Plant Health Composition

Abstract
The present invention relates to a method for improving the plant health of at least one plant variety, which method comprises treating the plant and/or the locus where the plant is growing or is intended to grow with an amide compound of the formula I (compound I). The present invention also relates to a method for improving the plant health of at least one plant variety, which method comprises treating the plant and/or the locus where the plant is growing or is intended to grow with a mixture comprising an amide compound having the formula I (compound I) and at least one compound selected from the group consisting of a further fungicide II (compound II), a further fungicide III (compound IIb), an insecticide (compound III) and a herbicide (compound IV).
Description

The present invention relates to a method for improving the plant health of at least one plant variety, which method comprises treating the plant and/or the locus where the plant is growing or is intended to grow with an amide having the formula I (compound I)




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    • in which the substituents are as defined below:

    • R4 is methyl, difluoromethyl, or trifluoromethyl;

    • R5 is hydrogen or fluorine;

    • M is a thienyl ring or a phenyl ring, wherein the phenylring is substituted or not substituted with a fluorine atom;

    • Q is a direct bond, a cyclopropylene or an anellated bicyclo[2.2.1]heptane ring;

    • R1 is cyclopropyl, 1,3-dimethylbutyl, isopropyl, phenyl substituted with two or three halogen atoms or a trifluoromethylthio radical.





The present invention relates to a method for improving the plant health of at least one plant variety, which method comprises treating the plant and/or the locus where the plant is growing or is intended to grow with a mixture comprising an amide of the formula I (compound I) and a further fungicide II (compound II) or an insecticide (compound III) or a herbicide (compound IV).


The present invention also relates to a method for improving the plant health of at least one plant variety, which method comprises treating the plant and/or the locus where the plant is growing or is intended to grow with a ternary mixture comprising an amide of the formula I (compound I) and as a second component a further fungicide II (compound II) or an insecticide (compound III) and as a third component either a further fungicide III (compound IIb) or optionally a herbicide (compound IV).


The present invention also relates to a method for improving the plant health of at least one plant variety, which method comprises treating the plant and/or the locus where the plant is growing or is intended to grow with a ternary mixture comprising an amide of the formula I (compound I) and an insecticide (compound III) and a herbicide (compound IV).


The present invention also relates to a method for improving the plant health of at least one plant variety, which method comprises treating the plant and/or the locus where the plant is growing or is intended to grow with a quaternary mixture comprising an amide of the formula I (compound I) and a further fungicide II (compound II) and a further fungicide III (compound IIb) and a herbicide (compound IV).


The present invention also relates to the use of an amide having the formula I (compound I) for improving the the plant health of at least one plant variety.


In crop protection, there is a continuous need for compositions that improve the health of plants. Healthier plants are desirable since they result among others in better crop yields and/or a better quality of the plants or crops. Healthier plants also better resist to abiotic stress.


It was therefore an object of the present invention to provide a pesticidal composition which solves the problems outlined above, and which should, in particular, improve plant health.


We have found that this object is achieved by a method for improving the health of a plant, which comprises treating the plant and/or the locus where the plant is growing or is intended to grow with an amide (compound I) having the formula I (compound I)




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    • in which the substituents are as defined below:

    • R4 is methyl or trifluoromethyl;

    • R5 is hydrogen or fluorine;

    • M is a thienyl ring or a phenyl ring, wherein the phenylring is substituted or not substituted with a fluorine atom;

    • Q is a direct bond, a cyclopropylene or an anellated bicyclo[2.2.1]heptane ring;

    • R1 is cyclopropyl, 1,3-dimethylbutyl, isopropyl, phenyl substituted with two or three halogen atoms or a trifluoromethylthio radical.





It was also found that certain fungicidal mixtures showed synergistic plant health effects in the method of the present invention.


Within these mixtures, also synergistic mixtures with synergistic fungicidal activity have been found.


WO 01/82701 discloses a method for inducing resistance of plants against virus infection by repeated application of strobilurin type active compounds. However, repeated application of fungicides may select resistant populations of the harmful fungi.


PCT/EP/2008/051672 discloses that certain anilids induce virus tolerance.


WO 07/104658 comprises a method of inducing tolerance of plants against bacterioses by application of strobilurins with anilid compounds to plants.


WO 05/018324 discloses plant health effects of certain anilid compunds.


Combinations of amides of formula I with several fungicides are disclosed in WO 07/017416, PCT/EP2008/051331, PCT/EP2008/051375, WO 08/000377, WO 07/128756, EP application No. 08152059.5, EP application No. 08155881.9, EP application No. 07119858.4 and PCT/EP2008/051955. However, herein no hints towards synergistic plant health effects are given.


In addition, none of these references discloses the synergistic plant health effects of the mixtures as defined at the outset or describes the synergistic fungicidal mixtures in detail.


The amides of formula I (compound I) are known as fungicides (cf., for example, EP-A 545 099, EP-A 589 301, EP-A 737682, EP-A 824099, WO 99/09013, WO 03/010149, WO 03/070705, WO 03/074491, WO 2004/005242, WO 04/035589, WO 04/067515, WO 06/087343,). They can be prepared in the manner described therein.


The further fungicide II (compound II), the insecticides (compound III) and the herbicides (compound IV) as well as their pesticidal action and methods for producing them are generally known. For instance, the commercially available compounds may be found in The Pesticide Manual, 13th Edition, British Crop Protection Council (2003) among other publications.


The below remarks as to preferred embodiments of amides of the formula I (compound I) and respective mixtures comprising the compounds (I), to their preferred use and methods of using them, are to be understood either each on their own or preferably in combination with each other.


In a preferred embodiment, the amide of the formula I (compound I) is a compound of the formula Ia




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which is N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, herein after referred to as “Ia”


According to another preferred embodiment, the amide of the formula I (compound I) is a compound of the formula Ib




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which is N-[2-(4′-trifluoromethylthio)-biphenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, herein after referred to as “Ib”


According to a further preferred embodiment, the amide of the formula I (compound I) is a compound of the formula Ic




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which is N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide (common name: bixafen), herein after referred to as “Ic”


According to a further preferred embodiment, the amide of the formula I (compound I) is a compound of the formula Id




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which is N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, herein after referred to as “Id”


According to a further preferred embodiment, the amide of the formula I (compound I) is a compound of the formula Ie




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which is N-(2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, wherein this compound can be found as racemat of its cis-isomers and trans-isomers (common name: sedaxane).


According to a further preferred embodiment, the amide of the formula I (compound I) is a compound of the formula If




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which is N-[1,2,3,4-tetrahydro-9-(1-methylethyl)-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (common name: isopyrazam), herein after referred to as “If”


According to a further preferred embodiment, the amide of the formula I (compound I) is a compound of the formula Ig




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Ig, which is N-[2-(1,3-dimethylbutyl)-3-thienyl]-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide (common name: penthiopyrad), herein after referred to as “Ig”


In a more preferred embodiment, compound (I) is selected from the group consisting of Ia, Ic, Ie, If and Ig.


In an even more preferred embodiment, compound (I) is selected from the group consisting of Ia, Ic, If and Ig, most preferably compound (I) is the compound Ia.


As mentioned at the outset, the present invention also relates to a method for improving the plant health of at least one plant variety, which method comprises treating the plant and/or the locus where the plant is growing or is expected to grow with a compound (I) or with a specified mixture. In one embodiment, this mixture comprises

  • (1) an amide of the formula I (compound I); and
  • (2) a further fungicide II (compound II), wherein the further fungicide II is selected from the group consisting of
    • (i) strobilurines, selected from azoxystrobin (S1), dimoxystrobin (S2), fluoxastrobin (S3), kresoxim-methyl (S4), metominostrobin (S5), orysastrobin (S6), picoxystrobin (S7), pyraclostrobin (S8) and trifloxystrobin (S9);
    • (ii) carboxylic amides, selected from boscalid, fenhexamid, metalaxyl, dimethomorph, fluopicolide (picobenzamid), zoxamide, mandipropamid and carpropamid;
    • (iii) azoles, selected from cyproconazole (A1), difenoconazole (A2), epoxiconazole (A3), flusilazole (A4), fluquinconazole (A5), flutriafol (A6), ipconazole (A7), metconazole (A8), propiconazole (A9), prothioconazole (A10), tebuconazole (A11), cyazofamid (A12), prochloraz (A13), ethaboxam (A14) and triazoxide (A15);
    • (iv) heterocyclic compounds, selected from famoxadone, fluazinam, cyprodinil, pyrimethanil, fenpropimorph, iprodione, acibenzolar-S-methyl, proquinazid, quinoxyfen, fenpiclonil, captan, fenpropidin, captafol and anilazin;
    • (v) carbamates and dithiocarbannates, selected from mancozeb, metiram, iprovalicarb, maneb, propineb, flubenthiavalicarb (benthiavalicarb) and propamocarb;
    • (vi) organo-chloro compounds, selected from thiophanate methyl, chlorothalonil, tolylfluanid and flusulfamid;
    • (vii) inorganic active ingredients, selected from Bordeaux composition, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate and sulfur;
    • (viii) various, selected from spiroxamine, guazatin, cymoxanil, cyflufenamid, valiphenal, metrafenone; fosetly-aluminium and dithianon;
    • (3) and as a third component optionally a further fungicide III (compound IIb), wherein the further fungicide III is selected from the group consisting of
    • (iii) azoles, selected from cyproconazole (A1), difenoconazole (A2), epoxiconazole (A3), flusilazole (A4), fluquinconazole (A5), flutriafol (A6), ipconazole (A7), metconazole (A8), propiconazole (A9), prothioconazole (A10), tebuconazole (A11), cyazofamid (A12), prochloraz (A13), ethaboxam (A14) and triazoxide (A15);
    • (4) or as a third component optionally a herbicide (compound IV), wherein the herbicide is selected from the group consisting of glyphosate (H1), glyphosinate (H2) and sulfonisate (H3).


      in plant health synergistically effective amounts.


The term “plant health effective amount” denotes an amount of the compound (I) or the mixtures of compound (I) and at least one compound selected from the group consisting of the compounds (II), (IIb), (III) and (IV), which is sufficient for achieving plant health effects as defined herein below. More exemplary information about amounts, ways of application and suitable ratios to be used is given below. Anyway, the skilled artisan is well aware of the fact that such an amount can vary in a broad range and is dependent on various factors, e.g. the treated cultivated plant or material and the climatic conditions.


The term “synergistic” means that the simultaneous, that is joint or separate, application of the compound (I) and at least one compound of the group consisting of the compounds (II), (IIb), (III) and (IV), or the successive application of the compound (I) and at least one compound of the group consisting of the compounds (II), (IIb), (III) and (IV), provides enhanced plant health effects compared to the plant health effects that are possible with the individual compounds.


Preferably, the further fungicide II (compound II) is selected from the group consisting of

  • (i) strobilurines, selected from azoxystrobin (S1), dimoxystrobin (S2), orysastrobin (S6), picoxystrobin (S7), pyraclostrobin (S8) and trifloxystrobin (S9);
  • (ii) carboxcyclic amides, selected from boscalid and dimethomorph;
  • (iii) azoles, selected from cyproconazole (A1), difenoconazole (A2), epoxiconazole (A3), metconazole (A8), propiconazole (A9), prothioconazole (A10) and tebuconazole (A11);
  • (iv) heterocyclic compounds, selected from cyprodinil, pyrimethanil, fenpropimorph, iprodione, quinoxyfen and acibenzolar-S-methyl;
  • (v) carbamates and dithiocarbamates, selected from mancozeb, metiram, propineb and iprovalicarb;
  • (viii) various, selected from dithianon and metrafenone.


Preferably, the further fungicide III (compound IIb) is selected from the group consisting of

  • (iii) azoles, selected from cyproconazole (A1), difenoconazole (A2), epoxiconazole (A3), metconazole (A8), propiconazole (A9), prothioconazole (A10) and tebuconazole (A11).


The preferred herbicide (compound IV) is glyphosate (H1).


More preferably, the further fungicide II (compound II) is selected from the group consisting of:

  • (i) strobilurines, selected from azoxystrobin (S1), orysastrobin (S6), pyraclostrobin (S8), trifloxystrobin (S9)
  • (iii) azoles, selected from epoxiconazole (A3), metconazole (A8), propiconazole (A9), prothioconazole (A10) and tebuconazole (A11).


Most preferably, the further fungicide II (compound II) is selected from the group consisting of azoxystrobin (S1), orysastrobin (S6), pyraclostrobin (S8), and trifloxystrobin (S9), wherein orysastrobin (S6) and pyraclostrobin (S8) are the utmost preferred fungicides II.


Most preferably, the further fungicide III (compound IIb) is selected from the group consisting of epoxiconazole (A3), metconazole (A8), propiconazole (A9), prothioconazole (A10) and tebuconazole (A11).


In the terms of the present invention “mixture” is not restricted to a physical mixture containing compounds (I) and at least one compound selected from the group consisting of compounds (II), (IIb), (III) and (IV) but refers to any preparation form of compounds (I) and at least one compound selected from the group consisting of compounds (II), (IIb), (III) and (IV), the use of which is time- and locus-related.


In one embodiment of the invention “mixture” refers to a physical mixture of the compound (I) (=one compound I) and one compound selected from the group consisting of compounds (II), (IIb), (III) and (IV), (=one of the specific fungicides II or the specific fungicides IIb or one of the insecticides III or one of the herbicides IV as defined).


In another embodiment of the invention, “mixture” refers to ternary mixtures comprising a compound (I) and one compound (II) and one compound selected from the group consisting of (IIb), (III) and (IV).


In another embodiment of the invention, “mixture” refers to quaternary mixtures comprising a compound (I) and one compound (II) and two compounds selected from the group consisting of (IIb), (III) and (IV).


In another embodiment of the invention, “mixture” refers to the compounds (I) and at least one compound selected from the group consisting of compounds (II), (IIb), (III) ornd (IV), formulated separately but applied to the same plant or locus, where the plant grows or intends to grow in a temporal relationship, i.e. simultaneously or subsequently, the subsequent application having a time interval which allows a combined action of the compounds.


Furthermore, the individual compounds of the mixtures according to the invention such as parts of a kit or parts of the binary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate (tank mix).


In another embodiment, these mixtures comprise

  • (I) an amide compound of the formula I (compound I) and
  • (III) an insecticide (compound III) selected from the group consisting of fipronil (Fip) and ethiprole (Ethi).


    in synergistically plant health effective amounts.


The preferred insecticide (compound III) is fipronil (Fip).


Preferably, all above-mentioned mixtures comprise either Ia, Ib, Ic, Id, Ie, If or Ig as compound (I).


More preferably, these mixtures comprise either Ia, Ic, If or Ig as compound (I). Most preferably, these mixtures comprise either Ia, Ic or If as compound (I).


In a particular preferred embodiment, these mixtures comprise Ia as compound (I).


Thus, with respect to their intended use in the methods of the present invention, the following secondary mixtures of compound (I) and compounds (II) or (III) or (IV), listed in the table below are a preferred embodiment of the present invention:













TABLE 1







No.
(I)
(II) or (III) or (IV)









M-1
Ia
azoxystrobin



M-2
Ia
orysastrobin



M-3
Ia
pyraclostrobin



M-4
Ia
trifloxystrobin



M-5
Ia
epoxiconazole



M-6
Ia
metconazole



M-7
Ia
prothioconazole



M-8
Ia
tebuconazole



M-9
Ia
propiconazole



M-10
Ia
fipronil



M-11
Ia
boscalid



M-12
Ia
dimethomorph



M-13
Ia
cyproconazole



M-14
Ia
difenoconazole



M-15
Ia
cyprodinil



M-16
Ia
pyrimethanil



M-17
Ia
fenpropimorph



M-18
Ia
iprodione



M-19
Ia
quinoxyfen



M-20
Ia
acibenzolar-S-methyl



M-21
Ia
mancozeb



M-22
Ia
metiram



M-23
Ia
propineb



M-24
Ia
iprovalicarb



M-25
Ia
dithianon



M-26
Ia
metrafenone



M-27
Ic
azoxystrobin



M-28
Ic
orysastrobin



M-29
Ic
pyraclostrobin



M-30
Ic
trifloxystrobin



M-31
Ic
epoxiconazole



M-32
Ic
metconazole



M-33
Ic
prothioconazole



M-34
Ic
tebuconazole



M-35
Ic
propiconazole



M-36
Ic
fipronil



M-37
Ic
boscalid



M-38
Ic
dimethomorph



M-39
Ic
cyproconazole



M-40
Ic
difenoconazole



M-41
Ic
cyprodinil



M-42
Ic
pyrimethanil



M-43
Ic
fenpropimorph



M-44
Ic
iprodione



M-45
Ic
quinoxyfen



M-46
Ic
acibenzolar-S-methyl



M-47
Ic
mancozeb



M-48
Ic
metiram



M-49
Ic
propineb



M-50
Ic
iprovalicarb



M-51
Ic
dithianon



M-52
Ic
metrafenone



M-53
If
azoxystrobin



M-54
If
orysastrobin



M-55
If
pyraclostrobin



M-56
If
trifloxystrobin



M-57
If
epoxiconazole



M-58
If
metconazole



M-59
If
prothioconazole



M-60
If
tebuconazole



M-61
If
propiconazole



M-62
If
fipronil



M-63
If
boscalid



M-64
If
dimethomorph



M-65
If
cyproconazole



M-66
If
difenoconazole



M-67
If
cyprodinil



M-68
If
pyrimethanil



M-69
If
fenpropimorph



M-70
If
iprodione



M-71
If
quinoxyfen



M-72
If
acibenzolar-S-methyl



M-73
If
mancozeb



M-74
If
metiram



M-75
If
propineb



M-76
If
iprovalicarb



M-77
If
dithianon



M-78
If
metrafenone



M-79
Ig
azoxystrobin



M-80
Ig
orysastrobin



M-81
Ig
pyraclostrobin



M-82
Ig
trifloxystrobin



M-83
Ig
epoxiconazole



M-84
Ig
metconazole



M-85
Ig
prothioconazole



M-86
Ig
tebuconazole



M-87
Ig
propiconazole



M-88
Ig
fipronil



M-89
Ig
boscalid



M-90
Ig
dimethomorph



M-91
Ig
cyproconazole



M-92
Ig
difenoconazole



M-93
Ig
cyprodinil



M-94
Ig
pyrimethanil



M-95
Ig
fenpropimorph



M-96
Ig
iprodione



M-97
Ig
quinoxyfen



M-98
Ig
acibenzolar-S-methyl



M-99
Ig
mancozeb



M-100
Ig
metiram



M-101
Ig
propineb



M-102
Ig
iprovalicarb



M-103
Ig
dithianon



M-104
Ig
metrafenone



M-105
Ia
glyphosate



M-106
Ib
glyphosate



M-107
Ic
glyphosate



M-108
Id
glyphosate



M-109
Ie
glyphosate



M-110
If
glyphosate



M-111
Ig
glyphosate










Within the mixtures of table 1, the following mixtures are especially preferred: M-1, M-2, M-3, M-4, M-5, M-6, M-7, M-8, M-9, M-10, M-27, M-28, M-29, M-30, M-31, M-32, M-33, M-34, M-35, M-36, M-53, M-54, M-55, M-56, M-57, M-58, M-59, M-60, M-61, M-61, M-62, M-79, M-80, M-81, M-82, M-83, M-84, M-85, M-86, M-87, M-88, M-105, M-106, M-107, M-108, M-109, M-110 and M-111.


Within this subset, the following mixtures are more preferred:


M-1, M-2, M-3, M-4,M-10, M-27, M-28, M-29, M-30, M-36, M-53, M-54, M-55, M-56, M-62, M-79, M-80, M-81, M-82, M-88, M-105, M-107, M-110 and M-111


The following mixtures are even more preferred: M-1, M-2, M-3, M-4, M-27, M-28, M-29, M-30, M-53, M-54, M-55, M-56, M-79, M-80, M-81, M-82 and M-105


The following mixtures are most preferred: M-2, M-3, M-28, M-29, M-54, M-55, M-80, M-81 and M-105.


Utmost preference is given to mixtures M-2, M-3 and M-105.


With respect to their intended use within the methods of the present invention, the following ternary mixtures of compound (I) and compounds (II) or (III) in combination with compounds (IIb) or (IV) listed in the table 2 below are a prefered embodiment of the present invention.


The mixtures disclosed in table 2 are also a further embodiment of the present invention.














TABLE 2









(II)
(IIb)





or
or



No.
(I)
(III)
(IV)









N-1
Ia
S1
A1



N-2
Ia
S1
A2



N-3
Ia
S1
A3



N-4
Ia
S1
A4



N-5
Ia
S1
A5



N-6
Ia
S1
A6



N-7
Ia
S1
A7



N-8
Ia
S1
A8



N-9
Ia
S1
A9



N-10
Ia
S1
A10



N-11
Ia
S1
A11



N-12
Ia
S1
A12



N-13
Ia
S1
A13



N-14
Ia
S1
A14



N-15
Ia
S1
A15



N-16
Ia
S2
A1



N-17
Ia
S2
A2



N-18
Ia
S2
A3



N-19
Ia
S2
A4



N-20
Ia
S2
A5



N-21
Ia
S2
A6



N-22
Ia
S2
A7



N-23
Ia
S2
A8



N-24
Ia
S2
A9



N-25
Ia
S2
A10



N-26
Ia
S2
A11



N-27
Ia
S2
A12



N-28
Ia
S2
A13



N-29
Ia
S2
A14



N-30
Ia
S2
A15



N-31
Ia
S3
A1



N-32
Ia
S3
A2



N-33
Ia
S3
A3



N-34
Ia
S3
A4



N-35
Ia
S3
A5



N-36
Ia
S3
A6



N-37
Ia
S3
A7



N-38
Ia
S3
A8



N-39
Ia
S3
A9



N-40
Ia
S3
A10



N-41
Ia
S3
A11



N-42
Ia
S3
A12



N-43
Ia
S3
A13



N-44
Ia
S3
A14



N-45
Ia
S3
A15



N-46
Ia
S4
A1



N-47
Ia
S4
A2



N-48
Ia
S4
A3



N-49
Ia
S4
A4



N-50
Ia
S4
A5



N-51
Ia
S4
A6



N-52
Ia
S4
A7



N-53
Ia
S4
A8



N-54
Ia
S4
A9



N-55
Ia
S4
A10



N-56
Ia
S4
A11



N-57
Ia
S4
A12



N-58
Ia
S4
A13



N-59
Ia
S4
A14



N-60
Ia
S4
A15



N-61
Ia
S5
A1



N-62
Ia
S5
A2



N-63
Ia
S5
A3



N-64
Ia
S5
A4



N-65
Ia
S5
A5



N-66
Ia
S5
A6



N-67
Ia
S5
A7



N-68
Ia
S5
A8



N-69
Ia
S5
A9



N-70
Ia
S5
A10



N-71
Ia
S5
A11



N-72
Ia
S5
A12



N-73
Ia
S5
A13



N-74
Ia
S5
A14



N-75
Ia
S5
A15



N-76
Ia
S6
A1



N-77
Ia
S6
A2



N-78
Ia
S6
A3



N-79
Ia
S6
A4



N-80
Ia
S6
A5



N-81
Ia
S6
A6



N-82
Ia
S6
A7



N-83
Ia
S6
A8



N-84
Ia
S6
A9



N-85
Ia
S6
A10



N-86
Ia
S6
A11



N-87
Ia
S6
A12



N-88
Ia
S6
A13



N-89
Ia
S6
A14



N-90
Ia
S6
A15



N-91
Ia
S7
A1



N-92
Ia
S7
A2



N-93
Ia
S7
A3



N-94
Ia
S7
A4



N-95
Ia
S7
A5



N-96
Ia
S7
A6



N-97
Ia
S7
A7



N-98
Ia
S7
A8



N-99
Ia
S7
A9



N-100
Ia
S7
A10



N-101
Ia
S7
A11



N-102
Ia
S7
A12



N-103
Ia
S7
A13



N-104
Ia
S7
A14



N-105
Ia
S7
A15



N-106
Ia
S8
A1



N-107
Ia
S8
A2



N-108
Ia
S8
A3



N-109
Ia
S8
A4



N-110
Ia
S8
A5



N-111
Ia
S8
A6



N-112
Ia
S8
A7



N-113
Ia
S8
A8



N-114
Ia
S8
A9



N-115
Ia
S8
A10



N-116
Ia
S8
A11



N-117
Ia
S8
A12



N-118
Ia
S8
A13



N-119
Ia
S8
A14



N-120
Ia
S8
A15



N-121
Ia
S9
A1



N-122
Ia
S9
A2



N-123
Ia
S9
A3



N-124
Ia
S9
A4



N-125
Ia
S9
A5



N-126
Ia
S9
A6



N-127
Ia
S9
A7



N-128
Ia
S9
A8



N-129
Ia
S9
A9



N-130
Ia
S9
A10



N-131
Ia
S9
A11



N-132
Ia
S9
A12



N-133
Ia
S9
A13



N-134
Ia
S9
A14



N-135
Ia
S9
A15



N-136
Ib
S1
A1



N-137
Ib
S1
A2



N-138
Ib
S1
A3



N-139
Ib
S1
A4



N-140
Ib
S1
A5



N-141
Ib
S1
A6



N-142
Ib
S1
A7



N-143
Ib
S1
A8



N-144
Ib
S1
A9



N-145
Ib
S1
A10



N-146
Ib
S1
A11



N-147
Ib
S1
A12



N-148
Ib
S1
A13



N-149
Ib
S1
A14



N-150
Ib
S1
A15



N-151
Ib
S2
A1



N-152
Ib
S2
A2



N-153
Ib
S2
A3



N-154
Ib
S2
A4



N-155
Ib
S2
A5



N-156
Ib
S2
A6



N-157
Ib
S2
A7



N-158
Ib
S2
A8



N-159
Ib
S2
A9



N-160
Ib
S2
A10



N-161
Ib
S2
A11



N-162
Ib
S2
A12



N-163
Ib
S2
A13



N-164
Ib
S2
A14



N-165
Ib
S2
A15



N-166
Ib
S3
A1



N-167
Ib
S3
A2



N-168
Ib
S3
A3



N-169
Ib
S3
A4



N-170
Ib
S3
A5



N-171
Ib
S3
A6



N-172
Ib
S3
A7



N-173
Ib
S3
A8



N-174
Ib
S3
A9



N-175
Ib
S3
A10



N-176
Ib
S3
A11



N-177
Ib
S3
A12



N-178
Ib
S3
A13



N-179
Ib
S3
A14



N-180
Ib
S3
A15



N-181
Ib
S4
A1



N-182
Ib
S4
A2



N-183
Ib
S4
A3



N-184
Ib
S4
A4



N-185
Ib
S4
A5



N-186
Ib
S4
A6



N-187
Ib
S4
A7



N-188
Ib
S4
A8



N-189
Ib
S4
A9



N-190
Ib
S4
A10



N-191
Ib
S4
A11



N-192
Ib
S4
A12



N-193
Ib
S4
A13



N-194
Ib
S4
A14



N-195
Ib
S4
A15



N-196
Ib
S5
A1



N-197
Ib
S5
A2



N-198
Ib
S5
A3



N-199
Ib
S5
A4



N-200
Ib
S5
A5



N-201
Ib
S5
A6



N-202
Ib
S5
A7



N-203
Ib
S5
A8



N-204
Ib
S5
A9



N-205
Ib
S5
A10



N-206
Ib
S5
A11



N-207
Ib
S5
A12



N-208
Ib
S5
A13



N-209
Ib
S5
A14



N-210
Ib
S5
A15



N-211
Ib
S6
A1



N-212
Ib
S6
A2



N-213
Ib
S6
A3



N-214
Ib
S6
A4



N-215
Ib
S6
A5



N-216
Ib
S6
A6



N-217
Ib
S6
A7



N-218
Ib
S6
A8



N-219
Ib
S6
A9



N-220
Ib
S6
A10



N-221
Ib
S6
A11



N-222
Ib
S6
A12



N-223
Ib
S6
A13



N-224
Ib
S6
A14



N-225
Ib
S6
A15



N-226
Ib
S7
A1



N-227
Ib
S7
A2



N-228
Ib
S7
A3



N-229
Ib
S7
A4



N-230
Ib
S7
A5



N-231
Ib
S7
A6



N-232
Ib
S7
A7



N-233
Ib
S7
A8



N-234
Ib
S7
A9



N-235
Ib
S7
A10



N-236
Ib
S7
A11



N-237
Ib
S7
A12



N-238
Ib
S7
A13



N-239
Ib
S7
A14



N-240
Ib
S7
A15



N-241
Ib
S8
A1



N-242
Ib
S8
A2



N-243
Ib
S8
A3



N-244
Ib
S8
A4



N-245
Ib
S8
A5



N-246
Ib
S8
A6



N-247
Ib
S8
A7



N-248
Ib
S8
A8



N-249
Ib
S8
A9



N-250
Ib
S8
A10



N-251
Ib
S8
A11



N-252
Ib
S8
A12



N-253
Ib
S8
A13



N-254
Ib
S8
A14



N-255
Ib
S8
A15



N-256
Ib
S9
A1



N-257
Ib
S9
A2



N-258
Ib
S9
A3



N-259
Ib
S9
A4



N-260
Ib
S9
A5



N-261
Ib
S9
A6



N-262
Ib
S9
A7



N-263
Ib
S9
A8



N-264
Ib
S9
A9



N-265
Ib
S9
A10



N-266
Ib
S9
A11



N-267
Ib
S9
A12



N-268
Ib
S9
A13



N-269
Ib
S9
A14



N-270
Ib
S9
A15



N-271
Ic
S1
A1



N-272
Ic
S1
A2



N-273
Ic
S1
A3



N-274
Ic
S1
A4



N-275
Ic
S1
A5



N-276
Ic
S1
A6



N-277
Ic
S1
A7



N-278
Ic
S1
A8



N-279
Ic
S1
A9



N-280
Ic
S1
A10



N-281
Ic
S1
A11



N-282
Ic
S1
A12



N-283
Ic
S1
A13



N-284
Ic
S1
A14



N-285
Ic
S1
A15



N-286
Ic
S2
A1



N-287
Ic
S2
A2



N-288
Ic
S2
A3



N-289
Ic
S2
A4



N-290
Ic
S2
A5



N-291
Ic
S2
A6



N-292
Ic
S2
A7



N-293
Ic
S2
A8



N-294
Ic
S2
A9



N-295
Ic
S2
A10



N-296
Ic
S2
A11



N-297
Ic
S2
A12



N-298
Ic
S2
A13



N-299
Ic
S2
A14



N-300
Ic
S2
A15



N-301
Ic
S3
A1



N-302
Ic
S3
A2



N-303
Ic
S3
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N-304
Ic
S3
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N-305
Ic
S3
A5



N-306
Ic
S3
A6



N-307
Ic
S3
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N-308
Ic
S3
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N-309
Ic
S3
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N-310
Ic
S3
A10



N-311
Ic
S3
A11



N-312
Ic
S3
A12



N-313
Ic
S3
A13



N-314
Ic
S3
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N-315
Ic
S3
A15



N-316
Ic
S4
A1



N-317
Ic
S4
A2



N-318
Ic
S4
A3



N-319
Ic
S4
A4



N-320
Ic
S4
A5



N-321
Ic
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A6



N-322
Ic
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A7



N-323
Ic
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N-324
Ic
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N-325
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S4
A10



N-326
Ic
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A11



N-327
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A12



N-328
Ic
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A13



N-329
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N-330
Ic
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A15



N-331
Ic
S5
A1



N-332
Ic
S5
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N-333
Ic
S5
A3



N-334
Ic
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N-335
Ic
S5
A5



N-336
Ic
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A6



N-337
Ic
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N-338
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N-339
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N-340
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N-341
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A11



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N-343
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N-344
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Ic
S5
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N-346
Ic
S6
A1



N-347
Ic
S6
A2



N-348
Ic
S6
A3



N-349
Ic
S6
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N-350
Ic
S6
A5



N-351
Ic
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A6



N-352
Ic
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A7



N-353
Ic
S6
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N-354
Ic
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N-355
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A10



N-356
Ic
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A11



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N-361
Ic
S7
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N-362
Ic
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N-363
Ic
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N-364
Ic
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N-365
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N-366
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N-367
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N-368
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N-369
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N-370
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N-371
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N-373
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N-374
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N-376
Ic
S8
A1



N-377
Ic
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N-378
Ic
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A3



N-379
Ic
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A4



N-380
Ic
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A5



N-381
Ic
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A6



N-382
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N-383
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N-384
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N-385
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N-386
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N-388
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Ic
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N-392
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N-394
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N-395
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N-396
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N-397
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N-398
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N-399
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N-400
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S1
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S1
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S1
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S1
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Ie
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N-553
Ie
S1
A13



N-554
Ie
S1
A14



N-555
Ie
S1
A15



N-556
Ie
S2
A1



N-557
Ie
S2
A2



N-558
Ie
S2
A3



N-559
Ie
S2
A4



N-560
Ie
S2
A5



N-561
Ie
S2
A6



N-562
Ie
S2
A7



N-563
Ie
S2
A8



N-564
Ie
S2
A9



N-565
Ie
S2
A10



N-566
Ie
S2
A11



N-567
Ie
S2
A12



N-568
Ie
S2
A13



N-569
Ie
S2
A14



N-570
Ie
S2
A15



N-571
Ie
S3
A1



N-572
Ie
S3
A2



N-573
Ie
S3
A3



N-574
Ie
S3
A4



N-575
Ie
S3
A5



N-576
Ie
S3
A6



N-577
Ie
S3
A7



N-578
Ie
S3
A8



N-579
Ie
S3
A9



N-580
Ie
S3
A10



N-581
Ie
S3
A11



N-582
Ie
S3
A12



N-583
Ie
S3
A13



N-584
Ie
S3
A14



N-585
Ie
S3
A15



N-586
Ie
S4
A1



N-587
Ie
S4
A2



N-588
Ie
S4
A3



N-589
Ie
S4
A4



N-590
Ie
S4
A5



N-591
Ie
S4
A6



N-592
Ie
S4
A7



N-593
Ie
S4
A8



N-594
Ie
S4
A9



N-595
Ie
S4
A10



N-596
Ie
S4
A11



N-597
Ie
S4
A12



N-598
Ie
S4
A13



N-599
Ie
S4
A14



N-600
Ie
S4
A15



N-601
Ie
S5
A1



N-602
Ie
S5
A2



N-603
Ie
S5
A3



N-604
Ie
S5
A4



N-605
Ie
S5
A5



N-606
Ie
S5
A6



N-607
Ie
S5
A7



N-608
Ie
S5
A8



N-609
Ie
S5
A9



N-610
Ie
S5
A10



N-611
Ie
S5
A11



N-612
Ie
S5
A12



N-613
Ie
S5
A13



N-614
Ie
S5
A14



N-615
Ie
S5
A15



N-616
Ie
S6
A1



N-617
Ie
S6
A2



N-618
Ie
S6
A3



N-619
Ie
S6
A4



N-620
Ie
S6
A5



N-621
Ie
S6
A6



N-622
Ie
S6
A7



N-623
Ie
S6
A8



N-624
Ie
S6
A9



N-625
Ie
S6
A10



N-626
Ie
S6
A11



N-627
Ie
S6
A12



N-628
Ie
S6
A13



N-629
Ie
S6
A14



N-630
Ie
S6
A15



N-631
Ie
S7
A1



N-632
Ie
S7
A2



N-633
Ie
S7
A3



N-634
Ie
S7
A4



N-635
Ie
S7
A5



N-636
Ie
S7
A6



N-637
Ie
S7
A7



N-638
Ie
S7
A8



N-639
Ie
S7
A9



N-640
Ie
S7
A10



N-641
Ie
S7
A11



N-642
Ie
S7
A12



N-643
Ie
S7
A13



N-644
Ie
S7
A14



N-645
Ie
S7
A15



N-646
Ie
S8
A1



N-647
Ie
S8
A2



N-648
Ie
S8
A3



N-649
Ie
S8
A4



N-650
Ie
S8
A5



N-651
Ie
S8
A6



N-652
Ie
S8
A7



N-653
Ie
S8
A8



N-654
Ie
S8
A9



N-655
Ie
S8
A10



N-656
Ie
S8
A11



N-657
Ie
S8
A12



N-658
Ie
S8
A13



N-659
Ie
S8
A14



N-660
Ie
S8
A15



N-661
Ie
S9
A1



N-662
Ie
S9
A2



N-663
Ie
S9
A3



N-664
Ie
S9
A4



N-665
Ie
S9
A5



N-666
Ie
S9
A6



N-667
Ie
S9
A7



N-668
Ie
S9
A8



N-669
Ie
S9
A9



N-670
Ie
S9
A10



N-671
Ie
S9
A11



N-672
Ie
S9
A12



N-673
Ie
S9
A13



N-674
Ie
S9
A14



N-675
Ie
S9
A15



N-676
If
S1
A1



N-677
If
S1
A2



N-678
If
S1
A3



N-679
If
S1
A4



N-680
If
S1
A5



N-681
If
S1
A6



N-682
If
S1
A7



N-683
If
S1
A8



N-684
If
S1
A9



N-685
If
S1
A10



N-686
If
S1
A11



N-687
If
S1
A12



N-688
If
S1
A13



N-689
If
S1
A14



N-690
If
S1
A15



N-691
If
S2
A1



N-692
If
S2
A2



N-693
If
S2
A3



N-694
If
S2
A4



N-695
If
S2
A5



N-696
If
S2
A6



N-697
If
S2
A7



N-698
If
S2
A8



N-699
If
S2
A9



N-700
If
S2
A10



N-701
If
S2
A11



N-702
If
S2
A12



N-703
If
S2
A13



N-704
If
S2
A14



N-705
If
S2
A15



N-706
If
S3
A1



N-707
If
S3
A2



N-708
If
S3
A3



N-709
If
S3
A4



N-710
If
S3
A5



N-711
If
S3
A6



N-712
If
S3
A7



N-713
If
S3
A8



N-714
If
S3
A9



N-715
If
S3
A10



N-716
If
S3
A11



N-717
If
S3
A12



N-718
If
S3
A13



N-719
If
S3
A14



N-720
If
S3
A15



N-721
If
S4
A1



N-722
If
S4
A2



N-723
If
S4
A3



N-724
If
S4
A4



N-725
If
S4
A5



N-726
If
S4
A6



N-727
If
S4
A7



N-728
If
S4
A8



N-729
If
S4
A9



N-730
If
S4
A10



N-731
If
S4
A11



N-732
If
S4
A12



N-733
If
S4
A13



N-734
If
S4
A14



N-735
If
S4
A15



N-736
If
S5
A1



N-737
If
S5
A2



N-738
If
S5
A3



N-739
If
S5
A4



N-740
If
S5
A5



N-741
If
S5
A6



N-742
If
S5
A7



N-743
If
S5
A8



N-744
If
S5
A9



N-745
If
S5
A10



N-746
If
S5
A11



N-747
If
S5
A12



N-748
If
S5
A13



N-749
If
S5
A14



N-750
If
S5
A15



N-751
If
S6
A1



N-752
If
S6
A2



N-753
If
S6
A3



N-754
If
S6
A4



N-755
If
S6
A5



N-756
If
S6
A6



N-757
If
S6
A7



N-758
If
S6
A8



N-759
If
S6
A9



N-760
If
S6
A10



N-761
If
S6
A11



N-762
If
S6
A12



N-763
If
S6
A13



N-764
If
S6
A14



N-765
If
S6
A15



N-766
If
S7
A1



N-767
If
S7
A2



N-768
If
S7
A3



N-769
If
S7
A4



N-770
If
S7
A5



N-771
If
S7
A6



N-772
If
S7
A7



N-773
If
S7
A8



N-774
If
S7
A9



N-775
If
S7
A10



N-776
If
S7
A11



N-777
If
S7
A12



N-778
If
S7
A13



N-779
If
S7
A14



N-780
If
S7
A15



N-781
If
S8
A1



N-782
If
S8
A2



N-783
If
S8
A3



N-784
If
S8
A4



N-785
If
S8
A5



N-786
If
S8
A6



N-787
If
S8
A7



N-788
If
S8
A8



N-789
If
S8
A9



N-790
If
S8
A10



N-791
If
S8
A11



N-792
If
S8
A12



N-793
If
S8
A13



N-794
If
S8
A14



N-795
If
S8
A15



N-796
If
S9
A1



N-797
If
S9
A2



N-798
If
S9
A3



N-799
If
S9
A4



N-800
If
S9
A5



N-801
If
S9
A6



N-802
If
S9
A7



N-803
If
S9
A8



N-804
If
S9
A9



N-805
If
S9
A10



N-806
If
S9
A11



N-807
If
S9
A12



N-808
If
S9
A13



N-809
If
S9
A14



N-810
If
S9
A15



N-811
Ig
S1
A1



N-812
Ig
S1
A2



N-813
Ig
S1
A3



N-814
Ig
S1
A4



N-815
Ig
S1
A5



N-816
Ig
S1
A6



N-817
Ig
S1
A7



N-818
Ig
S1
A8



N-819
Ig
S1
A9



N-820
Ig
S1
A10



N-821
Ig
S1
A11



N-822
Ig
S1
A12



N-823
Ig
S1
A13



N-824
Ig
S1
A14



N-825
Ig
S1
A15



N-826
Ig
S2
A1



N-827
Ig
S2
A2



N-828
Ig
S2
A3



N-829
Ig
S2
A4



N-830
Ig
S2
A5



N-831
Ig
S2
A6



N-832
Ig
S2
A7



N-833
Ig
S2
A8



N-834
Ig
S2
A9



N-835
Ig
S2
A10



N-836
Ig
S2
A11



N-837
Ig
S2
A12



N-838
Ig
S2
A13



N-839
Ig
S2
A14



N-840
Ig
S2
A15



N-841
Ig
S3
A1



N-842
Ig
S3
A2



N-843
Ig
S3
A3



N-844
Ig
S3
A4



N-845
Ig
S3
A5



N-846
Ig
S3
A6



N-847
Ig
S3
A7



N-848
Ig
S3
A8



N-849
Ig
S3
A9



N-850
Ig
S3
A10



N-851
Ig
S3
A11



N-852
Ig
S3
A12



N-853
Ig
S3
A13



N-854
Ig
S3
A14



N-855
Ig
S3
A15



N-856
Ig
S4
A1



N-857
Ig
S4
A2



N-858
Ig
S4
A3



N-859
Ig
S4
A4



N-860
Ig
S4
A5



N-861
Ig
S4
A6



N-862
Ig
S4
A7



N-863
Ig
S4
A8



N-864
Ig
S4
A9



N-865
Ig
S4
A10



N-866
Ig
S4
A11



N-867
Ig
S4
A12



N-868
Ig
S4
A13



N-869
Ig
S4
A14



N-870
Ig
S4
A15



N-871
Ig
S5
A1



N-872
Ig
S5
A2



N-873
Ig
S5
A3



N-874
Ig
S5
A4



N-875
Ig
S5
A5



N-876
Ig
S5
A6



N-877
Ig
S5
A7



N-878
Ig
S5
A8



N-879
Ig
S5
A9



N-880
Ig
S5
A10



N-881
Ig
S5
A11



N-882
Ig
S5
A12



N-883
Ig
S5
A13



N-884
Ig
S5
A14



N-885
Ig
S5
A15



N-886
Ig
S6
A1



N-887
Ig
S6
A2



N-888
Ig
S6
A3



N-889
Ig
S6
A4



N-890
Ig
S6
A5



N-891
Ig
S6
A6



N-892
Ig
S6
A7



N-893
Ig
S6
A8



N-894
Ig
S6
A9



N-895
Ig
S6
A10



N-896
Ig
S6
A11



N-897
Ig
S6
A12



N-898
Ig
S6
A13



N-899
Ig
S6
A14



N-900
Ig
S6
A15



N-901
Ig
S7
A1



N-902
Ig
S7
A2



N-903
Ig
S7
A3



N-904
Ig
S7
A4



N-905
Ig
S7
A5



N-906
Ig
S7
A6



N-907
Ig
S7
A7



N-908
Ig
S7
A8



N-909
Ig
S7
A9



N-910
Ig
S7
A10



N-911
Ig
S7
A11



N-912
Ig
S7
A12



N-913
Ig
S7
A13



N-914
Ig
S7
A14



N-915
Ig
S7
A15



N-916
Ig
S8
A1



N-917
Ig
S8
A2



N-918
Ig
S8
A3



N-919
Ig
S8
A4



N-920
Ig
S8
A5



N-921
Ig
S8
A6



N-922
Ig
S8
A7



N-923
Ig
S8
A8



N-924
Ig
S8
A9



N-925
Ig
S8
A10



N-926
Ig
S8
A11



N-927
Ig
S8
A12



N-928
Ig
S8
A13



N-929
Ig
S8
A14



N-930
Ig
S8
A15



N-931
Ig
S9
A1



N-932
Ig
S9
A2



N-933
Ig
S9
A3



N-934
Ig
S9
A4



N-935
Ig
S9
A5



N-936
Ig
S9
A6



N-937
Ig
S9
A7



N-938
Ig
S9
A8



N-939
Ig
S9
A9



N-940
Ig
S9
A10



N-941
Ig
S9
A11



N-942
Ig
S9
A12



N-943
Ig
S9
A13



N-944
Ig
S9
A14



N-945
Ig
S9
A15



N-946
Ia
Fip
H1



N-947
Ia
Ethi
H1



N-948
Ib
Fip
H1



N-949
Ib
Ethi
H1



N-950
Ic
Fip
H1



N-951
Ic
Ethi
H1



N-952
Id
Fip
H1



N-953
Id
Ethi
H1



N-954
Ie
Fip
H1



N-955
Ie
Ethi
H1



N-956
If
Fip
H1



N-957
If
Ethi
H1



N-958
Ig
Fip
H1



N-959
Ig
Ethi
H1



N-960
Ia
A1
H1



N-961
Ia
A2
H1



N-962
Ia
A3
H1



N-963
Ia
A4
H1



N-964
Ia
A5
H1



N-965
Ia
A6
H1



N-966
Ia
A7
H1



N-967
Ia
A8
H1



N-968
Ia
A9
H1



N-969
Ia
A10
H1



N-970
Ia
A11
H1



N-971
Ia
A12
H1



N-972
Ia
A13
H1



N-973
Ia
A14
H1



N-974
Ia
A15
H1



N-975
Ib
A1
H1



N-976
Ib
A2
H1



N-977
Ib
A3
H1



N-978
Ib
A4
H1



N-979
Ib
A5
H1



N-980
Ib
A6
H1



N-981
Ib
A7
H1



N-982
Ib
A8
H1



N-983
Ib
A9
H1



N-984
Ib
A10
H1



N-985
Ib
A11
H1



N-986
Ib
A12
H1



N-987
Ib
A13
H1



N-988
Ib
A14
H1



N-989
Ib
A15
H1



N-990
Ic
A1
H1



N-991
Ic
A2
H1



N-992
Ic
A3
H1



N-993
Ic
A4
H1



N-994
Ic
A5
H1



N-995
Ic
A6
H1



N-996
Ic
A7
H1



N-997
Ic
A8
H1



N-998
Ic
A9
H1



N-999
Ic
A10
H1



N-1000
Ic
A11
H1



N-1001
Ic
A12
H1



N-1002
Ic
A13
H1



N-1003
Ic
A14
H1



N-1004
Ic
A15
H1



N-1005
Id
A1
H1



N-1006
Id
A2
H1



N-1007
Id
A3
H1



N-1008
Id
A4
H1



N-1009
Id
A5
H1



N-1010
Id
A6
H1



N-1011
Id
A7
H1



N-1012
Id
A8
H1



N-1013
Id
A9
H1



N-1014
Id
A10
H1



N-1015
Id
A11
H1



N-1016
Id
A12
H1



N-1017
Id
A13
H1



N-1018
Id
A14
H1



N-1019
Id
A15
H1



N-1020
Ie
A1
H1



N-1021
Ie
A2
H1



N-1022
Ie
A3
H1



N-1023
Ie
A4
H1



N-1024
Ie
A5
H1



N-1025
Ie
A6
H1



N-1026
Ie
A7
H1



N-1027
Ie
A8
H1



N-1028
Ie
A9
H1



N-1029
Ie
A10
H1



N-1030
Ie
A11
H1



N-1031
Ie
A12
H1



N-1032
Ie
A13
H1



N-1033
Ie
A14
H1



N-1034
Ie
A15
H1



N-1035
If
A1
H1



N-1036
If
A2
H1



N-1037
If
A3
H1



N-1038
If
A4
H1



N-1039
If
A5
H1



N-1040
If
A6
H1



N-1041
If
A7
H1



N-1042
If
A8
H1



N-1043
If
A9
H1



N-1044
If
A10
H1



N-1045
If
A11
H1



N-1046
If
A12
H1



N-1047
If
A13
H1



N-1048
If
A14
H1



N-1049
If
A15
H1



N-1050
Ig
A1
H1



N-1051
Ig
A2
H1



N-1052
Ig
A3
H1



N-1053
Ig
A4
H1



N-1054
Ig
A5
H1



N-1055
Ig
A6
H1



N-1056
Ig
A7
H1



N-1057
Ig
A8
H1



N-1058
Ig
A9
H1



N-1059
Ig
A10
H1



N-1060
Ig
A11
H1



N-1061
Ig
A12
H1



N-1062
Ig
A13
H1



N-1063
Ig
A14
H1



N-1064
Ig
A15
H1



N-1065
Ia
S1
H1



N-1066
Ia
S2
H1



N-1067
Ia
S3
H1



N-1068
Ia
S4
H1



N-1069
Ia
S5
H1



N-1070
Ia
S6
H1



N-1071
Ia
S7
H1



N-1072
Ia
S8
H1



N-1073
Ia
S9
H1



N-1074
Ib
S1
H1



N-1075
Ib
S2
H1



N-1076
Ib
S3
H1



N-1077
Ib
S4
H1



N-1078
Ib
S5
H1



N-1079
Ib
S6
H1



N-1080
Ib
S7
H1



N-1081
Ib
S8
H1



N-1082
Ib
S9
H1



N-1083
Ic
S1
H1



N-1084
Ic
S2
H1



N-1085
Ic
S3
H1



N-1086
Ic
S4
H1



N-1087
Ic
S5
H1



N-1088
Ic
S6
H1



N-1089
Ic
S7
H1



N-1090
Ic
S8
H1



N-1091
Ic
S9
H1



N-1092
Id
S1
H1



N-1093
Id
S2
H1



N-1094
Id
S3
H1



N-1095
Id
S4
H1



N-1096
Id
S5
H1



N-1097
Id
S6
H1



N-1098
Id
S7
H1



N-1099
Id
S8
H1



N-1100
Id
S9
H1



N-1101
Ie
S1
H1



N-1102
Ie
S2
H1



N-1103
Ie
S3
H1



N-1104
Ie
S4
H1



N-1105
Ie
S5
H1



N-1106
Ie
S6
H1



N-1107
Ie
S7
H1



N-1108
Ie
S8
H1



N-1109
Ie
S9
H1



N-1110
If
S1
H1



N-1111
If
S2
H1



N-1112
If
S3
H1



N-1113
If
S4
H1



N-1114
If
S5
H1



N-1115
If
S6
H1



N-1116
If
S7
H1



N-1117
If
S8
H1



N-1118
If
S9
H1



N-1119
Ig
S1
H1



N-1120
Ig
S2
H1



N-1121
Ig
S3
H1



N-1122
Ig
S4
H1



N-1123
Ig
S5
H1



N-1124
Ig
S6
H1



N-1125
Ig
S7
H1



N-1126
Ig
S8
H1



N-1127
Ig
S9
H1










Within the ternary mixtures of table 2, the following mixtures are especially preferred according to the present invention:


N-1, N-2, N-3, N-4, N-5, N-6, N-7, N-8, N-9, N-10, N-11, N-12, N-13, N-14, N-15, N-16, N-17, N-18, N-19, N-20, N-21, N-22, N-23, N-24, N-25, N-26, N-27, N-28, N-29, N-30, N-31, N-32, N-33, N-34, N-35, N-36, N-37, N-38, N-39, N-40, N-41, N-42, N-43, N-44, N-45, N-46, N-47, N-48, N-49, N-50, N-51, N-52, N-53, N-54, N-55, N-56, N-57, N-58, N-59, N-60, N-61, N-62, N-63, N-64, N-65, N-66, N-67, N-68, N-69, N-70, N-71, N-72, N-73, N-74, N-75, N-76, N-77, N-78, N-79, N-80, N-81, N-82, N-83, N-84, N-85, N-86, N-87, N-88, N-89, N-90, N-91, N-92, N-93, N-94, N-95, N-96, N-97, N-98, N-99, N-100, N-101, N-102, N-103, N-104, N-105, N-106, N-107, N-108, N-109, N-110, N-111, N-112, N-113, N-114, N-115, N-116, N-117, N-118, N-119, N-120, N-121, N-122, N-123, N-124, N-125, N-126, N-127, N-128, N-129, N-130, N-131, N-132, N-133, N-134, N-135, N-960, N-961, N-962, N-963, N-964, N-965, N-966, N-967, N-968, N-969, N-970, N-971, N-972, N-973, N-974, N-1065, N-1066, N-1067, N-1068, N-1069, N-1070, N-1071, N-1072, N-1073, N-1083, N-1084, N-1085, N-1086, N-1087, N-1088, N-1089, N-1090, N-1091, N-1110, N-1111, N-1112, N-1113, N-1114, N-1115, N-1116, N-1117, N-1118, N-1119, N-1120, N-1121, N-1122, N-1123, N-1124, N-1125, N-1126 and N-1127.


Within the mixtures of table 2, the mixture N-78, which comprises the amide compound of the formula Ia, orysastrobin (S6) as a further fungicide II and epoxiconazole (A3) as a further fungicide III, is of utmost preference.


Within the mixtures of table 2, the mixture N-108, which comprises the amide compound of the formula Ia, pyraclostrobin (S8) as a further fungicide II and epoxiconazole (A3) as a further fungicide III, is of utmost preference.


Within the mixtures of table 2, the mixture N-962, which comprises the amide compound of the formula Ia, epoxiconazole (A3) as a further fungicide II and glyphosate (H1), is of utmost preference.


Within the mixtures of table 2, the mixture N-1070, which comprises the amide compound of the formula Ia, orysastrobin (S6) as a further fungicide II and glyphosate (H1), is of utmost preference.


Within the mixtures of table 2, the mixture N-1072, which comprises the amide compound of the formula Ia, pyraclostrobin (S8) as a further fungicide II and glyphosate (H1), is of utmost preference.


Within the mixtures of table 2, the mixture N-1088, which comprises the amide compound of the formula Ic (bixafen), orysastrobin (S6) as a further fungicide II and glyphosate (H1), is of utmost preference.


Within the mixtures of table 2, the mixture N-1090, which comprises the amide compound of the formula Ic (bixafen), pyraclostrobin (S8) as a further fungicide II and glyphosate (H1), is of utmost preference.


Within the mixtures of table 2, the mixture N-1115, which comprises the amide compound of the formula If (isopyrazam), orysastrobin (S6) as a further fungicide II and glyphosate (H1), is of utmost preference.


Within the mixtures of table 2, the mixture N-1117, which comprises the amide compound of the formula If (isopyrazam), pyraclostrobin (S8) as a further fungicide II and glyphosate (H1), is of utmost preference.


Within the mixtures of table 2, the mixture N-1124, which comprises the amide compound of the formula Ig (penthiopyrad), orysastrobin (S6) as a further fungicide II and glyphosate (H1), is of utmost preference.


Within the mixtures of table 2, the mixture N-1126, which comprises the amide compound of the formula Ig (penthiopyrad), pyraclostrobin (S8) as a further fungicide II and glyphosate (H1), is of utmost preference.


With respect to their intended use within the methods of the present invention, the following quaternary mixtures of a strobilurin compound (2)(i) in combination with mixtures listed in table 2 above are a preffered embodiment of the present invention:


A quaternary mixture (Q-1 to Q-105) comprising the strobilurin compound S1 and a ternary mixture, wherin the ternary mixture in each case corresponds to a row of table 2 selected from the mixtures No. N-960 to N-1064.


A quaternary mixture (Q-106 to Q-210) comprising the strobilurin compound S2 and a ternary mixture, wherin the ternary mixture in each case corresponds to a row of table 2 selected from the mixtures No. N-960 to N-1064.


A quaternary mixture (Q-211 to Q-315) comprising the strobilurin compound S3 and a ternary mixture, wherin the ternary mixture in each case corresponds to a row of table 2 selected from the mixtures No. N-960 to N-1064.


A quaternary mixture (Q-316 to Q-420) comprising the strobilurin compound S4 and a ternary mixture, wherin the ternary mixture in each case corresponds to a row of table 2 selected from the mixtures No. N-960 to N-1064.


A quaternary mixture (Q-421 to Q-525) comprising the strobilurin compound S5 and a ternary mixture, wherin the ternary mixture in each case corresponds to a row of table 2 selected from the mixtures No. N-960 to N-1064.


A quaternary mixture (Q-526 to Q-630) comprising the strobilurin compound S6 and a ternary mixture, wherin the ternary mixture in each case corresponds to a row of table 2 selected from the mixtures No. N-960 to N-1064.


A quaternary mixture (Q-631 to Q-735) comprising the strobilurin compound S7 and a ternary mixture, wherin the ternary mixture in each case corresponds to a row of table 2 selected from the mixtures No. N-960 to N-1064.


A quaternary mixture (Q-736 to Q-840) comprising the strobilurin compound S8 and a ternary mixture, wherin the ternary mixture in each case corresponds to a row of table 2 selected from the mixtures No. N-960 to N-1064.


A quaternary mixture (Q-841 to Q-945) comprising the strobilurin compound S9 and a ternary mixture, wherin the ternary mixture in each case corresponds to a row of table 2 selected from the mixtures No. N-960 to N-1064.


Within the quaterny mixtures disclosed above, the mixture comprising the amide compound of the formula Ia, pyraclostrobin (S8) as a further fungicide II, epoxiconazole (A3) as a further fungicide III and additionally glyphosate (H1), is of utmost preference.


Within the quaterny mixtures disclosed above, the mixture comprsing the amide compound of the formula (Ia), orysastrobin (S6) as a further fungicide II, epoxiconazole (A3) as a further fungicide III and additionally glyphosate (H1), is of utmost preference.


In all mixtures used according to the methods of the present invention, compounds (I) and compounds (II), (IIb), (III) or (IV), are employed in amounts to afford a synergistic effect. The weight ratio of compound (I) to compounds (II), (IIb), (III) or (IV), is preferably from 200:1 to 1:200, more preferably from 100:1 to 1:100, more preferably from 50:1 to 1:50 and in particular from 20:1 to 1:20. The utmost preferred ratio is 1:10 to 10:1. The weight ratio refers to the total weight of compounds (I) and compounds (II), (IIb), (III) or (IV), in the mixture.


All mixtures set forth above are also an embodiment of the present invention.


All embodiments of the mixtures set forth above are herein below referred to as “mixtures according to the present invention”.


As mentioned above, the compounds (I) or the mixtures according to the present invention are used for improving the health of plants when applied to plant or parts of plants or to their actual or intended locus of growth.


Thus, the invention also relates to a method for improving the health of plants, which comprises treating the plant, a part of the plant, the locus where the plant is growing or is expected to grow with the compounds (I) or the mixtures according to the present invention.


If a mixture according to the present invention is used in this inventive method, the plant and/or the locus where the plant is growing or is expected to grow are preferably treated simultaneously (together or separately) or subsequently with the the amide compound of the formula I (compound I) and at least one further compound selected from the group consisting of compounds (II), (IIb), (III) and (IV).


Of course, the subsequent application is carried out with a time interval which allows a combined action of the applied compounds. Preferably, the time interval for a subsequent application of compound (I) and compounds (II), (IIb), (III) and/or (IV), ranges from a few seconds up to 3 months, preferably, from a few seconds up to 1 month, more preferably from a few seconds up to 2 weeks, even more preferably from a few seconds up to 3 days and in particular from 1 second up to 24 hours.


The term “BBCH principal growth stage” refers to the extended BBCH-scale which is a system for a uniform coding of phenologically similar growth stages of all mono- and dicotyldedonous plant species in which the entire developmental cycle of the plants is subdivided into clearly recoginizable and distinguishable longer-lasting developmental phases. The abbreviation BBCH dervies from Biologische Bundesanstalt, Bundessor-tenamt and CHemical industry.


“Locus” means soil, area, material or environment where the plant is growing or intended to grow.


As a matter of course, compounds (I) and in case mixtures are employed, compounds selected from the group consisting of compounds (II), (IIb), (III) and (IV), are used in an effective and non-phytotoxic amount. This means that they are used in a quantity which allows to obtain the desired effect but which does not give rise to any phytotoxic symptom on the treated plant or on the plant raised from the treated propagule or treated soil.


The plants to be treated are generally plants of economic importance and/or mengrown plants. Thus, they are preferably selected from agricultural, silvicultural and ornamental plants, more preferably from agricultural plants.


Generally the term “plants” also includes plants which have been modified by breeding, mutagenesis or genetic engineering. Genetically modified plants are plants, which genetic material has been modified by the use of recombinant DNA techniques. The use of recombinant DNA techniques makes modification possible that cannot readily be obtained by cross breeding under natural circumstances, mutations or natural recombination.


Thus, also the preferred soybeans mentioned herein can be a non-transgenic plant, e.g. as obtained by traditional breeding, or can have at least one transgenic event. In one embodiment it is preferred that the soybean plant be a transgenic plant having preferably a transgenic event that confers resistance to a pesticide, preferably against the herbicide glyphosate. Accordingly, it is preferred that the transgenic plant be one having a transgenic event that provides glyphosate resistance. Some examples of such preferred transgenic plants having transgenic events that confer glyphosate resistance are described in U.S. Pat. No. 5,914,451, U.S. Pat. No. 5,866,775, U.S. Pat. No. 5,804,425, U.S. Pat. No. 5,776,760, U.S. Pat. No. 5,633,435, U.S. Pat. No. 5,627,061, U.S. Pat. No. 5,463,175, U.S. Pat. No. 5,312,910, U.S. Pat. No. 5,310,667, U.S. Pat. No. 5,188,642, U.S. Pat. No. 5,145,783, U.S. Pat. No. 4,971,908 and U.S. Pat. No. 4,940,835. More preferably, the transgenic soybean plant has the characteristics of “Roundup-Ready” (RR) transgenic soybeans (available from Monsanto Company, St. Louis, Mo.).


“Silvicultural plants” in the terms of the present invention are trees, more specifically trees used in reforestation or industrial plantations. Industrial plantations generally serve for the commercial production of forest products, such as wood, pulp, paper, rubber, Christmas trees, or young trees for gardening purposes. Examples for silvicultural plants are conifers, like pines, in particular Pinus spec., fir and spruce, eucalyptus, tropical trees like teak, rubber tree, oil palm, willow (Salix), in particular Salix spec., poplar (cottonwood), in particular Populus spec., beech, in particular Fagus spec., birch and oak.


In another embodiment of the invention, the plant health of which is to be improved by the treatment with the composition of the invention is an ornamental plant. “Ornamental plants” are plants which are commonly used in gardening, e.g. in parks, gardens and on balconies. Examples are turf, geranium, pelargonia, petunia, begonia, and fuchsia, to name just a few among the vast number of ornamentals.


“Agricultural plants” are plants of which a part (such as seeds) or allis harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fibers (e.g. cotton, linen), combustibles (e.g. wood, bioethanol, biodiesel, biomass) or other chemical compounds. Agricultural plants may also include horticultural plants, i.e. plants grown in gardens (and not on fields), such as certain fruits and vegetables. Preferred agricultural plants are for example cereals, e. g. wheat, rye, barley, triticale, oats, sorghum or rice, beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, oil-seed rape, canola, linseed, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, canola, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers.


In one embodiment of the present invention, fruit crops are preferred. Within fruit crops, apples, strawberries and citrus (e.g. orange and lemon) are especially preferred.


More preferred agricultural plants are field crops, such as potatoes, sugar beets, cereals such as wheat, rye, barley, oats, sorghum, rice, corn, cotton, rape, oilseed rape and canola, legumes such as soybeans, peas and field beans, sunflowers, sugar cane; ornamentals; or vegetables, such as cucumbers, tomatoes, or onions, leeks, lettuce, squashes, most preferred agricultural plants are potatoes, sugar beets, cereals such as wheat, rye, barley, oats, sorghum, rice, corn, cotton, soybeans, oilseed rape, canola, sunflower and utmost preferred plant is soybean.


In a preferred embodiment, the aforementioned method for improving the health of a plant comprises treating an agricultural plant and/or the locus where the plant is growing or is expected to grow with a compound (I) or a mixture according to the invention, wherein the agricultural plant is selected from the group consisting of transgenic or non-transgenic potatoes, sugar beets, cereals such as wheat, rye, barley, oats, sorghum, rice, corn, cotton, soybeans, oilseed rape, canola, sunflower with a composition of the invention, wherein soybean is utmost preferred. Such plants can be transgenic or non-transgenic plants.


If mixtures according to the present invention are used, the plant, the locus where the plant is growing or is expected to grow are preferably treated simultaneously (together or separately) or subsequently with the components present in the mixtures of the present invention.


“Plant health” is intended to mean a condition of the plant which is determined by several aspects alone or in combination with each other.


One indicator (indicator 1) for the condition of the plant is the yield, which is crop and/or fruit yield. “Crop” and “fruit” are to be understood as any plant product which is further utilized after harvesting, e.g. fruits in the proper sense, vegetables, nuts, grains, seeds, wood (e.g. in the case of silviculture plants), flowers (e.g. in the case of gardening plants, ornamentals) etc., that is anything of economic value that is produced by the plant. One way of tetermining the yield is the Thousand Grain Weight (TGW) of the harvested grains.


In one embodiment of the present invention, the plant yield becomes manifest by an increase in Thousand Grain Weight (TGW), straw yield, grain yield, tillering, harvest index and the single ear grain yield.


Another indicator (indicator 2) for the condition of the plant is the plant vigour. The plant vigour becomes manifest in several aspects, too, some of which are visual appearance, e.g. leaf color, fruit color and aspect, amount of dead basal leaves and/or extent of leaf blades, plant weight, plant height, extent of plant verse (lodging), number, strongness and productivity of tillers or branches or halms, panicles' length, seed set, extent of root system, strongness of roots, extent of nodulation, in particular of rhizobial nodulation, point of time of germination, emergence, flowering, grain maturity and/or senescence, protein content, sugar content and the like.


In one embodiment of the present invention, the plant vigour becomes manifest by an increase in plant height, number of halms with ear, tillering, plant shoot growth, number of grains per ear and the grean leaf area.


Another indicator (indicator 3) for the condition of the plant is the plant's tolerance or resistance to abiotic stress factors. Abiotic stress, especially over longer terms, can have harmful effects on plants. Abiotic stress is caused for example by extremes in temperature such as heat or cold or strong variations in temperature or temperatures unusual for the specific season, drought, extreme wetness like flooding or waterlogging, anaerobic conditions, high salinity, radiation (e.g. increased UV radiation due to the decreasing ozone protective layer), increased ozone levels and organic pollution (e.g. by phythotoxic amounts of pesticides) or inorganic pollution (e.g. by heavy metal contaminants). As a result, the quantity and the quality of the stressed plants, their crops and fruits decrease. As far as quality is concerned, reproductive development is usually severely affected with consequences on the crops which are important for fruits or seeds. Synthesis, accumulation and storage of proteins are mostly affected by temperature; growth is slowed by almost all stresses; polysaccharide synthesis, both structural and storage is reduced or modified: these effects bring to a decrease in biomass and to changes in the nutritional value of the product.


In one embodiment of the present invention, the tolerance of a plant against drought stress (abiotic stress) becomes manifest by an increase of water use effiency and a reduction of the plant's transpiration.


In one preferred embodiment, the present invention provides the use of the compound (I) of formula I or a mixture according to the present invention for increasing the yield of a plant, preferably of an agricultural, silvicultural and/or ornamental plant, more preferably of an agricultural plant.


The present invention further provides a method for increasing the yield of a plant, preferably of an agricultural, silvicultural and/or ornamental plant, more preferably of an agricultural plant.


In a more preferred embodiment, the aforementioned method for increasing the yield of the plant comprises treating the plant and/or the locus where the plant is growing or is expected to grow with a compound (I) or a mixture according to the present invention, wherein the plant is preferably selected from the group consisting of field crops, such as potatoes, sugar beets, cereals such as wheat, rye, barley, oats, sorghum, rice, corn, cotton, rape, oilseed rape and canola, legumes such as soybeans, peas and field beans, sunflowers, sugar cane; ornamentals; or vegetables, such as cucumbers, tomatoes, or onions, leeks, lettuce, squashes, more preferably agricultural plants are potatoes, sugar beets, cereals such as wheat, rye, barley, oats, sorghum, rice, corn, cotton, soybeans, oilseed rape, canola, sunflower.


In a especially preferred embodiment. the aforementioned method for increasing the plant health of the plant comprises treating the plant and/or the locus where the plant is growing or is expected to grow with a compound (I) or a mixture according to the present invention, wherein the plant is wheat, maize (corn) and soybeans.


In a particular preferred embodiment, the aforementioned method for increasing the yield of the plant comprises treating the plant and/or the locus where the plant is growing or is expected to grow with a compound (I) or a mixture according to the present invention, wherein the plant is transgenic or non-transgenic soybean.


According to the present invention, “increased yield” of a plant, in particular of an agricultural, silvicultural and/or ornamental plant, more preferably of an agricultural plant means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the composition of the invention.


According to the present invention, it is preferred that the yield be increased by at least 0.5%, more preferred at least 1%, even more preferred at least 2%, still more preferred at least 4%.


The improvement of the yield increase according to the present invention particularly means that the improvement of any one or several or all of the above mentioned plant characteristics are improved independently of the pesticidal action of the compound (I) or the mixture according to the present invention.


In another preferred embodiment, the present invention provides the use of the compound (I) or a mixture of the present invention for increasing the yield and/or improving the vigor of a plant, e.g. of an agricultural, silvicultural and/or ornamental plant, more preferably an agricultural plant.


The present invention further provides a method for increasing the yield and/or improving the vigor of a plant, preferably of an agricultural, silvicultural and/or ornamental plant, more preferably of an agricultural plant.


In a more preferred embodiment, the aforementioned method for increasing or improving the vigour of the plant comprises treating the plant and/or the locus where the plant is growing or is expected to grow with a compound (I) or a mixture according to the present invention, wherein the plant is preferably selected from the group consisting of field crops, such as potatoes, sugar beets, cereals such as wheat, rye, barley, oats, sorghum, rice, corn, cotton, rape, oilseed rape and canola, legumes such as soybeans, peas and field beans, sunflowers, sugar cane; ornamentals; or vegetables, such as cucumbers, tomatoes, or onions, leeks, lettuce, squashes, more preferably agricultural plants are potatoes, sugar beets, cereals such as wheat, rye, barley, oats, sorghum, rice, corn, cotton, soybeans, oilseed rape, canola, sunflower.


In a particular preferred embodiment, the afore-mentioned method for increasing the vigour of the plant treating the plant and/or the locus where the plant is growing or is expected to grow with a compound (I) or a mixture according to the present invention, wherein the plant is transgenic or non-transgenic soybean.


According to the present invention, “improved plant vigour” means that certain crop characteristics are increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions, but without the application of the composition of the present invention.


Improved plant vigour can be characterized, among others, by at least one of the following improved properties of the plant:

    • improved vitality of the plant,
    • improved quality of the plant and/or of the plant products, e.g. enhanced protein content, enhanced fruit size, more uniform fruit or grain color etc.,
    • improved storability of harvested plant or plant parts,
    • improved visual appearance,
    • delay of senescence, thus, longer lasting photosynthetic active leaf apparatus,
    • enhanced root growth and/or more developed root system,
    • enhanced nodulation, in particular rhizobial nodulation,
    • longer panicles,
    • bigger pods,
    • improved pod set,
    • improved seed set,
    • improved fruit set,
    • reduced flower abortion,
    • reduced pod abortion,
    • reduced seed abortion,
    • bigger leaf blade,
    • less dead basal leaves,
    • improved leaf area index,
    • increased or improved plant stand density,
    • less plant verse (lodging),
    • increased plant weight,
    • increased plant height,
    • increased shoot growth
    • tillering increase,
    • increase in branching
    • stronger and/or more productive tillers or branches,
    • less non-productive tillers,
    • enhanced photosynthetic activity and/or enhanced pigment content and thus greener leaf color,
    • reduced production of ethylene and/or the inhibition of its reception by the plant,
    • earlier and improved germination
    • improved emergence,
    • earlier flowering,
    • earlier fruiting,
    • earlier grain maturity,
    • more uniform ripening,
    • less fertilizers needed,
    • improved harvest index,
    • improved shelf life,
    • increased water-use efficiency
    • increase in green leaf area
    • better harvestability.


The improvement of the plant vigour according to the present invention particularly means that the improvement of any one or several or all of the above mentioned plant characteristics are improved independently of the pesticidal action of the compound (I) or a mixture according to the present invention.


In a more preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for improving the vitality of the plant.


In a more preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for increasing the water-use efficiency of the plant.


In another preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for improveing the quality of the plant and/or of the plant products, e.g. enhanced protein content.


In another preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for improved storability of harvested plants or plant parts.


In another preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for delayed senescence and consequently longer photosynthetic activity of the leaf apparatus.


In another more preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for enhancing root growth and/or inducing the formation of a more developed root system of a plant.


In another preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for improved seed or fruit set.


In another preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for reduced flower abortion and/or pod abortion and/or seed abortion.


In another preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for bigger leaf blades.


In another preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for less dead basal leaves.


In another preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for reduced plant verse (lodging).


In another preferred embodiment of the invention, the compound of formula I or a mixture of the present invention is used for increased plant weight.


In another preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for increased plant height.


In another preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for stronger and/or more productive tillers or branches.


In another preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for enhanced photosynthetic activity and/or enhanced pigment content and thus greener leaf colour.


In another preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for improved emergence.


In another preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for increased shoot growth. In another preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for reduction of ethylene production and/or inhibition of ethylene reception by the plant.


In another preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for more uniform ripening of the plant, plant parts or fruits.


In another preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for improved harvestability.


In a most preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for enhancing improved vitality of the plant.


In another most preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for delayed senescence and consequently longer photosynthetic activity of the leaf apparatus.


In another most preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for bigger leaf blades.


In another most preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for less dead basal leaves.


In another most preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for improved seed or fruit set.


In another most preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for increased plant weight.


In another most preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for increased plant height.


In another most preferred embodiment of the invention, the compound (I) or a mixture of the present invention is used for increased shoot growth.


In yet another preferred embodiment, the present invention provides the use of the compound (I) or a mixture of the present invention for enhancing the plant's tolerance or resistance to abiotic stress factors.


The present invention further provides a method for enhancing a plant's tolerance or resistance to abiotic stress factors, which comprises treating the plant and/or the locus where the plant is growing or is expected to grow with a compound (I) or a mixture according to the present invention.


In a more preferred embodiment, the aforementioned method for enhancing a plant's tolerance or resistance to abiotic stress factors comprises treating the plant and/or the locus where the plant is growing or is expected to grow with a compound (I) or a mixture according to the present invention, wherein the plant is preferably selected from the group consisting of field crops, such as potatoes, sugar beets, cereals such as wheat, rye, barley, oats, sorghum, rice, corn, cotton, soybeans, rape, oilseed rape and canola, legumes such as soybeans, peas and field beans, sunflowers, sugar cane; ornamentals; or vegetables, such as cucumbers, tomatoes, or onions, leeks, lettuce, squashes, more preferably agricultural plants are potatoes, sugar beets, cereals such as wheat, rye, barley, oats, sorghum, rice, corn, cotton, soybeans, oilseed rape, canola, sunflower.


In a particular preferred embodiment, the afore-mentioned method for enhancing a plant's tolerance or resistance to abiotic stress factors treating the plant, the locus where the plant is growing or is expected to grow with a compound (I) or a mixture according to the present invention, wherein the plant is transgenic or non-transgenic soybean.


Abiotic stress factors have been defined above.


According to the present invention, “enhanced tolerance or resistance of a plant to abiotic stress factors” means (1.) that certain negative factors caused by abiotic stress are diminished in a measurable or noticeable amount as compared to plants exposed to the same conditions, but without being treated with the and (2.) that the negative effects are not diminished by a direct action of the composition on the stress factors, e.g. by its fungicidal or insecticidal action which directly destroys the microorganisms or pests, but rather by a stimulation of the plants' own defensive reactions against said stress factors.


Negative factors caused by abiotic stress are also well-known and can often be observed as reduced plant vigor (see above), e.g. dotted leaves, “burned leaves”, reduced growth, less flowers, less biomass, less crop yields, reduced nutritional value of the crops, later crop maturity, to give just a few examples.


In preferred embodiment, the tolerance of and/or resistance against abiotic stress factors is enhanced. Thus, according to a further embodiment of the present invention, the inventive compositions are used for stimulating the plant's own defensive reactions against abiotic stress such as extremes in temperature, e.g. heat or cold or strong variations in temperature or temperatures unusual for the specific season, drought, extreme wetness, high salinity, radiation (e.g. increased UV radiation due to the decreasing ozone protective layer), increased ozone levels, organic pollution (e.g. by phythotoxic amounts of pesticides) and/or inorganic pollution (e.g. by heavy metal contaminants).


In a more preferred embodiment, the compound (I) or a mixture according to the present invention is used for stimulating a plant's own defensive reactions against abiotic stress, where the abiotic stress factors are preferably selected from extremes in temperature, drought and extreme wetness.


In a more preferred embodiment, the compound (I) or a mixture according to the present invention is used for stimulating a plant's own defensive reactions against abiotic stress, where the abiotic stress factor is drought stress.


In another more preferred embodiment, the compound (I) or a mixture according to the present invention is used for reducing or inhibiting the injury caused to plants by phythotoxic amounts of pesticides such as fungicides, herbicides and/or insecticides.


During the present invention, it has been found that certain mixtures selected from the mixtures according to the present invention as described above, have not yet been explicitly described in the prior art—these mixtures however, have not only synergistic plant health effects as described hereinabove, but also provide synergistic fungicidal effects.


Thus, we also found a method for controlling pythopathogenic fungi, wherein the fungi, their habitat, breeding grounds, their locus or the plants to be protected against fungal attack, the soil or seed are treated with a pesticidally effective amount of these mixtures.


In one embodiment of the invention, the fungicidal mixtures for controlling pythopathogenic fungi are applied to seed, in an amount of from 0.001 g to 1 kg per 100 kg of seeds.


“Locus” means a plant, seed, soil, area, material or environment in which a pest is growing or may grow.


In general, “pesticidally effective amount” means the amount of the inventive mixtures or of compositions comprising the mixtures needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various mixtures/compositions used in the invention. A pesticidally effective amount of the mixtures/compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.


These mixtures comprise


(1) an amide of formula I (compound I); and


(2) a further fungicide II (compound II) selected from the group consisting of

    • (ii) carboxylic amides, selected from boscalid, fenhexamid, metalaxyl, fluopicolide (picobenzamid), zoxamide, mandipropamid and carpropamid
    • (iii) azoles, selected from cyproconazole (A1), epoxiconazole (A3), flusilazole (A4), ipconazole (A7), propiconazole (A9), prothioconazole (A10), tebuconazole (A11), cyazofamid (A12) and triazoxide (A15)
    • (iv) heterocyclic compounds, selected from fluazinam, cyprodinil, acibenzolar-S-methyl, proquinazid, quinoxyfen, fenpicionil, captan, folpet and fenpropidin,
    • (v) carbamates and dithiocarbamates, selected from iprovalicarb, maneb, propineb and flubenthiavalicarb (benthiavalicarb);
    • (vi) organo-chloro compounds such as flusulfamid;
    • (vii) inorganic active ingredients such as sulfur; and
    • (viii) various, selected from spiroxamine, cymoxanil, cyflufenamid and valiphenal.


In another embodiment of the invention, Tthese mixtures comprise

  • (1) an amide of formula I (compound I); and
  • (2) a further fungicide II (compound II) selected from the group consisting of
    • (ii) carboxylic amides, selected from boscalid, fenhexamid, metalaxyl, fluopicolide (picobenzamid), zoxamide, mandipropamid and carpropamid
    • (iii) azoles, selected from cyproconazole (A1), epoxiconazole (A3), flusilazole (A4), ipconazole (A7), propiconazole (A9), prothioconazole (A10), tebuconazole (A11), cyazofamid (A12) and triazoxide (A15)
    • (iv) heterocyclic compounds, selected from fluazinam, cyprodinil, acibenzolar-S-methyl, proquinazid, quinoxyfen, fenpiclonil, captan, folpet and fenpropidin,
    • (v) carbamates and dithiocarbamates, selected from iprovalicarb, maneb, propineb and flubenthiavalicarb (benthiavalicarb);
    • (vi) organo-chloro compounds such as flusulfamid;
    • (vii) inorganic active ingredients such as sulfur; and
    • (viii) various, selected from spiroxamine, cymoxanil, cyflufenamid and valiphenal, and
  • (3) optionally a herbicide (compound IV) selected from glyphosate, sulfonisate and glyphosinate.


This subset of mixtures is herein below defined as “novel mixtures according to the present invention”. Naturally this subset is comprised by the mixtures according to the present invention. Thus, this term is mentioned only, if this subset needs to be addressed separately.


The weight ratio of the compound (I) to compound (II) or (IV) is preferably from 200:1 to 1:200, more preferably from 100:1 to 1:100, more preferably from 50:1 to 1:50 and in particular from 20:1 to 1:20. The utmost preferred ratio is 1:10 to 10:1. The weight ratio refers to the total weight of compounds (I) and compounds (II) in the mixture.


With respect to their intended use, the following secondary mixtures of compound (I) and compound (II) or (IV) listed in the table 3 below are especially preferred.













TABLE 3







No.
(I)
(II) or (IV)









O-1
Ia
boscalid



O-2
Ia
fenhexamid



O-3
Ia
fluopicolide



O-4
Ia
zoxamide



O-5
Ia
mandipropamid



O-6
Ia
carpropamid



O-7
Ia
cyazofamid,



O-8
Ia
flusilazole



O-9
Ia
ipconazole



O-10
Ia
triazoxide



O-11
Ia
fluazinam,



O-12
Ia
cyprodinil



O-13
Ia
acibenzolar-S-methyl



O-14
Ia
proquinazid



O-15
Ia
quinoxyfen



O-16
Ia
fenpiclonil



O-17
Ia
captan



O-18
Ia
fenpropidin



O-19
Ia
iprovalicarb



O-20
Ia
maneb



O-21
Ia
propineb



O-22
Ia
flubenthiavalicarb



O-23
Ia
flusulfamid



O-24
Ia
sulfur



O-25
Ia
spiroxamine



O-26
Ia
cymoxanil



O-27
Ia
cyflufenamid



O-28
Ia
valiphenal



O-29
Ia
metalaxyl



O-30
Ia
tebuconazole



O-31
Ia
cyproconazole



O-32
Ia
epoxiconazole



O-33
Ia
propiconazole



O-34
Ia
prothioconazole



O-35
Ib
boscalid



O-36
Ib
fenhexamid



O-37
Ib
fluopicolide



O-38
Ib
zoxamide



O-39
Ib
mandipropamid



O-40
Ib
carpropamid



O-41
Ib
cyazofamid,



O-42
Ib
flusilazole



O-43
Ib
ipconazole



O-44
Ib
triazoxide



O-45
Ib
fluazinam,



O-46
Ib
cyprodinil



O-47
Ib
acibenzolar-S-methyl



O-48
Ib
proquinazid



O-49
Ib
quinoxyfen



O-50
Ib
fenpiclonil



O-51
Ib
captan



O-52
Ib
fenpropidin



O-53
Ib
iprovalicarb



O-54
Ib
maneb



O-55
Ib
propineb



O-56
Ib
flubenthiavalicarb



O-57
Ib
flusulfamid



O-58
Ib
sulfur



O-59
Ib
spiroxamine



O-60
Ib
cymoxanil



O-61
Ib
cyflufenamid



O-62
Ib
valiphenal



O-63
Ib
metalaxyl



O-64
Ib
tebuconazole



O-65
Ib
cyproconazole



O-66
Ib
epoxiconazole



O-67
Ib
propiconazole



O-68
Ib
prothioconazole



O-69
Ic
boscalid



O-70
Ic
fenhexamid



O-71
Ic
fluopicolide



O-72
Ic
zoxamide



O-73
Ic
mandipropamid



O-74
Ic
carpropamid



O-75
Ic
cyazofamid,



O-76
Ic
flusilazole



O-77
Ic
ipconazole



O-78
Ic
triazoxide



O-79
Ic
fluazinam,



O-80
Ic
cyprodinil



O-81
Ic
acibenzolar-S-methyl



O-82
Ic
proquinazid



O-83
Ic
quinoxyfen



O-84
Ic
fenpiclonil



O-85
Ic
captan



O-86
Ic
fenpropidin



O-87
Ic
iprovalicarb



O-88
Ic
maneb



O-89
Ic
propineb



O-90
Ic
flubenthiavalicarb



O-91
Ic
flusulfamid



O-92
Ic
sulfur



O-93
Ic
spiroxamine



O-94
Ic
cymoxanil



O-95
Ic
cyflufenamid



O-96
Ic
valiphenal



O-97
Ic
metalaxyl



O-98
Ic
tebuconazole



O-99
Ic
cyproconazole



O-100
Ic
epoxiconazole



O-101
Ic
propiconazole



O-102
Ic
prothioconazole



O-103
Id
boscalid



O-104
Id
fenhexamid



O-105
Id
fluopicolide



O-106
Id
zoxamide



O-107
Id
mandipropamid



O-108
Id
carpropamid



O-109
Id
cyazofamid,



O-110
Id
flusilazole



O-111
Id
ipconazole



O-112
Id
triazoxide



O-113
Id
fluazinam,



O-114
Id
cyprodinil



O-115
Id
acibenzolar-S-methyl



O-116
Id
proquinazid



O-117
Id
quinoxyfen



O-118
Id
fenpiclonil



O-119
Id
captan



O-120
Id
fenpropidin



O-121
Id
iprovalicarb



O-122
Id
maneb



O-123
Id
propineb



O-124
Id
flubenthiavalicarb



O-125
Id
flusulfamid



O-126
Id
sulfur



O-127
Id
spiroxamine



O-128
Id
cymoxanil



O-129
Id
cyflufenamid



O-130
Id
valiphenal



O-131
Id
metalaxyl



O-132
Id
tebuconazole



O-133
Id
cyproconazole



O-134
Id
epoxiconazole



O-135
Id
propiconazole



O-136
Id
prothioconazole



O-137
Ie
boscalid



O-138
Ie
fenhexamid



O-139
Ie
fluopicolide



O-140
Ie
zoxamide



O-141
Ie
mandipropamid



O-142
Ie
carpropamid



O-143
Ie
cyazofamid,



O-144
Ie
flusilazole



O-145
Ie
ipconazole



O-146
Ie
triazoxide



O-147
Ie
fluazinam,



O-148
Ie
cyprodinil



O-149
Ie
acibenzolar-S-methyl



O-150
Ie
proquinazid



O-151
Ie
quinoxyfen



O-152
Ie
fenpiclonil



O-153
Ie
captan



O-154
Ie
fenpropidin



O-155
Ie
iprovalicarb



O-156
Ie
maneb



O-157
Ie
propineb



O-158
Ie
flubenthiavalicarb



O-159
Ie
flusulfamid



O-160
Ie
sulfur



O-161
Ie
spiroxamine



O-162
Ie
cymoxanil



O-163
Ie
cyflufenamid



O-164
Ie
valiphenal



O-165
Ie
metalaxyl



O-166
Ie
tebuconazole



O-167
Ie
cyproconazole



O-168
Ie
epoxiconazole



O-169
Ie
propiconazole



O-170
Ie
prothioconazole



O-171
If
boscalid



O-172
If
fenhexamid



O-173
If
fluopicolide



O-174
If
zoxamide



O-175
If
mandipropamid



O-176
If
carpropamid



O-177
If
cyazofamid,



O-178
If
flusilazole



O-179
If
ipconazole



O-180
If
triazoxide



O-181
If
fluazinam,



O-182
If
cyprodinil



O-183
If
acibenzolar-S-methyl



O-184
If
proquinazid



O-185
If
quinoxyfen



O-186
If
fenpiclonil



O-187
If
captan



O-188
If
fenpropidin



O-189
If
iprovalicarb



O-190
If
maneb



O-191
If
propineb



O-192
If
flubenthiavalicarb



O-193
If
flusulfamid



O-194
If
sulfur



O-195
If
spiroxamine



O-196
If
cymoxanil



O-197
If
cyflufenamid



O-198
If
valiphenal



O-199
If
metalaxyl



O-200
If
tebuconazole



O-201
If
cyproconazole



O-202
If
epoxiconazole



O-203
If
propiconazole



O-204
If
prothioconazole



O-205
Ig
boscalid



O-206
Ig
fenhexamid



O-207
Ig
fluopicolide



O-208
Ig
zoxamide



O-209
Ig
mandipropamid



O-210
Ig
carpropamid



O-211
Ig
cyazofamid,



O-212
Ig
flusilazole



O-213
Ig
ipconazole



O-214
Ig
triazoxide



O-215
Ig
fluazinam,



O-216
Ig
cyprodinil



O-217
Ig
acibenzolar-S-methyl



O-218
Ig
proquinazid



O-219
Ig
quinoxyfen



O-220
Ig
fenpiclonil



O-221
Ig
captan



O-222
Ig
fenpropidin



O-223
Ig
iprovalicarb



O-224
Ig
maneb



O-225
Ig
propineb



O-226
Ig
flubenthiavalicarb



O-227
Ig
flusulfamid



O-228
Ig
sulfur



O-229
Ig
spiroxamine



O-230
Ig
cymoxanil



O-231
Ig
cyflufenamid



O-232
Ig
valiphenal



O-233
Ig
metalaxyl



O-234
Ig
tebuconazole



O-235
Ig
cyproconazole



O-236
Ig
epoxiconazole



O-237
Ig
propiconazole



O-238
Ig
prothioconazole



O-239
Ia
glyphosate



O-240
Ib
glyphosate



O-241
Ic
glyphosate



O-242
Id
glyphosate



O-243
Ie
glyphosate



O-244
If
glyphosate



O-245
Ig
glyphosate










Within the mixtures of table 3, the following mixtures are especially preferred:


O-1, O-2, O-3, O-4, O-5, O-6, O-7, O-8, O-9, O-10, O-11, O-12, O-13, O-14, O-15, O-16, O-17, O-18, O-19, O-20, O-21, O-22, O-23, O-24, O-25, O-26, O-27, O-28, O-29, O-30, O-31, O-32, O-33, O-34, O-69, O-70, O-71, O-72, O-73, O-74, O-75, O-76, O-77, O-78, O-79, O-80, O-81, O-82, O-83, O-84, O-85, O-86, O-87, O-88, O-89, O-90, O-91, O-92, O-93, O-94, O-95, O-96, O-97, O-98, O-99, O-100, O-101, O-102, O-103, O-104, O-105, O-106, O-107, O-108, O-109, O-110, O-111, O-112, O-113, O-114, O-115, O-116, O-117, O-118, O-119, O-120, O-121, O-122, O-123, O-124, O-125, O-126, O-127, O-128, O-129, O-130, O-131, O-132, O-133, O-134, O-135, O-136, O-137, O-138, O-139, O-140, O-141, O-142, O-143, O-144, O-145, O-146, O-147, O-148, O-149, O-150, O-151, O-152, O-153, O-154, O-155, O-156, O-157, O-158, O-159, O-160, O-161, O-162, O-163, O-164, O-165, O-166, O-167, O-168, O-169, O-170, O-171, O-172, O-173, O-174, O-175, O-176, O-177, O-178, O-179, O-180, O-181, O-182, O-183, O-184, O-185, O-186, O-187, O-188, O-189, O-190, O-191, O-192, O-193, O-194, O-195, O-196, O-197, O-198, O-199, O-200, O-201, O-202, O-203, O-204, O-205, O-206, O-207, O-208, O-209, O-210, O-211, O-212, O-213, O-214, O-215, O-216, O-217, O-218, O-219, O-220, O-221, O-222, O-223, O-224, O-225, O-226, O-227, O-228, O-239, O-241, O-244 and O-245.


Within this subset, the following mixtures are preferred:


O-1, O-2, O-3, O-4, O-5, O-6, O-7, O-8, O-9, O-10, O-11, O-12, O-13, O-14, O-15, O-16, O-17, O-18, O-19, O-20, O-21, O-22, O-23, O-24, O-25, O-26, O-27, O-28, O-29, O-30, O-31, O-32, O-33, O-34, O-69, O-70, O-71, O-72, O-73, O-74, O-75, O-76, O-77, O-78, O-79, O-80, O-81, O-82, O-83, O-84, O-85, O-86, O-87, O-88, O-89, O-90, O-91, O-92, O-93, O-94, O-95, O-96, O-97, O-98, O-99, O-100, O-101, O-102, O-171, O-172, O-173, O-174, O-175, O-176, O-177, O-178, O-179, O-180, O-181, O-182, O-183, O-184, O-185, O-186, O-187, O-188, O-189, O-190, O-191, O-192, O-193, O-194, O-195, O-196, O-197, O-198, O-199, O-200, O-201, O-202, O-203, O-204, O-205, O-206, O-207, O-208, O-209, O-210, O-211, O-212, O-213, O-214, O-215, O-216, O-217, O-218, O-219, O-220, O-221, O-222, O-223, O-224, O-225, O-226, O-227, O-228 and O-239, The following mixtures are even more preferred: O-1, O-2, O-3, O-4, O-5, O-6, O-7, O-8, O-9, O-10, O-11, O-12, O-13, O-14, O-15, O-16, O-17, O-18, O-19, O-20, O-21, O-22, O-23, O-24, O-25, O-26, O-27, O-28, O-29, O-30, O-31, O-32, O-33, O-34 O-239.


Herein, we have found that the simultaneous, that is joint or separate application of compound (I) and compound (II) or (IV) or successive application of compound (I) and compound (II) or (IV) allows enhanced control of pests, that means harmful plant diseases, compared to the control rates that are possible with the individual compounds (synergistic mixtures).


In addition, we have found that the simultaneous, that is joint or separate application of compound (I) and compound (II) or (III) and compound (IIb) or (IV) listed in the table 2 or the successive application of compound (I) and compound (II) or (III) and compound (IIb) or (IV) allows an enhanced control of pests, that means harmful plant diseases, compared to the control rates that are possible with the individual compounds (synergistic mixtures).


With respect to their intended use for controlling pest, the ternary mixtures of compound (I) and at least one compound selected from the group consisting of compounds (II), (IIb), (III) or (IV) listed in the table 2 above are especially preferred.


Within the ternary mixtures of table 2, the following mixtures are especially preferred with respect to their intended use for controlling pest:


N-1, N-2, N-3, N-4, N-5, N-6, N-7, N-8, N-9, N-10, N-11, N-12, N-13, N-14, N-15, N-16, N-17, N-18, N-19, N-20, N-21, N-22, N-23, N-24, N-25, N-26, N-27, N-28, N-29, N-30, N-31, N-32, N-33, N-34, N-35, N-36, N-37, N-38, N-39, N-40, N-41, N-42, N-43, N-44, N-45, N-46, N-47, N-48, N-49, N-50, N-51, N-52, N-53, N-54, N-55, N-56, N-57, N-58, N-59, N-60, N-61, N-62, N-63, N-64, N-65, N-66, N-67, N-68, N-69, N-70, N-71, N-72, N-73, N-74, N-75, N-76, N-77, N-78, N-79, N-80, N-81, N-82, N-83, N-84, N-85, N-86, N-87, N-88, N-89, N-90, N-91, N-92, N-93, N-94, N-95, N-96, N-97, N-98, N-100, N-101, N-102, N-103, N-104, N-105, N-106, N-107, N-108, N-109, N-110, N-111, N-112, N-113, N-114, N-115, N-116, N-117, N-118, N-119, N-120, N-121, N-122, N-123, N-124, N-125, N-126, N-127, N-128, N-129, N-130, N-131, N-132, N-133, N-134, N-135, N-960, N-961, N-962, N-963, N-964, N-965, N-966, N-967, N-968, N-969, N-970, N-971, N-972, N-973, N-974, N-1065, N-1066, N-1067, N-1068, N-1069, N-1070, N-1071, N-1072, N-1073, N-1083, N-1084, N-1085, N-1086, N-1087, N-1088, N-1089, N-1090, N-1091, N-1110, N-1111, N-1112, N-1113, N-1114, N-1115, N-1116, N-1117, N-1118, N-1119, N-1120, N-1121, N-1122, N-1123, N-1124, N-1125, N-1126 and N-1127.


Advantageously, the inventive mixtures are suitable for controlling the following plant diseases:



Albugo spp. (white rust) on ornamentals, vegetables (e. g. A. candida) and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A. alternata), tomatoes (e. g. A. solani or A. alternate) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A. hordei on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.) on corn (e. g. D. maydis), cereals (e. g. B. sorokiniana: spot blotch), rice (e. g. B. oryzae) and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn, rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, anamorph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. graminicola), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. liriodendri, teleomorph: Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Bottyosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pisi), such as cucurbits (e. g. E. cichoracearum), cabbages, rape (e. g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohllum (syn. Helminthosporium) spp. on corn (e. g. E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani on soybeans and F. verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and corn; Gibberella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica); Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsid), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad-leaved trees (e. g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples; Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia yallundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or ‘rotbrenner’, anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, and asparagus (e. g. P. asparagi); Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum); Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. rolfsii or S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum and sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae); Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.


The inventive mixturs are also suitable for controlling harmful fungi in the protection of materials (e. g. wood, paper, paint dispersions, fiber or fabrics) and in the protection of stored products. As to the protection of wood and construction materials, the particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichorma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.


They are particularly important for controlling a multitude of fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grape-fruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants.


Preferably, these mixtures are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, cereals such as wheat, rye, barley, oats, sorghum, rice, corn, cotton, rape, canola, legumes such as soybeans, peas and field beans, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, onions, leeks, lettuce, beans or squashes.


The treatment of a plant or its growth locus or its propagation material, such as a seed, with the compound of formula I or a mixture according to the present invention of the invention can be accomplished in several ways. The components (I) and (II or III) may be applied directly to the propagules, especially the seed, and/or to the soil in which the seed is to be planted or before planting or transplanting, or for example, at the time of planting along with the seed (for example in-furrow application).


The compound (I) or a mixture according to the present invention may also comprise a solvent or solid carrier and compound (I) and in case a mixture is used compound (II) or (III) (and/or their salts) can be converted into customary types of agrochemical formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules together or separately. The formulation type depends on the particular intended purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention.


Examples for formulation types are suspensions (SC, OD, FS), pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, DP, DS) or granules (GR, FG, GG, MG), which can be water-soluble or wettable, as well as gel formulations for the treatment of plant propagation materials such as seeds (GF). Usually the formulation types (e.g. SC, OD, FS, WG, SG, WP, SP, SS, WS, GF) are employed diluted. Formulation types such as DP, DS, GR, FG, GG and MG are usually used undiluted.


The formulations are prepared in a known manner (cf. U.S. Pat. No. 3,060,084, EP-A 707 445 (for liquid concentrates), Browning: “Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, S. 8-57 and ff. WO 91/13546, U.S. Pat. No. 4,172,714, U.S. Pat. No. 4,144,050, U.S. Pat. No. 3,920,442, U.S. Pat. No. 5,180,587, U.S. Pat. No. 5,232,701, U.S. Pat. No. 5,208,030, GB 2,095,558, U.S. Pat. No. 3,299,566, Klingman: Weed Control as a Science (J. Wiley & Sons, New York, 1961), Hance et al.: Weed Control Handbook (8th Ed., Blackwell Scientific, Oxford, 1989) and Mollet, H. and Grubemann, A.: Formulation technology (Wiley VCH Verlag, Weinheim, 2001).


The agrochemical formulations may also comprise auxiliaries which are customary in agrochemical formulations. The auxiliaries used depend on the particular application form and active substance, respectively.


Examples for suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e.g. for seed treatment formulations).


Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, glycols, ketones such as cyclohexanone and gamma-butyrolactone, fatty acid dimethylamides, fatty acids and fatty acid esters and strongly polar solvents, e. g. amines such as N-methylpyrrolidone.


Solid carriers are mineral earths such as silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e. g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.


Suitable surfactants (adjuvants, wtters, tackifiers, dispersants or emulsifiers) are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsoulfonic acid (Borresperse® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Morwet® types, Akzo Nobel, U.S.A.), dibutylnaphthalene-sulfonic acid (Nekal® types, BASF, Germany),and fatty acids, alkylsulfonates, alkylarylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, furthermore condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxy-ethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkyiphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and proteins, denatured proteins, polysaccharides (e. g. methylcellulose), hydrophobically modified starches, polyvinyl alcohols (Mowiol® types, Clariant, Switzerland), polycarboxylates (Sokolan® types, BASF, Germany), polyalkoxylates, polyvinylamines (Lupasol® types, BASF, Germany), polyvinylpyrrolidone and the copolymers therof.


Examples for thickeners (i.e. compounds that impart a modified flowability to formulations, i. e. high viscosity under static conditions and low viscosity during agitation) are polysaccharides and organic and anorganic clays such as Xanthan gum (Kelzan®, CP Kelco, U.S.A.), Rhodopol® 23 (Rhodia, France), Veegum® (R.T. Vanderbilt, U.S.A.) or Attaclay® (Engelhard Corp., NJ, USA).


Bactericides may be added for preservation and stabilization of the formulation. Examples for suitable bactericides are those based on dichlorophene and benzylalcohol hemi formal (Proxel® from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acticide® MBS from Thor Chemie).


Examples for suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.


Examples for anti-foaming agents are silicone emulsions (such as e. g. Silikon® SRE, Wacker, Germany or Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and mixtures thereof.


Suitable colorants are pigments of low water solubility and water-soluble dyes. Examples to be mentioned and the designations rhodamin B, C. I. pigment red 112, C. I. solvent red 1, pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.


Examples for tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose®, Shin-Etsu, Japan).


Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the compounds I (and optionally compound II) and, if appropriate, further active substances, with at least one solid carrier.


Granules, e. g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e. g., ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.


Examples for formulation types are:


1. Composition Types for Dilution with Water


i) Water-Soluble Concentrates (SL, LS)


10 parts by weight of compound (I) and optionally at least one compound selected from the group consisting of compounds (II), (IIb), (III) and (IV) according to the invention are dissolved in 90 parts by weight of water or in a water-soluble solvent. As an alternative, wetting agents or other auxiliaries are added. The active substance dissolves upon dilution with water. In this way, a formulation having a content of 10% by weight of active substance is obtained.


ii) Dispersible Concentrates (DC)


20 parts by weight of compound (I) and optionally at least one compound selected from the group consisting of compounds (II), (IIb), (III) and (IV) according to the invention are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, e. g. polyvinylpyrrolidone. Dilution with water gives a dispersion. The active substance content is 20% by weight.


iii) Emulsifiable Concentrates (EC)


15 parts by weight of compound (I) and optionally at least one compound selected from the group consisting of compounds (II), (IIb), (III) and (IV) according to the invention are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The composition has an active substance content of 15% by weight.


iv) Emulsions (EW, EO, ES)


25 parts by weight of compound (I) and optionally at least one compound selected from the group consisting of compounds (II), (IIb), (III) and (IV) according to the invention are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifying machine (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The composition has an active substance content of 25% by weight.


v) Suspensions (SC, OD, FS)


In an agitated ball mill, 20 parts by weight of compound (I) and optionally at least one compound selected from the group consisting of compounds (II), (IIb), (III) and (IV) according to the invention are comminuted with addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. The active substance content in the composition is 20% by weight.


vi) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)


50 parts by weight of compound (I) and optionally at least one compound selected from the group consisting of compounds (II), (IIb), (III) and (IV) according to the invention are ground finely with addition of 50 parts by weight of dispersants and wetting agents and prepared as water-dispersible or water-soluble granules by means of technical appliances (e.g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance. The composition has an active substance content of 50% by weight.


vii) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, SS, WS)


75 parts by weight of compound (I) and optionally at least one compound selected from the group consisting of compounds (II), (IIb), (III) and (IV) according to the invention are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetting agents and silica gel. Dilution with water gives a stable dispersion or solution of the active substance. The active substance content of the composition is 75% by weight.


viii) Gel (GF)


In an agitated ball mill, 20 parts by weight of compound (I) and optionally at least one compound selected from the group consisting of compounds (II), (IIb), (III) and (IV) according to the invention are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance, whereby a composition with 20% (w/w) of active substance is obtained.


2. Composition Types to be Applied Undiluted


ix) Dustable Powders (DP, DS)


5 parts by weight of compound (I) and optionally at least one compound selected from the group consisting of compounds (II), (IIb), (III) and (IV) according to the invention are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable composition having an active substance content of 5% by weight.


x) Granules (GR, FG, GG, MG)


0.5 parts by weight of compound (I) and optionally at least one compound selected from the group consisting of compounds (II), (IIb), (III) and (IV) according to the invention is ground finely and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted having an active substance content of 0.5% by weight.


xi) ULV Solutions (UL)


10 parts by weight of compound (I) and optionally at least one compound selected from the group consisting of compounds (II), (IIb), (III) and (IV) according to the invention are dissolved in 90 parts by weight of an organic solvent, e. g. xylene. This gives a composition to be applied undiluted having an active substance content of 10% by weight.


The agrochemical formulations generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substance(s). The active substance(s) are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).


Compositions, which are especially useful for the purposes of treatment of plant propagation materials, particularly seeds seed treatment are e.g.:


A Soluble concentrates (SL, LS)


D Emulsions (EW, EO, ES)


E Suspensions (SC, OD, FS)


F Water-dispersible granules and water-soluble granules (WG, SG)


G Water-dispersible powders and water-soluble powders (WP, SP, WS)


H Gel-Formulations (GF)


I Dustable powders (DP, DS)


These compositions can be applied to plant propagation materials, particularly seeds, diluted or undiluted.


The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying or treating agrochemical compounds and compositions thereof, respectively, on to plant propagation material, especially seeds, are known in the art, and include dressing, coating, pelleting, dusting and soaking application methods of the propagation material (and also in furrow treatment). In a preferred embodiment, the compounds or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.


The compounds of formula I or the compounds mixtures of the present invention can be used as such or in the form of their compositions, e. g. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading, brushing, immersing or pouring. The application forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the compounds of formula I or the compounds mixtures of the present invention.


Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the compounds of formula I or the compounds mixtures of the present invention, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.


The active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1% by weight of compounds of formula I or the compounds mixtures of the present invention.


The compounds (I) or the compound mixtures of the present invention may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives.


In another embodiment, the inventive compositions are used for reducing or inhibiting the injury caused to plants by phythotoxic amounts of pesticides such as fungicides, herbicides and/or insecticides.


The compositions according to the present invention comprise a plant health effective amount of a compound (I) or a plant health effective amount of compound (I) and at least one compound selected from the group consisting of compounds (II), (IIb), (III) and (IV) wherein compound (I) and at least one compound selected from the group consisting of compounds (II), (IIb), (III) and (IV) provide synergistic plant health effects.


The compositions according to the present invention comprising the novel mixtures according to the present invention comprise a pesticidally effective amount of compound (I) and compound (II) (or III), wherein compound (I) and (II) provide synergistic pesticidal effects.


In the methods according to the invention, the application rates of the mixtures according to the invention are from 0.3 g/ha to 2000 g/ha, preferably 0.005 kg/ha to 2.0 kg/ha, more preferably from 20 to 1000 g/ha, in particular from 20 to 500 g/ha, depending on the type of compound and the desired effects.


Various types of oils, wetters, adjuvants, herbicides, bactericides, other fungicides and/or pesticides may be added to the active substance(s) or the compositions comprising them, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compound I or the mixtures according to the invention according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.


Adjuvants which can be used are in particular organic modified polysiloxanes such as Break Thru S 240®; alcohol alkoxylates such as Atplus 245®, Atplus MBA 1303®, Plurafac LF 300® and Lutensol ON 30®; EO/PO block polymers, e. g. Pluronic RPE 2035® and Genapol B®; alcohol ethoxylates such as Lutensol XP 80®; and dioctyl sulfosuccinate sodium such as Leophen RA®.


The compound (I) according to the invention or the mixtures according to the invention can, in the use form as fungicides, also be present together with other active substances, e.g. with herbicides, insecticides, growth regulators, fungicides or else with fertilizers or inoculants, as pre-mix or, if appropriate, not until immediately prior to use (tank mix).


If a mixture according to the present invention is used, the compounds (I) and optionally compounds (II), (IIb), (III) or (IV) can be used individually or already partially or completely mixed with one another to prepare the composition according to the invention. It is also possible for them to be packaged and used further as combination composition such as a kit of parts.


In one embodiment of the invention, the kits may include one or more, including all, components that may be used to prepare the composition e.g. in form of an agrochemical formulation. These kits may include compound I and/or an adjuvant component and/or a insecticide component and/or a growth regulator component and/or a herbicide and/or an inoculant. One or more of the components may already be combined together or pre-formulated. In those embodiments where more than two components are provided in a kit, the components may already be combined together and as such are packaged in a single container such as a vial, bottle, can, pouch, bag or canister. In other embodiments, two or more components of a kit may be packaged separately, i.e., not pre-formulated. As such, kits may include one or more separate containers such as vials, cans, bottles, pouches, bags or canisters, each container containing a separate component for an agrochemical composition. In both forms, a component of the kit may be applied separately from or together with the further components or as a component of a combination composition according to the invention for preparing the composition according to the invention.


The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank or a spray plane. Here, the agrochemical composition is made up with water and/or buffer to the desired application concentration, it being possible, if appropriate, to add further auxiliaries, and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 50 to 500 liters of the ready-to-use spray liquor are applied per hectare of agricultural useful area, preferably 80 to 400 liters. According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate (tank mix).


The following examples are intended to illustrate the invention, but without imposing any limitation.







EXAMPLES
Example 1

Mitcherlich pots of known weight were filled with 5.5 kg of sandy dry soil (pH 6.8) and fertilized (P, K and Mg) to optimal growing conditions. The culture was spring wheat (cv. Passat); 12 plants per pot. The experiment was conducted with 6 replications in a vegetation hall. Experiments were carried out under semi controlled conditions at very low disease-pressure with insignificant infection rates, protected from any undesired rain or water impact. The water consumption of each pot was calculated on the basis of the recorded measurements of the weight of the pots prior to each irrigation event up to the defined set point.


Nitrogen fertilizer (totally 1.75 g N/pot) was added in equal amounts at 3 stages to allow optimal growth conditions throughout the life cycle. All plants/pots were grown at optimal water supply by watering 2-3 times a day to 60% of the water holding capacity of the soil.


Compound Ia (62.5 g/L, 2 L in 400 L water/ha) was applied at growth stage 39/49 (BBCH scale), which is an EC formulation of compound Ia. Control plants were not treated.


Plant Height, as an indicator of plant vigor, was measured after heading. At maturity of the plants the grain, as an indicator of yield, was harvested and uniformly dried to 5% moisture content. Straw yield, as an another indicator of plant yield, was also determined and the number of halms with ear per pot was counted at maturity. Number of grains per pot was counted after harvest. Thousand Grain Weight (TGW), as yet another indicator of plant yield, was calculated based on grain yield per pot and number of grains per pot.














TABLE 4






Plant
Number of

Straw
Grain


Compound
height
halms with
TGW
yield
yield/pot


applied
(cm)
ear/pot
(g)
(g/pot)
(g/pot)







Control
74.7
32.3
31.4
65.9
59.8


(untreated)


Compound Ia
76.2
37.5
32.0
70.0
74.2



(+2%)
(+16%)
(+2%)
(+6%)
(+6%)









The results in table 4 illustrate that compound Ia improves the tillering of the wheat crop. The promotion of plant shoot growth can also be seen in the increase in straw yield and plant height. Besides the number of grains that are formed per ear as well as the grain weight (TGW), the number of halms with ears is generally determining the final grain yield of a cereal crop. As can be seen in table 4, all measured parameters were increased by the application of compound la in the example given. Consequently, compound Ia clearly increases the health of a plant leading to an increased plant vigor and increase in yield.


Example 2

Spring wheat (cv. Passat) was cultivated in Mitcherlich pots as described above in example 1. The experiment was conducted with 6 replications in a vegetation hall. Experiments were carried out under semi controlled conditions at very low disease-pressure with insignificant infection rates, protected from any undesired rain or water impact. The water consumption of each pot was calculated on the basis of the recorded measurements of the weight of the pots prior to each irrigation event up to the defined set point.


Nitrogen fertilizer (totally 1.75 g N/pot) was added in equal amounts at 3 stages to allow optimal growth conditions throughout the life cycle. All plants/pots were grown at optimal water supply by watering 2-3 times a day to 60% of the water holding capacity of the soil until growth stage 55 (BBCH). Then, pots were only watered to 60% of the maximum water holding capacity of the soil after clear water stress symptoms on the plants were visible to apply severe drought stress.


Compound Ia (62.5 g/l, 2 L in 400 L water/ha) was applied at growth stage 39/49 (BBCH scale), which is an EC formulation of compound Ia. Control plants were not treated.


After ripening of the plants, the grain was harvested and uniformly dried to 5% moisture content. Grain yield per pot, grain yield per ear, number of grains per ear and number of grains per pot were determined as indicators of plant vigor and plant yield. The relation of grain yield to straw added to the grain yield was used to calculate the harvest index.












TABLE 5






Harvest index
Single ear grain
Number of


Compound
(grain yield g/grain +
yield
grains per


applied
straw yield g)
(g/ear)
ear







Control
0.41
1.27
48.3


(untreated)


Compound Ia
0.42
1.31
49.9



(+3%)
(+3%)
(+3%)









The results in table 5 illustrate that compound Ia improves the seed set in wheat plants, especially under drought stress like in the present example. More grains per ear are generated, which resulted in an increased yield per ear. As a result, compound Ia clearly increases the plant vigor as well as the yield even under severe abiotic stress conditions like drought stress. Consequently, compound Ia increases the overall plant health according to the present invention.


Example 3

Spring wheat (cv. Passat) was cultivated in Mitcherlich pots as described above in example 1. The experiment was conducted with 6 replications in a vegetation hall. Experiments were carried out under semi controlled conditions at very low disease-pressure with insignificant infection rates, protected from any undesired rain or water impact. The water consumption of each pot was calculated on the basis of the recorded measurements of the weight of the pots prior to each irrigation event up to the defined set point. Pots without crop coverage were used to estimate the evaporation of the soil.


Nitrogen fertilizer (totally 1.75 g N/pot) was added in equal amounts at 3 stages to allow optimal growth conditions throughout the life cycle. All plants/pots were grown at optimal water supply by watering 2-3 times a day to 60% of the water holding capacity of the soil until growth stage 55 (BBCH). Then, pots were only watered to 30% of the maximum water holding capacity of the soil to apply moderate drought stress. Compound Ia (62.5 g/l, 2 L in 400 L water/ha) was applied at growth stage 39/49 (BBCH scale), which is an EC formulation of comound Ia. Control plants were not treated.


At maturity of the plants the grain was harvested and uniformly dried to 5% moisture content. Number of grains per pot was counted after harvest. Thousand Grain Weight (TGW), as an indicator of plant yield, was calculated based on grain yield per pot and number of grains per pot. Transpiration was calculated on the basis of the amount of water added to the respective pots and the estimated soil evaporation. Water use efficiency, as an indicator of drought stress tolerance of a plant, was calculated based on the respective transpiration per pot.












TABLE 6





Compound
Transpiration
Water use efficiency
Thousand Grain


applied
(L water/pot)
(kg grain/L water)
Weight (g)







Control (un-
27.6
1.96
29.8


treated)


Compound Ia
26.5
2.02
31.2



(−4%)
(+3%)
(+4%)









Compound Ia improved seed development in terms of grain weight. In the applied drought stress condition compound la lead to a reduction of transpiration of water. Conseqeuntly, compound Ia treated wheat plants used less water to produce the increase in grain yield and less water per kg of grain. In addition, the reduction of transpiration and the increase in water use effiency led to an increase in plant vigor. The improved water use efficiency shows the improved tolerance against abiotic stresses, especially drought stress, by the compound la and its beneficial effect on additional plant health effects such as plant vigor and yield according to the present invention.


Example 4

Soybeans were grown in 2008 in two field trials at the BASF experimental station in Dinuba, 10181 Avenue 416, Calif., U.S.A. In one trial, the variety Pioneer 93-M-11 was planted at a seeding rate of 88 kg/ha. In a second trial, the variety Crow C300 42 was planted at the same seeding rate. Both trials were setup as randomized complete block design with 5 replications, each. Plot size was 42 m2. Compound la was used as an EC formulation (62.5 g a.i./L) with a dose rate of 0.64 L per hectar (40 g a.i./ha). The formulation was applied in a total spray volume of 300 L/ha. Compound Ia was sprayed at growth stage 34/37 (BBCH) with a tractor mounted spray boom with VS11003 spray nozzles at 3 bar spray pressure.


No disease symptoms were visible at the application time and no symptoms were detected at later stages.


Green leaf area, as an indicator of plant vigor, was assessed in the second trial (variety Crow C300 42) when all pods had reached their final size by estimating the green leaf area in 10 randomly chosen plants per plot. At maturity the grain was harvested and the grain yield per plot, as an indicator of plant yield, was determined (kg/plot). Finally, the grain yield per hectare was calculated (dt/ha). Thousand Grain Weight (TGW) was determined in the second trial (Crow C300 42).









TABLE 7







Green leaf area, TGW, and grain yield in maize,


one trial, Dinuba, CA, 2008











Compound applied
% Green leaf area
TGW (g)















Control
84.0
167.5



(untreated)



Compound Ia
88.4
177.0



(increase as %
(+5.2%)
(+5.7%)



of untreated)

















TABLE 8







Soybean grain yield in dt/ha, two field trials, Dinuba, CA, 2008











Soybean grain
Soybean grain




yield (Trial 1)
yield (Trial 2)


Compound applied
Pioneer 93M11
Crow C300 42
Mean













Control
40.7
63.0
51.9


(untreated)


Compound Ia
45.5
67.1
56.3


(increase as %
(+11.6%)
(+6.5%)
(+8.5%)


of untreated)









Compound Ia increased photosynthetic active green leaf area by more than 5% versus the untreated control. A higher proportion of photosynthetic active leaf area results in a higher grain yield, as was observed in the present example. Grain size and grain weight was improved by compound Ia, respectively, as indicated by the increase in compound Ia treated plants over the untreated control (table 7).


Finally, compound Ia improved the seed yield in soybeans as shown in table 8. The grain yield in soybeans was improved by the comound la treatment by 8.5% on an average of the two trials with one trial showing an increase of up to almost 12%.


As can be seen, the application of compound Ia clearly increases the health of a plant leading to an increase in plant vigor and yield.


Example 5

Maize was grown in 2008 in a field trial at the BASF experimental station in Dinuba, 10181 Avenue 416, Calif., U.S.A. The variety Dekalb RX940 was planted at a seeding rate of 10 plants/m2. Four rows per plot were planted with a row spacing of 0.75 m. The trial was setup as a randomized bloc design with 5 replications, each. Plot size was 43 m2. Compound Ia was used as an EC formulation (62.5 g a.i./L) with a dose rate of 0.8 L per hectar (50 g a.i./ha). The formulation was applied in a total spray volume of 400 L/ha. Compound Ia was sprayed at a growth stage 51/55 (BBCH) with a tractor mounted spray boom with VS11003 spray nozzles at 3 bar spray pressure.


No disease symptoms were visible at the application time and no symptoms were detected at later stages.


Green leaf area, as an indicator of plant vigor, was assessed beginning of ripening by estimating the green leaf area in 10 randomly chosen plants per plot.


At maturity the grain was harvested and the grain yield per plot, as an indicator of plant yield, was determined (kg/plot). Finally, the grain yield per hectare, as an aditional indicator of plant yield, was calculated (dt/ha). Furthermore, the Thousand Grain Weight (TGW) was determined in the second trial (Crow C300 42).









TABLE 9







Green leaf area, TGW, and grain yield in maize,


one trial, Dinuba, CA, 2008










Compound





applied
% Green leaf area
TGW (g)
Grain yield (dt/ha)













Control
43.0
306.9
148.1


(untreated)


Compound Ia
49.0
317.0
154.7


(increase as %
(+13.9%)
(+3.3%)
(+4.5%)


of untreated)









Compound Ia increased photosynthetic active green leaf area by almost 14% compared to the untreated control. Consequently, a higher proportion of the leaf area remains photosynthetic active. More storage compounds (i.e. carbohydrates) are synthesized which then are trans-located to the grains. Bigger and more grains per cob are formed. The increase in grain size is indicated by the increase in TGW shown in table 9. Consequently, the treatment with compound Ia leads to an increase in maize grain yield. In the present example, the plots treated with compound Ia showed an yield increase of 4.5% compared to the untreated plots. As can be seen, the application of compound Ia clearly increases the health of a plant.


Example 6

Maize was grown in 2008 in a field trial at the BASF experimental station in Dinuba, 10181 Avenue 416, Calif., U.S.A. The variety Pioneer 34-N-45 was planted at a seeding rate of 35.000 plants/ha. The trial was setup as a randomized bloc design with 5 replications, each. Plot size was 43 m2.


The maize plants were either untreted, treated with epoxiconazol (A3), with compound Ia, and with a mixture comprising compound Ia and epoxiconazol. Epoxiconazol was applied as the commercial formulation OPUS™ (125 g a.i./L, SC formulation) at a dose rate of 0.4 L/ha (50 g a.i./ha). Compound Ia was used as an EC formulation (62.5 g a.i./L) with a dose rate of 0.8 L per hectar (50 g a.i./ha). Epoxiconazol was applied together with compound Ia (as a mixture) using a co-formulation of both compounds (EC formulation, 62.5 g a.i./L each) with a product rate of 0.8 L/ha. The formulation was applied in a total spray volume of 300 L/ha. Compound Ia was sprayed at growth stage 51/55 (BBCH) with a tractor mounted spray boom with VS11003 spray nozzles at 3 bar spray pressure.


No disease symptoms were visible at the application time and no symptoms were detected at later stages.


At maturity the grain was harvested and the grain yield per plot, as an indicator of plant yield, was determined (kg/plot). Finally, the grain yield per hectare was calculated (dt/ha).


The efficacy was calculated as % increase of the grain yield (dt/ha) by each treatment compared to the untreated control.


The expected efficacies of the combinations of the active compounds were estimated using Colby's formula (Colby, S. R., Calculating synergistic and antagonistic responses of herbicide combinations, Weeds, 15, pp. 20-22, 1967) and compared with the observed efficacies.






E=x+y−x·y/100   Colby's formula:

  • E expected efficacy, expressed in % of the untreated control, when using the mixture of the active compounds A and B at the concentrations a and b
  • x efficacy, expressed in % of the untreated control, when using the active ingredient A at the concentration a
  • y efficacy, expressed in % of the untreated control, when using the active ingredient B at the concentration b









TABLE 10







TGW, observed and expected efficacy according to Colby's formula.
















Grain
Ob-





a.i.
Formu-
yield
served
Expected
Syner-


Compound
rate
lation
(dt/
efficacy
efficacy
gism


applied
(g/ha)
type
ha)
(%)
(%)
(%)





1. Control


154.3





(untreated)


2. Compound Ia
50
EC
154.9
0.4


3. Epoxiconazol
50
SC
155.8
0.9


(A3)


4. Epoxiconazol
50 +
EC
161.7
4.8
1.3
3.5


(A3) +
50


compound Ia









The results demonstrate that the efficacy in the combination ratios of the active compounds shown in table 10 is higher than the expected efficacy calculated using Colby's formula. Consequently, the secondary mixture described in table 10 is a synergistic plant health increasing mixture according to the invention.


Example 7

Soybeans were grown in 2008 at the CEDUP “Caetano Vieira da Costa” in Sao José do Cerrito, Santa Catarina, Brazil. The variety M-SOY 6001 RR was planted in 2007, 11 Nov., at a seeding rate of 300.000 plants per ha. Row spacing was 50 cm. The trial was setup as a randomized bloc design with 4 replications. Plot size was 12.5 m2.


Fungicide treatments were applied at BBCH GS 70-79 (pods reached 15-20 mm of final lenght). The fungicides were used as formulations.


Compound Ia was applied as an EC formulation (62.5 g/L—EC) at 0.64 L/ha (40 g ai/ha). Epoxiconazol (A3) and pyraclostrobin (S8) were coformulated in an SC formulation (160 g/L of epoxiconazol+260 g/L of pyraclostrobin—SC) and sprayed at a dose rate of 0.25 I/ha (40 g a.i./ha epoxiconazol and 65 g a.i./ha pyraclostrobin. The adjuvant DASH HC was added to the spray tank with 0.3% (v/v).


Finally, compound Ia was applied in a mixture together with epoxiconazol and pyraclostrobin forming a ternary mixture according to the present invention, using a coformulation of all three compounds (50 g/L of compound Ia+50 g/L of epoxiconazol+81 g/L of pyraclostrobin—EC). This formulation was sprayed at a rate of 0.8 L/ha (40 g a.i./ha compound Ia+40 g a.i./ha epoxiconazol+65 g a.i./ha pyraclostrobin). The formulations were diluted in water. Total spray volume for foliar application was 150 L/ha.


The trial was conducted under low disease pressure. No differences could be observed between the chemical treatments.


Plots were harvested at maturity of the soybean crop and the yield (thousand grain weight) was determined (table 11). The efficacy in yield increase was calculated as % increase of the Thousand Grain Weight (TGW) by the treatments compared to the untreated control.


The expected efficacies of the combinations of the active compounds were estimated using Colby's formula as defined above and compared with the observed efficacies.















TABLE 11









Ob-





a.i.
Formu-

served
Expected
Syner-


Compound
rate
lation
TGW
efficacy
efficacy
gism


applied
(g/ha)
type
(g)
(%)
(%)
(%)





















1. Control


153





(untreated)


2. Compound Ia
40
EC
153
0


3. Epoxiconazol
40 +
SC
158
3.3


(A3) +
65


pyraclostrobin


(S8)


4. Epoxiconazol
40 +
EC
165
7.8
3.3
4.5


(A3) +
65 +


pyraclostrobin
40


(S8) +


compound Ia





*including adjuvant DASH HC 0.3% v/v






The results demonstrate that when applying a ternary mixture according to the invention, comprising epoxiconazol (A3), pyraclostrobin (S8) and the amide compound Ia, the yield not only increases but in addition, that the observed efficacy is higher than the expected efficacy calculated using Colby's formula. Consequently, the mixture described in table 11 is a synergistic plant health increasing mixture according to the invention.

Claims
  • 1-19. (canceled)
  • 20. A method for improving the plant health of at least one plant variety, which method comprises treating the plant and/or the locus where the plant is growing or is intended to grow with an amide having the formula I (compound I)
  • 21. The method as claimed in claim 20, wherein the amide of formula I (compound I) is selected from the group consisting of N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-[2-(4′-trifluoromethylthio)-biphenyl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide (common name: bixafen), N-[2-(1,3-dimethylbutyl)-phenyl]-1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N-(2-bicyclopropyl-2-yl-phenyl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide (common name: sedaxane), N-[1,2,3,4-tetrahydro-9-(1-methylethyl)-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (common name: isopyrazam) and N-[2-(1,3-dimethylbutyl)-3-thienyl]-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide (common name: penthiopyrad).
  • 22. The method as claimed in claim 20, wherein the amide of formula I (compound I) is selected from the group consisting of N-(3′,4′,5′-trifluorobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-difluoromethyl-1-methylpyrazole-4-carboxamide (common name: bixafen), N-[1,2,3,4-tetrahydro-9-(1-methylethyl)-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide (common name: isopyrazam) and N-[2-(1,3-dimethylbutyl)-3-thienyl]-1-methyl-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide (common name: penthiopyrad).
  • 23. The method as claimed in claim 22, wherein a mixture of the amide compound of formula I (compound I) and a further fungicide II (compound II) is applied in plant health synergistically effective amounts, wherein the further fungicide II is selected from the group consisting of (i) a strobilurine selected from the group consisting of azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin;(ii) a carboxylic amide selected from the group consisting of boscalid, fenhexamid, metalaxyl, dimethomorph, fluopicolide (picobenzamid), zoxamide, mandipropamid and carpropamid;(iii) an azole selected from the group consisting of cyproconazole, difenoconazole, epoxiconazole, flusilazole, fluquinconazole, flutriafol, ipconazole, metconazole, propiconazole, prothioconazole, tebuconazole, cyazofamid, prochloraz, ethaboxam and triazoxide;(iv) a heterocyclic compounds selected from the group consisting of famoxadone, fluazinam, cyprodinil, pyrimethanil, fenpropimorph, iprodione, acibenzolar-S-methyl, proquinazid, quinoxyfen, fenpiclonil, captan, fenpropidin, captafol and anilazin;(v) a carbamate and dithiocarbamate selected from the group consisting of mancozeb, metiram, iprovalicarb, maneb, propineb, flubenthiavalicarb (benthiavalicarb) and propamocarb(vi) an organo-chloro compound selected from the group consisting of thiophanate methyl, chlorothalonil, tolylfluanid and flusulfamid;(vii) an inorganic active ingredient selected from the group consisting of Bordeaux composition, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate and sulfur;(viii) an additional compound selected from the group consisting of spiroxamine, guazatin, cymoxanil, cyflufenamid, valiphenal, metrafenone, fosetly-aluminium and dithianon.
  • 24. The method as claimed in claim 23, wherein the further fungicide II (compound II) is selected from the group consisting of (i) a strobilurine selected from the group consisting of azoxystrobin, dimoxystrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin;(ii) a carboxcyclic amide selected from the group consisting of boscalid and dimethomorph(iii) an azole selected from the group consisting of cyproconazole, difenoconazole, epoxiconazole, metconazole, propiconazole, prothioconazole and tebuconazole;(iv) a heterocyclic compound selected from the group consisting of cyprodinil, pyrimethanil, fenpropimorph, iprodione, quinoxyfen and acibenzolar-S-methyl;(v) a carbamate and dithiocarbamate selected from the group consisting of mancozeb, metiram, propineb and iprovalicarb;(viii) an additional compound selected from the group consisting of dithianon and metrafenone.
  • 25. The method as claimed in claim 23, wherein the further fungicide II (compound II) is selected from the group consisting of orysastrobin, pyraclostrobin, azoxystrobin and trifloxystrobin.
  • 26. The method as claimed in claim 24, additionally comprising an insecticide (compound III), selected from fipronil and ethiprole.
  • 27. The method as claimed in claim 24, additionally comprising a further fungicide III (compound IIb), selected from the group consisting of cyproconazole, difenoconazole, epoxiconazole, flusilazole, fluquinconazole, flutriafol, ipconazole, metconazole, propiconazole, prothioconazole, tebuconazole, cyazofamid, prochloraz, ethaboxam and triazoxide.
  • 28. The method as claimed in claim 24, additionally comprising a herbicide (compound IV) selected from the group consisting of glyphosate, sulfosinate and glyphosinate.
  • 29. The method as claimed in claim 20, wherein the plant is selected from the group consisting of agricultural plants, silvicultural plants and ornamental plants.
  • 30. The method as claimed in claim 24, wherein the amide compound of the formula I (compound I) and at least one further compound selected from the group consisting of compounds (II), (IIb), (III) and (IV) are applied simultaneously, either as a mixture or separately, or subsequently to the plant and/or the locus where the plant is growing or intended to grow.
  • 31. The method according to claim 24, wherein the amide compound of formula I (compound I) is applied to said plants and/or the locus in which they grow at an application rate of from about 0.005 kg/ha to about 2.0 kg/ha to said plants and/or the locus in which they grow.
  • 32. A fungicidal mixture comprising in synergistically effective amounts an amide having the formula I (compound I)
Priority Claims (2)
Number Date Country Kind
PCT/EP2008/051375 Feb 2008 EP regional
08161625.2 Aug 2008 EP regional
PCT Information
Filing Document Filing Date Country Kind 371c Date
PCT/EP2009/051241 2/4/2009 WO 00 11/30/2010