Patent Grant
7956009
The present invention relates to novel active compound combinations which consist of a known fluoro-benzothiazole derivative and further known fungicidally active compounds, and which are highly suitable for controlling phytopathogenic fungi.
It is already known that isopropyl 1-({[1-(6-fluoro-1,3-benzothiazol-2-yl)ethyl]-amino}carbonyl)-2-methylpropylcarbamate has fungicidal properties (cf. EP-A1-775 696). The activity of this compound is good; however, at low application rates it is in some cases not satisfactory.
Furthermore, it is already known that a large number of triazole derivatives; aniline derivatives, dicarboximides and other heterocycles can be employed 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). Likewise, the activity of these compounds is not always satisfactory at low application rates.
Finally, it is also known that 1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazo-lidineimine can be used for controlling animal pests such as insects (cf. Pesticide Manual, 9th Edition (1991), page 491). However, fungicidal properties have hitherto not been described for this compound.
Furthermore, it is already known that 1-(3,5-dimethyl-isoxazol-4-sulphonyl)-2-chloro-6,6-difluoro-[1,3]-dioxolo-[4,5f]-benzimidazole has fungicidal properties (cf. WO 97-06171).
Furthermore, it is already known that substituted azodioxacycloalkenes have fungicidal properties (cf. EP-B-712 396).
Finally, it is also known that substituted halogenopyrimidines have fungicidal properties (cf. DE-A1-196 46 407, EP-B-712 396).
It has now been found that the novel active compound combinations comprising a fluorobenzothiazole derivative of the formula
and
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have very good fungicidal properties.
Surprisingly, the fungicidal activity of the active compound combinations according to the invention is considerably higher 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 activities.
From the structural formula of the active compound of the formula (I), it can be seen that the compound has two asymmetrically substituted carbon atoms. Accordingly, the product can be present as a mixture of different isomers or else in the form of a single isomer.
Preferred compounds of the formula (I) are compounds in which the amino acid moiety is formed from i-propyloxycarbonyl-L-valine and the fluoro-benzothiazoleethylamine moiety is racemic, but has, in particular, the (R) configuration.
The formula (II) includes the compounds
and
The formula (IV) includes the aniline derivatives of the formulae
and
It is evident from the structural forrnula for the active compound of the formula (V) that the compound has three asymmetrically substituted carbon atoms. The product may therefore be present as a mixture of different isomers, or else in the form of a single component. Particular preference is given to the compounds
N-(R)-[1-(4-chloro-phenyl)-ethyl]-(1S)-2,2-dichloro-1-ethyl-3t-methyl-1R-cyclopro-panecarboxamide of the formula
and
N-(R)-[1-(4-chloro-phenyl)-ethyl]-(1R)-2,2-dichloro-1-ethyl-3t-methyl-1R-cyclopro-panecarboxamide of the formula
The formula (VII) includes the compounds
The formula (XVI) includes the compounds
The compound of the formula (XVII) can be present as methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-DL-alaninate (metalaxyl, XVIIa) or as methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-D-alaninate (metalaxyl-M, XVIIIb).
The hydroxyethyl-triazole derivative of the formula (XXI) can be present in the “thiono” form of the formula
or in the tautomeric “mercapto” form of the formula
For simplicity's sake, only the “thioino” form is given in each case.
The guanidine derivative of the formula (XXV) is a substance mixture with the common name guazatine.
From the structural formula for the active compouds of the formula (XXXXIX), it can be seen that the compounds can be present as E or Z isomers. Accordingly, the product 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 (XXXXIX) in which the compounds of the formula (XXXXIX) are present as E isomer. Particular preference is given to the compounds of the formulae
and their isomers.
The following active compounds are particularly preferred mixing partners of the compounds of the formula (I):
The components which are present in the active combinations according to the invention in addition to a halogeno-benzimidazole of the formula (XXVII) are also known.
Specifically, the active compounds are described in the following publications:
In addition to an active compound of the formula (I), the active compound combinations according to the invention comprise at least one active compound of the compounds of groups (1) to (51). Additionally, they may comprise further fungicidally active additives.
The synergistic effect is particularly pronounced when the active compounds in the active compound combinations according to the invention are present in certain weight ratios. However, the weight ratios of the active compounds in the active compound combinations can be varied within a relatively wide range. In general,
The active compound combinations according to the invention have very good fungicidal properties and can be employed 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 Phytophthora infestans and Plasmopara viticola.
The fact that the active compound combinations are well tolerated by plants at the concentrations required for controlling plant diseases permits the treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil. The active compound combinations according to the invention can be employed for foliar application or else as seed dressings.
The active compound combinations according to the invention may also be employed to increase the yield of crops. However, they have reduced toxicity and are tolerated well 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 plants 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 multi-layer coating.
The active compound combinations according to the invention can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and microencapsulations in polymeric substances and in coating compositions for seeds, and ULV 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 use, for example, organic solvents as auxiliary solvents. Essentially, suitable liquid solvents include: 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, 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 dimethylfornamide and dimethyl sulphoxide, or else water. Liquefied gaseous extenders or carriers are to be understood as meaning liquids which are gaseous at ambient temperature and under atmospheric pressure, for example aerosol propellants such as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example 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 lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and 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 additives can be 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 formulations 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, as such or in their formulations, can also be applied in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, to broaden the activity spectrum or to prevent the development of resistance, for example. In many cases, synergistic effects are obtained, i.e. the activity of the mixture is greater than the activity of the individual components.
A mixture with other known active compounds such as herbicides or with fertilizers and growth regulators is also possible.
The active compound combinations 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 and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering, spreading, 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.
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 the active compound combination 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 the 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 the active compound combination are generally between 0.1 and 10,000 g/ha, preferably between 1 and 5000 g/ha.
The good fungicidal activity of the active compound combinations according to the invention is evident from the examples below. While the individual active compounds exhibit weaknesses with regard to the fungicidal activity, the combinations have an activity which exceeds the sum of individual activities.
A synergistic effect of fungicides is always present when the fungicidal activity of the active compound combinations exceeds the total of the activities of the active compounds when applied individually.
The expected activity for a given combination of two active compounds can be calculated as follows (cf. Colby, S. R., “Calculating Synergistic and Antagonistic Responses of Herbicide Combinations”, Weeds 15, (1967), 20-22):
The efficacy is calculated in %. 0% is an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
If the actual fungicidal activity exceeds the calculated value, then the activity of the combination is superadditive, i.e. a synergistic effect exists. In this case, the efficacy which was actually observed must be greater than the value for the expected efficacy (E) calculated from the abovementioned formula.
The examples that follow illustrate the invention. However, the invention is not limited to the examples.
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, or a commercial formulation of active compound or active compound combination is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the active compound preparation 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 cabin 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 activity found for the active compound combination according to the invention is greater than the calculated activity, i.e. there is a synergistic effect. At a mixing ratio of 1:1 and an application rate of 0.1 g/ha, the combination of the compound of the formula (I) and the halogeno-benzimidazole of the formula No. XXVII has an actual efficacy of 73%. At 63%, the expected value, calculated using Colby's formula, is considerably lower.
Active compounds, application rates and test results are shown in the tables below.
| Number | Date | Country | Kind |
|---|---|---|---|
| 199 59 947 | Dec 1999 | DE | national |
| 100 21 412 | May 2000 | DE | national |
This application is a division of U.S. application Ser. No. 11/336,501, filed Jan. 20, 2006, which is a division of Ser. No. 10/619,730 filed Jul. 7, 2003, now U.S. Pat. No. 7,115,593, issued Oct. 3, 2006, which is a division of Ser. No. 10/149,353, now U.S. Pat. No. 6,624,183, issued Sep. 23, 2003, which was filed under 35 U.S.C. 371 as a national stage application of International Application No. PCT/EP00/11989, filed Nov. 30, 2000, which was published in German as International Patent Publication WO 01/44215 on Jun. 21, 2001, which is entitled to the right of priority of German Patent Applications 199 59 947.5, filed Dec. 13, 1999, and 100 21 412.6, filed May 3, 2000.
| Number | Name | Date | Kind |
|---|---|---|---|
| 1972961 | Tisdale et al. | Sep 1934 | A |
| 2553770 | Kittleson | May 1951 | A |
| 3290353 | Battershell et al. | Dec 1966 | A |
| 3513241 | Hoyer et al. | May 1970 | A |
| 3745170 | Fujinami et al. | Jul 1973 | A |
| 3755350 | Sauli | Aug 1973 | A |
| 3823240 | Sauli | Jul 1974 | A |
| 3903090 | Fujinami et al. | Sep 1975 | A |
| 3912752 | Meiser et al. | Oct 1975 | A |
| 3952002 | Kramer et al. | Apr 1976 | A |
| 3991071 | Brookes et al. | Nov 1976 | A |
| 4009278 | Fujinami et al. | Feb 1977 | A |
| 4048318 | Meiser et al. | Sep 1977 | A |
| 4079062 | Van Reet et al. | Mar 1978 | A |
| 4147791 | Meiser et al. | Apr 1979 | A |
| 4154945 | Brookes et al. | May 1979 | A |
| 4160838 | Van Reet et al. | Jul 1979 | A |
| 4291049 | Bosone et al. | Sep 1981 | A |
| 4331670 | Nishiyama et al. | May 1982 | A |
| 4347253 | Harr | Aug 1982 | A |
| 4425357 | Bosone et al. | Jan 1984 | A |
| 4432989 | Spencer | Feb 1984 | A |
| 4436744 | Harr | Mar 1984 | A |
| 4457937 | Sandmeier et al. | Jul 1984 | A |
| 4496551 | Moberg | Jan 1985 | A |
| 4510136 | Moberg | Apr 1985 | A |
| 4532341 | Holmwood et al. | Jul 1985 | A |
| 4608385 | Noguchi et al. | Aug 1986 | A |
| 4626595 | Holmwood et al. | Dec 1986 | A |
| 4664696 | Schaub | May 1987 | A |
| 4723984 | Holmwood et al. | Feb 1988 | A |
| 4780551 | Nyfeler et al. | Oct 1988 | A |
| 4789672 | Holmwood et al. | Dec 1988 | A |
| 4849439 | Schaub | Jul 1989 | A |
| 4851405 | Kramer et al. | Jul 1989 | A |
| 4871390 | Holmwood et al. | Oct 1989 | A |
| 4897107 | Holmwood et al. | Jan 1990 | A |
| 4904298 | Holmwood et al. | Feb 1990 | A |
| 4910200 | Curtze et al. | Mar 1990 | A |
| 4911746 | Holmwood et al. | Mar 1990 | A |
| 4920139 | Fujimoto | Apr 1990 | A |
| 4925840 | Nyfeler et al. | May 1990 | A |
| 4931560 | Hubele | Jun 1990 | A |
| 4931581 | Schurter et al. | Jun 1990 | A |
| 4957933 | Geffken et al. | Sep 1990 | A |
| 4988734 | Kraatz et al. | Jan 1991 | A |
| 4992438 | Ito et al. | Feb 1991 | A |
| 4995898 | Nasu et al. | Feb 1991 | A |
| 4997941 | Hubele | Mar 1991 | A |
| 5021581 | Clough et al. | Jun 1991 | A |
| 5059623 | Kruger et al. | Oct 1991 | A |
| 5081141 | Colle et al. | Jan 1992 | A |
| 5087635 | Shaber | Feb 1992 | A |
| 5145843 | Arnold et al. | Sep 1992 | A |
| 5145856 | Clough et al. | Sep 1992 | A |
| 5153200 | Hubele | Oct 1992 | A |
| 5190928 | Schurter et al. | Mar 1993 | A |
| 5221691 | Clough et al. | Jun 1993 | A |
| 5223523 | Adams, Jr. et al. | Jun 1993 | A |
| 5240940 | Arnold et al. | Aug 1993 | A |
| 5264440 | Clough et al. | Nov 1993 | A |
| 5266585 | Hubele et al. | Nov 1993 | A |
| 5304572 | Michelotti et al. | Apr 1994 | A |
| 5334607 | Sauter et al. | Aug 1994 | A |
| 5340802 | Shiosaki et al. | Aug 1994 | A |
| 5342837 | Clough et al. | Aug 1994 | A |
| 5356908 | Geffken et al. | Oct 1994 | A |
| 5389308 | Busel et al. | Feb 1995 | A |
| 5395837 | Clough et al. | Mar 1995 | A |
| 5407902 | Oda et al. | Apr 1995 | A |
| 5438059 | Clough et al. | Aug 1995 | A |
| 5453531 | Seitz et al. | Sep 1995 | A |
| 5468747 | Clough et al. | Nov 1995 | A |
| 5523311 | Schurter et al. | Jun 1996 | A |
| 5679676 | Kruger et al. | Oct 1997 | A |
| 5789430 | Jautelat et al. | Aug 1998 | A |
| 5859039 | Jautelat et al. | Jan 1999 | A |
| 5883250 | Kruger et al. | Mar 1999 | A |
| 6020354 | Assmann et al. | Feb 2000 | A |
| 6103717 | Heinemann et al. | Aug 2000 | A |
| 6127547 | Assmann et al. | Oct 2000 | A |
| 6130251 | Seitz et al. | Oct 2000 | A |
| 6160001 | Assmann et al. | Dec 2000 | A |
| 6235743 | Gayer et al. | May 2001 | B1 |
| 6268508 | Assmann et al. | Jul 2001 | B1 |
| 6355634 | Isenring et al. | Mar 2002 | B1 |
| 6359133 | Gayer et al. | Mar 2002 | B2 |
| 6387939 | Assmann et al. | May 2002 | B1 |
| 6558685 | Kober et al. | May 2003 | B1 |
| 20010018442 | Gayer et al. | Aug 2001 | A1 |
| Number | Date | Country |
|---|---|---|
| 2012656 | Sep 1971 | DE |
| 610764 | Aug 1994 | DE |
| 775696 | May 1997 | DE |
| H09-183703 | Jul 1997 | JP |
| 9823155 | Jun 1998 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20070161688 A1 | Jul 2007 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 11336501 | Jan 2006 | US |
| Child | 11714497 | US | |
| Parent | 10619730 | Jul 2003 | US |
| Child | 11336501 | US | |
| Parent | 10149353 | US | |
| Child | 10619730 | US |
