CN1111090A - 杀真菌混合物 - Google Patents
杀真菌混合物 Download PDFInfo
- Publication number
- CN1111090A CN1111090A CN94116391.1A CN94116391A CN1111090A CN 1111090 A CN1111090 A CN 1111090A CN 94116391 A CN94116391 A CN 94116391A CN 1111090 A CN1111090 A CN 1111090A
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- Prior art keywords
- ethylenebis
- compound
- acid
- chemical compounds
- mixture
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Abstract
包含增效活性量的下列组分的杀真菌混合物：
a)式I肟醚甲酰胺
b)选自
-亚乙基双(二硫代氨基甲酸镁)(锌配合物)(IIa)
-亚乙基双(二硫代氨基甲酸镁)(IIb)
-亚乙基双(二硫代氨基甲酸锌)氨合物(IIc)和
-亚乙基双(二硫代氨基甲酸锌)(IId)
的二硫代氨基甲酸盐。
Description
本发明涉及包含增效活性量的下列组分的杀真菌混合物：
a）式Ⅰ肟醚甲酰胺
b）选自
-亚乙基双（二硫代氨基甲酸镁）（锌配合物）（Ⅱa）
-亚乙基双（二硫代氨基甲酸镁）（Ⅱb）
-亚乙基双（二硫代氨基甲酸锌）氨合物（Ⅱc）和
-亚乙基双（二硫代氨基甲酸锌）（Ⅱd）的二硫代氨基甲酸盐。
本发明还涉及用化合物Ⅰ和Ⅱ的混合物控制有害真菌的方法；以及化合物Ⅰ和化合物Ⅱ在此类混合物的生产中的用途。
文献中公开了式Ⅰ化合物、其制备方法及其抗有害真菌的作用（EP-A 477631）。
类似地，人们也知道二硫代氨基甲酸盐Ⅱ（Ⅱa：俗名：mancozeb，US-A 3379610；Ⅱb：俗名：maneb，US-A 2504404；Ⅱc：曾用俗名metriam,US-A 3248400；Ⅱd：俗名zineb，US-A 2457674，它们的制备方法及其抗有害真菌的作用。
就减少施用比率和拓宽已知化合物的作用谱而言，本发明是基于这样的混合物的：它具有较小的活性化合物总施用量和增强的抗有害真菌作用（增效混合物）。
因此，发现了本文开头定义的混合物，还发现同时合并或分别施用化合物Ⅰ和化合物Ⅱ或者依次施用化合物Ⅰ和化合物Ⅱ与独立施用各化合物相比，能更好地控制有害真菌。
式Ⅰ化合物相对于C=X双键（相对于羧酸官能团）可以有E或Z构形。因此，它可以纯E或Z异构体或以E/Z异构体混合物的形式用在本发明混合物中。优选使用E/Z异构体混合物或E异构体，特别优选E异构体。
由于NH基是碱性的，化合物Ⅰ能够与无机或有机酸或者与金属离子形成盐或加成物。
无机酸的例子有氢卤酸如氢氟酸、氢氯盐、氢溴酸和氢碘酸、硫酸、磷酸和硝酸。
适宜的有机酸是例如甲酸、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、烷磺酸（具有1-20个碳原子的直链或支链烷基的磺酸）、芳磺酸或二磺酸（带有1个或两个磺酸基的苯基和萘基之类的芳香基团）、烷磷酸（具有1-20个碳原子的直链或支链烷基的磷酸）、芳磷酸或二磷酸（带有1个或两个磷酸基的苯基和萘基之类的芳香基团），所述烷基和芳基还可再带有取代基，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。
适宜的金属离子具体是第二类主族元素离子，尤其是钙和镁离子；第三和第四类主族元素离子，尤其是铝、锡和铅离子；以及第一到第八类副族元素离子，尤其是铬、锰、铁、钴、镍、铜、锌等。特别优选第四类副族元素的离子。在这种情况下，金属可以不同的合适的化合价存在。
最好在混合物的制备中使用纯的活性化合物Ⅰ和Ⅱ，必要时还可在混合物中加进其它抗有害真菌或其它害虫（如昆虫、蜘蛛或线虫）的活性化合物，或者加进除草剂或生长调节活性化合物或肥料。
化合物Ⅰ和Ⅱ的混合物以及同时联合或分别使用化合物Ⅰ和Ⅱ对于广谱的植物病源性真菌特别是子囊菌纲和担子菌纲的真菌具有突出的作用。在某些情况下，它们是系统活性的，因而也可用作落叶剂和土壤杀真菌剂。
它们对于控制各种作物如棉花、蔬菜（例如：黄瓜、菜豆和南瓜）、大麦、青草、燕麦、咖啡、玉米、果树、水稻、黑麦、大豆、葡萄、小麦、观赏植物、甘蔗和许多种子上的许多真菌都特别重要。
特别是，它们适用于下列植物病原性真菌的防治：谷类上的禾白粉菌，南瓜上的Erysiha cichoracearum和Sphaerotheca fuliginea，苹果上的Podosphaera leucotricha，谷类上的柄锈菌属，棉花和草坪上的丝核菌属，谷类和甘蔗上的黑粉菌属，苹果上的黑星菌属（痂）、谷类上的长蠕孢属，小麦上的Septoria nodorum，草梅和葡萄树上的Botrytis cinerea（灰霉），落花生上的Cercospora archidicola，小麦和大麦上的Pseudocercosporella herpotrichoides，水稻上的Pyricularia oryzae，葡萄树上的Plasmopara viticola，蔬菜和水果上的交链孢菌属和镰孢菌属和轮枝孢菌属。
它还适用于材料保护（例如，木材保藏），例如用来抗Peacilomyces variotii。
化合物Ⅰ和Ⅱ可同时联合或分别施用，或先后施用，分别施用时，其先后顺序一般不影响防治效果。
通常，化合物Ⅰ和Ⅱ施用时重量比为2000∶1至5∶1，优选1000∶1至5∶1，特别是500∶1至5∶1（Ⅱ∶Ⅰ）。
根据期望达到的效果，本发明混合物的施用比率为化合物Ⅰ∶0.005-0.5kg/英亩，优选0.01-0.5kg/英亩，特别是0.01-0.3kg/英亩，化合物Ⅱ的施用比率相应地为0.1-10kg/英亩，优选0.5-5kg/英亩，特别是1-4kg/英亩。
在处理种子时，通常混合物的施用比率为0.001-100g/kg种子，优选0.01-50g/kg，特别是0.01-10g/kg。
如果用来防治植物病源性有害真菌，则在将植物播种前后或在植物出苗前后将化合物Ⅰ和Ⅱ联合或分别或者将化合物Ⅰ与化合物Ⅱ的混合物喷洒或撒播在种子上。
本发明的杀菌增效混合物和化合物Ⅰ和Ⅱ可制成例如可直接喷洒溶液、粉剂和混悬液的形式，或者高百分比水溶液、油溶液或其它混悬液、分散体、乳液、油分散体、糊、撒粉组合物、撒施组合物或颗粒剂的形式，以喷洒、喷雾、撒粉、撒施或浇水的方式用药。其施用形式取决于目标用途。在各种情况下应当确保本发明混合物尽可能精细均匀地分散。
可用本身已知的方法例如通过加入溶剂和/或载体的方式来制备所述制剂。通常往制剂里混入添加剂如乳化剂或分散剂。
适宜的表面活性物质是芳族磺酸和脂肪酸的碱金属、碱土金属或铵盐，所述芳族磺酸的例子有木素磺酸、苯酚磺酸、萘磺酸和二丁基萘磺酸；烷基和烷芳基磺酸酯；烷基·月桂基醚和脂肪醇磺酸酯；以及磺化的十六、十七和十八烷醇或脂肪醇甘醇醚盐，磺化的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；聚氧化乙烯辛基苯酚醚；乙氧基化的异辛基、辛基或壬基苯酚、烷基苯酚或三丁基苯酚聚乙二醇醚；烷芳基聚醚醇，异十三烷醇；脂肪醇-环氧乙烷缩合物；乙氧基化的蓖麻油；聚氧化乙烯或聚氧化丙烯烷基醚；月桂醇聚乙二醇醚乙酸酯；山梨醇酯，木素亚硫酸废液或甲基纤维素。
将化合物Ⅰ或Ⅱ或化合物Ⅰ与Ⅱ的混合物与固体载体混合或一同研磨可制得粉剂、撒施组合物和撒粉组合物。
将一种或多种活性化合物粘合到固体载体上通常可制得颗粒剂（例如：包衣的、浸透的或均匀的颗粒剂）。
所用的填料或固体载体是，例如矿物土如硅胶、硅酸、硅酸盐、滑石、高岭土、石灰石、石灰、白垩、粘土、黄土、白云石、硅藻土、氧化镁、塑料粉，和肥料如硫酸铵、磷酸铵、硝酸铵、尿素，和蔬菜产品如谷粉、树皮粉、木粉和果壳粉、纤维素粉或其它固体载体。
该制剂通常含有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。在此情况下，所用活性化合物的纯度为90-100%，最好为95-100%（按NMR谱或HPLC测定）。
化合物Ⅰ或Ⅱ及混合物或相应制剂可通过用杀真菌活性量的混合物或化合物Ⅰ和Ⅱ（分别施用时）处理有害真菌或要求无真菌的植物、种子、土壤、表面、材料或空间。施用可在受真菌侵害之前或之后进行。
本发明混合物抗有害真菌的增效活性实例。
通过下列试验可以显示出所述化合物和混合物的杀真菌作用。
分别或联合制备了活性化合物在下述混合物中的20%浓度乳液：70%（重量）环已酮，20%（重量）Nekanil
LN(Lutensol
A96,润湿剂，基于乙氧基化的烷基苯酚而具有乳化剂和分散剂的作用）和10%（重量）Emulphor
EL(Emulan
EL，基于乙氧基化的脂肪醇的乳化剂）。用水稀释至所需浓度。
测定受害叶子面积百分数进行评估。将这些百分数值转变为作用程度。按照。Colby公式[R.S.Colby，Weeds15，（1967）20-20]确定预期的活性化合物混合物的作用程度，并与观察到的作用程度比较。
Colby公式 E=x+y-x×y/100
E是预期的作用程度，表示为未处理对照组的百分数，活性化合物在混合物中的浓度为a和b。
x是作用程度，表示为未处理对照组的百分数，所用活性化合物A的浓度为a。
y是作用程度，表示为未处理对照组的百分数，所用活性化合物B的浓度为b。
作用程度为0时，经处理的植物所受侵害与未处理的对照植物的相同；作用程度为100时，经处理的植物未显示出受侵害。
抗小麦上的Fusarium culmorum活性
用含80%活性化合物和20%乳化剂（干重）的水喷洒液喷洒生长在盆中的小麦（Kanzler）的初生叶上，直至有液滴落下。第二天，用Fusarium Culmorum的孢子混悬液接种，然后置于高空气湿度（>90%）的22-24℃的温室中。6天之后，用眼观察评估病害的发展程度。
*）用Colby公式计算
从试验结果得知，观察到的所有比例的混合物的作用程度都高于Colby公式预计的作用程度。
Claims (12)
1、包含增效活性量的下列组分的杀真菌混合物：
a)式Ⅰ肟醚甲酰胺
b)选自
-亚乙基双(二硫代氨基甲酸镁)(锌配合物)(Ⅱa)
-亚乙基双(二硫代氨基甲酸镁)(Ⅱb)
-亚乙基双(二硫代氨基甲酸锌)氨合物(Ⅱc)和
-亚乙基双(二硫代氨基甲酸锌)(Ⅱd)的二硫代氨基甲酸盐。
2、如权利要求1所述的杀真菌混合物，它含有权利要求1所述的式Ⅰ肟醚甲酰胺和亚乙基双（二硫代氨基甲酸镁）（锌配合物）（Ⅱa）。
3、如权利要求1所述的杀真菌混合物，它含有权利要求1所述的式Ⅰ肟醚甲醚胺和亚乙基双（二硫代氨基甲酸镁）（Ⅱb）。
4、如权利要求1所述的杀真菌混合物，它含有权利要求1所述的式Ⅰ肟醚甲酰胺和亚乙基双（二硫代氨基甲酸锌）氨合物（Ⅱc）。
5、如权利要求1所述的杀真菌混合物，它含有权利要求1所述的式Ⅰ肟醚甲酰胺和亚乙基双（二硫代氨基甲酸锌）（Ⅱd）。
6、如权利要求1所述的混合物，其中化合物Ⅱ与化合物Ⅰ的重量比为2000∶1至5∶1。
7、防治有害真菌的方法，它包括用权利要求1所述的式Ⅰ化合物和式Ⅱ化合物处理有害真菌、其环境或者要求无真菌的植物、种子、土壤、表面、材料或空间。
8、如权利要求7的方法，其中权利要求1所述的化合物Ⅰ和Ⅱ同时合并或分别施用，或先后施用。
9、如权利要求7的方法，其中用0.005-0.5kg/英亩权利要求1所述的化合物Ⅰ处理有害真菌、其环境或者要求无真菌的植物、种子、土壤、表面、材料或空间。
10、如权利要求7的方法，其中用0.1-10kg/英亩权利要求1所述的化合物Ⅱ处理有害真菌、其环境或者要求无真菌的植物、种子、土壤、表面、材料或空间。
11、使用权利要求1所述的化合物Ⅰ来生产权利要求1所述的杀真剂活性的增效混合物的方法。
12、使用权利要求1所述的化合物Ⅱ来生产权利要求1所述的杀真剂活性的增效混合物的方法。
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4332569.6 | 1993-09-24 | ||
| DE4332569 | 1993-09-24 | ||
| DEP4406645.7 | 1994-03-01 | ||
| DE4406645 | 1994-03-01 | ||
| US08/364,930 US5504110A (en) | 1993-09-24 | 1994-12-28 | Fungicidal mixtures |
| CN95101893.0A CN1126029A (zh) | 1993-09-24 | 1995-01-03 | 杀真菌混合物 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1111090A true CN1111090A (zh) | 1995-11-08 |
Family
ID=37101996
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94116391.1A Pending CN1111090A (zh) | 1993-09-24 | 1994-09-24 | 杀真菌混合物 |
| CN95101893.0A Pending CN1126029A (zh) | 1993-09-24 | 1995-01-03 | 杀真菌混合物 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95101893.0A Pending CN1126029A (zh) | 1993-09-24 | 1995-01-03 | 杀真菌混合物 |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3630724B2 (zh) |
| CN (2) | CN1111090A (zh) |
| CA (1) | CA2132048A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100352347C (zh) * | 2003-06-10 | 2007-12-05 | 沈阳化工研究院 | 烯肟菌酯与硫代氨基甲酸盐的杀菌组合物 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR9610003A (pt) * | 1995-08-17 | 1999-07-06 | Basf Ag | Mistura fungicida processo para controlar fungos nocivos e uso de um composto |
-
1994
- 1994-09-14 CA CA002132048A patent/CA2132048A1/en not_active Abandoned
- 1994-09-16 JP JP22182794A patent/JP3630724B2/ja not_active Expired - Fee Related
- 1994-09-24 CN CN94116391.1A patent/CN1111090A/zh active Pending
-
1995
- 1995-01-03 CN CN95101893.0A patent/CN1126029A/zh active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100352347C (zh) * | 2003-06-10 | 2007-12-05 | 沈阳化工研究院 | 烯肟菌酯与硫代氨基甲酸盐的杀菌组合物 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07165509A (ja) | 1995-06-27 |
| JP3630724B2 (ja) | 2005-03-23 |
| CN1126029A (zh) | 1996-07-10 |
| CA2132048A1 (en) | 1995-03-25 |
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