Plant Health Composition

Information

  • Patent Application
  • 20110105579
  • Publication Number
    20110105579
  • Date Filed
    February 04, 2009
    15 years ago
  • Date Published
    May 05, 2011
    13 years ago
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 propagules with an amide compound having the formula I (compound I). The present invention also N relates to a method for improving the plant health of at least one plant variety, which method comprises treating the plant propagules 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 Il (compound II), a further fungicide III (compound lib) and an insecticide III (compound III).
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 propagules 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 phenyl ring 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.


In addition, the present invention relates to a method for improving the plant health of at least one plant variety, which method comprises treating the plant propagules with a secondary mixture comprising an amide of the formula I (compound I) and a further fungicide II (compound II) or an insecticide (compound III).


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 propagules with a ternary mixture comprising an amide of the formula I (compound I) and a further fungicide II (compound II) and as a third component either a further fungicide III (compound IIb) or an insecticide (compound III).


The present invention also relates to the use of an amide having the formula I (compound I) for improving 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, plant parts and/or their products. 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.


Surprisingly, we have found that this object is achieved by treating plant propagules with an amide of 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.


It was also found that certain mixtures with further fungicides (compound II or IIb) or insecticides (compound III) showed synergistic plant health effects in the method of the present invention. Within these mixtures, also synergistic mixtures with synergistic 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 07/104,658 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 compounds. The particular anilid compounds of formula I are not explicitly disclosed therein.


Combinations comprising a specific amide of formula I and strobilurine fungicides are disclosed in WO 07/017,416. However, this publication is silent about potential plant health effects.


Combinations of amides of formula I with several fungicides are disclosed in WO 07/017,416, PCT/EP2008/051331, PCT/EP2008/051375, WO 08/000,377, WO 07/128,756, 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 04/005242, WO 04/035589, WO 04/067515, WO 06/087343). They can be prepared in the manner described therein.


The further fungicides (compound II or IIb) or the insecticides (compound III) 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 the compounds selected from the group consisting of compounds (I), (II), (IIb) and (III) and respective mixtures comprising the compounds selected from the group consisting of compounds (I), (II), (IIb) and (III), 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 (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 (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 (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 (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 (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 in its cis-isomers and trans-isomers (common name: sedaxane).


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




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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, If and Ig.


In a another more preferred embodiment, compound (I) is selected from the group consisting of Ia, Id, Ie and Ig, most preferably compound (I) is 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 propagules 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 compound (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), trifloxystrobin (S9), enestroburin (S10), pyribencarb (S11), (E)-2-[2-(2,5-Dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester (S12) and 2-{2-[(E)-3-(2,6-Dichloro-phenyl)-1-methylprop-2-en-(E)-ylideneaminooxymethyl]-phenyl}-2-[(E)-methoxyimino]-N-methylacetamide (S13);
    • (ii) 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), triazoxide (A15), tetraconazole (A16), triadimefon (A17), triadimenol (A18), triticonazole (A19), uniconazole (A20), 1-(4-chloro-phenyl)-2-([1,2,4]triazol-1-yl)cycloheptanol (A21), azaconazole (A22), bitertanol (A23), bromuconazole (A24), cifenoconazole (A25), diniconazole (A26), diniconazole-M (A27), fenbuconazole (A28), hexaconazole (A29), imibenconazole (A30), myclobutanil (A31), oxpoconazole (A32), paclobutrazole (A33), penconazole (A34), simeconazole (A35), imazalil (A36), pefurazoate (A37), triflumizol (A38), etridiazole (A39), hymexazole (A40) and 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-yn-yloxy-acetamide (A41);
    • (iii) various, selected from metalaxyl (V1), metalaxyl-M (mefenoxam) (V2), silthiofam (V3), pyrimethanil (V4), dimethomorph (V5), iprodione (V6), fludioxonil (V7), thiram (V8), thiophanate-methyl (V9), carbendazim (V10), fosetyl-aluminium (V11), phosphorous acid and its salts (V12), metiram (V13), mancozeb (V14), famoxadone (V15) and fenamidone (V16);
  • (3) and optionally as a third component a further fungicide III (compound IIb), wherein compound (IIb) is selected from the group consisting of
    • (ii) 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), triazoxide (A15), tetraconazole (A16), triadimefon (A17), triadimenol (A18), triticonazole (A19), uniconazole (A20), 1-(4-chloro-phenyl)-2-([1,2,4]triazol-1-yl)-cycloheptanol (A21), azaconazole (A22), bitertanol (A23), bromuconazole (A24), cifenoconazole (A25), diniconazole (A26), diniconazole-M (A27), fenbuconazole (A28), hexaconazole (A29), imibenconazole (A30), myclobutanil (A31), oxpoconazole (A32), paclobutrazole (A33), penconazole (A34), simeconazole (A35), imazalil (A36), pefurazoate (A37), triflumizol (A38), etridiazole (A39), hymexazole (A40) and 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-yn-yloxy-acetamide (A41);
    • (iii) various, selected from metalaxyl (V1), metalaxyl-M (mefenoxam) (V2), silthiofam (V3), pyrimethanil (V4), dimethomorph (V5), iprodione (V6), fludioxonil (V7), thiram (V8), thiophanate-methyl (V9), carbendazim (V10), fosetyl-aluminium (V11), phosphorous acid and its salts (V12), metiram (V13), mancozeb (V14), famoxadone (V15) and fenamidone (V16);
  • (4) or optionally as a third component an insecticide (compound III), wherein compound (III) is selected from the group consisting of chloranthraniliprole (Ch), fipronil (Fip) and ethiprole (Ethi).


    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 compounds (II), (IIb) and (III), 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 selected from the group consisting of compounds (II), (IIb) and (III), or the successive application of the compound (I) and at least one compound selected from the group consisting of compounds (II), (IIb) and (III), provides enhanced plant health effects compared to the plant health effects that are possible with the individual compounds.


Preferably, compound (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), trifloxystrobin (S9) and enestroburin (S10);
    • (ii) 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), triazoxide (A15), triadimenol (A18), triticonazole (A19), myclobutanil (A31), imazalil (A36) and hymexazole (A40);
    • (iii) various selected from metalaxyl (V1), metalaxyl-M (mefenoxam) (V2), silthiofam (V3), pyrimethanil (V4), dimethomorph (V5), iprodione (V6), fludioxonil (V7), thiram (V8), thiophanate-methyl (V9), carbendazim (V10), fosetyl-aluminium (V11), phosphorous acid and its salts (V12), metiram (V13), mancozeb (V14), famoxadone (V15) and fenamidone (V16).


In another embodiment, compound (II) is preferably selected from the group consisting of

    • (i) strobilurines selected from azoxystrobin (S1), fluoxastrobin (S3), orysastrobin (S6), picoxystrobin (S7), pyraclostrobin (S8), trifloxystrobin (S9) and enestroburin (S10);
    • (ii) azoles, selected fromdifenoconazole (A2), epoxiconazole (A3), fluquinconazole (A5), flutriafol (A6), ipconazole (A7), metconazole (A8), prothioconazole (A10), tebuconazole (A11), prochloraz (A13), ethaboxam (A14), triadimenol (A18), triticonazole (A19), myclobutanil (A31), imazalil (A36) and hymexazole (A40);
    • (iii) various, selected from metalaxyl (V1), metalaxyl-M (mefenoxam) (V2), silthiofam (V3), pyrimethanil (V4), dimethomorph (V5), iprodione (V6), fludioxonil (V7), thiram (V8), thiophanate-methyl (V9), carbendazim (V10), fosetyl-aluminium (V11), phosphorous acid and its salts (V12), metiram (V13) and mancozeb (V14).


More preferably, compound (II) is selected from the group consisting of azoxystrobin (S1), orysastrobin (S6), pyraclostrobin (S8), trifloxystrobin (S9), difenoconazole (A2), epoxiconazole (A3), fluquinconazole (A5), flutriafol (A6), metconazole (A8), prothioconazole (A10), tebuconazole (A11), prochloraz (A13), triticonazole (A19), metalaxyl (V1), metalaxyl-M (mefenoxam) (V2), silthiofam (V3), pyrimethanil (V4), dimethomorph (V5), fludioxonil (V7), thiram (V8), thiophanate-methyl (V9), fosetyl-aluminium (V11) and phosphorous acid and its salts (V12).


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


In the terms of the present invention “mixture” is not restricted to a physical mixture comprising compound (I) and at least one compound selected form the group consisting of compounds (II), (IIb) and (III) but refers to any preparation form of compound (I) and at least one compound selected from the group consisting of compounds (II), (IIb) and (III), 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 form the group consisting of compounds (II), (IIb) and (III) (=one of the specific fungicides II or one of the specific fungicides IIb or one of the insecticides III 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 compounds (IIb) and (III).


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


In another embodiment of the invention, the amide compound of the formula I (compound I) and at least one further compound selected from the group consisting of compounds (II), (IIb) and (III) are applied simultaneously, either as a mixture or separately, or subsequently to the plant propagules.


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). This applies also in case ternary mixtures are used according to the invention.


In another embodiment, these mixtures comprise

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


    in synergistically plant health effective amounts.


The preferred insecticides (compound III) are fipronil (Fip) or chloranthraniliprole (Ch).


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, Id, Ie or Ig as compound (I). Most preferably, these mixtures comprise either Ia, Id or Ie. 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 listed in table 1 comprising one compound (I) and one compound (II) or one compound (III) are a preferred embodiment of the present invention.













TABLE 1







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









M-1
Ia
orysastrobin



M-2
Ia
pyraclostrobin



M-3
Ia
trifloxystrobin



M-4
Ia
azoxystrobin



M-5
Ia
difenoconazole



M-6
Ia
epoxiconazole



M-7
Ia
fluquinconazole



M-8
Ia
flutriafol



M-9
Ia
metconazole



M-10
Ia
prothioconazole



M-11
Ia
tebuconazole



M-12
Ia
triticonazole



M-13
Ia
prochloraz



M-14
Ia
metalaxyl



M-15
Ia
mefenoxam



M-16
Ia
silthiofam



M-17
Ia
pyrimethanil



M-18
Ia
dimethomorph



M-19
Ia
fludioxonil



M-20
Ia
thiram



M-21
Ia
thiophanate-methyl



M-22
Id
orysastrobin



M-23
Id
pyraclostrobin



M-24
Id
trifloxystrobin



M-25
Id
azoxystrobin



M-26
Id
difenoconazole



M-27
Id
epoxiconazole



M-28
Id
fluquinconazole



M-29
Id
flutriafol



M-30
Id
metconazole



M-31
Id
prothioconazole



M-32
Id
tebuconazole



M-33
Id
triticonazole



M-34
Id
prochloraz



M-35
Id
metalaxyl



M-36
Id
mefenoxam



M-37
Id
silthiofam



M-38
Id
pyrimethanil



M-39
Id
dimethomorph



M-40
Id
fludioxonil



M-41
Id
thiram



M-42
Id
thiophanate-methyl



M-43
Ie
orysastrobin



M-44
Ie
pyraclostrobin



M-45
Ie
trifloxystrobin



M-46
Ie
azoxystrobin



M-47
Ie
difenoconazole



M-48
Ie
epoxiconazole



M-49
Ie
fluquinconazole



M-50
Ie
flutriafol



M-51
Ie
metconazole



M-52
Ie
prothioconazole



M-53
Ie
tebuconazole



M-54
Ie
triticonazole



M-55
Ie
prochloraz



M-56
Ie
metalaxyl



M-57
Ie
mefenoxam



M-58
Ie
silthiofam



M-59
Ie
pyrimethanil



M-60
Ie
dimethomorph



M-61
Ie
fludioxonil



M-62
Ie
thiram



M-63
Ie
thiophanate-methyl



M-64
Ig
orysastrobin



M-65
Ig
pyraclostrobin



M-66
Ig
trifloxystrobin



M-67
Ig
azoxystrobin



M-68
Ig
difenoconazole



M-69
Ig
epoxiconazole



M-70
Ig
fluquinconazole



M-71
Ig
flutriafol



M-72
Ig
metconazole



M-73
Ig
prothioconazole



M-74
Ig
tebuconazole



M-75
Ig
triticonazole



M-76
Ig
prochloraz



M-77
Ig
metalaxyl



M-78
Ig
mefenoxam



M-79
Ig
silthiofam



M-80
Ig
pyrimethanil



M-81
Ig
dimethomorph



M-82
Ig
fludioxonil



M-83
Ig
thiram



M-84
Ig
thiophanate-methyl



M-85
Ia
fipronil



M-86
Ia
chloranthraniliprole



M-87
Id
fipronil



M-88
Id
chloranthraniliprole



M-89
Ie
fipronil



M-90
Ie
chloranthraniliprole



M-91
Ig
fipronil



M-92
Ig
chloranthraniliprole



M-93
Ia
fosetyl-aluminium



M-94
Id
fosetyl-aluminium



M-95
Ie
fosetyl-aluminium



M-96
Ig
fosetyl-aluminium



M-97
Ia
phosphorous acid and its





salts



M-98
Id
phosphorous acid and its





salts



M-99
Ie
phosphorous acid and its





salts



M-100
Ig
phosphorous acid and its





salts



M-101
Ic
orysastrobin



M-102
Ic
pyraclostrobin



M-103
Ic
trifloxystrobin



M-104
Ic
azoxystrobin



M-105
Ic
difenoconazole



M-106
Ic
epoxiconazole



M-107
Ic
fluquinconazole



M-108
Ic
flutriafol



M-109
Ic
metconazole



M-110
Ic
prothioconazole



M-111
Ic
tebuconazole



M-112
Ic
triticonazole



M-113
Ic
prochloraz



M-114
Ic
metalaxyl



M-115
Ic
mefenoxam



M-116
Ic
silthiofam



M-117
Ic
pyrimethanil



M-118
Ic
dimethomorph



M-119
Ic
fludioxonil



M-120
Ic
thiram



M-121
Ic
thiophanate-methyl



M-122
Ic
fipronil



M-123
Ic
chloranthraniliprole



M-124
Ic
fosetyl-aluminium



M-125
Ic
phosphorous acid and its





salts



M-126
If
orysastrobin



M-127
If
pyraclostrobin



M-128
If
trifloxystrobin



M-129
If
azoxystrobin



M-130
If
difenoconazole



M-131
If
epoxiconazole



M-132
If
fluquinconazole



M-133
If
flutriafol



M-134
If
metconazole



M-135
If
prothioconazole



M-136
If
tebuconazole



M-137
If
triticonazole



M-138
If
prochloraz



M-139
If
metalaxyl



M-140
If
mefenoxam



M-141
If
silthiofam



M-142
If
pyrimethanil



M-143
If
dimethomorph



M-144
If
fludioxonil



M-145
If
thiram



M-146
If
thiophanate-methyl



M-147
If
fipronil



M-148
If
chloranthraniliprole



M-149
If
fosetyl-aluminium



M-150
If
phosphorous acid and its





salts










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-11, M-12, M-13, M-14, M-15, M-16, M-17, M-18, M-19, M-20, M-21, M-22, M-23, M-24, M-25, M-43, M-44, M-45, M-46, M-64, M-65, M-66, M-67, M-85, M-86, M-87, M-88, M-89, M-90, M-91, M-92, M-93 and M-97.


Within this subset, the following mixtures are preferred: M-1, M-2, M-3, M-4, M-22, M-23, M-24, M-25, M-43, M-44, M-45, M-46, M-64, M-65, M-66, M-67, M-85, M-86, M-87, M-88, M-89, M-90, M-91 and M-92.


The following mixtures are more preferred: M-1, M-2, M-3, M-4, M-22, M-23, M-24, M-25, M-43, M-44, M-45, M-46, M-64, M-65, M-66 and M-67.


The following mixtures are most preferred: M-1, M-22, M-43 and M-64. Utmost preference is given to mixture Ml.


Within the mixtures of table 1, the following mixtures are also especially preferred: M-101, M-102, M-103, M-104, M-112, M-122, M-123, M-126, M-127, M-128, M-129, M-137, M-147 and M-148.


Within this subset, the following mixtures are preferred: M-101, M-102, M-103, M-104, M-126, M-127, M-128 and M-129.


Within this subset, the following mixtures are more preferred: M-101, M-102, M-126 and M-127.


With respect to their intended use within the methods of the present invention, the following ternary mixtures listed in table 2, comprising one compound (I) and one compound (II) and as a third component either one compound (IIb) or one compound (III) are a preferred embodiment of the present invention.


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














TABLE 2










(IIb)






or



No.
(I)
(II)
(III)









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
S1
A19



N-17
Ia
S2
A1



N-18
Ia
S2
A2



N-19
Ia
S2
A3



N-20
Ia
S2
A4



N-21
Ia
S2
A5



N-22
Ia
S2
A6



N-23
Ia
S2
A7



N-24
Ia
S2
A8



N-25
Ia
S2
A9



N-26
Ia
S2
A10



N-27
Ia
S2
A11



N-28
Ia
S2
A12



N-29
Ia
S2
A13



N-30
Ia
S2
A14



N-31
Ia
S2
A15



N-32
Ia
S2
A19



N-33
Ia
S3
A1



N-34
Ia
S3
A2



N-35
Ia
S3
A3



N-36
Ia
S3
A4



N-37
Ia
S3
A5



N-38
Ia
S3
A6



N-39
Ia
S3
A7



N-40
Ia
S3
A8



N-41
Ia
S3
A9



N-42
Ia
S3
A10



N-43
Ia
S3
A11



N-44
Ia
S3
A12



N-45
Ia
S3
A13



N-46
Ia
S3
A14



N-47
Ia
S3
A15



N-48
Ia
S3
A19



N-49
Ia
S4
A1



N-50
Ia
S4
A2



N-51
Ia
S4
A3



N-52
Ia
S4
A4



N-53
Ia
S4
A5



N-54
Ia
S4
A6



N-55
Ia
S4
A7



N-56
Ia
S4
A8



N-57
Ia
S4
A9



N-58
Ia
S4
A10



N-59
Ia
S4
A11



N-60
Ia
S4
A12



N-61
Ia
S4
A13



N-62
Ia
S4
A14



N-63
Ia
S4
A15



N-64
Ia
S4
A19



N-65
Ia
S5
A1



N-66
Ia
S5
A2



N-67
Ia
S5
A3



N-68
Ia
S5
A4



N-69
Ia
S5
A5



N-70
Ia
S5
A6



N-71
Ia
S5
A7



N-72
Ia
S5
A8



N-73
Ia
S5
A9



N-74
Ia
S5
A10



N-75
Ia
S5
A11



N-76
Ia
S5
A12



N-77
Ia
S5
A13



N-78
Ia
S5
A14



N-79
Ia
S5
A15



N-80
Ia
S5
A19



N-81
Ia
S6
A1



N-82
Ia
S6
A2



N-83
Ia
S6
A3



N-84
Ia
S6
A4



N-85
Ia
S6
A5



N-86
Ia
S6
A6



N-87
Ia
S6
A7



N-88
Ia
S6
A8



N-89
Ia
S6
A9



N-90
Ia
S6
A10



N-91
Ia
S6
A11



N-92
Ia
S6
A12



N-93
Ia
S6
A13



N-94
Ia
S6
A14



N-95
Ia
S6
A15



N-96
Ia
S6
A19



N-97
Ia
S7
A1



N-98
Ia
S7
A2



N-99
Ia
S7
A3



N-100
Ia
S7
A4



N-101
Ia
S7
A5



N-102
Ia
S7
A6



N-103
Ia
S7
A7



N-104
Ia
S7
A8



N-105
Ia
S7
A9



N-106
Ia
S7
A10



N-107
Ia
S7
A11



N-108
Ia
S7
A12



N-109
Ia
S7
A13



N-110
Ia
S7
A14



N-111
Ia
S7
A15



N-112
Ia
S7
A19



N-113
Ia
S8
A1



N-114
Ia
S8
A2



N-115
Ia
S8
A3



N-116
Ia
S8
A4



N-117
Ia
S8
A5



N-118
Ia
S8
A6



N-119
Ia
S8
A7



N-120
Ia
S8
A8



N-121
Ia
S8
A9



N-122
Ia
S8
A10



N-123
Ia
S8
A11



N-124
Ia
S8
A12



N-125
Ia
S8
A13



N-126
Ia
S8
A14



N-127
Ia
S8
A15



N-128
Ia
S8
A19



N-129
Ia
S9
A1



N-130
Ia
S9
A2



N-131
Ia
S9
A3



N-132
Ia
S9
A4



N-133
Ia
S9
A5



N-134
Ia
S9
A6



N-135
Ia
S9
A7



N-136
Ia
S9
A8



N-137
Ia
S9
A9



N-138
Ia
S9
A10



N-139
Ia
S9
A11



N-140
Ia
S9
A12



N-141
Ia
S9
A13



N-142
Ia
S9
A14



N-143
Ia
S9
A15



N-144
Ia
S9
A19



N-145
Id
S1
A1



N-146
Id
S1
A2



N-147
Id
S1
A3



N-148
Id
S1
A4



N-149
Id
S1
A5



N-150
Id
S1
A6



N-151
Id
S1
A7



N-152
Id
S1
A8



N-153
Id
S1
A9



N-154
Id
S1
A10



N-155
Id
S1
A11



N-156
Id
S1
A12



N-157
Id
S1
A13



N-158
Id
S1
A14



N-159
Id
S1
A15



N-160
Id
S1
A19



N-161
Id
S2
A1



N-162
Id
S2
A2



N-163
Id
S2
A3



N-164
Id
S2
A4



N-165
Id
S2
A5



N-166
Id
S2
A6



N-167
Id
S2
A7



N-168
Id
S2
A8



N-169
Id
S2
A9



N-170
Id
S2
A10



N-171
Id
S2
A11



N-172
Id
S2
A12



N-173
Id
S2
A13



N-174
Id
S2
A14



N-175
Id
S2
A15



N-176
Id
S2
A19



N-177
Id
S3
A1



N-178
Id
S3
A2



N-179
Id
S3
A3



N-180
Id
S3
A4



N-181
Id
S3
A5



N-182
Id
S3
A6



N-183
Id
S3
A7



N-184
Id
S3
A8



N-185
Id
S3
A9



N-186
Id
S3
A10



N-187
Id
S3
A11



N-188
Id
S3
A12



N-189
Id
S3
A13



N-190
Id
S3
A14



N-191
Id
S3
A15



N-192
Id
S3
A19



N-193
Id
S4
A1



N-194
Id
S4
A2



N-195
Id
S4
A3



N-196
Id
S4
A4



N-197
Id
S4
A5



N-198
Id
S4
A6



N-199
Id
S4
A7



N-200
Id
S4
A8



N-201
Id
S4
A9



N-202
Id
S4
A10



N-203
Id
S4
A11



N-204
Id
S4
A12



N-205
Id
S4
A13



N-206
Id
S4
A14



N-207
Id
S4
A15



N-208
Id
S4
A19



N-209
Id
S5
A1



N-210
Id
S5
A2



N-211
Id
S5
A3



N-212
Id
S5
A4



N-213
Id
S5
A5



N-214
Id
S5
A6



N-215
Id
S5
A7



N-216
Id
S5
A8



N-217
Id
S5
A9



N-218
Id
S5
A10



N-219
Id
S5
A11



N-220
Id
S5
A12



N-221
Id
S5
A13



N-222
Id
S5
A14



N-223
Id
S5
A15



N-224
Id
S5
A19



N-225
Id
S6
A1



N-226
Id
S6
A2



N-227
Id
S6
A3



N-228
Id
S6
A4



N-229
Id
S6
A5



N-230
Id
S6
A6



N-231
Id
S6
A7



N-232
Id
S6
A8



N-233
Id
S6
A9



N-234
Id
S6
A10



N-235
Id
S6
A11



N-236
Id
S6
A12



N-237
Id
S6
A13



N-238
Id
S6
A14



N-239
Id
S6
A15



N-240
Id
S6
A19



N-241
Id
S7
A1



N-242
Id
S7
A2



N-243
Id
S7
A3



N-244
Id
S7
A4



N-245
Id
S7
A5



N-246
Id
S7
A6



N-247
Id
S7
A7



N-248
Id
S7
A8



N-249
Id
S7
A9



N-250
Id
S7
A10



N-251
Id
S7
A11



N-252
Id
S7
A12



N-253
Id
S7
A13



N-254
Id
S7
A14



N-255
Id
S7
A15



N-256
Id
S7
A19



N-257
Id
S8
A1



N-258
Id
S8
A2



N-259
Id
S8
A3



N-260
Id
S8
A4



N-261
Id
S8
A5



N-262
Id
S8
A6



N-263
Id
S8
A7



N-264
Id
S8
A8



N-265
Id
S8
A9



N-266
Id
S8
A10



N-267
Id
S8
A11



N-268
Id
S8
A12



N-269
Id
S8
A13



N-270
Id
S8
A14



N-271
Id
S8
A15



N-272
Id
S8
A19



N-273
Id
S9
A1



N-274
Id
S9
A2



N-275
Id
S9
A3



N-276
Id
S9
A4



N-277
Id
S9
A5



N-278
Id
S9
A6



N-279
Id
S9
A7



N-280
Id
S9
A8



N-281
Id
S9
A9



N-282
Id
S9
A10



N-283
Id
S9
A11



N-284
Id
S9
A12



N-285
Id
S9
A13



N-286
Id
S9
A14



N-287
Id
S9
A15



N-288
Id
S9
A19



N-289
Ie
S1
A1



N-290
Ie
S1
A2



N-291
Ie
S1
A3



N-292
Ie
S1
A4



N-293
Ie
S1
A5



N-294
Ie
S1
A6



N-295
Ie
S1
A7



N-296
Ie
S1
A8



N-297
Ie
S1
A9



N-298
Ie
S1
A10



N-299
Ie
S1
A11



N-300
Ie
S1
A12



N-301
Ie
S1
A13



N-302
Ie
S1
A14



N-303
Ie
S1
A15



N-304
Ie
S1
A19



N-305
Ie
S2
A1



N-306
Ie
S2
A2



N-307
Ie
S2
A3



N-308
Ie
S2
A4



N-309
Ie
S2
A5



N-310
Ie
S2
A6



N-311
Ie
S2
A7



N-312
Ie
S2
A8



N-313
Ie
S2
A9



N-314
Ie
S2
A10



N-315
Ie
S2
A11



N-316
Ie
S2
A12



N-317
Ie
S2
A13



N-318
Ie
S2
A14



N-319
Ie
S2
A15



N-320
Ie
S2
A19



N-321
Ie
S3
A1



N-322
Ie
S3
A2



N-323
Ie
S3
A3



N-324
Ie
S3
A4



N-325
Ie
S3
A5



N-326
Ie
S3
A6



N-327
Ie
S3
A7



N-328
Ie
S3
A8



N-329
Ie
S3
A9



N-330
Ie
S3
A10



N-331
Ie
S3
A11



N-332
Ie
S3
A12



N-333
Ie
S3
A13



N-334
Ie
S3
A14



N-335
Ie
S3
A15



N-336
Ie
S3
A19



N-337
Ie
S4
A1



N-338
Ie
S4
A2



N-339
Ie
S4
A3



N-340
Ie
S4
A4



N-341
Ie
S4
A5



N-342
Ie
S4
A6



N-343
Ie
S4
A7



N-344
Ie
S4
A8



N-345
Ie
S4
A9



N-346
Ie
S4
A10



N-347
Ie
S4
A11



N-348
Ie
S4
A12



N-349
Ie
S4
A13



N-350
Ie
S4
A14



N-351
Ie
S4
A15



N-352
Ie
S4
A19



N-353
Ie
S5
A1



N-354
Ie
S5
A2



N-355
Ie
S5
A3



N-356
Ie
S5
A4



N-357
Ie
S5
A5



N-358
Ie
S5
A6



N-359
Ie
S5
A7



N-360
Ie
S5
A8



N-361
Ie
S5
A9



N-362
Ie
S5
A10



N-363
Ie
S5
A11



N-364
Ie
S5
A12



N-365
Ie
S5
A13



N-366
Ie
S5
A14



N-367
Ie
S5
A15



N-368
Ie
S5
A19



N-369
Ie
S6
A1



N-370
Ie
S6
A2



N-371
Ie
S6
A3



N-372
Ie
S6
A4



N-373
Ie
S6
A5



N-374
Ie
S6
A6



N-375
Ie
S6
A7



N-376
Ie
S6
A8



N-377
Ie
S6
A9



N-378
Ie
S6
A10



N-379
Ie
S6
A11



N-380
Ie
S6
A12



N-381
Ie
S6
A13



N-382
Ie
S6
A14



N-383
Ie
S6
A15



N-384
Ie
S6
A19



N-385
Ie
S7
A1



N-386
Ie
S7
A2



N-387
Ie
S7
A3



N-388
Ie
S7
A4



N-389
Ie
S7
A5



N-390
Ie
S7
A6



N-391
Ie
S7
A7



N-392
Ie
S7
A8



N-393
Ie
S7
A9



N-394
Ie
S7
A10



N-395
Ie
S7
A11



N-396
Ie
S7
A12



N-397
Ie
S7
A13



N-398
Ie
S7
A14



N-399
Ie
S7
A15



N-400
Ie
S7
A19



N-401
Ie
S8
A1



N-402
Ie
S8
A2



N-403
Ie
S8
A3



N-404
Ie
S8
A4



N-405
Ie
S8
A5



N-406
Ie
S8
A6



N-407
Ie
S8
A7



N-408
Ie
S8
A8



N-409
Ie
S8
A9



N-410
Ie
S8
A10



N-411
Ie
S8
A11



N-412
Ie
S8
A12



N-413
Ie
S8
A13



N-414
Ie
S8
A14



N-415
Ie
S8
A15



N-416
Ie
S8
A19



N-417
Ie
S9
A1



N-418
Ie
S9
A2



N-419
Ie
S9
A3



N-420
Ie
S9
A4



N-421
Ie
S9
A5



N-422
Ie
S9
A6



N-423
Ie
S9
A7



N-424
Ie
S9
A8



N-425
Ie
S9
A9



N-426
Ie
S9
A10



N-427
Ie
S9
A11



N-428
Ie
S9
A12



N-429
Ie
S9
A13



N-430
Ie
S9
A14



N-431
Ie
S9
A15



N-432
Ie
S9
A19



N-433
Ig
S1
A1



N-434
Ig
S1
A2



N-435
Ig
S1
A3



N-436
Ig
S1
A4



N-437
Ig
S1
A5



N-438
Ig
S1
A6



N-439
Ig
S1
A7



N-440
Ig
S1
A8



N-441
Ig
S1
A9



N-442
Ig
S1
A10



N-443
Ig
S1
A11



N-444
Ig
S1
A12



N-445
Ig
S1
A13



N-446
Ig
S1
A14



N-447
Ig
S1
A15



N-448
Ig
S1
A19



N-449
Ig
S2
A1



N-450
Ig
S2
A2



N-451
Ig
S2
A3



N-452
Ig
S2
A4



N-453
Ig
S2
A5



N-454
Ig
S2
A6



N-455
Ig
S2
A7



N-456
Ig
S2
A8



N-457
Ig
S2
A9



N-458
Ig
S2
A10



N-459
Ig
S2
A11



N-460
Ig
S2
A12



N-461
Ig
S2
A13



N-462
Ig
S2
A14



N-463
Ig
S2
A15



N-464
Ig
S2
A19



N-465
Ig
S3
A1



N-466
Ig
S3
A2



N-467
Ig
S3
A3



N-468
Ig
S3
A4



N-469
Ig
S3
A5



N-470
Ig
S3
A6



N-471
Ig
S3
A7



N-472
Ig
S3
A8



N-473
Ig
S3
A9



N-474
Ig
S3
A10



N-475
Ig
S3
A11



N-476
Ig
S3
A12



N-477
Ig
S3
A13



N-478
Ig
S3
A14



N-479
Ig
S3
A15



N-480
Ig
S3
A19



N-481
Ig
S4
A1



N-482
Ig
S4
A2



N-483
Ig
S4
A3



N-484
Ig
S4
A4



N-485
Ig
S4
A5



N-486
Ig
S4
A6



N-487
Ig
S4
A7



N-488
Ig
S4
A8



N-489
Ig
S4
A9



N-490
Ig
S4
A10



N-491
Ig
S4
A11



N-492
Ig
S4
A12



N-493
Ig
S4
A13



N-494
Ig
S4
A14



N-495
Ig
S4
A15



N-496
Ig
S4
A19



N-497
Ig
S5
A1



N-498
Ig
S5
A2



N-499
Ig
S5
A3



N-500
Ig
S5
A4



N-501
Ig
S5
A5



N-502
Ig
S5
A6



N-503
Ig
S5
A7



N-504
Ig
S5
A8



N-505
Ig
S5
A9



N-506
Ig
S5
A10



N-507
Ig
S5
A11



N-508
Ig
S5
A12



N-509
Ig
S5
A13



N-510
Ig
S5
A14



N-511
Ig
S5
A15



N-512
Ig
S5
A19



N-513
Ig
S6
A1



N-514
Ig
S6
A2



N-515
Ig
S6
A3



N-516
Ig
S6
A4



N-517
Ig
S6
A5



N-518
Ig
S6
A6



N-519
Ig
S6
A7



N-520
Ig
S6
A8



N-521
Ig
S6
A9



N-522
Ig
S6
A10



N-523
Ig
S6
A11



N-524
Ig
S6
A12



N-525
Ig
S6
A13



N-526
Ig
S6
A14



N-527
Ig
S6
A15



N-528
Ig
S6
A19



N-529
Ig
S7
A1



N-530
Ig
S7
A2



N-531
Ig
S7
A3



N-532
Ig
S7
A4



N-533
Ig
S7
A5



N-534
Ig
S7
A6



N-535
Ig
S7
A7



N-536
Ig
S7
A8



N-537
Ig
S7
A9



N-538
Ig
S7
A10



N-539
Ig
S7
A11



N-540
Ig
S7
A12



N-541
Ig
S7
A13



N-542
Ig
S7
A14



N-543
Ig
S7
A15



N-544
Ig
S7
A19



N-545
Ig
S8
A1



N-546
Ig
S8
A2



N-547
Ig
S8
A3



N-548
Ig
S8
A4



N-549
Ig
S8
A5



N-550
Ig
S8
A6



N-551
Ig
S8
A7



N-552
Ig
S8
A8



N-553
Ig
S8
A9



N-554
Ig
S8
A10



N-555
Ig
S8
A11



N-556
Ig
S8
A12



N-557
Ig
S8
A13



N-558
Ig
S8
A14



N-559
Ig
S8
A15



N-560
Ig
S8
A19



N-561
Ig
S9
A1



N-562
Ig
S9
A2



N-563
Ig
S9
A3



N-564
Ig
S9
A4



N-565
Ig
S9
A5



N-566
Ig
S9
A6



N-567
Ig
S9
A7



N-568
Ig
S9
A8



N-569
Ig
S9
A9



N-570
Ig
S9
A10



N-571
Ig
S9
A11



N-572
Ig
S9
A12



N-573
Ig
S9
A13



N-574
Ig
S9
A14



N-575
Ig
S9
A15



N-576
Ig
S9
A19



N-577
Ia
S1
V1



N-578
Ia
S1
V2



N-579
Ia
S1
V3



N-580
Ia
S1
V4



N-581
Ia
S1
V5



N-582
Ia
S1
V6



N-583
Ia
S1
V7



N-584
Ia
S1
V8



N-585
Ia
S1
V9



N-586
Ia
S1
V10



N-587
Ia
S1
V11



N-588
Ia
S1
V12



N-589
Ia
S1
V13



N-590
Ia
S1
V14



N-591
Ia
S1
V15



N-592
Ia
S1
V16



N-593
Ia
S2
V1



N-594
Ia
S2
V2



N-595
Ia
S2
V3



N-596
Ia
S2
V4



N-597
Ia
S2
V5



N-598
Ia
S2
V6



N-599
Ia
S2
V7



N-600
Ia
S2
V8



N-601
Ia
S2
V9



N-602
Ia
S2
V10



N-603
Ia
S2
V11



N-604
Ia
S2
V12



N-605
Ia
S2
V13



N-606
Ia
S2
V14



N-607
Ia
S2
V15



N-608
Ia
S2
V16



N-609
Ia
S3
V1



N-610
Ia
S3
V2



N-611
Ia
S3
V3



N-612
Ia
S3
V4



N-613
Ia
S3
V5



N-614
Ia
S3
V6



N-615
Ia
S3
V7



N-616
Ia
S3
V8



N-617
Ia
S3
V9



N-618
Ia
S3
V10



N-619
Ia
S3
V11



N-620
Ia
S3
V12



N-621
Ia
S3
V13



N-622
Ia
S3
V14



N-623
Ia
S3
V15



N-624
Ia
S3
V16



N-625
Ia
S4
V1



N-626
Ia
S4
V2



N-627
Ia
S4
V3



N-628
Ia
S4
V4



N-629
Ia
S4
V5



N-630
Ia
S4
V6



N-631
Ia
S4
V7



N-632
Ia
S4
V8



N-633
Ia
S4
V9



N-634
Ia
S4
V10



N-635
Ia
S4
V11



N-636
Ia
S4
V12



N-637
Ia
S4
V13



N-638
Ia
S4
V14



N-639
Ia
S4
V15



N-640
Ia
S4
V16



N-641
Ia
S5
V1



N-642
Ia
S5
V2



N-643
Ia
S5
V3



N-644
Ia
S5
V4



N-645
Ia
S5
V5



N-646
Ia
S5
V6



N-647
Ia
S5
V7



N-648
Ia
S5
V8



N-649
Ia
S5
V9



N-650
Ia
S5
V10



N-651
Ia
S5
V11



N-652
Ia
S5
V12



N-653
Ia
S5
V13



N-654
Ia
S5
V14



N-655
Ia
S5
V15



N-656
Ia
S5
V16



N-657
Ia
S6
V1



N-658
Ia
S6
V2



N-659
Ia
S6
V3



N-660
Ia
S6
V4



N-661
Ia
S6
V5



N-662
Ia
S6
V6



N-663
Ia
S6
V7



N-664
Ia
S6
V8



N-665
Ia
S6
V9



N-666
Ia
S6
V10



N-667
Ia
S6
V11



N-668
Ia
S6
V12



N-669
Ia
S6
V13



N-670
Ia
S6
V14



N-671
Ia
S6
V15



N-672
Ia
S6
V16



N-673
Ia
S7
V1



N-674
Ia
S7
V2



N-675
Ia
S7
V3



N-676
Ia
S7
V4



N-677
Ia
S7
V5



N-678
Ia
S7
V6



N-679
Ia
S7
V7



N-680
Ia
S7
V8



N-681
Ia
S7
V9



N-682
Ia
S7
V10



N-683
Ia
S7
V11



N-684
Ia
S7
V12



N-685
Ia
S7
V13



N-686
Ia
S7
V14



N-687
Ia
S7
V15



N-688
Ia
S7
V16



N-689
Ia
S8
V1



N-690
Ia
S8
V2



N-691
Ia
S8
V3



N-692
Ia
S8
V4



N-693
Ia
S8
V5



N-694
Ia
S8
V6



N-695
Ia
S8
V7



N-696
Ia
S8
V8



N-697
Ia
S8
V9



N-698
Ia
S8
V10



N-699
Ia
S8
V11



N-700
Ia
S8
V12



N-701
Ia
S8
V13



N-702
Ia
S8
V14



N-703
Ia
S8
V15



N-704
Ia
S8
V16



N-705
Ia
S9
V1



N-706
Ia
S9
V2



N-707
Ia
S9
V3



N-708
Ia
S9
V4



N-709
Ia
S9
V5



N-710
Ia
S9
V6



N-711
Ia
S9
V7



N-712
Ia
S9
V8



N-713
Ia
S9
V9



N-714
Ia
S9
V10



N-715
Ia
S9
V11



N-716
Ia
S9
V12



N-717
Ia
S9
V13



N-718
Ia
S9
V14



N-719
Ia
S9
V15



N-720
Ia
S9
V16



N-721
Id
S1
V1



N-722
Id
S1
V2



N-723
Id
S1
V3



N-724
Id
S1
V4



N-725
Id
S1
V5



N-726
Id
S1
V6



N-727
Id
S1
V7



N-728
Id
S1
V8



N-729
Id
S1
V9



N-730
Id
S1
V10



N-731
Id
S1
V11



N-732
Id
S1
V12



N-733
Id
S1
V13



N-734
Id
S1
V14



N-735
Id
S1
V15



N-736
Id
S1
V16



N-737
Id
S2
V1



N-738
Id
S2
V2



N-739
Id
S2
V3



N-740
Id
S2
V4



N-741
Id
S2
V5



N-742
Id
S2
V6



N-743
Id
S2
V7



N-744
Id
S2
V8



N-745
Id
S2
V9



N-746
Id
S2
V10



N-747
Id
S2
V11



N-748
Id
S2
V12



N-749
Id
S2
V13



N-750
Id
S2
V14



N-751
Id
S2
V15



N-752
Id
S2
V16



N-753
Id
S3
V1



N-754
Id
S3
V2



N-755
Id
S3
V3



N-756
Id
S3
V4



N-757
Id
S3
V5



N-758
Id
S3
V6



N-759
Id
S3
V7



N-760
Id
S3
V8



N-761
Id
S3
V9



N-762
Id
S3
V10



N-763
Id
S3
V11



N-764
Id
S3
V12



N-765
Id
S3
V13



N-766
Id
S3
V14



N-767
Id
S3
V15



N-768
Id
S3
V16



N-769
Id
S4
V1



N-770
Id
S4
V2



N-771
Id
S4
V3



N-772
Id
S4
V4



N-773
Id
S4
V5



N-774
Id
S4
V6



N-775
Id
S4
V7



N-776
Id
S4
V8



N-777
Id
S4
V9



N-778
Id
S4
V10



N-779
Id
S4
V11



N-780
Id
S4
V12



N-781
Id
S4
V13



N-782
Id
S4
V14



N-783
Id
S4
V15



N-784
Id
S4
V16



N-785
Id
S5
V1



N-786
Id
S5
V2



N-787
Id
S5
V3



N-788
Id
S5
V4



N-789
Id
S5
V5



N-790
Id
S5
V6



N-791
Id
S5
V7



N-792
Id
S5
V8



N-793
Id
S5
V9



N-794
Id
S5
V10



N-795
Id
S5
V11



N-796
Id
S5
V12



N-797
Id
S5
V13



N-798
Id
S5
V14



N-799
Id
S5
V15



N-800
Id
S5
V16



N-801
Id
S6
V1



N-802
Id
S6
V2



N-803
Id
S6
V3



N-804
Id
S6
V4



N-805
Id
S6
V5



N-806
Id
S6
V6



N-807
Id
S6
V7



N-808
Id
S6
V8



N-809
Id
S6
V9



N-810
Id
S6
V10



N-811
Id
S6
V11



N-812
Id
S6
V12



N-813
Id
S6
V13



N-814
Id
S6
V14



N-815
Id
S6
V15



N-816
Id
S6
V16



N-817
Id
S7
V1



N-818
Id
S7
V2



N-819
Id
S7
V3



N-820
Id
S7
V4



N-821
Id
S7
V5



N-822
Id
S7
V6



N-823
Id
S7
V7



N-824
Id
S7
V8



N-825
Id
S7
V9



N-826
Id
S7
V10



N-827
Id
S7
V11



N-828
Id
S7
V12



N-829
Id
S7
V13



N-830
Id
S7
V14



N-831
Id
S7
V15



N-832
Id
S7
V16



N-833
Id
S8
V1



N-834
Id
S8
V2



N-835
Id
S8
V3



N-836
Id
S8
V4



N-837
Id
S8
V5



N-838
Id
S8
V6



N-839
Id
S8
V7



N-840
Id
S8
V8



N-841
Id
S8
V9



N-842
Id
S8
V10



N-843
Id
S8
V11



N-844
Id
S8
V12



N-845
Id
S8
V13



N-846
Id
S8
V14



N-847
Id
S8
V15



N-848
Id
S8
V16



N-849
Id
S9
V1



N-850
Id
S9
V2



N-851
Id
S9
V3



N-852
Id
S9
V4



N-853
Id
S9
V5



N-854
Id
S9
V6



N-855
Id
S9
V7



N-856
Id
S9
V8



N-857
Id
S9
V9



N-858
Id
S9
V10



N-859
Id
S9
V11



N-860
Id
S9
V12



N-861
Id
S9
V13



N-862
Id
S9
V14



N-863
Id
S9
V15



N-864
Id
S9
V16



N-865
Ie
S1
V1



N-866
Ie
S1
V2



N-867
Ie
S1
V3



N-868
Ie
S1
V4



N-869
Ie
S1
V5



N-870
Ie
S1
V6



N-871
Ie
S1
V7



N-872
Ie
S1
V8



N-873
Ie
S1
V9



N-874
Ie
S1
V10



N-875
Ie
S1
V11



N-876
Ie
S1
V12



N-877
Ie
S1
V13



N-878
Ie
S1
V14



N-879
Ie
S1
V15



N-880
Ie
S1
V16



N-881
Ie
S2
V1



N-882
Ie
S2
V2



N-883
Ie
S2
V3



N-884
Ie
S2
V4



N-885
Ie
S2
V5



N-886
Ie
S2
V6



N-887
Ie
S2
V7



N-888
Ie
S2
V8



N-889
Ie
S2
V9



N-890
Ie
S2
V10



N-891
Ie
S2
V11



N-892
Ie
S2
V12



N-893
Ie
S2
V13



N-894
Ie
S2
V14



N-895
Ie
S2
V15



N-896
Ie
S2
V16



N-897
Ie
S3
V1



N-898
Ie
S3
V2



N-899
Ie
S3
V3



N-900
Ie
S3
V4



N-901
Ie
S3
V5



N-902
Ie
S3
V6



N-903
Ie
S3
V7



N-904
Ie
S3
V8



N-905
Ie
S3
V9



N-906
Ie
S3
V10



N-907
Ie
S3
V11



N-908
Ie
S3
V12



N-909
Ie
S3
V13



N-910
Ie
S3
V14



N-911
Ie
S3
V15



N-912
Ie
S3
V16



N-913
Ie
S4
V1



N-914
Ie
S4
V2



N-915
Ie
S4
V3



N-916
Ie
S4
V4



N-917
Ie
S4
V5



N-918
Ie
S4
V6



N-919
Ie
S4
V7



N-920
Ie
S4
V8



N-921
Ie
S4
V9



N-922
Ie
S4
V10



N-923
Ie
S4
V11



N-924
Ie
S4
V12



N-925
Ie
S4
V13



N-926
Ie
S4
V14



N-927
Ie
S4
V15



N-928
Ie
S4
V16



N-929
Ie
S5
V1



N-930
Ie
S5
V2



N-931
Ie
S5
V3



N-932
Ie
S5
V4



N-933
Ie
S5
V5



N-934
Ie
S5
V6



N-935
Ie
S5
V7



N-936
Ie
S5
V8



N-937
Ie
S5
V9



N-938
Ie
S5
V10



N-939
Ie
S5
V11



N-940
Ie
S5
V12



N-941
Ie
S5
V13



N-942
Ie
S5
V14



N-943
Ie
S5
V15



N-944
Ie
S5
V16



N-945
Ie
S6
V1



N-946
Ie
S6
V2



N-947
Ie
S6
V3



N-948
Ie
S6
V4



N-949
Ie
S6
V5



N-950
Ie
S6
V6



N-951
Ie
S6
V7



N-952
Ie
S6
V8



N-953
Ie
S6
V9



N-954
Ie
S6
V10



N-955
Ie
S6
V11



N-956
Ie
S6
V12



N-957
Ie
S6
V13



N-958
Ie
S6
V14



N-959
Ie
S6
V15



N-960
Ie
S6
V16



N-961
Ie
S7
V1



N-962
Ie
S7
V2



N-963
Ie
S7
V3



N-964
Ie
S7
V4



N-965
Ie
S7
V5



N-966
Ie
S7
V6



N-967
Ie
S7
V7



N-968
Ie
S7
V8



N-969
Ie
S7
V9



N-970
Ie
S7
V10



N-971
Ie
S7
V11



N-972
Ie
S7
V12



N-973
Ie
S7
V13



N-974
Ie
S7
V14



N-975
Ie
S7
V15



N-976
Ie
S7
V16



N-977
Ie
S8
V1



N-978
Ie
S8
V2



N-979
Ie
S8
V3



N-980
Ie
S8
V4



N-981
Ie
S8
V5



N-982
Ie
S8
V6



N-983
Ie
S8
V7



N-984
Ie
S8
V8



N-985
Ie
S8
V9



N-986
Ie
S8
V10



N-987
Ie
S8
V11



N-988
Ie
S8
V12



N-989
Ie
S8
V13



N-990
Ie
S8
V14



N-991
Ie
S8
V15



N-992
Ie
S8
V16



N-993
Ie
S9
V1



N-994
Ie
S9
V2



N-995
Ie
S9
V3



N-996
Ie
S9
V4



N-997
Ie
S9
V5



N-998
Ie
S9
V6



N-999
Ie
S9
V7



N-1000
Ie
S9
V8



N-1001
Ie
S9
V9



N-1002
Ie
S9
V10



N-1003
Ie
S9
V11



N-1004
Ie
S9
V12



N-1005
Ie
S9
V13



N-1006
Ie
S9
V14



N-1007
Ie
S9
V15



N-1008
Ie
S9
V16



N-1009
Ig
S1
V1



N-1010
Ig
S1
V2



N-1011
Ig
S1
V3



N-1012
Ig
S1
V4



N-1013
Ig
S1
V5



N-1014
Ig
S1
V6



N-1015
Ig
S1
V7



N-1016
Ig
S1
V8



N-1017
Ig
S1
V9



N-1018
Ig
S1
V10



N-1019
Ig
S1
V11



N-1020
Ig
S1
V12



N-1021
Ig
S1
V13



N-1022
Ig
S1
V14



N-1023
Ig
S1
V15



N-1024
Ig
S1
V16



N-1025
Ig
S2
V1



N-1026
Ig
S2
V2



N-1027
Ig
S2
V3



N-1028
Ig
S2
V4



N-1029
Ig
S2
V5



N-1030
Ig
S2
V6



N-1031
Ig
S2
V7



N-1032
Ig
S2
V8



N-1033
Ig
S2
V9



N-1034
Ig
S2
V10



N-1035
Ig
S2
V11



N-1036
Ig
S2
V12



N-1037
Ig
S2
V13



N-1038
Ig
S2
V14



N-1039
Ig
S2
V15



N-1040
Ig
S2
V16



N-1041
Ig
S3
V1



N-1042
Ig
S3
V2



N-1043
Ig
S3
V3



N-1044
Ig
S3
V4



N-1045
Ig
S3
V5



N-1046
Ig
S3
V6



N-1047
Ig
S3
V7



N-1048
Ig
S3
V8



N-1049
Ig
S3
V9



N-1050
Ig
S3
V10



N-1051
Ig
S3
V11



N-1052
Ig
S3
V12



N-1053
Ig
S3
V13



N-1054
Ig
S3
V14



N-1055
Ig
S3
V15



N-1056
Ig
S3
V16



N-1057
Ig
S4
V1



N-1058
Ig
S4
V2



N-1059
Ig
S4
V3



N-1060
Ig
S4
V4



N-1061
Ig
S4
V5



N-1062
Ig
S4
V6



N-1063
Ig
S4
V7



N-1064
Ig
S4
V8



N-1065
Ig
S4
V9



N-1066
Ig
S4
V10



N-1067
Ig
S4
V11



N-1068
Ig
S4
V12



N-1069
Ig
S4
V13



N-1070
Ig
S4
V14



N-1071
Ig
S4
V15



N-1072
Ig
S4
V16



N-1073
Ig
S5
V1



N-1074
Ig
S5
V2



N-1075
Ig
S5
V3



N-1076
Ig
S5
V4



N-1077
Ig
S5
V5



N-1078
Ig
S5
V6



N-1079
Ig
S5
V7



N-1080
Ig
S5
V8



N-1081
Ig
S5
V9



N-1082
Ig
S5
V10



N-1083
Ig
S5
V11



N-1084
Ig
S5
V12



N-1085
Ig
S5
V13



N-1086
Ig
S5
V14



N-1087
Ig
S5
V15



N-1088
Ig
S5
V16



N-1089
Ig
S6
V1



N-1090
Ig
S6
V2



N-1091
Ig
S6
V3



N-1092
Ig
S6
V4



N-1093
Ig
S6
V5



N-1094
Ig
S6
V6



N-1095
Ig
S6
V7



N-1096
Ig
S6
V8



N-1097
Ig
S6
V9



N-1098
Ig
S6
V10



N-1099
Ig
S6
V11



N-1100
Ig
S6
V12



N-1101
Ig
S6
V13



N-1102
Ig
S6
V14



N-1103
Ig
S6
V15



N-1104
Ig
S6
V16



N-1105
Ig
S7
V1



N-1106
Ig
S7
V2



N-1107
Ig
S7
V3



N-1108
Ig
S7
V4



N-1109
Ig
S7
V5



N-1110
Ig
S7
V6



N-1111
Ig
S7
V7



N-1112
Ig
S7
V8



N-1113
Ig
S7
V9



N-1114
Ig
S7
V10



N-1115
Ig
S7
V11



N-1116
Ig
S7
V12



N-1117
Ig
S7
V13



N-1118
Ig
S7
V14



N-1119
Ig
S7
V15



N-1120
Ig
S7
V16



N-1121
Ig
S8
V1



N-1122
Ig
S8
V2



N-1123
Ig
S8
V3



N-1124
Ig
S8
V4



N-1125
Ig
S8
V5



N-1126
Ig
S8
V6



N-1127
Ig
S8
V7



N-1128
Ig
S8
V8



N-1129
Ig
S8
V9



N-1130
Ig
S8
V10



N-1131
Ig
S8
V11



N-1132
Ig
S8
V12



N-1133
Ig
S8
V13



N-1134
Ig
S8
V14



N-1133
Ig
S8
V15



N-1136
Ig
S8
V16



N-1137
Ig
S9
V1



N-1138
Ig
S9
V2



N-1139
Ig
S9
V3



N-1140
Ig
S9
V4



N-1141
Ig
S9
V5



N-1142
Ig
S9
V6



N-1143
Ig
S9
V7



N-1144
Ig
S9
V8



N-1145
Ig
S9
V9



N-1146
Ig
S9
V10



N-1147
Ig
S9
V11



N-1148
Ig
S9
V12



N-1149
Ig
S9
V13



N-1150
Ig
S9
V14



N-1151
Ig
S9
V15



N-1152
Ig
S9
V16



N-1153
Ia
A1
V1



N-1154
Ia
A1
V2



N-1155
Ia
A1
V3



N-1156
Ia
A1
V4



N-1157
Ia
A1
V5



N-1158
Ia
A1
V6



N-1159
Ia
A1
V7



N-1160
Ia
A1
V8



N-1161
Ia
A1
V9



N-1162
Ia
A1
V10



N-1163
Ia
A1
V11



N-1164
Ia
A1
V12



N-1165
Ia
A1
V13



N-1166
Ia
A1
V14



N-1167
Ia
A1
V15



N-1168
Ia
A1
V16



N-1169
Ia
A2
V1



N-1170
Ia
A2
V2



N-1171
Ia
A2
V3



N-1172
Ia
A2
V4



N-1173
Ia
A2
V5



N-1174
Ia
A2
V6



N-1175
Ia
A2
V7



N-1176
Ia
A2
V8



N-1177
Ia
A2
V9



N-1178
Ia
A2
V10



N-1179
Ia
A2
V11



N-1180
Ia
A2
V12



N-1181
Ia
A2
V13



N-1182
Ia
A2
V14



N-1183
Ia
A2
V15



N-1184
Ia
A2
V16



N-1185
Ia
A3
V1



N-1186
Ia
A3
V2



N-1187
Ia
A3
V3



N-1188
Ia
A3
V4



N-1189
Ia
A3
V5



N-1190
Ia
A3
V6



N-1191
Ia
A3
V7



N-1192
Ia
A3
V8



N-1193
Ia
A3
V9



N-1194
Ia
A3
V10



N-1195
Ia
A3
V11



N-1196
Ia
A3
V12



N-1197
Ia
A3
V13



N-1198
Ia
A3
V14



N-1199
Ia
A3
V15



N-1200
Ia
A3
V16



N-1201
Ia
A4
V1



N-1202
Ia
A4
V2



N-1203
Ia
A4
V3



N-1204
Ia
A4
V4



N-1205
Ia
A4
V5



N-1206
Ia
A4
V6



N-1207
Ia
A4
V7



N-1208
Ia
A4
V8



N-1209
Ia
A4
V9



N-1210
Ia
A4
V10



N-1211
Ia
A4
V11



N-1212
Ia
A4
V12



N-1213
Ia
A4
V13



N-1214
Ia
A4
V14



N-1215
Ia
A4
V15



N-1216
Ia
A4
V16



N-1217
Ia
A5
V1



N-1218
Ia
A5
V2



N-1219
Ia
A5
V3



N-1220
Ia
A5
V4



N-1221
Ia
A5
V5



N-1222
Ia
A5
V6



N-1223
Ia
A5
V7



N-1224
Ia
A5
V8



N-1225
Ia
A5
V9



N-1226
Ia
A5
V10



N-1227
Ia
A5
V11



N-1228
Ia
A5
V12



N-1229
Ia
A5
V13



N-1230
Ia
A5
V14



N-1231
Ia
A5
V15



N-1232
Ia
A5
V16



N-1233
Ia
A6
V1



N-1234
Ia
A6
V2



N-1235
Ia
A6
V3



N-1236
Ia
A6
V4



N-1237
Ia
A6
V5



N-1238
Ia
A6
V6



N-1239
Ia
A6
V7



N-1240
Ia
A6
V8



N-1241
Ia
A6
V9



N-1242
Ia
A6
V10



N-1243
Ia
A6
V11



N-1244
Ia
A6
V12



N-1245
Ia
A6
V13



N-1246
Ia
A6
V14



N-1247
Ia
A6
V15



N-1248
Ia
A6
V16



N-1249
Ia
A7
V1



N-1250
Ia
A7
V2



N-1251
Ia
A7
V3



N-1252
Ia
A7
V4



N-1253
Ia
A7
V5



N-1254
Ia
A7
V6



N-1255
Ia
A7
V7



N-1256
Ia
A7
V8



N-1257
Ia
A7
V9



N-1258
Ia
A7
V10



N-1259
Ia
A7
V11



N-1260
Ia
A7
V12



N-1261
Ia
A7
V13



N-1262
Ia
A7
V14



N-1263
Ia
A7
V15



N-1264
Ia
A7
V16



N-1265
Ia
A8
V1



N-1266
Ia
A8
V2



N-1267
Ia
A8
V3



N-1268
Ia
A8
V4



N-1269
Ia
A8
V5



N-1270
Ia
A8
V6



N-1271
Ia
A8
V7



N-1272
Ia
A8
V8



N-1273
Ia
A8
V9



N-1274
Ia
A8
V10



N-1275
Ia
A8
V11



N-1276
Ia
A8
V12



N-1277
Ia
A8
V13



N-1278
Ia
A8
V14



N-1279
Ia
A8
V15



N-1280
Ia
A8
V16



N-1281
Ia
A9
V1



N-1282
Ia
A9
V2



N-1283
Ia
A9
V3



N-1284
Ia
A9
V4



N-1285
Ia
A9
V5



N-1286
Ia
A9
V6



N-1287
Ia
A9
V7



N-1288
Ia
A9
V8



N-1289
Ia
A9
V9



N-1290
Ia
A9
V10



N-1291
Ia
A9
V11



N-1292
Ia
A9
V12



N-1293
Ia
A9
V13



N-1294
Ia
A9
V14



N-1295
Ia
A9
V15



N-1296
Ia
A9
V16



N-1297
Ia
A10
V1



N-1298
Ia
A10
V2



N-1299
Ia
A10
V3



N-1300
Ia
A10
V4



N-1301
Ia
A10
V5



N-1302
Ia
A10
V6



N-1303
Ia
A10
V7



N-1304
Ia
A10
V8



N-1305
Ia
A10
V9



N-1306
Ia
A10
V10



N-1307
Ia
A10
V11



N-1308
Ia
A10
V12



N-1309
Ia
A10
V13



N-1310
Ia
A10
V14



N-1311
Ia
A10
V15



N-1312
Ia
A10
V16



N-1313
Ia
A11
V1



N-1314
Ia
A11
V2



N-1315
Ia
A11
V3



N-1316
Ia
A11
V4



N-1317
Ia
A11
V5



N-1318
Ia
A11
V6



N-1319
Ia
A11
V7



N-1320
Ia
A11
V8



N-1321
Ia
A11
V9



N-1322
Ia
A11
V10



N-1323
Ia
A11
V11



N-1324
Ia
A11
V12



N-1325
Ia
A11
V13



N-1326
Ia
A11
V14



N-1327
Ia
A11
V15



N-1328
Ia
A11
V16



N-1329
Ia
A12
V1



N-1330
Ia
A12
V2



N-1331
Ia
A12
V3



N-1332
Ia
A12
V4



N-1333
Ia
A12
V5



N-1334
Ia
A12
V6



N-1335
Ia
A12
V7



N-1336
Ia
A12
V8



N-1337
Ia
A12
V9



N-1338
Ia
A12
V10



N-1339
Ia
A12
V11



N-1340
Ia
A12
V12



N-1341
Ia
A12
V13



N-1342
Ia
A12
V14



N-1343
Ia
A12
V15



N-1344
Ia
A12
V16



N-1345
Ia
A13
V1



N-1346
Ia
A13
V2



N-1347
Ia
A13
V3



N-1348
Ia
A13
V4



N-1349
Ia
A13
V5



N-1350
Ia
A13
V6



N-1351
Ia
A13
V7



N-1352
Ia
A13
V8



N-1353
Ia
A13
V9



N-1354
Ia
A13
V10



N-1355
Ia
A13
V11



N-1356
Ia
A13
V12



N-1357
Ia
A13
V13



N-1358
Ia
A13
V14



N-1359
Ia
A13
V15



N-1360
Ia
A13
V16



N-1361
Ia
A14
V1



N-1362
Ia
A14
V2



N-1363
Ia
A14
V3



N-1364
Ia
A14
V4



N-1365
Ia
A14
V5



N-1366
Ia
A14
V6



N-1367
Ia
A14
V7



N-1368
Ia
A14
V8



N-1369
Ia
A14
V9



N-1370
Ia
A14
V10



N-1371
Ia
A14
V11



N-1372
Ia
A14
V12



N-1373
Ia
A14
V13



N-1374
Ia
A14
V14



N-1375
Ia
A14
V15



N-1376
Ia
A14
V16



N-1377
Ia
A15
V1



N-1378
Ia
A15
V2



N-1379
Ia
A15
V3



N-1380
Ia
A15
V4



N-1381
Ia
A15
V5



N-1382
Ia
A15
V6



N-1383
Ia
A15
V7



N-1384
Ia
A15
V8



N-1385
Ia
A15
V9



N-1386
Ia
A15
V10



N-1387
Ia
A15
V11



N-1388
Ia
A15
V12



N-1389
Ia
A15
V13



N-1390
Ia
A15
V14



N-1391
Ia
A15
V15



N-1392
Ia
A15
V16



N-1393
Ia
A19
V1



N-1394
Ia
A19
V2



N-1395
Ia
A19
V3



N-1396
Ia
A19
V4



N-1397
Ia
A19
V5



N-1398
Ia
A19
V6



N-1399
Ia
A19
V7



N-1400
Ia
A19
V8



N-1401
Ia
A19
V9



N-1402
Ia
A19
V10



N-1403
Ia
A19
V11



N-1404
Ia
A19
V12



N-1405
Ia
A19
V13



N-1406
Ia
A19
V14



N-1407
Ia
A19
V15



N-1408
Ia
A19
V16



N-1409
Id
A1
V1



N-1410
Id
A1
V2



N-1411
Id
A1
V3



N-1412
Id
A1
V4



N-1413
Id
A1
V5



N-1414
Id
A1
V6



N-1415
Id
A1
V7



N-1416
Id
A1
V8



N-1417
Id
A1
V9



N-1418
Id
A1
V10



N-1419
Id
A1
V11



N-1420
Id
A1
V12



N-1421
Id
A1
V13



N-1422
Id
A1
V14



N-1423
Id
A1
V15



N-1424
Id
A1
V16



N-1425
Id
A2
V1



N-1426
Id
A2
V2



N-1427
Id
A2
V3



N-1428
Id
A2
V4



N-1429
Id
A2
V5



N-1430
Id
A2
V6



N-1431
Id
A2
V7



N-1432
Id
A2
V8



N-1433
Id
A2
V9



N-1434
Id
A2
V10



N-1435
Id
A2
V11



N-1436
Id
A2
V12



N-1437
Id
A2
V13



N-1438
Id
A2
V14



N-1439
Id
A2
V15



N-1440
Id
A2
V16



N-1441
Id
A3
V1



N-1442
Id
A3
V2



N-1443
Id
A3
V3



N-1444
Id
A3
V4



N-1445
Id
A3
V5



N-1446
Id
A3
V6



N-1447
Id
A3
V7



N-1448
Id
A3
V8



N-1449
Id
A3
V9



N-1450
Id
A3
V10



N-1451
Id
A3
V11



N-1452
Id
A3
V12



N-1453
Id
A3
V13



N-1454
Id
A3
V14



N-1455
Id
A3
V15



N-1456
Id
A3
V16



N-1457
Id
A4
V1



N-1458
Id
A4
V2



N-1459
Id
A4
V3



N-1460
Id
A4
V4



N-1461
Id
A4
V5



N-1462
Id
A4
V6



N-1463
Id
A4
V7



N-1464
Id
A4
V8



N-1465
Id
A4
V9



N-1466
Id
A4
V10



N-1467
Id
A4
V11



N-1468
Id
A4
V12



N-1469
Id
A4
V13



N-1470
Id
A4
V14



N-1471
Id
A4
V15



N-1472
Id
A4
V16



N-1473
Id
A5
V1



N-1474
Id
A5
V2



N-1475
Id
A5
V3



N-1476
Id
A5
V4



N-1477
Id
A5
V5



N-1478
Id
A5
V6



N-1479
Id
A5
V7



N-1480
Id
A5
V8



N-1481
Id
A5
V9



N-1482
Id
A5
V10



N-1483
Id
A5
V11



N-1484
Id
A5
V12



N-1485
Id
A5
V13



N-1486
Id
A5
V14



N-1487
Id
A5
V15



N-1488
Id
A5
V16



N-1489
Id
A6
V1



N-1490
Id
A6
V2



N-1491
Id
A6
V3



N-1492
Id
A6
V4



N-1493
Id
A6
V5



N-1494
Id
A6
V6



N-1495
Id
A6
V7



N-1496
Id
A6
V8



N-1497
Id
A6
V9



N-1498
Id
A6
V10



N-1499
Id
A6
V11



N-1500
Id
A6
V12



N-1501
Id
A6
V13



N-1502
Id
A6
V14



N-1503
Id
A6
V15



N-1504
Id
A6
V16



N-1505
Id
A7
V1



N-1506
Id
A7
V2



N-1507
Id
A7
V3



N-1508
Id
A7
V4



N-1509
Id
A7
V5



N-1510
Id
A7
V6



N-1511
Id
A7
V7



N-1512
Id
A7
V8



N-1513
Id
A7
V9



N-1514
Id
A7
V10



N-1515
Id
A7
V11



N-1516
Id
A7
V12



N-1517
Id
A7
V13



N-1518
Id
A7
V14



N-1519
Id
A7
V15



N-1520
Id
A7
V16



N-1521
Id
A8
V1



N-1522
Id
A8
V2



N-1523
Id
A8
V3



N-1524
Id
A8
V4



N-1525
Id
A8
V5



N-1526
Id
A8
V6



N-1527
Id
A8
V7



N-1528
Id
A8
V8



N-1529
Id
A8
V9



N-1530
Id
A8
V10



N-1531
Id
A8
V11



N-1532
Id
A8
V12



N-1533
Id
A8
V13



N-1534
Id
A8
V14



N-1535
Id
A8
V15



N-1536
Id
A8
V16



N-1537
Id
A9
V1



N-1538
Id
A9
V2



N-1539
Id
A9
V3



N-1540
Id
A9
V4



N-1541
Id
A9
V5



N-1542
Id
A9
V6



N-1543
Id
A9
V7



N-1544
Id
A9
V8



N-1545
Id
A9
V9



N-1546
Id
A9
V10



N-1547
Id
A9
V11



N-1548
Id
A9
V12



N-1549
Id
A9
V13



N-1550
Id
A9
V14



N-1551
Id
A9
V15



N-1552
Id
A9
V16



N-1553
Id
A10
V1



N-1554
Id
A10
V2



N-1555
Id
A10
V3



N-1556
Id
A10
V4



N-1557
Id
A10
V5



N-1558
Id
A10
V6



N-1559
Id
A10
V7



N-1560
Id
A10
V8



N-1561
Id
A10
V9



N-1562
Id
A10
V10



N-1563
Id
A10
V11



N-1564
Id
A10
V12



N-1565
Id
A10
V13



N-1566
Id
A10
V14



N-1567
Id
A10
V15



N-1568
Id
A10
V16



N-1569
Id
A11
V1



N-1570
Id
A11
V2



N-1571
Id
A11
V3



N-1572
Id
A11
V4



N-1573
Id
A11
V5



N-1574
Id
A11
V6



N-1575
Id
A11
V7



N-1576
Id
A11
V8



N-1577
Id
A11
V9



N-1578
Id
A11
V10



N-1579
Id
A11
V11



N-1580
Id
A11
V12



N-1581
Id
A11
V13



N-1582
Id
A11
V14



N-1583
Id
A11
V15



N-1584
Id
A11
V16



N-1585
Id
A12
V1



N-1586
Id
A12
V2



N-1587
Id
A12
V3



N-1588
Id
A12
V4



N-1589
Id
A12
V5



N-1590
Id
A12
V6



N-1591
Id
A12
V7



N-1592
Id
A12
V8



N-1593
Id
A12
V9



N-1594
Id
A12
V10



N-1595
Id
A12
V11



N-1596
Id
A12
V12



N-1597
Id
A12
V13



N-1598
Id
A12
V14



N-1599
Id
A12
V15



N-1600
Id
A12
V16



N-1601
Id
A13
V1



N-1602
Id
A13
V2



N-1603
Id
A13
V3



N-1604
Id
A13
V4



N-1605
Id
A13
V5



N-1606
Id
A13
V6



N-1607
Id
A13
V7



N-1608
Id
A13
V8



N-1609
Id
A13
V9



N-1610
Id
A13
V10



N-1611
Id
A13
V11



N-1612
Id
A13
V12



N-1613
Id
A13
V13



N-1614
Id
A13
V14



N-1615
Id
A13
V15



N-1616
Id
A13
V16



N-1617
Id
A14
V1



N-1618
Id
A14
V2



N-1619
Id
A14
V3



N-1620
Id
A14
V4



N-1621
Id
A14
V5



N-1622
Id
A14
V6



N-1623
Id
A14
V7



N-1624
Id
A14
V8



N-1625
Id
A14
V9



N-1626
Id
A14
V10



N-1627
Id
A14
V11



N-1628
Id
A14
V12



N-1629
Id
A14
V13



N-1630
Id
A14
V14



N-1631
Id
A14
V15



N-1632
Id
A14
V16



N-1633
Id
A15
V1



N-1634
Id
A15
V2



N-1635
Id
A15
V3



N-1636
Id
A15
V4



N-1637
Id
A15
V5



N-1638
Id
A15
V6



N-1639
Id
A15
V7



N-1640
Id
A15
V8



N-1641
Id
A15
V9



N-1642
Id
A15
V10



N-1643
Id
A15
V11



N-1644
Id
A15
V12



N-1645
Id
A15
V13



N-1646
Id
A15
V14



N-1647
Id
A15
V15



N-1648
Id
A15
V16



N-1649
Id
A19
V1



N-1650
Id
A19
V2



N-1651
Id
A19
V3



N-1652
Id
A19
V4



N-1653
Id
A19
V5



N-1654
Id
A19
V6



N-1655
Id
A19
V7



N-1656
Id
A19
V8



N-1657
Id
A19
V9



N-1658
Id
A19
V10



N-1659
Id
A19
V11



N-1660
Id
A19
V12



N-1661
Id
A19
V13



N-1662
Id
A19
V14



N-1663
Id
A19
V15



N-1664
Id
A19
V16



N-1665
Ie
A1
V1



N-1666
Ie
A1
V2



N-1667
Ie
A1
V3



N-1668
Ie
A1
V4



N-1669
Ie
A1
V5



N-1670
Ie
A1
V6



N-1671
Ie
A1
V7



N-1672
Ie
A1
V8



N-1673
Ie
A1
V9



N-1674
Ie
A1
V10



N-1675
Ie
A1
V11



N-1676
Ie
A1
V12



N-1677
Ie
A1
V13



N-1678
Ie
A1
V14



N-1679
Ie
A1
V15



N-1680
Ie
A1
V16



N-1681
Ie
A2
V1



N-1682
Ie
A2
V2



N-1683
Ie
A2
V3



N-1684
Ie
A2
V4



N-1685
Ie
A2
V5



N-1686
Ie
A2
V6



N-1687
Ie
A2
V7



N-1688
Ie
A2
V8



N-1689
Ie
A2
V9



N-1690
Ie
A2
V10



N-1691
Ie
A2
V11



N-1692
Ie
A2
V12



N-1693
Ie
A2
V13



N-1694
Ie
A2
V14



N-1695
Ie
A2
V15



N-1696
Ie
A2
V16



N-1697
Ie
A3
V1



N-1698
Ie
A3
V2



N-1699
Ie
A3
V3



N-1700
Ie
A3
V4



N-1701
Ie
A3
V5



N-1702
Ie
A3
V6



N-1703
Ie
A3
V7



N-1704
Ie
A3
V8



N-1705
Ie
A3
V9



N-1706
Ie
A3
V10



N-1707
Ie
A3
V11



N-1708
Ie
A3
V12



N-1709
Ie
A3
V13



N-1710
Ie
A3
V14



N-1711
Ie
A3
V15



N-1712
Ie
A3
V16



N-1713
Ie
A4
V1



N-1714
Ie
A4
V2



N-1715
Ie
A4
V3



N-1716
Ie
A4
V4



N-1717
Ie
A4
V5



N-1718
Ie
A4
V6



N-1719
Ie
A4
V7



N-1720
Ie
A4
V8



N-1721
Ie
A4
V9



N-1722
Ie
A4
V10



N-1723
Ie
A4
V11



N-1724
Ie
A4
V12



N-1725
Ie
A4
V13



N-1726
Ie
A4
V14



N-1727
Ie
A4
V15



N-1728
Ie
A4
V16



N-1729
Ie
A5
V1



N-1730
Ie
A5
V2



N-1731
Ie
A5
V3



N-1732
Ie
A5
V4



N-1733
Ie
A5
V5



N-1734
Ie
A5
V6



N-1735
Ie
A5
V7



N-1736
Ie
A5
V8



N-1737
Ie
A5
V9



N-1738
Ie
A5
V10



N-1739
Ie
A5
V11



N-1740
Ie
A5
V12



N-1741
Ie
A5
V13



N-1742
Ie
A5
V14



N-1743
Ie
A5
V15



N-1744
Ie
A5
V16



N-1745
Ie
A6
V1



N-1746
Ie
A6
V2



N-1747
Ie
A6
V3



N-1748
Ie
A6
V4



N-1749
Ie
A6
V5



N-1750
Ie
A6
V6



N-1751
Ie
A6
V7



N-1752
Ie
A6
V8



N-1753
Ie
A6
V9



N-1754
Ie
A6
V10



N-1755
Ie
A6
V11



N-1756
Ie
A6
V12



N-1757
Ie
A6
V13



N-1758
Ie
A6
V14



N-1759
Ie
A6
V15



N-1760
Ie
A6
V16



N-1761
Ie
A7
V1



N-1762
Ie
A7
V2



N-1763
Ie
A7
V3



N-1764
Ie
A7
V4



N-1765
Ie
A7
V5



N-1766
Ie
A7
V6



N-1767
Ie
A7
V7



N-1768
Ie
A7
V8



N-1769
Ie
A7
V9



N-1770
Ie
A7
V10



N-1771
Ie
A7
V11



N-1772
Ie
A7
V12



N-1773
Ie
A7
V13



N-1774
Ie
A7
V14



N-1775
Ie
A7
V15



N-1776
Ie
A7
V16



N-1777
Ie
A8
V1



N-1778
Ie
A8
V2



N-1779
Ie
A8
V3



N-1780
Ie
A8
V4



N-1781
Ie
A8
V5



N-1782
Ie
A8
V6



N-1783
Ie
A8
V7



N-1784
Ie
A8
V8



N-1785
Ie
A8
V9



N-1786
Ie
A8
V10



N-1787
Ie
A8
V11



N-1788
Ie
A8
V12



N-1789
Ie
A8
V13



N-1790
Ie
A8
V14



N-1791
Ie
A8
V15



N-1792
Ie
A8
V16



N-1793
Ie
A9
V1



N-1794
Ie
A9
V2



N-1795
Ie
A9
V3



N-1796
Ie
A9
V4



N-1797
Ie
A9
V5



N-1798
Ie
A9
V6



N-1799
Ie
A9
V7



N-1800
Ie
A9
V8



N-1801
Ie
A9
V9



N-1802
Ie
A9
V10



N-1803
Ie
A9
V11



N-1804
Ie
A9
V12



N-1805
Ie
A9
V13



N-1806
Ie
A9
V14



N-1807
Ie
A9
V15



N-1808
Ie
A9
V16



N-1809
Ie
A10
V1



N-1810
Ie
A10
V2



N-1811
Ie
A10
V3



N-1812
Ie
A10
V4



N-1813
Ie
A10
V5



N-1814
Ie
A10
V6



N-1815
Ie
A10
V7



N-1816
Ie
A10
V8



N-1817
Ie
A10
V9



N-1818
Ie
A10
V10



N-1819
Ie
A10
V11



N-1820
Ie
A10
V12



N-1821
Ie
A10
V13



N-1822
Ie
A10
V14



N-1823
Ie
A10
V15



N-1824
Ie
A10
V16



N-1825
Ie
A11
V1



N-1826
Ie
A11
V2



N-1827
Ie
A11
V3



N-1828
Ie
A11
V4



N-1829
Ie
A11
V5



N-1830
Ie
A11
V6



N-1831
Ie
A11
V7



N-1832
Ie
A11
V8



N-1833
Ie
A11
V9



N-1834
Ie
A11
V10



N-1835
Ie
A11
V11



N-1836
Ie
A11
V12



N-1837
Ie
A11
V13



N-1838
Ie
A11
V14



N-1839
Ie
A11
V15



N-1840
Ie
A11
V16



N-1841
Ie
A12
V1



N-1842
Ie
A12
V2



N-1843
Ie
A12
V3



N-1844
Ie
A12
V4



N-1845
Ie
A12
V5



N-1846
Ie
A12
V6



N-1847
Ie
A12
V7



N-1848
Ie
A12
V8



N-1849
Ie
A12
V9



N-1850
Ie
A12
V10



N-1851
Ie
A12
V11



N-1852
Ie
A12
V12



N-1853
Ie
A12
V13



N-1854
Ie
A12
V14



N-1855
Ie
A12
V15



N-1856
Ie
A12
V16



N-1857
Ie
A13
V1



N-1858
Ie
A13
V2



N-1859
Ie
A13
V3



N-1860
Ie
A13
V4



N-1861
Ie
A13
V5



N-1862
Ie
A13
V6



N-1863
Ie
A13
V7



N-1864
Ie
A13
V8



N-1865
Ie
A13
V9



N-1866
Ie
A13
V10



N-1867
Ie
A13
V11



N-1868
Ie
A13
V12



N-1869
Ie
A13
V13



N-1870
Ie
A13
V14



N-1871
Ie
A13
V15



N-1872
Ie
A13
V16



N-1873
Ie
A14
V1



N-1874
Ie
A14
V2



N-1875
Ie
A14
V3



N-1876
Ie
A14
V4



N-1877
Ie
A14
V5



N-1878
Ie
A14
V6



N-1879
Ie
A14
V7



N-1880
Ie
A14
V8



N-1881
Ie
A14
V9



N-1882
Ie
A14
V10



N-1883
Ie
A14
V11



N-1884
Ie
A14
V12



N-1885
Ie
A14
V13



N-1886
Ie
A14
V14



N-1887
Ie
A14
V15



N-1888
Ie
A14
V16



N-1889
Ie
A15
V1



N-1890
Ie
A15
V2



N-1891
Ie
A15
V3



N-1892
Ie
A15
V4



N-1893
Ie
A15
V5



N-1894
Ie
A15
V6



N-1895
Ie
A15
V7



N-1896
Ie
A15
V8



N-1897
Ie
A15
V9



N-1898
Ie
A15
V10



N-1899
Ie
A15
V11



N-1900
Ie
A15
V12



N-1901
Ie
A15
V13



N-1902
Ie
A15
V14



N-1903
Ie
A15
V15



N-1904
Ie
A15
V16



N-1905
Ie
A19
V1



N-1906
Ie
A19
V2



N-1907
Ie
A19
V3



N-1908
Ie
A19
V4



N-1909
Ie
A19
V5



N-1910
Ie
A19
V6



N-1911
Ie
A19
V7



N-1912
Ie
A19
V8



N-1913
Ie
A19
V9



N-1914
Ie
A19
V10



N-1915
Ie
A19
V11



N-1916
Ie
A19
V12



N-1917
Ie
A19
V13



N-1918
Ie
A19
V14



N-1919
Ie
A19
V15



N-1920
Ie
A19
V16



N-1921
Ig
A1
V1



N-1922
Ig
A1
V2



N-1923
Ig
A1
V3



N-1924
Ig
A1
V4



N-1925
Ig
A1
V5



N-1926
Ig
A1
V6



N-1927
Ig
A1
V7



N-1928
Ig
A1
V8



N-1929
Ig
A1
V9



N-1930
Ig
A1
V10



N-1931
Ig
A1
V11



N-1932
Ig
A1
V12



N-1933
Ig
A1
V13



N-1934
Ig
A1
V14



N-1935
Ig
A1
V15



N-1936
Ig
A1
V16



N-1937
Ig
A2
V1



N-1938
Ig
A2
V2



N-1939
Ig
A2
V3



N-1940
Ig
A2
V4



N-1941
Ig
A2
V5



N-1942
Ig
A2
V6



N-1943
Ig
A2
V7



N-1944
Ig
A2
V8



N-1945
Ig
A2
V9



N-1946
Ig
A2
V10



N-1947
Ig
A2
V11



N-1948
Ig
A2
V12



N-1949
Ig
A2
V13



N-1950
Ig
A2
V14



N-1951
Ig
A2
V15



N-1952
Ig
A2
V16



N-1953
Ig
A3
V1



N-1954
Ig
A3
V2



N-1955
Ig
A3
V3



N-1956
Ig
A3
V4



N-1957
Ig
A3
V5



N-1958
Ig
A3
V6



N-1959
Ig
A3
V7



N-1960
Ig
A3
V8



N-1961
Ig
A3
V9



N-1962
Ig
A3
V10



N-1963
Ig
A3
V11



N-1964
Ig
A3
V12



N-1965
Ig
A3
V13



N-1966
Ig
A3
V14



N-1967
Ig
A3
V15



N-1968
Ig
A3
V16



N-1969
Ig
A4
V1



N-1970
Ig
A4
V2



N-1971
Ig
A4
V3



N-1972
Ig
A4
V4



N-1973
Ig
A4
V5



N-1974
Ig
A4
V6



N-1975
Ig
A4
V7



N-1976
Ig
A4
V8



N-1977
Ig
A4
V9



N-1978
Ig
A4
V10



N-1979
Ig
A4
V11



N-1980
Ig
A4
V12



N-1981
Ig
A4
V13



N-1982
Ig
A4
V14



N-1983
Ig
A4
V15



N-1984
Ig
A4
V16



N-1985
Ig
A5
V1



N-1986
Ig
A5
V2



N-1987
Ig
A5
V3



N-1988
Ig
A5
V4



N-1989
Ig
A5
V5



N-1990
Ig
A5
V6



N-1991
Ig
A5
V7



N-1992
Ig
A5
V8



N-1993
Ig
A5
V9



N-1994
Ig
A5
V10



N-1995
Ig
A5
V11



N-1996
Ig
A5
V12



N-1997
Ig
A5
V13



N-1998
Ig
A5
V14



N-1999
Ig
A5
V15



N-2000
Ig
A5
V16



N-2001
Ig
A6
V1



N-2002
Ig
A6
V2



N-2003
Ig
A6
V3



N-2004
Ig
A6
V4



N-2005
Ig
A6
V5



N-2006
Ig
A6
V6



N-2007
Ig
A6
V7



N-2008
Ig
A6
V8



N-2009
Ig
A6
V9



N-2010
Ig
A6
V10



N-2011
Ig
A6
V11



N-2012
Ig
A6
V12



N-2013
Ig
A6
V13



N-2014
Ig
A6
V14



N-2015
Ig
A6
V15



N-2016
Ig
A6
V16



N-2017
Ig
A7
V1



N-2018
Ig
A7
V2



N-2019
Ig
A7
V3



N-2020
Ig
A7
V4



N-2021
Ig
A7
V5



N-2022
Ig
A7
V6



N-2023
Ig
A7
V7



N-2024
Ig
A7
V8



N-2025
Ig
A7
V9



N-2026
Ig
A7
V10



N-2027
Ig
A7
V11



N-2028
Ig
A7
V12



N-2029
Ig
A7
V13



N-2030
Ig
A7
V14



N-2031
Ig
A7
V15



N-2032
Ig
A7
V16



N-2033
Ig
A8
V1



N-2034
Ig
A8
V2



N-2035
Ig
A8
V3



N-2036
Ig
A8
V4



N-2037
Ig
A8
V5



N-2038
Ig
A8
V6



N-2039
Ig
A8
V7



N-2040
Ig
A8
V8



N-2041
Ig
A8
V9



N-2042
Ig
A8
V10



N-2043
Ig
A8
V11



N-2044
Ig
A8
V12



N-2045
Ig
A8
V13



N-2046
Ig
A8
V14



N-2047
Ig
A8
V15



N-2048
Ig
A8
V16



N-2049
Ig
A9
V1



N-2050
Ig
A9
V2



N-2051
Ig
A9
V3



N-2052
Ig
A9
V4



N-2053
Ig
A9
V5



N-2054
Ig
A9
V6



N-2055
Ig
A9
V7



N-2056
Ig
A9
V8



N-2057
Ig
A9
V9



N-2058
Ig
A9
V10



N-2059
Ig
A9
V11



N-2060
Ig
A9
V12



N-2061
Ig
A9
V13



N-2062
Ig
A9
V14



N-2063
Ig
A9
V15



N-2064
Ig
A9
V16



N-2065
Ig
A10
V1



N-2066
Ig
A10
V2



N-2067
Ig
A10
V3



N-2068
Ig
A10
V4



N-2069
Ig
A10
V5



N-2070
Ig
A10
V6



N-2071
Ig
A10
V7



N-2072
Ig
A10
V8



N-2073
Ig
A10
V9



N-2074
Ig
A10
V10



N-2075
Ig
A10
V11



N-2076
Ig
A10
V12



N-2077
Ig
A10
V13



N-2078
Ig
A10
V14



N-2079
Ig
A10
V15



N-2080
Ig
A10
V16



N-2081
Ig
A11
V1



N-2082
Ig
A11
V2



N-2083
Ig
A11
V3



N-2084
Ig
A11
V4



N-2085
Ig
A11
V5



N-2086
Ig
A11
V6



N-2087
Ig
A11
V7



N-2088
Ig
A11
V8



N-2089
Ig
A11
V9



N-2090
Ig
A11
V10



N-2091
Ig
A11
V11



N-2092
Ig
A11
V12



N-2093
Ig
A11
V13



N-2094
Ig
A11
V14



N-2095
Ig
A11
V15



N-2096
Ig
A11
V16



N-2097
Ig
A12
V1



N-2098
Ig
A12
V2



N-2099
Ig
A12
V3



N-2100
Ig
A12
V4



N-2101
Ig
A12
V5



N-2102
Ig
A12
V6



N-2103
Ig
A12
V7



N-2104
Ig
A12
V8



N-2105
Ig
A12
V9



N-2106
Ig
A12
V10



N-2107
Ig
A12
V11



N-2108
Ig
A12
V12



N-2109
Ig
A12
V13



N-2110
Ig
A12
V14



N-2111
Ig
A12
V15



N-2112
Ig
A12
V16



N-2113
Ig
A13
V1



N-2114
Ig
A13
V2



N-2115
Ig
A13
V3



N-2116
Ig
A13
V4



N-2117
Ig
A13
V5



N-2118
Ig
A13
V6



N-2119
Ig
A13
V7



N-2120
Ig
A13
V8



N-2121
Ig
A13
V9



N-2122
Ig
A13
V10



N-2123
Ig
A13
V11



N-2124
Ig
A13
V12



N-2125
Ig
A13
V13



N-2126
Ig
A13
V14



N-2127
Ig
A13
V15



N-2128
Ig
A13
V16



N-2129
Ig
A14
V1



N-2130
Ig
A14
V2



N-2131
Ig
A14
V3



N-2132
Ig
A14
V4



N-2133
Ig
A14
V5



N-2134
Ig
A14
V6



N-2135
Ig
A14
V7



N-2136
Ig
A14
V8



N-2137
Ig
A14
V9



N-2138
Ig
A14
V10



N-2139
Ig
A14
V11



N-2140
Ig
A14
V12



N-2141
Ig
A14
V13



N-2142
Ig
A14
V14



N-2143
Ig
A14
V15



N-2144
Ig
A14
V16



N-2145
Ig
A15
V1



N-2146
Ig
A15
V2



N-2147
Ig
A15
V3



N-2148
Ig
A15
V4



N-2149
Ig
A15
V5



N-2150
Ig
A15
V6



N-2151
Ig
A15
V7



N-2152
Ig
A15
V8



N-2153
Ig
A15
V9



N-2154
Ig
A15
V10



N-2155
Ig
A15
V11



N-2156
Ig
A15
V12



N-2157
Ig
A15
V13



N-2158
Ig
A15
V14



N-2159
Ig
A15
V15



N-2160
Ig
A15
V16



N-2161
Ig
A19
V1



N-2162
Ig
A19
V2



N-2163
Ig
A19
V3



N-2164
Ig
A19
V4



N-2165
Ig
A19
V5



N-2166
Ig
A19
V6



N-2167
Ig
A19
V7



N-2168
Ig
A19
V8



N-2169
Ig
A19
V9



N-2170
Ig
A19
V10



N-2171
Ig
A19
V11



N-2172
Ig
A19
V12



N-2173
Ig
A19
V13



N-2174
Ig
A19
V14



N-2175
Ig
A19
V15



N-2176
Ig
A19
V16



N-2177
Ia
S1
Fip



N-2178
Ia
S2
Fip



N-2179
Ia
S3
Fip



N-2180
Ia
S4
Fip



N-2181
Ia
S5
Fip



N-2182
Ia
S6
Fip



N-2183
Ia
S7
Fip



N-2184
Ia
S8
Fip



N-2185
Ia
S9
Fip



N-2186
Ia
S1
Ch



N-2187
Ia
S2
Ch



N-2188
Ia
S3
Ch



N-2189
Ia
S4
Ch



N-2190
Ia
S5
Ch



N-2191
Ia
S6
Ch



N-2192
Ia
S7
Ch



N-2193
Ia
S8
Ch



N-2194
Ia
S9
Ch



N-2195
Id
S1
Fip



N-2196
Id
S2
Fip



N-2197
Id
S3
Fip



N-2198
Id
S4
Fip



N-2199
Id
S5
Fip



N-2200
Id
S6
Fip



N-2201
Id
S7
Fip



N-2202
Id
S8
Fip



N-2203
Id
S9
Fip



N-2204
Id
S1
Ch



N-2205
Id
S2
Ch



N-2206
Id
S3
Ch



N-2207
Id
S4
Ch



N-2208
Id
S5
Ch



N-2209
Id
S6
Ch



N-2210
Id
S7
Ch



N-2211
Id
S8
Ch



N-2212
Id
S9
Ch



N-2213
Ie
S1
Fip



N-2214
Ie
S2
Fip



N-2215
Ie
S3
Fip



N-2216
Ie
S4
Fip



N-2217
Ie
S5
Fip



N-2218
Ie
S6
Fip



N-2219
Ie
S7
Fip



N-2220
Ie
S8
Fip



N-2221
Ie
S9
Fip



N-2222
Ie
S1
Ch



N-2223
Ie
S2
Ch



N-2224
Ie
S3
Ch



N-2225
Ie
S4
Ch



N-2226
Ie
S5
Ch



N-2227
Ie
S6
Ch



N-2228
Ie
S7
Ch



N-2229
Ie
S8
Ch



N-2230
Ie
S9
Ch



N-2231
Ig
S1
Fip



N-2232
Ig
S2
Fip



N-2233
Ig
S3
Fip



N-2234
Ig
S4
Fip



N-2235
Ig
S5
Fip



N-2236
Ig
S6
Fip



N-2237
Ig
S7
Fip



N-2238
Ig
S8
Fip



N-2239
Ig
S9
Fip



N-2240
Ig
S1
Ch



N-2241
Ig
S2
Ch



N-2242
Ig
S3
Ch



N-2243
Ig
S4
Ch



N-2244
Ig
S5
Ch



N-2245
Ig
S6
Ch



N-2246
Ig
S7
Ch



N-2247
Ig
S8
Ch



N-2248
Ig
S9
Ch



N-2249
Ia
A1
Fip



N-2250
Ia
A2
Fip



N-2251
Ia
A3
Fip



N-2252
Ia
A4
Fip



N-2253
Ia
A5
Fip



N-2254
Ia
A6
Fip



N-2255
Ia
A7
Fip



N-2256
Ia
A8
Fip



N-2257
Ia
A9
Fip



N-2258
Ia
A10
Fip



N-2259
Ia
A11
Fip



N-2260
Ia
A12
Fip



N-2261
Ia
A13
Fip



N-2262
Ia
A14
Fip



N-2263
Ia
A15
Fip



N-2264
Ia
A19
Fip



N-2265
Ia
A1
Ch



N-2266
Ia
A2
Ch



N-2267
Ia
A3
Ch



N-2268
Ia
A4
Ch



N-2269
Ia
A5
Ch



N-2270
Ia
A6
Ch



N-2271
Ia
A7
Ch



N-2272
Ia
A8
Ch



N-2273
Ia
A9
Ch



N-2274
Ia
A10
Ch



N-2275
Ia
A11
Ch



N-2276
Ia
A12
Ch



N-2277
Ia
A13
Ch



N-2278
Ia
A14
Ch



N-2279
Ia
A15
Ch



N-2280
Ia
A19
Ch



N-2281
Id
A1
Fip



N-2282
Id
A2
Fip



N-2283
Id
A3
Fip



N-2284
Id
A4
Fip



N-2285
Id
A5
Fip



N-2286
Id
A6
Fip



N-2287
Id
A7
Fip



N-2288
Id
A8
Fip



N-2289
Id
A9
Fip



N-2290
Id
A10
Fip



N-2291
Id
A11
Fip



N-2292
Id
A12
Fip



N-2293
Id
A13
Fip



N-2294
Id
A14
Fip



N-2295
Id
A15
Fip



N-2296
Id
A19
Fip



N-2297
Id
A1
Ch



N-2298
Id
A2
Ch



N-2299
Id
A3
Ch



N-2300
Id
A4
Ch



N-2301
Id
A5
Ch



N-2302
Id
A6
Ch



N-2303
Id
A7
Ch



N-2304
Id
A8
Ch



N-2305
Id
A9
Ch



N-2306
Id
A10
Ch



N-2307
Id
A11
Ch



N-2308
Id
A12
Ch



N-2309
Id
A13
Ch



N-2310
Id
A14
Ch



N-2311
Id
A15
Ch



N-2312
Id
A19
Ch



N-2313
Ie
A1
Fip



N-2314
Ie
A2
Fip



N-2315
Ie
A3
Fip



N-2316
Ie
A4
Fip



N-2317
Ie
A5
Fip



N-2318
Ie
A6
Fip



N-2319
Ie
A7
Fip



N-2320
Ie
A8
Fip



N-2321
Ie
A9
Fip



N-2322
Ie
A10
Fip



N-2323
Ie
A11
Fip



N-2324
Ie
A12
Fip



N-2325
Ie
A13
Fip



N-2326
Ie
A14
Fip



N-2327
Ie
A15
Fip



N-2328
Ie
A19
Fip



N-2329
Ie
A1
Ch



N-2330
Ie
A2
Ch



N-2331
Ie
A3
Ch



N-2332
Ie
A4
Ch



N-2333
Ie
A5
Ch



N-2334
Ie
A6
Ch



N-2335
Ie
A7
Ch



N-2336
Ie
A8
Ch



N-2337
Ie
A9
Ch



N-2338
Ie
A10
Ch



N-2339
Ie
A11
Ch



N-2340
Ie
A12
Ch



N-2341
Ie
A13
Ch



N-2342
Ie
A14
Ch



N-2343
Ie
A15
Ch



N-2344
Ie
A19
Ch



N-2345
Ig
A1
Fip



N-2346
Ig
A2
Fip



N-2347
Ig
A3
Fip



N-2348
Ig
A4
Fip



N-2349
Ig
A5
Fip



N-2350
Ig
A6
Fip



N-2351
Ig
A7
Fip



N-2352
Ig
A8
Fip



N-2353
Ig
A9
Fip



N-2354
Ig
A10
Fip



N-2355
Ig
A11
Fip



N-2356
Ig
A12
Fip



N-2357
Ig
A13
Fip



N-2358
Ig
A14
Fip



N-2359
Ig
A15
Fip



N-2360
Ig
A19
Fip



N-2361
Ig
A1
Ch



N-2362
Ig
A2
Ch



N-2363
Ig
A3
Ch



N-2364
Ig
A4
Ch



N-2365
Ig
A5
Ch



N-2366
Ig
A6
Ch



N-2367
Ig
A7
Ch



N-2368
Ig
A8
Ch



N-2369
Ig
A9
Ch



N-2370
Ig
A10
Ch



N-2371
Ig
A11
Ch



N-2372
Ig
A12
Ch



N-2373
Ig
A13
Ch



N-2374
Ig
A14
Ch



N-2375
Ig
A15
Ch



N-2376
Ig
A19
Ch










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-136, N-137, N-138, N-139, N-140, N-141, N-142, N-143, N-144, N-577, N-578, N-579, N-580, N-581, N-582, N-583, N-584, N-585, N-586, N-587, N-588, N-589, N-590, N-591, N-592, N-593, N-594, N-595, N-596, N-597, N-598, N-599, N-600, N-601, N-602, N-603, N-604, N-605, N-606, N-607, N-608, N-609, N-610, N-611, N-612, N-613, N-614, N-615, N-616, N-617, N-618, N-619, N-620, N-621, N-622, N-623, N-624, N-625, N-626, N-627, N-628, N-629, N-630, N-631, N-632, N-633, N-634, N-635, N-636, N-637, N-638, N-639, N-640, N-641, N-642, N-643, N-644, N-645, N-646, N-647, N-648, N-649, N-650, N-651, N-652, N-653, N-654, N-655, N-656, N-657, N-658, N-659, N-660, N-661, N-662, N-663, N-664, N-665, N-666, N-667, N-668, N-669, N-670, N-671, N-672, N-673, N-674, N-675, N-676, N-677, N-678, N-679, N-680, N-681, N-682, N-683, N-684, N-685, N-686, N-687, N-688, N-689, N-690, N-691, N-692, N-693, N-694, N-695, N-696, N-697, N-698, N-699, N-700, N-701, N-702, N-703, N-704, N-705, N-706, N-707, N-708, N-709, N-710, N-711, N-712, N-713, N-714, N-715, N-716, N-717, N-718, N-719, N-720, N-1153, N-1154, N-1155, N-1156, N-1157, N-1158, N-1159, N-1160, N-1161, N-1162, N-1163, N-1164, N-1165, N-1166, N-1167, N-1168, N-1169, N-1170, N-1171, N-1172, N-1173, N-1174, N-1175, N-1176, N-1177, N-1178, N-1179, N-1180, N-1181, N-1182, N-1183, N-1184, N-1185, N-1186, N-1187, N-1188, N-1189, N-1190, N-1191, N-1192, N-1193, N-1194, N-1195, N-1196, N-1197, N-1198, N-1199, N-1200, N-1201, N-1202, N-1203, N-1204, N-1205, N-1206, N-1207, N-1208, N-1209, N-1210, N-1211, N-1212, N-1213, N-1214, N-1215, N-1216, N-1217, N-1218, N-1219, N-1220, N-1221, N-1222, N-1223, N-1224, N-1225, N-1226, N-1227, N-1228, N-1229, N-1230, N-1231, N-1232, N-1233, N-1234, N-1235, N-1236, N-1237, N-1238, N-1239, N-1240, N-1241, N-1242, N-1243, N-1244, N-1245, N-1246, N-1247, N-1248, N-1249, N-1250, N-1251, N-1252, N-1253, N-1254, N-1255, N-1256, N-1257, N-1258, N-1259, N-1260, N-1261, N-1262, N-1263, N-1264, N-1265, N-1266, N-1267, N-1268, N-1269, N-1270, N-1271, N-1272, N-1273, N-1274, N-1275, N-1276, N-1277, N-1278, N-1279, N-1280, N-1281, N-1282, N-1283, N-1284, N-1285, N-1286, N-1287, N-1288, N-1289, N-1290, N-1291, N-1292, N-1293, N-1294, N-1295, N-1296, N-1297, N-1298, N-1299, N-1300, N-1301, N-1302, N-1303, N-1304, N-1305, N-1306, N-1307, N-1308, N-1309, N-1310, N-1311, N-1312, N-1313, N-1314, N-1315, N-1316, N-1317, N-1318, N-1319, N-1320, N-1321, N-1322, N-1323, N-1324, N-1325, N-1326, N-1327, N-1328, N-1329, N-1330, N-1331, N-1332, N-1333, N-1334, N-1335, N-1336, N-1337, N-1338, N-1339, N-1340, N-1341, N-1342, N-1343, N-1344, N-1345, N-1346, N-1347, N-1348, N-1349, N-1350, N-1351, N-1352, N-1353, N-1354, N-1355, N-1356, N-1357, N-1358, N-1359, N-1360, N-1361, N-1362, N-1363, N-1364, N-1365, N-1366, N-1367, N-1368, N-1369, N-1370, N-1371, N-1372, N-1373, N-1374, N-1375, N-1376, N-1377, N-1378, N-1379, N-1380, N-1381, N-1382, N-1383, N-1384, N-1385, N-1386, N-1387, N-1388, N-1389, N-1390, N-1391, N-1392, N-1393, N-1394, N-1395, N-1396, N-1397, N-1398, N-1399, N-1400, N-1401, N-1402, N-1403, N-1404, N-1405, N-1406, N-1407, N-1408, N-2182 and N-2191.


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


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-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-657, N-658, N-659, N-660, N-661, N-662, N-663, N-664, N-665, N-666, N-667, N-668, N-669, N-670, N-671, N-672, N-689, N-690, N-691, N-692, N-693, N-694, N-695, N-696, N-697, N-698, N-699, N-700, N-701, N-702, N-703, N-704, N-2182, N-2184, N-2192 and N-2193.


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


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-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 and N-128.


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


N-657, N-658, N-659, N-660, N-661, N-662, N-663, N-664, N-665, N-666, N-667, N-668, N-669, N-670, N-671, N-672, N-689, N-690, N-691, N-692, N-693, N-694, N-695, N-696, N-697, N-698, N-699, N-700, N-701, N-702, N-703 and N-704.


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


N-2182, N-2184, N-2192 and N-2193.

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


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-657, N-658, N-659, N-660, N-661, N-662, N-663, N-664, N-665, N-666, N-667, N-668, N-669, N-670, N-671 and N-672.


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


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-689, N-690, N-691, N-692, N-693, N-694, N-695, N-696, N-697, N-698, N-699, N-700, N-701, N-702, N-703 and N-704.


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


N-1393, N-1394, N-1395, N-1396, N-1397, N-1398, N-1399, N-1400, N-1401, N-1402, N-1403, N-1404, N-1405, N-1406, N-1407, N-1408, N-2264 and N-2280.

In all mixtures used according to the method of the present invention, compound (I) and at least one of the compound selected from the compounds (II), (IIb) and (III), are employed in amounts to afford a synergistic effect. The weight ratio of compound (I) to a compound selected from the group consisting of compounds (II), (IIb) and (III), 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 compound (I) and a compound selected from the group consisting of compounds (II), (IIb) and (III) 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 propagules.


Thus, the invention relates to a method for improving the health of plants, which comprises treating the plant propagules from which the plant grows with a compound (I) or with the mixtures according to the present invention.


If a mixture according to the present invention is used in this inventive method, the plant propagules are preferably treated simultaneously (together or separately) or subsequently with the amide compound of the formula I (compound I) and a compound selected from the group consisting of compounds (II), (IIb) and (III).


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 a compound selected from the group consisting of compounds (II), (IIb) and (III), 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, Bundessortenamt and Chemical industry.


The term “propagules” or “plant propagules” is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting. In a preferred embodiment, the term “propagules” or “plant propagules” denotes for seed.


As a matter of course, compound (I) and in case mixtures are employed, a compound selected from the group consisting of compounds (II), (IIb) and (III) 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 men-grown 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 modifications 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 compound (I) or a mixture of the present 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 (e.g. seeds) or all is 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; and on the plant propagation material, such as seeds, and the crop material of these plants.


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 most preferred embodiment, the aforementioned method for improving the health of a plant comprises treating the plant propagules, preferably the seeds of an agricultural plant 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 an compound (I) or a mixture according to the present invention, wherein soybean is utmost preferred.


“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.


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, 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, crop establishment, flowering, grain maturity and/or senescence, protein content, sugar content and the like.


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 preferred embodiment, the present invention provides the use of compound (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 propagules, more preferably the seed 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 with a compound (I) or a mixture according to the present invention.


In a particular preferred embodiment, the aforementioned method for increasing the yield of the plant comprises treating the plant propagules, more preferably the seed of transgenic or non-transgenic soybean with a compound (I) or a mixture according to the present invention.


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 propagules, more preferably the seed 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 with a compound (I) or a mixture according to the present invention.


In a particular preferred embodiment, the aforementioned method for increasing the vigour of the plant treating the plant propagules, more preferably the seed of transgenic or non-transgenic soybean with a compound of formula I (compound I) or a mixture according to the present invention.


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,
    • improved visual appearance,
    • delay of senescence,
    • enhanced root growth and/or more developed root system,
    • enhanced nodulation, in particular rhizobial nodulation,
    • longer panicles,
    • bigger leaf blade,
    • less dead basal leaves,
    • increased or improved plant stand density,
    • less plant verse (lodging),
    • increased plant weight,
    • increased plant height,
    • tillering increase,
    • stronger and/or more productive tillers,
    • less non-productive tillers,
    • enhanced photosynthetic activity and/or enhanced pigment content and thus greener leaf color,
    • earlier and improved germination
    • improved emergence and establishment,
    • increased shoot growth,
    • earlier flowering,
    • earlier fruiting,
    • earlier grain maturity,
    • less fertilizers needed,
    • less seeds needed.


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 of formula I or a mixture of the present invention is used for enhancing improved vitality of the plant.


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


In another more preferred embodiment of the invention, the compound of formula 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 of formula I or a mixture of the present invention is used for enhancing nodulation, in particular rhizobial nodulation.


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


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


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


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 of formula I or a mixture of the present invention is used for increased plant height.


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


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


In another preferred embodiment of the invention, the compound of formula I or a mixture of the present invention is used for earlier and improved germination.


In another preferred embodiment of the invention, the compound of formula I or a mixture of the present invention is used for improved emergence and plant establishment.


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


In a most preferred embodiment of the invention, the compound of formula 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 of formula 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 most preferred embodiment of the invention, the compound of formula I or a mixture of the present invention is used for enhancing nodulation, in particular rhizobial nodulation.


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


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


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


In another most preferred embodiment of the invention, the compound of formula I or a mixture of the present invention is used for earlier and improved germination


In another most preferred embodiment of the invention, the compound of formula 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 of formula 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 propagules, preferably the seed of the plant with a compound (I) or a mixture according to the present invention.


In a more preferred embodiment, the afore-mentioned method for enhancing a plant's tolerance or resistance to abiotic stress factors comprises treating the plant propagules, more preferably the seed 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 with a compound (I) or a mixture according to the present invention.


In a particular preferred embodiment, the afore-mentioned method for enhancing a plant's tolerance or resistance to abiotic stress factors treating the plant propagules, more preferably the seed of transgenic or non-transgenic soybean with a compound (I) or a mixture according to the present invention.


Abiotic stress factors have been defined above.


According to the present invention, “enhanced plant's tolerance or resistance 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 a 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 a 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 an especially preferred embodiment of the invention, the tolerance against cold stress is enhanced.


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 prior art—these mixtures however, have not only synergistic plant health effects as described herein above, 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.


“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 the formula I (compound I); and
  • (2) a further fungicide II (compound II) selected from the group consisting ipoconazole, ethaboxam, mefenoxam, metalaxyl, fludioxinil, difenocona-zole, myclobutanil, hymexazol, triadimenol, famoxadone, fenamidone and fosetly-aluminium.


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 the compound (II) 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) listed in the table 3 below are especially preferred.













TABLE 3







No.
(I)
(II)









O-1
Ia
ipoconazole



O-2
Ia
ethaboxam



O-3
Ia
mefenoxam



O-4
Ia
epoxiconazole



O-5
Ia
dimethomorph



O-6
Ia
fludioxonil



O-7
Ia
metalaxyl



O-8
Ia
fludioxinil



O-9
Ia
difenoconazole



O-10
Ia
flutriafol



O-11
Ia
myclobutanil



O-12
Ia
hymexazol



O-13
Ia
triadimenol



O-14
Ib
ipoconazole



O-15
Ib
ethaboxam



O-16
Ib
mefenoxam



O-17
Ib
epoxiconazole



O-18
Ib
dimethomorph



O-19
Ib
fludioxonil



O-20
Ib
metalaxyl



O-21
Ib
fludioxinil



O-22
Ib
difenoconazole



O-23
Ib
flutriafol



O-24
Ib
myclobutanil



O-25
Ib
hymexazol



O-26
Ib
triadimenol



O-27
Ic
ipoconazole



O-28
Ic
ethaboxam



O-29
Ic
mefenoxam



O-30
Ic
epoxiconazole



O-31
Ic
dimethomorph



O-32
Ic
fludioxonil



O-33
Ic
metalaxyl



O-34
Ic
fludioxinil



O-35
Ic
difenoconazole



O-36
Ic
flutriafol



O-37
Ic
myclobutanil



O-38
Ic
hymexazol



O-39
Ic
triadimenol



O-40
Id
ipoconazole



O-41
Id
ethaboxam



O-42
Id
mefenoxam



O-43
Id
epoxiconazole



O-44
Id
dimethomorph



O-45
Id
fludioxonil



O-46
Id
metalaxyl



O-47
Id
fludioxinil



O-48
Id
difenoconazole



O-49
Id
flutriafol



O-50
Id
myclobutanil



O-51
Id
hymexazol



O-52
Id
triadimenol



O-53
Ie
ipoconazole



O-54
Ie
ethaboxam



O-55
Ie
mefenoxam



O-56
Ie
epoxiconazole



O-57
Ie
dimethomorph



O-58
Ie
fludioxonil



O-59
Ie
metalaxyl



O-60
Ie
fludioxinil



O-61
Ie
difenoconazole



O-62
Ie
flutriafol



O-63
Ie
myclobutanil



O-64
Ie
hymexazol



O-65
Ie
triadimenol



O-66
If
ipoconazole



O-67
If
ethaboxam



O-68
If
mefenoxam



O-69
If
epoxiconazole



O-70
If
dimethomorph



O-71
If
fludioxonil



O-72
If
metalaxyl



O-73
If
fludioxinil



O-74
If
difenoconazole



O-75
If
flutriafol



O-76
If
myclobutanil



O-77
If
hymexazol



O-78
If
triadimenol



O-79
Ig
ipoconazole



O-80
Ig
ethaboxam



O-81
Ig
mefenoxam



O-82
Ig
epoxiconazole



O-83
Ig
dimethomorph



O-84
Ig
fludioxonil



O-85
Ig
metalaxyl



O-86
Ig
fludioxinil



O-87
Ig
difenoconazole



O-88
Ig
flutriafol



O-89
Ig
myclobutanil



O-90
Ig
hymexazol



O-91
Ig
triadimenol



O-92
Ia
famoxadone



O-93
Ib
famoxadone



O-94
Ic
famoxadone



O-95
Id
famoxadone



O-96
Ie
famoxadone



O-97
If
famoxadone



O-98
Ig
famoxadone



O-99
Ia
fenamidone



O-100
Ib
fenamidone



O-101
Ic
fenamidone



O-102
Id
fenamidone



O-103
Ie
fenamidone



O-104
If
fenamidone



O-105
Ig
fenamidone



O-106
Ia
fosetly-





aluminium



O-107
Ib
Foselty-





aluminium



O-108
Ic
fosetly-





aluminium



O-109
Id
fosetly-





aluminium



O-110
Ie
fosetly-





aluminium



O-111
If
fosetly-





aluminium



O-112
Ig
fosetyl-





aluminium










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-27, O-28, O-29, O-30, O-31, O-32, O-33, O-34, O-35, O-36, O-37, O-38, O-39, O-40, O-41, O-42, O-43, O-44, O-45, O-46, O-47, O-48, O-49, O-50, O-51, O-52, O-53, O-54, O-55, O-56, O-57, O-58, O-59, O-60, O-61, O-62, O-63, O-64, O-65, O-66, O-67, O-68, 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-99, O-106, O-94, O-101, O-108, O-95, O-102, O-109, O-96, O-103, O-110, O-97, O-104, O-111, O-98, O-105, O-112.


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-40, O-41, O-42, O-43, O-44, O-45, O-46, O-47, O-48, O-49, O-50, O-51, O-52, O-53, O-54, O-55, O-56, O-57, O-58, O-59, O-60, O-61, O-62, O-63, O-64, O-65, 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-99, O-106, O-92, O-99, O-106, O-95, O-102, O-109, O-96, O-103, O-110, O-98, O-105.


The following mixtures are 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-40, O-41, O-42, O-43, O-44, O-45, O-46, O-47, O-48, O-49, O-50, O-51, O-52, O-53, O-54, O-55, O-56, O-57, O-58, O-59, O-60, O-61, O-62, O-63, O-64 and O-65, O-92, O-99, O-106, O-92, O-99, O-106, O-95, O-102, O-109, O-96, O-103.


The following mixtures are most 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-92, O-99 and O-106.


Utmost preference is given to O-11, O-92, O-99 and O-106.


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


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. alternate), 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 cassficola (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 Botryosphaeria obtuse; Elsinoe spp. on pome fruits (E. pyri), soft fruits (E. veneta: anthracnose) and vines (E. ampeline: 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; Exserohilum (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. taxa, 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. capsici), 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 trans-mitted 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 mixtures 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 goose-berries; 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, 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, 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 compounds (II), (IIb) and (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 Nmethylpyrrolidone.


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, wetters, 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.), dibutylnaphthalenesulfonic 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, alkylphenyl 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 thereof.


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, U.S.A.).


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 one compound selected from the group consisting of compounds (II), (IIb) and (III), 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 one compound selected from the group consisting of compounds (II), (IIb) and (III), 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 one compound selected from the group consisting of compounds (II), (IIb) and (III), 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 one compound selected from the group consisting of compounds (II), (IIb) and (III), 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 one compound selected from the group consisting of compounds (II), (IIb) and (III), 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 one compound selected from the group consisting of compounds (II), (IIb) and (III), 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-Soluable Powders (WP, SP, SS, WS)


75 parts by weight of compound (I), and optionally one compound selected from the group consisting of compounds (II), (IIb) and (III), 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 one compound selected from the group consisting of compounds (II), (IIb) and (III), 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 one compound selected from the group consisting of compounds (II), (IIb) and (III), 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 one compound selected from the group consisting of compounds (II), (IIb) and (III), 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 one compound selected from the group consisting of compounds (II), (IIb) and (III), 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 according to the present invention 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) and (III), wherein compound (I) and at least one compound selected from the group consisting of compounds (II), (IIb) and (III) 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), wherein compound (I) and (II) provide synergistic pesticidal effects.


In the methods according to the invention, the application rates of the novel mixtures according to the invention are from 0.3 g/ha to 2000 g/ha, preferably 5 g/ha to 2000 g/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 effect.


In the treatment of plant propagules, preferably seed, application rates of compound (I) are generally from 0.001 to 1000 g per 250 kg of plant propagules, preferably seed, preferably from 0.01 to 500 g per 100 kg, in particular from 0.1 g to 250 g per 100 kg of plant propagules, preferably seed.


In the treatment of plant propagules, preferably seed, application rates of mixture of the present invention are generally from 0.001 to 1000 g per 250 kg of plant propagules, preferably seed, preferably from 0.01 to 500 g per 100 kg, in particular from 0.1 g to 250 g per 100 kg of plant propagules, preferably seed.


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 premix or, if appropriate, not until immediately prior to use (tank mix).


If a mixture according to the present invention is used, the compound (I) and the compounds selected from the group consisting of compounds (II), (IIb) and (III) 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

Corn (Zea maydis var. M314A10) seeds were treated in a Hege 11 seed treater in a total slurry volume of 1000 ml/100 kg seed. Treatments comprised:


1) Water (control)


2) Pyraclostrobin (S8) (2.5 g a.i./100 kg);


3) Compound Ia (1 g a.i./100 kg);


4) Pyraclostrobin (S8) (2.5 g a.i./100 kg)+compound Ia (1 g a.i./100 kg).


CF Clear Binder (19 ml/100 kg seed) and color coat blue (13 ml/100 kg seed) were added to all treatments including the check. Following seed treatment, seeds were allowed to dry overnight. Seeds were planted in plastic pots (10 cm×10 cm×12 cm). Experiments were conducted using natural soil (sandy loam soil, source NC, U.S.A.). Pots were placed inside the greenhouse in a completely randomized design. Seedlings were grown at 25° C., until they reached growth stages 10 (first leaf through coleoptile, BBCH Scale). At growth stages 10, seedlings were placed in a completely randomized design in a low temperature incubator (Thermo Electron Corporation) and exposed to −5° C. during 3 hrs. At the time of cold exposure, pots were at field capacity. Percentage of seedling mortality for each treatment was recorded 3 days after the cold treatment.


The efficacy of induced cold tolerance (E) was calculated as % decrease of seedling mortality in the treatments compared to the untreated control:






E=1−a/b·100


a corresponds to the seedling mortality (%) of the treated plants and


b corresponds to the seedling mortality (%) of the untreated (control) plants


An efficacy of 0 means the seedling mortality of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means the treated plants showed a decrease in seedling mortality of 100%.


The expected efficacy of the combination 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 efficacy.






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 4







Mortality of seedlings (%) after exposure to cold temperature










Application rate
Seedling mortality (mean %)


Compound applied
(g a.i./100 kg seed)
GS 10 (3 hrs)












Water (control)
0
27 (a)


Pyraclostrobin (S8)
2.5
21 (c)


Compound Ia
1
23 (b)


Pyraclostrobin +
2.5
14 (d)


compound Ia
1





Means followed by the same letter (a), (b), (c) or (d) do not significantly differ (P = 0.05).






As can be seen in table 4, after the application of compound Ia the seedling mortality, as an indicator of plant vigor, was significantly decreased, demonstrating the applicablitiy of the compound Ia for increasing the health of plants according to the present invention.


The mixture (which corresponds to the above defined mixture M-2 in table 1) of pyraclostrobin (S8) and compound Ia provided even greater protection against cold temperatures (abiotic stress) than each component individually (tables 4 and 5). The observed protection against cold temperature (increase in cold stress tolerance) based on the combination (mixture) of pyraclostrobin (S8) and compound Ia was greater than the expected values based on the Colby equation, thus demonstrating a synergistic plant health effect of the fungicide mixture (S8+compound Ia).









TABLE 5







Efficacy (%) of cold tolerance after cold temperature exposure.












Expected
Observed efficacy



Application rate
efficacy
(%)


Compound applied
(g a.i./100 kg seed)
(%)
GS 10 (3 hrs)













Water (control)
0

0


Pyraclostrobin (S8)
2.5

22


Compound Ia
1

15


Pyraclostrobin +
2.5
33.7
48


compound Ia
1









Example 2

Soybeans were grown in 2008 in the Rondonopolis region, Mato Grosso, Brazil. The variety TMG 103 RR was planted at a seeding rate of 45 kg/ha. The trial was setup as randomized bloc design with 4 replications. Plot size was 10 m2. The soybean seed was treated prior to planting with either orysastrobin (S6), compound Ia or was left untreated (Control). Compound Ia was used as an FS formulation (100 g a.i./L) with a dose rate of 500 ml/100 kg seed (50 g a.i./100 kg). Orysastrobin (S6) was applied as an FS formulation (250 g a.i./L) with a dose rate of 300 ml per 100 kg seed (75 g a.i./100 kg). In the combination treatments of compound Ia and orysastrobin, both formulations were applied in a sequence. The formulations were applied in a total slurry volume of 600 ml/100 kg of seed.


The observed efficacy (E) of the compounds on crop emergence and crop establishment as an indicator of plant vitality and plant vigor was determined by counting the plants in a row on a distance of 5 m at 12 and 33 days after planting.


The efficacy of the fungicidal treatments was calculated as the increase in the number of plants in the treatments compared to the control (%):






E=(a/b−1)·100


a corresponds to the number in the treated and


b corresponds to the number of plants in the untreated (control) plots


The expected efficacy of the combination of the active compounds was estimated using Colby's formula (see example 1 above)


As can be seen in table 6, after the application of compound Ia the number of plants, as an indicator of plant vigor, was significantly increased, demonstrating the applicablitiy of the compound Ia for increasing the health of plants according to the present invention.


The combination (mixture) of orysastrobin and compound Ia (which corresponds to the above defined mixture M-1 in table 1) provided even greater improvement of crop emergence (number of plants 12 days after planting) and crop establishment (number of plants 33 days after planting) than each component individually (table 6). The observed efficacy for crop emergence, as an indicator of plant vigor, for the mixture of orysastrobin and compound Ia was greater than expected values based on the Colby equation, thus demonstrating a synergistic effect of the fungicide mixture according to the present invention (table 7).









TABLE 6







Emergance and crop establishement determined


as plant population density











Application
Number of plants
Number of plants



rate
per 5 m distance
per 5 m distance



(g a.i./
(mean)
(mean)



100 kg
12 days after
33 days after


Fungicide treatment
seed)
planting
planting















(Control (untreated)
0
35
(c)
34
(d)


Orysastrobin (S6)
75
55
(ab)
52
(ab)


Compound Ia
50
49
(b)
45
(bc)


Orysastrobin +
75
62
(a)
58
(a)


compound Ia
50





Means followed by the same letter (a), (b), (c) or (d) do not significantly differ (P = 0.05, Tukey's HSD)













TABLE 7







Efficacy of the treatments













Application
Expected
Observed
Expected
Observed



rate
efficacy
efficacy
efficacy
efficacy


Fungicide
(g a.i./100 kg
(%)
(%)
(%)
(%)










treatment
seed)
12 days after planting
33 days after planting















Control
0

0

0


(untreated)


Orysastrobin
75

57.1

52.9


(S6)


Compound Ia
50

40.0

32.3


Orysastrobin +
75
74.3
77.1
68.1
70.6


compound Ia
50








Claims
  • 1-18. (canceled)
  • 19. A method for improving the plant health of at least one plant variety, which method comprises treating the plant propagules with an amide having the formula I (compound I)
  • 20. The method as claimed in claim 19, 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).
  • 21. The method as claimed in claim 19, 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).
  • 22. The method as claimed in claim 19, 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-(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) 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 19, 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 compound (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, trifloxystrobin, enestroburin, pyribencarb, (E)-2-[2-(2,5-Dimethylphenoxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2-{2-[(E)-3-(2,6-Dichloro-phenyl)-1-methyl-prop-2-en-(E)-ylideneaminooxymethyl]-phenyl}-2-[(E)-methoxyimino]-N-methyl-acetamide;(ii) an azole selected from the group consisting of cyproconazole, difenoconazole, epoxiconazole, flusilazole, fluquinconazole, flutriafol, ipconazole, metconazole, propiconazole, prothioconazole, tebuconazole, cyazofamid, prochloraz, ethaboxam, triazoxide, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1-(4-chloro-phenyl)-2-([1,2,4]triazol-1-yl)-cycloheptanol, azaconazole, bitertanol, bromuconazole, cifenoconazole, diniconazole, diniconazole-M, fenbuconazole, hexaconazole, imibenconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, simeconazole, imazalil, pefurazoate, triflumizol, etridiazole, hymexazole and 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;(iii) and additional compound selected from the group consisting of metalaxyl, metalaxyl-M (mefenoxam), silthiofam, pyrimethanil, dimethomorph, iprodione, fludioxonil, thiram, thiophanate-methyl, carbendazim, fosetyl-aluminium, phosphorous acid and its salts, metiram, mancozeb, famoxadone and fenamidone.
  • 24. The method as claimed in claim 23, wherein compound (II) is selected from the group consisting of orysastrobin, pyraclostrobin, trifloxystrobin, azoxystrobin, difenoconazole, epoxiconazole, fluquinconazole, flutriafol, metconazole, prothioconazole, tebuconazole, triticonazole, prochloraz, metalaxyl, metalaxyl-M (mefenoxam), silthiofam, pyrimethanil, dimethomorph, fludioxonil, thiram, thiophanate-methyl, fosetyl-aluminium, phosphorous acid and its salts.
  • 25. The method as claimed in claim 23, wherein compound (II) is selected from the group consisting of orysastrobin, pyraclostrobin, azoxystrobin and trifloxystrobin.
  • 26. The method as claimed in claim 19, additionally comprising a further fungicide III (compound IIb), selected from the group consisting of (ii) an azole selected from the group consisting of cyproconazole, difenoconazole, epoxiconazole, flusilazole, fluquinconazole, flutriafol, ipconazole, metconazole, propiconazole, prothioconazole, tebuconazole, cyazofamid, prochloraz, ethaboxam, triazoxide, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1-(4-chloro-phenyl)-2-([1,2,4]triazol-1-yl)-cycloheptanol, azaconazole, bitertanol, bromuconazole, cifenoconazole, diniconazole, diniconazole-M, fenbuconazole, hexaconazole, imibenconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, simeconazole, imazalil, pefurazoate, triflumizol, etridiazole, hymexazole and 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;(iii) an additional compound selected from the group consisting of metalaxyl, metalaxyl-M (mefenoxam), silthiofam, pyrimethanil, dimethomorph, iprodione, fludioxonil, thiram, thiophanate-methyl, carbendazim, fosetyl-aluminium, phosphorous acid and its salts, metiram, mancozeb, famoxadone and fenamidone.
  • 27. The method as claimed in claim 19, additionally comprising an insecticide (compound III), selected from the group consisting of chloranthraniliprole, fipronil and ethiprole.
  • 28. The method as claimed in claim 19, wherein the plant is selected from agricultural plants, silvicultural plants and ornamental plants.
  • 29. The method according to claim 19, comprising applying to the plant propagules an amount of from 0.001 g to 1000 g per 250 kg seed of the amide compound (I).
  • 30. The method as claimed in 23, 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) and (III) are applied simultaneously, either as a mixture or separately, or subsequently to the plant propagules.
  • 31. A fungicidal mixture comprising in synergistically effective amounts (I) an amide having the formula I (compound I)
  • 32. A method for controlling pests, wherein the pest, their habitat, breeding grounds, their locus or the plants to be protected against pest attack, the soil or seed are treated with an effective amount of a mixture as defined in claim 32.
Priority Claims (2)
Number Date Country Kind
PCT/EP2008/051375 Feb 2008 EP regional
08161623.7 Aug 2008 EP regional
PCT Information
Filing Document Filing Date Country Kind 371c Date
PCT/EP09/51255 2/4/2009 WO 00 12/8/2010