Patent Application
20130237418
1. Field of the Invention
The invention relates to novel selective herbicidal active compound combinations which comprise substituted thien-3-ylsulphonylamino(thio)carbonyltriazolin(ethi)ones and at least one compound which improves crop plant compatibility and which can be used with particularly good results for the selective control of weeds in various crops of useful plants.
2. Description of Related Art
Substituted thien-3-ylsulphonylamino(thio)carbonyltriazoline(ethi)ones are already known as effective herbicides (cf. WO-A-01/05788). However, the activity of these compounds and/or their compatibility with crop plants are not entirely satisfactory under all conditions.
Surprisingly, it has now been found that certain substituted thien-3-ylsulphonylamino(thio)carbonyltriazolin(ethi)ones, when used together with the crop-plant-compatibility-improving compounds (safeners/antidotes) described below, prevent damage to crop plants extremely well and can be used particularly advantageously as broad-spectrum combination preparations for the selective control of weeds in crops of useful plants, such as, for example, in cereals and maize.
The invention provides selective herbicidal compositions, characterized by an effective amount of an active compound combination comprising
In the definitions, the hydrocarbon chains, such as in alkyl or alkanediyl, are in each case straight-chain or branched—including in combination with hetero atoms, such as in alkoxy.
Preferred meanings of the groups listed above in connection with the formula (I) are defined below.
R3 represents hydrogen, hydroxyl, mercapto, amino, cyano, fluorine, chlorine, bromine, represents in each case optionally fluorine-, chlorine-, cyano-, methoxy-, ethoxy-, n- or i-propoxy-, acetyl-, propionyl-, n- or i-butyroyl. methoxycarbonyl-, ethoxycarbonyl-, n- or i-propoxycarbonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, represents in each case optionally fluorine-, chlorine- and/or bromine-substituted ethenyl, propenyl, butenyl, ethynyl, propynyl or butynyl, represents in each case optionally fluorine-, chlorine-, cyano-, methoxy-, ethoxy-, n- or i-propoxy-, methoxycarbonyl-, ethoxycarbonyl-, n- or i-propoxycarbonyl-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, acetylamino or propionylamino, represents propenyloxy, butenyloxy, ethynyloxy, propynyloxy, butynyloxy, propenyl-thio, butenylthio, propynyhhio, butynylthio, propenylamino, butenylamino, propynylamino or butynylamino, represents dimethylamino, diethylamino or dipropylamino, represents in each case optionally fluorine-, chlorine-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, cyclopropyloxy, cyclobutyloxy, cyclopentyl-oxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclo-hexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclo-hexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopropylmethylthio, cyclobutylmethylthio, cyclo-pentylmethylthio, cyclohexylmethylthio, cyclopropylmethylamino, cyclo-butylmethylamino, cyclopentylmethylamino or cyclohexylmethylamino, or represents in each case optionally fluorine-, chlorine-, bromine-, methyl-, trifluoromethyl-, methoxy- or methoxycarbonyl-substituted phenyl, benzyl, phenoxy, benzyloxy, phenylthio, benzylthio, phenylamino or benzylamino.
Most preferably, R1 and R2 represent methyl, ethyl, n- or i-propyl.
Preferred active compound components of group 1 are in particular also the sodium, potassium, magnesium, calcium, ammonium, C1-C4-alkylammonium-, di-(C1-C4-alkyl)ammonium-, tri-(C1-C4-alkyl)ammonium, tetra-(C1-C4-alkyl)ammonium, tri-(C1-C4-alkyl)sulphonium-, C5- or C6-cycloalkylammonium and di-(C1-C2-alkyl)-benzylammonium salts of compounds of the formula (I) in which Q1, Q2, R1, R2, R3 and R4 have the meanings given above as being preferred.
Examples of compounds of the formula (I) which are very particularly preferred as active compound components according to the invention are listed in Table I below.
Very particular emphasis as active compound components according to the invention is also given to the sodium salts of the compounds from Table 1.
Preferred meanings of the groups listed above in connection with the compounds improving crop plant compatibility (“herbicide safeners”) of the formulae (IIa), (IIb), (IIc), (IId) and (IIe) are defined below.
Examples of compounds of the formula (IIa) which are very particularly preferred as herbicide safeners according to the invention are listed in Table 2 below.
Examples of compounds of the formula (IIb) which are very particularly preferred as herbicide safeners according to the invention are listed in Table 3 below.
Examples of the compounds (IIc) which are very particularly preferred as herbicide safeners according to the invention are listed in Table 4 below.
Examples of the compounds of the formula (IId) which are very particularly preferred as herbicide safeners according to the invention are listed in Table 5 below.
Examples of the compounds of the formula (IIe) which are very particularly preferred as herbicide safeners according to the invention are listed in Table 6 below.
The compounds of the general formula (IIa) to be used as safeners according to the invention are known and/or can be prepared by processes known per se (cf. WO-A-91/07874, WO-A-95/07897).
The compounds of the general formula (IIb) to be used as safeners according to the invention are known and/or can be prepared by processes known per se (cf. EP-A-191736).
The compounds of the general formula (IIc) to be used as safeners according to the invention are known and/or can be prepared by processes known per se (cf. DE-A-22180974, DE-A-2350547).
The compounds of the general formula (IId) to be used as safeners according to the invention are known and/or can be prepared by processes known per se (cf. DE-A-19621522/U.S. Pat. No. 6,235,680/WO 97/4016).
The compounds of the general formula (IIe) to be used as safeners according to the invention are known and/or can be prepared by processes known per se (cf. WO-A-99/66795/U.S. Pat. No. 6,251,827).
Examples of the selectively herbicidal combinations according to the invention of in each case one active compound of the formula (I) and in each case one of the safeners defined above are listed in Table 7 below.
Surprisingly, it has now been found that the above-defined active compound combinations of substituted thien-3-ylsulphonylamino(thio)carbonyltriazolin(ethi)ones of the general formula (I) and/or their salts and safeners (antidotes) of group (2) listed above, whilst being tolerated very well by crop plants, have particularly high herbicidal activity and can be used in various crops, in particular in cereal (especially wheat) and maize, but also in soya beans, potatoes and rice, for the selective control of weeds.
Here, it has to be considered to be surprising that, from a large number of known safeners or antidotes which are capable of antagonizing the damaging effect of a herbicide on the crop plants, that are in particular the abovementioned compounds of group (2) which neutralize the damaging effect of substituted thien-3-ylsulphonylamino(thio)carbonyltriazolin(ethi)ones on the crop plants virtually completely without negatively affecting the herbicidal activity with respect to the weeds.
Emphasis is given here to the particularly advantageous effect of the particularly and most preferred combination partners from group (2), in particular in respect of sparing cereal plants, such as, for example, wheat, barley and rye, but also maize and rice, as crop plants.
The active compound combinations according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindemia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cuburbita, Helianthus.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.
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 manner to other plants. According to the invention, crop plants are all plants and plant varieties including transgenic plants and plant varieties, where on transgenic plants and plant varieties it is also possible for synergistic effects to occur.
The advantageous effect of the crop plant compatibility of the active compound combinations according to the invention is particularly highly pronounced at certain concentration ratios. However, the weight ratios of the active compounds in the active compound concentrations can be varied within relatively wide ranges. In general, 0.001 to 1000 parts by weight, preferably 0.01 to 100 parts by weight, and particularly preferably 0.1 to 50 parts by weight and most preferably 1 to 25 parts by weight of one of the compounds which improve crop plant compatibility mentioned under group 2 above (antidotes/safeners) are present per part by weight of active compound of the formula (I) or its salts.
The active compounds or active compound combinations can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspoemulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules 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 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. Suitable liquid solvents are essentially: 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, and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethy) sulphoxide, and also 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, 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, and also 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 fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and protein hydrolysates; suitable dispersants are: for example lignosulphite 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, and also 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 formulations generally comprise from 0.1 to 95 percent by weight of active compounds including the safeners, preferably between 0.5 and 90%.
The active compound combinations according to the invention are generally used in the form of finished formulations. However, the active compounds contained in the active compound combinations can also be mixed in individual formulations when used, i.e. in the form of tank mixes.
The novel active compound combinations, as such or in their formulations, can furthermore be used as a mixture with other known herbicides, finished formulations or tank mixes again being possible. A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, growth factors, plant nutrients and agents which improve soil structure, is also possible. For certain intended uses, in particular in the post-emergence method, it may furthermore be advantageous to include, as further additives in the formulations, mineral or vegetable oils which are tolerated by plants (for example the commercial preparation “Rako Binol”), or ammonium salts such as, for example, ammonium sulphate or ammonium thiocyanate.
The novel active compound combinations can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by washing, spraying, atomizing, dusting or scattering.
The amounts of the active compound combinations according to the invention applied can be varied within a certain range; they depend, inter alia. on the weather and on soil factors. In general, the application rates are between 0.001 and 5 kg per ha, preferably between 0.001 and 1 kg per ha, particularly preferably between 0.003 and 0.5 kg per ha.
The active compound combinations according to the invention can be applied before and after emergence of the plants, that is to say by the pre-emergence and post-emergence method.
The active compound or safener components are in each case dissolved in a few ml (generally 2-3 ml) of solvent (generally acetone or N,N-dimethyl-formamide), and the solutions are combined and then—if appropriate after addition of an emulsifier—diluted with water to the desired concentration. In general, an aqueous spray liquor was prepared using 0.1% of the additive Renex-36.
The test plants are grown under controlled conditions (temperature, light, atmospheric humidity) in a greenhouse. The test plants are sprayed when they have reached a height of 5-15 cm. The concentration of the spray liquor is chosen such that the particular amounts of active compound desired are applied in 5001 of water/ha.
After spraying, the pots with the test plants are kept in a greenhouse chamber under controlled conditions (temperature, light, atmospheric humidity) until the test has ended. About three weeks after the application, the degree of damage to the crop plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
Active compounds, application rates, test plants and results are shown in the tables below, the terms being used in the tables being as defined below:
maize=maize cv. “Pioneer”
a.i.=active ingredient=active compound/safener
Here, an aqueous spray liquor comprising 0.5% of the additive Renex-36 was prepared.
The compound I-2 was used as 10 WP. In each case, Marlipal® was added in an amount of 500 ml/ha.
Evaluation was carried out as early as 7 days after the application.
Maize 1=maize of the cultivar “Prinz”
Maize 2=maize of the cultivar “Pioneer”
Maize 3=maize of the cultivar “LIXIS”
Mefenpyr-diethyl was used as 100 EC.
The compounds of Ex. Nos. I-2 and I-13 were used as 10 WP.
Mefenpyr-diethyl was used as 100 EC and the compound of Ex. No. I-2 was used as 10 WP.
| Number | Date | Country | Kind |
|---|---|---|---|
| 101 46 590.4 | Sep 2001 | DE | national |
This application is a Continuation of U.S. application Ser. No. 10/489,092, filed Sep. 7, 2004, which is a §371 National Stage Application of PCT/EP2002/010104, filed Sep. 10, 2002, which claims priority to German Application No. 101 46 590.4, filed Sep. 21, 2001, the content of all of which are incorporated herein by reference in their entireties.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10489092 | Sep 2004 | US |
| Child | 13873656 | US |
