CA2292475A1 - Substituted arylalkyl uracils - Google Patents
Substituted arylalkyl uracils Download PDFInfo
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- CA2292475A1 CA2292475A1 CA002292475A CA2292475A CA2292475A1 CA 2292475 A1 CA2292475 A1 CA 2292475A1 CA 002292475 A CA002292475 A CA 002292475A CA 2292475 A CA2292475 A CA 2292475A CA 2292475 A1 CA2292475 A1 CA 2292475A1
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- formula
- general formula
- alkyl
- arylalkyluracils
- optionally substituted
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-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/456—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to other ring carbon atoms
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- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/52—Two oxygen atoms
- C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
- C07D239/545—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/557—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. orotic acid
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to substituted arylalkyl uracils of general formula (I), in which A is a straight-chain or branched alkane dyil, Ar is a substituted phenyl or naphthyl, both of which are optionally substituted, R1 is a hydrogen, amino or an optionally substituted alkyl, R2 is a cyano, carboxy, carbamoyl, thiocarbamoyl or an optionally substituted alkoxycarbonyl, and R3 is hydrogen, a halogen or alkyl. The invention also relates to a method for producing said compounds and their use as herbicides.
Description
Le A 32 451-Foreien Countries ,.
/~1 I:ILE, PTHIS AM~Eid~EO
TRANSLATION
Substituted arylalkyluracils The invention relates to new substituted arylalkyluracils, processes for their preparation and their use as herbicides.
A large number of substituted benzyluracils are already known from the (patent) literature (cf. US 5391541, WO 9504461, WO 9701543). However, these compounds have acquired no particular importance.
New substituted arylalkyluracils of the general formula (I) R' I
RZ N\ /O
CI) R3 N~A~Ar O
in which A represents straight-chain or branched alkanediyl, Ar represents in each case optionally substituted phenyl or naphthyl, R 1 represents hydrogen, amino or optionally substituted alkyl, R2 represents cyano, carboxyl, carbamoyl, thiocarbamoyl or optionally substituted alkoxycarbonyl and R3 represents hydrogen, halogen or alkyl, have now been found. --Le A 32 451-Foreign Countries The new substituted arylalkyluracils of the general formula (I) are obtained by a process in which N-arylalkyl-1-alkoxycarbonylamino-maleimides of the general formula (II) O~R
~ H
O~N~
(II) N
O ~A-Ar in which A, Ar and R3 have the abovementioned meanings and R represents alkyl, are reacted with a metal hydroxide in the presence of water and optionally in the I S presence of an organic solvent, and the arylalkyluracils obtained here, of the general formula (Ia) OH H
O N' /O
(la) R3 N~A~Ar O
in which A, Ar and R3 have the abovementioned meanings, Le A 32 451-Foreign Countries are optionally converted into other compounds of the formula (I) within the definition of the substituents, by customary methods.
The compounds of the general formula (I) and of the formula (Ia) can be converted S into other compounds of the general formula (I) according to the above definition by customary methods, for example by amination or alkylation (for example R1: H -~
NH2, H -~ CH3; R2: COOH -~ COOCH3, COOCH3 -~ CONH2); dehydration (for example R2: CONH2 -~ CN); addition of hydrogen sulfide (for example R2: CN -~
CSNH2, cf. the Preparation Examples).
'The new substituted arylalkyluracils of the general formula (I) are distinguished by a potent and selective herbicidal activity.
in the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkinyl, are in each case straight-chain or branched.
halogen in general represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
The invention preferably relates to compounds of the formula (I) in which A represents straight-chain or branched alkanediyl having 1 to 4 carbon atoms, Ar represents phenyl or naphthyl, in each case optionally substituted by amino, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-fluoroalkyl, C1-C4-chloroalkyl, C1-C4-fluorochloroalkyl and/or Cl-C4-alkoxy, C1-C4-fluoroalkoxy, C 1-C4-chloroalkoxy, C 1-C4-fluorochloroalkoxy, Rl represents hydrogen, amino or alkyl which has 1 to 4 carbon atoms and is optionally substituted by cyano, fluorine or chlorine, Le A 32 451-Foreign Countries R2 represents cyano, carboxyl, carbamoyl, thiocarbamoyl or alkoxycarbonyl which has 1 to 4 carbon atoms in the alkoxy group and is optionally substituted by cyano, fluorine or chlorine and R3 represents hydrogen, fluorine, chlorine, bromine or alkyl having 1 to 4 carbon atoms.
The invention particularly relates to compounds of the formula (I), in which A represents methylene, ethane-1,1-diyl (ethylidene), ethane-1,2-diyl (dimethylene), propane-1,1-diyl (propylidene), propane-1,2-diyl or propane-1,3-diyl (trimethylene), Ar represents phenyl which is optionally substituted by amino, nitro, cyano, 1 S carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy and/or trifluoromethoxy, R 1 represents hydrogen, amino, methyl or ethyl, R2 represents cyano, carboxyl, carbamoyl, thiocarbamoyl, methoxycarbonyl or ethoxycarbonyl and R3 represents hydrogen, chlorine, bromine or methyl.
The definitions of radicals given above, given generally or in preferred ranges, apply both to the end products of the formula (I) and accordingly to the particular starting substances or intermediate products required for the preparation. These definitions of radicals can be combined as desired with one another, that is to say also between the preferred ranges stated.
Le A 32 451-Foreign Countries If, for example, methyl [1-(2,4-difluoro-benzyl)-2,5-dioxo-2,5-dihydro-1H-pyrrol-3-yl]-carbamate is used as the starting substance, the course of the reaction in the process according to the invention can be outlined by the following equation:
O~CH3 H
H O~ H
O~N~ N
O
i / O - O
N
O O , F
F
F
F
Formula (II) provides a general definition of the N-arylalkyl-1-alkoxycarbonylamino-maleimides to be used as starting substances in the process according to the invention for the preparation of compounds of the formula (I). In formula (II), A, Ar and R3 preferably or in particular have those meanings which have already been mentioned above as preferred or as particularly preferred for A, Ar and R3 in connection with the description of the compounds of the formula (I) according to the invention; R
preferably represents C1-C4-alkyl, in particular methyl or ethyl.
1 S The starting substances of the general formula (II) are not yet known from the literature; as new substances, the present application also relates to them.
The new N-arylalkyl-1-alkoxycarbonylamino-maleimides of the formula (II) are obtained by a process in which alkyl (2,5-dioxo-2,5-dihydro-furan-3-yl)-carbamates of the general formula (III) Le A 32 451-Foreign Countries O~R
~ H
O~N
(III) O
O
in which R3 has the abovementioned meaning and R represents alkyl, are reacted with arylalkylamines of the general formula (IV) H2N_A_Ar (IV) in which A and Ar have the abovementioned meaning, optionally in the presence of a diluent, such as, for example, acetic acid, at temperatures between 0°C and 200°C, preferably between 50°C and 150°C (cf. the Preparation Examples).
The precursors of the general formula (III) are known and/or can be prepared by known processes (cf. DE 19604229).
The precursors of the general formula (IV) are known synthesis chemicals.
The process according to the invention for the preparation of the new compounds of the general formula (I) is carried out using a metal hydroxide. Metal hydroxides Le A 32 451-Foreign Countries _7_ which are employed here are, preferably, alkali metal hydroxides, such as, for example, lithium, sodium, potassium, rubidium or caesium hydoxide, alkaline earth metal hydroxides, such as, for example, magnesium, calcium or barium hydroxide, or earth metal hydroxides, such as, for example, aluminium hydroxide. Alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, are particularly suitable.
The metal hydroxides are employed in the presence of water, that is to say in general in aqueous solution, the concentration in general being between 0.01 and 10 mol, preferably between 0.1 and 1.0 mol of metal hydroxide per litre of water.
Possible diluents for carrying out the process according to the invention are, above all, polar organic solvents. These include, preferably, ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether (in particular dioxane); ketones, such as acetone, butanone or methyl isobutyl ketone; nitrites, such as acetonitrile, propionitrile or butyronitrile;
amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate, sulfoxides, such as dimethyl sulfoxide, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether.
The reaction temperatures can be varied within a substantial range in carrying out the process according to the invention. The reaction is in general carried out at temperatures between 0°C and 150°C, preferably between 20°C and 120°C.
The process according to the invention is in general carried out under normal pressure. However, it is also possible to carry out the process according to the invention under increased or reduced pressure - in general between 0.1 bar and 10 bar.
Le A 32 451-Foreien Countries _g_ For carrying out the process according to the invention, the starting substances are in general employed in approximately equimolar amounts. However, it is also possible for one of the components to be used in a relatively large excess. The reaction is in general carried out in a suitable diluent and the reaction mixture is in general stirred at the required temperature for several hours. Working up and, if appropriate, secondary reactions are carried out by customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weedkillers. By weeds in the broadest sense there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyleden 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 crops of the eg nera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Le A 32 451-Foreign Countries Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monocotyledon crops of the eg nera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
Depending on the concentration, the compounds are suitable for total weed control, for example on industrial terrain and rail tracks and on paths and areas with or without tree growth. Equally, the compounds can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea 1 S plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns and turf and pastures and for selective geed control in annual crops.
'Ihe compounds of the formula (I) according to the invention are particularly suitable for selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops both by the pre-emergence and by the post-emergence method.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspoemulsion concentrates, natural and synthetic substances impregnated with active compound, and microencapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is to say liquid solvents and/or solid carriers, optionally with the use of surfactants, that is to say emulsifiers and/or dispersants and/or foam-formers.
Le A 32 451-Foreign Countries If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. Liquid solvents which are mainly suitable are: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as 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.
Suitable solid Garners are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic and organic meals, and granules of organic material, such as sawdust, coconut shells, maize cobs and tobacco stalks;
suitable emulsifiers and/or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: for example lignin-sulfite waste liquors and methylcellulose.
Adhesives, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use dyestuffs, such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyestuffs, such as alizarin dyestuffs, azo Le A 32 451-Forei~ Countries dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general comprise between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, asulam, atrazine, azimsulfuron, benazolin, benfuresate, bensulfuron(-methyl), bentazon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bromobutide, bromofenoxim, bromoxynil, butachlor, butylate, cafenstrole, carbetamide, chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clopyralid, clopyrasulfuron, cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, etobenzanid, fenoxaprop(-ethyl), flamprop(-isopropyl), flamprop(-isopropyl-1), flamprop(-methyl), flazasulfuron, fluazifop(-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurenol, fluridone, fluroxypyr, flurprimidol, flurtamone, fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), hexazinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron, metazachlor, Le A 32 451-Foreign Countries methabenzthiazuron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon orbencarb, oryzalin, oxadiazon, oxyfluorfen, paraquat, pendimethalin, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propyzamide, prosulfocarb, prosulfuron, pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyributicarb, pyridate, pyrithiobac(-sodium), quinchlorac, quinmerac, quizalofop(-ethyl), quizalofop(-p-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.
A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, 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 customary manner, for example by watering, spraying, atomizing, spreading.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the examples which follow.
Le A 32 451-Foreign Countries Preparation Examples:
Examule 1 OH H
O N O
I N
H ~ ~ -CI
O CI
A mixture of 6.9 g (21 mmol) of ethyl [1-(2,3-dichloro-benzyl)-2,5-dioxo-2,5-dihydro-1H-pyrrol-3-yl)-carbamate, 1.0 g of sodium hydroxide, 100 ml of water and 300 ml of dioxane is heated under reflux for 4 hours and then concentrated under a waterpump vacuum. The residue is then shaken with 1N hydrochloric acid and ethyl acetate and the organic phase is separated off, dried with sodium sulfate and filtered.
The filtrate is concentrated under a waterpump vacuum, the residue is digested with diethyl ether and the product obtained as crystals is isolated by filtration with suction.
4.3 g (65% of theory) of 1-(2,3-dichloro-benzyl)-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidine-4-carboxylic acid of melting point 229°C are obtained.
Example 2 O N O
I ~ \ I
H ~ ~ -cl O CI
A mixture of 4.1 g (13 mmol) of 1-(2,3-dichloro-benzyl)-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidine-4-carboxylic acid (cf. Example 1 ), 5.0 g (40 mmol) of dimethyl sulfate, 10.8 g of potassium carbonate and 100 ml of acetonitrile is heated under reflux for 18 hours and then concentrated under a waterpump vacuum. The residue is shaken with water and ethyl acetate and the organic phase is separated off, Le A 32 451-Foreign Countries washed with water, dried with sodium sulfate and filtered. The solvent is distilled off carefully from the filtrate under a waterpump vacuum.
2.3 g (52% of theory) of methyl 1-(2,3-dichloro-benzyl)-3-methyl-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidine-4-carboxylate of melting point 88°C are obtained.
Example 3 NHZ i H3 N O
° I ~ ~
N
H CI
O CI
2.1 g (6.1 mmol) of methyl 1-(2,3-dichloro-benzyl)-3-methyl-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidine-4-carboxylate are dissolved in 50 ml of tetrahydrofuran, a solution of 2.0 g of ammonium chloride in 40 ml of concentrated aqueous ammonia solution is added and the mixture is stirred at room temperature (about 20°C) for 5 hours. After addition of a further 1.0 g of ammonium chloride in 20 ml of concentrated aqueous ammonia solution, the reaction mixture is stirred at room temperature for a further 12 hours and then concentrated under a waterpump vacuum.
The residue is dissolved in water and the solution is acidified with 1N
hydrochloric acid. The product obtained as crystals here is isolated by filtration with suction.
1.2 g (50% of theory) of 1-(2,3-dichloro-benzyl)-3-methyl-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidine-4-carboxamide of melting point 209°C are obtained.
Le A 32 451-Foreign Countries Example 4 NC N O
N
H CI
O CI
A solution of 0.5 ml of trifluoroacetic anhydride in 1 ml of methylene chloride is added to a mixture, cooled to 0°C, of 1.0 g (3 mmol) of 1-(2,3-dichloro-benzyl)-3-methyl-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidine-4-carboxamide, 1.5 ml of pyridine and 10 ml of methylene chloride, while stirring, and the reaction mixture is stirred in a thawing ice-bath for 12 hours. It is then poured onto water and shaken with methylene chloride. The organic phase is separated off, washed with water, dried with sodium sulfate and filtered. The filtrate is concentrated under a waterpump vacuum, the residue is digested with diisopropyl ether and the product obtained as crystals is isolated by filtration with suction.
0.5 g (54% of theory) of 1-(2,3-dichloro-benzyl)-3-methyl-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidine-4-carbonitrile of melting point 152°C is obtained.
Le A 32 451-Foreign Countries The compounds of the formula ()7 listed in the following Table 1, for example, can also be prepared analogously to Preparation Examples 1 to 4 and in accordance with the general description of the preparation process according to the invention.
R' t RZ N\ /O
(I) R3 N~A~Ar O
Table 1: Examples of the compounds of the formula (I) Ex- A Ar Rl R2 R3 Physical ample data No.
CH2 ~ CH3 COOH H (amorphous) /
'CI
CI
6 CHCH3 ~ CH3 CN H
'CI
CI
/~1 I:ILE, PTHIS AM~Eid~EO
TRANSLATION
Substituted arylalkyluracils The invention relates to new substituted arylalkyluracils, processes for their preparation and their use as herbicides.
A large number of substituted benzyluracils are already known from the (patent) literature (cf. US 5391541, WO 9504461, WO 9701543). However, these compounds have acquired no particular importance.
New substituted arylalkyluracils of the general formula (I) R' I
RZ N\ /O
CI) R3 N~A~Ar O
in which A represents straight-chain or branched alkanediyl, Ar represents in each case optionally substituted phenyl or naphthyl, R 1 represents hydrogen, amino or optionally substituted alkyl, R2 represents cyano, carboxyl, carbamoyl, thiocarbamoyl or optionally substituted alkoxycarbonyl and R3 represents hydrogen, halogen or alkyl, have now been found. --Le A 32 451-Foreign Countries The new substituted arylalkyluracils of the general formula (I) are obtained by a process in which N-arylalkyl-1-alkoxycarbonylamino-maleimides of the general formula (II) O~R
~ H
O~N~
(II) N
O ~A-Ar in which A, Ar and R3 have the abovementioned meanings and R represents alkyl, are reacted with a metal hydroxide in the presence of water and optionally in the I S presence of an organic solvent, and the arylalkyluracils obtained here, of the general formula (Ia) OH H
O N' /O
(la) R3 N~A~Ar O
in which A, Ar and R3 have the abovementioned meanings, Le A 32 451-Foreign Countries are optionally converted into other compounds of the formula (I) within the definition of the substituents, by customary methods.
The compounds of the general formula (I) and of the formula (Ia) can be converted S into other compounds of the general formula (I) according to the above definition by customary methods, for example by amination or alkylation (for example R1: H -~
NH2, H -~ CH3; R2: COOH -~ COOCH3, COOCH3 -~ CONH2); dehydration (for example R2: CONH2 -~ CN); addition of hydrogen sulfide (for example R2: CN -~
CSNH2, cf. the Preparation Examples).
'The new substituted arylalkyluracils of the general formula (I) are distinguished by a potent and selective herbicidal activity.
in the definitions, the saturated or unsaturated hydrocarbon chains, such as alkyl, alkenyl or alkinyl, are in each case straight-chain or branched.
halogen in general represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
The invention preferably relates to compounds of the formula (I) in which A represents straight-chain or branched alkanediyl having 1 to 4 carbon atoms, Ar represents phenyl or naphthyl, in each case optionally substituted by amino, nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-fluoroalkyl, C1-C4-chloroalkyl, C1-C4-fluorochloroalkyl and/or Cl-C4-alkoxy, C1-C4-fluoroalkoxy, C 1-C4-chloroalkoxy, C 1-C4-fluorochloroalkoxy, Rl represents hydrogen, amino or alkyl which has 1 to 4 carbon atoms and is optionally substituted by cyano, fluorine or chlorine, Le A 32 451-Foreign Countries R2 represents cyano, carboxyl, carbamoyl, thiocarbamoyl or alkoxycarbonyl which has 1 to 4 carbon atoms in the alkoxy group and is optionally substituted by cyano, fluorine or chlorine and R3 represents hydrogen, fluorine, chlorine, bromine or alkyl having 1 to 4 carbon atoms.
The invention particularly relates to compounds of the formula (I), in which A represents methylene, ethane-1,1-diyl (ethylidene), ethane-1,2-diyl (dimethylene), propane-1,1-diyl (propylidene), propane-1,2-diyl or propane-1,3-diyl (trimethylene), Ar represents phenyl which is optionally substituted by amino, nitro, cyano, 1 S carboxyl, carbamoyl, thiocarbamoyl, fluorine, chlorine, bromine, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy and/or trifluoromethoxy, R 1 represents hydrogen, amino, methyl or ethyl, R2 represents cyano, carboxyl, carbamoyl, thiocarbamoyl, methoxycarbonyl or ethoxycarbonyl and R3 represents hydrogen, chlorine, bromine or methyl.
The definitions of radicals given above, given generally or in preferred ranges, apply both to the end products of the formula (I) and accordingly to the particular starting substances or intermediate products required for the preparation. These definitions of radicals can be combined as desired with one another, that is to say also between the preferred ranges stated.
Le A 32 451-Foreign Countries If, for example, methyl [1-(2,4-difluoro-benzyl)-2,5-dioxo-2,5-dihydro-1H-pyrrol-3-yl]-carbamate is used as the starting substance, the course of the reaction in the process according to the invention can be outlined by the following equation:
O~CH3 H
H O~ H
O~N~ N
O
i / O - O
N
O O , F
F
F
F
Formula (II) provides a general definition of the N-arylalkyl-1-alkoxycarbonylamino-maleimides to be used as starting substances in the process according to the invention for the preparation of compounds of the formula (I). In formula (II), A, Ar and R3 preferably or in particular have those meanings which have already been mentioned above as preferred or as particularly preferred for A, Ar and R3 in connection with the description of the compounds of the formula (I) according to the invention; R
preferably represents C1-C4-alkyl, in particular methyl or ethyl.
1 S The starting substances of the general formula (II) are not yet known from the literature; as new substances, the present application also relates to them.
The new N-arylalkyl-1-alkoxycarbonylamino-maleimides of the formula (II) are obtained by a process in which alkyl (2,5-dioxo-2,5-dihydro-furan-3-yl)-carbamates of the general formula (III) Le A 32 451-Foreign Countries O~R
~ H
O~N
(III) O
O
in which R3 has the abovementioned meaning and R represents alkyl, are reacted with arylalkylamines of the general formula (IV) H2N_A_Ar (IV) in which A and Ar have the abovementioned meaning, optionally in the presence of a diluent, such as, for example, acetic acid, at temperatures between 0°C and 200°C, preferably between 50°C and 150°C (cf. the Preparation Examples).
The precursors of the general formula (III) are known and/or can be prepared by known processes (cf. DE 19604229).
The precursors of the general formula (IV) are known synthesis chemicals.
The process according to the invention for the preparation of the new compounds of the general formula (I) is carried out using a metal hydroxide. Metal hydroxides Le A 32 451-Foreign Countries _7_ which are employed here are, preferably, alkali metal hydroxides, such as, for example, lithium, sodium, potassium, rubidium or caesium hydoxide, alkaline earth metal hydroxides, such as, for example, magnesium, calcium or barium hydroxide, or earth metal hydroxides, such as, for example, aluminium hydroxide. Alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, are particularly suitable.
The metal hydroxides are employed in the presence of water, that is to say in general in aqueous solution, the concentration in general being between 0.01 and 10 mol, preferably between 0.1 and 1.0 mol of metal hydroxide per litre of water.
Possible diluents for carrying out the process according to the invention are, above all, polar organic solvents. These include, preferably, ethers, such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether (in particular dioxane); ketones, such as acetone, butanone or methyl isobutyl ketone; nitrites, such as acetonitrile, propionitrile or butyronitrile;
amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate, sulfoxides, such as dimethyl sulfoxide, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether.
The reaction temperatures can be varied within a substantial range in carrying out the process according to the invention. The reaction is in general carried out at temperatures between 0°C and 150°C, preferably between 20°C and 120°C.
The process according to the invention is in general carried out under normal pressure. However, it is also possible to carry out the process according to the invention under increased or reduced pressure - in general between 0.1 bar and 10 bar.
Le A 32 451-Foreien Countries _g_ For carrying out the process according to the invention, the starting substances are in general employed in approximately equimolar amounts. However, it is also possible for one of the components to be used in a relatively large excess. The reaction is in general carried out in a suitable diluent and the reaction mixture is in general stirred at the required temperature for several hours. Working up and, if appropriate, secondary reactions are carried out by customary methods (cf. the Preparation Examples).
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weedkillers. By weeds in the broadest sense there are to be understood all plants which grow in locations where they are undesired. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyleden 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 crops of the eg nera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
Monocotyledon weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Le A 32 451-Foreign Countries Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
Monocotyledon crops of the eg nera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
Depending on the concentration, the compounds are suitable for total weed control, for example on industrial terrain and rail tracks and on paths and areas with or without tree growth. Equally, the compounds can be employed for controlling weeds in perennial crops, for example forests, ornamental tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea 1 S plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hop fields, on lawns and turf and pastures and for selective geed control in annual crops.
'Ihe compounds of the formula (I) according to the invention are particularly suitable for selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops both by the pre-emergence and by the post-emergence method.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspoemulsion concentrates, natural and synthetic substances impregnated with active compound, and microencapsulations in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is to say liquid solvents and/or solid carriers, optionally with the use of surfactants, that is to say emulsifiers and/or dispersants and/or foam-formers.
Le A 32 451-Foreign Countries If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. Liquid solvents which are mainly suitable are: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as 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.
Suitable solid Garners are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly disperse silica, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite, and synthetic granules of inorganic and organic meals, and granules of organic material, such as sawdust, coconut shells, maize cobs and tobacco stalks;
suitable emulsifiers and/or foam-formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: for example lignin-sulfite waste liquors and methylcellulose.
Adhesives, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use dyestuffs, such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyestuffs, such as alizarin dyestuffs, azo Le A 32 451-Forei~ Countries dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general comprise between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulfuron, asulam, atrazine, azimsulfuron, benazolin, benfuresate, bensulfuron(-methyl), bentazon, benzofenap, benzoylprop(-ethyl), bialaphos, bifenox, bromobutide, bromofenoxim, bromoxynil, butachlor, butylate, cafenstrole, carbetamide, chlomethoxyfen, chloramben, chloridazon, chlorimuron(-ethyl), chlornitrofen, chlorsulfuron, chlortoluron, cinmethylin, cinosulfuron, clethodim, clodinafop(-propargyl), clomazone, clopyralid, clopyrasulfuron, cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, dicamba, diclofop(-methyl), difenzoquat, diflufenican, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dinitramine, diphenamid, diquat, dithiopyr, diuron, dymron, EPTC, esprocarb, ethalfluralin, ethametsulfuron(-methyl), ethofumesate, ethoxyfen, etobenzanid, fenoxaprop(-ethyl), flamprop(-isopropyl), flamprop(-isopropyl-1), flamprop(-methyl), flazasulfuron, fluazifop(-butyl), flumetsulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, fluometuron, fluorochloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurenol, fluridone, fluroxypyr, flurprimidol, flurtamone, fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), hexazinone, imazamethabenz(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, imazosulfuron, ioxynil, isopropalin, isoproturon, isoxaben, isoxaflutole, isoxapyrifop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron, metazachlor, Le A 32 451-Foreign Countries methabenzthiazuron, metobenzuron, metobromuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron(-methyl), molinate, monolinuron, naproanilide, napropamide, neburon, nicosulfuron, norflurazon orbencarb, oryzalin, oxadiazon, oxyfluorfen, paraquat, pendimethalin, phenmedipham, piperophos, pretilachlor, primisulfuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propyzamide, prosulfocarb, prosulfuron, pyrazolate, pyrazosulfuron(-ethyl), pyrazoxyfen, pyributicarb, pyridate, pyrithiobac(-sodium), quinchlorac, quinmerac, quizalofop(-ethyl), quizalofop(-p-tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron(-methyl), sulfosate, tebutam, tebuthiuron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulfuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasulfuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulfuron.
A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, 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 customary manner, for example by watering, spraying, atomizing, spreading.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the examples which follow.
Le A 32 451-Foreign Countries Preparation Examples:
Examule 1 OH H
O N O
I N
H ~ ~ -CI
O CI
A mixture of 6.9 g (21 mmol) of ethyl [1-(2,3-dichloro-benzyl)-2,5-dioxo-2,5-dihydro-1H-pyrrol-3-yl)-carbamate, 1.0 g of sodium hydroxide, 100 ml of water and 300 ml of dioxane is heated under reflux for 4 hours and then concentrated under a waterpump vacuum. The residue is then shaken with 1N hydrochloric acid and ethyl acetate and the organic phase is separated off, dried with sodium sulfate and filtered.
The filtrate is concentrated under a waterpump vacuum, the residue is digested with diethyl ether and the product obtained as crystals is isolated by filtration with suction.
4.3 g (65% of theory) of 1-(2,3-dichloro-benzyl)-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidine-4-carboxylic acid of melting point 229°C are obtained.
Example 2 O N O
I ~ \ I
H ~ ~ -cl O CI
A mixture of 4.1 g (13 mmol) of 1-(2,3-dichloro-benzyl)-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidine-4-carboxylic acid (cf. Example 1 ), 5.0 g (40 mmol) of dimethyl sulfate, 10.8 g of potassium carbonate and 100 ml of acetonitrile is heated under reflux for 18 hours and then concentrated under a waterpump vacuum. The residue is shaken with water and ethyl acetate and the organic phase is separated off, Le A 32 451-Foreign Countries washed with water, dried with sodium sulfate and filtered. The solvent is distilled off carefully from the filtrate under a waterpump vacuum.
2.3 g (52% of theory) of methyl 1-(2,3-dichloro-benzyl)-3-methyl-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidine-4-carboxylate of melting point 88°C are obtained.
Example 3 NHZ i H3 N O
° I ~ ~
N
H CI
O CI
2.1 g (6.1 mmol) of methyl 1-(2,3-dichloro-benzyl)-3-methyl-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidine-4-carboxylate are dissolved in 50 ml of tetrahydrofuran, a solution of 2.0 g of ammonium chloride in 40 ml of concentrated aqueous ammonia solution is added and the mixture is stirred at room temperature (about 20°C) for 5 hours. After addition of a further 1.0 g of ammonium chloride in 20 ml of concentrated aqueous ammonia solution, the reaction mixture is stirred at room temperature for a further 12 hours and then concentrated under a waterpump vacuum.
The residue is dissolved in water and the solution is acidified with 1N
hydrochloric acid. The product obtained as crystals here is isolated by filtration with suction.
1.2 g (50% of theory) of 1-(2,3-dichloro-benzyl)-3-methyl-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidine-4-carboxamide of melting point 209°C are obtained.
Le A 32 451-Foreign Countries Example 4 NC N O
N
H CI
O CI
A solution of 0.5 ml of trifluoroacetic anhydride in 1 ml of methylene chloride is added to a mixture, cooled to 0°C, of 1.0 g (3 mmol) of 1-(2,3-dichloro-benzyl)-3-methyl-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidine-4-carboxamide, 1.5 ml of pyridine and 10 ml of methylene chloride, while stirring, and the reaction mixture is stirred in a thawing ice-bath for 12 hours. It is then poured onto water and shaken with methylene chloride. The organic phase is separated off, washed with water, dried with sodium sulfate and filtered. The filtrate is concentrated under a waterpump vacuum, the residue is digested with diisopropyl ether and the product obtained as crystals is isolated by filtration with suction.
0.5 g (54% of theory) of 1-(2,3-dichloro-benzyl)-3-methyl-2,6-dioxo-1,2,3,6-tetrahydro-pyrimidine-4-carbonitrile of melting point 152°C is obtained.
Le A 32 451-Foreign Countries The compounds of the formula ()7 listed in the following Table 1, for example, can also be prepared analogously to Preparation Examples 1 to 4 and in accordance with the general description of the preparation process according to the invention.
R' t RZ N\ /O
(I) R3 N~A~Ar O
Table 1: Examples of the compounds of the formula (I) Ex- A Ar Rl R2 R3 Physical ample data No.
CH2 ~ CH3 COOH H (amorphous) /
'CI
CI
6 CHCH3 ~ CH3 CN H
'CI
CI
7 CH2CH2 ~ CH3 CN H
/
'CI
CI
/
'CI
CI
8 CH2 ~ CH3 CN Cl 'CI
CI
Le A 32 451-Foreign Countries (continuation) Table 1:
Exam A Ar - Rl R2 R3 physical ple data No.
CI
Le A 32 451-Foreign Countries (continuation) Table 1:
Exam A Ar - Rl R2 R3 physical ple data No.
9 CH2 ~ CH3 CN CH3 /
'CI
CI
/ CI
CI
11 CH2 ~ CH3 CSNH2 H Melting / point: 190°C
'CI
CI
/ CI
CI
13 CH2 ~ CI CH3 CN H
/
CI
CI
Le A 32 451-Foreign Countries (continuation) Table 1:
Exam A Ar Rl R2 R3 Physical pleNo data 1 S CH2 ~ CI CH3 CN H
/
CI
16 CH2 ~ CI CH3 CN H
/
17 CH2 ~ CH3 CN H
/
CI
18 CH2 ~ CH3 CN H
/
CI
19 CH2 ~ CH3 CN H
/
'CN
CI
20 CH2 ~ CH3 CN H
/
-CI
CN
21 CH2 ~ CH3 CN H
'CN
F
Le A 32 451-Foreign Countries (continuation) Table 1:
Exam A Ar Ri R2 R3 Physical pleNo data 22 CH2 ~ CH3 CN H
'F
CI
23 CH2 ~ CH3 CN H
-CI
F
24 CH2 ~ CH3 CN H
CI
25 CH2 ~ CH3 CN H
CI
26 CH2 CI CH3 CN H Melting point:
156°C
CI
27 CH2 CI CH3 CSNH2 H Melting point:
166°C
CI
28 CH2 ~i H COOH H Melting point:
239°C
CI
Le A 32 451-Foreign Countries (continuation) Table 1:
Exam A . Ar Rl R2 R3 Physical ple data No.
29 CH2 CI CH3 COOCH3 H Melting point:
CI
30 CH2 CI CH3 COON H Melting point:
CI
31 CH2 CI CH3 CONH2 H Melting point:
CI
Le A 32 451-Foreign Countries Starting substances of the formula (II):
Example (II-1) O~CZHs ~ H
O~N~
H
CI CI
A mixture of 5.0 g (28 mmol) of 2,3-dichloro-benzylamine, 5.3 g (28 mmol) of ethyl (2,5-dioxo-2,5-dihydro-furan-3-yl)-carbamate and 50 ml of acetic acid is heated at the boiling point under reflux for about 40 hours and then concentrated under a waterpump vacuum. The residue is digested with diethyl ether and the product obtained as crystals is isolated by filtration with suction.
6.6 g (69% of theory) of ethyl [1-(2,3-dichloro-benzyl)-2,5-dioxo-2,5-dihydro-pyrrol-3-yl]-carbamate of melting point 179°C are obtained.
Le A 32 451-Foreign Countries The compounds of the formula (II) listed in the following Table 2, for example, can also be prepared analogously to Example (lI-1).
OAR
~ H
O~N~
R3 / O (II) N
O ~A--~
S
Table 2: Examples of the compounds of the formula (II) Example A Ar R R' Physical data No.
II-2 CH2 \ CH3 Cl /
CI
II-3 CH2 \ CH3 CH3 /
~CI
CI
CI
CI
\
CI
Le A 32 451-Foreign Countries (continuation) Table 2:
Example A Ar R R' Physical data No.
II-6 CH2 ~ CI CH3 H
CI
II-7 CHCH3 ~ CH3 H
/
I
CI
II-8 CH2CH2 ~ CH3 H
/
I
CI
lI-9 CH2 ~ CI CH3 H
CI
CI
Le A 32 451-Foreign Countries Use Examples:
Example A
Pre-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, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is watered with the preparation of the active compound. It is expedient to keep constant the amount of water per unit area here. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0 % - no action (like untreated control) 100 % - total destruction In this test, at an application amount of 250 g/ha, for example, the compound according to Preparation Example 4 shows a potent action against weeds, such as Setaria (100%) and Amaranthus (95%), coupled with a good tolerance by crop plants, such as, for example, maize (20%) arid sugar beet (20%).
Le A 32 451-Foreign Countries - 24a -Table A
Pre-emergence test / greenhouse Active compound Application Maize Sugarbeet Setaria Amaranthus according to preparation amount no. (g ai./ha) CN N O
I N \ I
H CI
O CI
(4) Le A 32 451-Foreign Countries 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, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5-15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is so chosen that the particular amounts of active compound desired are applied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0 % = no action (like untreated control) 100 % = total destruction In this test, at an application amount of 250 g/ha, for example, the compound according to Preparation Example 4 shows a potent action against weeds, such as Abutilon (100%), Amaranthus (80%), Galium (80%) and Sinapis (80%).
Le A 32 4S1-Foreign Countries - 2Sa -Table B
Post-emergence test / greenhouse Active compound Application Abutilon Amaranthus Galium Sinapis according to preparation amount no. (g ai./ha) CN N O
N w I
H CI
O CI
(4)
'CI
CI
/ CI
CI
11 CH2 ~ CH3 CSNH2 H Melting / point: 190°C
'CI
CI
/ CI
CI
13 CH2 ~ CI CH3 CN H
/
CI
CI
Le A 32 451-Foreign Countries (continuation) Table 1:
Exam A Ar Rl R2 R3 Physical pleNo data 1 S CH2 ~ CI CH3 CN H
/
CI
16 CH2 ~ CI CH3 CN H
/
17 CH2 ~ CH3 CN H
/
CI
18 CH2 ~ CH3 CN H
/
CI
19 CH2 ~ CH3 CN H
/
'CN
CI
20 CH2 ~ CH3 CN H
/
-CI
CN
21 CH2 ~ CH3 CN H
'CN
F
Le A 32 451-Foreign Countries (continuation) Table 1:
Exam A Ar Ri R2 R3 Physical pleNo data 22 CH2 ~ CH3 CN H
'F
CI
23 CH2 ~ CH3 CN H
-CI
F
24 CH2 ~ CH3 CN H
CI
25 CH2 ~ CH3 CN H
CI
26 CH2 CI CH3 CN H Melting point:
156°C
CI
27 CH2 CI CH3 CSNH2 H Melting point:
166°C
CI
28 CH2 ~i H COOH H Melting point:
239°C
CI
Le A 32 451-Foreign Countries (continuation) Table 1:
Exam A . Ar Rl R2 R3 Physical ple data No.
29 CH2 CI CH3 COOCH3 H Melting point:
CI
30 CH2 CI CH3 COON H Melting point:
CI
31 CH2 CI CH3 CONH2 H Melting point:
CI
Le A 32 451-Foreign Countries Starting substances of the formula (II):
Example (II-1) O~CZHs ~ H
O~N~
H
CI CI
A mixture of 5.0 g (28 mmol) of 2,3-dichloro-benzylamine, 5.3 g (28 mmol) of ethyl (2,5-dioxo-2,5-dihydro-furan-3-yl)-carbamate and 50 ml of acetic acid is heated at the boiling point under reflux for about 40 hours and then concentrated under a waterpump vacuum. The residue is digested with diethyl ether and the product obtained as crystals is isolated by filtration with suction.
6.6 g (69% of theory) of ethyl [1-(2,3-dichloro-benzyl)-2,5-dioxo-2,5-dihydro-pyrrol-3-yl]-carbamate of melting point 179°C are obtained.
Le A 32 451-Foreign Countries The compounds of the formula (II) listed in the following Table 2, for example, can also be prepared analogously to Example (lI-1).
OAR
~ H
O~N~
R3 / O (II) N
O ~A--~
S
Table 2: Examples of the compounds of the formula (II) Example A Ar R R' Physical data No.
II-2 CH2 \ CH3 Cl /
CI
II-3 CH2 \ CH3 CH3 /
~CI
CI
CI
CI
\
CI
Le A 32 451-Foreign Countries (continuation) Table 2:
Example A Ar R R' Physical data No.
II-6 CH2 ~ CI CH3 H
CI
II-7 CHCH3 ~ CH3 H
/
I
CI
II-8 CH2CH2 ~ CH3 H
/
I
CI
lI-9 CH2 ~ CI CH3 H
CI
CI
Le A 32 451-Foreign Countries Use Examples:
Example A
Pre-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, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is watered with the preparation of the active compound. It is expedient to keep constant the amount of water per unit area here. The concentration of the active compound in the preparation is of no importance, only the amount of active compound applied per unit area being decisive.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0 % - no action (like untreated control) 100 % - total destruction In this test, at an application amount of 250 g/ha, for example, the compound according to Preparation Example 4 shows a potent action against weeds, such as Setaria (100%) and Amaranthus (95%), coupled with a good tolerance by crop plants, such as, for example, maize (20%) arid sugar beet (20%).
Le A 32 451-Foreign Countries - 24a -Table A
Pre-emergence test / greenhouse Active compound Application Maize Sugarbeet Setaria Amaranthus according to preparation amount no. (g ai./ha) CN N O
I N \ I
H CI
O CI
(4) Le A 32 451-Foreign Countries 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, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5-15 cm are sprayed with the preparation of the active compound in such a way as to apply the particular amounts of active compound desired per unit area. The concentration of the spray liquor is so chosen that the particular amounts of active compound desired are applied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in comparison to the development of the untreated control.
The figures denote:
0 % = no action (like untreated control) 100 % = total destruction In this test, at an application amount of 250 g/ha, for example, the compound according to Preparation Example 4 shows a potent action against weeds, such as Abutilon (100%), Amaranthus (80%), Galium (80%) and Sinapis (80%).
Le A 32 4S1-Foreign Countries - 2Sa -Table B
Post-emergence test / greenhouse Active compound Application Abutilon Amaranthus Galium Sinapis according to preparation amount no. (g ai./ha) CN N O
N w I
H CI
O CI
(4)
Claims (8)
1. Arylalkyluracils of the general formula (I), characterized in that A represents straight-chain or branched alkanediyl, Ar represents in each case optionally substituted phenyl or naphthyl, R1 represents hydrogen, amino or optionally substituted alkyl, R2 represents cyano, carboxyl, carbamoyl, thiocarbamoyl or optionally substituted alkoxycarbonyl and R3 represents hydrogen, halogen or alkyl.
2. Process for the preparation of arylalkyluracils of the general formula (I) in which R1, R2, R3, A and Ar have the meanings given in Claim 1, characterized in that N-arylalkyl-1-alkoxycarbonylaminomaleimides of the general formula (II) in which A, Ar and R3 have the abovementioned meanings and R represents alkyl, are reacted with a metal hydroxide in the presence of water, and the arylalkyluracils obtained here, of the general formula (Ia) in which A, Ar and R3 have the abovementioned meanings, are optionally converted into other compounds of the formula (I) within the definition of the substituents.
3. Herbicidal compositions, characterized by a content of at least one arylalkyluracil of the formula (I) according to Claim 1.
4. Method of controlling undesirable plants, characterized in that aarylalkyluracils of the formula (I) according to Claim 1 are allowed to act on undesirable plants and/or their environment.
5. Use of arylalkyluracils of the formula (I) according to Claim 1 for controlling undesirable plants.
6. Process for the preparation of herbicidal compositions, characterized in that arylalkyluracils of the formula (I) according to Claim 1 are mixed with extenders and/or surface-active substances.
7. N-Arylalkyl-1-alkoxycarbonylamino-maleimides of the general formula (II) characterized in that A represents straight-chain or branched alkanediyl, Ar represents in each case optionally substituted phenyl or naphthyl, R3 represents hydrogen, halogen or alkyl and R represents alkyl.
8. Arylalkyluracils of the general formula (Ia) characterized in that A, Ar and R3 have the meanings given in Claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1997123525 DE19723525A1 (en) | 1997-06-05 | 1997-06-05 | Substituted arylalkyl uracils |
| DE19723525.5 | 1997-06-05 | ||
| PCT/EP1998/003060 WO1998055462A1 (en) | 1997-06-05 | 1998-05-25 | Substituted arylalkyl uracils |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2292475A1 true CA2292475A1 (en) | 1998-12-10 |
Family
ID=7831440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002292475A Abandoned CA2292475A1 (en) | 1997-06-05 | 1998-05-25 | Substituted arylalkyl uracils |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0986543A1 (en) |
| AU (1) | AU7915598A (en) |
| BR (1) | BR9810418A (en) |
| CA (1) | CA2292475A1 (en) |
| DE (1) | DE19723525A1 (en) |
| WO (1) | WO1998055462A1 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400508A (en) * | 1980-11-18 | 1983-08-23 | Ube Industries, Ltd. | Orotic acid derivatives |
| ATE111901T1 (en) * | 1990-01-18 | 1994-10-15 | Nissan Chemical Ind Ltd | URACIL DERIVATIVES AND PESTICIDES CONTAINING THEM AS ACTIVE SUBSTANCES. |
-
1997
- 1997-06-05 DE DE1997123525 patent/DE19723525A1/en not_active Withdrawn
-
1998
- 1998-05-25 AU AU79155/98A patent/AU7915598A/en not_active Abandoned
- 1998-05-25 WO PCT/EP1998/003060 patent/WO1998055462A1/en not_active Application Discontinuation
- 1998-05-25 CA CA002292475A patent/CA2292475A1/en not_active Abandoned
- 1998-05-25 BR BR9810418-7A patent/BR9810418A/en not_active Application Discontinuation
- 1998-05-25 EP EP98929371A patent/EP0986543A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP0986543A1 (en) | 2000-03-22 |
| AU7915598A (en) | 1998-12-21 |
| BR9810418A (en) | 2000-07-25 |
| DE19723525A1 (en) | 1998-12-10 |
| WO1998055462A1 (en) | 1998-12-10 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |