IE910321A1 - Herbicidally active urea derivatives and a process for the¹preparation thereof - Google Patents

Abstract

Novel, herbicidally active substituted sulfonylurea derivatives of the general formula (I), wherein R1 stands for hydrogen, halogen, C1-4 alkoxy, halo-C1-4 alkoxy, C1-3 alkylsulfonyl or a group of the formula COR6; R2 means hydrogen, C1-3 alkyl or phenyl; R3 represents C1-6 alkyl, C3-6 alkenyl, C1-3 alkoxyalkyl group, C2-4 alkyl substituted by one or more halogen(s) or benzyl; R4 and R5 mean independently of each other a C1-4 alkyl, C1-4 alkoxy group, halogen, C1-3 alkylamino or di(C1-3alkyl) amino or C1-3 alkylthio; R6 stands for a C1-4 alkoxy, C3-6 alkenyloxy, C1-3 alkylamino, di(C1-3 alkyl) amino, piperazinyl or morpholinyl group; X means oxygen of sulfur; and E stands for a methine group or nitrogen, their salts as well as herbicide compositions containing these compounds optionally together with an antidote are disclosed. The compositions are highly effective against a number of weeds and selective when used in cultures of cultivated @.

Description

This invention relates to novel, herbicidally active substituted 5 sulfonylurea derivatives of the general formula (I) (I) wherein R^ stands for hydrogen, halogen, C-^alkoxy, halo-C-^alkoxy, Cj, ^alkylsulfonyl or a group of the formula COR^; R2 means hydrogen, C-^alkyl or phenyl; R^ represents Chalky!, C^alkenyl, C^_-jalkoxyalkyl group; C2_Zlalkyl substituted by one or more halogen(s); or benzyl group; R^ a°d R^ mean independently of each other a C^_^alkyl, C-^alkoxy group; halogen; C|_jalkylamino or di(C^_-jalkyl)amino; or C^_^alkylthio R6 stands for a C^alkoxy, C^alkenyloxy, C^alkoxyalkyl, C^alkylamino, diCC^ ^alkyl)amino, piperazinyl or morpholinyl group; X means oxygen or sulfur; and E stands for a methine group or nitrogen, their salts formed with alkaline metals, alkaline-earth metals, amines or quaternary ammonium bases. The invention is further directed to herbicide compositions containing such compounds optionally together with an antidote.

The invention further relates to a process for the preparation of novel compounds of the general formula (I), wherein Rp R2, R^, R^, R^, Rg, X and E are as defined above.

In the above definitions (throughout the specification): - alkyl group is meant to include a straight or branched chain alkyl group, such as methyl, ethyl, propyl, isopropyl, as well as any of the isomeric butyl groups; - alkoxy group usually means methoxy, ethoxy, propoxy, isopropoxy or any of the four isomeric butoxy groups, particularly methoxy, ethoxy, or propoxy group; A 4716-803 KY - 2 - alkenyl group may be e.g. allyl, isopropenyl, 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, l-isobutenyl or a pentenyl group, particularly allyl or 4-pentenyl group; - halogen in itself or halogen of a haloalkoxy group may be fluorine, chlorine or bromine, particularly chlorine.

Suitable alkaline metal or alkaline-earth metal hydroxides forming salts with the compounds of the general formula (I) are potassium, sodium, magnesium or calcium hydroxide, mainly sodium and potassium hydroxide.

Useful amines for salt formation include primary, secondary or 10 tertiary amines, such as methylamine, ethylamine, propylamine, isopropylamine, any of the four isomeric butylamines, dimethylamine, diethylamine, isopropylamine, diisopropylamine, pyrrolidine, piperidine, morpholine, trimethylamine, pyridine, quinoline or isoquinoline, particularly isopropylamine and diethanolamine.

Quaternary ammonium bases used for salt formation are e.g. tetraethylammonium, trietbylbenzylammonium, trimethylbenzylammonium halide or any kind of tetrabutylammonium halides.

Herbicidally active sulfonylurea derivatives are commonly known compounds.

The known sulfonylureas are characterized thereby that the nitrogen in 3-position, substituted by a heterocyclic group, bears hydrogen or a C^_^alkyl group, preferably a· methyl group; or a C^_^alkoxy group, preferably a methoxy group; or a C2_8alkenyl, C2_Ztalkynyl group or an aralkyl group. Other substituents have been published in a surprisingly low number or patent specifications.

Sulfonylureas of such type are e.g. discribed in the European Patent Specification No. 152,379 and in the published Japanese Patent Applications Nos. 95 8126872 and 96 0078981.

Sulfonylureas exert an excellent herbicidal effect against a '30 number of mono- and dicotyledonous weeds, chiefly broad-leaf and grass weeds /_~9.M. Green et al.: Proc. S. Weed Sci. Soc. 34, 214 (1981)7, particularly in wheat and barley cultures. Their advantage consists in the very low effective doses (usually 5 to 50 g/hectare). Their disadvantage appears therein that upon the use thereof cultivated plants are damaged to a higher or lower degree. It has turned out in the practice of their use that their antidotation is advisable in cereals and essential in maize cultures. In the European Patent Application No. 127,469 antidotes are published which can be used after sowing in the preemergent period and are capable to protect wheat and millet from the harmful effect of sulfonylurea-type herbicides. Methyl 2-Λ (aminocarbonyl)aminosulfonyl7benzoate and its ammonium salt as well as methyl 3-/. (aminocarbonyl)amino5 sulfonyl7-2-thiophenecarboxylate were found to be most favourable.

According to the United States Patent Specification Nn. 4,343,649 1,8-naphthalic acid anhydride, oc -(cyanomethoxyimino) benzene:acetonitrile or N,N-diallyl-dichloroacetamide may be used to give a favourable result in the increase of selectivity of the herbicidally active 2-chloro-N10 -_/_(4-methoxy-6-methyl-l,3,5-triazin-2-yl)aminocarbonyl7benzenesulfonamide, 2,5-dichloro-N-_/~(4,6-dimethoxypyridin-2-yl)aminocarbonyl7benzenesulfonamide or 2-carbomethoxy-N-/. (4,6-dimethylpyrimidin-2-yl)aminocarbonyl7 benzenesulfonamide.

Herbicide compositions containing a sulfonylurea derivative as active ingredient together with glycine derivatives as antidotes are published in the Hungarian Patent Specification No. 201,445.

The aim of the present invention was to develop herbicide compositions containing novel active ingredients.' which possess more favourable physical and chemical properties, higher selectivity and lower persistency in comparison to the known sulfonylureas.

In the course of our investigations, compositions containing novel sulfonylurea derivatives of the general formula (I) have been developed which are characterized in that the atom (nitrogen in 3-position) of the sulfonylurea group substituted by a heterocyclic group bears an R2-CH-0Rj group wherein R2 and R^ are as defined above.

It has been found that compositions containing the novel compounds of the general formula (I) are particularly useful for weed control purposes since they show an excellent herbicidal effect in a suitable low dose, are appropriately selective against cultivated plants or can be made selective by using known antidotes and simultaneously, they are easily decomposed in the soil.

According to another aspect of the invention, there is provided a process for the preparation of the new compounds of general Formula (I) in inert organic solvents or a mixture thereof. This process comprises a) reacting an isocyanate or isothiocyanate of the general Formula (IV) (IV) Ε91321 2-NCX wherein R^ is as defined above, with an aminopyrimidine or aminotriazine derivative of the general formula (III) (III) wherein R2, R^, R^, R5 and E are as defined for formula (I), optionally in the presence of a base as catalyst, at a temperature of 0 to 50 °C, preferably between 20 °C and 30°C; or b) reacting a sulfonylcarbamate derivative of the general formula (V), -NH - COOR (V) wherein R^ is as defined for formula (I) and R stands for phenyl group, with an aminopyrimidine or aminotriazine derivative of the general formula (III), wherein R2, R-j, R^, R$ and E are as defined above, at a temperature of 25 to 120 °C, preferably between 60°C and 90°C; or c) reacting a carbamoyl chloride of the general formula (VI) (VI) IE 91321 - 5 wherein Rp R?, R^, R5 and E are as defined above and R means phenyl group, with an alkaline metal salt of a sulfonamide of the general formula (II) (II) wherein R^ is as defined for as catalyst at a temperature between 0 °C and 50 °C; or d) reacting a N-pyrimidinyl- or formula (VII) formula (I), in the presence of a base between -10 °C and 50 °C, perferably N-triazinylcarbamate of the general N ~ COOR CH-OR3 (VII) wherein R2, Rp R^, R5 and E are as defined above and R means phenyl group, with a sulfonamide of the general formula (II), wherein R^ is as defined for formula (I), in the presence of a catalytic amount of a base at a temperature of 20 to 80 °C, preferably between 20 °C and 40 °C; or e) reacting a sulfonyl chloride of the general formula (VIII) (VIII) wherein R^ is as defined for formula (I), with an aminopyrimidine or aminotriazine derivative of the general formula (III), wherein R2, Rp R^ and R^ are as defined above, and alkaline metal cyanates at a temperature of 20 °C to 120 °C, preferably between 60 °C and 90 °C.

IE 91321 - 6 If desired, the compounds of general formula (I) prepared by using the above process variants may be converted to their salts with alkaline metal or alkaline-earth metal hydroxides, amines or quaternary ammonium halides, e.g. by reacting the desired compound with the appropriate base in a suitable solvent, which is then evaporated In the preparation of compounds of the general formula (I) methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, tetrahydrofuran, acetonitrile, dioxane, benzene, toluene, xylene, chlorobenzene, dimethylformamide, nitromethane, nitroethane, N-methylpyrrolidone, dimethoxyethane,' diethyl ether, diisopropyl ether, dibutyl ether, hexane, petroleum ether, ethyl acetate, butyl acetate, dibutyl phthalate as well as mineral and vegetable oils may be used as inert organic solvents but useful solvents are not restricted to those listed above.

In the above process variants the reaction temperature may be varied in a wide range usually from -20 °C up to the boiling of the solvent used; however, it is preferred to react the components at a temperature between 0 °C and 90 °C, particularly at 15 to 45 °C since this temperature range is useful to prepare also the heat-sensitive derivatives of the general formula (I). The reactions are suitably carried out under atmospheric pressure, however an elevated or reduced pressure may also be used; the reactions can further be performed in the presence of air or under an inert gas e.g. nitrogen.

For shortening the reaction time or for completing the reaction a few drops of a base should be used as catalyst.

As catalytically active bases particularly tertiary amines such as triethylamine, tributylamine, Ν,Ν-dimethylaniline as well as nitrogencontaining heterocyclic compounds, e.g. pyridine or 1,4-diazabicyclo-/2.2.27octane (DABCO) may be empleyed although alkaline metal hydroxides or alkaline metal alkoxides such as sodium hydroxide or sodium methoxide are also useful. The catalysts being useful in the practice of the process variants are not restricted to those listed above.

The products prepared by using the above process variants can be separated by the complete or partial evaporation of the solvent and recrystallization; or by triturating an evaporation residue with a solvent or solvent mixture weakly dissolving the product. If necessary, the compounds obtained can be purified by chromatography on a suitable load, such as aluminium oxide, silica gel and the like.

IE 91321 - 7 The herbicide compositions according to the invention usually contain the active ingredient of general formula (I) in an amount of 0.0.1 to 95 % by weight, preferably' 2 to BO % by weight in the form of known formulations, e.g. solutions, emulsions, dusting powders, suspensions, wettable powders, pastes, soluble powders, granules, suspension concentrates or emulsifiable concentrates, natural or synthetic materials impregnated with the active ingredient or compositions encapsulated in polymeric substances.

The compositions are prepared by mixing and/or triturating 10 the active ingredients with binding agents, solvents and/or carriers, optionally by the simultaneous use of surfactants and/or dispersing as well as adhesion-promoting agents.

Useful solvents are: aromatic hydrocarbons, preferably Cy_^2 fractions, e.g. toluene, xylene mixtures or substituted naphthalenes; chlorinated aliphatic or aromatic hydrocarbons, preferably chloroethylene, methylene chloride or chlorobenzene; aliphatic hydrocarbons such as cyclohexane, paraffins or mineral oil fractions; mineral or vegetable oils; alcohols, e.g. ethanol or ethylene glycol; or their ethers Such as ethylene glycol monomethyl ether, ethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; strongly polar solvents, e.g. N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide; phthalic acid esters, e.g. dibutyl phthalate or dioleyl phthalate; as well as epoxidized vegatable oils such as epoxidized cocus oil or soybean oil; or water.

Suitable carriers are: inorganic powders such as kaolin, calcite, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, perlite, amorphous silicon dioxide, aluminium oxide, highly disperse silicic acid, pumice, brick powder, sepiolite, bentonite, or sand; organic powders, e.g. flour-like powders prepared from plant parts such as corn-stalk or coconut-shell as well as corn flour; various types of starch, processed starch; sugar, e.g. glucose; powdered or ground synthetic resins, e.g. phenol or urea resins, In addition, a high number of inorganic or organic pre-granulated materials may be used.

Nonionic, cationic and/or anionic tensides may be employed as surfactants which possess favourable emulsifying, dispersing and wetting properties. Mixtures of tensides may also be used. The anionic tensides are water-soluble soaps, e.g. sodium or potassium salt of IE 31321 - 8 oleic or stearic acid as well as the salts of natural fatty acid mixtures; however, it is more suitable to use synthetic tensides, particularly fatty alcohol sulfonates, fatty alcohol sulfates, sulfonate-benzimidazole derivatives or alkylarylsulfonates. The calcium or triethanolamine salts of ligninsulfonic acid, dodecylsulfuric acid esters, sulfonic acids prepared from natural fatty acids as well as sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts, dodecylbenzenesulfonic acid or tributylnaphthalenesulfonic acid may be mentioned as examples.

In addition, phosphates, e.g. salts of the phosphate ester of p-nonylphenol -(4-14)ethylene oxide adduct are also suitable.

As cationic tensides quaternary ammonium salts may be taken in consideration which contain lower alkyl groups substituted by halogen or hydroxyl group and/or a benzyl group bound to the quaternary nitrogen in addition to a Cg_28alkyl group. Examples of tensides of this type are e.g. stearyltrimethyl-ammonium chloride or benzyl-bis(2-chloroethyl)ethylammonium bromide.

The nonionic tensides are mainly polyoxyethylene glycol ethers, polyoxyethylene glycol esters as well as esters of polyvalent alcohols and their condensation products, nonylphenol polycthoxyethanols, castor oil polyglycol ethers and polypropylene-polyethylene oxide adducts.

Ligninsulfonate, sulfite liquor and methylcellulose are e.g. useful dispersing agents.

The compositions may contain adhesion-promoting agents, e.g. carboxymethylcellulose, natural and artificial, powder-like, granular or latex-like polymers, e.g. polyvinyl alcohol, polyvinyl acetate as well as native phospholipids such as cephalin, lecithin or synthetic phospholipids.

In addition, the compositions according to the invention may contain other additives such as stabilizers, antifoam agents, viscosity30 regulating substances, preserving agents as well as inorganic or organic pigments.

Activating, synergistic, antidoting substances may also be incorporated to the compositions according to the invention.

The herbicide compositions containing known antidotes, such as DKA-24 (N-dichloroacetyl-N-allylglycine N'-allylamide), AD-67 (Ndichloroacetyl-l-oxa-4-azaspiro/4,j?7decane), R-25788 (N,N-diallyl-dichloroacetamide), MG-191, TI-35 or CGA-92194 are also within the scope of the invention. (TI-35 is N-(dichloroacetyl)-hexamethylene imine, CGA-92194 is N-(l,3-dioxolan-2-ylmethoxy)-imino-benzeneacetonitrile.) - 9 If desired, the compounds of the general formula (I) according to the invention and the compositions containing same can be used in combination with other agrochemicals, which may be herbicides, fungicides, insecticides, miticides, nematocides, antiviral agents, plant growtfi-reguiating agents or attractants.

The compositions according to the invention preferably contain 0,01 to 95 %, more preferably 2 to 80 % by weight of active ingredient of the general formula (I) or a total of active ingredient and antidote, to 99.9 % by weight of liquid or solid carrier and 0 to 30, preferably 0.1 to 25 % by weight of surfactant and other additives. In the compositions containing also an antidote, the ratio of the antidote to the active ingredient may be 1:1 to 50:1.

Compositions with the components listed hereinafter are particularly preferred (percentages are throughout given by weight): 15 1. Solutions Active ingredient 1 to 30 %, preferably 5 to 25 % Solvent 1 to 90 %, preferably 0 to 85 % Surfactant 2. Emulsifiable concentrate 0 to 99 %, preferably 0 to 95 % 20 Active ingredient 1 to 20 %, preferably 5 to 10 % Surfactant 1 to 30 %, preferably 5 to 20 % Liquid carrier 50 to 94 %, preferably 70 to 85 % 3. Wettable powder Active ingredient 0.5 to 90 %, preferably 20 to 80 % 25 Surfactant 0.5 to 20 %, preferably 5 to 15 % Solid carrier 4. Suspension concentrate 5 to 95 %, preferably 15 to 90 % Active ingredient 5 to 75 %, preferably 10 to 50 % Water 25 to 95 %, preferably 30 to 80 % 30 Surfactant 5. Powder 1 to 40 %, preferably 5 to 20 % Active ingredient 0.5 to 10 %, preferably 0.5 to 5 % Solid carrier 6. Granules 90 to 99.5 %, preferably 95 to 99 % 35 Active ingredient . 0.5 to 30 %, preferably 1 to 15 % Solid carrier 70 to 99.5 %, preferably 85 to 95 % - 10 g9^321 The compositions according to the invention can be diluted to an active ingredient concentration of 0.01 % by weight with water before the use. The compositions may be applied, onto the locus to be treated after or without dilution by using the common methods, e.g. spraying, dusting, atomization, spreading, sprinkling or the ultra low volume method. The compositions containing the novel sulfonylureas of the general formula (I) according to the invention possess an excellent herbicidal effect against both monocotyledonous and dicotyledonous, annual as well as perennial weeds. The compositions according to the invention can be applied before sowing or both in the preemergent or postemergent period.

When carrying out the treatment before emergence of the weeds on the soil without plants, the sprouting plants shoot up and develop up to the cotyledon (seed-leaf) phase, then their growth stops and they perish partially or totally after 3 to 6 weeks. When carrying out the treatment after shooting up (emergence) of the weeds, the growth of the weeds stops after the treatment and the weeds perish partially or totally after 1 to 4 weeks. It is characteristic of the compositions according to the invention that they already show effect in an extraordinarily low applied amount. Depending on the weeds treated, the herbicidal effect is very good in doses of as low as 0.01 to 2.0 kg/hectare. The important large-scale cultures, e.g. wheat, maize, barley, rice and so-y sorts were found to be resistant; thus, the compositions according to the invention are excellently useful for the control of both mono- and di25 cotyledonous, annual and perennial weeds, which are difficult to kill or cannot be killed at all in the above cultures. Cultivated plants are not restricted to those mentioned above. Depending on the active ingredient employed, 0.05 to 2.0 kg/hectare doses of compositions according to the invention can be used for a total weed control, too.

A particular advantage of compositions containing sulfonylureas of the general formula (I) as active ingredient appears therein that, after getting to the soil, they are rapidly decomposed therefore, when the compositions are postemergently used, the field area employed can be sown with other cultivated plants immediately after harvesting the host-plant or after a shorter period in comparison to the compositions containing known, commercially available sulfonylureas.

The preparation and use of the active ingredients /compounds of the general formula (I)/ and compositions according to the invention - 11 are illustrated in detail in the following, non-limiting Examples.

Example 1 Preparation of 3-ethoxymethyl-l-(2-methoxycarbonylphenylsulfonyl)-35 (4-methoxy-6-methyl-l,3,5-triazin-2-yl)urea (compound No. 8) After adding 0.01 g of DABCO catalyst to a solution containing 3.96 g (20 mmol) of 2-ethoxymethylamino-4-methoxy-6-methyl-l,3,5-triazine in 50 ml of anhydrous diethyl ether, 5.3 g (22 mmol) of 2-methoxycarbonyl10 phenylsulfonyl isocyanate dissolved in 20 ml of anhydrous diethyl ether are dropped to the above solution at room temperature under stirring.

The reaction mixture is stirred for 6 hours while precipitation of the product begins. Next day the crystalline precipitate is filtered, washed with a little diethyl ether and then dried at room temperature to give 6.5 g (74 % yield) of the title product, m.p.: 105-106 °C.

Example 2 Preparation of 3-ethoxymethyl-l-(2-chlorophenylsulfonyl)-3-(4-methoxy-6-methyl-l,3,5-triazin-2-yl)urea (compound No. 4) 3.96 g (20 mmol) of 2-(ethoxymethyl)amino-4-methoxy-6-methyl1,3,5-triazine are added to the solution of 6.23 g (20 mmol) of phenyl-N-(2-chlorophenylsulfonyl)carbamate in 120 ml of anhydrous benzene.

The mixture is stirred at 75 to 80 °C for 8 hours, then evaporated to dryness. After recrystallizing the residue from diethyl ether 5.06 g (61 %) of the title compound are obtained, m.p.: 123-123 °C.

Example 3 Preparation of 3-(4,6-dimethylpyrimidin-2-yl)-l-(2-chlorophenylsulfonyl)30 -3-(ethoxymethyl)urea (compound No. 2) 4.87 g (20 mmol) of N-(4,6-dimethylpyrimidin-2-yl)-N-(ethoxymethyl) carbamoyl chloride dissolved in 10 ml of dimethylformamide are dropwise added to a solution containing 4.27 g (20 mmol) of 2-chlorobenzenesulfon35 amide sodium salt in 25 ml of anhydrous, redistilled dimethylformamide at 5 to 10 °C while stirring. After the addition, the mixture is stirred at room temperature for 3 hours, then poured onto 250 ml of icewater.

The precipitate is filtered, washed with a little water, dried and.Then . - 12 recrystallized from a mixture of ethyl acetate and diethyl ether to obtain the title product in a yield of 3.34 g (42 %), m.p.: 118-119 °C.

Example 4 Preparation of 3-(4,6-dimethylpyrimidin-2-yl)-3-ethoxymethyl-l-(2-methoxycarbonylphenylsulfonyl)urea (compound No. 6) After adding 3.1 g (10 mmol) of phenyl-N-(4,6-dimethylpyrimidin-2-yl)-N-(ethoxymethyl)carbamate to the solution of 2.15 g (10 mmol) of 2-methoxycarbonylbenzenesulfonamide and 1.52 g (10 mmol) of 1,8-diazabicyclo/_~5.4.0_7undec-7-ene in 25 ml of anhydrous dioxane, the reaction mixture is stirred at 30 to 35 °C for 10 hours, then poured into 200 ml of water. After adjusting the pH value to 6.5 the precipitate is filtered, dried and then recrystallized from a mixture of chloroform and hexane to give 1.59 g (37.6 %) of the title compound, m.p.: 124 to 126 °C.

Example 5 Preparation of 3-(4,6-dimethylpyrimidin-2-yl)-3-methoxymethyl-l-(2-methoxycarbonylphenylsulfonyl)urea (compound No. 5) A mixture containing 4.3 g (20 mmol) of 2-methoxycarbonylbenzenesulfonyl chloride, 3.67 g (22 mmol) of 4,6-dimethyl-2-(methoxymethyl)aminopyrimidine and 3.24 g (40 mmol) of potassium cyanate in 30 ml of anhydrous acetonitrile is heated at 81 °C under vigorous stirring for 2 hours. After filtering off the precipitated inorganic salt, the filtrate is evaporated, the residue is resuspended in 30 ml of water, then the precipitate filtered off is dried and recrystallized from a mixture of ethyl«acetate and diethyl ether to give the title compound in a yield of 5.4 g (66.2 %), m.p.: 133-135 °C.

The compounds listed in Table I are prepared similarly as described in the above Examples.

IE 91321 - 13 Table I Compounds of the general formula (I), wherein X = oxygen Compound No.R1 r2R3R4R5 E M.p. °C 1 Cl H CH3 CH3 CH3 CH 126-8 2 H HC2H5 ch3 ch3 CH 118-9 3 Cl H ch3 ch3 CH30 N 130-5 4 Cl H c?h3 ch3 CH30 N 123-4 5 COOCH} H ch3 ch3 ch3 CH 133-5 6 C00CH3 HC2H5 ch3 ch3 N 124-6 7 COOCH3 H ch3 ch3 CH30 N 112-5 8 cooch3 H c?h3 ch3 ch3o N 105-6 9 COOCH3 H C4H9 ch3 CH30 N 100-2 10 C00CH3 HC4H9 ch3 CH30 N 103-4 11 H H ch3 ch3 CH30 N 125-7 Example 6 Preparation of a wettable powder (10 WP) Example 6 Preparation of a wettable powder (10 WP) 20 Components weighed in: g Active ingredient prepared according to Example 2 20 Silicate carrier (Zeolex 444) 80 Siliceous earth (diatomaceous earth) 80 Sodium aliphatic sulfonate wetting agent (Netzer IS) 4 Cresol formaldehyde sulfonate dispersing agent (Dispergiermittel 1494) 6 Sulfite liquor powder (Borresperse NA) 10 The powder mixture is crushed in a laboratory ball mill for 30 minutes, then ground to fine particles in an Alpine 63 C-type laboratory contraplex mill at a speed degree of 70. The thus obtained wettable powder composition contains the compound No. 4 of Table I as active ingredient in an amount of 10 % by weight.

Floatability (in 1 % concentration): 86.5 %.

Wet sieve residue (on a sieve of DIN 10): 0.27 %.

Example 7 Preparation of a wettable powder (50 WP) IE 91321 - 14 Components weighed in: g Active ingredient prepared according to Example 3 150 Synthetic silicate carrier (Zeolex 444) 30 Siliceous earth 50 Sodium aliphatic sulfonate (Netzer IS) 4 Cresol-formaldehydesulfonate 6 Sulfite liquor powder 10 The process described in Example 6 is followed.

The thus obtained wettable powder composition contains the compound No. 2 of Table I as active ingredient in an amount of 50 % by weight.

Floatability (in 1 % concentration): 82.9 %.

Wet sieve residue (on a sieve of DIN 100): 0.43 %.

Example 8 Preparation of a wettable powder (85 WP) Components weighed in: g 20 Active ingredient prepared according to Example 4 170 Synthetic silica carrier (Sip?rnat. 50 S) 20 Sodium oleyl methyl laurate (Arkopon T plv.) 4 Cresol-formaldehydesulfonate 6 The process described in Example 6 is followed.

The thus obtained wettable powder composition contains the compound No. 6 of Table I as active ingredient in an amount of 85 % by weight.

Floatability (in 1 % concentration): 82.9 %.

Wet sieve residue (on a sieve of DIN 100): 0.43 %.

Example 9 Preparation of an emulsifiable concentrate (5 EC) Components weighed in: g Active ingredient prepared according to Example 1 5 Xylene 70 Cyclohexanone 15 Calcium dodecylbenzenesulfonate (Emulsogen IP 400) 8 Fatty acid polyglycol ester (Emulsogen EL 400) 2 91321 - 15 The active ingredient is dissolved in the mixture of xylene and cyclohexanone under stirring and 8 g of Emulsogen IP 400 as well as 2 g of Emulsogen EL 400 emulsifying agents are added. After homogenization the mixture is filtered.

The thus obtained emulsifiable concentrate contains the compound No. 8 of Table I as active ingredient in an amount of 5 % by weight.

Emulsion stability (1 % concentrate in CIPAC A and CIPAC D water) stable after 2 hours.

A reversible creamification is observed after 24 hours.

Example 10 Preparation of dusting powder (5 D) Components weighed in: _2.

Talc 20 Silicate (Sipernat 50 S) 30 Active ingredient prepared according to Example 5 50 Limestone grist (M 10) 900 The mixture of the active ingredient prepared according to Example 5, the synthetic silicate carrier and talc are crushed in a laboratory ball mill, then ground to fine particles in an Alpine 63 C-type laboratory contraplex mill. The grist is homogenized with limestone grist in a laboratory powder mixer.

The thus obtained dusting powder contains the compound No. 5 of Table I as active ingredient in an amount of 5 % by weight.

Sieve residue (on a sieve of DIN 100): 0.12 %.

Example 11 Preparation of a suspension concentrate (5 FW) Components weighed in: g Active ingredient prepared according to Example 2 10 Sunflower oil 168 Organophilic bentonite (Ivegel) 2 Polyethylene alkyl ether, polyoxyethylene castor oil, ethoxylated fatty acids and sodium sulfosuccinate (Sorpol 3815) 91321 - 16 The active ingredient, sunflower oil, organophilic bentonite (Ivegel) and Sorpol 3815 emulsifying agent are weighed into a laboratory bead-mill. The suspension concentrate is ground together with 65 % by volume of glass-bead load of 1.0 to 1.5 mm in diameter at 775 rpm for minutes.

The thus obtained suspension concentrate contains the compound No. 4 of Table I as active ingredient in an amount of 5 % by weight.

Stability (1 % concentrate in CIPAC and CIPAC D water): stable after 30 minutes.

Example 12 Preparation of suspension concentrate (40 FVJ) Components weighed in: q Active ingredient prepared according to Example 1 80 Synthetic silicate (Zeolex 444) 6 Sodium oleyl methyl tauride (Arkopon T plv.) 4 Nonylphenyl polyglycol ether (Arkopal N 100) 10 % Xanthan gum (Kelzen S) solution 10 Water 80 g of the active ingredient prepared according to Example 1, synthetic silicate (Zeolex 444), sodium oleyl methyl tauride (Arkopon T) and nonylphenyl polyglycol ether (Arkopal N 100) wetting dispersing agent as well as 80 g of water are weighed in a laboratory bead-mill. After homogeinization, the suspension concentrate is ground together with 70 % by volume of glass-bead load of 1.0 to 1.5 mm in diameter for 30 minutes. After grinding and separating from the load, the .mixture is homogenized with 20 g of 2 % xanthan gum (Kelzen S) solution in an Ultra turrax equipment under vigorous stirring.

The thus prepared suspension concentrate contains the compound No. 8 of Table I as active ingredient in an amount of 40 % by weight. Floatability (in 1 % concentration): 97.3 % Particle size (below 10 ^u): 91.6 % Example 13 Preparation of water-dispersible granules (75 WDG) Components weighed in: Compound No. 3 of Table I as active ingredient Synthetic silicate carrier Polyvinylpyrrolidone (K 30 product of BASF) Alkylphenol ether phosphate (Atlox 5330 product of ICI) Mixture of polyalkylene glycol ether and polymethylene 375 alkylaryl ether (Atlox 4896 product of ICI) Water 180 375 g of compound No. 3 of Table I as active ingredient are pre-crushed (pre-ground) with 55 g of synthetic silicate carrier in a laboratory ball mill, then the mixture is ground to fine particles in an Alpine 63 C-type contraplex mill at a speed degree of 80. The granulating liquid is prepared by dissolving 20 g of polyvinylpyrrolidone, 30 g of alkylphenol ether phosphate and 20 g of a mixture of polyalkylene glycol ether and polymethylene alkylaryl ether in 180 ml of water. The ground powder mixture is introduced to an FPG 0.5 type batch-operation (periodically operated) granulating apparatus with fluidizing atomization and brought into a fluidized, state by regulating the air stream entering with a temperature of 60 to 65 °C. When the inlet temperature reaches 30 °C, the evaporation of the granulating liquid is started under a pressure of 1.5 bar and the volume of the air flow is increased depending on the particle growth. After introducing the granulating liquid the drying is continued until the outlet temperature reaches 36 to 38 °C.

The thus prepared granules contain the compound No. 3 of Table I as active ingredient in an amount of 75 % by weight.

Floatability (in 1 % concentration after 30 minutes): 93.7 % Particle size between 0.2 and 1 mm: at least 75 % Exaple 14 Preparation of water-dispersible granules (25 WDG) IE 91321 - 18 Components weighed in: P Compound No. 7 of Table I as active ingredient 125 Synthetic silicate carrier 250 Maltodextrin binding agent 75 Ligninsulfonate (Sorpol 9D 47 K product of Toko) 30 Polyoxyethylene polyalkylaryl phenyl ether sulfate (Sorpol 5096 product of Toko) 20 The compound No. 7 of Table I as active ingredient, synthetic silicate carrier, maltodextrin binding agent as well as ligninsulfonate (Sorpol 90 47 K product of Toko) and polyoxyethylene polyalkylaryl phenyl sulfate (Sorpol 5096 product of Toko) tenside are weighed in a laboratory ball mill. After grinding for 30 minutes, the powder mixture is ground to fine particles in an Alpine 63 C-type contraplex mill. The grist is introduced into an FPG 0.5-type batch-operation (periodically operated) fluidization apparatus with fluidizing atomization and brought into a fluidized state by regulating the air stream having an inlet temperature of about 60 °C.

The granulation is carried out by atomized water when the outlet temperature reaches 28 to 30 °C. After obtaining the desired particle size of about 0.5 mm, the atomization of the water is stopped and the drying is continued until the outlet temperature reaches 36 to 38 °C.

The thus prepared granules contain the compound No. 7 of the Table I as active ingredient in an amount of 25 % by weight.

Floatability (in 1 % concentration after 30 minutes): 91.85 % Particle size between 0.2 and 1.0 mm: at least 95 %.

Example 15 Preparation of a suspension concentrate (14.5 FW) Components weighed in: g Compound No. 8 of Table I as active ingredient 2 DKA-24 (N-dichloroacetyl-N-allylglycine N'-allylamide) as antidote 12.5 Zeolex 444 carrier 11.6 Monoethylene glycol 15 Arkopon T wetting agent 3 Arkopol N-090 (nonylphen/1 polyglycol ether) dispersing agent 6 IE 91321 Water % by weight xanthan gum solution as thickening agent 39.9 g The suspension concentrate containing the active ingredient (compound No. 8 of Table I) and the DKA-24 antidote in a total amount of 14.5 % by weight in a weight ratio of 1:6.25 is prepared as described in Example 12.

Example 16 Preparation of a suspension concentrate (27.0 FW) Components weighed in: P Compound No. 8 of Table I as active ingredient 2 R-25788 (Ν,Ν-diallyl-dichloroacetamide) as antidote 25 Zeolex 444 carrier 5 Monoethyleneglycol 10 Arkopon T wetting agent 2.5 Arkopol N-090 dispersing agent 5.5 Water 42 % by weight xanthan gum solution thickening agent 8 The process described in Example 12 is followed to obtain a suspension concentrate containing the active ingredient (compound No. 8 of Table I) and the R-25788 antidote in a total amount of 27 % by weight in a weight ratio of 1:12.5.

Example 17 Preparation of a wettable powder (20.25 WP) Components weighed in: Compound No. 4 of Table I as active ingredient AD-67 (N-dichloroacetyl-l-oxa-4-azaspiro/4.57decane) as antidote Zeolex 444 carrier Siliceous (diatomaceous) earth Netzer IS wetting agent Dispergiermittel 1494 dispersing agent 1.5 18.75 34.75 33.0 Sulfite liquor powder dispersing agent 5 g The process described in Example 6 is followed to obtain a wettable powder composition containing the active ingredient (No. 4 of Table I) and the AD-67 antidote in a total amount of 20.25 % by weight in a weight ratio of 1:12.5.

Example IS Preparation of water-dispersible granules (13.5 WDG) Components weighed in: q Compound No. 6 of Table I as active ingredient 1 CGA-92194 /N-(l,3-dioxolan-2-ylmethoxy)imino-benzeneacetonitrile/ as antidote 12.5 Synthetic silicate carrier 61.5 Maltodextrin binding agent 15 Ligninsulfonate (Sorpol 90 47 K) 6 Polyoxyethylene polyalkylaryl phenyl ether sulfate (Sorpol 5096) 4 The process described in Example 14 is followed to obtain water- dispersible granules containing the active ingredient (compound No. 6 of Table I) and the antidote (CGA-92194) in a total amount of 13.5 % by weight in a weight ratio of 1:12.5. 25 Example 19 Preparation of a wettable powder (51.2 WP) Components weighed in: 9 Compound No. 2 of Table I as active ingredient 20 30 DKA-24 as antidote 31.2 Zeolex 444 carrier 14.4 Siliceous earth carrier 24.4 Netzer IS wetting agent 2 Cresol-formaldehydesulfonate 3 35 Sulfite liquor powder dispersing agent 5 The process described in Example 6 is followed to obtain a wettable powder composition containing the active ingredient (compound No. 2 of Table I) and the antidote (DKA-24) in a total amount of 51.2 % by weight in a weight ratio of 1:1.56.

Example 20 Preparation of a wettable powder (24.75 WP) Components weighed in: q Compound No. 2 of Table 1 as active ingredient 6 MG-191 (2-dichloromethyl-2-methyl-l,3-dioxolane) as antidote 18.75 Zeolex 444 carrier 33 Siliceous earth carrier 32.25 Netzer IS wetting agent 2 Dispergiermittel 1494 dispersing agent 3 Sulfite liquor powder dispersing agent 5 The process described in Example 6 is followed to give a wettable powder composition containing the active ingredient (compound No. 2 of Table I) and the antidote (MG-191) in a total amount of 24.75 % by weight in a weight ratio of 1:3.125.

Example 21 Preparation of a dusting powder (5.2 D) Components weighed in: _Q Compound No. 5 of Table I as active ingredient 2 AD-67 as antidote 50 Talc 19 Synthetic silicate carrier (Sipernat 50 S) 29 Limestone grist (M 10-type) 900 The process described in Example 10 is followed to give a dusting powder containing the active ingredient (compound No. 5 of Table I) and the antidote (AD-67) in a total amount of 5.2 % by weight in a weight ratio of 1:25. - 22 Example 22 Preparation of a wettable powder (21 WP) Components weighed in: g Compound No. 6 of Table I as active ingredient 1 DKA-24 as antidote 20 Zeolex 444 carrier 30 Siliceous earth carrier 39.5 Dispergiermittel 1494 dispersing agent 3 Netzer IS wetting agent 2 Sulfite liquor powder 4.5 The process described in Example 6 is followed to obtain a wettable powder containing the active ingredient (compound No. 6 of Table I) and the antidote (DKA-24) in a total amount of 21 % by weight in a weight ratio of 1:20.

Example 23 Preparation of a dusting powder (6 D) Components weighed in: £ Compound No. 4 of Table I as active ingredient 10 DKA-24 as antidote 50 Talc 15 Synthetic silicate carrier (Sipernat 50 S) 25 Limestone grist (M 10-type) 900 The process described in Example 10 is followed to give a dusting powder composition containing the active ingredient (compound No. 4 of Table I) and the antidote (DKA-24) in a total amount of 6 % by weight in a weight ratio of 1:5.

Example 24 Preparation of a suspension concentrate (22 FW) - 23 Components weighed in: 2 Compound No. 2 of Table I as active ingredient 2 DKA-24 as antidote 20 Zeolex 444 carrier 6 Arkopon T wetting agent 4 Arkopol N-100 wetting agent 10 % by weight xanthan gum solution as thickening agent 10 Water 48 The process described in Example 12 is followed to give a suspension concentrate containing the active ingredient (compound No. 5 of Table I) and the antidote (DKA-24) in a total amount of 22 % by weight in a weight ratio of 1:10.

Example 25 Greenhouse test of the postemergent effect (effect on emerged plants) The seeds of the test plants were sowed into a mixture containing 20 1/3 part of sand, 1/3 part of clay and 1/3 part of floresca chernozem soil placed in 200 ml plastic bottles containing 4 holes at their bottom.

After sowing, the soil and the smalT plants, respectively emerged were daily sprinkled at a temperature of 20 to 26 °C under natural illumination supplemented with an illumination of 4 hours. The 10 WP composition prepared from the compounds Nos. 3, 5, 6, 7 and 8, respectively of Table I according to Example 6 were sprayed by using 1000 litres per hectare of water under a pressure of 4 bar onto the 2 to 4-leaf plants by using a greenhouse sprayer.

The damages (injuries) of the test plants were evaluated in the 2nd and 4th weeks following the spraying. The damages of the various test plants are given as percentage; 0 % means no damage and 100 % means total perishment.

The results are summarized in Table II. It can be seen that the compositions according to the invention possess a good herbicidal effect and a favourable selectivity against the cultivated plants. The compounds Nos. 3, 7 and 8 proved to be particularly effective.

In the first column of Table II and the following Tables, the Roman numeral I refers to Table I and the Arabic numeral refers to the number of the compound in Table I.

Table II · Postemeroent effect Compound No. in Table I) Dose Perishmerit of the test plants (%) TRIE g/ha ORYS STEM ECHC GALA ΜΑΤΙ ZEAM HELA GLYM 1/3 270 30 100 80 100 100 20 100 80 0 90 0 100 60 80 100 0 100 30 0 30 0 100 0 40 90 0 40 30 0 10 0 100 0 30 30 0 0 0 0 1/5 270 100 100 100 80 100 100 100 100 100 1/6 270 90 100 100 35 70 100 100 80 100 90 so; 100 100 30 50 90 100 50 90 1/7 270 10 100 100 60 100 10 100 70 0 90 10 100 100 50 100 10 100 60 0 30 0 100 20 25 90 0 40 0 0 10 0 100 0 0 30 0 40 0 0 1/8 270 20 100 100 70 100 100 100 90 0 90 20 100 90 50 100 20 100 60 0 30 0 100 30 40 90 10 100 40 0 10 0 100 0 30 90 0 70 10 0 Abbreviations in Table II: ORYS Oryza sativ a STEM Stellaria media ECHC Echinochloa e.g. GALA Galium aparine ΜΑΤΙ Matricana inodor ZEAM Zea mays HELA Helianthus annuus GLYM Glycine max TRIE Triticum aesticum IE 91321 - 25 Example 26 Greenhouse test of the preemergent effect The seeds of the test plants were sowed in 3 repetitions into a medium-impermeable forest soil placed in a bottom-perforated paper 2 box of 7 cm in height with a footing area of 200 cm . The boxes of the separate treatments were placed on plastic trays equipped with a wetting cloth. After sowing, before the emergence of the plants, the 10 WP composition prepared from compound No. 7 of Table I according to Example 6 was applied with a water amount corresponding to 1200 litres per hectare onto the soil surface in the boxes by using a greenhouse microsprayer. The supplementation with water was ensured by maintaining the wetting cloth in a wet state. The experiment was carried out at a temperature of 20 to 28 °C under natural illumination supplemented with an illumination of 4 hours. The herbicidal effect of the compound No. 7 of Table I was evaluated in the 4th and 6th weeks after spraying. The results are summarized in Table III.

Table III Preemergent effect Compound No. Dose Perishment of test plants (%) (in Table I) g/ha Solanuni Digitaria ECHC STEM TRIE migrum adans 1/7 250 70 50 20 100 0 1000 100 60 40 100 0 Example 27 Investigation of the effect on cultivated plants in the plant-cultivating chamber 400 g of field top soil each (with a pH value of 6.5, permeability of 50 and humus content of 1.4 %) were weighed in plastic cultivating bottles of 0.8 dm^ surface each lined with PVC foil. Onto this soil 10 seeds of Pi-3737 maize each, 100 seeds of streaked sunflower IREG, each. 50 seeds of SA-114 sorghum each and 1 g of red millet each were sowed.

After covering the seeds with 100 g of soil each, the treatments were carried out. In the course of these treatments 10, 20, 40, 80, 160 IE 91321 - 26 or 320, respectively g per hectare doses of water-dispersible granules (75 WDG) prepared according to Example 13 from the compounds Nos. 2, 4, , 6 and 8, respectively, as well as of Ally, Tell, Granstar, Glean, Logran and SL-950, respectively, control compositions were applied in four repetitions. The treated soil surface was again covered with additional 100 g of soil in each bottle.

The bottles were placed in plant-cultivating chambers, sprinkled daily up to their water capacity and cultivated under HGMF/D 400 sunshine subsisting lamps with a daily illumunaion period of 16 hours. The ex10 periment was evaluated on the 10th day after sowing when the green weight of sunflower, sorghum and millet as well as the green weight and shoot length of maize were determined. The results obtained are summarized in Table IV with the designation Sowing I.

The seeds of maize, sunflower and millet were repeatedly sowed 6 times into the soil of the experiment evaluated. The results of evaluation of these latter experiments are summarized in Tables V to IX with the designations Sowing II, III, IV, V, VI.

From sowing I up to the evaluation of sowing VI 76 days elapsed.

IE 91321 - 27 Ο CM m Ο M3 Ο Ο 00 Ο M3 M3 M3 co m Γ~ Γ-Ι M3 ιη m M3 Ο ιη Ό CO CO CM M3 M3 Γin M3 m ο m r~m co in m O o co M3 in σ\ q-i O -H o q-i ¢-1 TZ) □ co l±J i—1 CL o HP Pl s -H 0 P o 03 0 3 O n l-p 03 qp +J c 03 D 03 tn Pl +» 03 c r~ 0 -P 03 Ό C +> > co l·—1 4-1 03 o 03 N rP Ή 03 _Q CO 03 co E CO H— -H Γ- c A 03 Γ- 0 Α Pl 1 03 •Ip CL CL ω co CD 0 -P 03 Γ* > DD •P •P 0) 03 3 tn C -p 03 c 03 03 P E DD -P CO 03 03 r~ P -P -P cp 03 O JZ -P -P c E CL O iP > CD Pl O r-i «Η □ ω P-l O o co co -=J□D DD •r-H C P LD CD CM co oo r—i m m co co m Γ— o CM VO Γ- r-H Γ- iP CM Γ- Cv i—I Cv A Γ- rP CM CV I rP CM CO VO VO A A CO CO CM ι-Ρ Γ- CO CO CO rP CV Γ- rP A Γ- CO rcv ro cm co r~ r-t ΓΟΟ σ\ Cv o VO cv cm CM VO ι-H CO LA A CM CO LA LA rP CO rCD VO vO rP CO CM CM o vo A Cv CM CM Γ- <3* Ο Γ— co cm CO Cv VO vo r- ra ko vo O LA VO vO ΓCM CD <—I rP Cv VO rP r—I I—I rP o r-i VO O Γ— Cv A rP Γ- Cv CO A Cv CM CO co CD ΓΙΑ CO CO VO A CM rP CO VO ΓΑ vo vo Γ- rP CM O CO iP CO CD VO Q CO cv vO CO co CD P C E -P CO P P co 0 C CO o A -P ID CO .. CO r—i Pi Cv c rP vo CM A 03 rp 03 1 co rP rP 0D O —J P < HP HP HP HH HP LD H— —I CD CD I IE 91321 - 28, CD CXI l—l Γ~ <4- UK 1 CO KO CM KO Γ- 10 CJK O CO QJ CD ro c qj ω ω α. cn ro c QJ > cn +-> c QJ ro ω f-l QJ C0 KO [— O LTK CM CO 0 QJ O c cn «0 o o co co CM KO 0 UK LCK I—1 rH r·* ok Γ CO Γ** OS KO C3 rH Γ-* KO CO KO rH O rH cm r*· co la Ο O A ' CO A rH M3 0\ ro Continuation of Table IV <0 □ 0 QJ <4—I 0 CD c o Q.

CD f-l O cn □ c ro o c o Ό QJ ra CD c CD CD CD •0 QJ c QJ QJ CD C QJ E CL O (0 CD > CD a CD C0 ro •0 Ό OJ □J c QJ > •0 ro ¢0 o QJ cn o □ C0 CM l»K C0 KO o CO C0 A <7 M3 rH rH CM KO CO CM CM r-H KO r**· cm r*·* KO A CM M3 CO M3 rH Γ- CM CM CM M3 A A rH r-l A OK rH CM rH r-I o co CO rH \0 A M3 A i—4 rH lA CM A rH O OK A a oo A r-l CM rH A M3 OK M3 A K0 r-H A CO CO CO Οκ ι—I M3 M3 K0 CO M3 CK Α Γ*- r-l £2 A A CO M3 ,—Ι Α r* οκ a α Γ-* r- M3 Ο Γ- ^K M3 I <ί r- r—’ CO KO O M3 co A CM CO A IE 91321 - 29 Table V Results of sowing II ω •H C ω E +-> cd ω n I— AJ γre lA ο lA CJ LA ΓCM co la I-1 1-1 CJ o LA γCJ co co ια vO re co cv CJ CO co vo re r-H cj A CO A ι—I OK rH CD O A A CD C\ CO CN Γ— κΟ A Ο I O i—t CN CN CN A OK CD O CO ΓΙΑ CN 1—1 O CA re vo o vO o rCJ O\ CO ND A r— CN ΓΙΑ co VO LA CJ co re CTV VO LA vo LA VO r-H ΓCJ co CO CO rro re CN o cn o rA CN CN A O ND KO A r-l co r- <+ co i—ι CD Ok Γ— o o CD A OK c o CD LA Γ-t OK m ι cd _i _i cn Granstar lo7 13o 137 80 116 139 61 IE 91321 - 30o CM re re co CA O vO CA CM CA vo re cm Green weight of sunflower Green weight of sorghum o vo σ co co CD > rH -P ω co p o ω cn o a o CM re co vo o co Γ— VO Cv r-ι r- cm CM LA CA vo re cm Γ— CM LA CO CO CO lA Γ— O CA ΓCM co LA vo CO ip rOv vo O ov re P CO LA LA OV ΓCA o LA Γ— re co cm p la co CM O cm rco co vo CM P ip VO CM CM Γ— co CO LA re ca vo CM lA CO CO ι—I VO co re co vo ov CO O CO I Γ- ov CO P- vo Ov ip r- la CO vo LA LA vo ip LA re για rla re vo re rre la ca r- vo ov P OV ι—I OV CO OV vo ro co 00 CM P Γ*- CO lA vo LA Ov vo la r- go ov CA CO LA -p c CD E p co ω p P ro c c co o lA P tn >x CO ip P CA c P CO vo CM LA ω ip cn t co P ip tu o _J P < P P P P P CO P _j CO co IE 91321 - 31 Treatments Green weight of maize Green weight of sunflower Green weight of sorghum o CM A o KO o co CO CM CO co o CM A ω > o •H O CO CO cw CM O ω co o O rH co O CM A CO KO O CO o <± CD CM KO r-H Α Γ- CM rH rCM KO rH Ok A A KO CM Os KO A KO Γ-* SO Γ- KO CO Os r— co ko AAA CO CO O A CM rrOs O CM CD Ok Os Os OK rH OK KO SO KO Γo rH A A KO a ko r* A KO co a rr- co ko r< rOs rH so co a CO r- o r- cm OK r-ι KO CM a ko r* ok a r- o i-H Γ— KO rH so co Γ- KO A CO rH A OK σ Α A rH KO CM CO κθ CO rH SO Os MO Ok so A CO rH O CO KO CM ko CM OK CM A CO OK CO CO O OK OK KO A Γ- OK ko rr- cm Α ΓOK O A OK A CM CO A r-H OK KO A σ rco KO Os CM rH rH KO A rKO rH A r<± A rKO OK r^ co CO co co co co co CM O Α ΓΟΟ A CM CM A Os rH CO rH A CO rH CM CM A A OK CO CO Os CO rH SO CO Γ- SO rH A CO CM Γ- A CO KO rH SO CO Γ— Γ- A A OK Os Os Γ- A Γ- Os CO Γ- Os OK Γ- KO CO A A A A CM rH CO OK A r-H rH *-H ΟΟ CO CO ΟΟ KO A KO a Γ- A CM SO CO co KO CO CO Γ— co OK rH Os rH rH ι—I CM Γ— A A CM o CTS A Γ—- Γ— co Os CO CK a Os CO Γ- OS r—1 CK o rH r-H rH rH rH CD A Γ- A A Γ- Α CO CO CD rH Os CO o rH CK Os Γ- O r-H CO CO rH rH r—l rH rH C-j Cd c C ra co A 4-» ω >> ra rH Ci Os c rH co KO CM A ω rH CJ) 1 ra r-H *—\ r-H ω o —J Ci c I—I 1—! Η-1 1—1 1—1 CD 1— _J OD CD i:; Green weight of maize Green weight of sunflower Green weight of sorghum σ CM A co VO o co co CM \ o CD CM A -P c •P TO ω ρ cn c •P > •P -P L3 CD tp O cn <0 a o CM co o CM A CO VO CO CO σ CM CM co co co CV CM CM A »P CM VO rp CV fA CO CM CO vO a cv A CM CV (P rn r—> vO Ον Γ— O O, VO CM CO A «Ρ vo co i—I CM CO rP CO OV ^0 Cv rPCOC3 CV A vo cv CMVOOOCOVOr— OVA CvCOOvr-Or-OVOOv A ov co a AOvCO A Γco co ovaco COr-'ACOCMOCvr-CV ΓΑ ΓΑ <± Ov A VO A A ΓO < A VO Γ— VO VO vo vo CM VO Γ— cv A cv o cv A A co A vo CM ΓΑ co A co co VO A co o Γ— co vo A CM o CO o CO CM A A A A A Γ- A CM Γ- rp A VO Γ— A <3· Α A CO rp A Γ— r-H vo VO O rP a A co Γ- A A vO vo A A CM VO CM A Γ- VO A CO Γ—· VO A A Γ- Γ- CV A VO VO Γ— Γ— Α vo A M3 A VO V0 Ov Γ- A A A CM A VO νθ VO Γ- cv A Γ— A Γ— 1 Γ— 1 »P Γ- rP ov Γ— CM CV Α rP Γ— rp o Γ— iP A a rp o A vO CM Γ- A o GO rp A Γ— Γ- 1 ΟΟ A A VO A Γ- Α CM CO CV o rP rp A fp A CV A Γ- Γ- Γ— Γ— A CV cv CM ip rp rP rp CM Γ— A CV CM CV CD O Γ- CO OV OV OV CO rp rP Γ— CM o A CO A Ov CO Ov Ov vo vo vo A Ov Γ— ω -p c E -P co P co <± vo CM A HP HP HP IP IP P co c a -P C co A cn CO ι—1 P cv c 03 rP CD 1 co rp 03 o _J P co 1— co CD Green weight of maize Green weight of sunflower Green weight of sorghum Treatments Dose of the active ingredient (g/ha) o CVI re o VO O CO o o OJ re o vo o co o o OJ re o vo o CO o o A CO re co OJ CO OJ o re a vo re r- re oi ι—i re oi LA o o CA re LA vo o re re LA o OJ O vo CA re o ip ip rp ip Ip ip <± co VO o iP OJ ip σ co (P OJ fp re co ip VO CO LA CO P VO co LA Ov Ov OJ Ov CA re <± OJ Γ- VO Γ— CO o Γ— O p o p o CO co ip rP iP iP ip rp r- <± vo CO re ov CA LA vo ov co re 04 ov CO 04 CO LA Γ— CO r* co ip ip P rp P VO co CA Γ- P P re CO r- LA iP vo re ΟΟ re co LA ip iP rP ip ip |p re vo re r* P Γ- iP vo ip co Γ- ΙΑ «-I A ip <± co <· r-4 ip Γ- iP o P vo VO LA CM <± Γ— o A CD <± r- iP Γ- σ CO A CO r- O CVJ rp ip ip iP ov o A LA re iP P ov CO vo o ip CO ip co A CA r— CM ov iP fp rp ip vo o o VO rp A Γ- CO re CO co LA Ov re co ip ip VO Ov co Γ- co ip ip rP iP Ov ip iP CO CO o ip Γ- CO re ov σ o Ov CO r— CA Γ- rp iP ip ov VO Γ— vo ov Γ— a ip re Cvj A Γ- CO OV vo ov o co Γ- r- vo rp ip ip ip rP vo A Ip CA CVJ re Γ- re CO CO OV CM CA Ov ov ΟΟ a vo Γ- ΟΟ A CO Γ- A CA OV Γ- ΟΟ A CVI A CD rP CM CD P Γ- ip ip A A ip Γ- VO Ip re cm Γ- Γ— co VO σ Γ— A OV A CO A A ip A σ CD P ι—1 iP vo re P iP r- Γ— A co Cvj CO CO Γ- ov ov σ A o r- co O A A ι—1 ip fp Γ- a Γ— CO VO A A a 00 A CD οο CA o o CO A co a o A iP iP r·—1 ip fp ip vo CA vo A A A A CM Γ— A Γ— co CA CA A Η co A A CO A r—1 r—l Pj CO C o P c CO A tn >» CO C-t A c ip CO VO CVJ A ω ip cn 1 co fp \ — rp ω o _J ¢-1 P P P P P CD P _j cn co Green weight of maize Green weight of sunflower Green weight of sorghum Treatments Dose of the active ingredient (g/ha) o CM A CD VO o co o CM CO co . CM ; A , O VO O ! co : o . CM : A ' O VO o co CO co CM CO A A A CV vo co A Ov co Γ- CM O P CM A A Ov CM A 00 σ ip co CM A co VO OV vO CO vo r- o co P A O ov CO A co fp P rP iP fp CM o CV A Γ- VO CM A /P CD co co CV CO P ΟΟ Ov CM O Γ- CO i—i i-1 P fp cv P CM A co VO A A ov Α A p Ο P VO CM P CM O A OV O »P P P fp fp P P P rP A A o VO Γ— CM ov A Os -X CM CM o iP CD CM rP CM CV iP CD Os rP iP rp rP fp fp P rp ip A A cv CO P A o VO CM CM CV CO A o σ CO A CD CO Os P P P P P P ι—1 P P CM fp VO Cv CD OV CM rP A Γ- VO Γ- Ov VO CO CO co CO A Cs ov cv fp ΟΟ A CM vo A O VO A co Γ- Γ- CO CO OV vo Ov A Γ- O P r- Γ— CM OV vo a CM CD A ΟΟ r— CV A o cv Γ- Os A • Os co iP ip ip co CM A <3* vo Α CM A A CM r- co CO CM CM P VO Cv Γ— CO CD rp rp ip P P fp rp Cv vo CV A CO CM CO Γ- CM A Γ- Γ— co CD A co CO Os Α OS OS ΟΟ P rp rP CO ip CO co Γ- fp CM a CM vo co co OV ΟΟ CO ip A A Os rp fp P o A P A A Ov cv CM CV Γ- A co co Ov CO CM CM CM o o Ov rP P ip rp vo fp CO A rP VO CO CM A Γ— VO co co A CV CO CM CM fp Ov r-H iP ip A VO rp Γ— Cv ip vO VO co CO VO CO Γ— o Ov co cv Cv CM σ ov ov fp rP iP Γ- CM vo σ co A VO A vo A ΟΟ Ov cv o a a CO Ov OS o Os ip »P rp rp A CO ip CM A A a Ov VO A rp fp OV Os CO O rp o CO OV a o ip P P ip rp rp rp co o fp rp o a CV o r- Γ— A o o σ o a o OV o Ov CV Os fp rP P P P iP fp P ra c o 4-> c ro A ω >> ra rp P Os c rp co vo CM A ω ip CD 1 ra rp \ \ \ rp ω · O p <£ P P P P P CO ρ· cn C_D - 35 Example 28 Test of the herbicidal activity in a field experiment carried out in a winter-wheat culture A postemergent weed control experiment was performed on Winter2 wheat in parcels of 10 m each near to the river Sebes-Koros.

The test was carried out on a meadow-clay soil-type having pH value of 6.3 containing 3.4 % of organic material. Winter-wheat was used as green crop. The seeds were sowed on 24th Octobrr in a well-processes dry seed-bed to a depth of 6 to 7 cm with a row distance formed by direct sowing.

The test was performed postemergently on 20th April. The weed species and their development stage at the time of treatment were: burweed (Galium aparine, abbreviated GALAP) in 4 to 6-leaf-whorl stage; red blind15 nettle (Lamium purpureum, LAMPU) in flowering stage; meadow-veronica (Veronica arvensis, VERAR) in budding period at the beginning of flowering; medicinal earth-gall (Fumaria officinalis, FUMOF) in the 6-leaf stage; chickweed (Stellaria media, STEME) in the flowering state; eastern larkspur (Consolida orientalis, CONOR) of 10 cm in height, in the stem-forming period; white goosefoot (Chenopodium album, CHEAL) in 2 to 6-leaf stage; fallow bindweed (Bilderdyckia convolvulus, BILCO) in a 2 to 3-leaf stage.

On establishing the experiment a parcel-spraying machine was used with propane-butane gas pressure. Doses of 10 to 30 g of active ingredient per hectare of the compounds Nos. 4, 5, 6 and 8, respectively, of Table I were applied in 500 litres per hectare of spray liquid in the form of FW suspension concentrates formulated according to Example 11. The same doses of Logran 75 DF and Granstar 75 DF, respectively, were used for comparison.

The herbicidal and phytotoxic effects of the treatments carried out within these examinations were evaluated by using a score (scale) from 0 (inactive) up to 100 (total perishment). These evaluations were performed 4 times (on 27th April, 4th May, 25th May and 18th June) in the vegetative period following the treatment by measuring the number of spikes (piece/ m ), spike-length (cm) and the weight of 1000 grains (g).

The results, which are the average values of 4 repetitions, are summarized in Tables X to XVI.

" JO co PhytotoxiCi, o\® ca LU X CJ a: a z a CJ LU X UJ H CZ) ce -+-> < cjqc CD LU q-i> q-i CD co co D CL.

-Q t-i =5 < CL <£ CO c o q-l -r-l - Ο -H CO CD O ΕΞ ι—I •r-l CO I— > CD CD CO tn a a σ. +-> c CD ca ω f-l a co a a r—l UK ——I cn tn ok --1 O UK O —-1 uk co ok co o co co CO KO CN f-l --1 KO σκ Ok a tt ok OK CO Γ' Ok r-l NO r-l tn UK -Να CJ co o m KO CO Ok CN m co co co in co co tn vo ok co m co ok co in in cn co tn Ko ok co Ok tn OK CO cn in ok co co CN tn in ok co m in Ok co co co m in co in ok ι S' 1 tn OK ——I OK ο in Γ' co m m CO r—l in Ok γ-i rn ok Ok KO Ok CN Ok tn Ok Ok CO Ok m Ok CN Ok Ok tn CO CO m CN I—I o •cj o CO co KO tn co κΟ r-l CO CO cn tn ok co in ko i—t -e ok co co m m ok 100 100 100 tn co ko in in Ok Ok t-l t-l > J—t »—I I—I I—I co co IE 91321 x_____ £ A* O o > cd o cd cd CM US CD CD CD 0 CM US cd us rs rs rs rs Q_ μ co c LxJ X o A CM O os σκ \o a o A CO OK \a σ\ MJ 0 Os so 0 CM CO Os QC σ CD CD CD CD Os rs Os CD 0 Ό OS CD CO O OS CD 0 so Os CD .MJ CD CD CD CO 00 OS CD CM US OS CD SO Os O -st OS CD US MJ CO US UJ X Ld tn ΓCD US I CM OS CD 0 OS I 0 Os CD US Ο I CM. CD Table XI A’u. 0° ο ξ ,ω0 ω os ι—I o •rH JD 0 O CDS' Α CO CD A A -e ο so rs co so US Γ~· CM KO CM A Γ- P* Os 0 co 0 0 co OS SO co CM 0 OS CD CD M3 CM CO OK rs os mj rs co os CD CD us rs os o CD US CO OS CD CD A OK KO CM Γ- CO so ao cm 0 ao Os OS so rs os CD CD rs rCM OS CD CD CL. < _J ' < CD c O O 0 ro ro E D •rH r-H i— ra > CD CM PM3 KO os co 0 co 0 CD US CM CD CM US Os Os rs Os I CD CM I-H PH I-H PH ω ra ω iz o \ α σι -p c ω E -P ra CD ρ ίW HH PH CD CM CD CD IE CO -=L Lui CJ DC o Lui tn os tn in o r—t tn m m m so so ΙΛ <ί ΙΛ ΓΓη CO r-i in CM CM o m so CM -st so in CM CO so Γ- 00 in cm r- co so CO r- co CO I r-i in CM CM r-i in tn in <3· m tn rKO Ov Γ* co σν σ OV ο α σν ον σν Table XII ω ζ 4-1 Qj ro < Ό Ql Lui ω > •rH _Q P -s c Σ CL < _J < O c • a 4—1 -H □ ro Qj 0 ή ro (— > ω qj ro tn zz o \ □ □) +> c Qj E -H ro QJ N co in co m CM CM co co m r-t cm cm m ο ο CM Ρ κο A CO P o SO \o ο a ο ο ο ο σ ο A A Ον Ο co o CM σ οο ο ο Α Ο Ο Ρ CM CM vo ο ρ ο σ CM Ο A ΓCM CM O P CO CO CM Ρ P A A CO CO CM CM CM «3· OV CM O A CM O A CM <± [—>. CM P o CM o co vo vo CM A O A A CM IE 91321 .-39x»\· o 4-» O XI Q_ < QJ X CO QC o z o o QJ X OYW I— in u tu. +-1 r, +u tn 03 so -=3- m -=3<3 rH <3 CO rl CM SO Γ— <3 CO <3 CO rH m OS co co in cn so cm m co os o co co co CO CO OS I CM CM C3 rH l/S OS m <3- m Os <3 O V) ri m r— co os m os rH m OS r-H m OS CM CM Os co co 100 co o co co in os r-H CM Os <3 O so m -=3 -=3 X ID P XI ro CD •rH oor •rH< -°s ω> Q_ X < X <1 CL < < CO c □ •rH =Η Ή o ro 03 ι—I E ro •rH > I— 03 ro tn x o \ □ 03 +-> E +-> ro QJ (-1 co α ο o o in co σ o m co os rH o in CD rH CM CM CM O CO CD O CD CD OS CD rH CM M l-H l-H > o cd co cd o in co co in co o m cm m l-H HH l-H > l-H l-H l-H co CM CD US Os ·—I ‘-1 rH CM CM o m x co CD Os <3- corn cm m rH in m co ri cm m m co in m os r-H CM rH m m i· cm cm m l-H l-H l-H > l-H l-H l-H o -=3 CD co IE 91321 o δ;' oi H ' co < UJ X CJ X CD □ CJ UJ X UJ cn CD CD CD CD CD CD CD a CJ M3 M3 CM M3 CD CD CD a CD CD CD CJ CO 0 0 M3 as as 0 ao 0 cd 0 <4- 0 CD CD CD CD CD 0 0 CD CM M3 CM O CD CD CD CD CD cd ra CM I co 1—I o o CM CD CD CD CD 0 ra ι CM 0 CD CD CD CM 0 CD 0 CD CD CO Os I 0 . CM 0 > X ω JD ro =\=u. -h g; o ω cz 0. ω x < ro x TD UJ 0 > CJ •rH JD f-l ω -ΰ -Οχ < <£ X < —I < CD C o 0 o 0 ' ro QJ D £Ξ <"H 0 CO 0 > QJ QJ ra CO JZ o \ q ro c QJ ro QJ f-l CD CD CD CD rs 0 us cm rs 0 0 CD CD CD CM 0 CD CO CO CM O 0 0 CO OS X a c ro f-l ro o SO 0 0 crs cd 0 <4· CD CM CD c ro f-l CT O MJ < 0 CD ra 0 CD SO 0 0 0 ra cd r-I SO 0 0 0«—I CM 0 CO SO SO 0 CD 0 0 0 CD O 0 CD 0 0 Os CD 0 CD οο 0 σ CM <4 0 CD CD <4 X a c ro f-l ro o O 0 0 CD 0 <4 0 O CD CO c ra f-l ro o n-t o •r-4 x ο α a co o o\° co co co co UK UK co co r*^ P Table XVI Results of examinations of the spikes Treatment Dose Number of g/ha spikes/m2 Spike-length .Number of Weight of · in cm grains/spike 1000 grains(g) Untreated 1/8 1/4 1/6 1/5 Logran 75 WG Logran 75 WG Logran 75 WG Logran 75 WG Granstar 75 OF Granstar 75 OF Granstar 75 OF Granstar 75 OF - 509 10 607 20 590 40 620 80 604 10 620 20 609 40 619 80 630 10 424 20 432 40 301 80 266 10 399 20 ' 250 40 248 80 261 10 614 20 645 40 630 80 641 10 600 20 590 40 639 80 629 7,0 7.7 7,9 8,2 7.8 7.8 7.9 7,0 7,0 7,5 .8 5,4 5,4 .9 5,2 2,8 .4 7.8 7.9 8.5 7,9 7,8 0,4 0,0 7,0 19,4 21.3 19,0 22,0 20,9 21,6 20,6 21.4 22,0 14,0 13.4 7,2 6,0 .4 10,0 7,0 6,1 ,6 21.4 21.4 22,0 20,8 .4 21,1 21,0 39,4 40.3 41.4 40.9 40,0 40,0 41,2 42,0 40.6 42.1 42,0 44.1 44.2 43.7 44,4 43.9 44,0 42.3 40,0 42.4 41.3 40,0 40.4 39,0 41,3 - 43 From the results illustrated in TablesX to XVI it can clearly be seen that a difference appeared between the effectivity of the compositions according to the invention and that of the commercially available compositions used for comparison. Compositions containing compounds Nos. 4 and 8 of Table I proved to be highly effective by late postemergent treatments on developed weeds in extremely strong infections. The selectivity against cultivated plants of both compounds is also favourable. Due to their high phytotoxicity as well as weak, eventually unuseful weed control action, herbicide compositions containing the compounds Nos. 5 and 6 of Table I are not suitable for weed control in a winter-wheat culture.

Example 29 Investigation of the effect of antidoted compositions on cultivated plants in a plant-cultivating chamber g of field top soil each (with a pH value of 6.5, permeability of 50 and humus content of 1.4 %) were weighed in plastic cultivating bottles of 0.8 dm surface each lined with PVC foil. Onto this soil 10 seeds of Pi-3737 maize each and 10 seeds of streaked sunflower IREG each were sowed. The seeds were covered by 100 g of soil, then the treatments were carried out in 4 repetitions. In the course of these treatments 20 to 160 g per hectare doses of active ingredients Nos. 2, 4, 5, 6 or 8, respectively of Table I together with 250 to 500 g per hectare of the antidotes DKA-24, AD-67, R-25788, MG-191 or CGA-92194, respectively were applied in the form of compositions formulated according to Examples 15 to 21. The treated soil surface was covered with additional 100 g of soil in each bottle.

The bottles were placed in a plant-cultivating chamber and cultivated with a daily illumination period of 16 hours. The plants were daily sprinkled up to their water capacity.

The experiment was evaluated by determining (measuring) the shoot-length and green weight on the 13th day following the treatment.

The results are summarized in Tables XVII to XIX.

IE 91321 44. Table XVII Ί* ϋ o m o c«in o vo in CCJ ο ο ιη Ο ιη CVJ CO H t- vo σκ cS Η σ» 'kJ· co c— ok vo m ο in cvj co co c— ο rH in vo tc— in tιη c— cvj σκ cm σκ in co c— σκ c~- vo co ru ω q-ι P CD Ό c CD N CO I— m I· m ι •pH □_ q-i o co •P CD S c ω CD p co CD +3 CD -P C CD E Q.

O ip CD > CD CD cn -p c CD E +-> CO CD P Ή CD CD CD P -P c CD CJ ID CD -P CO CD P -P c: CD CD (Di CO I -P c CD CJ P CD Q. cn co CD N •P co tp CD •P I •P CD c CD CD P o LI> «=)- VO o 1 o CsJ OK <· o co in H rH co tr- ιη vd CVJ o . υ tr- VO 1 in 0 OK m OK I# cvj H O C— CV1 ct— vo I Q <4 ό OK H CO o in cvi o O cj in I -aj O in CJ CD > -P CJ -P CO CD CD . co q-ι -p CD Ό CO CD -3 CD PX cn CD) CO CD C a -p in -p c CD E P co CD P I— vo OK vo OK o in M· o rH co cCJ co c— OK in o i—i OK O co o «4· r~t OK CVJ ok m co OK in o <· r~I o m in H ι—I tCVl CVJ r~) i—I o o CVJ vo rH in vo dv co m c— ι—I VO CJ VO o CVJ o co Η OK VO in o <· IE 91321 to o <· o cstn (\l cs CJ mJ- OS SO SO 00- 0- SO CO US Η H C- CS 0- CO SO CO US co · so c0Table XVIII Development of the shoot-length of Pi-3737 maize under effect tn p c qj ro ω f-l qj -P q-i o to o Η O OS US i—I r-H O P CJ to 13 o -P us c Cl o ω Ό to ω o +-3 co o ra ω p CO US 0- -P US c Cl □ 1 to o A O US CJ QJ ro ro •P c to ω o o o to ra A to H o CD N us CJ rH ra ro c QJ to o o US CJ I -P O o to o IfS CJ en o ro -p c QJ OTD.ro QJ J= QJ NX cn ro ct o c Q -H I -I—3 ra ω -p c ω co SO us cs US •=4· 0- 0- rs co Mf 0tr CD CS us 00 rs us t- SO CJ SO us t- 0- o 0- US o 0- cs cs rs CS SO CO CO ω cs 04 cs co co CJ cs US CO M CJ co H 0- CJ o cs co Mi- cs SO co H· . rs OS rs rs so cs co OJ CO US 0- co rs H cj rs co CO rs cs us 0- ι—i so 0co 0- mi- cs Mt CO CJ CS H CO SO SO H CS Mio o o o mJ* mJ- OJ SO ι—I co <· o OJ M3 CM A m}er-J e'o Mh ό Mt Table XIX Development of the green weight of streaked sunflower IREG under effect of the treatments ' <4OV P . CM Os Ί < o o in P • 03 o P 03 P o c ITS o CM ω Ό CD P ra ω p rH o o P OS US c H □ 1 o P o A in S CM CD CD ra P c co o CD co o o b- in P US Q) □_ CM 1 o CO in ra CM P ω 3 O o fp p c— o c in D SO cn P o 1 o <3 in CM p □3 •H 0 3 1 o: <- o 0 CM in 0 I 0 U 03 -J P o A in 0 CM > •P -H O +-> ro 0 0 4-1 •P o TD ω ro 0 P c ro CD · o C □3 □ •P P C 0) E P ra cd ρ h- 00 C— m m <· CM in c~* b- co SO M* rH m lH «Μ- rH O in os SO co SO *3· CM in in OS o rt- b- o r4 in os CO in in SO ri so OS in so a rH SO o. rH SO in cn cn b- IT- O os so co co . OS b- in m co in in co rH b- co in co τ- so CM co r- os ο <- b- co so co b- in i—1 <· o o b- b- b- CD so o rH SO in rt o ι—1 OS OS CM CD o rH in CO SO in A4 OS co in OS rH CD b- <· Τ'- in SO CO OS co cm co rH SO rH 1—[ so co τ- Τ- O o o o ο Ο xf- - CM SO rH CM Ή· co M3 CM us R ro \ \ Η-1 l—l 1—1 I—) h-1 tsD o A - 47 Example 30 Test of the effect of antidoted compositions on cultivated plants in a plant-cultivating chamber. 400 g of field top soil each (with a pH value of 6.5, permeability of 50 and humus content of 1.4 %) were weighed in plastic cultivating bottles of 0.8 dm^ surface each lined with PVC foil. Onto this soil 10 seeds of Pi-3747 maize each and 50 seeds of SA-114 sorghum each were sowed. The seeds were covered by 100 g of soil, then the treatments were carried out in 4 repetitions. In the course of these treatments 20, 40 or 80, respectively g per hectare dose of the compounds Nos. 2, 4, 5, 6 or 8, respectively, of Table I together with 400 g per hectare of DKA-24 antidote were applied in the form of compositions formulated according to Examples 22 to 24. The same doses of Glean, Granstar, Ally or Tell, respectively were applied together with DKA-24 antidote for comparison.

The sprayed soil surface was again covered with additional 100 g of soil in each bottle.

The bottles were placed in a plant-cultivating chamber and cultivated with a daily illumination period of 16 hours. The plants were daily sprinkled up to their water capacity.

The experiment was evaluated by determining (measuring) the shootlength and green weight on the 12th day following the treatment. The results obtained are summarized in Table XX. - 48 Shoot-length of maize (cm) Green weight of maize (g) Green weight of sorghum (g)

Claims (11)

1. A subsituted sulfonylurea derivative of the general formula (I) wherein stands for hydrogen, halogen, C^alkoxy, halo-C^alkoxy, 15 C^ ^alkylsulfonyl or a group of the formula COR^; R 2 means hydrogen, C^alkyl or phenyl; R^ represents C^_^alkyl, Cj^alkenyl, C^_-jalkoxyalkyl group, C 2 alkyl subsutituted by one or more halogen(s) or benzyl group, R^ and R^ mean independently of each other a C^alkyl, C-^alkoxy 20 group, halogen, C^alkylamino or dKC^alkyDamino, or C^alkylthio; R 6 stands for a C^alkoxy, C^alkenyloxy, C^alkoxyalkyl, C^alkylamino, di(C^_^alkyl)amino, piperazinyl or morpholinyl group; X means oxygen or sulfur; and 25 E stands for a methine group or nitrogen, as well as its salts. (Claim priority: 31.01.1990.)

2. A herbicide composition containing substituted sulfonylurea 30 derivative, which comprises as active ingredient a substituted sulfonylurea derivative of the general formula (I), wherein - 51 stands for hydrogen, halogen, C^alkoxy, halo-C^alkoxy, C^alkylsulfonyl or a group of the formula COR^; R 2 means hydrogen, C^alkyl or phenyl; R-j represents C^alkyl, C^alkenyl, Cp-jalkoxyalkyl group, 5 C 2 _ z ,alkyl subsutituted by one or more halogen(s) A or benzyl; R^ and R^ mean independently of each other a C^alkyl, C-^alkoxy group, halogen, C^_-jalkylamino or di(Cj_^alkyl)amino or C^alkylthio; Rg stands for a C^_^alkoxy, C^alkenyloxy, C^alkoxyalkyl, Cj^alkyl 10 amino, di(C^ ^alkyDamino, piperazinyl or morpholinyl group, X means oxygen or sulfur, and E stands for a methine group or nitrogen, or a salt thereof. (Claim priority: 31. 01. 1990.) 15

3. A composition as claimed in Claim 2 in the form of wettable powder. (Priority: 31. 01. 1990.)

4. A composition as claimed in Claim 2 in the form of granules. 20 (Priority: 31. 01. 1990.)

5. An antidote-containing herbicide composition containing a substituted sulfonylurea derivative as active ingredient and an antidote, which comprises a substituted sulfonylurea 25 derivative of the general formula (I), wherein Rp R 2 , Rp R^, R^, X and E are as : defined, in Claim 1 or its salt as active ingredient and an antidote, preferably DKA-24 (chemically N-dichloroacetyl-Nallylglycine N'-allylamide), AD-67 (chemically N-dichloroacetyl-1oxa-4-azaspiro/4.5/decane), R-25788 (chemically N,N-diallyl-dichloro30 acetamide), MG-191 (chemically 2-dichloromethyl-2-methyl-l,3-dioxolane), CGA-92194 (chemically N-(l,3-dioxolan-2-ylmethoxy)imino-benzeneacetonitrile) or TI-35, respectively, in a total amount of 0.01 to 95 % by weight, preferably 2 to 80 % by weight in an 1:1 to 1:50 weight ratio (of the active ingredient to the antidote). 35 (Priority: 19.12.1990.) IE 91321 - 52

6. A process for the preparation of a substituted sulfonylurea derivative of the general formula (I) o; ' 2 -NH-C-N (I) R 2 - CH—OR 2 wherein stands for hydrogen, halogen, C-^alkoxy, halo-C|_ 4 alkoxy, C|_^alkylsulfonyl or a group of the formula COR^; 15 R 2 means hydrogen, C^alkyl or phenyl; R^ represents C^_^alkyl, C^alkenyl, C-^alkoxyalkyl group, C 2 ^alkyl subsutituted by one or more halogen(s). or benzyl; R^ and R^ mean independently of each other a C^alkyl, C^alkoxy group, halogen, C-^-jalkylamino or di(C 1 _ 3 alkyl)amino, or C^-jalkyl20 thio; Rg stands for a C-^alkoxy, C^alkenyloxy, C^_^alkoxyalkyl, C^_-jalkyl amino, di(C 1 _ 5 alkyl)amino, piperazinyl or morpholinyl group; X means oxygen or sulfur; and E stands for a methine group or nitrogen, as well as its salts, which comprises 25 a) reacting an isocyanate or isothiocianate of the general formula (IV), NCX wherein R^ is as defined above, with an aminopyrimidine or aminotriazine derivative of the general formula III 91321 - 53 (III) ,R HN “^O E N R 2 - CH —OR 3 R' wherein the substituents are as defined above, at a temperature of 0 to 50 °C, preferably at 20 to 30 °C, or b) reacting a sulfonylcarbamate of the general formula (V) (V) \X^S02 - NH - COOR wherein is as defined above and R stands for phenyl group, with an aminopyrimidine or aminotriazine derivative of the general formula (III) at a temperature of 25 to 120 °C, preferably at 60 to 90 °C, or c) reacting a carbamoyl chloride of the general formula (VI) (VI) wherein the substituents are as defined above, with an alkaline 20 metal salt of a sulfonamide derivative of the general formula (II) SO2 — NH2 (II) - 5¼ wherein the substituents are as defined above, at a temperature between -10 °C and 50 °C, preferably at 0 to 25 °C, or d) reacting an N-pyrimidinyl- or N-triazinylcarbamate of the geeral formula (VII) —N Ε N ~ COOR R 5 ^— N -i R 2 -CH- OR 3 (VII) wherein the substituents are as defined above, with a sulfonamide derivative of the general formula (II), wherein the substituents are as defined above, at a temperature between 20 to 80 °C, preferably at 20 to 40 °C, or 15 e) reacting a sulfonyl chloride of the general formula (VIII) . , R 1 Cl (VIII) wherein the substituents are as defined above, with an aminopyrimidine or aminotriazine derivative of the general formula (III), wherein the substituents are as defined above, at a temperature of 20 to 120 °C, 25 preferably at 60 to 90 °C in an inert organic solvent or in a mixture of inert organic solvents, then optionally converting the compound of the general formula (I) thus obtained to its salt with an alkaline metal or alkaline-earth metal hydroxide, amine or quaternary ammonium halide, separating the compound of general formula (I) or its salt 30 obtained by evaporating the solvent(s) and, if necessary, recrystallizing it by a method known per se. (Priority: 31.01.1990.)

7. A substituted sulfonylurea derivative of the general formula (I) given and defined in Claim 1 or a salt thereof, substantially as hereinbefore described and exemplified.

8. A process for the preparation of a substituted sulfonylurea derivative of the general formula (I) given and defined in Claim 1 or a salt thereof, substantially as hereinbefore described and exemplified.

9. A substituted sulfonylurea derivative of the general formula (I) given and defined in Claim 1 or a salt thereof, whenever prepared by a process claimed in a preceding claim.

10. A herbicide composition according to Claim 2, substantially as hereinbefore described and exemplified.

11. An antidote-containing herbicide composition according to Claim 5, substantially as hereinbefore described and exemplified.