WO1993016062A1 - Melanges d'ethers de cyclohexenone-oximes optiquement actifs, leur procede de preparation et produits intermediaires pour leur preparation, ainsi que leur utilisation comme herbicides - Google Patents

Melanges d'ethers de cyclohexenone-oximes optiquement actifs, leur procede de preparation et produits intermediaires pour leur preparation, ainsi que leur utilisation comme herbicides Download PDF

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WO1993016062A1
WO1993016062A1 PCT/EP1993/000212 EP9300212W WO9316062A1 WO 1993016062 A1 WO1993016062 A1 WO 1993016062A1 EP 9300212 W EP9300212 W EP 9300212W WO 9316062 A1 WO9316062 A1 WO 9316062A1
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alkyl
optically active
halogen
group
alkoxy
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PCT/EP1993/000212
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German (de)
English (en)
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Ulf Misslitz
Norbert Meyer
Juergen Kast
Harald Rang
Hardo Siegel
Helmut Walter
Karl-Otto Westphalen
Matthias Gerber
Uwe Kardorff
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Basf Aktiengesellschaft
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Priority to BR9305882A priority Critical patent/BR9305882A/pt
Priority to EP93917358A priority patent/EP0625974A1/fr
Priority to JP5513724A priority patent/JPH07505866A/ja
Publication of WO1993016062A1 publication Critical patent/WO1993016062A1/fr
Priority to KR1019940702774A priority patent/KR950700271A/ko

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/02—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom not condensed with other 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
    • C07C251/54—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by singly-bound oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/47—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D309/06—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the present invention relates to new mixtures of optically active cyclohexenone oxime ethers with R and S configuration in the oxime ether part of the general formula I.
  • R 1 is a Ci-C ⁇ alkyl group
  • n 0 to 3 or 1 to 5 if all X is halogen; 2 a C ⁇ -C 4 alkoxy-C ⁇ -C 6 - * _-H * ⁇ * ----- ⁇ - * -4 ⁇ ⁇ kyl distr;
  • a C 3 -C -cycloalkyl group or a C 5 -C -cycloalkenyl group where these groups can, if desired, carry one to three substituents, selected from a group consisting of C 1 -C 4 alkyl, C 1 -C 4 alkox , Ci-C ⁇ alkylthio, -C-C 4 haloalkyl, hydroxyl and halogen;
  • a 5-membered saturated heterocycle which contains one or two oxygen and / or sulfur atoms as heteroatoms and which, if desired, can also carry one to three substituents, selected from a group consisting of C 1 -C 4 -alkyl, C ⁇ - C 4 -alkoxy, C 4 alkylthio and C ⁇ -C4-haloalkyl; a 6- or 7-membered saturated or mono- or di-unsaturated heterocycle which contains one or two oxygen or sulfur atoms or one oxygen and one sulfur atom as heteroatoms,
  • the heterocycle can also carry one to three substituents selected from a group consisting of hydroxyl, halogen, C ⁇ -C 4 alkyl, C ⁇ -C 4 alkoxy, C ⁇ -C 4 ⁇ alkylthio and C ⁇ -C 4 - Haloalkyl;
  • heteroaromatic if desired, can carry one to three substituents selected from a group be ⁇ standing from halogen, cyano, C alkyl, C] -C4 ⁇ alkoxy, C ⁇ -C 4 alkylthio, C ⁇ -C 4 - Haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkenyloxy and C ⁇ -C 4 alkoxy-C ⁇ -C 4 alkyl;
  • a phenyl or pyridyl group these aromatics optionally being able to carry one to three substituents selected from a group consisting of halogen, nitro, cyano, C 1 -C 4 -alkyl, C 4 -C 4 -alkoxy, C 1 -C 3 -alkylthio,
  • R a is hydrogen, C ⁇ -C 4 alkyl, C 3 -C 6 alkenyl or C3-Ce alkynyl and
  • R b is hydrogen, -CC 4 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C ⁇ -Cg-acyl or benzoyl, which, if desired, can in turn carry one to three residues, selected from a group consisting of nitro, cyano, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio and C ⁇ -C 4 haloalkyl;
  • the invention relates to a process for the preparation of these compounds, their use as herbicides and herbicidal compositions which contain these compounds as active substances.
  • the invention further relates to new mixtures of optically active hydroxylamines with R and S configuration of the formula III
  • X for nitro, cyano, halogen, C ⁇ -C 4 alkyl, C ⁇ -C 4 halogen alkyl "and n for 0 to 3 or 1 to 5 in the event that all X are halogen,
  • R c , R d and R e stand inter alia for the following meanings:
  • R e substituted 5- to 7-membered heterocycle
  • R e substituted 5- to 7-membered heterocycle
  • the invention was therefore based on new mixtures of cyclohexenone oxime ethers with improved selectivity against grass weeds in grassy crops such as rice and maize.
  • mixtures of optically active cyclohexenone oxime ethers I can be obtained in various ways, preferably in a manner known per se from already known cyclohexenones of the formula II (DE-A 38 38 309, EP-A 243 313,
  • EP-A 456 112 and the corresponding mixtures of optically active hydroxylamines of the formula III (cf. EP-A 169 521):
  • a suitable salt of the hydroxylamines III, in particular their hydrochloride, is preferably used and the reaction is carried out in the heterogeneous phase in an inert solvent, for example in dimethyl sulfoxide, in an alcohol such as methanol, ethanol and isopropanol, in an aromatic hydrocarbon such as benzene and Toluene, in a chlorinated hydrocarbon such as chloroform and 1,2-dichloroethane, in an aliphatic hydrocarbon such as hexane and cyclohexane, in an ester such as ethyl acetate or in an ether such as diethyl ether, dioxane and tetrahydrofuran.
  • an inert solvent for example in dimethyl sulfoxide, in an alcohol such as methanol, ethanol and isopropanol, in an aromatic hydrocarbon such as benzene and Toluene, in a chlorinated hydrocarbon such as chloroform and 1,2-
  • the reaction is carried out in the presence of a base, a base amount of about 0.5 to 2 mol equivalents, based on the ammonium compound, normally being sufficient.
  • Suitable bases are, for example, carbonates, bicarbonates, acetates, alcoholates or oxides of alkali or alkaline earth metals, in particular sodium hydroxide, potassium hydroxide, magnesium oxide or calcium oxide.
  • Organic bases such as pyridine and tert.
  • Amines such as triethylamine are suitable.
  • the reaction is preferably carried out in methanol using sodium hydrogen carbonate as the base.
  • a variant of the method consists in the reaction without base with the free hydroxylamine bases III, z. B. in the form of an aqueous solution; depending on the solvent used for the compound II, a one- or two-phase reaction mixture is obtained.
  • Suitable solvents for this variant are, for example, alcohols such as methanol, ethanol, isopropanol and cyclohexanol, aliphatic and aromatic, optionally chlorinated hydrocarbons such as hexane, cyclohexane,
  • cyclohexenone II and the mixture of optically active hydroxylamines III or their salts are expediently used in an approximately stoichiometric ratio, but in some cases an excess of one or the other component, up to about 10 mol%, can also be advantageous .
  • the reaction temperature is generally between 0 ° C and the boiling point of the reaction mixture, preferably between 20 and 80 ° C.
  • the reaction is complete after a few hours.
  • the product can be prepared in the usual way, e.g. B. by concentrating the mixture, distributing the residue in methylene chloride / water and distilling off the solvent under reduced pressure.
  • the optically active cyclohexenone oxime ether I can form salts of alkali or alkaline earth metal compounds and enol esters.
  • Alkali metal salts of the compounds I can be obtained by treating the 3-hydroxycyclohexenone compounds with sodium or potassium hydroxide or alcoholate in aqueous solution or in an organic solvent such as methanol, ethanol, acetone and toluene.
  • metal salts such as manganese, copper, zinc, iron, calcium, magnesium and barium salts can be prepared from the sodium salts in a conventional manner, as can ammonium and phosphonium salts using ammonia,
  • esters of the compounds I are also available in the usual way (see e.g. Organikum, VEB Deutscher erlag dermaschineen, 17th edition, Berlin 1988, pp. 405-408).
  • the new mixtures of optically active hydroxylamines III can be prepared from known precursors in a number of known process steps:
  • VII L a leaving group, e.g. B. halogen such as chlorine, bromine and
  • optically active alkylating agent V ⁇ Tetrahedron Lett is preferably coupled. 22., 5493 (1988); J. Org. Chem. 51, 3587 (1987); EP-A 172 719; EP-A 230 379; No. 4,841,079 ⁇ , but if desired also the optically active carbinol IV ⁇ Chem. Pharm. Bull. 3_3_, 1955 (1985) ⁇ according to the Mitsunobu variant ⁇ Synthesis 1, 1981; J. Med. Chem. H, 187 (1990) ⁇ , with a cyclic hydroxyimide VI and cleaves the resulting protected hydroxylamine derivative VII to free optically active hydroxylamine III, e.g. B. with 2-aminoethanol.
  • D is z.
  • the reaction of the optically active alkylating agent V with the hydroxyimides VI is advantageously carried out in the presence of a base.
  • a base In principle, all bases which are capable of deprotonating the hydroxyimides VI without attacking the imide system are suitable. These are especially the so-called non-nucleophilic bases.
  • Examples include mineral bases such as alkali metal and alkaline earth metal carbonates, alkali metal and alkaline earth metal hydrogen carbonates, organic bases such as aliphatic, cycloaliphatic and aromatic tertiary amines. Mixtures of these bases can also be used.
  • the base is generally added in equivalent amounts up to an excess of 5 equivalents, based on the hydroxyimide. A higher excess is possible, but usually does not bring any additional advantages. It is also possible to use a small amount of base. However, a base amount of 1 to 3, in particular 1 to 2 equivalents, based on the hydroxyimide VI, is preferably used.
  • nucleophilic bases e.g. B. alkali metal and alkaline earth metal hydroxides, especially sodium and potassium hydroxide, is also possible.
  • base in equivalent amounts with respect to the hydroxyimide VI in order to prevent nucleophilic attack of the hydroxyl ions on the carbonyl function of the imide grouping.
  • optically active alkylating agent V is expediently reacted with the hydroxyimides VI in a solvent which is reacted under the reaction conditions behaves inertly.
  • Advantageous solvents are e.g. B. polar, aprotic solvents such as dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, sulfolane and cyclic ureas.
  • the amount of solvent is generally not critical.
  • the reaction of the optically active alkylating agents V with the hydroxyimides VI can also be carried out using phase transfer catalysis.
  • two-phase solvents preferably chlorinated hydrocarbons, are used with water.
  • Suitable phase transfer catalysts are the quaternary ammonium and phosphonium salts, polyethylene glycols, polyethylene glycol ethers and crown ethers, as are used, for example, for such purposes.
  • Phase Transfer Catalysis pp. 37-45 and pp. 86-93, Verlag Chemie, Weinheim 1980.
  • phase transfer catalysts are expediently used in amounts of 1 to 10% by volume, preferably in amounts of 3 to 5% by volume, based on the volume of the reaction mixture.
  • the reaction of the optically active alkylating agents V with the hydroxyimides VI generally takes place in the temperature range between 0 and 140 ° C., preferably between 2 and 100 ° C., in particular between 40 and 80 ° C.
  • the procedure is advantageously such that the hydroxyimide VI is initially introduced together with the base in the solvent and the alkylating agent V is metered into this solution. It may prove to be advantageous if the hydroxyimide is added at a lower temperature, for example at 0 to 50 ° C., and the reaction mixture is heated to the actual reaction temperature only after this addition.
  • the hydroxylamine derivatives VII can be temporarily stored or immediately converted into the optically active hydroxylamines III with a free amino group.
  • This conversion can be carried out according to methods known per se, as described, for example, in DE-A 36 15 973 and the documents cited therein.
  • the method according to DE-A 36 15 973 is preferably used after the optically active hydroxylamines III have been released by means of ethanolamine. It is also possible to release the optically active hydroxylamines III with the aid of other bases such as aqueous mineral bases, with amines, hydrazines, hydroxylamines or with aqueous acids.
  • optically active hydroxylamines III can be isolated from the reaction mixtures obtained by these processes by means of customary workup methods, for example by extraction or by crystallization. To increase the tendency of these hydroxylamines III to crystallize, it can often be beneficial to convert them into their salts with mineral acid or organic acids. For this purpose, dilute solutions of these acids are generally mixed with
  • Hydroxylamine derivatives implemented, expediently in equivalent amounts.
  • the hydroxylammonium salts obtained can, like the optically active hydroxylamines III (with free amino group), be further processed directly to give the optically active cyclohexenone oxime ethers of the formula I or, if desired, can also be stored.
  • the optical purity of the intermediates III and the cyclohexenone oxime ether I depends on the optical purity of the carbinols IV or alkylating agent V used.
  • R-configured carbinols IV or R-configured alkylating agents V are used, with the highest possible optical purity, so that in the preparation of the optically active hydroxylamines III and the optically active cyclohexenone oxime ethers I, isomer mixtures are obtained whose Proportion of isomers with R con figuration on the methyl-substituted C atom (in the oxime ether part) is at least 75 mol%, in particular 90 to 100 mol%.
  • optically active cyclohexenone oxime ethers I can be obtained in the preparation as isomer mixtures, both E / Z isomer mixtures (position of the oxime ether part relative to R 1 ) and diastereoisomer mixtures being possible.
  • the isomer mixtures can be prepared by the customary methods, for. B. by chromatography or by crystallization.
  • optically active cyclohexenone oxime ethers I can be written in several tautomeric forms, all of which are encompassed by the invention.
  • alkyl, alkoxy, alkylthio, haloalkyl, alkenyl, alkenyloxy, alkynyl and alkynyloxy parts can be straight-chain or branched.
  • the haloalkyl parts can carry identical or different halogen atoms.
  • Halogen fluorine, chlorine, bromine and iodine
  • C ⁇ -C-alkyl methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;
  • C ⁇ -C4-alkoxy methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1, 1-dimethylethoxy;
  • - C ⁇ -C 4 alkylthio methylthio, ethylthio, n-propylthio, 1-methylethylthio, n-butylthio, 1-methylpropylthio, 2-methylpropylthio and 1, 1-dimethylethylthio;
  • C ⁇ -C 4 haloalkyl fluoromethyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl, trichloromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-di-fluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2 , 2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;
  • C 2 -C 6 alkenyl ethenyl and C 3 -C 6 alkenyl such as 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1- propenyl, l-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pen , tenyl, 3-pentenyl, 4-pentenyl, 1-methyl -l-butenyl, 2-methyl-1-butenyl, 3-methyl-l-butenyl, l-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, l-methyl -3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-l-propenyl, 1,2-di -but
  • C 2 -Ce alkenyloxy ethenyloxy and Cs-Cs alkenyloxy such as 2-propenyloxy, 2-butenyloxy, 3-butenyloxy, l-methyl-2-propenyloxy, 2-methyl-2-propenyloxy, 2-pentenyloxy, 3 -Pentenyloxy, 4-pentenyloxy, l-methyl-2-butenyloxy, 2-methyl-2-butenyloxy, 3-methyl-2-butenyloxy, l-methyl-3-butenyloxy, 2 ⁇ methyl-3-butenyloxy, 3 -Methyl-3-butenyloxy, 1, l-dimethyl-2-propenyloxy, 1,2-dimethyl-2-propenyloxy, l-ethyl-2-propenyloxy, 2-hexenyloxy, 3-hexenyloxy, 4-hexenyloxy , 5-hexenyloxy, 1-methyl-2-pentenylox
  • cyclohexenones of the formula I are preferred, in which the variables have the following meaning:
  • R 1 C ⁇ -C 6 alkyl such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, preferably ethyl and propyl;
  • Halogen preferably fluorine, chlorine and bromine
  • haloalkyl preferably difluoromethyl, trifluoromethyl, 2,2, 2-trifluoroethyl and pentafluoroethyl; halogen is particularly preferred; n is 0 to 3 or 1 to 5 if all X is halogen; 0 to 3 is particularly preferred;
  • R2 - a C ⁇ -C 6 alkyl group such as methyl, ethyl, n-propyl,
  • a C 3 -C cycloalkyl group or a C 5 -C cycloalkenyl group such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl and
  • a 5-membered saturated heterocycle such as tetrahydrofuranyl, tetrahydrothienyl, dioxolanyl, dithiolanyl and oxathiolanyl, in particular tetrahydrofuranyl, tetrahydrothienyl and dioxolanyl, where these rings can be unsubstituted or can carry one to three substituents selected from one group selected from a group selected from C ⁇ -C 4 alkyl, C ⁇ -C 4 alkoxy, C ⁇ -C 4 alkylthio and C ⁇ -C 4 haloalkyl; a 5-membered heteroaromatic such as pyrrolyl, pyrazolyi, imidazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, furanyl and thienyl, in particular isoxazolyl and furanyl, where the 5-membered heteroaromatic may be un
  • C 2 -C 6 alkenyl such as enthenyl and C 3 -C 5 alkenyl, preferably 1-methylethen-l-yl,
  • C 2 ⁇ C 6 alkenyloxy such as ethenyloxy and C 3 -C 5 alkenyloxy, especially 1-methylethen-l-yloxy
  • a) can be saturated, for example tetrahydropyran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl and dioxepan-5-yl
  • b) can be mono- or di-unsaturated, for example dihydropyran 3-yl, dihydropyran-4-yl, dihydrothiopyran-3-yl and dihydrothiopyran-4-yl, it being possible for the heterocycles to be unsubstituted or to carry one to three substituents selected from a group consisting of hydroxyl, halogen, C-.
  • tetrahydropyran-3-yl, tetrahydropyran-4-yl and tetrahydrothiopyran-3-yl are very particularly preferred;
  • a phenyi or pyridyl group both of which can be unsubstituted or can carry one to three substituents, selected from a group consisting of C ⁇ -C 4 alkyl, C ⁇ -C 4 alkoxy, C ⁇ -C 4 alkylthio, C ⁇ -C 4 haloalkyl, C 3 -C 6 alkenyloxy, preferably
  • 2-propenyloxy and 2-butenyloxy C 3 -Cg-alkynyloxy such as 2-propynyloxy, 2-butynyloxy, 3-butynyloxy, l-methyl-2-propynyloxy, 2-pentynyloxy, 3-pentynyloxy, 4-pentynyloxy, 1-methyl-3-butynyloxy, 2-methyl-3-butynyloxy, 1-methyl-2-butynyloxy, 1, 1-dimethyl-2-propynyloxy, 1-ethyl-2-propynyloxy, 2-hexynyloxy, 3-hexynyloxy, 4-hexynyloxy, 5-hexynyloxy, l-methyl-2-pentynyloxy, l-methyl-3-pentynyloxy, l-methyl-4-pentynyloxy, 2-methyl-3-pentynyloxy, 2-methyl-4-pentynyloxy
  • C ⁇ -C 4 alkyl preferably methyl and ethyl
  • C 3 -C 6 alkenyl preferably 2-propenyl and 2-butenyl
  • C 3 -C 6 alkynyl preferably 2-propynyl and 2-butynyl
  • R b represents hydrogen, C ⁇ -C 4 alkyl, preferably methyl and ethyl,
  • C 3 -C 6 alkenyl preferably 2-propenyl and 2-butenyl
  • C 3 -C 6 alkynyl preferably 2-propynyl and 2-butynyl
  • C ⁇ -C 6 ⁇ acyl such as acetyl, propionyl, butyryl, 2nd -Methyl-propionyl, n-pentanoyl, 2-methylbutyryl, 3-methylbutyryl, 2,2-dimethylpropionyl, n-hexanoyl, 2-methylpentanoyl, 3-methylpentanoyl, 4-methylpentanoyl, 2,2-dimethylbutyryl, 2 , 3-dimethylbutyryl, 3, 3-dimethylbutyryl and 2-et ylbutyryl, preferably acetyl and propionyl,
  • Suitable salts of the compounds of the formula I are agriculturally useful salts, for example alkali metal salts, in particular the sodium or potassium salt, alkaline earth metal salts in particular the calcium, magnesium or barium salt, manganese, copper, zinc or iron salt and ammonium salt , Phosphonium, sulfonium or sulfoxonium salts, for example ammonium salts, tetraalkylammonium salts, benzyltrialkylammonium salts, trialkylsulfonium salts or trialkylsulfoxonium salts.
  • alkali metal salts in particular the sodium or potassium salt
  • alkaline earth metal salts in particular the calcium, magnesium or barium salt, manganese, copper, zinc or iron salt and ammonium salt
  • Phosphonium, sulfonium or sulfoxonium salts for example ammonium salts, tetraalkylammonium salts, benzyltrialkylammonium salts
  • esters of C ⁇ -C ⁇ o-carboxylic acids include, in particular, C ⁇ -C 6 -alkyl carboxylic acids such as methyl carboxylic acid (acetic acid), ethyl carboxylic acid (propionic acid), propyl carboxylic acid (butyric acid), 1-methylethyl carboxylic acid (isobutyric acid), butyl carbyl carbonate, 1-methyl propyl carbonate - Acid, 2-methylpropylcarboxylic acid, 1, 1-dimethylethylcarboxylic acid, pentylcarboxylic acid, 1-methylbutylcarboxylic acid, 2-methylbutylcarboxylic acid, 3-methylbutylcarbonic acid, 1, 1-dimethylpropylcarboxylic acid, 1,2-dimethylpropylcarboxylic acid, 2.2 -Dimethylpropylcarboxylic acid, 1-ethylpropylcarboxylic acid, benzoic acid as well as halogen substituted benzoic acids
  • Table 1 lists further optically active hydroxylamines III which were prepared or can be prepared in the same way.
  • Tables 2 to 8 contain optically active cyclohexenone oxime ether I according to the invention.
  • cyclohexenone oxime ethers I are also suitable for the selective control of undesired grasses in Gramineae crops.
  • optically active cyclohexenone oxime ether I or the herbicidal compositions comprising it can be, for example, in the form of directly sprayable solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents or Granules by spraying, atomizing, dusting, scattering or pouring can be used.
  • the application forms depend on the purposes; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.
  • the compounds I are generally suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions.
  • Mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g.
  • strongly polar solvents such as N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or water.
  • Aqueous use forms can be prepared from emulsion concentrates, dispersions, pastes, wettable powders or water-dispersible granules by adding water.
  • the substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. It can but also from active substance, wetting, adhesive, dispersing or emulsifying agents and possibly solvents or existing concentrates which are suitable for dilution with water.
  • alkali, alkaline earth, ammonium salts of aromatic sulfonic acids e.g. Lignin, phenol, naphthalene and d-butylnaphthalenesulfonic acid, as well as of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols, as well as fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl or nonylphenol, alkylphenol, tributylpheny
  • Powders, materials for spreading and dusting can be produced by mixing or grinding the active substances together with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.
  • Solid carriers are mineral earths such as silica gel, silica, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, Ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • the formulations generally contain between 0.01 and 95% by weight, preferably between 0.5 and 90% by weight, of active ingredient.
  • the active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).
  • IX a stable oily dispersion of 20 parts by weight of compound no. 6.12, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of a phenolsulfonic acid urea -formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil;
  • By finely distributing the mixture in 10,000 parts by weight Water gives a spray mixture which contains 0.1% by weight of the active ingredient.
  • the herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active ingredients are less compatible with certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit, if possible, while the active ingredients on the leaves growing below them unwanted plants or the uncovered floor area (post-directed, lay-by).
  • the application rates of active ingredient are 0.001 to 3.0, preferably 0.01 to 1 kg / ha of active substance (a.S.) depending on the control target, season, target plants and growth stage.
  • optically active cyclohexenone oxime ethers I or agents containing them can also be used in a further number of crop plants for eliminating unwanted plants.
  • the following crops are considered, for example:
  • Coffea arabica Coffea canephora, coffee
  • Nicotiana tabacum (N. rustica) tobacco Olea europaea olive tree Oryza sativa rice Phaseolus lunatus moon bean Phaseolus vulgaris bush beans Picea abies red spruce Pinus spp. jaw
  • the optically active cyclohexenone oxime ethers I can be mixed with numerous representatives of other herbicidal or growth-regulating active ingredient groups and applied together.
  • Benzo hexane derivatives come as mixing partners -l, 3-dione derivatives, which in
  • 2-position e.g. bear a carboxy or carbimino group, quinoline carboxylic acid derivatives, imidazolinones, sulfonamides, sulfonylureas, aryloxy, heteroaryloxyphenoxypropionic acids and their salts, esters and amides and others are considered.
  • Pests or phytopathogenic fungi or bacteria are also of interest. Also of interest is the miscibility with mineral salt solutions which are used to correct nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.
  • Plastic flower pots with loamy sand with about 3.0% humus as substrate served as culture vessels.
  • the seeds of the test plants were sown separately according to species.
  • the active ingredients suspended or emulsified in water were applied directly after sowing using finely distributing nozzles.
  • the vessels were lightly rained to encourage germination and growth and then covered with transparent plastic hoods until the plants had grown. This covering causes the test plants to germinate uniformly, provided that this has not been impaired by the active substances.
  • test plants were already grown in the test vessels or transplanted into the test vessels a few days beforehand. Depending on the growth habit, the active ingredients suspended or emulsified in water were only applied at a growth height of 3 to 15 cm.
  • the application rate for post-emergence treatment was 0.06 and 0.03 kg / ha a.S.
  • the plants were kept at 10-25 ° C and 20-35 ° C depending on the species.
  • the test period extended over 2 to 4 weeks. During this time, the plants were cared for and their reaction to the individual treatments was evaluated.
  • Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts, and 0 means no damage or normal growth.
  • the plants used in the greenhouse experiments are composed of the following types:
  • compounds 4.12 and 4.20 could be used to control undesirable grasses very well, while at the same time being compatible with the example culture of rice.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pyridine Compounds (AREA)

Abstract

Mélanges d'éthers de cyclohexénone-oximes optiquement actifs, à configuration R et S dans la partie éther d'oxime, de formule (I), où R1 = alkyle en C¿1?-C6; X = NO2, CN, halogène, alkyle en C1-C4, halogénoalkyle en C1-C4; n = 0 à 3 ou 1 à 5, dans le cas où tous les X sont des halogènes; R?2 = C¿1-C4-alcoxy-C1-C6-alkyle, C1-C4-alkylthio-C1-C6-alkyle, cycloalkyle en C3-C7 éventuellement substitué, cycloalcényle en C5-C7 éventuellement substitué, hétérocycle saturé à 5 chaînons, éventuellement substitué, portant 1 ou 2 atomes d'oxygène et/ou de soufre, hétérocycle à 6 ou 7 chaînons, éventuellement substitué, ayant 1 ou 2 atomes d'oxygène et/ou de soufre non voisins, pouvant être saturé ou une ou deux fois insaturé, groupe hétéro-aromatique à 5 chaînons, éventuellement substitué, renfermant 1 ou 2 atomes de N et un atome de O ou un atome de S, phényle ou pyridyle, les deux pouvant porter encore 1 à 3 substituants: halogène, NO2, CN, alkyle, alcoxy, alkylthio, halogénoalkyle, alcényloxy, alcinyloxy et/ou -NRaRb; Ra = H, alkyle, alcényle ou alcinyle, et Rb = H, alkyle, alcényle, alcinyle, acyle ou benzoyle éventuellement substitué; ainsi que les sels utilisables en agriculture et les esters d'acides carboxyliques en C¿1?-C10 et d'acides anorganiques des composés (I), sous réserve que les mélanges renferment, dans la partie éther d'oxime, au moins 75 % molaire en isomères de configuration R.
PCT/EP1993/000212 1992-02-13 1993-01-30 Melanges d'ethers de cyclohexenone-oximes optiquement actifs, leur procede de preparation et produits intermediaires pour leur preparation, ainsi que leur utilisation comme herbicides WO1993016062A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BR9305882A BR9305882A (pt) 1992-02-13 1993-01-30 Misturas de éteres de ciclo-hexenona oxima oticamente ativos éteres de ciclohexenona oxima oticamente ativos processo para a fabricação das misturas agente herbicida processo para combater o crescimento de plantas indesejadas misturas de hidroxilaminas oticamente ativas hidroxilaminas oticamente ativas e processo para a fabricação das misturas
EP93917358A EP0625974A1 (fr) 1992-02-13 1993-01-30 Melanges d'ethers de cyclohexenone-oximes optiquement actifs, leur procede de preparation et produits intermediaires pour leur preparation, ainsi que leur utilisation comme herbicides
JP5513724A JPH07505866A (ja) 1992-02-13 1993-01-30 光学活性シクロヘキセノンオキシムエーテル，その製造方法および中間生成物ならびにその除草剤としての用途
KR1019940702774A KR950700271A (ko) 1992-02-13 1994-08-12 광학 활성 시클로헥세논 옥심 에테르의 혼합물, 이의 제조 방법 및 제조용 중간체 및 제초제로서의 이의 용도(Mixtures of Optically Active Cyclohexenone Oxime Ethers, Process and Intermediate Products for Their Production and Their Use as herbicides)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4204206.2 1992-02-13
DE4204206A DE4204206A1 (de) 1992-02-13 1992-02-13 Mischungen aus optisch aktiven cyclohexenonoximethern, verfahren und zwischenprodukte zu ihrer herstellung und ihre verwendung als herbizide

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WO1993016062A1 true WO1993016062A1 (fr) 1993-08-19

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Country Status (11)

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EP (1) EP0625974A1 (fr)
JP (1) JPH07505866A (fr)
KR (1) KR950700271A (fr)
BR (1) BR9305882A (fr)
CA (1) CA2129121A1 (fr)
DE (1) DE4204206A1 (fr)
HU (1) HU216276B (fr)
RU (1) RU94044433A (fr)
TW (1) TW232646B (fr)
WO (1) WO1993016062A1 (fr)
ZA (1) ZA93970B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
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EP0666254A1 (fr) * 1994-02-07 1995-08-09 Basf Aktiengesellschaft 2-Aroylcydohexanedoines, procédé pour leur préparation ainsi que leur utilisation comme herbicide ou comme agent régulateur de la croissance des plantes
US5674812A (en) * 1994-03-31 1997-10-07 Basf Aktiengesellschaft 5(sulfo-/carbamoylmethyl)cyclohexenone oxime ethers
EP1296556A2 (fr) * 2000-07-03 2003-04-02 Valent U.S.A. Corporation Clethodime (-) optiquement pure, compositions et procedes permettant de commander la croissance des plantes a l'aide de cette clethodime
CN110483439A (zh) * 2019-08-28 2019-11-22 郑州手性药物研究院有限公司 6-氨基甲基-1,1-二氧-1,2-苯并噻唑-3-酮的合成方法
CN110483497A (zh) * 2019-08-28 2019-11-22 郑州手性药物研究院有限公司 6-氨基甲基-1,1-二氧-1,2-苯并噻唑-3-酮中间体及其合成方法
CN114591230A (zh) * 2022-03-07 2022-06-07 沈阳万菱生物技术有限公司 一种环己烯酮类化合物及其应用和一种农药除草剂

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* Cited by examiner, † Cited by third party
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DE4244390A1 (de) * 1992-12-29 1994-06-30 Basf Ag Verfahren zur Herstellung von Oximino-Derivaten und neue Oximino-Derivate
DE4415887A1 (de) * 1994-05-05 1995-06-01 Basf Ag Verfahren zur Herstellung von O-Phenoxyalkyloximen und O-Phenoxyalkylhydroxylaminen
DK0861026T3 (da) * 1995-09-20 2003-04-22 Basf Ag Synergistiske herbicide blandinger indeholdende cyclohexenonoximethere
CN113973824A (zh) * 2020-01-16 2022-01-28 郑州恒诚仪器耗材有限公司 环己烷-1,3-二酮类化合物作为除草剂的用途
CN114105842A (zh) * 2020-08-28 2022-03-01 郑州手性药物研究院有限公司 环己二烯肟醚类化合物及其应用
WO2021143617A1 (fr) * 2020-01-16 2021-07-22 郑州手性药物研究院有限公司 Composé d'éther d'oxime cyclohexadiène, son procédé de synthèse et son utilisation
CN116806829A (zh) * 2020-04-10 2023-09-29 辽宁先达农业科学有限公司 农药组合物及其应用和除草剂
CN112568223B (zh) * 2020-04-13 2023-04-21 辽宁先达农业科学有限公司 除草组合物及其应用和除草剂
CN115417791B (zh) * 2022-09-23 2023-10-27 郑州手性药物研究院有限公司 一种肟醚类1,3-环己二酮化合物及其合成方法和应用

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EP0048911A2 (fr) * 1980-09-26 1982-04-07 Roche Diagnostics GmbH Oximes o-substituées dérivées de l'acide alpha-cétocarboxylique, procédé de préparation et médicaments qui les contiennent
EP0184546A1 (fr) * 1984-09-13 1986-06-11 Sandoz Ag Oximes ou éthers d'hydroxylamine et leur utilisation comme pesticides
EP0456112A1 (fr) * 1990-05-09 1991-11-13 BASF Aktiengesellschaft Ethers de cyclohexènonoxime, leur procédé de préparation et leur emploi comme herbicides

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
EP0048911A2 (fr) * 1980-09-26 1982-04-07 Roche Diagnostics GmbH Oximes o-substituées dérivées de l'acide alpha-cétocarboxylique, procédé de préparation et médicaments qui les contiennent
EP0184546A1 (fr) * 1984-09-13 1986-06-11 Sandoz Ag Oximes ou éthers d'hydroxylamine et leur utilisation comme pesticides
EP0456112A1 (fr) * 1990-05-09 1991-11-13 BASF Aktiengesellschaft Ethers de cyclohexènonoxime, leur procédé de préparation et leur emploi comme herbicides

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0666254A1 (fr) * 1994-02-07 1995-08-09 Basf Aktiengesellschaft 2-Aroylcydohexanedoines, procédé pour leur préparation ainsi que leur utilisation comme herbicide ou comme agent régulateur de la croissance des plantes
US5559218A (en) * 1994-02-07 1996-09-24 Basf Aktiengesellschaft 2-aroylcyclohexanediones and their use as herbicides or plant growth-regulating agents
US5674812A (en) * 1994-03-31 1997-10-07 Basf Aktiengesellschaft 5(sulfo-/carbamoylmethyl)cyclohexenone oxime ethers
EP1296556A2 (fr) * 2000-07-03 2003-04-02 Valent U.S.A. Corporation Clethodime (-) optiquement pure, compositions et procedes permettant de commander la croissance des plantes a l'aide de cette clethodime
EP1296556A4 (fr) * 2000-07-03 2004-01-14 Valent Usa Corp Clethodime (-) optiquement pure, compositions et procedes permettant de commander la croissance des plantes a l'aide de cette clethodime
CN110483439A (zh) * 2019-08-28 2019-11-22 郑州手性药物研究院有限公司 6-氨基甲基-1,1-二氧-1,2-苯并噻唑-3-酮的合成方法
CN110483497A (zh) * 2019-08-28 2019-11-22 郑州手性药物研究院有限公司 6-氨基甲基-1,1-二氧-1,2-苯并噻唑-3-酮中间体及其合成方法
CN110483497B (zh) * 2019-08-28 2022-12-30 郑州手性药物研究院有限公司 6-氨基甲基-1,1-二氧-1,2-苯并噻唑-3-酮中间体及其合成方法
CN110483439B (zh) * 2019-08-28 2022-12-30 郑州手性药物研究院有限公司 6-氨基甲基-1,1-二氧-1,2-苯并噻唑-3-酮的合成方法
CN114591230A (zh) * 2022-03-07 2022-06-07 沈阳万菱生物技术有限公司 一种环己烯酮类化合物及其应用和一种农药除草剂

Also Published As

Publication number Publication date
DE4204206A1 (de) 1993-08-19
TW232646B (fr) 1994-10-21
HU9402353D0 (en) 1994-11-28
EP0625974A1 (fr) 1994-11-30
RU94044433A (ru) 1996-06-20
HU216276B (hu) 1999-05-28
KR950700271A (ko) 1995-01-16
HUT68901A (en) 1995-08-28
BR9305882A (pt) 1997-08-19
CA2129121A1 (fr) 1993-08-19
ZA93970B (en) 1994-08-12
JPH07505866A (ja) 1995-06-29

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