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WO1997000253A1 - Tetrazoles substitues, leur procede de preparation et leur utilisation comme herbicides et regulateurs de la croissance vegetale - Google Patents

Tetrazoles substitues, leur procede de preparation et leur utilisation comme herbicides et regulateurs de la croissance vegetale Download PDF

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Publication number
WO1997000253A1
WO1997000253A1 PCT/EP1996/002532 EP9602532W WO9700253A1 WO 1997000253 A1 WO1997000253 A1 WO 1997000253A1 EP 9602532 W EP9602532 W EP 9602532W WO 9700253 A1 WO9700253 A1 WO 9700253A1
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Prior art keywords
alkyl
alkoxy
substituted
unsubstituted
formula
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PCT/EP1996/002532
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German (de)
English (en)
Inventor
Hansjörg Lehmann
Philip John Dudfield
Klaus Bauer
Hermann Bieringer
Christopher Rosinger
Mark James Ford
Peter West
Original Assignee
Hoechst Schering Agrevo Gmbh
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Application filed by Hoechst Schering Agrevo Gmbh filed Critical Hoechst Schering Agrevo Gmbh
Priority to AU63024/96A priority Critical patent/AU6302496A/en
Publication of WO1997000253A1 publication Critical patent/WO1997000253A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

Definitions

  • 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 object of the invention is to provide active ingredients which, owing to the biological action, manufacturability or application properties, e.g. Storage stability in formulations, as alternatives or with advantages compared to the known active ingredients can be used.
  • the present invention relates to compounds of the formula (I) or their salts,
  • a CH or N, X is hydrogen, halogen, cyano, nitro, hydroxy, an aliphatic
  • Hydrocarbon or hydrocarbonoxy radical which is unsubstituted or substituted, or aryl or aryloxy, each of the latter 2 radicals being unsubstituted or substituted, or amino, mono- or disubstituted amino, or acyloxy,
  • R 1 is hydrogen, an aliphatic hydrocarbon radical which is unsubstituted or substituted, or acyl or the equivalent of a cation,
  • R 2 is hydrogen, an aliphatic hydrocarbon radical which is unsubstituted or substituted, or aryl or heteroaryl, each of the latter 2 radicals being unsubstituted or substituted,
  • R 3 , R 4 independently of one another are hydrogen, alkyl, alkoxy, halogen, haloalkyl, haloalkoxy, alkylamino or dialkylamino, each of the above C-containing radicals X, R 1 and R 2 including any substituents preferably having 1 to 20 C atoms, especially 1 to 10
  • C atoms preferably 1 to 6 C atoms, are preferred.
  • the compounds of the general formula (I) can exist in various isomeric forms, such as the tautomers (la) and (Ib), and in enantiomeric configurations.
  • the latter result, for example, from the ⁇ -C atom (see C in la and Ib)
  • the alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio radicals and the corresponding unsaturated and / or substituted radicals in the carbon skeleton can each be straight-chain or branched.
  • the lower carbon skeletons for example having 1 to 6 carbon atoms or, in the case of unsaturated groups, having 2 to 6 carbon atoms, are preferred for these radicals.
  • Alkyl radicals also in the composite meanings such as alkoxy, haloalkyl, etc., mean, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i -Hexyl and 1,3-dimethylbutyl, heptyls such as n-heptyl, 1-methylhexyl and 1,4-dimethylpentyl;
  • Alkenyl and alkynyl radicals have the meaning of the possible unsaturated radicals corresponding to the alkyl radicals;
  • Alkenyl means, for example, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl , 1-methyl-but-3-en-1-yl and 1-methyl-but-2
  • C ⁇ cloalkyl means a carboc ⁇ clic, saturated ring system with preferably 3-8 C atoms, e.g. Cyclopropyl, cyclopentyl or cyclohexyl.
  • Halogen means, for example, fluorine, chlorine, bromine or iodine.
  • Haloalkoxy is, for example, OCF 3 , OCHF 2 , OCH 2 F, CF 3 CF 2 O, OCH 2 CF 3 and OCH 2 CH 2 CI; The same applies to haloalkenyl and other halogen-substituted radicals.
  • a hydrocarbon radical is a straight-chain, branched or cyclic and saturated or unsaturated aliphatic or aromatic hydrocarbon radical, for example alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl or aryl;
  • Aryl here means a mono-, bi- or polycyclic aromatic system, for example phenyl, naphthyl, tetrahydronaphthyl, indenyl, indanyl, Pentalenyl, fluorenyl and the like, preferably phenyl;
  • a hydrocarbon radical is preferably alkyl, alkenyl or alkynyl having up to 12 carbon atoms or cycloalkyl having 3, 4, 5, 6 or 7 ring atoms or
  • a heterocyclic radical or ring can be saturated, unsaturated or heteroaromatic; it preferably contains one or more hetero units in the ring, ie heteroatoms or ring members, which also include substituted heteroatoms, preferably from the group N, O, S, SO, SO 2 ; it is preferably an aliphatic heterocyclyl radical with 3 to 7 ring atoms or a heteroaromatic radical with 5 or 6 ring atoms and contains 1, 2 or 3 hetero units.
  • the heterocyclic radical can be, for example, a heteroaromatic radical or ring (heteroaryl), such as, for example, a mono-, bi- or pol ⁇ cyclic aromatic system in which at least 1 ring contains one or more heteroatoms, for example pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, thienyl, Thiazolyl, oxazolyl, furyl, pyrrolyl, pyrazolyl and imidazolyl, or is a partially or completely hydrogenated radical such as oxiranyl, pyrrolidyl, piperidyl, piperazinyl, dioxolanyl, morpholinyl, tetra hydrofuryl.
  • heteroaryl such as, for example, a mono-, bi- or pol ⁇ cyclic aromatic system in which at least 1 ring contains one or more heteroatoms, for example pyridyl, pyrimidinyl, pyr
  • Possible substituents for a substituted heterocyclic radical are the substituents mentioned below, and additionally oxo.
  • the oxo group can also occur on the hetero ring atoms, which can exist in different oxidation states, for example in the case of N and S.
  • Substituted radicals such as substituted hydrocarbon radicals, for example substituted alkyl, alkenyl, alkynyl, aryl, phenyl and benzyl, or substituted heterocyclyl or heteroaryl, mean, for example, a substituted radical derived from the unsubstituted basic body, the substituents being, for example, one or more, preferably 1, 2 or 3 radicals from the group halogen, alkoxy, haloalkoxy, alkylthio, hydroxy, amino, nitro, carboxy, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl, carbamoyl, mono- and dialkylaminocarbonyl, substituted amino, such as acylamino, mono- and dialkylamino, and alkylsulfinyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl and, in
  • radicals with carbon atoms those with 1 to 4 carbon atoms, in particular 1 or 2 carbon atoms, are preferred.
  • Substituents from the group halogen for example fluorine and chlorine, (C 1 -C 4 ) alkyl, preferably methyl or ethyl, (C 1 -C 4 ) haloalkyl, preferably trifluoromethyl, (C-
  • the substituents methyl, methoxy and chlorine are particularly preferred.
  • Mono- or disubstituted amino means a chemically stable radical from the group of substituted amino radicals which are, for example, N-substituted by one or two identical or different radicals from the group alkyl, alkoxy, acyl and aryl; preferably monoalkylamino, dialkylamino, acylamino, arylamino, N-alkyl-N-arylamino and N-heterocycles; alkyl radicals having 1 to 4 carbon atoms are preferred; Aryl is preferably phenyl or substituted phenyl; the definition given below applies to acyl, preferably (C 1 -C 4 ) alkanoyl. The same applies to substituted hydroxylamino or hydrazino.
  • Optionally substituted phenyl is preferably phenyl which is unsubstituted or one or more times, preferably up to three times, by identical or different radicals from the group halogen, (C 1 -C 4 ) alkyl, (C r C 4 ) alkoxy, (C 1 -C 4 ) haloalkyl, (C 1 -C 4 ) haloalkoxy and nitro, for example o-, m- and p-tolyl, dimethylphenyl, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4- Trifluoro- and trichlorophenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.
  • An acyl residue means the residue of an organic acid, for example the residue of a carboxylic acid and residues derived therefrom, such as thiocarboxylic acid, optionally N-substituted iminocarboxylic acids or the residue of carbonic acid monoesters, optionally N-substituted carbamic acid, sulfonic acids, sulfinic acids, phosphonic acids, phosphinic acids.
  • acyl means formyl, alkylcarbonyl such as [(C r C 4 ) alkyl] carbonyl, phenylcarbonyl, alkyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl, N-alkyl-1-iminoalkyl and other residues of organic acids.
  • radicals in each case in the alkyl or phenyl part can be further substituted, for example in the alkyl part by one or more radicals from the group halogen, alkoxy, phenyl and phenoxy;
  • substituents in the phenyl part are the substituents already mentioned above generally for substituted phenyl.
  • the compounds can form salts.
  • the compounds (I) in which R 1 is hydrogen can form salts with bases in which the hydrogen from group R 1 is replaced by a cation suitable for agriculture.
  • These salts are, for example, metal salts, in particular alkali metal salts or alkaline earth metal salts, in particular sodium and potassium salts, or also ammonium salts or salts with organic amines. Salt formation with inorganic or organic acids can also take place if the compounds of the formula (I) contain basic groups, such as, for example, amino and alkylamino groups. Suitable acids for this are strong inorganic and organic acids, for example HCl, HBr, H 2 SO 4 or HNO 3 .
  • 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 formulas (I).
  • the possible stereoisomers defined by their specific spatial shape, such as enantiomers, Diastereomers, Z and E isomers are all encompassed by the formula (I) and can be obtained by conventional methods from mixtures of the stereoisomers or can also be prepared by stereoselective reactions in combination with the use of stereochemically pure starting materials.
  • R 3 , R 4 independently of one another are hydrogen, (C r C 4 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, (C r C 4 ) alkoxy, halogen, (C r C 4 ) Haloalkyl, (C 1 -C 4 ) haloalkoxy, (C r C 4 ) alkylamino or di - [(C r C 4 ) alkyl] amino.
  • X is hydrogen, halogen, cyano, hydroxy, nitro, (C 1 -C 4 ) alkyl
  • R 1 is hydrogen, (C r C 6 ) alkyl, [(C r C 6 ) alkyl] carbonyl, [(C r C 6 ) alkoxy] carbonyl, di - [(C r C 4 ) alkyl] aminocarbonyl, (C 1 -C 4 ) alkylaminocarbonyl, the latter 5 residues in the alkyl part being unsubstituted or substituted by one or more residues from the group halogen, cyano, (C-
  • R 2 (C r C 4 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, (C 3 -C 6 ) cycloalkyl, each of the latter 4 radicals being unsubstituted or by one or more radicals from the group halogen, cyano, (C 1 -C 4 ) alkoxy, (C 1 -C 4 ) alkoxy-carbonyl and, in the case of cyclic radicals, also (C 1 -C 4 ) alkyl, or phenyl or heteroaryl, wherein each of the latter 2 radicals unsubstituted or by one or more radicals from the group halogen, cyano, hydroxy, nitro, (C 1 -C 4 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl , (C r C 4 ) haloalkyl, (
  • R 3 , R 4 independently of one another are hydrogen, (C r C 4 ) alkyl, (C 1 -C 4 ) alkoxy, (C r C 4 ) haloalkoxy, (C r C 4 ) alkylamino or di - [(C r C 4 ) Mean alkyl] amino.
  • X is hydrogen, halogen, hydroxy, cyano, (C r C 4 ) alkyl, (C 1 -C 4 ) haloalkyl, methoxy- (C r C 4 ) alkyl, ethoxy- (C r C 4 ) alkyl, (C r C 4 ) alkoxy, methoxy- (C r C 4 ) alkoxy, ethoxy- (C r C 4 ) alkoxy, (C r C 4 ) alkylthio, (C 1 -C 4 ) alkylcarbonyloxy or (C 1 -C 4 ) alkoxycarbonyloxy, or a group of the formula NR'R "in which R 'and R" independently of one another are H, (C r C 4 ) alkyl, benzyl, phenyl, (C r C 4 ) alkanoyl, (C r C 4 ) alkoxycarbonyl, (C 1 -C
  • R 1 is hydrogen, (C r C 4 ) alkyl, [(C r C 4 ) alkyl] carbonyl, [(C r C 4 ) alkoxyjcarbonyl, di - [(C 1 -C 4 ) alkyl] aminocarbonyl, (C 1 -C 4 ) alkylaminocarbonyl, each of the last 5 radicals in the alkyl part being unsubstituted or substituted by one or more radicals from the group halogen, (C 1 -C 4 ) alkoxy and (C 1 -C 4 ) alkylthio, or Phenylcarbonyl which is unsubstituted in the phenyl part or by one or more radicals from the group halogen, (C r C 4 ) alkyl, (C r C 4 ) haloalkyl, (C r C 4 ) alkoxy, (C r C 4 ) alkylthio, ( C r C 4 )
  • R 2 (C r C 4 ) alkyl, allyl, propargyl, (C 3 -C 6 ) cycloalkyl, each of the latter 4 radicals unsubstituted or by one or more radicals from the group halogen, cyano and (C 1 -C 4 ) Alkoxy and, in the case of cyclic radicals, also (C 1 -C 4 ) alkyl, or phenyl or heteroaryl, where each of the latter 2 radicals is unsubstituted or by one or more radicals from the group halogen, cyano, nitro, (C r C 4 ) alkyl, (C r C 4 ) haloalkyl, (C r C 4 ) alkoxy, (C r C 4 ) haloalkoxy, amino, (C r C 2 ) alkylamino and di - [(C r C 2 ) alkyl] -amino is substituted.
  • Preferred compounds of the formula (I) or their salts are those in which
  • X is hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, methyl,
  • R 1 is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, phenoxycarbonyl, acetyl, propionyl, Propylcarbonyl, isopropylcarbonyl, where each of the latter 18 radicals is unsubstituted or substituted by radicals from the group consisting of fluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy and cyano, or dimethylaminocarbonyl, diethylaminocarbonyl or M + .
  • R 2 isopropyl, tert-butyl, cyclopropyl, cyclopentyl or cyclohexyl, each of these radicals being unsubstituted or substituted by one or more radicals from the group consisting of fluorine, chlorine, bromine, cyano, methoxy, ethoxy and propoxy, or phenyl or heteroaryl the series pyridyl, pyrimidinyl, pyrrolyl, imidazolyl, pyrazolyl, quinolinyl, isoquinolinyl, indolyl, furyl, thienyl, thiazolyl, oxazolyl, isoxazolyl, benzimidazolyl, benzothiophenyl, benzothiazolyl, pyranyl and benzofuranyl, where phenyl and heteroaryl are unsubstituted or substituted by one or more radicals from the group consisting of fluorine, chlorine, bro
  • X is hydrogen, fluorine, chlorine, bromine, hydroxy, methoxy or acetoxy
  • R 1 is hydrogen, methyl or acetyl or M + , where M + is Na + or K + .
  • Another object of the present invention is the process for the preparation of compounds of general formula (I) or their salts, characterized in that
  • the reaction of compounds of formula (II) and (III) according to variant a) is usually carried out in the presence of an organic or inorganic base.
  • Suitable bases for this reaction are, for example, organic bases such as sodium amide, lithium diisopropylamide (LDA), butyllithium or lithium hexamethyldisilazane.
  • suitable inorganic bases are alkali metal hydroxides, alkali metal hydrides, alkali metal alcoholates, alkaline earth metal hydroxides and alkaline earth metal hydrides.
  • the compound of the formula (II) can, for example, be used in equimolar amounts or in a slight excess in relation to the compound of the formula (IM).
  • a non-aqueous, aprotic, inert solvent in a temperature range between -100 and 50 ° C., preferably between -70 and 20 ° C.
  • Aliphatic and aromatic hydrocarbons such as n-pentane, n-hexane, cyclohexane, n-pentane, benzene, toluene or xylene, or ethers, such as diethyl ether, dimethoxyethane, diglyme or tetrahydrofuran, can be used as solvents, taking into account the respective solubilities.
  • a halogenating agent preferably N-haloimides such as N-chlorosuccinimide or N-bromosuccinimide
  • catalysts for example, radical formers such as azobis-isobutyronitrile (AIBN) and peroxides, for example dibenzoyl peroxide, and / or bases such as, for example, sodium amide, lithium diisopropylamide (LDA), butyllithium or lithium hexamethyldisilazane.
  • AIBN azobis-isobutyronitrile
  • peroxides for example dibenzoyl peroxide
  • bases such as, for example, sodium amide, lithium diisopropylamide (LDA), butyllithium or lithium hexamethyldisilazane.
  • Suitable solvents are usually halogenated hydrocarbons such as methylene chloride, chloroform and CCI 4 , ethers such as diethyl ether, tetrahydrofuran (THF) and dimethoxyethane or aprotic polar solvents such as dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide (DMSO) and acetonitrile.
  • halogenated hydrocarbons such as methylene chloride, chloroform and CCI 4
  • ethers such as diethyl ether, tetrahydrofuran (THF) and dimethoxyethane
  • aprotic polar solvents such as dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide (DMSO) and acetonitrile.
  • inert solvents mean in each case solvents which are inert under the respective reaction conditions but do not have to be inert under any reaction conditions.
  • the compounds of the formula (I) according to the invention and their salts, hereinafter referred to collectively as (compounds) of the 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 applied by pre-sowing, pre-emergence or post-emergence.
  • Some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned in detail, which can be controlled by the compounds according to the invention without the name being intended to restrict them to certain species.
  • 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 monocotyledonous and dicotyledonous weeds, crop plants of economically important crops such as, for example, wheat, barley, rye, rice, maize, sugar beet, cotton and soybeans are only insignificantly 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 substances according to the invention have excellent growth-regulating properties in crop plants. They intervene regulating the plant's own metabolism and can thus influence plant constituents in a targeted manner and to facilitate harvesting, e.g. 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 according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations.
  • the invention therefore also relates to herbicidal and plant growth-regulating compositions which comprise compounds of the formula (I).
  • the compounds of formula (I) can be formulated in different ways, depending on which biological and / or chemical-physical parameters are specified. Possible formulation options are, for example: 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 (SO, dispersions based on oil or water, oil-miscible solutions, capsule suspensions (CS), dusts (DP), mordants, 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
  • combinations with other pesticidally active substances such as insecticides, acaricides, herbicides, fungicides, and with safeners, fertilizers and / or growth regulators can also be prepared, for example in the form of a ready-to-use formulation or as a tank mix.
  • Spray powders are preparations which are uniformly dispersible in water and, in addition to the active ingredient, in addition to a diluent or inert substance, are also surfactants of an ionic and / or nonionic type (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonatesulfonates, alkylbenzene sulfonates, alkylbenzene sulfonates, alkylbenzene sulfonates, alkyl benzene sulfonates, alkyl benzene sulfonates, alkyl benzene sulfonates, alkyl benzene sulfonates, alkyl benzene sulfonates, alkyl benzene
  • Emulsifiable concentrates are made by dissolving the active ingredient in an organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of the organic solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers).
  • organic solvent e.g. Butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons or mixtures of the 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. Sorbitan fatty acid esters or polyoxethylene sorbitan esters such as e.g. Polyoxyethylene sorbitan fatty acid esters.
  • Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • finely divided solid substances e.g. 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 those described above for the others Formulation types already listed can be produced.
  • Emulsions e.g. Oil-in-water emulsions (EW) can be used, for example, with stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants, such as those e.g. already listed above for the other formulation types.
  • EW Oil-in-water emulsions
  • 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. 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. Polyvinyl alcohol, sodium polyacrylic acid or mineral oils
  • Water-dispersible granules are generally produced using the customary methods, 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).
  • the active ingredient concentration in wettable powders is, for example, about 10 to 90% by weight, the remainder to 100% by weight consists of customary 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% by weight of active ingredient, preferably mostly 5 to 20% by weight of active ingredient
  • sprayable solutions contain 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 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, for example, in Weed Research 26, 441 -445 (1986) or "The Pesticide Manual", 10th edition, The British Crop Protection Council and the Royal Soc. of Chemistry, 1994, England, and the literature cited therein.
  • herbicides known from the literature which can be combined with the compounds of the formula (I) are the following active ingredients (note: the compounds are either with the "common name” according to the International Organization for Standardization (ISO) or with the chemical name , if necessary together with a usual 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; azimsulfurone (DPX-A8947); aziprotryn; barban; BAS 516 H, ie 5-fluor
  • the formulations present in the commercial form are optionally diluted in the customary manner, for example for wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules using water.
  • Preparations in the form of dust, ground granules or scattering granules and sprayable solutions are usually no longer diluted with other inert substances before use.
  • the required application rate of the compounds of formula (I) varies with the external conditions, such as temperature, humidity, the type of herbicide used, and others. It can vary within wide limits, for example between 0.1 and 10.0 kg / ha or more of active substance, but is preferably between 0.5 and 5 kg / ha.
  • Melting point melting point in ° C or other information on
  • n a number from 1 to 3
  • 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), 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyl taurine as a wetting and dispersing agent and grind 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 ground in a friction ball mill 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 75 parts by weight of a compound of formula (I),
  • Seeds or rhizome pieces of monocotyledonous and dicotyledonous weed plants are 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 are 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 compounds according to the invention have good herbicidal pre-emergence activity against a broad spectrum of grasses and weeds.
  • Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds are placed in sandy loam soil in plastic pots, covered with soil and grown in the greenhouse under good growth conditions. Three weeks after sowing, the test plants are treated at the three-leaf stage.
  • the compounds according to the invention formulated as wettable powder or as emulsion concentrates are applied to the green in various dosages with a water application rate of the equivalent of 600 to 800 l / ha Plant parts sprayed and after approx. 3 to 4 weeks of standing of the test plants in the greenhouse under optimal growth conditions, the effect of the preparations was assessed visually 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.

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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)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des composés qui répondent à la formule (I), leurs sels, leur procédé de préparation et leur utilisation comme herbicides et régulateurs de la croissance végétale. Dans la formule, A désigne CH ou N; X désigne hydrogène, halogène, cyano, nitro, hydroxy, un reste hydrocarbure ou oxyhydrocarbure aliphatique substitué ou non, aryle ou aryloxy substitué ou non, amino, amino monosubstitué ou disubstitué ou acyloxy; R1 désigne hydrogène, un reste hydrocarbure aliphatique substitué ou non, acyle ou l'équivalent d'un cation; R2 désigne hydrogène, un reste aliphatique hydrocarbure substitué ou non, aryle ou hétéroaryle substitué ou non; et R3, R4 désignent indépendamment hydrogène, alkyle, alcoxy, halogène, haloalkyle, haloalcoxy, alkylamino ou dialkylamino.
PCT/EP1996/002532 1995-06-14 1996-06-11 Tetrazoles substitues, leur procede de preparation et leur utilisation comme herbicides et regulateurs de la croissance vegetale WO1997000253A1 (fr)

Priority Applications (1)

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AU63024/96A AU6302496A (en) 1995-06-14 1996-06-11 Substituted tetrazoles, process for preparing the same and their use as herbicides and plant growth regulators

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19521653A DE19521653A1 (de) 1995-06-14 1995-06-14 Substituierte Tetrazole, Verfahren zu ihrer Herstellung und ihre Verwendung als Herbizide und Pflanzenwachstumsregulatoren
DE19521653.9 1995-06-14

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WO1997000253A1 true WO1997000253A1 (fr) 1997-01-03

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DE (1) DE19521653A1 (fr)
WO (1) WO1997000253A1 (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009519233A (ja) * 2005-11-23 2009-05-14 ブリストル−マイヤーズ スクイブ カンパニー ヘテロ環式ｃｅｔｐ阻害剤
CN115894396A (zh) * 2022-11-11 2023-04-04 安徽农业大学 一种手性1,5-二取代四氮唑化合物及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1765408B1 (fr) 2004-07-08 2015-12-09 Novo Nordisk A/S Conjugues de polypeptides a effet prolonge comprenant un motif tetrazolique

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0410590A1 (fr) * 1989-07-27 1991-01-30 AgrEvo UK Limited Herbicides dérivés de pyrimidines
EP0461079A2 (fr) * 1990-06-07 1991-12-11 Sandoz Ltd. Phtalides substitués et phtalides hétérocycliques
WO1992001677A1 (fr) * 1990-07-19 1992-02-06 Schering Agrochemicals Limited Herbicides de triazinyle et pyrimidinyle
WO1992016511A1 (fr) * 1991-03-13 1992-10-01 Schering Agrochemicals Limited Herbicides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0410590A1 (fr) * 1989-07-27 1991-01-30 AgrEvo UK Limited Herbicides dérivés de pyrimidines
EP0461079A2 (fr) * 1990-06-07 1991-12-11 Sandoz Ltd. Phtalides substitués et phtalides hétérocycliques
WO1992001677A1 (fr) * 1990-07-19 1992-02-06 Schering Agrochemicals Limited Herbicides de triazinyle et pyrimidinyle
WO1992016511A1 (fr) * 1991-03-13 1992-10-01 Schering Agrochemicals Limited Herbicides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009519233A (ja) * 2005-11-23 2009-05-14 ブリストル−マイヤーズ スクイブ カンパニー ヘテロ環式ｃｅｔｐ阻害剤
CN115894396A (zh) * 2022-11-11 2023-04-04 安徽农业大学 一种手性1,5-二取代四氮唑化合物及其制备方法

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ZA965013B (en) 1996-12-17
DE19521653A1 (de) 1996-12-19
AU6302496A (en) 1997-01-15

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