[go: up one dir, main page]

CN1201657C - 甲氧基丙烯酸甲酯类化合物杀菌剂 - Google Patents

甲氧基丙烯酸甲酯类化合物杀菌剂 Download PDF

Info

Publication number
CN1201657C
CN1201657C CN 03120882 CN03120882A CN1201657C CN 1201657 C CN1201657 C CN 1201657C CN 03120882 CN03120882 CN 03120882 CN 03120882 A CN03120882 A CN 03120882A CN 1201657 C CN1201657 C CN 1201657C
Authority
CN
China
Prior art keywords
compound
composition
powdery mildew
mildew
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
CN 03120882
Other languages
English (en)
Other versions
CN1456054A (zh
Inventor
许天明
陈定花
孔小林
朱卫钢
郑昀红
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Chemical Industry Research Institute Co Ltd
Sinochem Lantian Co Ltd
Original Assignee
Chemical Industry Inst Of Zhejiang Prov
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemical Industry Inst Of Zhejiang Prov filed Critical Chemical Industry Inst Of Zhejiang Prov
Priority to CN 03120882 priority Critical patent/CN1201657C/zh
Publication of CN1456054A publication Critical patent/CN1456054A/zh
Priority to PCT/CN2004/000226 priority patent/WO2004084632A1/zh
Priority to BRPI0409037-3A priority patent/BRPI0409037A/pt
Priority to AU2004224838A priority patent/AU2004224838A1/en
Priority to TR2005/03847T priority patent/TR200503847T1/xx
Application granted granted Critical
Publication of CN1201657C publication Critical patent/CN1201657C/zh
Priority to ZA200508026A priority patent/ZA200508026B/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C07C69/736—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • 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
    • A01N37/00—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
    • A01N37/36—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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明涉及含有结构式I所示2-(2-((2，5-二甲基苯氧基)甲基苯基))-3-甲氧基丙烯酸甲酯及其立体异构体的杀真菌化合物的组合物，其使用方法，以及上述活性成分的化合物及其制备方法。生物活性测定表明：化合物I对防治农业上真菌产生的病害有很高的生物活性，对防治白粉病、霜霉病、炭咀病有特效。

Description

甲氧基丙烯酸甲酯类化合物杀菌剂
                              本发明技术领域
本发明涉及一种甲氧基丙烯酸甲酯类农用杀菌剂。本发明进一步涉及一种具有高效杀菌效果的甲氧基丙烯酸甲酯化合物，其制备方法，其杀菌剂组合物及其用途。
为了获得在很小的剂量下就可以控制各种真菌病害化合物，本发明发明者们合成了其中的一些化合物，这些化合物具有广谱杀菌活性可用于防治作物上的由藻菌纲、卵菌纲、子囊菌纲和半知菌纲等多种真菌引起的病害，而且由于这一化合物具有很高的生物活性使得在很低的剂量下就可以获得很好防治效果。本类化合物对白粉病、霜霉病、炭疽病表现出很好的生物活性外，对葡萄的黑痘病、葡萄白锈病也有防治作用。
本发明提供的化合物不但具有很高的生物活性，而且对环境非常友好，对环境没有污染。本发明提供化合物不但具有很高的生物活性，而且同世界类似产品比较生产成本低，是一个非常有前途的农用杀菌剂新品种。
                                背景技术
在US 4,914,128号专利申请中公开了一些甲氧基丙烯酸甲酯类化合物，并公开了其中的化合物具有杀菌活性。
本申请人意外地发现，其通式结构中的一些未具体公开的化合物，具有优异的杀真菌活性，并由此完成了本发明。
甲氧基丙烯酸甲酯类杀菌剂是从天然化合物通过结构改造而来的高效农用杀真菌剂。它们特点是杀菌广、对其它生物毒性低、环境相容性好。世界上有许多农药大公司进行这方面研究，发现了几个有很好市场前景的甲氧基丙烯酸甲酯类化合物。该类杀菌剂市场占有比例越来越大，将可能取代三唑类杀菌剂成为农用杀菌剂第一大品种。
                               本发明概述
本发明提供了新的甲氧基丙烯酸甲酯类化合物和其制备方法，及其杀菌剂组合物和用途。本发明甲氧基丙烯酸甲酯杀菌剂化合物的化学名称为：
(E)-2-(2-((2，5-二甲基苯氧基)甲基苯基))-3-甲氧基丙烯酸甲酯
结构式为：
本发明的化合物可以通过以下方法制备：
方法一  反应如下：
化合物I可以这样来制备：在适当的溶剂中，加入式II的2，5-二甲基苯酚和式III的2-(2-卤代甲基苯基)-3-甲氧基丙烯酸甲酯，再加入适当的碱，在适当的温度下和适当时间内反应制得。其中III中的X离去基团如卤素，优选为氯、溴或碘。
优选溶剂为丙酮或四氢呋喃。
其中碱包括有机碱和无机碱：有机碱包括三乙胺、吡啶等；无机碱包括氢氧化钠、氢氧化钾、氢化钠、碳酸钠、碳酸钾等。本发明优选碱为碳酸钠或碳酸钾。
优选温度为0～100℃。
方法二  反应如下：
Figure C0312088200051
方法二制备化合物I过程为：在适当的溶剂中，加入式II的2，5-二甲基苯酚和式IV化合物，再加入适当的碱，在适当的温度下和适当时间内反应制得V。其中IV中的X离去基团如卤素，优选氯、溴或碘。V在适当的溶剂中，再加入适当的碱，加入适量的甲酸甲酯，在适当的温度下和适当时间内反应制得VI。VI在适当的溶剂中，加入甲基化试剂，如硫酸二甲酯、碘甲烷等，再加入适当的碱，在适当的温度下和适当时间内反应制得化合物I。
其中在制备V时：优选溶剂为丙酮或四氢呋喃。
其中碱包括有机碱和无机碱：有机碱包括三乙胺、吡啶等；无机碱包括氢氧化钠、氢氧化钾、氢化钠、碳酸钠、碳酸钾等。本发明优选碱为碳酸钠或碳酸钾。
优选温度为0～100℃。
在制备VI时优选碱为甲醇钠或氢化钠等；优选溶剂为乙醚或甲醇。优选温度为零下5～100℃。
其中在制备I时：优选溶剂为丙酮或四氢呋喃。
其中碱包括有机碱和无机碱：有机碱包括三乙胺、吡啶等；无机碱包括氢氧化钠、氢氧化钾、氢化钠、碳酸钠、碳酸钾等。本发明优选碱为碳酸钠或碳酸钾。
优选温度为0～100℃。
本发明的化合物I是有效的杀真菌剂。特别适合于防治下列植物病害：
大麦和小麦白粉病、蔬菜白粉病、瓜类白粉病、果树白粉病、葡萄白粉病、草莓白粉病及花卉白粉病；小麦和大麦条锈病、叶锈病和其它锈病。
黄瓜霜霉病，葡萄霜霉病；瓜类上的炭疽病等病害。
本发明还提供了如上所定义的化合物的杀菌组合物及其制备方法。
本发明的组合物，优选含从0.1～99.0％重量的式(I)的活性成份。需要时可在组合物中加入合适的载体和表面活性剂成分。
本发明组合物的制备方法是将化合物I和至少一种载体混合。这种组合物还可以含有其它的农药活性成分。
本发明的载体系满足下述条件的物质：它与活性成分配制后便于施用于待处理的位点，例如可以是植物、种子或土壤；或者有利于贮存、运输或操作。载体可以是固体或液体，和可使用任何通常在配制杀虫、杀菌组合物中所用的载体。
合适的固体载体包括天然和合成的硅酸盐、例如硅藻土、滑石、硅镁土、硅酸铝(高岭土)、蒙脱石和云母；碳酸钙、硫酸钙、硫酸铵；合成的氧化硅酸钙或硅酸铝；元素如碳和硫；天然的和合成的树脂如苯并呋喃树脂，聚氯乙烯和苯乙烯聚合物和共聚物；固体多氯苯酚；沥青；蜡如蜂蜡、石腊。
合适的液体载体包括水；醇如异丙醇和乙醇；酮如丙酮、甲基乙基酮、甲基异丁基酮和环己酮；醚；芳烃如苯、甲苯和二甲苯；石油馏分如煤油和矿物油；氯代烃如四氯化碳、全氯乙烯和三氯乙烷，通常，这些液体的混合物也是合适的。
杀虫、杀菌组合物通常加工成浓缩物的形式并以此用于运输，在施用之前由使用者将其稀释。少量的表面活性剂载体的存在有助于稀释过程。这样，按照本发明的组合物中，优选含有表面活性剂。
表面活性剂可以是乳化剂、分散剂或润湿剂：它可以是离子表面活性剂或非离子表面活性剂。如：聚丙烯酸和木质素磺酸的钠盐或钙盐；分子中含至少12个碳原子的脂肪酸或脂肪胺或酰胺；环氧乙烷和或环氧丙烷的缩合物；甘醇，山梨醇、蔗糖或季戊四醇脂肪酸脂及这些酯与环氧乙烷和或环氧丙环的缩合物；脂肪醇或烷基苯酚如对辛基苯酚或对辛基苯酚与环氧乙烷和或环氧丙烷的缩合物；这些缩合产物的硫酸盐或磺酸盐；在分子中含有至少10个碳原子的硫酸或磺酸酯的碱金属或碱土金属盐，优选钠盐，例如硫酸月桂酯钠，硫酸仲烷基酯钠，磺化蓖麻油钠盐，磺酸烷基芳基酯钠如十二烷基苯磺酸钠盐。
本发明的组合物的实例是可湿性粉剂、粉剂、颗粒剂、可乳化的浓缩剂、乳剂、悬浮浓缩剂、气雾剂和烟雾剂。可湿性粉剂通常含20-80％重量活性成分，且通常除固体惰性载体之外，还含有2～10％重量分散剂，且若需要或加入0～10％重量稳定剂和或其它添加剂如渗透剂或粘着剂。粉剂通常可成型为具有可湿性粉剂相似的组成但有分散剂的粉剂浓缩剂，在地里进一步用固体载体稀释，得到通常含0.5～10％重量活性成分的组合物。粒剂通常制成具有10和100目大小，且可用成团或注入技术制备。通常，粒剂含0.1～80％重量的活性成分和0～10％重量添加剂如稳定剂、表面活性剂、缓释剂等。所谓的“可流动干粉”由具有相对高浓度活性成分的相对小的颗粒组成。可乳化浓缩剂除溶剂外，当需要时通常含有共溶剂，1～50％W/V活性成分，2～20％W/V乳化剂和0～20％W/V其他添加剂如稳定剂、渗透剂和腐蚀抑制剂。悬浮浓缩齐通常含有10～80％重量的活性成分、0.5～15％重量的分散剂、0.1～10％重量的其它添加剂如消泡剂、腐蚀抑制剂、稳定剂、渗透剂和粘着剂。
水分散剂和乳化剂，例如通过用水稀释按照本发明的可湿性粉剂或浓缩物得到的组合物，也列入本发明范围。所说的乳剂可具有油包水或水包油两个类型。
通过在组合物中加入其他一种或多种杀真菌剂，使其能比单独的化合物(I)具有更广的活性。此外，其他杀真菌剂可对化合物(I)的杀菌活性具有增效作用。可以包含在本发明组合物中的杀真菌剂化合物的实例中：克菌丹、灭菌丹、嘧霉胺、十三吗啉、氯苯嘧啶醇、咯菌腈、氧化亚酮、恶醚唑、代森锌、代森锰锌、福美双、敌菌丹、异菌脲、甲基菌核利、甲乙菌核利、己唑醇、腈菌唑、戊唑醇、戊菌隆、霜脲氰、双胍辛醋酸盐、硫菌威、环菌胺、氟吗啉、氟哇唑、SSF-129，picoxystrobin，metrafenone、pyraclostrobin、resveratro、dimoxystrobin、UBF-307、BASF490F、ICIA5504、TH-164、RH7592、酯菌脲、烯唑醇、氟酰脲、多菌灵、苯菌灵、三唑酮、环唑醇、乙霉威、甲基托布津、土菌消、丁苯吗啉、霜霉威、甲霜灵、呋霜灵、苯霜灵、恶酰胺、磺菌威、啶斑肟、苯锈啶、嘧菌胺、烯酰吗啉、拌种咯、拌种强、丙环唑、百菌清、二嗪哝、硫酸铜、抑菌灵、乙磷铝、恶霉灵、等。
可以与本发明的化合物混合形成组合物的杀虫剂有：杀虫剂溴螨酯、三氯杀螨醇、甲基1605、1605、杀螟松、地亚农、丁硫克百威、毒死蜱、锐尽特、除尽、灭多威、杀虫单、杀虫双、巴丹、阿维菌素、氯菊酯、氯氰菊酯、胺菊酯、七氟菊酯、氟氯氰菊酯、氰戊菊酯、氟虫脲、杀虫脲、定虫脲、唑螨酯、吡虫啉、双氧威、三唑磷、喹螨酯、杀螨隆、哒螨灵、四螨嗪等。
                                具体实施方式
通过以下具体的实例来对本发明进行详细的说明，除非另外指明本申请中的 份数一重 量计：
合成实施例：
在室温下将12.2g2，5-二甲基苯酚加到500ml盛有150ml干燥丙酮的三口瓶中，然后加入13.8g碳酸钾，室温搅拌20分钟，然后慢慢加入28.5g(E)-2-(2-(溴甲基)苯基)-3-甲氧基丙烯酸甲酯。然后回流反应3小时结束，过滤，浓缩，得粗品。用乙酸乙酯和石油醚的混合液(1∶4)为洗脱液进行柱层析得到化合物I 26.08g，为白色固体，收率为80％。熔点：108～110℃
1HNMR：2.235(3H，s)，2.279(3H，s)，3.706(3H，s)，3.835(3H，s)，4.944(2H，s)，6.584(1H，s)6.655-6.673(1H，d)，7.013-7.032(1H，d)，7.164-7.168(2H，d)，7.300-7.7.382(2H，m)，7.596(1H，s)，7.617(1H，s)
注：1HNMR谱是用CDCl3溶剂记录。在实验中所用的缩写如下：
NMR＝核磁共振s＝单峰d＝双峰m＝多峰
制剂实施例
制剂实施例1
本发明的化合物40公斤、硅藻土53公斤、C12-20醇硫酸酯4公斤、十二烷基苯磺酸钠3公斤，将以上成分均匀混合，粉碎，得含有效成分40％的可湿性粉剂。
制剂实施例2
本发明的化物30公斤、二甲苯33公斤、二甲基甲酰胺30公斤、聚氧乙烯烷基丙醚7公斤，将以上成分均匀混合、溶解、得含有效成分30％的乳剂。
制剂实施例3
本发明的化合物10公斤、滑石粉89公斤、聚氧乙烯烷基丙醚公斤，将以上成分均匀混合，粉碎，得含有效成分10％的粉剂。
制剂实施例4
本发明的化合物5公斤、粘土73公斤、膨润土20公斤、二辛基硫代丁二酸钠1公斤、磷酸钠1公斤，将以上成分均匀混合，充分粉碎后，加入适量水。再充分混合，造粒，干燥后，得含有效成分5％的颗粒剂。
制剂实施例5
本发明的化合物10公斤，木质素磺酸钠4公斤，十二烷基苯磺酸钠1公斤，黄原酸1公斤，水84公斤，将以上成分均匀混合，湿式研磨到粒度为1微米以下，得到含有效成分为10％的胶悬剂。
制剂实施例6
本发明化合物8公斤、代森锰锌50公斤、高岭土30公斤、十二烷基苯磺酸钠4公斤、木质素磺酸钠8公斤，将上述成分混合，充分粉碎后，得混剂含量为58％的可湿性粉剂。
制剂实施例7
本发明化合物1公斤、三唑酮20公斤、高岭土64公斤、十二烷基苯磺酸钠6公斤、木质素磺酸钠9公斤，将以上成分均匀混合，充分粉碎后，得混合含量为21％的可湿性粉剂。
药效实施例：
本发明的化合物，同现有杀菌剂比具有佷好生物活性，可以在很低的剂量下很好地防治由真菌引起的病害，对白粉病、锈病、霜霉病、炭疽病有特别好的效果。如小麦、大麦的白粉病、黄瓜白粉、南瓜白粉、草莓白粉病、葡萄白粉病，小麦、大麦锈病，葡萄霜霉病、黄瓜霜霉病，黄瓜炭疽病。另位对葡萄黑痘病、白锈病也有一定的抑制作用。
药效实施例1：防治黄瓜白粉病保护与治疗作用试验(室内)
试验药剂为本发明化合物I(含量5％的乳油)设10、5、2.5、1.25、0.625、0.3125ppm六个浓度。对照ZA-1963(即先正达公司picoxystrobin，即相似专利中商品化的化合物)(含量5％的乳油)设10、5、2.5、1.25、0.625、0.3125ppm六个浓度。对照药剂20％三唑酮乳油，设100、50、25ppm。选择生长至2叶一心期的盆栽两片真叶平展的黄瓜健苗喷药，预防试验喷药后24小时接种，治疗试验接种后24小时喷药。接种后黄瓜幼移置人工气候箱内保湿培养，7天后调查防效。结果见表1：
            表1黄瓜白粉病保护与治疗作用试验结果：
药剂 浓度(ppm)                黄瓜白粉病
    预防效果(％)     治疗效果(％)
    化合物(I)     10     100     98.89
    5     100     97.53
    2.5     97.22     88.89
1.25 90.28     85.71
    0.625     85.31     64.81
    0.315     63.11     29.63
ZA-1963     10     98.15     86.11
    5     88.89     68.52
    2.5     81.75     36.11
    1.25     75.60     23.42
    0.625     47.63     8.33
    0.315     41.67     0.0
    三唑酮     100     100
    50     81.25
    25     45.40
保护及治疗试验结果表明：化合物I预防略优于治疗。0.625ppm预防为85.31％，治疗为64.81％。同时发现化合物(I)的预防和治疗效果的明显活性优于ZA-1963，特别是治疗作用。化合物I的生物活性远远好于三唑酮。
药效实施例2防治小麦白粉病保护与治疗作用试验(室内)
试验药剂为本发明化合物I(含量5％的乳油)设25、12.5、6.25、3.125、1.563、0.781ppm六个浓度。对照ZA-1963(即先正达公司picoxystrobin，即相似专利中商品化的化合物)(含量5％的乳油)设25、12.5、6.25、3.125、1.563、0.781ppm六个浓度。对照药剂20％三唑酮乳油，设100、50、25ppm。选择生长至2叶一心期的盆栽小麦喷药，预防试验喷药后24小时接种，治疗试验接种后24小时喷药。接种后小麦移置人工气候箱内保湿培养，7天后调查防效。结果见表2
              表2小表白粉病保护与治疗作用试验结果
药剂 浓度(ppm)                小麦白粉病
    预防效果(％)     治疗效果(％)
化合物(I)     25     100     100
    12.5     100     100
    6.25     100     100
    3.125     100     100
    1.563     98.33     97.33
    0.781     87.43     84.13
ZA-1963     25     100     99.77
    12.5     99.60     98.31
    6.25     91.30     82.95
    3.125     93.61     73.15
    1.563     78.18     71.97
    0.781     53.05     38.97
    三唑酮     100
    50
    25
保护及治疗试验结果表明：发现化合物I的预防和治疗效果的明显活性优于ZA-1963，治疗作用更加明显。化合物I的生物活性远远好于三唑酮。
药效实施例3对小麦白粉病模拟田间试验
化合物(I)处理浓度为50，25，12.5，6.25，3.125ppm，对照药剂ZA-1963的处理浓度与化合物I相同，三唑酮的处理浓度为100，50，25ppm。将盆栽小麦培养至4-5叶期，任其自然发病至中期，按上述所设浓度进行叶面喷雾处理，10天后调查防效。结果见表3
      表3对小麦白粉病模拟田间试验
    药剂     浓度(mg/l)     防效(％)
    化合物(I)     50     100
    25     100
    12.5     100
    6.25     95.60
    3.125     70.37
    ZA-1963     50     93.61
    25     83.26
    12.5     64.25
    6.25     49.57
    3.125     41.83
三唑酮     100     64.93
    50     13.85
模拟田间试验结果表明，化合物I对盆栽小麦自然发病至中期时施药，仍表现出很高的防治作用，并且防效优于对照药剂ZA-1963和三唑酮。
药效实施例4持效期试验
化合物I和对照药剂ZA-1963的处理浓度为50，25mg/l，测试对象为小麦白粉病。在盆栽小麦两片真叶平展时喷药，喷药后24小时接种小麦白粉菌，接种后的小麦移至温室内保湿培养，处理后7、10、15、20、25、30天调查防效。结果见表4
                     表4持效期试验结果
药剂     浓度mg/l                    防效(％)
    7天     10天     15天     20天
化合物(I)     50     100     100     99.6     88.16
    25     100     100     98.51     87.23
ZA-1963     50     100     100     96.43     85.21
    25     100     100     96.31     84.68
持效期试验表明：在温室人工接种的条件下，化合物I的持效期比ZA-1963略长。
药效实施例5对南瓜白粉病的防效试验(田间)
田间防效南瓜白粉病试验2002年6月在浙江绍兴市现代农业园区的大棚内进行。
化合物I(10％水悬剂)设50，25，12.5，6.25ppm四个浓度，对照药剂为20％粉锈宁EC设浓度为100ppm。另设清水对照。每处理4次重复。施药7天后调查。结果见表5
                 表5对南瓜白粉病的防效试验(田间)结果
药剂 浓度(ppm) 病情指数     病指增加数 防效(％)
化合物(I)     50   17     1.5     91.8
    25   22.75     1     96.4
    12.5   22.5     2.5     90.9
    6.25   23.75     2     92.7
    粉锈宁     200   20     7.25     72.7
    CK   44.25     27.5     27.5
注：CK防效栏为病指增加值。
从表5中可以看出：化合物在6.25ppm对南瓜白粉有很高的活性，明显优于对照药剂粉锈宁。
药效实施例6对黄瓜白粉病的防效试验(田间)
田间防治黄瓜白粉病试验2002年6月在浙江绍兴市现代农业园区的大棚内进行。
化合物I(10％水悬剂)设50，25，12.5，6.25ppm四个浓度，对照药剂为20％粉锈宁EC设浓度为100ppm。另设清水对照。每处理4次重复。施药7天后调查。结果见表6
                表6对黄瓜白粉病的防效试验(田间)结果
药剂 浓度(ppm) 病情指数     病指增加数 防效(％)
化合物(I)     50   21.25     0.5     98.6
    25   26.75     1.25     96.5
    12.5   21.25     2.75     92.2
    6.25   24.5     2.75     92.2
    粉锈宁     200   37.25     11     68.8
    CK   59.5     35.25     35.25
注：CK防效栏为病指增加值。
从表6中可以看出：化合物I在6.25ppm对黄瓜白粉有很高的活性，明显优于对照药剂粉锈宁。
药效实施例7化合物(I)对黄瓜霜霉病防效试验(室内)
化合物I处理浓度为100，50，25，12.5，6.25ppm，对照药剂ZA-1963的处理浓度与化合物I相同，甲霜灵处理浓度为500ppm。选择生长至2叶一心期的盆栽两片真叶平展的黄瓜健苗喷药，预防试验喷药后24小时接种，治疗试验接种后24小时喷药。接种后黄瓜幼移置人工气候箱内保湿培养，7天后调查防效，结果见表7
 表7对黄瓜霜霉病的防效试验(室内)结果
药剂 浓度(ppm) 防效(％)
化合物(I) 100  100
 50  100
 25  100
 12.5  97.18
 6.25  91.55
 3.125  77.46
 ZA-1963  100  91.55
 50  60.56
 25  46.48
 12.5  40.84
 6.25  26.76
 3.125  9.86
甲霜灵  500  70.11
在温室条件下化合物I对黄瓜霜霉病的防效在相同浓度下明显优于对照药剂ZA-1963，明显优于甲霜灵。
药效实施例8对葡萄霜霉病的防效试验(田间)
田间防治葡萄霜霉病试验2002年7月在安微省马鞍山市当涂县石桥乡农业科技示范场进行。
化合物I(5％乳油)设200，100，50，25，12.5ppm五个浓度，对照药剂72％杜邦克露可湿性粉剂设1000ppm浓度。另设空白对照，每处理重复4次。喷药7天后调查。结果如表8
                 表8对葡萄霜霉病的防效试验(田间)结果
    药剂     浓度(ppm)     药前基数     病指数     防效(％)
    化合物(I)     12.5     1.61     4.89     50.94
    25     1.89     4.33     62.97
    50     2.00     3.89     68.58
    100     2.28     3.20     77.34
    200     2.22     2.47     82.05
    克露     1000     1.55     1.68     82.49
    CK     1.89     11.70
从结果可以看出，化合物I在防治葡萄霜霉在200ppm与对照药克露1000ppm相当。药效实施例9对黄瓜霜霉病的防效试验(田间)
田间防治黄瓜霜霉病试验2002年7月在安微省马鞍山市当涂县石桥乡农业科技示范场进行。
化合物I(5％乳油)设200，100，50，25，12.5ppm五个浓度，对照药剂72％杜邦克露可湿性粉剂设1000ppm。另设空白对照，每处理重复4次。喷药7天后调查。结果如表9
           表9对黄瓜霜霉病的防效试验(田间)结果
  药剂   浓度(ppm)     药前基数     病指数     防效(％)
  化合物(I)   12.5     0.96     3.89     51.38
  25     1.07     3.04     65.91
  50     1.04     2.59     70.01
  100     0.93     1.84     76.12
  200     0.89     1.28     82.67
  克露   1000     0.93     1.13     85.33
  CK     0.78     6.48
从结果可以看出，化合物I在防治黄瓜霜霉在200ppm与对照药克露1000ppm相当。
药效实施例10对黄瓜炭疽病防效果试验(室内)
化合物I和对照药剂ZA-1963的处理浓度为500，250，125，62.5，31.25ppm。测试对象为黄瓜炭疽病，盆栽黄瓜苗生长至一张真叶期时喷药，喷药24小时后接种炭疽病孢子悬浮液，接种后移入人工气候箱内，保持湿度100％，温度为20度，接种24小时后保持相对湿度为85％。7天后进行调查。结果见表10
表10对黄瓜炭疽病试验结果。(室内)
药剂  浓度(ppm)  防效(％)
化合物(I)  500  98.51
 250  89.94
 125  88.02
 62.5  69.83
 31.25  68.41
ZA-1963  500  93.20
 250  86.38
 125  80.94
 62.5  73.86
 31.25  63.24
在温室条件下化合物I对黄瓜炭疽病的防效在相同浓度下略优于对照药剂ZA-1963

Claims (9)

1.一种甲氧基丙烯酸甲酯类化合物杀菌剂组合物，其特征在于组合物中包含具有化学结构式(I)的化合物及其异构体：
Figure C031208820002C1
2.根据权利要求1所述的杀菌剂组合物，其特征在于有效成分(I)在制剂中所占有的比例为0.1％～99.0％重量。
3.根据权利要求1或2所述的杀菌剂组合物，其特征在于可将有效成分(I)配制成乳剂、粉剂、可湿性粉剂、胶悬剂、颗粒剂。
4.根据上述任一权利要求的组合物的使用方法，其特征在于可单独使用上述组合物也可和1种或2种以上的杀菌剂、杀虫剂、除草剂或植物生长调节剂复配成二元或三元混合制剂应用。
5.根据权利要求4的组合物的使用方法，其特征在于使用到作物上防治在各种作物上由藻菌纲、卵菌纲、子囊菌纲和半知菌纲等多种真菌引起的病害。
6.根据权利要求4的组合物的使用方法，其特征在于使用到作物上防治麦类白粉病、瓜类白粉病、麦类锈病、蔬菜白粉病、水果白粉病、花类白粉病；黄瓜霜霉病、葡萄霜霉病；黄瓜炭疽病。
7.一种杀菌剂化合物，其特征在于化合物为权利要求1的式(I)的化合物及其异构体
Figure C031208820002C2
8.根据权利要求7的化合物的制备方法，其特征在于在碱性条件下使(II)化合物与(III)化合物反应得到化合物(I)
其中III中X为离去基团，必要时反应可在溶剂存在下进行。
9.根据权利要求7的化合物的制备方法，其特征在于反应的过程如下：
其中IV中的X为离去基团，且在需要时可加入适当的溶剂。
CN 03120882 2003-03-25 2003-03-25 甲氧基丙烯酸甲酯类化合物杀菌剂 Expired - Lifetime CN1201657C (zh)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CN 03120882 CN1201657C (zh) 2003-03-25 2003-03-25 甲氧基丙烯酸甲酯类化合物杀菌剂
PCT/CN2004/000226 WO2004084632A1 (en) 2003-03-25 2004-03-19 Fungicides containing methoxy acrylic acid methyl ester compound
BRPI0409037-3A BRPI0409037A (pt) 2003-03-25 2004-03-19 fungicidas que contém composto metil éster de ácido metóxi acrìlico
AU2004224838A AU2004224838A1 (en) 2003-03-25 2004-03-19 Fungicides containing methoxy acrylic acid methyl ester compound
TR2005/03847T TR200503847T1 (tr) 2003-03-25 2004-03-19 Metoksi akrilik asit metil ester bileşiği içeren fungusitler.
ZA200508026A ZA200508026B (en) 2003-03-25 2005-10-04 Fungicides containing methoxy acrylic acid methyl ester compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 03120882 CN1201657C (zh) 2003-03-25 2003-03-25 甲氧基丙烯酸甲酯类化合物杀菌剂

Publications (2)

Publication Number Publication Date
CN1456054A CN1456054A (zh) 2003-11-19
CN1201657C true CN1201657C (zh) 2005-05-18

Family

ID=29411572

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 03120882 Expired - Lifetime CN1201657C (zh) 2003-03-25 2003-03-25 甲氧基丙烯酸甲酯类化合物杀菌剂

Country Status (6)

Country Link
CN (1) CN1201657C (zh)
AU (1) AU2004224838A1 (zh)
BR (1) BRPI0409037A (zh)
TR (1) TR200503847T1 (zh)
WO (1) WO2004084632A1 (zh)
ZA (1) ZA200508026B (zh)

Families Citing this family (180)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101524076B (zh) * 2005-08-17 2012-11-07 浙江省化工研究院有限公司 杀菌剂组合物
CN100401889C (zh) * 2005-08-17 2008-07-16 浙江化工科技集团有限公司 杀菌剂组合物
CN101642119B (zh) * 2009-08-24 2013-06-05 陕西上格之路生物科学有限公司 一种含苯醚菌酯的农用杀菌组合物
WO2011132967A2 (ko) * 2010-04-21 2011-10-27 주식회사 오스코텍 알파-아릴메톡시아크릴레이트 유도체, 이의 제조방법 및 이를 포함하는 약학적 조성물
CN102115458B (zh) * 2010-11-25 2019-12-13 大连九信精细化工有限公司 3-甲氧基-2-芳香基丙烯酸甲酯类化合物的合成方法
CN102919240B (zh) * 2010-12-08 2014-08-13 陕西美邦农药有限公司 一种含十三吗啉的杀菌组合物
CN102835399B (zh) * 2012-09-27 2014-04-30 陕西上格之路生物科学有限公司 一种含苯菌酮的杀菌组合物
CN103975927B (zh) * 2013-04-07 2016-06-08 海南正业中农高科股份有限公司 一种含有环氟菌胺与唑菌酯或苯醚菌酯的杀菌组合物及应用
CN103598193B (zh) * 2013-10-23 2015-04-01 江苏丰登作物保护股份有限公司 一种含啶氧菌酯和福美双的杀菌组合物及其应用
EP3214937B1 (en) 2014-11-07 2024-07-03 Basf Se Pesticidal mixtures
WO2016174042A1 (en) 2015-04-27 2016-11-03 BASF Agro B.V. Pesticidal compositions
EP3371177A1 (en) 2015-11-02 2018-09-12 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
US20180317490A1 (en) 2015-11-04 2018-11-08 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
BR112018009579A2 (pt) 2015-11-13 2018-11-06 Basf Se composto da fórmula i, mistura, composição agroquímica, uso de composto e método de combate a fungos
WO2017081310A1 (en) 2015-11-13 2017-05-18 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
MX2018006244A (es) 2015-11-19 2018-11-09 Basf Se Oxadiazoles sustituidos para combatir hongos fitopatogenos.
CR20180332A (es) 2015-11-19 2018-10-18 Basf Se Oxadiazoles sustituidos para combatir hongos fitopatógenos
EP3202267A1 (en) 2016-02-05 2017-08-09 Basf Se Pesticidal mixtures
EP3205208A1 (en) 2016-02-09 2017-08-16 Basf Se Mixtures and compositions comprising paenibacillus strains or fusaricidins and chemical pesticides
WO2017153200A1 (en) 2016-03-10 2017-09-14 Basf Se Fungicidal mixtures iii comprising strobilurin-type fungicides
US11425909B2 (en) 2016-03-16 2022-08-30 Basf Se Use of tetrazolinones for combating resistant phytopathogenic fungi on fruits
US11241012B2 (en) 2016-03-16 2022-02-08 Basf Se Use of tetrazolinones for combating resistant phytopathogenic fungi on soybean
UA125210C2 (uk) 2016-03-16 2022-02-02 Басф Се Застосування тетразолінонів для боротьби зі стійкими фітопатогенними грибами на злакових культурах
US10986839B2 (en) 2016-04-11 2021-04-27 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
CN105766919A (zh) * 2016-04-22 2016-07-20 广东中迅农科股份有限公司 含有氟菌唑和苯醚菌酯的杀菌组合物
WO2018050421A1 (en) 2016-09-13 2018-03-22 Basf Se Fungicidal mixtures i comprising quinoline fungicides
WO2018054711A1 (en) 2016-09-26 2018-03-29 Basf Se Pyridine compounds for controlling phytopathogenic harmful fungi
WO2018054723A1 (en) 2016-09-26 2018-03-29 Basf Se Pyridine compounds for controlling phytopathogenic harmful fungi
WO2018054721A1 (en) 2016-09-26 2018-03-29 Basf Se Pyridine compounds for controlling phytopathogenic harmful fungi
WO2018065182A1 (en) 2016-10-04 2018-04-12 Basf Se Reduced quinoline compounds as antifuni agents
WO2018073110A1 (en) 2016-10-20 2018-04-26 Basf Se Quinoline compounds as fungicides
WO2018114393A1 (en) 2016-12-19 2018-06-28 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
EP3339297A1 (en) 2016-12-20 2018-06-27 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
EP3338552A1 (en) 2016-12-21 2018-06-27 Basf Se Use of a tetrazolinone fungicide on transgenic plants
BR112019014061A2 (pt) 2017-01-23 2020-02-04 Basf Se compostos de fórmula i, intermediários b, intermediários c, intermediários ii e intermediários d, composição, uso, método para combater fungos fitopatogênicos, semente e processo para a síntese dos compostos de fórmula i
WO2018149754A1 (en) 2017-02-16 2018-08-23 Basf Se Pyridine compounds
BR112019015338B1 (pt) 2017-02-21 2023-03-14 Basf Se Compostos de fórmula i, composição agroquímica, semente revestida, uso dos compostos e método para combater fungos nocivos fitopatogênicos
CN110461854A (zh) 2017-03-31 2019-11-15 巴斯夫欧洲公司 制备手性2,3-二氢噻唑并[3,2-a]嘧啶-4-鎓化合物的方法
BR112019020879A2 (pt) 2017-04-06 2020-04-28 Basf Se compostos, composição, uso de um composto de formula i, método para combater fungos fitopatogênicos, semente e intermediários
WO2018184970A1 (en) 2017-04-07 2018-10-11 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2018188962A1 (en) 2017-04-11 2018-10-18 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
CA3059301A1 (en) 2017-04-20 2018-10-25 Pi Industries Ltd. Novel phenylamine compounds
EP3618629A1 (en) 2017-05-02 2020-03-11 Basf Se Fungicidal mixture comprising substituted 3-phenyl-5-(trifluoromethyl)-1,2,4-oxadiazoles
EP3619207B1 (en) 2017-05-04 2021-06-23 Basf Se Substituted 5-(haloalkyl)-5-hydroxy-isoxazolines for combating phytopathogenic fungi
WO2018202491A1 (en) 2017-05-04 2018-11-08 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
WO2018202737A1 (en) 2017-05-05 2018-11-08 Basf Se Fungicidal mixtures comprising triazole compounds
WO2018210661A1 (en) 2017-05-15 2018-11-22 Basf Se Heteroaryl compounds as agrochemical fungicides
WO2018210660A1 (en) 2017-05-15 2018-11-22 Basf Se Heteroaryl compounds as agrochemical fungicides
WO2018210658A1 (en) 2017-05-15 2018-11-22 Basf Se Heteroaryl compounds as agrochemical fungicides
WO2018210659A1 (en) 2017-05-15 2018-11-22 Basf Se Heteroaryl compounds as agrochemical fungicides
IL270873B2 (en) 2017-05-30 2023-04-01 Basf Se "The history of pyridine and pyrazine compounds, a preparation containing them and their use as fungicides
WO2018219797A1 (en) 2017-06-02 2018-12-06 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2018234139A1 (en) 2017-06-19 2018-12-27 Basf Se 2-[[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]aryloxy](thio)acetamides for combating phytopathogenic fungi
WO2019002158A1 (en) 2017-06-30 2019-01-03 Basf Se SUBSTITUTED TRIFLUOROMETHYLOXADIAZOLES FOR THE CONTROL OF PHYTOPATHOGENIC FUNGI
WO2019025250A1 (en) 2017-08-04 2019-02-07 Basf Se SUBSTITUTED TRIFLUOROMETHYLOXADIAZOLES FOR COMBATING PHYTOPATHOGENIC FUNGI
WO2019038042A1 (en) 2017-08-21 2019-02-28 Basf Se SUBSTITUTED TRIFLUOROMETHYLOXADIAZOLES FOR THE CONTROL OF PHYTOPATHOGENIC FUNGI
EP3915379A1 (en) 2017-08-29 2021-12-01 Basf Se Pesticidal mixtures
WO2019042932A1 (en) 2017-08-31 2019-03-07 Basf Se METHOD FOR CONTROLLING RICE PARASITES IN RICE
EP3453706A1 (en) 2017-09-08 2019-03-13 Basf Se Pesticidal imidazole compounds
US11076596B2 (en) 2017-09-18 2021-08-03 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
WO2019057660A1 (en) 2017-09-25 2019-03-28 Basf Se INDOLE AND AZAINDOLE COMPOUNDS HAVING 6-CHANNEL SUBSTITUTED ARYL AND HETEROARYL CYCLES AS AGROCHEMICAL FUNGICIDES
US11399543B2 (en) 2017-10-13 2022-08-02 Basf Se Substituted 1,2,3,5-tetrahydroimidazo[1,2-a]pyrimidiniumolates for combating animal pests
US11147275B2 (en) 2017-11-23 2021-10-19 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
WO2019115511A1 (en) 2017-12-14 2019-06-20 Basf Se Fungicidal mixture comprising substituted 3-phenyl-5-(trifluoromethyl)-1,2,4-oxadiazoles
EP3723485A1 (en) 2017-12-15 2020-10-21 Basf Se Fungicidal mixture comprising substituted pyridines
CN111670180A (zh) 2017-12-20 2020-09-15 Pi工业有限公司 氟烯基化合物，制备方法及其用途
WO2019121143A1 (en) 2017-12-20 2019-06-27 Basf Se Substituted cyclopropyl derivatives
AU2019211978B2 (en) 2018-01-09 2024-08-22 Basf Se Silylethynyl hetaryl compounds as nitrification inhibitors
WO2019137995A1 (en) 2018-01-11 2019-07-18 Basf Se Novel pyridazine compounds for controlling invertebrate pests
WO2019150311A1 (en) 2018-02-02 2019-08-08 Pi Industries Ltd. 1-3 dithiol compounds and their use for the protection of crops from phytopathogenic microorganisms
WO2019154665A1 (en) 2018-02-07 2019-08-15 Basf Se New pyridine carboxamides
CN111683933A (zh) 2018-02-07 2020-09-18 巴斯夫欧洲公司 新型吡啶羧酰胺类
EP3530118A1 (en) 2018-02-26 2019-08-28 Basf Se Fungicidal mixtures
EP3530116A1 (en) 2018-02-27 2019-08-28 Basf Se Fungicidal mixtures comprising xemium
KR102730587B1 (ko) 2018-02-28 2024-11-14 바스프 에스이 질화작용 저해제로서의 n-관능화 알콕시 피라졸 화합물의 용도
WO2019166558A1 (en) 2018-02-28 2019-09-06 Basf Se Use of pyrazole propargyl ethers as nitrification inhibitors
WO2019166252A1 (en) 2018-02-28 2019-09-06 Basf Se Fungicidal mixtures comprising fenpropidin
PE20211753A1 (es) 2018-02-28 2021-09-06 Basf Se Uso de alcoxipirazoles como inhibidores de la nitrificacion
EA202092018A1 (ru) 2018-03-01 2021-02-01 Басф Агро Б.В. Фунгицидные композиции мефентрифлуконазола
EP3533333A1 (en) 2018-03-02 2019-09-04 Basf Se Fungicidal mixtures comprising pydiflumetofen
EP3533331A1 (en) 2018-03-02 2019-09-04 Basf Se Fungicidal mixtures comprising pydiflumetofen
EP3536150A1 (en) 2018-03-06 2019-09-11 Basf Se Fungicidal mixtures comprising fluxapyroxad
WO2019175712A1 (en) 2018-03-14 2019-09-19 Basf Corporation New uses for catechol molecules as inhibitors to glutathione s-transferase metabolic pathways
WO2019175713A1 (en) 2018-03-14 2019-09-19 Basf Corporation New catechol molecules and their use as inhibitors to p450 related metabolic pathways
WO2019219464A1 (en) 2018-05-15 2019-11-21 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
KR102727205B1 (ko) * 2018-05-15 2024-11-06 바스프 에스이 벤즈피리목산 및 옥사조술필을 포함하는 혼합물 및 이의 용도 및 이의 적용 방법
WO2019224092A1 (en) 2018-05-22 2019-11-28 Basf Se Pesticidally active c15-derivatives of ginkgolides
WO2020002472A1 (en) 2018-06-28 2020-01-02 Basf Se Use of alkynylthiophenes as nitrification inhibitors
PL3826983T3 (pl) 2018-07-23 2024-09-09 Basf Se Zastosowanie podstawionych 2-tiazolin jako inhibitorów nitryfikacji
CN112424147B (zh) 2018-07-23 2023-06-30 巴斯夫欧洲公司 取代噻唑烷化合物作为硝化抑制剂的用途
AR115984A1 (es) 2018-08-17 2021-03-17 Pi Industries Ltd Compuestos de 1,2-ditiolona y sus usos
EP3613736A1 (en) 2018-08-22 2020-02-26 Basf Se Substituted glutarimide derivatives
EP3628158A1 (en) 2018-09-28 2020-04-01 Basf Se Pesticidal mixture comprising a mesoionic compound and a biopesticide
AU2019348280A1 (en) 2018-09-28 2021-04-22 Basf Se Method of controlling pests by seed treatment application of a mesoionic compound or mixture thereof
EP3628156A1 (en) 2018-09-28 2020-04-01 Basf Se Method for controlling pests of sugarcane, citrus, rapeseed, and potato plants
EP3628157A1 (en) 2018-09-28 2020-04-01 Basf Se Method of controlling insecticide resistant insects and virus transmission to plants
EP3643705A1 (en) 2018-10-24 2020-04-29 Basf Se Pesticidal compounds
WO2020095161A1 (en) 2018-11-05 2020-05-14 Pi Industries Ltd. Nitrone compounds and use thereof
EP3670501A1 (en) 2018-12-17 2020-06-24 Basf Se Substituted [1,2,4]triazole compounds as fungicides
EP3696177A1 (en) 2019-02-12 2020-08-19 Basf Se Heterocyclic compounds for the control of invertebrate pests
KR20210131350A (ko) 2019-02-20 2021-11-02 바스프 에스이 피라졸 화합물을 포함하는 살충 혼합물
EP3730489A1 (en) 2019-04-25 2020-10-28 Basf Se Heteroaryl compounds as agrochemical fungicides
EP3769623A1 (en) 2019-07-22 2021-01-27 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
BR112021019416A2 (pt) 2019-05-29 2021-12-07 Basf Se Compostos, composição, métodos de proteção de safras e de combate, controle, prevenção ou proteção contra infestações, método não terapêutico de tratamento de animais infestados, semente e uso
WO2020244970A1 (en) 2019-06-06 2020-12-10 Basf Se New carbocyclic pyridine carboxamides
WO2020244969A1 (en) 2019-06-06 2020-12-10 Basf Se Pyridine derivatives and their use as fungicides
WO2020244968A1 (en) 2019-06-06 2020-12-10 Basf Se Fungicidal n-(pyrid-3-yl)carboxamides
EP3766879A1 (en) 2019-07-19 2021-01-20 Basf Se Pesticidal pyrazole derivatives
WO2021063735A1 (en) 2019-10-02 2021-04-08 Basf Se New bicyclic pyridine derivatives
WO2021063736A1 (en) 2019-10-02 2021-04-08 Basf Se Bicyclic pyridine derivatives
JP7785003B2 (ja) 2019-12-23 2025-12-12 ビーエーエスエフ ソシエタス・ヨーロピア 酵素によって増強された農薬化合物の根からの取り込み
WO2021170463A1 (en) 2020-02-28 2021-09-02 BASF Agro B.V. Methods and uses of a mixture comprising alpha-cypermethrin and dinotefuran for controlling invertebrate pests in turf
BR112022017563A2 (pt) 2020-03-04 2022-10-18 Basf Se Uso de compostos, composição agroquímica e método para combater fungos fitopatogênicos nocivos
BR112022020612A2 (pt) 2020-04-14 2022-11-29 Basf Se Mistura fungicida, composição agroquímica, uso não terapêutico da mistura e método para controlar fungos fitopatogênicos nocivos
EP3903582A1 (en) 2020-04-28 2021-11-03 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors ii
EP3903584A1 (en) 2020-04-28 2021-11-03 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors iv
BR112022021631A2 (pt) 2020-04-28 2022-12-06 Basf Se Compostos, composição, métodos para combater ou controlar pragas invertebradas, para proteger plantas em crescimento e para tratar ou proteger um animal, semente e uso de um composto
EP3903583A1 (en) 2020-04-28 2021-11-03 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors iii
EP3903581A1 (en) 2020-04-28 2021-11-03 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors i
EP3909950A1 (en) 2020-05-13 2021-11-17 Basf Se Heterocyclic compounds for the control of invertebrate pests
EP3945089A1 (en) 2020-07-31 2022-02-02 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors v
WO2021249800A1 (en) 2020-06-10 2021-12-16 Basf Se Substituted [1,2,4]triazole compounds as fungicides
EP3960727A1 (en) 2020-08-28 2022-03-02 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors vi
EP3939961A1 (en) 2020-07-16 2022-01-19 Basf Se Strobilurin type compounds and their use for combating phytopathogenic fungi
WO2022017836A1 (en) 2020-07-20 2022-01-27 BASF Agro B.V. Fungicidal compositions comprising (r)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1- (1,2,4-triazol-1-yl)propan-2-ol
EP3970494A1 (en) 2020-09-21 2022-03-23 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors viii
TW202229241A (zh) 2020-09-26 2022-08-01 印度商皮埃企業有限公司 殺線蟲化合物及其用途
US20230397607A1 (en) 2020-10-27 2023-12-14 BASF Agro B.V. Compositions comprising mefentrifluconazole
WO2022090071A1 (en) 2020-11-02 2022-05-05 Basf Se Use of mefenpyr-diethyl for controlling phytopathogenic fungi
WO2022090069A1 (en) 2020-11-02 2022-05-05 Basf Se Compositions comprising mefenpyr-diethyl
WO2022106304A1 (en) 2020-11-23 2022-05-27 BASF Agro B.V. Compositions comprising mefentrifluconazole
EP4018830A1 (en) 2020-12-23 2022-06-29 Basf Se Pesticidal mixtures
EP4288398A1 (en) 2021-02-02 2023-12-13 Basf Se Synergistic action of dcd and alkoxypyrazoles as nitrification inhibitors
EP4043444A1 (en) 2021-02-11 2022-08-17 Basf Se Substituted isoxazoline derivatives
BR112023023592A2 (pt) 2021-05-11 2024-03-12 Basf Se Mistura fungicida, composição agroquímica, uso da mistura e método para controlar fungos nocivos fitopatogênicos
WO2022243107A1 (en) 2021-05-18 2022-11-24 Basf Se New substituted pyridines as fungicides
CN117355520A (zh) 2021-05-18 2024-01-05 巴斯夫欧洲公司 用作杀真菌剂的新型取代喹啉类
US20240270727A1 (en) 2021-05-18 2024-08-15 Basf Se New substituted pyridines as fungicide
US20240270658A1 (en) 2021-05-21 2024-08-15 Basf Se Use of an N-Functionalized Alkoxy Pyrazole Compound as Nitrification Inhibitor
US20240351959A1 (en) 2021-05-21 2024-10-24 Basf Se Use of ethynylpyridine compounds as nitrification inhibitors
EP4094579A1 (en) 2021-05-28 2022-11-30 Basf Se Pesticidal mixtures comprising metyltetraprole
CA3223077A1 (en) 2021-06-21 2022-12-29 Barbara Nave Metal-organic frameworks with pyrazole-based building blocks
EP4119547A1 (en) 2021-07-12 2023-01-18 Basf Se Triazole compounds for the control of invertebrate pests
AU2022321882A1 (en) 2021-08-02 2024-02-15 Basf Se (3-pirydyl)-quinazoline
US20250019361A1 (en) 2021-08-02 2025-01-16 Basf Se (3-quinolyl)-quinazoline
EP4140986A1 (en) 2021-08-23 2023-03-01 Basf Se Pyrazine compounds for the control of invertebrate pests
EP4140995A1 (en) 2021-08-27 2023-03-01 Basf Se Pyrazine compounds for the control of invertebrate pests
EP4151631A1 (en) 2021-09-20 2023-03-22 Basf Se Heterocyclic compounds for the control of invertebrate pests
WO2023072671A1 (en) 2021-10-28 2023-05-04 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors ix
WO2023072670A1 (en) 2021-10-28 2023-05-04 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors x
EP4194453A1 (en) 2021-12-08 2023-06-14 Basf Se Pyrazine compounds for the control of invertebrate pests
EP4198033A1 (en) 2021-12-14 2023-06-21 Basf Se Heterocyclic compounds for the control of invertebrate pests
EP4198023A1 (en) 2021-12-16 2023-06-21 Basf Se Pesticidally active thiosemicarbazone compounds
EP4238971A1 (en) 2022-03-02 2023-09-06 Basf Se Substituted isoxazoline derivatives
WO2023203066A1 (en) 2022-04-21 2023-10-26 Basf Se Synergistic action as nitrification inhibitors of dcd oligomers with alkoxypyrazole and its oligomers
AU2023317620A1 (en) 2022-08-02 2025-02-13 Basf Se Pyrazolo pesticidal compounds
EP4342885A1 (en) 2022-09-20 2024-03-27 Basf Se N-(3-(aminomethyl)-phenyl)-5-(4-phenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-amine derivatives and similar compounds as pesticides
EP4361126A1 (en) 2022-10-24 2024-05-01 Basf Se Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors xv
WO2024104813A1 (en) 2022-11-14 2024-05-23 Basf Se Fungicidal mixture comprising substituted pyridines
EP4619399A1 (en) 2022-11-16 2025-09-24 Basf Se New substituted tetrahydrobenzoxazepine
CN120202195A (zh) 2022-11-16 2025-06-24 巴斯夫欧洲公司 作为杀真菌剂的取代的苯并二氮杂䓬类
AU2023381249A1 (en) 2022-11-16 2025-05-29 Basf Se Fungicidal mixture comprising substituted pyridines
WO2024104822A1 (en) 2022-11-16 2024-05-23 Basf Se Substituted tetrahydrobenzodiazepine as fungicides
EP4619393A1 (en) 2022-11-16 2025-09-24 Basf Se Substituted benzodiazepines as fungicides
EP4389210A1 (en) 2022-12-21 2024-06-26 Basf Se Heteroaryl compounds for the control of invertebrate pests
WO2024165343A1 (en) 2023-02-08 2024-08-15 Basf Se New substituted quinoline compounds for combatitng phytopathogenic fungi
AU2024238668A1 (en) 2023-03-17 2025-09-25 Basf Se Substituted pyridyl/pyrazidyl dihydrobenzothiazepine compounds for combatting phytopathogenic fungi
EP4455137A1 (en) 2023-04-24 2024-10-30 Basf Se Pyrimidine compounds for the control of invertebrate pests
CN121335882A (zh) 2023-04-26 2026-01-13 巴斯夫欧洲公司 嗜球果伞素型化合物用于对抗含有线粒体细胞色素b蛋白中赋予对Qo抑制剂XVI的抗性的氨基酸取代F129L的植物病原真菌的用途
EP4467535A1 (en) 2023-05-25 2024-11-27 Basf Se Lactam pesticidal compounds
EP4488270A1 (en) 2023-07-06 2025-01-08 Basf Se Triazole compounds for the control of invertebrate pests
EP4488269A1 (en) 2023-07-06 2025-01-08 Basf Se Triazole compounds for the control of invertebrate pests
EP4488273A1 (en) 2023-07-06 2025-01-08 Basf Se Triazole compounds for the control of invertebrate pests
EP4574819A1 (en) 2023-12-22 2025-06-25 Basf Se Diazinone compounds for the control of invertebrate pests
EP4640052A1 (en) 2024-04-24 2025-10-29 Basf Se Mixtures of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors with at least one further pesticide i
WO2025223904A1 (en) 2024-04-24 2025-10-30 Basf Se Mixtures of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors with at least one further pesticide i
WO2026021911A1 (en) 2024-07-23 2026-01-29 Basf Se New substituted benzothiazine pyridine compounds for combatting phytopathogenic fungi
WO2026021909A1 (en) 2024-07-23 2026-01-29 Basf Se New substituted benzothiazine pyridine compounds for combatting phytopathogenic fungi
WO2026021910A1 (en) 2024-07-23 2026-01-29 Basf Se New substituted benzothiazine pyridine compounds for combatting phytopathogenic fungi
WO2026021912A1 (en) 2024-07-23 2026-01-29 Basf Se New substituted benzothiazine pyridine compounds for combatting phytopathogenic fungi

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3545319A1 (de) * 1985-12-20 1987-06-25 Basf Ag Acrylsaeureester und fungizide, die diese verbindungen enthalten

Also Published As

Publication number Publication date
BRPI0409037A (pt) 2006-03-28
ZA200508026B (en) 2006-10-25
TR200503847T1 (tr) 2006-04-21
WO2004084632A1 (en) 2004-10-07
AU2004224838A1 (en) 2004-10-07
CN1456054A (zh) 2003-11-19

Similar Documents

Publication Publication Date Title
CN1201657C (zh) 甲氧基丙烯酸甲酯类化合物杀菌剂
CN1553770A (zh) 以芳基脒衍生物和已知杀真菌化合物为主剂的杀真菌组合物
CN1917760A (zh) 包含吡啶基乙基苯甲酰胺衍生物和能抑制麦角甾醇生物合成的化合物的杀真菌组合物
KR20150100865A (ko) 곡류에서의 진균 방제를 위한 상승작용적 살진균 혼합물
CN101080170A (zh) 在豆科植物中防治真菌病害的方法
CN101052302A (zh) 农业或园艺杀菌组合物以及控制植物病害的方法
CN1078043C (zh) 杀菌剂与杀虫剂的复配物,含该复配物的组合物及其用途
TW200808183A (en) Azolymethyloxiranes, their use for controlling phytopathogenic fungi, and compositions comprising them
JP2003522100A (ja) 殺菌剤６−（２−ハロ−４−アルコキシフェニル）−トリアゾロピリミジン
CN100340167C (zh) 增效组合物
CN1918125A (zh) 包含吡啶基乙基苯甲酰胺衍生物和能抑制植物病原真菌生物中呼吸链的电子传递的化合物的杀真菌组合物
CN1066610C (zh) 杀微生物剂
CN1284456C (zh) 以吡啶甲基苯甲酰胺衍生物和缬酰胺衍生物为主剂的杀真菌组合物
CN1074251C (zh) 杀真菌组合物
CN1250079C (zh) 杀真菌组合物
CN1250080C (zh) 基于霜霉威和吡啶基甲基苯甲酰胺衍生物的杀真菌组合物
UA72459C2 (en) 6-(2-halo-4-alkoxyphenyl)triazolepyrimidines, a method for preparation and a fungicide composition
CN1968604A (zh) 除草组合物
CN1307877C (zh) 包含咪唑菌酮和土菌消的杀真菌组合物
CN1393134A (zh) 含氰菌胺杀菌剂、杀虫剂组合物
CN1163143C (zh) 杀真菌混合物
CN1565182A (zh) 氟吗啉与烯肟菌酯及含有增效剂的杀菌组合物
CN1536962A (zh) 植物病原菌防治用组合物以及植物病原菌的防治方法
CN1711022A (zh) 用于防治稻病原体的杀真菌混合物
CN1212767C (zh) 杀真菌组合物

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C56 Change in the name or address of the patentee

Owner name: ZHEJIANG CHEM-TECH GROUP CO., LTD.

Free format text: FORMER NAME: CHEMICAL INDUSTRY INST. OF ZHEJIANG PROV.

Owner name: ZHEJIANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY C

Free format text: FORMER NAME: ZHEJIANG CHEM-TECH GROUP CO., LTD.

CP01 Change in the name or title of a patent holder

Address after: 310023, Zhejiang, Hangzhou Province, leaving the camp door

Patentee after: ZHEJIANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Ltd.

Address before: 310023, Zhejiang, Hangzhou Province, leaving the camp door

Patentee before: ZHEJIANG CHEM TECH GROUP Co.,Ltd.

Address after: 310023, Zhejiang, Hangzhou Province, leaving the camp door

Patentee after: ZHEJIANG CHEM TECH GROUP Co.,Ltd.

Address before: 310023, Zhejiang, Hangzhou Province, leaving the camp door

Patentee before: ZHEJIANG CHEMICAL INDUSTRY Research Institute

ASS Succession or assignment of patent right

Owner name: ZHEJIANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY,

Effective date: 20121012

Owner name: SINOCHEM LANTIAN CO., LTD.

Free format text: FORMER OWNER: ZHEJIANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY, LTD.

Effective date: 20121012

C41 Transfer of patent application or patent right or utility model
COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: 310023 HANGZHOU, ZHEJIANG PROVINCE TO: 310051 HANGZHOU, ZHEJIANG PROVINCE

TR01 Transfer of patent right

Effective date of registration: 20121012

Address after: 310051 Binjiang District Jiangnan Road, Zhejiang, No. 96, No.

Patentee after: SINOCHEM LANTIAN Co.,Ltd.

Patentee after: ZHEJIANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Ltd.

Address before: 310023, Zhejiang, Hangzhou Province, leaving the camp door

Patentee before: ZHEJIANG RESEARCH INSTITUTE OF CHEMICAL INDUSTRY Ltd.

PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: Methyl Methoxyacrylate compound fungicide

Effective date of registration: 20211011

Granted publication date: 20050518

Pledgee: Industrial and Commercial Bank of China Limited Hangzhou Zhaohui sub branch

Pledgor: SINOCHEM LANTIAN Co.,Ltd.

Registration number: Y2021330001830

PE01 Entry into force of the registration of the contract for pledge of patent right
PC01 Cancellation of the registration of the contract for pledge of patent right

Date of cancellation: 20220507

Granted publication date: 20050518

Pledgee: Industrial and Commercial Bank of China Limited Hangzhou Zhaohui sub branch

Pledgor: SINOCHEM LANTIAN Co.,Ltd.

Registration number: Y2021330001830

PC01 Cancellation of the registration of the contract for pledge of patent right
CX01 Expiry of patent term

Granted publication date: 20050518

CX01 Expiry of patent term