WO1995006039A1 - Novel phenyl glyoxylic acid derivatives, processes for producing them and their use as herbicides and plant growth regulators - Google Patents

Novel phenyl glyoxylic acid derivatives, processes for producing them and their use as herbicides and plant growth regulators Download PDF

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Publication number
WO1995006039A1
WO1995006039A1 PCT/EP1994/002629 EP9402629W WO9506039A1 WO 1995006039 A1 WO1995006039 A1 WO 1995006039A1 EP 9402629 W EP9402629 W EP 9402629W WO 9506039 A1 WO9506039 A1 WO 9506039A1
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Prior art keywords
formula
alkoxy
alkyl
group
halogen
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PCT/EP1994/002629
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German (de)
French (fr)
Inventor
Rainer SCHÜTZE
Klaus Bauer
Hermann Bieringer
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Hoechst Schering Agrevo Gmbh
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Priority to AU76527/94A priority Critical patent/AU7652794A/en
Publication of WO1995006039A1 publication Critical patent/WO1995006039A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/38—Sulfur atoms
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
    • 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
    • C07D239/60—Three or more oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/30—Only oxygen atoms

Definitions

  • New phenylglyoxylic acid derivatives processes for their preparation and their use as herbicides and plant growth regulators
  • the invention relates to the technical field of herbicides and plant growth regulators, in particular herbicides for the selective control of weeds and weeds in crops of useful plants.
  • the present invention relates to compounds of the formula (I)
  • R 1 H (C., - C 8 alkyl, which is unsubstituted or by one or more radicals from the group halogen, nitro, cyano, (C 1 -C 4 ) alkoxy, aryl and substituted aryl, or (C 3 -C 6 ) alkenyl, (C 3 -C 6 ) alkynyl or aryl, where the aryl radical is unsubstituted or by one or more radicals from the group halogen, nitro, (C 1 -C 4 ) -Alkyl, (C., ⁇ ) - alkoxy and [(C 1 -C 4 ) -alkoxy] carbonyl, or a cation suitable for agriculture, for example a metal cation, in particular alkali or alkaline earth metal cation, or an unsubstituted or substituted ammonium ion,
  • R 2 and R 3 independently of one another (C r C 4 ) alkyl, (C r C 4 ) haloalkyl, (C r C 4 ) -
  • R 4 H halogen, (C r C 4 ) alkyl, (C r C 4 ) alkoxy, (C r C 4 ) alkoxycarbonyl, nitro, cyano, or a group of the formula Q defined below,
  • R 5 , R 6 each independently of one another are H, (C r C 4 ) -alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, (C 1 -C 4 ) -alkoxy or aryl, or (C 3 -C 6 ) alkenyl, (C 3 -C 6 ) alkynyl or aryl which is unsubstituted or by one or more radicals from the group halogen, nitro, (C r C 4 ) alkyl, (C r C 4 ) - Alkoxy and (C r C 4 ) -haloalkoxy is substituted, or together with the N atom connecting them a heterocyclic radical with 3 to 7 ring atoms, which in addition to the N atom as a hetero ring atom has one or two further hetero ring atoms from the group N, O and S may be present in the possible oxidation states and may be unsubstituted or substitute
  • R 2 ' , R 3' , X 'and Y' are defined analogously to the meanings of the corresponding radicals R 2 , R 3 , X and Y in formula (I).
  • hydrocarbon-containing radicals such as. B. alkyl, alkoxy, haloalkyl and alkylthio radicals and the corresponding unsaturated and / or substituted radicals in the hydrocarbon part may each be straight-chain or branched.
  • Alkyl radicals also in the composite meanings such as alkoxy, haloalkyl, etc., mean methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl;
  • Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals, such as 2-propenyl, 2- or 3-butenyl, 2-propynyl, 2- or 3-butynyl.
  • Halogen means fluorine, chlorine, bromine or iodine.
  • Haloalkyl means alkyl which is substituted by one or more atoms from the group halogen; Haloalkyl is, for example, CF 3 , CHF 2 , CH 2 CF 3 .
  • Aryl is, for example, phenyl, naphthyl, tetrahydronaphthyl, indanyl, fluorenyl and the like, preferably phenyl.
  • Substituted aryl or substituted phenyl preferably means aryl or phenyl, which is substituted by one or more, preferably 1 to 3, radicals from the group halogen, alkyl, haloalkyl, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkanoyl, carbamoyl, mono- and di-alkylaminocarbonyl , Mono- and dialkylamino, alkylsulfinyl or alkylsulfonyl is substituted, the alkyl-containing radicals having 1 to 4 carbon atoms, in particular 1 to 2 carbon atoms, being preferred; methyl, methoxy and chlorine are particularly preferred.
  • Heterocyclic radicals for the group NR 5 R 6 are, for example, saturated, unsaturated and heteroaromatic radicals of optionally substituted compounds from the group pyrrole, imidazole, pyrazole, triazole, oxazole, propanesultam, butanesulfame, pyrrolidone, pyrazolone and their partially or completely hydrogenated system such as piperidine , Piperazine or morpholine.
  • the invention also relates to all stereoisomers which are encompassed by formula (I) and mixtures thereof.
  • Such compounds of the formula (I) contain one or more asymmetric carbon atoms or else double bonds which are not indicated separately in the general formula (I).
  • the possible stereoisomers defined by their specific spatial shape such as enantiomers, diastereomers, Z and E isomers, are all encompassed by the formulas (I) and can be obtained by conventional methods from mixtures of the stereoisomers or by stereoselective reactions in combination with the Use of stereochemically pure starting materials.
  • Preferred compounds of the formula (I) according to the invention are those in which R 1 is H, (Ci "C 5 ) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen and (C r C 4 ) alkoxy, ( C 3 -C 6 ) alkenyl, (C 3 -C 6 ) alkynyl, an alkali metal cation, an alkaline earth metal cation or an ammonium ion (NH 4 ⁇ ), preferably H, (C- Cs.-alkyl which is unsubstituted or singly or repeatedly by Halogen or (C., ⁇ ) - alkoxy is substituted,
  • R 2 and R 3 independently of one another (C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl, (C - C 4 ) alkoxy, (C 1 -C 4 ) haloalkoxy or halogen, preferably (-C-C 4 ) alkoxy or (C 1 -C 4 ) alkyl, in particular OCH 3 ,
  • R 4 H halogen, (CC 4 ) -alkyl, (C r C 4 ) -alkoxy, (CC 4 -alkoxycarbonyl, nitro, cyano or a group of the formula Q, preferably H, Cl, CH 3 , OCH 3 , CO 2 CH 3 , NO 2 or a group of the formula Q, X 0 or S, preferably O,
  • Y is CH or N, preferably CH
  • R 2 ' , R 3' , X 'and Y' are defined analogously to R 2 , R 3 , X and Y in formula (I).
  • R 2 and R 3 independently of one another (C-
  • R 4 H halogen, (C r C 4 ) alkyl, (C r C 4 ) alkoxy, Nitro, cyano or a group Q, preferably H, Cl, CH 3 , OCH 3 , CO 2 CH 3 , NO 2 or a group Q,
  • X is an oxygen atom
  • Y is a group of the formula CH
  • W is an oxygen atom
  • R 2 ' , R 3' , X 'and Y' are defined as R 2 , R 3 , X and Y in formula (I).
  • R 2 and R 3 each OCH 3 ,
  • R 4 H halogen, CH 3 , OCH 3 , CO 2 CH 3 , nitro or a group Q,
  • the invention further relates to processes for the preparation of the compounds of the formula (I) according to the invention, characterized in that
  • Nuc is a leaving group, such as. B. Cl or CH 3 -SO 2 -, reacted, wherein in the formulas (II) to (VI) above R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X and Y as in formula (I) are defined.
  • reaction with chloroformate (variant c) is carried out, for example, in dipolar aprotic solvents, preferably N, N-dimethylformamide, at room temperature under the action of a base.
  • dipolar aprotic solvents preferably N, N-dimethylformamide
  • 2-mercaptophenylglyoxylic acid takes place, for. B. in polar protic solvents, preferably water under the action of alkali metal hydroxides.
  • polar protic solvents preferably water under the action of alkali metal hydroxides.
  • the reaction of the 2-hydroxyphenylglyoxylic acid is generally carried out in dipolar aprotic solvents, preferably N, N-dimethylformamide.
  • the optionally substituted 2-mercaptophenylglyoxylic acid is obtained by methods known from the literature by reacting (subst.) Thiophenol with oxalyl chloride and cyclizing the resulting oxalic acid thiohaloester chloride in an intramolecular Friedel-Crafts acylation to give the (subst.) Benzothiophendione, which is then hydrolysed and acidified which provides (subst.) 2-mercaptophenylglyoxylic acid.
  • the (subst.) 2-hydroxyphenylglyoxylic acid can also be obtained by methods known from the literature (Chem. Reports 17, 973 (1886)) by basic hydrolysis of isatin, the resulting 2-aminophenylglyoxylic acid and the diazonium salt being subjected to a phenol boil.
  • ⁇ available methylthioethers can be prepared by oxidation with oxone (potassium peroxodisulfate).
  • the compounds of formula (I) according to the invention have excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants. Perennial weeds that are difficult to control and that sprout from rhizomes, rhizomes or other permanent organs are also well captured by the active ingredients. It does not matter whether the substances are pre-seeded, pre-emergence or Post-emergence procedures are applied.
  • the spectrum of activity extends to species such as: B. Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida on the annual side as well as Convolvulus, Cirsium, Rumex and Artemisia for the perennial weeds.
  • the compounds according to the invention are applied to the surface of the earth before germination, either the weed seedlings emerge completely or the weeds grow to the cotyledon stage, but then stop growing and finally die completely after three to four weeks.
  • the compounds according to the invention have excellent herbicidal activity against mono- and dicotyledon weeds, crop plants of economically important crops, such as, for. B. wheat, barley, rye, rice, corn, sugar beet, cotton and soy are only slightly or not at all damaged. For these reasons, the present compounds are very suitable for the selective control of undesired plant growth in agricultural crops.
  • the compounds of the formula (I) according to the invention have excellent growth-regulating properties in crop plants. They intervene regulatively in the plant's own metabolism and can thus be used to specifically influence plant constituents and to facilitate harvesting, e.g. B. by triggering desiccation and stunted growth. Furthermore, they are also suitable for general control and inhibition of undesired vegetative growth without killing the plants. Inhibiting vegetative growth plays a major role in many monocotyledonous and dicotyledonous crops, as this can reduce or completely prevent storage.
  • the compounds of formula (I) according to the invention can be used in the customary formulations in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules.
  • the invention therefore also relates to herbicidal and plant growth-regulating compositions which comprise compounds of the formula (I) or their salts.
  • the compounds of formula (I) can be formulated in different ways, depending on which biological and / or chemical-physical parameters are specified.
  • formulation options come in, for example Question: wettable powder (WP), water-soluble powder (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC) , Oil or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), pickling agents, granules for spreading and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible Granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
  • WP wettable powder
  • SP water-soluble powder
  • EC emulsifiable concentrates
  • Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, contain not only a diluent or an inert substance, but also ionic and / or nonionic surfactants (wetting agents, dispersing agents), e.g. B.
  • the herbicidal active ingredients are finely ground, for example in conventional apparatus such as hammer mills, fan mills and air jet mills, and mixed at the same time or subsequently with the formulation auxiliaries.
  • Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent e.g. B. butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers).
  • organic solvent e.g. B. butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents
  • surfactants of ionic and / or nonionic type emulsifiers
  • alkylarylsulfonic acid calcium salts such as
  • Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as e.g. B. sorbitan fatty acid esters or polyoxethylene sorbitan esters such. B. polyoxyethylene sorbitan fatty acid ester.
  • Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. B. talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • Suspension concentrates can be water or oil based. You can, for example, by wet grinding using commercially available bead mills and optionally adding surfactants, such as z. B. already listed above for the other types of formulation.
  • Emulsions e.g. B. oil-in-water emulsions (EW) can be, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants such as z. B. are already listed above for the other types of formulation.
  • Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. As polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.
  • adhesives e.g. As polyvinyl alcohol, sodium polyacrylic acid or mineral oils
  • Water-dispersible granules are generally produced using the customary processes, such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
  • the agrochemical preparations generally contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of active compound of the formula (I) or salts thereof.
  • the active ingredient concentration is z. B. about 10 to 90 wt .-%, the rest of 100 wt .-% consists of conventional formulation components.
  • the active substance concentration can be about 1 to 90, preferably 5 to 80,% by weight.
  • Dust-like formulations contain 1 to 30, preferably mostly 5 to 20% by weight of active ingredient, sprayable solutions about 0.05 to 80, preferably 2 to 50% by weight of active ingredient.
  • the active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulating aids, fillers, etc. are used.
  • the active ingredient content of the water-dispersible granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreezes and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and the pH and Agents influencing viscosity.
  • active substances can be used, for example, as described in e.g. B. from Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 9th edition, The British Crop Protection Council, 1990/91, Bracknell, England, and literature cited therein.
  • herbicides known from the literature which can be combined with the compounds of formula (I), z.
  • the following active substances are to be named (note: the compounds are identified either with the "common name” according to the International Organization for Standardization (ISO) or with the chemical name, if appropriate together with a customary code number): acetochlor; acifluorfen; aclonifen; AKH 7088, ie [[[[1- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidene] amino] oxy] acetic acid and methyl acetate; alachlor; alloxydim; ametryn; amidosulfuron; amitrole; AMS, ie ammonium sulfamate; anilofos; asulam; atrazine; aziprotryn; barban; BAS 516 H, ie 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluorflu
  • the formulations present in the commercial form are optionally diluted in the customary manner, for. B. with wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Preparations in the form of dust, ground or scatter granules and sprayable solutions are usually no longer diluted with other inert substances before use.
  • the compounds of the invention can, for example, directly on the harmful plants or harmful plants and crop plants at the same time in the post-emergence process or on the area on which the plants grow, for. B. on arable soil with plant seeds or accumulated plants or on acreages, such as. B. a rice cultivation area, applied in the pre- or post-emergence process.
  • the required application rate of the compounds of formula (I) varies. It can fluctuate within wide limits, e.g. B. between 0.001 and 10.0 kg / ha or more of active substance, but is preferably between 0.005 and 5 kg / ha.
  • the mixture is heated under reflux for 2 hours, allowed to cool to room temperature, the solution is brought to pH 1 with concentrated hydrochloric acid and extracted twice with 50 ml of ethyl acetate.
  • the combined organic phases are dried over MgSO 4 , the drying agent is filtered off and the solvent is distilled off under reduced pressure.
  • Ph phenyl
  • a dusting agent is obtained by mixing 10 parts by weight of a compound of the formula (I) and 90 parts by weight of talc as an inert substance and comminuting in a hammer mill.
  • a wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of a compound of the formula (I),
  • quartz containing kaolin as an inert substance
  • potassium lignosulfonate 1 part by weight sodium oleoylmethyl taurine as wetting and dispersing agent and ground in a pin mill.
  • a dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of a compound of the formula (I) with 6 parts by weight of alkylphenol polyglycol ether ( ® Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight.
  • Parts of paraffinic mineral oil (boiling range e.g. approx. 255 to above 277 ° C) and mixed in one Grinding ball mill ground to a fineness of less than 5 microns.
  • An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol as emulsifier.
  • a water-dispersible granulate is obtained by:
  • Seeds or rhizome pieces of monocotyledonous and dicotyledonous weed plants were placed in sandy loam in plastic pots and covered with soil.
  • the compounds according to the invention formulated in the form of wettable powders or emulsion concentrates were then applied as an aqueous suspension or emulsion with a water application rate of the equivalent of 600 to 800 l / ha in different dosages to the surface of the covering earth.
  • the pots were placed in the greenhouse and kept under good growth conditions for the weeds. After the test plants had emerged, the optical damage to the plants or the emergence damage was assessed after a test period of 3 to 4 weeks in comparison to untreated controls. As the test results show, the compounds according to the invention have good herbicidal pre-emergence activity against a broad spectrum of grasses and weeds.
  • the compounds of Examples 1, 2, 3, 4, 11, 12, 14, 56, 59, 60, 61, 62, 66, 67, 68, 75, 77 and 78 have very good herbicidal activity against harmful plants such as Sinapis alba, Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus and Panicum miliaceum in the pre-emergence process with an application rate of 0.3 kg and less active substance per hectare.
  • Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds were placed in plastic pots in sandy loam soil, covered with soil and grown in the greenhouse under good growth conditions.
  • the test plants were treated at the three-leaf stage three weeks after sowing.
  • the compounds according to the invention formulated as wettable powder or as emulsion concentrates, were sprayed onto the green parts of the plant in various dosages with a water application rate of the equivalent of 600 to 800 l / ha, and after about 3 to 4 weeks of standing of the test plants in the greenhouse under optimal growth conditions, the action of the preparations visually rated in comparison to untreated controls.
  • the agents according to the invention also have good herbicidal activity against a broad spectrum of economically important grasses and weeds, even after emergence.
  • the compounds of Examples 1, 2, 3, 4, 11, 12, 14, 56, 59, 60, 61, 62, 66, 67, 68, 75, 77 and 78 have very good herbicidal activity against harmful plants such as Sinapis alba, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Chrysanthemum segetum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus and Panicum miliaceum, Avena sativa in the post-emergence process with an application rate of 0.3 kg and less active substance per hectare.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth 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)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Compounds of formula (I) are disclosed, wherein: R1 represents H, (C¿1?-C8)-alkyl, where appropriate substituted with a halogen, cyano, (C1-C4)-alkoxy, aryl and substituted aryl, or (C3-C6)-alkenyl, (C3-C6)-alkinyl or (subst.) aryl or an agriculturally suitable cation; R?2 and R3¿ independently of one another represent (C¿1?-C4)-alkyl, -haloalkyl, -alkoxy or -haloalkoxy, -halogen, or mono- or di[(C1-C4)-alkyl]amino; R?4¿ represents H, a halogen, (C¿1?-C4)-alkyl, -alkoxy or -alkoxy carbonyl, nitro, cyano or a group Q; X represents O or S, Y represents CH or N, W represents O, S, N-OR?5, N-NR5R6; R5, R6¿ represent H, (subst.) (C¿1?-C4)-alkyl, (C3-C6)-alkenyl, (C3-C6)-alkinyl or (subst.) aryl or, together with the N atom, a (subst.) heterocyclic group with 3-7 ring atoms; and Q represents a group of formula (a), wherein R?2', R3'¿, X' and Y' are defined by analogy with R2, R3, X and Y in formula (I). The proposed compounds are suitable for use as herbicides and plant growth regulators. They can be manufactured by the processes disclosed in claim 5.

Description

Beschreibungdescription
Neue Phenylglyoxylsäurederivate, Verfahren zu ihrer Herstellung und ihre Verwendung als Herbizide und PflanzenwachstumsregulatorenNew phenylglyoxylic acid derivatives, processes for their preparation and their use as herbicides and plant growth regulators
Die Erfindung betrifft das technische Gebiet der Herbizide und Pflanzenwachstumsregulatoren, insbesondere der Herbizide zur selektiven Bekämpfung von Unkräutern und Ungräsern in Nutzpflanzenkulturen.The invention relates to the technical field of herbicides and plant growth regulators, in particular herbicides for the selective control of weeds and weeds in crops of useful plants.
Es ist bekannt, daß einige Heteroaryioxy- bzw. Heteroarylmercaptobenzoesäure- derivate herbizide und pflanzenwachstumsregulierende Eigenschaften besitzen; vgl. EP-A-223 406, EP-A-249 708, EP-A-287 072, EP-A-287 079, EP-A-315 889, EP-A-321 846, EP-A-426 476, EP-A-435 170, EP-A-472 1 13,It is known that some heteroaryioxy or heteroaryl mercaptobenzoic acid derivatives have herbicidal and plant growth-regulating properties; see. EP-A-223 406, EP-A-249 708, EP-A-287 072, EP-A-287 079, EP-A-315 889, EP-A-321 846, EP-A-426 476, EP -A-435 170, EP-A-472 1 13,
Es wurden nun 2-Heteroaryloxy- bzw. 2-Heteroaryimercaptophenylglyoxyl- säurederivate gefunden, die als Herbizide und Wachstumsregulatoren geeignet sind.There have now been found 2-heteroaryloxy or 2-heteroaryimercaptophenylglyoxylic acid derivatives which are suitable as herbicides and growth regulators.
Gegenstand der vorliegenden Erfindung sind Verbindungen der Formel (I),The present invention relates to compounds of the formula (I)
Figure imgf000003_0001
Figure imgf000003_0001
worinwherein
R1 H, (C.,-C8.-Alkyl, das unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, Nitro, Cyano, (C1-C4)-Alkoxy, Aryl und substituiertes Aryl substituiert ist, oder (C3-C6)-Alkenyl, (C3-C6)-Alkinyl oder Aryl, wobei der Arylrest unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, Nitro, (C1-C4)-Alkyl, (C.,^)- Alkoxy und [(C1-C4)-Alkoxy]carbonyl substituiert ist, oder ein für die Landwirtschaft geeignetes Kation, beispielsweise ein Metallkation, insbesondere Alkali- oder Erdalkalimetallkation, oder ein unsubstituiertes oder substituiertes Ammoniumion,R 1 H, (C., - C 8 alkyl, which is unsubstituted or by one or more radicals from the group halogen, nitro, cyano, (C 1 -C 4 ) alkoxy, aryl and substituted aryl, or (C 3 -C 6 ) alkenyl, (C 3 -C 6 ) alkynyl or aryl, where the aryl radical is unsubstituted or by one or more radicals from the group halogen, nitro, (C 1 -C 4 ) -Alkyl, (C., ^) - alkoxy and [(C 1 -C 4 ) -alkoxy] carbonyl, or a cation suitable for agriculture, for example a metal cation, in particular alkali or alkaline earth metal cation, or an unsubstituted or substituted ammonium ion,
R2 und R3 unabhängig voneinander (CrC4)-Alkyl, (CrC4)-Haloalkyl, (CrC4)-R 2 and R 3 independently of one another (C r C 4 ) alkyl, (C r C 4 ) haloalkyl, (C r C 4 ) -
Alkoxy, (C1-C4)-Haloalkoxy, Halogen,
Figure imgf000004_0001
oder Di[(CrC4)- Alkyl]amino,Alkoxy, (C 1 -C 4 ) haloalkoxy, halogen,
Figure imgf000004_0001
or di [(C r C 4 ) alkyl] amino,
R4 H, Halogen, (CrC4)-Alkyl, (CrC4)-Alkoxy, (CrC4)-Alkoxycarbonyl, Nitro, Cyano, oder eine Gruppe der weiter unten definierten Formel Q,R 4 H, halogen, (C r C 4 ) alkyl, (C r C 4 ) alkoxy, (C r C 4 ) alkoxycarbonyl, nitro, cyano, or a group of the formula Q defined below,
X O oder S,X O or S,
Y CH oder N,Y CH or N,
W O, S, N-OR5, N-NR5R6,WO, S, N-OR 5 , N-NR 5 R 6 ,
R5, R6 jeder unabhängig voneinander H, (CrC4)-Alkyl, das unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, (C1-C4)-Alkoxy oder Aryl substituiert ist, oder (C3-C6)-Alkenyl, (C3-C6)-Alkinyl oder Aryl, das unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, Nitro, (CrC4)-Alkyl, (CrC4)-Alkoxy und (CrC4)-Haloalkoxy substituiert ist, oder gemeinsam mit dem sie verbindenden N-Atom einen heterocyclischen Rest mit 3 bis 7 Ringatomen, der neben dem N-Atom als Heteroringatom ein oder zwei weitere Heteroringatome aus der Gruppe N, O und S in den möglichen Oxidationsstufen enthalten und unsubstituiert oder durch (C1-C4)-Alkyl, (C-,-C4)-Alkoxy oder Halogen substituiert sein kann, und eine Gruppe der FormelR 5 , R 6 each independently of one another are H, (C r C 4 ) -alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, (C 1 -C 4 ) -alkoxy or aryl, or (C 3 -C 6 ) alkenyl, (C 3 -C 6 ) alkynyl or aryl which is unsubstituted or by one or more radicals from the group halogen, nitro, (C r C 4 ) alkyl, (C r C 4 ) - Alkoxy and (C r C 4 ) -haloalkoxy is substituted, or together with the N atom connecting them a heterocyclic radical with 3 to 7 ring atoms, which in addition to the N atom as a hetero ring atom has one or two further hetero ring atoms from the group N, O and S may be present in the possible oxidation states and may be unsubstituted or substituted by (C 1 -C 4 ) -alkyl, (C -, - C 4 ) -alkoxy or halogen, and a group of the formula
Figure imgf000005_0001
Figure imgf000005_0001
worinwherein
R2', R3', X' und Y' analog den Bedeutungen der entsprechenden Reste R2, R3, X bzw. Y in Formel (I) definiert sind, bedeuten.R 2 ' , R 3' , X 'and Y' are defined analogously to the meanings of the corresponding radicals R 2 , R 3 , X and Y in formula (I).
In der Formel (I) und im folgenden können kohlenwasserstoffhaltige Reste wie z. B. Alkyl-, Alkoxy-, Haloalkyl- und Alkylthioreste sowie die entsprechenden ungesättigten und/oder substituierten Reste im Kohlenwasserstoffteil jeweils geradkettig oder verzweigt sein. Alkylreste, auch in den zusammengesetzten Bedeutungen wie Alkoxy, Haloalkyl usw., bedeuten Methyl, Ethyl, n- oder i-Propyl, n-, i-, t- oder 2-Butyl; Alkenyl- und Alkinylreste haben die Bedeutung der den Alkylresten entsprechenden möglichen ungesättigten Reste, wie 2-Propenyl, 2- oder 3-Butenyl, 2-Propinyl, 2- oder 3-Butinyl. Halogen bedeutet, Fluor, Chlor, Brom oder Jod. Haloalkyl bedeutet Alkyl, das durch ein oder mehrere Atome aus der Gruppe Halogen substituiert ist; Haloalkyl ist beispielsweise CF3, CHF2, CH2CF3. Aryl ist beispielsweise Phenyl, Naphthyl, Tetrahydronaphthyl, Indanyl, Fluorenyl und ähnliches, vorzugsweise Phenyl. Substituiertes Aryl oder substituiertes Phenyl bedeutet vorzugsweise Aryl bzw. Phenyl, das durch einen oder mehrere, vorzugsweise 1 bis 3 Reste aus der Gruppe Halogen, Alkyl, Haloalkyl, Haloalkoxy, Nitro, Cyano, Alkoxycarbonyl, Alkanoyl, Carbamoyl, Mono- und Di-alkylaminocarbonyl, Mono- und Dialkylamino, Alkylsulfinyl oder Alkylsulfonyl substituiert ist, wobei bei den alkylhaltigen Resten solche mit 1 bis 4 C-Atomen, insbesondere 1 bis 2 C-Atomen bevorzugt sind; besonders bevorzugt sind dabei Methyl, Methoxy und Chlor. Heterocyclische Reste für die Gruppe NR5R6 sind beispielsweise gesättigte, ungesättigte und heteroaromatische Reste von gegebenenfalls substituierten Verbindungen aus der Gruppe Pyrrol, Imidazol, Pyrazol, Triazol, Oxazole, Propansultam, Butansulfam, Pyrrolidon, Pyrazolon sowie deren partiell oder ganz hydrierten System wie Piperidin, Piperazin oder Morpholin.In the formula (I) and below, hydrocarbon-containing radicals such as. B. alkyl, alkoxy, haloalkyl and alkylthio radicals and the corresponding unsaturated and / or substituted radicals in the hydrocarbon part may each be straight-chain or branched. Alkyl radicals, also in the composite meanings such as alkoxy, haloalkyl, etc., mean methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl; Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals, such as 2-propenyl, 2- or 3-butenyl, 2-propynyl, 2- or 3-butynyl. Halogen means fluorine, chlorine, bromine or iodine. Haloalkyl means alkyl which is substituted by one or more atoms from the group halogen; Haloalkyl is, for example, CF 3 , CHF 2 , CH 2 CF 3 . Aryl is, for example, phenyl, naphthyl, tetrahydronaphthyl, indanyl, fluorenyl and the like, preferably phenyl. Substituted aryl or substituted phenyl preferably means aryl or phenyl, which is substituted by one or more, preferably 1 to 3, radicals from the group halogen, alkyl, haloalkyl, haloalkoxy, nitro, cyano, alkoxycarbonyl, alkanoyl, carbamoyl, mono- and di-alkylaminocarbonyl , Mono- and dialkylamino, alkylsulfinyl or alkylsulfonyl is substituted, the alkyl-containing radicals having 1 to 4 carbon atoms, in particular 1 to 2 carbon atoms, being preferred; methyl, methoxy and chlorine are particularly preferred. Heterocyclic radicals for the group NR 5 R 6 are, for example, saturated, unsaturated and heteroaromatic radicals of optionally substituted compounds from the group pyrrole, imidazole, pyrazole, triazole, oxazole, propanesultam, butanesulfame, pyrrolidone, pyrazolone and their partially or completely hydrogenated system such as piperidine , Piperazine or morpholine.
Gegenstand der Erfindung sind auch alle Stereoisomeren, die von Formel (I) umfaßt sind, und deren Gemische. Solche Verbindungen der Formel (I) enthalten ein oder mehrere asymmetrische C-Atome oder auch Doppelbindungen, die in der allgemeinen Formeln (I) nicht gesondert angegeben sind. Die durch ihre spezifische Raumform definierten möglichen Stereoisomeren, wie Enantiomere, Diastereomere, Z- und E-Isomere sind jedoch alle von den Formeln (I) umfaßt und können nach üblichen Methoden aus Gemischen der Stereoisomeren erhalten werden oder auch durch stereoselektive Reaktionen in Kombination mit dem Einsatz von stereochemisch reinen Ausgangsstoffen hergestellt werden.The invention also relates to all stereoisomers which are encompassed by formula (I) and mixtures thereof. Such compounds of the formula (I) contain one or more asymmetric carbon atoms or else double bonds which are not indicated separately in the general formula (I). However, the possible stereoisomers defined by their specific spatial shape, such as enantiomers, diastereomers, Z and E isomers, are all encompassed by the formulas (I) and can be obtained by conventional methods from mixtures of the stereoisomers or by stereoselective reactions in combination with the Use of stereochemically pure starting materials.
Bevorzugt sind erfindungsgemäße Verbindungen der Formel (I), in denen R1 H, (Ci"C5)-Alkyl, das unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen und (CrC4)-Alkoxy substituiert ist, (C3-C6)- Alkenyl, (C3-C6)-Alkinyl, ein Alkalimetallkation, ein Erdalkalimetallkation oder ein Ammoniumion (NH4 Θ), vorzugsweise H, (C- Cs.-Alkyl das unsubstituiert oder einfach oder mehrfach durch Halogen oder (C.,^)- Alkoxy substituiert ist,Preferred compounds of the formula (I) according to the invention are those in which R 1 is H, (Ci "C 5 ) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen and (C r C 4 ) alkoxy, ( C 3 -C 6 ) alkenyl, (C 3 -C 6 ) alkynyl, an alkali metal cation, an alkaline earth metal cation or an ammonium ion (NH 4 Θ ), preferably H, (C- Cs.-alkyl which is unsubstituted or singly or repeatedly by Halogen or (C., ^) - alkoxy is substituted,
R2 und R3 unabhängig voneinander (C1-C4)-Alkyl, (C1-C4)-Haloalkyl, (C--C4)- Alkoxy, (C1-C4)-Haloalkoxy oder Halogen, vorzugsweise (Cι-C4)-Alkoxy oder (C1-C4)-Alkyl, insbesondere OCH3,R 2 and R 3 independently of one another (C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl, (C - C 4 ) alkoxy, (C 1 -C 4 ) haloalkoxy or halogen, preferably (-C-C 4 ) alkoxy or (C 1 -C 4 ) alkyl, in particular OCH 3 ,
R4 H, Halogen, (C C4)-Alkyl, (CrC4)-Alkoxy, (C C4.-Alkoxycarbonyl, Nitro, Cyano oder eine Gruppe der Formel Q, vorzugsweise H, Cl, CH3, OCH3, CO2CH3, NO2 oder eine Gruppe der Formel Q, X 0 oder S, vorzugsweise O,R 4 H, halogen, (CC 4 ) -alkyl, (C r C 4 ) -alkoxy, (CC 4 -alkoxycarbonyl, nitro, cyano or a group of the formula Q, preferably H, Cl, CH 3 , OCH 3 , CO 2 CH 3 , NO 2 or a group of the formula Q, X 0 or S, preferably O,
Y CH oder N, vorzugsweise CH,Y is CH or N, preferably CH,
W O undW O and
Q eine Gruppe der FormelQ is a group of the formula
Figure imgf000007_0001
Figure imgf000007_0001
worinwherein
R2', R3', X' und Y' analog R2, R3, X bzw. Y in Formel (I) definiert sind, bedeuten.R 2 ' , R 3' , X 'and Y' are defined analogously to R 2 , R 3 , X and Y in formula (I).
Weiter bevorzugt sind erfindungsgemäße Verbindungen der Formel (I), in denenFurther preferred compounds of formula (I) according to the invention are those in which
R1 H, (C -C5)-Alkyl, das unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen oder (C1-C )-Alkoxy substituiert ist, vorzugsweise CH3, C2H5, n-C3H7 oder i-C3H7,R 1 H, (C -C 5 ) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen or (C 1 -C) alkoxy, preferably CH 3 , C 2 H 5 , nC 3 H 7 or iC 3 H 7 ,
R2 und R3 unabhängig voneinander (C-|-C4)- Alkoxy, (C1-C4)-Alkyl, vorzugsweise OCH3,R 2 and R 3 independently of one another (C- | -C 4 ) alkoxy, (C 1 -C 4 ) alkyl, preferably OCH 3 ,
R4 H, Halogen, (CrC4)-Alkyl, (CrC4)-Alkoxy,
Figure imgf000007_0002
Nitro, Cyano oder eine Gruppe Q, vorzugsweise H, Cl, CH3, OCH3, CO2CH3, NO2 oder eine Gruppe Q,R 4 H, halogen, (C r C 4 ) alkyl, (C r C 4 ) alkoxy,
Figure imgf000007_0002
Nitro, cyano or a group Q, preferably H, Cl, CH 3 , OCH 3 , CO 2 CH 3 , NO 2 or a group Q,
X ein Sauerstoffatom, Y eine Gruppe der Formel CH,X is an oxygen atom, Y is a group of the formula CH,
W ein Sauerstoffatom, undW is an oxygen atom, and
Q eine Gruppe der FormelQ is a group of the formula
Figure imgf000008_0001
Figure imgf000008_0001
wobeiin which
R2', R3', X' und Y' wie R2, R3, X bzw. Y in Formel (I) definiert sind, bedeuten.R 2 ' , R 3' , X 'and Y' are defined as R 2 , R 3 , X and Y in formula (I).
Weiterhin bevorzugt sind erfindungsgemäße Verbindungen der Formel (I), in denenFurther preferred compounds of the formula (I) according to the invention are those in which
R1 CH3, C2H5 oder n- oder i-C3H7,R 1 CH 3 , C 2 H 5 or n- or iC 3 H 7 ,
R2 und R3 jeweils OCH3,R 2 and R 3 each OCH 3 ,
R4 H, Halogen, CH3, OCH3, CO2CH3, Nitro oder eine Gruppe Q,R 4 H, halogen, CH 3 , OCH 3 , CO 2 CH 3 , nitro or a group Q,
X O,X O,
Y CH,Y CH,
W O und WHERE and
Figure imgf000009_0001
Figure imgf000009_0001
bedeuten.mean.
Weiterer Gegenstand der Erfindung sind Verfahren zur Herstellung der erfindungsgemäßen Verbindungen der Formel (I), dadurch gekennzeichnet, daß manThe invention further relates to processes for the preparation of the compounds of the formula (I) according to the invention, characterized in that
a) im Falle W = N-OR5, eine Verbindung der Formel (I), in der W. = O ist, mit einem Hydroxylamin der Formel (II)a) in the case of W = N-OR 5, a compound of formula (I) in which W. = O, with a hydroxylamine of the formula (II)
NH2 - OR5 (II)NH 2 - OR 5 (II)
umsetzt, oderimplements, or
b) im Falle W = N-NR5R6, eine Verbindung der Formel (I), in der W = O ist, mit einem Hydrazin der Formel (III)b) in the case of W = N-NR 5 R 6 , a compound of the formula (I) in which W = O, with a hydrazine of the formula (III)
Figure imgf000009_0002
Figure imgf000009_0002
umsetzt oderimplements or
c) im Falle W = O und R1 ungleich H, eine Verbindung der Formel (II), in der W = O und R1 = H sind, mit einem Chlorameisensäureester der Formel (IV)c) in the case of W = O and R 1 not equal to H, a compound of the formula (II) in which W = O and R 1 = H, with a chloroformate of the formula (IV)
Cl - CO - OR1 (IV) umsetzt oder d) im Falle W = O und R1 = H, ein Phenylglyoxylsäurederivat der Formel (V)Cl - CO - OR 1 (IV) or d) in the case of W = O and R 1 = H, a phenylglyoxylic acid derivative of the formula (V)
R 4 R 4
Figure imgf000010_0001
mit einem Pyrimidin- bzw. triazinderivat der Formel (VI)
Figure imgf000010_0001
with a pyrimidine or triazine derivative of the formula (VI)
Figure imgf000010_0002
Figure imgf000010_0002
worin Nuc eine Abgangsgruppe, wie z. B. Cl oder CH3-SO2- bedeutet, umsetzt, wobei in den obigen Formeln (II) bis (VI) R1 , R2, R3, R4, R5, R6, X und Y wie in Formel (I) definiert sind.wherein Nuc is a leaving group, such as. B. Cl or CH 3 -SO 2 -, reacted, wherein in the formulas (II) to (VI) above R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X and Y as in formula (I) are defined.
Das Verfahren zur Herstellung der erfindungsgemäßen Verbindung der Formel (I), worin W = N-OR5 oder N-NR5R6 (Varianten a und b) wird beispielsweise einem polar protischen Lösungsmittel, vorzugsweise Alkoholen wie Methanol und Ethanol, unter Einwirkung von organischen oder anorganischen Säuren durchgeführt.The process for the preparation of the compound of the formula (I) according to the invention in which W = N-OR 5 or N-NR 5 R 6 (variants a and b) is, for example, a polar protic solvent, preferably alcohols such as methanol and ethanol, under the action of organic or inorganic acids.
Die Umsetzung mit Chlorameisensäureester (Variante c) wird beispielsweise in dipolar aprotischen Lösungsmitteln, vorzugsweise N,N-Dimethylformamid bei Raumtemperatur unter Baseneinwirkung durchgeführt.The reaction with chloroformate (variant c) is carried out, for example, in dipolar aprotic solvents, preferably N, N-dimethylformamide, at room temperature under the action of a base.
Die erfindungsgemäßen Verbindungen der Formel (I) mit W = O und R = H erhält man beispielsweise durch Umsetzung von (subst.) 2-Mercaptophenyl- glyoxylsäure (Formel (V), X = S) bzw. 2-Hydroxyphenylglyoxylsäure (Formel (V), X = O) mit Chlortriazinderivaten (Formel (VI)), Y = N, Nuc = CD oder Methylpyrimidinylsulfonderivaten (Formel (VI)), Y = CH, Nuc = CH3SO2).The compounds of the formula (I) according to the invention with W = O and R = H are obtained, for example, by reacting (subst.) 2-mercaptophenylglyoxylic acid (formula (V), X = S) or 2-hydroxyphenylglyoxylic acid (formula (V), X = O) with chlorotriazine derivatives (formula (VI)), Y = N, Nuc = CD or methylpyrimidinylsulfone derivatives (formula (VI)), Y = CH, Nuc = CH 3 SO 2 ).
Die Umsetzung der 2-Mercaptophenylglyoxylsäure erfolgt z. B. in polar protischen Lösungsmitteln, vorzugsweise Wasser unter Einwirkung von Alkalihydroxiden. Die Umsetzung der 2-Hydroxyphenylglyoxylsäure wird in der Regel in dipolar aprotischen Lösungsmitteln, vorzugsweise N,N-Dimethylformamid, durchgeführt.The implementation of 2-mercaptophenylglyoxylic acid takes place, for. B. in polar protic solvents, preferably water under the action of alkali metal hydroxides. The reaction of the 2-hydroxyphenylglyoxylic acid is generally carried out in dipolar aprotic solvents, preferably N, N-dimethylformamide.
Zur gegebenenfalls substituierten 2-Mercaptophenylglyoxylsäure kommt man nach literaturbekannten Methoden, indem man (subst.) Thiophenol mit Oxalylchlorid umsetzt und das entstehende Oxalsäurethiohalbesterchlorid in einer intramolekularen Friedel-Crafts-Acylierung zum (subst.) Benzothiophendion cyclisiert, das dann basisch hydrolysiert wird und nach Ansäuern die (subst.) 2-Mercaptophenylglyoxylsäure liefert.The optionally substituted 2-mercaptophenylglyoxylic acid is obtained by methods known from the literature by reacting (subst.) Thiophenol with oxalyl chloride and cyclizing the resulting oxalic acid thiohaloester chloride in an intramolecular Friedel-Crafts acylation to give the (subst.) Benzothiophendione, which is then hydrolysed and acidified which provides (subst.) 2-mercaptophenylglyoxylic acid.
Zur (subst.) 2-Hydroxyphenylglyoxylsäure gelangt man ebenfalls nach literaturbekannten Verfahren (Chem. Berichte 17, 973 (1886), indem man Isatin basisch hydrolysiert, die entstandene 2-Aminophenylglyoxylsäure diazotiert und das Diazoniumsalz einer Phenolverkochung unterzieht.The (subst.) 2-hydroxyphenylglyoxylic acid can also be obtained by methods known from the literature (Chem. Reports 17, 973 (1886)) by basic hydrolysis of isatin, the resulting 2-aminophenylglyoxylic acid and the diazonium salt being subjected to a phenol boil.
Einige Chlortriazinderivate der Formel (VI) (Y = N, Nuc = CD sind kommerziell erhältlich. Die Sulfone (VI) (Y = CH, Nuc = CD können aus den kommerziellSome chlorotriazine derivatives of the formula (VI) (Y = N, Nuc = CD) are commercially available. The sulfones (VI) (Y = CH, Nuc = CD can be obtained commercially)
~ erhältlichen Methylthioethern durch Oxidation mit Oxone (Kaliumperoxodisulfat) hergestellt werden. ~ available methylthioethers can be prepared by oxidation with oxone (potassium peroxodisulfate).
Die erfindungsgemäßen Verbindungen der Formel (I) weisen eine ausgezeichnete herbizide Wirksamkeit gegen ein breites Spektrum wirtschaftlicher wichtiger mono- und dikotyler Schadpflanzen auf. Auch schwer bekämpfbare perennierende Unkräuter, die aus Rhizomen, Wurzelstöcken oder anderen Dauerorganen austreiben, werden durch die Wirkstoffe gut erfaßt. Dabei ist es gleichgültig, ob die Substanzen im Vorsaat-, Vorauflauf- oder Nachauflaufverfahren ausgebracht werden.The compounds of formula (I) according to the invention have excellent herbicidal activity against a broad spectrum of economically important mono- and dicotyledonous harmful plants. Perennial weeds that are difficult to control and that sprout from rhizomes, rhizomes or other permanent organs are also well captured by the active ingredients. It does not matter whether the substances are pre-seeded, pre-emergence or Post-emergence procedures are applied.
Im einzelnen seien beispielsweise einige Vertreter der mono- und dikotylenSome of the representatives of the mono- and dicotyls are, for example
Unkrautflora genannt, die durch die erfindungsgemäßen Verbindungen kontrolliert werden können, ohne daß durch die Nennung eine Beschränkung auf bestimmte Arten erfolgen soll.Weed flora mentioned, which can be controlled by the compounds according to the invention, without any restriction to certain species being made by the name.
Auf der Seite der monokotylen Unkrautarten werden z. B. Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria sowie Cyperusarten aus der annuellen Gruppe und auf Seiten der perennierenden Spezies Agropyron, Cynodon, Imperata sowie Sorghum und auch ausdauernde Cyperusarten gut erfaßt.On the side of the monocot weed species, e.g. B. Avena, Lolium, Alopecurus, Phalaris, Echinochloa, Digitaria, Setaria and Cyperus species from the annual group and on the part of the perennial species Agropyron, Cynodon, Imperata and Sorghum and also perennial Cyperus species well recorded.
Bei dikotylen Unkrautarten erstreckt sich das Wirkungsspektrum auf Arten wie z. B. Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon und Sida auf der annuellen Seite sowie Convolvulus, Cirsium, Rumex und Artemisia bei den perennierenden Unkräutern.In dicotyledon weed species, the spectrum of activity extends to species such as: B. Galium, Viola, Veronica, Lamium, Stellaria, Amaranthus, Sinapis, Ipomoea, Matricaria, Abutilon and Sida on the annual side as well as Convolvulus, Cirsium, Rumex and Artemisia for the perennial weeds.
Unter den spezifischen Kulturbedingungen im Reis vorkommende Unkräuter wie z. B. Sagittaria, Alisma, Eleocharis, Scirpus und Cyperus werden von den erfindungsgemäßen Wirkstoffen ebenfalls hervorragend bekämpft.Weeds occurring in the rice under the specific crop conditions, such as. B. Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus are also superbly combated by the active compounds according to the invention.
Werden die erfindungsgemäßen Verbindungen vor dem Keimen auf die Erdoberfläche appliziert, so wird entweder das Auflaufen der Unkrautkeimlinge vollständig verhindert oder die Unkräuter wachsen bis zum Keimblattstadium heran, stellen jedoch dann ihr Wachstum ein und sterben schließlich nach Ablauf von drei bis vier Wochen vollkommen ab.If the compounds according to the invention are applied to the surface of the earth before germination, either the weed seedlings emerge completely or the weeds grow to the cotyledon stage, but then stop growing and finally die completely after three to four weeks.
Bei Applikation der Wirkstoffe auf die grünen Pflanzenteile im Nachauflaufverfahren tritt ebenfalls sehr rasch nach der Behandlung ein drastischer Wachstumsstop ein und die Unkrautpflanzen bleiben in dem zum Applikationszeitpunkt vorhandenen Wachstumsstadium stehen oder sterben nach einer gewissen Zeit ganz ab, so daß auf diese Weise eine für die Kulturpflanzen schädliche Unkrautkonkurrenz sehr früh und nachhaltig beseitigt wird.When the active ingredients are applied to the green parts of the plants in the post-emergence process, there is also a drastic growth stop very quickly after the treatment and the weed plants remain in the growth stage at the time of application or die completely after a certain time, so that one for them Crops harmful weed competition is eliminated very early and sustainably.
Obgleich die erfindungsgemäßen Verbindungen eine ausgezeichnete herbizide Aktivität gegenüber mono- und dikotylen Unkräutern aufweisen, werden Kulturpflanzen wirtschaftlich bedeutender Kulturen wie z. B. Weizen, Gerste, Roggen, Reis, Mais, Zuckerrübe, Baumwolle und Soja nur unwesentlich oder gar nicht geschädigt. Die vorliegenden Verbindungen eignen sich aus diesen Gründen sehr gut zur selektiven Bekämpfung von unerwünschtem Pflanzenwuchs in landwirtschaftlichen Nutzpflanzungen.Although the compounds according to the invention have excellent herbicidal activity against mono- and dicotyledon weeds, crop plants of economically important crops, such as, for. B. wheat, barley, rye, rice, corn, sugar beet, cotton and soy are only slightly or not at all damaged. For these reasons, the present compounds are very suitable for the selective control of undesired plant growth in agricultural crops.
Darüberhinaus weisen die erfindungsgemäßen Verbindungen der Formel (I) hervorragende wachstumsregulatorische Eigenschaften bei Kulturpflanzen auf. Sie greifen regulierend in den pflanzeneigenen Stoffwechsel ein und können damit zur gezielten Beeinflussung von Pflanzeninhaltsstoffen und zur Ernteerleichterung, z. B. durch Auslösen von Desikkation und Wuchstauchung, eingesetzt werden. Desweiteren eignen sie sich auch zur generellen Steuerung und Hemmung von unerwünschtem vegetativen Wachstum, ohne dabei die Pflanzen abzutöten. Eine Hemmung des vegetativen Wachstums spielt bei vielen mono- und dikotylen Kulturen eine große Rolle, da das Lagern hierdurch verringert oder völlig verhindert werden kann.In addition, the compounds of the formula (I) according to the invention have excellent growth-regulating properties in crop plants. They intervene regulatively in the plant's own metabolism and can thus be used to specifically influence plant constituents and to facilitate harvesting, e.g. B. by triggering desiccation and stunted growth. Furthermore, they are also suitable for general control and inhibition of undesired vegetative growth without killing the plants. Inhibiting vegetative growth plays a major role in many monocotyledonous and dicotyledonous crops, as this can reduce or completely prevent storage.
Die erfindungsgemäßen Verbindungen der Formel (I) können in Form von Spritzpulvern, emulgierbaren Konzentraten, versprühbaren Lösungen, Stäubemitteln oder Granulaten in den üblichen Zubereitungen angewendet werden. Gegenstand der Erfindung sind deshalb auch herbizide und pflanzenwachstumsregulierende Mittel, die Verbindungen der Formel (I) oder deren Salze enthalten.The compounds of formula (I) according to the invention can be used in the customary formulations in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules. The invention therefore also relates to herbicidal and plant growth-regulating compositions which comprise compounds of the formula (I) or their salts.
Die Verbindungen der Formel (I) können auf verschiedene Art formuliert werden, je nachdem welche biologischen und/oder chemisch-physikalischen Parameter vorgegeben sind. Als Formulierungsmöglichkeiten kommen beispielsweise in Frage: Spritzpulver (WP), wasserlösliche Pulver (SP), wasserlösliche Konzentrate, emulgierbare Konzentrate (EC), Emulsionen (EW), wie Öl-in¬ Wasser- und Wasser-in-ÖI-Emulsionen, versprühbare Lösungen, Suspensionskonzentrate (SC), Dispersionen auf Öl- oder Wasserbasis, ölmischbare Lösungen, Kapselsuspensionen (CS), Stäubemittel (DP), Beizmittel, Granulate für die Streu- und Bodenapplikation, Granulate (GR) in Form von Mikro-, Sprüh-, Aufzugs- und Adsorptionsgranulaten, wasserdispergierbare Granulate (WG), wasserlösliche Granulate (SG), ULV-Formulierungen, Mikrokapseln und Wachse.The compounds of formula (I) can be formulated in different ways, depending on which biological and / or chemical-physical parameters are specified. As formulation options come in, for example Question: wettable powder (WP), water-soluble powder (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC) , Oil or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusts (DP), pickling agents, granules for spreading and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible Granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.
Diese einzelnen Formulierungstypen sind im Prinzip bekannt und werden beispielsweise beschrieben in: Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hauser Verlag München, 4. Aufl. 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N.Y., 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.These individual formulation types are known in principle and are described, for example, in: Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th Edition 1986, Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, NY , 1973; K. Martens, "Spray Drying" Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.
Die notwendigen Formulierungshilfsmittel wie Inertmaterialien, Tenside, Lösungsmittel und weitere Zusatzstoffe sind ebenfalls bekannt und werden beispielsweise beschrieben in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, "Solvente Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Grenzflächenaktive Äthylenoxidaddukte", Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hauser Verlag München, 4. Aufl. 1986.The necessary formulation aids such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, "Introduction to Clay Colloid Chemistry"; 2nd Ed., J. Wiley & Sons, N.Y .; C. Marsden, "Solvent Guide"; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J .; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Interface-active ethylene oxide adducts", Wiss. Publishing company, Stuttgart 1976; Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.
Auf der Basis dieser Formulierungen lassen sich auch Kombinationen mit anderen pestizid wirksamen Stoffen, wie z. B. Insektiziden, Akariziden, Herbiziden, Fungiziden, Safenern, Düngemitteln und/oder Wachstumsregulatoren herstellen, z. B. in Form einer Fertigformulierung oder als Tankmix. Spritzpulver sind in Wasser gleichmäßig dispergierbare Präparate, die neben dem Wirkstoff außer einem Verdünnungs- oder Inertstoff noch Tenside ionischer und/oder nichtionischer Art (Netzmittel, Dispergiermittel), z. B. polyoxyethylierte Alkylphenole, polyoxethylierte Fettalkohole, polyoxethylierte Fettamine, Fettalkoholpolyglykolethersulfate, Alkansulfonate, Alkylbenzolsulfonate, ligninsulfonsaures Natrium, 2,2'-dinaphthylmethan-6,6'-disulfonsaures Natrium, dibutylnaphthalin-sulfonsaures Natrium oder auch oleoylmethyltaurinsaures Natrium enthalten. Zur Herstellung der Spritzpulver werden die herbiziden Wirkstoffe beispielsweise in üblichen Apparaturen wie Hammermühlen, Gebläsemühlen und Luftstrahlmühlen feingemahlen und gleichzeitig oder anschließend mit den Formulierungshilfsmitteln vermischt.Based on these formulations, combinations with other pesticidally active substances, such as. B. Insecticides, acaricides, herbicides, fungicides, safeners, fertilizers and / or growth regulators, for. B. in the form of a finished formulation or as a tank mix. Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, contain not only a diluent or an inert substance, but also ionic and / or nonionic surfactants (wetting agents, dispersing agents), e.g. B. polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, sodium dibutylnaphthalene-sulfonate sodium or also. To produce the wettable powders, the herbicidal active ingredients are finely ground, for example in conventional apparatus such as hammer mills, fan mills and air jet mills, and mixed at the same time or subsequently with the formulation auxiliaries.
Emulgierbare Konzentrate werden durch Auflösen des Wirkstoffes in einem organischen Lösungsmittel z. B. Butanol, Cyclohexanon, Dimethylformamid, Xylol oder auch höhersiedenden Aromaten oder Kohlenwasserstoffen oder Mischungen der organischen Lösungsmittel unter Zusatz von einem oder mehreren Tensiden ionischer und/oder nichtionischer Art (Emulgatoren) hergestellt. Als Emulgatoren können beispielsweise verwendet werden: Alkylarylsulfonsaure Calzium-Salze wieEmulsifiable concentrates are made by dissolving the active ingredient in an organic solvent e.g. B. butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers). Examples of emulsifiers which can be used are: alkylarylsulfonic acid calcium salts such as
Ca-dodecylbenzolsulfonat oder nichtionische Emulgatoren wie Fettsäurepolyglykolester, Alkylarylpolyglykolether, Fettalkoholpolyglykolether, Propylenoxid-Ethylenoxid-Kondensationsprodukte, Alkylpolyether, Sorbitanester wie z. B. Sorbitanfettsäureester oder Polyoxethylensorbitanester wie z. B. Polyoxyethylensorbitanfettsäureester.Ca-dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters such as e.g. B. sorbitan fatty acid esters or polyoxethylene sorbitan esters such. B. polyoxyethylene sorbitan fatty acid ester.
Stäubemittel erhält man durch Vermählen des Wirkstoffes mit fein verteilten festen Stoffen, z. B. Talkum, natürlichen Tonen, wie Kaolin, Bentonit und Pyrophyllit, oder Diatomeenerde. Suspensionskonzentrate können auf Wasser- oder Ölbasis sein. Sie können beispielsweise durch Naß-Vermahlung mittels handelsüblicher Perlmühlen und gegebenenfalls Zusatz von Tensiden, wie sie z. B. oben bei den anderen Formulierungstypen bereits aufgeführt sind, hergestellt werden.Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. B. talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth. Suspension concentrates can be water or oil based. You can, for example, by wet grinding using commercially available bead mills and optionally adding surfactants, such as z. B. already listed above for the other types of formulation.
Emulsionen, z. B. ÖI-in-Wasser-Emulsionen (EW), lassen sich beispielsweise mittels Rührern, Kolloidmühlen und/oder statischen Mischern unter Verwendung von wäßrigen organischen Lösungsmitteln und gegebenenfalls Tensiden, wie sie z. B. oben bei den anderen Formulierungstypen bereits aufgeführt sind, herstellen.Emulsions e.g. B. oil-in-water emulsions (EW) can be, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants such as z. B. are already listed above for the other types of formulation.
Granulate können entweder durch Verdüsen des Wirkstoffes auf adsorptionsfähiges, granuliertes Inertmaterial hergestellt werden oder durch Aufbringen von Wirkstoffkonzentraten mittels Klebemitteln, z. B. Polyvinylalkohol, polyacrylsaurem Natrium oder auch Mineralölen, auf die Oberfläche von Trägerstoffen wie Sand, Kaolinite oder von granuliertem Inertmaterial. Auch können geeignete Wirkstoffe in der für die Herstellung von Düngemittelgranulaten üblichen Weise - gewünschtenfalls in Mischung mit Düngemitteln - granuliert werden.Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. As polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.
Wasserdisbergierbare Granulate werden in der Regel nach den üblichen Verfahren wie Sprühtrocknung, Wirbelbett-Granulierung, Teller-Granulierung, Mischung mit Hochgeschwindigkeitsmischern und Extrusion ohne festes Inertmaterial hergestellt.Water-dispersible granules are generally produced using the customary processes, such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
Die agrochemischen Zubereitungen enthalten in der Regel 0, 1 bis 99 Gew.-%, insbesondere 0,1 bis 95 Gew.-%, Wirkstoff der Formel (I) oder deren Salze.The agrochemical preparations generally contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight, of active compound of the formula (I) or salts thereof.
In Spritzpulvern beträgt die Wirkstoff konzentration z. B. etwa 10 bis 90 Gew.-%, der Rest zu 100 Gew.-% besteht aus üblichen Formulierungsbestandteilen. Bei emulgierbaren Konzentraten kann die Wirkstoffkonzentration etwa 1 bis 90, vorzugsweise 5 bis 80 Gew.-% betragen. Staubförmige Formulierungen enthalten 1 bis 30, vorzugsweise meistens 5 bis 20 Gew.-% an Wirkstoff, versprühbare Lösungen etwa 0,05 bis 80, vorzugsweise 2 bis 50 Gew.-% Wirkstoff. Bei wasserdispergierbaren Granulaten hängt der Wirkstoffgehalt zum Teil davon ab, ob die wirksame Verbindung flüssig oder fest vorliegt und welche Granulierhilfsmittel, Füllstoffe usw. verwendet werden. Bei den in Wasser dispergierbaren Granulaten liegt der Gehalt an Wirkstoff beispielsweise zwischen 1 und 95 Gew.-%, vorzugsweise zwischen 10 und 80 Gew.-% .In wettable powders, the active ingredient concentration is z. B. about 10 to 90 wt .-%, the rest of 100 wt .-% consists of conventional formulation components. In the case of emulsifiable concentrates, the active substance concentration can be about 1 to 90, preferably 5 to 80,% by weight. Dust-like formulations contain 1 to 30, preferably mostly 5 to 20% by weight of active ingredient, sprayable solutions about 0.05 to 80, preferably 2 to 50% by weight of active ingredient. In the case of water-dispersible granules, the active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulating aids, fillers, etc. are used. The active ingredient content of the water-dispersible granules is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
Daneben enthalten die genannten Wirkstofformulierungen gegebenenfalls die jeweils üblichen Haft-, Netz-, Dispergier-, Emulgier-, Penetrations-, Konservierungs-, Frostschutz- und Lösungsmittel, Füll-, Träger- und Farbstoffe, Entschäumer, Verdunstungshemmer und den pH-Wert und die Viskosität beeinflussende Mittel.In addition, the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreezes and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and the pH and Agents influencing viscosity.
Als Kombinationspartner für die erfindungsgemäßen Wirkstoffe in Mischungsformulierungen oder im Tank-Mix sind beispielsweise bekannte Wirkstoffe einsetzbar, wie sie in z. B. aus Weed Research 26, 441-445 (1986), oder "The Pesticide Manual", 9th edition, The British Crop Protection Council, 1990/91 , Bracknell, England, und dort zitierter Literatur beschrieben sind. Als literaturbekannte Herbizide, die mit den Verbindungen der Formel (I) kombiniert werden können, sind z. B. folgende Wirkstoffe zu nennen (Anmerkung: Die Verbindungen sind entweder mit dem "common name" nach der International Organization for Standardization (ISO) oder mit dem chemischen Namen, gegebenenfalls zusammen mit einer üblichen Codenummer bezeichnet): acetochlor; acifluorfen; aclonifen; AKH 7088, d. h. [[[1-[5-[2-Chloro-4- (trifluoromethyl)-phenoxy]-2-nitrophenyl]-2-methoxyethylidene]-amino]-oxy]- essigsäure und -essigsäuremethylester; alachlor; alloxydim; ametryn; amidosulfuron; amitrol; AMS, d. h. Ammoniumsulfamat; anilofos; asulam; atrazin; aziprotryn; barban; BAS 516 H, d. h. 5-Fluor-2-phenyl-4H-3,1- benzoxazin-4-on; benazolin; benfluralin; benfuresate; bensulfuron-methyl; bensulide; bentazone; benzofenap; benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox; bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butamifos; butenachlor; buthidazole; butralin; butylate; carbetamide; CDAA, d. h. 2-Chlor- N,N-di-2-propenylacetamid; CDEC, d. h. Diethyldithiocarbaminsäure-2- chlorallylester; CGA 184927, d. h. 2-[4-[(5-Chlor-3-fluor-2-pyridinyl)-oxy]- phenoxyl-propansäure und 2-propynylester; chlomethoxyfen; chloramben; chlorazifop-butyl, pirifenop-butyl; chlorbromuron; chlorbufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron ethyl; chlornitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlorthal-dimethyl; chlorthiamid; cinmethylin; cinosulfuron; clethodim; clomazone; clomeprop; cloproxydim; clopyralid; cyanazine; cycloate; cycloxydim; cycluron; cyperquat; cyprazine; cyprazole; 2,4-DB; dalapon; desmedipham; desmetryn; di-allate; dicamba; dichlobenil; dichlorprop; diclofop-methyl; diethatyl; difenoxuron; difenzoquat; diflufenican; dimefuron; dimethachlor; dimethametryn; dimethazone, clomazon; dimethipin; dimetrasulfuron, cinosulfuron; dinitramine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 177, d. h. 5-Cyano-1-(1 ,1-dimethylethyl)-N-methyl-3H-pyrazole-4-carboxamid; endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl; ethidimuron; ethiozin; ethofumesate; F5231 , d. h. N-_2-Chlor-4-fluor-5-[4-(3-fluorpropyl)-4,5- dihydro-5-oxo-1 H-tetrazol-1-yl]-phenyl]-ethansulfonamid; F6285, d. h. 1-[5-(N- Methylsulfonyl)-amino-2,4-dichlorophenyl]-3-methyl-4-difluoromethyl-1 ,2,4- triazol-5-on; fenoprop; fenoxan, clomazon; fenoxaprop-ethyl; fenuron; flamprop-methyl; flazasulfuron; fluazifop und dessen Esterderivate; fluchloralin; flumetsulam; N-[2,6-Difluorphenyl]-5-methyl-(1 ,2,4)-triazolo[1 ,5a]pyrimidin-2- sulfonamid; flumeturon; flumipropyn; fluorodifen; fluoroglycofen-ethyl; fluridone; flurochloridone; fluroxypyr; flurtamone; fomesafen; fosamine; furyloxyfen; glufosinate; glyphosate; halosafen; haloxyfop und dessen Esterderivate; hexazinone; Hw 52, d. h. N-(2,3-Dichlorphenyl)-4-(ethoxymethoxy)-benzamid; imazamethabenz-methyl; imazapyr; imazaquin; imazethamethapyr; imazethapyr; imazosulfuron; ioxynil; isocarbamid; isopropalin; isoproturon; isouron; isoxaben; isoxapyrifop; karbutilate; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidid; metamitron; metazachlor; methabenzthiazuron; metham; methazole; methoxyphenone; methyidymron; metobromuron; metolachlor; metoxuron; metribuzin; metsulfuron-methyl; MH; molinate; monalide; monocarbamide dihydrogensulfate; monolinuron; monuron; MT 128, d. h. 6-Chlor-N-(3-chlor-2-propenyl)-5-methyl-N-phenyl-3-pyridazinamin; MT 5950, d. h. N-[3-Chlor-4-(1-methylethyl)-phenyl]-2-methylpentanamid; naproanilide; napropamide; naptalam; NC 310, d. h. 4-(2,4-dichlorbenzoyl)-1 -methyl-5- benzyloxypyrazol; neburon; nicosulfuron; nipyraclophen; nitralin; nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiazon; oxyfluorfen; paraquat; pebulate; pendimethalin; perfluidone; phenmedipham; phenisopham; phenmedipham; picloram; piperophos; piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl; procyazine; prodiamine; profluralin; proglinazine-ethyl; prometon; prometryn; propachlor; propanil; propaquizafop und dessen Esterderivate; propazine; propham; propyzamide; prosulfalin; prosulfocarb; prynachlor; pyrazolinate; pyrazon; pyrazosulfuron-ethyl; pyrazoxyfen; pyridate; quinclorac; quinmerac; quinofop und dessen Esterderivate, quizalofop und dessen Esterderivate; quizalofop-ethyl; quizalofop-p-tefuryl; renriduron; dymron; S 275, d. h. 2-[4-Chlor-2-fluor-5-(2-propynyloxy)-phenyl]-4,5,6,7-tetrahydro-2H- indazol; S 482, d. h. 2-[7-Fluor-3,4-dihydro-3-oxo-4-(2-propynyl)-2H-1 ,4- benzoxazin-6-yl]-4,5,6,7-tetrahydro-1 H-isoindol-1 ,3(2H)-dion; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, d. h. 2-[[7-[2-Chlor-4- (trifluor-methyl)-phenoxy]-2-naphthalenyl]-oxy]-propansäure und -methylester; sulfometuron-methyl; sulfazuron; flazasulfuron; TCA; tebutam; tebuthiuron; terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryn; TFH 450, d. h. N,N-Diethyl-3-[(2-ethyl-6-methylphenyl)-sulfonyl]-1 H-1 ,2,4- triazol-1-carboxamid; thiazafluron; thifensulfuron-methyl; thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide; tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin; trimeturon; vernolate; WL 1 10547, d. h. 5-Phenoxy-1-[3-(trifluormethyl)-phenyl]-1 H- tetrazol. Zur Anwendung werden die in handelsüblicher Form vorliegenden Formulierungen gegebenenfalls in üblicher Weise verdünnt z. B. bei Spritzpulvern, emulgierbaren Konzentraten, Dispersionen und wasserdispergierbaren Granulaten mittels Wasser. Staubförmige Zubereitungen, Boden- bzw. Streugranulate sowie versprühbare Lösungen werden vor der Anwendung üblicherweise nicht mehr mit weiteren inerten Stoffen verdünnt.As a combination partner for the active substances according to the invention in mixture formulations or in the tank mix, known active substances can be used, for example, as described in e.g. B. from Weed Research 26, 441-445 (1986), or "The Pesticide Manual", 9th edition, The British Crop Protection Council, 1990/91, Bracknell, England, and literature cited therein. As herbicides known from the literature, which can be combined with the compounds of formula (I), z. For example, the following active substances are to be named (note: the compounds are identified either with the "common name" according to the International Organization for Standardization (ISO) or with the chemical name, if appropriate together with a customary code number): acetochlor; acifluorfen; aclonifen; AKH 7088, ie [[[[1- [5- [2-chloro-4- (trifluoromethyl) phenoxy] -2-nitrophenyl] -2-methoxyethylidene] amino] oxy] acetic acid and methyl acetate; alachlor; alloxydim; ametryn; amidosulfuron; amitrole; AMS, ie ammonium sulfamate; anilofos; asulam; atrazine; aziprotryn; barban; BAS 516 H, ie 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin; benfluralin; benfuresate; bensulfuron-methyl; bensulide; bentazone; benzofenap; benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox; bromacil; bromobutide; bromofenoxim; bromoxynil; bromuron; buminafos; busoxinone; butachlor; butamifos; butenachlor; buthidazole; butralin; butylates; carbetamide; CDAA, ie 2-chloro-N, N-di-2-propenylacetamide; CDEC, ie 2-chloroallyl ester of diethyldithiocarbamic acid; CGA 184927, ie 2- [4 - [(5-chloro-3-fluoro-2-pyridinyl) -oxy] - phenoxyl-propanoic acid and 2-propynyl ester; chlomethoxyfen; chloramben; chlorazifop-butyl, pirifenop-butyl; chlorbromuron; chlorobufam; chlorfenac; chlorflurecol-methyl; chloridazon; chlorimuron ethyl; chloronitrofen; chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron; chlororthal dimethyl; chlorothiamide; cinmethylin; cinosulfuron; clethodim; clomazone; clomeprop; cloproxydim; clopyralid; cyanazine; cycloate; cycloxydim; cycluron; cyperquat; cyprazine; cyprazole; 2,4-DB; dalapon; desmedipham; desmetryn; di-allate; dicamba; dichlobenil; dichlorprop; diclofop-methyl; diethatyl; difenoxuron; difenzoquat; diflufenican; dimefuron; dimethachlor; dimethametryn; dimethazone, clomazone; dimethipin; dimetrasulfuron, cinosulfuron; dinitramine; dinoseb; dinoterb; diphenamide; dipropetryn; diquat; dithiopyr; diuron; DNOC; eglinazine-ethyl; EL 177, ie 5-cyano-1- (1, 1-dimethylethyl) -N-methyl-3H-pyrazole-4-carboxamide; endothal; EPTC; esprocarb; ethalfluralin; ethametsulfuron-methyl; ethidimuron; ethiozin; ethofumesate; F5231, ie N-_2-chloro-4-fluoro-5- [4- (3-fluoropropyl) -4,5-dihydro-5-oxo-1H-tetrazol-1-yl] phenyl] ethanesulfonamide; F6285, ie 1- [5- (N-methylsulfonyl) amino-2,4-dichlorophenyl] -3-methyl-4-difluoromethyl-1, 2,4-triazol-5-one; fenoprop; fenoxan, clomazone; fenoxaprop-ethyl; fenuron; flamprop-methyl; flazasulfuron; fluazifop and its ester derivatives; fluchloralin; flumetsulam; N- [2,6-difluorophenyl] -5-methyl- (1,2,4) -triazolo [1,5a] pyrimidine-2-sulfonamide; flumeturon; flumipropyn; fluorodifen; fluoroglycofen-ethyl; fluridone; flurochloridone; fluroxypyr; flurtamone; fomesafen; fosamine; furyloxyfen; glufosinate; glyphosate; halosafen; haloxyfop and its ester derivatives; hexazinone; Hw 52, ie N- (2,3-dichlorophenyl) -4- (ethoxymethoxy) benzamide; imazamethabenz-methyl; imazapyr; imazaquin; imazethamethapyr; imazethapyr; imazosulfuron; ioxynil; isocarbamide; isopropaline; isoproturon; isouron; isoxaben; isoxapyrifop; carbutilates; lactofen; lenacil; linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidide; metamitron; metazachlor; methabenzthiazuron; metham; methazole; methoxyphenone; methyidymron; metobromuron; metolachlor; metoxuron; metribuzin; metsulfuron-methyl; MH; molinate; monalide; monocarbamide dihydrogen sulfates; monolinuron; monuron; MT 128, ie 6-chloro-N- (3-chloro-2-propenyl) -5-methyl-N-phenyl-3-pyridazinamine; MT 5950, ie N- [3-chloro-4- (1-methylethyl) phenyl] -2-methylpentanamide; naproanilide; napropamide; naptalam; NC 310, ie 4- (2,4-dichlorobenzoyl) -1-methyl-5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclophen; nitraline; nitrofen; nitrofluorfen; norflurazon; orbencarb; oryzalin; oxadiazon; oxyfluorfen; paraquat; pebulate; pendimethalin; perfluidone; phenmedipham; phenisopham; phenmedipham; picloram; piperophos; piributicarb; pirifenop-butyl; pretilachlor; primisulfuron-methyl; procyazine; prodiamine; profluralin; proglinazine-ethyl; prometon; prometryn; propachlor; propanil; propaquizafop and its ester derivatives; propazine; propham; propyzamide; prosulfalin; prosulfocarb; prynachlor; pyrazolinates; pyrazone; pyrazosulfuron-ethyl; pyrazoxyfen; pyridate; quinclorac; quinmerac; quinofop and its ester derivatives, quizalofop and its ester derivatives; quizalofop-ethyl; quizalofop-p-tefuryl; renriduron; dymron; S 275, ie 2- [4-chloro-2-fluoro-5- (2-propynyloxy) phenyl] -4,5,6,7-tetrahydro-2H-indazole; S 482, ie 2- [7-fluoro-3,4-dihydro-3-oxo-4- (2-propynyl) -2H-1,4-benzoxazin-6-yl] -4,5,6,7- tetrahydro-1 H-isoindole-1,3 (2H) -dione; secbumeton; sethoxydim; siduron; simazine; simetryn; SN 106279, ie 2 - [[7- [2-chloro-4- (trifluoromethyl) phenoxy] -2-naphthalenyl] oxy] propanoic acid and methyl ester; sulfometuron-methyl; sulfazuron; flazasulfuron; TCA; tebutam; tebuthiuron; terbacil; terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryn; TFH 450, ie N, N-diethyl-3 - [(2-ethyl-6-methylphenyl) sulfonyl] -1 H-1, 2,4-triazole-1-carboxamide; thiazafluron; thifensulfuron-methyl; thiobencarb; tiocarbazil; tralkoxydim; tri-allate; triasulfuron; triazofenamide; tribenuron-methyl; triclopyr; tridiphane; trietazine; trifluralin; trimeturon; vernolate; WL 1 10547, ie 5-phenoxy-1- [3- (trifluoromethyl) phenyl] -1 H-tetrazole. For use, the formulations present in the commercial form are optionally diluted in the customary manner, for. B. with wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Preparations in the form of dust, ground or scatter granules and sprayable solutions are usually no longer diluted with other inert substances before use.
Die erfindungsgemäßen Verbindungen können beispielsweise direkt auf die Schadpflanzen oder Schadpflanzen und Nutzpflanzen zugleich im Nachauflaufverfahren oder auf die Fläche, auf der die Pflanzen wachsen, z. B. auf Ackerboden mit Pflanzensamen bzw. aufgelaufenen Pflanzen oder auf Anbauflächen, wie z. B. eine Reisanbaufläche, im Vor- oder Nachauflaufverfahren appliziert werden.The compounds of the invention can, for example, directly on the harmful plants or harmful plants and crop plants at the same time in the post-emergence process or on the area on which the plants grow, for. B. on arable soil with plant seeds or accumulated plants or on acreages, such as. B. a rice cultivation area, applied in the pre- or post-emergence process.
Mit den äußeren Bedingungen wie Temperatur, Feuchtigkeit, der Art des verwendeten Herbizids, u.a. variiert die erforderliche Aufwandmenge der Verbindungen der Formel (I). Sie kann innerhalb weiter Grenzen schwanken, z. B. zwischen 0,001 und 10,0 kg/ha oder mehr Aktivsubstanz, vorzugsweise liegt sie jedoch zwischen 0,005 und 5 kg/ha.With the external conditions such as temperature, humidity, the type of herbicide used, etc. the required application rate of the compounds of formula (I) varies. It can fluctuate within wide limits, e.g. B. between 0.001 and 10.0 kg / ha or more of active substance, but is preferably between 0.005 and 5 kg / ha.
A. Chemische BeispieleA. Chemical examples
a) Benzo[b]thiophen-2,3-diona) Benzo [b] thiophene-2,3-dione
27,5 g (0,25 mol) Thiophenol werden in 200 ml Diethylether gelöst und zu dieser Lösung 48,0 g (0,38 mol) Oxalylchlorid in 200 ml Diethylether gelöst hinzugetropft. Anschließend erwärmt man 2 Stunden zum Rückfluß, destilliert den Ether unter vermindertem Druck ab und trocknet den Rückstand 16 Stunden im Vakuumexsikkator über Kaliumhydroxid. Der verbliebene Rückstand wird in 450 ml Schwefelkohlenstoff gelöst, auf 0°C abgekühlt und bei dieser Temperatur 40 g (0,299 mol) Aluminiumtrichlorid langsam hinzugegeben. Dann läßt man auf Raumtemperatur aufwärmen, erhitzt noch 30 Minuten zum Rückfluß, läßt abkühlen und gibt eiskalte Salzsäure hinzu, bis keine Gasentwicklung mehr zu beobachten ist. Der Schwefelkohlenstoff wird durch Wasserdampfdestillation entfernt. Durch Umkristallisieren des Rückstandes aus Methanol erhält man 22,70 g (55,3 % d.Th.) Benzo[b]thiophen-2,3-dion vom Schmelzpunkt 1 18°C.27.5 g (0.25 mol) of thiophenol are dissolved in 200 ml of diethyl ether and 48.0 g (0.38 mol) of oxalyl chloride dissolved in 200 ml of diethyl ether are added dropwise to this solution. The mixture is then heated under reflux for 2 hours, the ether is distilled off under reduced pressure and the residue is dried over potassium hydroxide in a vacuum desiccator for 16 hours. The remaining residue is dissolved in 450 ml of carbon disulfide, cooled to 0 ° C. and 40 g (0.299 mol) at this temperature. Aluminum trichloride added slowly. The mixture is then allowed to warm to room temperature, heated to reflux for a further 30 minutes, allowed to cool and ice-cold hydrochloric acid is added until no more gas evolution can be observed. The carbon disulfide is removed by steam distillation. By recrystallizing the residue from methanol, 22.70 g (55.3% of theory) of benzo [b] thiophene-2,3-dione, melting point 1 18 ° C., is obtained.
2-[(4,6-Dimethoxypyrimidin-2-yl)mercapto]-phenylglyoxylsäure (siehe Beispiel 1 , Tab. 1 ) 4,92 g (0,03 mol) Benzo[b]thiophen-2,3-dion werden in 50 ml Wasser suspendiert und 2,4 g (0,06 mol) Natriumhydroxid hinzugefügt und 1 Stunde zum Rückfluß erhitzt. Anschließend läßt man auf 50°C abkühlen und fügt dann 6,54 g (0,03 mol) 4,6-Dimethoxy-2- methylsulfonylpyrimidin hinzu. Man erhitzt 2 Stunden zum Rückfluß, läßt auf Raumtemperatur abkühlen, bringt die Lösung mit konzentrierter Salzsäure auf pH 1 und extrahiert zweimal mit je 50 ml Essigester. Die vereinigten organischen Phasen werden über MgSO4 getrocknet, vom Trockenmittel abfiltriert und das Lösungsmittel unter vermindertem Druck abdestilliert.2 - [(4,6-Dimethoxypyrimidin-2-yl) mercapto] phenylglyoxylic acid (see Example 1, Tab. 1) 4.92 g (0.03 mol) of benzo [b] thiophene-2,3-dione are added in Suspended 50 ml of water and added 2.4 g (0.06 mol) of sodium hydroxide and heated to reflux for 1 hour. The mixture is then allowed to cool to 50 ° C. and 6.54 g (0.03 mol) of 4,6-dimethoxy-2-methylsulfonylpyrimidine are then added. The mixture is heated under reflux for 2 hours, allowed to cool to room temperature, the solution is brought to pH 1 with concentrated hydrochloric acid and extracted twice with 50 ml of ethyl acetate. The combined organic phases are dried over MgSO 4 , the drying agent is filtered off and the solvent is distilled off under reduced pressure.
Der Rückstand wird an Kieselgel chromatographiert (zuerst mit CH2CI2 / EE = 4:1 , dann mit Methanol) vom methanolischen Eluat wird das Lösungsmittel unter vermindertem Druck abdestilliert, der Rückstand in Natriumhydrogencarbonatlosung gelöst. Anschließend bringt man mit 2 N Salzsäure auf pH 2 und erhält durch Filtration 4,0 g (41 ,6 % d.Th.) 2-[4,6-Dimethoxypyrimidin-2-yl]-mercaptophenylglyoxylsäure vom Schmelzpunkt 68°C. c) 2-[(4,6-Dimethoxypyrimidin-2-yl)-mercapto]- phenylglyoxylsäuremethylester (siehe Beispiel 2, Tab. 1 )The residue is chromatographed on silica gel (first with CH 2 Cl 2 / EA = 4: 1, then with methanol), the solvent is distilled off from the methanolic eluate under reduced pressure and the residue is dissolved in sodium hydrogen carbonate solution. The mixture is then brought to pH 2 with 2 N hydrochloric acid and 4.0 g (41.6% of theory) of 2- [4,6-dimethoxypyrimidin-2-yl] mercaptophenylglyoxylic acid of melting point 68 ° C. are obtained by filtration. c) 2 - [(4,6-Dimethoxypyrimidin-2-yl) mercapto] - phenylglyoxylic acid methyl ester (see Example 2, Tab. 1)
9,9 g (0,031 mol) 2-[4,6-Dimethoxypyrimidin-2-yl]- mercaptophenylglyoxylsäure werden in 50 ml DMF gelöst, 3,3 g (0,032 mol) Triethylamin hinzugefügt und dann bei Raumtemperatur 2,9 g (0,031 mol) Chlorameisensäuremethylester hinzugetropft. Man rührt 30 Minuten bei Raumtemperatur nach, destilliert das DMF unter vermindertem Druck ab, nimmt den Rückstand in Essigester auf, filtriert vom Ungelösten ab, destilliert das Lösungsmittel unter reduziertem Druck ab und chromatographiert den Rückstand an Kieselgel mit CH2CI2 / Essigester (4:1 ). Man erhält so 7,2 g (69,7 % d.Th.) 2-[(4,6- Dimethoxypyrimidin-2-yl)-mercapto]-phenylglyoxylsäuremethylestervom Schmelzpunkt 102°C.9.9 g (0.031 mol) of 2- [4,6-dimethoxypyrimidin-2-yl] mercaptophenylglyoxylic acid are dissolved in 50 ml of DMF, 3.3 g (0.032 mol) of triethylamine are added and then 2.9 g (0.031 mol) methyl chloroformate added dropwise. The mixture is stirred at room temperature for 30 minutes, the DMF is distilled off under reduced pressure, the residue is taken up in ethyl acetate, the undissolved solution is filtered off, the solvent is distilled off under reduced pressure and the residue is chromatographed on silica gel with CH 2 Cl 2 / ethyl acetate (4 :1 ). 7.2 g (69.7% of theory) of 2 - [(4,6-dimethoxypyrimidin-2-yl) mercapto] phenylglyoxylic acid methyl ester of melting point 102 ° C. are thus obtained.
d) 1-[2-(4,6-Dimethoxypyrimidin-2-yl-thio)-phenyl]-ethoxyiminoessig- säuremethylester (siehe Beispiel 56, Tab. 1 )d) Methyl 1- [2- (4,6-dimethoxypyrimidin-2-yl-thio) phenyl] ethoxyiminoacetic acid (see Example 56, Table 1)
3,34 g (0,01 mol) 2-[(4,6-Dimethoxypyrimidin-2-yl)-mercapto]- phenylglyoxylsäuremethylester werden in 100 ml Methanol gelöst, 1 ,07 g (0,01 1 mol) O-Ethylhydroxylaminhydrochlorid hinzugefügt und anschließend 8 Stunden zum Rückfluß erwärmt. Das Methanol wird dann unter reduziertem Druck abdestilliert, der Rückstand in Essigester aufgenommen, die organische Phase mit Natriumhydrogencarbonatlosung gewaschen, die organischen Phase über MgSO4 getrocknet, vom Trockenmittel abfiltriert und das Lösungsmittel unter vermindertem Druck abdestilliert. Nach Ausrühren des Rückstandes mit Diethylether erhält man 2,67 g (70,3 % d.Th.) 1-[2-(4,6-Dimethoxypyrimidin-2-ylthio)- ethoxyiminoessigsäuremethylester vom Schmelzpunkt 90°C. e) 2-[(4,6-Dimethoxypyrimidin-2-yl)-oxy]-phenylglyoxylsäure3.34 g (0.01 mol) of 2 - [(4,6-dimethoxypyrimidin-2-yl) mercapto] - methyl phenylglyoxylate are dissolved in 100 ml of methanol, 1.07 g (0.01 1 mol) of O-ethylhydroxylamine hydrochloride added and then heated to reflux for 8 hours. The methanol is then distilled off under reduced pressure, the residue is taken up in ethyl acetate, the organic phase is washed with sodium hydrogen carbonate solution, the organic phase is dried over MgSO 4 , the drying agent is filtered off and the solvent is distilled off under reduced pressure. After stirring the residue with diethyl ether, 2.67 g (70.3% of theory) of 1- [2- (4,6-dimethoxypyrimidin-2-ylthio) - ethoxyiminoacetic acid methyl ester of melting point 90 ° C. is obtained. e) 2 - [(4,6-Dimethoxypyrimidin-2-yl) -oxy] -phenylglyoxylic acid
(siehe Beispiel 66, Tab. 1 ) 8,3 g (0,05 mol) 2-Hydroxyphenylglyoxylsäure werden zusammen mit 13,8 g (0, 10 mol) Kaliumcarbonat in 250 ml DMF für 45 Minuten auf 60°C erwärmt, danach fügt man bei dieser Temperatur 10,9 g (0,05 mol) 4,6-Dimethoxy-2-methylsulfonylpyrimidin hinzu und rührt anschließend 6 Stunden bei 80°C nach. Danach wird das Lösungsmittel bei reduziertem Druck abdestilliert, der Rückstand in Wasser aufgenommen und die wäßrige Lösung mit Essigester gewaschen. Die Wasserphase wird mit 2 N Salzsäure auf pH 3 eingestellt und mit Essigester extrahiert. Nach Trocknen der organischen Phase über MgSO4, Abfiltrieren des Trockenmittels und Abdestillieren des Lösungsmittels bei reduziertem Druck erhält man 8,1 g (53,1 % d.Th.) 2-[(4,6-Dimethoxypyrimidin-2-yl)- oxyjphenylglyoxylsäure vom Schemlzpunkt 213°C.(see Example 66, Table 1) 8.3 g (0.05 mol) of 2-hydroxyphenylglyoxylic acid are heated together with 13.8 g (0.10 mol) of potassium carbonate in 250 ml of DMF at 60 ° C. for 45 minutes, then 10.9 g (0.05 mol) of 4,6-dimethoxy-2-methylsulfonylpyrimidine are added at this temperature and the mixture is then stirred at 80 ° C. for 6 hours. The solvent is then distilled off under reduced pressure, the residue is taken up in water and the aqueous solution is washed with ethyl acetate. The water phase is adjusted to pH 3 with 2 N hydrochloric acid and extracted with ethyl acetate. After drying the organic phase over MgSO 4 , filtering off the drying agent and distilling off the solvent under reduced pressure, 8.1 g (53.1% of theory) of 2 - [(4,6-dimethoxypyrimidin-2-yl) - oxyphenylglyoxylic acid with a melting point of 213 ° C.
f) 2-[(4,6-Dimethoxy-1 ,3,5-triazin-2-yl)-thio]-phenylglyoxylsäuref) 2 - [(4,6-Dimethoxy-1, 3,5-triazin-2-yl) thio] phenylglyoxylic acid
(siehe Beispiel 13, Tab. 1 ) 7,1 g (0,043 mol) Benzo[b]thiophen-2,3-dion und 3,46 g (0,086 mol) Natriumhydroxid werden in 100 ml Wasser für 1 Stunde zum Rückfluß erhitzt. Anschließend läßt man auf 50°C abkühlen und fügt dann 7,6 g (0,043 mol) 2-Chlor-4,6-dimethoxy-1 ,3,5-triazin hinzu und erhitzt noch 2 Stunden zum Rückfluß. Nach Abkühlen auf Raumtemperatur wird die Lösung mit 2 N Salzsäure auf pH 1 gebracht und die wäßrige Phase mit Essigester extrahiert. Die organische Phase wird über MgSO4 getrocknet und das Lösungsmittel unter vermindertem Druck abdestilliert. Nach Umkristallisieren aus Essigester erhält man 8,1 g (58,3 % d.Th.) 2-[(4,6- Dimethoxy-1 ,3,5-triazin-2-yl)-thio]-phenylglyoxylsäure vom Schmelzpunkt 155°C. g) 3-Methoxyiminobenzo[b]thiophen-2-on(see Example 13, Table 1) 7.1 g (0.043 mol) of benzo [b] thiophene-2,3-dione and 3.46 g (0.086 mol) of sodium hydroxide are heated to reflux in 100 ml of water for 1 hour. The mixture is then allowed to cool to 50 ° C. and then 7.6 g (0.043 mol) of 2-chloro-4,6-dimethoxy-1,3,5-triazine are added and the mixture is heated under reflux for a further 2 hours. After cooling to room temperature, the solution is brought to pH 1 with 2 N hydrochloric acid and the aqueous phase is extracted with ethyl acetate. The organic phase is dried over MgSO 4 and the solvent is distilled off under reduced pressure. After recrystallization from ethyl acetate, 8.1 g (58.3% of theory) of 2 - [(4,6-dimethoxy-1, 3,5-triazin-2-yl) thio] phenylglyoxylic acid with a melting point of 155 are obtained ° C. g) 3-methoxyiminobenzo [b] thiophen-2-one
2 g (0,012 mol) Benzo[b]thiophen-2,3-dion werden in 50 ml Methanol gelöst, 1 ,02 g (0,012 mol) O-Methylhydroxylaminhydrochlorid hinzugefügt und 30 Minuten zum Rückfluß erhitzt. Anschließend destilliert man das Methanol unter reduziertem Druck ab, löst den Rückstand in Essigester, wäscht die organische Phase einmal mit Wasser, trocknet die organische Phase über MgSO4 und filtriert vom Trockenmittel ab. Nach Abdestillieren des Essigesters bei vermindertem Druck erhält man 1 ,87 g (80,6 %) d.Th.) 3-Methoxyiminobenzo[b]thiophen-2-on vom Schmelzpunkt 76°C.2 g (0.012 mol) of benzo [b] thiophene-2,3-dione are dissolved in 50 ml of methanol, 1.02 g (0.012 mol) of O-methylhydroxylamine hydrochloride are added and the mixture is heated under reflux for 30 minutes. The methanol is then distilled off under reduced pressure, the residue is dissolved in ethyl acetate, the organic phase is washed once with water, the organic phase is dried over MgSO 4 and the desiccant is filtered off. After distilling off the ethyl acetate at reduced pressure, 1.87 g (80.6%) of theory) 3-methoxyiminobenzo [b] thiophen-2-one with a melting point of 76 ° C. is obtained.
h) 1-[2-(4,6-Dimethoxy-1 ,3,5-triazin-2-ylthio)-phenyl]methoxyiminoessig- säure (siehe Beispiel 63, Tab. 1 )h) 1- [2- (4,6-Dimethoxy-1, 3,5-triazin-2-ylthio) phenyl] methoxyiminoacetic acid (see Example 63, Table 1)
1 ,24 g (0,0064 mol) 3-Methoxyiminobenzo[b]thiophen-2-on werden mit 0,51 g (0,013 mol) Natriumhydroxid in 50 ml Wasser 90 Minuten zum Rückfluß erhitzt. Man läßt auf 50°C abkühlen, tropft bei dieser Temperatur 1 ,13 g (0,0064 mol) 2-Chlor-4,6-di-methoxy-1 ,3,5-triazin hinzu und erhitzt 1 Stunde zum Rückfluß. Nach Zugabe von weiteren 100 mg Natriumhydroxid erhitzt man nach 30 Minuten zum Rückfluß läßt auf Raumtemperatur abkühlen und bringt die Lösung mit 2 N Salzsäure auf pH 1 .1.24 g (0.0064 mol) of 3-methoxyiminobenzo [b] thiophen-2-one are refluxed with 0.51 g (0.013 mol) of sodium hydroxide in 50 ml of water for 90 minutes. The mixture is allowed to cool to 50 ° C., 1.13 g (0.0064 mol) of 2-chloro-4,6-di-methoxy-1,3,5-triazine are added dropwise at this temperature and the mixture is heated under reflux for 1 hour. After adding a further 100 mg of sodium hydroxide, the mixture is refluxed after 30 minutes and allowed to cool to room temperature and the solution is brought to pH 1 with 2 N hydrochloric acid.
Die wäßrige Phase wird 2 mal mit je 50 ml Essigester extrahiert, die organische Phase über MgSO4 getrocknet, vom Trockenmittel abfiltriert und das Lösungsmittel bei reduziertem Druck abdestilliert. Nach Ausrühren des Rückstandes mit Diethylether erhält man durch Filtration 1 ,05 g (46,8 % d.Th.) 1-[2-(4,6-Dimethoxy-1 ,3,5-triazin-2-ylthio)- phenylj-methoxyiminoessigsäure vom Schmelzpunkt 174°C (Zers.). Die anderen Verbindungen der nachfolgenden Tabelle 1 werden analog zu den Verfahren der Beispiele a) - h) erhalten.The aqueous phase is extracted twice with 50 ml of ethyl acetate each time, the organic phase is dried over MgSO 4 , the drying agent is filtered off and the solvent is distilled off under reduced pressure. After the residue has been stirred with diethyl ether, 1.05 g (46.8% of theory) of 1- [2- (4,6-dimethoxy-1,3,5-triazin-2-ylthio) phenylj is obtained by filtration -methoxyiminoacetic acid with a melting point of 174 ° C. (dec.). The other compounds in Table 1 below are obtained analogously to the processes of Examples a) - h).
Abkürzungen zu Tabellen 1 :Abbreviations to tables 1:
Smp. = Schmelzpunkt n = Alkyl = geradkettiges Alkyl i = iso s = sekundär t = tertiärMp = melting point n = alkyl = straight-chain alkyl i = iso s = secondary t = tertiary
Q1 = ein Rest der Formel - 0Q 1 = a radical of the formula - 0
Figure imgf000025_0001
H
Figure imgf000025_0001
H
O C HO C H
Q = ein Rest der Formel _ /(Q = a remainder of the formula _ / (
O C HO C H
Ph = PhenylPh = phenyl
*) = Für die mit Öl bezeichneten Verbindungen sind NMR-Daten am Ende der Tabelle aufgeführt. *) = NMR data for the compounds marked with oil are listed at the end of the table.
Tabelle 1 : Verbindungen der Formel (I)Table 1: Compounds of formula (I)
Figure imgf000026_0001
Figure imgf000026_0001
Figure imgf000026_0002
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000026_0002
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
NMR-DatenNMR data
Beispiel 3 1H-NMR (CDCI3): δ = 1 ,3 (t; 3 H, CH3), 3,65 (s; 6 H, OCH3),Example 3 1 H-NMR (CDCI 3 ): δ = 1, 3 (t; 3 H, CH 3 ), 3.65 (s; 6 H, OCH 3 ),
4,30 (q; 2 H, OCH2), 5,65 (s; 1 H, Pyrimidin 5-H), 7,40 bis 8,00 (m; 4 H, Phenyl).4.30 (q; 2 H, OCH 2 ), 5.65 (s; 1 H, pyrimidine 5-H), 7.40 to 8.00 (m; 4 H, phenyl).
Beispiel 4 1H-NMR (CDCI3): δ = 3,70 (s; 6 H, OCH3), 4,20 bis 4,95Example 4 1 H-NMR (CDCI 3 ): δ = 3.70 (s; 6 H, OCH 3 ), 4.20 to 4.95
(m; 4 H, CH2CH2), 5,65 (s; 1 H, Pyrimidin 5 H), 7,40 bis 8,00 (m; 4 H, Phenyl).(m; 4 H, CH 2 CH 2 ), 5.65 (s; 1 H, pyrimidine 5 H), 7.40 to 8.00 (m; 4 H, phenyl).
Beispiel 1 1 1H-NMR (CDCI3): δ = 3,65 (s; 6 H, OCH3), 4,60 bis 4,80 (m; 2 H, OCH2), 5,10 bis 5,30 (m; 2 H, CH2 = ), 5,65 (s; 1 H, Pyrimidin 5-H), 5,70 bis 6,15 (m; 1 H, CH = ), 7,40 bis 7,95 (m; 4 H, Phenyl).Example 1 1 1 H-NMR (CDCI 3 ): δ = 3.65 (s; 6 H, OCH 3 ), 4.60 to 4.80 (m; 2 H, OCH 2 ), 5.10 to 5, 30 (m; 2 H, CH 2 =), 5.65 (s; 1 H, pyrimidine 5-H), 5.70 to 6.15 (m; 1 H, CH =), 7.40 to 7, 95 (m; 4H, phenyl).
Beispiel 12 1H-NMR (CDCI3): δ = 3,60 (s; 6 H, OCH3), 5,20 (s; 2 H, OCH2), 5,60 (s; 1 H, Pyrimidin 5-H), 7,25 (s; 5 H, C6H5), 7,55 bis 7,95 (m; 4 H, C6H4).Example 12 1 H-NMR (CDCI 3 ): δ = 3.60 (s; 6 H, OCH 3 ), 5.20 (s; 2 H, OCH 2 ), 5.60 (s; 1 H, pyrimidine 5 -H), 7.25 (s; 5 H, C 6 H 5 ), 7.55 to 7.95 (m; 4 H, C 6 H 4 ).
Beispiel 60 1 H-NMR (CDCI3): δ = 3,55 (s; 6 H, Pyrimidin-OCH3), 3,70Example 60 1 H-NMR (CDCI 3 ): δ = 3.55 (s; 6 H, pyrimidine-OCH 3 ), 3.70
(s; 3 H, OCH3), 5,15 (s; 2 H, OCH2), 5,60 (s; 1 H, Pyrimidin 5-H), 7,20 (s; 1 H, Pyrimidin 5-H), 7,20 (s; 5 H, C6H5), 7,25 bis 7,80 (m; 4 H, C6H4). Beispiel 75 ^-NMR (CDCI3): δ = 3,75 (s; 6 H, OCH3), 4,30 bis 5,00(s; 3 H, OCH 3 ), 5.15 (s; 2 H, OCH 2 ), 5.60 (s; 1 H, pyrimidine 5-H), 7.20 (s; 1 H, pyrimidine 5- H), 7.20 (s; 5 H, C 6 H 5 ), 7.25 to 7.80 (m; 4 H, C 6 H 4 ). Example 75 ^ -NMR (CDCI 3 ): δ = 3.75 (s; 6 H, OCH 3 ), 4.30 to 5.00
(m; 4 H, CH2-CH2), 5,75 (s; 1 H, Pyrimidin 5-H), 7,20 bis 8,00 (m; 4 H, Phenyl).(m; 4 H, CH 2 -CH 2 ), 5.75 (s; 1 H, pyrimidine 5-H), 7.20 to 8.00 (m; 4 H, phenyl).
Beispiel 78 1H-NMR (CDCI3): δ = 3,70 (s; 6 H, OCH3), 5,25 (s; 2 H, OCH2), 5,70 (s; 1 H, Pyrimidin 5-H), 7,25 (s; 5 H, C6H5), 7,20 bis 8,00 (m; 4 H, C6H4).Example 78 1 H-NMR (CDCI 3 ): δ = 3.70 (s; 6 H, OCH 3 ), 5.25 (s; 2 H, OCH 2 ), 5.70 (s; 1 H, pyrimidine 5 -H), 7.25 (s; 5 H, C 6 H 5 ), 7.20 to 8.00 (m; 4 H, C 6 H 4 ).
Beispiel 149 1H-NMR (CDCI3): δ = 3,75 (s; 6 H, Pyrimidin OCH3),Example 149 1 H-NMR (CDCI 3 ): δ = 3.75 (s; 6 H, pyrimidine OCH 3 ),
3,80 (s; 3 H, OCH3), 5,10 (s; 2 H, OCH2), 5,65 (s; 1 H, Pyrimidin 5-H), 7,30 (s; 5H; C6H5), 7,20 bis 7,55 (m; 4 H, C6H4).3.80 (s; 3 H, OCH 3 ), 5.10 (s; 2 H, OCH 2 ), 5.65 (s; 1 H, pyrimidine 5-H), 7.30 (s; 5H; C 6 H 5 ), 7.20 to 7.55 (m; 4 H, C 6 H 4 ).
B. FormulierungsbeispieleB. Examples of formulation
a) Ein Stäubemittel wird erhalten, indem man 10 Gew.-Teile einer Verbindung der Formel (I) und 90 Gew.-Teile Talkum als Inertstoff mischt und in einer Schlagmühle zerkleinert.a) A dusting agent is obtained by mixing 10 parts by weight of a compound of the formula (I) and 90 parts by weight of talc as an inert substance and comminuting in a hammer mill.
b) Ein in Wasser leicht dispergierbares, benetzbares Pulver wird enthalten, indem man 25 Gewichtsteile einer Verbindung der Formel (I),b) A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of a compound of the formula (I),
64 Gewichtsteile kaolinhaltigen Quarz als Inertstoff, 10 Gewichtsteile ligninsulfonsaures Kalium und 1 Gew.-Teil oleoylmethyltaurinsaures Natrium als Netz- und Dispergiermittel micht und in einer Stiftmühle mahlt.64 parts by weight of quartz containing kaolin as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight sodium oleoylmethyl taurine as wetting and dispersing agent and ground in a pin mill.
c) Ein in Wasser leicht dispergierbares Dispersionskonzentrat wird erhalten, indem man 20 Gewichtsteile einer Verbindung der Formel (I) mit 6 Gew.- Teilen Alkylphenolpolyglykolether (®Triton X 207), 3 Gew.-Teilen Isotridecanolpolyglykolether (8 EO) und 71 Gew.-Teilen paraffinischem Mineralöl (Siedebereich z. B. ca. 255 bis über 277°C) mischt und in einer Reibkugelmühle auf eine Feinheit von unter 5 Mikron vermahlt.c) A dispersion concentrate which is readily dispersible in water is obtained by mixing 20 parts by weight of a compound of the formula (I) with 6 parts by weight of alkylphenol polyglycol ether ( ® Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71 parts by weight. Parts of paraffinic mineral oil (boiling range e.g. approx. 255 to above 277 ° C) and mixed in one Grinding ball mill ground to a fineness of less than 5 microns.
d) Ein emulgierbares Konzentrat wird erhalten aus 15 Gew.-Teilen einer Verbindung der Formel (I), 75 Gew.-Teilen Cyclohexanon als Lösungsmittel und 10 Gew.-Teilen oxethyiiertes Nonylphenol als Emulgator.d) An emulsifiable concentrate is obtained from 15 parts by weight of a compound of the formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol as emulsifier.
e) Ein in Wasser dispergierbares Granulat wird erhalten indem mane) A water-dispersible granulate is obtained by:
75 Gewichtsteile einer Verbindung der Formel (I), 10 " ligninsulfonsaures Calcium,75 parts by weight of a compound of the formula (I), 10 "calcium lignosulfonic acid,
5 " Natriumlaurylsulfat,5 "sodium lauryl sulfate,
3 " Polyvinylalkohol und3 "polyvinyl alcohol and
7 " Kaolin7 "kaolin
mischt, auf einer Stiftmühle mahlt und das Pulver in einem Wirbelbett durch Aufsprühen von Wasser als Granulierflüssigkeit granuliert.mixes, grinds on a pin mill and granulates the powder in a fluidized bed by spraying water as granulating liquid.
f) Ein in Wasser dispergierbares Granulat wird auch erhalten, indem manf) A water-dispersible granulate is also obtained by
25 Gewichtsteile einer Verbindung der Formel (I),25 parts by weight of a compound of the formula (I),
5 " 2,2'-dinaphthylmethan-6,6'-disulfonsaures Natrium,5 "2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium,
2 " oleoylmethyltaurinsaures Natrium,2 "oleoylmethyl tauric acid sodium,
1 Gewichtsteil Polyvinylalkohol, 17 Gewichtsteile Calciumcarbonat und 50 " Wasser1 part by weight of polyvinyl alcohol, 17 parts by weight of calcium carbonate and 50 "water
auf einer Kolloidmühle homogenisiert und vorzerkleinert, anschließend auf einer Perlmühle mahlt und die so erhaltene Suspension in einem Sprühturm mittels einer Einstoffdüse zerstäubt und trocknet. C. Biologische Beispielehomogenized on a colloid mill and pre-comminuted, then ground on a bead mill and the suspension thus obtained is atomized and dried in a spray tower using a single-component nozzle. C. Biological examples
1. Unkrautwirkung im Vorauflauf1. Pre-emergence weed action
Samen bzw. Rhizomstucke von mono- und dikotylen Unkrautpflanzen wurden in Plastiktöpfen in sandiger Lehmerde ausgelegt und mit Erde abgedeckt. Die in Form von benetzbaren Pulvern oder Emulsionskonzentraten formulierten erfindungsgemäßen Verbindungen wurden dann als wäßrige Suspension bzw. Emulsion mit einer Wasseraufwandmenge von umgerechnet 600 bis 800 l/ha in unterschiedlichen Dosierungen auf die Oberfläche der Abdeckerde appliziert.Seeds or rhizome pieces of monocotyledonous and dicotyledonous weed plants were placed in sandy loam in plastic pots and covered with soil. The compounds according to the invention formulated in the form of wettable powders or emulsion concentrates were then applied as an aqueous suspension or emulsion with a water application rate of the equivalent of 600 to 800 l / ha in different dosages to the surface of the covering earth.
Nach der Behandlung wurden die Töpfe im Gewächshaus aufgestellt und unter guten Wachstumsbedingungen für die Unkräuter gehalten. Die optische Bonitur der Pflanzen- bzw. der Auflaufschäden erfolgte nach dem Auflaufen der Versuchspflanzen nach einer Versuchszeit von 3 bis 4 Wochen im Vergleich zu unbehandelten Kontrollen. Wie die Testergebnisse zeigen, weisen die erfindungsgemäßen Verbindungen eine gute herbizide Vorauflaufwirksamkeit gegen ein breites Spektrum von Ungräsern und Unkräutern auf. Beispielsweise haben die Verbindungen der Beispiele 1 , 2, 3, 4, 1 1 , 12, 14, 56, 59, 60, 61 , 62, 66, 67, 68, 75, 77 und 78 sehr gute herbizide Wirkung gegen Schadplanzen wie Sinapis alba, Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus und Panicum miliaceum im Vorauflaufverfahren bei einer Aufwandmenge von 0,3 kg und weniger Aktivsubstanz pro Hektar.After the treatment, the pots were placed in the greenhouse and kept under good growth conditions for the weeds. After the test plants had emerged, the optical damage to the plants or the emergence damage was assessed after a test period of 3 to 4 weeks in comparison to untreated controls. As the test results show, the compounds according to the invention have good herbicidal pre-emergence activity against a broad spectrum of grasses and weeds. For example, the compounds of Examples 1, 2, 3, 4, 11, 12, 14, 56, 59, 60, 61, 62, 66, 67, 68, 75, 77 and 78 have very good herbicidal activity against harmful plants such as Sinapis alba, Chrysanthemum segetum, Avena sativa, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus and Panicum miliaceum in the pre-emergence process with an application rate of 0.3 kg and less active substance per hectare.
2. Unkrautwirkung im Nachauflauf2. Post-emergence weed action
Samen bzw. Rhizomstucke von mono- und dikotylen Unkräutern wurden in Plastiktöpfen in sandigem Lehmboden ausgelegt, mit Erde abgedeckt und im Gewächshaus unter guten Wachstumsbedingungen angezogen. Drei Wochen nach der Aussaat wurden die Versuchspflanzen im Dreiblattstadium behandelt. Die als Spritzpulver bzw. als Emulsionskonzentrate formulierten erfindungsgemäßen Verbindungen wurden in verschiedenen Dosierungen mit einer Wasseraufwandmenge von umgerechnet 600 bis 800 l/ha auf die grünen Pflanzenteile gesprüht und nach ca. 3 bis 4 Wochen Standzeit der Versuchspflanzen im Gewächshaus unter optimalen Wachstumsbedingungen die Wirkung der Präparate optisch im Vergleich zu unbehandelten Kontrollen bonitiert. Die erfindungsgemäßen Mittel weisen auch im Nachauflauf eine gute herbizide Wirksamkeit gegen ein breites Spektrum wirtschaftlich wichtiger Ungräser und Unkräuter auf. Beispielsweise haben die Verbindungen der Beispiele 1 , 2, 3, 4, 1 1 , 12, 14, 56, 59, 60, 61 , 62, 66, 67, 68, 75, 77 und 78 sehr gute herbizide Wirkung gegen Schadplanzen wie Sinapis alba, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Chrysanthemum segetum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus und Panicum miliaceum, Avena sativa im Nachauflaufverfahren bei einer Aufwandmenge von 0,3 kg und weniger Aktivsubstanz pro Hektar. Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds were placed in plastic pots in sandy loam soil, covered with soil and grown in the greenhouse under good growth conditions. The test plants were treated at the three-leaf stage three weeks after sowing. The compounds according to the invention, formulated as wettable powder or as emulsion concentrates, were sprayed onto the green parts of the plant in various dosages with a water application rate of the equivalent of 600 to 800 l / ha, and after about 3 to 4 weeks of standing of the test plants in the greenhouse under optimal growth conditions, the action of the preparations visually rated in comparison to untreated controls. The agents according to the invention also have good herbicidal activity against a broad spectrum of economically important grasses and weeds, even after emergence. For example, the compounds of Examples 1, 2, 3, 4, 11, 12, 14, 56, 59, 60, 61, 62, 66, 67, 68, 75, 77 and 78 have very good herbicidal activity against harmful plants such as Sinapis alba, Stellaria media, Echinochloa crus-galli, Lolium multiflorum, Chrysanthemum segetum, Setaria spp., Abutilon theophrasti, Amaranthus retroflexus and Panicum miliaceum, Avena sativa in the post-emergence process with an application rate of 0.3 kg and less active substance per hectare.

Claims

PatentansprücheClaims
Verbindungen der Formel (I)Compounds of formula (I)
Figure imgf000039_0001
Figure imgf000039_0001
worin R1 H, (C^Cβl-Alky!, das unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, Nitro, Cyano, (CrC4)-Alkoxy, Aryl und substituiertes Aryl substituiert ist, oder (C3-C6)-Alkenyl, (C3-C6)-Alkinyl oder Aryl, wobei der Arylrest unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, Nitro, (CrC4)-Alkyl, (CrC4)-Alkoxy und [(CrC4)-Alkoxy]carbonyl substituiert ist, oder ein für die Landwirtschaft geeignetes Kation,wherein R 1 H, (C ^ C β l-alky !, which is unsubstituted or substituted by one or more radicals from the group halogen, nitro, cyano, (C r C 4 ) alkoxy, aryl and substituted aryl, or ( C 3 -C 6 ) alkenyl, (C 3 -C 6 ) alkynyl or aryl, where the aryl radical is unsubstituted or by one or more radicals from the group halogen, nitro, (C r C 4 ) alkyl, (C r C 4 ) alkoxy and [(C r C 4 ) alkoxy] carbonyl, or a cation suitable for agriculture,
R2 und R3 unabhängig voneinander (CrC4)-Alkyl, (C1-C4)-Haloalkyl,R 2 and R 3 independently of one another (C r C 4 ) alkyl, (C 1 -C 4 ) haloalkyl,
(CrC4)-Alkoxy, (C1-C4)-Haloalkoxy, Halogen, (CrC4)-Alkylamino
Figure imgf000039_0002
(C r C 4 ) alkoxy, (C 1 -C 4 ) haloalkoxy, halogen, (C r C 4 ) alkylamino
Figure imgf000039_0002
R4 H, Halogen, (CrC4)-Alkyl, (CrC4)-Alkoxy, (CrC4)-Alkoxycarbonyl, Nitro, Cyano, oder eine Gruppe der weiter unten definierten Formel Q,R 4 H, halogen, (C r C 4 ) alkyl, (C r C 4 ) alkoxy, (C r C 4 ) alkoxycarbonyl, nitro, cyano, or a group of the formula Q defined below,
X O oder S,X O or S,
Y CH oder N,Y CH or N,
W O, S, N-OR5, N-NR5R6, R5, R6 jeder unabhängig voneinander H, (C-j-C4)-Alkyl, das unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, (C1-C4)-Alkoxy oder Aryl substituiert ist, oder (C3-C6)-Alkenyl, (C3-C6)-Alkinyl oder Aryl, das unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen, Nitro, (C1-C4)-Alkyl, (C1-C4)-Alkoxy und (C1-C4)-Haloalkoxy substituiert ist, oder gemeinsam mit dem sie verbindenden N-Atom einen heterocyclischen Rest mit 3 bis 7 Ringatomen, der neben dem N-Atom als Heteroringatom ein oder zwei weitere Heteroringatome aus der Gruppe N, O und S in den möglichen Oxidationsstufen enthalten und unsubstituiert oder durch (CrC4)-Alkyl, (C.,-C4)- Alkoxy oder Halogen substituiert sein kann, undWO, S, N-OR 5 , N-NR 5 R 6 , R 5, R 6 are each independently H, (C-j-C4) alkyl which is unsubstituted or substituted by one or more radicals from the group halogen, (C 1 -C 4) alkoxy or aryl, or ( C 3 -C 6 ) alkenyl, (C 3 -C 6 ) alkynyl or aryl which is unsubstituted or by one or more radicals from the group halogen, nitro, (C 1 -C 4 ) alkyl, (C 1 - C 4 ) -alkoxy and (C 1 -C 4 ) -haloalkoxy is substituted, or together with the N atom connecting them a heterocyclic radical with 3 to 7 ring atoms, which in addition to the N atom as a hetero ring atom comprises one or two further hetero ring atoms the group N, O and S in the possible oxidation states and may be unsubstituted or substituted by (C r C 4 ) -alkyl, (C., - C 4 ) - alkoxy or halogen, and
Q eine Gruppe der FormelQ is a group of the formula
Figure imgf000040_0001
Figure imgf000040_0001
worinwherein
R2 , R3', X' und Y' analog den Bedeutungen der entsprechenden Reste R2, R3, X bzw. Y in Formel (I) definiert sind, bedeuten.R 2 , R 3 ' , X' and Y 'are defined analogously to the meanings of the corresponding radicals R 2 , R 3 , X and Y in formula (I).
Verbindungen nach Anspruch 1 , dadurch gekennzeichnet, daßCompounds according to claim 1, characterized in that
R1 H, (C.,-C5)-Alkyl, das unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen und (C1-C4)-Alkoxy substituiert ist, (C3-C6)-Alkenyl, (C3-C6)-Alkinyl, ein Alkalimetallkation, Erdalkalimetallkation oder ein Ammoniumion, R2 und R3 unabhängig voneinander (C1-C4)-Alkyl, (C1-C4)-Haloalkyl, (C1-C4)-Alkoxy, (C1-C4)-Haloalkoxy oder Halogen,R 1 H, (C., - C5) -alkyl which is unsubstituted or substituted by one or more radicals from the group halogen and (C 1 -C 4 ) -alkoxy, (C 3 -C 6 ) -alkenyl, ( C 3 -C 6 ) alkynyl, an alkali metal cation, alkaline earth metal cation or an ammonium ion, R 2 and R 3 independently of one another (C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl, (C 1 -C 4 ) alkoxy, (C 1 -C 4 ) haloalkoxy or halogen,
R4 H, Halogen, (CrC4)-Alkyl, (CrC4)-Alkoxy, (CrC4)-Alkoxycarbonyl, Nitro, Cyano oder eine Gruppe Q,R 4 H, halogen, (C r C 4 ) alkyl, (C r C 4 ) alkoxy, (C r C 4 ) alkoxycarbonyl, nitro, cyano or a group Q,
X O oder S,X O or S,
Y CH oder N undY CH or N and
W OWHERE
bedeuten.mean.
3. Verbindungen nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß3. Compounds according to claim 1 or 2, characterized in that
R1 H, (C.|-C5.-Alkyl, das unsubstituiert oder durch einen oder mehrere Reste aus der Gruppe Halogen oder (C,-C4)-Alkoxy substituiert ist,R 1 H, (C. | -C5.-alkyl which is unsubstituted or substituted by one or more radicals from the group halogen or (C, -C 4 ) alkoxy,
R2 und R3 unabhängig voneinander (CrC4)-Alkoxy oder (CrC4)-Alkyl,R 2 and R 3 independently of one another (C r C 4 ) alkoxy or (C r C 4 ) alkyl,
R4 H, Halogen, (CrC4)-Alkyl, (CrC4)-Alkoxy, (C1-C4)-Alkoxycarbonyl, Nitro, Cyano oder eine Gruppe Q,R 4 H, halogen, (C r C 4 ) alkyl, (C r C 4 ) alkoxy, (C 1 -C 4 ) alkoxycarbonyl, nitro, cyano or a group Q,
X O undX O and
Y CHY CH
bedeuten. Verbindungen nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daßmean. Compounds according to one of claims 1 to 3, characterized in that
Methyl, Ethyl, n-Propyl oder i-Propyl,Methyl, ethyl, n-propyl or i-propyl,
OCH3,OCH 3 ,
Figure imgf000042_0001
Figure imgf000042_0001
H, Chlor, CH3, OCH3, CO2CH3, Nitro oder eine Gruppe Q undH, chlorine, CH 3 , OCH 3 , CO 2 CH 3 , nitro or a group Q and
Figure imgf000042_0002
Figure imgf000042_0002
bedeuten.mean.
Verfahren zur Herstellung von Verbindungen der Formel (I) wie sie in Anspruch 1 definiert sind, dadurch gekennzeichnet, daß man a) im Falle W = N-OR5, eine Verbindung der Formel (I), in der W = O ist, mit einem Hydroxylamin der Formel (II)Process for the preparation of compounds of the formula (I) as defined in claim 1, characterized in that a) in the case W = N-OR 5 , a compound of the formula (I) in which W = O, with a hydroxylamine of the formula (II)
NH2 - OR5 (II)NH 2 - OR 5 (II)
umsetzt, oderimplements, or
b) im Falle W = N-NR5R6, eine Verbindung der Formel (I), in der W = O ist, mit einem Hydrazin der Formel (III)b) in the case of W = N-NR 5 R 6 , a compound of the formula (I) in which W = O, with a hydrazine of the formula (III)
NH2 - NR5R6 (III) umsetzt oder c) im Falle W = O und R1 ungleich H, eine Verbindung der Formel (II), in der W = O und R1 = H sind, mit einem Chlorameisensäureester der Formel (IV)NH 2 - NR 5 R 6 (III) or c) in the case of W = O and R 1 not equal to H, a compound of the formula (II) in which W = O and R 1 = H, with a chloroformate of the formula (IV)
Cl - CO - OR1 (IV)Cl - CO - OR 1 (IV)
umsetzt oderimplements or
d) * im Falle W = 0 und R1 = H, ein Phenylglyoxylsäurederivat der Formel (V)d) * in the case of W = 0 and R 1 = H, a phenylglyoxylic acid derivative of the formula (V)
R 4 R 4
Figure imgf000043_0001
mit einem Pyrimidin- bzw. triazinderivat der Formel (VI)
Figure imgf000043_0001
with a pyrimidine or triazine derivative of the formula (VI)
Figure imgf000043_0002
Figure imgf000043_0002
worin Nuc eine Abgangsgruppe, wie z. B. Cl oder CH3-SO2- bedeutet, umsetzt, wobei in den obigen Formeln (II) bis (VI) R1 , R2, R3, R4, R5, R6, X und Y wie in Formel (I) definiert sind.wherein Nuc is a leaving group, such as. B. Cl or CH 3 -SO 2 -, reacted, wherein in the formulas (II) to (VI) above R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , X and Y as in formula (I) are defined.
6. Herbizides oder pflanzenwachstumsregulierendes Mittel, dadurch gekennzeichnet, daß es mindestens eine Verbindung der Formel (I) nach einem der Ansprüche 1 bis 4 und im Pflanzenschutz übliche Formulierungshilfsmittel enthält. 7. Verfahren zur Bekämpfung von Schadpflanzen oder zur Wachstumsregulierung von Pflanzen, dadurch gekennzeichnet, daß man ein wirksame Menge von mindestens einer Verbindung der Formel (I) nach einem der Ansprüche 1 bis 4 auf die Schadpflanzen bzw. Pflanzen, deren Pflanzensamen oder die Fläche, auf der die Pflanzen wachsen, appliziert.6. Herbicidal or plant growth regulating agent, characterized in that it contains at least one compound of the formula (I) according to one of Claims 1 to 4 and formulation auxiliaries customary in crop protection. 7. A method for controlling harmful plants or for regulating the growth of plants, characterized in that an effective amount of at least one compound of the formula (I) according to one of Claims 1 to 4 is applied to the harmful plants or plants, their plant seeds or the area, on which the plants grow.
8. Verwendung der Verbindungen der Formel (I) nach einem der Ansprüche 1 bis 4 als Herbizide oder Pflanzenwachstumsregulatoren. 8. Use of the compounds of formula (I) according to one of claims 1 to 4 as herbicides or plant growth regulators.
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EP0472113A1 (en) * 1990-08-22 1992-02-26 Kumiai Chemical Industry Co., Ltd. Pyrimidine derivatives and herbicidal compositions containing the same
GB2249092A (en) * 1990-10-25 1992-04-29 Ici Plc Oxime ether fungicides
EP0549344A1 (en) * 1991-12-27 1993-06-30 Sumitomo Chemical Company, Limited Triazine derivatives as herbicides
EP0555488A1 (en) * 1991-07-31 1993-08-18 Kumiai Chemical Industry Co., Ltd. Pyrimidine or triazine derivative and herbicide

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0468684A2 (en) * 1990-07-27 1992-01-29 Zeneca Limited Propenoic acid derivatives, process for their preparation and their use as fungicides
EP0472113A1 (en) * 1990-08-22 1992-02-26 Kumiai Chemical Industry Co., Ltd. Pyrimidine derivatives and herbicidal compositions containing the same
GB2249092A (en) * 1990-10-25 1992-04-29 Ici Plc Oxime ether fungicides
EP0555488A1 (en) * 1991-07-31 1993-08-18 Kumiai Chemical Industry Co., Ltd. Pyrimidine or triazine derivative and herbicide
EP0549344A1 (en) * 1991-12-27 1993-06-30 Sumitomo Chemical Company, Limited Triazine derivatives as herbicides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5747528A (en) * 1996-02-21 1998-05-05 Warner-Lambert Company Chroman derivatives as anti-oxidants
JP2008019241A (en) * 2007-03-01 2008-01-31 Mitsubishi Tanabe Pharma Corp Oxime derivative and method for producing the same

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AU7652794A (en) 1995-03-21

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