|Title of Invention||
"SYNERGISTIC HERBICIDAL COMPOSTITIONS"
|Abstract||The present invention relates to novel synergistic herbicidal combinations of N isopropyi-N-(4-fluorophenyl)(5-trifluoromethyl-l,3,4-thiadiazol-2-yloxy)acetamide with fenoxaprop-ethyl and or clodinafop-propargyl.|
|Full Text||The nvention relates to novel synergistic herbicidal combinations of a known hetaryloxyacetamide with other known herbicides belonging to other classes which can be used particularly advantageously for selective weed control in a variety of crop plants.
The patents listed below describe hetaryloxyacetamides which are particularly active against monocotyledonous weeds (= grass weeds), but additionally also act against some dicotyledonous weeds. They are virtually exclusively soil-acting and have little foliar activity, and some of them are very selective in mono- and dicotyledonous crop plants such as cereals, maize, rice, soybeans and cotton [cf. for example EP-A 5 501 (« US 4 509 971 and US 4 833 243); EP-A 18 497 (= US 4 645 525 and US 4 756 741); EP-A29 171 (= US 4 408 055); EP-A 94 514 (- US 585 471); EP-A 100 044 (- US 4 549 899); EP-A 100 045 (= US 4 540 430); EP-A 161 602 (- US 4 784 682); EP-A 195 237 (« US 4 788 291); DE-A 3 724 467; EP-A 348 734 (= US 4 988 380); EP-A 348 737 (= US 4 968 342 and 5 090 991); DE-A 4 113 421 and DE-A 4 137 827; and also WO 91/06544].
In addition, DE 4 223 465 describes synergistic mixtures of hetaryloxyacetamides with N-phenylureas, N-benzothiazoiiylureas, 2.6-dinitroanilines, s-triazines, as-triazinones, sulfonylureas, imidazoiinones, pyridinecarboxamides and diphenyl ethers. However, none of the mixtures described therein has as yet achieved any practical significance. A disadvantage of the mixtures described in DE 4 223 465 Is that their action is not always distinct in case of strong overgrowth by a variety of weeds.
It is an object of the present invention to provide on the basis of N-isopropyl-N-(4-fluoropheayi)(5-tnjQuoromethyl-l>3,4-thiadiazoi-2-ylo:cy)acetamide of the formula (I)
novel synergistic herbicidal mixtures which are superior in their activity to prior art mixtures and additionally act against a broad spectrum of weeds.
This object is achieved by combinations of known herbicides with the active compound of the: formula (I) surprisingly found, in biological tests, to show pronounced synergistic effects with regard to activity against weeds and to be especially advantageously useful as effective broad range combination product; for th; selective control of weeds • both of monocotyledonous arid of dicotyledonous weeds by the pre-emergence and post-emergence method- in monocotyledonous and di
The present invention accordingly provides synergistic herbicidal compositions, characterized in that they comprise an effective amount of an active compound combination of N-isopropyl-N-(4-fluorophenyl)(5-trifluoromethyl-1,3,4-thiadi.izol-2-ylo:>cy)acetarnide of the formula (I)
and at least one herbicidally active compound of the formula (II) or (III)
The compound of the formula (I) is known from EP-A 348 737 and US 4 968 342.
Fenoxaprop-ethyl is ethyl 2-[4-(6-chlorobenzoxazol-2-yI)oxypher1oxy]pro-pionate, described in DE 2 640 730.
Clodmafop-propargyl is propinyl (R)-2-[4-[(5-chloro-3-fIuo::opyridm-2-yl)-oxyjphenoxyjpropionate, disclosed in EP-A 248 968.
Hetaryloxyacetamides including the active compound of the formula (I) are particularly active against monocotyledonous weeds (*= grass weeds), but additionally also act against some dicotyledonous weeds.
The active compounds (II) and (III) mentioned can be used for the selective control of a broad spectrum of grass weeds in economically important crop plants such as, for example, cereals, maize:, soybeans, cotton, beet and rice. However, their activity against: certain harmful monocotyledons is not always satisfactory. Important problem weeds, such as, for example, Apera spica-venti, are of:en not sufficiently controlled.
Surprisingly, it has now been found that the active compound combinations of the hetaryloxyacetamide of the formula (I) and the active compounds (II) and/or (III) defined above have a particularly hi$i activity aid can be used selectively in maw crop plant;;.
Surprisingly, the herbicidal activity of the active compound combinations according to the invention is considerably higher than the sum of the activities of the individual active compounds.
This means that not merely a complementation of action is present, but a true synerjjstic effect, which was unforeseeable. The novel active compound combinations are well tolerated by many crop plants, and even •weeds Vvfoich are otherwise difficult to control, such as Apera spica-venti, are controlled well by the novel active compound combinations. The novel active compound combinations are therefore a useful addition to the range of the selective herbicides.
The active compound combinations according to the invention can be used for example in connection with the following plaits:
Dicotyledonous crop plants of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linurn, Ipomoea;, Vicia, Nicotian*., Lycopersicon, Arachis, Brassies., Lactuca, Cucumis and Cucurbita.
Mojiocotvledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cypenis, Sorghum, Agropyron, Cynodon, Monocboria, Fimbrisi-ylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactylo Oryza, Zca, Triticum, H jrdeum,
Avena. Secale. Sorgjium, Panicum, Sacchan};m, Ananas, Asparagus and AJlium.
However, the use of the active compound combinations according to the invention is in no way restricted to these genera, but also extends in the same manr.er to other plants.
The synergistic effect of the active compound combinations according to the invention is especially pronounced at specific concentration ratios. However, the weight ratios of the active compounds in the active compound combinations can be varied within relatively wide ranges. In general, 0.001 to 1000 parts by weight, preferably 0,01 to 100 parts by weight, especially preferably 0.1 to 30 parts by weight, of active compound of the formula (II) and/or (HI) are used per pjirt by weight of active compound of the formula (I).
The active compounds or active compound combinations can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, po'-vders, dusts, pastes, soluble powders, granules., suspoemulsion concentrates, natural and synthetic . materials impregnated witi active
compound, and microencapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifier.5 and/or dispersants and/or foam-formers.
If water is used as an extender, organic solvents can, for example, also be used as au>iliary solvents. Liquid solvents which are mainly suitable are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and 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 as well as their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, stron.dy polar solvents such as dimethylformamide and dimethyl sulphoxide, and water.
Suitable solid carriers are: for example ammonium salts and 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 non-ionic and anionic emulsifiers, such as polyoxyethylene forty acid esters, polyoxyethylen ? fatty alcohol ethers, for example alkylaryl polygjycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolyzates; suitable dispersants are: for example lignin-sulphite waste liquors and methybellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices such as gum Jirabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins, ;ind synthetic phospholipids can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Pru.ssi.an Blue, aad organic dyestuf£> such as alizarin dyestufis, azo dyestufis 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 percent by weight of active compound, preferably between 0.5 and 90%.
In general, the active compound combinations according to the invention are applied in the form of ready mixes. However, the active compounds in the active compound combinations can also be formulated individually and mixed upon application, that is to say applied in the form of tank mixes.
The new active compound combinations as such or in the form of their formulations can aleo be used as mixtures with fuuhcr known tierbiCides, finished formulations or tank mixes again being possible. Mixtures with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repeilants, growth promoters, plant nutrients and soil conditioners, are also possible. Furthermore, it maybe advantageous for specific purposes, in particular when using the post-emergence method, to incorporate mineral or vegetable oils tolerated by plants (for example "Oleo Dupont HE", which is commercially available) or ammonium salts such as., for example, ammonium sulfete or ammonium thiocyanate, as further additives in the formulations.
The novel active compound combinations according to the invention can be used as such, in the form of their formulations or in the use; forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, pov/ders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing, dusting or spreading.
The rates of application of the active compound combinations according to the invention can be varied within a certain range; they depend, inter aliia, on the weather and on the condition of the soil. In general, the rates of application are between 0.01 and 10 k§ per ha, preferably between 0.03 and 5 kg per ha, in particular between 0.05 and 3.0 kg per ha.
The active compound combinations according to the invention can be applied before and af:er the emergence cf the plants, i.e. by the pre-emergence and post-emergence method
The §x>od herbicidal activity of the novel active compound combinations is evident from the examples below. While the individual active compounds show weaknesses in i:heir herbicidal activity, the combinations all exhibit very efficient control of weeds, and this control exceeds a simple sum of the activities.
In herbicides, a uynergistic effect is always present when the herbicidal activity
of th The expected activity for a given combination of two herbicides can be calculated as follows (cf. Colby, S. R.; "Calculating synergistlc and.antagonistic responses of herbicide combinations", Weeds 15, pages 20-22, 1967):
If X = % damage by herbicide A (active compound of group 1) at
the rate of application of p kg/ha and
Y » % damage by herbicide B (active compound of group 2) at the rate of application of q kg/ha and
E - the cxpect rate of application of p and q kg/ha,
thenE- X+ Y- (J1L}.
If the actual damage exceeds the calculated value, the combination is super-additive with regard to its activity., i.e. it shows a synergistic effect.
The e?:amples below reveal thait the herbicidal activity of the active ccmpound combinations according to the invention found exceeds the calculated value, i.e. that the novel active compound combinations have a synergistic action.
To prepare the active compound preparations required for the tests, suitable amounts of a water-dispersible powder formulation (WP) of the hetaryloxyacetc.mide of the formula (I) and a commercially available formulation of the compounds (II) and/or (III), respectively, are weighed out and diluted with water to the desired concentration; by mixing, various combinations c f the two active compounds were prepared.
A) g ost-em ergence tests/ greenhouse
Test plants which have a height of 5 to 15 cm are sprayed with the active compound preparation:; in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is chosen such that the particular amounts of gtctive compound desired sire applied in 500 1 of water per ha. After the treatment, the test plants are kept in the greenhouse under controlled conditions (temperature, atmospheric humidity, li^it) until the evaluation. After three weeks, the degree of damage to the plants is rated in % damage in compari;>on to the development of untreated control plants.
The figures denote:
0% = no action/damage (like untreated control) 100% * total destruction
Active compounds, application rates and results are listed in the tables below.
Herbicidal activity of (I), clodinafop-propargyi aid tank mixes of (]') and ciodinafop-propargyl against Apera spica-venti by the post-emergence method (Table Remove)
Herbicidal activity of (I), fenoxaprop-ethyl and tank mixes of (I) arid fenoxaprop-ethyl againtt Apera spica-venti by the post-emergence method
found -calc. =
activity or damage (in percent) found;
activity or damage (in percent) calculated using the COLBY
The compounds fenoxaprcp-ethyl (3!I) und clodinafop-propargyl (III) have been used in form of the following commercially available formulations:
RALON 060 EW (emulsion-in-water) (AgrEvo);
TOPIK 240 EC (emulsion concentrate)(Novartis).
1 . Synergistic herbicidal compositions, characterized in that they comprise an effective amount of an active compound combination of N- .sopropyl-N-(4-f[uorophenyl)(5-trifluorornethyl-l,3,4-thiadiazol-2-yloxy)acetarnide of the formula (I)
and at least one herbici:ially active compound of the formula (II) or (III)
Synergisdc herbicidal compositions according to Claim 1, characterized in that 0 001 to 1000 parts by weight of active compound of ths formula (II) and/or (III) are employed per part by weight of N-isopropyI*N-(4-fluoroph«nyl)(5-trifluoromethyl-l,354-thiadiazol'2-yloxy)acetjimide (I),
Synergistic herbicidal compositions according to Claim 1, chaj'acterized in that 0,01 to 100 parts by weight of active compound of the formula (II) and/or (III) are employed per pan: by weight of active compound of
the fonr.ula (I).
Synergistic herbicidai compositions according to Claim 1, characterized
in that C.I to 30 parts by weight of active compound of the formula (II)
and/or (HI) are employed per part by weight of active compound of the
Method of controlling weeds, characterized in that an active compound
combins.tion according to Claims 1 to 4 is allowed to act on weeds
and/'or their habitat.
Use of active compound combinations according to Claims 1 to 4 for
Process for preparing herbicidal compositions, characterized in that an
active compound combination according to Claims 1 to 4 is mixed with
extenders and/or surfactants.
Svnergistic herbicidal compositions substantially as hereinbefore
described with reference to the foregoing examples.
Process for preparing herbicidal compositions substantially as
hereinbefore described with reference to the foregoing example^.
|Indian Patent Application Number||1949/DEL/1997|
|PG Journal Number||12/2008|
|Date of Filing||14-Jul-1997|
|Name of Patentee||BAYER AKTIENGESELLSCHAFT|
|Applicant Address||D-51368 LEVERKUSEN GERMANY|
|PCT International Classification Number||A01N 43/80|
|PCT International Application Number||N/A|
|PCT International Filing date|