MXPA99001934A - Herbicides based on 4-bromo-1-methyl-5-trifluoromethyl-3-(2-fluoro-4-chloro-5-isopropoxycarbonylphenyl)pyrazole - Google Patents

Abstract

The invention concerns novel synergistic herbicides based on 4-bromo-1-methyl-5-trifluoromethyl-3-(2-fluoro-4-chloro-5-isopropoxycarbonylphenyl)pyrazole and heteroaryloxyacetamides.

Description

HERBICIDE AGENTS BASED ON 4-BROMO-1-METHYL-5-TRIFLUOR-METHYL-3- (2-FLUOR-4-CHLORO-5-ISOPROPOXICARBONYLPHENYL) -PIRA-2QL. Field of the invention The task of the present application was to make available a new combination of synergistic herbicidal active compounds based on a new active product of the 3-phenylpyrazole class as well as an active product of the heteroaryloxyacetamide class. with marked effect against both monocotyledonous and dicotyledonous weeds. Description of the prior art. Both the 3-phenylpyrazole class and the heteroaryloxyacetamide class have been tested for their herbicidal activity. EP 361 114 describes in general 3- (4-chlorophenyl) -pyrazoles as herbicides for the control of various weeds in pre-emergence as well as post-emergence, especially in rice crops. JP 03 163 063 also describes the use of 3-substituted phenolpyrazoles for the herbicidal use in agriculture. Finally, US 5 281 571 3-substituted phenylprazoles are described for herbicidal use. Possible components of REF are also cited in this publication. 29565 mixture, among which are described 2-chloro-N, N-di-alkylacetamide, N, N-dimethyl-2, 2-diphenylacetate ida, N- (2,4-dimethylthien-3-yl) - N- (1-methoxyprop-2-yl) -2-chloroacetamide, N- (1H-pyrazol-1-ylmethyl-N- (2,4-dimethylthien-3-yl) -2-chloroacetamide, N- (l-pyrazol-1-ylmethyl) -N- (4,6-dimethoxypyrimidin-5-yl) -2-chloracetamide and N- (2, 4-dimethyl-5- [[[(trifluor ethyl)) sulfonyl] amino] -phenyl] -acetamide However, no mixture has been described with an acetamide herbicide and with a defined 3-phenylpyrazole Detailed description of the invention Surprisingly it has now been found in biological assays, and herein lies the solution of the task, than 4-bromo-l-methyl-5-trifluoromethyl-3- (2-fluoro-4-chloro-5-iso-propoxycarbonylphenyl) pyrazole of the formula (I) presents both alone and in admixture with a herbicide of the class of heteroaryloxyacetamides, when excellent synergistic properties are used together in terms of effectiveness against weeds. The active product can be used in a particularly advantageous manner alone or as a preparation in combination of broad activity, for the selective fight against weeds - both monocotyledonous weeds and dicotyledonous weeds, in the pre-emergence procedure and post-emergence crops in monocotilédoneas and dicotyledonous useful plant crops, such as for example maize, wheat, barley, rice, soybeans and cotton, whereby a series of economically important weeds (problematic) are combated in a safe manner. The object of the invention are herbicidal, synergistic agents, characterized by an active content in a combination of active products constituted by 4-bromo-l-methyl-5-trifluoromethyl-3- (2-fluoro-4-chloro-5-isopropoxy -carbonylphenyl) pyrazole of the formula (I) C and an active product of the formula (II) wherein Het means a substituted heteroaromatic radical, if any, substituted from the group consisting of 1,3-thiazol-2-yl, 1,2,4-thiadiazol-2-yl, 1,3,4-thiadiazol-2-yl, benzoxazol-2-yl and benzothiazol-2-yl, R 1 means alkyl with 1 to 4 carbon atoms, alkenyl with 3 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms substituted respectively, and R 2 means alkyl with 1 to 4 carbon atoms, alkenyl having 2 to 4 carbon atoms or phenyl substituted, respectively, if appropriate. Particularly preferred are the herbicidal compositions according to the invention of the compound of the formula (I) mentioned above with the N-isopropyl-N- (4-fluorophenyl) -amide of (5-trifluoromethyl-1,3,4-thiadiazole-2) acid. -il-oxy) -acetic of the formula (II-l) The compound of formula (II-1) is known, for example, from EP-A 348 737 and US 4 968 342. Heteroaryloxyacetamides defined under group (II) preferably act against monocotyledonous weeds (= weeds). They also act, however, in addition against some bad dicotyledonous grass. It has been found now, surprisingly, that the combinations of active products previously defined, constituted by heteroaryloxyacetamides of the formula (II) and by 4-bromo-l-methyl-5-trifluoromethyl-3- (2-fluoro-4-chloro-5- isopropoxycarbonylphenyl) pyrazole, have a particularly high herbicidal activity and can be used selectively in many crops. Surprisingly, the herbicidal activity of the active compound combinations according to the invention is considerably greater than the sum of the effects of the individual active products. Therefore a real synergistic effect is not predictable and not only a complement of the effects. The new combinations of active products are perfectly compatible with many crops, attacking new combinations of active ingredients also with weeds that are difficult to combat otherwise, such as Galium aparine and Loliu types. The new combinations of active products therefore represent a valuable enrichment of the selective herbicides. The active compound combinations according to the invention can be used, for example, on the following plants: Dicotyledonous bad herbs of the kinds; Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Ga-linsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portu-lac, Xanthium, Convolvulus, Ipo oea, Polygonum, Sesba-nia, Ambrosia, Cirsium, Carduus, Sonchus, Rorippa , Rota-la, Lindemia, Lamium, Veronica, Abutilon, Emex, Aids, Datura, Viola, Geleopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxum. Dicotyledonous crops of the classes; Gossypium, Glyci-ne, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vivia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuc, Cucumis, Cucurbita. Bad monocotyledonous herbs of the kinds; Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Loliu, Bromus, Oats, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fim-bristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecuus, Apera. Monocotyledonous crops of the classes; Oryza, Zea, Triticuym, Hordeum, Oats, Sécale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Alliu. The use of the combinations of active compounds according to the invention is, however, not limited in any way to these classes, but they also extend equally over other plants. The synergistic effect of the combinations of active products according to the invention is especially marked with certain proportions of concentration. However, the proportions by weight of the active products in the combinations of active products can vary within a relatively wide range. In general, from 1 part by weight of active compound of the formula (I) are from 0.001 to 1000 parts by weight, preferably from 0.01 to 100 parts by weight and, more preferably, from 0.1 to 30 parts by weight. parts by weight of active compound of the formula (II). The active ingredients can be converted into customary formulations, such as solutions, emulsions, sprayable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with the active compound , as well as micro-encapsulations in polymer materials. These formulations are prepared in known manner, for example by mixing the active ingredients with extender materials, that is, with liquid solvents and / or solid excipients, if appropriate, using surfactants, that is, emulsifiers and dispersants. and / or foam generating means. In the case of using water as an extender, organic solvents can also be used, for example, as auxiliary solvents. Suitable liquid solvents 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, fractions of crude oil, mineral and vegetable oils, alcohols, such as butanol, or glycol, as well as their esters and ethers, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, or cyclohexanone , strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, as well as water. Suitable solid excipients 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 silicic acid, highly dispersed, aluminum oxide and silicates as solid excipients for granulates come into consideration: for example, broken and fractionated natural minerals such as calcite, marble, pumice, sepiolite, dolomite, as well as synthetic granules of inorganic and organic flours, as well as Granules of organic materials, such as sawdust, coconut husks, corn ears and tobacco stems; suitable emulsifiers and / or foam generators are, for example, nonionic and anionic emulsifiers, such as polyoxyethylenated esters of fatty acids, for example, alkylaryl polyglycol ether, alkylsulphonates, alkyl sulfates, arylsulfonates, as well as albumin hydrolysates; Suitable dispersants are, for example, sulfitic leaching of lignin and methylcellulose. Adhesives such as carboxymethylcellulose, natural and synthetic polymers powdery, granulated or in the form of latex, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids, such as cephalin and lecithin, and synthetic phospholipids can be used in the formulations. . Other additives can be mineral and vegetable oils. Dyes, such as inorganic pigments, for example, iron oxide, titanium oxide, ferrocyanic blue and organic dyes, such as alizarin dyes, metal azo and phthalocyanine dyes and trace nutrients, such as iron salts, can be employed. , manganese, boron, copper, cobalt, molybdenum and zinc. The formulations generally contain between 0.1 to 95% by weight of active substance, preferably between 0.5 and 90%. The active compound combinations according to the invention will be used, in general, as ready-to-use formulations. The active products, contained in the combinations of active products, can be mixed in the case of their application, in individual formulations, that is to say that they can be used in the form of tank mixtures. The new combinations of active products can find application as such or in their formulations as well as in a mixture of other known herbicides, while ready-to-use formulations or tank mixtures are possible. A mixture with other known active substances is also possible, such as fungicides, insecticides, acaricides, nematicides, protective substances against ingestion by birds, growth substances, nutrient substances of the plants and means for improving the structure of the ground. For certain purposes of application, especially in the post-emergence process, it can also be advantageous to incorporate in the formulations, in the form of other additional products, vegetable mineral oils compatible with the plants (for example the commercial product "Oil Dupont HE ") or ammonium salts, such as, for example, ammonium sulfate or ammonium rodanide. The novel active compound combinations according to the invention can be used as such, in the form of their formulations or of the forms of application prepared therefrom by further dilutions, such as ready-to-use solutions, suspensions, emulsions, powders, pastes. and granulates. The use is carried out in the usual way, for example, by watering, spraying, spraying, spreading. The application rates of the active compound combinations according to the invention may vary within certain limits; These depend, among other things, on the climatology and the terrain factors. In general, the application amounts are preferably between 0.05 and 5 kg per ha, more preferably between 0.1 g and 3.0 kg per ha. The active compound combinations according to the invention can be applied both before and after the outbreak of the plants, ie in pre-emergence and post-emergence procedures. The good herbicidal effect of the new combinations can be seen by means of the following examples.

While the individual active products have weak points in their herbicidal effect, the combinations present, as a rule, a very good weed-destroying effect, which goes beyond the mere sum of the effects. A synergistic effect is presented in the herbicides provided that the herbicidal effect of the combination of the active products is greater than that of the active products applied individually. The expected effect for a given combination of two herbicides can be calculated as follows (see COLBY, SR, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, pages 20-22, 1967): If X =% damage caused by herbicide A (active product of formula I) with an application amount p kg / ha and Y =% damage caused by herbicide B (active product of formula II) with an application amount of q kg / ha and E = the expected damages caused by herbicides A and B with application quantities p and q kg / ha, then E = X + Y- (XY / 100). If the actual damages are greater than those calculated, then the combination will be over-additive in its effect, that is, it shows a synergistic effect. It is clear from the following examples that the herbicidal effect of the combinations of active products according to the invention, on weeds, is greater than that calculated, that is to say that the new combinations of active products have a synergistic effect. Application examples In order to obtain the active compound preparations necessary for the tests, corresponding amounts of a water-dispersible powder formulation (WP) of the heteroaryloxyacetamide of the formula (II-1) or respectively a commercially available formulation of the active compound are used. the formula (I) and diluted with water to the desired concentration; by mixing, various combinations of both active products were prepared. The tests were carried out in the following manner: A) Pre-shoot / greenhouse test. Seeds of the test plants were planted in normal soils and after 24 hours they were watered with the preparation of the active product. In this case, the quantity of water per unit of surface is con- stantly constant. The concentration of the active products in the preparation does not play any role, the fundamental being just the amount of application of active product per unit area. After the treatment, the test plants are kept in the greenhouse under controlled conditions (temperature, humidity, light) until the evaluation. After three weeks, the degree of deterioration of the plants is evaluated in% deterioration compared to the development of the untreated control plants. Means: 0% = no effect / deterioration (like untreated controls) 100% = total destruction. B) Post-emergence / greenhouse test. Powders of test plants having a height of 5 to 15 cm are sprayed with the active compound preparations in such a way that the desired quantities of active compound are applied in each case per unit area. The concentration of the sprayable broths is chosen in such a way that the quantities of active products desired in each case are applied in 500 liters of water per hectare. After treatment, the test plants are kept in the greenhouse under controlled conditions (temperature, humidity, light) until the evaluation. After three weeks, the degree of deterioration of the plants is evaluated in% deterioration compared to the development of the untreated control plants. It means: 0% = no effect / deterioration (like untreated controls), 100% = total destruction. The active products, the application quantities and the results can be seen respectively in the following tables. Table l; Herbicidal effect against Apera spica-venti of (I) (II-1) and of the tank mixture of (I) and (Il-1) in the pre-sprout procedure.

Table i; (Continuation) Table 2; Herbicidal effect against Stellaria media of (I), (II-1) and of the tank mixture of (I) and (II-1) in the post-emergence procedure.

Table 2; (Continuation) .

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (5)

CLAIMS Having described the invention as above, property is claimed as contained in the following:

1. - Herbicidal agents, characterized in that they have an active content of a combination of active compounds constituted by 4-bromo-l-methyl-5-trifluoro-methyl-3- (2-fluoro-4-chloro-5-isopropoxycarbonylphenyl) pyrazole (I ) and by an active product of the formula (II) wherein Het means a substituted heteroaromatic radical, if any, substituted from the group consisting of 1,3-thiazol-2-yl, 1,2,4-thiadiazol-2-yl, 1,3,4-thiadiazol-2-yl, benzoxazol-2-yl and benzothiazol-2-yl, R 1 means alkyl with 1 to 4 carbon atoms, alkenyl with 3 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms substituted respectively, and R 2 means alkyl with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms or phenyl substituted respectively, if appropriate.

2. - Herbicidal agents, characterized in that they have an active content of a combination of active products constituted by 4-bromo-l-methyl-5-trifluoromethyl-3- (2-fluoro-4-chloro-5-isopropoxycarbonylphenyl) pi -razol (I) and the N-isopropyl-N- (4-fluorophenyl) -amide of (5-trifluoromethyl-1,3,4-thiadiazol-2-yl-oxy) -acetic acid (Il-i).

3. - Herbicidal agents according to claims 1 and 2, characterized in that they can be used both in the pre-emergence procedure and in the post-emergence procedure.

4. - Herbicidal agents according to claims 1 and 2, characterized in that they contain, relative to a part by weight of the active compound of the formula (I), from 0.001 to 1,000 parts by weight of active compound of the formula (II).

5. - Herbicidal agents according to claims 1 and 2, characterized in that they contain between 0.1 and 95% by weight of the combination of the active products.