CN100384327C - 包括ps-ⅱ抑制剂和sar诱导剂的除草剂组合物 - Google Patents

包括ps-ⅱ抑制剂和sar诱导剂的除草剂组合物 Download PDF

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CN100384327C
CN100384327C CNB03825977XA CN03825977A CN100384327C CN 100384327 C CN100384327 C CN 100384327C CN B03825977X A CNB03825977X A CN B03825977XA CN 03825977 A CN03825977 A CN 03825977A CN 100384327 C CN100384327 C CN 100384327C
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salicylate
acid
herbicidal composition
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F·P·西尔弗曼
Z·志國
P·D·佩特拉塞克
D·F·海曼
P·瓦里奥尔
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Abstract

包括PSII抑制剂和SAR诱导剂的除草剂组合物及其使用方法。

Description

包括PS-Ⅱ抑制剂和SAR诱导剂的除草剂组合物
发明背景
许多除草剂已经用于在耕种田地或果园中消灭不希望的植物(杂草)。这些除草剂被喷雾到土壤上(出土前)或被喷雾到杂草上(出土后)。
除草剂是昂贵的，它们的使用可能会导致无意的后果如损害农作物、造成地下水污染、环境损害、导致耐除草剂杂草的发展、和人以及哺乳动物的健康问题。
现在有许多类型的除草剂，可以根据它们的作用方式对其进行分组。一类特别令人感兴趣的除草剂是光合作用的光系统II(PSII)抑制剂。这些包括三嗪如莠去津；三嗪酮如嗪草酮；尿嘧啶如除草定；腈如溴苯腈；苯并噻二唑如灭草松；以及脲如敌草隆。PSII抑制剂通过在光合成过程中抑制电子的转移来起作用。抑制作用阻断了光合成、CO2的固定、和ATP或NADPH的生成。由于生成了能够引发脂质过氧化作用的自由基物种，并最终使细胞死亡而导致植物死亡。
本发明的目的是：(1)减少有效处理所需要的除草剂的量，(2)减短除草剂施用和植物死亡之间的时间，和(3)增加PSII抑制剂如莠去津及其盐用来预防耐除草剂杂草发展的的效能。
发明概述
本发明涉及除草剂组合物，其包括PSII抑制剂和水杨酸盐或系统获得抗性(SAR)诱导剂。
本发明涉及改变PSII抑制剂除草活性的方法，其包括向PSII抑制剂中加入有效量的水杨酸盐或SAR诱导剂。更具体地讲，本发明涉及增强PSII抑制剂除草活性的方法，其包括向PSII抑制剂中加入有效量的水杨酸盐或SAR诱导剂。在本发明方法的实施过程中，水杨酸盐或SAR诱导剂和PSII抑制剂同时或几乎同时施用于土壤或待处理的植物上。
本发明还涉及控制植物生长的方法，其包括在植物上施用除草有效量的包括PSII抑制剂和水杨酸盐或SAR诱导剂的除草剂组合物。
发明详述
水杨酸盐定义为在2位-或邻位上具有羟基的任何取代的或者未取代的苯甲酸，或其生物学可接受的盐或者生物或化学前体。苯甲酸上的取代包括在3-、4-、5-和/或6-位上的单、二、三或四取代：取代基可以是选自以下所述的任意的组合：在两个相邻点连接到苯甲酸上的含3或4个碳的烷基桥；1-4个碳的低级烷氧基；卤素氟，氯，溴或者碘；氨基，其中氮可以带有0、1、或2个相同或不同的各有1-4个碳的低级烷基；硝基；甲酰基；乙酰基；羟甲基；甲氧羰基；碳酰胺基或磺酰胺基，其中氮可以带有0、1、或2个相同或不同的各有1-4个碳的低级烷基取代基；氰基；烷硫基-、烷基硫氧基或烷基磺酰基，其中烷基由1-4个碳组成或是单-、二-或三氟甲基基团。在术语″水杨酸盐″的定义中也包括杂环衍生物，其中2-羟基苯甲酸的一个或多个环碳原子替换为一个或多个氮原子。有代表性的这种衍生物是羟基-吡啶羧酸，如3-羟基吡考啉酸。生物学可接受的盐包括那些常见的碱金属钠和钾盐、碱土金属镁或钙盐、锌盐、或者铵或单一的烷基铵阳离子如单-、二-、三-或四甲铵或其它最多带有7个碳的铵阳离子的盐。2-羟基化的苯甲酸的生物或化学前体包括至少一个邻位处于游离态的未羟基化的苯甲酸和其衍生物，其中羟基通过所述化合物所施用的植物的自然代谢过程而以生物学的方式引入。2-羟基化的苯甲酸的生物或化学前体还包括以下苯甲酸化合物，其中2-位上的羟基被以化学方法保护，这种保护基团是不稳定的并且很容易脱除，一旦化合物已经被施用到植物上，它或者通过植物正常代谢作用的酶催化过程或者通过缓慢的自发水解而脱除。这种保护基团的实例包括1-7个碳的单羧酸酯，和包含3-13个碳的三烷基甲硅烷基醚。
优选的水杨酸盐包括水杨酸钠，水杨酸，4-氯水杨酸，5-氯水杨酸，3，5-二氯水杨酸和3-羟基吡考啉酸。
SAR诱导剂定义为能在植物中提高对疾病产生剂的抵抗力的任何化合物，所述疾病产生剂包括但是不局限于病毒，细菌，真菌，或其组合。植物对病原体的抗病性应答的组分是涉及到诱发发病的蛋白质。另外，SAR诱导剂可以诱导对于食用植物的昆虫的抗性，正如Enyedi等人在(1992；Cell，70：879-886)所定义。示范性的SAR诱导剂覆盖许多结构体系的化合物，但是却通过它们诱导与发病有关的蛋白质、诱导对植物病害和/或食用植物的害虫的抗性能力而成为一体。一类SAR诱导剂是水杨酸盐。另一类SAR诱导剂包括苯并噻二唑衍生物，如以Actigard销售的Acibenzolar-S-甲基。又一例SAR诱导剂是2，6-二氯异烟酸。激卫素(Elicitors)构成另一类也许可具有这一用途的试验性的SAR诱导剂。
本发明的组合物包含50％-0.0001％的PSII抑制剂和50.0％-0.001％的水杨酸盐或SAR诱导剂，优选5.0％-0.001％的PSII抑制剂和1.0％-0.01％的水杨酸盐或SAR诱导剂，最优选0.5％-0.05％的PSII抑制剂和0.4％-0.05％的水杨酸盐或SAR诱导剂。
本发明的组合物分散或溶于水中，形成用于施用的浓度15％-0.0015％，优选5.0％-0.002％，最优选1.0％-0.05％。
本发明的组合物也可以配制成除草剂浓缩物的形式，其具有足以用于商业用途的储存稳定性，并在使用之前用水稀释。这种浓缩物包含浓度为99％-0.01％的本发明的除草剂加上水杨酸盐或SAR诱导剂组合物，优选50％-0.1％，最优选40％-1％。所有的百分比都是重量百分比。
在本发明的另一实施方案中，PSII抑制剂可以配制为浓缩物的形式，水杨酸盐或其它的SAR诱导剂可以配制为分离的浓缩物形式。然后，这两种浓缩物在使用之前混合并稀释。
有代表性的PSII抑制剂是莠去津，6-氯-N-乙基-N′-(1-甲基乙基)-1，3，5-三嗪-2，4-二胺；灭草松，3-(1-甲基乙基)-1H-2，1，3-苯并噻二嗪-4(3H)-酮-2，2-二氧化物，和它们的盐。这些包括以Aatrex 销售的莠去津制剂，和任何单独包含有PSII抑制剂或其盐或包含其与其它除草剂组合的制剂。
用于本发明的SAR诱导剂包括水杨酸盐和ActigardTM(Acibenzolar-S-甲基＝1，2，3-苯并噻二唑-7-硫代羟酸(carbothioic acid)-S-甲酯；CAS登记号为135158-54-2)，由NC，Greensboro的SyngentaCrop Protection公司出售。
本发明的组合物包括准备好立即使用的液体组合物，和在使用之前需要，通常用水作为溶剂进行稀释的固体或液体浓缩组合物。
固体组合物可以呈颗粒或扑粉形式，其中活性成分与细分散的固体稀释剂(如高岭土，膨润土，硅藻土，白云石，碳酸钙，滑石，粉末氧化镁，漂白土或石膏)混合。它们也可以呈可分散性粉剂或颗粒的形式，包括用于促进粉末或颗粒分散在液体中的润湿剂。呈粉末形式的固体组合物可以以叶用粉尘的形式施用。
液体组合物可以包括其中活性成分处于任选包含有表面活性剂的水中的溶液、悬浮液或分散液，或者可以包括活性成分处于与水不溶混的有机溶剂中的溶液或分散液，其以液滴或胶束的形式分散在水中。本发明组合物优选的活性成分是水溶性的除草剂，或者其很容易悬浮在水中，优选使用水性组合物和浓缩物。
本发明的组合物可以包含另外的表面活性剂，包括例如，用于增加以上所讨论的浓缩组合物的相容性或稳定性的表面活性剂。这种表面活性剂可以是阳离子的，阴离子的，或非离子的，或两性的，或者是其混合物。阳离子试剂是，例如，季铵化合物(如，溴化十六烷基三甲基铵)。适当的阴离子试剂是皂类，硫酸的脂肪族单酯盐，例如十二烷硫酸钠；和磺化芳族化合物的盐，例如十二烷基苯磺酸钠，木素磺酸、丁基萘磺酸钠盐、钙盐、和铵盐，和二异丙基和三异丙基萘磺酸钠盐的混合物。适当的非离子试剂是环氧乙烷与脂肪醇如油醇和鲸蜡醇的缩合产物，或与烷基酚如辛基-或壬基酚或辛基甲酚的缩合产物。其它的非离子试剂是源自于长链脂肪酸和己糖醇酸酐的偏酯，例如脱水山梨糖醇单月桂酸酯；所述偏酯与环氧乙烷的缩合产物；卵磷脂；和聚硅酮表面活性剂(具有包括硅氧烷链骨架的水溶性的或可分散的表面活性剂，如Silwet)。适当的在矿物油中的混合物是
Figure C0382597700062
Figure C0382597700063
。
通常用于农业组合物的其它的助剂包括相容剂，消泡剂，螯合剂，中和剂和缓冲剂，防腐剂，染料，添味剂，扩展剂，渗透助剂，粘着剂，分散剂，增稠剂，凝固点降低剂，抗菌剂等。组合物也可以包含其它相容的组分，例如，其它的除草剂，植物生长调节剂，杀真菌剂，杀虫剂等，并可以与液体肥料或固体、颗粒化肥载体如硝酸铵、尿素等一起配制。
本发明组合物的施用量将取决于很多因素，包括，例如，活性成分、生长要受抑制的植物品种、成长阶段和杂草物种的密度、配制和使用方法，如喷雾、加入到灌溉用水中或其它传统方法。但是，作为一般的原则，作为喷雾剂的施用量为每公顷1000-10升稀释的喷雾剂溶液，优选每公顷200-100升。
可以用本发明的组合物进行处理的有代表性的植物种包括但是不局限于，烟草(烟草)和苘麻(绒毛叶)，但是并不打算仅将本发明的组合物和方法用于这些物种。
本发明可以通过以下有代表性的实施例进行说明。
方法
在所有的实施例中，都使用去离子超纯水来制备溶液。喷雾剂溶液在混合后尽快使用。
用于这些研究的除草剂和喷雾助剂包括：农作物油浓缩物(COC；Orchex 796，83％；Ag Plus 300f，7％)，莠去津，阿特拉律，Basagran(灭草松)。水杨酸盐或SAR诱导剂包括水杨酸钠(NaSA)，水杨酸(SA)，其它取代的水杨酸盐，2，6-二氯异烟酸和Actigard。
在所有的除草剂施用过程中，植物上都喷以足以确保充分覆盖的量，达到喷雾剂溶液溢出的程度。把COC以0.25％的比率(v/v)加入到所有的喷雾剂溶液中。对于所有同时包含除草剂和水杨酸盐或SAR诱导剂的处理剂来说，都将这些物质混合并以单一喷雾剂溶液施用(通常称作桶混制剂)。喷雾后，把植物移到温室中并以随机完成区组排列。通过根据受影响的叶面积的百分数来评价损害程度而评价植物在喷雾后的除草作用(植物毒性)。对所有的数据都进行方差分析，并且在α＝0.05下用邓肯多程检验法测定平均离距。
实施例1
水杨酸盐的加入增加了莠去津在烟草上的除草活性(表1)。在除草剂施用后3天，作用很明显，并且在施用后持续6天。
Figure C0382597700081
实施例2
水杨酸盐增强了Aatrex
Figure C0382597700082
一种商品莠去津制剂在绒毛叶(velvetleaf)上的作用(表2)。
Figure C0382597700083
实施例3：
水杨酸盐增强了灭草松，一种商品灭草松制剂在烟草上的作用(表3)。
Figure C0382597700091
实施例4
Figure C0382597700092
是一种Acibenzolar-S-甲基制剂，一种商品SAR诱导剂。Actigard在烟草上的莠去津活性促进作用依赖于剂量(表4)。这表明，除SA以外的SAR诱导剂也可以增强莠去津的除草活性。
Figure C0382597700101
实施例5
除了水杨酸及其盐之外，其它的水杨酸盐可以增强莠去津的除草活性(表5)。在试验的水杨酸盐当中，用3-氯水杨酸，3-氟水杨酸，4-氟水杨酸，5-氟水杨酸，和3，5-二氟水杨酸可以比水杨酸具有更强的增效作用。在莠去津活性增强方面与水杨酸活性相同的水杨酸盐是3-甲氧基水杨酸、3-硝基水杨酸，5-溴水杨酸，5-硝基水杨酸，6-氟水杨酸，和3，5-二溴水杨酸。在试验的水杨酸盐当中，用苯甲酸钠，3-甲基水杨酸，4-甲基水杨酸，5-甲基水杨酸，和6-甲基水杨酸没有观察到莠去津的增效作用。
Figure C0382597700111
对于SAR诱导剂，也测定了其作为莠去津增效剂的作用(表7)。在试验的SAR诱导剂当中，用Acibenzolar-S-甲基，2，6-二氯异烟酸，烯丙苯噻唑，乳氟禾草灵，和4-氯水杨酸，5-氯水杨酸，3，5-二氯水杨酸观察到了比等摩尔水杨酸更强的增效作用。水杨酸盐4-氯水杨酸，5-氯水杨酸和3，5-二氯水杨酸是已知的SAR诱导剂(Conrath等人，1995.Proc.Natl.Acad.Sci.USA 92：7143-7147)。这些数据表明，莠去津的增效作用可以概括到SAR诱导剂。
Figure C0382597700121
实施例6
加入水杨酸盐或SAR诱导剂能在不利的环境条件下增加PSII抑制剂的活性。例如，加入水杨酸盐会在低光照下增强莠去津的除草活性，并在黑暗中给予一定的活性(表7)。
Figure C0382597700131
水杨酸盐也可在温度范围(15-35℃)下增强莠去津除草活性(表8)。因此，向PSII抑制除草剂中加入水杨酸盐或SAR诱导剂可以提供在不太有利的环境条件下使用除草剂的方法，从而增加其效用。
Figure C0382597700141
实施例7
莠去津通常用于玉米和小粒谷类作物中的杂草。如表9所示，水杨酸盐和莠去津的叶面施药对于玉米秧苗没有副作用。

Claims (12)

1.除草剂组合物，其包括莠去津和水杨酸盐，其中莠去津占组合物的1.0重量％-0.05重量％，水杨酸盐占组合物的0.5重量％-0.05重量％。
2.权利要求1的除草剂组合物，其溶于水。
3.权利要求2的除草剂组合物，其中水占组合物的0.1重量％-99.9重量％。
4.权利要求1的除草剂组合物，其中所述水杨酸盐是水杨酸钠。
5.权利要求1的除草剂组合物，其中所述水杨酸盐是水杨酸。
6.权利要求1的除草剂组合物，其中所述水杨酸盐是羟基吡啶羧酸。
7.权利要求6的除草剂组合物，其中羟基吡啶羧酸是3-羟基吡考啉酸。
8.权利要求1的除草剂组合物，其中水杨酸盐是2，6-二氯异烟酸。
9.权利要求1的除草剂组合物，其中水杨酸盐是4-氯水杨酸。
10.权利要求1的除草剂组合物，其中水杨酸盐是5-氯水杨酸。
11.权利要求1的除草剂组合物，其中水杨酸盐是3，5-二氯水杨酸。
12.控制植物生长的方法，其包括在植物上施用除草有效量的权利要求1的除草剂组合物。
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