Herbicidal Mixture of a Pyrozolium Salt and Benzothiadiozinone Derivative

The present invention relates to new and valuable herbicides containing compositions of different active ingredients.

It is known that pyrazolium salts, dinitrophenol derivatives, hydroxybenzonitriles, hydroxybenzaldoxime aryl ethers, benzothiadiazinone dioxides and phenoxycarboxylic acids have a herbicidal action. However, this action is not always satisfactory.

I have now found that a composition of

A. A COMPOUND OF THE FORMULA ##SPC1##

Where R denotes alkoxy, or phenyl which may be substituted by halogen or lower alkyl,

And/or

B. A COMPOUND OF THE FORMULA ##SPC2##

Where R denotes lower alkyl and R.sup.1 denotes hydrogen, or a salt thereof, e.g., salts of ammonium, sodium, potassium, lithium, calcium, magnesium, ethylamine, dimethylamine, diethylamine, diethanolamine, ethanolamine, dimethylethanolamine and trimethylamine,

And/or

C. A COMPOUND OF THE FORMULA ##SPC3##

Where X denotes chloro, bromo, iodo, nitro, cyano or lower alkyl, n denotes one of the integers 0, 1, 2 and 3, and R denotes hydrogen, or a salt thereof, e.g., the sodium and lithium salts, R further denotes ##EQU1## R.sup.2 and R.sup.3 denoting hydrogen, lower alkyl or substituted or unsubstituted aryl, R further denotes ##SPC4##

Y denoting chloro, bromo or iodo and

R.sup.1 denoting lower alkyl, ##EQU2## or hydrogen, or a salt thereof, e.g., the sodium salt, and/or

D. A COMPOUND OF THE FORMULA ##SPC5##

Or ##SPC6##

Where X and Y denote chloro or methyl, n denotes one of the integers 0, 1, 2 and 3, R denotes hydrogen or lower alkyl, m denotes one of the integers 0, 1 and 2, and R.sup.1 denotes alkyl or hydrogen, or a salt thereof, e.g., sodium, potassium, dimethylamine, diethanolamine and diethylamine, has a better herbicidal action than its individual components.

The compositions may contain one or more compounds of the formula a and one or more compounds of the formulas b, c and d in a ratio by weight of from 0:1:10 to 10:1 parts in the case of 2-component mixtures, and in a ratio by weight of 0.1 to 10:0.1 to 10:0.1 to 10 parts in the case of 3-component mixtures.

The amount used of the agents according to the invention may vary and depends in essence on the type of effect to be achieved; it is generally from 0.1 to 30 (and more), preferably from 0.2 to 6, kg per hectare of active ingredient. The agents according to the invention may be used once or several times before or after planting, before sowing, and before, during or after emergence of the crop plants and unwanted plants.

The compositions are selective in Triticum aestivum, Hordeum vulgare, Secale cereale, Zea mays, Oryza sativa, Pisum sativum, Phaseolus vulgaris, Solanum tuberosum, Glycine max. etc.

The compositions may also be used as total herbicides on ditches, aquatic areas, railroad tracks, and barren or waste land, etc.

Preferred compositions according to the invention are: a+b, a+c, a+d, a+b+c, a+b+d, a+c+d and b+c+d.

Application may be effected for instance in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting of watering. The forms of application depend entirely on the purpose for which the agents are being used; in any case they should ensure a fine distribution of the active ingredient.

For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, etc. and oils of vegetable or mineral origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated fatty alcohol glycol ether, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octyphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silica gel, silicic acid, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient.

There may be added to the compositions or individual active ingredients (if desired, immediately before use (tankmix)) oils of various types, herbicides, fungicides, nematocides, insecticides, bactericides, trace elements, fertilizers, antifoams (e.g., silicones), growth regulators, antidotes and other herbicidally effective compounds such as substituted anilines, substituted aryloxycarboxylic acids and salts, esters and amides thereof

substituted ethers

substituted arsonic acids and their salts, esters and amides

substituted benzimidazoles

substituted benzisothiazoles

substituted benzothiadiazinone dioxides

substituted benzoxazines

substituted benzoxazinones

substituted benzothiadiazoles

substituted biurets

substituted quinolines

substituted carbamates

substituted aliphatic carboxylic acids and their salts, esters and amides

substituted aromatic carboxylic acids and their salts, esters and amides

substituted carbamoylalkylthiol- or -dithiophosphates

substituted quinazolines

substituted cycloalkylamidocarbothiolic acids and their salts, esters and amides

substituted cycloalkylcarbonamidothiazoles

substituted dicarboxylic acids and their salts, esters and amides

substituted dihydrobenzofuranyl sulfonates

substituted disulfides

substituted dipyridylium salts

substituted dithiocarbamates

substituted dithiophosphoric acids and their salts, esters and amides

substituted ureas

substituted hexahydro-1H-carbothioates

substituted hydantoins

substituted hydrazides

substituted hydrazonium salts

substituted isoxazole pyrimidones

substituted imidazoles

substituted isothiazole pyrimidones

substituted ketones

substituted naphthoquinones

substituted aliphatic nitriles

substituted aromatic nitriles

substituted oxadiazoles

substituted oxadiazinones

substituted oxadiazolidine diones

substituted oxadiazine diones

substituted phenols and their salts and esters

substituted phosphonic acids and their salts, esters and amides

substituted phosphonium chlorides

substituted phosphonalkyl glycines

substituted phosphites

substituted phosphoric acids and their salts, esters and amides

substituted piperidines

substituted pyrazoles

substituted pyrazole alkylcarboxylic acids and their salts, esters and amides

substituted pyrazolium salts

substituted pyrazolium alkyl sulfates

substituted pyridazines

substituted pyridazones

substituted pyridine carboxylic acids and their salts, esters and amides

substituted pyridines

substituted pyridine carboxylates

substituted pyridinones

substituted pyrimidines

substituted pyrimidones

substituted pyrrolidine carboxylic acid and its salts, esters and amides

substituted pyrrolidines

substituted pyrrolidones

substituted arylsulfonic acids and their salts, esters and amides

substituted styrenes

substituted tetrahydrooxadiazine diones

substituted tetrahydroxadiazole diones

substituted tetrahydromethanoindenes

substituted tetrahydroxadiazole thiones

substituted tetrahydrothiadiazine thiones

substituted tetrahydrothiadiazole diones

substituted aromatic thiocarbonylamides

substituted thiocarboxylic acids and their salts, esters and amides

substituted thiol carbamates

substituted thioureas

substituted thiophosphoric acids and their salts, esters and amides

substituted triazines

substituted triazoles

substituted uracils, and

substituted uretidine diones.

The last-mentioned herbicidal compounds may also be applied before or after the active ingredients or compositions thereof according to the invention.

These agents may be added to the herbicides according to the invention in a ratio by weight of from 1:10 to 10:1. The same applies to oils, fungicides, nematocides, insecticides, bactericides, antidotes and growth regulators.

The new compositions have a strong herbicidal action and may therefore be used as weedkillers or for controlling the growth or unwanted plants. Whether the new active ingredients are used as total or selective agents depends in essence on the amount of ingredient used per unit area.

By weeds and unwanted plant growth are meant all monocotyledonous and dicotyledonous plants which grow in loci where they are not desired.

The agents according to the invention may therefore be used for controlling for instance Gramineae, such as Cynodon spp. Dactylis spp. Digitaria spp. Avena spp. Echinochloa spp. Bromus spp. Setaria spp. Uniola spp. Panicum spp. Poa spp. Alopecurus spp. Leptochloa spp. Lolium spp. Brachiaria spp. Sorghum spp. Eleusine spp. Agropyron spp. Cenchrus spp. Phalaris spp. Eragrostis spp. Apera spp. Phragmites communis etc.; Cyperaceae, such as Carex spp. Eleocharis spp. Cyperus spp. Scirpus spp. etc.; dicotyledonous weeds, such as Malvaceae, e.g. Abutilon theoprasti Hibiscus spp. Sida spp. Malva spp. etc.; Compositae, such as Ambrosia spp. Centaurea spp. Lactuca spp. Tussilago spp. Senecio spp. Lapsana communis Sonchus spp. Tagetes spp. Xanthium spp. Erigeron spp. Iva spp. Anthemis spp. Galinsoga spp. Mataricaria spp. Taraxacum spp. Artemisia spp. Chrysanthemum ssp. Bidens spp. Cirsium spp. etc.; Convolvulaceae, such as Convolvulus spp. Cuscuta spp. Ipomoea spp. Jaquemontia tamnifolia etc.; Cruciferae, such as Barbarea vulgaris Arabidopsis thaliana Brassica spp. Descurainia spp. Capsella spp. Draba spp. Sisymbrium spp. Coronopus didymus Thlaspi spp. Lepidium spp. Sinapis arvensis Raphanus spp. etc.; Geraniaceae, such as Erodium spp. Geranium spp. etc.; Portulacaceae, such as Portulaca spp. etc.; Primulaceae, such as Anagallis arvensis Lysimachia spp. etc. Rubiaceae, such as Richardia spp. Diodia spp. Galium spp. etc.; Scrophulariaceae, such as Linaria spp. Digitalis spp. Veronica spp. etc.; Solanaceae, such as Physalis spp. Nicandra spp. Solanum spp. Datura spp. etc.; Urticaceae, such as Urtica spp. Violaceae, such as Viola spp. etc.; Zygophyllaceae, such as Tribulus terrrestris etc.; Euphorbiaceae, such as Mercurialis annua Euphorbia spp. Umbelliferae, such as Daucus carota Ammi majus Aethusa cynapium etc.; Commelinaceae, such as Commelina spp. etc.; Labiatae, such as Lamium spp. Galeopsis spp. etc.; Leguminosae, such as Medicago spp. Sesbania exaltata Trifolium spp. Cassia spp. Vicia spp. Lathyrus spp. etc.; Plantaginaceae, such as Plantago spp. etc.; Polygonaceae, such as Polygonum spp. Fagopyrum spp. Rumex spp. etc.; Aizoacea, such as Mollugo verticillata etc.; Amaranthaeceae, such as Amaranthus spp. etc.; Boraginaceae, such as Amsinchkia spp. Anchusa spp. Myostis spp. Lithospermum spp. etc.; Caryophyllaceae, such as Stellaria spp. Silene spp. Spergula spp. Cerastium spp. Saponaria spp. Agrostemma githago Scleranthus annuus etc.; Chenopodiaceae, such as Chenopodium spp. Atriplex spp. Kochia spp. Monolepsis nuttalliana Salsola Kali etc.; Lythraceae, such as Cuphea spp. etc.; Oxalidaceae, such as Oxalis spp. Ranunculaceae, such as Ranunculus spp. Adonis spp. Delphinium spp. etc.; Papaveraceae, such as Papaver spp. Fumaria officinalis etc.; Onagraceae, such as Jussiaea spp. etc.; Rosaceae, such as Alchemillia spp. Potentilla spp. etc.; Potamogetonaceae, such as Potamogeton spp. etc.; Najadaceae, such as Najas spp. etc.; Equisetaceae Equisetum spp. etc.; Marsileaceae, such as Marsilea quadrifolia etc.; Polypodiaceae, Pteridium quilinum Alismataoeae, such as Alisma spp. Sagittaria sagittifolia etc.

In the greenhouse and in the open, compositions of the following agents were tested on the abovementioned plants; it was ascertained that their action corresponds to that of the compositions in the examples below:

3-methyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide

3-ethyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide

3-propyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide

3-butyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide

3-isobutyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide

3-Isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, sodium salt

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, dimethylamine salt

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, diethanolamine salt

3,5-dibromo-4-hydroxybenzaldoxime-O-(2',4'-dinitrophenyl)-ether

3,5-dibromo-4-hydroxybenzaldoxime-0-(2',4'-dinitrophenyl)-ether, sodium salt

3,5-dibromo-4-hydroxybenzaldoxime-0-(2'-cyano-4'-nitrophenyl)-ether

3,5-dibromo-4-hydroxybenzaldoxime-0-(2'-nitro-4'-cyanophenyl)-ether

3,5-dibromo-4-hydroxybenzaldoxime-0-(2'-cyano-4'-nitrophenyl)-ether, sodium salt

3,5-diiodo-4-hydroxybenzaldoxime-0-(2'-cyano-4'-nitrophenyl)ether

3,5-diiodo-4-hydroxybenzaldoxime-0-(2'-cyano-4'-nitrophenyl)ether, sodium salt

3,5-diiodo-4-hydroxybenzonitrile

3,5-diiodo-4-hydroxybenzonitrile, lithium salt

3,5-diiodo-4-hyroxybenzonitrile, sodium salt

3,5-dibromo-4-hydroxybenzonitrile

3,5-dibromo-4-hydroxybenzonitrile, sodium salt

3,5-dibromo-4-octanoyloxybenzonitrile

2-methyl-4,6-dinitrophenol, sodium salt

2-sec-butyl-4,6-dinitrophenyl acetate

2-tert-butyl-4,6-dinitrophenyl acetate

2-tert-butyl-5-methyl-4,6-dinitrophenyl acetate

2-isopropyl-3-methyl-4,6-dinitrophenol

2-sec-butyl-4,6-dinitrophenol, sodium salt

2-sec-amyl-4,6-dinitrophenol

2-(1-methylbutyl)-4,6-dinitrophenol

1,2-dimethyl-3,5-diphenylpyrazoliummethyl sulfate

1,2-dimethyl-3,5-diphenylpyrazolium-p-tolyl sulfonate

.alpha.-(2,4-dichlorophenoxy)-propionic acid, dimethylamine salt

.alpha.-(2,4-dichlorophenoxy)-propionic acid, sodium salt

isooctyl .alpha.-(2,4-dichlorophenoxy)-propionate

.alpha.-(2-methyl-4-chlorophenoxy)-propionic acid, dimethylamine salt

.alpha.-(2-methyl-4-chlorophenoxy)-propionic acid, diethanolamine salt

.alpha.-(2-methylphenoxy)-propionic acid, dimethylamine salt

.alpha.-(2-methylphenoxy)-propionic acid, sodium salt

isooctyl .alpha.-(2-methylphenoxy)-propionate

.alpha.-(2,4,5-trichlorophenoxy)-propionic acid, potassium salt

amyl .alpha.-(2,4,5-trichlorophenoxy)-propionate

.alpha.-(4-chlorophenoxy)-propionic acid, dimethylamine salt

.alpha.-(2-methyl-4-chlorophenoxypropionic acid, sodium salt

.alpha.-(2-methyl-4-chlorphenoxy-propionic acid, potassium salt

amyl 2,4,5-trichlorophenoxyacetate

isooctyl 2,4,5-trichlorophenoxyacetate

2,4,5-trichlorophenoxyacetic acid, diethylamine salt

2,4,5-trichlorophenoxyacetic acid, potassium salt

2,4-dichlorophenoxyacetic acid, dimethylamine salt

2,4-dichlorophenoxyacetic acid, sodium salt

isooctyl 2,4-dichlorophenoxyacetate

2-methyl-4-chlorophenoxyacetic acid, dimethylamine salt

isooctyl 2-methyl-4-chlorophenoxyacetate

4-chlorophenoxyacetic acid, dimethylamine salt

2-chlorophenoxyacetic acid, dimethylamine salt

.gamma.-(2,4-dichlorophenoxy)-butyric acid, dimethylamine salt

isooctyl .gamma.-(2,4-dichlorophenoxy)-butyrate

.gamma.-(2-methyl-4-chlorophenoxy)-butyric acid, sodium salt

.gamma.-(2,4,5-trichlorophenoxy)-butyric acid, dimethylamine salt

.gamma.-(4-chlorophenoxy)-butyric acid

.gamma.-(2,4-dichlorophenoxycrotonic acid, dimethylamine salt

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, methylamine salt

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, trimethylamine salt

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, ethylamine salt

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, diethylamine salt

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, ethanolamine salt

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, aniline salt

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, pyridine salt

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, phenylenediamine salt

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, cyclohexylamine salt

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, dodecylhexamethylenimine salt

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, hydrazine salt

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, magnesium salt,

3-iospropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, calcium salt

3-isopropyl-2,1,3-benzothiadazinone-(4)-2,2-dioxide, ammonium salt

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, potassium salt

3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, lithium salt

3-isobutyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, sodium salt

3-isobutyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, dimethylamine salt

3-isobutyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, diethanolamine salt

3-sec-butyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, sodium salt

3-sec-butyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, dimethylamine salt

3-sec-butyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, diethanolamine salt

3-n-butyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, sodium salt

3-n-butyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, dimethylamine salt

3-n-butyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, diethanolamine salt

3-n-propyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, sodium salt

3-n-propyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, dimethylamine salt

3-n-propyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, diethanolamine salt

3-methyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, sodium salt

3-methyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, dimethylamine salt

3-methyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, diethanolamine salt

3-ethyl-2,1,3benzothiadiazinone-(4)-2,2-dioxide, sodium salt

3-ethyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, dimethylamine salt

3-ethyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, diethanolamine salt

3-sec-butyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide

3,5-dibromo-4-acetyloxybenzaldoxime-0-(2'-cyano-4'-nitrophenyl)ether

3,5-dibromo-4-propionyloxybenzaldoxime-0-(2'-cyano-4'-nitrophenyl)-ether

3,5-dibromo-4-phenylcarbamoyloxybenzaldoxime-0-(2'-cyano-4'-nitrophenyl)-et her

3,5-dibromo-4-isopropylcarbamoyloxybenzaldoxime-0-(2'-cyano-4'-nitrophenyl) -ether

In the greenhouse, various plants were treated at a growth height of from 2 to 21 cm with the following amounts of the following individual active ingredients and compositions thereof as oil dispersions:

I 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate

Ii 1,2-dimethyl-3,5-diphenylpyrazolium-p-tolyl sulfonate

Iii 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide

Iv 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, sodium salt

V 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, dimethylamine salt

Vi 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, diethanolamine salt

each of these compounds at rates of 0.5, 0.75, 1 and 1.5 kg/ha; I+III, I+IV, I+V, I+VI, II+IV and II+V

each of these compositions at rates of 0.5+1, 1+0.5 and 0.75+0.75 kg/ha.

After 12 to 15 days it was ascertained that the compositions had a better herbicidal action than their components, combined with the same crop plant compatibility.

The results are given below:

In the greenhouse, various plants were treated at a growth height of from 3 to 25 cm with the following amounts of the following individual active ingredients and compositions thereof as emulsions:

I 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate

Ii 1,2-dimethyl-3,5-diphenylpyrazolium-p-tolyl sulfonate

Iii 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide

Iv 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, sodium salt

V 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, dimethylamine salt

Vi 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, diethanolamine salt

each of these compounds at rates of 0.5, 1.5, 2.5 and 3 kg/ha; I+III, I+IV, I+V, I+VI, II+IV and II+V

each of these compositions at rates of 2.5+0.5, 0.5+2.5 and 1.5+1.5 kg/ha.

After 14 to 18 days it was ascertained that the compositions had a better herbicidal action than their components, combined with the same crop plant compatibility.

The results are given below:

In the greenhouse, various plants were treated at a growth height of from 2 to 21 cm with the following amounts of the following inndividual active ingredients and compositions thereof as dispersions:

I 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate

Ii 1,2-dimethyl-3,5-diphenylpyrazolium-p-tolyl sulfonate

V 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, dimethylamine salt

Vii 2-sec-butyl-4,6-dinitrophenyl acetate

Viii 3,5-diiodo-4-hydroxybenzonitrile

Ix 3,5-dibromo-4-hydroxybenzaldoxime-O-(2',4'-dinitrophenyl)-ether

X 3,5-dibromo-4-hydroxybenzaldoxime-0-(2'-cyano-4'-nitrophenyl)-ether, sodium salt

each of these compounds at rates of 0.25, 1 and 1.5 kg/ha;

I+v+vii, i+v+viii, i+v+ix, ii+v+vii, ii+v+viii, ii+v+ix and I+V+X

each of these compositions at rates of 1+0.25+0.25, 0.25+1+0.25 and 0.25+0.25+1 kg/ha.

After 12 to 16 days it was ascertained that the compositions had a better herbicidal action than their components, combined with the same crop plant compatibility.

The results are given below:

In the open, various plants were treated at a growth height of from 2 to 18 cm with the following amounts of the following individual active ingredients and compositions thereof as emulsions:

I 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate

Iii 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide

Iv 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, sodium salt

V 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, dimethylamine salt

Vi 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, diethanolamine salt

Xi .alpha.-(2-methyl-4-chlorophenoxy)-propionic acid, dimethylamine salt

Xii .alpha.-(2,4-dichlorophenoxy)-propionic acid, dimethylamine salt

Xiii .alpha.-(2,4,5-trichlorophenoxy)-propionic acid, potassium salt

Xiv 2-methyl-4-chlorophenoxyacetic acid, dimethylamine salt

Xv 2,4-dichlorophenoxyacetic acid, diethanolamine salt

Xvi 2,4,5-trichlorophenoxyacetic acid, potassium salt each of these compounds at rates of 0.5, 1,2 and 3 kg/ha; III+I+XVI, IV+I+XIII, V+I+XI, V+I+XII, V+I+XIV and VI+I+XV each of these compositions of rate of I+I+I, 0.5+2+0.5, 2+0.5+0.5 and 0.5+0.5+2 kg/ha.

After 14 to 17 days it was ascertained that the compositions had a better herbicidal action than their components, combined with the same crop plant compatibility.

The results are given below: Active ingredient I III IV V VI kg/ha 0.5 1 2 3 0.5 1 2 3 0.5 1 2 3 0.5 1 2 3 0.5 1 2 3 __________________________________________________________________________ Crop plants Triticum aestivum 0 0 0 5 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Hordeum vulgare 0 0 0 10 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Secale cereale 0 0 0 12 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Unwanted plants Avena fatua 35 65 90 100 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Galium aparine 0 6 13 26 35 60 85 95 30 60 85 95 30 50 86 100 35 65 85 95 Stellaria media 5 10 16 30 30 60 82 95 20 55 80 92 20 50 90 95 20 60 95 100 __________________________________________________________________________ 0 = damage 100 = complete destruction Active Ingredient XI XII XIII XIV XV kg/ha 0.5 1 2 3 0.5 1 2 3 0.5 1 2 3 0.5 1 2 3 0.5 1 2 3 __________________________________________________________________________ Crop plants Triticum aestivum 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Hordeum vulgare 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Secale cereale 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Unwanted plants Avena fatura 0 0 5 15 0 0 5 15 0 0 10 30 0 0 0 10 0 0 0 10 Galium aparine 30 50 85 100 20 65 80 100 40 57 95 100 10 20 27 30 10 20 30 40 Stellaria media 35 45 90 100 0 10 20 40 45 60 95 100 15 20 38 45 5 10 28 40 __________________________________________________________________________ 0 = no damage 100 = complete destruction Active ingredient XVI III+I+XVI IV+I+XII kg/ha 1 0.5 2 0.5 1 0.25 2 0.5 0.5 1 2 3 1 2 0.5 0.5 1 2 0.5 0.5 1 0.5 0.5 2 1 0.5 0.5 2 __________________________________________________________________________ Crop plants Triticum aestivum 0 0 7 15 0 0 0 7 0 0 0 0 Hordeum vulgare 0 0 10 30 0 0 0 10 0 0 0 0 Secale cereale 0 0 10 17 0 0 0 10 0 0 0 0 Unwanted plants Avena fatua 0 0 0 20 100 100 70 70 100 100 70 80 Galium aparine 30 60 80 100 100 100 100 100 100 100 100 100 Stellaria media 35 50 90 100 100 100 100 100 100 100 100 100 Active ingredient V+I+XI V+I+XII kg/ha 1 0.5 2 0.5 1 0.5 2 0.5 1 2 0.5 0.5 1 2 0.5 0.5 1 0.5 0.5 2 1 0.5 0.5 2 Crop plants Triticum aestivum 0 0 0 0 0 0 0 0 Hordeum vulgare 0 0 0 0 0 0 0 0 Secale cereale 0 0 0 0 0 0 0 0 Unwanted plants Avena fatua 100 100 72 76 100 100 71 76 Galium aparine 100 100 100 100 100 100 100 100 Stellaria media 100 100 100 100 100 72 100 100 __________________________________________________________________________ 0 = no damage 100 = complete destruction Active ingredient V+I+XIV VI+I+XV 1 0.5 2 0.5 1 0.5 2 0.5 kg/ha 1 2 0.5 0.5 1 2 0.5 0.5 1 0.5 0.5 2 1 0.5 0.5 2 __________________________________________________________________________ Crop plants Triticum aestivum 0 0 0 0 0 0 0 0 Hordeum vulgare 0 0 0 0 0 0 0 0 Secale cereale 0 0 0 0 0 0 0 0 Unwanted plants Avena fatua 100 100 70 70 100 100 70 71 Galium aparine 100 90 100 92 100 92 100 100 Stellaria media 100 88 100 100 100 78 100 87 __________________________________________________________________________ 0 = no damage 100 = complete destruction

In the greenhouse, various plants were treated at a growth height of from 2 to 18 cm with the following amounts of the following individual active ingredients and compositions thereof as solutions:

I 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate

Vii 2-sec-butyl-4,6-dinitrophenyl acetate

Xii .alpha.-(2,4-dichlorophenoxy)-propionic acid, dimethylamine salt

each of these compounds at rates of 0.5, 1 and 2 kg/ha; I+VII+XII at rates of 1+0.5+0.5, 0.5+1+0.5 and 0.5+0.5+1 kg/ha.

After 14 to 16 days it was ascertained that the compositions had a better herbicidal action than their components, combined with the same crop plant compatibility.

The results are given below: Active ingredient I VII XII I+VII+XII 1 0.5 0.5 kg/ha 0.5 1 2 0.5 1 2 0.5 1 2 0.5 1 0.5 0.5 0.5 1 __________________________________________________________________________ Crop plants Triticum aestivum 0 0 0 0 0 0 0 0 0 0 0 0 Hordeum vulgare 0 0 0 0 0 0 0 0 0 0 0 0 Secale cereale 0 0 0 0 0 0 0 0 0 0 0 0 Unwanted plants Avena fatua 35 65 90 0 0 10 0 0 5 100 69 70 Galium aparine 0 6 13 25 40 55 20 65 80 88 97 100 Stellaria media 5 10 16 20 40 50 0 10 20 66 80 70 __________________________________________________________________________ 0 = no damage 100 = complete destruction

In the greenhouse, various plants were treated at a growth height of from 2 to 24 cm with the following amounts of the following individual active ingredients and compositions thereof as emulsions:

I 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate

Vii 2-sec-butyl-4,6-dinitrophenyl acetate

Viii 3,5-diiodo-4-hydroxybenzonitrile, lithium salt

Ix 3,5-dibromo-4-hydroxybenzaldoxime-0-(2',4'-dinitrophenyl)ether, sodium salt

X 3,5-dibromo-4-hydroxybenzaldoxime-0-(2'-cyano-4'-nitrophenyl)-ether, sodium salt

Xi .alpha.-(2-methyl-4-chlorophenoxy)-propionic acid, dimethylamine salt

Xii .alpha.-(2,4-dichlorophenoxy)-propionic acid, dimethylamine salt

Xiii .alpha.-(2,4,5-trichlorophenoxy)-propionic acid, isooctyl ester

Xiv 2-methyl-4-chlorophenoxyacetic acid, dimethylamine salt

Xv 2,4-dichlorophenoxyacetic acid, dimethylamine salt

Xvi 2,4,5-trichlorophenoxyacetic acid, isooctyl ester

Xvii .gamma.-(2,4-dichlorophenoxy)-butyric acid, dimethylamine salt

Xviii 3,5-dibromo-4-hydroxybenzonitrile, sodium salt

each of these compounds at rates of 0.5, 0.75, 1 and 1.5 kg/ha; I+VII, I+VIII, I+IX, I+X, I+XI, I+XII, I+XIII, I+XIV, I+XV, I+XVI, I+XVII and I+XVIII

each of these compositions at rates of 0.5+1, 1+0.5 and 0.75+0.75 kg/ha.

After 12 to 15 days it was ascertained that the compositions had a better herbicidal action than their components, combined with the same crop plant compatibility.

The results are given below: Active ingredient I+XIV I+XV I+XVI I+XVII I+XVIII 0.5 1 0.75 0.5 1 0.75 0.5 1 0.75 0.5 1 0.75 0.5 1 0.75 1 0.5 0.75 1 0.5 0.75 1 0.5 0.75 1 0.5 0.75 1 0.5 0.75 __________________________________________________________________________ Crop plants Triticum aestivum 0 0 0 0 0 0 0 0 0 0 0 0 10 5 7 Hordeum vulgare 0 0 0 0 0 0 0 0 0 0 0 0 5 0 0 Secale cereale 0 0 0 0 0 0 0 0 0 0 0 0 8 0 0 Unwanted plants Avena fatua 82 100 88 80 100 89 82 100 88 81 100 88 82 100 89 Galium aparine 60 58 62 60 56 62 98 80 90 58 59 61 92 69 85 Stellaria media 64 65 58 57 55 51 66 60 58 54 56 50 100 80 94 __________________________________________________________________________ 0 = no damage 100 = complete destruction Active ingredient I+IX I+X I+XI I+XII I+XIII 0.5 1 0.75 0.5 1 0.75 0.5 1 0.75 0.5 1 0.75 0.5 1 0.75 kg/ha 1 0.5 0.75 1 0.5 0.75 1 0.5 0.75 1 0.5 0.75 0.5 0.75 __________________________________________________________________________ Crop plants Triticum aestivum 0 0 0 0 0 0 0 0 0 0 0 0 5 0 0 Hordeum vulgare 0 0 0 0 0 0 0 0 0 0 0 0 7 0 0 Secale cereale 0 0 0 0 0 0 0 0 0 0 0 0 10 0 0 Unwanted plants Avena fatua 80 100 88 80 100 88 81 100 89 80 100 87 83 100 88 Galium aparine 90 76 90 100 80 94 90 76 90 100 95 100 100 87 93 Stellaria media 93 80 75 100 84 79 91 80 79 100 77 80 100 85 90 __________________________________________________________________________ 0 = no damage 100 = complete destruction Active ingredient XVI XVII XVIII I+VII I+VIII 0.5 1 0.75 0.5 1 0.75 kg/ha 0.5 0.5 1 1.5 0.5 0.75 1 1.5 0.5 0.75 1 1.5 1 0.5 0.75 1 0.5 0.75 __________________________________________________________________________ Crop plants Triticum aestivum 0 0 0 0 0 0 0 0 5 7 10 12 0 0 0 10 0 0 Hordeum vulgare 0 0 0 5 0 0 0 0 0 0 5 6 0 0 0 10 0 0 Secale cereale 0 0 0 7 0 0 0 0 0 0 8 10 0 0 0 20 0 0 Unwanted plants Avena fatua 0 0 0 0 0 0 0 0 0 0 0 0 87 100 98 81 100 88 Galium aparine 30 45 60 80 12 15 18 25 20 40 50 67 86 76 86 98 76 100 Stellaria media 10 16 20 36 5 6 8 15 25 54 70 78 100 90 91 99 82 89 __________________________________________________________________________ 0 = no damage 100 = complete destruction

In the greenhouse, various plants were treated at a growth height of from 2 to 20 cm with the following amounts of the following individual active ingredients and compositions thereof as dispersions, emulsions, solutions and tankmixes:

I 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate

Iii 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide

Iv 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, sodium salt

V 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, dimethylamine salt

Vi 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, diethanolamine salt

Vii 2-sec-butyl-4,6-dinitrophenyl acetate

Viii 3,5-diiodo-4-hydroxybenzonitrile, sodium salt

Ix 3,5-dibromo-4-hydroxybenzaldoxime-0-(2',4'-dinitrophenyl)ether

X 3,5-dibromo-4-hydroxybenzaldoxime-0-(2'-cyano-4'-nitrophenyl)-ether, sodium salt

Xi .alpha.-(2-methyl-4-chlorophenoxy)-propionic acid, dimethylamine salt

Xii .alpha.-(2,4-dichlorophenoxy)-propionic acid, sodium salt

Xiii .alpha.-(2,4,5-trichlorophenoxy)-propionic acid, potassium salt

Xiv 2-methyl-4-chlorophenoxyacetic acid, dimethylamine salt

Xv 2,4-dichlorophenoxyacetic acid, dimethylamine salt

Xvi 2,4,5-trichlorophenoxyacetic acid, potassium salt

Xvii .gamma.-(2,4-dichlorophenoxy)-butyric acid, dimethylamine salt

Xviii 3,5-dibromo-4-hydroxybenzonitrile, sodium salt

each of these compounds at rates of 0.25, 1 and 1.5 kg/ha;

I + iii + vii, i + iii + viii, i + iii + ix, i + iii + x, i + iii + xi, i + iii + xii, i + iii + xiii, i + iii + xiv, i + iii + xv, i + iii + xvii, i + iv + xi, i + iv + xii, i + iv + xiv, i + iv + xv, i + iv + xvi, i + iv + xvii, i + v + vii, i + v + viii, i + v + xviii, i + v ix, i + v + x, i + v + xv, i + v + xvi, i + v + xvii, i + vi + vii, i + vi + viii, i + vi + ix, i + vi + x, i + vi + xi, i + vi + viii, i + vii + xi, i + vii + xii, i + vii + xiii, i + vii + xiv, i + vii + xv, i + vii + xvi, i + vii + xvii, i + viii + xi, i + viii + xii, i + viii + xiii, i + viii + xiv, i + viii + xv, i + viii + xvi, i + viii + xvii, i + xviii + xi, i + xviii + xii, i + xviii + xiii, i + xviii + xiv, i + xviii + xv, i + xviii + xv, i + xviii + xvii, i + ix + xi, i + ix + xii, i + ix + xiii, i + ix + xiv, i + ix + xv, i + ix + xv, i + ix + xvii, i + x + xi, i + ix + xii, i + ix + xiii, i + ix + xiv, i + ix + xv, i + ix + xv, i + ix + xvii, i + x + xi, i + x + xii, i + x + xiii, i + x + xiv, i + x + xv, i + x + xvi, i + x + xvii, iii + vii + xi, iii + vii + xii, iii + vii + xiii, iii + vii + xiv, iii + vii + xv, iii + vii + xv, iii + vii + xvii, iii + vii + xi, iii + viii + xvii, iii + viii + xiii, iii + viii + xiv, iii + viii + xv, iii + viii + xvi, iii + viii + xvii, iii + ix + xi, iii + ix + xii, iii + ix + xiii, iii + ix + xiv, iii + ix + xv, iii + ix + xv, iii + ix + xvii, iii + x + xi, iii + x + xii, iii + x + xiii, iii + x + xiv, iii + x + xv, iii + x + xvi, iii + x + xvii, iv + viii + xi, iv + viii + xii, iv + viii + xiii, iv + viii + xiv, iv + viii + xv, iv + viii + xvi, iv + viii + xvii, iv + ix + xi, iv + ix + xii, iv + ix + xiii, iv + ix + xiv, iv + ix + xv, iv + ix + xvi, iv + ix + xvii, iv + x + xi, iv + x + xii, iv + x + xiii, iv + x + xiv, iv + x + xv, iv + x + xvi, iv + x + xvii, v + vii + xi, v + vii + xii, v + vii + xiii, v + vii + xiv, v + vii + xv, v + vii + xvi, v + vii + xvii, v + viii + xi, v + viii + xii, v + viii + xiii, v + viii + xiii, v + viii + xv, v + viii + xv, v + viii + xvii, v + ix + xi, v + ix + xii, v + ix + xiii, v + ix + xiv, v + ix + xv, v + ix + xvi, v + ix + xvii, iii + xviii + xi, iii + xviii + xii, iii + xviii + xiii, iii + xviii + xiv, iii + xviii + xv, iii + xviii + xvi, iii + xviii + xvii, iv + vii + xi, iv + vii + xii, iv + vii + xiii, iv + vii + xiv, iv + vii + xv, iv + vii + xvi, iv + vii + xvii, iii + xviii + xi, iii + xviii + xii, iii + xviii + xiv, iii + xvii + xv, iii + xviii + xvi, iii + xvii + xvii, v + x + xi, v + x + xii, v + x + xiii, v + x + xiv, v + x + xv, v + x + xvi, v + x + xvii

each of these compositions at rates of 1+0.25+0.25, 0.25+1+0.25 and 0.25+0.25+1 kg/ha.

After 12 to 15 days it was ascertained that the compositions had a better herbicidal action than their components, combined with the same crop plant compatibility.

The results are given below: Active ingredient I III IV V VI VII VIII kg/ha 0.25 1 1.5 0.25 1 1.5 0.25 1 1.5 0.25 1 1.5 0.25 1 1.5 0.25 1 1.5 0.25 1 1.5 __________________________________________________________________________ Crop plants Triticum aestivum 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 10 20 Hordeum vulgare 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 10 10 Secale cereale 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 5 0 20 20 Unwanted plants Avena fatua 20 65 80 0 0 0 0 0 0 0 0 0 0 0 0 0 10 15 0 0 0 Galium aparine 0 6 10 15 60 75 15 66 75 20 50 60 25 65 80 18 40 50 15 60 70 Stellaria media 0 10 14 25 60 70 10 65 70 25 50 70 10 60 85 20 60 75 25 55 80 __________________________________________________________________________ 0 = no damage 100 = complete destruction

In the greenhouse, various plants were treated at a growth height of from 2 to 20 cm with the following amounts of the following individual active ingredients and compositions thereof:

I 1,2-dimethyl-3,5-diphenylpyrazolium methyl sulfate

Iii 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide

Iv 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, sodium salt

V 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, dimethylamine salt

Vi 3-isopropyl-2,1,3-benzothiadiazinone-(4)-2,2-dioxide, diethanolamine salt

Xi .alpha.-(2-methyl-4-chlorophenoxy)-propionic acid, sodium salt

Xii .alpha.-(2,4-dichlorophenoxy)-propionic acid, dimethylamine salt

Xiv 2-methyl-4-chlorophenoxyacetic acid, dimethylamine salt

Xv 2,4-dichlorophenoxyacetic acid, dimethylamine salt

Xvi 2,4,5-trichlorophenoxyacetic acid, isooctyl ester

each of compounds I to VI at rates of 0.5 and 1.5 kg/ha, and each of compounds XI to XVI at rates of 0.25 and 1.5 kg/ha; I + III + XV + XIV, I + IV + XV + XIV, I + V + XV + XIV, I + VI + XV + XIV, I + III + XV + XI, I + IV + XV + XI, I + V + XV + XI, I + VI + XV + XI, I + III + XI + XVI, I + IV + XI + XVI, I + V + XI + XVI, I + VI + XI + XVI, I + III + XV + XVI, I + IV + XV + XVI, I + V + XV + XVI, I + VI + XV + XVI, I + VI + XIV + XVI, I + IV + XIV + XVI, I + V + XIV + XVI, I + VI + XIV + XVI, I + III + XII + XVI, I + IV + XII + XVI, I + V + XII + XVI, I + VI + XII + XVI

each of these compositions at a rate of 0.5+0.5+0.25+0.25 kg/ha.

After 12 to 15 days it was ascertained that the compositions had a better herbicidal action than their components, combined with the same crop plant compatibility.

The results are given below: Active ingredient I III IV V VI XI XII XIV XV XVI kg/ha 0.5 1.5 0.5 1.5 0.5 1.5 0.5 1.5 0.5 1.5 0.25 1.5 0.25 1.5 0.25 1.5 0.25 1.5 0.25 1.5 __________________________________________________________________________ Crop plants: Triticum aestivum 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Hordeum vulgare 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 5 Secale cereale 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 7 Unwanted plants: Avena fatua 35 80 0 0 0 0 0 0 0 0 0 0 0 5 0 0 0 0 0 0 Galium aparine 0 10 35 75 30 75 30 60 35 80 15 70 10 75 5 25 5 25 15 80 Stellaria media 5 14 30 70 20 70 20 70 20 85 20 70 15 75 10 35 3 20 5 36 __________________________________________________________________________ 0 = no damage 100 = complete destruction