ITMI942276A1 - SYNERGIC COMPOSITIONS FOR THE FIGHT AGAINST THE DEVELOPMENT OF UNWANTED VEGETATION IN RICE CULTIVATIONS - Google Patents

Abstract

Synergic herbicide compositions with a content of N-phenoxysulfonyl-N '- (4, 6-disubstituted-pyrimid-2yl) -replacements and esters of 2-fluoro-4-cyanophenoxyphenoxy-propionic acid as well as possibly one or more herbicides from paddy field.

Description

"Synergistic compositions for the fight against the development of unwanted vegetation in rice crops"

DESCRIPTION

The invention lies in the field of plant protection agents which can be used against monocotyledonous and dicotyledonous weeds. In German patent applications P 38.16.704.2 (EP-A-0.342.569), P 38.16.703.4 (EP-A-0.342.568) and P 39.09.053.1 (EP-A-0.388.771) phenoxy-sulfonylureas are described heterocyclically substitutes with which it is possible to fight a wide spectrum of monocotyledonous and dicotyledonous weeds. They can be used both as soil herbicides as well as through the leaves and also show a particularly high selectivity in monocotyledonous cultivated plants, such as wheat, maize and rice.

From P 39.33.543.7 and P 40.31.799.4 and P 42.09.475.5 mixtures of active ingredients are known which show a synergistic enhancement of success in the fight against important problematic weeds in wheat and rice.

However, in rice there is a whole series of very important monocotyledonous weeds from an economic point of view, such as Cyperus serotinus, Sagittaria spp., Eleocharis spp., Scirpus spp., Echinochtoa spp. and others, which cannot be optimally fought with the mixtures mentioned alone.

Surprisingly, it has now been possible to identify in biological tests active herbicidal principles which, in simultaneous use with the single compounds previously mentioned, have distinctly synergistic characteristics from the point of view of efficacy against weeds and therefore are superior to the combinations known from the applications for patent P 39.33.543.7 and P 42.09.475.5

Object of the present invention are herbicidal compositions characterized in that they have an effective content of

A) compounds of general formula (I) or their salts

0)

in which

a ^) R ^ represents ethoxy, propoxy or isopropoxy e

2

R represents halogen, NO2, CF3, CN, 1 to 4 carbon alkyl, 1 to 4 carbon alkoxy, 1 to 4 carbon alkylthio or alkoxy (1 to 4 carbon atoms) -carbonyl and

n means 0, 1, 2 or 3, or

a2) represents halogen, methoxy, ethyl or propyl each time in position 2 on the phenyl residue,

2

R represents alkoxy (1 to 4 carbon atoms) -carbonyl in position 6 in the phenyl residue e

n = 1

as well as in all cases) and a2)

R represents hydrogen, 1 to 8 alkyl

carbon or alkoxy atoms from 1 to 4

saturated or unsaturated carbon atoms,

R, R, independently of each other, represent hydrogen, halogen, alkyl from 1 to 4 carbon atoms, alkoxy from 1 to 4

carbon atoms, alkylthio 1 to 4

carbon atoms, where the three residues

mentioned last are not replaced or replaced by halogen, by

alkoxy of 1 to 4 carbon atoms or

by alkylthio from 1 to 4 atoms of

carbon,

Y represents 0 or S e

E represents CH σ N,

in combination with the compound of formula II (DEH-112, ester of 2-fluoro-4-cyanophenoxyphenoxypropionic acid, B) or its salts

(M) wherein R® represents hydrogen or alkyl from 1 to 6 carbon atoms.

As further combination companions, one or more known rice herbicides of different structural classes can be used if necessary. Of particular interest are compounds of the class of sulfonylureas, ureas, amides, cyclohexandions, thiocarbamates or chloroacetanilides.

As particular examples of such combination companions, the following compounds are mentioned, without a limitation being meant in this:

Cl, AC-014

C2, Anilofos

C3, Bentazone

C4, Bensulfuron-methyl

C5, Benzofenap

C6, Bromobutide

C7, Butachlor

C8, Butenachlor

C9, Cinmethyline

IOC, Cinosulfuron

Cl1, α-Chloro-N- (3-methoxy-2-thienyl) -methyl-2 ', 6'dimethylacetanilide (NSK-850)

C12, Daimuron (1- (1-methyl-1-phenylethyl) -3-p-tolylurea

C13,1-Diethylcarbamoyl-3- {2,4,6-trimethylphenylsulfonyl-1, 2,4-triazole (CH-900)

C14, Dimepiperato

C15, Dimetamethrin

C16, Ditiopyr

C17, DPX-47

C18, Esprocarb

C19,4-Ethoxybenzo-2 ', 3'-dihydrochloranilide (HW-52)

C20, Phenoxaprop-ethyl or phenoxaprop-P-ethyl C21, Imazosul furori

C22, JC 940 (l- (2-chlorobenzyl) -3- (a, a-dimethylbenzyl) -urea

C23, MCPB

C24, Mefenacet

C25, Molinate

C26, Naproanilide

C27, Piperofos

C28, Prethylachlor

C29, Propanyl

C30, Pyrazosulfuron-ethyl

C31, Pirazossifen

C32, Pirazolato

C33, Quinclorac

C34, Simetrin

C35, Sulcotrione (Chlororaesulone, ICI-A0051)

C36, Tiobencarb

C37, 2, 4-D

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

Compound A is known from the German patent applications mentioned at the beginning. The mixture

of formula B was disclosed in European patent application EP 0.302.203.

In the formulas cited for compounds A and B, the stereochemistry was not indicated in detail. To the extent that stereoisomers may occur, they are also included in the formulas

all forms of geometric isomers, enantiomers and diastereomers, as well as their mixtures.

Compound DPX-47 = DPX-A8947, N - (((4-6-dimethoxypyrimidin-2-yl) -amino-carboxyl) -1-methyl

-4- (2-methyl-2H-tetrazol-5-yl) -1-H-pyrazol-5-sulfonamide has the following structural formula:

The compound AC-014, 1- (2- (cyclopropylcarbonylphenyl) -sulfomoyl) -3- (4,6-dimethoxy-pyrimidine-2-yl) -urea has the following structural formula

and it is known from US patent 5.009.699 of June 22, 1990.

Compound JC 940 is known from Japanese patent application J-60087254.

The compound imazosulfuron (TH-913) is known from the European patent application EP-A-0.238.070 (see example 1).

Compound NSK-850 (α-chloro-N- {3-methoxy-2-thienyl) -methyl-2 ', 6'-dimethylacetanilide) is described by M. Ogasawara et al. in "Weed Research", (Tokyo), 1989, pages 131 to 137.

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

The compound CH-900 (1-diethylcarbamoyl-3- (2,4,6-trimethylfenylsulfonyl) -1,2,4-triazole) is described in the European patent EP-332.133.

The compound Sulcotrione (chloromesulone, 2- (2-chloro-4-mesylbenzoyl) -cyclohexan-1,3-dione) is known from the European patent EP 0.298.680 (see page 13, compound No. 51A). The other type C compounds are described in "The Pesticide Manual", British Crop Protection Council, 9th Ed., 1991.

Of particular interest are herbicidal compositions according to the invention with compounds of the above formula (I) or their salts, in which a ^) R ^ represents ethoxy, propoxyl or isopropoxy and

R is oriented in position 6 and has the meaning mentioned above, and n means 0 or 1, or

in all cases a ^) and ajj

R ^ represents hydrogen, 1 to 4 alkyl

carbon atoms, in particular hydrogen ο methyl,

Α and

R, R represent halogen, alkyl 1 to 4

carbon atoms, 1 to 4 carbon alkoxy or 1 to 4 carbon alkylthio, where the three last-mentioned residues are unsubstituted or substituted by halogen, by 1 to 4 carbon alkoxy or by alkylthio from 1 to 4 carbon atoms,

Y represents 0, and

E represents CH.

Alkyl and saturated or unsaturated alkoxy correspondingly means straight or branched chain alkyl or alkoxy respectively, halogen means F, Cl, Br and I, preferably F and Cl.

The compounds of formula (I) can form salts in which the hydrogen of the -SC ^ -NH group is replaced by a cation suitable in the agricultural field. These salts are generally metal salts, in particular alkaline and alkaline earth salts, possibly alkylated ammonium salts or organic amine salts.

Preferred herbicidal compositions contain, as compounds A, one or more compounds of formula Al, A2 and A3, where the formulas have the following meaning:

(A 1)

(A 2)

(A3)

As special examples of the claimed active ingredient mixtures are cited here, without this being intended as a limitation:

1. Αχ B

2. Αχ B CIO (NSK 850)

3. A1 B Cll (CH 900)

4. A ^ B C25 (Pretylachlor)

Combinations according to the invention, used together, show extraordinarily good efficacy against a broad spectrum of economically important harmful monocotyledonous and dicotyledonous plants. Even difficult-to-fight perennial weeds that germinate from rhizomes, roots or other permanent organs are well attacked by combinations of active ingredients. In this respect it is equivalent that the substances are spread in the pre-sowing, pre-emergence or post-emergence procedure. In particular, some representatives of the monocotyledonous and dicotyledonous weed flora will be cited by way of example, which can be controlled by means of the agents according to the invention without limiting them to specific species from their citation.

On the part of the monocotyledonous weed species, for example, the species of Echinochloa as well as Cyperus in the group of annuals are well attacked, and as regards the perennial species, permanent species of Cyperus are well attacked.

The weeds that occur in the specific conditions of rice cultivation, such as Sagittaria, Alisma, Rotala, Monochoria, Eleocharis, Scirpus, Cyperus and so on, are strongly combated by the combinations of active ingredients conforming to the invention.

If the herbicides according to the invention are applied before germination on the surface of the soil, then either the emergence of weed shoots is completely prevented, or the weeds grow up to the cotyledonal stage, their growth however then stops and finally they die completely after three to four weeks have passed.

In the application of the combinations of active ingredients on the green parts of the plants or in the irrigation water of the rice crop in the post-emergence method, a drastic arrest of growth also occurs very quickly after the treatment. The weeds remain at the growth stage presented at the time of application or die after a certain time more or less quickly, so that in this way it is possible to eliminate harmful competition from weeds for cultivated plants very early and in permanently through the use of the new agents according to the invention.

Although the preparations according to the invention demonstrate excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, the rice cultivated plant is damaged only insubstantially or not at all. The agents, for these reasons, are especially suitable in rice for a very good selective fight against the development of unwanted vegetation.

In terms of range of action and intensity of action, they are superior to known herbicides and herbicide combinations and can be used in smaller application quantities. Further advantages of these new combinations are their continued protracted action, which lasts for several weeks and thus makes subsequent herbicide applications against new germinating weeds unnecessary. In this way it is possible to save a second work step as with a single application the growth of competing weeds is eliminated.

With the combinations of active ingredients according to the invention, a herbicidal action is obtained which goes beyond what is to be expected on the basis of the action of the individual components. These enhancements of the effects allow to considerably reduce the quantities used of the single active ingredients. The combination of herbicides can also improve the duration of their action or cause an acceleration of the speed of action. These characteristics offer the user considerable advantages in the practical fight against weeds. It is possible to fight weeds in a cheaper and faster way, with a lesser effort and in a more lasting way, and in this way it is possible to obtain a greater income from a plant of cultivated plants.

Furthermore, it has been discovered that in a series of combinations of active ingredients there is a marked action of "safener" or antidote, ie that the phytotoxic side effects of the active ingredients used are reduced or completely avoided in cultivated plants, such as for example in rice.

The mixing ratios A: B can fluctuate within wide limits and are usually between 1: 1 and 1:40. The choice of the mixing ratio depends on the mixing companions used, the stage of development of the weeds, the spectrum of the weeds and the climatic conditions.

Preferably, mixing ratios for A: B from 1: 5 to 1:30 are used. The application quantities of the herbicide A in the mixtures of active ingredients are preferably between 10 and 100 g / ha, the application quantities of B are between 50 and 600 g / ha. The application quantities for compounds of group C, since they are partly of different structure classes, are considerably different and, depending on the active ingredient, range from a few grams up to 3 kg of active substance per hectare.

The combinations of active ingredients according to the invention can be presented either as mixed formulations of the two components, which are then diluted in the usual way with water or which are used in the form of granulates, or as so-called "tank mixes" (extemporaneous mixtures) by diluting with water together with the separately formulated components.

Compounds A and B or their combinations with C can be formulated in various ways according to which biological and / or chemical and physical parameters are preset.

For example, sprayable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), aqueous solutions (SL), emulsions (EW), such as oil emulsions in water and water in oil, sprayable solutions or emulsions sprayed on it, oil-based or aqueous dispersions, concentrates for suspension (SC), (suspo-emulsions), solutions miscible with oils, encapsulated suspensions (CS), sprinklers (DP), tanning agents, granulates for application to the ground or by sprinkling, granulates (GR) in the form of microgranulates, sprayable granulates, granulates obtained by coating and granulates obtained by adsorption, water soluble granules (SG), water dispersible granules (WG), formulations ULV (ultra-low volume), microcapsules or waxes.

These individual types of formulations are known in principle and are described for example in: Winnacker-Kiichler, "Chemische Technologie", volume 7, C. Hauser Verlag Miinchen, fourth edition 1986; van Valkenburg, "Pesticides Formulations", Marcel Dekker N. Y., second edition 1972 - 73; K. Martens, "Spray Drying Handbook", third edition 1979, G. Goodwin Ltd London.

The required formulation aids, such as inert materials, surfactants, solvents and further additives, are also known and are described for example in: Watkins, "Handbook of Insecticide Dust Diluents and Carriere", second edition, Darland Books, Caldwell N. J .; H. v.

Olphen, "Introduction to Clay Colloid Chemistry", second edition, J.Wiley & Sons. N. Y. Marsden, "Solvents Guide", second edition, Interscience, N. Y. 1950; McCutcheon's, "Detergent and Emulsifiers Annual", MC Pubi. Corp., Ridgewood N. J .; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Pubi. Co. Ine., N. Y. 1964; Schonfeldt, "Grenzflachenaktive Àthylenoxidaddukte", Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Kiichler, "Chemische Technologie", volume 7, C.

Hauser Verlag Munchen, fourth edition 1986.

On the basis of these formulations, it is also possible to produce combinations with other substances with pesticidal efficacy, such as other herbicides, fungicides or insecticides, as well as fertilizers and / or growth regulators, for example in the form of a ready formulation or ^ tankmix "( extemporaneous mixture).

Sprayable powders are preparations that can be dispersed uniformly in water which, in addition to the principles and in addition to a diluent or an inert substance, still contain ionic and / or non-ionic surfactants (wetting agents, dispersants), for example polyoxyethylated alkylphenols, alcohols polyoxyethylated fats or polyoxyethylated fatty animins, polyglycolethersulphates of fatty alcohols, alkanesulfonates, alkylbenzenesulphonates, sodium lignosulfonate, 2,2'-dinaphthylmethan-6, 6'-sodium disulfonate, sodium dibutylnaphthalenesulphonate or sodium oleyl methyltaurate. For the preparation of the sprayable powders, the herbicidal active ingredients are for example finely ground in conventional equipment such as hammer mills, blower mills, air jet mills and, simultaneously or subsequently, are mixed with the formulation auxiliaries.

Emulsifiable concentrates are obtained by dissolving the active ingredient in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or even higher-boiling aromatic compounds or hydrocarbons, with the addition of one or more ionic and / or non-ionic surfactants. ionic (emulsifiers). As emulsifiers, for example: calcium salts of alkylaryl sulphonic acids, such as Ca-dodecylbenzenesulphonate or non-ionic emulsifiers, such as polyglycolesters of fatty acids, alkylaryl polyglycol ethers, polyglycol ethers of fatty alcohol, condensation products of propylene oxide-ethylene oxide, alkyl polyethers, fatty acid esters with sorbitan, fatty acid esters with polyoxyethylene sorbitan or polyoxyethylene sorbitol esters.

Sprinklers are obtained by grinding the active ingredient with finely divided solid substances, for example talc, natural clays, such as kaolin, bentonite, pyrophyllite or diatomaceous earth.

Suspension concentrates can be water-based or oil-based. They can for example be prepared by wet grinding with the use of normal commercial bead mills and possible addition of surfactants, as have already been presented for example above with regard to other types of formulations.

The emulsions, for example oil-in-water (EW) emulsions, can for example be produced by means of agitators, colloid mills and / or static mixers with the use of aqueous organic solvents and possibly surfactants, as have already been presented for example more on about the other types of formulations.

The granulates can be prepared by spraying a solution of the active ingredient on adsorbent granulated inert material or by applying concentrates of the active ingredient by means of a binder, for example polyvinyl alcohol, sodium polyacrylate or even mineral oils on the surface of carrier substances, such as sand. , kaolinite, or granulated inert material. It is also possible to prepare suitable formulations of the active ingredients in the usual way for the preparation of fertilizer granules - possibly in mixture with fertilizing substances -.

Water dispersible granulates are usually prepared according to the usual processes, such as spray drying, fluidized bed granulation, plate granulation, mixing with high speed mixers and extrusion, without solid inert material.

Agro-chemical preparations generally contain from 0.1 to 99% by weight, in particular from 2 to 95% by weight, of the active ingredients A and B and possibly C. The concentrations of the active ingredients A, B and C can be different in formulations.

In sprayable powders, the concentration of the active principle amounts for example to about 10 to 95% by weight, the rest at 100% by weight consists of usual formulation components. In the emulsifiable concentrates, the concentration of the active ingredients can have values of about 1 to 85% by weight, preferably from 5 to 80% by weight. Formulations in powder form contain about 1 to 25% by weight, mostly from 5 to 20% by weight, of active ingredient, the sprayable solutions about 0.2 to 25% by weight, preferably from 2 to 20 % by weight of active ingredient. In granulates, for example in water-dispersible granulates, the content of active ingredient depends in part on whether the active compound is present in liquid or solid form and on which granulation aids and which fillers are used. As a rule, the content in the water-dispersible granulates is between 10 and 90% by weight. In the sprinkling granulates, which are sprinkled directly into the irrigation water, content of active principle from 1 to 10% is generally preferred.

Furthermore, the formulations of active ingredients mentioned may possibly contain wetting agents, dispersants, adhesives, emulsifiers, penetrating agents, preservatives, frost protection agents and solvents, inert fillers, vehicles and dyes, antifoamers, evaporation inhibitors and agents that affect the pH and viscosity from time to time usual.

For use, the formulations which occur in normal commercial form are optionally diluted in the usual way, for example, in the case of spray powders, emulsifiable concentrates, dispersions and granulates that can be dispersed in water, by means of water. Preparations in the form of powders, granulates for the soil or respectively for sprinkling, as well as sprayable solutions, are generally no longer diluted with further inert substances before use.

According to external conditions, such as temperature, humidity, type of herbicide used and others, the amount of application of compounds A and B varies. The amount of necessary application of the additionally used rice herbicides (C) also varies according to external conditions.

The following examples serve to illustrate the invention:

A. Examples of wording

a) A sprinkler is obtained by mixing 10 parts by weight of a mixture of active ingredients and 90 parts by weight of talc as an inert substance and grinding everything in an impact mill. b) A wettable powder easily dispersible in water is obtained by mixing 25 parts by weight of active ingredients A B, 64 parts by weight of quartz containing kaolin as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleylmethyltaurine as bathers and dispersants and grinding everything in a punch mill.

c) A concentrate for dispersion easily dispersible in water is obtained by mixing 20 parts by weight of active ingredients A B with 6 parts by weight of alkylphenol polyglycol ether ((R) Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight of paraffinic mineral oil (boiling range for example from about 255 to over 277 ° C) and grinding the whole in a friction ball mill to a fineness of less than 5 microns.

d) An emulsifiable concentrate is obtained from 15 parts by weight of a mixture of active ingredients A B, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol as emulsifier.

e) A water dispersible granulate is obtained by mixing

75 parts by weight of active ingredients A B 10 "of calcium lignosulfonate 5" of sodium lauryl sulfate 3 of polyvinyl alcohol and

7 of kaolin.

grinding them on a punch mill and granulating the powder into a fluidized bed by spraying water over it as a granulation liquid.

f) A granulate dispersed in water is obtained by homogenizing

25 parts by weight of active ingredients A B 5 "of 2,2'-dinaphthylmethan-6,6'-sodium disulfonate

2 of sodium oleylmethyltaurate 1 part by weight of polyvinyl alcohol

17 parts by weight of calcium carbonate and 50 parts of water

on a colloid mill and subjecting the mixture to a pre-reduction in size, subsequently grinding it in a pearl mill and spraying the suspension thus obtained in a spraying tower, using a single-component nozzle, and drying it.

Biological example

1. Action on pre-emergence weeds

seeds and rhizome pieces of monocotyledonous and dicotyledonous weeds respectively were placed in plastic pots with a diameter of 9 cm in sandy silty earth and covered with earth. Weeds that occur in paddy fields were grown in water-saturated soil, where the pots were filled with enough water that the water reached the surface of the soil or a few millimeters above it.

The combinations of active ingredients according to the invention formulated in the form of wettable powders or emulsion concentrates as well as, in parallel tests, the correspondingly formulated individual active ingredients, were then applied in the form of aqueous suspensions or respectively of emulsions with a quantity of application in water equal, recalculated, to from 600 to 800 l / ha, in different dosages on the surface of the cover earth or, in rice, they have been poured into flood water.

After treatment, the pots were placed in the greenhouse and kept in good growing conditions for the weeds. The optical evaluation of the damage to the plants and respectively of the damage in emergence was carried out after the emergence of the experimental plants, after a test duration of 3 to 4 weeks, in comparison with untreated witnesses. The herbicidal agents according to the invention exhibited good herbicidal efficacy in pre-emergence against a broad spectrum of weeds and weeds.

In all cases, in the combinations a difference was made between the calculated degree of action and the one found. The calculated degree of action, which must be theoretically observed, of a combination is determined according to the formula of S. R. Colby: "Calculation of synergistic and antagonistic responses of herbicide combinations", Weeds 15 (1967), pages 20 - 22.

The formula, for binary combinations, looks like this:

and for combinations of three herbicides it has, correspondingly, the form:

where you have

X = percentage damage due to herbicide A at an application quantity equal to X kg / ha;

Y = percentage damage due to the further herbicide B at an application quantity equal to Y kg / ha;

Z = percentage damage due to the further herbicide C at an application quantity equal to Z kg / ha;

E = damage to be expected from herbicides A B (or respectively C) to X Y (or respectively Z) kg / ha.

If the actual damage is greater than the calculated one, then the action of the combination of active ingredients is more than additive, i.e. there is a synergistic effect.

The combinations of active ingredients according to the invention exhibit a herbicidal action which is higher than that to be expected on the basis of the observed effects of the individual components in the case of isolated use, according to Colby. Therefore, the combinations of active ingredients are synergistic.

2. Action on weeds in post-emergence

Seeds and rhizome pieces of monocotyledonous and dicotyledonous weeds respectively were placed in plastic pots in sandy loamy soil, covered with earth and placed in greenhouses under good growing conditions. The weeds that occur in paddy fields were grown in pots in which water reached up to 3-cm above the soil surface and were grown during the test phase.

Approximately two to three weeks after planting, test plants are treated at the two to three leaf stage.

The combinations of active ingredients according to the invention formulated as sprayable powders or as concentrates for emulsion respectively as well as, in parallel tests, the individual active ingredients formulated accordingly, are sprayed in different dosages with a recalculated amount of water use on from 300 to 600 l / ha on the green parts of the plants and, after about 3 to 4 weeks of waiting for the test plants in the greenhouse under optimal growth conditions, the action of the preparations is optically evaluated in comparison with untreated witnesses. In the weeds that occur in paddy fields, the active ingredients are also introduced directly into the flood water (application in a similar way to the so-called use of granules) or are sprayed on the plants and in the flood water. The agents according to the invention also show good herbicidal efficacy against a broad spectrum of economically important weeds and weeds in post-emergence. The effects of the agents according to the invention based on Colby's analysis are synergistic.

3. Tolerability by cultivated plants

In further greenhouse trials, seeds from a greater number of cultivated plants and weeds were scattered in sandy fertile soil and covered with soil. The rice was planted and grown as paddy rice in water-saturated soils.

A part of the pots is immediately treated as described in point 1., the others are placed in the greenhouse until the plants have developed from two to three true leaves and are then sprayed with the combinations of active ingredients according to the invention and, for comparison, only with a single active ingredient at different dosages as described in point 2. In paddy rice, the application is carried out in part by pouring the active ingredients, or their formulation respectively, into the flood water.

Two weeks after application and the waiting time in the greenhouse, it is determined by optical evaluation that the combinations of active ingredients according to the invention leave various crops without damage in the pre-emergence and post-emergence method even at high dosages of the active ingredients. They save grass crops, such as wheat and rice. The combinations of active ingredients according to the invention therefore exhibit a high selectivity in use for combating the development of undesirable vegetation in economically important crops in the agricultural field.

Below are the results of selected tests, in tabular form:

Abbreviations:

to the. = active substance (referred to the pure active ingredient)

ECCR = Echinochloa crus galli

Al - 1 - [(2-ethoxyphenoxy) sulfonyl] -3- (4,6-dimethoxy-pyrimidinyl) -urea as 20% sprayable powder

B = DEH 112 as 10% emulsifiable concentrate

C2 = Anilofos as sprayable powder at 10%% damage = 0-100: no damage - full damage.

Abbreviations:

to the. = active substance (referred to the pure active ingredient)

ECCR = Echinochloa crus galli

Al = 1 - [(2-ethoxyphenoxy) sulfonyl] -3- (4,6-dimethoxy-pyrimidinyl) -urea as 20% sprayable powder

B DEH 112 as 10% emulsifiable concentrate

C2 Anilofos as sprayable powder at 10% damage 0-100: no damage - full damage.

Abbreviations:

to the. = active substance (referred to the pure active ingredient) transplanted rice = Paddy Rice (Var: Nihonbare) Al = 1 - [(2-ethoxyphenoxy) solionyl] -3- (4,6-dimethoxy-pyrimidinyl) -urea as sprayable powder 20%

Β = DEH 112 as 10% emulsifiable concentrate

C2 = Anilofos as 10% sprayable powder

G = Growth Inhibition

0-10: null inhibition - complete

Sprout weight = evaluation of the weight on the rice cultivated plant in%, referred to untreated rice plants

SD = standard deviation of the mean value.

Claims (10)

CLAIMS 1. Herbicidal compositions characterized by having an effective content of A) compounds of general formula (I) or their salts (I) in which a ^) R ^ represents ethoxy, propoxyl or isopropoxy e R represents halogen, NO2, CF3, CN, 1 to 4 carbon alkyl, 1 to 4 carbon alkoxyl, 1 to 4 carbon alkylthio or alkoxy (1 to 4 carbon atoms) -carbonyl and n means 0, 1, 2 or 3, or a2) represents halogen, methoxy, ethyl or propyl each time in position 2 on the phenyl residue, R represents alkoxy (1 to 4 carbon atoms) -carbonyl in position 6 in the phenyl residue e as well as in all cases a ^) and aj) R ^ represents hydrogen, alkyl from 1 to 8 carbon or alkoxy atoms from 1 to 4 saturated or unsaturated carbon atoms, R4, R5, independently of each other, represent hydrogen, halogen, alkyl from 1 to 4 carbon atoms, 1 to 4 carbon alkoxy, 1 to 4 alkylthio carbon atoms, where the three residues cited last are not substituted or substituted by halogen, by alkoxy of 1 to 4 carbon atoms or by alkylthio of 1 to 4 carbon atoms carbon, Y represents 0 or S e E represents CH or N, in combination with B) a compound B of formula II or its salts (Π) wherein R ^ represents hydrogen or alkyl 1 to 6 carbon atoms. 2. Compositions according to claim 1 characterized in that it contains compounds of formula (I) or their salts, in which a ^) represents ethoxy, propoxyl or isopropoxy and n R is oriented in position 6 and has the meaning mentioned above, and n means 0 or 1, or in all cases a ^) e) R represents hydrogen, alkyl from 1 to 4 carbon atoms, R ^, R ^ represent halogen, alkyl 1 to 4 carbon atoms, 1 to 4 carbon alkoxy or 1 to 4 carbon alkylthio, where the three last-mentioned residues are unsubstituted or substituted by halogen, by 1 to 4 carbon alkoxy or by alkylthio from 1 to 4 carbon atoms, Y represents 0, and E represents CH. 3. Compositions according to claim 1 or 2 characterized in that they contain a compound of formula Al, A2 and A3 or their salts (Al) (A2) (A3) 4. Compositions according to one or more of claims 1 to 3 characterized in that they contain from 0.1 to 99% by weight of the active ingredients A and B in addition to usual formulation aids. 5. Compositions according to one or more of claims 1 to 4 characterized in that they contain the active ingredients A and B in a weight ratio from 1: 1 to 1:40. 6. Process for the preparation of a composition according to one or more of claims 1 to 5 characterized in that a compound A is formulated with a compound B similarly to a usual formulation of agents for the protection of plants of the group containing sprayable powders , emulsified concentrates, aqueous solutions, emulsions, sprayable solutions, oil-based or aqueous dispersions, suspo-emulsions, concentrates for suspension, solutions miscible with oils, suspensions in the form of capsules, granulates in the form of microgranulates, sprayable granules, granules for coating and granulates for adsorption, sprinklers, tanning agents, granulates for use on the ground or for spreading, water dispersible granulates, ULV formulations, microcapsules or waxes. 7. Method for combating unwanted plants characterized in that an effective amount of an agent according to one or more of claims 1 to 5 is applied to these or their planting surfaces. 8. Method according to claim 7 characterized in that weeds are selectively combated in crops of useful plants. Method according to claim 8 characterized in that the cultivation of useful plants is rice. 10. Use of the herbicides according to one or more of claims 1 to 5 for the selective control of weeds in rice.