CN1070339C - 杀真菌活性化合物的组合物 - Google Patents
杀真菌活性化合物的组合物 Download PDFInfo
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- CN1070339C CN1070339C CN94101569A CN94101569A CN1070339C CN 1070339 C CN1070339 C CN 1070339C CN 94101569 A CN94101569 A CN 94101569A CN 94101569 A CN94101569 A CN 94101569A CN 1070339 C CN1070339 C CN 1070339C
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Abstract
式(Ⅰ)缬氨酰胺衍生物与已知的杀真菌活性物质的新活性化合物组合物,及其用于杀灭所述植物致病真菌的用途
其中,R1和R2具有说明书中给定的定义。
Description
本发明涉及新的活性化合物组合物,它一方面包括缬氨酰胺衍生物,另一方面还包括其它已知的真杀菌活性化合物,该类组合物特别适用于杀灭植物致病的真菌。
缬氨酰胺衍生物具有杀真菌性能是已知的(参见EP-A472,996)。该物质有着良好的活性,但在某些情况下,当使用低施用剂量时仍有些问题有待解决。
另外,已知大量的吡咯衍生物、芳族羧酸衍生物、吗啉化合物和其它杂环类化合物可用来杀灭真菌(参见K·H·Bchel"pflanzenschutz und Schdlingsbekmpfung"[Crop protec-tion and pest Control]第87 136,140,141页,和146页至153页Georg Thieme Verlag,Stuttgart 1977)。然而,当使用低施用剂量时,所述物质的活性并不总是令人满意的。
基中:
R1代表异丙基或仲丁基,
R2代表氯、甲基、乙基或甲氧基
(A)式(Ⅱ)的抑菌灵
(C)式(Ⅳ)的四氯-间苯二氰
(H)王铜
(K)式(Ⅹ)的吗啉衍生物
(L)式(Ⅺ)的二噻农
(O)式(ⅩⅣ)的百维灵或其盐酸盐(CH3)2NCH2-CH2-CH2-NHCO-OCH2CH3 (ⅩⅣ)
(P)式(ⅩⅤ)的fosetyl或其铝加合物
(Q)式(ⅩⅥ)的瑞毒霉
(S)式(ⅩⅧ)的氟啶胺
(T)甲氧丙烯酸酯,如
(U)甲氧亚氨基乙酸酯,如
式(ⅩⅩ)的(E)-甲氧亚氨基[α-(邻-甲苯氧基)-邻-甲苯基]乙酸甲酯
(Ⅴ)呋氨丙灵=N-(2-呋喃甲酰基)-N-(2,6-二甲苯基)-DL-氨基丙酸甲酯
(X)氯唑灵=3-三氯甲基-5-乙氧基-1,2,4-噻二唑
(Y)戊菌隆=1-(4-氯苄基)-1-环戊基(-3-苯基)脲
令人惊奇的是,本发明的活性化合物组合物的杀真菌活性明显高于所述各个活性化合物的活性总和。这意味着实际上发生了不可预知的增效作用,而不仅仅是相互加合的活性。
从式(Ⅰ)的活性化合物的结构式可以看出,该类化合物有两个非对称取代的碳原子。因此产物可以各种异构体的混合物形式或者以单纯一种异构体形式存在。
优选的式(Ⅰ)化合物是其中氨基酸部分由异丙氧羰基-L-缬氨酸或仲-丁氧羰基-L-缬氨酸形成的且苯乙胺部分或者是外消旋的或具有S(-)构型,但优选R(+)构型的化合物。
特别优选的式(Ⅰ)化合物是其中R1代表异丙基的化合物。
特别提到的是下列化合物及其如上述的异构体:
式(Ⅳ)的[2-甲基-1-[[[-1-(4-乙苯基)乙基]氨基]羰基]-丙基]-氨基甲酸1-甲基乙酯
和式(Ⅴ)的[2-甲基-1-[[[-1-(4-甲氧苯基)-乙基]氨基]羰基]-丙基]-氨基甲酸1-甲基乙酯式(Ⅰ)的活性化合物是已知的(参见EP-A 472,996)。其它出现在本发明的组合物中的杀真菌活性化合物也是已知的。各个活性化合物见下列出版物所述:
(A):K.H.Bchel"pflanzenschutz und
Schdlingsbekmpfung"[Crop Protection and pest
Control],第141页,Georg Thieme verlag,Stuttgart
1977;
(B):K.H.Bchel,loc.cit.,第141页(G)p.153
(C):K.H.Bchel,loc.cit.,第146页(H)p.122
(D):K.H.Bchel,loc.cit.,第138页(I)p.132,140
(E):K.H.Bchel,loc.cit.,第136页(K)EP-A 219,756
(F):K.H.Bchel,loc.cit.,第137页(L)p,145
(G):K.H.Bchel,loc.cit.,第153页
(H):K.H.Bchel,loc.cit.,第122页
(I):K.H.Bchel,loc.cit.,第132页
(K):EP-A 219,756
(L):K.H.Bchel,loccit., 第145页
(M):K.H.Bchel,loc.cit.,第140页
(O):DE 1,567,169:*
(P):FR 2,254,276:**
(Q):GB 1,500,581
(R):GB 2,058,059
(S):EP 0 31257
(T):Brighton Crop protection Conference(1992)5-6,435-
37
(U):Brighton Crop Protection Conference(1992)5-6,403-
05
(V):GB 1 448 810
(W):EP-0 040 345,DE 2 324 010,DE 2 201 063
(X):US 3 260 588
(Y):DE 2 732 257.
本发明活性化合物组合物除了包括至少一种式(Ⅰ)的活性化合物外,还包括至少一种(A)至(U)的活性化合物。另外,它们还可包括其它可以混合的杀真菌活性组份。
当本发明活性化合物组合物中的活性化合物以一定比例(重量)存在时,增效作用更显著。但是活性化合物组合物中活性化合物的重量比可在相当宽的范围内变化。一般地,每重量份的式(Ⅰ)活性化合物使用下列量的其它活性化合物:
1至50重量份,优选2.5至10重量份活性化合物(A),
1至50重量份,优选2.5至10重量份活性化合物(B),
1至50重量份,优选1至10重量份活性化合物(C),
1至50重量份,优选5至20重量份活性化合物(D),
1至200重量份,优选1至100重量份活性化合物(E),
1至50重量份,优选5至20重量份活性化合物(F),
1至200重量份,优选1至100重量份活性化合物(G),
1至200重量份,优选1至50重量份活性化合物(H),
1至100重量份,优选1至50重量份活性化合物(I),
0.5至10重量份,优选1至5重量份活性化合物(K),
1至50重量份,优选1至20重量份活性化合物(L),
1至50重量份,优选1至20重量份活性化合物(M),
0.5至20重量份,优选1至10重量份活性化合物(N),
1至100重量份,优选1至50重量份活性化合物(O),
1至50重量份,优选1至20重量份活性化合物(P),
0.5至20重量份,优选1至10重量份活性化合物(Q),
0.5至20重量份,优选1至10重量份活性化合物(R),
1至20重量份,优选1至10重量份活性化合物(S),
0.5至20重量份,优选1至10重量份活性化合物(T),
0.5至20重量份,优选1至10重量份活性化合物(U),
0.5至20重量份,优选1至10重量份活性化合物(V),
0.5至20重量份,优选0.5至10重量份活性化合物(W),
0.5至20重量份,优选0.5至10重量份活性化合物(X),
0.5至20重量份,优选0.5至10重量份活性化合物(Y)。
本发明的活性化合物组合物具有很好的杀真菌性能,并能用于杀灭植物致病的真菌,特别如:根肿病菌纲、卵菌亚纲、壶菌纲、接合菌亚纲、子囊菌纲、担子菌纲和半知菌纲
本发明的活性化合物组合物特别适用于保护性防治西红柿和马铃薯上的马铃薯晚疫病和早疫病,以及葡萄上的葡萄霜霉病。
作物对于所述活性化合物组合物在杀灭植物病害所需浓度的好的耐受性使处理植物的地上部分,及植物繁殖的根状茎和种子,以及生长的土壤成为可能。
本发明活性化合物组合物可以配制成常规制剂,例如:液剂、乳剂、悬浮剂、粉剂、泡沫剂、糊剂、颗粒剂、气雾剂、聚合物质中的微细胶囊剂和用于种子包衣的组合物及ULV制剂。
这些制剂是用已知方法生产的,例如:通过将活性化合物或活性化合物组合物与填充剂即液体溶剂、加压液化的气体和/或固体载体混合,任选地使用表面活性剂即乳化剂和/或分散剂和/或发泡剂而制得。在使用水作为填充剂时,也可以使用有机溶剂,例如用作辅助溶剂。适用的液体溶剂主要有:芳族,如二甲苯、甲苯或烷基萘,氯化芳族或氯化脂族烃,如氯苯、二氯乙烷或二氯甲烷,脂族烃,如环己烷或链烷烃,例如矿物油馏份,醇类例如丁醇或乙二醇以及它们的醚类或酯类,酮类,例如丙酮、甲乙酮、甲基异丁酮或环己酮,强极性溶剂如二甲基甲酰胺,二甲基亚砜及水。所述液化的气体填充剂或载体是指在环境温度和大气压下是气体的那些液体。例如气雾喷射剂,例如丁烷、丙烷、氮气和二氧化碳。合适的固体载体有:例如研磨的天然矿物,如高岭土、粘土、滑石、白垩、石英、绿坡镂土、蒙脱土或硅藻土,研磨的合成矿物如高分散二氧化硅、氧化铝和硅酸盐。适合作为颗粒剂的固体载体例如:粉碎和筛分的天然岩石如方解石、大理石、浮石、海泡石和白云石及无机合成颗粒和有机粉末,及有机材料的颗粒如锯屑、椰子壳、玉米芯和烟草茎的颗粒。适合的乳化剂和/或发泡剂有:例如非离子和阴离子乳化剂如聚氧乙烯脂肪酸酯、聚氧乙烯脂肪醇醚如烷芳基聚乙二醇醚、烷基磺酸酯、烷基硫酸酯、芳基磺酸酯及白蛋白水解产物。合适的分散剂有:例如木质素亚硫酸废液和甲基纤维素。
在制剂中可以使用粘合剂,例如羧甲基纤维素和天然及合成的粉末状、颗粒状或胶乳状聚合物,例如阿拉伯树胶、聚乙烯醇和聚乙酸乙烯酯,及天然磷脂,例如脑磷脂和卵磷脂和合成磷脂。其它的添加剂可以是矿物油和植物油。
可以使用着色剂,例如无机颜料如氧化铁、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以及微量营养物如铁盐、镁盐、硼盐、铜盐、钴盐、钼盐和锌盐。
制剂一般包括0.1%至95%(重量)的活性化合物,优选0.5%至90%(重量)之间。
本发明的活性化合物或组合物可以作为与其它已知活性化合物的混合物存在于制剂中,其它已知活性化合物包括杀真菌剂、杀虫剂、杀螨剂和除草剂以及存在于与肥料或植物生长调节剂形成的混合物中。
所述活性化合物可以直接使用,或者以其制剂形式或由其制备的使用形式使用,例如现用溶液、乳油、乳液、悬浮液,可湿性粉剂,可溶性粉剂和颗粒剂。它们可以常规方式使用,例如通过泼浇、喷雾、喷烟雾、散播,在干燥种子处理中涂刷,种子处理的溶液,种子处理的水溶性粉剂或浆液处理的水分散性粉剂,或进行种子包衣。
在处理作物部分时,该活性化合物在使用形式中的浓度可在相当宽的范围内变化。通常在1%至0.0001%(重量)之间,优选0.5%至0.001%(重量)之间。
在处理种子时,每千克种子一般需要活性化合物的量为0.001至50克,优选0.01至10克。
对于土壤处理,在作用区域要求活性化合物的浓度为0.00001%至0.1%(重量),优选0.0001%至0.02%(重量)。
本发明活性化合物组合物的良好杀真菌活性可见实例。虽然各个活性化合物在杀真菌活性等方面有弱点,但所述组合物的活性超过了活性化合物的简单加合效果。
由于所述活性化合物组合物的杀真菌活性超过了使用的各个活性化合物活性的总和,则该杀真菌剂常显示增效作用。
对于给定两种活性化合物的组合物的预期活性可按如下计算(参见:Colby,S·R·,“除草组合物的增效和拮抗作用计算”,Weeds 15,第20-22页,1967):如果:
X是用使用浓度为mppm的活性化合物A的药效,与未处理对照的百分数表示的有效率,
Y是用使用浓度为nppm的活性化合物B的药效,与未处理对照的百分数表示的有效率,
E是预期使用浓度为mppm和nppm的活性化合物A和B时的药效,与未处理对照的百分数表示的有效率,则
如果实际杀真菌活性超过计算值,那么组合物的活性是超过加合作用的,即存在一种增效作用。在这种情况下,实际观测到的有效率必定超过用上述公式计算的预期有效率(E)。
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PL (1) | PL180530B1 (zh) |
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ZA (1) | ZA94947B (zh) |
Cited By (2)
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CN101755777B (zh) * | 2009-11-10 | 2013-02-27 | 深圳诺普信农化股份有限公司 | 一种防治植物卵菌病害的组合物 |
CN104705340A (zh) * | 2015-03-16 | 2015-06-17 | 广东中迅农科股份有限公司 | 一种含有双炔酰菌胺和噻唑膦的农药组合物 |
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DE4304172A1 (de) * | 1993-02-12 | 1994-08-25 | Bayer Ag | Fungizide Wirkstoffkombinationen |
CN1216440A (zh) * | 1996-04-26 | 1999-05-12 | 巴斯福股份公司 | 杀菌混剂 |
TW438575B (en) * | 1996-08-28 | 2001-06-07 | Basf Ag | Compositions and methods for controlling harmful fungi |
GB9718366D0 (en) | 1997-08-29 | 1997-11-05 | Ciba Geigy Ag | Novel combinations |
US6228883B1 (en) * | 1997-09-18 | 2001-05-08 | Gustafson, Inc. | Seed treatment fungicides for control of plant diseases |
BR9813669B1 (pt) * | 1997-12-18 | 2014-01-14 | Mistura fungicida, e, processo para controlar fungos nocivos | |
UA70327C2 (uk) * | 1998-06-08 | 2004-10-15 | Баєр Акціенгезельшафт | Спосіб боротьби з фітопатогенними хворобами сільськогосподарських рослин та фунгіцидна композиція |
GB9819317D0 (en) * | 1998-09-04 | 1998-10-28 | Novartis Ag | Organic compounds |
US6057365A (en) * | 1998-12-22 | 2000-05-02 | Rohm And Haas Company | Fungicidal compositions containing N-acetonylbenzamides |
DE19904081A1 (de) | 1999-02-02 | 2000-08-03 | Bayer Ag | Fungizide Wirkstoffkombinationen |
AU2164101A (en) | 1999-12-13 | 2001-06-25 | Bayer Aktiengesellschaft | Fungicidal combinations of active substances |
US6696497B2 (en) | 2000-02-23 | 2004-02-24 | Basf Aktiengesellschaft | Fungicidal mixtures |
PL205954B1 (pl) * | 2001-01-22 | 2010-06-30 | Basf Ag | Mieszanina grzybobójcza, sposób zwalczania szkodliwych grzybów i środek grzybobójczy |
DE10141618A1 (de) * | 2001-08-24 | 2003-03-06 | Bayer Cropscience Ag | Fungizide Wirkstoffkombinationen |
DE10141617A1 (de) * | 2001-08-24 | 2003-03-06 | Bayer Cropscience Ag | Fungizide Wirkstoffkombinationen |
CA2492451C (en) * | 2002-07-18 | 2011-10-11 | Basf Aktiengesellschaft | Fungicidal mixtures |
ATE348520T1 (de) * | 2002-07-23 | 2007-01-15 | Basf Ag | Fungizide mischungen |
GB0227966D0 (en) * | 2002-11-29 | 2003-01-08 | Syngenta Participations Ag | Organic Compounds |
US20040156742A1 (en) * | 2003-02-11 | 2004-08-12 | Milan Jolanda Bianca | Synergistically-effective cyclohexylethan-1-yl ester mixtures as malodour counteractants as measured physiologically and psychometrically and methods for using same |
US20050106192A1 (en) * | 2003-11-13 | 2005-05-19 | Parekh Prabodh P. | Synergistically-effective composition of zinc ricinoleate and one or more substituted monocyclic organic compounds and use thereof for preventing and/or suppressing malodors |
DE102004017981A1 (de) * | 2004-04-14 | 2005-11-03 | Bayer Cropscience Ag | Fungizide Wirkstoffkombinationen |
BRPI0519755A2 (pt) * | 2004-12-21 | 2009-03-10 | Critical Care Connections Inc | composiÇÕes ou combinaÇÕes nutrientes terapÊuticas e uso dos mesmos |
JP2009529565A (ja) * | 2006-03-14 | 2009-08-20 | ビーエーエスエフ ソシエタス・ヨーロピア | 細菌症に対する植物の耐性を誘導する方法 |
ES2610030T3 (es) * | 2006-03-24 | 2017-04-25 | Basf Se | Método para combatir la enfermedad de la yesca |
TR200901842T1 (tr) * | 2006-09-12 | 2009-06-22 | Nippon Soda Co., Ltd. | Stabil süspansiyon formunda haşere kontrol ajanı |
MX2009012880A (es) * | 2007-06-29 | 2009-12-10 | Basf Se | Estrobilurinas para aumentar la resistencia de plantas al estres abiotico. |
US8012554B2 (en) | 2007-09-12 | 2011-09-06 | Pactiv Corporation | Bags having odor management capabilities |
GB0906515D0 (en) | 2009-04-15 | 2009-05-20 | Syngenta Participations Ag | Fungical compositions |
EP2292094A1 (en) | 2009-09-02 | 2011-03-09 | Bayer CropScience AG | Active compound combinations |
CN105923643B (zh) * | 2016-04-12 | 2018-01-16 | 郑州鸿跃环保科技有限公司 | 一种从铝电解槽大修渣中回收氟化钙的方法及回收系统 |
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1993
- 1993-02-12 DE DE4304172A patent/DE4304172A1/de not_active Withdrawn
-
1994
- 1994-01-31 DE DE59408221T patent/DE59408221D1/de not_active Expired - Lifetime
- 1994-01-31 EP EP94101357A patent/EP0610764B1/de not_active Expired - Lifetime
- 1994-01-31 ES ES94101357T patent/ES2133426T3/es not_active Expired - Lifetime
- 1994-02-04 JP JP6032071A patent/JPH06247810A/ja active Pending
- 1994-02-04 US US08/192,333 patent/US5491165A/en not_active Expired - Lifetime
- 1994-02-07 KR KR1019940002291A patent/KR100348708B1/ko not_active IP Right Cessation
- 1994-02-09 CN CNA2004100322726A patent/CN1539279A/zh active Pending
- 1994-02-09 IL IL10860394A patent/IL108603A/xx not_active IP Right Cessation
- 1994-02-09 CN CN94101569A patent/CN1070339C/zh not_active Expired - Fee Related
- 1994-02-09 CN CNA2006100944850A patent/CN1989970A/zh active Pending
- 1994-02-10 BR BR9400484A patent/BR9400484A/pt not_active IP Right Cessation
- 1994-02-10 PL PL94302198A patent/PL180530B1/pl not_active IP Right Cessation
- 1994-02-11 HU HU9400383A patent/HU213954B/hu unknown
- 1994-02-11 ZA ZA94947A patent/ZA94947B/xx unknown
- 1994-02-14 RU RU94004980/04A patent/RU2176449C2/ru active
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1995
- 1995-11-06 US US08/554,142 patent/US5650423A/en not_active Expired - Lifetime
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1997
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1998
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1999
- 1999-06-09 GR GR990401531T patent/GR3030458T3/el unknown
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2000
- 2000-04-03 US US09/541,922 patent/US6245772B1/en not_active Expired - Fee Related
- 2000-08-21 CN CN00126216A patent/CN1329828A/zh active Pending
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2001
- 2001-02-05 US US09/776,817 patent/US6495575B2/en not_active Expired - Fee Related
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2002
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EP0493683A1 (en) * | 1990-12-20 | 1992-07-08 | American Cyanamid Company | Fungicidal amino acid amides |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101755777B (zh) * | 2009-11-10 | 2013-02-27 | 深圳诺普信农化股份有限公司 | 一种防治植物卵菌病害的组合物 |
CN104705340A (zh) * | 2015-03-16 | 2015-06-17 | 广东中迅农科股份有限公司 | 一种含有双炔酰菌胺和噻唑膦的农药组合物 |
Also Published As
Publication number | Publication date |
---|---|
PL180530B1 (pl) | 2001-02-28 |
US20020173542A1 (en) | 2002-11-21 |
BR9400484A (pt) | 1994-09-27 |
GR3030458T3 (en) | 1999-10-29 |
CN1539279A (zh) | 2004-10-27 |
IL108603A0 (en) | 1994-05-30 |
ZA94947B (en) | 1994-08-25 |
IL108603A (en) | 2000-07-16 |
EP0610764B1 (de) | 1999-05-12 |
KR100348708B1 (ko) | 2004-12-23 |
HU9400383D0 (en) | 1994-05-30 |
EP0610764A1 (de) | 1994-08-17 |
US6057363A (en) | 2000-05-02 |
US20010006964A1 (en) | 2001-07-05 |
CN1989970A (zh) | 2007-07-04 |
DE59408221D1 (de) | 1999-06-17 |
CN1329828A (zh) | 2002-01-09 |
US7105569B2 (en) | 2006-09-12 |
DE4304172A1 (de) | 1994-08-25 |
US6245772B1 (en) | 2001-06-12 |
HUT66297A (en) | 1994-11-28 |
ES2133426T3 (es) | 1999-09-16 |
US6495575B2 (en) | 2002-12-17 |
PL302198A1 (en) | 1994-08-22 |
US5776976A (en) | 1998-07-07 |
RU2176449C2 (ru) | 2001-12-10 |
US5491165A (en) | 1996-02-13 |
JPH06247810A (ja) | 1994-09-06 |
CN1091238A (zh) | 1994-08-31 |
HU213954B (en) | 1997-11-28 |
US5650423A (en) | 1997-07-22 |
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