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WO2007046440A1 - Composition herbicide - Google Patents

Composition herbicide Download PDF

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Publication number
WO2007046440A1
WO2007046440A1 PCT/JP2006/320777 JP2006320777W WO2007046440A1 WO 2007046440 A1 WO2007046440 A1 WO 2007046440A1 JP 2006320777 W JP2006320777 W JP 2006320777W WO 2007046440 A1 WO2007046440 A1 WO 2007046440A1
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WIPO (PCT)
Prior art keywords
compound
name
generic name
methyl
generic
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PCT/JP2006/320777
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English (en)
Japanese (ja)
Inventor
Manabu Saeki
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Nissan Chemical Corp
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Nissan Chemical Corp
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Priority to JP2007541023A priority Critical patent/JPWO2007046440A1/ja
Publication of WO2007046440A1 publication Critical patent/WO2007046440A1/fr
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Classifications

    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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<
    • A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/16—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the present invention relates to a herbicide composition and a herbicidal method with reduced phytotoxicity to crops, particularly paddy rice.
  • Compound (A) is patent-pending as a herbicide for paddy rice, has an extremely low dosage and exhibits an effect on many weeds, and has high safety against paddy rice under normal planting conditions. Under shallow planting and leakage conditions, it may cause phytotoxicity to paddy rice.
  • Daimlon, dimethylpiperate, and esprocalp are compounds that have been put to practical use as herbicides for paddy rice, but have been reported so far to reduce the phytotoxicity of compound (A) on paddy rice. ,.
  • Patent Document 1 discloses that pyrazole sulfonylureas having a dioxazine ring bonded to a pyrazole ring have herbicidal activity. However, Patent Document 1 does not specifically disclose pyrazole sulfonylureas such as compound (A) in which a substituent is bonded to the dioxazine ring on the virazole ring.
  • Patent Document 1 JP-A-7-118269
  • the present inventors have found that a mixture of the compound (A) and Daimlone, dimethylpiperate or esprocarp has an effect of reducing phytotoxicity exceeding expectations. They found that when compound (A) was mixed with certain herbicides, they complemented each other's herbicidal spectrum without antagonizing each other, thereby completing the present invention.
  • the present invention relates to a herbicide composition described in the following [1] and [2] (hereinafter referred to as the present composition), and a herbicidal method described in [3] and [4] (hereinafter referred to as the present invention). It is called a method.)
  • R 1 is a C alkyl group, a C haloalkyl group, a C alkoxy C alkyl group, a
  • 1-3 1-3 1-3 1-3 represents a phenyl group or a pyridyl group
  • R 2 is a hydrogen atom, C alkyl group, C haloalkyl group, C alkoxy group or halo.
  • a force representing a 1-3 group or a C haloalkyl group, or R 3 and R 4 together represent CH;
  • X and Y are each independently a C alkyl group, C haloalkyl group, C alkoxy group,
  • 1-3 1-3 1-3 represents a Si group, a C haloalkoxy group, a halogen atom or a di (C alkyl) amino group,
  • z represents a nitrogen atom or a methine group.
  • a herbicidal composition for paddy rice containing the compound (A) and at least one compound selected from among the mainstays of Daimlon, Dimepiperate, and Esprocalp.
  • a paddy field weeding method wherein the compound (A) and at least one compound selected from Daimlon, dimethylpiperate and esprocarp are applied simultaneously or with a time difference.
  • B (generic name), etobenzanid (generic name), cuminoluron (cumyluron. Common name), benzobicyclon / -common name, pyriftalide (pyriftalid / -common name), bispyribac / -common name, pyrachlor (pyraclonilZ--common name), anilofos /- (Generic name), OK—701 (study name), penoxsulam Z (generic name), AVH—301 (study name), KUH-021 (study name;), TH-547 (study name), Bentazone (BentazoneZ) (Generic name), 2, 4— PA (—generic name), metamihop (generic name), flucetosulfuron (generic name), HOK—201 (—generic name), mesotrione (mesotrioneZ—generic name), properties ( PropanilZ (common name), quinoclam
  • a paddy rice herbicide composition comprising the compound (A) and at least one compound selected from the group B.
  • [7] A herbicidal method in which the compound (A) and the at least one compound selected from group B power are applied simultaneously or with a time difference.
  • [8] A method for weeding paddy fields, wherein the compound (A) and the at least one compound selected from the group B force are applied simultaneously or at a time difference.
  • the phytotoxicity to crops, particularly paddy rice, caused by the compound (A) which is an active ingredient of the herbicide is reduced by Daimlon, dimethylpiperate and esprocalp, and the herbicidal effect on various weeds Does not drop.
  • Mixtures of compound (A) with certain herbicides complement each other in the herbicidal spectrum without antagonism. For these reasons, the utility in an actual application scene according to the present invention is extremely high.
  • Ph in the formula represents a phenol group
  • Me represents a methyl group
  • Bu represents a butyl group
  • Compound (A) can be produced by the method shown in the following reaction formulas 1 to 3.
  • Reaction Formula 1 is 4- (5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfonamide (2) in the presence or absence of a base, 2-phenoxycarbo-laminopyrimidine (or triazine). ) A method for producing compound (1) by reacting with (3) is shown.
  • (3) is usually used in an amount of 0.5 to 10-fold mol, preferably 0.9 or 1.1-fold mol based on (2).
  • Bases used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride, pyridine, 4-dimethylaminopyridine, triethylamine, N, N dimethylamine, 1,8 diazabicyclo [5. 4. 0] 7undecene and 1,4-diazabicyclo [2.2.2] octane and other organic bases, n-butyllithium and sec-butyllithium and other organic lithiums, lithium diisopropylamide and Organic lithium amides such as lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide can be mentioned.
  • the base is usually used in an amount of 0 to 10-fold mol, preferably 0 to 2-fold mol based on (2).
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl And mixed solvents thereof.
  • the reaction temperature is usually 90 ° C and 200 ° C, preferably 0 ° C and 120 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • Reaction formula 2 is 4- (5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfonyl carnomate (4) in the presence or absence of a base and 2-aminopyrimidine (or Triazine)
  • a method for producing compound (1) by reacting with (5) is shown.
  • (5) is usually used in an amount of 0.5 to 10-fold mol, preferably 0.9 or 1.1-fold mol with respect to (4).
  • Bases used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride, pyridine, 4-dimethylaminopyridine, triethylamine, N, N dimethylamine, 1,8 diazabicyclo [5. 4. 0] 7undecene and 1,4-diazabicyclo [2.2.2] octane and other organic bases, n-butyllithium and sec-butyllithium and other organic lithiums, lithium diisopropylamide and Organic lithium amides such as lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide can be mentioned.
  • the base is usually used in an amount of 0 to 10-fold mol, preferably 0 to 2-fold mol based on (4).
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloro Halogenated hydrocarbons such as loetane, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoleketone and methylisobutylketone, and tolyl such as acetonitrile and propio-tolyl And mixed solvents thereof.
  • the reaction temperature is usually 90 ° C and 200 ° C, preferably 0 ° C and 120 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • Reaction scheme 3 is 4- (5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfol isocyanate (6) in the presence or absence of a base in the presence of 2 aminopyrimidine ( Alternatively, a method for producing compound (1) by reacting with triazine (5) is shown.
  • (5) is usually used in an amount of 0.5 to 10-fold mol, preferably 0.9 or 1.1-fold mol based on (6).
  • Bases used in this reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride, pyridine, 4-dimethylaminopyridine, triethylamine, N, N dimethylamine, 1,8 diazabicyclo [5. 4. 0] 7undecene and 1,4-diazabicyclo [2.2.2] octane and other organic bases, n-butyllithium and sec-butyllithium and other organic lithiums, lithium diisopropylamide and Organic lithium amides such as lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide can be mentioned.
  • the base is usually 0 to 10 times mol, preferably 0, relative to (3). 2 times mole used.
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl And mixed solvents thereof.
  • the reaction temperature is usually 90 ° C and 200 ° C, preferably 0 ° C and 120 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • 4- (5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole-5 sulfonamide (2) used in the method shown in Reaction Formula 1 is the method shown in Reaction Formulas 4 and 6. Can be manufactured. Also, 4- (5H, 6H-1, 4, 2, dioxazin-3-yl) pyrazole-5-sulfolcarbamate (4) and 4 (5H, 6H-1) , 4, 2 dioxazine-3-yl) pyrazole-5-sulfol isocyanate (6) is made from 4- (5H, 6H- 1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfonamide (2) It can be synthesized with reference to the methods described in JP-A-59-219281 and JP-A-55-13266.
  • Reaction Scheme 4 is a method of reacting 5-chlorocap 4- (5H, 6H-1, 4, 2 dioxazine 3-yl) pyrazole (7) with sodium hydrosulfide.
  • 6H- 1, 4, 2—dioxazine 3-yl) pyrazole (8) (step A), (8) is reacted with chlorine or sodium hypochlorite and other chlorinated agents to give 4- (5H , 6H-1, 4, 2 dioxazine-3-yl) pyrazole-5-sulfourel chloride (9) (step B), (9) is reacted with aqueous ammonia or ammonium carbonate (step C).
  • sodium sulfate is usually used in an amount of 1.0 to 10-fold mol, preferably 2 to 5-fold mol based on (7).
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl , N, N dimethylformamide, N, N dimethylacetamide and N-methyl
  • Examples include amides such as rho-2-pyrrolidone, sulfur-containing polar solvents such as dimethyl sulfoxide and sulfolane, water, and mixed solvents thereof.
  • the reaction temperature is usually 90 ° C and 200 ° C, preferably 0 ° C and 120 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • Step B chlorine or sodium hypochlorite is usually used in an amount of 1 V, 100 times mol, preferably 2! And 10 times mol of (8).
  • This reaction can use a solvent as needed.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • halogenated hydrocarbons such as carbon tetrachloride, black mouth form and 1,2-dichloro mouth ethane, water, and a mixed solvent thereof may be used. Can be mentioned.
  • the reaction temperature is usually -90! And 100 ° C, preferably -10! And 50 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • ammonia or ammonium carbonate is usually 1.
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-amides such as 2-pyrrolidone, sulfur-containing polar solvents such as dimethyl sulfoxide and sulfolane, water, and mixed solvents thereof It is done.
  • ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran
  • ketones such as acetone, methinoretinoketone and methylisobutylketone
  • -tolyls such as acetonitrile and propio-to
  • the reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • Reaction formula 5 is a reaction of 5 benzyl mercapto-4- (5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole (10) with a chlorinating agent such as chlorine or sodium hypochlorite.
  • chlorine or sodium hypochlorite is usually 1 to 1 relative to (10).
  • This reaction can use a solvent as needed.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • halogenated hydrocarbons such as carbon tetrachloride, black mouth form and 1,2-dichloro mouth ethane, water, and a mixed solvent thereof may be used. Can be mentioned.
  • the reaction temperature is usually -90! And 100 ° C, preferably -10! And 50 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • (9) can be derived into 4- (5H, 6H-1, 4, 2 dioxazine 3 yl) pyrazole-5-sulfonamide (2) by the step C in Reaction Scheme 4. Further, (1) can be produced by reacting (9) and (5) with reference to the method described in JP-A-7-118267.
  • n-butyllithium or lithium diisopropylamide is usually used in an amount of 1 to 100-fold mol, preferably 1 to 5-fold mol based on (11).
  • This reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene
  • ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran are used. And mixed solvents thereof.
  • the reaction temperature is usually 120 ° C and 100 ° C, preferably 78 ° C and 10 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • disulfur diacid is usually used in an amount of 1.0 to 100 times mol, preferably 1 to 10 times mol, relative to (11).
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene
  • ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran are used.
  • jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran are used.
  • these mixed solvents I can get lost.
  • the reaction temperature is usually 120 ° C and 100 ° C, preferably 78 ° C and 10 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • N-chlorosuccinimide is usually used in an amount of 1.0 to 100 times mol, preferably 1 to 10 times mol to (12).
  • the solvent used in this reaction is not particularly limited as long as it is inert to the reaction.
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, and 1,2-dichloroethane, water, and These mixed solvents are mentioned.
  • the reaction temperature is usually -90! And 100 ° C, preferably -10! And 50 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • [0020] (9) can be derived from 4 step 5 of Reaction Scheme 4 to 4 (5H, 6H—1, 4, 2 dioxazine 3 yl) pyrazole-5 sulfonamide (2).
  • 01 [0021] 5-Chromium used in the methods shown in Reaction Formulas 4 to 6 — 4— (5H, 6H— 1, 4, 2 Dioxazine-3-yl) pyrazole (7), 5 Benzyl mercapto-4— (5H, 6H-1, 4, 2 dioxazine-3 yl) pyrazole (10) and 4- (5H, 6H—1, 4, 2 dioxazine-3 yl) pyrazole (11) are It can be manufactured by the method shown in 15.
  • (14) is usually used in an amount of 1.0 to 100 times mol, preferably 1 to 5 times mol, relative to (13).
  • Examples of the base used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride and other inorganic bases, pyridine, 4-dimethylaminopyridine, Triethylamine, N, N dimethyldiamine, 1,8 diazabicyclo [5. 4.
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N-dimethylformamide, N, N dimethylacetamide and N-methyl-2-pyrrolidone, sulfur-containing polar solvents such as dimethyl sulfoxide and sulfolane, water, and mixed solvents thereof .
  • ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran
  • ketones such as acetone, methinoretinoketone and methylisobutylketone
  • -tolyls such as acetonitrile and propio-tolyl Amides such
  • the reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.
  • reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours. (Reaction formula 8)
  • R 4 , R 5 , R 6 and L have the same meaning as described above, and X 2 represents a halogen atom, a C alkylsulfo-oxy group or a C haloalkyl sulfo-oxy group.
  • pyrazole 4 carboxylic acid chloride (15) is reacted with alkoxyamine (16) to give pyrazole 4 hydroxamic acid ester (17) (step F), and (17) is reacted with a base (step G), 4- (5H, 6H-1, 4, 2 dioxazine 3 yl) pyrazole (7), (10) or (11) is produced.
  • (16) is usually used in an amount of 1 to 100 times mol, preferably 2 to 5 times mol to (15).
  • Examples of the base used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride and other inorganic bases, pyridine, 4-dimethylamino. Pyridine, triethylamine, N, N dimethyladiline, 1,8 diazabicyclo [5. 4.
  • octane and other organic bases n-butyllithium and sec Examples include organolithiums such as butyllithium, organolithiums such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide.
  • the base is usually used in an amount of 0 to 10 times mol, preferably 0 to 2 times mol for (15).
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as, jetyl ether, diisopropyl ether, Ethers such as dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, -tolyls such as acetonitrile and propio-tolyl, N, N-dimethylformamide, N, N-dimethylacetate Amides and amides such as N-methyl 2-pyrrolidone, water, and mixed solvents thereof can be mentioned.
  • the reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • Bases used in the reaction in Step G include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride, pyridine, 4-dimethylaminopyridine, triethylamine, N , N-dimethylaniline, 1,8-diazabicyclo [5. 4.
  • inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and sodium hydride, pyridine, 4-dimethylaminopyridine, triethylamine, N , N-dimethylaniline, 1,8-diazabicyclo [5. 4.
  • octane and other organic bases n-butyllithium and sec—
  • organic lithiums such as butyl lithium
  • organic lithium amides such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide
  • metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide.
  • the base is usually used in an amount of 0 to 10 times mol, preferably 0 to 2 times mol of (17).
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone, water, and mixed solvents thereof.
  • the reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • X 1 and L represent the same meaning as described above, and R 7 and R 8 each independently represent a hydrogen atom or a C alkyl group. ]
  • pyrazole 4 carboxylic acid chloride (15) is reacted with aryloxyamine (16a) to give pyrazole 4 hydroxamic acid ester (17a) (steps H) and (17a) as halogen or N— 4 (5-Haloalkyl-5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole (7a), (10a) or (11a) by reacting with halogenated succinimide (Step 1), (7a) , (10a) or (11a) is reduced ( ⁇ ) and 4- (5 alkyl-5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole (7b), (10b) or ( l Shows how to produce ib).
  • (16a) is usually used in an amount of 1 to 100 times mol, preferably 2 to 5 times mol to (15).
  • Examples of the base used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride and other inorganic bases, pyridine, 4-dimethylaminopyridine, Triethylamine, N, N Dimethyla Diphosphorus, 1,8 diazabicyclo [5. 4. 0] —7 undecene and 1,4 diazabicyclic mouth [2.2.2] octane and other organic bases, n butyl lithium and sec butyl lithium, etc.
  • Examples thereof include organic lithium amides such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide.
  • the base is usually used in an amount of 0 to 10 times mol, preferably 0 to 2 times mol for (15).
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N-dimethylformamide, N, N dimethylacetamide and N-methyl-2-pyrrolidone, water, and mixed solvents thereof.
  • the reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • halogen or N-halogenosuccinimide is usually used in an amount of 1 to 100-fold mol, preferably 1 to 5-fold mol based on (17a).
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl , Carboxylic acid esters such as methyl acetate or ethyl acetate, alcohols such as methanol, ethanol or ethylene glycol, amides such as N, N-dimethylformamide, N, N dimethylacetamide and N-methyl-2-pyrrolidone , Water, and mixed solvents thereof
  • the reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • the reducing agent and reduction system used in the reaction of @J include alkali metal such as metallic sodium Z liquid ammonia, metallic lithium Z liquid ammonia and metallic sodium Zt-butyl alcohol-tetrahydrofuran mixed solvent, zinc Z acetic acid Zinc Z Hydroxide Potassium Z System using zinc metal such as Z water, triphenyltin hydride, diphenyltin hydride, tri-n-butyltin hydride, di-n-butyltin hydride, hydrogen Systems using organotin hydrides such as triethyltin and trimethyltin hydride, systems combining the above organotin compounds with free radical initiators such as azobisisobutyl thiol, silanes such as chlorosilane, triethylsilane and trimethylsilane , Lithium aluminum hydride, aluminum hydride sodium , Systems using metal hydr
  • the reducing agent is usually used in an amount of 1 to 100 times mol, preferably 1 to 5 times mol for (7a), (10a) or (11a).
  • the solvent is not particularly limited as long as it is inert to each of the above reduction systems.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1
  • Halogenated hydrocarbons such as 2-dichloroethane, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and-such as acetonitrile and propiotolyl Tolyls
  • carboxylic esters such as methyl acetate or ethyl acetate
  • alcohols such as methanol, ethanol or ethylene glycol
  • amides such as N, N dimethylformamide, N, N dimethylacetamide and N
  • the reaction temperature is usually -90! And 200 ° C, preferably -78! And 100 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • Reaction scheme 10 is 4- (5-haloalkyl-5H, 6H-1, 4, 2 dioxazine-3-yl) pyrazole (7c), (10c) or (11c) in the presence or absence of a base, Dehydrohalogenated to the corresponding 4 (5 alkylidene-5H, 6H-1, 4, 2 dioxazine 3 yl) pyrazole (7d), (10d) or (l id) (step K), ( 7d), (10d) or (l id) is reduced (Step L), and the corresponding 4 (5 alkyl 5H, 6H—1, 4, 2 dioxazine-3-yl) pyrazole (7e), (10e ) Or (l ie) is shown.
  • Bases used in the reaction of Step K include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and sodium hydride, pyridine, 4- Organic bases such as dimethylaminopyridine, triethylamine, N, N-dimethylamine, 1,8 diazabicyclo [5.4.0] -7 undecene and 1,4 diazabicyclo [2.2.2] octane, n —Organic lithiums such as butyllithium and sec-butyllithium, organolithiums such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. Can be mentioned.
  • the base is usually 0 to 100 times mol, preferably 0 to 5 times mol for (7c), (10c) or (11c). used.
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N dimethylformamide, N, N dimethylacetamide and N-methyl 2-pyrrolidone, water, and mixed solvents thereof.
  • the reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • Examples of the reducing agent and reducing system used in the reaction in Step L include metallic sodium Z liquid ammonia, metallic lithium Z liquid ammonia, metallic lithium Z ethylamine and other alkali metal systems, aluminum mercury Z jetyl ether monohydrate and aluminum.
  • Metal hydride complexes such as lithium aluminum hydride, sodium aluminum hydride, sodium bis (2-methoxyethoxy) aluminum hydride, sodium borohydride and sodium cyanoborohydride Systems using compounds, systems using borane derivatives such as diborane, trimethylamine borane and pyridine borane, hydrazine hydrate Z air, hydrazine hydrate Z potassium hexocyano (in) and hydroxylamine o-sulfonic acid Z Systems using diimides generated in reaction systems such as sodium hydroxide and sodium, heterogeneous catalytic reduction systems such as hydrogen Z palladium carbon and hydrogen Z Raney nickel, and hydrogen Z chlorotri
  • Solvent is above
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1, 2- Halogenated hydrocarbons such as dichloroethane, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, -tolyls such as acetonitrile and propio-tolyl, Carboxylic acid esters such as methyl acetate or ethyl acetate, alcohols such as methanol, ethanol or ethylene glycol, amides such as N, N dimethylformamide, N, N dimethylacetamide and N
  • the reaction temperature is usually -90! And 200 ° C, preferably -78! And 100 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • Reaction scheme 11 is a reaction of pyrazole 4 hydroxamic acid ester (17a) or (17b) with acid (H +) to give 4- (5-alkyl-511, 6H—1, 4, 2 dioxazine 3yl) pyrazole ( A method for producing 7b), (10b) or (1 lb) is indicated.
  • acids used in this reaction include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid.
  • the acid is usually used in an amount of 0.01- to 100-fold mol, preferably 0.05 to 10-fold mol based on (17a) or (17b).
  • This reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N dimethylformamide, N, N dimethylacetamide and N-methyl 2-pyrrolidone, water, and mixed solvents thereof.
  • the reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • Scheme 12 shows the reaction of pyrazole 4 hydroxamic acid (13) with halogenaryl (18) in the presence or absence of a base to form pyrazol 4 hydroxamic acid ester (17a ) Is shown.
  • (18) is usually used in an amount of 1 to 100-fold mol, preferably 1 to 5- fold mol based on (13).
  • Examples of the base used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride and other inorganic bases, pyridine, 4-dimethylamino. Pyridine, triethylamine, N, N dimethyladiline, 1,8 diazabicyclo [5. 4.
  • octane and other organic bases n-butyllithium and sec Butylliciu And organic lithium amides such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide.
  • the base is usually used in an amount of 0 !, 100 times mol, preferably 0 !, and 5 times mol with respect to (13).
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N dimethylformamide, N, N dimethylacetamide and N-methyl 2-pyrrolidone, water, and mixed solvents thereof.
  • the reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • Scheme 13 shows the reaction of pyrazol 4 hydroxamic acid (13) in the presence or absence of a base with rholine, rhohydrin (19) or oxilan (20) to form a pyrazo 1-luo 4 hydroxamic acid ester used in Scheme 11
  • the method of manufacturing (17b) is shown.
  • (19) or (20) is usually used in an amount of 1 to 100-fold mol, preferably 2 to 5-fold mol with respect to (13).
  • Bases used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, Inorganic bases such as sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride, pyridine, 4-dimethylaminopyridine, triethylamine, N, N dimethylaniline, 1,8 diazabicyclo [5.
  • Organic bases such as octane, organic lithiums such as n-butyllithium and sec-butyllithium, lithium diisopropylamide and lithium bis (trimethylsilyl) amide
  • organic lithium amides examples include organic lithium amides, and metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide.
  • the base is usually used in an amount of 0 !, 100 times mol, preferably 0 !, and 5 times mol with respect to (13).
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N dimethylformamide, N, N dimethylacetamide and N-methyl 2-pyrrolidone, water, and mixed solvents thereof.
  • the reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.
  • reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • (21) is usually used in an amount of 1 to 100 times mol, preferably 1 to 5 times mol, of (13).
  • Examples of the base used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and sodium hydride.
  • Organic bases pyridine, 4-dimethylaminopyridine, triethylamine, N, N dimethylaniline, 1,8 diazabicyclo [5. 4. 0] —7 undecene and 1,4 diazabicycline [2.2.2] octane N, organic lithiums such as butyl lithium and sec butyl lithium, organic lithium amides such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide, and sodium methoxide, sodium ethoxide and potassium t -Metal alkoxides such as butoxide.
  • the base is usually used in an amount of 0 !, 100 times mol, preferably 0 !, and 5 times mol with respect to (13).
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N dimethylformamide, N, N dimethylacetamide and N-methyl 2-pyrrolidone, water, and mixed solvents thereof.
  • the reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.
  • Acids or bases used in the reaction of Step M include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid and P-toluenesulfonic acid, water Inorganic bases such as sodium oxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride, pyridine, 4-dimethylaminopyridine, triethylamine, N, N dimethylamine, 1 , 8 Diazabicyclo [5. 4.
  • inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid
  • organic acids such as acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid and P-toluenesulfonic acid
  • water Inorganic bases such as sodium oxide, potassium hydroxide, potassium
  • Organic bases such as 7-undecene and 1,4-Diazabicyclo [2.2.2] octane, Organolithiums such as n-butyllithium and sec-butyllithium, Lithium diisopropylamide and Organic lithium amides such as lithium bis (trimethylsilyl) amide And sodium methoxide, and metal alkoxides such as sodium Umuetokishido and potassium t- butoxide.
  • the acid or base is usually used in an amount of 0 to 100-fold mol, preferably 0 to 5-fold mol based on (17c). Used.
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ketones such as acetone, methinoretinoketone and methylisobutylketone, and -tolyls such as acetonitrile and propio-tolyl Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone, water, and mixed solvents thereof.
  • the reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • the halogenating agent or alkyl sulfonating agent is usually 1 to 100 times mol, preferably 1 to 5 times mol of (7f), (10 f) or (l lf). Used in moles.
  • halogenating agent used in this reaction examples include hydrohalic acids such as hydrogen chloride, hydrogen bromide and hydrogen iodide, phosphorus halides such as phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and phosphorus tribromide. , Phosphonic acid triphenyl z benzil chloride and triphenylphosphine Z tetrasalt-carbon, etc., methanesulfonyl chloride and halogenated sulfone such as P-toluenesulphonyl, and thiol chloride And thionyl halides such as thiol bromide.
  • hydrohalic acids such as hydrogen chloride, hydrogen bromide and hydrogen iodide
  • phosphorus halides such as phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and phosphorus tribromide.
  • alkyl sulfonating agent used in this reaction examples include halogenated sulfones such as methane chloride chloride and p-toluene chloride.
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as: ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran; ketones such as acetone, methinoretinoleketone and methylisobutylketone;-such as acetonitrile and propio-tolyl Examples include tolyls, amides such as N, N dimethylformamide, N, N dimethylacetamide and N-methyl-2-pyrrolidone, water, and mixed solvents thereof.
  • the reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • hydroxylamine is usually used in an amount of 1 to 100-fold mol, preferably 1 to 5-fold mol based on (15).
  • Examples of the base used in this reaction include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and sodium hydride and other inorganic bases, pyridine, 4-dimethylamino. Pyridine, triethylamine, N, N dimethyladiline, 1,8 diazabicyclo [5. 4.
  • octane and other organic bases n-butyllithium and sec Examples include organolithiums such as butyllithium, organolithiums such as lithium diisopropylamide and lithium bis (trimethylsilyl) amide, and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide.
  • the base is usually used in an amount of 0! And 100 times mol, preferably 0! And 5 times mol of (15).
  • the reaction proceeds even without solvent, but a solvent can be used if necessary.
  • the solvent is not particularly limited as long as it is inert to the reaction.
  • hydrocarbons such as hexane, cyclohexane, benzene and toluene, carbon tetrachloride, chloroform, and 1,2-dichloroethane.
  • Halogenated hydrocarbons such as ether, ethers such as jetyl ether, diisopropyl ether, dioxane and tetrahydrofuran, acetone, methinoretinoleketone And ketones such as methyl isobutyl ketone, -tolyls such as acetonitrile and propio-tolyl, amides such as N, N dimethylformamide, N, N dimethylacetamide and N-methyl-2-pyrrolidone, water, and these The mixed solvent is mentioned.
  • the reaction temperature is usually -90! And then 200 ° C, preferably 0! And 100 ° C.
  • the reaction time is usually 0.05 to 100 hours, preferably 0.5 to 10 hours.
  • the target product obtained by the above reaction can be isolated and purified by operations such as filtration, extraction, washing, column chromatography, recrystallization and distillation.
  • the raw material is 3 black mouth 4— (5,5 dimethyl-5H, 6H-1, 4, 2 dioxazine-3-yl) -1-methylbiazole-5-sulfonamide (0.47 g, 1.5 mmol)
  • the target product (0.42 g) was obtained in the same manner as in Synthesis Example 1. Melting point 189-191 ° C. Proton nuclear magnetic resonance chemical shift value ⁇ (ppm) (in CDCl) 1.41 (s, 6H), 3.78 (s, 2H), 3.97 (s
  • the aqueous layer was extracted with methylene chloride.
  • the obtained methylene chloride solutions were combined, washed with a saturated aqueous solution of sodium chloride and dried over anhydrous sodium sulfate.
  • Triethylamine (2.9 g, 29 mmol) was added at 0 ° C to a suspension of allyloximine hydrochloride (2.3 g, 21 mmol) in tetrahydrofuran (20 ml) and stirred at room temperature for 5 minutes.
  • Benzylthio-3 chloro-1-methylpyrazole-4 A solution of rubonic acid chloride (2. lg, 7. Ommol) in tetrahydrofuran (10 ml) was added dropwise. After stirring at room temperature for 1 hour, water (100 ml) was added and extracted with ethyl acetate.
  • the target product (1.5 g) was obtained in the same manner as (1) of Reference Example 1 using 5 benzylthio-1,3 dimethylbirazole 4 force ruponic acid chloride (1.6 g, 5.7 mmol) as a raw material. Oily substance. Proton nuclear magnetic resonance chemical shift value ⁇ (ppm) (in CDCl) 2.50 (s, 3H), 3.34
  • the starting material (0.74 g) was used in the same manner as (2) in Reference Example 1, using (5-benzylthio-1,3 dimethylbiazole-4-yl) -N allyloxycarboxylate (0.92 g, 2.9 mmol) as the raw material.
  • Got. Melting point 79-81 ° C.
  • Lithium aluminum hydride (0.090 g, 2.4 mmol) in a suspension of jetyl ether (20 ml) with stirring at 5 ° C, 2— (1,3 dimethyl-5-benzylthiopyrazole-4-yl) Carbo-laminooxy) ethyl ester of propanoate (0.88 g, 2.3 mmol)
  • 1 tel 5 ml
  • the reaction mixture was poured into ice water (20 ml), adjusted to pH 1 with 10% hydrochloric acid, and extracted with ethyl acetate.
  • N-aryloxy 3,5 dichloro 1-methylbiazole 4 carboxylic acid amide (20 Og, 80. Ommol) solution in acetonitrile (200 ml) [this, N bromoconoxyimide (1 7. lg, 96. Ommol) was added and stirred at room temperature for 1 hour. Sodium hydrogen sulfite saturated aqueous solution (100 ml) was added, and acetonitrile was distilled off. Next, extraction with ethyl acetate was performed, and the resulting ethyl acetate solution was washed successively with water and a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and the solvent was distilled off.
  • hydroxynoreamine hydrochloride (13.3 g, 191 mmol) in water (40 ml) at 5 or 15 ° C in 85% potassium hydroxide (12.6 g, 191 mmol) in water (40 ml) was stirred and stirred at room temperature for 15 minutes.
  • the tetrahydrofuran solution was added dropwise at 3 to 15 ° C. over 0.25 hours.
  • 35% hydrochloric acid (20 ml) was added to adjust the pH to 3 or 4, and the mixture was extracted with ethyl acetate.
  • the target product (0.45 g) was obtained in the same manner as in Reference Example 1 using 5-benzylthio 1 (pyridyl-2-yl) pyrazole 4 carboxylic acid chloride (3.63 g, 11. Ommol) as a raw material. Oily substance. Proton nuclear magnetic resonance chemical shift value ⁇ (ppm) (in CDC1) 1.43 (d, J
  • the ethyl acetate layer was washed successively with water and saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate, and evaporated to an oil. was gotten.
  • Compound (A) and at least one compound selected from the power of Daimlon, Dimepiperate and Esprocarb Combinations include Compound 1Z Daimlone, Compound 1Z Dimepiperate, Compound 1Z Esprocarp, Compound 2Z Daimlon
  • the compounds listed in Table 2 as compounds of the group IV can be mentioned. Further, when applying at least one kind of compound (ii) and at least one kind of compound selected from Daimron, Dimepiperate and Esprocarp at the same time, the compounds listed in Table 2 can be applied simultaneously.
  • each compound may be applied individually or as a mixed composition in application.
  • each When each is applied individually, it can be applied at the same time, or can be processed separately as long as they are close in time.
  • the application rate of compound ( ⁇ ) is usually lg-10 kgZha, preferably 10 g-lkgZha. Daimlon, dimethylpiperate and esprocarp medium strength
  • the application rate of at least one compound selected is usually lg—10 kgZha, preferably 10 g—3 kgZha.
  • composition of the present invention is usually mixed with an appropriate solid carrier or liquid carrier, and if desired, a surface active agent, a penetrating agent, a spreading agent, a thickening agent, an antifreezing agent, a binder, an anti-caking agent, a disintegration.
  • any dosage form such as dustable powder, granule and gel.
  • the preparations of any of the above dosage forms can be enclosed in a water-soluble package. If necessary, it can be mixed with other herbicides, insecticides, fungicides, plant growth regulators, fertilizers, etc. during formulation or spraying.
  • solid carrier examples include quartz, kaolinite, neurophyllite, sericite, talc, bentonite, acid clay, attapulgite, zeolite, and diatomaceous earth, calcium carbonate, ammonium sulfate, sodium sulfate and salt.
  • Inorganic salts such as potassium, synthetic silicic acid and synthetic silicate.
  • liquid carrier examples include alcohols such as ethylene glycol, propylene glycol, and isopropanol, aromatic hydrocarbons such as xylene, alkylbenzene, and alkylnaphthalene, ethers such as butylcetosolve, ketones such as cyclohexanone, —Esters such as butaguchi ratataton, acid amides such as N-methylpyrrolidone and N-octylpyrrolidone, vegetable oils such as soybean oil, rapeseed oil, cottonseed oil and castor oil, and water.
  • alcohols such as ethylene glycol, propylene glycol, and isopropanol
  • aromatic hydrocarbons such as xylene, alkylbenzene, and alkylnaphthalene
  • ethers such as butylcetosolve
  • ketones such as cyclohexanone
  • Esters such as butaguchi ratataton
  • acid amides such as N
  • These solid and liquid carriers may be used alone or in combination of two or more.
  • surfactant examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene fatty acid ether.
  • Nonionic surfactants such as stealth, sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters, alkyl sulfates, alkylbenzene sulfonates, lignin sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, alkyl naphthalene sulfonates , Formalin condensate salt of naphthalene sulfonic acid, salt of formalin condensate of alkyl naphthalene sulfonic acid, polyoxyethylene alkyl aryl ether sulfate and phosphate, polyoxyethylene styryl ether ether sulfate and phosphate, poly Carboxylic acid surfactants such as carboxylates and polystyrene sulfonates, cationic surfactants such as alkylamine salts and alkyl quaternary ammonium
  • the content of these surfactants is not particularly limited, but is preferably in the range of 0.05 to 20 parts by mass with respect to 100 parts by mass of the preparation of the present invention. These surfactants may be used alone or in combination of two or more.
  • a plurality of other herbicides, insecticides, fungicides, plant growth regulators, fertilizers and the like can be used in combination.
  • the herbicidal spectrum can be expanded, and the effects of the present invention can be made more stable.
  • the present composition 0.1 to 80 parts
  • anti-caking agents include anti-caking agents and decomposition inhibitors.
  • composition of the present invention 0.1-30 parts
  • composition of the present invention 0.1-70 parts
  • antifreezing agents include antifreezing agents and thickeners.
  • composition of the present invention 0.1-90 parts
  • Other examples include a binder and a decomposition inhibitor.
  • composition of the present invention 0.01-70 parts
  • antifreezing agents include antifreezing agents and spreading agents.
  • the present composition 0.01 to 80 parts
  • Other examples include a binder and a decomposition inhibitor.
  • composition of the present invention 0.01-30 parts
  • Other examples include a drift inhibitor and a decomposition inhibitor.
  • the above preparation is diluted with water 1 to: LOOOO times or not diluted, and the active ingredient strength is 0.001 to 50 kg per hectare (ha), preferably ⁇ or 0.001 to LOkg. Scatter.
  • the above is uniformly mixed and ground to obtain a wettable powder.
  • Nonionic surfactant Kao Co., Ltd. trade name
  • Example 6 dustable powder
  • the above is uniformly mixed and pulverized to obtain a powder.
  • the above is uniformly mixed and ground to obtain a wettable powder.
  • Nonionic surfactant Kao Co., Ltd. trade name
  • the above is uniformly mixed and pulverized to obtain a powder.
  • the above is uniformly mixed and ground to obtain a wettable powder.
  • Nonionic surfactant Kao Co., Ltd. trade name
  • the above is uniformly mixed and pulverized to obtain a powder.
  • composition of the present invention as a herbicide will be specifically described in the following test examples.
  • [0138] phytotoxicity test under standing seedlings and leakage conditions
  • the seedling condition was 4 cm submersion conditions after alluvial soil was put into a 1Z10000 are plastic pot and water was mixed.
  • a 2.5-leaf rice seedling was fixed on the rice pad with the roots exposed.
  • water leakage conditions were the same as in Test Example 1, and 2.5-leaf rice seedlings were transplanted.
  • a suspension of a predetermined concentration of the reagent was dropped with a wettable powder prepared according to the formulation example on the 6th day after transplantation.
  • the phytotoxicity of rice was investigated according to the above criteria.
  • all of Compound (A) + Dimron, Compound (A) + Dimepiperate, and Compound (A) + Esprocalp showed a phytotoxicity-reducing effect on rice compared to Compound (A) alone. It was.
  • composition of the present invention is useful, for example, as a herbicide for paddy fields.

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

Abstract

L’invention concerne une nouvelle composition herbicide et un procédé de désherbage. La composition herbicide selon l’invention contient à la fois un composé (A) représenté par la formule générale (1) et au moins un composé choisi parmi dymron, dimepipérate, et esprocarb. Le procédé de désherbage selon l'invention comprend l'application d'un composé (A) et d'au moins un composé choisi parmi dymron, dimepipérate, et esprocarb, soit de manière simultanée, soit à intervalle : [Formule chimique 1]
PCT/JP2006/320777 2005-10-18 2006-10-18 Composition herbicide Ceased WO2007046440A1 (fr)

Priority Applications (1)

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JP2007541023A JPWO2007046440A1 (ja) 2005-10-18 2006-10-18 除草剤組成物

Applications Claiming Priority (4)

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JP2005-303144 2005-10-18
JP2005303144 2005-10-18
JP2005311700 2005-10-26
JP2005-311700 2005-10-26

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WO2007046440A1 true WO2007046440A1 (fr) 2007-04-26

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JP (1) JPWO2007046440A1 (fr)
KR (1) KR20080064160A (fr)
TW (1) TW200731927A (fr)
WO (1) WO2007046440A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011039276A1 (fr) 2009-10-01 2011-04-07 Bayer Cropscience Ag Oxathiazinyl-(hétéro) arylsulfonylurées, procédé et produits intermédiaires pour leur préparation et leur utilisation en tant que pesticides et régulateurs de croissance des plantes
US20120220461A1 (en) * 2009-11-04 2012-08-30 Nissan Chemical Industries, Ltd. Crystal forms of sulfonylurea compound and method for producing the same
JP2012197271A (ja) * 2011-03-07 2012-10-18 Sumitomo Chemical Co Ltd 水稲作における雑草防除方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07118269A (ja) * 1993-09-27 1995-05-09 Bayer Ag Ｎ−アジニル−ｎ′−（ヘト）アリールスルホニル−尿素
WO2005103044A1 (fr) * 2004-04-27 2005-11-03 Nissan Chemical Industries, Ltd. Composé de sulfonylurée de pyrazole et herbicide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07118269A (ja) * 1993-09-27 1995-05-09 Bayer Ag Ｎ−アジニル−ｎ′−（ヘト）アリールスルホニル−尿素
WO2005103044A1 (fr) * 2004-04-27 2005-11-03 Nissan Chemical Industries, Ltd. Composé de sulfonylurée de pyrazole et herbicide

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011039276A1 (fr) 2009-10-01 2011-04-07 Bayer Cropscience Ag Oxathiazinyl-(hétéro) arylsulfonylurées, procédé et produits intermédiaires pour leur préparation et leur utilisation en tant que pesticides et régulateurs de croissance des plantes
US20120220461A1 (en) * 2009-11-04 2012-08-30 Nissan Chemical Industries, Ltd. Crystal forms of sulfonylurea compound and method for producing the same
US8765640B2 (en) * 2009-11-04 2014-07-01 Nissan Chemical Industries, Ltd. Crystal forms of sulfonylurea compound and method for producing the same
JP2012197271A (ja) * 2011-03-07 2012-10-18 Sumitomo Chemical Co Ltd 水稲作における雑草防除方法

Also Published As

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TW200731927A (en) 2007-09-01
KR20080064160A (ko) 2008-07-08
JPWO2007046440A1 (ja) 2009-04-23

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