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CN1109499C - 杀菌剂活性物质组合 - Google Patents

杀菌剂活性物质组合 Download PDF

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Publication number
CN1109499C
CN1109499C CN98804274A CN98804274A CN1109499C CN 1109499 C CN1109499 C CN 1109499C CN 98804274 A CN98804274 A CN 98804274A CN 98804274 A CN98804274 A CN 98804274A CN 1109499 C CN1109499 C CN 1109499C
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active compound
group
formula
weight ratio
derivatives
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CN98804274A
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CN1252690A (zh
Inventor
S·杜茨曼恩
K·斯泰泽尔
M·尧特拉特
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Bayer Pharma AG
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Bayer AG
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Abstract

本发明公开了式(I)的2-[2-(1-氯代环丙基)-3-(2-氯代苯基)-2-羟基丙基]-2，4-二氢-[1，2，4]-三唑-3-硫酮和本说明书中所列的活性物质组(1)到(24)的新的活性物质组合，它们具有很好的杀真菌性能。

Description

杀菌剂活性物质组合
本发明涉及新颖的杀菌活性化合物组合，包括已知的2-[2-(1-氯代环丙基)-3-(2-氯代苯基)-2-羟基丙基]-2，4-二氢-[1，2，4]-三唑-3-硫酮和其它已知的杀菌活性化合物，它们很适合于防治植物病原真菌。
文献中已描述过2-[2-(1-氯代环丙基)-3-(2-氯代苯基)-2-羟基丙基]-2，4-二氢-[1，2，4]-三唑-3-硫酮有较好的杀真菌性能(参见，WO96-16 048)，但在低使用剂量时，在某些情况下，此化合物的活性并不理想。
此外，据文献报道许多三唑衍生物、苯胺衍生物、二羰基亚胺和其它杂环可用于防治真菌(EP-A 0 040 345，DE-A 2 201 063，DE-A 2 324010，《农药手册》[Pesticide Manual]，第9版(1991)，第249和827页，US-A 3 903 090和EP-A 0 206 999)，在低使用剂量时，这些化合物的活性同样不能令人满意。
还已知1-[(6-氯-3-吡啶基)-甲基]-N-硝基-2-咪唑烷亚胺可用于动物害虫如昆虫的防治(参见，《农药手册》，第9版(1991)，第491页)，但迄今未见有关此化合物杀真菌性能的描述。
现已发现，本发明的新颖的活性化合物组合具有非常好的杀真菌性能，它们包括：
式(I)的2-[2-(1-氯代环丙基)-3-(2-氯代苯基)-2-羟基丙基]-2，4-二氢-[1，2，4]-三唑-3-硫酮
Figure C9880427400111
和
(1)式(II)的三唑衍生物
其中，X代表氯或苯基，Y代表
       或
Figure C9880427400123
和/或
(2)式(III)的三唑衍生物
Figure C9880427400124
                  (戊唑醇)
和/或
(3)式(IV)的苯胺衍生物
其中，R1代表氢或甲基，
和/或
(4)式(V)的N-[1-(4-氯-苯基)-乙基]-2，2-二氯-1-乙基-3-甲基环丙烷-甲酰胺
和/或
(5)式(VI)的亚丙基-1，2-双-(二硫代氨基甲酸)锌
           N＞＝1    (甲基代森锌)
和/或
(6)式(VII)的至少一种硫代氨基甲酸酯
Me＝Zn或Mn，或Zn和Mn的混合物
和/或
(7)式(VIII)的苯胺衍生物
和/或
(8)式(IX)的化合物
和/或
(9)式(X)的苯并噻二唑衍生物
和/或
(10)式(XI)的8-叔丁基-2-(N-乙基-N-正丙基-氨基)-甲基-1，4-二氧杂螺[5，4]癸烷
                  (螺噁茂胺)
和/或
(11)式(XII)的化合物
                  (腈嘧菌酯)
和/或
(12)式(XIII)的化合物
                  (亚胺菌)
和/或
(13)式(XIV)的化合物
Figure C9880427400161
和/或
(14)式(XV)的二羰基亚胺
                  (腐霉利)
和/或
(15)式(XVI)的嘧啶衍生物
其中，R2代表甲基或环丙基
和/或
(16)式(XVII)的苯基衍生物
Figure C9880427400171
                  (XVII)
                  (百菌清)
和/或
(17)式(XVIII)的吗啉衍生物
和/或
(18)式(XIX)的苯邻二甲酰亚胺衍生物
                  (灭菌丹)
和/或
(19)式(XX)的磷化合物
                  (三乙膦酸铝)
和/或
(20)式(XXI)的苯基吡咯衍生物
其中，R3和R4分别代表氯或一起代表基团-O-CF2-O-
和/或
(21)式(XXII)的1-[(6-氯-3-吡啶基)-甲基]-N-硝基-2-咪唑烷亚胺
Figure C9880427400183
                  (吡虫啉)
和/或
(22)式(XXIII)的苯基脲衍生物
Figure C9880427400184
                  (戊菌隆)
和/或
(23)式(XXIV)的苯甲酰胺衍生物
Figure C9880427400191
和/或
(24)式(XXV)的胍衍生物
Figure C9880427400192
其中，m代表整数0到5
R5代表氢(17％到23％)或基团
出人意外的是，本发明活性化合物组合的杀真菌活性比单个活性化合物的活性之和要高得多，因此，其中存在一种不可预知的、真正的协同作用而非活性的简单加和。
式(I)的2-[2-(1-氯代环丙基)-3-(2-氯代苯基)-2-羟基丙基]-2，4-二氢-[1，2，4]-三唑-3-硫酮为已知的(参见，WO 96-16 048)，该化合物可以以下式的“硫酮”式存在
或以下式的互变异构体“硫醇”式存在
Figure C9880427400202
为简单起见，在本发明中仅给出“硫酮”式。
式(II)包括化合物：
1-(4-氯-苯氧基)-3，3-二甲基-1-(1，2，4-三唑-1-基)-丁烷-2-酮
                                  (三唑酮)
1-(4-氯-苯氧基)-3，3-二甲基-1-(1，2，4-三唑-1-基)-丁烷-2-醇
                  (三唑醇)
和
1-(4-苯基-苯氧基)-3，3-二甲基-1-(1，2，4-三唑-1-基)-丁烷-2-醇
Figure C9880427400212
                  (双苯三唑醇)
式(IV)包括式(IVa)和(IVb)的苯胺衍生物：
                  (苯氟磺胺)
和
                  (甲苯氟磺胺)
式(V)的活性化合物很明显有三个不对称取代碳原子，因此产品可能以各种异构体的混合物存在，或以单一异构成分存在。特别优选的化合物有：
N-(R)-[1-(4-氯-苯基)-乙基]-(1S)-2，2-二氯-1-乙基-3t-甲基-1r-环丙烷甲酰胺
Figure C9880427400221
和
N-(R)-[1-(4-氯-苯基)-乙基]-(1R)-2，2-二氯-1-乙基-3t-甲基-1r-环丙烷甲酰胺
式(VII)包括化合物：
(VIIa)       Me＝Zn  (代森锌)
(VIIb)       Me＝Mn  (代森锰)
和
(VIIc)       (VIIa)和(VIIb)的混合物(代森锰锌)
式(XVI)包括化合物：
(XVIa)        R2＝CH3  (嘧霉胺)
和
(XVIb)        R2＝        (嘧菌环胺)
Figure C9880427400223
式(XXI)包括化合物：
4-(2，3-二氯苯基)-吡咯-3-腈
Figure C9880427400231
                  (拌种咯)
和
4-(2，2-二氟-1，3-苯并二氧戊环-7-基)-1氢-吡咯-3-腈
                  (咯菌清)
式(XXV)的胍衍生物是通用名为双胍辛乙酸盐(guazatine)的混合物。
除了式(I)的活性化合物，存在于本发明的组合中的其它成分也均为已知的。具体地说，它们在下列文献中有描述：
(1)式(II)的化合物
DE-A 2 201 063
DE-A 2 324 010
(2)式(III)的化合物
EP-A 0 040 345
(3)式(IV)的化合物
《农药手册》，第9版(1991)，第249和827页
(4)式(V)的化合物和其单个异构体
EP-A 0 341 475
(5)式(VI)的化合物
《农药手册》，第9版(1991)，第726页
(6)式(VII)的化合物
《农药手册》，第9版(1991)，第529、531和866页
(7)式(VIII)的化合物
EP-A 0 339 418
(8)式(IX)的化合物
EP-A 0 472 996
(9)式(X)的化合物
EP-A 0 313 512
(10)式(XI)的化合物
EP-A 0 281 842
(11)式(XII)的化合物
EP-A 0 382 375
(12)式(XIII)的化合物
EP-A 0 515 901
(13)式(XIV)的化合物
EP-A196 02 095
(14)式(XV)的化合物
US-A 3 903 090
(15)式(XVI)的化合物
EP-A 0 270 1 1 1
EP-A 0 310 550
(16)式(XVII)的化合物
《农药手册》，第9版(1991)，第159页
(17)式(XVIII)的化合物
EP-A 0 219 756
(18)式(XIX)的化合物
《农药手册》，第9版(1991)，第431页
(19)式(XX)的化合物
《农药手册》，第9版(1991)，第443页
(20)式(XXI)的化合物
EP-A 0 236 272
EP-A 0 206 999
(21)式(XXII)的化合物
《农药手册》，第9版(1991)，第491页
(22)式(XXIII)的化合物
DE-A 2 732 257
(23)式(XXIV)的化合物
EP-A 0 600 629
(24)式(XXII)的物质
《农药手册》，第9版(1991)，第461页
除式(I)的活性化合物外，本发明的组合还包含(1)到(24)化合物组中的至少一个活性化合物。另外，可能还包含更多的杀真菌活性成分。
本发明的活性化合物组合中的活性化合物以某种重量比存在时，协同作用尤其明显。然而，活性化合物组合中的活性化合物的重量比有一相对宽的变化范围。一般而言，相对于每份重量的式(I)活性化合物，存在：
0.1至20份重量，优选0.2至10份重量的组(1)活性化合物，
0.1至20份重量，优选0.2至10份重量的组(2)活性化合物，
0.2至150份重量，优选1至100份重量的组(3)活性化合物，
0.1至10份重量，优选0.2至5份重量的组(4)活性化合物，
1至50份重量，优选5至20份重量的组(5)活性化合物，
1至50份重量，优选2至20份重量的组(6)活性化合物，
0.1至50份重量，优选1至30份重量的组(7)活性化合物，
0.2至50份重量，优选1至20份重量的组(8)活性化合物，
0.02至50份重量，优选0.2至10份重量的组(9)活性化合物，
0.1至50份重量，优选0.2至20份重量的组(10)活性化合物，
0.1至50份重量，优选0.2至20份重量的组(11)活性化合物，
0.1至50份重量，优选0.2至20份重量的组(12)活性化合物，
0.1至50份重量，优选0.2至20份重量的组(13)活性化合物，
0.1至50份重量，优选1至30份重量的组(14)活性化合物，
0.1至50份重量，优选0.2至20份重量的组(15)活性化合物，
0.1至50份重量，优选2至20份重量的组(16)活性化合物，
1至20份重量，优选2至10份重量的组(17)活性化合物，
1至50份重量，优选2至20份重量的组(18)活性化合物，
1至50份重量，优选2至20份重量的组(19)活性化合物，
0.1至10份重量，优选0.2至5份重量的组(20)活性化合物，
0.05至20份重量，优选0.1至10份重量的组(21)活性化合物，
0.1至10份重量，优选0.2至5份重量的组(22)活性化合物，
0.1至10份重量，优选0.2至5份重量的组(23)活性化合物，
和/或
0.1至10份重量，优选0.2至5份重量的组(24)活性化合物。
本发明的活性化合物组合有很好的杀真菌性能，可用于防治植物病原真菌，如：根肿菌纲、卵菌纲、壶菌纲、接合菌纲、子囊菌纲、担子菌纲、半知菌纲等。
本发明活性化合物组合尤其适合于防治谷类植物病害如白粉菌、柄锈菌和镰刀菌，和葡萄栽培中的病害如钩丝壳霉病、单轴霉病和葡萄孢，也可用在双子叶作物上防治白粉病和霜霉病真菌以及叶斑中的病原有机物。
在防治所需浓度下植物对活性化合物组合有很好的耐药性，因此可用于植物地上部分、繁殖茎和种子处理。也能用于叶面处理或种子包衣。
本发明活性化合物组合可制成常见剂型，如溶液、乳剂、悬浮剂、粉剂、泡沫剂、糊剂、颗粒剂、气雾剂和包于聚合物中和包于用于种子的包衣组合物中的微囊剂以及超低容量喷雾剂型。
这些型剂可以用已知的方式生产，例如，将活性化合物与扩充剂，即液体溶剂、加压下的液化气和/或固体载体混合，并任选使用表面活性剂，即乳化剂和/或分散剂和/或泡沫形成剂。在用水作扩充剂的情况下，也可以用有机溶剂作助溶剂。适合的液体溶剂主要有：芳族化合物，如二甲苯，甲苯或烷基萘，氯代芳族化合物或氯代脂肪烃，如氯代苯类、氯乙烯类或二氯甲烷，脂族烃，如环己烷或石蜡，例如石油馏份，醇类，如丁醇或乙二醇以及其醚和酯，酮类，如丙酮、甲乙酮、甲基异丁基酮或环己酮，强极性溶剂，如二甲基甲酰胺或二甲基亚砜，以及水。液化气扩充剂或载体应理解为是指在常温和常压下是气体的液体，例如气雾剂抛射剂如卤代烃，或是丁烷、丙烷、氮气和二氧化碳。适合的固体载体是：例如磨碎的天然岩石如高岭土、粘土、滑石、白垩、石英、硅镁土、蒙脱石或硅藻土，和磨碎的合成矿物质，如高分散二氧化硅、矾土和硅酸盐。适合用于颗粒剂的固体载体有：例如压碎并分级的天然矿物质如方解石、大理石、浮石、海泡石和白云石，以及有机和无机粉的合成颗粒，和如下有机物的颗粒：锯木屑、椰壳、玉米穗轴和烟茎。适合的乳化剂和/或泡沫形成剂是：例如非离子和阴离子乳化剂，如聚氧乙烯脂肪酸酯、聚氧乙烯脂肪醇醚，例如，烷芳基聚乙二醇醚，烷基磺酸盐，烷基硫酸盐，芳基磺酸盐以及白蛋白水解产物。适合的分散剂是：例如，木素亚硫酸废液和甲基纤维素。
制剂中可以使用粘合剂如羧甲基纤维素和粉状、颗粒或乳胶形式的天然和合成聚合物，如阿拉伯胶、聚乙烯醇和聚乙酸乙烯酯，以及天然磷脂，如脑磷脂和卵磷脂，和合成磷脂。其它的粘合剂可以是矿物油和植物油。
也可能使用染料，如无机颜料，例如氧化铁、氧化钛和普鲁士蓝，和有机染料，如茜素染料、偶氮染料和金属酞菁染料，和微量营养素如铁、锰、硼、铜、钴、钼和锌的盐。
制剂中通常含有按重量计0.1至95％的活性化合物，优选0.5至90％。
剂型中，本发明活性化合物组合可以以与其它已知活性化合物混合的混合物形式存在，其它已知的活性化合物如杀真菌剂、杀虫剂、杀螨剂和除草剂，也可作为与肥料及植物生长调节剂的混合物。
本发明活性化合物组合可以以其原样、其制剂形式或由此制剂制备的使用形式使用，如直接可用溶液、乳油、乳剂、悬浮剂、可湿性粉剂、可溶性粉剂颗粒剂。它们可以以常规的方式使用，例如通过浇水、喷雾、弥雾、撒施、涂抹，也可以作为用于干种子处理的粉剂、作为用于种子处理的溶液、用于种子处理的水溶性粉剂、用于淤浆处理的水溶性粉剂，或进行包衣。
当使用本发明活性化合物组合时，取决于施用的类型，施用剂量可以在相对宽的范围内变化。在处理植物部分时，活性化合物组合的施用剂量通常在0.1至10,000g/ha，优选10至1000g/ha之间。在处理种子时，活性化合物的施用剂量通常在0.001至50g/kg种子，优选0.01至10g/kg种子之间。在处理土壤时，活性化合物的施用剂量通常在0.1至10,000g/ha，优选1至5000g/ha之间。
从下面的实施例中可以明显看到，本发明活性化合物组合显示很好的杀真菌活性，而单个活性化合物的杀真菌活性较弱，本发明组合的活性超过各化合物活性的简单加和。
当活性化合物组合的杀真菌活性超过各活性化合物单独使用时的活性之和时，则总是存在杀菌剂的协同作用。
两个活性化合物组合后的预期活性可按下面方法计算(参考：Colby，S.R.，“Calculating Synergistic and Antagonistic Responsesof Herbicide Combinations”，Weed 15，(1967)，20-22)
如果
X为在 m g/ha使用剂量下施用活性化合物A产生的效力，
Y为在 n g/ha使用剂量下施用活性化合物B产生的效力，
E为在 m+ n g/ha使用剂量下施用活性化合物A+B产生的效力，
则 E = X + Y - X &CenterDot; Y 100
效力以％计算，0％是指效力与对照的相当，100％是指没有观察到侵染。
如果实际的杀真菌活性超过了计算值，则组合的活性是超加合的，即，存在协同作用。在此情况下，实际观察到的效力一定比按上述公式计算得到的期望效力(E)值要大。
下面的实施例举例说明本发明。
实施例1
单丝壳菌试验(黄瓜)/保护性
溶剂：      47份重量的丙酮
乳化剂：    3份重量的烷基芳基聚乙二醇醚
为了制得合适的活性化合物，将一份按重量计的活性化合物或活性化合物的组合与上述量的溶剂和乳化剂混合，并用水稀释到所需浓度，或者将活性化合物或活性化合物组合的商品剂型用水稀释到所需浓度。
为了测试保护性活性，将幼苗用所述使用剂量的活性化合物制剂喷雾，待喷液层变干后，将幼苗用单丝壳菌(Sphaerotheca fuliginea)的孢子悬浮液接种，然后把黄瓜苗置于温度约23℃、空气湿度约70％的温室中。
接种10天后进行效果评价，0％是指效力与对照的相当，100％是指没有观察到侵染。
活性化合物、使用剂量和试验结果列于下表中：表1单丝壳菌试验(黄瓜)/保护性表1(续)单丝壳菌试验(黄瓜)/保护性
Figure C9880427400311
表1(续)单丝壳菌试验(黄瓜)/保护性表1(续)单丝壳菌试验(黄瓜)/保护性表1(续)单丝壳菌试验(黄瓜)/保护性
Figure C9880427400341
表1(续)单丝壳菌试验(黄瓜)/保护性表1(续)单丝壳菌试验(黄瓜)/保护性表1(续)单丝壳菌试验(黄瓜)/保护性
Figure C9880427400371
表1(续)单丝壳菌试验(黄瓜)/保护性
Figure C9880427400381
表1(续)单丝壳菌试验(黄瓜)/保护性实测值＝实测的效力计算值＝用Colby式计算得的效力
实施例2
黑星菌试验(苹果)/保护性
溶剂：      47份重量的丙酮
乳化剂：    3份重量的烷基芳基聚乙二醇醚
为了制得合适的活性化合物，将一份按重量计的活性化合物或活性化合物的组合与上述量的溶剂和乳化剂混合，并用水稀释到所需浓度，或者将活性化合物或活性化合物组合的商品剂型用水稀释到所需浓度。
为了测试保护性活性，将幼苗用所述使用剂量的活性化合物制剂喷雾，待喷液层变干后，将幼苗用苹果黑星病(Venturia inaequalis)的病原有机物的分生孢子悬浮液接种，并将其置于温度约20℃、空气湿度为100％的保温室中1天。
然后将试验植物置于温度约21℃、空气湿度约90％的温室中。
接种12天后进行效果评价，0％是指效力与对照的相当，100％是指没有观察到侵染。
活性化合物、使用剂量和试验结果列于下表中：表2黑星菌试验(苹果)/保护性实测值＝实测的效力计算值＝用Colby式计算得的效力
实施例3
白粉菌试验(大麦)/治疗性
溶剂：      10份重量的N-甲基-吡咯烷酮
乳化剂：    0.6份重量的烷基芳基聚乙二醇醚
为了制得合适的活性化合物，将一份按重量计的活性化合物或活性化合物的组合与上述量的溶剂和乳化剂混合，并用水稀释到所需浓度，或者将活性化合物或活性化合物组合的商品剂型用水稀释到所需浓度。
为了测试治疗性活性，将幼苗用大麦白粉菌(Erysiphe graminisf.sp.hordei)孢子喷粉。接种48小时后，将幼苗用所述使用剂量的活性化合物制剂喷雾。
然后将试验植物置于温度约20℃、空气湿度约80％的温室中以促进白粉病斑的生长。
接种7天后进行效果评价，0％是指效力与对照的相当，100％是指没有观察到侵染。
活性化合物、使用剂量和试验结果列于下表中：表3白粉病试验(大麦)/治疗性
实施例4
白粉菌试验(大麦)/保护性
溶剂：      10份重量的N-甲基-吡咯烷酮
乳化剂：    0.6份重量的烷基芳基聚乙二醇醚
为了制得合适的活性化合物，将一份按重量计的活性化合物或活性化合物的组合与上述量的溶剂和乳化剂混合，并用水稀释到所需浓度，或者将活性化合物或活性化合物组合的商品剂型用水稀释到所需浓度。
为了测试保护性活性，将幼苗用所述使用剂量的活性化合物制剂喷雾。
待喷液层变干后，将幼苗用大麦白粉菌(Erysiphe graminis f.sp.hordei)的孢子喷粉。
然后将试验植物置于温度约20℃、空气湿度约80％的温室中以促进白粉病斑的生长。
接种7天后进行效果评价，0％是指效力与对照的相当，100％是指没有观察到侵染。
活性化合物、使用剂量和试验结果列于下表中：表4白粉菌试验(大麦)/保护性
实施例5
白粉菌试验(小麦)/治疗性
溶剂：      10份重量的N-甲基-吡咯烷酮
乳化剂：    0.6份重量的烷基芳基聚乙二醇醚
为了制得合适的活性化合物，将一份按重量计的活性化合物或活性化合物的组合与上述量的溶剂和乳化剂混合，并用水稀释到所需浓度，或者将活性化合物或活性化合物组合的商品剂型用水稀释到所需浓度。
为了测试治疗性活性，将幼苗用小麦白粉菌(Erysiphe graminisf.sp.tritici)孢子喷粉。接种48小时后，将幼苗用所述使用剂量的活性化合物制剂喷雾。
然后将试验植物置于温度约20℃、空气湿度约80％的温室中以促进白粉病斑的生长。
接种7天后进行效果评价，0％是指效力与对照的相当，100％是指没有观察到侵染。
活性化合物、使用剂量和试验结果列于下表中：表5白粉菌试验(小麦)/治疗性
Figure C9880427400471
表5(续)白粉菌试验(小麦)/治疗性表5(续)白粉菌试验(小麦)/治疗性
Figure C9880427400491
表5(续)白粉菌试验(小麦)/治疗性
Figure C9880427400501
表5(续)白粉菌试验(小麦)/治疗性
实施例6
白粉菌试验(小麦)/保护性
溶剂：      10份重量的N-甲基-吡咯烷酮
乳化剂：    0.6份重量的烷基芳基聚乙二醇醚
为了制得合适的活性化合物，将一份按重量计的活性化合物或活性化合物的组合与上述量的溶剂和乳化剂混合，并用水稀释到所需浓度，或者将活性化合物或活性化合物组合的商品剂型用水稀释到所需浓度。
为了测试保护性活性，将幼苗用所述使用剂量的活性化合物制剂喷雾。
待喷液层变干后，将幼苗用小麦白粉菌(Erysiphe graminis f.sp.tritici)的孢子喷粉。
然后将试验植物置于温度约20℃、空气湿度约80％的温室中以促进白粉病斑的生长。
接种7天后进行效果评价，0％是指效力与对照的相当，100％是指没有观察到侵染。
活性化合物、使用剂量和试验结果列于下表中：表6白粉菌试验(小麦)/治疗性
Figure C9880427400531
实施例7
小球腔菌试验(小麦)/保护性
溶剂：      10份重量的N-甲基-吡咯烷酮
乳化剂：    0.6份重量的烷基芳基聚乙二醇醚
为了制得合适的活性化合物，将一份按重量计的活性化合物或活性化合物的组合与上述量的溶剂和乳化剂混合，并用水稀释到所需浓度，或者将活性化合物或活性化合物组合的商品剂型用水稀释到所需浓度。
为了测试保护性活性，将幼苗用所述使用剂量的活性化合物制剂喷雾，待喷液层变干后，将幼苗用小球腔菌(Leptosphaeria nodorum)孢子悬浮液喷雾。并将其置于温度20℃、空气湿度为100％的保温室中48小时。
然后将试验植物置于温度约15℃、空气湿度约80％的温室中。
接种10天后进行效果评价，0％是指效力与对照的相当，100％是指没有观察到侵染。
活性化合物、使用剂量和试验结果列于下表中：表7小球腔菌试验(小麦)/保护性
实施例8
柄锈菌试验(小麦)/保护性
溶剂：      10份重量的N-甲基-吡咯烷酮
乳化剂：    0.6份重量的烷基芳基聚乙二醇醚
为了制得合适的活性化合物，将一份按重量计的活性化合物或活性化合物的组合与上述量的溶剂和乳化剂混合，并用水稀释到所需浓度，或者将活性化合物或活性化合物组合的商品剂型用水稀释到所需浓度。
为了测试保护性活性，将幼苗用柄锈菌(Puccinia recondita)在0.1％的琼脂水溶液中的孢子悬浮液接种，待喷液层变干后，将幼苗用所述使用剂量的活性物质喷雾，并将其置于温度20℃、空气湿度为100％的保温室中24小时。
然后将试验植物置于温度约20℃、空气湿度约80％的温室中，以促进锈病斑的生长。
接种10天后进行效果评价，0％是指效力与对照的相当，100％是指没有观察到侵染。
活性化合物、使用剂量和试验结果列于下表中：表8柄锈菌试验(小麦)/保护性
Figure C9880427400571
实施例9
黄色镰孢菌(Fusarium culmorum)试验(小麦)/种子处理
活性化合物以干种子拌种剂施用。该制剂可通过将单独的活性化合物或组合的活性化合物与磨细的矿物质混合来制备，得到能在种子表面均匀分布的细粉状混合物。
种子拌种时，将侵染种子和种子拌种剂在封闭的玻璃烧瓶内摇动3分钟。
2×100粒小麦播种于1厘米深的标准土壤中，在温度约18℃、空气湿度约95％的温室内培养，种子栽培箱每日需15小时光照。
播种3周后，评价麦苗的病症，0％是指效力与对照的相当，100％是指没有观察到侵染。
活性化合物、使用剂量和试验结果列于下表中：表9黄色镰孢菌试验(小麦)/种子处理
实施例10
雪腐镰孢菌(Fusarium nivale)试验(黑小麦)/种子处理
活性化合物以干种子拌种剂施用。该制剂可通过将单独的活性化合物或组合的活性化合物与磨细的矿物质混合来制备，得到能在种子表面均匀分布的细粉状混合物。
种子拌种时，将侵染种子和种子拌种剂在封闭的玻璃烧瓶内摇动3分钟。
2×100粒小麦播种于1厘米深的标准土壤中，在温度约10℃、空气湿度约95％的温室内培养，种子栽培箱每日需15小时光照。
播种3周后，评价麦苗的病症，0％是指效力与对照的相当，100％是指没有观察到侵染。
活性化合物、使用剂量和试验结果列于下表中：表10雪腐镰孢菌试验(黑小麦)/种子处理
实施例11
立枯丝核菌(Rhizoctonia solani)试验(棉花)/种子处理
活性化合物以干种子拌种剂施用。该制剂可通过将单独的活性化合物或组合的活性化合物与磨细的矿物质混合来制备，得到能在种子表面均匀分布的细粉状混合物。
种子拌种时，将侵染种子和种子拌种剂在封闭的玻璃烧瓶内摇动3分钟。
2×50粒棉花籽播种于2厘米深的感染立枯丝核菌的标准土壤中，在种子托盘上于温度约22℃的温室内培养，种子栽培箱每日需15小时光照。
播种8天后进行评价。0％是指效力与对照的相当，100％是指没有观察到侵染。
活性化合物、使用剂量和试验结果列于下表中：表11立枯丝核菌试验(棉花)/种子处理
Figure C9880427400631

Claims (4)

1.杀真菌组合物，其特征在于，它们含有如下活性化合物组合：
式(I)的2-[2-(1-氯代环丙基)-3-(2-氯代苯基)-2-羟基丙基]-2，4-二氢-[1，2，4]-三唑-3-硫酮
和
(1)式(II)的三唑衍生物
其中，X代表氯或苯基，Y代表
          或
和/或
(2)式(III)的三唑衍生物
          (戊唑醇)
和/或
(3)式(IV)的苯胺衍生物
其中，R1代表氢或甲基，
和/或
(4)式(V)的N-[1-(4-氯-苯基)-乙基]-2，2-二氯-1-乙基-3-甲基环丙烷-甲酰胺
和/或
(5)式(VI)的亚丙基-1，2-双-(二硫代氨基甲酸)锌
      n＞＝1    (甲基代森锌)
和/或
(6)式(VII)的至少一种硫代氨基甲酸酯
             Me＝Zn或Mn
                 或Zn和Mn的混合物
和/或
(7)式(VIII)的苯胺衍生物
和/或
(8)式(IX)的化合物
Figure C9880427400043
和/或
(9)式(X)的苯并噻二唑衍生物
和/或
(10)式(XI)的8-叔丁基-2-(N-乙基-N-正丙基-氨基)-甲基-1，4-二氧杂螺[5，4]癸烷
                   (螺噁茂胺)
和/或
(11)式(XII)的化合物
                   (腈嘧菌酯)
和/或
(12)式(XIII)的化合物
Figure C9880427400061
                  (亚胺菌)
和/或
(13)式(XIV)的化合物
Figure C9880427400062
和/或
(14)式(XV)的二羰基亚胺
                  (腐霉利)
和/或
(15)式(XVI)的嘧啶衍生物
其中，R2代表甲基或环丙基
和/或
(16)式(XVII)的苯基衍生物
                  (百菌清)
和/或
(17)式(XVIII)的吗啉衍生物
Figure C9880427400073
和/或
(18)式(XIX)的苯邻二甲酰亚胺衍生物
                  (灭菌丹)
和/或
(19)式(XX)的磷化合物
Figure C9880427400081
                  (三乙膦酸铝)
和/或
(20)式(XXI)的苯基吡咯衍生物
其中，R3和R4分别代表氯或一起代表基团-O-CF2-O-
和/或
(21)式(XXII)的1-[(6-氯-3-吡啶基)-甲基]-N-硝基-2-咪唑烷亚胺
Figure C9880427400083
                  (吡虫啉)
和/或
(22)式(XXIII)的苯基脲衍生物
                  (戊菌隆)
和/或
(23)式(XXIV)的苯甲酰胺衍生物
其中，式(I)的化合物与其它物质的重量比为：
与组(1)的活性化合物重量比在1∶0.1到1∶20之间，
与组(2)的活性化合物重量比在1∶0.1到1∶20之间，
与组(3)的活性化合物重量比在1∶0.2到1∶150之间，
与组(4)的活性化合物重量比在1∶0.1到1∶10之间，
与组(5)的活性化合物重量比在1∶1到1∶50之间，
与组(6)的活性化合物重量比在1∶1到1∶50之间，
与组(7)的活性化合物重量比在1∶0.1到1∶50之间，
与组(8)的活性化合物重量比在1∶0.2到1∶50之间，
与组(9)的活性化合物重量比在1∶0.02到1∶50之间，
与组(10)的活性化合物重量比在1∶0.1到1∶50之间，
与组(11)的活性化合物重量比在1∶0.1到1∶50之间，
与组(12)的活性化合物重量比在1∶0.1到1∶50之间，
与组(13)的活性化合物重量比在1∶0.1到1∶50之间，
与组(14)的活性化合物重量比在1∶0.1到1∶50之间，
与组(15)的活性化合物重量比在1∶0.1到1∶50之间，
与组(16)的活性化合物重量比在1∶1到1∶50之间，
与组(17)的活性化合物重量比在1∶1到1∶20之间，
与组(18)的活性化合物重量比在1∶1到1∶50之间，
与组(19)的活性化合物重量比在1∶1到1∶50之间，
与组(20)的活性化合物重量比在1∶0.1到1∶10之间，
与组(21)的活性化合物重量比在1∶0.05到1∶20之间，
与组(22)的活性化合物重量比在1∶0.1到1∶10之间，和
与组(23)的活性化合物重量比在1∶0.1到1∶10之间。
2.防治真菌的方法，其特征在于，将权利要求1中的活性化合物组合施用于真菌和/或它们的栖息地。
3.权利要求1中的活性化合物组合用防治真菌的应用。
4.制备杀真菌组合物的方法，其特征在于，将权利要求1中的活性化合物组合与扩充剂和/或表面活性剂混合。
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