WO2011145329A1 - Agent réduisant les dommages chimiques pour herbicide, composition herbicide suscitant des dommages chimiques réduits, et procédé pour réduire les dommages chimiques sur les plantes cultivées - Google Patents

Agent réduisant les dommages chimiques pour herbicide, composition herbicide suscitant des dommages chimiques réduits, et procédé pour réduire les dommages chimiques sur les plantes cultivées Download PDF

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WO2011145329A1
WO2011145329A1 PCT/JP2011/002724 JP2011002724W WO2011145329A1 WO 2011145329 A1 WO2011145329 A1 WO 2011145329A1 JP 2011002724 W JP2011002724 W JP 2011002724W WO 2011145329 A1 WO2011145329 A1 WO 2011145329A1
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compounds
group
parts
compound
herbicide
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PCT/JP2011/002724
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English (en)
Japanese (ja)
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平岡学
高橋優樹
高橋亨
池内利祐
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クミアイ化学工業株式会社
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Priority to JP2012515752A priority Critical patent/JP5814233B2/ja
Publication of WO2011145329A1 publication Critical patent/WO2011145329A1/fr

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    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
    • 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
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/06—Oxygen or sulfur directly attached to a cycloaliphatic ring system
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing carboxylic groups or thio analogues thereof, directly attached by the carbon atom to a cycloaliphatic ring; Derivatives thereof
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • 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
    • 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
    • A01N43/86—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 six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof

Definitions

  • the present invention is a herbicide safener capable of reducing or preventing adverse effects and reducing environmental impact without using a plurality of different types of herbicidal active ingredients in combination, herbicide compositions with reduced medicinal damage, and harmful effects of crops. It relates to the mitigation method.
  • pyrimisulfan exhibits high herbicidal activity against low-dose annual weeds such as grasshoppers, eggplants, stalks, leeks and black-headed halibuts, perennial weeds such as pine bees, urikawa and omodaka, especially paddy weeds, It is known as having a broad herbicidal spectrum (see Patent Document 1).
  • herbicide safeners for enhancing the selectivity of herbicidally active compounds.
  • herbicide safeners that have been put into practical use include fenclolimus for preilacrole of chloroacetanilide compounds, chlorazole for fenoxaprop-ethyl of allyloxy compounds, and the like, and also safeners for safeners of sulfonylurea compounds.
  • a benzoyloxime ether compound see Patent Document 2 has also been proposed.
  • these safeners are used only for specific herbicidally active compounds, and can not be used widely and generally.
  • Patent Document 1 An attempt has been proposed to achieve both high herbicidal effect and safety for rice by using pyrimisulfan in combination with certain other herbicidally active compounds such as pretilachlor and butacrol.
  • Patent Document 1 At present, no technology has yet been established for achieving both high herbicidal effects and safety for rice without using multiple herbicidally active compounds in combination (see 3).
  • JP-A-2000-44546 (claims and others)
  • European Patent EP-A122 231 (claims and others)
  • JP-A-2000-281513 (claims and others)
  • the subject matter of the present invention is that, when the herbicidal active ingredient is simply applied, when it is simply applied, developmental disorders and growth inhibition of the target crop such as rice, etc. and symptoms of adverse effects such as suppression of division and transversal appear.
  • Herbicide safener that can reduce or prevent the harmful symptoms of the target crop without combining multiple herbicidal active ingredients of different types and without sacrificing the herbicidal effect It is an object of the present invention to provide a herbicidal composition having reduced medicinal damage and a method for reducing the harmful effect of a crop.
  • the present inventors have known sulfonylurea compounds, sulfonamide compounds, chloroacetanilide compounds, which are known herbicidally active compounds.
  • the present invention provides a herbicide safener, a herbicide composition with reduced medicinal damage, and a method for alleviating harmful damage to grasses particularly by the herbicide as follows.
  • the salt of the compound represented by the general formula (I) is an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an isopropyl ammonium salt, a trimethyl sulfonium salt, a salt with triethanolamine or a dimethyl distearyl ammonium salt.
  • (9) (A) the herbicide safener according to any one of the above (1) to (8); (B) Sulfonylurea compounds, sulfonamide compounds, chloroacetanilide compounds, thiocarbamate compounds, pyrimidinyloxy (thio) benzoic acid compounds, tetrazolinone compounds, triazole compounds, pyrazole compounds, cyclohexanedione compounds Or one or more herbicidally active compounds selected from phenoxycarboxylic acid compounds, oxazinone compounds, difluoromethanesulfonyl anilide compounds and isoxazoline compounds, or salts thereof, And a herbicidal composition having reduced medicinal damage characterized by containing
  • the sulfonylurea compound is preferably benzosulfuron methyl, pyrazosulfuron ethyl, halosulfuron methyl, azimsulfuron, cinosulfuron, cyclosulfamuron, flucetosulfuron, imazosulfuron, ethoxysulfuron or propylisulfuron (9)
  • the herbicidal composition with which the drug damage as described in was reduced.
  • the herbicide safener of the present invention and the herbicide composition for which herbicides have been reduced are useful for a wide range of herbicidally active compounds, and when they are simply applied, the growth disorders, growth suppression, and division control of target crops such as rice are suppressed. , Even if they cause adverse effects such as yellowing, they can reduce or prevent adverse effects of the target crop without sacrificing sufficient herbicidal effects, so reduce or prevent the adverse effects of the target crop. They are useful as herbicide safeners or herbicide compositions with reduced medicinal damage, in particular as rice safeners or paddy safeners or pesticide compositions.
  • the method of the present invention is a combined application of the safener of the present invention even at the application rate of a herbicidally active compound which causes adverse effects such as developmental disorders and growth suppression and yellowing of the target crop, especially rice. Since it can reduce or prevent adverse effects, it is useful as a method for reducing the adverse effects of a herbicidally active compound on crops.
  • R represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group
  • Group represents a C 1 to C 4 alkyl group such as t-butyl group or a hydroxycyclohexyl group
  • X represents a carboxyl group, a hydroxyl group, a carbamoyl group, a dimethylcarbamoyl group, a C 1 to C 4 alkoxycarbonyl group or a benzyloxycarbonyl group
  • Particularly preferable compounds are those in which X in the compound represented by the general formula (I) is bonded to the 4-position of the group containing R, and specifically, for example, 4-tert-butylcyclohexanecarboxylic acid in which R is methyl and X is carboxyl, 4-tert-butylcyclohexanol in which R is methyl and X is hydroxyl, and R is methyl and X is carbamoyl 4-tert-Butylcyclohexanecarboxamide, 4-tert-butyl-N, N-dimethylcyclohexanecarboxamide in which R is methyl and X is dimethylcarbamoyl, 4-tert- in which R is methyl and X is methoxycarbonyl Methyl butylcyclohexanecarboxylate, benzyl 4-tert-butylcyclohexanecarboxylate in which R is methyl and X is benzyloxycarbonyl,
  • the compound represented by the general formula (I), which is used as a main component in the herbicide safener of the present invention, may be a salt, particularly a salt which can be used as a component of the herbicide.
  • a salt which can be used as a component of the herbicide.
  • Specific examples thereof include alkali metal salts, alkaline earth metal salts, ammonium salts, isopropyl ammonium salts, trimethylsulfonium salts, salts with triethanolamine, and dimethyl distearyl ammonium salts.
  • the compounds represented by the general formula (I) used in the present invention also include geometric isomers (cis and trans) and a mixture of all proportions thereof.
  • calcium salt, triethanolamine salt or dimethyl distearyl ammonium salt is particularly preferable, and in this case, the above X is a carboxyl group.
  • R 1 represents a methyl group
  • X 1 represents a C 1 to C 4 alkoxycarbonyl group bonded to 4-position of a group containing R 1 , a benzyloxycarbonyl group, a carbamoyl group or dimethylcarbamoyl Represents a group.
  • R 2 represents a methyl group
  • X 2 represents a carboxyl group bonded to the 4-position of the group containing R.
  • the compounds represented by the above general formula (I) can be produced, for example, by the methods shown below, but are not limited to these methods.
  • Step 1 That is, the compound represented by the general formula (II) comprises the compound represented by the general formula (III) and a halogenating agent, an acid anhydride, an acid halide or a dehydration condensation agent in a solvent or in the absence of a solvent It can be produced by reacting.
  • the halogenating agent usable in this step is, for example, oxalyl chloride or thionyl chloride and the like
  • the acid anhydride is, for example, acetic anhydride or trifluoroacetic anhydride
  • the acid halide is, for example, acetyl chloride or propyl chloride, etc.
  • DCC dicyclohexyl carbodiimide
  • WSC N- (3-dimethylaminopropyl) -N'-ethyl carbodiimide
  • N, N-carbonyldiimidazole 2-chloro-1,3-dimethylimidazolium chloride Or 2-chloro-1-pyridinium iodide and the like.
  • the amount of the halogenating agent, the acid anhydride and the acid halide may be appropriately selected from the range of 0.01 to 20 moles, preferably 1 to 20 moles, per mole of the compound represented by the general formula (III). It is 10 moles.
  • the amount of the dehydrating condensing agent to be used may be appropriately selected from the range of 0.5 to 10 mol, preferably 1.0 to 1.2 mol, per 1 mol of the compound represented by the general formula (III) .
  • the solvent may be any solvent which does not inhibit the reaction, and examples thereof include halogen hydrocarbons such as dichloromethane and chloroform, ethers such as diethyl ether or tetrahydrofuran, and aromatic hydrocarbons such as benzene or toluene.
  • halogen hydrocarbons such as dichloromethane and chloroform
  • ethers such as diethyl ether or tetrahydrofuran
  • aromatic hydrocarbons such as benzene or toluene.
  • the amount of the solvent used is 0.01 to 100 L, preferably 0.1 to 10 L, per 1 mol of the compound represented by the general formula (III).
  • the reaction temperature may be selected from the range of -20.degree. C. to the boiling point range of the inert solvent used, preferably in the range of 0.degree. C. to 100.degree.
  • the reaction time varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually 10 minutes to 48 hours.
  • the compound represented by the general formula (II), which is the object of this reaction may be collected from the reaction system by a conventional method, and may be purified by an operation such as column chromatography or recrystallization as necessary it can.
  • Step 2 The compound represented by the general formula (II) is reacted with a C 1 to C 4 alcohol, benzyl alcohol, ammonia or dimethylamine in a solvent in the presence or absence of a base to obtain a compound represented by general formula (Ia) Can be produced.
  • the amount of C 1 -C 4 alcohol, benzyl alcohol, ammonia or dimethylamine used here is appropriately selected from the range of 0.5 to 10 moles with respect to 1 mole of the compound represented by the general formula (II)
  • the amount is preferably 1.0 to 1.2 moles.
  • Examples of the base that can be used in this step include organics such as triethylamine, pyridine, 4-dimethylaminopyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), etc.
  • organics such as triethylamine, pyridine, 4-dimethylaminopyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), etc.
  • metal carbonates such as sodium carbonate, potassium carbonate, magnesium carbonate and calcium carbonate
  • metal hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate
  • metal acetates such as sodium acetate, potassium acetate, calcium acetate and magnesium acetate
  • Metal carboxylates represented by the formula: metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tertiary butoxide, potassium methoxide and potassium tertiary butoxide; sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide
  • Metal hydroxides such as Um
  • lithium hydride, sodium hydride, potassium hydride, and metal hydrides such as calcium hydride.
  • the amount of the base used may be appropriately selected from the range of 0.5 to 10 moles, preferably 1.0 to 1.2 moles, per mole of the compound represented by the general formula (II).
  • the solvent which can be used in this step may be any solvent which does not inhibit the progress of the reaction, for example, nitriles such as acetonitrile; ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, monoglyme, diglyme, etc .; Halogenated hydrocarbons such as chloroform, carbon tetrachloride and tetrachloroethane; Aromatic hydrocarbons such as benzene, chlorobenzene, nitrobenzene and toluene; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide etc. 1 And imidazolinones such as 3-dimethyl-2-imidazolinone; sulfur compounds such as dimethyl sulfoxide and the like, and mixed solvents of these can also be used.
  • nitriles such as acetonitrile
  • ethers such as diethyl
  • the reaction temperature may be selected from the range of -20.degree. C. to the boiling point range of the inert solvent used, preferably in the range of 0.degree. C. to 100.degree.
  • a phase transfer catalyst such as quaternary ammonium salt may be used to react in a two-phase system.
  • the reaction time varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually 10 minutes to 48 hours.
  • the compound represented by the general formula (Ia), which is the object of the reaction can be collected from the reaction system by a conventional method, and can be purified by an operation such as column chromatography or recrystallization if necessary. .
  • the compound represented by the general formula (Ib) can be produced by reacting the compound represented by the general formula (III) with an alkylating agent in the presence of a base.
  • the amount of the alkylating agent used in this step may be appropriately selected from the range of 3.0 to 10.0 mol, preferably 3.0 to 10.0 mol, per 1 mol of the compound represented by the general formula (III). 6.0 moles.
  • the amount of the base used may be appropriately selected from the range of 3.0 to 10 moles, preferably 3.0 to 6.0 moles, per mole of the compound represented by the general formula (III).
  • alkylating agent such as dimethyl sulfuric acid and diethyl sulfuric acid; methyl iodide, ethyl iodide, benzyl chloride, benzyl bromide, propargyl bromide, halogenated alkyl such as bromoethyl acetate, chloroacetonitrile, etc.
  • dialkyl sulfuric acid such as dimethyl sulfuric acid and diethyl sulfuric acid
  • methyl iodide ethyl iodide
  • benzyl chloride methyl iodide
  • benzyl bromide benzyl chloride
  • propargyl bromide propargyl bromide
  • halogenated alkyl such as bromoethyl acetate, chloroacetonitrile, etc.
  • sulfonic acid esters such as ethoxyethyl p-toluenesulfonic acid and cyclopentyl me
  • the reaction temperature may be selected from the range of -20.degree. C. to the boiling point range of the inert solvent used, preferably in the range of 0.degree. C. to 100.degree.
  • the reaction time varies depending on the reaction temperature, the reaction substrate, the reaction amount and the like, but is usually 10 minutes to 48 hours.
  • the compound represented by the general formula (Ib), which is the object of the reaction can be collected from the reaction system by a conventional method, and can be purified by operations such as column chromatography and recrystallization as necessary. .
  • the compound represented by the general formula (Ic) can be produced by reacting the compound represented by the general formula (III) with a basic substance.
  • Examples of the basic substance that can be used in this reaction include sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia, isopropylamine, triethanolamine, trimethylsulfonium hydroxide and the like.
  • the amount of the basic substance used may be appropriately selected from the range of 1.0 to 10.0 mol, preferably 1.0 to 3.0 mol, per 1 mol of the compound represented by the general formula (III). It is.
  • the reaction can optionally be carried out using a solvent.
  • the solvent may be any solvent which does not inhibit the progress of the reaction, and alcohols such as methanol, ethanol, propanol or isopropanol, ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, dimethoxyethane or diethylene glycol dimethyl ether, benzene Aromatic hydrocarbons such as chlorobenzene, nitrobenzene or toluene, water and the like can be used, and these solvents can be used alone or in combination.
  • the reaction temperature is from -10 ° C to the boiling point range of the inert solvent used, preferably from 0 ° C to the boiling point of the inert solvent used.
  • the reaction time is not constant depending on the reaction temperature, reaction amount and the like, it may be generally selected from the range of 1 to 48 hours.
  • an alkaline earth is obtained by a salt exchange reaction between an alkali metal salt of a compound represented by the general formula (Ic) and a quaternary ammonium salt such as dimethyldistearyl ammonium chloride or an alkaline earth metal salt such as calcium chloride. It can also be converted to other salts such as metalloid salts and quaternary ammonium salts.
  • a quaternary ammonium salt such as dimethyldistearyl ammonium chloride or an alkaline earth metal salt such as calcium chloride. It can also be converted to other salts such as metalloid salts and quaternary ammonium salts.
  • the amount of quaternary ammonium salt or alkali metal salt to be used may be appropriately selected from the range of 1.0 to 10.0 mol per mol of the alkali metal salt of the compound represented by the general formula (Ic), preferably Is 1.0 to 3.0 moles.
  • the solvent that can be used in this salt exchange reaction, the reaction temperature and the reaction time are the same as in the above-mentioned Production Method 2.
  • the herbicidal composition of the present invention with reduced drug damage is: Component (A): Herbicide safener (B) containing the compound represented by the above general formula (I) as a main component: 1 or 2 or more of specific herbicidally active compounds It is a thing.
  • herbicidally active compound of the component (B) used in combination with the component (A) include, for example, clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl, diclohop-P.
  • Potassium salt (mecoprop-P), clopyralid, fupyrari Roxipyr (fluroxypyr), picloram (tricloram), triclopyr (triclopyr), triclopyr-buttol (triclopyr-butotyl), quinclorac (quinclorac), quinmerac (quinmerac), naptalam (including salts with sodium etc.), Diflufenzopyr, flamprop-M (including methyl, ethyl and isopropyl ester), flamprop (including methyl, ethyl and isopropyl ester), chlorflurenol (chlorflurenol- methyl), cinmethylin (cummethylin), cumylron (cumyluron), Immuron (daimuron), methyl dymuron (methyldymuron), diphenzocoat (diphenzoquat), etobenzanide (etobenzanid), fosamine (fosamine), pyributicarb (pyribut
  • Particularly preferable compounds as the herbicidally active compounds of the component (B) are for example, sulfonylurea compounds such as bensulfuron methyl, pyrazosulfuron ethyl, halosulfuron methyl, azimsulfuron, cinosulfuron, cyclosulfamuron, flucetosulfuron, imazosulfuron, ethoxysulfuron or propylisulfuron;
  • sulfonamide compounds such as penoxsulam
  • chloroacetanilide compounds such as butachlor, pretilachlor or tenicrol
  • thiocarbamate compounds such as thiobencarb, esprocarb or molinate
  • pyrimidinyloxy (thio) benzoic acid compounds such as pyriminobac methyl, pyriphthalide, bispyribac sodium or pyribenzoxime
  • Eg tetrazolinone compounds such as ben
  • fenoxasulfone ie 3- (2,5-dichloro-4-ethoxybenzylsulfonyl) -4,5-dehydro-5,5-dimethoxyisoxazole, is described in WO 01/012613.
  • pyroxasulfone that is, 3-[(5-difluoromethoxy-1-methyl-3-trifluoromethylpyrazol-4-yl) methylsulfonyl] -4,5-dihydro-5,5-dimethylisoxazole is It is described in WO 02/062770.
  • salts of the herbicidally active compounds for example, salts of alkali metals such as sodium or potassium; salts of alkaline earth metals such as calcium, magnesium or barium; salts of transition metals such as manganese, copper, zinc or iron Ammonium salts; salts with inorganic acids such as hydrochloric acid, hydrobromic acid, phosphoric acid or sulfuric acid; C 1 -C 4 alkyl sulfonic acids such as methanesulfonic acid; aromatic sulfonic acids such as benzenesulfonic acid or toluenesulfonic acid Mention may be made of salts with organic acids such as oxalic acid, maleic acid, fumaric acid, lactic acid, tartaric acid, adipic acid or benzoic acid.
  • organic acids such as oxalic acid, maleic acid, fumaric acid, lactic acid, tartaric acid, adipic acid or benzoic acid.
  • herbicidal composition of the present invention other herbicidally active compounds other than the above may be used in combination.
  • the use ratio of the component (A) to the component (B) can be appropriately varied depending on the types of both, the type and growth period of the target crop, for example, the transplanting period in rice etc.
  • the mass of the component (A) is usually 0.1 to 200 times the mass of the component (B).
  • the application amount of the component (A) is not particularly limited in the herbicidal composition of the present invention, it is usually 10 to 5000 g, preferably 50 to 3000 g, more preferably 100 to 2000 g, per hectare of farmland. It is chosen in the range of
  • the application amount of the component (B) is not particularly limited, but per hectare of farmland,
  • the amount of sulfonylurea compound is 1 to 200 g, preferably 5 to 100 g, 5 to 50 g, preferably 10 to 30 g, for sulfonamide compounds
  • For chloroacetanilide compounds 50 to 3000 g, preferably 100 to 2000 g
  • In the thiocarbamate compound 500 to 5000 g, preferably 1000 to 4000 g
  • pyrimidinyloxy (thio) benzoic acid compounds 5-500 g, preferably 10-200 g, 50 to 1000 g, preferably 100 to 500 g, for tetrazolinone compounds, 50 to 1000 g, preferably 100 to 500 g, for triazole compounds 100 to 5000 g, preferably 500 to 3000 g, for pyrazole compounds
  • For cyclohexanedione compounds 5-1000 g, preferably 10-500
  • the herbicidal composition of the present invention can contain, as required, additional components that are usually used in pesticide formulations.
  • Carriers such as solid carriers or liquid carriers, surfactants, binders, binders, tackifiers, thickeners, colorants, spreaders, spreading agents, antifreeze agents, anti-caking agents, and the like.
  • Disintegrants, antidegradants and the like can be mentioned.
  • preservatives, plant fragments and the like may be used as additive components. These additive components may be used alone or in combination of two or more.
  • Solid carriers include, for example, natural mineral substances such as quartz, clay, kaolinite, pyrophyllite, cericite, talc, bentonite, acid clay, attapulgite, zeolite, diatomaceous earth, etc .; inorganic substances such as calcium carbonate, ammonium sulfate, sodium sulfate, potassium chloride Salts; Organic solid carriers such as synthetic silicic acid, synthetic silicates, starch, cellulose, plant powder, etc. Plastic carriers such as polyethylene, polypropylene, polyvinylidene chloride, etc. may be mentioned.
  • liquid carrier examples include monohydric alcohols such as methanol, ethanol, propanol, isopropanol and butanol, and polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol and glycerin.
  • monohydric alcohols such as methanol, ethanol, propanol, isopropanol and butanol
  • polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol and glycerin.
  • Polyhydric alcohol compounds such as propylene glycol ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone and cyclohexanone; Ethyl ether, dioxane, ethylene glycol monoethyl ether, dipropyl ether, Ethers such as tetrahydrofuran; Aliphatic hydrocarbon waters such as normal paraffin, naphthene, isoparaffin, kerosene, mineral oil Aromatic hydrocarbons such as benzene, toluene, xylene, solvent naphtha and alkyl naphthalene; Halogenated hydrocarbons such as dichloroethane, chloroform and carbon tetrachloride; Ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, adipic acid Esters such as
  • surfactant for example, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene resin acid ester, polyoxyethylene fatty acid diester, polyoxyethylene alkyl ether, polyoxy acid Ethylene alkyl phenyl ether, polyoxyethylene dialkyl phenyl ether, polyoxyethylene alkyl phenyl ether formalin condensation product, polyoxyethylene polyoxypropylene block polymer, alkyl polyoxyethylene polypropylene block polymer ether, polyoxyethylene fatty acid amide, polyoxyethylene fatty acid Bis phenyl ether, polyalkylene benzyl phenyl ether, polyoxyalkyl Non-ionic surfactants such as styryl phenyl ether, acetylene diol, polyoxyalkylene addition acetylene diol, polyoxyethylene ether type silicone, ester type silicone, fluorinated surfact
  • binders and tackifiers for example, carboxymethylcellulose and its salts, dextrin, water-soluble starch, xanthan gum, guar gum, sucrose, polyvinyl pyrrolidone, gum arabic, polyvinyl alcohol, polyvinyl acetate, sodium polyacrylate, average molecular weight 6000
  • examples thereof include polyethylene glycol of ⁇ 20,000 and polyethylene oxide having an average molecular weight of 100,000 ⁇ 5,000,000, phospholipids (eg, cephalin, lecithin etc.) and the like.
  • thickeners examples include water-soluble polymers such as xanthan gum, guar gum, welan gum, carboxymethylcellulose, polyvinylpyrrolidone, carboxyvinyl polymers, acrylic polymers, starch compounds and water-soluble polysaccharides; high purity bentonite, fumed silica Inorganic fine powders such as (fumed silica, white carbon) and the like can be mentioned.
  • colorant examples include inorganic pigments such as iron oxide, titanium oxide and Prussian blue; organic dyes such as alizarin dye, azo dye and metal phthalocyanine dye.
  • silicone surfactant for example, silicone surfactant, cellulose powder, dextrin, modified starch, polyaminocarboxylic acid chelate compound, crosslinked polyvinyl pyrrolidone, copolymer of maleic acid and styrenes, (meth) acrylic acid copolymer And a half ester of a polymer comprising a polyhydric alcohol and a dicarboxylic acid anhydride, a water-soluble salt of polystyrene sulfonic acid, and the like.
  • the spreading agent for example, paraffin, terpene, polyamide resin, polyacrylate, polyoxyethylene, wax, polyvinyl alkyl ether, alkylphenol formalin condensate, synthetic resin emulsion and the like can be mentioned.
  • antifreezing agent examples include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and glycerin.
  • anti-caking agent examples include polysaccharides such as starch, alginic acid, mannose and galactose, polyvinyl pyrrolidone, fumed silica (fumed silica, white carbon), ester gum, petroleum resin and the like.
  • disintegrants include sodium tripolyphosphate, sodium hexametaphosphate, metal salts of stearic acid, cellulose powder, dextrin, copolymers of methacrylic acid ester type, polyvinyl pyrrolidone, polyamino carboxylic acid chelate compounds, sulfonated styrene, isobutylene, and maleic anhydride
  • disintegrants include sodium tripolyphosphate, sodium hexametaphosphate, metal salts of stearic acid, cellulose powder, dextrin, copolymers of methacrylic acid ester type, polyvinyl pyrrolidone, polyamino carboxylic acid chelate compounds, sulfonated styrene, isobutylene, and maleic anhydride
  • examples include acid copolymers, starch / polyacrylonitrile graft copolymers and the like.
  • decomposition inhibitor examples include zeolite, fresh lime, desiccant such as magnesium oxide, and ultraviolet absorbers such as salicylic acid type and benzophenone type.
  • preservative examples include potassium sorbate, 1,2-benzthiazolin-3-one and the like.
  • plant fragments examples include sawdust, coconut shell, corn cob, tobacco stem and the like.
  • the content ratio thereof is usually 5 to 95%, preferably 20 to 90% by weight on a carrier basis, and 0.1% to 20% on a surfactant. It is selected in the range of 30%, preferably 0.5 to 10%, and in the case of other additives 0.1 to 30%, preferably 0.5 to 10%.
  • the herbicide composition of the present invention may be any solution such as liquid, emulsion, wettable, powder, oil, water dispersible granule, flowable, milk suspension, granule, jumbo, suspoemulsion, microcapsule, etc. It is formulated and used in a dosage form. At the time of this formulation, a mixture composition with pesticides other than the component (B), for example, other herbicides, insecticides, fungicides, plant growth regulators, fertilizers and the like can also be used.
  • pesticides other than the component (B) for example, other herbicides, insecticides, fungicides, plant growth regulators, fertilizers and the like can also be used.
  • the herbicide composition of the present invention may be in the form of packaging any of the above-mentioned preparations in a water-soluble film, and application in this form contributes to labor saving and can enhance safety.
  • the herbicide composition of the present invention can be applied at any time from before weed development to the growing stage to co-express weed control and reduction of damage to the target crop. Is preferred because the application effect of the herbicide composition of the present invention is most remarkable.
  • the above-mentioned component (A) and component (B) may be applied simultaneously or in close proximity.
  • the proximity application means applying the component (A) while bringing the period from the application of the component (B) into proximity before the phytotoxicity of the target crop caused by the component (B) appears.
  • it can be applied in the form of ready mix, for example, the composition of the present invention which has been formulated in advance may be used, or the above components (A) and (B) may be separated. It can also be applied in the form of an on-site preparation which is prepared and mixed at the time of use, ie in the form of a tank mix.
  • the manufacturing method in particular of the herbicide composition of this invention is not restrict
  • (1) A method in which an appropriate amount of water is added to a mixture of all the raw materials, and the mixture is kneaded, and then extruded, granulated and dried from a screen with holes of a certain size.
  • (2) A method in which a safener, a herbicidally active compound and a surfactant are dissolved or suspended in an organic solvent and adsorbed on a carrier.
  • Examples 1 to 10 Hydroponic test Add various safeners, ie, component (A), to a 25% aqueous solution of Murashige-Skuog medium salt (made by Wako Pure Chemical Industries, Ltd.) to a concentration of 10 ppm, and further weed a predetermined amount
  • the active ingredient, component (B) was added. 50 mL of the solution was aliquoted into Erlenmeyer flasks to prepare various liquid media.
  • a liquid culture medium hereinafter referred to as "treatment-free culture medium" containing 50 mL of only a 25% aqueous solution of Murashige-Skoog culture medium salt was prepared.
  • an untreated area means the crop division which grew a crop by the said untreated culture medium.
  • Examples 11 to 34 Hydroponic test Add various safeners, ie component (A) to a concentration of 2.5 ppm to a 25% aqueous solution of Murashige-Skuog medium salt (Wako Pure Chemical Industries, Ltd.) and further add a predetermined amount The herbicidal active ingredient of (1) was added. 50 mL of the solution was aliquoted into Erlenmeyer flasks to prepare various liquid media. Also, in the same manner, a liquid culture medium (hereinafter referred to as "treatment-free culture medium”) containing 50 mL of only a 25% aqueous solution of Murashige-Skoog culture medium salt was prepared.
  • treatment-free culture medium containing 50 mL of only a 25% aqueous solution of Murashige-Skoog culture medium salt was prepared.
  • an untreated area means the crop division which grew a crop by the said untreated culture medium.
  • Examples 35 to 40 Pot test 2 parts of fenoxasulfone, 0.5 parts of pyrimisulfan, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 25 parts of bentonite and 70.5 parts of calcium carbonate were mixed with an appropriate amount of water and kneaded Thereafter, the mixture was extruded and granulated through a screen with an opening diameter of 1 mm using an extrusion granulator. The granules were dried by a fluid bed dryer at a product temperature of 70 ° C. and sieved to obtain granules containing fenoxasulfone and pyrimisulfan.
  • the rice (gold south wind) grown up to the 2-leaf stage with seedling growth soil was cut with the length of 1 cm left at the root. Root-cut rice was transplanted into a Wagner pot with an area of 1/5000 a filled with soil so that the depth of the stem and leaf base was 1 cm. The rice was poured into a transplanted Wagner pot and managed so that the depth from the water surface to the soil surface was 4 cm.
  • 20 mg of the herbicide containing the above-mentioned herbicide compound, ie component (B) is treated, and further after treatment with a prescribed amount of various safeners, ie, component (A) on the water surface , Grown rice in a greenhouse.
  • an untreated area means the crop division which grown the crop, without applying the granule containing the said (B) component, and also treating the (A) component.
  • part means “part by mass”.
  • Example 41 An appropriate amount of water is added to 2 parts of 4-tert-butylcyclohexanol, 2 parts of fenoxasulfone, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 25 parts of bentonite and 69 parts of calcium carbonate and kneaded. It extruded and granulated from the screen of 1 mm of opening diameters using the extrusion granulator. The granules were dried by a fluid bed dryer at a product temperature of 70 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanol and fenoxasulfone.
  • Example 42 An appropriate amount of water is added to 5 parts of 4-tert-butylcyclohexanecarboxylic acid, 2 parts of fenoxasulfone, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 25 parts of bentonite and 66 parts of calcium carbonate and then kneaded.
  • the mixture was extruded and granulated through a screen with an opening diameter of 1 mm using an extrusion granulator.
  • the granules were dried by a fluid bed dryer at a product temperature of 70 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanecarboxylic acid and fenoxasulfone.
  • Example 43 An appropriate amount of water is added to 10 parts of 2,2'-bis (4-hydroxycyclohexyl) propane, 2 parts of fenoxasulfone, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 25 parts of bentonite and 61 parts of calcium carbonate After addition and kneading, the mixture was extruded and granulated through a screen with an opening diameter of 1 mm using an extrusion granulator. The granules were dried by a fluid bed dryer at a product temperature of 70 ° C. and sieved to obtain granules containing 2,2′-bis (4-hydroxycyclohexyl) propane and fenoxasulfone.
  • Example 44 By mixing and grinding 10 parts of 4-tert-butylcyclohexanecarboxylic acid, 10 parts of fenoxasulfone, 5 parts of fumed silica (white carbon), 10 parts of alkylnaphthalene sulfonic acid sodium salt and 65 parts of clay using an impact crusher Thus, a wettable powder containing 4-tert-butylcyclohexanecarboxylic acid and fenoxasulfone was obtained.
  • Example 45 2 parts of 4-tert-butylcyclohexanecarboxylic acid, 4 parts of fenoxasulfone, 5 parts of polyoxyethylene styryl phenyl ether sulfate sodium salt, 10 parts of propylene glycol, 0.3 parts of xanthan gum and 78.7 parts of water with a wet grinder By mixing and grinding glass beads as a grinding medium, a flowable containing 4-tert-butylcyclohexanecarboxylic acid and fenoxasulfone was obtained.
  • Example 46 An appropriate amount of water is added to 8 parts of 4-tert-butylcyclohexanecarboxylic acid, 8 parts of fenoxasulfone, 3 parts of enzyme-modified dextrin, 3 parts of acetylene diol, 12 parts of water-containing plastic hollow beads, 20 parts of anhydrous sodium sulfate and 46 parts of urea After kneading and kneading, it was extruded and granulated through a screen with an opening diameter of 5 mm using an extrusion granulator. After being sized to a length of 3 to 20 mm, the product is dried by a fluid bed dryer at a product temperature of 60 ° C. and sieved to obtain a floating diffusion type granule containing 4-tert-butylcyclohexanecarboxylic acid and fenoxasulfone. Obtained.
  • Example 47 An appropriate amount of water is added to 5 parts of 4-tert-butylcyclohexanol, 2 parts of fenoxasulfone, 1 part of bensulfuron methyl, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 25 parts of bentonite and 65 parts of calcium carbonate After addition and kneading, the mixture was extruded and granulated through a screen with an opening diameter of 1 mm using an extrusion granulator. The granules were dried by a fluid bed dryer at a product temperature of 70 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanol, fenoxasulfone and bensulfuron methyl.
  • Example 48 An appropriate amount of water is added to 10 parts of 4-tert-butylcyclohexanol, 1 part of pyrimisulfan, 3 parts of pregelatinized starch, 1 part of sodium dodecylbenzene sulfonate and 85 parts of clay, and the mixture is kneaded using an extrusion granulator. It extruded and granulated from the screen of 1 mm of opening diameters. The mixture was dried by a fluid bed dryer at an article temperature of 60 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanol and pyrimisulfan.
  • Example 49 5 parts of 4-tert-butylcyclohexanecarboxylic acid, 2 parts of pyrimisulfan, 5 parts of polyoxyethylene styryl phenyl ether sulfate sodium salt, 10 parts of propylene glycol, 0.3 parts of xanthan gum and 77.7 parts of water by a wet grinder By mixing and grinding glass beads as a grinding medium, a flowable containing 4-tert-butylcyclohexanecarboxylic acid and pyrimisulfan was obtained.
  • Example 50 2 parts of 2,2'-bis (4-hydroxycyclohexyl) propane, 3 parts of pyrimisulfan, 3 parts of enzyme-modified dextrin, 3 parts of acetylene diol, 12 parts of water-containing plastic hollow beads, 20 parts of anhydrous sodium sulfate and 57 parts of urea An appropriate amount of water was added and the mixture was kneaded and then extruded and granulated through a screen with an opening diameter of 5 mm using an extrusion granulator. After being sized to a length of 3 to 20 mm, it is dried by a fluid bed dryer at an article temperature of 60 ° C. and sifted to give a suspension containing 2,2′-bis (4-hydroxycyclohexyl) propane and pyrimisulfan. A diffusion type granule was obtained.
  • Example 51 An appropriate amount of water was added to 10 parts of 4-tert-butylcyclohexanecarboxylic acid, 1 part of pyriminobac-methyl, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 25 parts of bentonite and 62 parts of calcium carbonate Thereafter, the mixture was extruded and granulated through a screen with an opening diameter of 1 mm using an extrusion granulator. The granules were dried by a fluid bed dryer at a product temperature of 70 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanecarboxylic acid and pyriminobacmethyl.
  • Example 52 10 parts of 4-tert-butylcyclohexanol, 2 parts of pyriminobac methyl, 3 parts of bensulfuron methyl, 3 parts of enzyme-modified dextrin, 3 parts of acetylene diol, 12 parts of water-containing plastic hollow beads, 20 parts of anhydrous sodium sulfate and 47 parts of urea
  • An appropriate amount of water was added to the mixture and the mixture was kneaded, and then extruded and granulated through a screen with an opening diameter of 5 mm using an extrusion granulator. After being sized to a length of 3 to 20 mm, the product is dried by a fluid bed dryer at a product temperature of 60 ° C. and sifted to give a floating diffusion containing 4-tert-butylcyclohexanol, pyriminovac methyl and bensulfuron methyl. A mold granule was obtained.
  • Example 53 5 parts of 2,2'-bis (4-hydroxycyclohexyl) propane, 5 parts of thiobencarb, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 5 parts of fumed silica (white carbon), 10 parts of diatomaceous earth, bentonite An appropriate amount of water was added to 25 parts and 48 parts of calcium carbonate and the mixture was kneaded, and then extruded and granulated through a screen with an opening diameter of 1 mm using an extrusion granulator. The mixture was dried by a fluid bed dryer at an article temperature of 50 ° C. and sieved to obtain granules containing 2,2′-bis (4-hydroxycyclohexyl) propane and thiobencarb.
  • Example 54 An appropriate amount of water is added to 10 parts of 4-tert-butylcyclohexanecarboxylic acid, 3 parts of fentrazamide, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 25 parts of bentonite and 60 parts of calcium carbonate and kneaded. It extruded and granulated from the screen of 1 mm of opening diameters using the granulator. The mixture was dried by a fluid bed dryer at a product temperature of 70 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanecarboxylic acid and fentrazamide.
  • Example 55 10 parts of 4-tert-butylcyclohexanecarboxylic acid, 1 part of oxadiclomephone, 5 parts of polyoxyethylene styryl phenyl ether sulfate sodium salt, 10 parts of propylene glycol, 0.3 parts of xanthan gum and 73.7 parts of water with a wet grinder The resulting beads were mixed and ground as a grinding medium to obtain a flowable containing 4-tert-butylcyclohexanecarboxylic acid and oxadiclomephone.
  • Example 56 5 parts of 4-tert-butylcyclohexanecarboxylic acid, 2 parts of cafenstrol, 4 parts of benzobicyclone, 5 parts of polyoxyethylene styryl phenyl ether sulfate sodium salt, 10 parts of propylene glycol, 0.3 parts of xanthan gum and 73.7 parts of water Using a wet grinder, glass beads were mixed and ground as a grinding medium to obtain a flowable agent containing 4-tert-butylcyclohexanecarboxylic acid, cafenstrol and benzobicyclone.
  • Example 57 5 parts of 4-tert-butylcyclohexanol, 5 parts of butachlor, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 5 parts of fumed silica (white carbon), 10 parts of diatomaceous earth, 25 parts of bentonite and calcium carbonate 48 An appropriate amount of water was added to the part and kneaded, and then extruded and granulated through a screen with an opening diameter of 1 mm using an extrusion granulator. The granules were dried by a fluid bed dryer at an article temperature of 50 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanol and butachlor.
  • Example 58 An appropriate amount of water is added to 20 parts of 4-tert-butylcyclohexanecarboxylic acid, 1 part of penoxsulam, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 25 parts of bentonite and 52 parts of calcium carbonate and kneaded. It extruded and granulated from the screen of 1 mm of opening diameters using the granulator. The granules were dried by a fluid bed dryer at a product temperature of 70 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanecarboxylic acid and penoxsulam.
  • Example 59 3 parts of 4-tert-butylcyclohexanecarboxylic acid, 1 part of oxadiclomephone, 3 parts of chromeprop, 5 parts of polyoxyethylene styryl phenyl ether sulfate sodium salt, 10 parts of propylene glycol, 0.3 parts of xanthan gum and 77.7 parts of water
  • the glass beads were mixed and ground using a grinding machine as a grinding medium to obtain a flowable containing 4-tert-butylcyclohexanecarboxylic acid, oxadiclomephone and chromeprop.
  • Example 60 An appropriate amount of water is added to 4 parts of 4-tert-butylcyclohexanecarboxylic acid, 8 parts of benzofenap, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 25 parts of bentonite and 61 parts of calcium carbonate and kneaded. The mixture was extruded and granulated through a screen with an opening diameter of 1 mm using an extrusion granulator. The granules were dried by a fluid bed dryer at an article temperature of 70 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanecarboxylic acid and benzophenap.
  • Example 61 An appropriate amount of water is added to 5 parts of 4-tert-butylcyclohexanecarboxamide, 2 parts of fenoxasulfone, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 25 parts of bentonite and 66 parts of calcium carbonate, and It extruded and granulated from the screen of 1 mm of opening diameters using the extrusion granulator. The mixture was dried by a fluid bed dryer at an article temperature of 70 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanecarboxamide and fenoxasulfone.
  • Example 62 By mixing and grinding 10 parts of 4-tert-butylcyclohexanecarboxamide, 10 parts of fenoxasulfone, 5 parts of fumed silica (white carbon), 10 parts of alkylnaphthalene sulfonic acid sodium salt and 65 parts of clay using an impact crusher, A wettable powder containing 4-tert-butylcyclohexanecarboxamide and fenoxasulfone was obtained.
  • Example 63 2 parts of 4-tert-butylcyclohexanecarboxamide, 4 parts of fenoxasulfone, 5 parts of polyoxyethylene styryl phenyl ether sulfate sodium salt, 10 parts of propylene glycol, 0.3 parts of xanthan gum and 78.7 parts of water by a wet crusher, The glass beads were mixed and ground as grinding media to obtain a flowable containing 4-tert-butylcyclohexanecarboxamide and fenoxasulfone.
  • Example 64 An appropriate amount of water is added to 8 parts of 4-tert-butylcyclohexanecarboxamide, 8 parts of fenoxasulfone, 3 parts of enzyme-modified dextrin, 3 parts of acetylene diol, 12 parts of water-containing plastic hollow beads, 20 parts of anhydrous sodium sulfate and 46 parts of urea After kneading, the mixture was extruded and granulated through a screen with an opening diameter of 5 mm using an extrusion granulator. The particles are sized to a length of 3 to 20 mm, dried at a product temperature of 60 ° C. by a fluid bed dryer, and sieved to obtain floating diffusion type granules containing 4-tert-butylcyclohexanecarboxamide and fenoxasulfone.
  • the particles are sized to a length of 3 to 20 mm, dried at a product temperature of 60 ° C. by a fluid bed dryer,
  • Example 65 An appropriate amount of water is added to 5 parts of 4-tert-butylcyclohexanecarboxamide, 2 parts of fenoxasulfone, 1 part of bensulfuron methyl, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 25 parts of bentonite and 65 parts of calcium carbonate After addition and kneading, the mixture was extruded and granulated through a screen with an opening diameter of 1 mm using an extrusion granulator. The granules were dried by a fluid bed dryer at a product temperature of 70 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanecarboxamide, fenoxasulfone and bensulfuron methyl.
  • Example 66 An appropriate amount of water is added to 10 parts of 4-tert-butylcyclohexanecarboxamide, 1 part of pyrimisulfan, 3 parts of pregelatinized starch, 1 part of sodium dodecylbenzene sulfonate and 85 parts of clay, and the mixture is kneaded using an extrusion granulator. It extruded and granulated from the screen of 1 mm of opening diameters. The mixture was dried by a fluid bed dryer at an article temperature of 60 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanecarboxamide and pyrimisulfan.
  • Example 67 5 parts of 4-tert-butylcyclohexanecarboxamide, 2 parts of pyrimisulfan, 5 parts of polyoxyethylene styryl phenyl ether sulfate sodium salt, 10 parts of propylene glycol, 0.3 parts of xanthan gum and 77.7 parts of water by a wet crusher, The glass beads were mixed and ground as a grinding medium to obtain a flowable containing 4-tert-butylcyclohexanecarboxamide and pyrimisulfan.
  • Example 68 An appropriate amount of water is added to 2 parts of 4-tert-butylcyclohexanecarboxamide, 3 parts of pyrimisulfan, 3 parts of enzyme-modified dextrin, 3 parts of acetylene diol, 12 parts of water-containing plastic hollow beads, 20 parts of anhydrous sodium sulfate and 57 parts of urea After kneading, the mixture was extruded and granulated through a screen with an opening diameter of 5 mm using an extrusion granulator.
  • the granules are sized to 3 to 20 mm in length, dried by a fluid bed dryer at an article temperature of 60 ° C., and sieved to obtain a floating diffusion type granule containing 4-tert-butylcyclohexanecarboxamide and pyrimisulfan.
  • Example 69 An appropriate amount of water is added to 10 parts of 4-tert-butylcyclohexanecarboxamide, 1 part of pyriminobac-methyl, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 25 parts of bentonite and 62 parts of calcium carbonate and kneaded The mixture was extruded and granulated through a screen with an opening diameter of 1 mm using an extrusion granulator. The mixture was dried by a fluid bed dryer at an article temperature of 70 ° C., and sieved to obtain granules containing 4-tert-butylcyclohexanecarboxamide and pyriminobac-methyl.
  • Example 70 10 parts of 4-tert-butylcyclohexanecarboxamide, 2 parts of pyriminobac methyl, 3 parts of benzosulfuron methyl, 3 parts of enzyme-modified dextrin, 3 parts of acetylene diol, 12 parts of water-containing plastic hollow beads, 20 parts of anhydrous sodium sulfate and 47 parts of urea An appropriate amount of water was added to the mixture and the mixture was kneaded, and then extruded and granulated through a screen with an opening diameter of 5 mm using an extrusion granulator.
  • the product After being sized to a length of 3 to 20 mm, the product is dried by a fluid bed dryer at a product temperature of 60 ° C., and sifting to give a floating diffusion containing 4-tert-butylcyclohexanecarboxamide, pyriminovac methyl and bensulfuron methyl. A mold granule was obtained.
  • Example 71 5 parts of 4-tert-butylcyclohexanecarboxamide, 5 parts of thiobencarb, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 5 parts of fumed silica (white carbon), 10 parts of diatomaceous earth, 25 parts of bentonite and calcium carbonate 48 An appropriate amount of water was added to the part and kneaded, and then extruded and granulated through a screen with an opening diameter of 1 mm using an extrusion granulator. The mixture was dried by a fluid bed dryer at an article temperature of 50 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanecarboxamide and thiobencarb.
  • Example 72 An appropriate amount of water is added to 10 parts of 4-tert-butylcyclohexanecarboxamide, 3 parts of fentrazamide, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 25 parts of bentonite and 60 parts of calcium carbonate and kneaded. Using a granulator, the mixture was extruded and granulated through a screen with an opening diameter of 1 mm. The mixture was dried by a fluid bed dryer at an article temperature of 70 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanecarboxamide and fentrazamide.
  • Example 73 Using 10 parts of 4-tert-butylcyclohexanecarboxamide, 1 part of oxadiclomephone, 5 parts of polyoxyethylene styryl phenyl ether sulfate sodium salt, 10 parts of propylene glycol, 0.3 parts of xanthan gum and 73.7 parts of water using a wet grinder The glass beads were mixed and ground as a grinding medium to obtain a flowable containing 4-tert-butylcyclohexanecarboxamide and oxadiclomephone.
  • Example 74 5 parts of 4-tert-butylcyclohexanecarboxamide, 2 parts of cafenstrol, 4 parts of benzobicyclon, 5 parts of polyoxyethylene styryl phenyl ether sulfate sodium salt, 10 parts of propylene glycol, 0.3 parts of xanthan gum and 73.7 parts of water
  • glass beads were mixed and ground as grinding media to obtain a flowable agent containing 4-tert-butylcyclohexanecarboxamide, cafentrol and benzobicyclone.
  • Example 75 5 parts of 4-tert-butylcyclohexanecarboxamide, 5 parts of butachlor, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 5 parts of fumed silica (white carbon), 10 parts of diatomaceous earth, 25 parts of bentonite and calcium carbonate 48
  • An appropriate amount of water was added to the part and kneaded, and then extruded and granulated through a screen with an opening diameter of 1 mm using an extrusion granulator.
  • the mixture was dried by a fluid bed dryer at an article temperature of 50 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanecarboxamide and butachlor.
  • Example 76 An appropriate amount of water is added to 20 parts of 4-tert-butylcyclohexanecarboxamide, 1 part of penoxsulam, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 25 parts of bentonite and 52 parts of calcium carbonate, and kneaded. Using a granulator, the mixture was extruded and granulated through a screen with an opening diameter of 1 mm. The mixture was dried by a fluid bed dryer at an article temperature of 70 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanecarboxamide and penoxsulam.
  • Example 77 3 parts of 4-tert-butylcyclohexanecarboxamide, 1 part of oxadiclomephone, 3 parts of chromeprop, 5 parts of polyoxyethylene styryl phenyl ether sulfate sodium salt, 10 parts of propylene glycol, 0.3 parts of xanthan gum and 77.7 parts of water
  • a flowable agent containing 4-tert-butylcyclohexanecarboxamide, oxadiclomephone and chromeprop was obtained by mixing and grinding glass beads as a grinding medium.
  • Example 78 An appropriate amount of water is added to 4 parts of 4-tert-butylcyclohexanecarboxamide, 8 parts of benzofenap, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 25 parts of bentonite and 61 parts of calcium carbonate, and It extruded and granulated from the screen of 1 mm of opening diameters using the extrusion granulator. The mixture was dried by a fluid bed dryer at an article temperature of 70 ° C. and sieved to obtain granules containing 4-tert-butylcyclohexanecarboxamide and benzophenap.
  • Example 79 Containing 4-tert-butylcyclohexanecarboxylic acid by mixing and grinding 10 parts of 4-tert-butylcyclohexanecarboxylic acid, 2 parts of alkylnaphthalenesulfonic acid sodium salt, 30 parts of diatomaceous earth and 58 parts of clay with an impact crusher We obtained a wettable powder. Separately, an appropriate amount of water is added to 2 parts of fenoxasulfone, 1 part of enzyme-modified dextrin, 1 part of dioctyl sulfosuccinate sodium salt, 25 parts of bentonite and 61 parts of calcium carbonate, and the mixture is kneaded using an extrusion granulator.
  • Example 80 The granules containing phenoxasulfone prepared in Example 79 are applied to paddy weeds, and after 3 days, the wettable powder containing 4-tert-butylcyclohexanecarboxylic acid prepared in Example 79 is converted to paddy weeds. I applied it.
  • Example 81 The wettable powder containing 4-tert-butylcyclohexanecarboxylic acid prepared in Example 79 is applied to paddy weeds, and after 7 days, the granules containing fenoxasulfone prepared in Example 79 are converted to paddy weeds. I applied it.
  • Example 82 Containing 4-tert-butylcyclohexanecarboxamide by mixing and grinding 10 parts of 4-tert-butylcyclohexanecarboxamide, 2 parts of alkylnaphthalenesulfonic acid sodium salt, 30 parts of diatomaceous earth and 58 parts of clay with an impact crusher We obtained a wettable powder.
  • Example 83 The flowable containing pyrimisulfan prepared in Example 82 was applied to paddy weeds, and after 5 days, the wettable powder containing 4-tert-butylcyclohexanecarboxamide prepared in Example 82 was applied to paddy weeds. .
  • Example 84 The wettable powder containing 4-tert-butylcyclohexanecarboxamide prepared in Example 82 was applied to paddy field weeds, and after 5 days, the flowable containing pyrimisulfan prepared in Example 82 was applied to paddy field weeds. .
  • Example 85 Preparation of methyl 4-tert-butylcyclohexanecarboxylate: To 160 mL of methanol under ice cooling, 1.8 g (22.7 mmol) of acetyl chloride was added and stirred for 10 minutes, then 5.36 g of 4-tert-butylcyclohexanecarboxylic acid (29. 1 mmol) was added and stirred at room temperature for 18 hours. The reaction solution was poured into water, extracted with diethyl ether, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine.
  • Example 86 Preparation of benzyl 4-tert-butylcyclohexanecarboxylate 4.0 g (21.7 mmol) of 4-tert-butylcyclohexane carboxylic acid was dissolved in 25 mL of N, N-dimethylformamide, 6.0 g (43.5 mmol) of potassium carbonate, 4.8 g (28.1 mmol) of benzyl bromide was added and stirred at room temperature for 20 hours. The reaction solution was poured into water, extracted with ethyl acetate, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine.
  • Example 87 Preparation of 4-tert-butylcyclohexanecarboxamide 10.0 g (54.3 mmol) of 4-tert-butylcyclohexanecarboxylic acid is dissolved in 50 mL of methylene chloride, a catalytic amount of N, N-dimethylformamide is added, and chloride is added under ice-cooling 20.7 g (163 mmol) of oxalyl was added dropwise and stirred at room temperature for 3 hours. The solvent was distilled off under reduced pressure, and the mixture was added dropwise to an excess of 30% aqueous ammonia under ice-cooling, and stirred at room temperature for 10 minutes. The solution was extracted four times with 30 mL of methylene chloride.
  • Example 88 Preparation of 4-tert-butyl-N, N-dimethylcyclohexanecarboxamide 1.0 g (5.4 mmol) of 4-tert-butylcyclohexanecarboxylic acid is dissolved in 10 mL of methylene chloride and a catalytic amount of N, N-dimethylformamide, chloride Add 2.1 g (16.5 mmol) of oxalyl and heat to reflux. After 3 hours, the mixture was added to an excess 40% aqueous solution of dimethylamine under ice-cooling and stirred at room temperature for 5 minutes. To this solution was added 100 mL of 0.5 M aqueous citric acid solution, and extracted four times with 20 mL of methylene chloride.
  • Example 89 Preparation of 4-tert-butylcyclohexanecarboxylic acid calcium salt 20 mL of distilled water is added to 5.0 g (27.2 mmol) of 4-tert-butylcyclohexanecarboxylic acid, and 4.0 g of 33% aqueous sodium hydroxide solution is added dropwise at room temperature Stir for 3 hours. To the reaction solution, 3.5 g of 50% aqueous solution of calcium chloride dihydrate was added dropwise, and 90 mL of distilled water was further added, and the mixture was stirred at room temperature for 30 minutes. The resulting precipitate was filtered and dried under reduced pressure until there was no weight change to obtain 6.0 g of calcium 4-tert-butylcyclohexanecarboxylate as colorless crystals.
  • Example 91 Preparation of 4-tert-butylcyclohexanecarboxylic acid dimethyl distearyl ammonium salt
  • 1.5 g (8.14 mmol) of 4-tert-butylcyclohexanecarboxylic acid is dissolved in 90 mL of tetrahydrofuran, and 3.6 mL of 10% aqueous sodium hydroxide solution is added, The mixture was stirred at 80 ° C. for 30 minutes. The reaction solution was cooled to room temperature, 4.77 g (8.14 mmol) of dimethyl distearyl ammonium chloride was added, and the mixture was stirred at 80 ° C. for 2 hours and then at room temperature for 12 hours.

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Abstract

L'invention concerne un agent réduisant les dommages chimiques pour herbicide, qui est capable de réduire ou de prévenir les dommages chimiques et de réduire la charge pour l'environnement sans utiliser une pluralité de différents ingrédients à activité herbicide en combinaison ; une composition herbicide qui suscite des dommages chimiques réduits, et un procédé pour réduire les dommages chimiques sur une plante cultivée. L'invention concerne spécifiquement un agent réduisant les dommages chimiques pour herbicide, qui se caractérise en ce qu'il contient un composé représenté par la formule générale (I) (dans laquelle R représente un groupe alkyle en C1-C4 ou un groupe hydroxycyclohexyle, et X représente un groupe carboxyle, un groupe hydroxyle, un groupe carbamoyle, un groupe diméthylcarbamoyle, un groupe (alcoxy en C1-C4)carbonyle ou un groupe benzyloxycarbonyle) ou l'un de ses sels comme composant principal. L'invention concerne également spécifiquement une composition herbicide qui suscite des dommages chimiques réduits, qui se caractérise en ce qu'elle contient l'agent réduisant les dommages chimiques décrit ci-dessus pour herbicide et un ou plusieurs composés à activité herbicide spécifiques.
PCT/JP2011/002724 2010-05-18 2011-05-17 Agent réduisant les dommages chimiques pour herbicide, composition herbicide suscitant des dommages chimiques réduits, et procédé pour réduire les dommages chimiques sur les plantes cultivées WO2011145329A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015511488A (ja) * 2012-03-12 2015-04-20 ヤマト農磁株式会社 田植機搭載型液剤散布装置、およびそれを用いる田植え同時液剤散布方法（関連出願の相互参照）本出願は、２０１２年３月１２日に出願された「ｒｉｃｅｔｒａｎｓｐｌａｎｔｅｒ−ｍｏｕｎｔｅｄｌｉｑｕｉｄｒｅａｇｅｎｔａｐｐｌｉｃａｔｉｏｎｄｅｖｉｃｅ」と題する先行中国特許出願第ｃｎ２０１２１００６４１１７．７号に基づいて前記特許出願からの優先権の恩典を主張するものであり、前記出願のすべての内容を本願明細書の内容に組み込むものとする。

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB703516A (en) * 1950-12-26 1954-02-03 Bataafsche Petroleum Tertiary alkyl cyclohexane carboxylic acids and salts thereof
JPH10298144A (ja) * 1997-04-23 1998-11-10 T Hasegawa Co Ltd トランス−４−アルキルシクロヘキサンカルボン酸エステル類の製法
WO2007091502A1 (fr) * 2006-02-08 2007-08-16 Kumiai Chemical Industry Co., Ltd. Agent de contrôle de la phytotoxicité pour l'agriculture de montagne et procédé de contrôle de la phytotoxicité utilisant celui-ci
JP2010163420A (ja) * 2008-08-29 2010-07-29 Zenkoku Nogyo Kyodo Kumiai Rengokai 除草剤組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB703516A (en) * 1950-12-26 1954-02-03 Bataafsche Petroleum Tertiary alkyl cyclohexane carboxylic acids and salts thereof
JPH10298144A (ja) * 1997-04-23 1998-11-10 T Hasegawa Co Ltd トランス−４−アルキルシクロヘキサンカルボン酸エステル類の製法
WO2007091502A1 (fr) * 2006-02-08 2007-08-16 Kumiai Chemical Industry Co., Ltd. Agent de contrôle de la phytotoxicité pour l'agriculture de montagne et procédé de contrôle de la phytotoxicité utilisant celui-ci
JP2010163420A (ja) * 2008-08-29 2010-07-29 Zenkoku Nogyo Kyodo Kumiai Rengokai 除草剤組成物

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Title
BRUCE R. ET AL.: "alpha-Carbon Isomerization in Amide Dehydrations", J. ORG. CHEM., vol. 27, 1962, pages 4608 - 4610 *
SHIBUYA INDEX, 2009, pages 248 - 249 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015511488A (ja) * 2012-03-12 2015-04-20 ヤマト農磁株式会社 田植機搭載型液剤散布装置、およびそれを用いる田植え同時液剤散布方法（関連出願の相互参照）本出願は、２０１２年３月１２日に出願された「ｒｉｃｅｔｒａｎｓｐｌａｎｔｅｒ−ｍｏｕｎｔｅｄｌｉｑｕｉｄｒｅａｇｅｎｔａｐｐｌｉｃａｔｉｏｎｄｅｖｉｃｅ」と題する先行中国特許出願第ｃｎ２０１２１００６４１１７．７号に基づいて前記特許出願からの優先権の恩典を主張するものであり、前記出願のすべての内容を本願明細書の内容に組み込むものとする。

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