KR100352810B1 - Compositions for combating weeds in rice crops - Google Patents

Abstract

The present invention, in addition to any one or more rice herbicides, is a herbicide comprising synergistic amounts of anilofos (A) and 2-fluoro-4-cyanophenoxyphenoxypropionic acid esters (DEH-112, B) It relates to a composition.

Description

Herbicide composition for controlling weeds of rice crops {COMPOSITIONS FOR COMBATING WEEDS IN RICE CROPS}

Anilofos is a rice herbicide that can be used to selectively control annual turf and forage from transplanted rice. (See Pesticide Manual, British Crop Port. Council, 9th Ed., P 36).

Japanese Laid-Open Publication No. 54 160731 (German Publication No. 2821509 or British Patent 2020978) discloses 2,4 D. MCPB, naproanilide. Anilophos, mixed with dymron and bentazone, has been described as synergistic in controlling weeds in rice crops. Combinations with other active compounds are described in patent application No. 42 36 475.2.

On the other hand, other weeds are known in Japan and Southeast Asia that cannot be permanently or properly controlled using the above-mentioned combinations. These are particularly perennial organisms in the soil, as well as weeds such as Sagittaria spp., Eleocharis spp., Cyperus serotinus and Scirpus Juncoides . Also included are other weeds that germinate predominantly from and hence are more difficult to control than weeds that germinate from seeds. Surprisingly, biological greenhouse experiments with various herbicidal compounds have found mixtures with novel synergistic activity.

The present invention provides an effective amount of a compound of the following general formula (I) (anilophos, A) and a compound of the following general formula (II) (DEH-112, 2-fluoro-4-cyanophenoxyphenoxypropionic acid ester , B) and a mixture of salts thereof.

In the above formula,

R is hydrogen or (C ₁ -C ₆ ) -alkyl.

If desired, one or more known rice herbicides (C) of the class having very different structures may be further mixed and used. Of particular interest are compounds of the sulfonylureas, amides, cyclohexanediones, thiocarbamates or chloroacetanilide classes.

Specific examples of the above additionally mixed herbicides which may be mentioned without limitation are the following compounds:

C1, AC-014

C2, Ventazone

C3, bensulfuron-methyl

C4, Benzophene

C5, bromobutide

C6, Butachlor

C7, Butenachlor

C8, Cynmethyline

C9, cynosulfuron

C10, α -chloro-N- (3-methoxy-2-thienyl) methyl-2 ', 6'-dimethylacetanilide (NSK-850)

C11, dimuron (1- (1-methyl-1-phenylethyl) -3-p-tolyl-urea)

C12, 1-dimethylcarbamoyl-3- (2,4,6-trimethylphenylsulfonyl-1,2,4-triazole)

(CH-900)

C13, dimepiperate

C14, dimethacrylate

C15, Dithiopyr

C16, DPX-47

C17, Espprocab

C18, 4-ethoxybenz-2,3'-dihydrochloroanilide (HW-52)

C19, phenoxaprop-ethyl or phenoxaprop-P-ethyl

C20, imazosulfuron

C21, JC 940 (1- (2-chlorobenzyl) 3- ( α, α -dimethylbenzyl) urea

C22, MCPB

C23, mefenacet

C24, Molinate

C25, naproanilide

C26, piperofoss

C27, pretilachloro

C28, propanyl

C29, pyrazosulfuron-ethyl

C30, Pirazofen

C31, pyrazolate

C32, Queen Cloak

C33, simethrin

C34, Sulkotlion (Chloromesulone, ICI-A0051)

C35, thioubencab

C36, 2,4-D

However, other rice herbicides can also be used advantageously with the mixtures according to the invention.

Compound A is described in Pesticide Manual, British Crop Prot. Council, 9th Ed., P 36. Compound B is described in European Patent Application EP 0 302 203.

In the general formulas referring to compounds A and B, stereochemistry is not mentioned in detail. When stereoisomers are produced, all geometric isomers, enantiomers and diastereomers and mixtures thereof are also included in the above general formula.

Compound DPX-47 = DPX-A8947, N-((4,6-dimethoxypyrimidin-2-yl) aminocarboxy) -1-methyl-4- (2-methyl-2H tetrazol 5 day) -1- H-pyrazole-5-sulfonamide has the following structural formula:

Compound AC-014, 1- (2- (cyclopropylcarbonylphenyl) sulfamoyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea has the formula: U.S. Patent 5,009,699 (June 22, 1990):

Compound imazosulfuron (TH-913) is described in patent application EP-A-0 238 070 (see Example 1).

Compound NSK-850 ( α -chloro-N- (3-methoxy-2-thienyl) -methyl 2 ', 6'-dimethylacetanilide) has been described by M. Ogasawara et al. In "Weed Research" ( Tokyo). 1989, pp 131-137.

Compound HW-52 (4-ethoxybenz-2,3-dihydrochloroanilide) is described in N. Ichizen et al., "Weed Research", (Tokyo). 1990, pp 261-267.

Compound CH-90O (1-diethylcarbamoyl-3- (2,4,6-trimethylphenylsulfonyl) -1,2,4-triazole) is described in EP-332 133.

Compound sulfotions (chloromesulone, 2- (2-chloro-4-mesylbenzoyl) cyclohexane-1,3-dione) are described in EP 0 298 680 (see compound number 51A on page 13). Other compounds of type C are described in "The Pesticidc Manual", British Crop Protection Council, 9th Ed., 1991.

Specific examples of the active compound mixtures claimed herein, which may be mentioned without limitation, are as follows:

1.A + B

2.A + B + C1 (AC-014)

3.A + B + C3 (bensulfuron-methyl)

4.A + B + C19 (imazosulfuron)

5.A + B + C27 (pyrazosulfuron-ethyl)

When applied together, the mixtures according to the invention show very good activity against a number of economically important monocotyledonous and dicotyledonous weeds. Even difficult to control perennial weeds germinating from rhizomes, roots or other perennial organisms are easily overcome by the mixture of the active compounds. It is not important whether the mixture is applied before sowing, before germination or after germination. The monocotyledonous and dicotyledonous weeds that can be controlled by the composition according to the present invention are not limited to a particular kind and some representative examples may be mentioned in more detail by the examples.

During the year, monocotyledonous weed species such as Echinochloa and Cyperus species and perennial species, i.e. cold-resistant Cypressus species, are readily controlled.

Weeds grown in rice under certain crop conditions, for example, fructose , Alisma , Rotala , Monochoria , Eleocharis , sirpus , cypressus and the like according to the invention It is controlled in an excellent way by mixtures of the active compounds.

When the herbicide composition according to the present invention is applied to the soil surface before germination, germination of weed seedlings is completely inhibited, or weeds grow up to the cotyledon stage, but their growth stops shortly and finally dies after 3 to 4 weeks. .

When the mixture of the active compounds according to the invention is applied to a part of a green plant or to irrigation water after rice crop germination, growth stops very rapidly after treatment. Since weeds remain in the growth stage when applied, or die somewhat quickly after a certain time, competitive weeds that are harmful to crops can be removed very early by continuing to use the novel compositions according to the invention.

The composition according to the invention has excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, but only slightly or no damage to crop rice. For this reason, the compositions are particularly well suited to selectively inhibit undesirable plant growth in rice.

The composition is superior to known herbicides and mixtures thereof with respect to various actions and efficacy and can be used at low application rates. Another advantage of the new mixtures is their continuous action, which lasts for several weeks, eliminating the need for subsequent application of herbicides to prevent weeds from germinating. In other words, the growth of competing weeds can be eliminated in a single application, so there is no need to process them again.

With the mixture of the active compounds according to the invention, the herbicidal action is achieved beyond what is expected on the basis of the action of the individual components. Thus, the use of such mixtures can significantly reduce the amount of individual active compound used. The use of a mixture of herbicides can also speed up the action. This property provides a significant benefit to the user when actually controlling weeds. Users can control weeds more cheaply, faster, and with less effort, more permanently, resulting in greater yields in one crop group.

It has also been found that in the mixture of many active compounds there is a considerable degree of action of a toxic agent or antidote. That is, it has been found that the phytotoxic side effects of the active compounds used can be reduced or completely avoided in crops such as rice.

The mixing ratio of A, B and C can vary within wide ranges. In particular, it depends on the mixture partner used, weed growth stage, weed range and climatic conditions. The application rate of herbicide A in the mixture is 50 to 500 g active substance / ha, and the application rate of B is 50 to 600 g active substance / ha. In addition, the application rate of other rice herbicides optionally added may vary widely depending on the difference in structure.

The mixture of active compounds according to the invention can be present as a mixed blend of divalent components and applied in conventionally diluted form with water or as granules, or separately prepared components can be prepared in a so-called tank mixture by dilution with water.

Mixtures of compounds can be formulated in a variety of ways depending on the biological and / or physicochemical parameters described. Suitable formulation candidates are, for example: wettable powders (WP), emulsifiable concentrates (EC), aqueous solutions (SL), emulsions (EW) (e.g. oil-in-water and water-in-oil emulsions), sprays or Spray emulsions, oily or aqueous dispersions, suspension emulsions, dusting agents (DP), seed-dressing agents, in particular granules for soil application or spraying, water-dispersible granules (WG), ULV blends, microcapsules or waxes.

Such individual types of combinations are known in principle, for example binnaker-quihler ( "Chemische Technologie" (chemical Technology) Volume 7, C. Hauser Verlag Munich, 4th edition 1986; Van valkenburg, "Pesticide Formulations", Marcel Dekker NY, 2nd Ed. 1972-73; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979. G. Goodwin Ltd. London.

Necessary compounding aids are known, for example impurity substances, surfactants, solvents and other additives and are described, for example, in Watkins, "Handbook of Insecticide Dust Diluents and Carriers," 2nd Ed., Darland Books. , Caldwell NJ; HV Olphen, "Introduction to Clay Colloid Chemisty", 2nd Ed., J. Wiley Sons, NY, Marsden, "Solvents Guide", 2nd Ed., Interscience, NY 1950; McCutcheon, "Detergents and Emulsifiers Annual", NC Publ. Corp., Ridgewood NJ; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., NY 1964; Schonfeld ( ) [" (Surface-Active Ethylene Oxide Adducts), Wiss. Verlagsgesell., Stuttgart 1976; Winnacker- "Chemische Technologie" (Chemical Technology), Volume 7, C. Hauser Verlag Munich, 4th edition 1986.

On the basis of the above formulations, mixtures with other pesticidal active substances, for example other herbicides, fungicides or pesticides, and also fertilizers and / or growth regulators, can be prepared, for example, in the form of the final formulation or in a tank mixture.

Wettable powders may be uniformly dispersed in water and, in addition to active compounds, with the exception of diluents or inert materials, wetting agents (e.g. polyoxyethylenated alkylphenols, polyoxyethylenated fatty alcohols or fatty amines, alkanesulfonates, alkylbenzenes) Sulfonates) and dispersants such as sodium lignosulfonate, sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, sodium dibutylnaphthalenesulfonate or optionally sodium oleoylmethyl taurate It is a formulation containing.

Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent such as butanol, cyclohexanone, dimethylformamide, xylene or alternatively a relatively high boiling aromatic or hydrocarbon with the addition of one or more emulsifiers. Emulsifiers that may be used are, for example, alkylarylsulfonic acid calcium salts such as Ca dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide Ethylene oxide condensates, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters).

Dust compositions are obtained by grinding the active compound with finely ground solid materials such as talc; natural clays such as kaolin, bentonite and pyrophyllite; or diatomaceous earth.

Granules can be used to spray active compounds onto adsorbent granulated inert materials, or to concentrate concentrates of the active compounds by adhesives such as polyvinyl alcohol, sodium polyacrylate or optionally mineral oils such as sand, kaolinite or granulated inert materials. It can be prepared by applying to the surface of the carrier. Suitable active compounds may also be granulated, optionally in a mixture with fertilizers, in a manner customary for the preparation of fertilizer granules.

Agrochemical formulations generally contain from 0.1 to 99% by weight, in particular from 2 to 95% by weight of active compounds A and B and optionally C. The concentration of active compounds A, B and optionally C in the combination may vary.

In wettable powders, the active compound concentration is, for example, about 10-95% by weight in 100% by weight, with the remainder being a conventional blending component. For emulsifiable concentrates, the concentration of the active compound may be about 1 to 85% by weight, preferably 5 to 80% by weight. The formulation in dust form contains about 1 to 25% by weight, at most 5 to 20% by weight of active compound, and the spray solution contains about 0.2 to 25% by weight, preferably 2 to 20% by weight of active compound. For granules, such as water-dispersible granules, the active compound content depends in part on whether the active compound is present as a liquid or as a solid and whether granular aids and fillers are used. Generally, for water-dispersible granules the content is 5 to 90% by weight. In the case of spraying granules which are sparged directly in irrigation water, they are generally from 1 to 50%, preferably from 2 to 25% of the active compound.

The combinations of the active compounds mentioned also optionally in each case optionally contain an adhesive, a wetting agent, a dispersant, an emulsifier, a penetrant, a solvent, a filler or a carrier.

In application, the formulations present in the commercially available form are optionally diluted in conventional manner, for example with wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules. It is common for the preparations in the form of dust, soil or spray granules and spray solutions to be no longer diluted with further inert substances before application.

The required application rates of compounds A and B vary, in particular, depending on external conditions such as temperature, humidity, type of herbicide used.

The following examples are intended to illustrate the invention.

A. Formulation Examples (Combination Examples)

(a) A dust composition was obtained by mixing 10 parts by weight of a mixture of the active compounds according to the invention and 90 parts by weight of talc as an inert material and grinding with a hammer mill.

(b) an easily water-dispersible wettable powder comprising: 5 parts by weight of a mixture of active compounds, 64 parts by weight of kaolin-containing quartz as inert material, 10 parts by weight of potassium lignosulfonate, and sodium oleoylmethyltau as wetting agent and dispersant Obtained by mixing 1 part by weight and grinding on a pin disk mill.

(c) easy to be - ^(? Triton (Triton) × 207) 20 parts by weight of a mixture of a dispersible dispersion concentrate active compounds, alkylphenol polyglycol ether, 6 parts by weight, isophthalic tree decanol polyglycol ether (8 EO) 3 wt. Part and 71 parts by weight of paraffinic mineral oil (boiling range, for example about 255 to 277 ° C.) were mixed and obtained by grinding with a powder of 5 microns or less in a wear ball mill.

(d) An emulsifiable concentrate was obtained from 15 parts by weight of a mixture of active compounds, 75 parts by weight of cyclohexanone as a solvent and 10 parts by weight of ethoxylated nonylphenol as an emulsifier.

(e) the water-dispersible granules were mixed with 75 parts by weight of the active compound mixture, 10 parts by weight of calcium lignosulfonate, 5 parts by weight of sodium lauryl sulfate, 3 parts by weight of polyvinyl alcohol and 7 parts by weight of kaolin, and Obtained by grinding in a mill and spraying water as granulation liquid to granulate the powder in a fluidized bed.

(f) 25 parts by weight of the mixture of the active compound, 5 parts by weight of sodium 2,2'-dinaphthylmethane-6,6'-disulfonate, and 2 parts by weight of sodium oleoylmethyltaurate. , 1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 parts by weight of water are homogenized and pre-crushed in a colloid mill, ground in a bead mill, sprayed, and the resulting suspension is sprayed in a spray tower by one material nozzle. Obtained by drying.

B. Biological Examples

1. Weed action before germination

Some of the seeds or rhizomes of monocotyledonous and dicotyledonous weeds were placed in sandy loam soil in a plastic pot 9 cm in diameter and covered with soil. Weeds growing on rice cultivation were grown in water-saturated soils, and pots were filled with water to or even up to several millimeters above the soil surface.

The mixtures of the active compounds according to the invention, formulated in the form of wettable powders or emulsifiable concentrates, and in similar tests are applied to the surface of the soil covered with the respective active compounds correspondingly formulated, or equivalent to 300 to 600 l / ha for rice. The water application rate was poured into irrigation water in different application amounts as an aqueous suspension or emulsion.

After treatment, the pots were kept in greenhouses under good growth conditions in the weeds. Visual assessment of plant damage or germination damage was performed after germination of the test plants after the 3-4 week test period compared to the untreated control. The herbicide compositions according to the invention have good pre-germination herbicidal activity against a wide range of grass weeds and weeds.

In all cases, the functionality of the mixture differs between the calculated and measured values. The theoretically expected calculation of the functionality of the mixture is determined by the formula of S. R. Colby: Calculation of synergistic and antagonistic responses of herbicide combinations, Weeds 15, pp 20-22 (1967).

The formula is as follows for a mixture of two components:

The mixture of three herbicidal active compounds is as follows:

In the above formula,

X =% damage by herbicide A at X kg / ha application rate;

Y =% damage by herbicide B at application rate of Y kg / ha;

Z =% damage by herbicide C at application rate Z kg / ha;

E = X + Y (or X + Y + Z) Percentage of damage expected by herbicide A + B (or A + B + C) at kg / ha application rate.

If the actual damage rate is greater than what is arithmetically expected, then the action of the mixture is greater than the sum of the components. In other words, there is a synergistic effect.

The mixture of active compounds according to the invention has a higher herbicidal action than expected based on the action observed when the individual components are applied alone (calculated according to Colby's formula).

2. Weed action after germination

Some of the seeds or rhizomes of monocotyledonous and dicotyledonous weeds were placed in sandy loam soil in plastic pots, covered with soil and grown in greenhouses under good growth conditions. Weeds growing on rice cultivation were grown in pots with water up to 3 cm above the soil surface, and during the trial phase. About 2 to 3 weeks after sowing the test plants were treated in the 2-3 leaf stage.

The active compound mixture according to the invention, formulated in the form of a wettable powder or an emulsifiable concentrate, and the parts of the greenhouse plant in varying dosages at the respective water application rates corresponding to 300 to 600 l / ha of the respective active compounds correspondingly formulated in a similar test Sprayed and the action of the formulation was visually evaluated in comparison with the untreated control after the test plants were allowed to stand in the greenhouse under optimal growth conditions for about 3-4 weeks. In addition, for rice or weeds growing on rice fields, the active compounds were added directly to irrigation water (similar to so-called granulation applications) or plants and sprayed on irrigation water. The composition according to the invention has good herbicidal activity against a wide range of economically important grass weeds and weeds even after germination. According to Colby analysis, the composition according to the invention is synergistic.

3. Crop Resistance

In further tests in the greenhouse, a relatively large number of crop plants and weed seeds were placed in sandy loam soil and covered with soil. Rice was grown and grown with paddy rice in soil saturated with water.

Several pots are immediately treated as mentioned in 1 above, the rest are placed in a greenhouse until the plants grow to 2 to 3 leaves, followed by the active compound mixture according to the invention as mentioned in 2 above, and Sprayed with only one individual active compound in different application amounts for comparison. In the case of rice, the application was also carried out in some cases by pouring the active compound or combination thereof into irrigation water.

Two weeks after application and standing in the greenhouse, it was found by visual evaluation that the mixture of the active compounds according to the invention does not damage various crops before and after germination even at high application amounts of the active compounds. Mixtures of the active compounds protect Gramineae crops such as wheat and rice. The mixture of active compounds according to the invention is thus applied and has a high selectivity in competition with the growth of undesirable plants in crops.

In the following, the results of the selected tests are presented in a table:

Claims (8)

Compounds of the following general formula (I) in an applied amount of 38 to 1350 g active substance / ha (anilofos, A) and compounds of the following general formula (II) in an applied amount of 38 to 400 g active substance / ha Herbicide compositions comprising a mixture of DEH-112, 2-fluoro-4-cyanophenoxyphenoxypropionic acid ester, B) or salts thereof: In the above formula, R is hydrogen or (C ₁ -C ₆ ) -alkyl. The method of claim 1, Containing from 1 to 99% by weight of the mixture of claim 1 together with conventional blending aids. Composition. The method of claim 1, Additionally containing one or more rice herbicides Composition. The method of claim 1, Further containing one or more compounds selected from the group consisting of bensulforon-methyl, pyrazolesulfuron-ethyl, imazosulfuron and AC-014 Composition. Wettable powders, emulsifiable concentrates, aqueous solutions, emulsions, sprays (tank mixtures), oily or aqueous dispersions, suspension emulsions, dust compositions, seed-dressing compositions, soil application or spraying granules, water-dispersible granules, ULV blends, A method of making a composition according to any one of claims 1 to 4, comprising combining the composition similarly to conventional plant protection agent combinations selected from the group consisting of microcapsules and waxes. The composition according to any one of claims 1 to 4, wherein the composition is Sagittaria , Alisma , Rotala , Monochoria , Eleocharis , Sirpus ( Applying to weeds or their habitats selected from the group consisting of Scirpus , Cyperus and Echinochloa , The control method of the weeds. The method of claim 6, Selective control of weeds selected from the group consisting of fructose, alisma, rotala, monochoria, eleocharis, sirpus, cypressus and echinocloe in useful crops Way. The method of claim 7, wherein Useful crops Way.