WO2005105755A1 - Processus de production de 5-difluorométhoxy -4-thiométhylpyrazoles - Google Patents

Processus de production de 5-difluorométhoxy -4-thiométhylpyrazoles Download PDF

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WO2005105755A1
WO2005105755A1 PCT/JP2005/007847 JP2005007847W WO2005105755A1 WO 2005105755 A1 WO2005105755 A1 WO 2005105755A1 JP 2005007847 W JP2005007847 W JP 2005007847W WO 2005105755 A1 WO2005105755 A1 WO 2005105755A1
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group
alkyl
difluoromethoxy
general formula
branched
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PCT/JP2005/007847
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Yukio Uchida
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Ihara Chemical Industry Co., Ltd.
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    • 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
    • C07D231/20—One oxygen atom attached in position 3 or 5

Definitions

  • the present invention relates to a method for producing a 5-difluoromethoxy-4 thiomethylpyrazolide conjugate.
  • the 5-difluoromethoxy-4-thiomethylpyrazole compound obtained by the present invention is useful as an intermediate for producing pharmaceuticals and agricultural chemicals.
  • Non-Patent Document 1 a method of reacting a 5-hydroxypyrazole compound with chlorodifluoromethane in an N, N dimethylformamide solvent in the presence of potassium hydrogen carbonate (Non-Patent Document 1), and a method in which a reaction is carried out in a mixed solvent of dioxane and water in the presence of sodium hydroxide (see Patent Document 1).
  • the 5-hydroxy-4-thiomethylpyrazole compound exists as a keto-enol tautomer, and the keto-type compound is a product obtained by adding Michael with a sulfur compound to an olefin having an electron withdrawing group.
  • Michael addition it is known that this type of Michael addition is reversible, and the sulfur compound is eliminated when the adduct is heated with a strong base (see Non-Patent Document 2).
  • a 5-difluoromethoxy-4-thiomethylvirazole compound is to be obtained from a 5-hydroxy-4-thiomethylpyrazole compound using chlorodifluoromethane under strong base conditions, for example, the reaction is carried out in an alcohol solvent. It is known that the raw material is decomposed in competition with the progress of the reaction (see Non-Patent Document 2).
  • Patent Document 1 International Publication No.W095Z19967
  • Non-patent document 1 J. Medicinal Chemis try), Vol. 43-No. 16, 2975-2981 (2000)
  • Non-Patent Document 2 Role of Sulfur Compounds in Organic Synthesis (Sankyo Shuppan Co., Ltd.), Chapter 5.5.2, pp. 171-174, (1981)
  • the present invention provides a novel method for efficiently producing a 5-difluoromethoxy-4-thiomethylpyrazole compound using chlorodifluoromethane with respect to a 5-hydroxy-4-thiomethylpyrazole compound.
  • the method of the present invention provides a novel industrial production method of 5 difluoromethoxy-4-thiomethylpyrazolide conjugate.
  • a 5-difluoromethoxy-4-thiomethylpyrazolide compound can be produced by a simple operation using a 5-hydroxy-4-thiomethylpyrazole compound and a halogenated difluoromethane as raw materials.
  • the decomposition time of raw materials and products is small, and the reaction time is greatly shortened, so that the method has high industrial utility value.
  • halogenated difluoromethane represented by the general formula (3) is reacted in the presence of di (C1-C3 alkyl) ketone or (C1-C3 alkyl) nitrile and sodium hydroxide.
  • a method for producing a 5 difluoromethoxy 4 thiomethylpyrazole compound represented by the formula: [2] The production method according to the above [1], wherein X in the general formula (2) is chlorine.
  • the present invention relates to a 5-hydroxy-4 thiomethylpyrazole compound represented by the general formula (1) and a halogenated difluoromethane represented by the general formula (2), wherein di (C1-C3 alkyl) ketone or (C1- A process for producing a 5-difluoromethoxy-4-thiomethylpyrazole compound represented by the general formula (3), characterized by reacting in the presence of (C3 alkyl) nitrile and sodium hydroxide.
  • R in the general formula (1) includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n- A linear or branched C1-C6 alkyl group such as an xyl group; for example, a monocyclic or condensed-ring C6-C10 aromatic hydrocarbon group such as a fluor group or a naphthyl group (the aromatic hydrocarbon group is For example, halogen atoms such as bromo, chloro, fluoro, and odo; for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n A straight-chain or branched C1-C6 alkyl group such as a hexyl group; a hydroxyl group
  • Aromatic heterocyclic group (the aromatic heterocyclic group is, for example, a halogen atom such as promo, chloro, fluoro, oxade; etc .; for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group)
  • Linear or branched C1-C6 alkyl groups such as sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group; hydroxyl group; for example, methoxy group, ethoxy group, n-propoxy group, A linear or branched (C1-C6 alkoxy)-(C1-C6 alkyl) group such
  • a substituent such as a cyano group
  • a hydrofuryl group a vinyl group, a thiol group, a thianyl group, a pyrrolidinyl group, an indole group, or a piperidinyl group.
  • a heterocyclic group having 5 to 14, preferably 5 to 10 monocyclic or condensed rings having no aromaticity is, for example, a methyl group, ethyl, A linear or branched C1-C6 alkyl group such as a group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group; hydroxyl group; for example, methoxy group A straight-chain or branched C1-C6 alkoxy group such as a group, an ethoxy group, an n-propoxy group, an isopropoxy group; a straight-chain or branched C1-C6 hydride such as a hydroxymethyl group or a hydroxyethyl group; Roxyalkyl group; linear or branched (C1-C6 alkoxy) -mono (C1-C6
  • a nitrogen atom, an oxygen atom, or a sulfur nuclear atom such as a pyridylcarbyl group, a chlorocarbol group, or a furylcarbol group.
  • Having 1 to 4 at least one heteroatom and having at least one substituent such as a monocyclic or condensed ring heteroarylcarbonyl group having 5 to 14, preferably 5 to 10 atoms constituting the ring; Possess May be.
  • Attracting atomic group specifically, for example, a linear or branched C1-C6 haloalkyl group such as a difluoromethyl group and a trifluoromethyl group; a carboxyl group; for example, a methoxycarbol group, an ethoxycarbol group, and the like.
  • a straight-chain or branched (C1-C6 alkoxy) carboxy group for example, a halogen atom such as bromo, chloro, fluoro, and odo; a nitro group; a formyl group; for example, a methylcarbyl group and an ethylcarbyl group
  • a straight-chain or branched (C1-C6 alkyl) carboxy group an aminocarbon group; for example, a straight-chain or branched (C1-C6 alkyl) amino group such as a methylaminocarbon group; Linear or branched di (C1-C6 alkyl) amino carboyl groups such as nocarbol groups;
  • a group that attracts a partner force electron by an inducing effect as a substituent such as a chromophore group, an acetylethyl group, a nitrophenyl group, an acetylnaphthyl group, etc.
  • An atomic group that attracts a partner electron by an induced effect as a substituent for example, a linear or branched C1-C6 haloalkyl group exemplified as an atomic group that attracts a partner electron by an induced effect; Carboxyl group; straight-chain or branched (C1-C6 alkoxy) force rubonyl group; halogen atom; nitro group; formyl group; straight-chain or branched (C1-C6 alkyl) carboxy group; aminocarboyl group; Or one or more branched (C1-C6 alkyl) aminocarboyl groups; linear or branched di (C1-C6 alkyl) aminocarboyl groups; an atomic group such as a cyano group), a nitrogen atom, an oxygen atom, a sulfur atom
  • the substituent represented by R in the general formula (1) is, for example, a methyl group, an ethyl group, an n-propyl group.
  • Linear or branched C1-C6 alkyl groups such as pill, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl; phenyl, naphthyl
  • a monocyclic or condensed ring C6-C10 aromatic hydrocarbon group for example, a halogen atom such as bromo, chloro, fluoro, and odo; a methyl group and an ethyl group
  • a straight-chain or branched C1-C6 alkyl group such as n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group; hydroxy group; Linear or branched C1-C6 alkoxy group such as ethoxy group, n-propoxy group, isopropoxy group; linear or
  • C1 ⁇ C6 A straight-chain or branched C1-C6 haloalkyl group such as a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group; a carboxyl group; a straight-chain group such as a methoxycarbyl group and an ethoxycarbol group; Chain or branched (C1-C6 alkoxy) carboxy group; nitro group; for example, straight-chain or branched (C1-C6 alkoxy) group such as methoxycarbylmethyl group, 1-methoxycarboxyletyl group, 1 ethoxycarboleluryl group, etc.
  • Carbonyl- (C1-C6 alkyl) group may have a substituent such as a cyano group.
  • a furyl group for example, a furyl group, a benzofuryl group, a pyridyl group, a chel group, a benzochel group, an oxazolyl group, a benzoxazolyl group, a thiazolyl group, a benzothiazolyl group, an isooxazolyl group, a thiadiazolyl group, a virazyl group, and a pyrimidyl group.
  • a straight-chain or branched (C1-C6 alkoxy) mono (C1-C6 alkyl) group such as methoxymethyl group, 1-methoxyethyl group, and 1-ethoxyethyl group; for example, fluoromethyl
  • Straight-chain or branched C1 to C6 haloalkyl group such as group, difluoromethyl group, trifluoromethyl group
  • carboxyl group for example, straight-chain or branched (C1-C6) group such as methoxycarbyl group, ethoxycarbol group and the like.
  • a heterocyclic group preferably having 5 to 10 monocyclic or condensed-ring aromatic groups (the heterocyclic group having no aromatic group is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group).
  • Linear or branched C1-C6 alkyl groups such as n-, n-, sec-, t-, n-pentyl, and n-hexyl groups; hydroxyl groups; for example, methoxy, ethoxy, n-
  • a linear or branched C1-C6 alkoxy group such as a propoxy group or an isopropoxy group; for example, a linear or branched C1-C6 hydroxyalkyl group such as a hydroxymethyl group or a hydroxyethyl group; for example, a methoxymethyl group
  • a straight-chain or branched (C1-C6 alkoxy) -mono (C1-C6 alkyl) group such as a methoxyethyl group or an ethoxyxyl group; for example, a straight-chain or branched group such as a fluoromethyl group, a difluoromethyl group, and a trifluoromethyl group; C1
  • a heterocyclic group having or not having an aromatic property can be exemplified.
  • the compound represented by the general formula (1) is a sulfide; and when n is 2, the compound represented by the general formula (1) is a sulfone. .
  • the 5-hydroxy-4 thiomethylpyrazole compound represented by the general formula (1) is a known compound. Or can be easily synthesized, for example, by reacting 5-hydroxypyrazoles with formaldehyde and sulfur conjugates as described in Reference Examples 1 to 4 below. .
  • X in the general formula (2) represents a halogen atom such as fluoro, chloro, bromo, and odo. Therefore, specific examples of the halogenated difluoromethane represented by the general formula (2) that can be used in this reaction include trifluoromethane, chlorodifluoromethane, bromodifluoromethane, and difluoroiodomethane. Preferred are chlorodifluoromethane and bromodifluoromethane. Particularly preferred are chlorodifluoromethane.
  • the halogenated difluoromethane represented by the general formula (2) is a known compound.
  • the reaction proceeds at any molar ratio of the halogenated difluoromethane represented by the general formula (2) to the 5-hydroxy-4 thiomethylpyrazole compound represented by the general formula (1).
  • the halogenated difluoromethane power represented by the general formula (2) is usually 0.1 to 10.0 mol, preferably 1.0 mol, per 1 mol of the 5-hydroxy-4-thiomethylpyrazole compound represented by the general formula (1).
  • the range is, for example, about 5.0 to 5.0 mol, and more preferably 1.3 to 2.2 mol.
  • This reaction is performed using sodium hydroxide.
  • sodium hydroxide examples include a commercially available 96% sodium hydroxide, which is good as long as it is a solid sodium hydroxide, and a bead-like 99% hydroxyl available as an industrial product. In particular, 99% sodium hydroxide is preferred.
  • the amount of sodium hydroxide used may be any amount as long as the reaction proceeds sufficiently. Among them, 1.0 to 20 mol, preferably 1.5 to 10 mol, more preferably 2.0 to 3 mol per mol of the 5-hydroxy-4 thiomethylpyrazole compound represented by the general formula (1). 0 mol range.
  • the additive acts to trap water produced as a by-product of the reaction in the reaction system as an additive. Or by coexisting sodium carbonate in the reaction system, especially scale-up In some cases, the yield can be stably increased. Further, the addition of the additive also suppresses the hydrolysis of halogenated difluoromethane, and consequently leads to a reduction in the amount of used difluoromethane.
  • the amount of the additive to be used is not particularly limited, but is preferably 0.01 to 20 mol, preferably 0.1 to 1 mol of the 5-hydroxy-14-thiomethylpyrazole compound represented by the general formula (1). A sufficient effect is exhibited in a range of from about 10 to 10 mol, more preferably from 0.2 to 0.5 mol.
  • the additive acts to capture water produced as a by-product in the reaction system as the reaction progresses, and that the additive progresses.
  • the additive functions to trap water produced as a by-product in the reaction system, other than the above examples may be used in some cases, and the present invention also includes these.
  • the reaction is carried out by, for example, di (C1-C3 alkyl) ketone such as acetone or methylethylketone; or (C1-C3 alkyl) nitrile such as acetonitrile or propio-tolyl. Perform in the presence. Normally, an excess amount is used also as a solvent for the reaction so that the reaction system can be sufficiently stirred, and specifically, is usually used per 1 mol of the starting material represented by the general formula (1).
  • Di (C1-C3 alkyl) ketone and (C1-C3 alkyl) nitrile are used alone or in a solvent that does not hinder the reaction, for example, aromatic hydrocarbons such as toluene, xylene, and benzene. Hydrogen; halogenated aliphatic hydrocarbons such as dichloromethane and chloroform; ether solvents such as getyl ether and diisopropyl ether; and aliphatic hydrocarbons such as pentane and n-hexane can also be used.
  • aromatic hydrocarbons such as toluene, xylene, and benzene.
  • Hydrogen halogenated aliphatic hydrocarbons such as dichloromethane and chloroform
  • ether solvents such as getyl ether and diisopropyl ether
  • aliphatic hydrocarbons such as pentane and n-hexane
  • the ratio (volume ratio) is 1 or more (that is, the volume is equal to or more than that of a solvent to be mixed with an aromatic hydrocarbon or the like), and di (C1 to C3 alkyl) ketone and (C1 to C3 alkyl) nitrile are Even when used in a mixture with a solvent that does not inhibit the reaction, the amount used is within the above range (di (C1 to C3 alkyl) ketone, (C1 to C3) per mole of the starting compound represented by the general formula (1).
  • (Alkyl) nitrile is usually from 0.05 to: L01, preferably from 0.3 to 51, more preferably from 0.5 to 21. Box).
  • the total amount of the solvent may be an amount that can sufficiently stir the reaction system, and is usually 0.05 to: L01, preferably 1 mol, per mol of the starting compound represented by the general formula (1). It may be in the range of 0.5 to 21.
  • the reaction must be carried out at a reaction temperature of ⁇ 10 ° C. to 35 ° C., and preferably 0 ° C. to 10 ° C. in combination with the reaction rate.
  • reaction time of this reaction is not particularly limited, the reaction rate varies depending on the introduction rate of the halogenated difluoromethane represented by the general formula (2). Usually, the reaction is completed in 1 hour to 30 hours.
  • each component to the reactor and the reaction method are not particularly limited.
  • a base is added to the organic layer, the starting material represented by the general formula (1) is added thereto, suspended, and then the reaction is carried out by introducing halogenated difluoromethane. And a method for obtaining a product represented by the general formula (3).
  • the 5-hydroxy-4-thiomethylpyrazole compound represented by the general formula (1) and the halogenated difluoromethane represented by the general formula (2) are reacted with dihydromethane in the presence of sodium hydroxide.
  • a 5-difluoromethoxy-4 thiomethylpyrazolide conjugate represented by the general formula (3) is produced.
  • the resulting 5-difluoromethoxy-4-thiomethylpyrazoyl conjugate represented by the general formula (3) is a compound useful as an intermediate for pharmaceuticals and agricultural chemicals.
  • Example 2 The reaction was carried out in the same manner as in Example 2 except that 99% sodium hydroxide was replaced by 99% potassium hydroxide in Example 2 (the number of moles used was the same). As a result, in the analysis one hour after the start of the blowing, only 10% of the target product was generated, the raw material had disappeared, and the remainder was a decomposition product.
  • Example 2 The reaction was carried out in the same manner as in Example 2, except that sodium hydroxide was replaced with potassium hydrogen carbonate in Example 2 (the number of moles used was the same). As a result, in the analysis 24 hours after the start of the blowing, only 1% or less of the target product was produced, and the remainder was raw material.
  • the aqueous layer was re-extracted with 20 ml of ethyl acetate, and the combined organic layer was washed successively with 10 ml of water and 10 ml of saturated saline.
  • the obtained organic layer was dried over sodium sulfate, and the solvent was distilled off, thereby obtaining the title compound (1.2 g, yield 88%) as a pale yellow liquid.
  • the aqueous layer was re-extracted with 2 Oml of ethyl acetate, and the combined organic layers were sequentially washed with 10 ml of water and 10 ml of saturated saline.
  • the obtained organic layer was dried over sodium sulfate, and the solvent was distilled off, thereby obtaining 2.1 g (yield: 99%) of the title compound as pale yellow crystals.
  • the obtained crystals were recrystallized from n-hexane-2 propanol and obtained as white crystals.
  • Example 8 Method for synthesizing 4 -— [(3 cyano 5 difluoromethoxy 1-ferbilazolo 4-yl) -methylsulfonyl] toluene
  • Example 9 3 — [(5 difluoromethoxy) using sodium carbonate as an additive
  • the suspension was cooled on ice, and while maintaining the temperature in the range of 5 to 15 ° C, 130 g (1.5 mol) of chlorodifluoromethane was introduced over 4 hours, and the reaction was carried out at the same temperature for 6 hours. After completion of the reaction, 1, OOO ml of water was added, and the organic layer was separated. After re-extracting the aqueous layer with 300 ml of acetonitrile, the organic layers were combined. Internal standard analysis method using gas chromatography in the organic layer As a result of calculating the reaction yield by the above, the yield was 91%.
  • a novel industrial method for producing 5-difluoromethoxy-4thiomethylpyrazolide conjugate is provided.
  • a 5-hydroxy-4-thiomethylpyrazole compound and a halogenated difluoromethane are used as raw materials to prepare a 5-difluoromethoxy-4-thiomethylpyrazolide conjugate by a simple operation.

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Abstract

Un processus pour produire facilement du 5-difluorométhoxy-4-thiométhyl- pyrazoles en masse, à savoir un processus de production de 5-difluorométhoxy-4-thiométhylpyrazoles représenté par la formule générale (3) : (3) [où R1 est un alkyle ou similaire, R2 est un groupe attractif d'électrons, R3 est un alkyle ou similaire et n vaut 0 ou 2], caractérisé par la réaction d'un 5-hydroxy-4-thiométhylpyrazole représenté par la formule générale (1) : (1) [où R1, R2, R3 et n sont chacun tels que définis ci-dessus] avec un halogénure de difluorométhyle représenté par la formule générale (2) : CHF2X (2) [où X est halogène] en présence soit de cétone de dialkyle, soit d'un nitrile d'alkyle et d'hydroxyde de sodium. Selon le processus, les composés objectifs peuvent être produits par une opération simple. De plus, le processus souffre peu de la décomposition des matières premières des produits et apporte une réduction remarquable du temps de réaction, il a ainsi une forte efficacité industrielle.
PCT/JP2005/007847 2004-04-28 2005-04-25 Processus de production de 5-difluorométhoxy -4-thiométhylpyrazoles WO2005105755A1 (fr)

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WO2006068092A1 (fr) * 2004-12-20 2006-06-29 Ihara Chemical Industry Co., Ltd. Procede de production de sels de (4,5-dihydroisoxazol-3-yl)thiocarboxamidine
US7465805B2 (en) 2004-10-05 2008-12-16 Syngenta Limited Isoxazoline derivatives and their use as herbicides
EP2065373A1 (fr) 2007-11-30 2009-06-03 Bayer CropScience AG Dérivés de chirale 3-(benzylsulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole et dérivés de 5,5-dimethyl-3-[(1H-pyrazol-4-ylmethyl) sulfinyl]-4,5-dihydroisoxazole, leur procédé de fabrication ainsi que leur utilisation en tant qu'herbicides et régulateurs de croissance des plantes
JP2010527974A (ja) * 2007-05-25 2010-08-19 アボット ゲーエムベーハー ウント カンパニー カーゲー 代謝型グルタミン酸受容体２（ｍｇｌｕ２受容体）の陽性調節剤としての複素環化合物
WO2021002484A2 (fr) 2019-10-31 2021-01-07 クミアイ化学工業株式会社 Herbicide et procédé de production d'un intermédiaire de celui-ci
WO2022137370A1 (fr) * 2020-12-23 2022-06-30 クミアイ化学工業株式会社 Procédé de production de dérivé de sulfone
CN114716428A (zh) * 2022-05-06 2022-07-08 山东潍坊润丰化工股份有限公司 制备砜吡草唑中间体的方法
WO2023074828A1 (fr) 2021-10-29 2023-05-04 クミアイ化学工業株式会社 Composé disulfure, composé polysulfure et utilisation associée

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Cited By (16)

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Publication number Priority date Publication date Assignee Title
US7465805B2 (en) 2004-10-05 2008-12-16 Syngenta Limited Isoxazoline derivatives and their use as herbicides
US7714142B2 (en) 2004-12-20 2010-05-11 Ihara Chemical Industry Co., Ltd. Process for production of (4,5-dihydroisoxazol-3-Y) thio-carboxamidine salts
JPWO2006068092A1 (ja) * 2004-12-20 2008-06-12 イハラケミカル工業株式会社 （４，５−ジヒドロイソオキサゾロ−３−イル）チオカルボキサミジン塩化合物の製造方法
WO2006068092A1 (fr) * 2004-12-20 2006-06-29 Ihara Chemical Industry Co., Ltd. Procede de production de sels de (4,5-dihydroisoxazol-3-yl)thiocarboxamidine
US9242933B2 (en) 2007-05-25 2016-01-26 AbbVie Deutschland GmbH & Co. KG Heterocyclic compounds as positive modulators of metabotropic glutamate receptor 2 (mGlu2 receptor)
JP2010527974A (ja) * 2007-05-25 2010-08-19 アボット ゲーエムベーハー ウント カンパニー カーゲー 代謝型グルタミン酸受容体２（ｍｇｌｕ２受容体）の陽性調節剤としての複素環化合物
US8420570B2 (en) 2007-11-30 2013-04-16 Bayer Cropscience Ag Chiral 3-(benzylsulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole derivatives and 5,5-dimethyl-3-[(1H-pyrazol-4-ylmethyl)sulfinyl]-4,5-dihydroisoxazole derivatives, method for the production thereof, and use of same as herbicides and plant growth regulations
US8895471B2 (en) 2007-11-30 2014-11-25 Bayer Cropscience Ag Chiral3-(benzylsulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole derivatives and 5,5-dimethyl-3-[(1h-pyrazol-4-ylmethyl)sulfinyl]-4,5-dihyddroisoxazole derivatives, method for the production thereof, and use of same as herbicides and plant growth regulators
EP2065373A1 (fr) 2007-11-30 2009-06-03 Bayer CropScience AG Dérivés de chirale 3-(benzylsulfinyl)-5,5-dimethyl-4,5-dihydroisoxazole et dérivés de 5,5-dimethyl-3-[(1H-pyrazol-4-ylmethyl) sulfinyl]-4,5-dihydroisoxazole, leur procédé de fabrication ainsi que leur utilisation en tant qu'herbicides et régulateurs de croissance des plantes
WO2021002484A2 (fr) 2019-10-31 2021-01-07 クミアイ化学工業株式会社 Herbicide et procédé de production d'un intermédiaire de celui-ci
KR20220097436A (ko) 2019-10-31 2022-07-07 구미아이 가가쿠 고교 가부시키가이샤 제초제 및 그 중간체의 제조방법
KR20230053729A (ko) 2019-10-31 2023-04-21 구미아이 가가쿠 고교 가부시키가이샤 제초제 및 그 중간체의 제조방법
WO2022137370A1 (fr) * 2020-12-23 2022-06-30 クミアイ化学工業株式会社 Procédé de production de dérivé de sulfone
WO2023074828A1 (fr) 2021-10-29 2023-05-04 クミアイ化学工業株式会社 Composé disulfure, composé polysulfure et utilisation associée
CN114716428A (zh) * 2022-05-06 2022-07-08 山东潍坊润丰化工股份有限公司 制备砜吡草唑中间体的方法
CN114716428B (zh) * 2022-05-06 2024-02-06 山东潍坊润丰化工股份有限公司 制备砜吡草唑中间体的方法

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