Patent Grant
9288988
The present invention relates to novel active compound combinations comprising firstly known carboxamides and secondly further known fungicidally active compounds, which novel active compound combinations are highly suitable for controlling unwanted phytopathogenic fungi.
It is already known that certain carboxamides have fungicidal properties. Thus, for example, N-(3′,4′-di -chloro-5-fluoro-1,1′-biphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide is known from DE-A 102 15 292, 3-(trifluoromethyl)-N-{3′-fluoro-4′-[(E)-(methoxyimino)methyl]-1,1′-biphenyl-2-yl}-1-methyl-1H-pyrazole-4-carboxamide is known from WO 02/08197 and N-(3′,4′-dichloro-1,1′-biphenyl-2-yl)-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide is known WO 00/14701. The activity of these compounds is good; however, at low application rates it is sometimes unsatisfactory. Furthermore, it is already known that numerous triazole derivatives, aniline derivatives, dicarboximides and other heterocycles can be used for controlling fungi (cf. EP-A 0 040 345, DE-A 22 01 063, DE-A 23 24 010, Pesticide Manual, 9th Edition (1991), pages 249 and 827, EP-A 0 382 375 and EP-A 0 515 901). However, the action of these compounds is likewise not always sufficient at low application rates. Furthermore, it is already known that 1-(3,5-dimethylisoxazole-4-sulphonyl)-2-chloro-6,6-difluoro-[1,3]-dioxolo-[4,5f]-benzimidazole has fungicidal properties (cf. WO 97/06171). Finally, it is also known that substituted halopyrimidines have fungicidal properties (cf. DE-A1-196 46 407, EP-B 0 712 396).
The present invention now provides novel active compound combinations having very good fungicidal properties and comprising a carboxamide of the general formula (I) (group 1)
in which
in which
in which
in which R22 represents hydrogen or methyl;
Group (5) Valinamides Selected from
in which
in which
in which
in which
in which
in which
in which
in which
in which
in which
in which
Surprisingly, the fungicidal action of the active compound combinations according to the invention is considerably better than the sum of the activities of the individual active compounds. Thus, an unforeseeable true synergistic effect is present, and not just an addition of actions.
The formula (I) provides a general definition of the compounds of group (1).
Preference is given to carboxamides of the formula (I) in which
Particular preference is given to carboxamides of the formula (I) in which
Very particular preference is given to carboxamides of the formula (I) in which
Very particular preference is given to using, in mixtures, compounds of the formula (Ia)
in which R1, R2, R3, R6, R7 and R8 are as defined above.
Very particular preference is given to using, in mixtures, compounds of the formula (Ib)
in which R1, R2, R3, R9 and R10 are as defined above.
The formula (I) embraces in particular the following preferred mixing partners of group (1):
Emphasis is given to active compound combinations according to the invention which, in addition to carboxamide (1-1) N-(3′,4′-dichloro-5-fluoro-1,1′-biphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H -pyrazole-4-carboxamide (group 1) comprise one or more, preferably one, mixing partner of groups (2) to (23).
Emphasis is given to active compound combinations according to the invention which, in addition to carboxamide (1-7) N-(4′-bromo-1,1′-biphenyl-2-yl)-4-(difluoromethyl)-2-methyl-1,3-thiazole-5-carboxamide (group 1) comprise one or more, preferably one, mixing partner of groups (2) to (23).
Emphasis is given to active compound combinations according to the invention which, in addition to carboxamide (1-8) 4-(difluoromethyl)-2-methyl-N-[4′-(trifluoromethyl)-1,1′-biphenyl-2-yl]-1,3-thiazole-5-carboxamide (group 1) comprise one or more, preferably one, mixing partner of groups (2) to (23).
Emphasis is given to active compound combinations according to the invention which, in addition to carboxamide (1-9) N-(4′-chloro-3′-fluoro-1,1′-biphenyl-2-yl)-4-(difluoromethyl)-2-methyl-1,3-thiazole-5-carboxamide (group 1) comprise one or more, preferably one, mixing partner of groups (2) to (23).
The formula (II) embraces the following preferred mixing partners of group (2):
The formula (III) embraces the following preferred mixing partners of group (3):
The formula (IV) embraces the following preferred mixing partners of group (4):
Preferred mixing partners of group (5) are
The formula (V) embraces the following preferred mixing partners of group (6):
Preferred mixing partners of group (7) are
The formula (VI) embraces the following preferred mixing partners of group (8):
The formula (VII) embraces the following preferred mixing partners of group (9):
The formula (VIII) embraces the following preferred mixing partners of group (10):
The formula (IX) embraces the following preferred mixing partners of group (11):
Preferred mixing partners of group (12) are
Preferred mixing partners of group (13) are
Preferred mixing partners of the group (14) are
The formula (X) embraces the following preferred mixing partners of group (15):
The formula (XI) embraces the following preferred mixing partners of group (16):
Preferred mixing partners of group (17) are
The formula (XII) embraces the following preferred mixing partners of group (18) which are known from WO 96/23793 and can in each case be present as E or Z isomers. Accordingly, compounds of the formula (XII) can be present as a mixture of different isomers or else in the form of a single isomer. Preference is given to compounds of the formula (XII) in the form of their E isomers:
Preferred mixing partners of group (19) are
Preferred mixing partners of group (20) are
Preferred mixing partners of group (21) are
Preferred mixing partners of group (22) are
Preferred mixing partners of group (23) are
Compound (6-7), carpropamid, has three asymmetrically substituted carbon atoms. Accordingly, compound (6-7) can be present as a mixture of different isomers or else in the form of a single component. Particular preference is given to the compounds
(1S,3R)-2,2-dichloro-N-[(1R)-1-(4-chlorophenyl)ethyl]-1-ethyl-3-methylcyclopropanecarboxamide of the formula
and
Particularly preferred mixing partners are the following active compounds:
Very particularly preferred mixing partners are the following active compounds:
Preferred active compound combinations consisting of two groups of active compounds and comprising in each case at least one carboxamide of the formula (I) (group 1) and at least one active compound from the stated group (2) to (23) are described below. These combinations are the active compound combinations A to T.
Among the preferred active compound combinations A to T, emphasis is given to those comprising a carboxamide of the formula (I) (group 1)
in which R1, R2, R3 and A are as defined above.
Particular preference is given to active compound combinations A to T comprising a carboxamide of the formula (I) (group 1)
in which
Very particular preference is given to active compound combinations A to T in which the carboxamide of the formula (I) (group 1) is selected from the list below:
Especially preferred are active compound combinations A to T in which the carboxamide of the formula (I) (group 1) is selected from the list below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations A also comprise a strobilurin of the formula (II) (group 2)
in which A1, L and R14 are as defined above.
Particular preference is given to active compound combinations A in which the strobilurin of the formula (II) (group 2) is selected from the list below:
Very particular preference is given to active compound combinations A in which the strobilurin of the formula (II) (group 2) is selected from the list below:
Emphasis is given to the active compound combinations A listed in Table 1 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations B also comprise a triazole of the formula (III) (group 3)
in which Q, m, R16, R17, A4, A5, R18 and R19 are as defined above.
Preference is given to active compound combinations B in which the triazole of the formula (III) (group 3) is selected from the list below:
Particular preference is given to active compound combinations B in which the triazole of the formula (III) (group 3) is selected from the list below:
Emphasis is given to the active compound combinations B listed in Table 2 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations C also comprise a sulphenamide of the formula (IV) (group 4)
in which R22 is as defined above.
Preference is given to active compound combinations C in which the sulphenamide of the formula (IV) (group 4) is selected from the following list:
Emphasis is given to the active compound combinations C listed in Table 3 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations D also comprise a valinamide (group 5) selected from
Preference is given to active compound combinations D in which the valinamide (group 5) is selected from the following list:
Emphasis is given to the active compound combinations D listed in Table 4 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations E also comprise a carboxamide of the formula (V) (group 6)
in which X, Y and Z are as defined above.
Preference is given to active compound combinations E in which the carboxamide of the formula (V) (group 6) is selected from the list below:
Particular preference is given to active compound combinations E in which the carboxamide of the formula (V) (group 6) is selected from the list below:
Very particular preference is given to active compound combinations E in which the carboxamide of the formula (V) (group 6) is selected from the list below:
Emphasis is given to the active compound combinations E listed in Table 5 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations F also comprise a dithiocarbamate (group 7) selected from
Preference is given to active compound combinations F in which the dithiocarbamate (group 7) is selected from the following list:
Particular preference is given to active compound combinations F in which the dithiocarbamate (group 7) is selected from the following list:
Emphasis is given to the active compound combinations F listed in Table 6 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations G also comprise an acylalanine of the formula (VI) (group 8)
in which * and R26 are as defined above.
Preference is given to active compound combinations G in which the acylalanine of the formula (VI) (group 8) is selected from the following list:
Particular preference is given to active compound combinations G in which the acylalanine of the formula (VI) (group 8) is selected from the following list:
Emphasis is given to the active compound combinations G listed in Table 7 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations H also comprise an anilinopyrimidine (group 9) selected from
Emphasis is given to the active compound combinations H listed in Table 8 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations I also comprise a benzimidazole of the formula (VIII) (group 10)
in which R28, R29, R30 and R31 are as defined above.
Preference is given to active compound combinations I in which the benzimidazole of the formula (VIII) (group 10) is selected form the following list:
Particular preference is given to active compound combinations I in which the benzimidazole of the formula (VIII) (group 10) is:
Emphasis is given to the active compound combinations I listed in Table 9 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations J also comprise a carbamate (group 11) of the formula (IX)
in which R32 and R33 are as defined above.
Preference is given to active compound combinations J in which the carbamate (group 11) is selected from the following list:
Emphasis is given to the active compound combinations J listed in Table 10 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations K also comprise a dicarboximide (group 12) selected from
Preference is given to active compound combinations K in which the dicarboximide (group 12) is selected from the following list:
Emphasis is given to the active compound combinations K listed in Table 11 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations L also comprise a guanidine (group 13) selected from
Preference is given to active compound combinations L in which the guanidine (group 13) is selected from the following list:
Emphasis is given to the active compound combinations L listed in Table 12 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations M also comprise an imidazole (group 14) selected from
Preference is given to active compound combinations M in which the imidazole (group 14) is selected from the following list:
Emphasis is given to the active compound combinations M listed in Table 13 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations N also comprise a morpholine (group 15) of the formula (X)
in which R34, R35 and R36 are as defined above.
Preference is given to active compound combinations N in which the morpholine (group 15) of the formula (X) is selected from the following list:
Particular preference is given to active compound combinations N in which the morpholine (group 15) of the formula (X) is selected from the following list:
Emphasis is given to the active compound combinations N listed in Table 14 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations O also comprise a pyrrole (group 16) of the formula (XI)
in which R37, R38 and R39 are as defined above.
Preference is given to active compound combinations O in which the pyrrole (group 16) of the formula (XI) is selected from the following list:
Particular preference is given to active compound combinations O in which the pyrrole (group 16) of the formula (XI) is selected from the following list:
Emphasis is given to the active compound combinations O listed in Table 15 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations P also comprise a phosphonate (group 17) selected from
Emphasis is given to the active compound combinations P listed in Table 16 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations Q also comprise a fungicide (group 19) selected from
Preference is given to active compound combinations Q in which the fungicide (group 19) is selected from the following list:
Particular preference is given to active compound combinations Q in which the fungicide (group 19) is selected from the following list:
Emphasis is given to the active compound combinations Q listed in Table 17 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations R also comprise a (thio)urea derivative (group 20) selected from
Preference is given to active compound combinations R in which the (thio)urea derivative (group 20) is selected from the following list:
Emphasis is given to the active compound combinations R listed in Table 18 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations S also comprise a triazolopyrimidine (group 22) of the formula (XIV)
in which R43, R44, R45, R46, R47, R48, R49 and R50 are as defined above.
Preference is given to active compound combinations S in which the triazolopyrimidine (group 22) of the formula (XIV) is selected from the list below:
Particular preference is given to active compound combinations S in which the triazolopyrimidine (group 22) of the formula (XIV) is selected from the list below:
Emphasis is given to the active compound combinations S listed in Table 19 below:
In addition to a carboxamide of the formula (I) (group 1), the active compound combinations T also comprise an iodochromone (group 23) of the formula (XV)
in which R51 and R52 are as defined above.
Preference is given to active compound combinations T in which the iodochromone (group 23) of the formula (XV) is selected from the following list:
Particular preference is given to active compound combinations T in which the iodochromone (group 23) of the formula (XV) is selected from the following list:
Emphasis is given to the active compound combinations T listed in Table 20 below:
In addition to an active compound of the formula (I), the active compound combinations according to the invention comprise at least one active compound from the compounds of groups (2) to (23). In addition, they may also comprise further fungicidally active additives.
If the active compounds in the active compound combinations according to the invention are present in certain weight ratios, the synergistic effect is particularly pronounced. However, the weight ratios of the active compounds in the active compound combinations can be varied within a relatively wide range. In general, the combinations according to the invention comprise active compounds of the formula (I) and a mixing partner from one of the groups (2) to (23) in the mixing ratios listed in an exemplary manner in Table 21 below.
The mixing ratios are based on ratios by weight. The ratio is to be understood as active compound of the formula (I): mixing partner.
In each case, the mixing ratio is to be chosen such that a synergistic mixture is obtained. The mixing ratios between the compound of the formula (I) and a compound of one of the groups (2) to (23) may also vary between the individual compounds of a group.
The active compound combinations according to the invention have very good fungicidal properties and are suitable for controlling phytopathogenic fungi, such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes, etc.
The active compound combinations according to the invention are particularly suitable for controlling Erysiphe graminis, Pyrenophora teres and Leptosphaeria nodorum.
Some pathogens causing fungal diseases which come under the generic names listed above may be mentioned by way of example, but not by way of limitation:
Pythium species, such as, for example, Pythium ultimum; Phytophthora species, such as, for example, Phytophthora infestans; Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis ; Plasmopara species, such as, for example, Plasmopara viticola; Bremia species, such as, for example, Bremia lactucae; Peronospora species, such as, for example, Peronospora pisi or P. brassicae; Erysiphe species, such as, for example, Erysiphe graminis; Sphaerotheca species, such as, for example, Sphaerotheca fuliginea; Podosphaera species, such as, for example, Podosphaera leucotricha; Venturia species, such as, for example, Venturia inaequalis; Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidia form: Drechslera, syn: Helminthosporium); Cochliobolus species, such as, for example, Cochliobolus sativus (conidia form: Drechslera, syn: Helminthosporium); Uromyces species, such as, for example, Uromyces appendiculatus; Puccinia species, such as, for example, Puccinia recondita; Sclerotinia species, such as, for example, Sclerotinia sclerotiorum; Tilletia species, such as, for example, Tilletia caries; Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae; Pellicularia species, such as, for example, Pellicularia sasakii; Pyricularia species, such as, for example, Pyricularia oryzae; Fusarium species, such as, for example, Fusarium culmorum; Botrytis species, such as, for example, Botrytis cinerea; Septoria species, such as, for example, Septoria nodorum; Leptosphaeria species, such as, for example, Leptosphaeria nodorum; Cercospora species, such as, for example, Cercospora canescens; Alternaria species, such as, for example, Alternaria brassicae; Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides, Rhizoctonia species, such as, for example, Rhizoctonia solani.
The fact that the active compound combinations are well tolerated by plants at the concentrations required for controlling plant diseases permits a treatment of entire plants (above-ground parts of plants and roots), of propagation stock and seed, and of the soil. The active compound combinations according to the invention can be used for foliar application or else as seed dressings.
The active compound combinations according to the invention are also suitable for increasing the yield of crops. In addition, they show reduced toxicity and are well tolerated by plants.
According to the invention, it is possible to treat all plants and parts of plants. Plants are to be understood here as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including plant cultivars which can or cannot be protected by plant breeders' certificates. Parts of plants are to be understood as meaning all above-ground and below-ground parts and organs of plants, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stems, trunks, flowers, fruit bodies, fruits and seeds and also roots, tubers and rhizomes. Parts of plants also include harvested material and vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.
The treatment of the plants and parts of plants according to the invention with the active compounds is carried out directly or by action on their environment, habitat or storage area according to customary treatment methods, for example by dipping, spraying, evaporating, atomizing, broadcasting, brushing-on and, in the case of propagation material, in particular in the case of seeds, furthermore by one- or multilayer coating.
As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding, such as crossing or protoplast fusion, and parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering, if appropriate in combination with conventional methods (genetically modified organisms), and parts thereof, are treated. The term “parts” or “parts of plants” or “plant parts” has been explained above.
Particularly preferably, plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention.
Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive (“synergistic”) effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible which exceed the effects which were actually to be expected.
The transgenic plants or plant cultivars (i.e. those obtained by genetic engineering) which are preferably to be treated according to the invention include all plants which, in the genetic modification, received genetic material which imparted particularly advantageous useful properties (“traits”) to these plants. Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, better quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products. Further and particularly emphasized examples of such properties are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, cotton, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton and oilseed rape. Traits that are emphasized in particular are increased defence of the plants against insects, by toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof) (hereinbelow referred to as “Bt plants”). Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosates or phosphinotricin (for example the “PAT” gene). The genes which impart the desired traits in question can also be present in combinations with one another in the transgenic plants. Examples of “Bt plants” which may be mentioned are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD® (for example maize, cotton, soya bean), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucoton® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosates, for example maize, cotton, soya bean), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned also include the varieties sold under the name Clearfield® (for example maize). Of course, these statements also apply to plant cultivars which have these genetic traits or genetic traits still to be developed, and which will be developed and/or marketed in the future.
Depending on their particular physical and/or chemical properties, the active compound combinations according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, dusts, foams, pastes, soluble powders, granules, aerosols, suspoemulsion concentrates, natural and synthetic substances impregnated with active compound and microencapsulations in polymeric substances and in coating compositions for seeds, and ULV cool and warm fogging formulations.
These formulations are produced in a known manner, for example by mixing the active compounds or active compound combinations with extenders, that is liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants, and/or foam formers.
If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. Essentially, suitable liquid solvents are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulphoxide, or else water.
Liquefied gaseous extenders or carriers are to be understood as meaning liquids which are gaseous at standard temperature and under atmospheric pressure, for example aerosol propellants such as butane, propane, nitrogen and carbon dioxide.
Suitable solid carriers are: for example ammonium salts, ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as finely divided silica, alumina and silicates. Suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks. Suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates. Suitable dispersants are: for example lignosulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other possible additives are mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The active compound content of the use forms prepared from the commercial formulations may be varied within wide ranges. The concentration of active compound of the use forms for controlling animal pests, such as insects and acarids, may be from 0.0000001 to 95% by weight of active compound and is preferably from 0.0001 to 1% by weight. Application is in a customary manner adapted to the use forms.
The formulations for controlling unwanted phytopathogenic fungi generally comprise between 0.1 and 95% by weight of active compounds, preferably between 0.5 and 90%.
The active compound combinations according to the invention can be used as such, in the form of their formulations or as the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders, soluble powders, dusts and granules. They are used in a customary manner, for example by watering (drenching), drip irrigation, spraying, atomizing, broadcasting, dusting, foaming, spreading-on, and as a powder for dry seed treatment, a solution for seed treatment, a water-soluble powder for seed treatment, a water-soluble powder for slurry treatment, or by encrusting.
The active compound combinations according to the invention can, in commercial formulations and in the use forms prepared from these formulations, be present as a mixture with other active compounds, such as insecticides, attractants, sterilants, bactericides, acaricides, nematicides, fungicides, growth regulators or herbicides.
When using the active compound combinations according to the invention, the application rates can be varied within a relatively wide range, depending on the kind of application. In the treatment of parts of plants, the application rates of active compound combinations are generally between 0.1 and 10 000 g/ha, preferably between 10 and 1000 g/ha. In the treatment of seeds, the application rates of active compound combination are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In the treatment of the soil, the application rates of active compound combination are generally between 0.1 and 10 000 g/ha, preferably between 1 and 5000 g/ha.
The active compound combinations can be used as such, in the form of concentrates or in the form of generally customary formulations, such as powders, granules, solutions, suspensions, emulsions or pastes.
The formulations mentioned can be prepared in a manner known per se, for example by mixing the active compounds with at least one solvent or diluent, emulsifier, dispersant and/or binder or fixative, water repellent, if desired desiccants and UV stabilizers, and, if desired, colorants and pigments and other processing auxiliaries.
The good fungicidal action of the active compound combinations according to the invention is demonstrated by the examples below. While the individual active compounds show weaknesses in their fungicidal action, the combinations show an action which exceeds a simple sum of actions.
A synergistic effect in fungicides is always present when the fungicidal action of the active compound combinations exceeds the total of the action of the active compounds when applied individually.
The expected fungicidal action for a given combination of two active compounds can be calculated as follows, according to S. R. Colby (“Calculating Synergistic and Antagonistic Responses of Herbicide Combinations”, Weeds 1967, 15, 20-22):
If
Here, the efficacy is determined in %. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
If the actual fungicidal action exceeds the calculated value, the action of the combination is superadditive, i.e. a synergistic effect is present. In this case, the actually observed efficacy must exceed the value calculated using the above formula for the expected efficacy (E).
The invention is illustrated by the examples below. However, the invention is not limited to the examples.
In the use examples shown below, in each case mixtures of the carboxamides of the general formula (I) (group 1) below with the mixing partners given in each case (structural formulae see above) were tested.
Carboxamides of the formula (I) used:
Pyrenophora teres Test (Barley)/Curative
To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for curative activity, young plants are sprayed with a conidia suspension of Pyrenophora teres. The plants remain in an incubation cabinet at 20° C. and 100% relative atmospheric humidity for 48 hours. The plants are then sprayed with the preparation of active compound at the stated application rate.
The plants are placed in a greenhouse at a temperature of about 20° C. and a relative atmospheric humidity of about 80%.
Evaluation is carried out 12 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.
Erysiphe Test (Barley)/Protective
To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are dusted with spores of Erysiphe graminis f. sp. hordei.
Plants are placed in a greenhouse at a temperature of about 20° C. and a relative atmospheric humidity of about 80% to promote the development of mildew pustules.
Evaluation is carried out 6 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.
Puccinia Test (Wheat)/Curative
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for curative activity, young plants are sprayed with a conidia suspension of Puccinia recondita. The plants remain in an incubation cabinet at 20° C. and 100% relative atmospheric humidity for 48 hours.
The plants are then sprayed with the preparation of active compound at the stated application rate.
The plants are placed in a greenhouse at a temperature of about 20° C. and a relative atmospheric humidity of about 80% to promote the development of rust pustules.
Evaluation is carried out 8 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.
Gibberella zeae Test (Barley)/Curative
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for curative activity, young plants are sprayed with a conidia suspension of Gibberella zeae. The plants remain in an incubation cabinet at 22° C. and 100% relative atmospheric humidity for 24 hours. The plants are then sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants remain in a greenhouse under translucent incubation hoods at a temperature of about 22° C. and a relative atmospheric humidity of about 100%.
Evaluation is carried out 6 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
The table below shows clearly that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.
Sphaerotheca fuliginea Test (Cucumber)/Protective
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Sphaerotheca fuliginea.
The plants are then placed in a greenhouse at about 23° C. and a relative atmospheric humidity of about 70%.
Evaluation is carried out 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.
Alternaria solani Test (Tomato)/Protective
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Alternaria solani.
The plants are then placed in an incubation cabinet at about 20° C. and 100% relative atmospheric humidity.
Evaluation is carried out 3 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.
Phytophthora infestans Test (Tomato)/Protective
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Phytophthora infestans. The plants are then placed in an incubation cabinet at about 20° C. and 100% relative atmospheric humidity.
Evaluation is carried out 3 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.
Botrytis cinerea Test (Bean)/Protective
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, 2 small pieces of agar colonized by Botrytis cinerea are placed onto each leaf. The inoculated plants are placed in a darkened chamber at about 20° C. and 100% relative atmospheric humidity.
The size of the infected areas on the leaves is evaluated 2 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.
Alternaria mali Test (In Vitro)/Microtitre Plates
The microtest is carried out in microtitre plates using potato dextrose broth (PDB) as liquid test medium. The active compounds are used as technical grade a.i., dissolved in acetone.
For inoculation, a spore suspension of Alternaria mali is used. After 5 days of incubation in the dark and with shaking (10 Hz), for each filled cavity of the microtitre plates, the light transmittance is determined with the aid of a spectrophotometer.
0% means an efficacy which corresponds to the growth in the controls, whereas an efficacy of 100% means that no fungal growth is observed.
The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.
Rhizoctonia solani Test (In Vitro)/Microtitre Plates
The microtest is carried out in microtitre plates using potato dextrose broth (PDB) as liquid test medium. The active compounds are used as technical grade a.i., dissolved in acetone.
For inoculation, a mycelium suspension of Rhizoctonia solani is used. After 5 days of incubation in the dark and with shaking (10 Hz), for each filled cavity of the microtitre plates, the light transmittance is determined with the aid of a spectrophotometer.
0% means an efficacy which corresponds to the growth in the controls, whereas an efficacy of 100% means that no fungal growth is observed.
The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.
Septoria tritici Test (In Vitro)/Microtitre Plates
The microtest is carried out in microtitre plates using potato dextrose broth (PDB) as liquid test medium. The active compounds are used as technical grade a.i., dissolved in acetone.
For inoculation, a spore suspension of Septoria tritici is used. After 7 days of incubation in the dark and with shaking (10 Hz), for each filled cavity of the microtitre plates, the light transmittance is determined with the aid of a spectrophotometer.
0% means an efficacy which corresponds to the growth in the controls, whereas an efficacy of 100% means that no fungal growth is observed.
The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.
Sphaerotheca fuliginea Test (Gherkin)/Protective
To produce a suitable preparation of active compound, the substance to be tested is homogenized in a mixture of acetone/Tween/water. The suspension is then diluted with water to the desired concentration.
Gherkin plants (Vert petit de Paris cultivar) are sown in starter cups on 50/50 peat soil/pozzolana soil substrate and cultivated at 20° C./23° C. At the 2-leaf stage, the plants are sprayed with the preparation of active compound at the stated application rate.
To test for protective activity, the plants are, after 24 h, sprayed with an aqueous spore suspension of Sphaerotheca fuliginea (100 000 spores/ml). The plants then remain at 20° C./25° C. and 60/70% relative atmospheric humidity.
Evaluation is carried out 21 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
The table below shows clearly that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.
| Number | Date | Country | Kind |
|---|---|---|---|
| 103 47 090 | Oct 2003 | DE | national |
| Number | Name | Date | Kind |
|---|---|---|---|
| 1972961 | Tisdale et al. | Sep 1934 | A |
| 2504404 | Flenner | Apr 1950 | A |
| 2553770 | Kittleson et al. | May 1951 | A |
| 2588428 | Stewart et al. | Mar 1952 | A |
| 3010968 | Loux | Nov 1961 | A |
| 3178447 | Kohn | Apr 1965 | A |
| 3206468 | Grenda | Sep 1965 | A |
| 3248400 | Flieg et al. | Apr 1966 | A |
| 3249499 | von Schmeling et al. | May 1966 | A |
| 3285929 | Klauke et al. | Nov 1966 | A |
| 3290353 | Battershell et al. | Dec 1966 | A |
| 3379610 | Lyon et al. | Apr 1968 | A |
| 3499951 | Schrader et al. | Mar 1970 | A |
| 3513241 | Hoyer et al. | May 1970 | A |
| 3546813 | Frohberger et al. | Dec 1970 | A |
| 3629428 | Seki et al. | Dec 1971 | A |
| 3631176 | Klopping | Dec 1971 | A |
| 3745170 | Fujinami et al. | Jul 1973 | A |
| 3745187 | Noguchi et al. | Jul 1973 | A |
| 3755350 | Sauli | Aug 1973 | A |
| 3856814 | Taninaka et al. | Dec 1974 | A |
| 3912752 | Meiser et al. | Oct 1975 | A |
| 3952002 | Kramer et al. | Apr 1976 | A |
| 3966750 | Mangold et al. | Jun 1976 | A |
| 3991071 | Brookes et al. | Nov 1976 | A |
| 4046911 | Hubele | Sep 1977 | A |
| 4064261 | Paget | Dec 1977 | A |
| 4068077 | Goetz et al. | Jan 1978 | A |
| 4079062 | Van Reet et al. | Mar 1978 | A |
| 4127673 | Yamada et al. | Nov 1978 | A |
| 4139616 | Ducret et al. | Feb 1979 | A |
| 4239760 | Sasse et al. | Dec 1980 | A |
| 4291049 | Bosone et al. | Sep 1981 | A |
| 4294850 | Hubele | Oct 1981 | A |
| 4432989 | Spencer | Feb 1984 | A |
| 4532341 | Holmwood et al. | Jul 1985 | A |
| 4598085 | Heeres et al. | Jul 1986 | A |
| 4664696 | Schaub | May 1987 | A |
| 4705800 | Nyfeler et al. | Nov 1987 | A |
| 4829085 | Wenderoth et al. | May 1989 | A |
| 4851405 | Krämer et al. | Jul 1989 | A |
| 4906652 | Karbach et al. | Mar 1990 | A |
| 4910200 | Curtze et al. | Mar 1990 | A |
| 4931560 | Hubele | Jun 1990 | A |
| 4931581 | Schurter et al. | Jun 1990 | A |
| 4988734 | Kraatz et al. | Jan 1991 | A |
| 5059623 | Krüger et al. | Oct 1991 | A |
| 5087635 | Shaber | Feb 1992 | A |
| 5112849 | Staub et al. | May 1992 | A |
| 5256683 | Hutt et al. | Oct 1993 | A |
| 5266585 | Hubele et al. | Nov 1993 | A |
| 5330995 | Eicken et al. | Jul 1994 | A |
| 5334607 | Sauter et al. | Aug 1994 | A |
| 5438070 | Eicken et al. | Aug 1995 | A |
| 5453531 | Seitz et al. | Sep 1995 | A |
| 5593996 | Pees et al. | Jan 1997 | A |
| 5599828 | Zeun et al. | Feb 1997 | A |
| 5650519 | Lacroix et al. | Jul 1997 | A |
| 5679676 | Krüger et al. | Oct 1997 | A |
| 5789428 | Shibata et al. | Aug 1998 | A |
| 5789430 | Jautelat et al. | Aug 1998 | A |
| 5859039 | Jautelat et al. | Jan 1999 | A |
| 5869517 | Müller et al. | Feb 1999 | A |
| 5948932 | Grote et al. | Sep 1999 | A |
| 5986135 | Pfrengle et al. | Nov 1999 | A |
| 5998450 | Eicken et al. | Dec 1999 | A |
| 5998455 | Knauf-Beiter et al. | Dec 1999 | A |
| 6020354 | Assmann et al. | Feb 2000 | A |
| 6103717 | Heinemann et al. | Aug 2000 | A |
| 6114362 | Dutzmann et al. | Sep 2000 | A |
| 6130224 | Eicken et al. | Oct 2000 | A |
| 6143745 | Eicken et al. | Nov 2000 | A |
| 6159992 | Müller et al. | Dec 2000 | A |
| 6169056 | Bayer et al. | Jan 2001 | B1 |
| 6191128 | Stenzel et al. | Feb 2001 | B1 |
| 6235743 | Gayer et al. | May 2001 | B1 |
| 6277791 | Assmann et al. | Aug 2001 | B1 |
| 6297263 | Dutzmann et al. | Oct 2001 | B1 |
| 6306414 | Koike | Oct 2001 | B1 |
| 6306850 | Dutzmann et al. | Oct 2001 | B1 |
| 6346538 | Schelberger et al. | Feb 2002 | B1 |
| 6350765 | Schelberger et al. | Feb 2002 | B1 |
| 6355634 | Isenring et al. | Mar 2002 | B1 |
| 6372748 | Schelberger et al. | Apr 2002 | B1 |
| 6407100 | Isenring et al. | Jun 2002 | B1 |
| 6423726 | Dutzmann et al. | Jul 2002 | B2 |
| 6479542 | Sembo et al. | Nov 2002 | B2 |
| 6559136 | Mauler-Machnik et al. | May 2003 | B1 |
| 6602823 | Röchling et al. | Aug 2003 | B1 |
| 7008903 | Dutzmann et al. | Mar 2006 | B2 |
| 7329633 | Dunkel et al. | Feb 2008 | B2 |
| 7358214 | Dunkel et al. | Apr 2008 | B2 |
| 7521397 | Dunkel et al. | Apr 2009 | B2 |
| 7538073 | Elbe et al. | May 2009 | B2 |
| 7655599 | Röchling et al. | Feb 2010 | B2 |
| 7799739 | Dunkel et al. | Sep 2010 | B2 |
| 7820708 | Dunkel et al. | Oct 2010 | B2 |
| 7879760 | Dunkel et al. | Feb 2011 | B2 |
| 8415274 | Wachendorff-Neumann et al. | Apr 2013 | B2 |
| 8486858 | Seitz et al. | Jul 2013 | B2 |
| 8652997 | Assmann et al. | Feb 2014 | B2 |
| 20020156108 | Eicken et al. | Oct 2002 | A1 |
| 20020173529 | Dutzmann et al. | Nov 2002 | A1 |
| 20020198222 | Bruns et al. | Dec 2002 | A1 |
| 20040039043 | Elbe et al. | Feb 2004 | A1 |
| 20040110771 | Blasco et al. | Jun 2004 | A1 |
| 20050009703 | Wachendorff-Neumann et al. | Jan 2005 | A1 |
| 20050009883 | Uhr et al. | Jan 2005 | A1 |
| 20050101639 | Ammermann et al. | May 2005 | A1 |
| 20050124815 | Elbe et al. | Jun 2005 | A1 |
| 20050143428 | Dunkel et al. | Jun 2005 | A1 |
| 20050165076 | Ammermann et al. | Jul 2005 | A1 |
| 20060004070 | Wachendorff-Neumann et al. | Jan 2006 | A1 |
| 20060014738 | Wachendorff-Neumann et al. | Jan 2006 | A1 |
| 20060035942 | Wachendorff-Neumann et al. | Feb 2006 | A1 |
| 20060079401 | Dutzmann et al. | Apr 2006 | A1 |
| 20060116414 | Dunkel et al. | Jun 2006 | A1 |
| 20060276342 | Krahmer et al. | Dec 2006 | A1 |
| 20070004921 | Dunkel et al. | Jan 2007 | A1 |
| 20070010399 | Rosinger et al. | Jan 2007 | A1 |
| 20070037799 | Dahmen et al. | Feb 2007 | A1 |
| 20070054804 | Suty-Heinze | Mar 2007 | A1 |
| 20070078171 | Andersch et al. | Apr 2007 | A1 |
| 20070142327 | Funke et al. | Jun 2007 | A1 |
| 20070155797 | Andersch et al. | Jul 2007 | A1 |
| 20070196406 | Dunkel et al. | Aug 2007 | A1 |
| 20070203025 | Bickers et al. | Aug 2007 | A1 |
| 20070213396 | Thielert et al. | Sep 2007 | A1 |
| 20070232598 | Funke et al. | Oct 2007 | A1 |
| 20070270416 | Funke et al. | Nov 2007 | A1 |
| 20070293550 | Röchling et al. | Dec 2007 | A1 |
| 20070298966 | Fischer et al. | Dec 2007 | A1 |
| 20080027114 | Funke et al. | Jan 2008 | A1 |
| 20080070863 | Funke et al. | Mar 2008 | A1 |
| 20080255071 | Suty-Heinze et al. | Oct 2008 | A1 |
| 20080261811 | Krohn et al. | Oct 2008 | A1 |
| 20080269051 | Suty-Heinze et al. | Oct 2008 | A1 |
| 20080269263 | Dahmen et al. | Oct 2008 | A1 |
| 20080274882 | Krohn et al. | Nov 2008 | A1 |
| 20090018015 | Wachendorff-Neumann et al. | Jan 2009 | A1 |
| 20090069178 | Suty-Heinze et al. | Mar 2009 | A1 |
| 20090069398 | Dunkel et al. | Mar 2009 | A1 |
| 20090105311 | Dunkel et al. | Apr 2009 | A1 |
| 20090118346 | Dunkel et al. | May 2009 | A1 |
| 20090170912 | Erdelen et al. | Jul 2009 | A1 |
| 20090170918 | Wolf | Jul 2009 | A1 |
| 20090286681 | Dahmen et al. | Nov 2009 | A1 |
| 20090306109 | Dutzmann et al. | Dec 2009 | A1 |
| 20110033433 | Davies et al. | Feb 2011 | A1 |
| 20110034496 | Höuser-Hahn et al. | Feb 2011 | A1 |
| 20110110906 | Andersch et al. | May 2011 | A1 |
| 20110124501 | Cristau et al. | May 2011 | A1 |
| 20110152097 | Stenzel et al. | Jun 2011 | A1 |
| 20120015910 | Wachendorff-Neumann et al. | Jan 2012 | A1 |
| 20130197018 | Wachendorff-Neumann et al. | Aug 2013 | A1 |
| Number | Date | Country |
|---|---|---|
| 7726387 | Feb 1988 | AU |
| 610 079 | May 1991 | AU |
| 2 476 462 | Apr 2011 | CA |
| 1 076 434 | Feb 1960 | DE |
| 1 081 446 | May 1960 | DE |
| 1 193 498 | May 1965 | DE |
| 1 209 799 | Jan 1966 | DE |
| 1 234 704 | Feb 1967 | DE |
| 1 493 736 | Apr 1969 | DE |
| 1 806 123 | Jun 1969 | DE |
| 2 012 656 | Sep 1971 | DE |
| 2 149 923 | Apr 1972 | DE |
| 2 250 077 | Apr 1973 | DE |
| 2 201 063 | Jul 1973 | DE |
| 2 207 576 | Aug 1973 | DE |
| 2 312 956 | Sep 1973 | DE |
| 23 24 010 | Jan 1975 | DE |
| 24 29 523 | Jan 1975 | DE |
| 24 56 627 | Jun 1975 | DE |
| 25 13 732 | Oct 1975 | DE |
| 25 15 091 | Oct 1975 | DE |
| 25 51 560 | May 1976 | DE |
| 25 43 279 | Apr 1977 | DE |
| 27 32 257 | Jan 1978 | DE |
| 27 35 872 | Feb 1978 | DE |
| 26 56 747 | Jun 1978 | DE |
| 28 02 488 | Jul 1979 | DE |
| 29 03 612 | Aug 1979 | DE |
| 140 041 | Feb 1980 | DE |
| 30 30 026 | Mar 1981 | DE |
| 30 42 303 | Aug 1981 | DE |
| 151 404 | Oct 1981 | DE |
| 34 06 993 | Sep 1984 | DE |
| 37 21 786 | Jan 1988 | DE |
| 37 35 555 | Sep 1988 | DE |
| 40 26 966 | Feb 1992 | DE |
| 44 23 612 | Jan 1996 | DE |
| 195 31 813 | Mar 1997 | DE |
| 195 39 324 | Apr 1997 | DE |
| 196 02 095 | Jul 1997 | DE |
| 196 46 407 | May 1998 | DE |
| 101 24 208 | Nov 2002 | DE |
| 102 15 292 | Aug 2003 | DE |
| 0 015 756 | Sep 1980 | EP |
| 0 019 450 | Nov 1980 | EP |
| 0 031 257 | Jul 1981 | EP |
| 0 040 345 | Nov 1981 | EP |
| 0 040 345 | Nov 1981 | EP |
| 0 068 813 | Jan 1983 | EP |
| 0 078 663 | May 1983 | EP |
| 0 112 284 | Jun 1984 | EP |
| 0 145 294 | Jun 1985 | EP |
| 0 155 509 | Sep 1985 | EP |
| 0 183 458 | Jun 1986 | EP |
| 0 196 038 | Oct 1986 | EP |
| 0 206 999 | Dec 1986 | EP |
| 0 219 756 | Apr 1987 | EP |
| 0 234 242 | Sep 1987 | EP |
| 0 236 272 | Sep 1987 | EP |
| 0 248 086 | Dec 1987 | EP |
| 0 253 213 | Jan 1988 | EP |
| 0 256 503 | Feb 1988 | EP |
| 0 258 161 | Mar 1988 | EP |
| 0 262 393 | Apr 1988 | EP |
| 0 270 111 | Jun 1988 | EP |
| 0 278 595 | Aug 1988 | EP |
| 0 298 196 | Jan 1989 | EP |
| 0 310 550 | Apr 1989 | EP |
| 0 313 512 | Apr 1989 | EP |
| 0 315 502 | May 1989 | EP |
| 0 329 397 | Aug 1989 | EP |
| 0 339 418 | Nov 1989 | EP |
| 0 341 475 | Nov 1989 | EP |
| 0 378 953 | Jul 1990 | EP |
| 0 382 375 | Aug 1990 | EP |
| 0 393 911 | Oct 1990 | EP |
| 0 398 692 | Nov 1990 | EP |
| 0 460 575 | Dec 1991 | EP |
| 0 515 901 | Dec 1992 | EP |
| 0 537 957 | Apr 1993 | EP |
| 0 545 099 | Jun 1993 | EP |
| 0 589 301 | Mar 1994 | EP |
| 0 596 254 | May 1994 | EP |
| 0 600 629 | Jun 1994 | EP |
| 0 604 019 | Jun 1994 | EP |
| 0 629 616 | Dec 1994 | EP |
| 0 639 574 | Feb 1995 | EP |
| 0 737 682 | Oct 1996 | EP |
| 0 897 904 | Feb 1999 | EP |
| 1 214 881 | Jun 2002 | EP |
| 935981 | Sep 1963 | GB |
| 988630 | Apr 1965 | GB |
| 1094567 | Dec 1967 | GB |
| 1103989 | Feb 1968 | GB |
| 1114155 | May 1968 | GB |
| 1 425 621 | Feb 1976 | GB |
| 1 591 267 | Jun 1981 | GB |
| 2 262 037 | Jun 1993 | GB |
| 07-206608 | Aug 1995 | JP |
| WO 9213830 | Aug 1992 | WO |
| WO 9504728 | Feb 1995 | WO |
| WO 9601559 | Jan 1996 | WO |
| WO 9604252 | Feb 1996 | WO |
| WO 9616048 | May 1996 | WO |
| WO 9618631 | Jun 1996 | WO |
| WO 9623793 | Aug 1996 | WO |
| WO 9706171 | Feb 1997 | WO |
| WO 9708952 | Mar 1997 | WO |
| WO 9710716 | Mar 1997 | WO |
| WO 9739630 | Oct 1997 | WO |
| WO 9808385 | Mar 1998 | WO |
| WO 9823155 | Jun 1998 | WO |
| WO 9914202 | Mar 1999 | WO |
| WO 9924413 | May 1999 | WO |
| WO 9931980 | Jul 1999 | WO |
| WO 9931985 | Jul 1999 | WO |
| WO 9942447 | Aug 1999 | WO |
| WO 9963813 | Dec 1999 | WO |
| WO 0187822 | Nov 2001 | WO |
| WO 0208197 | Jan 2002 | WO |
| WO 0238542 | May 2002 | WO |
| WO 0238565 | May 2002 | WO |
| WO 03014103 | Feb 2003 | WO |
| WO 03066609 | Aug 2003 | WO |
| WO 03066610 | Aug 2003 | WO |
| WO 03070705 | Aug 2003 | WO |
| Entry |
|---|
| Hirt, E.E., Office Action for U.S. Appl. No. 11/916,436, Inventors: Dunkel et al., § 371(c) Date: Nov. 7, 2008, U.S. Patent and Trademark Office, Alexandria, Virginia, mailed Jan. 30, 2012. |
| Holt, A.M., Office Action for U.S. Appl. No. 13/100,464, Inventors: Dahmen et al., Filing Date: May 4, 2011, U.S. Patent and Trademark Office, Alexandria, Virginia, mailed May 4, 2012. |
| Office Action mailed Jan. 4, 2011, in U.S. Appl. No. 11/997,079, inventor Dahmen, P., filed Jul. 28, 2008. |
| Colby, S.R., “Calculating Synergistic and Antagonistic Responses of Herbicide Combinations,” Weeds 15:20-22, Weed Society of America (1967). |
| “Dicholofluanid,” in The Pesticide Manual: A World Compendium, 9th edition, Worthing, C.E., ed., Hampshire, UK, p. 249(1991). |
| “Tolylfluanid,” in The Pesticide Manual: A World Compendium, 9th edition, Worthing, C.E., ed., Hampshire, UK, p. 827(1991). |
| Patent Abstracts of Japan, English language abstract for JP 07-206608 (listed on accompanying PTO/SB/08A as FP88), 2007. |
| STNEasy Database, Accession No. 1962:12696, English language abstract for DE 1 081 446 (listed on accompanying PTO/SB/08A as FP2), 2007. |
| STNEasy Database, Accession No. 1980:586371, English language abstract for DD 140 041 (listed on accompanying PTO/SB/08A as FP32), 2007. |
| STNEasy Database, Accession No. 1981:401897, English language abstract for DE 30 30 026 (listed on accompanying PTO/SB/08A as FP35), 2007. |
| STNEasy Database, Accession No. 1982:157395, English language abstract for DD 151 404 (listed on accompanying PTO/SB/08A as FP39), 2007. |
| STNEasy Database, Accession No. 1988:510440, English language abstract for EP 0 258 161 (listed on accompanying PTO/SB/08A as FP58), 2007. |
| International Search Report for International Application No. PCT/EP2004/010830, European Patent Office, Netherlands, completed Nov. 22, 2004. |
| Hirt, E.E., Office Action for U.S. Appl. No. 11/916,436, inventors: Dunkel et al., § 371(c) Date: Nov. 7, 2008, U.S. Patent and Trademark Office, Alexandria, Virginia, mailed Jul. 18, 2011. |
| European Search Report and Written Opinion for European Patent Application No. 10 163 282.6, European Patent Office, Munich, Germany, issued Feb. 2, 2011. |
| Unverified English translation of text portion of European Search Report and Written Opinion for European Patent Application No. 10 163 282.6, European Patent Office, Munich, Germany, issued Feb. 2, 2011. |
| Unverified English translation of claims of corresponding European Patent Application No. 10 163 282.6, filed Sep. 28, 2004, European Patent Office, Munich, Germany. |
| Rummens, F.H.A., “An Improved Definition of Synergistic and Antagonistic Effects,” Weed Science 23 (1):4-6, The Weed Science Society of America, United States (1975). |
| Prosecution History of European Patent Appl. No. 03735610.2 (European Counterpart of U.S. Appl. No. 10/518,742), Jul. 13, 2006-Sep. 25, 2009. |
| Partial English language translation of Prosecution History of European Patent Appl. No. 03735610.2, Jul. 13, 2006-Sep. 25, 2009. |
| Opposition Proceeding in European Patent No. EP-B-1482798, Mar. 5, 2007-Nov. 9, 2009. |
| Partial English language translation of Opposition Proceeding in European Patent No. EP-B-1482798, Feb. 26, 2007-Nov. 9, 2009. |
| Tomlin, C., ed, The Pesticide Manual, 1242-1245, British Crop Protection Council, Farnham, UK (1997). |
| “Metominostrobin data sheet,” Compendium of Pesticide Common Names, accessed at http://www.alanwood.net/pesticides/metominostrobin.html, accessed on Apr. 8, 2009, 1 page. |
| “Azoxystrobin data sheet,” Compendium of Pesticide Common Names, accessed at http://www.alanwood.net/pesticides/azoxystrobin.html, accessed on Apr. 8, 2009, 1 page. |
| “Kresoxim-methyl data sheet,” Compendium of Pesticide Common Names, accessed at http://www.alanwood.net/pesticides/kresoxim-methyl.html, accessed on Apr. 8, 2009, 1 page. |
| Dekeyser, M. and Davis, R.A., “Synthesis and Antifungal Activity of 5,6 Dihydro-3-methyl-1, 4-dioxin-2-carboxamides” J. Agric. Food. Chem. 46:287-2829 (1998). |
| Bauer, T.A. et al., “Response of Selected Weed Species to Postemergence Imazethapyr and Bentazon,” Weed Tech. 9:236-242, The Weed Science Society of America, United States (1995). |
| Blackshaw, R.E., “HOE-39866 Use in Chemical Fallow Systems,” Weed Tech. 3:420-428, The Weed Science Society of America, United States (1989). |
| Blackshaw, R.E., “Synergistic Mixes of DPX-A7881 and Clopyralid in Canola (Brassica napus),” Weed Tech. 3:690-695, The Weed Science Society of America, United States (1989). |
| Blackshaw, R.E., et al., “Herbicide Combinations for Postemergent Weed Control in Safflower (Carthamus tinctorius),” Weed Tech. 4:97-104, The Weed Science Society of America, United States (1990). |
| Blouin, D.C., et al., “Analysis of Synergistic and Antagonistic Effects of Herbicides Using Nonlinear Mixed-Model Methodology,” Weed Tech. 18:464-472, The Weed Science Society of America, United States (2004). |
| Bradley, P.R., et al., “Response of Sorghum (Sorghum bicolor) to Atrazine, Ammonium Sulfate, and Glyphosate,” Weed Tech. 14:15-18, The Weed Science Society of America, United States (2000). |
| Buker, III, R.S., et al., “Confirmation and Control of a Paraquat-Tolerant Goosegrass (Eleusine indica) Biotype,” Weed Tech. 16:309-313, The Weed Science Society of America, United States (2002). |
| Burke, I.C., et al., “CGA-362622 Antagonizes Annual Grass Control with Clethodim,” Weed Tech. 16:749-754, The Weed Science Society of America, United States (2002). |
| Flint, J.L., et al., “Analyzing Herbicide Interactions, a Statistical Treatment of Colby's Method,” Weed Tech. 2:304-309, The Weed Science Society of America, United States (1988). |
| Gillespie, G.R., and Nalewaja, J.D., “Wheat (Triticum aestivum) Response to Triallate Plus Chlorsulfuron,” Weed Tech. 3:20-23, The Weed Science Society of America, United States (1989). |
| Green, J.M., et al., “Metribuzin and Chlorimuron Mixtures for Preemergence Broadleaf Weed Control in Soybeans, Glycine max,” Weed Tech. 2:355-363, The Weed Science Society of America, United States (1988). |
| Harker, N.K., and O'Sullivan, P.A., “Synergistic Mixtures of Sethoxydim and Fluazifop on Annual Grass Weeds,” Weed Tech. 5:310-316, The Weed Science Society of America, United States (1991). |
| Kent, L.M., et al., “Effect of Ammonium Sulfate, Imazapyr, and Environment on the Phytotoxicity of Imazethapyr,” Weed Tech. 5:202-205, The Weed Science Society of America, United States (1991). |
| Kotoula-Syka, E., et al., “Interactions between SAN 582H and Selected Safeners on Grain Sorghum (Sorghum bicolor) and Corn (Zea mays),” Weed Tech. 10:299-304, The Weed Science Society of America, United States (1996). |
| Lanclos, D.Y., et al., “Glufosinate Tank-Mix Combinations in Glufosinate-Resistant Rice (Oryza sativa),” Weed Tech. 16:659-663, The Weed Science Society of America, United States (2002). |
| Norris, J.L., et al., “Weed Control from Herbicide Combinations with Three Formulations of Glyphosate,” Weed Tech. 15:552-558, The Weed Science Society of America, United States (2001). |
| Novosel, K.M., et al., “Metolachlor Efficacy as Influenced by Three Acetolactate Synthase-Inhibiting Herbicides,” Weed Tech. 12:248-253, The Weed Science Society of America, United States (1998). |
| Palmer, E.W., et al., “Broadleaf Weed Control in Soybean (Glycine max) with CGA-277476 and Four Postemergence Herbicides,” Weed Tech. 14:617-623, The Weed Science Society of America, United States (2000). |
| Salzman, F.P., and Renner, K.A., “Response of Soybean to Combinations of Clomazone, Metribuzin, Linuron, Alachlor, and Atrazine,” Weed Tech. 6:922-929, The Weed Science Society of America, United States (1992). |
| Scott, R.C., et al., “Spray Adjuvant, Formulation, and Environmental Effects on Synergism from Post-Applied Tank Mixtures of SAN 582H with Fluazifop-P, Imazethapyr, and Sethoxydim,” Weed Tech. 12:463-469, The Weed Science Society of America, United States (1998). |
| Shaw, D.R. and Arnold, J.C., “Weed Control from Herbicide Combinations with Glyphosate,” Weed Tech. 16:1-6, The Weed Science Society of America, United States (2002). |
| Snipes, C.E., and Allen, R.L., “Interaction of Graminicides Applied in Combination with Pyrithiobac,” Weed Tech. 10:889-892, The Weed Science Society of America, United States (1996). |
| Wehtje, G. and Walker, R.H., “Interaction of Glyphosate and 2,4-DB for the Control of Selected Morningglory (Ipomoea spp.) Species,” Weed Tech. 11:152-156, The Weed Science Society of America, United States (1997). |
| Zhang, W., et al., “Fenoxaprop Interactions for Barnyardgrass (Echinochloa crus-galli) Control in Rice,” Weed Tech. 19:293-297, The Weed Science Society of America, United States (2005). |
| Number | Date | Country | |
|---|---|---|---|
| 20130196981 A1 | Aug 2013 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10573066 | US | |
| Child | 13800076 | US |
