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WO1995029167A1 - Substituted cyclopropylcarbonyl-phenylaminosulphonyl ureas as herbicides - Google Patents

Substituted cyclopropylcarbonyl-phenylaminosulphonyl ureas as herbicides Download PDF

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WO1995029167A1
WO1995029167A1 PCT/EP1995/001394 EP9501394W WO9529167A1 WO 1995029167 A1 WO1995029167 A1 WO 1995029167A1 EP 9501394 W EP9501394 W EP 9501394W WO 9529167 A1 WO9529167 A1 WO 9529167A1
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chlorine
alkoxy
halogen
fluorine
formula
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PCT/EP1995/001394
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German (de)
French (fr)
Inventor
Johannes-R. Jansen
Mark-Wilhelm Drewes
Hans-Jochem Riebel
Markus Dollinger
Hans-Joachim Santel
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Bayer Aktiengesellschaft
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Priority to AU24062/95A priority Critical patent/AU2406295A/en
Publication of WO1995029167A1 publication Critical patent/WO1995029167A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D521/00—Heterocyclic compounds containing unspecified hetero rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
    • C07C225/22—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • the invention relates to new substituted cyclopropylcarbonylphenylaminosulfonylureas, processes for their preparation and their use as herbicides.
  • N- (4,6-dimethoxypyrimidin-2-yl) -N , - (2-cyclopropylcarbonylphenylaminosulfonyl) urea can be used as a selective herbicide (cf. EP-A 463287 / US-P 5009699).
  • Some alkylcarbonylphenylaminosulfonylureas are known from older patent applications, but have not gained any importance (cf. EP-A 264467 / US-P 4622065).
  • R 1 represents hydrogen, halogen or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino or dialkylamino each having 1 to 4 carbon atoms in the individual alkyl groups, each substituted by halogen or C 1 -C 3 alkoxy,
  • R 2 represents hydrogen or halogen
  • R 3 represents halogen or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino or dialkylamino, each optionally substituted by halogen or C 1 -C 3 alkoxy, each having 1 to 4 carbon atoms in the individual alkyl groups
  • R 4 represents hydrogen, halogen , Formyl or represents in each case optionally substituted by halogen or C 1 -C 3 alkoxy alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl or alkoxycarbonyl each having 1 to 4 carbon atoms in the individual alkyl groups
  • R 4 represents hydrogen, halogen , Formyl or represents in each case optionally substituted by halogen or C 1 -C 3 alkoxy alkyl, alkoxy, alkylthio, alky
  • R 5 represents cyclopropyl optionally substituted by halogen or C 1 -C 4 alkyl, and salts of the compounds of the formula (I) have been found, the compound being N- (4,6-dimethoxy-pyrimidin-2-yl) -N , - (2-Cyclopropylcarbonyl-phenylaminosulfonyl) urea (known from EP-A 463287 / US-P 5009699) is excluded by disclaimer.
  • the new substituted cyclopropylcarbonylphenylaminosulfonylureas of the general formula (I) or their salts are obtained if aminopyrimidines of the general formula (II)
  • R 1 , R 2 and R 3 have the meaning given above, with anilines of the general formula (IV)
  • R 4 and R 5 have the meaning given above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and if appropriate converting the compounds of the formula (I) thus obtained into salts by customary methods.
  • Another possible production method for the compounds of formula (I) according to the invention is outlined below, where R 1 , R 2 , R 3 , R 4 and R 5 have the meaning given above and R for alkyl (in particular for methyl or ethyl), aralkyl (in particular benzyl) or aryl (in particular phenyl):
  • the new substituted cyclopropylcarbonylphenylaminosulfonylureas of the general formula (I) are notable for their strong and selective herbicidal activity.
  • the new compounds of the formula (I) in some cases better tolerated by crop plants, have a considerably stronger herbicidal action than the structurally similar known compound N- (4,6-dimethoxypyrimidin-2-yl) -N '- (2-cyclopropylcarbonyl-phenylaminosulfonyl) -urea.
  • the invention preferably relates to compounds of the formula (I) in which
  • R 1 represents hydrogen, fluorine, chlorine, bromine or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino or dialkylamino, each optionally substituted by fluorine, chlorine, methoxy or ethoxy, each having 1 to 3 carbon atoms in the individual alkyl groups
  • R 2 represents hydrogen, fluorine, chlorine or bromine
  • R 3 represents fluorine, chlorine, bromine or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino or dialkylamino each having 1 to 3 carbon atoms in the individual alkyl groups, each substituted by fluorine, chlorine, methoxy or ethoxy
  • R 4 represents hydrogen, fluorine, chlorine, bromine, formyl or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl or alkoxycarbonyl, each optionally substituted by fluorine, chlorine, methoxy or ethoxy, each having 1 to 3 carbon atoms in the individual alkyl groups
  • R 5 represents cyclopropyl which is optionally substituted by fluorine, chlorine, methyl or ethyl, with the exception of the compound N- (4,6-dimethoxypyrimidin-2-yl)
  • the invention further preferably relates to sodium, potassium, magnesium, calcium, ammonium, C 1 -C 4 alkyl ammonium, di (C 1 -C 4 alkyl) ammonium, tri ( C 1 -C 4 alkyl) ammonium, C 5 - or C 6 cycloalkyl ammonium and di (C 1 -C 2 alkyl) benzyl ammonium salts of compounds of the formula (I), in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings preferably given above.
  • the invention relates in particular to compounds of the formula (I) in which
  • R 1 represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino,
  • R 2 represents hydrogen
  • R 3 represents chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino,
  • R 4 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, acetyl or methoxycarbonyl
  • R 5 represents cyclopropyl, with the exception of the compound N- (4,6-dimethoxy-pyrimidin-2-yl) -N '- (2-cyclopropylcarbonyl-phenylaminosulfonyl) urea, which was excluded by disclaimer above.
  • Very particularly preferred groups of compounds of the formula (I) are the compounds of the formulas (IA) and (IB)
  • R 1 , R 2 and R 3 have the meaning given above as being particularly preferred
  • R 4 represents fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, acetyl or methoxycarbonyl, and
  • R 5 represents cyclopropyl.
  • the general or preferred radical definitions given above apply both to the end products of the formula (I) and correspondingly to the starting materials or intermediates required in each case for the preparation.
  • radical definitions can be combined with one another as desired, that is to say also between the specified ranges of preferred compounds.
  • the hydrocarbon radicals mentioned in the radical definitions, such as alkyl, also in combinations with heteroatoms, such as in alkoxy, alkylthio or alkylamino, are straight-chain or branched, even if this is not expressly stated.
  • Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
  • aminopyrimidines of the formula (II) to be used as starting materials in the process according to the invention are known synthetic chemicals, some of which are commercially available.
  • A represents halogen, formyl or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl or alkoxycarbonyl each having 1 to 4 carbon atoms in the individual alkyl groups and optionally substituted by halogen or C 1 -C 3 -alkoxy.
  • A preferably represents fluorine, chlorine, bromine, formyl or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl or alkoxycarbonyl, each optionally substituted by fluorine, chlorine, methoxy or ethoxy, each having 1 to 3 carbon atoms in the individual alkyl groups; especially for fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, acetyl or methoxycarbonyl.
  • R 5 has the meaning given above, in the presence of a reaction auxiliary, such as, for example, boron (III) chloride and / or aluminum (III) chloride, and optionally in the presence of a diluent, such as, for example, dichloroethane, at temperatures between -20 ° C. and + 100 ° C (see the manufacturing examples).
  • a reaction auxiliary such as, for example, boron (III) chloride and / or aluminum (III) chloride
  • a diluent such as, for example, dichloroethane
  • diluents Practically all inert organic solvents can be used as diluents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl - And dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl and methyl iso-butyl ketone, esters
  • Acid acceptors which can be used in the process according to the invention are all acid binders which can customarily be used for such reactions.
  • Alkali metal hydroxides such as, for example, sodium and potassium hydroxide, alkaline earth metal hydroxides such as, for example, calcium hydroxide, alkali metal carbonates and alcoholates such as sodium and potassium carbonate, such as sodium and potassium tert-butoxide, and also aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, Dimethylaniline, dimethylbenzylamine, pyridine, 1,5-diazabicyclo [4,3,0] non-5-ene (DBN), 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU) and 1,4-diazabicyclo- [2,2,2] octane (DABCO).
  • DBN 1,5-diazabicyclo [4,3,0] non-5-ene
  • DBU 1,8-diazabic
  • reaction temperatures can be varied within a wide range in the process according to the invention. In general, temperatures between -30 ° C and + 80 ° C, preferably at temperatures between -10 ° C and + 60 ° C.
  • the process according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
  • the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in each case in a larger excess.
  • the reactions are generally carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the temperature required in each case.
  • Working up in the process according to the invention is carried out in each case by customary methods (cf. the preparation examples).
  • salts can be prepared from the compounds of the general formula (I) according to the invention.
  • Such salts are obtained in a simple manner by customary salt formation methods, for example by dissolving or dispersing a compound of the formula (I) in a suitable solvent, e.g. Methylene chloride, acetone, tert-butyl methyl ether or toluene, and addition of a suitable base.
  • a suitable solvent e.g. Methylene chloride, acetone, tert-butyl methyl ether or toluene
  • the salts can then be isolated - if appropriate after prolonged stirring - by concentration or suction.
  • the active compounds according to the invention can be used, for example, in the following plants: 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.
  • the compounds are suitable for total weed control, e.g. on industrial and track systems and on paths and squares with and without tree cover.
  • the compounds for weed control in permanent crops e.g. 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 pasture land and for selective purposes Weed control can be used in annual crops.
  • the compounds of formula (I) according to the invention are particularly suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops both in the pre-emergence and in the post-emergence process.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances.
  • These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents.
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride
  • aliphatic hydrocarbons such as cyclohexane or paraffins, for example 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.
  • Possible solid carriers are: e.g. Ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silicic acid, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g.
  • nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
  • Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate and natural phospholipi, can be used in the formulations de, such as cephalins and lecithins and synthetic phospholipids.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes 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 of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be used for combating weeds, in a mixture with known herbicides, finished formulations or tank mixes being possible.
  • herbicides are suitable for the mixtures, for example anilides, such as, for example, diflufenican and propanil; Aryl carboxylic acids such as dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids such as 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy-alkanoic acid esters, such as, for example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofopethyl; Azinones such as chloridazon and norflurazon; Carbamates such as chlorpropham, desmedipham, phenmedipham and propham; Chloroacetanilides such as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; Di
  • a mixture with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.
  • the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, sprinkling.
  • the active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing.
  • the amount of active ingredient used can vary over a wide range. It essentially depends 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, preferably between 5 g and 2 kg per ha.
  • Example (IV-1) the compounds of the formula (IV) listed in Table 2 below can also be prepared, for example.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, mix 1 part by weight of active compound with the stated amount of solvent, add the stated amount of emulsifier and dilute the concentrate with water to the desired concentration.
  • Test plants with a height of 5 - 15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area.
  • the concentration of the spray liquor is chosen so that the desired amounts of active compound are applied in 2000 l of water / ha.
  • the degree of damage to the plants is rated in% damage compared to the development of the untreated control. It means:
  • the compound according to Preparation Example 3 shows very good tolerance to crop plants, such as Beets, considerably stronger activity against weeds than the known compound (A) (see Table A-1).
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, mix 1 part by weight of active compound with the stated amount of solvent, add the stated amount of emulsifier and dilute the concentrate with water to the desired concentration.
  • Seeds of the test plants are sown in normal soil. After 24 hours, the active ingredient preparation is poured onto the floor. The amount of water per unit area is expediently kept constant. The concentration of active substance in the preparation is irrelevant, the only decisive factor is the amount of active substance applied 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:
  • the compound according to Preparation Example 6 shows very good tolerance to crop plants, such as Cotton, considerably more effective against weeds than the known compound (A) (see Table B-1).

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Abstract

The invention relates to novel substituted cyclopropylcarbonyl-phenylaminosulphonyl ureas of formula (I) in which the constituents R?1, R2, R3 and R4¿ have the meanings given in the description and R5 is optionally halogen or C¿1?-C4 alkyl-substituted cyclopropyl, and salts of the compounds of formula (I), excepting the compound N-(4,6-dimethoxy pyrimidine-2-yl)-N'-(2-cyclopropylcarbonyl-phenylaminosulphonyl) urea, and processes for producing the novel compounds and their use as herbicides.

Description

SUBSTITUIERTE CYCLOPROPYLCARBONYL-PHENYLAMINOSULFONYL-HARNSTOFFE ALS HERBIZIDE Die Erfindung betrifft neue substituierte Cyclopropylcarbonyl-phenylaminosulfonylharnstoffe, Verfahren zu ihrer Herstellung und ihre Verwendung als Herbizide. SUBSTITUTED CYCLOPROPYLCARBONYL-PHENYLAMINOSULFONYL UREAS AS HERBICIDES The invention relates to new substituted cyclopropylcarbonylphenylaminosulfonylureas, processes for their preparation and their use as herbicides.
Es ist bekannt, daß die Verbindung N-(4,6-Dimethoxy-pyrimidin-2-yl)-N,-(2-cyclopropylcarbonyl-phenylaminosulfonyl)-harnstoff, als selektives Herbizid eingesetzt werden kann (vgl. EP-A 463287 / US-P 5009699). Einige Alkylcarbonylphenylaminosulfonylharnstoffe sind aus älteren Patentanmeldungen bekannt, haben jedoch keine Bedeutung erlangt (vgl. EP-A 264467 / US-P 4622065). It is known that the compound N- (4,6-dimethoxypyrimidin-2-yl) -N , - (2-cyclopropylcarbonylphenylaminosulfonyl) urea can be used as a selective herbicide (cf. EP-A 463287 / US-P 5009699). Some alkylcarbonylphenylaminosulfonylureas are known from older patent applications, but have not gained any importance (cf. EP-A 264467 / US-P 4622065).
Es wurden nun die neuen substituierten Cyclopropylcarbonyl-phenylaminosulfonylharnstoffe der allgemeinen Formel (I)  The new substituted cyclopropylcarbonylphenylaminosulfonylureas of the general formula (I)
Figure imgf000003_0001
in welcher
Figure imgf000003_0001
in which
R1 für Wasserstoff, Halogen oder für jeweils gegebenenfalls durch Halogen oder C1-C3-Alkoxy substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylamino oder Dialkylamino mit jeweils 1 bis 4 Kohlenstoffatomen in den einzelnen Alkylgruppen steht, R 1 represents hydrogen, halogen or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino or dialkylamino each having 1 to 4 carbon atoms in the individual alkyl groups, each substituted by halogen or C 1 -C 3 alkoxy,
R2 für Wasserstoff oder Halogen steht, R3 für Halogen oder für jeweils gegebenenfalls durch Halogen oder C1-C3-Alkoxy substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylamino oder Dialkylamino mit jeweils 1 bis 4 Kohlenstoffatomen in den einzelnen Alkylgruppen steht, R4 für Wasserstoff, Halogen, Formyl oder für jeweils gegebenenfalls durch Halogen oder C1-C3-Alkoxy substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylcarbonyl oder Alkoxycarbonyl mit jeweils 1 bis 4 Kohlenstoffatomen in den einzelnen Alkylgruppen steht, und R 2 represents hydrogen or halogen, R 3 represents halogen or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino or dialkylamino, each optionally substituted by halogen or C 1 -C 3 alkoxy, each having 1 to 4 carbon atoms in the individual alkyl groups, R 4 represents hydrogen, halogen , Formyl or represents in each case optionally substituted by halogen or C 1 -C 3 alkoxy alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl or alkoxycarbonyl each having 1 to 4 carbon atoms in the individual alkyl groups, and
R5 für gegebenenfalls durch Halogen oder C1-C4-Alkyl substituiertes Cyclopropyl steht, sowie Salze der Verbindungen der Formel (I) gefunden, wobei die Verbindung N-(4,6-Dimethoxy-pyrimidin-2-yl)-N,-(2-cyclopropylcarbonyl-phenylaminosulfonyl)-harnstoff (bekannt aus EP-A 463287 / US-P 5009699) durch Disclaimer ausgenommen ist. Man erhält die neuen substituierten Cyclopropylcarbonyl-phenylaminosulfonyl- harnstoffe der allgemeinen Formel (I) bzw. deren Salze, wenn man Aminopyrimidine der allgemeinen Formel (II) R 5 represents cyclopropyl optionally substituted by halogen or C 1 -C 4 alkyl, and salts of the compounds of the formula (I) have been found, the compound being N- (4,6-dimethoxy-pyrimidin-2-yl) -N , - (2-Cyclopropylcarbonyl-phenylaminosulfonyl) urea (known from EP-A 463287 / US-P 5009699) is excluded by disclaimer. The new substituted cyclopropylcarbonylphenylaminosulfonylureas of the general formula (I) or their salts are obtained if aminopyrimidines of the general formula (II)
Figure imgf000004_0001
Figure imgf000004_0001
in welcher in which
R1, R2 und R3 die oben angegebene Bedeutung haben, mit Chlorsulfonylisocyanat (Cl-SO2-N=C=O), gegebenenfalls in Gegenwart eines Verdünnungsmittels, umsetzt und die hierbei gebildeten Chlorsulfonylharnstoffe der allgemeinen Formel (III)
Figure imgf000005_0002
R 1 , R 2 and R 3 have the meaning given above, with chlorosulfonyl isocyanate (Cl-SO 2 -N = C = O), if appropriate in the presence of a diluent, and the chlorosulfonylureas of the general formula (III) formed
Figure imgf000005_0002
in welcher in which
R1, R2 und R3 die oben angegebene Bedeutung haben, mit Anilinen der allgemeinen Formel (IV) R 1 , R 2 and R 3 have the meaning given above, with anilines of the general formula (IV)
Figure imgf000005_0001
Figure imgf000005_0001
in welcher in which
R4 und R5 die oben angegebene Bedeutung haben, gegebenenfalls in Gegenwart eines Säureakzeptors und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt und gegebenenfalls die so erhaltenen Verbindungen der Formel (I) nach üblichen Methoden in Salze überführt. Eine weitere mögliche Herstellungsmethode für die erfindungsgemäßen Verbindungen der Formel (I) ist nachstehend skizziert, wobei R1, R2, R3, R4 und R5 die oben angegebene Bedeutung haben und R für Alkyl (insbesondere für Methyl oder Ethyl), Aralkyl (insbesondere Benzyl) oder Aryl (insbesondere Phenyl) steht: R 4 and R 5 have the meaning given above, if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent, and if appropriate converting the compounds of the formula (I) thus obtained into salts by customary methods. Another possible production method for the compounds of formula (I) according to the invention is outlined below, where R 1 , R 2 , R 3 , R 4 and R 5 have the meaning given above and R for alkyl (in particular for methyl or ethyl), aralkyl (in particular benzyl) or aryl (in particular phenyl):
Figure imgf000006_0001
Figure imgf000006_0001
Figure imgf000006_0002
Figure imgf000006_0002
Die neuen substituierten Cyclopropylcarbonyl-phenylaminosulfonyl-harnstoffe der allgemeinen Formel (I) zeichnen sich durch starke und selektive herbizide Wirksamkeit aus. Überraschenderweise zeigen die neuen Verbindungen der Formel (I) bei teilweise besserer Verträglichkeit gegenüber Kulturpflanzen erheblich stärkere herbizide Wirkung als die strukturell ähnliche bekannte Verbindung N-(4,6-Dimethoxypyrimidin-2-yl)-N'-(2-cyclopropylcarbonyl-phenylaminosulfonyl)-harnstoff.  The new substituted cyclopropylcarbonylphenylaminosulfonylureas of the general formula (I) are notable for their strong and selective herbicidal activity. Surprisingly, the new compounds of the formula (I), in some cases better tolerated by crop plants, have a considerably stronger herbicidal action than the structurally similar known compound N- (4,6-dimethoxypyrimidin-2-yl) -N '- (2-cyclopropylcarbonyl-phenylaminosulfonyl) -urea.
Gegenstand der Erfindung sind vorzugsweise Verbindungen der Formel (I), in welcher The invention preferably relates to compounds of the formula (I) in which
R1 für Wasserstoff, Fluor, Chlor, Brom oder für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy oder Ethoxy substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylamino oder Dialkylamino mit jeweils 1 bis 3 Kohlenstoffatomen in den einzelnen Alkylgruppen steht, R2 für Wasserstoff, Fluor, Chlor oder Brom steht, R 1 represents hydrogen, fluorine, chlorine, bromine or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino or dialkylamino, each optionally substituted by fluorine, chlorine, methoxy or ethoxy, each having 1 to 3 carbon atoms in the individual alkyl groups, R 2 represents hydrogen, fluorine, chlorine or bromine,
R3 für Fluor, Chlor, Brom oder für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy oder Ethoxy substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylamino oder Dialkylamino mit jeweils 1 bis 3 Kohlenstoffatomen in den einzelnen Alkylgruppen steht, R4 für Wasserstoff, Fluor, Chlor, Brom, Formyl oder für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy oder Ethoxy substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylcarbonyl oder Alkoxycarbonyl mit jeweils 1 bis 3 Kohlenstoffatomen in den einzelnen Alkylgruppen steht, und R5 für gegebenenfalls durch Fluor, Chlor, Methyl oder Ethyl substituiertes Cyclopropyl steht, mit Ausnahme der oben durch Disclaimer ausgenommenen Verbindung N-(4,6- Dimethoxy-pyrimidin-2-yl)-N'-(2-cyclopropylcarbonyl-phenylaminosulfonyl)-harnstoff. Gegenstand der Erfindung sind weiter vorzugsweise Natrium-, Kalium-, Magnesium-, Calcium-, Ammonium-, C1-C4-Alkyl-ammonium-, Di-(C1-C4-alkyl)-ammonium-, Tri-(C1-C4-alkyl)-ammonium-, C5- oder C6-Cycloalkyl-ammonium- und Di-(C1-C2-alkyl)-benzyl-ammonium-Salze von Verbindungen der Formel (I), in welcher R1, R2, R3, R4 und R5 die oben vorzugsweise angegebenen Bedeutungen haben. Gegenstand der Erfindung sind insbesondere Verbindungen der Formel (I), in welcher R 3 represents fluorine, chlorine, bromine or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino or dialkylamino each having 1 to 3 carbon atoms in the individual alkyl groups, each substituted by fluorine, chlorine, methoxy or ethoxy, R 4 represents hydrogen, fluorine, chlorine, bromine, formyl or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl or alkoxycarbonyl, each optionally substituted by fluorine, chlorine, methoxy or ethoxy, each having 1 to 3 carbon atoms in the individual alkyl groups, and R 5 represents cyclopropyl which is optionally substituted by fluorine, chlorine, methyl or ethyl, with the exception of the compound N- (4,6-dimethoxypyrimidin-2-yl) -N '- (2-cyclopropylcarbonylphenylaminosulfonyl) which has been excluded by disclaimer above )-urea. The invention further preferably relates to sodium, potassium, magnesium, calcium, ammonium, C 1 -C 4 alkyl ammonium, di (C 1 -C 4 alkyl) ammonium, tri ( C 1 -C 4 alkyl) ammonium, C 5 - or C 6 cycloalkyl ammonium and di (C 1 -C 2 alkyl) benzyl ammonium salts of compounds of the formula (I), in which R 1 , R 2 , R 3 , R 4 and R 5 have the meanings preferably given above. The invention relates in particular to compounds of the formula (I) in which
R1 für Wasserstoff, Chlor, Methyl, Ethyl, Trifluormethyl, Methoxy, Ethoxy, Difluormethoxy, Methylthio, Ethylthio, Methylamino, Ethylamino oder Dimethylamino steht, R 1 represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino,
R2 für Wasserstoff steht, R3 für Chlor, Methyl, Ethyl, Trifluormethyl, Methoxy, Ethoxy, Difluormethoxy, Methylthio, Ethylthio, Methylamino, Ethylamino oder Dimethylamino steht, R 2 represents hydrogen, R 3 represents chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino,
R4 für Wasserstoff, Fluor, Chlor, Brom, Methyl, Ethyl, n- oder i-Propyl, Trifluormethyl, Methoxy, Methylthio, Methylsulfinyl, Methylsulfonyl, Acetyl oder Methoxycarbonyl steht, und R5 für Cyclopropyl steht, mit Ausnahme der oben durch Disclaimer ausgenommenen Verbindung N-(4,6- Dimethoxy-pyrimidin-2-yl)-N'-(2-cyclopropylcarbonyl-phenylaminosulfonyl)-harnstoff. R 4 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, acetyl or methoxycarbonyl, and R 5 represents cyclopropyl, with the exception of the compound N- (4,6-dimethoxy-pyrimidin-2-yl) -N '- (2-cyclopropylcarbonyl-phenylaminosulfonyl) urea, which was excluded by disclaimer above.
Ganz besonders bevorzugte Gruppen von Verbindungen der Formel (I) sind die Verbindungen der Formeln (IA) und (IB) Very particularly preferred groups of compounds of the formula (I) are the compounds of the formulas (IA) and (IB)
Figure imgf000008_0001
Figure imgf000008_0002
Figure imgf000008_0001
Figure imgf000008_0002
in welchen jeweils R1, R2 und R3 die oben als insbesondere bevorzugt angegebene Bedeutung haben, in which in each case R 1 , R 2 and R 3 have the meaning given above as being particularly preferred,
R4 für Fluor, Chlor, Brom, Methyl, Ethyl, n- oder i-Propyl, Trifluormethyl, Methoxy, Methylthio, Methylsulfinyl, Methylsulfonyl, Acetyl oder Methoxycarbonyl steht, und R 4 represents fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, acetyl or methoxycarbonyl, and
R5 für Cyclopropyl steht. Die oben aufgeführten allgemeinen oder in Vorzugsbereichen angegebenen Restedefinitionen gelten sowohl für die Endprodukte der Formel (I) als auch entsprechend für die jeweils zu Herstellung benötigten Ausgangsstoffe bzw. Zwischenprodukte. R 5 represents cyclopropyl. The general or preferred radical definitions given above apply both to the end products of the formula (I) and correspondingly to the starting materials or intermediates required in each case for the preparation.
Diese Restedefinitionen können untereinander, also auch zwischen den angegebenen Bereichen bevorzugter Verbindungen, beliebig kombiniert werden. Die bei den Restedefinitionen genannten Kohlenwasserstofifreste, wie Alkyl, auch in Kombinationen mit Heteroatomen, wie in Alkoxy, Alkylthio oder Alkylamino, sind auch dann, wenn dies nicht ausdrücklich angegeben ist, geradkettig oder verzweigt. These radical definitions can be combined with one another as desired, that is to say also between the specified ranges of preferred compounds. The hydrocarbon radicals mentioned in the radical definitions, such as alkyl, also in combinations with heteroatoms, such as in alkoxy, alkylthio or alkylamino, are straight-chain or branched, even if this is not expressly stated.
Halogen steht im allgemeinen für Fluor, Chlor, Brom oder Iod, vorzugsweise für Fluor, Chlor oder Brom, insbesondere für Fluor oder Chlor. Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
Verwendet man beispielsweise 4-Chlor-6-methoxy-2-amino-pyrimidin, Chlorsulfonylisocyanat und 2-Cyclopropylcarbonyl-6-fluor-anilin als Ausgangsstoffe, so kann der Reaktionsablauf beim erfindungsgemäßen Verfahren durch das folgende Formelschema skizziert werden: If, for example, 4-chloro-6-methoxy-2-aminopyrimidine, chlorosulfonyl isocyanate and 2-cyclopropylcarbonyl-6-fluoro-aniline are used as starting materials, the course of the reaction in the process according to the invention can be outlined using the following formula:
Figure imgf000009_0001
Figure imgf000009_0001
Die beim erfindungsgemäßen Verfahren als Ausgangsstoffe zu verwendenden Aminopyrimidine der Formel (II) sind bekannte, zum Teil im Handel erhältliche Synthesechemikalien.  The aminopyrimidines of the formula (II) to be used as starting materials in the process according to the invention are known synthetic chemicals, some of which are commercially available.
Die weiter als Ausgangsstoffe benötigten Aniline der Formel (IV) sind teilweise bekannt (vgl. US-P 5009699). Some of the anilines of the formula (IV) required as starting materials are known (cf. US Pat. No. 5009699).
Noch nicht aus der Literatur bekannt und als neue Stoffe ebenfalls Gegenstand der vorliegenden Anmeldung sind die Aniline der allgemeinen Formel (IVa)
Figure imgf000010_0002
Not yet known from the literature and the subject of the present application as new substances are the anilines of the general formula (IVa)
Figure imgf000010_0002
in welcher in which
A für Halogen, Formyl oder für jeweils gegebenenfalls durch Halogen oder C1- C3-Alkoxy substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylcarbonyl oder Alkoxycarbonyl mit jeweils 1 bis 4 Kohlenstoffatomen in den einzelnen Alkylgruppen steht. A represents halogen, formyl or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl or alkoxycarbonyl each having 1 to 4 carbon atoms in the individual alkyl groups and optionally substituted by halogen or C 1 -C 3 -alkoxy.
In der Formel (IVa) steht A vorzugsweise für Fluor, Chlor, Brom, Formyl oder für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy oder Ethoxy substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylcarbonyl oder Alkoxycarbonyl mit jeweils 1 bis 3 Kohlenstofifatomen in den einzelnen Alkylgruppen; insbesondere für Fluor, Chlor, Brom, Methyl, Trifluormethyl, Methoxy, Methylthio, Methylsulfinyl, Methylsulfonyl, Acetyl oder Methoxycarbonyl. In the formula (IVa), A preferably represents fluorine, chlorine, bromine, formyl or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl or alkoxycarbonyl, each optionally substituted by fluorine, chlorine, methoxy or ethoxy, each having 1 to 3 carbon atoms in the individual alkyl groups; especially for fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, acetyl or methoxycarbonyl.
Man erhält die neuen Aniline der Formel (IVa), wenn man entsprechende Anilin-derivate der allgemeinen Formel (V)
Figure imgf000010_0001
The new anilines of the formula (IVa) are obtained if corresponding aniline derivatives of the general formula (V)
Figure imgf000010_0001
in welcher A die oben angegebene Bedeutung hat, mit Nitrilen der allgemeinen Formel (VI) in which A has the meaning given above, with nitriles of the general formula (VI)
R5-CN (VI) in welcher R 5 -CN (VI) in which
R5 die oben angegebene Bedeutung hat, in Gegenwart eines Reaktionshilfsmittels, wie z.B. Bor(III)-chlorid und/oder Aluminium(III)-chlorid, und gegebenenfalls in Gegenwart eines Verdünnungsmittels, wie z.B. Dichlorethan, bei Temperaturen zwischen -20°C und +100°C umsetzt (vgl. die Herstellungsbeispiele). Die Ausgangsstoffe der Formeln (V) und (VI) sind bekannt. R 5 has the meaning given above, in the presence of a reaction auxiliary, such as, for example, boron (III) chloride and / or aluminum (III) chloride, and optionally in the presence of a diluent, such as, for example, dichloroethane, at temperatures between -20 ° C. and + 100 ° C (see the manufacturing examples). The starting materials of the formulas (V) and (VI) are known.
Das erfindungsgemäße Verfahren zur Herstellung der neuen Verbindungen der Formel (I) wird vorzugsweise unter Verwendung von Verdünnungsmitteln durchgeführt. Als Verdünnungsmittel kommen dabei praktisch alle inerten organischen Lösungsmittel infrage. Hierzu gehören vorzugsweise aliphatische und aromatische, gegebenenfalls halogenierte Kohlenwasserstoffe wie Pentan, Hexan, Heptan, Cyclohexan, Petrol-ether, Benzin, Ligroin, Benzol, Toluol, Xylol, Methylenchlorid, Ethylenchlorid, Chloroform, Tetrachlormethan, Chlorbenzol und o-Dichlorbenzol, Ether wie Diethyl- und Dibutylether, Glykoldimethylether und Diglykoldimethylether, Tetrahydrofuran und Dioxan, Ketone wie Aceton, Methyl-ethyl-, Methyl-isopropyl- und Methyl-iso-butyl-keton, Ester wie Essigsäuremethylester und -ethylester, Nitrile wie z.B. Aceto-nitril und Propionitril, Amide wie z.B. Dimethylformamid, Dimethylacetamid und N-Methylpyrrolidon sowie Dimethylsulfoxid, Tetramethylensulfon und Hexamethylphosphorsäuretriamid. The process according to the invention for the preparation of the new compounds of the formula (I) is preferably carried out using diluents. Practically all inert organic solvents can be used as diluents. These preferably include aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers such as diethyl - And dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, methyl ethyl, methyl isopropyl and methyl iso-butyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as Aceto-nitrile and propionitrile, amides such as e.g. Dimethylformamide, dimethylacetamide and N-methylpyrrolidone as well as dimethyl sulfoxide, tetramethylene sulfone and hexamethylphosphoric acid triamide.
Als Säureakzeptoren können bei dem erfindungsgemäßen Verfahren alle üblicherweise für derartige Umsetzungen verwendbaren Säurebindemittel eingesetzt werden. Vorzugsweise kommen Alkalimetallhydroxide wie z.B. Natrium- und Kaliumhydroxid, Erdalkalihydroxide wie z.B. Calciumhydroxid, Alkalicarbonate und -alkoholate wie Natrium- und Kalium-carbonat, wie Natrium- und Kalium-tert-butylat, ferner aliphatische, aromatische oder heterocyclische Amine, beispielsweise Triethylamin, Trimethylamin, Dimethylanilin, Dimethylbenzylamin, Pyridin, 1,5-Diazabicyclo[4,3,0]-non-5-en (DBN), 1,8-Diazabicyclo-[5,4,0]-undec-7-en (DBU) und 1,4-Diazabicyclo-[2,2,2]-octan (DABCO) in Betracht. Die Reaktionstemperaturen können bei dem erfindungsgemäßen Verfahren in einem größeren Bereich variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen -30°C und +80°C, vorzugsweise bei Temperaturen zwischen -10°C und +60°C. Das erfindungsgemäße Verfahren wird im allgemeinen unter Normaldruck durchgeführt. Es ist jedoch auch möglich, unter erhöhtem oder vermindertem Druck zu arbeiten. Acid acceptors which can be used in the process according to the invention are all acid binders which can customarily be used for such reactions. Alkali metal hydroxides such as, for example, sodium and potassium hydroxide, alkaline earth metal hydroxides such as, for example, calcium hydroxide, alkali metal carbonates and alcoholates such as sodium and potassium carbonate, such as sodium and potassium tert-butoxide, and also aliphatic, aromatic or heterocyclic amines, for example triethylamine, trimethylamine, Dimethylaniline, dimethylbenzylamine, pyridine, 1,5-diazabicyclo [4,3,0] non-5-ene (DBN), 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU) and 1,4-diazabicyclo- [2,2,2] octane (DABCO). The reaction temperatures can be varied within a wide range in the process according to the invention. In general, temperatures between -30 ° C and + 80 ° C, preferably at temperatures between -10 ° C and + 60 ° C. The process according to the invention is generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure.
Zur Durchführung des erfindungsgemäßen Verfahrens werden die jeweils benötigten Ausgangsstoffe im allgemeinen in angenähert äquimolaren Mengen eingesetzt. Es ist jedoch auch möglich, eine der beiden jeweils eingesetzten Komponenten in einem größeren Überschuß zu verwenden. Die Reaktionen werden im allgemeinen in einem geeigneten Verdünnungsmittel in Gegenwart eines Säureakzeptors durchgeführt, und das Reaktionsgemisch wird mehrere Stunden bei der jeweils erforderlichen Temperatur gerührt. Die Aufarbeitung erfolgt bei dem erfindungsgemäßen Verfahren jeweils nach üblichen Methoden (vgl. die Herstellungsbeispiele). To carry out the process according to the invention, the starting materials required in each case are generally used in approximately equimolar amounts. However, it is also possible to use one of the two components used in each case in a larger excess. The reactions are generally carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for several hours at the temperature required in each case. Working up in the process according to the invention is carried out in each case by customary methods (cf. the preparation examples).
Aus den erfindungsgemäßen Verbindungen der allgemeinen Formel (I) können gegebenenfalls Salze hergestellt werden. Man erhält solche Salze in einfacher Weise nach üblichen Salzbildungsmethoden, beispielsweise durch Lösen oder Dispergieren einer Verbindung der Formel (I) in einem geeigneten Lösungsmittel, wie z.B. Methylen-chlorid, Aceton, tert-Butyl-methylether oder Toluol, und Zugabe einer geeigneten Base. Die Salze können dann - gegebenenfalls nach längerem Rühren - durch Einengen oder Absaugen isoliert werden. If appropriate, salts can be prepared from the compounds of the general formula (I) according to the invention. Such salts are obtained in a simple manner by customary salt formation methods, for example by dissolving or dispersing a compound of the formula (I) in a suitable solvent, e.g. Methylene chloride, acetone, tert-butyl methyl ether or toluene, and addition of a suitable base. The salts can then be isolated - if appropriate after prolonged stirring - by concentration or suction.
Die erfindungsgemäßen Wirkstoffe können z.B. bei den folgenden Pflanzen verwendet werden: Dikotyle Unkräuter der Gattungen: 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. Dikotyle Kulturen der Gattungen: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita. The active compounds according to the invention can be used, for example, in the following plants: 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. Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
Monokotyle Unkräuter der Gattungen: 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. Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Iochasumirumum, Scalumumum, Scalumumum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monokotyle Kulturen der Gattungen: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium. Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.
Die Verwendung der erfindungsgemäßen Wirkstoffe ist jedoch keineswegs auf diese Gattungen beschränkt, sondern erstreckt sich in gleicher Weise auch auf andere Pflanzen. However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.
Die Verbindungen eignen sich in Abhängigkeit von der Konzentration zur Totalunkrautbekämpfung z.B. auf Industrie- und Gleisanlagen und auf Wegen und Plätzen mit und ohne Baumbewuchs. Ebenso können die Verbindungen zur Unkrautbekämpfung in Dauerkulturen, z.B. Forst, Ziergehölz-, Obst-, Wein-, Citrus-, Nuß-, Bananen-, Kaffee-, Tee-, Gummi-, Ölpalm-, Kakao-, Beerenfrucht- und Hopfenanlagen, auf Zier- und Sportrasen und Weideflächen und zur selektiven Unkrautbekämpfung in einjährigen Kulturen eingesetzt werden. Depending on the concentration, the compounds are suitable for total weed control, e.g. 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. 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 pasture land and for selective purposes Weed control can be used in annual crops.
Die erfindungsgemäßen Verbindungen der Formel (I) eignen sich insbesondere zur selektiven Bekämpfung von monokotylen und dikotylen Unkräutern in monokotylen und dikotylen Kulturen sowohl im Vorauflauf- als auch im Nachauflauf- Verfahren. The compounds of formula (I) according to the invention are particularly suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops both in the pre-emergence and in the post-emergence process.
Die Wirkstoffe können in die üblichen Formulierungen überführt werden, wie Lösungen, Emulsionen, Spritzpulver, Suspensionen, Pulver, Stäubemittel, Pasten, lösliche Pulver, Granulate, Suspensions-Emulsions-Konzentrate, Wirkstoff-imprägnierte Natur- und synthetische Stoffe sowie Feinstverkapselungen in polymeren Stoffen. Diese Formulierungen werden in bekannter Weise hergestellt, z. B. durch Vermischen der Wirkstoffe mit Streckmitteln, also flüssigen Lösungsmitteln und/oder festen Trägerstoffen, gegebenenfalls unter Verwendung von oberflächenaktiven Mitteln, also Emulgiermitteln und/oder Dispergiermitteln und/oder schaumerzeugenden Mitteln. Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösungsmittel als Hilfslösungsmittel verwendet werden. Als flüssige Lösungsmittel kommen im wesentlichen in Frage: Aromaten, wie Xylol, Toluol, oder Alkylnaphthaline, chlorierte Aromaten und chlorierte aliphatische Kohlenwasserstoffe, wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, mineralische und pflanzliche Öle, Alkohole, wie Butanol oder Glykol sowie deren Ether und Ester, Ketone wie Aceton, Methylethylketon, Methylisobutylketon oder Cyclohexanon, stark polare Lösungsmittel, wie Dimethylformamid und Dimethylsulfoxid, sowie Wasser. The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances. These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example 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.
Als feste Trägerstoffe kommen in Frage: z.B. Ammoniumsalze und natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate, als feste Trägerstoffe für Granulate kommen in Frage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengeln; als Emulgier- und/oder schaumerzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsäure-Ester, Polyoxyethylen-Fettalkohol-Ether, z.B. Alkylaryl-polyglykolether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel kommen in Frage: z.B. LigninSulfitablaugen und Methylcellulose. Possible solid carriers are: e.g. Ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silicic acid, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foaming agents are possible: e.g. nonionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
Es können in den Formulierungen Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulvrige, körnige oder latexförmige Polymere verwendet werden, wie Gummiarabicum, Polyvinylalkohol, Polyvinylacetat, sowie natürliche Phospholipi de, wie Kephaline und Lecithine und synthetische Phospholipide. Weitere Additive können mineralische und vegetabile Öle sein. Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate and natural phospholipi, can be used in the formulations de, such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.
Es können Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocyanblau und organische Farbstoffe, wie Alizarin-, Azo- und MetallphthalocyaninfarbStoffe und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink verwendet werden. Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
Die Formulierungen enthalten im allgemeinen zwischen 0, 1 und 95 Gewichtsprozent Wirkstoff, vorzugsweise zwischen 0,5 und 90 %. The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
Die erfindungsgemäßen Wirkstoffe können als solche oder in ihren Formulierungen auch in Mischung mit bekannten Herbiziden zur Unkrautbekämpfung Verwendung finden, wobei Fertigformulierungen oder Tankmischungen möglich sind. The active compounds according to the invention, as such or in their formulations, can also be used for combating weeds, in a mixture with known herbicides, finished formulations or tank mixes being possible.
Für die Mischungen kommen bekannte Herbizide infrage, beispielsweise Anilide, wie z.B. Diflufenican und Propanil; Arylcarbonsäuren, wie z.B. Dichlorpicolinsäure, Dicamba und Picloram; Aryloxyalkansäuren, wie z.B. 2,4-D, 2,4-DB, 2,4-DP, Fluroxypyr, MCPA, MCPP und Triclopyr; Aryloxy-phenoxy-alkansäureester, wie z.B. Diclofop-methyl, Fenoxaprop-ethyl, Fluazifop-butyl, Haloxyfop-methyl und Quizalofopethyl; Azinone, wie z.B. Chloridazon und Norflurazon; Carbamate, wie z.B. Chlorpropham, Desmedipham, Phenmedipham und Propham; Chloracetanilide, wie z.B. Alachlor, Acetochlor, Butachlor, Metazachlor, Metolachlor, Pretilachlor und Propachlor; Dinitroaniline, wie z.B. Oryzalin, Pendimethalin und Trifluralin; Diphenylether, wie z.B. Acifluorfen, Bifenox, Fluoroglycofen, Fomesafen, Halosafen, Lactofen und Oxyfluorfen; Harnstoffe, wie z.B. Chlortoluron, Diuron, Fluometuron, Isoproturon, Linuron und Methabenzthiazuron; Hydroxylamine, wie z.B. Alloxydim, Clethodim, Cycloxydim, Sethoxydim und Tralkoxydim; Imidazolinone, wie z.B. Imazethapyr, Imazamethabenz, Imazapyr und Imazaquin; Nitrile, wie z.B. Bromoxynil, Dichlobenil und Ioxynil; Oxyacetamide, wie z.B. Mefenacet; Sulfonylharnstoffe, wie z.B. Amidosulfuron, Bensulfüron-methyl, Chlorimuron-ethyl, Chlorsulfüron, Cinosulfüron, Metsulfuron-methyl, Nicosulfuron, Primisulfüron, Pyrazosulfuron-ethyl, Thifensulfuronmethyl, Triasulfuron und Tribenuron-methyl; Thiolcarbamate, wie z.B. Butylate, Cycloate, Diallate, EPTC, Esprocarb, Molinate, Prosulfocarb, Thiobencarb und Tri allate; Triazine, wie z.B. Atrazin, Cyanazin, Simazin, Simetryne, Terbutryne und Terbutylazin; Triazinone, wie z.B. Hexazinon, Metamitron und Metribuzin; Sonstige, wie z.B. Aminotriazol, Benfüresate, Bentazone, Cinmethylin, Clomazone, Clopyralid, Difenzoquat, Dithiopyr, Ethofümesate, Fluorochloridone, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate und Tridiphane. Known herbicides are suitable for the mixtures, for example anilides, such as, for example, diflufenican and propanil; Aryl carboxylic acids such as dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids such as 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy-alkanoic acid esters, such as, for example, diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofopethyl; Azinones such as chloridazon and norflurazon; Carbamates such as chlorpropham, desmedipham, phenmedipham and propham; Chloroacetanilides such as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; Dinitroanilines such as oryzalin, pendimethalin and trifluralin; Diphenyl ethers such as acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; Ureas such as chlorotoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; Hydroxylamines such as alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; Imidazolinones such as imazethapyr, imazamethabenz, imazapyr and imazaquin; Nitriles such as bromoxynil, dichlobenil and ioxynil; Oxyacetamides such as mefenacet; Sulfonylureas, such as, for example, amidosulfuron, bensulfüron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfüron, metsulfuron-methyl, nicosulfuron, primisulfüron, pyrazosulfuron-ethyl, thifensulfuronmethyl, triasulfuron and tribenuron-methyl; Thiol carbamates such as butylates, cycloates, dialates, EPTC, Esprocarb, Molinate, Prosulfocarb, Thiobencarb and Tri allate; Triazines such as atrazine, cyanazine, simazin, simetryne, terbutryne and terbutylazine; Triazinones such as hexazinone, metamitron and metribuzin; Others, such as, for example, aminotriazole, Benfüresate, Bentazone, Cinmethylin, Clomazone, Clopyralid, Difenzoquat, Dithiopyr, Ethofümesate, Fluorochloridone, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane.
Auch eine Mischung mit anderen bekannten Wirkstoffen, wie Fungiziden, Insektiziden, Akariziden, Nematiziden, Schutzstoffen gegen Vogelfraß, Pflanzennährstoffen und Bodenstrukturverbesserungsmitteln ist möglich. A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.
Die Wirkstoffe können als solche, in Form ihrer Formulierungen oder den daraus durch weiteres Verdünnen bereiteten Anwendungsformen, wie gebrauchsfertige Lösungen, Suspensionen, Emulsionen, Pulver, Pasten und Granulate angewandt werden. Die Anwendung geschieht in üblicher Weise, z.B. durch Gießen, Spritzen, Sprühen, Streuen. The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the usual way, e.g. by pouring, spraying, spraying, sprinkling.
Die erfindungsgemäßen Wirkstoffe können sowohl vor als auch nach dem Auflaufen der Pflanzen appliziert werden. Sie können auch vor der Saat in den Boden eingearbeitet werden. The active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing.
Die angewandte Wirkstoffmenge kann in einem größeren Bereich schwanken. Sie hängt im wesentlichen von der Art des gewünschten Effektes ab. Im allgemeinen liegen die Aufwandmengen zwischen 1 g und 10 kg Wirkstoff pro Hektar Bodenfläche, vorzugsweise zwischen 5 g und 2 kg pro ha. The amount of active ingredient used can vary over a wide range. It essentially depends 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, preferably between 5 g and 2 kg per ha.
Die Herstellung und die Verwendung der erfindungsgemäßen Wirkstoffe geht aus den nachfolgenden Beispielen hervor. The preparation and use of the active compounds according to the invention can be seen from the examples below.
Herstellungsbeispiele: Beispiel 1 Production examples: Example 1
Figure imgf000017_0001
Figure imgf000017_0001
5,0 g (36 mMol) 2-Amino-4-methoxy-6-methyl-pyrimidin werden bei 0°C bis 5°C unter Rühren zu einer Mischung aus 5,1 g (36 mMol) Chlorsulfonylisocyanat und 50 ml Methylenchlorid gegeben und das Gemisch wird ca. 30 Minuten bei dieser Temperatur gerührt. Dann werden 5,9 g (36 mMol) 2-Cyclopropylcarbonyl-anilin und 4,0 g (40 mMol) Triethylamin in 50 ml Methylenchlorid dazugegeben und das Reaktionsgemisch wird 18 Stunden bei 20°C gerührt. Anschließend wird mit Wasser gewaschen, mit Natriumsulfat getrocknet und filtriert. Das Filtrat wird eingeengt, der Rückstand mit wenig Ethanol verrieben und das kristallin angefallene Produkt durch Absaugen isoliert. 5.0 g (36 mmol) of 2-amino-4-methoxy-6-methyl-pyrimidine are added at 0 ° C. to 5 ° C. with stirring to a mixture of 5.1 g (36 mmol) of chlorosulfonyl isocyanate and 50 ml of methylene chloride and the mixture is stirred at this temperature for about 30 minutes. Then 5.9 g (36 mmol) of 2-cyclopropylcarbonyl-aniline and 4.0 g (40 mmol) of triethylamine in 50 ml of methylene chloride are added and the reaction mixture is stirred at 20 ° C. for 18 hours. It is then washed with water, dried with sodium sulfate and filtered. The filtrate is concentrated, the residue is triturated with a little ethanol and the crystalline product is isolated by suction.
Man erhält 7,0 g (48% der Theorie) N-(4-Methoxy-6-methyl-pyrimidin-2-yl)-N'-(2-cyclopropylcarbonyl-phenylaminosulfonyl)-harnstoff vom Schmelzpunkt 164°C. Analog Beispiel 1 sowie entsprechend der allgemeinen Beschreibung der erfindungsgemäßen Herstellungsverfahren können beispielsweise auch die in der nachstehenden Tabelle 1 aufgeführten Verbindungen der Formel (I) hergestellt werden. 7.0 g (48% of theory) of N- (4-methoxy-6-methyl-pyrimidin-2-yl) -N '- (2-cyclopropylcarbonyl-phenylaminosulfonyl) urea with a melting point of 164 ° C. are obtained. Analogously to Example 1 and in accordance with the general description of the production processes according to the invention, for example the compounds of the formula (I) listed in Table 1 below can also be prepared.
Figure imgf000017_0002
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000017_0002
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Ausgangsstoffe der Formel (IV): Beispiel (IV- 1) Starting materials of the formula (IV): Example (IV- 1)
Figure imgf000022_0001
250 ml Dichlorethan werden bei 0°C bis +5°C mit 30 g (0,25 Mol) Bor(III)-chlorid versetzt und zu dieser Mischung werden bei 0°C bis +5°C 26,8 g (0,25 Mol) 2-Methyl-anilin tropfenweise gegeben. Dann werden 25 g (0,375 Mol) Cyclopropylcyanid bei 0°C bis +5°C zugetropft und anschließend 36 g (0,275 Mol) Aluminium(III)-chlorid portionsweise eindosiert. Die Reaktionsmischung wird dann ca. 15 Stunden unter Rückfluß erhitzt, anschließend abkühlen gelassen und auf ca. 1 Liter Eiswasser gegossen. Es wird bis zur Auflösung der festen Komponenten gerührt, die organische Phase abgetrennt, mit Natriumsulfat getrocknet und filtriert. Das Filtrat wird im Wasserstrahlvakuum eingeengt, der Rückstand durch Digerieren mit Ligroin zur Kristallisation gebracht und das Produkt durch Absaugen isoüert. Man erhält 58 g (66% der Theorie) 2-Cyclopropylcarbonyl-6-methyl-anilin vom Schmelzpunkt 64°C.
Figure imgf000022_0001
250 ml of dichloroethane are mixed at 0 ° C to + 5 ° C with 30 g (0.25 mol) of boron (III) chloride and to this mixture at 0 ° C to + 5 ° C 26.8 g (0, 25 mol) 2-methyl-aniline added dropwise. Then 25 g (0.375 mol) of cyclopropyl cyanide are added dropwise at 0 ° C. to + 5 ° C. and then 36 g (0.275 mol) of aluminum (III) chloride are metered in in portions. The reaction mixture is then refluxed for about 15 hours, then allowed to cool and poured onto about 1 liter of ice water. The mixture is stirred until the solid components have dissolved, the organic phase is separated off, dried with sodium sulfate and filtered. The filtrate is concentrated in a water jet vacuum, the residue is crystallized by digestion with ligroin and the product is isolated by suction. 58 g (66% of theory) of 2-cyclopropylcarbonyl-6-methyl-aniline with a melting point of 64 ° C. are obtained.
Analog Beispiel (IV- 1) können beispielsweise auch die in der nachstehenden Tabelle 2 aufgeführten Verbindungen der Formel (IV) hergestellt werden.Analogously to Example (IV-1), the compounds of the formula (IV) listed in Table 2 below can also be prepared, for example.
Figure imgf000023_0001
Figure imgf000024_0002
Figure imgf000023_0001
Figure imgf000024_0002
Anwendungsbeispiele Examples of use
In den Anwendungsbeispielen wird die folgende Verbindung (A) als Vergleichssubstanz herangezogen: In the application examples, the following compound (A) is used as a reference substance:
Figure imgf000024_0001
Figure imgf000024_0001
N-(4,6-Dimethoxy-pyrimidin-2-yl)-N'-(2-cyclopropylcarbonyl-phenylaminosulfonyl)- harnstoff (bekannt aus EP-A 463287/US-P 5009699). N- (4,6-Dimethoxy-pyrimidin-2-yl) -N '- (2-cyclopropylcarbonyl-phenylaminosulfonyl) urea (known from EP-A 463287 / US-P 5009699).
Beispiel A Example A
Post-emergence-Test Post emergence test
Lösungsmittel: 5 Gewichtsteile Aceton Solvent: 5 parts by weight of acetone
Emulgator: 1 Gewichtsteil Alkylarylpolyglykolether Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, gibt die angegebene Menge Emulgator zu und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.  Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, mix 1 part by weight of active compound with the stated amount of solvent, add the stated amount of emulsifier and dilute the concentrate with water to the desired concentration.
Mit der WirkstofEzubereitung spritzt man Testpflanzen, welche eine Höhe von 5 - 15 cm haben so, daß die jeweils gewünschten Wirkstoffmengen pro Flächeneinheit ausgebracht werden. Die Konzentration der Spritzbrühe wird so gewählt, daß in 2000 1 Wasser/ha die jeweils gewünschten Wirkstoffmengen ausgebracht werden. Nach drei Wochen wird der Schädigungsgrad der Pflanzen bonitiert in % Schädigung im Vergleich zur Entwicklung der unbehandelten Kontrolle. Es bedeuten: Test plants with a height of 5 - 15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area. The concentration of the spray liquor is chosen so that the desired amounts of active compound are applied in 2000 l of water / ha. 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 % = keine Wirkung (wie unbehandelte Kontrolle) 0% = no effect (like untreated control)
100 % = totale Vernichtung  100% = total annihilation
In diesem Test zeigt beispielsweise die Verbindung gemäß Herstellungsbeispiel 3 bei sehr guter Verträglichkeit gegenüber Kulturpflanzen, wie z.B. Rüben, erheblich stärkere Wirkung gegen Unkräuter als die bekannte Verbindung (A) (vgl. Tabelle A-1). In this test, for example, the compound according to Preparation Example 3 shows very good tolerance to crop plants, such as Beets, considerably stronger activity against weeds than the known compound (A) (see Table A-1).
Weitere Testverbindungen und ihre Aufwandmengen sowie die verwendeten Testpflanzen und die Testergebnisse zeigt die nachfolgende Tabelle A-2.
Figure imgf000026_0001
Further test compounds and their application rates as well as the test plants used and the test results are shown in Table A-2 below.
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000027_0001
Beispiel B Example B
Pre-emergence-Test Pre-emergence test
Lösungsmittel: 5 Gewichtsteile Aceton Solvent: 5 parts by weight of acetone
Emulgator: 1 Gewichtsteil Alkylarylpolyglykolether Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit der angegebenen Menge Lösungsmittel, gibt die angegebene Menge Emulgator zu und verdünnt das Konzentrat mit Wasser auf die gewünschte Konzentration.  Emulsifier: 1 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, mix 1 part by weight of active compound with the stated amount of solvent, add the stated amount of emulsifier and dilute the concentrate with water to the desired concentration.
Samen der Testpflanzen werden in normalen Boden ausgesät. Nach 24 Stunden wird der Boden mit der Wirkstoffzubereitung begossen. Dabei hält man die Wassermenge pro Flächeneinheit zweckmäßigerweise konstant. Die Wirkstoffkonzentration in der Zubereitung spielt keine Rolle, entscheidend ist nur die Aufwandmenge des Wirkstoffs pro Flächeneinheit. Nach drei Wochen wird der Schädigungsgrad der Pflanzen bonitiert in % Schädigung im Vergleich zur Entwicklung der unbehandelten Kontrolle. Es bedeuten: Seeds of the test plants are sown in normal soil. After 24 hours, the active ingredient preparation is poured onto the floor. The amount of water per unit area is expediently kept constant. The concentration of active substance in the preparation is irrelevant, the only decisive factor is the amount of active substance applied 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 % = keine Wirkung (wie unbehandelte Kontrolle) 0% = no effect (like untreated control)
100 % = totale Vernichtung  100% = total annihilation
In diesem Test zeigt beispielsweise die Verbindung gemäß Herstellungsbeispiel 6 bei sehr guter Verträglichkeit gegenüber Kulturpflanzen, wie z.B. Baumwolle, erheblich stärkere Wirkung gegen Unkräuter als die bekannte Verbindung (A) (vgl. Tabelle B-1). In this test, for example, the compound according to Preparation Example 6 shows very good tolerance to crop plants, such as Cotton, considerably more effective against weeds than the known compound (A) (see Table B-1).
Weitere Testverbindungen und ihre Aufwandmengen sowie die verwendeten Test-pflanzen und die Testergebnisse zeigt die nachfolgende Tabelle B-2.
Figure imgf000029_0001
Further test compounds and their application rates as well as the test plants used and the test results are shown in Table B-2 below.
Figure imgf000029_0001
Tabelle B-2: Table B-2:
Pre-emergence-Test / Gewächshaus Pre-emergence test / greenhouse
Wirkstoff AufwandMais Abutilon Ambrosia Cheno- MatricariaActive ingredient expenditure Corn Abutilon Ambrosia Cheno-Matricaria
(gemäß Herstelmenge podium (according to the amount of podium
lungsbeispiel Nr.) (g/ha) Example No.) (g / ha)
(1) 60 0 80 95 90 95(1) 60 0 80 95 90 95
(9) 60 10 80 90 95 95(9) 60 10 80 90 95 95
(10) 60 0 60 95 95 90(10) 60 0 60 95 95 90
(15) 60 0 80 95 95 95(15) 60 0 80 95 95 95
(24) 60 0 80 90 95 90(24) 60 0 80 90 95 90
(27) 60 0 0 95 80 95 (27) 60 0 0 95 80 95

Claims

Patentansprüche Claims
1. Substituierte Cyclopropylcarbonyl-phenylaminosulfonyl-harnstoffe der allgemeinen Formel (I) 1. Substituted cyclopropylcarbonylphenylaminosulfonylureas of the general formula (I)
Figure imgf000031_0001
Figure imgf000031_0001
in welcher  in which
R1 für Wasserstoff, Halogen oder für jeweils gegebenenfalls durch Halogen oder C1-C3-Alkoxy substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylamino oder Dialkylamino mit jeweils 1 bis 4 Kohlenstoffatomen in den einzelnen Alkylgruppen steht, R2 für Wasserstoff oder Halogen steht, R 1 represents hydrogen, halogen or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino or dialkylamino, each optionally substituted by halogen or C 1 -C 3 alkoxy, each having 1 to 4 carbon atoms in the individual alkyl groups, R 2 represents hydrogen or halogen,
R3 für Halogen oder für jeweils gegebenenfalls durch Halogen oder C1-C3- Alkoxy substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylamino oder Dialkylamino mit jeweils 1 bis 4 Kohlenstoffatomen in den einzelnen Alkylgruppen steht, R4 für Wasserstoff, Halogen, Formyl oder für jeweils gegebenenfalls durchR 3 represents halogen or alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino or dialkylamino, each of which is optionally substituted by halogen or C 1 -C 3 -alkoxy, each having 1 to 4 carbon atoms in the individual alkyl groups, R 4 represents hydrogen, halogen , Formyl or for each optionally by
Halogen oder C1-C3 -Alkoxy substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylcarbonyl oder Alkoxycarbonyl mit jeweils 1 bis 4 Kohlenstoffatomen in den einzelnen Alkylgruppen steht, und R5 für gegebenenfalls durch Halogen oder C1-C4-Alkyl substituiertes Cyclopropyl steht, sowie Salze der Verbindungen der Formel (I), wobei die Verbindung N-(4,6- Dimethoxy-pyrimidin-2-yl)-N-(2-cyclopropylcarbonyl-phenylaminosulfonyl)- harnstoff ausgenommen ist. Halogen or C 1 -C 3 alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl or alkoxycarbonyl each having 1 to 4 carbon atoms in the individual alkyl groups, and R 5 is optionally halogen or C 1 -C 4 alkyl substituted cyclopropyl, and salts of the compounds of the formula (I), the compound N- (4,6-dimethoxypyrimidin-2-yl) -N- (2-cyclopropylcarbonylphenylaminosulfonyl) urea being excluded.
2. Verbindungen der Formel (I) gemäß Anspruch 1, dadurch gekennzeichnet, daß darin 2. Compounds of formula (I) according to claim 1, characterized in that therein
R1 für Wasserstoff, Fluor, Chlor, Brom oder für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy oder Ethoxy substituiertes Alkyl, Alkoxy, Alkyl- thio, Alkylsulfinyl, Alkylsulfonyl, Alkylamino oder Dialkylamino mit jeweils 1 bis 3 Kohlenstoffatomen in den einzelnen Alkylgruppen steht, R 1 stands for hydrogen, fluorine, chlorine, bromine or for alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino or dialkylamino, each optionally substituted by fluorine, chlorine, methoxy or ethoxy, each having 1 to 3 carbon atoms in the individual alkyl groups,
R2 für Wasserstoff, Fluor, Chlor oder Brom steht, R 2 represents hydrogen, fluorine, chlorine or bromine,
R3 für Fluor, Chlor, Brom oder für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy oder Ethoxy substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylamino oder Dialkylamino mit jeweils 1 bis 3R 3 for fluorine, chlorine, bromine or for alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylamino or dialkylamino each substituted by fluorine, chlorine, methoxy or ethoxy, each with 1 to 3
Kohlenstoffatomen in den einzelnen Alkylgruppen steht, Carbon atoms in the individual alkyl groups,
R4 für Wasserstoff, Fluor, Chlor, Brom, Formyl oder für jeweils gegebenenfalls durch Fluor, Chlor, Methoxy oder Ethoxy substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylcarbonyl oder Alkoxycarbonyl mit jeweils 1 bis 3 Kohlenstoffatomen in den einzelnenR 4 for hydrogen, fluorine, chlorine, bromine, formyl or for alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl or alkoxycarbonyl, each with 1 to 3 carbon atoms in each, optionally substituted by fluorine, chlorine, methoxy or ethoxy
Alkylgruppen steht, und Stands for alkyl groups, and
R5 für gegebenenfalls durch Fluor, Chlor, Methyl oder Ethyl substituiertes Cyclopropyl steht, ausgenommen die Verbindung N-(4,6-Dimethoxy-pyrimidin-2-yl)-N'-(2-cyclopropylcarbonyl-phenylaminosulfonyl)-harnstoff. R 5 represents cyclopropyl optionally substituted by fluorine, chlorine, methyl or ethyl, with the exception of the compound N- (4,6-dimethoxypyrimidin-2-yl) -N '- (2-cyclopropylcarbonylphenylaminosulfonyl) urea.
3. Verbindungen der Formel (I) gemäß Anspruch 1, dadurch gekennzeichnet, daß darin 3. Compounds of formula (I) according to claim 1, characterized in that therein
R1 für Wasserstoff, Chlor, Methyl, Ethyl, Trifluormethyl, Methoxy, Ethoxy, Difluormethoxy, Methylthio, Ethylthio, Methylamino, Ethylamino oder Dimethylamino steht, R 1 represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino,
R2 für Wasserstoff steht, R3 für Chlor, Methyl, Ethyl, Trifluormethyl, Methoxy, Ethoxy, Difluormethoxy, Methylthio, Ethylthio, Methylamino, Ethylamino oder Dimethylamino steht, R4 für Wasserstoff, Fluor, Chlor, Brom, Methyl, Ethyl, n- oder i-Propyl, Trifluormethyl, Methoxy, Methylthio, Methylsulfinyl, Methylsulfonyl,R 2 represents hydrogen, R 3 represents chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino, R 4 represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, Trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl,
Acetyl oder Methoxycarbonyl steht, und Is acetyl or methoxycarbonyl, and
R5 für Cyclopropyl steht, ausgenommen die Verbindung N-(4,6-Dimethoxy-pyrimidin-2-yl)-N'-(2-cyclopropylcarbonyl-phenylaminosulfonyl)-harnstoff. Verbindungen der Formeln (IA) und (IB) gemäß Anspruch 1, R 5 stands for cyclopropyl, with the exception of the compound N- (4,6-dimethoxy-pyrimidin-2-yl) -N '- (2-cyclopropylcarbonyl-phenylaminosulfonyl) urea. Compounds of the formulas (IA) and (IB) according to Claim 1,
Figure imgf000033_0001
Figure imgf000033_0002
Figure imgf000033_0001
Figure imgf000033_0002
in welchen jeweils R1 für Wasserstoff, Chlor, Methyl, Ethyl, Trifluormethyl, Methoxy, Ethoxy,in each of which R 1 represents hydrogen, chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy,
Difluormethoxy, Methylthio, Ethylthio, Methylamino, Ethylamino oder Dimethylamino steht, Difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino,
R2 für Wasserstoff steht, R3 für Chlor, Methyl, Ethyl, Trifluormethyl, Methoxy, Ethoxy, Difluormethoxy, Methylthio, Ethylthio, Methylamino, Ethylamino oder Dimethylamino steht, R 2 represents hydrogen, R 3 represents chlorine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methylthio, ethylthio, methylamino, ethylamino or dimethylamino,
R4 für Fluor, Chlor, Brom, Methyl, Ethyl, n- oder i-Propyl, Trifluormethyl, Methoxy, Methylthio, Methylsulfinyl, Methylsulfonyl, Acetyl oderR 4 for fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, acetyl or
Methoxycarbonyl steht, und Methoxycarbonyl stands, and
R5 für Cyclopropyl steht. R 5 represents cyclopropyl.
5. Verfahren zur Herstellung von substituierten Cyclopropylcarbonyl-phenylaminosulfonylharnstoffen der Formel (I) oder deren Salzen gemäß Anspruch 1, dadurch gekennzeichnet, daß man Aminopyrimidine der allgemeinen Formel (II) 5. A process for the preparation of substituted cyclopropylcarbonyl-phenylaminosulfonylureas of the formula (I) or salts thereof according to claim 1, characterized in that aminopyrimidines of the general formula (II)
Figure imgf000034_0001
Figure imgf000034_0001
in welcher  in which
R1, R2 und R3 die in Anspruch 1 angegebene Bedeutung haben, mit Chlorsulfonylisocyanat (Cl-SO2-N=C=O), gegebenenfalls in Gegenwart eines Verdünnungsmittels, umsetzt und die hierbei gebildeten Chlorsulfonylharnstoffe der allgemeinen Formel (III) R 1 , R 2 and R 3 have the meaning given in claim 1, are reacted with chlorosulfonyl isocyanate (Cl-SO 2 -N = C = O), optionally in the presence of a diluent, and the chlorosulfonylureas of the general formula (III) formed in this process
Figure imgf000034_0002
Figure imgf000034_0002
in welcher  in which
R1, R2 und R3 die in Anspruch 1 angegebene Bedeutung haben, mit Anilinen der allgemeinen Formel (IV) R 1 , R 2 and R 3 have the meaning given in claim 1, with anilines of the general formula (IV)
Figure imgf000035_0001
Figure imgf000035_0001
in welcher  in which
R4 und R5 die in Anspruch 1 angegebene Bedeutung haben, gegebenenfalls in Gegenwart eines Säureakzeptors und gegebenenfalls inR 4 and R 5 have the meaning given in claim 1, optionally in the presence of an acid acceptor and optionally in
Gegenwart eines Verdünnungsmittels umsetzt und gegebenenfalls die so erhaltenen Verbindungen der Formel (I) nach üblichen Methoden in Salze überführt. In the presence of a diluent and, if appropriate, converting the compounds of the formula (I) thus obtained into salts by customary methods.
6. Herbizide Mittel, gekennzeichnet durch einen Gehalt an mindestens einer Verbindung der Formel (I) gemäß Anspruch 1. 7. Verwendung von Verbindungen der allgemeinen Formel (I) gemäß Anspruch 1 zur Bekämpfung von unerwünschtem Pflanzenwachstum. 6. Herbicidal agents, characterized in that they contain at least one compound of the formula (I) according to Claim 1. 7. Use of compounds of the general formula (I) according to Claim 1 for combating undesired plant growth.
8. Verfahren zur Bekämpfung von Unkräutern, dadurch gekennzeichnet, daß man Verbindungen der allgemeinen Formel (I) gemäß Anspruch 1 auf die Unkräuter oder ihren Lebensraum einwirken läßt. 9. Verfahren zur Herstellung von herbiziden Mitteln, dadurch gekennzeichnet, daß man Verbindungen der allgemeinen Formel (I) gemäß Anspruch 1 mit Streckmitteln und/oder oberflächenaktiven Mitteln vermischt. 8. A method of combating weeds, characterized in that compounds of the general formula (I) according to Claim 1 are allowed to act on the weeds or their habitat. 9. A process for the preparation of herbicidal compositions, characterized in that compounds of the general formula (I) according to Claim 1 are mixed with extenders and / or surface-active agents.
10. Aniline der Formel (IVa), 10. anilines of the formula (IVa),
Figure imgf000035_0002
in welcher A für Halogen, Formyl oder für jeweils gegebenenfalls durch Halogen oder C1-C3-Alkoxy substituiertes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylcarbonyl oder Alkoxycarbonyl mit jeweils 1 bis 4 Kohlenstoffatomen in den einzelnen Alkylgruppen steht und
Figure imgf000035_0002
in which A stands for halogen, formyl or for alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl or alkoxycarbonyl, each optionally substituted by halogen or C 1 -C 3 -alkoxy, each having 1 to 4 carbon atoms in the individual alkyl groups and
R5 für gegebenenfalls durch Halogen oder C1-C4-Alkyl substituiertes Cyclopropyl steht. R 5 represents cyclopropyl optionally substituted by halogen or C 1 -C 4 alkyl.
PCT/EP1995/001394 1994-04-26 1995-04-13 Substituted cyclopropylcarbonyl-phenylaminosulphonyl ureas as herbicides WO1995029167A1 (en)

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