CN101253862A - 杀真菌混合物 - Google Patents
杀真菌混合物 Download PDFInfo
- Publication number
- CN101253862A CN101253862A CNA2008100096761A CN200810009676A CN101253862A CN 101253862 A CN101253862 A CN 101253862A CN A2008100096761 A CNA2008100096761 A CN A2008100096761A CN 200810009676 A CN200810009676 A CN 200810009676A CN 101253862 A CN101253862 A CN 101253862A
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- CN
- China
- Prior art keywords
- compound
- mixture
- acid
- fungicidal mixture
- harmful fungoid
- 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.)
- Granted
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- 230000000855 fungicidal effect Effects 0.000 title claims abstract description 8
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- 150000001875 compounds Chemical class 0.000 claims description 43
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- 238000002360 preparation method Methods 0.000 claims description 11
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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
- 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
- A01N37/44—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 nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
- A01N37/50—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 nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids the nitrogen atom being doubly bound to the carbon skeleton
Landscapes
- 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)
Abstract
本发明提供了一种杀真菌混合物，其中包含增效有效量的以下物质：a)具有结构式(I.a)或(I.b)的苯基苄基醚衍生物和b)(±)－(2－氯苯基)(4－氯苯基)(嘧啶－5－基)甲醇。
Description
本发明涉及一种杀真菌混合物，其中包含增效有效量的以下物质：
a)式I.a或I.b的苯基苄基醚衍生物
和
b)(±)-(2-氯苯基)(4-氯苯基)(嘧啶-5-基)甲醇
此外，本发明还涉及用化合物I(I.a和I.b)与化合物II的混合物来防治有害真菌的方法，以及化合物I和II在制备这种混合物时的应用。
化合物I、其制备方法及其抗有害真菌的活性已由文献公开(EP-A253213；EP-A254426)。
同样已知化合物II(GB-A-1218623；俗名Fenarimol)、其制备方法及其抗有害真菌的活性。
本发明的一个目的是提供在减少活性成分施用总量的同时具有改进的抗有害真菌作用的混合物(增效混合物)，以便减少施用量，并改善已知化合物的作用谱。
已经发现，该目的可由本文开头所定义的混合物实现。此外还发现，与单独施用单一化合物的情形相比，通过同时一起或分别施用化合物I和化合物II，或先后施用化合物I和化合物II能够更好地防治有害真菌。
化合物I和化合物II由于其碱性而能够与无机或有机酸或与金属离子形成盐或加合物。
无机酸的例子为氢卤酸，例如氢氟酸、氢氯酸、氢溴酸和氢碘酸、以及硫酸、磷酸和硝酸。
合适的有机酸为，例如甲酸、碳酸和链烷酸，如乙酸、三氟乙酸、三氯乙酸和丙酸，以及乙醇酸、硫氰酸、乳酸、琥珀酸、柠檬酸、苯甲酸、肉桂酸、草酸、烷基磺酸(含有1-20个碳原子的直链或支链烷基磺酸)，芳基磺酸或芳基二磺酸(其上连接有一个或两个磺基的芳基，如苯基和萘基)、烷基膦酸(具有1-20个碳原子的直链或支链烷基膦酸)、芳基膦酸或芳基二膦酸(其上连接有一个或两个磷酸基团的芳基，如苯基和萘基)，其中烷基或芳基还可携带其它取代基，例如，对-甲苯磺酸、水杨酸、对-氨基水杨酸、2-苯氧基苯甲酸，2-乙酰氧基苯甲酸等。
适当的金属离子尤为下列各族元素的离子：第二主族元素(特别是钙和镁)，第三和第四主族元素(特别是铝，锡和铅)，和第一到第八副族元素(特别是铬、锰、铁、钴、镍、铜、锌、以及其它)。特别优选的是第四周期副族元素的金属离子。这些金属可以是所能具有的各种价态。
在制备混合物时，优选采用纯活性成分I和II，其中根据需要可以混入对有害真菌或其它害虫(如昆虫，蛛形纲动物或线虫)具有活性的其它成份，或具有除草活性或植物生长调节活性的成份或肥料。
化合物I与II的混合物，或同时一起或分别使用化合物I和II，表现出对广谱的植物病原真菌，特别是属于子囊菌纲、担子菌纲、半知菌纲和藻状菌纲的真菌的优异活性。这些化合物中某些内吸地起作用，因而可用作叶面和土壤杀真菌剂。
它们对于防治各种作物，如棉花、蔬菜类(如黄瓜，菜豆，番茄，马铃薯和葫芦科)、大麦、牧草、燕麦、香蕉、咖啡、玉米、水果类、稻、黑麦、大豆、葡萄、小麦、观赏植物，甘蔗以及各种种子上的许多真菌特别重要。
它们特别适合于防治下列植物病原真菌：禾谷类上的禾白粉菌(Erysiphe graminis)、葫芦科上的二孢白粉菌(Erysiphecichoracearum)和苍耳单丝壳菌(Sphaerotheca fuliginea)、苹果上的苹果白粉病菌(Podosphaera leucotricha)、葡萄上的葡萄钩丝壳(Uncinula necator)，禾谷类上的柄锈菌(Puccinia)、棉花、稻和草坪上的丝核菌(Rhizoctonia)、禾谷类和甘蔗上的黑粉菌(Ustilago)、苹果上的苹果黑星菌(Venturia inaequalis)、禾谷类上的长蠕孢菌(Helminthosporium)、小麦上的颖枯病菌(Septoria nodorum)、草莓、蔬菜、观赏植物和葡萄上的灰霉菌(Botrytis cinera)、花生上的花生尾孢菌(Cercospora arachidicola)、小麦和大麦上的眼斑病菌(Pseudocercosporella herpotrichoides)、稻上的稻梨孢(Pyricularia oryzae)、马铃薯和蕃茄上的致病疫霉(Phytophthorainfestans)、葡萄上的葡萄生单轴霉(Plasmopara viticola)、啤酒花和黄瓜上的假霜霉属(Pseudoperonospora)、蔬菜和水果上的链格孢菌(Alternaria)，香蕉上的球腔菌(Mycosphaerella)，以及镰刀菌(Fusarium)和轮枝孢菌(Verticillium)。
而且，它们可用于保护材料(如，保护木材)免遭例如宛氏拟青霉(Paecilomyces variotii)的侵害。
化合物I与II可以同时，即，一起或分别施用，或先后施用，在分别施用的情形下，其施用次序一般对防治结果没有任何影响。
化合物I与II通常以10∶1-0.1∶1，优选5∶1-0.2∶1，特别是3∶1-0.3∶1的重量比使用。
本发明混合物的施用量，特别是在大田农作物的情况下，一般为0.01-8kg/ha，优选0.1-5kg/ha，尤为0.2-3.0kg/ha，这取决于所希望的效果。
化合物I的施用量为0.005-0.5kg/ha，优选0.05-0.5kg/ha，特别是0.05-0.3kg/ha。
相应地，就化合物II来说，施用量一般为0.05-0.5kg/ha，优选0.1-0.5kg/ha，特别是0.1-0.3kg/ha。
对于种子的处理，该混合物的施用量一般为0.001-250克/kg种子，优选0.01-100克/kg，特别是0.01-50克/kg种子。
如果要防治植物病原有害真菌，化合物I与II或化合物I与II的混合物可在植物播种之前或之后，或者在植物发芽之前或之后，通过对种子、植物或土壤喷雾或撒粉而分别或一起施用。
本发明的杀真菌增效混合物，或化合物I和II可以配制成，例如即可喷雾的溶液、粉剂和悬浮液形式，或高浓度的水性、油性或其它悬浮液、分散液、乳液，油分散体、糊剂、喷粉剂、撒播剂或颗粒剂的形式，并通过喷雾、弥雾、撒粉、撒播或浇泼使用。施用形式主要取决于预定用途，在任何情况下，应确保本发明混合物尽可能细微和均匀地分散。
这些制剂采用本领域公知的方式，如通过加入溶剂和/或载体来制备。通常将这种制剂与惰性添加剂，如乳化剂或分散剂混合。
合适的表面活性物质为下列酸的碱金属盐、碱土金属盐和铵盐：芳族磺酸，如木质素磺酸、苯酚磺酸、萘磺酸和二丁基萘磺酸，和脂肪酸、烷基-和烷芳基磺酸，烷基-、月桂基醚-和脂肪醇硫酸；以及硫酸化十六烷基醇、十七烷基醇和十八烷基醇或脂肪醇乙二醇醚的盐，磺化萘及其衍生物与甲醛的缩合产物，萘或萘磺酸与苯酚和甲醛的缩合产物，聚氧乙烯辛基苯酚醚，乙氧基化异辛基苯酚、辛基苯酚或壬基苯酚，烷基苯酚聚乙二醇醚、三丁基苯基聚乙二醇醚，烷芳基聚醚醇，异十三烷基醇、脂肪醇/氧化乙烯缩合物，乙氧基化蓖麻油，聚氧乙烯烷基醚或聚氧丙烯(原文如此)，十二烷基醇聚乙二醇醚乙酸盐，山梨醇酯，木素亚硫酸盐废液或甲基纤维素。
粉剂、撒播剂和喷粉剂可通过混合或一同研磨化合物I或II或化合物I和II的混合物与固体载体来制备。
颗粒剂(例如，包衣颗粒，浸渍颗粒和均质颗粒)通常通过将活性成分粘合到固体载体上来制备。
填料或固体载体是，例如矿质土类，如硅石、硅酸、硅胶、硅酸盐、滑石、高岭土、石灰石、石灰、白垩、红玄武土、黄土、陶土、白云石、硅藻土、硫酸钙、硫酸镁、氧化镁、研碎的合成物质、和肥料，如硫酸铵、磷酸铵、硝酸铵、尿素，以及植物源产物，如谷类作物粉末、树皮粉末、木材粉末和坚果壳粉，纤维素粉末或其它固体载体。
制剂通常包括0.1-95％重量，优选0.5-90％重量的化合物I或II之一或化合物I与II的混合物。所用活性成分的纯度为90％-100％，优选95％-100％(根据NMR谱或HPLC测定)。
本发明的组合物可以被调整成两部分，其中一部分含有在固体或液体载体中的式I化合物，另一部分含有在固体或液体载体中的式II化合物。
化合物I或II或其混合物或相应制剂通过用杀真菌有效量的混合物，或(在分别施用情形下)化合物I和II处理有害真菌、其聚集地、或欲免受它们侵染的植物、种子、土壤、表面，材料或空间的方式施用。
施用可在有害真菌侵染前或侵染后进行。
本发明混合物的增效作用可以通过下面的试验来证明：
将活性成分(单独或一起)配制成在63％重量环己酮与27％重量乳化剂的混合物中的10％乳液，然后用水稀释至所需浓度。
应用实施例1-抗小麦隐匿柄锈菌(Pucciniarecondita)(Weizenbraunrost)的活性。
用隐匿柄锈菌(Puccinia recondita)的孢子对“Fruehgold”品种的盆栽小麦秧苗叶撒粉。之后，将该盆在高大气湿度(90-95％)和20-22℃的室中放置24小时。期间，孢子萌发且发芽管(Keimschlaeuche)渗透到叶子组织中。第二天，用活性成分的含水制剂喷洒感染植物至滴流，所述制剂由包含10％活性化合物、63％环己酮和27％乳化剂的储备溶液制成。在喷液层干燥之后，将测试植物在温室中，在20-22℃和65-70％相对大气湿度下培养7天。之后，测定真菌在叶子上的感染程度。
通过测定感染叶面面积的百分数进行评价。将这些百分数换算成作用效力。作用效力(W)采用下述Abbot公式计算：
w＝(1-α/β)·100
α对应于处理植物的真菌感染，以％计，和
β对应于未处理(对照组)植物的真菌感染，以％计
效力0表示处理植物的感染程度与未处理对照植物感染程度相当；效力100表示处理植物未被感染。
采用Colby公式[R.S.Colby，Weeds，15，20-22(1967)]计算活性成分混合物的预期作用效力并与观测到的作用效力加以比较。
Colby公式：E＝x+y-x·y/100
E表示使用浓度分别为a和b的活性成分A和B的混合物的情况下的预期作用效力，以未处理对照组的％表示
x表示使用浓度为a的活性成分A的情况下的作用效力，以未处理对照组的％表示
y表示使用浓度为b的活性成分B的情况下的作用效力，以未处理对照组的％表示。
结果列于下表2和3中。
表2
| 实施例 | 活性成分 | 活性成分在喷雾液中的浓度(ppm) | 以未处理对照组的％表示的作用效力 |
| 1V | 对照组(未处理) | (100％感染) | 0 |
| 2V | Ia | 20010050 | 20200 |
| 3V | II | 2010 | 00 |
表3
| 实施例 | 按照本发明的混合物 | 所观察到的作用效力 | 计算出的作用效力*) |
| 4 | 200ppm Ia+20ppm II(混合物10∶1) | 65 | 20 |
| 5 | 100ppm Ia+20ppm II(混合物5∶1) | 70 | 20 |
| 6 | 50ppm Ia+10ppm Ib(混合物5∶1) | 35 | 0 |
*)采用Colby公式计算
试验结果表明，对于所有的混合比例，所观察的效力均超过采用Colby公式(来自Synerg 101.XLS)计算的效力。
Claims (6)
1.一种杀真菌混合物，其包含以下物质：
a)化合物I：式I.a的苯基苄基醚衍生物
和
b)化合物II：(±)-(2-氯苯基)(4-氯苯基)(嘧啶-5-基)甲醇
其中化合物I与化合物II的重量比为10∶1-0.1∶1。
2.根据权利要求1所要求的组合物，该组合物被调整成两部分，其中一部分含有在固体或液体载体中的权利要求1所述化合物I，而另一部分则含有在固体或液体载体中的权利要求1所述化合物II。
3.一种防治有害真菌的方法，该方法包括使用0.005-0.5kg/ha的权利要求1中所述化合物I和0.05-0.5kg/ha权利要求1所述化合物II处理有害真菌、有害真菌的聚集地、或欲免受有害真菌侵染的植物、种子、土壤、表面、材料或空间。
4.根据权利要求3所要求的方法，其中权利要求1所述化合物I和权利要求1所述化合物II同时一起或分别或先后施用。
5.权利要求1所述杀真菌混合物的制备方法，其中包括在该混合物中加入化合物I。
6.权利要求1所述杀真菌混合物的制备方法，其中包括在该混合物中加入化合物II。
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