CA1338985C - Cyclohexenone compounds, their preparation and their use for controlling undesirable plant growth - Google Patents
Cyclohexenone compounds, their preparation and their use for controlling undesirable plant growthInfo
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- CA1338985C CA1338985C CA000593380A CA593380A CA1338985C CA 1338985 C CA1338985 C CA 1338985C CA 000593380 A CA000593380 A CA 000593380A CA 593380 A CA593380 A CA 593380A CA 1338985 C CA1338985 C CA 1338985C
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- 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
- C07C251/52—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals of hydrocarbon radicals substituted by halogen atoms or by nitro or nitroso groups
-
- 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
- A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
- A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
- A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—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
- A01N43/06—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 five-membered rings
- A01N43/10—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 five-membered rings with sulfur as the ring hetero atom
-
- 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
- A01N43/80—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 1,2
-
- 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
- C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C251/36—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/40—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atoms of the oxyimino groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
- C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/28—Halogen atoms
-
- 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
Abstract
Cyclohexenone compounds of the formula I
where the substituents have the following meanings:
R1 is C3-C4-alkenyl, C3-C4-alkynyl, C2-C4-haloalkyl, C2-C4-halo-alkenyl, C2-C4-alkoxyalkyl or a radical CH2-R3, where R3 is a 5-ring heterocycle with one to three nitrogen atoms and/or one to two oxygen atoms and/or one sulfur atom as hetero-atoms, which may bear up to two double bonds and one or two of the following substituents: C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, halogen, trifluoromethyl, C1-C4-alkoxymethyl, C1-C4-alkylthiomethyl and/or vinyl, or phenyl which may bear one to three of the following groups:
C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, halogen, trifluoromethyl, nitro and/or C1-C4-dialkylamino, and R is C1-C4-alkyl, and their agriculturally acceptable salts, processes for their manu-facture, and their use.
where the substituents have the following meanings:
R1 is C3-C4-alkenyl, C3-C4-alkynyl, C2-C4-haloalkyl, C2-C4-halo-alkenyl, C2-C4-alkoxyalkyl or a radical CH2-R3, where R3 is a 5-ring heterocycle with one to three nitrogen atoms and/or one to two oxygen atoms and/or one sulfur atom as hetero-atoms, which may bear up to two double bonds and one or two of the following substituents: C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, halogen, trifluoromethyl, C1-C4-alkoxymethyl, C1-C4-alkylthiomethyl and/or vinyl, or phenyl which may bear one to three of the following groups:
C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, halogen, trifluoromethyl, nitro and/or C1-C4-dialkylamino, and R is C1-C4-alkyl, and their agriculturally acceptable salts, processes for their manu-facture, and their use.
Description
_ o.z. 0050/39798 Cyclohexenone compounds, their preparation and their use for controlling undesirable plant growth The present invention relates to cyclohexenone compounds of the formula I
OH ~OR 1 \
where R1 is C3- or C~-alkenyl, C3- or C4-alkynyl, C2-C4-haloalkyl, C2-C~-haloalkenyl, C2-C4-alkoxyalkyl or CH2-R3, R3 is a 5-membered heterocyclic ring which has 1 to 3 nitrogen atoms and/or 1 or 2 oxygen atoms and/or a sulfur atom as heteroatoms and not more than 2 double bonds and may carry one or two of the substituents Cl-C4-alkyl, C1-C4-alkoxy, C1-C~-alkylthio, halogen, trifluoromethyl, C1-C~-alkoxymethyl, Cl-C~-alkylthiomethyl and/or vinyl or a phenyl radical which may carry one to three of the groups C1-C~-alkyl, C1-C4-alkoxy, C1-C~-alkylthio, halogen, tri-fluoromethyl, nitro and/or C1-C~-dialkylamino, and R2 is C1-C4-alkyl, and their agriculturally acceptable salts.
The present invention furthermore relates to a proce~s for the preparation of these compounds and method~ for controlling undesirable plant growth using agents which contain the compound~ I.
The compounds I may occur in a plurality of taut-omeric and stereoisomeric ( E and Z isomerism) forms, all of which are embraced by the claim.
The literature describes 3-hydroxy-2-cyclohexen-l-ones which carry a substituted phenyl radical in the 5-position and are suitable for controlling undesirable gras~es in broad-leaved crops (DE-A 24 39 104). Phenyl-substituted cyclohexenone compounds, which are used for controlling gras~ weeds in crops such as corn, wheat, barley and rice are also disclosed ( DE-A 32 48 554, DE-A
33 29 017 and DE-A 30 47 924).
It is an ob~ect of the present invention to pro-vide compound~ which have high selectivity at a low application rate, ie. control undesirable plants without - 2 - o.z. 0050/39798 damaging the crops.
We have found that this ob~ect is achieved by the cyclohexenone compounds defined at the outset.
The cyclohexenones of the formula I can be ob-tAine~ in a known manner from known raw materials; forexample, the corresponding cyclohexenone of the formula II
OH ,9 ~R2 II
can be reacted with a hydroxylamine RlONH2.
Advantageously, the reaction is carried out in the heterogeneous phase in a solvent at not more than 80C in the presence of a base, and the hydroxylamine source used is the ammonium compound of the said hydroxy-lamine.
Examples of suitable bases are carbonates, bi-carbonates, acetates, alcoholates or oxides of alkali metals or alkaline earth metals, in particular sodium hydroxide, potassium hydroxide, magnesium oxide or cal-cium oxide. Organic bases, ~uch as pyridine or tertiary amines, can also be used. The base is added, for exam-ple, in an amount of from 0.5 to 2 moles, based on the ammonium compound (DE-A-34 33 767).
Examples of suitable solvents are dimethyl sul-foxide, alcohols, such as methanol, ethanol and iso-propanol, aromatic hydrocarbons, such as benzene and tol-uene, chlorohydrocarbons, such as chloroform and di-chloroethane, aliphatic hydrocarbons, such as hexane and cyclohex~ne, esters, such as ethyl acetate, and ethers, such as dioxane and tetrahydrofuran.
The reaction is complete after a few hours, and the end product can be isolated by evaporating down the mixture, distributing the residue in methylene chloride/
water and distilling off the solvent under reduced - 3 - o.z. 0050/39798 pressure.
It is also possible to use the free hydroxylamine base directly, for example in the form of an aqueous solution; dep~n~ing on the solvent used for the other 5reactant, a one-phase or two-phase reaction mixture is obtA i n~
Examples of suitable solvents for this reaction are alcohols, such as methanol, ethanol, isopropanol and cycloh~YAnol, aliphatic and aromatic hydrocarbons and 10chlorohydrocarbons, such as heYAne~ cycloheYAn~, meth-ylene chloride, toluene and dichloroethane, esters, such as ethyl acetate, nitriles, such as acetonitrile, and cyclic ethers, such as tetrahydrofuran.
Alkali metal salts of the compounds I can be ob-15tA i n~ by treating the 3-hydroxy compounds with sodium hydroxide, potassium hydroxide, a sodium alcoholate or a potassium alcoholate in aqueous solution or in an organic solvent, such as methanol, ethanol, acetone or toluene.
Other metal salts, for example the manganese, 20copper, zinc, iron, calcium, magnesium and barium salts, can be prepared from sodium salts in a conventional man-ner, as can ammonium, phosphonium, sulfonium and sulfox-onium salts by using ammonia or phosphonium, sulfonium or sulfoxonium hydroxides.
25The compounds of type II can be prepared, for example, from the corresponding cycloheYAne-1,3-diones of the formula III
OH
III
Y O
where Y is hydrogen or methoxycarbonyl, by known methods 30[Tetrahedron Lett. (1975), 2491].
It is also possible to prepare the compounds of the formula II via the enolester intermediates, which are obtAineA in the reaction of compounds of the formula III
with acyl chlorides in the presence of a base and are - 4 - o.z. 0050/39798 then sub~ected to a rearrangement reaction with certain imidazole or pyridine derivatives (JApAne~e Preliminary Published Application 79/063052).
A~--(R2COCI A ~< ll A ~ O
r o Y o Y o III II
Compounds of the formula I are obtained using known, commercial compounds are starting materials and by a number of known process steps, as shown in the scheme below and illustrated by a practical example.
~0 ~ceton~ ~J~ CH2Y (C02CH3) _~OH
NaOH NaOCH3 I I I
OH O 3 ~ OH 1`~--OR I
R2COCI ,~_</ R10--NH3Y ,~</
II I
Because of the biological activity, preferred cyclohexenone compounds I are those in which the radicals have the following meanings:
Rl is alkenyl, such as allyl, buten-2-yl, buten-3-yl and 2-methylbuten-2-yl, in particular allyl and buten-2-yl, alkynyl, such as prop-2-ynyl, but-2-ynyl, but-3-ynyl and l-methylprop-2-ynyl, in particular prop-2-ynyl and but-2-ynyl; haloalkyl, such as l-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-tri-chloroethyl and pentafluoroethyl, in particular 2-chloro-ethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl and penta-fluoroethyl; haloalkenyl, such as 2-chloroprop-2-enyl, 3-chloroprop-2-enyl or 3,3,2-trichloroprop-2-enyl, in par-icular 3-chloroprop-2-enyl; alkoxyalkyl, such as methoxy-methyl, ethoxymethyl, methoxyethyl and ethoxyethyl, in - 5 - o.z. 0050/39798 particular methoxyethyl and ethoxyethyl; phenyl which may carry one to three of the following substituents: nitro, trifluoromethyl, halogen, such as fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine, alkyl, such as methyl, ethyl, propyl, l-methyl-ethyl, butyl, l-methylpropyl, 2-methylpropyl or 1,1-di-methyl-ethyl, in particular methyl or ethyl, alkoxy, such as methoxy, ethoxy, propoxy, l-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy, in particular methoxy or l-methylethoxy, alkylthio, such as methylthio, ethylthio, propylthio, l-methylethylthio, butylthio, l-methylpropylthio, 2-methylpropylthio or 1,1-dimethylethylthio, in particular methylthio or ethylthio and/or dialkylamino, such as dimethylamino, ethylmethyl-amino or dimethylamino, in particular dimethylamino, or a radical -CH2-R3, where R3 is tetrahydrofuranyl, tetra-hydrothiophenyl, dioxolanyl, dithiolanyl, oxathiolanyl, dihydrofuranyl, dihydrothienyl, pyrrolinyl, pyrazolinyl, imidazolinyl, isoxazolinyl, oxazolinyl, isothiazolinyl, thiazolinyl, furanyl, thienyl, pyrrolyl, pyrazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, oxadiazol-yl, thiA~iAzolyl~ imidazolyl, oYA~iAzolyl, thiodiazolyl or triazolyl, in particular thiophenyl or isoxazolyl, and this heterocyclic structure may carry one or two of the following substituents: C1-C4-alkyl as stated above, in particular methyl, ethyl or isopropyl, Cl-C4-alkoxy as stated above, in particular methoxy, ethoxy or isoprop-oxy, C1-C~-alkylthio as stated above, in particular methylthio or ethylthio, halogen as stated above, in particular fluorine or chlorine, alkoxymethyl, such as methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxy-methyl, butoxymethyl, l-methylpropoxymethyl, 2-methyl-propoxyethyl or l,l-dimethylethoxymethyl, in particular methoxyethyl or ethoxymethyl, alkylthiomethyl, such as methylthiomethyl, ethylthiomethyl, propylthiomethyl, isopropylthiomethyl,butylthiomethyl,l-methylpropylthio-methyl, 2-methylpropylthiomethyl or l,l-dimethylethyl-.
OH ~OR 1 \
where R1 is C3- or C~-alkenyl, C3- or C4-alkynyl, C2-C4-haloalkyl, C2-C~-haloalkenyl, C2-C4-alkoxyalkyl or CH2-R3, R3 is a 5-membered heterocyclic ring which has 1 to 3 nitrogen atoms and/or 1 or 2 oxygen atoms and/or a sulfur atom as heteroatoms and not more than 2 double bonds and may carry one or two of the substituents Cl-C4-alkyl, C1-C4-alkoxy, C1-C~-alkylthio, halogen, trifluoromethyl, C1-C~-alkoxymethyl, Cl-C~-alkylthiomethyl and/or vinyl or a phenyl radical which may carry one to three of the groups C1-C~-alkyl, C1-C4-alkoxy, C1-C~-alkylthio, halogen, tri-fluoromethyl, nitro and/or C1-C~-dialkylamino, and R2 is C1-C4-alkyl, and their agriculturally acceptable salts.
The present invention furthermore relates to a proce~s for the preparation of these compounds and method~ for controlling undesirable plant growth using agents which contain the compound~ I.
The compounds I may occur in a plurality of taut-omeric and stereoisomeric ( E and Z isomerism) forms, all of which are embraced by the claim.
The literature describes 3-hydroxy-2-cyclohexen-l-ones which carry a substituted phenyl radical in the 5-position and are suitable for controlling undesirable gras~es in broad-leaved crops (DE-A 24 39 104). Phenyl-substituted cyclohexenone compounds, which are used for controlling gras~ weeds in crops such as corn, wheat, barley and rice are also disclosed ( DE-A 32 48 554, DE-A
33 29 017 and DE-A 30 47 924).
It is an ob~ect of the present invention to pro-vide compound~ which have high selectivity at a low application rate, ie. control undesirable plants without - 2 - o.z. 0050/39798 damaging the crops.
We have found that this ob~ect is achieved by the cyclohexenone compounds defined at the outset.
The cyclohexenones of the formula I can be ob-tAine~ in a known manner from known raw materials; forexample, the corresponding cyclohexenone of the formula II
OH ,9 ~R2 II
can be reacted with a hydroxylamine RlONH2.
Advantageously, the reaction is carried out in the heterogeneous phase in a solvent at not more than 80C in the presence of a base, and the hydroxylamine source used is the ammonium compound of the said hydroxy-lamine.
Examples of suitable bases are carbonates, bi-carbonates, acetates, alcoholates or oxides of alkali metals or alkaline earth metals, in particular sodium hydroxide, potassium hydroxide, magnesium oxide or cal-cium oxide. Organic bases, ~uch as pyridine or tertiary amines, can also be used. The base is added, for exam-ple, in an amount of from 0.5 to 2 moles, based on the ammonium compound (DE-A-34 33 767).
Examples of suitable solvents are dimethyl sul-foxide, alcohols, such as methanol, ethanol and iso-propanol, aromatic hydrocarbons, such as benzene and tol-uene, chlorohydrocarbons, such as chloroform and di-chloroethane, aliphatic hydrocarbons, such as hexane and cyclohex~ne, esters, such as ethyl acetate, and ethers, such as dioxane and tetrahydrofuran.
The reaction is complete after a few hours, and the end product can be isolated by evaporating down the mixture, distributing the residue in methylene chloride/
water and distilling off the solvent under reduced - 3 - o.z. 0050/39798 pressure.
It is also possible to use the free hydroxylamine base directly, for example in the form of an aqueous solution; dep~n~ing on the solvent used for the other 5reactant, a one-phase or two-phase reaction mixture is obtA i n~
Examples of suitable solvents for this reaction are alcohols, such as methanol, ethanol, isopropanol and cycloh~YAnol, aliphatic and aromatic hydrocarbons and 10chlorohydrocarbons, such as heYAne~ cycloheYAn~, meth-ylene chloride, toluene and dichloroethane, esters, such as ethyl acetate, nitriles, such as acetonitrile, and cyclic ethers, such as tetrahydrofuran.
Alkali metal salts of the compounds I can be ob-15tA i n~ by treating the 3-hydroxy compounds with sodium hydroxide, potassium hydroxide, a sodium alcoholate or a potassium alcoholate in aqueous solution or in an organic solvent, such as methanol, ethanol, acetone or toluene.
Other metal salts, for example the manganese, 20copper, zinc, iron, calcium, magnesium and barium salts, can be prepared from sodium salts in a conventional man-ner, as can ammonium, phosphonium, sulfonium and sulfox-onium salts by using ammonia or phosphonium, sulfonium or sulfoxonium hydroxides.
25The compounds of type II can be prepared, for example, from the corresponding cycloheYAne-1,3-diones of the formula III
OH
III
Y O
where Y is hydrogen or methoxycarbonyl, by known methods 30[Tetrahedron Lett. (1975), 2491].
It is also possible to prepare the compounds of the formula II via the enolester intermediates, which are obtAineA in the reaction of compounds of the formula III
with acyl chlorides in the presence of a base and are - 4 - o.z. 0050/39798 then sub~ected to a rearrangement reaction with certain imidazole or pyridine derivatives (JApAne~e Preliminary Published Application 79/063052).
A~--(R2COCI A ~< ll A ~ O
r o Y o Y o III II
Compounds of the formula I are obtained using known, commercial compounds are starting materials and by a number of known process steps, as shown in the scheme below and illustrated by a practical example.
~0 ~ceton~ ~J~ CH2Y (C02CH3) _~OH
NaOH NaOCH3 I I I
OH O 3 ~ OH 1`~--OR I
R2COCI ,~_</ R10--NH3Y ,~</
II I
Because of the biological activity, preferred cyclohexenone compounds I are those in which the radicals have the following meanings:
Rl is alkenyl, such as allyl, buten-2-yl, buten-3-yl and 2-methylbuten-2-yl, in particular allyl and buten-2-yl, alkynyl, such as prop-2-ynyl, but-2-ynyl, but-3-ynyl and l-methylprop-2-ynyl, in particular prop-2-ynyl and but-2-ynyl; haloalkyl, such as l-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-tri-chloroethyl and pentafluoroethyl, in particular 2-chloro-ethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl and penta-fluoroethyl; haloalkenyl, such as 2-chloroprop-2-enyl, 3-chloroprop-2-enyl or 3,3,2-trichloroprop-2-enyl, in par-icular 3-chloroprop-2-enyl; alkoxyalkyl, such as methoxy-methyl, ethoxymethyl, methoxyethyl and ethoxyethyl, in - 5 - o.z. 0050/39798 particular methoxyethyl and ethoxyethyl; phenyl which may carry one to three of the following substituents: nitro, trifluoromethyl, halogen, such as fluorine, chlorine, bromine or iodine, in particular fluorine or chlorine, alkyl, such as methyl, ethyl, propyl, l-methyl-ethyl, butyl, l-methylpropyl, 2-methylpropyl or 1,1-di-methyl-ethyl, in particular methyl or ethyl, alkoxy, such as methoxy, ethoxy, propoxy, l-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy, in particular methoxy or l-methylethoxy, alkylthio, such as methylthio, ethylthio, propylthio, l-methylethylthio, butylthio, l-methylpropylthio, 2-methylpropylthio or 1,1-dimethylethylthio, in particular methylthio or ethylthio and/or dialkylamino, such as dimethylamino, ethylmethyl-amino or dimethylamino, in particular dimethylamino, or a radical -CH2-R3, where R3 is tetrahydrofuranyl, tetra-hydrothiophenyl, dioxolanyl, dithiolanyl, oxathiolanyl, dihydrofuranyl, dihydrothienyl, pyrrolinyl, pyrazolinyl, imidazolinyl, isoxazolinyl, oxazolinyl, isothiazolinyl, thiazolinyl, furanyl, thienyl, pyrrolyl, pyrazolyl, isoxazolyl, oxazolyl, isothiazolyl, thiazolyl, oxadiazol-yl, thiA~iAzolyl~ imidazolyl, oYA~iAzolyl, thiodiazolyl or triazolyl, in particular thiophenyl or isoxazolyl, and this heterocyclic structure may carry one or two of the following substituents: C1-C4-alkyl as stated above, in particular methyl, ethyl or isopropyl, Cl-C4-alkoxy as stated above, in particular methoxy, ethoxy or isoprop-oxy, C1-C~-alkylthio as stated above, in particular methylthio or ethylthio, halogen as stated above, in particular fluorine or chlorine, alkoxymethyl, such as methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxy-methyl, butoxymethyl, l-methylpropoxymethyl, 2-methyl-propoxyethyl or l,l-dimethylethoxymethyl, in particular methoxyethyl or ethoxymethyl, alkylthiomethyl, such as methylthiomethyl, ethylthiomethyl, propylthiomethyl, isopropylthiomethyl,butylthiomethyl,l-methylpropylthio-methyl, 2-methylpropylthiomethyl or l,l-dimethylethyl-.
6 O.Z. 0050/39798 thiomethyl, in particular methylthiomethyl or ethylthiomethyl, trifluoro-methyl and/or vinyl, and R2 is C1-C4-alkyl, such as methyl, ethyl, propyl, l-methylethyl, butyl, l-methylpropyl, 2-methylpropyl or l,l-dimethylethyl, in particular ethyl or propyl.
Suitable salts of the compounds of the formula I are agriculturally acceptable salts, for example alkali metal salts, in particular potassium salts or sodium salts, alkaline earth metal salts, in particular calcium salts, and also manganese salts, copper salts, zinc salts, iron salts and 10 ammonium, tetraalkylammonium, benzyltrialkylammonium, trialkylsulfoxonium and trialkylsulfonium salts.
The cyclohexenones, or the herbicidal agents containing them, may be applied for instance in the form of directly sprayable solutions, powders, 15 suspensions (including high-percentage aqueous, oily or other suspen-sions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcast-ing agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribu-20 tion of the active ingredients according to the invention as possible.
For the preparation of solutions, emulsions, pastes and oil dispersions tobe sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vege-25 table or animal origin, aliphatic, cyclic and aromatic hydrocarbons suchas benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as 30 dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc.
are suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes, dispersions, wettable powders or water-dispersible granules by adding 35 water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concen-trates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing 40 agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl 7 O.z. 0050/39798 sulfonates, alkali metal and alkaline earth metal salts of dibutyl-naphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated 5 fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl-phenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol 10 polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated poly-oxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be 20 prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium 25 sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by30 weight of active ingredient.
The cyclohexenone compounds may be formulated for instance as follows:
I. 90 parts by weight of compound no. 1 is mixed with 10 parts by weight 35 of N-methyl-alpha-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 1 is dissolved in a mixture con-sisting of 80 parts by weight of xylene, 10 parts by weight of the adduct 40 of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanol-amide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and I mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous disper-sion is obtained containing 0.02% by weight of the active ingredient.
Suitable salts of the compounds of the formula I are agriculturally acceptable salts, for example alkali metal salts, in particular potassium salts or sodium salts, alkaline earth metal salts, in particular calcium salts, and also manganese salts, copper salts, zinc salts, iron salts and 10 ammonium, tetraalkylammonium, benzyltrialkylammonium, trialkylsulfoxonium and trialkylsulfonium salts.
The cyclohexenones, or the herbicidal agents containing them, may be applied for instance in the form of directly sprayable solutions, powders, 15 suspensions (including high-percentage aqueous, oily or other suspen-sions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcast-ing agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribu-20 tion of the active ingredients according to the invention as possible.
For the preparation of solutions, emulsions, pastes and oil dispersions tobe sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vege-25 table or animal origin, aliphatic, cyclic and aromatic hydrocarbons suchas benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as 30 dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc.
are suitable.
Aqueous formulations may be prepared from emulsion concentrates, pastes, dispersions, wettable powders or water-dispersible granules by adding 35 water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concen-trates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing 40 agent and possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl 7 O.z. 0050/39798 sulfonates, alkali metal and alkaline earth metal salts of dibutyl-naphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of sulfated 5 fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctyl-phenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol 10 polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated poly-oxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous granules, may be 20 prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium 25 sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain flours, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.
The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by30 weight of active ingredient.
The cyclohexenone compounds may be formulated for instance as follows:
I. 90 parts by weight of compound no. 1 is mixed with 10 parts by weight 35 of N-methyl-alpha-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.
II. 20 parts by weight of compound no. 1 is dissolved in a mixture con-sisting of 80 parts by weight of xylene, 10 parts by weight of the adduct 40 of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanol-amide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and I mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous disper-sion is obtained containing 0.02% by weight of the active ingredient.
8 O.Z. 0050/39798 III. 20 parts by weight of compound no. 2 is dissolved in a mixture con-sisting of 40 parts by weight of cyclohexanone, 30 parts by weight of iso-butanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles 5 of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
10 IV. 20 parts by weight of compound no. 8 is dissolved in a mixture con-sisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of 15 water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
V. 20 parts by weight of compound no. 3 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 20 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of the active ingredient.
VI. 3 parts by weight of compound no. 9 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.
30 VII. 30 parts by weight of compound no. 13 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
VIII. 20 parts of compound no. 12 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A
40 stable oily dispersion is obtained.
The active ingredients may be applied pre- or postemergence. If certain crop plants tolerate the active ingredients less well, application tech-g O.Z. 0050/39798 niques may be used in which the herbicidal agents are sprayed fromsuitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by 5 treatment).
The application rates depend on the objective to be achieved, the time of the year, the plants to be combated and their growth stage, and are from 0.01 to 3.0, preferably 0.05 to 1.0, kg of active ingredient per hectare.
In view of the number of application methods possible, the compounds according to the invention, or agents containing them, may be used in a further large number of crops for removing unwanted plants. The following crops are given by way of example:
O.Z. 0050/39798 Botanical name Common name Allium cepa onions Ananas comosus pineapples Arachis hypogaea peanuts (groundnuts) 5 Asparagus officinalis asparagus Avena sativa oats Beta vulgaris spp. altissima sugarbeets Beta vulgaris spp. rapa fodder beets Beta vulgaris spp. esculenta table beets, red beets 10 Brassica napus var. napus rapeseed Brassica napus var. napobrassica swedes Brassica napus var. rapa turnips Brassica rapa var. siIvestris Camellia sinensis tea plants 15 Carthamus tinctorius safflower Carya illinoinensis pecan trees Citrus limon lemons Citrus maxima grapefruits Citrus reticulata mandarins 20 Citrus sinensis orange trees Coffea arabica (Coffea canephora, Coffea liberica) coffee plants Cucumis melo melons Cucumis sativus cucumbers 25 Cynodon dactylon Bermudagrass Daucus carota carrots Elais guineensis oil palms Fragaria vesca strawberries Glycine max soybeans 30 Gossypium hirsutum (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium) cotton Helianthus annuus sunflowers Helianthus tuberosus Jerusalem artichoke Hevea brasiliensis rubber plants 35 Hordeum vulgare barley Humulus lupulus hops Ipomoea batatas sweet potatoes Juglans regia walnut trees Lactuca sativa lettuce 40 Lens culinaris lentils Linum usitatissimum flax Lycopersicon Iycopersicum tomatoes 11 O.Z. 0050/39798 Botanical name Common name Malus spp. apple trees Manihot esculenta cassava Medicago sativa alfalfa (lucerne) 5 Mentha piperita peppermint Musa spp. banana plants Nicotiana tabacum (N. rustica) tobacco Olea europaea olive trees Oryza sativa rice 10 Panicum miliaceum millet Phaseolus lunatus limabeans Phaseolus mungo mungbeans Phaseolus vulgaris snapbeans, green beans, dry beans 15 Pennisetum glaucum pearl millet Petroselinum crispum spp. tuberosum parsley Picea abies Norway spruce Abies alba fir trees Pinus spp. pine trees 20 Pisum sativum English peas Prunus avium cherry trees Prunus domestica plum trees Prunus dulcis almond trees Prunus persica peach trees 25 Pyrus communis pear trees Ribes sylvestre redcurrants Ribes uva-crispa gooseberries Ricinus communis castor-oil plants Saccharum officinarum sugar cane 30 Secale cereale rye Sesamum indicum sesame Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) sorghum Sorghum dochna sorgo 35 Spinacia oleracea spinach Theobroma cacao cacao plants Trifolium pratense red clover Triticum aestivum wheat Triticum durum durum wheat 40 Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Vicia faba tick beans Vigna sinensis (V. unguiculata) cow peas Vitis vinifera grapes Zea mays Indian corn, sweet corn, maize 12 O.Z. 0050/39798 To increase the spectrum of action and to achieve synergistic effects, the cyclohexenones of the formula I may be mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable components are diazines, 4H-3,1-5 benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran deriva-tives, cyclohexane-1,3-dione derivatives, quinolinecarboxylic acids, phenyloxy- or heteroaryloxy-phenylpropionic acids and salts, esters and 10 amides thereof, etc.
It may also be useful to apply the novel compounds of the formula I, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phyto-15 pathogenic fungi or bacteria. The compounds may also be mixed withsolutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.
Manufacturing examples The directions given in the synthesis examples below were employed, after appropriate modifications to the starting materials, to obtain further compounds of the formula I; the compounds obtained are listed in the tables below with physical data. Those compounds for which no data are 25 given may be produced analogously from the appropriate materials. In view of their close structural similarity with the compounds produced and investigated, they are expected to have a similar action.
Example 1 a) 4-(4-Ethylphenyl)-3-buten-2-one 20 ml of 10% strength sodium hydroxide solution is added to a mixture of 111.4 g (0.83 mol) of 4-ethylbenzaldehyde, 133 9 of acetone and 100 ml of water, and the mixture is stirred overnight at room tempera-ture. It is then diluted with 300 ml of ice water and extracted five times, each time with 100 ml of dichloromethane. The extracts are dried over sodium sulfate and concentrated.
Yield: 144 g of a yellow oil, which is reacted as follows:
13 O.Z. 0050/39798 b) 5-(4-Ethylphenyl)-3-hydroxy-2-cyclohexen-1-one 144 g (0.83 mol) of 4-(4-ethylphenyl)-3-buten-2-one dissolved in a small amount of methanol is dripped into 109 g (0.83 mol) of dimethyl malonate and 45 g (0.83 mol) of sodium methylate in 40 ml of methanol.
The mixture is stirred at reflux for 3 hours and for 10 hours at room temperature. The methanol is distilled off, and the residue is taken up in 2 liters of 10% strength potassium hydroxide solution and stirred for 8 hours at room temperature. At 60C, the mixture is acidified to pH 1 with concentrated hydrochloric acid. The mixture is stirred for a further 2 hours and suction filtered, and the precipi-tate is dried under reduced pressure.
Yield: 167 g of a yellow solid; m.p. 162 - 164C.
c) 2-Butyryl-5-(4-ethylphenyl)-3-hydroxy-2-cyclohexen-1-one 51 g (0.51 mol) of triethylamine and - with ice cooling - 54 g (0.51 mol) of butyryl chloride are dripped into a solution of 110 g (0.51 mol) of the 5-(4-ethylphenyl)-3-hydroxy-2-cyclohexen-1-one, obtained in accordance with the foregoing instructions, in 500 ml of tetra-hydrofuran. After 8 hours at room temperature, the mixture is filtered and the precipitate is washed with tetrahydrofuran. The filtrate is concentrated, the residue is taken up in 500 ml of ethyl acetate and 6.2 g of 4-N,N-dimethylaminopyridine is added. The homogeneous solu-tion is kept for 40 hours at room temperature, is then concentrated and the residue is taken up in 10% strength potassium hydroxide solu-tion. The undissolved constituents are separated off, and the fiItrate is acidified to pH 1. The product which precipitates out is filtered off and dried under reduced pressure.
Yield: 100 g of a yellow solid; m.p. 60 - 62C.
d) 2-(E)-3-Chloro-2-propenyloxyiminobutyl-5-(4-ethylphenyl)-3-hydroxy-2- cyclohexen-1-one 16.6 g (0.12 mol) of (E)-3-chloro-2-propenyloxyamine hydrochloride and 9.7 g (0.12 mol) of sodium bicarbonate are added to 30 g (0.11 mol) of the 2-butyryl-5-(4-ethylphenyl)-3-hydroxy-2-cyclohexen-1-one, obtained in accordance with the foregoing instructions, in 300 ml of methanol, and the solution is stirred overnight at room temperature. After con-centration, the residue is taken up in 300 ml of dichloromethane and washed twice with water, followed by drying over sodium sulfate and concentration.
~ 338985 14 O.Z. 0050/39798 Yield: 22 9 of a yellow solid (active ingredient no. 11 in the table below); m.p. 56 58C.
The compounds of the formula I given in the table below are characterized 5 by their melting point and/or 1H-NMR data. The 1H-NMR spectra were taken in deuterochloroform or hexadeuterosulfoxide as solvent, with tetramethyl-silane as internal standard. The chemical shifts were registered in ppm.
The multiplicities are given as follows: s = singlet, d = doublet, t =
triplet, q = quartet, m = multiplet.
_ _ I I
_ _ a~ . . . . .
r) ____ ___ __ ___ I I I I I I I -- I II I I
o ~ v ~ f7 v~ ~ V ~ V ~
O -- -- -- -- _ _ _ ~ _ _ _ _ _ ~ .... ... ~1~
O ~
____ ___ ____ ___ I I I II I II I I I I I I
V ~ V VV ~r ~n V ~ V v~ V V v~
____ ___ ____ ___ ___ ________ ___ I I T II I I I I I I I I I I
- - - - - - - - - - - -'O I I I I I I I I I ~: I I I I I
S ------_ ________ ___ O
~ ~ 0 0 0 0 0 0 0 ~/ _ 0~,~ ~0 o E ~ cr~
I I --~ ~ I I ~
`J E C ~
S ~ S S ~ ~ C--~L
O O
~ C~ Z
16 O.Z. 0050/39798 Use examples The action of the cyclohexenone derivatives of the formula I on plant growth is demonstrated by the following greenhouse experiments:
The vessels employed were plastic flowerpots having a volume of 300 cm3 and filled with a sandy loam containing about 3.0% humus. The seeds of the test plants were sown separately, according to species.
10 IV. 20 parts by weight of compound no. 8 is dissolved in a mixture con-sisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280C, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of 15 water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.
V. 20 parts by weight of compound no. 3 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 20 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of the active ingredient.
VI. 3 parts by weight of compound no. 9 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.
30 VII. 30 parts by weight of compound no. 13 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.
VIII. 20 parts of compound no. 12 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A
40 stable oily dispersion is obtained.
The active ingredients may be applied pre- or postemergence. If certain crop plants tolerate the active ingredients less well, application tech-g O.Z. 0050/39798 niques may be used in which the herbicidal agents are sprayed fromsuitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by 5 treatment).
The application rates depend on the objective to be achieved, the time of the year, the plants to be combated and their growth stage, and are from 0.01 to 3.0, preferably 0.05 to 1.0, kg of active ingredient per hectare.
In view of the number of application methods possible, the compounds according to the invention, or agents containing them, may be used in a further large number of crops for removing unwanted plants. The following crops are given by way of example:
O.Z. 0050/39798 Botanical name Common name Allium cepa onions Ananas comosus pineapples Arachis hypogaea peanuts (groundnuts) 5 Asparagus officinalis asparagus Avena sativa oats Beta vulgaris spp. altissima sugarbeets Beta vulgaris spp. rapa fodder beets Beta vulgaris spp. esculenta table beets, red beets 10 Brassica napus var. napus rapeseed Brassica napus var. napobrassica swedes Brassica napus var. rapa turnips Brassica rapa var. siIvestris Camellia sinensis tea plants 15 Carthamus tinctorius safflower Carya illinoinensis pecan trees Citrus limon lemons Citrus maxima grapefruits Citrus reticulata mandarins 20 Citrus sinensis orange trees Coffea arabica (Coffea canephora, Coffea liberica) coffee plants Cucumis melo melons Cucumis sativus cucumbers 25 Cynodon dactylon Bermudagrass Daucus carota carrots Elais guineensis oil palms Fragaria vesca strawberries Glycine max soybeans 30 Gossypium hirsutum (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium) cotton Helianthus annuus sunflowers Helianthus tuberosus Jerusalem artichoke Hevea brasiliensis rubber plants 35 Hordeum vulgare barley Humulus lupulus hops Ipomoea batatas sweet potatoes Juglans regia walnut trees Lactuca sativa lettuce 40 Lens culinaris lentils Linum usitatissimum flax Lycopersicon Iycopersicum tomatoes 11 O.Z. 0050/39798 Botanical name Common name Malus spp. apple trees Manihot esculenta cassava Medicago sativa alfalfa (lucerne) 5 Mentha piperita peppermint Musa spp. banana plants Nicotiana tabacum (N. rustica) tobacco Olea europaea olive trees Oryza sativa rice 10 Panicum miliaceum millet Phaseolus lunatus limabeans Phaseolus mungo mungbeans Phaseolus vulgaris snapbeans, green beans, dry beans 15 Pennisetum glaucum pearl millet Petroselinum crispum spp. tuberosum parsley Picea abies Norway spruce Abies alba fir trees Pinus spp. pine trees 20 Pisum sativum English peas Prunus avium cherry trees Prunus domestica plum trees Prunus dulcis almond trees Prunus persica peach trees 25 Pyrus communis pear trees Ribes sylvestre redcurrants Ribes uva-crispa gooseberries Ricinus communis castor-oil plants Saccharum officinarum sugar cane 30 Secale cereale rye Sesamum indicum sesame Solanum tuberosum Irish potatoes Sorghum bicolor (s. vulgare) sorghum Sorghum dochna sorgo 35 Spinacia oleracea spinach Theobroma cacao cacao plants Trifolium pratense red clover Triticum aestivum wheat Triticum durum durum wheat 40 Vaccinium corymbosum blueberries Vaccinium vitis-idaea cranberries Vicia faba tick beans Vigna sinensis (V. unguiculata) cow peas Vitis vinifera grapes Zea mays Indian corn, sweet corn, maize 12 O.Z. 0050/39798 To increase the spectrum of action and to achieve synergistic effects, the cyclohexenones of the formula I may be mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable components are diazines, 4H-3,1-5 benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran deriva-tives, cyclohexane-1,3-dione derivatives, quinolinecarboxylic acids, phenyloxy- or heteroaryloxy-phenylpropionic acids and salts, esters and 10 amides thereof, etc.
It may also be useful to apply the novel compounds of the formula I, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phyto-15 pathogenic fungi or bacteria. The compounds may also be mixed withsolutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added.
Manufacturing examples The directions given in the synthesis examples below were employed, after appropriate modifications to the starting materials, to obtain further compounds of the formula I; the compounds obtained are listed in the tables below with physical data. Those compounds for which no data are 25 given may be produced analogously from the appropriate materials. In view of their close structural similarity with the compounds produced and investigated, they are expected to have a similar action.
Example 1 a) 4-(4-Ethylphenyl)-3-buten-2-one 20 ml of 10% strength sodium hydroxide solution is added to a mixture of 111.4 g (0.83 mol) of 4-ethylbenzaldehyde, 133 9 of acetone and 100 ml of water, and the mixture is stirred overnight at room tempera-ture. It is then diluted with 300 ml of ice water and extracted five times, each time with 100 ml of dichloromethane. The extracts are dried over sodium sulfate and concentrated.
Yield: 144 g of a yellow oil, which is reacted as follows:
13 O.Z. 0050/39798 b) 5-(4-Ethylphenyl)-3-hydroxy-2-cyclohexen-1-one 144 g (0.83 mol) of 4-(4-ethylphenyl)-3-buten-2-one dissolved in a small amount of methanol is dripped into 109 g (0.83 mol) of dimethyl malonate and 45 g (0.83 mol) of sodium methylate in 40 ml of methanol.
The mixture is stirred at reflux for 3 hours and for 10 hours at room temperature. The methanol is distilled off, and the residue is taken up in 2 liters of 10% strength potassium hydroxide solution and stirred for 8 hours at room temperature. At 60C, the mixture is acidified to pH 1 with concentrated hydrochloric acid. The mixture is stirred for a further 2 hours and suction filtered, and the precipi-tate is dried under reduced pressure.
Yield: 167 g of a yellow solid; m.p. 162 - 164C.
c) 2-Butyryl-5-(4-ethylphenyl)-3-hydroxy-2-cyclohexen-1-one 51 g (0.51 mol) of triethylamine and - with ice cooling - 54 g (0.51 mol) of butyryl chloride are dripped into a solution of 110 g (0.51 mol) of the 5-(4-ethylphenyl)-3-hydroxy-2-cyclohexen-1-one, obtained in accordance with the foregoing instructions, in 500 ml of tetra-hydrofuran. After 8 hours at room temperature, the mixture is filtered and the precipitate is washed with tetrahydrofuran. The filtrate is concentrated, the residue is taken up in 500 ml of ethyl acetate and 6.2 g of 4-N,N-dimethylaminopyridine is added. The homogeneous solu-tion is kept for 40 hours at room temperature, is then concentrated and the residue is taken up in 10% strength potassium hydroxide solu-tion. The undissolved constituents are separated off, and the fiItrate is acidified to pH 1. The product which precipitates out is filtered off and dried under reduced pressure.
Yield: 100 g of a yellow solid; m.p. 60 - 62C.
d) 2-(E)-3-Chloro-2-propenyloxyiminobutyl-5-(4-ethylphenyl)-3-hydroxy-2- cyclohexen-1-one 16.6 g (0.12 mol) of (E)-3-chloro-2-propenyloxyamine hydrochloride and 9.7 g (0.12 mol) of sodium bicarbonate are added to 30 g (0.11 mol) of the 2-butyryl-5-(4-ethylphenyl)-3-hydroxy-2-cyclohexen-1-one, obtained in accordance with the foregoing instructions, in 300 ml of methanol, and the solution is stirred overnight at room temperature. After con-centration, the residue is taken up in 300 ml of dichloromethane and washed twice with water, followed by drying over sodium sulfate and concentration.
~ 338985 14 O.Z. 0050/39798 Yield: 22 9 of a yellow solid (active ingredient no. 11 in the table below); m.p. 56 58C.
The compounds of the formula I given in the table below are characterized 5 by their melting point and/or 1H-NMR data. The 1H-NMR spectra were taken in deuterochloroform or hexadeuterosulfoxide as solvent, with tetramethyl-silane as internal standard. The chemical shifts were registered in ppm.
The multiplicities are given as follows: s = singlet, d = doublet, t =
triplet, q = quartet, m = multiplet.
_ _ I I
_ _ a~ . . . . .
r) ____ ___ __ ___ I I I I I I I -- I II I I
o ~ v ~ f7 v~ ~ V ~ V ~
O -- -- -- -- _ _ _ ~ _ _ _ _ _ ~ .... ... ~1~
O ~
____ ___ ____ ___ I I I II I II I I I I I I
V ~ V VV ~r ~n V ~ V v~ V V v~
____ ___ ____ ___ ___ ________ ___ I I T II I I I I I I I I I I
- - - - - - - - - - - -'O I I I I I I I I I ~: I I I I I
S ------_ ________ ___ O
~ ~ 0 0 0 0 0 0 0 ~/ _ 0~,~ ~0 o E ~ cr~
I I --~ ~ I I ~
`J E C ~
S ~ S S ~ ~ C--~L
O O
~ C~ Z
16 O.Z. 0050/39798 Use examples The action of the cyclohexenone derivatives of the formula I on plant growth is demonstrated by the following greenhouse experiments:
The vessels employed were plastic flowerpots having a volume of 300 cm3 and filled with a sandy loam containing about 3.0% humus. The seeds of the test plants were sown separately, according to species.
10 For the preemergence treatment, the active ingredients were applied to the surface of the soil immediately after the seeds had been sown. The com-pounds were emulsified or suspended in water as vehicle, and sprayed through finely distributing nozzles. The application rate was 0.5 kg of active ingredient per hectare. After the agents had been applied, the 15 vessels were lightly sprinkler-irrigated to induce germination and growth.
Transparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the active ingredients.
20 For the postemergence treatment, the plants were grown, depending on growth form, to a height of 3 to 15 cm before being treated. In this treatment method, either plants which had been sown in the pots and grown there were selected, or they were cultivated separately as seedlings and transplanted to the pots a few days before being treated. The application 25 rate for postemergence treatment was 0.125 kg/ha. No covers were placed on the vessels in this method.
The pots were set up in the greenhouse, species from warmer climates in warmer areas (20 to 35C) and species from moderate climates at 10 to 30 25C. The experiments were run for from 2 to 4 weeks. During this time the plants were tended and their reactions to the various treatments assessed.
The assessment scale was 0 to 100, 100 denoting nonemergence or complete destruction of at least the visible plant parts, and 0 denoting no damage or normal growth.
The plants used in the greenhouse experiments were Avena fatua, Alopecurus myosuroides, Digitaria sanguinalis, Echinochloa crus-galli, Lolium multi-florum, Medicago sativa, Triticum aestivum and Zea mays.
40 Active ingredients 3 and 11, on preemergence application of 0.5 kg/ha, have a strong herbicidal action on grassy plants; mustard, as an example of a broadleaved species, remains undamaged.
17 O.Z. 0050/39798 For combating grassy vegetation, examples nos. 2 and 3 are suitable at a postemergence application rate of 0.125 kg/ha. Broadleaved crops, such as alfalfa, are not damaged. The novel active ingredients have a selective herbicidal action.
Active ingredients 3 and 11 may be used postemergence for combating unwanted grassy species in wheat. The crop plants only suffer minor damage, if any at all.
Transparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the active ingredients.
20 For the postemergence treatment, the plants were grown, depending on growth form, to a height of 3 to 15 cm before being treated. In this treatment method, either plants which had been sown in the pots and grown there were selected, or they were cultivated separately as seedlings and transplanted to the pots a few days before being treated. The application 25 rate for postemergence treatment was 0.125 kg/ha. No covers were placed on the vessels in this method.
The pots were set up in the greenhouse, species from warmer climates in warmer areas (20 to 35C) and species from moderate climates at 10 to 30 25C. The experiments were run for from 2 to 4 weeks. During this time the plants were tended and their reactions to the various treatments assessed.
The assessment scale was 0 to 100, 100 denoting nonemergence or complete destruction of at least the visible plant parts, and 0 denoting no damage or normal growth.
The plants used in the greenhouse experiments were Avena fatua, Alopecurus myosuroides, Digitaria sanguinalis, Echinochloa crus-galli, Lolium multi-florum, Medicago sativa, Triticum aestivum and Zea mays.
40 Active ingredients 3 and 11, on preemergence application of 0.5 kg/ha, have a strong herbicidal action on grassy plants; mustard, as an example of a broadleaved species, remains undamaged.
17 O.Z. 0050/39798 For combating grassy vegetation, examples nos. 2 and 3 are suitable at a postemergence application rate of 0.125 kg/ha. Broadleaved crops, such as alfalfa, are not damaged. The novel active ingredients have a selective herbicidal action.
Active ingredients 3 and 11 may be used postemergence for combating unwanted grassy species in wheat. The crop plants only suffer minor damage, if any at all.
Claims (6)
1. A cyclohexenone compound of the formula (I):
where the substituents have the following meanings:
R1 is C3-C4-alkenyl, C3-C4-alkynyl, C2-C4-haloalkyl, C2-C4-halo-alkenyl, C2-C4-alkoxyalkyl or a radical CH2-R3, where:
R3 is a 5-membered heterocyclic ring with one to three nitrogen atoms and/or one to two oxygen atoms and/or one sulfur atom as hetero-atoms, which may bear up to two double bonds and one or two of the following substituents: C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, halogen, trifluoromethyl, C1-C4-alkoxy-methyl, C1-C4-alkoxymethyl, C1-C4-alkylthiomethyl and/or vinyl, or phenyl which may bear one to three of the following groups:
C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, halogen, trifluoromethyl, nitro and/or C1-C4-dialkylamino, and R2 is C1-C4-alkyl, and its agriculturally acceptable salts.
where the substituents have the following meanings:
R1 is C3-C4-alkenyl, C3-C4-alkynyl, C2-C4-haloalkyl, C2-C4-halo-alkenyl, C2-C4-alkoxyalkyl or a radical CH2-R3, where:
R3 is a 5-membered heterocyclic ring with one to three nitrogen atoms and/or one to two oxygen atoms and/or one sulfur atom as hetero-atoms, which may bear up to two double bonds and one or two of the following substituents: C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, halogen, trifluoromethyl, C1-C4-alkoxy-methyl, C1-C4-alkoxymethyl, C1-C4-alkylthiomethyl and/or vinyl, or phenyl which may bear one to three of the following groups:
C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkylthio, halogen, trifluoromethyl, nitro and/or C1-C4-dialkylamino, and R2 is C1-C4-alkyl, and its agriculturally acceptable salts.
2. A compound of the formula (I) as set forth in claim 1, wherein R1 is C3-C4-alkenyl or C2-C4-haloalkenyl.
3. The use of a cyclohexenone compound of the formula (I) as set forth in claim 1 or 2 as a herbicidal agent.
4. A herbicidal composition containing conven-tional additives and a cyclohexenone derivative of the formula (I) as set forth in claim 1 or 2.
5. A herbicidal composition as claimed in claim 4, further containing other herbicidal or growth-regulating active ingredients.
6. A process for combating the growth of unwanted plants, wherein the unwanted plants and/or their habitat are treated with a herbicidally effective amount of a cyclo-hexenone derivative of the formula (I) as set forth in claim 1 or 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3808072.9 | 1988-03-11 | ||
| DE3808072A DE3808072A1 (en) | 1988-03-11 | 1988-03-11 | CYCLOHEXENON COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF, AND THEIR USE FOR CONTROLLING UNWANTED PLANT GROWTH |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1338985C true CA1338985C (en) | 1997-03-11 |
Family
ID=6349442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000593380A Expired - Fee Related CA1338985C (en) | 1988-03-11 | 1989-03-10 | Cyclohexenone compounds, their preparation and their use for controlling undesirable plant growth |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0332076B1 (en) |
| JP (1) | JPH024752A (en) |
| CA (1) | CA1338985C (en) |
| DE (2) | DE3808072A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE59102689D1 (en) * | 1990-05-09 | 1994-10-06 | Basf Ag | Cyclohexenone oxime ether, process for their preparation and their use as herbicides. |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3047924A1 (en) * | 1980-12-19 | 1982-07-15 | Basf Ag, 6700 Ludwigshafen | 5-ARYL-CYCLOHEXAN-1,3-DION DERIVATIVES, HERBICIDES THAT CONTAIN THESE COMPOUNDS, AND METHOD FOR THE PRODUCTION THEREOF |
| US4432786A (en) * | 1982-05-10 | 1984-02-21 | Chevron Research Company | Thienylmethoxyiminoalkyl cyclohexanedione herbicides |
| GB2124198A (en) * | 1982-06-18 | 1984-02-15 | Ici Plc | Plant growth regulating method |
| JPS59155353A (en) * | 1983-02-23 | 1984-09-04 | Nippon Soda Co Ltd | Cyclohexenone derivative, its preparation and herbicide |
| DE3329017A1 (en) * | 1983-08-11 | 1985-02-28 | Basf Ag, 6700 Ludwigshafen | CYCLOHEXAN-1,3-DIONE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE FOR COMBATING UNWANTED PLANT GROWTH |
-
1988
- 1988-03-11 DE DE3808072A patent/DE3808072A1/en not_active Withdrawn
-
1989
- 1989-03-03 EP EP89103750A patent/EP0332076B1/en not_active Expired - Lifetime
- 1989-03-03 DE DE58908337T patent/DE58908337D1/en not_active Expired - Lifetime
- 1989-03-10 JP JP1056555A patent/JPH024752A/en active Pending
- 1989-03-10 CA CA000593380A patent/CA1338985C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0332076A3 (en) | 1990-12-05 |
| EP0332076B1 (en) | 1994-09-14 |
| DE58908337D1 (en) | 1994-10-20 |
| JPH024752A (en) | 1990-01-09 |
| DE3808072A1 (en) | 1989-09-21 |
| EP0332076A2 (en) | 1989-09-13 |
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