直接用于种子处理的粉末。
可乳化性浓缩物
在植物保护中可以使用的具有任何所要求的稀释的乳液可以通过用水稀释从这种浓缩物中获得。
通过将活性成分与载体混合并且将该混合物在适合的研磨机中研磨而获得即用型尘剂。此类粉剂还可以用于种子的干法敷料。
挤出机颗粒
将活性成分与这些佐剂混合并且研磨,并且将混合物用水润湿。将混合物挤出并且然后在空气流中干燥。
包衣的颗粒活性成分(I:组分(B)=1:10) 8%
聚乙二醇(mol.wt.200) 3%
高岭土 89%
将该精细研磨的活性成分在一个混合器中均匀地施用到用聚乙二醇湿润的高岭土上。以此方式获得无尘的包衣的颗粒。
悬浮浓缩剂
将精细地研磨的活性成分与佐剂紧密地混合,得到悬浮浓缩剂,从该悬浮浓缩剂可以通过用水稀释获得任何所希望的稀释度的悬浮液。使用此类稀释体,可以对活的植物连同植物繁殖材料进行处理并且对其针对微生物侵染通过喷洒、倾倒或浸渍进行保护。
种子处理用的可流动性浓缩剂
将精细地研磨的活性成分与佐剂紧密地混合,得到悬浮浓缩剂,从该悬浮浓缩剂可以通过用水稀释获得任何所希望的稀释度的悬浮液。使用此类稀释体,可以对活的植物连同植物繁殖材料进行处理并且对其针对微生物侵染通过喷洒、倾倒或浸渍进行保护。
缓释的胶囊悬浮剂
将28份的具有化学式I的化合物和组分(B)的组合或这些化合物各自分开地与2份的芳香族溶剂和7份的甲苯二异氰酸酯/聚亚甲基-聚苯基异氰酸酯-混合物(8:1)进行混合。将该混合物在1.2份的聚乙烯醇、0.05份的消泡剂以及51.6份的水的混合物中进行乳化直至达到所希望的颗粒尺寸。向这个乳液中添加在5.3份的水中的2.8份的1,6-己二胺混合物。将该混合物搅拌直至聚合反应完成。
将获得的胶囊悬浮剂通过添加0.25份的一种增稠剂以及3份的分散剂进行稳定。该胶囊悬浮剂配制品包括28%的活性成分。该介质胶囊的直径是8微米-15微米。
将产生的配制品施用到种子上作为适合于用于此目的的一种装置中的水性悬浮液。
生物学实例
在孔板中的液体培养试验:
将一种真菌的菌丝体片段或分生孢子(从该真菌的液体培养物或从低温储存物新鲜制备)直接混入营养肉汤中。将试验化合物的DMSO溶液(最大10mg/ml)通过用0.025%的吐温20进行稀释50倍,并且将10μl的这种溶液用移液管移取到一个微量滴定板(96孔规格)中。然后将包含该真菌孢子/菌丝体片段的营养肉汤添加到其中,从而给出该试验化合物的终浓度。将这些试验板在24℃和96%rh的黑暗中进行孵育。取决于病害系统,2-4天之后通过光度法和观察法测定真菌生长的抑制,并且计算相对于未处理的百分抗真菌活性。
茄链格孢菌/液体培养:
将来自冷冻储存的真菌分生孢子直接混入营养肉汤(PDB(马铃薯葡萄糖肉汤))中。在将测试化合物的(DMSO)溶液置于微量滴定板(96孔规格)中以后,添加含有真菌孢子的营养肉汤。将这些测试板在24℃培育并且在施用后2-3天通过光度法和观察法测定对生长的抑制。
灰葡萄孢霉(Botryotinia fuckelian)(灰葡萄孢(Botrytis cinerea))/液体培
养:
将来自冷冻储存的真菌分生孢子直接混入营养肉汤(Vogels(沃格尔)肉汤)中。在将测试化合物的(DMSO)溶液置于微量滴定板(96孔规格)中以后,添加含有真菌孢子的营养肉汤。将这些测试板在24℃培育并且在施用后3天通过光度法和观察法测定对生长的抑制。
黄色镰刀菌/液体培养:
将来自冷冻储存的真菌分生孢子直接混入营养肉汤(PDB(马铃薯葡萄糖肉汤))中。在将测试化合物的(DMSO)溶液置于微量滴定板(96孔规格)中以后,添加含有真菌孢子的营养肉汤。将这些测试板在24℃培育并且在施用后3天通过光度法和观察法测定对生长的抑制。
小麦全蚀病菌/液体培养:
将来自低温储存物的菌丝体片段直接混入营养肉汤(PDB(马铃薯葡萄糖肉汤))中。在将测试化合物的(DMSO)溶液置于微量滴定板(96孔规格)中以后,添加含有真菌孢子的营养肉汤。将这些测试板在24℃培育并且在施用后3-4天通过光度法和观察法测定对生长的抑制。
雪腐明梭孢(雪霉叶枯菌)/液体培养:
将来自冷冻储存的真菌分生孢子直接混入营养肉汤(PDB(马铃薯葡萄糖肉汤))中。在将测试化合物的(DMSO)溶液置于微量滴定板(96孔规格)中以后,添加含有真菌孢子的营养肉汤。将这些测试板在24℃培育并且在施用后3-4天通过光度法和观察法测定对生长的抑制。
禾生球腔菌(小麦壳针孢)/液体培养:
将来自冷冻储存的真菌分生孢子直接混入营养肉汤(PDB(马铃薯葡萄糖肉汤))中。在将测试化合物的(DMSO)溶液置于微量滴定板(96孔规格)中以后,添加含有真菌孢子的营养肉汤。将这些测试板在24℃培育并且在施用后4天通过光度法和观察法测定对生长的抑制。
终极腐霉(苗期猝倒病)/液体培养:
将新培养的液体培养真菌的丝状体片段与卵孢子直接混入营养肉汤(PDB马铃薯葡萄糖肉汤)中。在将测试化合物的(DMSO)溶液置于微量滴定板(96孔规格)中以后,添加含有真菌菌丝体/孢子的混合物的营养肉汤。将这些测试板在24℃孵育并且在施用后2-3天通过观察法测定对生长的抑制。
结果
以下在表3至38中示出了来自以上概述的测试的结果的代表性实例。这些数据示出在如以上概述的针对一种或多种真菌的测试中,对于以下组合中的每一个观察到协同杀真菌活性:具有化学式(I)的化合物和(B1)具有化学式(II)、具有化学式(I)的化合物和(B2)胺苯吡菌酮、具有化学式(I)的化合物和(B4)欧塞匹林、具有化学式(I)的化合物和(B5)托普威、具有化学式(I)的化合物和(B6)氟菌螨酯、具有化学式(I)的化合物和(B9)具有化学式(III)的化合物、具有化学式(I)的化合物和(B10)丁香菌酯、具有化学式(I)的化合物和(B11)曼德斯宾、具有化学式(I)的化合物和(B12)异丁乙氧喹啉、具有化学式(I)的化合物和(B13)氯啶菌酯、具有化学式(I)的化合物和(B14)具有化学式(IV)的化合物。在所有情况下,测试的具有化学式(I)的化合物为化合物1.001(即3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-甲基-2-(2,4,6-三氯苯基)乙基]吡唑-4-甲酰胺)。
表3具有化学式(I)的化合物(化合物1.001)和(B1)具有化学式(II)的化合物的杀真菌活性–在这一情况下,其中R9是甲基-针对PDB中的终极腐霉
表4具有化学式(I)的化合物(化合物1.001)和(B1)具有化学式(II)的化合物的杀真菌活性–在这一情况下,其中R9是甲基-针对PDB中的黄色镰刀菌
表5具有化学式(I)的化合物(化合物1.001)和(B1)具有化学式(II)的化合物的杀真菌活性–在这一情况下,其中R9是甲基-针对PDB中的雪腐明梭孢(白小羊蹄菌(Michrodocium nivale))
表6具有化学式(I)的化合物(化合物1.001)和(B1)具有化学式(II)的化合物的杀真菌活性–在这一情况下,其中R9是甲基-针对沃格尔(Vogels)肉汤中的灰葡萄孢霉(灰葡萄孢)
表7具有化学式(I)的化合物(化合物1.001)和(B1)具有化学式(II)的化合物的杀真菌活性–在这一情况下,其中R9是甲基-针对PDB中的茄链格孢菌
表8具有化学式(I)的化合物(化合物1.001)和(B1)具有化学式(II)的化合物的杀真菌活性–在这一情况下,其中R9是甲基-针对PDB中的禾生球腔菌(小麦壳针孢)
表9具有化学式(I)的化合物(化合物1.001)和(B2)胺苯吡菌酮的杀真菌活性,针对PDB中的茄链格孢菌
表10具有化学式(I)的化合物(化合物1.001)和(B4)欧塞匹林的杀真菌活性,针对PDB中的终极腐霉
表11具有化学式(I)的化合物(化合物1.001)和(B4)欧塞匹林的杀真菌活性,针对PDB中的茄链格孢菌
表12具有化学式(I)的化合物(化合物1.001)和(B4)欧塞匹林的杀真菌活性,针对PDB中的禾生球腔菌(小麦壳针孢)
表13具有化学式(I)的化合物(化合物1.001)和(B5)托普威的杀真菌活性,针对PDB中的茄链格孢菌
表14具有化学式(I)的化合物(化合物1.001)和(B5)托普威的杀真菌活性,针对PDB中的禾生球腔菌(小麦壳针孢)
表15具有化学式(I)的化合物(化合物1.001)和(B6)氟菌螨酯的杀真菌活性,针对PDB中的黄色镰刀菌
表16具有化学式(I)的化合物(化合物1.001)和(B6)氟菌螨酯的杀真菌活性,针对PDB中的雪腐明梭孢(白小羊蹄菌)
表17具有化学式(I)的化合物(化合物1.001)和(B6)氟菌螨酯的杀真菌活性,针对沃格尔(Vogels)肉汤中的灰葡萄孢霉(灰葡萄孢)
表18具有化学式(I)的化合物(化合物1.001)和(B6)氟菌螨酯的杀真菌活性,针对PDB中的茄链格孢菌
表19具有化学式(I)的化合物(化合物1.001)和(B6)氟菌螨酯的杀真菌活性,针对PDB中的禾生球腔菌(小麦壳针孢)
表20具有化学式(I)的化合物(化合物1.001)和(B9)具有化学式(III)的化合物的杀真菌活性,针对PDB中的雪腐明梭孢(白小羊蹄菌)
表21具有化学式(I)的化合物(化合物1.001)和(B9)具有化学式(III)的化合物的杀真菌活性,针对沃格尔(Vogels)肉汤中的灰葡萄孢霉(灰葡萄孢)
表22具有化学式(I)的化合物(化合物1.001)和(B9)具有化学式(III)的化合物的杀真菌活性,针对PDB中的茄链格孢菌
表23具有化学式(I)的化合物(化合物1.001)和(B9)具有化学式(III)的化合物的杀真菌活性,针对PDB中的禾生球腔菌(小麦壳针孢)
表24具有化学式(I)的化合物(化合物1.001)和(B10)丁香菌酯的杀真菌活性,针对PDB中的黄色镰刀菌
表25具有化学式(I)的化合物(化合物1.001)和(B10)丁香菌酯的杀真菌活性,针对PDB中的雪腐明梭孢(白小羊蹄菌)
表26具有化学式(I)的化合物(化合物1.001)和(B10)丁香菌酯的杀真菌活性,针对PDB中的禾生球腔菌(小麦壳针孢)
表27具有化学式(I)的化合物(化合物1.001)和(B11)曼德斯宾的杀真菌活性,针对PDB中的黄色镰刀菌
表28具有化学式(I)的化合物(化合物1.001)和(B11)曼德斯宾的杀真菌活性,针对PDB中的雪腐明梭孢(白小羊蹄菌)
表29具有化学式(I)的化合物(化合物1.001)和(B11)曼德斯宾的杀真菌活性,针对沃格尔(Vogels)肉汤中的灰葡萄孢霉(灰葡萄孢)
表30具有化学式(I)的化合物(化合物1.001)和(B11)曼德斯宾的杀真菌活性,针对PDB中的茄链格孢菌
表31具有化学式(I)的化合物(化合物1.001)和(B11)曼德斯宾的杀真菌活性,针对PDB中的小麦全蚀病菌
表32具有化学式(I)的化合物(化合物1.001)和(B12)异丁乙氧喹啉的杀真菌活性,针对PDB中的雪腐明梭孢(白小羊蹄菌)
表33具有化学式(I)的化合物(化合物1.001)和(B12)异丁乙氧喹啉的杀真菌活性,针对沃格尔(Vogels)肉汤中的灰葡萄孢霉(灰葡萄孢)
表34具有化学式(I)的化合物(化合物1.001)和(B12)异丁乙氧喹啉的杀真菌活性,针对PDB中的茄链格孢菌
表35具有化学式(I)的化合物(化合物1.001)和(B13)氯啶菌酯的杀真菌活性,针对PDB中的黄色镰刀菌
表36具有化学式(I)的化合物(化合物1.001)和(B13)氯啶菌酯的杀真菌活性,针对PDB中的雪腐明梭孢(白小羊蹄菌)
表37具有化学式(I)的化合物(化合物1.001)和(B13)氯啶菌酯的杀真菌活性,针对沃格尔(Vogels)肉汤中的灰葡萄孢霉(灰葡萄孢)
表38具有化学式(I)的化合物(化合物1.001)和(B14)具有化学式IV的化合物的杀真菌活性,针对PDB中的雪腐明梭孢(白小羊蹄菌)
Claims (6)
1.一种适合于控制由植物病原菌引起的疾病的组合物,该组合物包括
作为组分(A)的化合物3-(二氟甲基)-N-甲氧基-1-甲基-N-[1-甲基-2-(2,4,6-三氯苯基)乙基]吡唑-4-甲酰胺或其农业化学上可接受的盐、立体异构体、非对映异构体、对映异构体和互变异构体;
以及作为成分(B)的选自下组的化合物,该组由以下各项组成
(B9)具有化学式(III)的化合物
(B5)托普威;
(B12)异丁乙氧喹啉;
(B14)具有化学式(IV)的化合物
(B3)异丙噻菌胺;
(B7)BLAD;
(B8)UK-2A普若赛德;
(B15)具有化学式V的化合物
(B16)双炔酰菌胺;或其农业化学上可接受的盐,
其中(A)与(B)的重量比是从1000:1至1:1000。
2.根据权利要求1所述的组合物,其中组分(A)和(B)以协同有效量存在。
3.根据权利要求1所述的组合物,其中(A)与(B)的重量比是从40:1至1:40。
4.根据权利要求1所述的组合物,其中(A)与(B)的重量比选自由1:4、1:5、4:35、1:10、2:35、4:75、1:20、1:35、2:75和1:40组成的组。
5.根据权利要求1所述的组合物,进一步包括农业上可接受的佐剂和/或载体。
6.控制有用植物上或其繁殖材料上由植物病原菌引起的疾病的方法,该方法包括将如权利要求1定义的组合物施用至这些有用植物、其场所或其繁殖材料。
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