CN103957712B - 农用化学制剂及其用途 - Google Patents
农用化学制剂及其用途 Download PDFInfo
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- CN103957712B CN103957712B CN201280054329.5A CN201280054329A CN103957712B CN 103957712 B CN103957712 B CN 103957712B CN 201280054329 A CN201280054329 A CN 201280054329A CN 103957712 B CN103957712 B CN 103957712B
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 229960003495 thiamine Drugs 0.000 description 1
- DPJRMOMPQZCRJU-UHFFFAOYSA-M thiamine hydrochloride Chemical compound Cl.[Cl-].CC1=C(CCO)SC=[N+]1CC1=CN=C(C)N=C1N DPJRMOMPQZCRJU-UHFFFAOYSA-M 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C1/00—Ammonium nitrate fertilisers
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
- C05C9/02—Fertilisers containing urea or urea compounds containing urea-formaldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
- C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
- Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- General Health & Medical Sciences (AREA)
- Plant Pathology (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Zoology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Agronomy & Crop Science (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Fertilizers (AREA)
Abstract
提供了一种杀虫组合物,该组合物包含:a)杀虫有效量的一种或更多种具有通式(I)的化合物,在通式(I)中:R1是烷基、卤素或CN;R2是4,5‑二氰咪唑‑2‑基、卤代烷基或S(O)mR7;R3是氢、卤素、NR8R9、S(O)nR10、C(O)R11、烷基、卤代烷基、OR12或N=CR13R14;R4和R6各自独立地表示氢、卤素、卤代烷基、CN或NO2;R5是氢、卤素、卤代烷基、卤代烷氧基或S(O)pR15;R7、R10、R12和R15各自独立地表示烷基或卤代烷基;R8和R9各自独立地表示氢、烷基、烯基、卤代烷基、烷氧基羰基或S(O)qCF3;R11和R14各自独立地表示氢或烷基;R13是任选地被一个或更多个卤素原子或者选自OH、烷基、烷氧基和氰基的成员取代的苯基;并且m、n、p和q独立地表示0、1或2;和b)至少一种氮基肥料。该氮基肥料降低通式(I)化合物对目的植物的植物毒性作用。本发明还提供了一种处理一位置处植物的方法,包括将通式(I)化合物和氮基肥料施用于该位置。
Description
技术领域
本发明涉及新农用化学制剂及其用途,更特别地涉及包含杀虫活性化合物和肥料的农用化学制剂。
特别地,本发明涉及包含一种或更多种N-芳基吡唑类杀虫剂和一种或更多种氮基肥料的组合物。本发明还涉及提高这样的组合物的杀虫效力和作物产量的方法。
背景技术
N-芳基吡唑是本领域已知的并且广泛地用作杀虫剂。在美国专利No.5,232,940中公开和描述了这样的化合物。它们的广谱使得能够有效防治一系列害虫,包括蚁、甲虫、蚤、蜱、蓟马(thrip)、根虫(rootworm)、象鼻虫、蝼蛄,以及特别是白蚁和蟑螂。N-芳基吡唑类通过阻断氯离子通道并因此干扰目的昆虫的中枢神经系统来起作用。
EP0822746公开了一种用于处理植物的方法,其通过将无植物毒性量的N-芳基吡唑类施用于所述植物来诱导生长调节应答。
已发现,包含一种或更多种N-芳基吡唑类和氮基肥料的制剂具有显著提高的杀虫效力和提高的植物作物产量。该肥料可以用作“安全剂”,即,使对N-芳基吡唑杀虫剂的不利作物应答最小化。因此,本制剂显著地降低或消除由施用杀虫有效量的N-芳基吡唑杀虫剂引起的副作用或作物损伤。换言之,该肥料提高作物对N-芳基吡唑杀虫剂的耐受性。还发现,在对植物的组合处理中施用N-芳基吡唑杀虫剂和氮基肥料表现出显著改进的昆虫防治和提高的植物作物产量。
发明内容
因此,在第一方面,本发明提供了包含以下的杀虫组合物:
a)杀虫有效量的一种或更多种具有通式(I)的化合物:
其中:
R1是烷基、卤素或CN;
R2是4,5-二氰咪唑-2-基、卤代烷基或S(O)mR7;
R3是氢、卤素、NR8R9、S(O)nR10、C(O)R11、烷基、卤代烷基、OR12、或N=CR13R14;
R4和R6各自独立地表示氢、卤素、卤代烷基、CN或NO2;
R5是氢、卤素、卤代烷基、卤代烷氧基或S(O)pR15;
R7、R10、R12和R15各自独立地表示烷基或卤代烷基;
R8和R9各自独立地表示氢、烷基、烯基、卤代烷基、烷氧基羰基或
S(O)qCF3;
R11和R14各自独立地表示氢或烷基;
R13是任选地被一个或更多个卤素原子或选自OH、烷基、烷氧基和氰基的成员取代的苯基;并且
m、n、p和q独立地表示0、1或2;
和
b)至少一种氮基肥料。
本发明采用氮基肥料来提高N-芳基吡唑活性成分的杀虫作用。氮是肥料中的必需元素,其在Farm Chemicals Handbook,1992年版,B23页中有详细描述。市售的氮基肥料包括铵盐(例如,磷酸铵、硫酸铵、氯化铵)、硝酸盐、无水氨、尿素、氮溶液(包括尿素硝铵(ureaammonium nitrate))及其组合。这些肥料可以通过本领域已知的方法来制备。
杀虫剂与肥料的混合物以颗粒剂、片剂、棒剂(stick)和板剂(plate)的形式在本领域中已知。然而,这些制品的性能并不令人满意,特别是对于大规模的农业施用而言。例如,美国专利No.5,783,203描述了包含肥料与昆虫烟碱能乙酰胆碱受体的激动剂或拮抗剂的混合物。这样的棒剂形式的混合物适于保护观赏性的室内植物。然而,该混合物并不适于农业用途。
在美国专利申请公开No.US 2006/0166939中描述了用于喷雾施用的杀虫肥料制剂。然而,当施用该制剂时,强酸盐的存在对植物造成损害。
已发现,使用本发明的组合物使组合物对环境的影响显著降低,并减少农民的工作量。更重要的是,与已知的N-芳基吡唑制剂相比,本发明的组合物表现出显著提高的杀虫效力,进而导致显著提高的作物产量。特别地,已发现氮基肥料的存在降低通式(I)活性化合物的植物毒性作用,导致降低对目的植物的损害和提高产量。
如前文所述,本发明的组合物包含一种或更多种具有通式(I)的杀虫活性化合物。在通式(I)化合物中,烷基、卤代烷基和卤代烷氧基部分可含有任意合适的碳原子数,这样的结构部分优选地具有1个至12个碳原子,更优选1个至8个碳原子,还更优选1个至4个碳原子。优选的基团是甲基、卤代甲基、卤代甲氧基、乙基、卤代乙基、卤代乙氧基、丙基、卤代丙基和卤代丙基。
类似地,存在于通式(I)化合物中的烯基部分可含有任意合适的碳原子数,这样的部分优选地具有1个至12个碳原子,更优选1个至8个碳原子,还更优选1个至4个碳原子。优选的基团是乙烯基和丙烯基。
存在于通式(I)化合物中的烷基、烯基、卤代烷基和卤代烷氧基可为直链的或支化的。
存在于通式(I)化合物中的含卤素基团可含有一个或更多个合适的卤素原子,优选氟或氯。
在通式(I)化合物中,R1优选地选自甲基、卤素(特别是氟或氯)或CN。特别优选的通式(I)化合物是其中R1为CN的那些。
此外,在通式(I)化合物中,R2优选地选自4,5-二氰咪唑-2-基、卤代甲基(特别是被一个或更多个氟或氯取代的甲基)或具有通式S(O)mR7的基团。在式S(O)mR7基团中,m可为0至2的整数,优选其中m为1的基团。R7可为烷基或卤代烷基,优选卤代烷基,特别是含有一个或更多个氟原子的卤代烷基。特别优选的通式(I)化合物是其中R7为具有一个或更多个氟取代基的甲基(特别是CF3)的那些。
存在于通式(I)化合物中的R3是选自氢、卤素、NR8R9、S(O)nR10、C(O)R11、烷基、卤代烷基、OR12或N=CR13R14的基团。如果作为卤素存在,则R3优选为氯或氟。在其中R3为式S(O)nR10基团的化合物中,n优选为1,并且R10优选为甲基或者具有一个或更多个卤素(优选氟或氯)的甲基。在其中R3为式C(O)R11基团的化合物中,R11优选为氢或甲基。或者,R3可为烷基,任选地具有一个或更多个卤素取代基,优选的基团是甲基或者具有一个或更多个卤素(优选氟或氯)的甲基。在其中R3为式OR12基团的通式(I)化合物中,R12是烷基,任选地具有一个或更多个卤素取代基,优选的基团是甲基或者具有一个或更多个卤素(优选氟或氯)的甲基。或者,R3可为式N=CR13R14基团,其中R13为任选地被一个或更多个卤素(优选氯或氟)、OH、烷基(优选甲基)、烷氧基(优选甲氧基)以及氰基取代的苯基部分。
特别优选的通式(I)化合物为其中R3是式NR8R9基团的那些。在这些基团中,R8和R9可独立地选自氢、烷基(优选甲基)、任选地具有一个或更多个甲基分支的烯基(优选乙烯基或丙烯基)、卤代烷基(优选具有一个或更多个氟原子或氯原子的甲基)、烷氧基羰基(优选甲氧基羰基)或S(O)qCF3(优选其中q为1)。特别优选R3为式NR8R9基团,其中R8和R9二者皆为氢(-NH2)。在替代性的实施方案中,R3为式NR8R9基团,其中R8为氢并且R9为烯基(特别是具有甲基分支的丙烯基)。
在通式(I)化合物中,R4和R6可为氢、卤素、卤代烷基(优选具有一个或更多个氟原子或氯原子的甲基)、CN或NO2。包含在本发明组合物中的特别优选的化合物是其中R4和R6二者都为卤素(特别是同一卤素,优选氯)的那些。
在通式(I)化合物中,R5可选自氢、卤素(优选氯或氟)、卤代烷基(优选具有一个或更多个氟原子或氯原子的甲基)、卤代烷氧基(优选具有一个或更多个氟原子或氯原子的甲氧基)或S(O)pR15。当R5优选为式S(O)pR15基团时,p优选为1,并且R15优选为甲基或者具有一个或更多个氟原子或氯原子的甲基。特别优选R5是具有三个卤素取代基的甲基,特别是CF3。
本发明组合物所包含的优选通式(I)化合物的实例包括以下化合物:
5-氨基-1-(2,6-二氯-α,α,α-三氟-对甲苯基)-4-[(三氟甲基)亚磺酰基]吡唑-3-甲腈(氟虫腈);
1-(2,6-二氯-α,α,α-三氟-对甲苯基)-5-(2-甲基烯丙基氨基)-4-[(三氟甲基)亚磺酰基]吡唑-3-甲腈(丁烯氟虫腈);
5-氨基-1-(2,6-二氯-α,α,α-三氟-对甲苯基)-4-[(乙基)亚磺酰基]吡唑-3-甲腈(乙虫腈);
1-[5-氨基-1-(2,6-二氯-α,α,α-三氟-对甲苯基)-4-(甲基亚磺酰基)吡唑-3-基]乙酮(乙酰虫腈);
(RS)-[O-1-(4-氯苯基)吡唑-4-基O-乙基S-丙基硫代磷酸酯](吡唑硫磷(pyraclofos));
1-(2,6-二氯-α,α,α-三氟-对甲苯基)-4-(氟甲基硫基)-5-[(吡嗪基甲基)氨基]吡唑-3-甲腈(吡嗪氟虫腈(pyrafluprole));
1-(2,6-二氯-α,α,α-三氟-对甲苯基)-4-(二氟甲基硫基)-5-[(2-吡啶基甲基)氨基]吡唑-3-甲腈(吡啶虫腈(pyriprole));
二甲基氨基甲酸3-甲基-1-苯基吡唑-5-基酯(吡唑威);以及
(E)-1-(2,6-二氯-α,α,α-三氟-对甲苯基)-5-(4-羟基-3-甲氧基亚苄基氨基)-4-三氟甲基硫基吡唑-3-甲腈(氟吡唑虫(vaniliprole))。
已发现,本发明的组合物是特别有效的配制5-氨基-1-(2,6-二氯-α,α,α-三氟-对甲苯基)-4-[(三氟甲基)亚磺酰基]吡唑-3-甲腈(通用名为氟虫腈)的方法。
通式(I)化合物可以以宽范围的量存在于本组合物中,存在的量取决于诸如最终使用和处理位置时施用组合物的方式等因素。优选地,通式(I)化合物以按重量计0.5%至80%、更优选按重量计1%至50%的量存在于组合物中。
本发明的组合物还包含一种或更多种氮基肥料。术语“氮基肥料”是指所有植物以显著量需要的用于植物生长的含氮的主要营养素。在组合物中可包含任意合适的氮基肥料。氮基肥料优选选自:铵盐(例如,硫酸铵)、硝酸盐、磷酸盐/酯、无水氨、氨水、流体氮肥、尿素、尿素-甲醛缩合制品(urea-formaldehyde condensation product)、尿素硝铵、氨基酸以及金属硝酸盐(例如,硝酸钠、硝酸钾、硝酸钙和硝酸镁)。任选地,可以添加微量营养素(优选锰、镁、铁、硼、铜、锌、钼和/或钴)的盐和植物激素(例如,维生素B1或吲哚-3-乙酸)。
氮基肥料可以以任意合适的量存在于组合物中,并且通常以按重量计0.5%至50%、更优选按重量计2%至40%、还更优选按重量计5%至20%的量存在。
通式(I)化合物和氮基肥料可以以相对于彼此的任意比例存在于组合物中或施用。特别地,组合物中这两种组分的重量比独立地优选为100∶1至1∶100,优选1∶20至20∶1。
通式(I)化合物和氮基肥料可以以单制剂或分开制剂施用。在后一种情况下,通式(I)杀虫活性化合物和氮基肥料可依次施用、分开施用或同时施用。
本发明的组合物可任选地包含一种或更多种辅助剂。在组合物中采用的辅助剂及其量将取决于制剂的类型和/或最终使用者施用制剂的方式。合适辅助剂为所有常用制剂辅料或组分,例如溶剂、表面活性剂、稳定剂、消泡剂、防冻剂、防腐剂、抗氧化剂、着色剂、增稠剂以及惰性填料。这样的辅助剂是本领域已知的并且是市售的。其在本发明组合物的制剂中的用途对于本领域技术人员而言是明显的。
所述组合物可包含一种或更多种溶剂。所述溶剂可为有机溶剂或无机溶剂。合适的溶剂选自所有能完全溶解所采用的农用化学活性物质的常用溶剂。它们是本领域已知的并且是市售的。实例包括:水;芳族溶剂,例如二甲苯(例如,SolvessoTM的市售溶剂制品);矿物油;动物油;植物油;醇类,例如甲醇、丁醇、戊醇和苯甲醇;酮类,例如,环己酮和γ-丁内酯;吡咯烷酮,例如NMP和NOP;乙酸酯,例如二乙酸二醇酯;二醇;脂肪酸二甲基酰胺;脂肪酸;以及脂肪酸酯。
所述组合物还任选地包含一种或更多种表面活性剂。合适的表面活性剂包括但不限于:木素磺酸、萘磺酸、苯酚磺酸、二丁基萘磺酸的碱金属盐、碱土金属盐及铵盐,烷基芳基磺酸酯、硫酸烷基酯、烷基磺酸酯、芳基磺酸酯、脂肪醇硫酸酯、脂肪酸及硫酸化的脂肪醇甘醇醚,此外还包括:磺化的萘及萘衍生物与甲醛的缩合物、萘或萘磺酸与苯酚、辛基苯酚、壬基苯酚的缩合物、烷基苯基聚二醇醚、三丁基苯基聚二醇醚、三硬脂酰基苯基聚二醇醚、烷基芳基聚醚醇、醇及脂肪醇/环氧乙烷缩合物、乙氧基化蓖麻油、聚氧乙烯烷基醚、乙氧基化聚氧丙烯、月桂醇聚二醇醚乙缩醛、山梨醇酯、木质素-亚硫酸盐废液以及甲基纤维素和环氧乙烷/环氧丙烷嵌段共聚物。
所述组合物还任选地包含一种或更多种聚合物稳定剂。可用于本发明的合适的聚合物稳定剂包括但不限于:聚丙烯、聚异丁烯、聚异戊二烯、单烯与二烯的共聚物、聚丙烯酸酯、聚苯乙烯、聚乙酸乙烯酯、聚氨酯或聚酰胺。合适的稳定剂是本领域已知的并且是市售的。
所述组合物可包含消泡剂。合适的消泡剂包括能够以该目的正常用于农用化学组合物中的那些物质,并且其对于本领域技术人员是很显然的。合适的消泡剂是本领域已知的并且是市售的。特别优选的消泡剂是聚二甲基硅氧烷与全氟烷基膦酸的混合物,如硅酮消泡剂(例如,由GE或Compton市售)。
所述组合物还可含有一种或更多种防腐剂。合适的防腐剂包括能够以该目的正常用于这类农用化学组合物的所有物质,并且其在本领域也是公知的。可提及的合适的实例包括(由Bayer AG市售)和(由Bayer AG市售)。
本组合物还可包含一种或更多种抗氧化剂。如本领域所已知,合适的抗氧化剂是能够以该目的正常用于农用化学组合物的所有物质。优选例如丁羟基甲苯。
本组合物还可包含一种或更多种固体粘附剂。这样的粘附剂是本领域已知的并且是市售的。其包括有机粘附剂和无机粘附剂,所述有机粘附剂包括胶粘剂,例如纤维素或经取代的纤维素,粉末、颗粒或晶格形式的天然聚合物及合成聚合物,所述无机粘附剂例如石膏、二氧化硅或水泥。
本组合物还可包含一种或更多种惰性填料。这样的惰性填料是本领域已知的并且是市售的。其包括例如天然地面矿物或合成地面矿物,所述天然地面矿物例如高岭土、氧化铝、滑石、白垩、石英、绿坡缕石(attapulgite)、蒙脱石以及硅藻土,所述合成地面矿物例如高度分散的硅酸、氧化铝、硅酸盐和磷酸钙及磷酸氢钙。用于颗粒的合适惰性填料包括例如经碾压和破碎化的天然矿物(例如方解石、大理石、浮石、海泡石和白云石)、或合成的地面无机物和有机物颗粒,以及有机物颗粒(例如,锯屑、椰壳、玉米棒和烟草秆)。
本组合物还可包含一种或更多种增稠剂。合适的增稠剂包括能够以该目的正常用于农用化学组合物的所有物质。合适的增稠剂的实例包括:胶状物(例如,黄原胶)、PVOH、纤维素及其衍生物、粘土水合硅酸盐、硅酸镁铝或其混合物。这样的增稠剂也是本领域已知的并且是市售的。
通式(I)杀虫活性化合物和氮基肥料及任选的任意其他杀虫剂可以作为固体活性成分以纯的形式施用和使用,例如,以特定粒径,或者优选地与如上文更详细描述的在配制技术中常用的至少一种辅助组分或辅料组分一起施用和使用。
本杀虫剂组合物可以为上文所述的任意合适的制剂。优选地,本组合物是颗粒剂、悬浮浓缩剂(suspension concentrate)、水分散性颗粒剂、水溶性颗粒剂、水分散性粉剂、水溶性粉剂或可流动混悬剂。
本发明的组合物可施用于目的植物或目标植物至其一个或更多个部分(例如,叶子或种子)或者其周围。
在一个实施方案中,如前文所述,通式(I)化合物与氮基肥料的组合作为组合物组合施用。
用于本发明的预混组合物实施方案的制剂类型的实例如下:
A)水溶性浓缩剂(SL)
将一种或更多种通式(I)杀虫活性化合物和氮基肥料溶解于水溶性溶剂中。可包含一种或更多种润湿剂和/或其他辅助剂。活性化合物在用水稀释后溶解。
B)可乳化浓缩剂(EC)
通过添加一种或更多种非阴离子乳化剂和阴离子乳化剂,将一种或更多种通式(I)杀虫活性化合物和氮基肥料溶解于溶剂中。搅动(例如,通过搅拌)混合物以得到均匀制剂。用水稀释,以得到稳定的乳剂。
C)乳剂(EW)
通过添加一种或更多种非阴离子乳化剂和阴离子乳化剂,将一种或更多种通式(I)杀虫活性化合物和氮基肥料溶解于一种或更多种合适的溶剂中。通过合适的方法(例如,乳化机)将所得混合物引入水中,得到均匀的乳剂。用水稀释,得到稳定的乳剂。
D)混悬剂(SC、OD、FS)
在搅拌球磨机中,通过添加一种或更多种分散剂和润湿剂以及水或溶剂,将一种或更多种通式(I)杀虫活性化合物和氮基肥料粉碎,以得到精细的活性化合物混悬剂。用水稀释,得到稳定的活性化合物混悬剂。
E)水分散性颗粒和水溶性颗粒(WG、SG)
通过添加一种或更多种分散剂和润湿剂,将一种或更多种通式(I)杀虫活性化合物和氮基肥料进行精细研磨,并通过合适的技术(例如,挤出、在喷雾塔中干燥或通过在流化床中处理)制备成水可分散颗粒或水溶性颗粒。用水稀释,得到稳定的活性化合物分散剂或溶液剂。
F)水分散性粉末和水溶性粉末(WP、SP)
通过添加一种或更多种分散剂、润湿剂和硅胶,将一种或更多种通式(I)杀虫活性化合物和氮基肥料在合适的设备(例如,转子-定子磨机)中进行研磨。用水稀释,得到活性化合物的稳定分散剂或溶液剂。
G)颗粒(GR、FG、GG、MG)
通过添加按重量计多至99.5份的载体,将一种或更多种通式(I)杀虫活性化合物和氮基肥料在合适的装置中进行精细研磨。然后通过合适的技术(例如挤出、喷雾干燥或使用流化床)来制备颗粒。
在另一方面,本发明提供了保护植物抵抗昆虫以提高作物产量的方法,该方法包括将前文限定的通式(I)杀虫活性化合物和氮基肥料施用于植物或其一部分或其周围。
本发明的组合物允许处理植物以防止或消除杀虫剂的侵害并增强该植物的生长。
特别地,可施用本发明的组合物以提高作物产量。合适的目的作物尤其包括:谷物,例如,小麦、大麦、黑麦、燕麦、稻、玉米、高粱、小米和树薯;甜菜,例如,糖甜菜和饲料甜菜;水果,例如,梨果、核果和软果(例如,苹果、梨、李、桃、杏、樱桃)或浆果(例如,草莓、树莓和黑莓);豆科植物,例如,豆子、扁豆(lentil)、豌豆和大豆;油料植物,例如,油菜、芥菜、罂粟、橄榄、向日葵、椰子、蓖麻油料植物、可可豆和花生;葫芦科植物(cucurbitaceae),例如,葫芦(marrow)、黄瓜和瓜类;纤维植物,例如,棉花、亚麻、大麻和黄麻;柑桔类水果植物,例如,橙、柠檬、葡萄柚和柑桔;蔬菜,例如,菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、番茄、土豆和辣椒;樟科植物(lauraceae),例如,牛油果、肉桂和樟树;以及烟草、坚果、咖啡、茄子、糖甘蔗、茶、胡椒、葡萄、啤酒花、香蕉、天然橡胶植物、桉属植物,以及观赏植物。特别优选的使用范围为以下作物:花生、可可豆、糖甘蔗、椰子、稻、棉花、粟(millet)、玉米、树薯、高粱和桉属植物。
一般来说,可制备并施用所述组合物使得通式(I)杀虫活性成分根据待处理位置的需要以任意合适的比例来施用。特别地,所述组合物可以制备成使得以10g至1000g每公顷、更优选约10g至500g每公顷、还更优选10g至200g每公顷的比例来施用通式(I)化合物。
如上文所述,通式(I)杀虫活性化合物和氮基肥料可以以任意合适的形式同时或以短的间隔(例如,在同一天)依次施用于期望防治的位置。在一个优选的实施方案中,通式(I)杀虫活性化合物和氮基肥料同时施用,特别是通过本发明组合物施用。通式(I)杀虫活性化合物和氮基肥料可以以任意顺序施用于植物或位置。每种化合物可施用仅一次或多次。优选地,每种化合物施用多次,特别是2次至5次,更优选3次。
通式(I)杀虫活性化合物和氮基肥料可以以相对于彼此的任意量施用。特别地,待施用于植物或位置的化合物的相对量如前文所述,通式(I)化合物与肥料的比例优选为1∶100至100∶1。
在通式(I)杀虫活性化合物和氮基肥料同时施用的情况下,它们可以获自分开的制剂来源,并任选地与其它杀虫剂混合在一起(称为罐混合物(tank-mix),即用型、喷雾液或浆料),或者它们可以作为单制剂混合物源(称为预混合物、浓缩物、配制复合物(或制品))获得,并任选地与其他杀虫剂混合。
在另一方面,本发明提供了如前文所限定的通式(I)杀虫活性化合物和氮基肥料用于处理一位置处植物的用途。如所提及的,该用途中通式(I)杀虫活性化合物和氮基肥料可分开使用或在单一组合物中组合使用。
如上文所提到的,如前文所述的一种或更多种通式(I)杀虫活性化合物和氮基肥料的使用可以提高被处理的目的植物的产量。本文所用术语“产量”是指由植物产生的任意植物产品的经济价值,所述植物产品例如:谷物、水果、蔬菜、坚果、种子、木材或花。在收获之后,植物产品还可进一步利用和/或加工。“产量”的提高可通过在以下性质上对所述植物与在相同条件下生长而未施用本发明杀虫肥料的植物进行比较来表征:
-增加的植物重量和/或高度;
-增加的生物质,例如,更高的鲜重和/或干重;
-更多和/或更强的分蘖;
-更大和/或更绿的叶子;
-较少的基生叶死亡;
-增加的枝条生长;
-较早的萌发;
-较早的开花;
-较早的谷物成熟期;
-更高的谷物产量;
-更多的果实和更高的果实产量(重量);
-增加的蛋白质含量;
-增加的油含量;
-增加的淀粉含量;
-增加的色素含量。
在另一方面,本发明提供了降低前文所限定的通式(I)化合物对一位置处植物的植物毒性作用的方法,该方法包括将如前文所限定的通式(I)化合物和氮基肥料施用于该位置。
此外,本发明还提供了氮基肥料用于降低如前文所限定的通式(I)化合物的植物毒性作用的用途。
具体实施方案
将仅通过举例说明的方式,参照以下实施例来进一步描述本发明。
实施例
组合物实施例1水溶性浓缩剂(SL)
将包含通式(I)化合物和氮基肥料的水溶性浓缩剂形成为具有列于下表中的组成:
组合物实施例2可乳化浓缩剂(EC)
将包含通式(I)化合物和氮基肥料的可乳化浓缩剂制备成具有列于下表中的组成:
组合物实施例3水分散性粉剂(WP)
将包含通式(I)化合物和氮基肥料的水分散性粉剂制备为具有列于下表中的组成:
组合物实施例4水分散性颗粒剂(WG)
将包含通式(I)化合物和氮基肥料的水分散性颗粒剂制备为具有列于下表中的组成:
组合物实施例5混悬剂
制备了包含通式(I)化合物和氮基肥料的混悬剂制剂。该混悬剂制剂的组成列于下表中:
组合物实施例6水溶性浓缩剂(SL)
制备了包含通式(I)化合物和氮基肥料的水溶性浓缩剂制剂。该浓缩剂制剂的组成列于下表中:
组合物实施例7水分散性颗粒剂(WG)
制备了包含通式(I)化合物和氮基肥料的水分散性颗粒剂,其组成列于下表中:
组合物实施例8可流动种子处理剂(seed treatment)(FS)
制备了具有下表所列组成的可流动种子处理剂组合物:
组合物实施例9水溶性浓缩剂(SL)
制备了包含通式(I)化合物和氮基肥料的水溶性浓缩剂。其组成列于下表中:
组合物实施例10作为可食用诱饵的颗粒剂(GR)
制备了包含通式(I)化合物和氮基肥料的颗粒剂组合物。其组成列于下表中:
测试1-针对大豆植物测试作物产量
在温室中播种大豆种子。在发育阶段和开花初期,用氟虫腈(BASF的)和上文实施例1至10的各制剂处理大豆植物。施用比例列于下表中。在成熟期收获了作物并测量籽粒产量(t/ha)。
*(式(I)+氮基肥料)的施用比例以g/ha计
由上述数据可知,在对大豆植物的处理中包含氮基肥料显著提高了籽粒产量。与未经处理的对照植物相比,当用含有活性成分而无氮基肥料的组合物处理时,籽粒产量因氟虫腈的植物毒性而降低。在对植物的处理中包含氮基肥料降低了活性成分的植物毒性作用。在较高的浓度下,该肥料组分有效地消除了氟虫腈的植物毒性并增加了籽粒产量。
测试2-针对稻植物测试作物产量
在30℃下,稻种子在水中萌发48小时,然后播种于盆中。出苗后,将氟虫腈(BASF的)和上文的实施例1至10中给出的各制剂施用于土壤。施用比例列于下表中。使植物成熟至收获期,在此时测量了籽粒产量(t/ha)。
*(式(I)+氮基肥料)的施用比例(以g/ha计)
测试3-对火蚁(Solenopsis invicta)的杀虫性能测试
布置约5000平方英尺(约465m2)的样地,每块样地平均含有九个火蚁丘,并在初夏进行处理。在处理之前对每块样地中的活蚁丘进行计数。每种处理进行了三次重复测试。施用了氟虫腈(BASF的)和上文的实施例1至10中给出的各制剂。在处理后的30、60和90天(“DAT”)(经过初秋)通过对活蚁丘进行计数并计算蚁丘数相对于处理前的减少评估了效力。结果示于下表中。
*(式(I)+氮基肥料)的施周比例(以g/ha计)
测试4-对肩突硬蜱(Ixodesscapularis)的杀虫性能测试
将芜菁叶盘置于培养皿中的琼脂中,用20个幼虫(2龄硬蜱(lxodes))感染。每种处理分配4份培养皿,用氟虫腈(BASF的)和上文的实施例1至10中给出的各制剂进行喷涂。在处理后的第四天或第五天测定了幼虫的死亡率。结果示于下表中。
*(式(I)+氮基肥料)的施用比例(以g/ha计)
Claims (27)
1.一种用于降低通式(I)化合物对一位置处植物的植物毒性作用的方法,
其中:
R1是烷基、卤素或CN;
R2是4,5-二氰咪唑-2-基、卤代烷基或S(O)mR7;
R3是氢、卤素、NR8R9、S(O)nR10、C(O)R11、烷基、卤代烷基、OR12、或N=CR13R1414;
R4和R6各自独立地表示氢、卤素、卤代烷基、CN或NO2;
R5是氢、卤素、卤代烷基、卤代烷氧基或S(O)pR15;
R7、R10、R12和R15各自独立地表示烷基或卤代烷基;
R8和R9各自独立地表示氢、烷基、烯基、卤代烷基、甲氧基羰基或S(O)qCF3;
R11和R14各自独立地表示氢或烷基;
R13是任选地被一个或更多个卤素原子或者选自OH、烷基、甲氧基和氰基的成员取代的苯基;并且
m、n、p和q独立地表示0、1或2;
所述烷基、卤代烷基、卤代烷氧基和烯基具有1至12个碳原子;
所述方法包括将所述通式(I)化合物与氮基肥料一起施用于所述位置。
2.根据权利要求1所述的方法,其中R1是氟、氯或CN。
3.根据权利要求2所述的方法,其中R1是CN。
4.根据前述权利要求中任一项所述的方法,其中R2是具有通式S(O)mR7的基团。
5.根据权利要求4所述的方法,其中R7是卤代烷基。
6.根据权利要求5所述的方法,其中R7是CF3。
7.根据权利要求1至3中任一项所述的方法,其中m为1。
8.根据权利要求1至3中任一项所述的方法,其中R3是式NR8R9的基团。
9.根据权利要求8所述的方法,其中R8与R9二者都是氢。
10.根据权利要求1至3中任一项所述的方法,其中R4与R6二者都是卤素。
11.根据权利要求10所述的方法,其中R4与R6二者都是氯。
12.根据权利要求1至3中任一项所述的方法,其中R5是卤代烷基。
13.根据权利要求12所述的方法,其中R5是CF3。
14.根据权利要求1至3中任一项所述的方法,其中所述通式(I)化合物选自:
5-氨基-1-(2,6-二氯-α,α,α-三氟-对甲苯基)-4-[(三氟甲基)亚磺酰基]吡唑-3-甲腈(氟虫腈);
1-(2,6-二氯-α,α,α-三氟-对甲苯基)-5-(2-甲基烯丙基氨基)-4-[(三氟甲基)亚磺酰基]吡唑-3-甲腈(丁烯氟虫腈);
5-氨基-1-(2,6-二氯-α,α,α-三氟-对甲苯基)-4-[(乙基)亚磺酰基]吡唑-3-甲腈(乙虫腈);以及
(E)-1-(2,6-二氯-α,α,α-三氟-对甲苯基)-5-(4-羟基-3-甲氧基亚苄基氨基)-4-三氟甲基硫基吡唑-3-甲腈(氟吡唑虫)。
15.根据权利要求14所述的方法,其中所述通式(I)化合物是氟虫腈。
16.根据权利要求1至3中任一项所述的方法,其中所述通式(I)化合物以按重量计1%至50%的量施用。
17.根据权利要求1至3中任一项所述的方法,其中所述氮基肥料选自铵盐、流体氮肥料、尿素、尿素-甲醛缩合制品、尿素硝铵、氨基酸、金属硝酸盐及其混合物。
18.根据权利要求1至3中任一项所述的方法,其还包括向所述位置施用一种或更多种微量营养素盐。
19.根据权利要求1至3中任一项所述的方法,其中所述氮基肥料以按重量计0.5%至50%的量施用。
20.根据权利要求1至3中任一项所述的方法,其中所述通式(I)化合物和所述氮基肥料以1∶20至20∶1的重量比施用。
21.根据权利要求1至3中任一项所述的方法,其中同时在一位置处向植物施用所述通式(I)化合物和所述氮基肥料。
22.根据权利要求21所述的方法,其中所述通式(I)化合物和所述氮基肥料一起作为组合物施用,其中所述组合物是颗粒剂、悬浮浓缩剂、水分散性颗粒剂、水溶性颗粒剂、水分散性粉剂、水溶性粉剂或可流动混悬剂。
23.根据权利要求1至3中任一项所述的方法,其中将所述通式(I)化合物和所述氮基肥料施用于所述植物的一个或更多个部分或所述植物周围环境。
24.根据权利要求1至3中任一项所述的方法,其中所述植物选自:谷物植物、水果植物、豆科植物、油料植物、葫芦科植物、纤维植物、蔬菜、樟科植物或观赏植物。
25.一种用于降低(RS)-[O-1-(4-氯苯基)吡唑-4-基O-乙基S-丙基硫代磷酸酯](吡唑硫磷)对一位置处植物的植物毒性作用的方法,所述方法包括将所述吡唑硫磷与氮基肥料一起施用于所述位置。
26.一种用于降低1-(2,6-二氯-α,α,α-三氟-对甲苯基)-4-(二氟甲基硫基)-5-[(2-吡啶基甲基)氨基]吡唑-3-甲腈(吡啶虫腈)对一位置处植物的植物毒性作用的方法,所述方法包括将所述吡啶虫腈与氮基肥料一起施用于所述位置。
27.氮基肥料用于降低通式(I)化合物的植物毒性作用的用途,
其中:
R1是烷基、卤素或CN;
R2是4,5-二氰咪唑-2-基、卤代烷基或S(O)mR7;
R3是氢、卤素、NR8R9、S(O)nR10、C(O)R11、烷基、卤代烷基、OR12、或N=CR13R14;
R4和R6各自独立地表示氢、卤素、卤代烷基、CN或NO2;
R5是氢、卤素、卤代烷基、卤代烷氧基或S(O)pR15;
R7、R10、R12和R15各自独立地表示烷基或卤代烷基;
R8和R9各自独立地表示氢、烷基、烯基、卤代烷基、甲氧基羰基或S(O)qCF3;
R11和R14各自独立地表示氢或烷基;
R13是任选地被一个或更多个卤素原子或者选自OH、烷基、甲氧基和氰基的成员取代的苯基;并且
m、n、p和q独立地表示0、1或2
所述烷基、卤代烷基、卤代烷氧基和烯基具有1至12个碳原子。
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AP (1) | AP2014007616A0 (zh) |
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CN106106477B (zh) * | 2016-06-27 | 2018-09-21 | 青岛润生农化有限公司 | 含甲维盐与乙酰虫腈的杀虫组合物 |
WO2020245235A1 (en) * | 2019-06-05 | 2020-12-10 | Bayer Aktiengesellschaft | Stabilized plant protection product formulations |
CN110256351B (zh) * | 2019-06-13 | 2024-03-15 | 北京大学 | 一种氟虫腈及其类似物的合成方法 |
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WO2008083709A1 (en) * | 2007-01-10 | 2008-07-17 | Bayer Cropscience Ag | Insecticidal fertilizer mixtures |
US7635404B1 (en) * | 2006-12-05 | 2009-12-22 | Kadant Grantek Inc. | Fertilizer combination products including fertilizer granules and cellulosic granules carrying pesticides and other active ingredients |
CN101622992A (zh) * | 2009-08-01 | 2010-01-13 | 深圳诺普信农化股份有限公司 | 一种杀虫剂水分散粒剂及其制备方法 |
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US7635404B1 (en) * | 2006-12-05 | 2009-12-22 | Kadant Grantek Inc. | Fertilizer combination products including fertilizer granules and cellulosic granules carrying pesticides and other active ingredients |
WO2008083709A1 (en) * | 2007-01-10 | 2008-07-17 | Bayer Cropscience Ag | Insecticidal fertilizer mixtures |
CN101622992A (zh) * | 2009-08-01 | 2010-01-13 | 深圳诺普信农化股份有限公司 | 一种杀虫剂水分散粒剂及其制备方法 |
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TN2014000179A1 (en) | 2015-09-30 |
ECSP14013338A (es) | 2015-05-29 |
GB201119286D0 (en) | 2011-12-21 |
CN103957712A (zh) | 2014-07-30 |
GB2496389A (en) | 2013-05-15 |
BR102012000681A2 (pt) | 2013-09-10 |
PE20142013A1 (es) | 2014-12-16 |
GB2496389B (en) | 2016-06-15 |
AR088797A1 (es) | 2014-07-10 |
AP2014007616A0 (en) | 2014-05-31 |
MA35622B1 (fr) | 2014-11-01 |
TW201325456A (zh) | 2013-07-01 |
CO6950489A2 (es) | 2014-05-20 |
IN2014CN03351A (zh) | 2015-07-03 |
WO2013067894A1 (en) | 2013-05-16 |
TWI568352B (zh) | 2017-02-01 |
CL2014001184A1 (es) | 2014-08-29 |
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