DE19530768A1 - Salts of N- (2-cyclopropylcarbonylphenylaminosulfonyl) -N '- (4,6-dimethoxy-2-pyrimidinyl) urea - Google Patents

Abstract

The invention relates to salts of N-(2-cyclopropylcarbonyl-phenylaminosulphonyl)-N'-(4,6-dimethoxy-2-pyr imidinyl)-urea (cyclosulphamurone) of the formula (I), a process for producing them and their use as herbicides. The salts of compound (I) are novel and have better technical properties than the basic compound (I).

Description

The invention relates to salts of N- (2-cyclopropylcarbonylphenylamino sulfonyl) -N ′ - (4,6-dimethoxy-2-pyrimidinyl) urea (cyclosulfamuron), a ver drive to their manufacture and their use as herbicides.

It is known that the compound N- (2-cyclopropylcarbonyl-phenylaminosulfonyl) - N '- (4,6-dimethoxy-2-pyrimidinyl) urea has herbicidal properties (cf. EP 463287 or US 5009699). However, the effect of this known compound is - especially because of the pH value of the application medium Hydrolysis reliability - not always entirely satisfactory. Salts of this compound were previously unknown.

Salts of N- (2-cyclopropylcarbonyl-phenylaminosulfonyl) - N ′ - (4,6-dimethoxy-2-pyrimidinyl) urea of the formula (I)

found; it was also found that the salts compared to the "free" Basic compound (I) possess superior technical properties.

The new salts of the compound of formula (I) are obtained if these ver bond (I) with bases, if appropriate in the presence of a diluent. Here, an acidic hydrogen atom in the compound (I) is replaced by an equivalent one of the cations formed from the base is replaced.

The new salts of N- (2-cyclopropylcarbonyl-phenylaminosulfonyl) -N ′ - (4,6-di methoxy-2-pyrimidinyl) urea of formula (I) are characterized by a consistently strong and selective herbicidal activity. With the new salts of N- (2-cyclopropylcarbonyl-phenylaminosulfonyl) -N ′ - (4,6-di methoxy-2-pyrimidinyl) urea of formula (I) can be more stable formulations than with the "free" compound of formula (I). The new salts of N- (2-cyclopropylcarbonyl-phenylaminosulfonyl) -N ′ - (4,6-dimethoxy- 2-pyrimidinyl) urea of the formula (I) are therefore a valuable addition to the State of the art.

The invention preferably relates to salts of the compound of the formula (I) Metals and with basic nitrogen compounds.

The invention particularly relates to salts of the compound of formula (I) with alkali metals such as As lithium, sodium, potassium, rubidium or cesium, very particularly with sodium or potassium, with alkaline earth metals, such as. As magnesium, calcium or Barium, especially with calcium, or with earth metals such as B. aluminum.

The invention further relates in particular to salts of the compound of the formula (I) with Ammonia, with C₁-C₆ alkyl amines, such as. B. with methylamine, ethylamine, n- or i-propylamine, n-, i-, s- or t-butylamine, n-, i-, s- or t-pentylamine, with di- (C₁-C₆-alkyl) - amines such as B. dimethylamine, diethylamine, dipropylamine, diisopropylamine, Dibutylamine, diisobuylamine, di-s-butylamine, dipentylamine, diisopentylamine, di-s- pentylamine and dihexylamine, with tri- (C₁-C₄-alkyl) amines, such as. B. trimethylamine,  Triethylamine, tripropylamine, tributylamine and N-ethyl-diisopropylamine, with C₃-C₆- Cycloalkyl amines, such as. B. cyclopentylamine or cyclohexylamine, with di- (C₃-C₆-cyclo alkyl) amines, such as. B. dicyclopentylamine or dicyclohexylamine, with N- (C₁- C₄-alkyl) - (C₃-C₆-cycloalkyl) amines, such as. B. N-methyl-cyclopentylamine, N-ethyl cyclopentylamine, N-methyl-cyclohexylamine or N-ethyl-cyclohexylamine, with N, N-di- (C₁-C₄-alkyl) - (C₃-C₆-cycloalkyl) amines, such as. B. N, N-dimethyl-cyclopentyl amine, N, N-diethyl-cyclopentylamine, N, N-dimethyl-cyclohexylamine or N, N-Di ethyl-cyclohexylamine, with N- (C₁-C₄-alkyl) -di (C₃-C₆-cycloalkyl) amines, such as e.g. B. N-methyl-dicyclopentylamine, N-ethyl-dicyclopentylamine, N-methyl-dicyclo hexylamine or N-ethyl-dicyclohexylamine, with phenyl-C₁-C₄-alkyl amines, such as. B. Benzylamine, 1-phenylethylamine or 2-phenylethylamine, with N- (C₁-C₄-alkyl) - (phenyl-C₁-C₄-alkyl) amines, such as. B. N-methyl-benzylamine or N-ethylbenzyl amine, or with N, N-di- (C₁-C₄-alkyl) - (phenyl-C₁-C₄-alkyl) amines, such as. B. N, N-Di methyl-benzylamine or N, N-diethyl-benzylamine, or with optionally fused and / or substituted by C₁-C₄-alkyl azines, such as. B. pyridine, Quinoline, 2-methyl-pyridine, 3-methyl-pyridine, 4-methyl-pyridine, 2,4-dimethyl-pyridine, 2,5-dimethyl-pyridine, 2,6-dimethyl-pyridine or 5-ethyl-2-methyl-pyridine.

As bases, which for the preparation of the salts of the compound of the invention Formula (I) that can be used are: Alkali metal or alkaline earth metal, acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates, such as sodium, potassium or Calcium acetate, lithium, sodium, potassium or calcium amide, sodium, potassium or Calcium carbonate, sodium, potassium or calcium hydrogen carbonate, lithium, Sodium, potassium or calcium hydride, lithium, sodium, potassium or calcium hydroxide, sodium or potassium methoxide, ethanolate, n- or i-propanolate, n-, i-, s- or t-butanolate.

The inventive method for the preparation of salts of the compound of Formula (I) is preferably carried out in the presence of a diluent. The usual inert organic diluents are generally used Solvent. These preferably include aliphatic, alicyclic and  aromatic, optionally halogenated hydrocarbons, such as Pentane, hexane, heptane, petroleum ether, ligroin, gasoline, benzene, toluene, xylene, chlorine benzene, dichlorobenzene, cyclohexane, methylcyclohexane, dichloromethane (methylene chloride), trichloromethane (chloroform) or carbon tetrachloride; Dialkyl ether, as in for example diethyl ether, diisopropyl ether, methyl t-butyl ether (MTBE), ethyl t-butyl ether, methyl t-pentyl ether (TAME), ethyl t-pentyl ether, tetrahydrofuran (THF), 1,4-dioxane, ethylene glycol dimethyl ether or diethyl ether, diethylene glycol dimethyl ether or diethyl ether; Dialkyl ketones such as acetone, butanone (Methyl ethyl ketone), methyl i-propyl ketone or methyl i-butyl ketone; Nitriles, as with for example acetonitrile, propionitrile, butyronitrile or benzonitrile; Amides, as with for example, N, N-dimethyl-formamide (DMF), N, N-dimethyl-acetamide, N-methyl formanilide, N-methyl-pyrrolidone or hexamethyl-phosphoric acid triamide; Esters, like for example methyl acetate, ethyl acetate, n- or i-propyl ester, -n-, -i- or -s-butyl ester; Sulfoxides such as dimethyl sulfoxide; Alkanols, such as as methanol, ethanol, n- or i-propanol, n-, i-, s- or t-butanol, ethylene glycol monomethyl ether or monoethyl ether, diethylene glycol monomethyl ether or -monoethyl ether.

The reaction temperatures can be carried out when carrying out the process according to the invention Process can be varied over a wide range. Generally you work at temperatures between 0 ° C and 100 ° C, preferably between 10 ° C and 50 ° C.

The process according to the invention is generally carried out under normal pressure leads. However, it is also possible to increase the process according to the invention or reduced pressure - generally between 0.1 bar and 10 bar to lead.

To carry out the process according to the invention, the starting materials in generally used in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess. The The reaction is generally carried out in a suitable diluent and the reaction mixture is generally required for several hours  stirred temperature. The workup is carried out using customary methods led (see the manufacturing examples).

The salts according to the invention can be used as defoliants, desiccants, and herbicides medium and in particular as a weed killer. Under Un Herb in the broadest sense is to be understood as all plants that grow up in places where they are undesirable. Whether the active substances according to the invention as total or selective Herbicides act essentially depends on the amount applied.

The active compounds according to the invention can, for. B. used in the following plants will:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Dicot cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, cucumis, cucurbita.

Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.  

However, the use of the active compounds according to the invention is by no means limited to these Limited genres, but extends in the same way to others Plants.

The compounds of the invention are suitable depending on the Concentration for total weed control e.g. B. on industrial and track systems and on paths and squares with and without tree cover. Likewise, the Compounds for weed control in permanent crops, e.g. B. forest, ornamental wood, Fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, Berry fruit and hop plants, on ornamental and sports turf and pastures and for selective weed control in annual crops.

The salts of compounds of formula (I) according to the invention are particularly suitable especially for the selective control of monocotyledon and dicotyledon weeds in monocot cultures, such as B. corn, rice and other cereals, both in Pre-emergence and post-emergence procedures.

The active ingredients can be converted into the usual formulations, such as Solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, sol Liche powder, granules, suspension emulsion concentrates, impregnated with active ingredient Natural and synthetic substances as well as very fine encapsulation in polymeric substances.

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients with extenders, i.e. liquid solvents and / or solid Carriers, if necessary using surface-active agents, that is Emulsifiers and / or dispersants and / or foaming agents.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as  Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable Oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as Acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar Solvents such as dimethylformamide and dimethyl sulfoxide, and water.

As solid carriers come into question: B. aminonium salts and natural Rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, Mont morillonite or diatomaceous earth and synthetic rock powder, such as highly disperse Silicic acid, aluminum oxide and silicates, come as solid carriers for granules in question: e.g. B. broken and fractionated natural rocks such as calcite, marble, Pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules made of organic material such as sawdust, Coconut shells, corn cobs and tobacco stems; as emulsifying and / or foam Generating funds are possible: z. B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkyl aryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as dispersants come into question: z. B. lignin sulfite and Methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospho lipids such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan and organic dyes such as alizarin, azo and metal phthalocyanine substances and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, Molybdenum and zinc can be used.  

The formulations generally contain between 0.1 and 95 percent by weight Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their formulations also used in a mixture with known herbicides for weed control find, where ready formulations or tank mixes are possible.

Known herbicides are suitable for the mixtures, for example anilides, such as e.g. B. Diflufenican and Propanil; Arylcarboxylic acids, such as. B. dichloropicolinic acid, Dicamba and picloram; Aryloxyalkanoic acids, such as. B. 2,4-D, 2,4-DB, 2,4-DP, Fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy-alkanoic acid esters, such as. B. Diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and Quizalofop-ethyl; Azinones, such as B. Chloridazon and Norflurazon; Carbamates like e.g. B. Chlorpropham, Desmedipham, Phenmedipham and Propham; Chloroacetanilides, such as As alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and Propachlor; Dinitroanilines such as e.g. B. Oryzalin, Pendimethalin and Trifluralin; Diphenyl ethers such as B. Acifluorfen, Bifenox, Fluoroglycofen, Fomesafen, Halosafen, Lactofen and oxyfluorfen; Ureas, such as B. chlorotoluron, diuron, fluometuron, Isoproturon, linuron and methabenzthiazuron; Hydroxylamines, such as. B. alloxydim, Clethodim, Cycloxydim, Sethoxydim and Tralkoxydim; Imidazolinones, e.g. B. Imazethapyr, imazamethabenz, imazapyr and imazaquin; Nitriles such as B. bromine oxynil, dichlobenil and ioxynil; Oxyacetamides such as e.g. B. Mefenacet; Sulfonyl ureas, such as B. amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorine sulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazo sulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; Thiel carbamates such as B. butylates, cycloates, dialallates, EPTC, Esprocarb, Molinate, Pro sulfocarb, thiobencarb and triallates, triazines, such as. B. atrazine, cyanazine, simazine, Simetryne, Terbutryne and Terbutylazin, Triazinone, such as. B. Hexazinon, Metamitron and metribuzin, others such as B. aminotriazole, benfuresate, bentazone, Cinmethylin, Clomazone, Clopyralid, Difenzoquat, Dithiopyr, Ethofumesate, Fluoro chloridones, glufosinates, glyphosates, isoxaben, pyndates, quinchlorac, quinmerac, Sulphosate and Tridiphane.  

A mixture with other known active ingredients, such as fungicides, Insecticides, acaricides, nematicides, bird repellants, plant nutrients substances and soil structure improvers are possible.

The active substances can be used as such, in the form of their formulations or in the form thereof application forms prepared by further dilution, such as ready-to-use Solutions, suspensions, emulsions, powders, pastes and granules are used will. The application is done in the usual way, e.g. B. by pouring, spraying, Spray, sprinkle.

The active compounds according to the invention can be used both before and after emergence of the plants are applied. They can also be planted in the soil before sowing be working.

The amount of active ingredient used can vary over a wide range. she depends essentially on the type of effect desired. In general the application rates are between 1 g and 10 kg of active ingredient per hectare of soil area, preferably between 5 g and 5 kg per ha.

The manufacture and use of the active compounds according to the invention are based on following examples.

Manufacturing examples example 1

Na salt of N- (2-cyclopropylcarbonyl-phenylaminosulfonyl) -N'- (4,6-dimethoxy-2-pyrimidinyl) urea (cyclosulfamuron) of the formula

0.40 g (10 mmol) sodium hydroxide (micro-pills or powder) are at room temperature (approx. 20 ° C) with stirring to a mixture of 4.2 g (10 mmol) N- (2- cyclopropylcarbonyl-phenylaminosulfonyl) -N ′ - (4,6-dimethoxy-2-pyrimid-inyl) added urea and 100 ml of methylene chloride and the reaction mixture is approx. Stirred for 18 hours at room temperature. Then the Irristallin accrued product isolated by suction.

4.1 g (92% of theory) of N- (2-cyclopropylcarbonylphenylamino) are obtained sulfonyl) -N ′ - (4,6-dimethoxy-2-pyrimidinyl) urea sodium salt of melting point 206 ° C.  

Examples of use Example A Pre-emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

Seeds of the test plants are sown in normal soil. After about 24 hours the soil is poured with the active ingredient preparation. You keep the water quantity per unit area expediently constant. The drug concentration in the preparation does not matter, only the application rate of the Active ingredient per unit area.

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
It means:
0% = no effect (like untreated control)
100% = total annihilation.

In this test, for example, shows the compound according to Production Example 1 strong action against weeds.  

Example B Post emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the specified amount of solvent, specifies the added amount of emulsifier and dilute the concentrate with water to the ge wanted concentration.

Test plants with a height of 5-15 cm are sprayed with the active substance preparation have so that the desired amounts of active ingredient per unit area be applied. The concentration of the spray liquor is chosen so that in 2000 l water / ha the desired amounts of active ingredient are applied.

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
It means:
0% = no effect (like untreated control)
100% = total annihilation.

This test shows, for example, the compound according to Preparation Example 1 very good tolerance to crops, such as. B. wheat, very strong Effect against weeds.

Claims (10)

1. Salts of N- (2-cyclopropylcarbonyl-phenylaminosulfonyl) -N '- (4,6-dimethoxy-2-pyrimidinyl) urea (cyclosulfamuron) of the formula 2. Salts of compound (I) according to claim 1 with metals or with basic Nitrogen compounds. 3. salts of the compound (I) according to claim 1 with alkali metals, Alkaline earth metals or earth metals. 4. Salts of the compound (1) according to claim 1 with sodium, potassium or Calcium. 5. N- (2-cyclopropylcarbonyl-phenylaininosulfonyl) -N '- (4,6-dimethoxy-2- pyrimidinyl) urea sodium salt according to claim 4. 6. Process for the preparation of salts of N- (2-cyclopropylcarbonyl-phenyl aminosulfonyl) -N ′ - (4,6-dimethoxy-2-pyrimidinyl) urea of the formula (I) according to claim 1, characterized in that the urea Formula (I) with bases, optionally in the presence of a diluent implements. 7. Herbicidal agents, characterized by a content of at least one salt des N- (2-cyclopropylcarbonyl-phenylaminosulfonyl) -N ′ - (4,6-dimetlioxy-2- pyrimidinyl) urea of the formula (I) according to Claim 1.   8. Use of salts of N- (2-cyclopropylcarbonyl-phenylaminosulfonyl) - N ′ - (4,6-dimethoxy-2-pyrimidinyl) urea of the formula (I) according to Claim 1 to combat unwanted plant growth. 9. A method of combating weeds, characterized in that salts of N- (2-cyclopropylcarbonyl-phenylaminosulfonyl) -N ′ - (4,6-di methoxy-2-pyrimidinyl) urea of formula (I) according to claim 1 on the Weeds or affect their habitat. 10. A process for the preparation of herbicidal compositions, characterized in that that one salts of N- (2-cyclopropylcarbonyl-phenylaminosulfonyl) -N '- (4,6-di methoxy-2-pyrimidinyl) urea of formula (1) according to claim 1 with Extenders and / or surfactants mixed.