CN103501603A - 用胍提高农药性能的方法 - Google Patents
用胍提高农药性能的方法 Download PDFInfo
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- CN103501603A CN103501603A CN201280021652.2A CN201280021652A CN103501603A CN 103501603 A CN103501603 A CN 103501603A CN 201280021652 A CN201280021652 A CN 201280021652A CN 103501603 A CN103501603 A CN 103501603A
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- A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
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- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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Abstract
本发明涉及一种提高农药性能的方法,该方法包括使助剂和农药接触的步骤,其中所述农药以小于10wt%的浓度存在于所得含有所述助剂和所述农药的组合物中,并且其中所述助剂含有如下所定义的式(A)的胍和/或其盐。本发明还涉及包含植物生长素除草剂和所述助剂的组合物;所述助剂在提高农药性能中的用途;和一种防治不希望植物的方法,其包括使除草有效量的所述组合物作用于植物、其生长环境或所述植物的种子。
Description
本发明涉及一种提高农药性能的方法,该方法包括使助剂和农药接触的步骤,其中所述助剂含有如下所定义的式(A)的胍和/或其盐。本发明还涉及包含植物生长素除草剂和所述助剂的组合物;所述助剂在提高农药性能中的用途;和一种防治不希望植物的方法,其包括使除草有效量的所述组合物作用于植物、其生长环境或所述植物的种子。本文中下文所述的本发明优选实施方案应理解为优选彼此独立或彼此组合。
已知各种提高农药性能的方法:
WO2011/039172公开了一种制备阴离子农药和阳离子多胺的盐的方法。该多胺降低阴离子农药的挥发性。
WO2011/008453公开了草甘膦(glyphosate)的各种胍衍生物。
EP0988790公开了包含协同增效有效量的唑并嘧啶(azolopyrimidine)衍生物和至少一种其它杀真菌剂如多果定(dodine)(十二烷基胍)的杀真菌组合物。
仍可进一步改善已知助剂以进一步提高农药的性能。
本发明目的为发现一种提高农药性能的方法。另一目的为降低农药的挥发性和/或农药的生物学效力。
该目的由一种提高农药性能的方法实现,该方法包括使助剂和农药接触的步骤,其中所述农药以小于10wt%的浓度存在于所得含有所述助剂和所述农药的组合物中,并且其中所述助剂含有式(A)的胍和/或其盐:
其中
R1、R2、R3、R4和R5独立地为H、C1-C30烷基、C2-C15亚烷基、C2-C30链烯基、C6-C12芳基、C7-C30烷基芳基、-(CH2)m-(NR6(CH2)n)x-NR7R8或-(CH2)m-CH(NH2)CH(NH2)R8、聚乙烯亚氨基或其杂取代衍生物;
R6和R7独立地为氢或C1-C6烷基;
R8为C1-C30烷基或-C(NH)NH2;和
m、n和x独立地为1-10的整数。
术语杂取代衍生物指C1-C30烷基、C2-C15亚烷基、C2-C30链烯基、C6-C12芳基、C7-C30烷基芳基、-(CH2)m-(NR6(CH2)n)x-NR7R8或-(CH2)m-CH(NH2)CH(NH2)R8或聚乙烯亚氨基的衍生物,其中至少一个碳原子被至少一个含有杂原子(例如O、N或S)的官能团替换。含有杂原子的官能团的实例为酮基、醛基、胺基、羟基或硫醇基团,其中优选酮基、羟基和胺基。优选C1-C30烷基和C2-C15亚烷基的杂取代衍生物,尤其是C1-C30烷基和C2-C15亚烷基的酮基、羟基和/或胺基取代的衍生物。
术语C2-C15亚烷基通常指式(A)的环状胍,其中选自R1、R2、R3、R4和R5的两个残基一起形成C2-C15亚烷基。例如,在三氮杂双环癸烯(1,5,7-三氮杂双环[4.4.0]癸-5-烯或TBD)中,R1和R2一起形成1,3-亚丙基),R3和R4一起形成1,3-亚丙基,且R5为H。
术语杂取代的C2-C15亚烷基通常指式(A)的环状胍,其中选自R1、R2、R3、R4和R5的两个残基一起形成杂取代的C2-C15亚烷基。例如,在肌酸酐(也称为2-亚氨基-1-甲基咪唑啉-4-酮)中,R1为H,R2为甲基,R4为H且R3和R5一起形成被酮基取代的1,2-亚乙基。
优选地,R1为H、C1-C30烷基、C2-C30链烯基、C6-C12芳基、C7-C30烷基芳基、-(CH2)m-(NR6(CH2)n)x-NR7R8或-(CH2)m-CH(NH2)CH(NH2)R8或聚乙烯亚氨基;和R2、R3、R4和R5独立地为H、C1-C22烷基或C1-C22链烯基。更优选地,R1为H、C1-C30烷基、C2-C30链烯基、C6-C12芳基、C7-C30烷基芳基、-(CH2)m-(NR6(CH2)n)x-NR7R8或-(CH2)m-CH(NH2)CH(NH2)R8或聚乙烯亚氨基;和R2、R3、R4和R5为H。
在另一优选形式中,R1为H、C1-C30烷基、C2-C30链烯基、C6-C12芳基、C7-C30烷基芳基、-(CH2)m-(NR6(CH2)n)x-NR7R8或-(CH2)m-CH(NH2)CH(NH2)R8、聚乙烯亚氨基或其杂取代衍生物;和R2、R3、R4和R5独立地为H、C1-C22烷基、C2-C10亚烷基、C1-C22链烯基或其杂取代衍生物。更优选地,R1为H、C1-C30烷基、C2-C30链烯基、C6-C12芳基、C7-C30烷基芳基、-(CH2)m-(NR6(CH2)n)x-NR7R8或-(CH2)m-CH(NH2)CH(NH2)R8、聚乙烯亚氨基或其杂取代衍生物;和R2、R3、R4和R5为H或C2-C6亚烷基或其杂取代衍生物。
在一些实施方案中,R1、R2、R3、R4和R5独立地为H或C1-C30烷基,例如C1-C4烷基或C1-C3烷基。在一些其它实施方案中,R1、R2、R3、R4和R5独立地为H、C2-C10亚烷基或C1-C30烷基或其杂取代衍生物。
最优选R1、R2、R3、R4和R5独立地为甲基或H,尤其是H。
在一些实施方案中,R1、R2、R3、R4和R5可独立地为C8-C30烷基或链烯基,优选C12-C18烷基或C12-C18链烯基。代表性烷基包括辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、椰油基和牛油基。代表性链烯基包括辛烯基、壬烯基、癸烯基、十一碳烯基、十二碳烯基、十三碳烯基、十四碳烯基、十五碳烯基、十六碳烯基、十七碳烯基和十八碳烯基。
在一些其它实施方案中,R1、R2、R3、R4和R5可独立地为-(CH2)m-CH(NH2)CH(NH2)R8,m为1和R8为C8-C30烷基或链烯基,例如以上列举的那些。在一些实施方案中,R1、R2、R3、R4和R5可独立地为-(CH2)m-(NR6(CH2)n)x-NR7R8,R6和R7为氢,R8为C8-C30烷基或C8-C30链烯基,例如以上列举的那些,m和n为2,且x为1-5的整数。
式(A)的胍的具体实例为胍;2-十二烷基胍;2-十六烷基胍;(C12-18烃基)胍;N,N,N,N-四甲基-(C12-18烃基)胍;N,N,N,N-四甲基-(C12烃基)胍;2-(C12烃基)胍;2-3,6,9,12,15,18-六氮杂三十烷基胍;1,1,3,3-四甲基-2-3,6,9,12,15,18-六氮杂三十烷基胍;(Z)-1,1,3,3-四甲基-2-(十八碳-9-烯基)胍;2-十六烷基-1,1,3,3-四甲基胍;2-(2,3-二氨基丙基)(C12-18烃基)胍;2-(2,3-二氨基丙基)(C12-18烃基)-1,1,3,3-四甲基胍;N-(1,1-二氨基-2,5,8,11,14,17-六氮杂十九碳-1-烯-19-基)十七烷酰胺;多果定;guatazine;双胍辛醋酸盐(iminoctadine);及其盐,其中优选盐。式(A)的胍的其它具体实例为三氮杂双环癸烯、精氨酸、肌酸酐和肌酸及其盐,其中优选盐。式(A)的胍的优选实例为胍(R1、R2、R3、R4和R5为H)、多果定、双胍辛醋酸盐及其盐,其中优选盐。尤其优选的式(A)的胍为胍及其盐,其中优选盐。在另一尤其优选的形式中,式(A)为三氮杂双环癸烯及其盐,其中优选盐。在另一尤其优选的形式中,式(A)为精氨酸及其盐,其中优选盐。在另一尤其优选的形式中,式(A)为肌酸酐及其盐,其中优选盐。在另一尤其优选的形式中,式(A)为肌酸及其盐,其中优选盐。
在一个优选实施方案中,助剂含有式(A)的胍的盐。在另一优选实施方案中,助剂含有式(A)的胍的盐以及式(A)的胍。
术语“盐”是指包含至少一种阴离子和至少一种阳离子的化学化合物。阴离子与阳离子之比通常取决于离子的电荷并得到中性盐。通常,盐在溶解于水中时离解成阴离子和阳离子。
式(A)的胍的盐通常包含由下式所示的胍鎓阳离子:
式(A)的胍的盐通常包含所述胍鎓阳离子和阴离子抗衡离子。合适的阴离子抗衡离子可以衍生于无机酸或有机酸,其中优选无机酸。
有机酸的实例为单羧酸(例如甲酸、乙酸、丙酸、丁酸、异丁酸、己酸、庚酸、辛酸、壬酸、癸酸、月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、丙烯酸、甲基丙烯酸、巴豆酸、异巴豆酸、苯乙酸、肉桂酸、苯甲酸、山梨酸、烟酸、尿刊酸和吡咯烷酮羧酸);二羧酸(例如草酸、丙二酸、琥珀酸、谷氨酸、己二酸、庚二酸、软木酸、壬二酸、癸二酸、马来酸、富马酸、邻苯二甲酸和对苯二甲酸);羟酸(例如乙醇酸、乳酸、苹果酸、酒石酸、柠檬酸和羟基苯甲酸);氨基酸(例如甘氨酸、丙氨酸、β-丙氨酸、缬氨酸、亮氨酸、苯基丙氨酸、酪氨酸、丝氨酸、苏氨酸、甲硫氨酸、半胱氨酸、胱氨酸、脯氨酸、羟基脯氨酸、2-哌啶酸、色氨酸、天冬氨酸、天冬酰胺、谷氨酸、谷氨酰胺、赖氨酸、组氨酸、鸟氨酸、精氨酸和氨基苯甲酸);低级烷基磺酸(例如甲磺酸和三氟甲磺酸);芳基磺酸(例如苯磺酸和对甲苯磺酸)。
无机酸的实例为氢卤酸(例如氢氟酸、盐酸、氢溴酸和氢碘酸)和无机酸(例如高氯酸、硫酸、硝酸、磷酸和碳酸)。
更优选地,阴离子抗衡离子选自硫酸根、硫酸氢根、磷酸根、磷酸二氢根、磷酸氢根、碳酸氢根、碳酸根、氨基磺酸根、氯离子、硝酸根、硫氰酸根。尤其优选的阴离子抗衡离子为硫酸氢根、磷酸根、磷酸二氢根、磷酸氢根、碳酸氢根和碳酸根。
优选的式(A)的胍的盐为硫酸胍、氨基磺酸胍、硫酸氢胍、磷酸胍、磷酸二氢胍、磷酸氢胍、碳酸氢胍、碳酸胍、氯化胍、硝酸胍、硫代硫酸胍、硫氰酸胍。尤其优选硫酸氢胍、磷酸胍、磷酸二氢胍、磷酸氢胍、碳酸氢胍、硫酸胍和碳酸胍。
式(A)的胍或其盐通常可溶于水。优选地,其在20℃下在水中的溶解度为至少1wt%,更优选至少5wt%,尤其是至少10wt%。
含有式(A)的胍的助剂通常为固体。优选地,该助剂在20℃下为固体。式(A)的胍通常为固体。优选地,式(A)的胍在20℃下为固体。
助剂通常含有至少50wt%,优选至少90wt%,尤其是至少98wt%式(A)的胍。在另一形式中,该助剂由式(A)的胍构成。
术语“农药”就本发明的含义而言是指可选自杀真菌剂、杀虫剂、杀线虫剂、除草剂和/或安全剂或生长调节剂,优选选自杀真菌剂、杀虫剂或除草剂,最优选选自除草剂的一种或多种化合物。也可使用两种或更多种上述类别的农药的混合物。本领域技术人员熟知这类农药,其可参见例如Pesticide Manual,第15版(2009),The British Crop Protection Council,London。
杀真菌剂的实例为:
A)嗜球果伞素类(strobilurin):
腈嘧菌酯(azoxystrobin)、醚菌胺(dimoxystrobin)、烯肟菌胺(enestroburin)、氟嘧菌酯(fluoxastrobin)、亚胺菌(kresoxim-methyl)、叉氨苯酰胺(metominostrobin)、肟醚菌胺(orysastrobin)、啶氧菌酯(picoxystrobin)、唑菌胺酯(pyraclostrobin)、pyrametostrobin、pyraoxystrobin、pyribencarb、肟菌酯(trifloxystrobin)、(2-氯-5-[1-(3-甲基苄氧基亚氨基)乙基]苄基)氨基甲酸甲酯和2-(2-(3-(2,6-二氯苯基)-1-甲基亚烯丙基氨基氧基甲基)苯基)-2-甲氧基亚氨基-N-甲基乙酰胺;
B)羧酰胺类:
-羧酰苯胺类:苯霜灵(benalaxyl)、精苯霜灵(benalaxyl-M)、麦锈灵(benodanil)、bixafen、啶酰菌胺(boscalid)、萎锈灵(carboxin)、呋菌胺(fenfuram)、环酰菌胺(fenhexamid)、氟酰胺(flutolanil)、呋吡唑灵(furametpyr)、isopyrazam、异噻菌胺(isotianil)、kiralaxyl、丙氧灭绣胺(mepronil)、甲霜灵(metalaxyl)、精甲霜灵(metalaxyl-M)(mefenoxam)、甲呋酰胺(ofurace)、霜灵(oxadixyl)、氧化萎锈灵(oxycarboxin)、penflufen、吡噻菌胺(penthiopyrad)、sedaxane、叶枯酞(tecloftalam)、溴氟唑菌(thifluzamide)、噻酰菌胺(tiadinil)、2-氨基-4-甲基噻唑-5-甲酰苯胺、N-(3',4',5'-三氟联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(4'-三氟甲硫基联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺和N-(2-(1,3,3-三甲基丁基)苯基)-1,3-二甲基-5-氟-1H-吡唑-4-甲酰胺;
-羧酰吗啉类:烯酰吗啉(dimethomorph)、氟吗啉(flumorph)、丁吡吗啉(pyrimorph);
-苯甲酰胺类:氟联苯菌(flumetover)、氟吡菌胺(fluopicolide)、氟吡菌酰胺(fluopyram)、苯酰菌胺(zoxamide);
-其它羧酰胺类:氯环丙酰胺(carpropamid)、双氯氰菌胺(diclocymet)、双炔酰菌胺(mandipropamid)、土霉素(oxytetracyclin)、硅噻菌胺(silthiofam)和N-(6-甲氧基吡啶-3-基)环丙烷甲酰胺;
C)唑类:
-三唑类:戊环菌(azaconazole)、双苯三唑醇(bitertanol)、糠菌唑(bromuconazole)、环唑醇(cyproconazole)、醚唑(difenoconazole)、烯唑醇(diniconazole)、精烯唑醇(diniconazole-M)、氧唑菌(epoxiconazole)、腈苯唑(fenbuconazole)、腈苯唑(fluquinconazole)、氟硅唑(flusilazole)、粉唑醇(flutriafol)、己唑醇(hexaconazole)、酰胺唑(imibenconazole)、环戊唑醇(ipconazole)、环戊唑菌(metconazole)、腈菌唑(myclobutanil)、咪唑(oxpoconazole)、多效唑(paclobutrazole)、戊菌唑(penconazole)、丙环唑(propiconazole)、丙硫菌唑(prothioconazole)、硅氟唑(simeconazole)、戊唑醇(tebuconazole)、氟醚唑(tetraconazole)、三唑酮(triadimefon)、唑菌醇(triadimenol)、戊叉唑菌(triticonazole)、烯效唑(uniconazole);
-咪唑类:氰霜唑(cyazofamid)、烯菌灵(imazalil)、稻瘟酯(pefurazoate)、丙氯灵(prochloraz)、氟菌唑(triflumizol);
-苯并咪唑类:苯菌灵(benomyl)、多菌灵(carbendazim)、麦穗宁(fuberidazole)、涕必灵(thiabendazole);
-其它:噻唑菌胺(ethaboxam)、氯唑灵(etridiazole)、土菌消(hymexazole)和2-(4-氯苯基)-N-[4-(3,4-二甲氧基苯基)异唑-5-基]-2-丙-2-炔氧基乙酰胺;
D)杂环化合物:
-嘧啶类:磺嘧菌灵(bupirimate)、环丙嘧啶(cyprodinil)、氟嘧菌胺(diflumetorim)、异嘧菌醇(fenarimol)、嘧菌腙(ferimzone)、嘧菌胺(mepanipyrim)、氯定(nitrapyrin)、氯苯嘧啶醇(nuarimol)、二甲嘧菌胺(pyrimethanil);
-哌嗪类:嗪氨灵(triforine);
-吗啉类:aldimorph、吗菌灵(dodemorph)、吗菌灵乙酸酯(dodemorphacetate)、丁苯吗啉(fenpropimorph)、克啉菌(tridemorph);
-哌啶类:苯锈啶(fenpropidin);
-二甲酰亚胺类:氟菌安(fluorimide)、异丙定(iprodione)、杀菌利(procymidone)、烯菌酮(vinclozolin);
-非芳族5员杂环类:唑酮菌(famoxadone)、咪唑菌酮(fenamidone)、flutianil、异噻菌酮(octhilinone)、噻菌灵(probenazole)、5-氨基-2-异丙基-3-氧代-4-邻甲苯基-2,3-二氢吡唑-1-硫代甲酸S-烯丙基酯;
-其它:噻二唑素-S-甲基(acibenzolar-S-methyl)、ametoctradin、amisulbrom、敌菌灵(anilazine)、灭瘟素(blasticidin-S)、敌菌丹(captafol)、克菌丹(captan)、灭螨锰(chinomethionat)、棉隆(dazomet)、双乙氧咪唑威(debacarb)、哒菌清(diclomezine)、苯敌快(difenzoquat)、苯敌快甲基硫酸酯(difenzoquat methylsulfate)、氰菌胺(fenoxanil)、灭菌丹(folpet)、喹菌酮(oxolinic acid)、粉病灵(piperalin)、丙氧喹啉(proquinazid)、咯喹酮(pyroquilon)、喹氧灵(quinoxyfen)、唑菌嗪(triazoxide)、三环唑(tricyclazole)、2-丁氧基-6-碘-3-丙基苯并吡喃-4-酮、5-氯-1-(4,6-二甲氧基嘧啶-2-基)-2-甲基-1H-苯并咪唑和5-氯-7-(4-甲基哌啶-1-基)-6-(2,4,6-三氟苯基)[1,2,4]三唑并[1,5-a]嘧啶;
E)氨基甲酸酯类
-硫代及二硫代氨基甲酸酯类:福美铁(ferbam)、代森锰锌(mancozeb)、代森锰(maneb)、威百亩(metam)、磺菌威(methasulphocarb)、代森联(metiram)、代森锌(propineb)、福美双(thiram)、代森锌(zineb)、福美锌(ziram);
-氨基甲酸酯类:苯噻菌胺(benthiavalicarb)、乙霉威(diethofencarb)、异丙菌胺(iprovalicarb)、百维灵(propamocarb)、百维灵盐酸盐(propamocarb hydrochlorid)、valiphenal和N-(1-(1-(4-氰基苯基)乙磺酰基)丁-2-基)氨基甲酸4-氟苯基酯;
F)其它活性物质
-胍类:胍、多果定、多果定游离碱、双胍盐(guazatine)、双胍乙酸盐(guazatine acetate)、双胍辛醋酸盐、双胍辛醋酸三乙酸盐(iminoctadinetriacetate)、双胍辛醋酸三(苯磺酸盐)(iminoctadine tris(albesilate));
-抗生素:春雷素(kasugamycin)、春雷素盐酸盐水合物(kasugamycinhydrochloride-hydrate)、链霉素(streptomycin)、多氧霉素(polyoxine)、井冈霉素(validamycin A);
-硝基苯基衍生物:乐杀螨(binapacryl)、敌螨通(dinobuton)、敌螨普(dinocap)、异丙消(nitrothal-isopropyl)、四氯硝基苯(tecnazen);
有机金属化合物:毒菌锡(fentin salt),如毒菌锡醋酸盐(fentin acetate)、毒菌锡氯(fentin chloride)或毒菌锡氢氧化物(fentin hydroxide);
-含硫杂环化合物:二噻农(dithianon)、稻瘟灵(isoprothiolane);
-有机磷化合物:稻瘟光(edifenphos)、藻菌磷(fosetyl)、藻菌磷铝(fosetyl-aluminum)、异稻瘟净(iprobenfos)、亚磷酸及其盐、定菌磷(pyrazophos)、甲基立枯磷(tolclofos-methyl);
-有机氯化合物:百菌清(chlorthalonil)、抑菌灵(dichlofluanid)、双氯酚(dichlorphen)、磺菌胺(flusulfamide)、六氯苯(hexachlorobenzene)、戊菌隆(pencycuron)、五氯酚(pentachlorophenol)及其盐、四氯苯酞(phthalide)、五氯硝基苯(quintozene)、甲基托布津(thiophanate-methyl)、对甲抑菌灵(tolylfluanid)、N-(4-氯-2-硝基苯基)-N-乙基-4-甲基苯磺酰胺;
-无机活性成分:波尔多液(Bordeaux混合剂)、醋酸铜、氢氧化铜、王铜、碱式硫酸铜、硫磺;
-其它:联苯、溴硝丙二醇(bronopol)、环氟菌胺(cyflufenamid)、清菌脲(cymoxanil)、二苯胺(diphenylamine)、苯菌酮(metrafenone)、米多霉素(mildiomycin)、喹啉铜(oxin-copper)、调环酸钙(prohexadione-calcium)、螺茂胺(spiroxamine)、tebufloquin、对甲抑菌灵(tolylfluanid)、N-(环丙基甲氧基亚氨基-(6-二氟甲氧基-2,3-二氟苯基)甲基)-2-苯基乙酰胺、N'-(4-(4-氯-3-三氟甲基苯氧基)-2,5-二甲基苯基)-N-乙基-N-甲基甲脒、N'-(4-(4-氟-3-三氟甲基苯氧基)-2,5-二甲基苯基)-N-乙基-N-甲基甲脒、N'-(2-甲基-5-三氟甲基-4-(3-三甲基硅烷基丙氧基)苯基)-N-乙基-N-甲基甲脒、N'-(5-二氟甲基-2-甲基-4-(3-三甲基硅烷基丙氧基)苯基)-N-乙基-N-甲基甲脒、2-{1-[2-(5-甲基-3-三氟甲基吡唑-1-基)乙酰基]哌啶-4-基}噻唑-4-甲酸甲基-(1,2,3,4-四氢萘-1-基)酰胺、2-{1-[2-(5-甲基-3-三氟甲基吡唑-1-基)乙酰基]哌啶-4-基}噻唑-4-甲酸甲基-(R)-1,2,3,4-四氢萘-1-基酰胺、甲氧基乙酸6-叔丁基-8-氟-2,3-二甲基喹啉-4-基酯和N-甲基-2-{1-[2-(5-甲基-3-三氟甲基-1H-吡唑-1-基)乙酰基]哌啶-4-基}-N-[(1R)-1,2,3,4-四氢萘-1-基]-4-噻唑羧酰胺。
生长调节剂的实例为:
脱落酸(abscisic acid)、先甲草胺(amidochlor)、嘧啶醇(ancymidol)、6-苄基氨基嘌呤、油菜素内酯(brassinolide)、地乐胺(butralin)、矮壮素阳离子(chlormequat)(氯化矮壮素(chlormequat chloride))、胆碱盐酸盐(choline chloride)、环丙酸酰胺(cyclanilide)、丁酰肼(daminozide)、敌草克(dikegulac)、噻节因(dimethipin)、2,6-二甲基吡啶、乙烯利(ethephon)、氟节胺(flumetralin)、调嘧醇(flurprimidol)、达草氟(fluthiacet)、调吡脲(forchlorfenuron)、赤霉酸(gibberellic acid)、抗倒胺(inabenfid)、吲哚-3-乙酸、抑芽丹(maleic hydrazide)、氟草磺(mefluidide)、助壮素(mepiquat)(助壮素(mepiquat chloride))、萘乙酸、N-6-苄基腺嘌呤、多效唑(paclobutrazol)、调环酸(调环酸钙)、茉莉酸诱导体(prohydrojasmon)、赛二唑素(thidiazuron)、抑芽唑(triapenthenol)、三硫代磷酸三丁基酯、2,3,5-三碘苯甲酸、抗倒酯(trinexapac-ethyl)及烯效唑(uniconazole);
除草剂的实例为:
-乙酰胺类:乙草胺(acetochlor)、甲草胺(alachlor)、丁草胺(butachlor)、克草胺(dimethachlor)、噻吩草胺(dimethenamid)、氟噻草胺(flufenacet)、苯噻草胺(mefenacet)、异丙甲草胺(metolachlor)、吡草胺(metazachlor)、草萘胺(napropamide)、萘丙胺(naproanilide)、烯草胺(pethoxamid)、丙草胺(pretilachlor)、毒草安(propachlor)、噻醚草胺(thenylchlor);
-氨基酸衍生物:双丙氨酰膦(bilanafos)、草甘膦(例如草甘膦游离酸、草甘膦铵盐、草甘膦异丙基铵盐、草甘膦三甲基锍盐、草甘膦钾盐、草甘膦二甲胺盐)、草铵膦(glufosinate)、草硫膦(sulfosate);
-芳氧基苯氧基丙酸酯类:炔草酯(clodinafop)、氰氟草酯(cyhalofop-butyl)、唑禾草灵(fenoxaprop)、吡氟禾草灵(fluazifop)、吡氟氯禾灵(haloxyfop)、恶唑酰草胺(metamifop)、喔草酯(propaquizafop)、喹禾灵(quizalofop)、精喹禾灵(quizalofop-P-tefuryl);
-联吡啶类:敌草快(diquat)、对草快(paraquat);
-(硫代)氨基甲酸酯类:黄草灵(asulam)、苏达灭(butylate)、长杀草(carbetamide)、异苯敌草(desmedipham)、哌草丹(dimepiperate)、扑草灭(eptam)(EPTC)、禾草畏(esprocarb)、草达灭(molinate)、坪草丹(orbencarb)、苯敌草(phenmedipham)、苄草丹(prosulfocarb)、稗草畏(pyributicarb)、杀草丹(thiobencarb)、野麦畏(triallate);
-环己二酮类:丁氧环酮(butroxydim)、烯草酮(clethodim)、噻草酮(cycloxydim)、profoxydim、稀禾定(sethoxydim)、醌肟草(tepraloxydim)、肟草酮(tralkoxydim);
-二硝基苯胺类:氟草胺(benfluralin)、丁氟消草(ethalfluralin)、黄草消(oryzalin)、胺硝草(pendimethalin)、氨基丙氟灵(prodiamine)、氟乐灵(trifluralin);
-二苯醚类:氟锁草醚(acifluorfen)、苯草醚(aclonifen)、治草醚(bifenox)、氯甲草(diclofop)、氯氟草醚(ethoxyfen)、氟黄胺草醚(fomesafen)、乳氟禾草灵(lactofen)、氟硝草醚(oxyfluorfen);
-羟基苄腈类:溴苯腈(bromoxynil)、敌草腈(dichlobenil)、碘苯腈(ioxynil);
-咪唑啉酮类:咪草酯(imazamethabenz)、咪草啶酸(imazamox)、甲基咪草烟(imazapic)、灭草烟(imazapyr)、灭草喹(imazaquin)、咪草烟(imazethapyr);
-苯氧基乙酸类:稗草胺(clomeprop)、2,4-二氯苯氧基乙酸(2,4-滴)、2,4-滴丁酸(2,4-DB)、2,4-滴丙酸(dichlorprop)、2甲4氯(MCPA)、酚硫杀(MCPA-thioethyl)、2甲4氯丁酸(MCPB)、2甲4氯丙酸(mecoprop);
-吡嗪类:杀草敏(chloridazon)、氟哒嗪草酯(flufenpyr-ethyl)、达草氟、达草灭(norflurazon)、达草止(pyridate);
-吡啶类:氯氨吡啶酸(aminopyralid)、二氯皮考啉酸(clopyralid)、吡氟草胺(diflufenican)、氟硫草定(dithiopyr)、氟草同(fluridone)、氟草烟(fluroxypyr)、毒莠定(picloram)、picolinafen、噻氟啶草(thiazopyr);
-磺酰脲类:磺氨黄隆(amidosulfuron)、四唑黄隆(azimsulfuron)、苄嘧黄隆(bensulfuron)、乙基氯嘧黄隆(chlorimuron-ethyl)、绿黄隆(chlorsulfuron)、醚黄隆(cinosulfuron)、环丙黄隆(cyclosulfamuron)、乙氧嘧黄隆(ethoxysulfuron)、啶嘧黄隆(flazasulfuron)、氟吡黄隆(flucetosulfuron)、氟啶黄隆(flupyrsulfuron)、甲酰胺黄隆(foramsulfuron)、吡氯黄隆(halosulfuron)、啶咪黄隆(imazosulfuron)、碘黄隆(iodosulfuron)、甲基二黄隆(mesosulfuron)、metazosulfuron、精甲基二黄隆(metsulfuron-methyl)、烟黄隆(nicosulfuron)、环丙氧黄隆(oxasulfuron)、氟嘧黄隆(primisulfuron)、氟丙黄隆(prosulfuron)、吡嘧黄隆(pyrazosulfuron)、玉嘧黄隆(rimsulfuron)、嘧黄隆(sulfometuron)、乙黄黄隆(sulfosulfuron)、噻黄隆(thifensulfuron)、醚苯黄隆(triasulfuron)、苯黄隆(tribenuron)、三氟啶黄隆(trifloxysulfuron)、氟胺黄隆(triflusulfuron)、三氟甲黄隆(tritosulfuron)、1-((2-氯-6-丙基咪唑并[1,2-b]哒嗪-3-基)磺酰基)-3-(4,6-二甲氧基嘧啶-2-基)脲;
-三嗪类:莠灭净(ametryn)、莠去津(atrazine)、草净津(cyanazine)、戊草津(dimethametryn)、乙赛克津(ethiozine)、六嗪同(hexazinon)、苯嗪草(metamitron)、赛克津(metribuzin)、扑草净(prometryn)、西玛津(simazine)、特丁津(terbuthylazine)、去草净(terbutryn)、苯氧苯氧丙胺津(triaziflam);
-脲类:绿麦隆(chlortoluron)、香草隆(daimuron)、敌草隆(diuron)、伏草隆(fluometuron)、异丙隆(isoproturon)、利谷隆(linuron)、噻唑隆(methabenzthiazuron)、丁唑隆(tebuthiuron);
-其它乙酰乳酸合酶抑制剂:双嘧苯甲酸钠(bispyribac-sodium)、唑嘧磺胺盐(cloransulam-methyl)、唑嘧磺胺(diclosulam)、双氟磺草胺(florasulam)、氟酮黄隆(flucarbazone)、氟唑啶草(flumetsulam)、唑草磺胺(metosulam)、ortho-sulfamuron、五氟磺草胺(penoxsulam)、丙苯黄隆(propoxycarbazone)、pyribambenz-propyl、嘧苯草肟(pyribenzoxim)、pyriftalid、肟啶草(pyriminobac-methyl)、pyrimisulfan、嘧硫苯甲酸(pyrithiobac)、pyroxasulfone、吡唑磺草胺(pyroxsulam);
-其它:氨唑草酮(amicarbazone)、杀草强(aminotriazole)、莎稗磷(anilofos)、氟丁酰草胺(beflubutamid)、草除灵(benazolin)、bencarbazone、呋草磺(benfuresate)、吡草酮(benzofenap)、噻草平(bentazone)、benzobicyclon、bicyclopyrone、除草定(bromacil)、溴丁酰草胺(bromobutide)、氟丙嘧草酯(butafenacil)、草胺磷(butamifos)、唑草胺(cafenstrole)、氟酮唑草(carfentrazone)、吲哚吲哚酮草酯(cinidon-ethyl)、敌草索(chlorthal)、环庚草醚(cinmethylin)、异恶草酮(clomazone)、苄草隆(cumyluron)、cyprosulfamide、麦草畏(dicamba)、苯敌快(difenzoquat)、二氟吡隆(diflufenzopyr)、稗内脐蠕孢菌(Drechslera monoceras)、草藻灭(endothal)、乙呋草黄(ethofumesate)、乙苯酰草(etobenzanid)、fenoxasulfone、四唑草胺(fentrazamide)、酰亚胺苯氧乙酸戊酯(flumiclorac-pentyl)、氟嗪酮(flumioxazin)、胺草唑(flupoxam)、氟咯草酮(fluorochloridone)、呋草酮(flurtamone)、茚草酮(indanofan)、异恶草胺(isoxaben)、异氟草(isoxaflutole)、环草定(lenacil)、敌稗(propanil)、拿草特(propyzamide)、二氯喹啉酸(quinclorac)、喹草酸(quinmerac)、硝磺酮(mesotrione)、甲砷酸(methylarsenic acid)、抑草生(naptalam)、炔丙唑草(oxadiargyl)、恶草灵(oxadiazon)、氯嗪草(oxaziclomefone)、戊唑草(pentoxazone)、pinoxaden、双唑草腈腈(pyraclonil)、氟唑草酯(pyraflufen-ethyl)、pyrasulfotole、吡唑特(pyrazoxyfen)、吡唑特(pyrazolynate)、灭藻醌(quinoclamine)、saflufenacil、磺草酮(sulcotrione)、磺胺草唑(sulfentrazone)、特草定(terbacil)、tefuryltrione、tembotrione、thiencarbazone、吡草磺(topramezone)、(3-[2-氯-4-氟-5-(3-甲基-2,6-二氧代-4-三氟甲基-3,6-二氢-2H-嘧啶-1-基)苯氧基]吡啶-2-基氧基)乙酸乙酯、6-氨基-5-氯-2-环丙基嘧啶-4-甲酸甲酯、6-氯-3-(2-环丙基-6-甲基苯氧基)哒嗪-4-醇、4-氨基-3-氯-6-(4-氯苯基)-5-氟-吡啶-2-甲酸、4-氨基-3-氯-6-(4-氯-2-氟-3-甲氧基苯基)吡啶-2-甲酸甲酯以及4-氨基-3-氯-6-(4-氯-3-二甲基氨基-2-氟苯基)吡啶-2-甲酸甲酯。
杀虫剂的实例为:
有机(硫代)磷酸酯类:高灭磷(acephate)、唑啶磷(azamethiphos)、谷硫磷(azinphos-methyl)、毒死蜱(chlorpyrifos)、甲基毒死蜱(chlorpyrifos-methyl)、毒虫畏(chlorfenvinphos)、二嗪农(diazinon)、敌敌畏(dichlorvos)、百治磷(dicrotophos)、乐果(dimethoate)、乙拌磷(disulfoton)、乙硫磷(ethion)、杀螟松(fenitrothion)、倍硫磷(fenthion)、异唑磷(isoxathion)、马拉硫磷(malathion)、甲胺磷(methamidophos)、杀扑磷(methidathion)、甲基一六零五(methyl-parathion)、速灭磷(mevinphos)、久效磷(monocrotophos)、砜吸磷(oxydemeton-methyl)、对氧磷(paraoxon)、一六零五(parathion)、稻丰散(phenthoate)、伏杀硫磷(phosalone)、亚胺硫磷(phosmet)、磷胺(phosphamidon)、甲拌磷(phorate)、辛硫磷(phoxim)、虫螨磷(pirimiphos-methyl)、丙溴磷(profenofos)、丙硫磷(prothiofos)、乙丙硫磷(sulprophos)、四氯烯磷(tetrachlorvinphos)、特丁磷(terbufos)、三唑磷(triazophos)、敌百虫(trichlorfon);
-氨基甲酸酯类:棉铃威(alanycarb)、涕灭威(aldicarb)、虫威(bendiocarb)、丙硫克百威(benfuracarb)、甲萘威(carbaryl)、虫螨威(carbofuran)、丁硫克百威(carbosulfan)、双氧威(fenoxycarb)、呋线威(furathiocarb)、灭虫威(methiocarb)、灭多虫(methomyl)、甲氨叉威(oxamyl)、抗蚜威(pirimicarb)、残杀威(propoxur)、硫双威(thiodicarb)、唑蚜威(triazamate);
-拟除虫菊酯类:丙烯除虫菊酯(allethrin)、氟氯菊酯(bifenthrin)、氟氯氰菊酯(cyfluthrin)、氯氟氰菊酯(cyhalothrin)、苯醚氰菊酯(cyphenothrin)、氯氰菊酯(cypermethrin)、α-氯氰菊酯(alpha-cypermethrin)、β-氯氰菊酯(beta-cypermethrin)、己体氯氰菊酯(zeta-cypermethrin)、溴氰菊酯(deltamethrin)、高氰戊菊酯(esfenvalerate)、醚菊酯(etofenprox)、甲氰菊酯(fenpropathrin)、杀灭菊酯(fenvalerate)、咪炔菊酯(imiprothrin)、λ-氯氟氰菊酯(lambda-cyhalothrin)、氯菊酯(permethrin)、炔酮菊酯(prallethrin)、除虫菊酯I和II(pyrethrin I and II)、吡咪唑菌(resmethrin)、灭虫硅醚(silafluofen)、τ-氟胺氰菊酯(tau-fluvalinat)、七氟菊酯(tefluthrin)、胺菊酯(tetramethrin)、四溴菊酯(tralomethrin)、四氟菊酯(transfluthrin)、profluthrin、dimefluthrin;
-昆虫生长调节剂:a)几丁质合成抑制剂:苯甲酰脲类:定虫隆(chloriluazuron)、灭蝇胺(cyramazin)、氟脲杀(diflubenzuron)、氟螨脲(flucycloxuron)、氟虫脲(flufenoxuron)、氟铃脲(hexaflumuron)、氟丙氧脲(lufenuron)、双苯氟脲(novaluron)、伏虫隆(teflubenzuron)、杀虫隆(triflumuron);噻嗪酮(buprofezin)、茂醚(diofenolan)、噻螨酮(hexythiazox)、特苯唑(etoxazole)、四螨嗪(clofentezine);b)蜕皮素拮抗剂:特丁苯酰肼(halofenozide)、甲氧苯酰肼(methoxyfenozide)、双苯酰肼(tebufenozide)、艾扎丁(azadirachtin);c)保幼激素类:蚊蝇醚(pyriproxyfen)、蒙五一五(methoprene)、双氧威(fenoxycarb);d)类脂生物合成抑制剂:螺螨酯(spirodiclofen)、螺甲螨酯(spiromesifen)、螺虫乙酯(spirotetramat);
-烟碱受体激动剂/拮抗剂化合物:噻虫胺(clothianidin)、呋虫胺(dinotefuran)、吡虫啉(imidacloprid)、噻虫嗪(thiamethoxam)、硝胺烯啶(nitenpyram)、吡虫清(acetamiprid)、噻虫啉(thiacloprid)、1-(2-氯噻唑-5-基甲基)-2-硝亚氨基-3,5-二甲基[1,3,5]六氢化三嗪(triazinane);
-GABA拮抗剂化合物:硫丹(endosulfan)、乙虫清(ethiprole)、锐劲特(fipronil)、氟吡唑虫(vaniliprole)、pyrafluprole、pyriprole、5-氨基-1-(2,6-二氯-4-甲基苯基)-4-胺亚磺酰基(sulfinamoyl)-1H-吡唑-3-硫代羧酰胺;
-大环内酯类杀虫剂:齐墩螨素(abamectin)、甲氨基阿维菌素(emamectin)、米尔螨素(milbemectin)、lepimectin、艾克敌105(spinosad)、spinetoram;
-线粒体电子传输抑制剂(METI)I杀螨剂:喹螨醚(fenazaquin)、哒螨酮(pyridaben)、吡螨胺(tebufenpyrad)、唑虫酰胺(tolfenpyrad)、flufenerim;
-METI II和III化合物:灭螨醌(acequinocyl)、嘧螨酯(fluacrypyrim)、灭蚁腙(hydramethylnon);
-去偶剂:氟唑虫清(chlorfenapyr);
-氧化磷酸化抑制剂:三环锡(cyhexatin)、杀螨硫隆(diafenthiuron)、杀螨锡(fenbutatin oxide)、克螨特(propargite);
-蜕皮干扰化合物:灭蝇胺(cyromazine);
-混合功能氧化酶抑制剂:增效醚(piperonyl butoxide);
-其它:benclothiaz、联苯肼酯(bifenazate)、杀螟丹(cartap)、氟啶虫酰胺(flonicamid)、啶虫丙醚(pyridalyl)、拒嗪酮(pymetrozine)、硫磺(sulfur)、硫环杀(thiocyclam)、氟虫酰胺(flubendiamide)、chlorantraniliprole、cyazypyr(HGW86);cyenopyrafen、flupyrazofos、丁氟螨酯(cyflumetofen)、磺胺螨酯(amidoflume)、imicyafos、双三氟虫脲(bistrifluron)及新喹唑啉(pyrifluquinazon)。
农药优选选自阴离子农药。术语“阴离子农药”是指以阴离子形式存在的农药。优选阴离子农药是指包含可质子化氢的农药。更优选阴离子农药是指包含羧酸、硫代碳酸、磺酸、亚磺酸、硫代磺酸或亚磷酸基团,尤其是羧酸基团的农药。上述基团可部分以中性形式(包含可质子化氢)存在。
通常,阴离子农药包含至少一个阴离子基团。优选所述阴离子农药包含一个或两个阴离子基团。特别地,所述阴离子农药包含恰好一个阴离子基团。阴离子基团的实例为羧酸根(-C(O)O-)。上述阴离子基团可部分以中性形式(包含可质子化氢)存在。例如,羧酸根可部分以羧酸(-C(O)OH)的中性形式存在。在含水组合物中优选如此,其中可存在羧酸根与羧酸的平衡。
下文给出了合适的阴离子农药。在名称涉及阴离子农药的中性形式或盐的情况下,意指阴离子农药的阴离子形式。例如,麦草畏的阴离子形式可由下式表示:
作为另一实例,草甘膦的阴离子形式可由下式中至少一个表示:
对专家而言已知当阴离子农药以溶解形式存在时,官能团的离解和由此阴离子电荷的位置可例如取决于pH。草甘膦的酸的离解常数pKa通常对第一磷酸而言为0.8,对羧酸而言为2.3,对第二磷酸而言为6.0,且对胺而言为11.0。
合适的阴离子农药为除草剂,其包含羧酸、硫代碳酸、磺酸、亚磺酸、硫代磺酸或亚磷酸基团,尤其是羧酸基团。实例为芳香酸类除草剂、苯氧基羧酸类除草剂或包含羧酸基团的有机磷除草剂。
合适芳香酸类除草剂为苯甲酸类除草剂,如二氟吡隆(diflufenzopyr)、抑草生(naptalam)、草灭平(chloramben)、麦草畏、2,3,6-三氯苯甲酸(草芽平(2,3,6-TBA))、杀草畏(tricamba);嘧啶氧基苯甲酸类除草剂,如双嘧苯甲酸(bispyribac)、肟啶草(pyriminobac);嘧啶硫基苯甲酸类除草剂,如嘧硫苯甲酸(pyrithiobac);邻苯二甲酸类除草剂,如敌草索(chlorthal);吡啶甲酸类除草剂,如氯氨吡啶酸(aminopyralid)、二氯皮考啉酸(clopyralid)、毒莠定(picloram);喹啉羧酸类除草剂,如二氯喹啉酸(quinclorac)、喹草酸(quinmerac);或其它芳香酸类除草剂,如环丙嘧啶酸(aminocyclopyrachlor)。优选为苯甲酸类除草剂,尤其是麦草畏。
合适的苯氧基羧酸类除草剂为苯氧基乙酸类除草剂,例如4-氯苯氧基乙酸(促生灵(4-CPA))、(2,4-二氯苯氧基)乙酸(2,4-滴(2,4-D))、(3,4-二氯苯氧基)乙酸(3,4-滴胺(3,4-DA))、2甲4氯(MCPA)(4-(4-氯邻甲苯氧基)丁酸)、酚硫杀、(2,4,5-三氯苯氧基)乙酸(2,4,5-涕(2,4,5-T));苯氧基丁酸类除草剂,例如氯苯氧丁酸(4-CPB)、4-(2,4-二氯苯氧基)丁酸(2,4-滴丁酸(2,4-DB))、4-(3,4-二氯苯氧基)丁酸(3,4-滴丁酸(3,4-DB))、4-(4-氯邻甲苯氧基)丁酸(2甲4氯丁酸(MCPB))、4-(2,4,5-三氯苯氧基)丁酸(2,4,5-涕丁酸(2,4,5-TB));苯氧基丙酸类除草剂,例如调果酸(cloprop)、2-(4-氯苯氧基)丙酸(氯苯氧丙酸(4-CPP))、2,4-滴丙酸、高2,4-滴丙酸(dichlorprop-P)、4-(3,4-二氯苯氧基)丁酸(3,4-滴丙酸(3,4-DP))、2,4,5-涕丙酸(fenoprop)、2甲4氯丙酸、高2甲4氯丙酸(mecoprop-P);芳氧基苯氧基丙酸类除草剂,例如炔禾灵(chlorazifop)、炔草酯(clodinafop)、氯丁草(clofop)、氰氟草酯(cyhalofop)、氯甲草(diclofop)、唑禾草灵、高唑禾草灵(fenoxaprop-P)、噻唑禾草灵(fenthiaprop)、吡氟禾草灵、精吡氟禾草灵(fluazifop-P)、吡氟氯禾灵、精吡氟氯禾灵(haloxyfop-P)、恶草醚(isoxapyrifop)、恶唑酰草胺、喔草酯、喹禾灵、精喹禾灵(quizalofop-P)、三氟苯氧丙酸(trifop)。优选为苯氧基乙酸类除草剂,尤其为2甲4氯。
包含羧酸基团的合适有机磷除草剂为双丙氨酰膦、草铵膦、精草铵膦(glufosinate-P)、草甘膦。优选为草甘膦。
包含羧酸的合适其它除草剂为包含羧酸的吡啶类除草剂,例如氟草烟、定草酯(triclopyr);包含羧酸的三唑并嘧啶类除草剂,例如唑嘧磺胺盐(cloransulam);包含羧酸的嘧啶基磺酰脲类除草剂,例如苄嘧黄隆、氯嘧黄隆(chlorimuron)、甲酰胺黄隆、吡氯黄隆、甲基二黄隆、氟嘧黄隆、嘧黄隆;咪唑啉酮类除草剂,例如咪草酯、咪草酯、咪草啶酸、甲基咪草烟、灭草烟、灭草喹和咪草烟;三唑啉酮类除草剂,例如氟酮黄隆、丙苯黄隆和thiencarbazone;芳族除草剂,例如氟锁草醚、治草醚、氟酮唑草、氟哒嗪草酯(flufenpyr)、酰亚胺苯氧乙酸(flumiclorac)、乙羧氟草醚(fluoroglycofen)、达草氟、乳氟禾草灵、氟唑草酯(pyraflufen)。此外,作为包含羧酸的其它除草剂,可提及氯甲丹(chlorflurenol)、茅草枯(dalapon)、草藻灭、氟燕灵(flamprop)、强氟燕灵、四氟丙酸(flupropanate)、抑草丁(flurenol)、油酸、壬酸、三氯醋酸(TCA)。
合适的阴离子农药为杀真菌剂,其包含羧酸、硫代碳酸、磺酸、亚磺酸、硫代磺酸或亚磷酸基团,尤其是羧酸基团。实例为多氧霉素(polyoxin)杀真菌剂,如polyoxorim。
合适的阴离子农药为杀虫剂,其包含羧酸、硫代碳酸、磺酸、亚磺酸、硫代磺酸或亚磷酸基团,尤其是羧酸基团。实例为苏云金素(thuringiensin)。
合适的阴离子农药为植物生长调节剂,其包含羧酸、硫代碳酸、磺酸、亚磺酸、硫代磺酸或亚磷酸基团,尤其是羧酸基团。实例为1-萘基乙酸、(2-萘基氧基)乙酸、吲哚-3-基乙酸、4-吲哚-3-基丁酸、草甘双磷(glyphosine)、茉莉酮酸、2,3,5-三碘苯甲酸、调环酸(prohexadione)、抗倒酯(trinexapac),优选为调环酸和抗倒酯。
优选的阴离子农药为阴离子除草剂,更优选麦草畏、草甘膦、2,4-滴、氯氨吡啶酸、环丙嘧啶酸和2甲4氯。尤其优选麦草畏和草甘膦。在另一优选实施方案中,优选麦草畏。在另一优选实施方案中,优选2,4-滴。在另一优选实施方案中,优选草甘膦。在另一优选实施方案中,优选2甲4氯。
在另一实施方案中,农药包含第一阴离子农药和第二阴离子农药。例如第二阴离子农药为如下阴离子农药,其中所述阴离子农药的至少一个阴离子基团选自一个或多个膦酸根。优选如下除草剂,其中所述除草剂的至少一个阴离子基团选自一个或多个膦酸根。实例为包含羧酸基团的有机磷除草剂。合适的包含羧酸基团的有机磷除草剂为双丙氨酰膦、草铵膦、精草铵膦、草甘膦。优选第二阴离子农药为草甘膦。
优选地,第一阴离子农药含有羧酸基团,且第二阴离子农药含有膦酸根。更优选地,第一阴离子农药为芳香酸类除草剂或苯氧基羧酸类除草剂,且第二阴离子农药为包含羧酸基团的有机磷除草剂。在另一优选实施方案中,第一和第二阴离子农药选自麦草畏、二氯喹啉酸、草甘膦、2,4-滴、氯氨吡啶酸和MCPP。例如第一和第二阴离子农药为麦草畏和草甘膦、2,4-滴和麦草畏、麦草畏和MCPP、2,4-滴和MCPP,或2,4-滴和草甘膦.
在另一优选实施方案中,农药包含植物生长素除草剂。各种合成和天然植物生长素除草剂是已知的,其中优选合成植物生长素除草剂。
天然植物生长素除草剂的实例为吲哚-3-乙酸(IAA)、苯乙酸(PAA)、4-氯吲哚-3-乙酸(4-Cl-IAA)和吲哚-3-丁酸(IBA)。
合成植物生长素除草剂的实例为2,4-滴及其盐和酯、2,4-滴丁酸及其盐和酯、氯氨吡啶酸及其盐如氯氨吡啶酸三(2-羟丙基)铵和其酯、草除灵、乙基草除灵(benazolin-ethyl)、草灭平及其盐和酯、稗草胺、二氯皮考啉酸及其盐和酯、麦草畏及其盐和酯、2,4-滴丙酸及其盐和酯、高2,4-滴丙酸及其盐和酯、氟草烟、丁氧基甲基氟草烟(fluroxypyr-butometyl)、氟氯胺啶(fluroxypyr-meptyl)、2甲4氯及其盐和酯、酚硫杀、2甲4氯丁酸及其盐和酯、2甲4氯丙酸及其盐和酯、高2甲4氯丙酸及其盐和酯、毒莠定及其盐和酯、二氯喹啉酸、喹草酸、草芽平及其盐和酯、定草酯及其盐和酯和环丙嘧啶酸及其盐和酯。
优选的植物生长素除草剂为2,4-滴及其盐和酯以及麦草畏及其盐和酯,其中更优选2,4-滴和麦草畏。
提高农药性能的方法包括使助剂和农药接触的步骤。由该步骤得到的组合物可以含有助剂和农药。含有助剂和农药的任何组合物在本文中称为“助剂化组合物(adjuvanted composition)”。助剂和农药的接触可通过以任意顺序混合而进行。
优选地,本发明方法包括使助剂和农药接触的步骤,其中所得含有助剂和农药的组合物为可喷雾含水组合物。
在另一优选实施方案中,本发明方法包括如下步骤:
a)使农药和辅助剂接触(得到所谓的“农化配制剂”),然后
b)使农化配制剂和助剂接触(得到助剂化组合物)。
优选地,在步骤b)中,使农化配制剂、液体载体(例如水)和助剂接触。使农化配制剂、液体载体和助剂接触的顺序可以为任意一种。这通常得到可喷雾含水组合物。
在步骤b)中,农化配制剂(其可为液体或固体)和液体载体(例如水)的重量比通常为1:1-1:1000,优选1:2-1:1000,更优选1:5-1:1000,尤其是1:10-1:1000。
在另一优选实施方案中,本发明方法包括使助剂和农药接触的步骤,其中农药以小于10wt%的浓度存在于所得含有助剂和农药的组合物(优选步骤b)中得到的助剂化组合物)中。该农药优选以小于5wt%,更优选小于2.5wt%,甚至更优选小于1wt%,尤其是小于0.5wt%的浓度存在于助剂化组合物农药(优选步骤b)中得到的助剂化组合物)中。
术语“可喷雾”组合物指可通过常规农化喷雾设备喷雾的组合物。可喷雾组合物通常在20℃下具有低动态粘度,例如在30mPas以下,优选在10mPas以下,更优选在3mPas以下,尤其是在1.5mPas以下。可喷雾组合物通常不含固体颗粒或非常小的颗粒。D50粒度通常在50μm以下,优选在20μm以下,尤其是在10μ以下。在另一实施方案中,至少90%颗粒具有在50μm以下,优选在25μm以下的粒度。
助剂和农药的总和的施用速率通常为2g/ha至100kg/ha,优选50g/ha至10kg/ha,尤其是200g/ha至5kg/ha。
本发明方法使用可以溶于和/或分散于水中的农药。优选地,农药溶于和/或分散于(优选溶于)助剂化组合物,例如由步骤b)得到的组合物中。
本发明方法为提高农药性能的方法。术语“提高”意指性能与不含助剂的相当方法相比更好。术语“性能”意指任何类型的农药特性,例如生物学活性、作物选择性、植物毒性、生态毒性、人类毒性(human toxicity)、储存稳定性或挥发性的降低。
本发明还涉及一种包含植物生长素除草剂和助剂的组合物,其含有如上所定义的式(A)的胍和/或其盐。优选实施方案,例如就R1、R2、R3、R4、R5、R6、R7、R8、m、n和x而言的优选实施方案如上所述。优选的植物生长素除草剂如合成和天然植物生长素除草剂如上所述。尤其优选的植物生长素除草剂为2,4-滴及其盐和酯以及麦草畏及其盐和酯,其中更优选2,4-滴和麦草畏。最优选植物生长素除草剂为麦草畏及其盐。
本发明组合物、农化配制剂或助剂化组合物可包含至少一种其它农药。所述其它农药可选自杀真菌剂、杀虫剂、杀线虫剂、除草剂和/或安全剂或生长调节剂,优选选自杀真菌剂、杀虫剂或除草剂,更优选为除草剂。优选其它农药为咪唑啉酮类除草剂和三嗪类除草剂。其它农药优选不含阴离子农药。
本发明组合物和方法适于用作除草剂。其适合原样使用或作为适当配制的组合物使用。本发明组合物和方法非常有效地防治非作物区域中的植物,尤其是在高施用率下。其用于防治诸如小麦、稻、玉米、大豆和棉花的作物中的阔叶杂草和禾草,且不会对作物植物造成任何显著伤害。该效应主要在低施用率下观测获得。
取决于所述施用方法,本发明组合物和方法可额外用于许多其它作物植物以清除不希望的植物。合适作物的实例如下:洋葱(Allium cepa)、凤梨(Ananas comosus)、落花生(Arachis hypogaea)、石刁柏(Asparagusofficinalis)、燕麦(Avena sativa)、甜菜(Beta vulgaris spec.altissima)、甜菜(Beta vulgaris spec.rapa)、欧洲油菜(Brassica napus var.napus)、芜青甘蓝(Brassica napus var.napobrassica)、芜青(Brassica rapa var.silvestris)、羽衣甘蓝(Brassica oleracea)、黑芥(Brassica nigra)、芥菜(Brassica juncea)、芸薹(Brassica campestris)、大叶茶(Camellia sinensis)、红花(Carthamustinctorius)、美国山核桃(Carya illinoinensis)、柠檬(Citrus limon)、甜橙(Citrus sinensis)、小果咖啡(Coffea arabica)(中果咖啡(Coffea canephora)、大果咖啡(Coffea liberica))、黄瓜(Cucumis sativus)、狗牙根(Cynodondactylon)、胡萝卜(Daucus carota)、油棕(Elaeis guineensis)、欧洲草莓(Fragaria vesca)、大豆(Glycine max)、陆地棉(Gossypium hirsutum)(树棉(Gossypium arboreum)、草棉(Gossypium herbaceum)、Gossypiumvitifolium)、向日葵(Helianthus annuus)、Hevea brasiliensis、大麦(Hordeumvulgare)、啤酒花(Humulus lupulus)、甘薯(Ipomoea batatas)、核桃(Juglansregia)、兵豆(Lens culinaris)、亚麻(Linum usitatissimum)、番茄(Lycopersicon lycopersicum)、苹果属(Malus spec.)、木薯(Manihotesculenta)、紫苜蓿(Medicago sativa)、芭蕉属(Musa spec.)、烟草(Nicotianatabacum)(黄花烟草(N.rustica))、油橄榄(Olea europaea)、稻(Oryza sativa)、金甲豆(Phaseolus lunatus)、菜豆(Phaseolus vulgaris)、欧洲云杉(Piceaabies)、松属(Pinus spec.)、开心果(Pistacia vera)、Pisum sativum、欧洲甜樱桃(Prunus avium)、Prunus persica、西洋梨(Pyrus communis)、杏(Prunusarmeniaca)、欧洲酸樱桃(Prunus cerasus)、扁桃(Prunus dulcis)和欧洲李(Prunus domestica)、Ribes sylvestre、蓖麻(Ricinus communis)、甘蔗(Saccharum officinarum)、黑麦(Secale cereale)、白芥(Sinapis alba)、马铃薯(Solanum tuberosum)、两色蜀黍(Sorghum bicolor)(高粱(S.vulgare))、可可树(Theobroma cacao)、红车轴草(Trifolium pratense)、普通小麦(Triticum aestivum)、小黑麦(Triticale)、硬粒小麦(Triticum durum)、蚕豆(Vicia faba)、葡萄(Vitis vinifera)、玉蜀黍(Zea mays)。
优选作物为:落花生、甜菜、欧洲油菜、羽衣甘蓝、芥菜、柠檬、甜橙、小果咖啡(中果咖啡、大果咖啡)、狗牙根、大豆、陆地棉(树棉、草棉、Gossypium vitifolium)、向日葵、大麦、核桃、兵豆、亚麻、番茄、苹果属、紫苜蓿、烟草(黄花烟草))、油橄榄、稻、金甲豆、菜豆、开心果、Pisum sativum、扁桃、甘蔗、黑麦、马铃薯、两色蜀黍(高粱)、小黑麦、普通小麦、硬粒小麦、蚕豆、葡萄和玉蜀黍。
本发明组合物和方法也可用于基因修饰植物,以便例如改变其性状或特征。术语“基因修饰植物”应理解为其遗传物质已以在自然环境下无法由杂交育种、突变、自然重组、育种、诱变或基因工程容易地获得方式利用DNA重组技术加以修饰的植物。通常将一个或多个基因整合到基因修饰植物的遗传物质中以改善植物的某些性能。这类基因修饰还包括但不限于蛋白质、寡肽或多肽的靶向翻译后修饰,例如通过糖基化或聚合物加成如异戊二烯化、乙酰化或法呢基化结构部分或PEG结构部分。
已通过育种、诱变和基因工程改性例如已赋予对某些类别的除草剂施用的耐受性的植物特别是与本发明组合物和方法一起使用。由于常规育种方法或遗传工程已形成对多类除草剂的耐受性,这些除草剂如植物生长素除草剂,例如麦草畏或2,4-滴;漂白除草剂如羟基苯基丙酮酸双加氧酶(HPPD)抑制剂或八氢番茄红素去饱和酶(PDS)抑制剂;乙酰乳酸合酶(ALS)抑制剂,如磺酰脲类或咪唑啉酮类;烯醇丙酮酰莽草酸3-磷酸合酶(EPSP)抑制剂,如草甘膦;谷氨酰胺合酶(GS)抑制剂,如草铵膦;原卟啉原-IX氧化酶(PPO)抑制剂;类脂生物合成抑制剂,如乙酰辅酶A羧化酶(ACCase)抑制剂或苯腈类(oxynil)除草剂(即溴苯腈或碘苯腈)。此外,已通过多次基因改性而使植物耐受多类除草剂,例如耐受草甘膦和草铵膦二者,或耐受草甘膦和选自其它类的除草剂(例如ALS抑制剂、HPPD抑制剂、植物生长素抑制剂或ACCase抑制剂)二者。这些除草剂耐受技术例如描述于Pest Management Science61,2005,246;61,2005,258;61,2005,277;61,2005,269;61,2005,286;64,2008,326;64,2008,332;WeedScience57,2009,108;Australian Journal of Agricultural Research58,2007,708;Science316,2007,1185;及其中引用的参考文献中。这些除草剂耐受技术的实例还描述于US2008/0028482、US2009/0029891、WO2007/143690、WO2010/080829、US6307129、US7022896、US2008/0015110、US7,632,985、US7105724和US7381861中,各自以引用方式并入本文。
已通过常规育种(诱变)方法赋予数种栽培植物对除草剂的耐受性,例如夏季油菜(Canola,BASF SE,德国)对咪唑啉酮类如咪草啶酸具有耐受性,或者向日葵(DuPont,美国)对磺酰脲类如苯黄隆具有耐受性。基因工程方法已用于赋予栽培植物如大豆、棉花、玉米、甜菜和油菜对除草剂如草甘膦、麦草畏、咪唑啉酮类和草铵膦的耐受性,其中一些处于研发阶段或者可以以商标或商品名(草甘膦耐受型,Monsanto,美国)和(咪唑啉酮类耐受性,BASF SE,德国)和(草铵膦耐受型,Bayer CropScience,德国)市购。
此外,还涵盖通过利用DNA重组技术而能合成一种或多种杀虫蛋白的植物,所述杀虫蛋白尤其是由芽孢杆菌属(Bacillus)细菌,特别是由苏云金芽孢杆菌(Bacillus thuringiensis)已知的那些,例如δ-内毒素如CryIA(b)、CryIA(c)、CryIF、CryIF(a2)、CryIIA(b)、CryIIIA、CryIIIB(b1)或Cry9c;或无性杀虫蛋白(VIP),例如VIP1、VIP2、VIP3或VIP3A;线虫定居细菌的杀虫蛋白,例如发光杆菌属(Photorhabdus)或致病杆菌属(Xenorhabdus);动物产生的毒素如蝎毒素、蜘蛛毒素、黄蜂毒素或其它昆虫特异性神经毒素;由真菌例如链霉菌属(Streptomycetes)产生的毒素;植物凝集素,如豌豆或大麦凝集素;凝集素;蛋白酶抑制剂,如胰蛋白酶抑制剂、丝氨酸蛋白酶抑制剂、马铃薯块茎储藏蛋白(patatin)抑制剂、半胱氨酸蛋白酶抑制剂或木瓜蛋白酶抑制剂;核糖体失活蛋白(RIP),如蓖麻蛋白、玉米-RIP、相思豆毒蛋白、丝瓜籽蛋白、皂草素或异株腹泻毒蛋白(bryodin);类固醇代谢酶,如3-羟基类固醇氧化酶、蜕皮甾类-IDP糖基转移酶、胆固醇氧化酶、蜕皮激素抑制剂或HMG-CoA还原酶;离子通道阻断剂,例如钠通道或钙通道阻断剂;保幼激素酯酶;利尿激素受体(helicokinin受体);茋合酶,联苄合酶,壳多糖酶或葡聚糖酶。在本发明上下文中,这些杀虫蛋白或毒素也可明确理解为前毒素、杂合蛋白、截短或改性的蛋白。杂合蛋白的特征在于蛋白域的新组合(例如参见WO2002/015701)。该类毒素或能合成该类毒素的基因修饰植物的其它实例例如公开于EP-A374753、WO93/07278、WO95/34656、EP-A427529、EP-A451878、WO03/18810和WO03/52073中。生产这些基因修饰植物的方法对本领域技术人员而言是公知的且例如描述于上述出版物中。基因修饰植物中所含的这些杀虫蛋白赋予产生这些蛋白的植物对所有分类学上为节肢动物的害虫,尤其是甲虫(鞘翅目(Coeleropta))、双翅目昆虫(双翅目(Diptera))和蛾(鳞翅目(Lepidoptera))以及线虫(线虫纲(Nematoda))的耐受性。能合成一种或多种杀虫蛋白的基因修饰植物例如描述于上述出版物中,且它们中的一些可市购,例如(产生毒素Cry1Ab的玉米栽培品种),Plus(产生毒素Cry1Ab和Cry3Bb1的玉米栽培品种),(产生毒素Cry9c的玉米栽培品种),RW(产生毒素Cry34Ab1、Cry35Ab1和酶膦丝菌素-N-乙酰转移酶[PAT]的玉米栽培品种);33B(产生毒素Cry1Ac的棉花栽培品种),I(产生毒素Cry1Ac的棉花栽培品种),II(产生毒素Cry1Ac和Cry2Ab2的棉花栽培品种);(产生VIP毒素的棉花栽培品种);(产生毒素Cry3A的马铃薯栽培品种); Bt11(例如CB)和法国Syngenta Seeds SAS的Bt176(产生毒素Cry1Ab和PAT酶的玉米栽培品种),法国Syngenta SeedsSAS的MIR604(产生毒素Cry3A的修饰译本的玉米栽培品种,参见WO03/018810),比利时Monsanto Europe S.A.的MON863(产生毒素Cry3Bb1的玉米栽培品种),比利时Monsanto Europe S.A.的IPC531(产生毒素Cry1Ac的修饰译本的棉花栽培品种)和比利时Pioneer OverseasCorporation的1507(产生毒素Cry1F和PAT酶的玉米栽培品种)。
此外,还涵盖通过利用DNA重组技术能合成一种或多种提高对细菌、病毒或真菌病原体的耐受性的蛋白质的植物。这类蛋白质的实例为所谓的“与发病机理相关的蛋白”(PR蛋白,参见例如EP-A392225),植物抗病基因(例如表达出对来自野生墨西哥马铃薯Solanum bulbocastanum的致病疫霉(Phytophthora infestans)的抗性基因的马铃薯栽培品种)或T4溶菌酶(例如能合成这些蛋白质以提高对细菌如梨火疫病菌(Erwinia amylovora)的耐受性的马铃薯栽培品种)。生产这类基因修饰植物的方法为本领域技术人员所公知的且例如描述于上述公开文献中。
此外,还涵盖通过利用DNA重组技术而能合成一种或多种蛋白质以提高生产能力(例如生物质生产、谷粒产量、淀粉含量、油含量或蛋白质含量),对干旱、盐度或其它生长限制性环境因素的耐受性或对害虫以及真菌、细菌或病毒病原体的耐受性的那些植物。
此外,还涵盖通过利用DNA重组技术而含有改善量的内含物或新内含物,尤其是改善人类或动物营养的内含物的植物,例如产生促进健康的长链ω-3脂肪酸或不饱和ω-9脂肪酸的油料作物(例如油菜,DOWAgro Sciences,加拿大)。
此外,已发现本发明组合物和方法也适于使植物部分脱叶和/或干燥,对此合适地为诸如棉花、马铃薯、油菜、向日葵、大豆或蚕豆,尤其是棉花的作物。就此而言,已发现用于使植物干燥和/或脱落的组合物、制备这些组合物的方法以及使用本发明组合物和方法使植物干燥和/或脱叶的方法。
作为干燥剂的本发明组合物和方法特别适于干燥作物如马铃薯、油菜、向日葵和大豆以及谷物的地上部分。这使得这些重要作物的完全机械化收获成为可能。
还具有经济益处的是促进柑橘类水果、橄榄和其它品种的仁果、核果和坚果的收获,这通过在一定时间期限内集中裂开或降低对树的粘附而成为可能。相同的机理,即促进果实部分或叶部分与植物的枝部分之间产生脱离组织对于有用植物,尤其是棉花的易控脱叶也是必要的。此外,缩短各棉花植株的成熟时间间隔可提高采收后的纤维质量。
本发明组合物和方法主要通过喷施叶片而施用至植物。此时,可使用例如水作为载体通过常规喷雾技术使用约100-1000L/ha(例如300-400L/ha)的喷雾液量进行施用。所述除草组合物也可通过低容量或超低容量法或以微颗粒剂形式施用。
本发明组合物和方法可在出苗前后施用或与作物植物种子一起施用。也可通过施用用本发明组合物预处理的作物植物的种子来施用所述化合物及组合物。如果某些作物植物对活性化合物A及C且适当的话C的耐受性较差,则可使用借助喷雾设备喷雾除草组合物的施用技术,从而使得其尽可能不与敏感作物植物叶片接触,同时活性化合物到达生长于下方的不希望植物的叶片或裸露土壤表面上(直接喷施、绕路到达(post-directed,lay-by))。
在又一实施方案中,本发明组合物或方法可通过处理种子而施用。种子处理包括基于本发明组合物和方法的基本上所有的本领域技术人员熟知的程序(拌种、种子包衣、种子撒粉、浸种、种子膜涂布、种子多层涂布、种子包壳、种子浸泡和种子造粒)。此时,所述除草组合物可经稀释或不经稀释施用。
术语种子包括所有类型种子,如谷粒、种子、果实、根茎、秧苗和类似形式。此处,优选术语种子包括谷粒和种子。
所用种子可为上述有用植物的种子,以及转基因植物或通过常规育种方法获得的植物的种子。
活性化合物的施用率为0.0001-3.0kg/ha,优选0.01-1.0kg/ha的活性物质(a.s.),这取决于防治目标、季节、目标植物和生长阶段。为了处理种子,农药通常以0.001-10kg/100kg种子的量使用。
此外,可有利地单独或与其它作物保护剂组合而一起施用本发明组合物,例如与用于防治害虫或植物病原性真菌或细菌的试剂或与调节生长的活性化合物组合而施用。同样感兴趣的是其与用于治疗营养缺乏及微量元素缺乏的矿物盐溶液的溶混性。也可添加无植物毒性的油和油浓缩物。
本发明组合物可转化成常用类型的农化组合物,例如溶液、乳液、悬浮液、粉剂、粉末、糊剂和颗粒。组合物的类型取决于具体预期目的;在每种情况下,应确保本发明化合物细且均匀分布。组合物类型的实例为悬浮液(SC、OD、FS)、可乳化浓缩物(EC)、乳液(EW、EO、ES)、糊剂、锭剂、润湿性粉末或粉剂(WP、SP、SS、WS、DP、DS)或可为水溶性或润湿性颗粒(GR、FG、GG、MG),以及用于处理诸如种子的植物繁殖材料的凝胶配制剂(GF)。组合物类型(例如SC、OD、FS、EC、WG、SG、WP、SP、SS、WS、GF)通常经稀释使用。组合物类型如DP、DS、GR、FG、GG和MG通常不经稀释即使用。所述组合物以已知方式制备。当所述农化组合物为含水组合物时,本发明盐可离解成阴离子和阳离子。
本发明组合物优选为呈可溶性浓缩物(SL)、油分散体(OD)、水溶性颗粒(SG)或水溶性粉末(SP)形式的农化组合物。
所述农化组合物也可包含农化组合物中常用的辅助剂。所用辅助剂分别取决于具体施用形式和活性物质。合适辅助剂的实例为溶剂,固体载体,分散剂或乳化剂(例如其它加溶剂、保护性胶体、表面活性剂和增粘剂),有机和无机增稠剂、杀菌剂、防冻剂、消泡剂,合适的话着色剂和增粘剂或粘合剂(例如用于种子处理配制剂)。
合适的溶剂为水,有机溶剂,例如中至高沸点的矿物油馏分如煤油和柴油,此外还有煤焦油,以及植物或动物来源的油,脂族、环状和芳族烃类,例如甲苯、二甲苯、石蜡、四氢萘、烷基化萘或其衍生物,醇类如甲醇、乙醇、丙醇、丁醇和环己醇,二醇类(例如乙二醇或1,2-丙二醇),酮类如环己酮和γ-丁内酯,脂肪酸二甲基酰胺,脂肪酸和脂肪酸酯以及强极性溶剂,例如胺类如N-甲基吡咯烷酮。优选的溶剂为水。
固体载体为矿土如硅酸盐、硅胶、滑石、高岭土、石灰石、石灰、白垩、红玄武土、黄土、粘土、白云石、硅藻土、硫酸钙、硫酸镁、硫酸铁、氧化镁;磨碎的合成物质;肥料如硫酸铵、磷酸铵、硝酸铵、脲类;以及植物来源的产品如谷粉、树皮粉、木粉和坚果壳粉,纤维素粉和其它固体载体。
合适的表面活性剂(助剂、润湿剂、增粘剂、分散剂或乳化剂)为芳族磺酸如木素磺酸(类型,挪威Borregard)、苯酚磺酸、萘磺酸(类型,美国Akzo Nobel)和二丁基萘磺酸(类型,德国BASF)以及脂肪酸的碱金属、碱土金属和铵盐,烷基磺酸盐和烷基芳基磺酸盐,烷基硫酸盐,月桂基醚硫酸盐,脂肪醇硫酸盐,以及硫酸化十六-、十七-和十八烷醇盐,硫酸化脂肪醇乙二醇醚,此外还有萘或萘磺酸与苯酚和甲醛的缩合物,聚氧乙烯辛基苯基醚,乙氧基化异辛基酚,辛基酚、壬基酚,烷基苯基聚乙二醇醚,三丁基苯基聚乙二醇醚,三硬脂基苯基聚乙二醇醚,烷基芳基聚醚醇,醇和脂肪醇/氧化乙烯缩合物,乙氧基化蓖麻油,聚氧乙烯烷基醚,乙氧基化聚氧丙烯,月桂醇聚乙二醇醚缩醛,山梨糖醇酯,木素亚硫酸盐废液和蛋白质,变性蛋白质,多糖(例如甲基纤维素),疏水改性的淀粉,聚乙烯醇(型,瑞士Clariant)、聚羧酸盐(型,德国BASF),聚烷氧基化物,聚乙烯基胺(型,德国BASF),聚乙烯基吡咯烷酮及其共聚物。其它合适的表面活性剂(尤其用于包含草甘膦的农化组合物)为烷氧基化C4-22烷基胺如乙氧基化牛油胺(POEA)和公开于EP1389040中的表面活性剂(例如实施例1-14中的那些)。
增稠剂(即赋予组合物以改性的流动性能,即静止状态下的高粘度和搅动状态下的低粘度的化合物)的实例为多糖以及有机和无机粘土如黄原胶(美国CP Kelco),23(法国Rhodia),(美国R.T.Vanderbilt)或(美国Engelhard Corp.,NJ)。可加入杀菌剂以保存和稳定该组合物。合适杀菌剂的实例为基于双氯酚和苄醇半缩甲醛的杀菌剂(ICI的或Thor Chemie的RS和Rohm&Haas的MK),以及异噻唑啉酮衍生物如烷基异噻唑啉酮类和苯并异噻唑啉酮类(Thor Chemie的MBS)。合适防冻剂的实例为乙二醇、丙二醇、尿素和甘油。消泡剂实例为聚硅氧烷乳液(例如SRE,德国Wacker或法国Rhodia),长链醇,脂肪酸,脂肪酸盐,有机氟化合物及其混合物。增粘剂或粘合剂的实例为聚乙烯基吡咯烷酮、聚乙酸乙烯酯、聚乙烯醇和纤维素醚(日本Shin-Etsu)。着色剂的实例为微水溶性颜料和水溶性染料二者。可提及的实例为以下列名称已知的染料:若丹明B、C.I.颜料红112和C.I.溶剂红1、以及颜料蓝15:4、颜料蓝15:3、颜料蓝15:2、颜料蓝15:1、颜料蓝80、颜料黄1、颜料黄13、颜料红112、颜料红48:2、颜料红48:1、颜料红57:1、颜料红53:1、颜料橙43、颜料橙34、颜料橙5、颜料绿36、颜料绿7、颜料白6、颜料棕25、碱性紫10、碱性紫49、酸性红51、酸性红52、酸性红14、酸性蓝9、酸性黄23、碱性红10、碱性红108。
粉末、撒播材料和粉剂可通过将本发明盐以及如果合适的话其它活性化合物与至少一种固体载体混合或同时研磨而制备。颗粒如涂覆颗粒、浸渍颗粒和均质颗粒可通过将活性化合物与固体载体粘合而制备。固体载体例如为矿土如硅胶、硅酸盐、滑石、高岭土、活性粘土(attaclay)、石灰石、石灰、白垩、红玄武土、黄土、粘土、白云石、硅藻土、硫酸钙、硫酸镁、氧化镁;磨碎的合成物质;肥料如硫酸铵、磷酸铵、硝酸铵、脲类;以及植物来源的产品如谷粉、树皮粉、木粉和坚果壳粉,纤维素粉和其它固体载体。
组合物类型的实例为:
1.用水稀释的组合物类型
i)水溶性浓缩物(SL、LS)
将50重量份农药溶解于50重量份水或水溶性溶剂中。作为替代方案,添加润湿剂或其它辅助剂。用水稀释后,该活性物质溶解。以此方式获得活性物质含量为10重量%的组合物。
ii)可分散浓缩物(DC)
将20重量份农药溶解于70重量份环己酮中,同时添加10重量份分散剂(例如聚乙烯基吡咯烷酮)。用水稀释以形成分散体。活性物质含量为20重量%。
iii)可乳化浓缩物(EC)
将15重量份农药溶解于75重量份二甲苯中,同时添加十二烷基苯磺酸钙和蓖麻油乙氧基物(在每种情况下添加5重量份)。用水稀释以形成乳液。该组合物的活性物质含量为15重量%。
iv)乳液(EW、EO、ES)
将25重量份农药溶解于35重量份二甲苯中,同时添加十二烷基苯磺酸钙和蓖麻油乙氧基化物(在每种情况下添加5重量份)。借助乳化机(Ultraturrax)将该混合物引入30重量份水中并制成均质乳液。用水稀释以形成乳液。该组合物的活性物质含量为25重量%。
v)悬浮液(SC、OD、FS)
在搅拌式球磨机中粉碎20重量份农药,同时添加10重量份分散剂和润湿剂以及70重量份水或有机溶剂,以形成细活性物质悬浮液。用水稀释以形成该活性物质的稳定悬浮液。所述组合物中的活性物质含量为20重量%。
vi)水分散性颗粒和水溶性颗粒(WG、SG)
细研磨50重量份农药,同时添加50重量份分散剂和润湿剂,并借助工业装置(如挤出机、喷雾塔、流化床)将其制成水分散颗粒或水溶性颗粒。用水稀释以形成该活性物质的稳定分散体或溶液。所述组合物的活性物质含量为50重量%。
vii)水分散性粉末和水溶性粉末(WP、SP、SS、WS)
将75重量份农药在转子-定子研磨机中研磨,同时添加25重量份分散剂、润湿剂和硅胶。用水稀释以形成该活性物质的稳定分散体或溶液。所述组合物中的活性物质含量为75重量%。
viii)凝胶(GF)
在搅拌式球磨机中粉碎20重量份农药,同时添加10重量份分散剂、1重量份胶凝剂润湿剂和70重量份水或有机溶剂,以形成活性物质的细悬浮液。用水稀释以形成该活性物质的稳定悬浮液,由此获得具有20%(w/w)活性物质的组合物。
2.不经稀释即施用的组合物类型
ix)可撒粉粉末(DP、DS)
细研磨5重量份农药并使其与95重量份细碎高岭土充分混合。这获得活性物质含量为5重量%的可撒粉组合物。
x)颗粒(GR、FG、GG、MG)
细研磨0.5重量份农药并使其与99.5重量份载体混合。现行方法为挤出、喷雾干燥或流化床法。这得到活性物质含量为0.5重量%的不经稀释即施用的颗粒。
xi)ULV溶液(UL)
将10重量份农药溶解于90重量份有机溶剂如二甲苯中。这得到活性物质含量为10重量%的不经稀释即施用的组合物。
优选组合物类型i)、iv)、vii)和x)。尤其优选组合物类型i)。
所述农化组合物通常包含0.01-95重量%,优选0.1-90重量%,最优选0.5-90重量%农药。这些活性物质以90-100%,优选95-100%(根据NMR谱)的纯度使用。为了处理植物繁殖材料,尤其是种子,通常使用水溶性浓缩物(LS)、可流动浓缩物(FS)、用于干燥处理的粉末(DS)、用于淤浆处理的水分散性粉末(WS)、水溶性粉末(SS)、乳液(ES)、可乳化的浓缩物(EC)和凝胶(GF)。这些组合物可经稀释或不经稀释即施用至植物繁殖材料,尤其是种子。所述组合物在稀释2-10倍后,在即用型制剂中获得0.01-60重量%,优选0.1-40重量%的活性物质浓度。
本发明盐的非常合适的农化组合物为:
a)水溶性浓缩物
10-70重量%除草盐以及任选至少一种其它农药、30-90重量%水、以及任选至多10重量%辅助剂如表面活性剂、增稠剂或着色剂,其中所有组分的量加和为100重量%。
b)润湿性粉末
10-90重量%除草盐以及任选至少一种其它农药、9-80重量%固体载体、1-10重量%表面活性剂以及任选辅助剂,其中所有组分的量加和为100重量%。
c)水分散性颗粒
10-90重量%除草盐以及任选至少一种其它农药、9-80重量%固体载体、1-10重量%表面活性剂以及任选辅助剂,其中所有组分的量加和为100重量%。
d)颗粒
0.5-20重量%除草盐以及任选至少一种其它农药、0.5-20重量%溶剂、40-99重量%固体载体以及任选辅助剂,其中所有组分的量加和为100重量%。
在另一优选实施方案中,本发明组合物为包含植物生长素除草剂的阴离子形式和助剂的阳离子形式的除草盐,其为式(A)的胍。除草盐可总共含有至少80wt%,优选至少90wt%,尤其是至少97wt%植物生长素除草剂的阴离子形式和助剂的阳离子形式。除草盐可包含其它阴离子或阳离子。
助剂的阳离子形式通常为由下式所示的胍鎓阳离子:
优选胍鎓阳离子的实例为胍鎓(R1、R2、R3、R4和R5为H)以及多果定和双胍辛醋酸盐的阳离子。
优选植物生长素除草剂的阴离子形式的实例可选自以上列举的合成和天然植物生长素除草剂,其中优选合成植物生长素除草剂。更优选的植物生长素除草剂的阴离子形式为选自2,4-滴、2,4-滴丁酸、氯氨吡啶酸、草除灵、草灭平、稗草胺、二氯皮考啉酸、麦草畏、2,4-滴丙酸、高2,4-滴丙酸、氟草烟、2甲4氯、2甲4氯丁酸、2甲4氯丙酸、高2甲4氯丙酸、毒莠定酯、二氯喹啉酸、喹草酸、草芽平、定草酯和环丙嘧啶酸的阴离子。在这些阴离子中,尤其优选2,4-滴和麦草畏,其中最优选麦草畏。
除草盐优选包含2,4-滴、2,4-滴丁酸、氯氨吡啶酸、草除灵、草灭平、稗草胺、二氯皮考啉酸、麦草畏、2,4-滴丙酸、高2,4-滴丙酸、氟草烟、2甲4氯、2甲4氯丁酸、2甲4氯丙酸、高2甲4氯丙酸、毒莠定酯、二氯喹啉酸、喹草酸、草芽平、定草酯或环丙嘧啶酸的阴离子形式和胍的阳离子形式,即胍鎓阳离子。除草盐更优选为麦草畏的阴离子形式和胍鎓阳离子的盐。
除草盐可以转化为常规类型的农化组合物,例如上述那些。含有除草剂盐的优选农化组合物为可溶性浓缩物(SL)、油分散体(OD)、水溶性颗粒(SG)或水溶性粉末(SP)。
施用可在播种之前或期间进行。分别用农化化合物及其组合物对植物繁殖材料,尤其是种子进行施用或处理的方法是本领域所已知的,且包括繁殖材料的拌种、包衣、造粒、撒粉、浸泡和犁沟内施用方法。在一个优选实施方案中,所述化合物或其组合物通过不引发萌芽的方法,如拌种、造粒、包衣和撒粉分别施用至植物繁殖材料。在一个优选实施方案中,将悬浮液型(FS)组合物用于种子处理。通常,FS组合物可包含1-800g/l活性物质、1-200g/l表面活性剂、0-200g/l防冻剂、0-400g/l粘合剂、0-200g/l颜料和至多1升溶剂(优选水)。
本发明组合物可原样使用或以其农化组合物形式使用,例如以如下形式使用:可直接喷雾的溶液、粉末、悬浮液、分散体、乳液、油分散体、糊剂、可撒粉产品、撒播用材料或颗粒,通过喷雾、雾化、撒粉、撒播、刷涂、浸泡或浇灌施用。施用形式完全取决于预期目的;旨在确保本发明活性物质在每种情况下均达到可能最细的分布。含水施用形式可由乳液浓缩物、糊剂或润湿性粉末(可喷雾粉末、油分散体)通过添加水而制备。可由呈原样或溶于油或溶剂中的这些物质借助润湿剂、增粘剂、分散剂或乳化剂在水中均化而制备乳液、糊剂或油分散体。或者,可制备包含活性物质、润湿剂、增粘剂、分散剂或乳化剂以及合适的话溶剂或油的浓缩物,且这类浓缩物适于用水稀释。即用型制剂中的活性物质浓度可在较宽范围内变化。一般为0.0001-10重量%,优选0.001-1重量%活性物质。所述活性物质也可成功用于超低容量法(ULV)中,其中可施用包含超过95重量%活性物质的组合物,或者甚至可施用无添加剂的活性物质。
当用于植物保护时,活性物质如除草盐的施用量取决于所需的效果类型为0.001-5kg/ha,优选为0.005-2kg/ha,更优选为0.05-0.9kg/ha,尤其为0.1-0.75kg/ha。在例如通过撒粉、包衣或浸泡种子处理植物繁殖材料如种子时,通常每100kg植物繁殖材料(优选种子)所需的活性物质的量为0.1-1000g,优选1-1000g,更优选1-100g,最优选5-100g。当用于保护材料或所储存产品时,活性物质的施用量取决于施用区域的类型和所需效果。在材料保护中,通常每立方米处理材料的施用量例如为0.001-2kg,优选0.005-1kg活性物质。
可向所述活性物质或包含所述活性物质的组合物中添加各种油、湿润剂、助剂、除草剂、杀菌剂、其它杀真菌剂和/或农药,适当的话在即将使用前添加(桶混合)。这些试剂可与本发明组合物以1:100-100:1,优选1:10-10:1的重量比混合。可使用的助剂尤其为有机改性的聚硅氧烷如Break Thru S醇烷氧基化物如AtplusAtplus MBAPlurafac LF和Lutensol ONEO/PO嵌段聚合物如Pluronic RPE和Genapol醇乙氧基化物如Lutensol XP以及磺基琥珀酸二辛基酯钠如Leophen
农药也可与其它活性物质一起存在,例如与除草剂、杀虫剂、生长调节剂、杀真菌剂或与肥料作为预混合物一起存在,或者合适的话在即将使用前才一起存在(桶混合)。
本发明还涉及一种制备本发明组合物的方法,该方法包括使植物生长素除草剂和助剂接触的步骤。其可以纯净形式或以其可得到配制剂,例如干燥或固体配制剂以及液体配制剂如含水配制剂的形式组合。优选地,植物生长素除草剂和助剂在水中接触。水可在组合之后对除草盐进行分离而除去。组合可以在常规温度如-20℃至100℃,优选3℃至90℃下进行。
本发明还涉及一种防治有害昆虫和/或植物病原性真菌的方法,其包括使其中或其上生长有或可生长有害昆虫和/或植物病原性真菌的植物、种子、土壤或植物生长环境,待保护以免所述有害昆虫和/或植物病原性真菌侵袭或侵染的植物、种子或土壤与有效量的本发明组合物接触。所述阴离子农药通常包含杀虫剂和/或杀真菌剂。例如,为了防治有害昆虫,所述农化配制剂包含杀虫剂。例如,为了防治植物病原性真菌,所述农化配制剂包含杀真菌剂。
本发明进一步涉及一种防治不希望的植物的方法,其包括使除草有效量的本发明组合物作用于植物、其生长环境或所述植物的种子上。在一个优选实施方案中,所述方法也可包括已赋予对施用其中阴离子农药为除草剂的农化配制剂的耐受性的植物。这些方法通常包括将有效量的包含所选除草剂的本发明农化配制剂施用至含有一种或多种对该除草剂具有耐受性的作物植物的栽培区域或作物田地。尽管可借助这些方法防治任意不希望的植物,但在一些实施方案中,这些方法可包括首先确定对所选除草剂敏感的区域或田地中的不希望植物。提供用于防治栽培区域中的不希望植物、防止在栽培区域中形成或出现不希望的植物、产生作物以及提高作物安全的方法。就最广泛的意义而言,不希望植物应理解为意指在不希望其出现的场所中生长的所有那些植物,包括但不限于通常视为杂草的植物物种。
此外,不希望的植物也可包括生长于指定位置上的不希望作物植物。例如,在主要包含大豆植物的田间的自生玉蜀黍植物可视为不希望的。可通过本发明方法加以防治的不希望植物包括在前一季节种植于特定田间或已种植于相邻区域中的植物,且包括作物植物,包括大豆、玉米、卡诺拉(canola)、棉花、向日葵等。在一些方面中,所述作物植物可耐受除草剂如草甘膦、ALS抑制剂或草铵膦除草剂。这些方法包括在种植区域种植对除草剂具有耐受性的作物植物,在一些实施方案中,对所述作物、种子、杂草、不希望的植物、土壤或其栽培区域施用有效量的所关注的除草剂。所述除草剂可在耐受植物栽培期间的任意时间施用。所述除草剂可在作物种植于栽培区域之前或之后施用。还提供防治栽培区域中的耐草甘膦杂草或作物植物的方法,包括将有效量的除草甘膦之外的除草剂施用至具有一种或多种对另一除草剂具有耐受性的植物的栽培区域。
术语“除草有效量”表示足以防治不希望植物且不会对处理植物造成显著损害的农药活性组分(如盐或其它农药)的量。该量可在宽范围内变化且取决于多种因素,例如待防治的物种、被处理的栽培植物或材料、气候条件和所用的具体农药活性组分。
术语“防治杂草”是指抑制杂草和/或不希望植物的生长、发芽、繁殖和/或增生;和/或将其杀死、去除、破坏或者以其它方式减少其产生和/或活性中的一种或多种。
本发明组合物或方法具有防治广谱经济上重要单子叶及双子叶有害植物如阔叶杂草、禾本科杂草或莎草科(cyperaceae)的优异除草活性。所述活性化合物也有效地作用于自根茎、根状茎及其它多年生组织产生枝条且其难以防治的多年生杂草。可提及的具体实例为可通过本发明组合物或方法防治的单子叶及双子叶杂草杂草植物群的一些代表,该列举并不限于特定物种。所述除草组合物可有效作用的杂草物种的实例尤其为单子叶杂草物种:野燕麦属(Avena spp.)、看麦娘属(Alopecurus spp.)、阿披拉草属(Aperaspp.)、臂形草属(Brachiaria spp.)、雀麦属(Bromus spp.)、马唐属(Digitariaspp.)、黑麦草属(Lolium spp.)、稗属(Echinochloa spp.)、千金子属(Leptochloa spp.)、飘拂草属(Fimbristylis spp.)、黍属(Panicum spp.)、虉草属(Phalaris spp.)、早熟禾属(Poa spp.)、狗尾草属(Setaria spp.)以及选自一年生组的莎草属(Cyperus)物种,和多年生物种偃麦草属(Agropyron)、狗牙根属(Cynodon)、白茅属(Imperata)和高粱属(Sorghum)和多年生莎草属物种。在双子叶杂草物种的情况下,作用谱延伸至属,例如一年生杂草的苘麻属(Abutilon spp.)、苋属(Amaranthus spp.)、藜属(Chenopodiumspp.)、菊属(Chrysanthemum spp.)、猪殃殃属(Galium spp.)、番薯属(Ipomoea spp.)、地肤属(Kochia spp.)、野芝麻属(Lamium spp.)、母菊属(Matricaria spp.)、牵牛属(Pharbitis spp.)、蓼属(Polygonum spp.)、黄花稔属(Sida spp.)、白芥属(Sinapis spp.)、茄属(Solanum spp.)、繁缕属(Stellariaspp.)、婆婆纳属(Veronica spp.)、鳢肠属(Eclipta spp.)、田菁属(Sesbaniaspp.)、合萌属(Aeschynomene spp.)、堇菜属(Viola spp.)和苍耳属(Xanthiumspp.),以及在多年生杂草的情况下的旋花属(Convolvulus)、蓟属(Cirsium)、酸模属(Rumex)和蒿属(Artemisia)。
本发明进一步涉及包含本发明组合物的种子。优选所述种子用包含本发明组合物的农化配制剂包衣。
本发明进一步涉及如上所定义的助剂在提高如上所定义的农药的性能中的用途。优选地,提高生物活性。在另一优选实施方案中,降低农药的挥发性。
本发明提供了各种优点:本发明方法和组合物导致农药具有低挥发性。此外,本发明的组合物可容易地由廉价的工业上可得且易于操作的化合物起始而制备。农药活性保持在与所述农药的已知盐或游离酸相当的水平。本发明降低由于降低的挥发性而导致的偏离目标作物伤害,甚至不会不利地影响农药活性。无论以桶混物还是以预混配制剂传送均维持低挥发特性。此外,本发明提高了该组合物的物理稳定性,例如通过降低结晶趋势或相分离趋势。式(A)的胍可以以工业规模得到,对人类、动物和环境具有非常低的毒性且具有非常低的植物毒性。
以下实施例进一步阐述本发明,但本发明不限于此。
实施例
实施例1–SL配制剂
在室温下将5.9g胍在搅拌下加入22.1g麦草畏(游离酸)在200ml水中的悬浮液。所得溶液可用作SL配制剂或可加入任选其它辅助剂。
实施例2–除草盐
为了制备麦草畏和胍的除草盐,将来自实施例1(不含辅助剂)的水溶液的水在真空下在室温下除去。麦草畏的胍鎓盐以高产率和纯度分离。
实施例3–SL配制剂
在室温下将13.9g三氮杂双环癸烯(1,5,7-三氮杂双环[4.4.0]癸-5-烯或TBD)在搅拌下加入22.1g麦草畏(游离酸)在200ml水中的悬浮液。所得溶液可用作SL配制剂或可加入任选其它辅助剂。
实施例4–桶混物
在室温下将0.2L含有22.1g麦草畏(游离酸)的SL配制剂用20L水稀释以制备可喷雾桶混物。在搅拌下向这些20.2L桶混物中加入5.9g胍。
实施例5–桶混物
在室温下将0.2L含有22.1g麦草畏(游离酸)的SL配制剂用80L水稀释以制备可喷雾桶混物。在搅拌下向这些80.2L桶混物中加入13.9g三氮杂双环癸烯。
实施例6–挥发性
使大豆在盆中生长直至第一个三出复叶展开和第二个三出复叶轻微展开(从种植直到准备处理约10天)。在每次处理中重复放置两棵植株,各自由具有8个玻璃陪替式培养皿(8x9cm)的托盘构成。生长出盆的根在置于托盘中之前修整以避免与陪替式培养皿接触或挥发性暴露。
用4480g麦草畏酸当量/ha(基于实施例1或3的SL配制剂或实施例4的桶混物)处理具有陪替式培养皿的托盘并立即用塑料拱顶覆盖。接下来,快速移除拱顶覆盖物并将两棵大豆植株置于各托盘中间。立即使用新的拱顶覆盖物并用粘合夹在各端固定以将拱顶固定在托盘上。温度计包括在托盘中以监测温度。如果温度升高至35℃以上,则拱顶托盘单元用遮蔽布覆盖。在2、7、14和21天评定损伤百分比(偏上性、翘曲和生长迟缓)。为了比较,在相同活性计量速率下使用麦草畏游离酸或(二甲基胺的麦草畏盐的SL配制剂(水溶性浓缩物为480g/l,可由Syngenta市购)而不是来自实施例3的麦草畏盐。
本发明麦草畏盐与麦草畏游离酸或相比导致对大豆的较低的损伤百分比。
Claims (16)
2.根据权利要求1的方法,其中所述农药溶解和/或分散于水中。
3.根据权利要求1或2的方法,其中所得含有所述助剂和所述农药的组合物为可喷雾含水组合物。
4.根据权利要求1-3中任一项的方法,其中所述农药以小于5wt%的浓度存在于所得含有所述助剂和所述农药的组合物中.
5.根据权利要求1-4中任一项的方法,其中所述式(A)的胍或其盐可溶于水中。
6.根据权利要求1-5中任一项的方法,其中所述助剂为固体。
7.根据权利要求1-6中任一项的方法,其中所述助剂包含具有衍生于无机酸或有机酸的阴离子抗衡离子的式(A)的胍的盐。
8.根据权利要求1-7中任一项的方法,其中所述助剂包含具有选自硫酸氢根、磷酸根、磷酸二氢根、磷酸氢根、碳酸氢根和碳酸根的阴离子抗衡离子的式(A)的胍的盐。
9.根据权利要求1-8中任一项的方法,其中R1、R2、R3、R4和R5为H。
10.根据权利要求1-9中任一项的方法,其中所述农药为阴离子农药,其包含羧酸、硫代碳酸、磺酸、亚磺酸、硫代磺酸或亚磷酸基团。
11.根据权利要求1-10中任一项的方法,其中所述农药为选自如下的植物生长素除草剂:2,4-滴及其盐和酯、2,4-滴丁酸及其盐和酯、氯氨吡啶酸及其盐如氯氨吡啶酸三(2-羟丙基)铵和其酯、草除灵、乙基草除灵、草灭平及其盐和酯、稗草胺、二氯皮考啉酸及其盐和酯、麦草畏及其盐和酯、2,4-滴丙酸及其盐和酯、高2,4-滴丙酸及其盐和酯、氟草烟、丁氧基甲基氟草烟、氟氯胺啶、2甲4氯及其盐和酯、酚硫杀、2甲4氯丁酸及其盐和酯、2甲4氯丙酸及其盐和酯、高2甲4氯丙酸及其盐和酯、毒莠定及其盐和酯、二氯喹啉酸、喹草酸、草芽平及其盐和酯、定草酯及其盐和酯和环丙嘧啶酸及其盐和酯。
12.一种组合物,包含植物生长素除草剂和如权利要求1-11中任一项的所定义的助剂。
13.根据权利要求12的组合物,其中所述组合物呈可溶性浓缩物(SL)、油分散体(OD)、水溶性颗粒(SG)或水溶性粉末(SP)形式的农化组合物。
14.根据权利要求12或13的组合物,其中所述组合物为包含植物生长素除草剂的阴离子形式和助剂的阳离子形式的除草盐。
15.根据权利要求12-14中任一项的组合物,其中所述植物生长素除草剂为麦草畏。
16.一种防治不希望植物的方法,其包括使除草有效量的如权利要求12-15中任一项所定义的组合物作用于植物、其生长环境或所述植物的种子。
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| PCT/EP2012/057578 WO2012150162A1 (en) | 2011-05-02 | 2012-04-25 | A method for enhancing the performance of a pesticide with guanidines |
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| CZ308168B6 (cs) * | 2014-12-22 | 2020-02-05 | Ústav experimentální botaniky AV ČR, v. v. i. | Herbicidní přípravek a způsob ošetření porostů |
| US12004509B2 (en) * | 2016-11-18 | 2024-06-11 | Indorama Ventures Oxides Australia Pty Limited | Co-formulation comprising a plant growth regulator and an oil, and methods of preparing and using said co-formulation |
| ES3051057T3 (en) | 2019-02-15 | 2025-12-26 | Nutrien Ag Solutions Canada Inc | The use of protoporphyrin ix derivatives to improve the health of plants |
| PH12022551140A1 (en) | 2019-11-15 | 2023-07-17 | Univ Arkansas | Glufosinate additive for improved weed control |
| WO2024175245A1 (de) * | 2023-02-23 | 2024-08-29 | Thor Gmbh | Synergistische zusammensetzungen enthaltend guanidin |
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| WO2012150162A1 (en) | 2012-11-08 |
| JP2014514341A (ja) | 2014-06-19 |
| EA201301217A1 (ru) | 2014-04-30 |
| MX2013011969A (es) | 2013-11-04 |
| CA2833190A1 (en) | 2012-11-08 |
| BR112013027778B1 (pt) | 2019-06-25 |
| US9198412B2 (en) | 2015-12-01 |
| AU2012251750B2 (en) | 2015-07-09 |
| CA2833190C (en) | 2020-04-28 |
| AU2012251750A1 (en) | 2013-11-28 |
| BR112013027778A2 (pt) | 2016-07-26 |
| EP2704566A1 (en) | 2014-03-12 |
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