WO1997045404A1 - Derives de cyclohexanedione et compositions herbicides - Google Patents

Derives de cyclohexanedione et compositions herbicides Download PDF

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Publication number
WO1997045404A1
WO1997045404A1 PCT/JP1997/001857 JP9701857W WO9745404A1 WO 1997045404 A1 WO1997045404 A1 WO 1997045404A1 JP 9701857 W JP9701857 W JP 9701857W WO 9745404 A1 WO9745404 A1 WO 9745404A1
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formula
group
derivative
general formula
cyclohexanedione
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PCT/JP1997/001857
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English (en)
Japanese (ja)
Inventor
Ken Morita
Toshiharu Ohno
Takurou Shimozono
Yoshihisa Watanabe
Hirokazu Yoshizawa
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Hokko Chemical Industry Co., Ltd.
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Priority to AU29773/97A priority Critical patent/AU2977397A/en
Publication of WO1997045404A1 publication Critical patent/WO1997045404A1/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
    • 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
    • A01N35/06—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 containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides
    • 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
    • A01N43/08—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 oxygen 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C317/18—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/12—Radicals substituted by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D309/06—Radicals substituted by oxygen atoms

Definitions

  • the present invention relates to a novel hexagonal hexandione derivative and a herbicidal composition containing the novel hexagonal hexandione derivative as an active ingredient.
  • the present invention also includes a method for herbicidal use using the cyclohexandione derivative. Therefore, the present invention is useful in the chemical industry and agriculture, particularly in the field of agrochemical manufacturing.
  • novel hexagonal hexanedione derivative provided by the present invention is similar in chemical structure to known hexagonal hexanediones including seven groups of hexagonal hexanedione derivatives of the following (1) to (6). It is known that any of the following known cyclohexanedione derivatives has herbicidal activity.
  • R represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a lower alkoxy lower alkyl group or a lower anoalkylthio lower anoalkyl group
  • R, R 2 are each a hydrogen atom or a lower alkyl group.
  • X is a chlorine atom Or a bromine atom) (see Japanese Patent Application Laid-Open No. Hei 62-47991).
  • R i, R 2 and R 3 each represent a hydrogen atom or a lower alkyl group
  • X represents a chlorine atom or a bromine atom
  • Y represents an oxygen atom or A sulfur atom
  • Z represents a lower alkylene group which may be substituted with a lower alkyl group
  • m represents an integer of 1 or 2
  • R represents a chlorine atom or a bromine atom
  • R t, R 2 , and R 3 each represent a hydrogen atom or a C> -C 4 alkyl group
  • R 4 represents a hydroxyl group or a hydrogen atom.
  • other shows the C 1 ⁇ C 4 a Ruki group, have Ru Oh is R, all of the R 2, R s your good beauty R 6 is C:!
  • R 3 and R 4 jointly represents one carboxy group
  • R 5 represents a hydrogen atom or a CI-alkyl group
  • R 6 represents a hydrogen atom, a C t -C 4 alkyl group, a C,- Represents a C 4 alkylthio group or a C, to C 4 alkyl sulfonyl group
  • R 7 represents a methyl group or an ethyl group
  • R ⁇ represents a halogen atom, a nitro group, etc.
  • X represents an oxygen atom or a sulfur atom, or a salt thereof (Japanese Unexamined Patent Application Publication No. PCTUS 89/05056, published in Japan) No. 17 26). 5 General formula (e)
  • R, R 2 and Ra each represent a hydrogen atom or a C ⁇ to C 4 alkyl group, and a hydroxyl group, a hydrogen atom or a C! To C 4 alkyl group.
  • R 5 represents a hydrogen atom or a C 4 to C 4 alkyl group
  • R 6 represents a hydrogen atom or Represents a C, -C alkyl group, etc.
  • R 7 represents a methyl group or an ethyl group
  • R 8 represents a nitrogen atom, a nitro group, etc.
  • R t is ⁇ ! ⁇ .
  • C Nono b alkyl-and main bets Kishechiru group or indicates et preparative key Shechiru group
  • R 7 - R i 2 Each Represents a hydrogen atom or a C 4 to C 4 alkyl group, and Q represents a halogen atom or a ditoro group (US Pat. No. 5,110,979) No.).
  • R indicates etc. halo gen atom, R t, R 2, R 3, R, and R 5, R 6 are each was or hydrogen atom of the C i to C 2 ⁇ Le Kill group
  • R 7 and R 8 each represent a halogen atom, a methoxethyl group, a methoxethyl group, or the like.
  • An object of the present invention is to replace the above-mentioned known compounds, have excellent herbicidal activity, but exhibit low phytotoxicity to crops and are safe and have excellent selectivity.
  • another object of the present invention is to provide the above-mentioned novel high-opening hexandione derivative which is useful for controlling major weeds generated in flooded sewage fields of rice and various crop fields.
  • An object of the present invention is to provide a herbicide composition for paddy rice and field crops, which is contained as an active ingredient.
  • the present inventors have synthesized a large number of cyclohexanedione derivatives to achieve the above-mentioned object, and have studied the herbicidal activity and usefulness of the synthesized cyclohexandione derivatives.
  • a novel cyclohexandione derivative represented by the following general formula (I) is obtained from rice and rice. And can show excellent herbicidal effects at low application rates on major weeds, especially on paddy fields, at the cultivation sites of various field crops, and do not harm the crops.
  • We studied diligently As a result, a novel cyclohexandione derivative represented by the following general formula (I) is obtained from rice and rice. And can show excellent herbicidal effects at low application rates on major weeds, especially on paddy fields, at the cultivation sites of various field crops, and do not harm the crops.
  • X represents a hydrogen atom or a halogen atom
  • Y represents a formula S ( ⁇ ) m —
  • R represents a lower alkyl group or a lower alkenyl group, provided that when R is a lower alkyl group, m is an integer of 0, 1 or 2, and R is M is zero in the case of a lower alkenyl group) or Y is a group of the formula
  • the lower alkyl group as R is a carbon atom. It is an alkyl group of 1 to 6 and may be linear or branched. So Examples of the lower alkyl group R include a methyl group, an ethyl group, an n-propynole group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-group.
  • R is a lower alkenyl group, it is an alkenyl group having 2 to 6 carbon atoms, and may be linear or branched.
  • the lower alkenyl group R include, for example, a vinyl group, a 1-probenyl group, an allyl group, a 1-methylvinyl group, and a 2-methylaryl group. Group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-pentenyl group, 2-hexenyl group and the like.
  • substituent Y in the compound of the general formula (I) is represented by the following formula: CH 2 ) n (Where n represents 0 or 1), and the alicyclic group is tetrahydro when n is zero. It represents a fran-2-inole group and a tetrahydropyran-2-inole group when n is 1;
  • X represents The offspring is preferably chlorine or bromine, such as chlorine, bromine, iodine or fluorine.
  • the first novel cyclohexanedione derivative of the general formula (I) includes the following four types of compounds of the types (A), (B), (C) and (D). I do.
  • X represents a chlorine, bromine, iodine, or fluorine atom
  • R ′ represents a linear or branched (C t to C 6 ) alkyl group.
  • X represents a chlorine, bromine, iodine or fluorine atom
  • R ′ represents a linear or branched (C, to C 6 ) alkyl group
  • X represents a chlorine, bromine, iodine, or fluorine atom
  • R b represents a linear or branched (C 2 -C 6 ) alkenyl group.
  • X represents chlorine. Bromine, iodine, or fluorine atom
  • n is 0 or 1 representing a tetrahydrofuran-2-inole group or a tetrahydropyran-2-inole group.
  • a hexandione derivative (Wherein n is 0 or 1) representing a tetrahydrofuran-2-inole group or a tetrahydropyran-2-inole group.
  • Preferred examples of the derivatives of the above general formula (la) include 2- (2 ′, 4′-dichloro mouth-3 ′-(methylthiome-tyloxy) benzoinole) -1,3-cyclohexanedione, 2 -[2 ', 4'-dibromo-3'-(methylthiomethioloxy) benzoinole]-1,3 -cyclohexanedione, 2-[2 ', 4''-(Ethylthiomethylooxy) benzoinole]-1,3-Cyclohexandione and 2- [2', 4'-Dibromo-3 '-(Ethynolethiomethioloxy) benzoinole] - It is a 1,3-six-hexoxedion.
  • Preferred examples of the derivatives of the above general formula (lb) are 2-(2 ', 4'-dichloro mouth-3 '-(methinoles norefino ninore metinoreoxy) benzo zore)-1 , 3-cyclohexandion, 2-[2 ', 4'-dibromo-3 '-(methyl benzene) -1, 3 -cyclohexandion, 2-(2 ', 4'-dichloro mouth-3 '-(methinoles) , 3 -Chick mouth Hexandion and 2-(2 ', 4'-Gibro- 3'-(Metinoresinorefininore Mechinorereshi) Benzoinore)- 1,3-six-hexoxedion.
  • Preferred examples of the derivative of the above general formula (Ic) include 2- (2 ′, 4′-cyclo mouth—3 ′-(arinolethiome methyloxy) benzoin) -1. 3-six mouth hexandion and 2-[2 ', 4'-dibromo-3 '— ( ⁇ ⁇ ⁇ ⁇ ⁇ ) Cyclohexandione.
  • Preferred examples of the derivative of the above general formula (Id) include 2- (2 ', 4'-dichloro mouth—3' — (tetrahydropyran-2—inole-methinoleoki). Benzoyl)]-1, 3 -six hexandion and 2-[2 ', 4' -jibromo-3 '-(tetrahydropyran -2yl-methinoreoxy) benzoinole] — 1,3-six-hexandione.
  • Table 1 shows typical specific examples of the derivative of the general formula (I) of the present invention.
  • the compound No. 0 shown in Table 1 is also referred to in the following Examples and Test Examples.
  • [Table 1] General formula (I)
  • All the compounds of the general formula (I) according to the first invention are new compounds.
  • the compound of the general formula (I) acts as an active ingredient effective for controlling various weeds generated in paddy fields and upland fields.
  • X represents a halogen atom
  • Y represents a group represented by the formula: s (o-R (where R represents a lower alkyl group or a lower alkenyl group, provided that R represents a lower alkyl group.
  • M is 0 if Is an integer of 1 or 2, and when R is a lower alkenyl group, m is zero), or Y is a group of the formula
  • a hexoxanedione derivative represented by the formula: is contained as an active ingredient together with a solid or liquid carrier.
  • a herbicidal composition characterized by the following is provided.
  • the substituent Y of the cyclohexanedione derivative represented by the general formula (I) is a lower alkylthio group, a lower alkenylthio group, a tetrahydrofuran-2-inole group or a tetrahydropropyl group.
  • a ran-2-yl group that is, when the derivative is a derivative represented by the above general formula (la), (Ic) or (Id), it is used as a starting material.
  • equation (II) is a lower alkylthio group, a lower alkenylthio group, a tetrahydrofuran-2-inole group or a tetrahydropropyl group.
  • X represents a halogen atom
  • Y ′ represents a lower alkylthio group, a lower alkenylthio group, a tetrahydrofuran-2-yl group or a tetraethyl group.
  • DCC dicyclohexyl-positive imide
  • the first step of reacting the compound of the formula (II) with the compound of the formula (III) to produce the compound of the formula (IV) uses an equivalent amount of each of the reaction components.
  • DCC dicyclohexylcarbodiimide
  • the reaction is carried out in a suitable organic solvent in the presence of pyridine.
  • the reaction temperature is suitably in the range of 0 to 50 ° C, and the reaction mixture is stirred until the reaction is substantially completed.
  • organic solvent examples include hydrocarbons such as benzene and toluene, and halogenated hydrocarbons such as chlorohonolem and dichloromethane, getyl ether, and tetrahydrofuran. It is possible to use ethers such as lan, ketones such as acetone, trilinoles such as acetonitrile, and esterenoles such as ethyl acetate. . Preferably, use ethyl acetate.
  • the hexahedral hexyl precipitated from the reaction solution The urea is removed by filtration, and the resulting filtrate containing the quinol ester compound of the formula (IV) is subjected to usual post-treatment such as concentration. If necessary, the phenol ester compound of the formula (IV) can be purified by a procedure such as chromatography.
  • a second step of subjecting the intermediate phenol ester compound of the formula (IV) to a rearrangement reaction is performed.
  • This step is carried out in the presence of an excess (preferably about 2 equivalents) of base and a catalytic amount (preferably 0.01 to 0.1 equivalents) of a cyanide source in the presence of a suitable solvent.
  • the middle enol ester compound is subjected to a rearrangement reaction.
  • the reaction temperature is a temperature close to the boiling point of the solvent, preferably in the range of 2 ° C to 40 ° C, and the reaction mixture is stirred until the rearrangement is substantially completed.
  • the base include organic salts such as triethylamine, triethanolamine, pyridin, and the like, or potassium carbonate and trinatium lime.
  • An inorganic base such as a space can be used.
  • the cyanide sources include cyanide sodium, cyanide force rim, and other cyanide force cyanide, acetate cyanohydridite, and the like.
  • Methylalkylketon cyanohydrin such as methylisobutylbutylketoncyanohydrin, or benzanoledehydrocyanohydrin, acetoaldehyde cyanohydrin Lindane, aldehydrocyanohydrin, such as drin, propionylanodehydrinohydrin, and zinc cyanide, trimethylsilyl Li Lucia Nai Can be used.
  • the solvent examples include hydrocarbons such as benzene, toluene, xylene, and the like, such as chloroform, dichloromethane, 1,2-dichloroethane, and chlorophenol.
  • Ethers such as hydrogenated hydrocarbons, getyl ether, tetrahydrofuran, and dioxane; ketones such as acetone and methylethyl ketone; and acetonitrile , Ethyl ester, dimethylformamide, etc. can be used.
  • the solvent is distilled off from the reaction solution under reduced pressure, and the target compound of the above formula (I ′) is collected. If desired, the desired compound can be purified by chromatographic or recrystallization operations.
  • the substituent Y of the cyclohexanedione derivative of the general formula (I) is a lower alkylsulfonyl group or a lower alkylsulfinyl group, that is, the derivative is represented by the above general formula (lb) If the derivative is
  • the first step of the second method can be performed in exactly the same manner as the first step of the first method.
  • reaction temperature is usually from 0 ° C to a temperature close to the boiling point of the solvent, preferably from 20 to 40 ° C.
  • the reaction mixture is stirred until the oxidation is substantially complete.
  • an inorganic oxidizing agent such as aqueous hydrogen peroxide or permanganic acid, or an organic oxidizing agent such as peracetic acid, perbenzoic acid, or 3-benzo-peroxybenzoic acid
  • an organic oxidizing agent such as peracetic acid, perbenzoic acid, or 3-benzo-peroxybenzoic acid
  • it is 3-cycloperoxybenzoic acid
  • the solvent include organic acids such as acetic acid, ketones such as acetone and methylethylketone, and nitrogenated hydrocarbons such as chlorophonolem and dichloromethane.
  • it is a mouth-to-mouth holm You.
  • the solution containing the resulting sulfinylated or snorefonylated enol ester compound of the formula (IV ⁇ ) is subjected to a usual post-treatment such as concentration, for the purpose. Collect things. If necessary, the enol ester compound of the formula (IV) can be purified by a procedure such as chromatography or recrystallization.
  • the third step of the second method is a step of subjecting a compound of the formula (IV ⁇ ) to a rearrangement reaction in the presence of a catalyst of a cyanide source to produce a cyclohexanedione derivative of the formula (lb).
  • This step can be performed in exactly the same manner as the second step of the first method.
  • the solvent is distilled off from the reaction solution under reduced pressure to collect a target compound of the formula (lb). If desired, the desired compound can be purified by chromatographic or recrystallization procedures.
  • Examples of the production of the compound of the formula (la) or the formula (Id) by the first method comprising the above two steps are shown in Examples 1 and 2 below.
  • Examples of the production of the compound of the formula (lb) by the second method consisting of the above three steps are shown in Examples 3 and 4 below.
  • the cyclohexanedione of the formula (II), which is a starting material, is a known one.
  • the starting material of the general formula (III) is a novel compound and can be synthesized by a known method. Examples of the production are shown in Reference Production Examples 1 and 2 below.
  • This enolester is 1- [2 ', 4'-dibromo-3'-(methylthiomethyl benzoyl) benzoin] oxy-six-hex hex-3-one .
  • reaction solution was washed with 100 ml of a 2% aqueous solution of sodium hydrogencarbonate, and the mouth layer was dried with anhydrous sodium sulfate.
  • the solvent was distilled off from the dried crotch-form layer under reduced pressure to give 1- [2 ',-jib-mo-3'-(methyl selenoninole methinoleoxy) benzene as white crystals. 3.0 g (94% yield, melting point 133-134 ° C) of hexen-3-one hexen-3-one were obtained.
  • ester (3.lg) was stirred for 2 hours at 50 ° C for 2 hours with a solution consisting of a mixture of 0.5g of sodium hydroxide, 15rol of water and 50ml of methanol. . Thereafter, 50 ml of water was added, and neutral sections were removed with 50 ml of toluene. Ethyl acetate (80 ml) was added to the aqueous layer, and the mixture was acidified with 1N hydrochloric acid and extracted.
  • a herbicidal composition is formulated by using the compound of the present invention of the general formula (I) as an active ingredient of a herbicide, a solid carrier, a liquid carrier, a surfactant, and other auxiliary agents for the formulation are usually used. And the appropriate formulation such as emulsions, wettable powders, liquid preparations, fluids (sol), powders, driftless preparations, granules, fine granules, tablets, etc.
  • a herbicidal composition can be prepared.
  • any carrier that is commonly used for agricultural and horticultural agents can be used, either solid or liquid, and is not limited to a specific one. Absent.
  • these carriers include mineral powders (kaolin, bentonite, cres, monmorillonite, talc, diatomaceous earth, mica, vermicelli , Quartz, calcium carbonate, phosphorus Limestone, white carbon, slaked lime, silica sand, ammonium sulfate, urea, etc.), vegetable powder (soybean flour, flour, wood flour, tobacco flour, starch, crystalline cellulose, etc.), High-molecular compounds (such as petroleum resin, polyvinyl chloride, ketone resin, and dammar gum) Examples include alumina, silicates, glycopolymers, highly-dispersible cake acids, and boxes. Can be
  • liquid carrier examples include water and alcohols (methyl alcohol, alcohol, alcohol, n-propanol, alcohol, isopro).
  • a herbicidal composition When a herbicidal composition is formulated in the form of an emulsion, a wettable powder, a flowable, or the like, various formulations for emulsification, dispersion, solubilization, moistening, foaming, lubrication, spreading, etc.
  • surfactants or emulsifiers
  • examples of such surfactants include non-ionic surfactants (polyoxyethylene phenol, polyethylene glycol, polyester, polyester, polyester, etc.).
  • Anion-type surfactants alkylbenzensulfonate, anorecils rufossuccinate, alkinoresulfate, polyoxyethylene sulfate, alali) Thioleuramine, etc.
  • positive ion-type surfactants anorequilamines (raurilamin, stearyl trimethine oleum ammonium chloride, anolequino resin) Thiobenzylammonium chloride), polyoxyethylene olenoalkylamines), amphoteric surfactant Strength agents such as carboxylic acid (betaine type), ester sulfate etc .; but not limited to these exemplified ones.
  • polyvinyl alcohol PVA
  • CMC canola benzoquinone cellulose
  • arabia rubber polyvinyl acetate
  • sodium anoregate gelatin
  • tragacanth rubber auxiliary agents
  • the compound of the present invention represented by the general formula (I) is used in an amount of 0.001% to 95% (% by weight; hereinafter the same) in producing the above-mentioned various preparations. , Preferably in the range of 0.01% to 75%.
  • DL powder and fine powder (F) 0.01% to 5%
  • granules 0.01% to 10%
  • wettable powders emulsions and liquids
  • 1% to The compound of the formula (I) can be contained in the range of 75%.
  • the formulation of the herbicidal composition thus prepared may be sprayed as it is on the soil surface, in soil or in water.
  • wettable powders, emulsions, and sols for example, they may be diluted with water or a suitable solvent, and the diluted chemical may be sprayed.
  • the compound of the formula (I) may be sprayed in an amount of about 0.3 g to 300 g per 10 ares. When used as an active ingredient, it may be sprayed in the range of about 0.3 g to 300 g in terms of active ingredient per 10 ares.
  • the herbicidal composition of the present invention is a wettable powder, an emulsion or a sol, it is diluted with water or an appropriate solvent and then applied as a paddy field herbicide.
  • the compound of formula (I) may be sprayed in an amount of about 0.3 g to 300 g per 10 ares as a converted amount of the active ingredient. If it is used by itself, it should be sprayed in the range of about 0.3 g to 300 g per 10 ares as the converted amount of the active ingredient.
  • weeds in rice fields or fields of field crops are sprayed in an amount ranging from 0.3 g to 300 g per 10 ares of paddy fields or fields, preferably from 0.3 g to 50 g.
  • a method for weed weeding comprising treating with a cyclohexanedione derivative represented by the following general formula (I).
  • the herbicidal composition containing the compound of the formula (I) as an active ingredient according to the present invention may further contain a known herbicide, an insecticide or a plant regulator.
  • a known herbicide an insecticide or a plant regulator.
  • the present invention is not limited to only these examples, and the composition of the present invention may contain other various additives in an arbitrary ratio, and may contain other herbicides. And the like can be formulated in any proportions and formulated into various forms.
  • the compound N 0. shown in the below-mentioned examples is the number shown in the above-mentioned Table 1, and in Examples, the part is All parts are by weight.
  • Test Examples 1 to 6 are shown to illustrate the herbicidal effect of the cyclohexanedione derivative of the formula (I) of the present invention.
  • Test Example 1 Test of herbicidal effect on Thai rice millet and phytotoxicity test on transplanted rice
  • a 1/5000 scale plastic pot was filled with paddy field soil (vegetable soil), and water was added for padding. Fifty seeds of the seeds of the seed were seeded on the surface layer of water-containing soil at 0 to 2 cm. In addition, two-leaf rice was planted in the soil, roots were inserted at a depth of 2 era, two plants were planted, and three plants were transplanted per pot. The pot was flooded and the water depth was kept at 3 cm.
  • a drug solution was prepared by diluting the emulsion prepared according to Example 7 with water to a predetermined concentration of the active ingredient, and the drug solution was applied to a pot. l O ra l was dripped.
  • the application rate of the compound of the present invention as an active ingredient was equivalent to application of 0.65 g per 1 are.
  • Weeding rate (%) X100 Average dry weight of weeds in untreated area
  • Comparative drugs A to G are herbicides prepared from the following known compounds in the same manner as the compounds of the present invention.
  • Test Example 1 The test procedure of Test Example 1 above was repeated, except that the emulsion prepared according to Example 7 was diluted with water to the prescribed concentration of the active ingredient, and the spray amount of the drug solution was equivalent to the pot. Weight was reduced in 5 ra l increments. In this test, the application rate of the compound of the present invention and the comparative compound as the active ingredients was equivalent to 0.32 g per are calculated.
  • a plastic pot with a size of 1/5000 is filled with paddy field soil (floated soil), and the rice vines and broadleaf weeds (Azena, Kika shigusa, Mizono Kobe) are filled. Then, 30 seeds of each firefly seed were sown at a depth of 1 to 2 cm. Sowing
  • the pot was flooded and the water depth was kept at 2 era.
  • 2.5-leaf rice was transplanted and grown in a greenhouse.
  • a medicinal solution prepared by diluting the emulsion prepared according to Example 7 with water so as to have a predetermined concentration of the active ingredient was dropped dropwise per pot.
  • the application rate of the active ingredient was equivalent to 0.16 g per are.
  • Field soil (alluvial loam) is packed in a pot made of unfired clay with a size of 1/5000 liters, and soil of 1 cm in surface layer is added to the soil of Meishishiba, Enokorogusa, Shiroza, Inubu, 50 weed seeds of each weed seed were mixed uniformly and the surface layer was lightly pressed.
  • a drug solution was prepared by diluting the emulsion prepared according to Example 7 with water. Two days after sowing, the diluted drug solution was sprayed on the soil surface of the pot at an amount of 100 liters per 10 ares. The active ingredient application rate was equivalent to 50 g per 10 ares.
  • Field soil (alluvial loam) was filled in a 1 / 10,000 ares pottery pot, and seeds (5 soybeans, 5 corns, and bees) of each crop shown in Table 6 below were filled. 10 seeds, 10 seeds of rape and 10 seeds of wheat) were sown in separate pots. The surface of the soil was lightly pressed. One day after sowing, a chemical solution prepared by diluting the emulsion prepared according to Example 7 with water was sprayed onto the soil surface of the pot in an amount of 100 liters per 10 ares. The application rate of the amount of the active ingredient was equivalent to 50 g per 10 ares. This test was performed twice in a single chemical concentration zone, and the degree of phytotoxicity to each crop was investigated 30 days after the chemical treatment based on the same evaluation index as in Test Example 1. The results are shown in Table 6.
  • the cyclohexandione derivative of the general formula (I) according to the present invention has excellent herbicidal activity and excellent selectivity between crops and weeds as compared with known analogous compounds. Is shown. That is, the compound of the present invention is a variety of undesirable weeds that are problematic in the herbicidal treatment of flooded paddy fields, for example, grass weeds such as rice vines, azaena, kikasidasa, and mizohacobena. It can effectively act on a wide variety of weeds such as broadleaf weeds, tamagayari, fireflies, squirrels, squirrels, etc. Complete weeding is possible. Moreover, there is no harm to paddy rice.
  • the compound of the present invention can be a problem in foliage treatment and soil treatment in upland fields, such as sonokazura, inubu, inutide, nokokobe, shiroza, aogaito, convouna, ichibi, Broadleaf weeds such as manore baasaagao, Tainubie, Inuibiye, Enokorogusa, Meishiba, Suzumenokatabira, Grass weeds such as wheat, etc. It can also act broadly on ryegaceae weeds and can almost completely eliminate them.
  • the compound of the present invention does not cause harm to main crops such as corn, wheat, rice, soybean, rapeseed and beet. Moreover, there is no toxicity to humans or fish. Therefore, it can be used safely.
  • the general formula (I) Silk mouth hexanedione derivatives have excellent herbicidal activity even at low application rates, and have the advantage of showing excellent selectivity between crops and weeds and not causing harm to crops. It is useful as a herbicide and as a field herbicide.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
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Abstract

Cette invention concerne de nouveaux dérivés de cyclohexanedione correspondant à la formule générale (I) où X représente halogéno. Y représente -S(O)m-R où R représente alkyle inférieur ou alcényle inférieur, étant entendu que m est un nombre entier égal à 0, 1 ou 2 lorsque R représente alkyle inférieur, et que m est égal à 0 lorsque R représente alcényle inférieur. Y peut également représenter tetrahydrofuran-2-yl ou tetrahydropyran-2-yl. Ces dérivés, qui ont une excellente activité herbicide même lorsqu'ils sont utilisés à faible dose, possèdent une excellente capacité de sélection leur permettant de distinguer les cultures des mauvaises herbes, ce qui en fait d'excellents herbicides.
PCT/JP1997/001857 1996-05-30 1997-05-30 Derives de cyclohexanedione et compositions herbicides WO1997045404A1 (fr)

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JP13646496 1996-05-30
JP8/136464 1996-05-30

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998034480A1 (fr) * 1997-02-07 1998-08-13 Novartis Ag Agent herbicide
WO1998041089A1 (fr) * 1997-03-14 1998-09-24 Novartis Ag Nouveaux herbicides
WO2001053275A2 (fr) * 2000-01-17 2001-07-26 Bayer Aktiengesellschaft Arylcetones substituees
WO2008031507A2 (fr) * 2006-09-13 2008-03-20 Bayer Cropscience Ag Compositions herbicides à phytotoxicité réduite

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6087238A (ja) * 1983-09-16 1985-05-16 ストウフアー・ケミカル・カンパニー ２‐（２‐置換ベンゾイル）‐１，３‐シクロヘキサンジオン
US4780127A (en) * 1982-03-25 1988-10-25 Stauffer Chemical Company Certain 2-(substituted benzoyl)-1,3-cyclohexanediones and their use as herbicides
JPH06321932A (ja) * 1993-05-07 1994-11-22 Hokko Chem Ind Co Ltd シクロヘキサンジオン誘導体および除草剤

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4780127A (en) * 1982-03-25 1988-10-25 Stauffer Chemical Company Certain 2-(substituted benzoyl)-1,3-cyclohexanediones and their use as herbicides
JPS6087238A (ja) * 1983-09-16 1985-05-16 ストウフアー・ケミカル・カンパニー ２‐（２‐置換ベンゾイル）‐１，３‐シクロヘキサンジオン
JPH06321932A (ja) * 1993-05-07 1994-11-22 Hokko Chem Ind Co Ltd シクロヘキサンジオン誘導体および除草剤

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998034480A1 (fr) * 1997-02-07 1998-08-13 Novartis Ag Agent herbicide
WO1998041089A1 (fr) * 1997-03-14 1998-09-24 Novartis Ag Nouveaux herbicides
WO2001053275A2 (fr) * 2000-01-17 2001-07-26 Bayer Aktiengesellschaft Arylcetones substituees
WO2001053275A3 (fr) * 2000-01-17 2003-04-17 Bayer Ag Arylcetones substituees
US6864219B2 (en) 2000-01-17 2005-03-08 Bayer Aktiengesellschaft Substituted aryl ketones
AU784813B2 (en) * 2000-01-17 2006-06-29 Bayer Aktiengesellschaft Substituted aryl ketones
WO2008031507A2 (fr) * 2006-09-13 2008-03-20 Bayer Cropscience Ag Compositions herbicides à phytotoxicité réduite
WO2008031507A3 (fr) * 2006-09-13 2009-04-16 Bayer Cropscience Ag Compositions herbicides à phytotoxicité réduite

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