Title of Invention	HERBICIDAL COMPOSITION FOR CONTROLLING GRASSES AND WEEDS
Abstract	Selectively herbicidal composition for controlling grasses and weeds in crops of useful plants, comprising a) a herbicidally effective amount of a compound of formula (I), wherein M is an alkali metal or alkaline earth metal; n is 1 or 2; r and s are each independently of the other 0, &half;, 1, 1&half;, 2, 2&half; or 3; and L is ethyl acetate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, Nmethyl-2-pyrrolidone, acetone, butanone, methylene chloride, trichloromethane, trichloroethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, chlorobenzene, toluene or xylene, and b) a herbicide-antagonistically effective amount of a compound of formula (II), wherein R<sub>1</sub> is chlorine, methoxy or methylthio, R<sub>2</sub> is ethyl or isopropyl and R<sub>3</sub> is ethyl, isopropyl, -C(CN)(CH<sub>3</sub>)-CH<sub>3</sub> or tert-butyl.

Title of Invention

HERBICIDAL COMPOSITION FOR CONTROLLING GRASSES AND WEEDS

Abstract

Selectively herbicidal composition for controlling grasses and weeds in crops of useful plants, comprising a) a herbicidally effective amount of a compound of formula (I), wherein M is an alkali metal or alkaline earth metal; n is 1 or 2; r and s are each independently of the other 0, &half;, 1, 1&half;, 2, 2&half; or 3; and L is ethyl acetate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, Nmethyl-2-pyrrolidone, acetone, butanone, methylene chloride, trichloromethane, trichloroethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, chlorobenzene, toluene or xylene, and b) a herbicide-antagonistically effective amount of a compound of formula (II), wherein R1 is chlorine, methoxy or methylthio, R2 is ethyl or isopropyl and R3 is ethyl, isopropyl, -C(CN)(CH3)-CH3 or tert-butyl.

Full Text	Herbicidal composition The present invention relates to novel selectively herbicidal compositions for controlling grasses and weeds in crops of useful plants, especially in crops of cotton, sugar cane and rice that comprise a herbicide and a safener (counter-agent, antidote) and that protect the useful plants but not the weeds against the phytotoxic action of the herbicide, and to the use of such a composition for weed control in crops of useful plants. The use of herbicides can result in considerable damage also being caused to cultivated plants, for example in dependence upon the concentration of the herbicide and the mode of its application, the cultivated plant, the nature of the soil and the climatic conditions, such as period of exposure to light, temperature and amounts of precipitation. In order to counter those and similar problems, various substances have already been proposed as safeners that are capable of antagonising the damaging action of the herbicide on the cultivated plant, that is to say of protecting the cultivated plant from that action, while the herbicidal action on the weeds to be controlled is virtually unimpaired. It has been found that the proposed safeners often have a very specific action both in respect of the cultivated plants and in respect of the herbicide and in some cases also in dependence upon the mode of application. This means that a specific safener is often suitable only for a specific cultivated plant and a particular class of herbicide or a specific herbicide. It has now been found that certain compounds from the class of the triazines, which are known perse for their good herbicidal action, at low rates of application are outstandingly suitable for protecting cultivated plants against the phytotoxic action of a certain class of sulfonylurea herbicides. It is known from US-A-6 180 563 that mixtures of such triazines with sulfonylureas exhibit a synergistic herbicidal action, that is to say the herbicidal action of the sulfonylurea on the weeds is enhanced in a superadditive manner by the addition of the triazine herbicide. It is therefore extremely surprising that such triazines, at herbicidally ineffective rates of application, are suitable as safeners for certain sulfonylurea herbicides. According to the invention, therefore, there is proposed a selectively herbicidal composition which, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of a) a herbicidally effective amount of a herbicide of formula I, wherein M is an alkali metal or alkaline earth metal; n is 1 or 2; r and s are each independently of the other 0, 1/2,1, 11/2, 2, 21/2 or 3; and L is ethyl acetate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, acetone, butanone, methylene chloride, trichloromethane, trichloro- ethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, chlorobenzene, toluene or xylene, and b) a herbicide-antagonistically effective amount of a compound of formula 11 wherein R1 is chlorine, methoxy or methylthio, R2 is ethyl or isopropyl and R3 is ethyl, isopropyl, -C(CN)(CH3)-CH3 or tert-butyl. M as an alkali metal or alkaline earth metal in the context of the present invention is preferably sodium, potassium, magnesium or calcium. The present invention includes all crystal modifications that can be formed by the compounds of formula I. Compounds of formula I that are preferred for the composition according to the invention are those wherein L is dioxane, tetrahydrofuran or water. Also preferred are compounds of formula I wherein n is 1, M being especially sodium. Preference is also given to compounds of formula I wherein M is sodium, n is 1, r is 0 and s is 0. For the method according to the invention special mention should also be made of the amorphous solid form of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0. The amorphous solid form can be used in the preparation of other crystal modifications, such as the C modification. As individual compounds from the scope of formula I that are especially preferred for use in the composition according to the invention there may be mentioned those compounds selected from a) the B modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 1, characterised by the X-ray powder pattern having d[Al/intensitv: 10.0/medium; 9.2/strong; 8.6/very weak; 8.1/weak; 7.2/strong; 6.9/strong; 6.4/medium; 5.82/strong; 5.75/strong; 5.64/very strong; 5.53/very weak; 5.13/medium; 4.97/very strong; 4.65/medium; 4.30/very strong; 4.22/weak; 4.15/very weak; 4.02/weak; 3.94/weak; 3.79/medium; 3.73/weak; 3.68/medium; 3.61/weak; 3.58/weak; 3.52/very strong; 3.42/very weak; 3.37/weak; 3.31/very weak; 3.27/very weak; 3.23/weak; 3.18/medium; 3.08/very weak; 3.03/very weak; 2.95/very weak; 2.87/strong; 2.82/very weak; 2.79/very weak; 2.73/very weak; 2.68/very weak; 2.65/very weak; 2.63/very weak; 2.60/weak; 2.57/weak; b) the J modification of the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is Vz and s is 0, characterised by the X-ray powder pattern having d[A]/intensitv: 15.7/weak; 10.2/very strong; 8.2/weak; 7.8/weak; 7.3/weak; 6.7/weak; 6.5/very weak; 6.2/medium; 5.64/very weak; 5.53/weak; 5.42/weak; 5.09/weak; 4.96/medium; 4.86/very weak; 4.60/medium; 4.37/medium; 4.24/weak; 4.11/very strong; 3.95/very weak; 3.90/weak; 3.81/very weak; 3.71/medium; 3.62/weak; 3.52/very weak; 3.43/strong; 3.37/weak; 3.32/very weak; 3.27/weak; 2.94/very weak; 2.82/medium; c) the K modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0, characterised by the X-ray powder pattern having dfAl/intensity: 13.4/weak; 10.1/very weak; 9.3/very strong; 7.8/weak; 6.9/very weak; 6.7/very weak; 5.63/very weak; 5.35/medium; 4.66/weak; 4.44/very weak; 4.35/weak; 4.12/strong; 3.94/strong; 3.87/very weak; 3.76/weak; 3.61/medium; 3.49/very weak; 3.40/very weak; d) the C modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 1, characterised by the X-ray powder pattern having drAl/intensity: 13.1/medium; 11.0/very strong; 8.8/weak; 7.7/very strong; 7.2/very strong; 7.0/weak; 6.4/weak; 6.2/strong; 5.96/weak; 5.90/weak; 5.64/strong; 5.47/weak; 5.34/medium; 5.19/weak; 4.79/weak; 4.74/medium; 4.64/very weak; 4.55/strong; 4.47/weak; 4.35/strong; 4.26/medium; 4.13/weak; 4.06/very weak; 3.92/very strong; 3.87/weak; 3.79/very strong; 3.67/weak; 3.61/medium; 3.58/strong; 3.47/weak; 3.32/very weak; 3.24/medium; 3.14/weak; 3.12/weak; 3.07/weak; 3.04/strong; 2.97/very weak; 2.92/very weak; 2.88/weak; 2.82/weak; 2.77/very weak; 2.74/very weak; 2.69/weak; 2.66/very weak; and e) the I modification of the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is 1 and s is 1, characterised by the X-ray powder pattern having d[AVintensitv: 11.6/weak; 9.8/very weak; 8.0/very strong; 7.6/medium; 6.7/strong; 6.4/very weak; 6.3/weak; 6.1/very weak; 5.80/medium; 5.66/very weak; 5.47/strong; 5.12/very weak; 5.08/very weak; 4.84/weak; 4.76/weak; 4.47/strong; 4.40/weak; 4.21/medium; 4.19/medium; 4.15/very weak; 4.00/very weak; 3.93/very weak; 3.84/medium; 3,72/very strong; 3.58/medium; 3.52/medium; 3.32/very weak; 3.28/very weak; 3.25/very weak; 3.11/very weak; 3.07/very weak; 2.95/very weak; 2.86/weak; 2.82/very weak; 2.75/very weak; 2.57/weak; 2.49/very weak. Preference is also given to a) the K modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0, prepared by drying the compound of formula I wherein M is sodium, n is 1, L is tetrahydro furan, r is Vz and s is 0 (J modification) at a temperature of from 35°C to GS^'C \n vacuo] b) the C modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 1, prepared by either i) bringing the substantially amorphous form (A modification) into contact with air of 98 % relative humidity, or ii) adding water to the K modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0, in a ratio of water to K modification of from 0.1 : 1 to 0.4 : 1 and separating off and drying the resulting product at a temperature of 30-90°C and a pressure of from 0.01 to 0.1 bar; c) the B modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 1, prepared by adding water to the compound of formula I wherein M is sodium, n is 1 and L, r and s are as defined for formula I, in a ratio of water to that compound of from 0.5 : 1 to 20 : 1, filtering, and drying the filtration residue at a temperature of 30-90°C and a pressure of from 0.01 to 0.1 bar, or preferably prepared by adding water to the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is 1/2 and s is 0 (K modification), or to the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is 1/2 and s is 0 (J modification), or to the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is 1 and s is 1 (I modification), or to the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 1 (C modification), in a ratio of water to K, J, I or C modification of from 0.5 : 1 to 20 : 1, filtering, and drying the filtration residue at a temperature of 30-90°C and a pressure of from 0.01 to 0.1 bar. Compounds of formula II that are especially preferred for the composition according to the invention are atrazine, terbuthylazine, simazine, prometryn, terbutryn, cyanazine and ametryn, very special preference being given to prometryn. Those compounds of formula II can each be combined with the crystal modifications of the compounds of formula I specifically mentioned above as being preferred to give especially advantageous herbicidally selective compositions. According to the invention very special preference is given to those compositions which comprise as compound of formula I either the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0 or the J or K crystal modification of the compound of formula I and, as compound of formula II, prometryn. The compounds of formula I can be prepared in accordance with a general process by reacting a compound of formula II in ethyl acetate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, acetone, butanone, methylene chloride, trichloromethane, trichloro-ethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, chlorobenzene, toluene or xylene, with a compound of formula V wherein M is as defined for formula I. The reaction of the compound of formula lla with the compound of formula III is carried out at temperatures of from -20°C to 180°C, a temperature range of 30 - 80°C being preferred. The compounds of formulae lla and III can be used in equivalent stoichiometric amounts, but a slight excess of isocyanate may be advantageous. The preparation of the starting compound of formula lla is described, for example, in EP-A-0 232 067, page 29. The compounds of formula III can be prepared, for example, by converting a compound of formula IV wherein R1 is -CH2-phenyl or isopropyl, by aqueous chiorination into the compound of formula V That compound is treated with aqueous ammonia and the resulting sulfonamide is then reacted with 30 % sodium methanolate. Such reactions are known and will be familiar to the person skilled in the art. Preferred crystal modifications of the compounds of formula I are prepared as follows: For example, the J modification of the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is 1/2 and s is 0 is prepared by adding a 5-25 % by weight solution of 4,6-dimethoxy-pyrimidine-2-isocyanate in anhydrous tetrahydrofuran at a temperature of 35-65°C to a 15-35 % by weight suspension of 3-(2-trifluoroethoxy)-pyridinyl-sulfonamide sodium salt in anhydrous tetrahydrofuran. After the addition of the 4,6-dimethoxy-pyrimidine-2-isocyanate, the reaction mixture is stirred until the conversion is complete. This process is preferably carried out at a temperature of 40-50°C. The J modification so obtained can be separated from the reaction mixture by filtration. The process for the preparation of the K modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0 is carried out as follows: a 5-25 % by weight solution of 4,6-dimethoxy-pyrimidine-2-isocyanate in anhydrous tetrahydrofuran is added at a temperature of 35-65°C to a 15-35 % by weight suspension of 3-(2-trifluoroethoxy)-pyridinyl-sulfon-amide sodium salt in anhydrous tetrahydrofuran, filtration is carried out and the filtration residue (J modification) is then dried at a temperature of 30-90°C and a pressure of from 0.01 to 0.1 bar. After the addition of the 4,6-dimethoxy-pyrimidine-2-isocyanate, the reaction mixture is stirred until the conversion is complete. For the drying, in this process variant a temperature of 40-60°C and a pressure of from 0.02 to 0.06 bar is preferred. The process for the preparation of the C modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 1 is carried out as follows: either the substantially amorphous form (A modification) is exposed to air of 98 % relative humidity, or water is added to the K modification in a ratio of water to K modification of from 0.1 : 1 to 0.4 : 1, filtration is carried out and the filtration residue is then dried at a temperature of 30-90°C and a pressure of from 0.01 to 0.1 bar. For the preparation of the C modification, the ratio of water to K modification may vary from 0.1 : 1 to 0.4 : 1; a ratio of from 0.1 : 1 to 0.3 : 1 is especially preferred. The addition of water can take place at a temperature of 0-60°C, especially at a temperature of 5-40°C. The drying of the C modification is preferably carried out at a temperature of 40-60°C and a pressure of 0.02-0.06 bar. The C modification can advantageously also be prepared by adding N-[(4,6-dimethoxy-2-pyrimidinyl)carbamoyl]-3-(2,2,2-trifluoroethoxy)-pyridine-2-sulfonamide to an aqueous sodium hydroxide solution, then concentrating by evaporation in vacuo at a temperature of 50°C, stirring the residue so obtained with diethyl ether, filtering, drying at temperatures of >120°C and then exposing the resulting substantially amorphous salt (A modification) to air of 98 % relative humidity. The process for the preparation of the I modification of the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is 1 and s is 1 is carried out as follows: a 5-25 % by weight solution of 4,6-dimethoxy-pyrimidine-2-isocyanate in anhydrous tetrahydrofuran is added at a temperature of from 0 to 30°C to a 10-35 % by weight suspension of 3"(2-tri-fluoroethoxy)-pyridinylsulfonamide sodium salt in anhydrous tetrahydrofuran and then 1-20 molar equivalents of water relative to the 3-(2-trifluoroethoxy)-pyridinylsulfonamide sodium salt are added. In this variant the addition of 2-5 molar equivalents of water is especially preferred. The process for the preparation of the B modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 1 is carried out as follows: water is added to the compound of formula I wherein M is sodium, n is 1 and L, r and s are as defined for formula I in a ratio of water to that compound of from 0.5 :1 to 20 :1, filtration is carried out and the filtration residue is dried at a temperature of 30-90°C and a pressure of from 0.01 to 0.1 bar. A preferred variant of the process for the preparation of the B modification is carried out as follows: water is added to the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0 (K modification), or to the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is 1/2 and s is 0 (J modification), or to the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is 1 and s is 1 (I modification), or to the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 1 (C modification), in a ratio of water to K, J, I or C modification of from 0.5 :1 to 20 :1, filtration is carried out and the filtration residue is then dried at a temperature of 30-90°C and a pressure of from 0.01 to 0.1 bar. The temperature for the addition of water can vary from 0 to 80°C; a temperature of 5-40°C is especially preferred. The drying of the filtration residue can be carried out at temperatures of 30-90°C and a pressure of from 0.01 to 0.1 bar; a temperature of 40-60°C and a pressure of 0.02-0.06 bar is preferred. It is especially advantageous to add seed crystals of the B modification to the suspension in order to accelerate crystal growth. Compounds of formula I and their preparation are described, for example, in WO 00/52006. Compounds of formula II are described, for example, in the Pesticide Manual, eleventh ed., British Crop Protection Council, 1997, under Entry Nos. 34, 692, 651, 693, 168 and 20. The invention relates also to a method for the selective control of weeds in crops of useful plants, which comprises treating the useful plants or seeds or cuttings thereof or the area under cultivation simultaneously or separately with a herbicidally effective amount of the herbicide of formula I and a herbicide-antagonistically effective amount of the safener of formula II. The composition according to the invention is suitable especially for controlling weeds in crops of useful plants, such as cereals, rape, sugar beet, sugar cane, plantation crops, rice, cotton, maize and soybeans, more especially cotton, sugar cane and rice, and for nonselective weed control. Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides by conventional methods of breeding or by genetic engineering, such as, for example, crops that are resistant to glyphosate, HPPD-inhibitors or ALS-inhibitors. The weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, e.g. Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica. Areas under cultivation are to be understood as including land where the crop plants are already growing or where seed material of those crop plants has already been sown as well as land intended for the cultivation of those crop plants. Depending upon the intended use, a safener of formula II can be used for pretreating the seed material of the crop plant (dressing the seed or cuttings) or introduced into the soil before or after sowing. It can, however, also be applied alone or together with the herbicide after emergence of the plants. The treatment of the plants or the seed material with the safener can therefore take place in principle independently of the time of application of the herbicide. The treatment of the plant may, however, be carried out also by simultaneous application of herbicide and safener (e.g. in the form of a tank mixture). The rate of application of safener relative to herbicide is largely dependent upon the mode of application. In the case of a field treatment, which is carried out either using a tank mixture comprising a combination of safener and herbicide or by separate application of safener and herbicide, the ratio of safener to herbicide is generally from 10:1 to 1:100, especially from 1:1 to 1:10, more especially from 1:4 to 1:9. For their known use as herbicides, the compounds of formula II are used at rates of application of about from 0.8 to 2.5 kg (recommended rate of application for prometryn according to the Pesticide Manual, eleventh ed., British Crop Protection Council, 1997). In the composition according to the invention, however, the compounds of formula II are used in much lower, herbicidally ineffective amounts. As a rule, according to the invention from 0.0005 to 0.01 kg/ha, especially from 0.0005 to 0.007 kg of compound of formula ll/ha, preferably from 0.0005 to 0.005 kg of compound of formula ll/ha, is applied in the case of field treatment. The rates of application of herbicide are generally from 0.0005 to 0.05 kg/ha, but especially from 0.001 to 0.01 kg/ha. In especially preferred herbicidal compositions according to the invention, the compounds of formula I and of formula II are applied in a total amount of from 0.003 to 0.008 kg/ha, especially from 0.004 to 0.0075 kg/ha. The compositions according to the invention are suitable for all methods of application customary in agriculture, such as, for example, pre-emergence application, post-emergence application and seed dressing. In the case of seed dressing, generally from 0.001 to 10 g of safener/kg of seed, especially from 0.05 to 2 g of safener/kg of seed, are applied. If the safener is applied in liquid form, by seed soaking, shortly before sowing, it is advantageous to use safener solutions containing the active ingredient in a concentration of from 1 to 10 000 ppm, especially from 100 to 1000 ppm. For application, the safeners of formula II or combinations of such safeners with the herbicides of formula I are advantageously processed together with the adjuvants customary in formulation technology into formulations, for example into emulsifible concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. The formulations are prepared in known manner, for example by intimately mixing and/or grinding the active ingredients with liquid or solid formulation adjuvants such as, for example, solvents or solid carriers. It is also possible additionally to use surface-active compounds (surfactants) in the preparation of the formulations. Solvents and solid carriers suitable for that purpose include, for example, those mentioned on page 6 of WO 97/34485. Depending upon the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485. In addition, the surfacta nts conventionally employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna 1981, and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81, are also suitable for the preparation of the herbicidal compositions according to the invention. The herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of active ingredient mixture comprising a compound of formula I with a compound of formula II, from 1 to 99.9 % by weight of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients. Various methods and techniques come into consideration for the use of safeners of formula II, or compositions containing them, for protecting cultivated plants against the damaging effects of herbicides of formula I, for example the following: i) Seed dressing a) Dressing the seeds with a wettable powder formulation of a compound of formula II by shaking in a vessel until the formulation is evenly distributed over the surface of the seeds (dry dressing). b) Dressing the seeds with an emulsifiable concentrate of the compound of formula il in accordance with method a) (wet dressing). c) Dressing by immersing the seed material in a liquor containing from 100 to 1000 ppm of the compound of formula II for from 1 to 72 hours and optionally subsequently drying the seed (immersion dressing). ii) Application in the form of a tank mixture A liquid formulation of a mixture of antidote and herbicide (in a respective quantity ratio of from 10:1 to 1:100) is used, the rate of application of herbicide being from 0.0005 to 0.5 kg per hectare. Such tank mixtures are applied before or after sowing. iii) Application to the seed furrow The compound of formula II is introduced into the open, sown seed furrow in the form of an emulsifiable concentrate, wettable powder or granules. When the seed furrow has been covered over, the herbicide is applied by the pre-emergence method in customary manner. iv) Controlled release of active ingredient A solution of the compound of formula II is applied to granular mineral carriers or polymerised granules (urea/formaldehyde) and dried. If desired, a coating can be applied (coated granules), which allows the active ingredient to be released in metered amounts over a specific period of time. Preferred formulations have especially the following compositions (% = percent by weight; "active ingredient mixture" denotes the mixture of compound of formula I with compound of formula II): Dusts: active ingredient mixture: 0.1 to 10%, preferably 0.1 to 5% solid carrier: 99.9 to 90%, preferably 99.9 to 99% Suspension concentrates: active ingredient mixture: 5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30% Wettable powders: active ingredient mixture: 0.5 to 90%, preferably 1 to 80% surfactant: 0.5 to 20%, preferably 1 to 15% solid carrier: 5 to 95%, preferably 15 to 90% Granules: active ingredient mixture: 0.1 to 30%, preferably 0.1 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85% The following Examples further illustrate, but do not limit, the invention. The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, yielding wettable powders which can be diluted with water to give suspensions of any desired concentration. e.g. CaCO3 or SiO2 The finely ground active ingredient is applied uniformly, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner. The finely ground active ingredient is intimately mixed with the adjuvants, yielding a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water. It is often more practical for the compound of formula I and the mixing partner of formula II to be formulated separately and then to be combined in the applicator in the desired mixing ratio in the form of a "tank mixture" in water shortly before application. Example F9: Preparation of wettable granules of the compound of formula I: The following substances are mixed together and then ground using a commercially available mill: 75 % crystal modification A of compound of formula I 4 % dibutylnaphthalenesulfonic acid sodium salt 8 % sodium lignosulfonate 0.5 % silicone antifoam ad 100 % silicon oxide. 22-26 % by weight water are then added to the mixture and granulation is carried out. After drying to a residual moisture content of Example F10: Preparation of wettable granules of the compound of formula I: The following substances are mixed together and then ground using a commercially available mill: 75 % crystal modification B of the compound of formula I 4 % dibutylnaphthalenesulfonic acid sodium salt 8 % sodium lignosulfonate 0.5 % silicone antifoam ad 100 % silicon oxide. 18-20 % by weight water are then added to the mixture and granulation is carried out. After drying to a residual moisture content of Example F11: Preparation of wettable granules of the compound of formula I: The following substances are mixed together and then ground using a commercially available mill: 75 % crystal modification K of the compound of formula I 4 % dibutylnaphthalenesulfonic acid sodium salt 8 % sodium lignosulfonate 0.5 % silicone antifoam ad 100 % silicon oxide. 43-48 % by weight water are then added to the mixture and granulation is carried out. After drying to a residual moisture content of Preparation Examples for the preparation of the compounds of formula I: Example PI: Preparation of the compound of formula I wherein M is sodium, n is 1, L is tetrahvdrofuran, r is 1/2 and s is 0 (J modification): A solution of 40 g of 4,6-dimethoxy-pyrimidine-2-isocyanate in 300 g of tetrahydrofuran (anhydrous) is added at a temperature of 40-45°C to a suspension of 59 g of 3-(2-trifluoro- ethoxy)-pyridinylsulfonamide sodium salt in 210 g of anhydrous tetrahydrofuran. The reaction mixture is then stirred at a temperature of 40°C until the conversion is complete. Finally the J modification is obtained by filtering and washing with anhydrous tetrahydrofuran. Table R1: X-rav powder pattern of modification J: 29 [degrees! dfAl Intensity 5.6 15.7 weak 8.6 10.2 very strong 10.7 8.2 weak 11.3 7.8 weak 12.1 7.3 weak 13.1 6.7 weak 13.6 6.5 very weak 14.4 6.2 medium 15.7 5.64 very weak 16.0 5.53 weak 16.3 5.42 weak 17.3 5.09 weak 29 [deqrees] d[Al] Intensity 17.9 4.96 medium 18.2 4.86 very weak 19.3 4.60 medium 20.3 4.37 medium 21.0 4.24 weak 21.6 4.11 very strong 22.5 3.95 very weak 22.8 3.90 weak 23.3 3.81 very weak 24.0 3.71 medium 24.5 3.62 weak 25.3 3.52 very weak 26.0 3.43 strong 26.4 3.37 weak 26.8 3.32 very weak 27.3 3.27 weak 30.3 2.94 very weak 31.7 2.82 medium Example P2: Preparation of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0 (K modification): Drying the J modification from Example PI at a temperature of 60°C and a pressure of 0.04 bar yields the K modification. That crystalline form is water- and solvent-free: thermo-gravimetric measurement shows a weight loss of less than 0.1 % by weight up to a temperature of 175°C. Table R2: X-ray powder pattern of modification K: 29 [degrees] d[A] Intensity 6.6 13.4 weak 8.8 10.1 very weak 9.5 9.3 very strong 11.4 7.8 weak 12.9 6.9 very weak 29 rdeareesi d[A] Intensity 13.3 6.7 very weak 15.7 5.63 very weak 16.6 5.35 medium 19.0 4.66 weak 20.0 4.44 very weak 20.4 4.35 weak 21.4 4.12 strong 22.6 3.94 strong 22.9 3.87 very weak 23.6 3.76 weak 24.6 3.61 medium 25.5 3.49 very weak 26.2 3.40 very weak Example P3: Preparation of the compound of formula I wherein M is sodium, n is 1, L is tetrahvdrofuran, r is 1 and s is 1 (I modification): A solution of 19.9 g of 4,6-dimethoxy-pyrimidine-2-isocyanate in 350 g of tetrahydrofuran (anhydrous) is added at a temperature of 25°C to a suspension of 34.2 g of 3-(2-trifluoro-ethoxy)-pyridinylsulfonamide sodium salt in 200 ml of anhydrous tetrahydrofuran. The reaction mixture is stirred at a temperature of 25°C until the conversion is complete. Then 10 g of water are added and the mixture is stirred for 18 hours. Finally the I modification is obtained by filtering and washing with anhydrous tetrahydrofuran. Table R3: X-ray powder pattern of modification I: 29 [degrees] d[A] Intensity 7.6 11.6 weak 9.0 9.8 very weak 11.0 8.0 very strong 11.6 7.6 medium 13.3 6.7 strong 13.7 6.4 very weak 14.0 6.3 weak 14.4 6.1 very weak 26 [dearees] d[A] Intensity 15.3 5.80 medium 15.6 5.66 very weak 16.2 5.47 strong 17.2 5.12 very weak 17.3 5.08 very weak 18.3 4.84 weak 18.6 4.76 weak 19.8 4.47 strong 20.1 4.40 weak 21.1 4.21 medium 21.2 4.19 medium 21.4 4.15 very weak 22.2 4.00 very weak 22.6 3.93 very weak 23.2 3.84 medium 23.9 3.72 very strong 24.8 3.58 medium 25.3 3.52 medium 26.9 3.32 very weak 27.2 3.28 very weak 27.5 3.25 very weak 28.7 3.11 very weak 29.0 3.07 very weak 30.2 2.95 very weak 31.2 2.86 weak 31.7 2.82 very weak 32.6 2.75 very weak 34.9 2.57 weak 36.0 2.49 very weak Example P4: Preparation of the compound of formula I wherein M is sodium, n is 1. r is 0 and s is 1 (B modification): The B modification is obtained selectively when 100 g of the K modification prepared according to Example P2 is suspended in 230 g of water for 15 minutes, then preferably inoculated with 1-3 g of seed crystals of the B modification and the suspension is stirred at a temperature of 20-25°C until transformation is complete. The suspension is then filtered and the filtration residue is dried to constant weight at a temperature of 60°C and a pressure of 0.04 bar. Table R4: X-ray powder pattern of modification B: 29 [degrees] d[A] Intensity 8.9 10.0 medium 9.6 9.2 strong 10.3 8.6 very weak 11.0 8.1 weak 12.2 7.2 strong 12.9 6.9 strong 13.8 6.4 medium 15.2 5.82 strong 15.4 5.75 strong 15.7 5.64 very strong 16.0 5.53 very weak 17.3 5.13 medium 17.8 4.97 very strong 19.1 4.65 medium 20.6 4.30 very strong 21.0 4.22 weak 21.4 4.15 very weak 22.1 4.02 weak 22.5 3.94 weak 23.4 3.79 medium 23.8 3.73 weak 24.2 3.68 medium 24.6 3.61 weak 29 [degrees] d[A] Intensity 24.8 3.58 weak 25.3 3.52 very strong 26.0 3.42 very weak 26.4 3.37 weak 26.9 3.31 very weak 27.3 3.27 very weak 27.6 3.23 weak 28.0 3.18 medium 28.9 3.08 very weak 29.4 3.03 very weak 30.3 2.95 very weak 31.2 2.87 strong 31.7 2.82 very weak 32.1 2.79 very weak 32.7 2.73 very weak 33.4 2.68 very weak 33.8 2.65 very weak 34.0 2.63 very weak 34.5 2.60 weak 34.9 2.57 weak In an analogous manner it is also possible to convert the crystal forms A, C, F, I and J into the B form, it being possible for those crystal forms still to be wet with solvent. In such cases the amount of water can be slightly increased. Example P5: Preparation of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0 (C modification): 100 g of the K modification prepared according to Example P2 are mixed with 20 g of water for 3 hours and then dried at a temperature of 60°C and a pressure of 0.04 bar. Table R5: X-ray powder pattern of modification C: 29 [degrees] d[A] Intensity 6.7 13.1 medium 29 [degrees] d[A] Intensity 8.1 11.0 very strong 10.1 8.8 weak 11.4 7.7 very strong 12.2 7.2 very strong 12.7 7.0 weak 13.9 6.4 weak 14.2 6.2 strong 14.9 5.96 weak 15.0 5.90 weak 15.7 5.64 strong 16.2 5.47 weak 16.6 5.34 medium 17.1 5.19 weak 18.5 4.79 weak 18.7 4.74 medium 19.1 4.64 very weak 19.5 4.55 strong 19.9 4.47 weak 20.4 4.35 strong 20.8 4.26 medium 21.5 4.13 weak 21.9 4.06 very weak 22.7 3.92 very strong 23.0 3.87 weak 23.5 3.79 very strong 24.2 3.67 weak 24.6 3.61 medium 24.9 3.58 strong 25.6 3.47 weak 26.9 3.32 very weak 27.5 3.24 medium 28.4 3.14 weak 28.6 3.12 weak 26 [degrees] d[A] Intensity 29.1 3.07 weak 29.3 3.04 strong 30.1 2.97 very weak 30.6 2.92 very weak 31.0 2.88 weak 31.6 2.82 weak 32.3 2.77 very weak 32.7 2.74 very weak 33.3 2.69 weak 33.7 2.66 very weak Example P6: Preparation of the compound of formula I wherein M is sodium, n is 1. r is 0 and s is 0, in substantially amorphous form (A modification): 1.56 g of N-[(4,6-dimethoxy-2-pyrimidinyl)carbamoyl]-3-(2,2,2-trifluoroethoxy)-pyridine-2-sulfonamide are added at a temperature of 20°C to a solution of 40 ml of aqueous 0.1 N sodium hydroxide solution. The reaction mixture is stirred at a temperature of 20°C for 18 hours. The residue obtained after concentration by evaporation In vacuo at a temperature of 50°C is then stirred with ether and filtered. The A modification is obtained by drying the filtrate at elevated temperatures (>120°C). Example P7: Preparation of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0 (C modification) from the A modification: Crystals of the A modification are exposed to a relative air humidity of 98 % for 4 hours at a temperature of 20°C. The C modification having the crystallographic data given under Example P5 is obtained. Example P8: Preparation of the compound of formula I wherein M is sodium, n is 1, r is 2, L is dioxane and s is 0 (G modification): 15 g of the A modification prepared, for example, according to Example P6 are stirred in 85 g of dioxane for 272 days at a temperature of 20°C and the mixture is then filtered. After filtration there is obtained as filtration residue the G modification having the X-ray crystallographic data given in Table R8: Table R8: X-ray powder pattern of modification G: 29 [degrees] d[A] Intensity 5.8 15.3 strong 7.0 12.7 very weak 8.4 10.5 weak 11.1 7.9 medium 12.8 6.9 medium 13.4 6.6 very weak 14.3 6.2 very strong 14.9 5.96 medium 17.4 5.08 medium 17.8 4.98 weak 18.3 4.84 medium 19.3 4.60 medium 19.7 4.51 medium 19.8 4.47 very weak 20.8 4.27 weak 21.0 4.23 medium 22.3 3.98 medium 22.7 3.91 medium 23.3 3.81 weak 23.9 3.71 strong 24.4 3.65 medium 24.9 3.57 weak 25.4 3.50 medium 26.2 3.39 very weak 26.7 3.33 weak 28.9 3.08 very weak 29.5 3.02 very weak 30.5 2.93 weak Example P9: Preparation of the compound of formula I wherein M is sodium, n is 1, r is 1, L is dioxane and s is 0 (F modification): The F modification is obtained by exposing the G modification prepared according to Example P8 to a temperature of 20-25°C and 50 % relative air humidity for a period of 8 days. Table R9: X-ray powder pattern of modification G: 26 [degrees] d[A] Intensity 6.0 14.7 very weak 7.0 12.6 very weak 8.1 10.9 medium 11.4 7.8 medium 12.0 7.4 very weak 12.7 7.0 weak 13.4 6.6 weak 14.3 6.2 weak 16.2 5.45 strong 18.0 4.91 medium 18.4 4.83 weak 18.6 4.76 very weak 20.8 4.28 very weak 21.7 4.10 weak 22.2 4.00 very weak 23.7 3.75 very strong 24.7 3.60 very weak The X-ray powder pattern gives the d-values (interplanar spacings), the associated intensities of the X-ray reflections and the diffraction angles 2 theta (apparatus-specific) of the crystal modification in question. The measurement of the X-ray powder patterns is carried out with a Guinier camera FR 552 from Enraf-Nonius using GuKalphal radiation. The patterns registered on X-ray film are evaluated with a Line-Scanner LS-18 from Johansson using Scanpi-Software. The ability of the compounds of formula II to protect cultivated plants against the phytotoxic action of herbicides of formula I is illustrated in the following Examples. Biological Examples Example B1: Post-emergence test: The test plants are grown in pots under greenhouse conditions up to an early post-application stage (1 to 2 leaves). A standard soil is used as cultivation substrate. At a post-emergence stage, the herbicides are applied to the test plants either alone or in admixture with safeners as a tank mixture. The rates of application are governed by the optimum concentrations determined under field or greenhouse conditions. The tests are evaluated after 1 or 2 weeks (100% action = plant completely dead; 0% action =: no phytotoxic action). The mixtures used in this test exhibit good results. Examples of the good safening action of prometryn on the compound of formula la (N-[3-(2-trifluoroethoxy)-pyridin-2-yl-sulfonyl]-N'-(4,6-dimethoxy-pyrimidin-2-yl)-urea sodium salt in the form of the J modification) are given in Table 1 below: Crop plant: cotton Weed: IPOHE (ivyleaf morningglory) Table 1: Safening action of prometryn on the compound of formula la: The results in Table 1 show that prometryn, which is known as a herbicide, at a rate of application of 0.56 g/ha is able to bring about a considerable reduction in the phytotoxic action of the compound of formula la on cotton for both the tested rates of application of compound of formula la. At the same time, the herbicidal action of the compound of formula la on the tested weed at a rate of application of 5 g/ha is reduced only very slightly. Prometryn alone exhibits no herbicidal action on cotton at the tested rate of application. What is claimed is: 1. A selectively herbicidal composition which, in addition to comprising customary inert formulation adjuvants, comprises as active ingredient a mixture of a) a herbicidally effective amount of a herbicide of formula I, wherein M is an alkali metal or alkaline earth metal; n is 1 or 2; r and s are each independently of the other 0, ½, 1, 1½, 2, 2½ or 3; and L is ethyl acetate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, acetone, butanone, methylene chloride, trichloromethane, trichloro- ethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, chlorobenzene, toluene or xylene, and b) a herbicide-antagonistically effective amount of a compound of formula II wherein R1 is chlorine, methoxy or methylthio, R2 is ethyl or isopropyl and R3 is ethyl, isopropyl, -C(CN)(CH3)-CH3 or tert-butyl. 2. A method of selectively controlling weeds and grasses in crops of useful plants, which comprises treating the useful plants or seeds or cuttings thereof or the area under cultivation with a herbicidally effective amount of a herbicide of formula I according to claim 1 and a herbicide-antagonistically effective amount of a compound of formula II according to claim 1. 3. A method according to claim 2, wherein the crop of useful plants is cotton, sugar cane and rice. 4. A selectively herbicidal composition substantially as herein described and exemplified.

Full Text

Herbicidal composition
The present invention relates to novel selectively herbicidal compositions for controlling grasses and weeds in crops of useful plants, especially in crops of cotton, sugar cane and rice that comprise a herbicide and a safener (counter-agent, antidote) and that protect the useful plants but not the weeds against the phytotoxic action of the herbicide, and to the use of such a composition for weed control in crops of useful plants.
The use of herbicides can result in considerable damage also being caused to cultivated plants, for example in dependence upon the concentration of the herbicide and the mode of its application, the cultivated plant, the nature of the soil and the climatic conditions, such as period of exposure to light, temperature and amounts of precipitation. In order to counter those and similar problems, various substances have already been proposed as safeners that are capable of antagonising the damaging action of the herbicide on the cultivated plant, that is to say of protecting the cultivated plant from that action, while the herbicidal action on the weeds to be controlled is virtually unimpaired. It has been found that the proposed safeners often have a very specific action both in respect of the cultivated plants and in respect of the herbicide and in some cases also in dependence upon the mode of application. This means that a specific safener is often suitable only for a specific cultivated plant and a particular class of herbicide or a specific herbicide.
It has now been found that certain compounds from the class of the triazines, which are known perse for their good herbicidal action, at low rates of application are outstandingly suitable for protecting cultivated plants against the phytotoxic action of a certain class of sulfonylurea herbicides.
It is known from US-A-6 180 563 that mixtures of such triazines with sulfonylureas exhibit a synergistic herbicidal action, that is to say the herbicidal action of the sulfonylurea on the weeds is enhanced in a superadditive manner by the addition of the triazine herbicide.
It is therefore extremely surprising that such triazines, at herbicidally ineffective rates of application, are suitable as safeners for certain sulfonylurea herbicides.

According to the invention, therefore, there is proposed a selectively herbicidal composition which, in addition to comprising customary inert formulation adjuvants, such as carriers, solvents and wetting agents, comprises as active ingredient a mixture of
a) a herbicidally effective amount of a herbicide of formula I,

wherein
M is an alkali metal or alkaline earth metal;
n is 1 or 2;
r and s are each independently of the other 0, 1/2,1, 11/2, 2, 21/2 or 3; and
L is ethyl acetate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide,
N-methyl-2-pyrrolidone, acetone, butanone, methylene chloride, trichloromethane, trichloro-
ethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether,
chlorobenzene, toluene or xylene, and
b) a herbicide-antagonistically effective amount of a compound of formula 11

wherein R1 is chlorine, methoxy or methylthio, R2 is ethyl or isopropyl and R3 is ethyl, isopropyl, -C(CN)(CH3)-CH3 or tert-butyl.
M as an alkali metal or alkaline earth metal in the context of the present invention is preferably sodium, potassium, magnesium or calcium. The present invention includes all crystal modifications that can be formed by the compounds of formula I.

Compounds of formula I that are preferred for the composition according to the invention are those wherein L is dioxane, tetrahydrofuran or water. Also preferred are compounds of formula I wherein n is 1, M being especially sodium.
Preference is also given to compounds of formula I wherein M is sodium, n is 1, r is 0 and s is 0.
For the method according to the invention special mention should also be made of the amorphous solid form of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0. The amorphous solid form can be used in the preparation of other crystal modifications, such as the C modification.
As individual compounds from the scope of formula I that are especially preferred for use in the composition according to the invention there may be mentioned those compounds selected from
a) the B modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 1, characterised by the X-ray powder pattern having d[Al/intensitv: 10.0/medium; 9.2/strong; 8.6/very weak; 8.1/weak; 7.2/strong; 6.9/strong; 6.4/medium; 5.82/strong; 5.75/strong; 5.64/very strong; 5.53/very weak; 5.13/medium; 4.97/very strong; 4.65/medium; 4.30/very strong; 4.22/weak; 4.15/very weak; 4.02/weak; 3.94/weak; 3.79/medium; 3.73/weak; 3.68/medium; 3.61/weak; 3.58/weak; 3.52/very strong; 3.42/very weak; 3.37/weak; 3.31/very weak; 3.27/very weak; 3.23/weak; 3.18/medium; 3.08/very weak; 3.03/very weak; 2.95/very weak; 2.87/strong; 2.82/very weak; 2.79/very weak; 2.73/very weak; 2.68/very weak; 2.65/very weak; 2.63/very weak; 2.60/weak; 2.57/weak;
b) the J modification of the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is Vz and s is 0, characterised by the X-ray powder pattern having d[A]/intensitv: 15.7/weak; 10.2/very strong; 8.2/weak; 7.8/weak; 7.3/weak; 6.7/weak; 6.5/very weak; 6.2/medium; 5.64/very weak; 5.53/weak; 5.42/weak; 5.09/weak; 4.96/medium; 4.86/very weak; 4.60/medium; 4.37/medium; 4.24/weak; 4.11/very strong; 3.95/very weak; 3.90/weak; 3.81/very weak; 3.71/medium; 3.62/weak; 3.52/very weak; 3.43/strong; 3.37/weak; 3.32/very weak; 3.27/weak; 2.94/very weak; 2.82/medium;
c) the K modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0, characterised by the X-ray powder pattern having dfAl/intensity: 13.4/weak; 10.1/very weak; 9.3/very strong; 7.8/weak; 6.9/very weak; 6.7/very weak; 5.63/very weak;

5.35/medium; 4.66/weak; 4.44/very weak; 4.35/weak; 4.12/strong; 3.94/strong; 3.87/very weak; 3.76/weak; 3.61/medium; 3.49/very weak; 3.40/very weak;
d) the C modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 1, characterised by the X-ray powder pattern having drAl/intensity: 13.1/medium; 11.0/very strong; 8.8/weak; 7.7/very strong; 7.2/very strong; 7.0/weak; 6.4/weak; 6.2/strong; 5.96/weak; 5.90/weak; 5.64/strong; 5.47/weak; 5.34/medium; 5.19/weak; 4.79/weak; 4.74/medium; 4.64/very weak; 4.55/strong; 4.47/weak; 4.35/strong; 4.26/medium; 4.13/weak; 4.06/very weak; 3.92/very strong; 3.87/weak; 3.79/very strong; 3.67/weak; 3.61/medium; 3.58/strong; 3.47/weak; 3.32/very weak; 3.24/medium; 3.14/weak; 3.12/weak; 3.07/weak; 3.04/strong; 2.97/very weak; 2.92/very weak; 2.88/weak; 2.82/weak; 2.77/very weak; 2.74/very weak; 2.69/weak; 2.66/very weak; and
e) the I modification of the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is 1 and s is 1, characterised by the X-ray powder pattern having d[AVintensitv: 11.6/weak; 9.8/very weak; 8.0/very strong; 7.6/medium; 6.7/strong; 6.4/very weak; 6.3/weak; 6.1/very weak; 5.80/medium; 5.66/very weak; 5.47/strong; 5.12/very weak; 5.08/very weak; 4.84/weak; 4.76/weak; 4.47/strong; 4.40/weak; 4.21/medium; 4.19/medium; 4.15/very weak; 4.00/very weak; 3.93/very weak; 3.84/medium; 3,72/very strong; 3.58/medium; 3.52/medium; 3.32/very weak; 3.28/very weak; 3.25/very weak; 3.11/very weak; 3.07/very weak; 2.95/very weak; 2.86/weak; 2.82/very weak; 2.75/very weak; 2.57/weak; 2.49/very weak.
Preference is also given to
a) the K modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is
0, prepared by drying the compound of formula I wherein M is sodium, n is 1, L is tetrahydro
furan, r is Vz and s is 0 (J modification) at a temperature of from 35°C to GS^'C \n vacuo]
b) the C modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is
1, prepared by either
i) bringing the substantially amorphous form (A modification) into contact with air of 98 % relative humidity, or
ii) adding water to the K modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0, in a ratio of water to K modification of from 0.1 : 1 to 0.4 : 1 and separating off and drying the resulting product at a temperature of 30-90°C and a pressure of from 0.01 to 0.1 bar;

c) the B modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 1, prepared by adding water to the compound of formula I wherein M is sodium, n is 1 and L, r and s are as defined for formula I, in a ratio of water to that compound of from 0.5 : 1 to 20 : 1, filtering, and drying the filtration residue at a temperature of 30-90°C and a pressure of from 0.01 to 0.1 bar, or preferably prepared by adding water to the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is 1/2 and s is 0 (K modification), or to the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is 1/2 and s is 0 (J modification), or to the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is 1 and s is 1 (I modification), or to the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 1 (C modification), in a ratio of water to K, J, I or C modification of from 0.5 : 1 to 20 : 1, filtering, and drying the filtration residue at a temperature of 30-90°C and a pressure of from 0.01 to 0.1 bar.
Compounds of formula II that are especially preferred for the composition according to the invention are atrazine, terbuthylazine, simazine, prometryn, terbutryn, cyanazine and ametryn, very special preference being given to prometryn. Those compounds of formula II can each be combined with the crystal modifications of the compounds of formula I specifically mentioned above as being preferred to give especially advantageous herbicidally selective compositions. According to the invention very special preference is given to those compositions which comprise as compound of formula I either the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0 or the J or K crystal modification of the compound of formula I and, as compound of formula II, prometryn.
The compounds of formula I can be prepared in accordance with a general process by reacting a compound of formula II

in ethyl acetate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, acetone, butanone, methylene chloride, trichloromethane, trichloro-ethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether, chlorobenzene, toluene or xylene, with a compound of formula V

wherein M is as defined for formula I.
The reaction of the compound of formula lla with the compound of formula III is carried out at temperatures of from -20°C to 180°C, a temperature range of 30 - 80°C being preferred. The compounds of formulae lla and III can be used in equivalent stoichiometric amounts, but a slight excess of isocyanate may be advantageous.
The preparation of the starting compound of formula lla is described, for example, in EP-A-0 232 067, page 29. The compounds of formula III can be prepared, for example, by converting a compound of formula IV

wherein R1 is -CH2-phenyl or isopropyl, by aqueous chiorination into the compound of formula V

That compound is treated with aqueous ammonia and the resulting sulfonamide is then reacted with 30 % sodium methanolate. Such reactions are known and will be familiar to the person skilled in the art.
Preferred crystal modifications of the compounds of formula I are prepared as follows:
For example, the J modification of the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is 1/2 and s is 0 is prepared by adding a 5-25 % by weight solution of 4,6-dimethoxy-pyrimidine-2-isocyanate in anhydrous tetrahydrofuran at a temperature of

35-65°C to a 15-35 % by weight suspension of 3-(2-trifluoroethoxy)-pyridinyl-sulfonamide sodium salt in anhydrous tetrahydrofuran.
After the addition of the 4,6-dimethoxy-pyrimidine-2-isocyanate, the reaction mixture is stirred until the conversion is complete. This process is preferably carried out at a temperature of 40-50°C. The J modification so obtained can be separated from the reaction mixture by filtration.
The process for the preparation of the K modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0 is carried out as follows: a 5-25 % by weight solution of 4,6-dimethoxy-pyrimidine-2-isocyanate in anhydrous tetrahydrofuran is added at a temperature of 35-65°C to a 15-35 % by weight suspension of 3-(2-trifluoroethoxy)-pyridinyl-sulfon-amide sodium salt in anhydrous tetrahydrofuran, filtration is carried out and the filtration residue (J modification) is then dried at a temperature of 30-90°C and a pressure of from 0.01 to 0.1 bar.
After the addition of the 4,6-dimethoxy-pyrimidine-2-isocyanate, the reaction mixture is stirred until the conversion is complete. For the drying, in this process variant a temperature of 40-60°C and a pressure of from 0.02 to 0.06 bar is preferred.
The process for the preparation of the C modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 1 is carried out as follows: either the substantially amorphous form (A modification) is exposed to air of 98 % relative humidity, or water is added to the K modification in a ratio of water to K modification of from 0.1 : 1 to 0.4 : 1, filtration is carried out and the filtration residue is then dried at a temperature of 30-90°C and a pressure of from 0.01 to 0.1 bar.
For the preparation of the C modification, the ratio of water to K modification may vary from 0.1 : 1 to 0.4 : 1; a ratio of from 0.1 : 1 to 0.3 : 1 is especially preferred. The addition of water can take place at a temperature of 0-60°C, especially at a temperature of 5-40°C. The drying of the C modification is preferably carried out at a temperature of 40-60°C and a pressure of 0.02-0.06 bar.

The C modification can advantageously also be prepared by adding N-[(4,6-dimethoxy-2-pyrimidinyl)carbamoyl]-3-(2,2,2-trifluoroethoxy)-pyridine-2-sulfonamide to an aqueous sodium hydroxide solution, then concentrating by evaporation in vacuo at a temperature of 50°C, stirring the residue so obtained with diethyl ether, filtering, drying at temperatures of >120°C and then exposing the resulting substantially amorphous salt (A modification) to air of 98 % relative humidity.
The process for the preparation of the I modification of the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is 1 and s is 1 is carried out as follows: a 5-25 % by weight solution of 4,6-dimethoxy-pyrimidine-2-isocyanate in anhydrous tetrahydrofuran is added at a temperature of from 0 to 30°C to a 10-35 % by weight suspension of 3"(2-tri-fluoroethoxy)-pyridinylsulfonamide sodium salt in anhydrous tetrahydrofuran and then 1-20 molar equivalents of water relative to the 3-(2-trifluoroethoxy)-pyridinylsulfonamide sodium salt are added. In this variant the addition of 2-5 molar equivalents of water is especially preferred.
The process for the preparation of the B modification of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 1 is carried out as follows: water is added to the compound of formula I wherein M is sodium, n is 1 and L, r and s are as defined for formula I in a ratio of water to that compound of from 0.5 :1 to 20 :1, filtration is carried out and the filtration residue is dried at a temperature of 30-90°C and a pressure of from 0.01 to 0.1 bar.
A preferred variant of the process for the preparation of the B modification is carried out as follows: water is added to the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0 (K modification), or to the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is 1/2 and s is 0 (J modification), or to the compound of formula I wherein M is sodium, n is 1, L is tetrahydrofuran, r is 1 and s is 1 (I modification), or to the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 1 (C modification), in a ratio of water to K, J, I or C modification of from 0.5 :1 to 20 :1, filtration is carried out and the filtration residue is then dried at a temperature of 30-90°C and a pressure of from 0.01 to 0.1 bar.
The temperature for the addition of water can vary from 0 to 80°C; a temperature of 5-40°C is especially preferred. The drying of the filtration residue can be carried out at temperatures of 30-90°C and a pressure of from 0.01 to 0.1 bar; a temperature of 40-60°C and a pressure

of 0.02-0.06 bar is preferred. It is especially advantageous to add seed crystals of the B modification to the suspension in order to accelerate crystal growth.
Compounds of formula I and their preparation are described, for example, in WO 00/52006. Compounds of formula II are described, for example, in the Pesticide Manual, eleventh ed., British Crop Protection Council, 1997, under Entry Nos. 34, 692, 651, 693, 168 and 20.
The invention relates also to a method for the selective control of weeds in crops of useful plants, which comprises treating the useful plants or seeds or cuttings thereof or the area under cultivation simultaneously or separately with a herbicidally effective amount of the herbicide of formula I and a herbicide-antagonistically effective amount of the safener of formula II.
The composition according to the invention is suitable especially for controlling weeds in crops of useful plants, such as cereals, rape, sugar beet, sugar cane, plantation crops, rice, cotton, maize and soybeans, more especially cotton, sugar cane and rice, and for nonselective weed control.
Crops are to be understood as also including those crops which have been rendered tolerant to herbicides or classes of herbicides by conventional methods of breeding or by genetic engineering, such as, for example, crops that are resistant to glyphosate, HPPD-inhibitors or ALS-inhibitors.
The weeds to be controlled may be both monocotyledonous and dicotyledonous weeds, e.g. Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
Areas under cultivation are to be understood as including land where the crop plants are already growing or where seed material of those crop plants has already been sown as well as land intended for the cultivation of those crop plants.

Depending upon the intended use, a safener of formula II can be used for pretreating the seed material of the crop plant (dressing the seed or cuttings) or introduced into the soil before or after sowing. It can, however, also be applied alone or together with the herbicide after emergence of the plants. The treatment of the plants or the seed material with the safener can therefore take place in principle independently of the time of application of the herbicide. The treatment of the plant may, however, be carried out also by simultaneous application of herbicide and safener (e.g. in the form of a tank mixture). The rate of application of safener relative to herbicide is largely dependent upon the mode of application.
In the case of a field treatment, which is carried out either using a tank mixture comprising a combination of safener and herbicide or by separate application of safener and herbicide, the ratio of safener to herbicide is generally from 10:1 to 1:100, especially from 1:1 to 1:10, more especially from 1:4 to 1:9.
For their known use as herbicides, the compounds of formula II are used at rates of application of about from 0.8 to 2.5 kg (recommended rate of application for prometryn according to the Pesticide Manual, eleventh ed., British Crop Protection Council, 1997).
In the composition according to the invention, however, the compounds of formula II are used in much lower, herbicidally ineffective amounts. As a rule, according to the invention from 0.0005 to 0.01 kg/ha, especially from 0.0005 to 0.007 kg of compound of formula ll/ha, preferably from 0.0005 to 0.005 kg of compound of formula ll/ha, is applied in the case of field treatment.
The rates of application of herbicide are generally from 0.0005 to 0.05 kg/ha, but especially from 0.001 to 0.01 kg/ha.
In especially preferred herbicidal compositions according to the invention, the compounds of formula I and of formula II are applied in a total amount of from 0.003 to 0.008 kg/ha, especially from 0.004 to 0.0075 kg/ha.
The compositions according to the invention are suitable for all methods of application customary in agriculture, such as, for example, pre-emergence application, post-emergence application and seed dressing. In the case of seed dressing, generally from 0.001 to 10 g of

safener/kg of seed, especially from 0.05 to 2 g of safener/kg of seed, are applied. If the safener is applied in liquid form, by seed soaking, shortly before sowing, it is advantageous to use safener solutions containing the active ingredient in a concentration of from 1 to 10 000 ppm, especially from 100 to 1000 ppm.
For application, the safeners of formula II or combinations of such safeners with the herbicides of formula I are advantageously processed together with the adjuvants customary in formulation technology into formulations, for example into emulsifible concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. The formulations are prepared in known manner, for example by intimately mixing and/or grinding the active ingredients with liquid or solid formulation adjuvants such as, for example, solvents or solid carriers. It is also possible additionally to use surface-active compounds (surfactants) in the preparation of the formulations. Solvents and solid carriers suitable for that purpose include, for example, those mentioned on page 6 of WO 97/34485.
Depending upon the nature of the compound of formula I to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485. In addition, the surfacta nts conventionally employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna 1981, and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81, are also suitable for the preparation of the herbicidal compositions according to the invention.
The herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of active ingredient mixture comprising a compound of formula I with a compound of formula II, from 1 to 99.9 % by weight of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

The compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients. Various methods and techniques come into consideration for the use of safeners of formula II, or compositions containing them, for protecting cultivated plants against the damaging effects of herbicides of formula I, for example the following: i) Seed dressing
a) Dressing the seeds with a wettable powder formulation of a compound of formula II by shaking in a vessel until the formulation is evenly distributed over the surface of the seeds (dry dressing).
b) Dressing the seeds with an emulsifiable concentrate of the compound of formula il in accordance with method a) (wet dressing).
c) Dressing by immersing the seed material in a liquor containing from 100 to 1000 ppm of the compound of formula II for from 1 to 72 hours and optionally subsequently drying the seed (immersion dressing).
ii) Application in the form of a tank mixture
A liquid formulation of a mixture of antidote and herbicide (in a respective quantity ratio of
from 10:1 to 1:100) is used, the rate of application of herbicide being from 0.0005 to 0.5 kg
per hectare. Such tank mixtures are applied before or after sowing.
iii) Application to the seed furrow
The compound of formula II is introduced into the open, sown seed furrow in the form of an
emulsifiable concentrate, wettable powder or granules. When the seed furrow has been
covered over, the herbicide is applied by the pre-emergence method in customary manner.
iv) Controlled release of active ingredient
A solution of the compound of formula II is applied to granular mineral carriers or
polymerised granules (urea/formaldehyde) and dried. If desired, a coating can be applied
(coated granules), which allows the active ingredient to be released in metered amounts
over a specific period of time.
Preferred formulations have especially the following compositions (% = percent by weight; "active ingredient mixture" denotes the mixture of compound of formula I with compound of formula II):

Dusts:
active ingredient mixture: 0.1 to 10%, preferably 0.1 to 5%
solid carrier: 99.9 to 90%, preferably 99.9 to 99%
Suspension concentrates:
active ingredient mixture: 5 to 75%, preferably 10 to 50%
water: 94 to 24%, preferably 88 to 30%
surfactant: 1 to 40%, preferably 2 to 30%
Wettable powders:
active ingredient mixture: 0.5 to 90%, preferably 1 to 80%
surfactant: 0.5 to 20%, preferably 1 to 15%
solid carrier: 5 to 95%, preferably 15 to 90%
Granules:
active ingredient mixture: 0.1 to 30%, preferably 0.1 to 15%
solid carrier: 99.5 to 70%, preferably 97 to 85%
The following Examples further illustrate, but do not limit, the invention.

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, yielding wettable powders which can be diluted with water to give suspensions of any desired concentration.

e.g. CaCO3 or SiO2
The finely ground active ingredient is applied uniformly, in a mixer, to the carrier moistened
with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

The finely ground active ingredient is intimately mixed with the adjuvants, yielding a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
It is often more practical for the compound of formula I and the mixing partner of formula II to be formulated separately and then to be combined in the applicator in the desired mixing ratio in the form of a "tank mixture" in water shortly before application.

Example F9: Preparation of wettable granules of the compound of formula I: The following substances are mixed together and then ground using a commercially available mill:
75 % crystal modification A of compound of formula I 4 % dibutylnaphthalenesulfonic acid sodium salt 8 % sodium lignosulfonate 0.5 % silicone antifoam ad 100 % silicon oxide.
22-26 % by weight water are then added to the mixture and granulation is carried out. After drying to a residual moisture content of Example F10: Preparation of wettable granules of the compound of formula I: The following substances are mixed together and then ground using a commercially available mill: 75 % crystal modification B of the compound of formula I
4 % dibutylnaphthalenesulfonic acid sodium salt
8 % sodium lignosulfonate 0.5 % silicone antifoam ad 100 % silicon oxide.
18-20 % by weight water are then added to the mixture and granulation is carried out. After drying to a residual moisture content of Example F11: Preparation of wettable granules of the compound of formula I: The following substances are mixed together and then ground using a commercially available mill: 75 % crystal modification K of the compound of formula I

4 % dibutylnaphthalenesulfonic acid sodium salt
8 % sodium lignosulfonate 0.5 % silicone antifoam ad 100 % silicon oxide.
43-48 % by weight water are then added to the mixture and granulation is carried out. After drying to a residual moisture content of Preparation Examples for the preparation of the compounds of formula I:
Example PI: Preparation of the compound of formula I wherein M is sodium, n is 1, L is
tetrahvdrofuran, r is 1/2 and s is 0 (J modification):
A solution of 40 g of 4,6-dimethoxy-pyrimidine-2-isocyanate in 300 g of tetrahydrofuran
(anhydrous) is added at a temperature of 40-45°C to a suspension of 59 g of 3-(2-trifluoro-
ethoxy)-pyridinylsulfonamide sodium salt in 210 g of anhydrous tetrahydrofuran. The reaction
mixture is then stirred at a temperature of 40°C until the conversion is complete. Finally the
J modification is obtained by filtering and washing with anhydrous tetrahydrofuran.
Table R1: X-rav powder pattern of modification J: 29 [degrees! dfAl Intensity
5.6 15.7 weak
8.6 10.2 very strong
10.7 8.2 weak
11.3 7.8 weak
12.1 7.3 weak
13.1 6.7 weak
13.6 6.5 very weak
14.4 6.2 medium
15.7 5.64 very weak
16.0 5.53 weak
16.3 5.42 weak
17.3 5.09 weak

29 [deqrees] d[Al] Intensity
17.9 4.96 medium
18.2 4.86 very weak
19.3 4.60 medium
20.3 4.37 medium
21.0 4.24 weak
21.6 4.11 very strong
22.5 3.95 very weak
22.8 3.90 weak
23.3 3.81 very weak
24.0 3.71 medium
24.5 3.62 weak
25.3 3.52 very weak
26.0 3.43 strong
26.4 3.37 weak
26.8 3.32 very weak
27.3 3.27 weak
30.3 2.94 very weak
31.7 2.82 medium
Example P2: Preparation of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0 (K modification):
Drying the J modification from Example PI at a temperature of 60°C and a pressure of 0.04 bar yields the K modification. That crystalline form is water- and solvent-free: thermo-gravimetric measurement shows a weight loss of less than 0.1 % by weight up to a temperature of 175°C.
Table R2: X-ray powder pattern of modification K:
29 [degrees] d[A] Intensity
6.6 13.4 weak
8.8 10.1 very weak
9.5 9.3 very strong
11.4 7.8 weak
12.9 6.9 very weak

29 rdeareesi d[A] Intensity
13.3 6.7 very weak
15.7 5.63 very weak
16.6 5.35 medium
19.0 4.66 weak
20.0 4.44 very weak
20.4 4.35 weak
21.4 4.12 strong

22.6 3.94 strong 22.9 3.87 very weak
23.6 3.76 weak 24.6 3.61 medium
25.5 3.49 very weak
26.2 3.40 very weak
Example P3: Preparation of the compound of formula I wherein M is sodium, n is 1, L is tetrahvdrofuran, r is 1 and s is 1 (I modification):
A solution of 19.9 g of 4,6-dimethoxy-pyrimidine-2-isocyanate in 350 g of tetrahydrofuran (anhydrous) is added at a temperature of 25°C to a suspension of 34.2 g of 3-(2-trifluoro-ethoxy)-pyridinylsulfonamide sodium salt in 200 ml of anhydrous tetrahydrofuran. The reaction mixture is stirred at a temperature of 25°C until the conversion is complete. Then 10 g of water are added and the mixture is stirred for 18 hours. Finally the I modification is obtained by filtering and washing with anhydrous tetrahydrofuran.
Table R3: X-ray powder pattern of modification I: 29 [degrees] d[A] Intensity
7.6 11.6 weak
9.0 9.8 very weak
11.0 8.0 very strong
11.6 7.6 medium
13.3 6.7 strong
13.7 6.4 very weak
14.0 6.3 weak
14.4 6.1 very weak

26 [dearees] d[A] Intensity
15.3 5.80 medium
15.6 5.66 very weak
16.2 5.47 strong
17.2 5.12 very weak
17.3 5.08 very weak
18.3 4.84 weak
18.6 4.76 weak
19.8 4.47 strong
20.1 4.40 weak
21.1 4.21 medium
21.2 4.19 medium
21.4 4.15 very weak
22.2 4.00 very weak
22.6 3.93 very weak
23.2 3.84 medium
23.9 3.72 very strong
24.8 3.58 medium
25.3 3.52 medium
26.9 3.32 very weak
27.2 3.28 very weak
27.5 3.25 very weak
28.7 3.11 very weak
29.0 3.07 very weak
30.2 2.95 very weak
31.2 2.86 weak
31.7 2.82 very weak
32.6 2.75 very weak
34.9 2.57 weak
36.0 2.49 very weak

Example P4: Preparation of the compound of formula I wherein M is sodium, n is 1. r is 0 and s is 1 (B modification):
The B modification is obtained selectively when 100 g of the K modification prepared according to Example P2 is suspended in 230 g of water for 15 minutes, then preferably inoculated with 1-3 g of seed crystals of the B modification and the suspension is stirred at a temperature of 20-25°C until transformation is complete. The suspension is then filtered and the filtration residue is dried to constant weight at a temperature of 60°C and a pressure of 0.04 bar.
Table R4: X-ray powder pattern of modification B:
29 [degrees] d[A] Intensity
8.9 10.0 medium
9.6 9.2 strong
10.3 8.6 very weak
11.0 8.1 weak
12.2 7.2 strong
12.9 6.9 strong
13.8 6.4 medium
15.2 5.82 strong
15.4 5.75 strong
15.7 5.64 very strong
16.0 5.53 very weak
17.3 5.13 medium
17.8 4.97 very strong
19.1 4.65 medium
20.6 4.30 very strong
21.0 4.22 weak
21.4 4.15 very weak
22.1 4.02 weak
22.5 3.94 weak
23.4 3.79 medium
23.8 3.73 weak
24.2 3.68 medium
24.6 3.61 weak

29 [degrees] d[A] Intensity
24.8 3.58 weak
25.3 3.52 very strong
26.0 3.42 very weak
26.4 3.37 weak
26.9 3.31 very weak
27.3 3.27 very weak
27.6 3.23 weak
28.0 3.18 medium
28.9 3.08 very weak
29.4 3.03 very weak
30.3 2.95 very weak
31.2 2.87 strong
31.7 2.82 very weak
32.1 2.79 very weak
32.7 2.73 very weak
33.4 2.68 very weak
33.8 2.65 very weak
34.0 2.63 very weak
34.5 2.60 weak
34.9 2.57 weak
In an analogous manner it is also possible to convert the crystal forms A, C, F, I and J into the B form, it being possible for those crystal forms still to be wet with solvent. In such cases the amount of water can be slightly increased.
Example P5: Preparation of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0 (C modification):
100 g of the K modification prepared according to Example P2 are mixed with 20 g of water for 3 hours and then dried at a temperature of 60°C and a pressure of 0.04 bar.
Table R5: X-ray powder pattern of modification C:
29 [degrees] d[A] Intensity
6.7 13.1 medium

29 [degrees] d[A] Intensity
8.1 11.0 very strong
10.1 8.8 weak
11.4 7.7 very strong
12.2 7.2 very strong 12.7 7.0 weak 13.9 6.4 weak
14.2 6.2 strong 14.9 5.96 weak
15.0 5.90 weak
15.7 5.64 strong
16.2 5.47 weak
16.6 5.34 medium
17.1 5.19 weak
18.5 4.79 weak
18.7 4.74 medium
19.1 4.64 very weak
19.5 4.55 strong
19.9 4.47 weak
20.4 4.35 strong
20.8 4.26 medium
21.5 4.13 weak
21.9 4.06 very weak
22.7 3.92 very strong
23.0 3.87 weak
23.5 3.79 very strong
24.2 3.67 weak
24.6 3.61 medium 24.9 3.58 strong
25.6 3.47 weak 26.9 3.32 very weak
27.5 3.24 medium
28.4 3.14 weak
28.6 3.12 weak

26 [degrees] d[A] Intensity
29.1 3.07 weak
29.3 3.04 strong
30.1 2.97 very weak
30.6 2.92 very weak 31.0 2.88 weak
31.6 2.82 weak 32.3 2.77 very weak 32.7 2.74 very weak 33.3 2.69 weak 33.7 2.66 very weak
Example P6: Preparation of the compound of formula I wherein M is sodium, n is 1. r is 0 and s is 0, in substantially amorphous form (A modification):
1.56 g of N-[(4,6-dimethoxy-2-pyrimidinyl)carbamoyl]-3-(2,2,2-trifluoroethoxy)-pyridine-2-sulfonamide are added at a temperature of 20°C to a solution of 40 ml of aqueous 0.1 N sodium hydroxide solution. The reaction mixture is stirred at a temperature of 20°C for 18 hours. The residue obtained after concentration by evaporation In vacuo at a temperature of 50°C is then stirred with ether and filtered. The A modification is obtained by drying the filtrate at elevated temperatures (>120°C).
Example P7: Preparation of the compound of formula I wherein M is sodium, n is 1, r is 0 and s is 0 (C modification) from the A modification:
Crystals of the A modification are exposed to a relative air humidity of 98 % for 4 hours at a temperature of 20°C. The C modification having the crystallographic data given under Example P5 is obtained.
Example P8: Preparation of the compound of formula I wherein M is sodium, n is 1, r is 2, L is dioxane and s is 0 (G modification):
15 g of the A modification prepared, for example, according to Example P6 are stirred in 85 g of dioxane for 272 days at a temperature of 20°C and the mixture is then filtered. After filtration there is obtained as filtration residue the G modification having the X-ray crystallographic data given in Table R8:

Table R8: X-ray powder pattern of modification G:
29 [degrees] d[A] Intensity
5.8 15.3 strong
7.0 12.7 very weak
8.4 10.5 weak
11.1 7.9 medium
12.8 6.9 medium
13.4 6.6 very weak
14.3 6.2 very strong
14.9 5.96 medium
17.4 5.08 medium
17.8 4.98 weak
18.3 4.84 medium
19.3 4.60 medium
19.7 4.51 medium
19.8 4.47 very weak
20.8 4.27 weak
21.0 4.23 medium
22.3 3.98 medium
22.7 3.91 medium
23.3 3.81 weak
23.9 3.71 strong
24.4 3.65 medium
24.9 3.57 weak
25.4 3.50 medium
26.2 3.39 very weak
26.7 3.33 weak
28.9 3.08 very weak
29.5 3.02 very weak
30.5 2.93 weak

Example P9: Preparation of the compound of formula I wherein M is sodium, n is 1, r is 1, L is dioxane and s is 0 (F modification):
The F modification is obtained by exposing the G modification prepared according to Example P8 to a temperature of 20-25°C and 50 % relative air humidity for a period of 8 days.
Table R9: X-ray powder pattern of modification G:
26 [degrees] d[A] Intensity
6.0 14.7 very weak
7.0 12.6 very weak
8.1 10.9 medium
11.4 7.8 medium
12.0 7.4 very weak
12.7 7.0 weak
13.4 6.6 weak
14.3 6.2 weak
16.2 5.45 strong
18.0 4.91 medium
18.4 4.83 weak
18.6 4.76 very weak
20.8 4.28 very weak
21.7 4.10 weak
22.2 4.00 very weak
23.7 3.75 very strong
24.7 3.60 very weak
The X-ray powder pattern gives the d-values (interplanar spacings), the associated intensities of the X-ray reflections and the diffraction angles 2 theta (apparatus-specific) of the crystal modification in question. The measurement of the X-ray powder patterns is carried out with a Guinier camera FR 552 from Enraf-Nonius using GuKalphal radiation. The patterns registered on X-ray film are evaluated with a Line-Scanner LS-18 from Johansson using Scanpi-Software.

The ability of the compounds of formula II to protect cultivated plants against the phytotoxic action of herbicides of formula I is illustrated in the following Examples.
Biological Examples
Example B1: Post-emergence test:
The test plants are grown in pots under greenhouse conditions up to an early post-application stage (1 to 2 leaves). A standard soil is used as cultivation substrate. At a post-emergence stage, the herbicides are applied to the test plants either alone or in admixture with safeners as a tank mixture. The rates of application are governed by the optimum concentrations determined under field or greenhouse conditions. The tests are evaluated after 1 or 2 weeks (100% action = plant completely dead; 0% action =: no phytotoxic action). The mixtures used in this test exhibit good results.
Examples of the good safening action of prometryn on the compound of formula la (N-[3-(2-trifluoroethoxy)-pyridin-2-yl-sulfonyl]-N'-(4,6-dimethoxy-pyrimidin-2-yl)-urea sodium salt in the form of the J modification) are given in Table 1 below:
Crop plant: cotton
Weed: IPOHE (ivyleaf morningglory)
Table 1: Safening action of prometryn on the compound of formula la:

The results in Table 1 show that prometryn, which is known as a herbicide, at a rate of application of 0.56 g/ha is able to bring about a considerable reduction in the phytotoxic

action of the compound of formula la on cotton for both the tested rates of application of compound of formula la. At the same time, the herbicidal action of the compound of formula la on the tested weed at a rate of application of 5 g/ha is reduced only very slightly. Prometryn alone exhibits no herbicidal action on cotton at the tested rate of application.

What is claimed is:
1. A selectively herbicidal composition which, in addition to comprising customary inert
formulation adjuvants, comprises as active ingredient a mixture of
a) a herbicidally effective amount of a herbicide of formula I,

wherein
M is an alkali metal or alkaline earth metal;
n is 1 or 2;
r and s are each independently of the other 0, ½, 1, 1½, 2, 2½ or 3; and
L is ethyl acetate, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide,
N-methyl-2-pyrrolidone, acetone, butanone, methylene chloride, trichloromethane, trichloro-
ethane, tetrahydrofuran, diethyl ether, 1,2-dimethoxyethane, dioxane, methyl tert-butyl ether,
chlorobenzene, toluene or xylene, and
b) a herbicide-antagonistically effective amount of a compound of formula II

wherein R1 is chlorine, methoxy or methylthio, R2 is ethyl or isopropyl and R3 is ethyl, isopropyl, -C(CN)(CH3)-CH3 or tert-butyl.
2. A method of selectively controlling weeds and grasses in crops of useful plants, which
comprises treating the useful plants or seeds or cuttings thereof or the area under cultivation
with a herbicidally effective amount of a herbicide of formula I according to claim 1 and a
herbicide-antagonistically effective amount of a compound of formula II according to claim 1.

3. A method according to claim 2, wherein the crop of useful plants is cotton, sugar cane and
rice.

4. A selectively herbicidal composition substantially as herein described and exemplified.

Documents:

2743-chenp-2004-abstract.pdf

2743-chenp-2004-claims filed.pdf

2743-chenp-2004-claims granted.pdf

2743-chenp-2004-correspondnece-others.pdf

2743-chenp-2004-correspondnece-po.pdf

2743-chenp-2004-description(complete) filed.pdf

2743-chenp-2004-description(complete) granted.pdf

2743-chenp-2004-form 1.pdf

2743-chenp-2004-form 26.pdf

2743-chenp-2004-form 3.pdf

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Patent Number

209393

Indian Patent Application Number

2743/CHENP/2004

PG Journal Number

38/2007

Publication Date

21-Sep-2007

Grant Date

28-Aug-2007

Date of Filing

03-Dec-2004

Name of Patentee

M/S. SYNGENTA PARTICIPATIONS AG

Applicant Address

Schwarzwaldallee 215, CH-4058 Basel

Inventors:

#	Inventor's Name	Inventor's Address
1	DUNNE Cheryl Lynn	Syngenta Crop Protection, Inc., VBRC, 7145 58th Avenue, Vero Beach, FL 32967
2	JOHNSON Michael Donald	Syngenta Crop Protection, Inc., 410 Swing Road, Greensboro, NC 27409
3	RAWLS Eric	Syngenta Crop Protection, Inc., VBRC, 7145 58th Avenue, Vero Beach, FL 32967

PCT International Classification Number

A01N 47/36

PCT International Application Number

PCT/EP2003/005857

PCT International Filing date

2003-06-04

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	942/02	2002-06-05	Switzerland