WO2000064890A1 - 3-(heterocycl-1-yl)-uraciles herbicides - Google Patents

3-(heterocycl-1-yl)-uraciles herbicides Download PDF

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Publication number
WO2000064890A1
WO2000064890A1 PCT/US2000/010723 US0010723W WO0064890A1 WO 2000064890 A1 WO2000064890 A1 WO 2000064890A1 US 0010723 W US0010723 W US 0010723W WO 0064890 A1 WO0064890 A1 WO 0064890A1
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alkyl
amino
alkoxy
formula
group
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PCT/US2000/010723
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English (en)
Inventor
Stefan Scheiblich
Trevor William Newton
Peter Johannes Servaas Van Eijk
Isabel Waldeck
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American Cyanamid Company
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Priority claimed from US09/495,322 external-priority patent/US6376426B1/en
Application filed by American Cyanamid Company filed Critical American Cyanamid Company
Priority to AU44774/00A priority Critical patent/AU4477400A/en
Publication of WO2000064890A1 publication Critical patent/WO2000064890A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • 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
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles

Definitions

  • the present invention relates to heterocyclyl-uracils in which the 3-position of the uracil moiety is directly attached to the nitrogen of the heterocyclyl group.
  • herbicidal compounds play an important role in agriculture and related fields. Growers seek herbicides that kill pest plants, but do not reduce crop yield. Although numerous selective herbicides have been described, there is, nevertheless, a considerable interest in new compounds having superior or different activities, because the known herbicidal compounds either are not suitable for application in certain crops, or are not sufficiently selective or active. Herbicidal heterocyclyl-uracils are known, for example, from JP-A 91-
  • heterocyclyl-uracils in which the heterocyclyl group is attached to the uracil group in the 3-position via the nitrogen atom have not yet been described.
  • R 1 and R 2 together with the interjacent nitrogen atom form an optionally substituted, optionally benzo-condensed 5-membered heterocyclic ring
  • R 3 represents a hydrogen atom, or an amino, a cyano or a hydroxy group, or an alkyl or alkoxy group optionally substituted by one or more substituents selected from halogen atoms, cyano and alkoxy groups,
  • R 4 represents a halogen atom, or a formyl, a hydroxyiminomethyl, a cyano, a carboxy, an alkoxycarbonyl, a carbamoyl, a thiocarbamoyl, an alkyl, an alkoxy, an alkylthio, a haloalkyl, a haloalkoxy or a haloalkylthio group
  • R 5 represents a hydrogen or halogen atom, or an alkyl group; or an agriculturally acceptable salt or N-oxide thereof.
  • the new compounds show excellent selective herbicidal activity in various crops.
  • alkyl, alkenyl or alkynyl groups may be linear or branched and may contain up to 12, preferably up to 6, and most preferably up to 4, carbon atoms.
  • Alkyl groups preferably contain one to six carbon atoms, alkenyl and alkynyl groups contain preferably two to 8 carbon atoms.
  • alkyl portion of a haloalkyl, haloalkenyl, haloalkoxy, alkylthio, haloalkylthio or alkoxy group suitably has up to 12 carbon atoms, preferably up to 6, and most preferably up to 4, carbon atoms.
  • the double bond of the alkenyl and haloalkenyl groups is as a rule located in the 1- or 2-position with respect to the point of their attachment.
  • the number of carbon atoms in the alkoxyalkyl, alkoxyalkoxy or dialkoxyalkyl groups is up to 12, preferably up to 6, e.g. methoxymethyl, methoxymethoxy, methoxyethyl, ethoxymethyl, ethoxyethoxy, dimethoxymethyl.
  • "Halogen” means a fluorine, chlorine, bromine or iodine atom, preferably fluorine, chlorine or bromine.
  • heteroaromatic or heteroaliphatic ring containing at least one nitrogen atom.
  • examples include azoles such as imidazole, pyrrole, pyrazole and triazole as well as the corresponding hydrogenated groups.
  • benzo-condensed shall mean a bicyclic aromatic ring system, in which one ring is a benzene ring and the other is a heterocyclyl group. Examples include indole, indazol, isoindol, carbazol, benzimidazol and benzotriazol.
  • Haloalkyl, haloalkenyl, haloalkylthio and haloalkoxy are preferably mono-, di-, tri-, tetra- or pentafluoroalkyl, -alkenyl, -alkylthio and -alkoxy, or monochloro- or dichloroalkenyl, or monobromoalkenyl, especially preferred are trifluoromethyl, tetrafluoroethyl, pentafluoroethyl, octafluorobutyl, 3,3,3- trifluoroprop-1 -enyl, 2-methyl-3,3,3-trifluoroprop-1 -enyl, 4,4,4-trifluorobut-1 -enyl, 1 ,2-difluorobuta-1 ,3-dienyl, 1- or 2-chlorovinyl, 2,2-dichlorovinyl, 1 ,2-dichlorovinyl, 1 ,
  • the substituent groups which are optionally present may be any of those customarily employed in the modification and/or development of pesticidal compounds and are especially substituents that maintain or enhance the herbicidal activity associated with the compounds of the present invention, or influence persistence of action, soil or plant penetration, or any other desirable property of such herbicidal compounds. There may be one or more of the same or different substituents present in each part of the molecules.
  • substituents include phenyl, halogen atoms, nitro, cyano, hydroxyl, C ⁇ -alkoxy, C ⁇ -haloalkoxy, C ⁇ -haloalkylthio and C ⁇ -alkoxycarbonyl groups.
  • herbicide and herbicidal are used to denote the inhibitive control or modification of undesired plant growth.
  • Inhibitive control and modification include all deviations from natural development such as, for example, total killing, growth retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, leaf burn and dwarfing.
  • herbicidally effective amount is used to denote any amount which achieves such control or modification when applied to the undesired plants themselves or the area in which these plants are growing.
  • plants is intended to include germinated seeds, emerging seedlings and established vegetation, including both roots and above-ground portion.
  • agriculturally acceptable salts is used herein to denote a salt or salts which readily ionize in aqueous media and includes sodium, potassium, calcium, ammonium, and magnesium salts and acid salts such as hydrochloride, sulfate and nitrate.
  • the compounds according to formula I include oils, gums, or, predominantly, crystalline solid materials.
  • dicotyledoneous species Abutilon, Amaranthus, Ambrosia, Anthemis, Brassica, Centaurea, Chenopodium, Chrysanthemum, Cirsium, Convolvus, Datura, Galeopsis, Galinsoga, Galium, Ipomoea, Lamium, Lepidium, Matricaria, Papaver, Pharbitis, Polygonum, Portulaca, Senecio, Sinapis, Sesbana, Solanum, Sonchus, Stellaria, Urtica, Veronica, Viola and Xanti ⁇ m; monocotyledoneous species: Alopecurus, Apera, Avena, Brachiaria,
  • the compounds of formula I can be used in particular for the control of Alopecurus myosuroides, Echinochloa crus-galli, Setaria viridis, Galium aparine, Stellaria media, Veronica persica, Lamium pu ⁇ ureum, Viola arvensis, Abutilon theophrasti, Ipomoea purpurea and Amaranthus retroflexus by pre- and post-emergence application.
  • R 3 represents an amino, a hydroxy or a methyl group
  • R 4 represents a halogen atom, or a cyano, a C ⁇ fluoroalkyl, a C ⁇ fluoroalkoxy or a C 1J( fluoroalkylthio group
  • R 5 represents a hydrogen or halogen atom, or a methyl group.
  • NR 1 R 2 represents a group selected from the formulae (1) and (2)
  • X represents N or CR ⁇
  • Y represents N or CR 7
  • R 6 represents a hydrogen or halogen atom, or a formyl, a nitro, a alkoxyiminoalkyl, a cyano, a carboxy, an amino, an alkylamino, an alkoxycarbonyl, a carbamoyl, a thiocarbamoyl an alkyl or an alkoxy group
  • R 7 represents a hydrogen or halogen atom or an alkyl group
  • L 1 and L 2 each independently represent hydrogen; halogen; nitro; amino; hydroxy; cyano; alkyl; alkoxyimino-alkyl; alkenyloxyimino-alkyl; alkenyloxyimino- alkoxycarbonyl-alkyl; alkoxycarbonyl-alkoxyimino-alkyl, hydroxy-alkyl; alkoxy-alkyl; di-(alkoxy)-alkyl, di-(alkylthio)-alkyl, alkylsulfonylamino-alkyl; halo- alkylsulfonylamino-alkyl; (alkyl) r amino-alkyl; (alkylcarbonyloxy) z -alkyl; haloalkyl; cyanoalkyl, cyanoalkenyl, formyl; alkylcarbonyl; or ZR 8 wherein Z is O, NR 9 or S(O) r or
  • alkyl haloalkyl; hydroxyalkyl; arylalkyl; cyanoalkyl; alkanoyloxyalkyl; alkoxyalkyl; cycloalkyl, alkenyl; alkoxyimino-alkoxycarbonyl-alkyl, di-(alkoxy)-alkyl or alkynyl;
  • R 9 is hydrogen; alkyl; alkenyl; alkynyl, amino, formyl or alkylcarbonyl;
  • R 10 is NR 12 , alkylidene or alkenylidene or a group of formula
  • R 11 is alkyl; haloalkyl; haloalkoxy, hydrogen; hydroxy; alkoxy; alkoxyalkyl; alkanoyloxyalkyl, alkanoyloxyalkoxy, alkoxyalkoxy; alkoxyalkylamino; dialkoxyalkylamino; aryl, aryloxy; azolyl, azolyloxy, cycolalkyl, cycloalkoxy, aralkyl; aralkoxy, alkoxycarbonyl; alkoxycarbonyloxy, hydroxycarboxyl; alkoxycarbonylalkyl; alkoxycarbonylalkoxy,; hydroxycarbonylalkoxy, (alkyl) r amino; (cycloalkyl) r amino; N- cycloalkyl-N-(alkyl) s amino; (alkyl) r hydrazino; alkoxycarbonyl-alkylamino; hydroxyalkylamino
  • R 12 is hydrogen; alkyl; alkenyl; alkynyl, amino, formyl, alkylcarbonyl, alkoxycarbonyl or alkyisulfonyl;
  • R 13 is hydrogen; alkyl, alkoxy; alkenyloxy; alkynyloxy or alkanoyloxy;
  • M or Q is alkoxy; alkyl; (alkyl) r amino; hydroxy; hydrogen; alkenyloxy; (alkenyl) r amino; alkynyloxy; or (alkynyl) r amino;
  • W is oxygen, sulfur or N-alkoxy;
  • P is phosphorus;
  • m represents 1 or 2;
  • n represents an integer from 1 to 4;
  • r represents an integer from 0 to 2;
  • s represents 0 or 1 ;
  • t represents an integer from 0 to 6; and
  • z represents 1 or 2.
  • L 1 and L 2 each independently represent hydrogen; halogen; nitro; amino; hydroxy; cyano; C ⁇ -alkyl; C ⁇ -alkoxyimino- C ⁇ -alkyl; alkenyloxyimino- C ⁇ -alkyl; C 2 _ 8 alkenyloxyimino- C ⁇ -alkoxycarbonyl- C ⁇ -alkyl; C ⁇ -alkoxycarbonyl-C ⁇ - aikoxyimino-alkyl, hydroxy- C ⁇ -alkyl; C ⁇ -alkoxy-C ⁇ -alkyl; di-(C ⁇ -alkoxy)-C ⁇ - alkyl, di-(alkylthio)-alkyl, C ⁇ -alkylsulfonylamino-C ⁇ -alkyl; halo-C ⁇ - alkylsulfonylamino-C ⁇ -alkyl; (C ⁇ -alkyl)n
  • ZR 8 wherein Z is O, NR 9 or S(O) r or a single bond
  • R 8 is -(R 10 ) ,-CWR 11 ; -(R 10 ) 8 -SO 2 R 11 ; W
  • R 10 is NR 12 , C,_ 4 alkylidene or C ⁇ alkenylidene
  • R 11 is C ⁇ -alkyl; halo-C ⁇ -alkyl; halo-C ⁇ -alkoxy, hydrogen; hydroxy; C ⁇ -alkoxy; C ⁇ -alkoxy- C ⁇ -alkyl; C ⁇ -alkoxy-C ⁇ -alkoxy; C ⁇ -alkoxy-C ⁇ -alkylamino; di- C ⁇ alkoxy-C ⁇ e -alkylamino; phenyl, phenoxy; C 3 ⁇ -cycolalkyl, C 3 .
  • R is hydrogen; C ⁇ -alkyl; C 2 . 8 -alkenyl; C 2 . 8 -alkynyl, formyl, C ⁇ -alkylsulfonyl, C 1-6
  • M or Q is C ⁇ -alkoxy; C ⁇ -alkyl; (C, ⁇ -alkyl) r amino; hydroxy; hydrogen; C 2 . 8 - alkenyloxy; (C 2 . 8 -alkenyl) r amino; C 2 . 8 -alkynyloxy; or (C 2 . 8 -alkynyl) r amino.
  • Especially preferred compounds of formula I include those wherein NR 1 R 2 represents a substituted ind(az)ol-1-yl group of formula (2) having a substituent L 2 at the 4-position which is not hydrogen.
  • R 3 represents an amino, a hydroxy or a methyl group
  • R 4 represents a halogen atom, or a cyano, a C ⁇ fluoroalkyl, a C ⁇ 4 fluoroalkoxy or a C 1-4 fluoroalkylthio group
  • R 5 represents a hydrogen or halogen atom, or a methyl group.
  • R 3 through R 6 , L 2 , X and n are as described herein below and above, especially a heterocycl-lyluracil of formula IA2
  • R 3 through R 5 have the meaning given, and R represents an alkyl, aryl or aralkyl group, with a heterocycl-1-ylcarbamate of formula III
  • R 1 and R 2 have the meaning given, and R represents an alkyl, aryl or aralkyl group.
  • R 4 and R 5 have the meaning given, and R' represents a hydrogen atom or an alkyl, aryl or aralkyl group, with a heterocycl-1-ylamine of formula V H
  • Suitable leaving groups include but are not limited to, halogen, nitro, hydroxy, tosylate, mesylate, alkyl- or arylsulfonyl and alkyl- or arylsulfonyloxy groups.
  • R 3 represents an alkyl group
  • the compounds of formula I may be obtained by reaction of the compound of formula 1C, with an alkylating agent of formula VI, wherein R 3 represents an alkyl group such as alkylhalides, in particular alkylbromides or alkyliodides, or dialkylsulfates, in the presence of a base at a suitable temperature.
  • the compounds of formula I may be obtained by reaction of the compound of formula 1C, with an nitrosylation agent followed by the reduction of the obtained N-nitrosamine or by reaction with 2,4-dinitrophenoxyamine in the presence of a base.
  • the nitrosylation reaction may be carried out in water, a dilute acid or an inert organic solvent at a suitable temperature.
  • the reaction with 2,4-dinitrophenoxyamine is as a rule carried out in an inert solvent.
  • the reactions mentioned hereinabove and herein below are conveniently carried out in an organic solvent.
  • any inert organic solvent is suitable, preferably aliphatic, cycloaliphatic or aromatic hydrocarbons, which may be halogenated such as hexane, iigroine, petrol ethers, cyclohexane, benzene, toluene, xylene, di-, tri- or tetrachloromethane, ethylenechloride, trichloroethylene and chlorobenzene; ethers such as diethylether, methylethylether, methyl-terf-butylether, diisopropylether, dibutylether, tetrahydrofuran and dioxane; ketones such as acetone and butane- one; nitriles such as acetonitrile and propionitrile
  • Suitable bases are inorganic and organic bases such as potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, sodium ethylate, sodium methylate, potassium fert-butylate, triethylamine, dimethylaminopyridine, pyridine, sodium hydride, sodium amide, butyllithium and lithium diisopropylamide.
  • the prepared compounds of formula I may be isolated and purified using conventional methods and techniques.
  • the starting compounds for the preparation of compounds of this invention are either known or can be prepared according to known methods.
  • the compounds of formula V may be obtained by a reacting a heterocyclic compound of formula VII
  • R 1 and R 2 have the meaning given with an amination agent such as O- mesitylsulfonyl-hydroxyiamine or O-diphenylphosphinyl-hydroxylamine in the presence of a strong base and an inert solvent at a suitable temperature.
  • an amination agent such as O- mesitylsulfonyl-hydroxyiamine or O-diphenylphosphinyl-hydroxylamine in the presence of a strong base and an inert solvent at a suitable temperature.
  • Suitable strong bases are inorganic and organic bases such as potassium terf-butylate, sodium hydride, hydride, sodium amide, potassium amide, methyllithium, butyllithium, lithium diisopropylamide and potassium hexamethyldisilazide.
  • the following acids are suitable for the preparation of the agronomically acceptable salts of the compounds of formula I: hydrohalides like hydrochloric or hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, mono- or bifunctional carboxylic acids and hydroxycarboxylic acids like acetic acid, maleic acid, succinic acid, fumaric acid, citric acid, salicylic acid, sorbic acid or lactic acid and sulfonic acids like p-toluenesulfonic acid or naphthalene-1 ,5-diyl-disulfonic acid.
  • the agronomically acceptable salts of the compounds of formula I are prepared according to conventional salt formation procedures, for example by dilution of a compound of formula I in a suitable organic solvent, addition of an acid and isolation of the salt formed by, for example, filtration and optional purification by washing with an inert solvent.
  • the invention further provides a herbicidal composition which comprises an active ingredient, which is at least one compound of formula I as defined above, and one or more carriers.
  • a method of making such a composition is also provided which comprises bringing a compound of formula I as defined above into association with the carrier(s).
  • Such a composition may contain a single active ingredient or a mixture of several active ingredients of the present invention. It is also envisaged that different isomers or mixtures of isomers may have different levels or spectra of activity and thus compositions may comprise individual isomers or mixtures of isomers.
  • a composition according to the invention preferably contains from 0.5% to 95% by weight (w w) of active ingredient.
  • a carrier in a composition according to the invention is any material with which the active ingredient is formulated to facilitate application to the locus to be treated, which may for example be a plant, seed or soil, or to facilitate storage, transport or handling.
  • a carrier may be a solid or a liquid, including material which is normally a gas but which has been compressed to form a liquid.
  • compositions may be manufactured into, e.g., emulsion or emulsifiable concentrates, solutions, oil in water emulsions, wettable powders, soluble powders, suspension concentrates, dusts, granules, water dispersible granules, aerosols, micro-capsules, gels and other formulation types by well- established procedures. These procedures may include intensive mixing and/or milling of the active ingredients with other substances, such as fillers, solvents, solid carriers, surface active compounds (surfactants), and optionally solid and/or liquid auxiliaries and/or adjuvants.
  • the form of application such as spraying, atomizing, dispersing or pouring and the type of composition may be chosen according to the desired objectives and the given circumstances.
  • Solvents may be aromatic hydrocarbons, e.g. Solvesso ® 200, substituted naphthalenes, phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, e.g. cyclohexane or paraffins, alcohols and glycols as well as their ethers and esters, e.g. ethanol, ethyleneglycol mono- and dimethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N-methyl-2- pyrrolidone, or ⁇ -butyrolactone, higher alkyl pyrrolidones, e.g. n-octylpyrrolidone or cyclohexylpyrrolidone, epoxidized plant oil esters, e.g. methylated coconut or soybean oil ester and water, or mixtures thereof.
  • aromatic hydrocarbons e.g. Solvesso ®
  • Solid carriers which may be used for dusts, wettable powders, water dispersible granules, or granules, may be mineral fillers, such as calcite, talc, kaolin, montmorillonite or attapulgite. The physical properties may be improved by addition of highly dispersed silica gel or polymers. Carriers for granules may be porous material, e.g. pumice, kaolin, sepiolite, bentonite; non-sorptive carriers may be calcite or sand. Additionally, a multitude of pre-granulated inorganic or organic materials may be used, such as dolomite or crushed plant residues.
  • Pesticidal compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application.
  • a carrier which is a surfactant facilitates this process of dilution.
  • at least one carrier in a composition according to the invention is a surfactant.
  • the composition may contain at two or more carriers, at least one of which is a surfactant.
  • Surfactants may be nonionic, anionic, cationic or zwitterionic substances with good dispersing, emulsifying and wetting properties depending on the nature of the compound according to general formula I to be formulated. Surfactants may also mean mixtures of individual surfactants. Wettable powders of this invention suitably contain 5 to 90% w/w of active ingredient to solid inert carrier, 3 to10% w/w of dispersing and wetting agents and, where necessary, 0 to 10% w/w of stabiiizer(s) and/or other additives such as penetrants or stickers.
  • Dusts may be formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and may be diluted in the field with further solid carrier to give a composition containing about 0.5 to 10% w/w of active ingredient.
  • Water dispersible granules and granules suitably may be prepared to have a size between 0.15 mm and 2.0 mm and may be manufactured by a variety of techniques. Generally, these types of granules will contain 0.5 to 90% w/w active ingredient and 0 to 20% w/w of additives such as stabilizer, surfactants, slow release modifiers and binding agents.
  • Emulsifiable concentrates of this invention may contain, in addition to a solvent or a mixture of solvents, 1 to 80% w/v active ingredient, 2 to 20% w/v emulsifiers and 0 to 20% w/v of other additives such as stabilizers, penetrants and corrosion inhibitors.
  • Suspension concentrates are suitably milled so as to obtain a stable, non- sedimenting flowable product and contain 5 to 75% w/v active ingredient, 0.5 to 15% w/v of dispersing agents, 0.1 to 10% w/v of suspending agents such as protective colloids and thixotropic agents, 0 to 10% w/v of other additives such as defoamers, corrosion inhibitors, stabilizers, penetrants and stickers, and water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or inorganic salts may be present dissolved in the formulation to assist in preventing sedimentation and crystallization or as antifreeze agents.
  • Aqueous dispersions and emulsions for example compositions obtained by diluting the formulated product according to the invention with water, also lie within the scope of the invention.
  • a carrier which will provide slow release of the pesticidal compounds into the environment of a plant which is to be protected.
  • the biological activity of the active ingredient can also be increased by including an adjuvant in the spray dilution.
  • An adjuvant is defined here as a substance which can increase the biological activity of an active ingredient but is not itself significantly biologically active.
  • the adjuvant can either be included in the formulation as a coformulant or carrier, or can be added to the spray tank together with the formulation containing the active ingredient.
  • compositions may preferably be in a concentrated form whereas the end user generally employs diluted compositions.
  • the compositions may be diluted to a concentration down to 0.001 % of active ingredient.
  • the doses usually are in the range from 0.01 to 10 kg a.i./ha.
  • Emulsion Concentrate (EC) Active Ingredient Compound of Example 4 30 % (w/v)
  • Emulsifier(s) e.g. Atlox ® 4856 B and Atlox ® 5 % (w/v)
  • Active Ingredient Compound of Example 4 50 % (w/v) Dispersing agent e.g. Soprophor ® FL 3) 3 % (w/v)
  • Antifoaming agent e.g. Rhodorsil ® 422 3) 0.2 % (w/v)
  • Antifreezing agent e.g. Propylene glycol 5 % (w/v)
  • Biocidal agent e.g. Proxel ® 5
  • WP Wettable Powder
  • Active Ingredient Compound of Example 4 60 % (w/w) Wetting agent e.g. Atlox ® 4995 1) 2 % (w/w) Dispersing agent e .g. Witcosperse ® D-60 6) 3 % (w/w)
  • Carrier / Filler e.g. Kaolin 35 % (w/w)
  • Active Ingredient Compound of Example 4 50 % (w/w)
  • Dispersing / Binding agent e.g. Witcosperse ® D-450 6
  • Wetting agent e .g. Morwet ® EFW 6
  • Antifoaming agent e.g. Rhodorsil ® EP 6703 3
  • Disintegrant e.g. Agrimer ® ATF ⁇ 2 % (w/w)
  • Carrier / Filler e.g. Kaolin 35 % (w/w)
  • compositions of this invention can also comprise other compounds having biological activity, e.g. compounds having similar or complementary pesticidal activity or compounds having plant growth regulating, fungicidal or insecticidal activity.
  • These mixtures of pesticides can have a broader spectrum of activity than the compound of formula I alone.
  • the other pesticide can have a synergistic effect on the pesticidal activity of the compound of formula I.
  • the active ingredients according to the invention can be employed alone or as formulations in combination with conventional herbicides. Such combinations of at least two herbicides can be included in the formulation or also added in a suitable form with the preparation of the tank mix. For such mixtures at least one of the following known herbicides can be used: ametrydione, metabenzthiazuron, metamitron, metribuzin, 2,4-D, 2,4-DB, 2,4-DP, alachlor, alloxydim, asulam, atrazin, bensulfuron, bentazon, bifenox, bromoxynil, butachlor, chloridazon, chlorimuron, chlorpropham, chlorsulfuron, chlortoluron, cinmethylin, clopyralid, cyanazin, cycloate, cycloxydim, dichlobenil, diclofop, eptame, ethiozin, fenoxaprop, fluazifop, fluometuron, fluridone,
  • Example 1 6-Methoxy-1 -(3-methy l-4-trifluoromethy ipyrimidin- 2,6-dion-1 -y l)-indole
  • I B 6-Methoxy-1-(4-trifluoromethylpyrimidin-2.6-dion-1-yl)-indole
  • IA 6-Methoxy-1-(4-trifluoromethylpyrimidin-2.6-dion-1-yl)-indole
  • IB 6-Methoxy-1-(4-trifluoromethylpyrimidin-2.6-dion-1-yl)-indole
  • a mixture of 1.45 g 1_B and 5 ml tetrahydrofuran (THF) is added to a suspension of 0.44 g of 60% sodium hydride in 10 ml THF at 0 °C. After 15 minutes a mixture 1.07 g O-mesitylsufonyl-hydroxylamine and 15 ml THF is added. Stirring at 0°C is continued for 1.5 hours. The mixture is poured into ice cold water, extracted with ethyl acetate, and purified by flash chromatography.
  • 6-Nitro-1-(3-methyl-4-trifluoromethylpyrimidin-2,6-dion-1-yl)-indole (3.5 g, obtained analogously to Example 1C) is dissolved in a mixture of ethyl acetate (100 mL) and ethanol (50 mL), Pd/C (10%wt) catalyst is added. A hydrogen pressure of 60 psi is applied and the hydrogenation is performed at room temperature. After removal of the hydrogenation catalyst by filtration and removal of the solvent by evaporation the amine was obtained after flash chromatography: 1.8 g, m.p. 181-184 °C.
  • This compound can be modified according to standard procedures as for example by acylation or suifonylation of the amino group.
  • Sodium hydride (60 %wt suspension in mineral oil; 0.33 g, 8.3 mmol) is suspended in dry tetrahydrofuran (THF, 10 mL) and is cooled to 0 °C.
  • reaction mixture is allowed to reach room temperature and is subsequently stirred for 3 h. Then the mixture is cooled again to 0 °C, and a second aliquot of O- mesitylenesulfonyihydroxylamine (1.25 g, 7 mmol) in THF (10 mL) is added slowly. The mixture is allowed to reach ambient temperature and is subsequently stirred overnight. The reaction mixture is worked up by adding it to water, extracting into ethyl acetate, and drying over sodium sulfate. The crude product (1.2 g) is obtained after filtration of the drying agent and evaporation of the solvent. This material is used for the next reaction step without purification.
  • the crude 168A (1.15 g, 6.88 mmol assumed) is dissolved in glacial acetic acid (15 mL) and 2-dimethyiamino-4-trifluoromethyl-[1 ,3]oxazin-6-one (1.43 g, 6.88 mmol) is added. The mixture was stirred for 4 h under reflux, after which the acetic acid iss removed in vacuo. The residue is dissolved in ethyl acetate, washed with saturated sodium carbonate solution and water, and is subsequently dried over sodium sulfate. The crude product (1.9 g) is obtained after removal of the drying agent by filtration and evaporation of the solvent. The product (100 mg) is purified by flash chromatography (ethyl acetate/petrol ether 3/7).
  • Sodium hydride (60 %wt suspension in mineral oil; 0.86 g, 21.5 mmol) is suspended in dry tetrahydrofuran (THF, 20 mL) and is cooled to 0 °C.
  • reaction mixture is allowed to reach room temperature and is subsequently stirred for 3 h. Then the mixture is cooled again to 0 °C, and a second aliquot of O- mesitylenesulfonylhydroxylamine (3.02 g, 14 mmol) in THF (25 mL) is added slowly. The mixture is allowed to reach ambient temperature and was subsequently stirred overnight.
  • the reaction mixture is worked up by adding it to water, extracting into ethyl acetate, and drying over sodium sulfate. The crude product (4 g) is obtained after filtration of the drying agent and evaporation of the solvent.
  • the aminated indole (2,2 g) is obtained as a black oil (mixture of starting material and product) after flash chromatography, using toluene as eluent.
  • the crude product (3 g) is obtained after removal of the drying agent by filtration and evaporation of the solvent.
  • the product (0.88 g) is obtained as a brown oil after flash chromatography (ethyl acetate/petrol ether 2/8).
  • the pre-emergence tests involve spraying a liquid formulation of the compound onto the soil in which the seeds of the plant species mentioned above has recently been sown.
  • the soil used in the tests is a prepared horticultural loam.
  • the formulations used in the tests are prepared from solutions of the test compounds in acetone containing 0.4% by weight of an alkylphenol/ethylene oxide condensate available under the trade mark TRITON X-155. These acetone solutions are diluted with water and the resulting formulations applied at dosage levels corresponding to 1000 g and 250 g/ha of active material per hectare in a volume equivalent to 900 litres per hectare. In these tests untreated sown soil are used as controls.
  • the post-emergence herbicidal activity of the compounds of the present invention is demonstrated by the following test, wherein monocotyledonous and dicotyledonous plants are treated with formulations prepared from solutions of the test compounds in acetone containing 0.4 % by weight of an alkylphenol/ethylene oxide condensate available under the trade mark TRITON X-155. These acetone solutions are diluted with water and the resulting formulations applied at dosage levels equivalent to about 1000, 800, 400, 250 or 100 g/ha per hectare of test compound per pot. After spraying, the plants are placed on greenhouse benches and are cared for in the usual manner, commensurate with conventional greenhouse practices.
  • the herbicidal effects of the test compounds are assessed visually twenty-one days after spraying the foliage and the soil and are recorded on a 0-9 scale.
  • a rating 0 indicates growth as untreated control, a rating 9 indicates death.
  • An increase of 1 unit on the linear scale approximates to a 10% increase in the level of effect.
  • the indazole uracil of Example 7 showed good performance both in pre- and post-emergence. In pre-emergence all of the weeds except Alopecurus were well controlled at 400 g/ha. Apart from wheat tolerance surprisingly good selectivity in maize was recorded at 100 g/ha with good control of Setaria, Abutilon, Cyperus, Ambrosia and Matricaria.
  • Example 7 displayed good cross spectrum control on both broadleaf weeds and grasses except Alopecurus with no observable crop tolerance. However, at 100 g/ha, good wheat tolerance was observed with excellent control of Setaria and all of the broadleaf weeds including Galium aparine.
  • Example 168 The indazole uracil of Example 168, showed good performance both in pre- and post-emergence. In pre-emergence all Alopecurus and four out of five broadleaf weeds were well controlled at 100 g/ha. Surprisingly good selectivity in maize and soy beans was recorded at 100 g/ha.
  • Example 168 displayed good cross spectrum control on both broadleaf weeds and grasses except Alopecurus and Echinochloa at 100 g/ha. At the lowest dose rate of 12.5 g/ha all broadleaf weeds were still well controlled.
  • the indole uracil of Example 169 showed excellent performance both in pre- and post-emergence. In pre-emergence all of the weeds except Alopecurus were well controlled at 100 g/ha. Surprisingly good selectivity in maize and soy beans was recorded at a dose rate of 25 g/ha with good control of Setaria, Abutilon, Galium, Matricaria and Stellaria.
  • Example 169 displayed good cross spectrum control on both broadleaf weeds and grasses at a dose rate of 100 g/ha. At the lowest dose rate of 12.5 g/ha excellent control of broadleaf weeds such as Abutilum, Galium, Ipomoea, Matricaria and Stellaria was recorded.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
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Abstract

L'invention porte sur de nouveaux 3-hétérocycl-1-yluraciles de la formule (I), dans laquelle R1 et R2, réunis à l'atome d'azote interjacent, forment un noyau hétérocyclique à 5 éléments, condensé par benzo, éventuellement substitué, et R3 à R5 ont la même signification donnée dans la revendication 1. L'invention porte également sur un procédé de production de ces substances et sur des compositions herbicides contenant ces composés utilisés comme ingrédients actifs.
PCT/US2000/010723 1999-04-23 2000-04-20 3-(heterocycl-1-yl)-uraciles herbicides WO2000064890A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU44774/00A AU4477400A (en) 1999-04-23 2000-04-20 Herbicidal 3-(heterocycl-1-yl)-uracils

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US29801999A 1999-04-23 1999-04-23
US09/298,019 1999-04-23
US09/495,322 2000-01-31
US09/495,322 US6376426B1 (en) 1999-04-23 2000-01-31 Herbicidal 3-(heterocycl-1-yl)-uracils

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WO2000064890A1 true WO2000064890A1 (fr) 2000-11-02

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WO (1) WO2000064890A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19652429A1 (de) * 1996-12-17 1998-06-18 Bayer Ag Heterocyclyluracile

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19652429A1 (de) * 1996-12-17 1998-06-18 Bayer Ag Heterocyclyluracile
WO1998027082A1 (fr) * 1996-12-17 1998-06-25 Bayer Aktiengesellschaft Heterocyclyluraciles

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