DE4236475A1 - Synergistic herbicides for selective weed control in rice crops - contain Anilofos and a second herbicide e.g. Bensulfuron methyl, Cinosulfuron or Fenoxapropethyl. - Google Patents

Abstract

Herbicides contain (A) Anilofos combined with (B) at least one of Bensulfuron methyl, pyrazosulfuron ethyl, Cinosulfuron, Imazosulfuron, AC014 (1-(2-cyclopropylcarbonyl -phenyl)-sulfamoyl)-3- (4,6-dimethoxy -pyrimidin-2-yl)urea), pyrazoxyfen, benzofenap (MY71), dymron, benfuresate, bromobutide, ACN, (quinoclamine), IC940 (1-(2-chloro-benzyl)3- alpha, alpha-dimethylbenzyl)urea) and fenoxapropethyl. USE/ADVANTAGE - The combination of (A) and (B) is esp. suitable for weed control in rice crops. The combination of (A) and (B) is synergistic. It is very well tolerated by rice and has a broad spectrum of activity against mono- and di-cotyledon weeds and against difficult to combat perennial weeds. The effect is long lasting, keeping up for several weeks, thus making it unnecessary to apply more herbicide against newly germinated weeds, thus saving effort and materials. Weeds commonly occurring in rice crops, e.g. Sagittaria, Alisma, Rotala, Monochoria, Eleocharis, Scirpus, Cyperus are controlled well by the combination, while the rice is scarcely affected.

Description

Anilofos is a selective rice herbicide that is used to control annual grasses and sedge can be used in transplanted rice. (Pesticide Manual, British Prot. Council, 9th Ed., P. 36.)

Already in 1981 it was pointed out that Anilofos with 2,4-dichlorophenoxyacetic acid (2,4-D) can be combined to make that Extending the spectrum of activity to broad-leaved weeds. In order to In addition to annual grasses such as Echinochloa spp. and Ischaemum sp. and Sedge like Cyperus difformis, Cyperus iria and Fimbristylis littoralis too broadleaved species such as Monochoria vaginalis, Sphenochlea zeylanica and Ludwigia octovalis can be fought well (1).

From Japanese laid-open publication 54 160731 (DOS 2821509 or Brit. Pat. 2020978) it is known that anilofos mixed with 2,4-D, MCPB, Naproanilide, Dymron and Bentazon have a synergistic effect in the Has weed control in rice.

On the other hand, there are more from the rice cultures in Japan and Southeast Asia Weeds known, not always with the combinations mentioned be adequately combated. This particularly includes weeds like Sagittaria spp., Eleocharis spp., Cyperus serotinus and Scirpus juncoides, however also other weed species, mainly from permanent organs in the soil germinate and can be controlled more difficult than weeds that germinate from seeds.  

Surprisingly, in biological greenhouse experiments various herbicidal active ingredients new synergistic Combinations found that when used together an extraordinary show good effectiveness against a wide range of different weeds and are also very well tolerated in rice. You are regarding range of effects and potency of the known herbicides and herbicide combinations superior and can be used in small amounts.

Other advantages of these new combinations are their lasting ones Permanent effect that lasts for several weeks and therefore subsequent ones Herbicide applications against newly germinating weeds are no longer necessary. So one can second operation can be saved by using a single application competing weed growth is eliminated.

The present invention relates to herbicidal compositions through an effective content of Anilofos (I)

in combination with at least one compound B (type B connection) from the Group which the connections

B1) bensulfuron-methyl, α- (4,6-dimethoxypyrimidin-2-yl carbamoylsulfamoyl) - methyl o-tolylate,

B2) pyrazosulfuron-ethyl, 5- (4,6-dimethoxypyrimidin-2-yl- carbomoylsulfamoyl) -1-methylpyrazole-4-carboxylic acid ethyl ester,

B3) Cinosulfuron, 3- (4,6-dimethoxy-1,3,5-triazin-2-yl) -1- [2- (2- methoxyethoxy) phenylsulfonyl] urea,

B4) imazosulfuron, 1- (2-chloroimidazo [1,2-a] pyridin-3-ylsulfonyl) -3- (4,6- dimethoxy-pyrimidin-2-yl) urea (TH-913, Example No. 1 from EP 0238070),

B5) AC 014, 1- (2- (cyclopropylcarbonylphenyl) sulfamoyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea,

B6) pyrazoxyfen, 2- [4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yloxy] - acetophenone,

B7) Benzofenap (MY71), 2- [4- (2,4-dichloro-m-toluoyl) -1,3-dimethylpyrazole-5- yloxy] -4′-methylacetophenone,

B8) dymron, 1- (1-methyl-1-phenylethyl) -3-o-tolylurea,

B9) Benfuresate, ethanesulfonic acid-2,3-dihydro-3,3-dimethylbenzofuran-5- ylester,

B10) bromobutide, 2-bromo-3,3-dimethyl-N- (1-methyl-1-phenylethyl) -butyramide,

B11) ACN, quinoclamine, 2-amino-3-chloro-1,4-naphthoquinone,

B12) IC 940, 1- (2-chlorobenzyl) -3- (α, α-dimethylbenzyl) urea and

B13) fenoxaprop-ethyl or fenoxaprop-P-ethyl, (±) or (2R) 2- [4- (6-chlorine ethyl benzoxazol-2-yloxy) phenoxy] propionate,

contains. The type B compounds are all from "The Pesticide Manual", 9. Brit edition. Crop. Prot. Council, known in 1991, except B5 (AC 014), which is known from the patent application US 5 009 699, B4 (TH-913), which from EP 00238070 is known and B12 (IC 940), which is from Japanese Patent application J-60087254 is known.

As specific examples of the active ingredient mixtures claimed named the following, without any restriction:

Anilofos + bensulfuron-methyl
Anilofos + bensulfuron-methyl + dymron

Anilofos + pyrazosulfuron-ethyl
Anilofos + pyrazosulfuron-ethyl + dymron

Anilofos + cinosulfuron
Anilofos + Cinosulfuron + Dymron

Anilofos + TH 913
Anilofos + TH 913 + Dymron

Anilofos + AC 014
Anilofos + AC 014 + Dymron.

In these combinations, the use of Dymron offers two clear advantages: on the one hand, Dymron reinforces the herbicidal activity against Cyperus spp. and grasses, on the other hand Dymron also acts as a safener on the Crop rice and reduces the potential damage from herbicides, such as B. sulfonylurea derivatives can arise.

Similarly, it was observed that using the combination Anilofos with Pyrazosulfuron a surprising safener effect of Anilofos going out. Possible rice damage caused by pyrazosulfuron alone or in Mixture with other herbicides are caused by anilofos diminished or completely canceled. So this combination of active ingredients showed novel properties that go beyond the previously known effects and were found completely unexpected and surprising.

The herbicidal compositions according to the invention have excellent herbicidal properties Efficacy against a wide range of economically important mono- and dicotyledonous harmful plants. Also difficult to fight perennials Weeds that come from rhizomes, rhizomes or other permanent organs drive out, are well grasped by the active ingredient combinations. It is no matter whether the substances in pre-sowing, pre-emergence or Post-emergence procedures are applied. In particular, are exemplary called some representatives of the monocotyledonous and dicotyledonous weed flora caused by the agents according to the invention can be controlled without the  Naming a restriction to certain types.

On the side of the monocot weed species, e.g. B. Echinochloa as well Cyperus species from the annual group and on the part of the perennial Species perennial Cyperus species well identified.

Those occurring in rice under the specific culture conditions Weeds, such as B. Sagittaria, Alisma, Rotala, Monochoria, Eleocharis, Scirpus, Cyperus etc., are from the active ingredient combinations according to the invention fought superbly.

Are the herbicidal compositions according to the invention before germination on the Applied earth surface, so is either the emergence of the weed seedlings completely prevented, or the weeds grow to the cotyledon stage approach, but then stop growing and eventually die after it expires from three to four weeks.

When applying the active ingredient combinations to the green parts of the plant in Post-emergence procedures also occur very quickly after treatment drastic growth stop. The weed plants stay in the for At the time of application, the existing growth stage remains or dies a certain time more or less quickly, so that in this way a weed competition harmful to crops very early and sustainably can be eliminated by using the new agents according to the invention.

Although the compositions according to the invention have excellent herbicidal activity crops against monocotyledonous and dicotyledonous weeds Rice only slightly or not at all damaged. The funds are suitable These reasons are particularly good for selective control of rice, especially in rice unwanted vegetation.  

The active compound combinations according to the invention have a herbicidal action achieved that goes beyond what is due to the effect of Individual components are to be expected. These increases in effectiveness allow to significantly reduce the amounts used for the individual active ingredients. The Combination of herbicides can also improve their long-term effectiveness or one Accelerate the speed of action. Such Properties offer the user considerable advantages in practical Weed control. It can make weeds cheaper, faster, with less Combat workload as well as more permanent and thereby in one Crop crops harvest more yield.

It was also found that a number of the active ingredient combinations There is a strong safener or antidote effect, d. H. that phytotoxic Side effects of the active ingredients used in crops, such as. B. the Rice, reduced or avoided altogether.

The mixing ratios of the different components can be within further boundaries fluctuate. They are particularly dependent on the one used Mix partner, from the stage of development of the weeds, from Weed spectrum and climatic conditions.

The active compound combinations according to the invention can be used both as Mixed formulations of the two components are present, which are then more common Diluted with water or applied as granules be, or as so-called tank mixes by common dilution of the separately formulated components are made with water.

The connections (combinations) can be formulated in different ways depending on which biological and / or chemical-physical Parameters are specified. Coming as formulation options for example in question: wettable powder (WP), emulsifiable concentrates (EC), aqueous solutions (SL), emulsions (EW) such as oil-in-water and water-in-oil  Emulsions, sprayable solutions or emulsions, dispersions on oil or Water-based, suspoemulsions, dusts (DP), mordants, but especially as Granules for soil or litter application or water-dispersible granules (WG), ULV formulations, microcapsules or waxes.

These individual types of formulation are known in principle and will described for example in: Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986; van Valkenburg, "Pesticides Formulations ", Marcel Dekker N.Y., 2nd edition 1972-73; K. Martens," Spray Drying Handbook ", 3rd edition, G. Goodwin Ltd. London.

The necessary formulation aids such as inert materials, surfactants, Solvents and other additives are also known and will be described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers ", 2nd edition, Darland Books, Caldwell N.J .; H. v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd edition, J. Wiley Sons, N.Y., Marsden, "Solvents Guide", 2nd edition, Interscience, N.Y. 1950; McCutcheon's, "Detergents and Emulsifiers Annual", MC Publ. Gorp., Ridgewood N.J .; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Interface Active Äthylenoxidaddukte ", Scientific Publishing Company, Stuttgart 1976; Winnacker-Küchler, "Chemical technology", volume 7, C. Hauser Verlag Munich, 4th ed. 1986.

Based on these formulations, combinations can also be made with other pesticidal substances, such as other herbicides, fungicides or Manufacture insecticides, fertilizers and / or growth regulators, e.g. B. in the form of a finished formulation or as a tank mix.

Spray powders (wettable powders) are evenly dispersible in water Preparations in addition to the active ingredient other than a diluent or inert still wetting agents, e.g. B. polyoxethylated alkylphenols, polyoxethylated Fatty alcohols or fatty amines, alkane or alkylbenzenesulfonates and  Dispersants, e.g. B. sodium lignosulfonate, 2,2'-dinaphthylmethane 6,6'-disulfonic acid sodium, dibutylnaphthalene-sulfonic acid sodium or also Contain oleoylmethyl tauric acid sodium.

Emulsifiable concentrates are made by dissolving the active ingredient in one organic solvents, e.g. B. butanol, cyclohexanone, dimethylformamide, Xylene or higher-boiling aromatics or hydrocarbons, under Addition of one or more emulsifiers produced. As emulsifiers can be used 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 condensation products, alkyl polyethers, Sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or Polyoxethylene sorbitol ester.

Dusts are obtained by grinding the active ingredient with finely divided solids, e.g. B. talc, natural clays such as kaolin, bentonite and Pyrophyllite or diatomaceous earth.

Granules can either by spraying the active ingredient adsorbable, granulated inert material or by Applying active ingredient concentrates using adhesives, e.g. B. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils on which Surface of carriers such as sand, kaolinite or granulated Inert material. Suitable active ingredients can also be used in the production of Fertilizer granules in the usual way - if desired in a mixture with Fertilizers - be granulated.

The agrochemical preparations usually contain 0.1 to 99 Weight percent, in particular 2 to 95 wt .-%, active ingredients A and B. Die Concentrations of active ingredients A and B can be found in the formulations to be different.  

In wettable powders, the active ingredient concentration is e.g. B. about 10 to 95 wt .-%, the rest of 100 wt .-% consists of conventional Formulation ingredients. With emulsifiable concentrates Active ingredient concentration about 1 to 85 wt .-%, preferably 5 to 80 wt .-% be. Dust-like formulations contain about 1 to 25% by weight, usually 5 to 20 wt .-% of active ingredient, sprayable solutions about 0.2 to 25% by weight, preferably 2 to 20% by weight of active ingredient. In the case of granules, e.g. B. water-dispersible granules, the active ingredient content depends in part on whether the active compound is liquid or solid and which Granulation aids and fillers can be used. As a rule, the Content of the water-dispersible granules between 5 and 90% by weight, with scattering granules between 1 and 50%, preferably between 2 and 25%.

In addition, the active ingredient formulations mentioned optionally contain the usual adhesive, wetting, dispersing, emulsifying, penetrating, Solvents, fillers or carriers.

Those available in the commercial form are used Formulations optionally diluted in a conventional manner, e.g. B. at Wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules using water. Dust-like preparations, Soil or scatter granules as well as sprayable solutions are before the Application usually no longer diluted with other inert substances.

With the external conditions such. B. temperature, humidity, the type of used herbicide u. a., the required application rate varies Mixtures.

The following examples serve to explain the invention:  

A. Examples of formulation

• a) A dusting agent is obtained by adding 10 parts by weight of a active ingredient combination according to the invention and 90 parts by weight of talc as Mixes inert material and crushes it in a hammer mill.
• b) a wettable powder which is readily dispersible in water is obtained, by 5 parts by weight of an active ingredient combination and 64 Parts by weight of quartz containing kaolin as an inert substance, 10 parts by weight ligninsulfonic acid potassium and 1 part by weight of oleoylmethyl tauric acid Mixes sodium as a wetting and dispersing agent and in a pin mill grinds.
• c) A dispersion concentrate which is readily dispersible in water is obtained by 20 parts by weight of an active ingredient combination with 6 Parts by weight of alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight Isotridecanol polyglycol ether (8 EO) and 71 parts by weight paraffinic Mineral oil (boiling range e.g. approx. 255 to above 277 ° C) mixes and in grinded to a fineness of less than 5 microns.
• d) An emulsifiable concentrate is obtained from 15 parts by weight of one Active ingredient combination, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethylated nonylphenol as an emulsifier.
• e) A water-dispersible granulate is obtained by
  75 parts by weight of the active ingredient combination,
  10 parts by weight of calcium lignosulfonic acid,
  5 parts by weight of sodium lauryl sulfate,
  3 parts by weight of polyvinyl alcohol and
  7 parts by weight of kaolin
  mixes, grinds on a pin mill and granulates the powder in a fluidized bed by spraying water as granulating liquid.
• f) A water-dispersible granulate is also obtained by
  25 parts by weight of the active ingredient combinations,
  5 parts by weight of 2,2′-dinaphthylmethane-6,6′-disulfonic acid sodium,
  2 parts by weight of oleoylmethyl tauric acid sodium,
  1 part by weight of polyvinyl alcohol,
  17 parts by weight of calcium carbonate and
  50 parts by weight of water
  homogenized on a colloid mill and pre-comminuted, then ground on a bead mill and the suspension thus obtained is atomized and dried in a spray tower using a single-component nozzle.

Biological examples 1. Pre-emergence weed action

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weed plants are grown in Plastic pots of 9 cm in diameter laid out in sandy loam and with Earth covered. Weeds found in rice cultivation are mixed with water cultivated saturated soil, with enough water being poured into the pots that the water is up to the surface of the ground or a few millimeters above it. In the Formulated in the form of wettable powders or emulsion concentrates Active ingredient combinations according to the invention and in parallel experiments appropriately formulated individual active ingredients are then aqueous Suspensions or as emulsions with a water application rate of converted 300 to 600 l / ha, in different doses to the Surface of the covering earth applied or in the irrigation water for rice poured.  

After the treatment, the pots are placed in the greenhouse and under good growing conditions for the weeds. The optical rating the damage to the plants or the emergence occurred after the emergence of the Test plants after a test period of 3 to 4 weeks compared to untreated controls. The herbicidal compositions according to the invention have a good herbicidal pre-emergence activity against a wide range of grass weeds and weeds.

In all cases, the combinations between the calculated and distinguished the efficiency found. The calculated, theoretically too The expected efficiency of a combination is determined using the formula of S. R. Colby: "Calculation of synergistic and antagonistic responses of herbicide combinations ", Weeds 15 (1967), pages 20-22.

For combinations of two, this formula is:

and accordingly for the combination of three herbicidal active ingredients:

in which
X =% damage by herbicide A at x kg / ha application rate;
Y =% damage by herbicide B at a rate of y kg / ha;
Z =% damage by another herbicide C at a rate of application of z kg / ha;
E = the damage to be expected from the herbicides A + B (or A + B + C) at x + y (or x + y + z) kg / ha.

If the actual damage is greater than the expected damage, then the effect of the combination more than additive, d. H. it is a synergistic Effect before.

The active compound combinations according to the invention have a herbicidal action, which is higher than it is due to the observed effects of the Individual components are to be expected when used alone (calculation according to Colby). The active ingredient combinations are therefore synergistic.

2. Post-emergence weed action

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds are grown in Plastic pots laid out in sandy clay soil, covered with earth and in Greenhouse grown under good growing conditions. In rice growing occurring weeds are grown in pots in which water up to 2 cm above the ground surface, and during the test phase cultured. The test plants are grown three weeks after sowing Three-leaf stage treated.

Formulated as wettable powder or emulsion concentrates Active ingredient combinations according to the invention and in parallel experiments Appropriately formulated individual active ingredients are available in different Dosages with a water application rate of the equivalent of 300 to 600 l / ha sprayed on the green parts of the plant and after about 3 to 4 weeks of standing the test plants in the greenhouse under optimal growth conditions the effect of the preparations visually compared to untreated controls rated. With rice or with weeds that occur in rice cultivation the active ingredients are also added directly to the irrigation water (application in Analogy to the so-called granulate application) or on plants and ins Irrigation water sprayed. The agents according to the invention also have Post-emergence good herbicidal activity against a wide range economically important grasses and weeds. The effects of  Agents according to the invention are synergistic according to the Colby analysis.

Claims (7)

1. Herbicidal agents, characterized by an effective content of anilofos in combination with at least one compound B (type B compounds) from the group comprising the compounds
B1) bensulfuron-methyl, B2) pyrazosulfuron-ethyl, B3) cinosulfuron, B4) imazosulfuron, B5) AC 014, 1, - (2- (cyclopropylcarbonylphenyl) sulfamoyl) -3- (4,6-dimethoxypyrimidin-2-yl) urea, B6) pyrazoxyfen, B7) Benzofenap (MY71), B8) dymron, B9) Benfuresate, B10) bromobutides, B11) ACN (Quinoclamine), B12) IC 940, 1- (2-chlorobenzyl) -3- (α, α-dimethylbenzyl) urea and B13) fenoxaprop-ethyl or fenoxaprop-P-ethyl, contains. 2. Composition according to claim 1, characterized in that they are 1 to 99 wt .-% of an agent according to claim 1 in addition to conventional Contain formulating agents. 3. Process for the preparation of an agent according to one or more of the Claims 1 and 2, characterized in that the agent analog a customary plant protection product formulation from the group, containing wettable powders, emulsifiable concentrates, aqueous solutions, Emulsions, sprayable solutions (tank mix), dispersions on oil and Water based, suspoemulsions, dusts, mordants, soil or Scatter granules, water-dispersible granules, ULV formulations, Microcapsules or waxes formulated. 4. Process for combating undesirable plants, thereby characterized in that one on these or their acreage effective amount of an agent according to one or more of the claims 1 to 3 applied. 5. The method according to claim 4, characterized in that weeds selectively controlled in crops. 6. The method according to claim 5, characterized in that the Crop crops are rice. 7. Use of the herbicidal compositions according to one or more of the Claims 1 to 3 for selective weed control in Crop crops.