WO2014103812A1 - ピラゾール化合物の結晶の製造方法 - Google Patents

ピラゾール化合物の結晶の製造方法 Download PDF

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WO2014103812A1
WO2014103812A1 PCT/JP2013/083807 JP2013083807W WO2014103812A1 WO 2014103812 A1 WO2014103812 A1 WO 2014103812A1 JP 2013083807 W JP2013083807 W JP 2013083807W WO 2014103812 A1 WO2014103812 A1 WO 2014103812A1
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pyrazole compound
organic solvent
water
compound
formula
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PCT/JP2013/083807
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English (en)
French (fr)
Japanese (ja)
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匡哉 谷本
広田　将司
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住友化学株式会社
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Priority to BR112015015120A priority Critical patent/BR112015015120A2/pt
Publication of WO2014103812A1 publication Critical patent/WO2014103812A1/ja

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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

Definitions

  • the present invention relates to a method for producing a crystal of a pyrazole compound.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a methyl group, a monofluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.
  • Patent Document 1 a solid containing a pyrazole compound represented by the formula (I) in which R 1 is a hydrogen atom and R 2 is a difluoromethyl group is represented by the formula (I) by recrystallization from toluene. A method for producing crystals of pyrazole compounds is described.
  • An object of the present invention is to provide a method for industrially advantageously producing a crystal of a pyrazole compound represented by the formula (I).
  • the present inventor has intensively studied to develop a method for producing a crystal of a pyrazole compound represented by the formula (I) in an industrially advantageous manner, and has reached the present invention.
  • the present invention is as follows.
  • Formula (I) (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a methyl group, a monofluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.)
  • a crystal of the pyrazole compound represented by formula (I) is precipitated by removing the organic solvent from a mixture of a solution in which the pyrazole compound represented by formula (I) is dissolved in an organic solvent and water. The manufacturing method of the crystal
  • [2] A solution in which a pyrazole compound represented by the formula (I) is dissolved in an organic solvent and water are mixed, and the organic solvent is removed from the obtained mixture to thereby remove the pyrazole compound represented by the formula (I).
  • [4] The production method according to any one of [1] to [3], wherein the solution in which the pyrazole compound represented by the formula (I) is dissolved in an organic solvent contains a dispersant.
  • crystals of the pyrazole compound represented by the formula (I) can be produced industrially advantageously.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents a methyl group, a monofluoromethyl group, or a difluoromethyl group. Or represents a trifluoromethyl group.
  • the pyrazole compound (I) has the formula (IR) (In the formula, R 1 and R 2 have the same meaning as described above.) R-form (hereinafter sometimes abbreviated as pyrazole compound (1-R)) and formula (IS) (In the formula, R 1 and R 2 have the same meaning as described above.) S-form (hereinafter sometimes abbreviated as pyrazole compound (1-S)) is present, but pyrazole compound (I) may be pyrazole compound (IR) or pyrazole. Compound (IS) may be sufficient, and the mixture which contains both in arbitrary ratios may be sufficient.
  • the pyrazole compound (I) may be a racemate or an optically active substance.
  • the present invention provides a pyrazole compound (I) characterized by precipitating crystals of a pyrazole compound (I) by removing the organic solvent from a mixture of a solution in which the pyrazole compound (I) is dissolved in an organic solvent and water. ) Crystal production method.
  • the organic solvent is an organic solvent that can dissolve the pyrazole compound (I), and an organic solvent having a lower boiling point than water or an organic solvent that can be azeotroped with water is easy to remove the organic solvent. From the viewpoint, it is preferable.
  • Such an organic solvent may be a water-miscible organic solvent or a water-immiscible organic solvent.
  • the water-miscible organic solvent include alcohol solvents having 1 to 3 carbon atoms such as methanol, ethanol, propanol and isopropanol, water-soluble cyclic ether solvents such as tetrahydrofuran and dioxane, acetonitrile, acetone and methyl cellosolve.
  • a water-immiscible organic solvent is an organic solvent that can form two layers of an aqueous layer and an organic layer when mixed with water, specifically, an aliphatic hydrocarbon solvent such as pentane, hexane, cyclohexane, etc.
  • Aromatic hydrocarbon solvents such as toluene, xylene and ethylbenzene, halogenated aliphatic hydrocarbon solvents such as dichloromethane, chloroform and 1,2-dichloroethane, halogenated aromatic hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene, Water-insoluble ether solvents such as diethyl ether, diisopropyl ether, tert-butyl methyl ether and cyclohexyl methyl ether, water-insoluble ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, water-insoluble with 4 or more carbon atoms such as butanol and pentyl alcohol Alcohol solvent, methyl acetate Ethyl acetate, water-insoluble ester solvents such as propyl acetate.
  • Aromatic hydrocarbon solvents such as toluene, xy
  • At least one selected from the group consisting of an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, a halogenated aromatic hydrocarbon solvent, and an alcohol solvent having 1 to 3 carbon atoms is preferable.
  • the aromatic hydrocarbon solvent and the carbon number More preferred is at least one selected from the group consisting of 1 to 3 alcohol solvents.
  • the organic solvent preferably contains an alcohol solvent having 1 to 3 carbon atoms.
  • the concentration of the pyrazole compound (I) in the solution in which the pyrazole compound (I) is dissolved in the organic solvent varies depending on the kind of the pyrazole compound (I) and the kind of the organic solvent, but is preferably 5% by weight to 70% by weight, More preferably, it is 60% by weight.
  • a solution can be prepared, for example, by subjecting the reaction mixture obtained by the method for producing the pyrazole compound (I) described later to post-treatment such as washing and concentration.
  • the solution in which pyrazole compound (I) is dissolved in an organic solvent, water, or both may contain a dispersant.
  • Dispersants include alkyl sulfate, alkyl sulfonate, alkyl aryl sulfonate, dialkyl sulfo succinate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether phosphate, naphthalene sulfonate Formalin condensate, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, polyoxyethylene polyoxypropylene block copolymer, sorbidan fatty acid ester, polyoxysorbidic fatty acid ester, polyhydric alcohol ester, etc. An activator is mentioned.
  • the amount of the dispersant used is usually 0.005 to 0.05 parts by weight with respect to 1 part by weight of the pyrazole compound (I).
  • a solution in which the pyrazole compound (I) is dissolved in an organic solvent is mixed with water, and the organic solvent is removed from the resulting mixture to precipitate crystals of the pyrazole compound (I). Crystals of pyrazole compound (I) may be precipitated by removing the organic solvent while adding a solution of (I) dissolved in the organic solvent to water.
  • a method for precipitating crystals of the pyrazole compound (I) by mixing a solution of the pyrazole compound (I) dissolved in an organic solvent and water and removing the organic solvent from the obtained mixture will be described below.
  • the solution and water are mixed by a method of adding the solution to water. Alternatively, it may be carried out by adding water to the solution.
  • the mixing temperature is usually in the range of room temperature to the low temperature of the boiling point of the organic solvent or water, preferably 20 ° C. to 80 ° C., more preferably 25 ° C. to 65 ° C.
  • the mixing time is usually 1 minute to 24 hours.
  • the amount of water used is preferably 0.5 to 100 parts by weight, more preferably 1 to 20 parts by weight with respect to 1 part by weight of the pyrazole compound (I).
  • Stirring is usually performed by stirring means such as an anchor blade, paddle blade, turbine blade, swept blade, and bull margin blade.
  • the mixture obtained by mixing a solution in which the pyrazole compound (I) is dissolved in an organic solvent and water is preferably a mixture in which the solution is dispersed in water.
  • the removal of the organic solvent from the mixture may be performed under reduced pressure conditions or normal pressure conditions.
  • the pyrazole compound (I) is thermally unstable or when the boiling point of the organic solvent is higher than that of water, it is preferable to remove the organic solvent under reduced pressure conditions.
  • seed crystals may be added to the mixture.
  • the removal of the organic solvent is preferably carried out in the range of 20 ° C. to 90 ° C., more preferably in the range of 25 ° C. to 75 ° C.
  • the removal time is usually 1 minute to 30 hours.
  • water When water is removed together with the organic solvent such as when the organic solvent forms an azeotrope with water, water is added to the mixture from the viewpoint of improving the slurry properties of the mixture in which crystals of the pyrazole compound (I) are precipitated. While adding, it is preferable to remove the organic solvent. In this case, the water removed together with the organic solvent may be condensed to separate the organic solvent and water, and the separated water may be added to the mixture.
  • the removal of the organic solvent is preferably performed while stirring, and the stirring is usually performed by stirring means such as an anchor blade, paddle blade, turbine blade, swept blade, and bull margin blade.
  • This method is preferable in that the maximum volume of the mixture of the solution and water can be reduced.
  • seed crystals may be added to water.
  • the amount of water used is preferably 0.5 to 100 parts by weight, more preferably 1 to 20 parts by weight, with respect to 1 part by weight of the pyrazole compound (I).
  • the addition of the solution in which the pyrazole compound (I) is dissolved in an organic solvent to water may be performed under reduced pressure conditions or under normal pressure conditions.
  • the pyrazole compound (I) is thermally unstable or when the boiling point of the organic solvent is higher than the boiling point of water, it is preferable to add the solution to water under reduced pressure conditions.
  • the addition of the solution in which the pyrazole compound (I) is dissolved in the organic solvent to the water is performed at a temperature higher than the temperature at which the organic solvent can be distilled out by evaporation.
  • an azeotrope is formed, it is carried out at or above the azeotropic temperature.
  • the reaction is preferably performed at 20 ° C to 90 ° C, more preferably 25 ° C to 75 ° C.
  • the time for adding the solution in which the pyrazole compound (I) is dissolved in the organic solvent to the water is preferably substantially the same as the time for removing the organic solvent.
  • water When water is removed together with the organic solvent such as when the organic solvent forms an azeotrope with water, water is added to the mixture from the viewpoint of improving the slurry properties of the mixture in which crystals of the pyrazole compound (I) are precipitated. While adding, it is preferable to remove the organic solvent. In this case, the water removed together with the organic solvent may be condensed to separate the organic solvent and water, and the separated water may be added to the mixture.
  • the removal of the organic solvent is preferably performed while stirring, and the stirring is usually performed by stirring means such as an anchor blade, paddle blade, turbine blade, swept blade, and bull margin blade.
  • the precipitated crystals of the pyrazole compound (I) can be taken out by cooling the obtained slurry as necessary, followed by separation treatment such as filtration and decantation.
  • the temperature for the separation treatment is preferably 0 ° C. to 50 ° C., more preferably 5 ° C. to 40 ° C.
  • the extracted crystals of pyrazole compound (I) may be washed with water or the like, if necessary.
  • the drying may be performed under normal pressure conditions or under reduced pressure conditions, and the temperature is usually 20 ° C. to 80 ° C.
  • the pyrazole compound (I) can be produced, for example, by the following production method 1 or 2.
  • chlorinating agents examples include thionyl chloride, oxalyl chloride and phosgene.
  • the amount of the chlorinating agent to be used is generally 1 mol-2 mol, preferably 1 mol-1.5 mol, per 1 mol of compound (II).
  • the reaction between the compound (II) and the chlorinating agent can be carried out in the presence of a tertiary amine or amide.
  • Tertiary amines or amides include pyridine, picoline, N, N-dimethylformamide and N-methyl-N-phenylformamide.
  • the amount of the tertiary amine or amide to be used is generally 0.001 mol to 0.05 mol, preferably 0.003 mol to 0.03 mol, per 1 mol of compound (II).
  • the reaction between the compound (II) and the chlorinating agent is usually performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it is inert to the reaction, and is an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, and cyclohexane, an aromatic hydrocarbon solvent such as toluene, xylene, and ethylbenzene, dichloromethane, chloroform, 1, 2 -Halogenated aliphatic hydrocarbon solvents such as dichloroethane and carbon tetrachloride, halogenated aromatic hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene, and diethyl ether, diisopropyl ether, tert-butyl methyl ether, cyclohexyl methyl ether And ether solvents such as dioxane, aromatic hydrocarbon solvents and halogenated aromatic hydro
  • the reaction between the compound (II) and the chlorinating agent is usually carried out in the range of 10 ° C. to 100 ° C., preferably in the range of 40 ° C. to 80 ° C., and the reaction time is usually 0.1 hour to 24 hours.
  • the compound (III) can be taken out by concentrating the obtained reaction mixture.
  • the obtained compound (III) may be purified by distillation or the like.
  • the reaction between compound (III) and compound (IV) is carried out in the presence of a base.
  • a base include alkali metal carbonates such as sodium carbonate and potassium carbonate, tertiary amines such as triethylamine and diisopropylethylamine, and nitrogen-containing aromatic compounds such as pyridine and 4-dimethylaminopyridine.
  • the amount of the base to be used is generally a catalyst amount to 5 mol, preferably 1 mol to 3 mol, per 1 mol of compound (IV).
  • Compound (IV) may be a salt such as hydrochloride or hydrobromide.
  • the amount of compound (III) to be used is generally 0.5 mol to 1.5 mol, preferably 0.8 mol to 1.3 mol, per 1 mol of compound (IV).
  • the reaction between compound (III) and compound (IV) is usually performed in the presence of a solvent.
  • the solvent is not particularly limited as long as it is inert to the reaction, and is an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, and cyclohexane, an aromatic hydrocarbon solvent such as toluene, xylene, and ethylbenzene, dichloromethane, chloroform, 1, Halogenated aliphatic hydrocarbon solvents such as 2-dichloroethane and carbon tetrachloride, halogenated aromatic hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene, diethyl ether, diisopropyl ether, tert-butyl methyl ether, cyclohexyl methyl ether, Examples include ether solvents such as tetrahydrofuran and dioxane, ester solvents such as
  • Aromatic hydrocarbon solvents Preferably, toluene, xylene, ethylbenzene, chlorobenzene and tetrahydrofuran is more preferable. Two or more solvents may be used in combination.
  • the amount of the solvent used is preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight, relative to 1 part by weight of compound (IV).
  • reaction between compound (III) and compound (IV) is usually carried out in the range of ⁇ 20 ° C. to 80 ° C., preferably 0 ° C. to 60 ° C., more preferably 20 ° C. to 55 ° C. 1 to 24 hours.
  • a solution containing compound (I) can be obtained by mixing an aqueous acid solution and then separating the solution into an organic layer and an aqueous layer.
  • the obtained solution is preferably water, an aqueous solution of sodium bicarbonate, an aqueous solution of sodium carbonate, an aqueous solution of ammonium chloride, an aqueous solution of sodium hydroxide, an aqueous solution of potassium hydroxide, or an aqueous solution of an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid. Washed. Such washing is usually performed at 0 to 70 ° C., preferably 20 to 60 ° C.
  • the obtained solution can be used in the present invention as it is.
  • dehydrating condensing agent examples include 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, carbodiimide compounds such as 1,3-dicyclohexylcarbodiimide, and (benzotriazol-1-yloxy) tris (dimethylamino) phosphonium. Hexafluorophosphate is mentioned.
  • the amount of the dehydrating condensing agent used is usually 1 mol to 5 mol with respect to 1 mol of the compound (II).
  • the amount of compound (IV) to be used is generally 0.5 mol to 3 mol with respect to 1 mol of compound (II).
  • solvents include ether solvents such as tetrahydrofuran, ethylene glycol dimethyl ether and tert-butyl methyl ether, aliphatic hydrocarbon solvents such as hexane, heptane and octane, aromatic hydrocarbon solvents such as toluene and xylene, and halogenated carbonization such as chlorobenzene.
  • Hydrogen solvents such as butyl acetate and ethyl acetate, nitrile solvents such as acetonitrile, acid amide solvents such as N, N-dimethylformamide, sulfoxide solvents such as dimethyl sulfoxide, and nitrogen-containing aromatic compound solvents such as pyridine Can be mentioned. Two or more solvents may be used in combination. The amount of the solvent used is usually 1 part by weight to 20 parts by weight with respect to 1 part by weight of the compound (II).
  • reaction between compound (II) and compound (IV) is usually carried out in the range of ⁇ 20 ° C. to 140 ° C., and the reaction time is usually 1 hour to 24 hours.
  • the resulting mixture can be filtered to take out the pyrazole compound (I) and the solid does not precipitate.
  • the pyrazole compound (I) can be taken out by extracting the obtained mixture with an organic solvent, separating the organic layer, and concentrating.
  • the obtained organic layer can be used in the present invention as it is or after washing.
  • an optically active substance of pyrazole compound (I) By using an optically active substance as compound (IV), an optically active substance of pyrazole compound (I) can be obtained.
  • a solution prepared by dissolving the obtained 1-methyl-3-difluoromethylpyrazole-4-carboxylic acid chloride in 9.36 g of toluene was subjected to (R) -1,1,3- at 45 ° C. to 50 ° C.
  • a solution prepared by mixing 9.29 g of trimethyl-4-aminoindane (optical purity: 95.2% ee), 5.81 g of triethylamine and 28.03 g of toluene was added dropwise over 1 hour. After completion of the dropwise addition, the obtained mixture was stirred at 45 ° C. to 50 ° C. for 2 hours. After mixing the obtained reaction mixture and water, the organic layer was separated.
  • the obtained 1-methyl-3-difluoromethylpyrazole-4-carboxylic acid chloride was subjected to (R) -1,1,3-trimethyl-4-aminoindane (optical purity: 90.2) at 0 ° C. to 5 ° C. % Ee) was added dropwise over 1 hour to a solution prepared by mixing 20.03 g, 12.52 g of triethylamine and 110.04 g of toluene. After completion of the dropwise addition, the obtained mixture was stirred at 0 ° C. to 5 ° C. for 1 hour, then heated to 20 ° C. to 25 ° C. and stirred at the same temperature for 2 hours. After mixing the obtained reaction mixture and water, the organic layer was separated.
  • Example 1 A 500-mL flask equipped with a stirrer equipped with three receding blades, a baffle, a condenser tube, and a thermometer was kept warm with warm water adjusted to 62 ° C. A flask was charged with 84.4 g of a toluene solution (concentration: 50 wt%) of pyrazole compound (a) (optical purity: 90.4% ee) and 0.3 g of sodium bis (2-ethylhexyl) sulfosuccinate. While stirring, 295.3 g of water was added to the obtained mixture.
  • the mixture in the flask was in a state where the toluene solution of the pyrazole compound (a) was uniformly dispersed in water. While stirring the mixture, the pressure in the flask was reduced to 30.3 kPa, and toluene was removed over 5 hours. While removing toluene, the temperature of the warm water was raised to 75 ° C. over 4 hours, and water was added so that the amount of liquid in the flask did not decrease. In order to promote crystallization of the pyrazole compound (a), 0.4 g of seed crystals were added.
  • Example 2 A 300-mL flask equipped with a stirrer equipped with three receding blades, a baffle, a condenser, and a thermometer was kept warm with warm water adjusted to 60 ° C. A flask was charged with 43.3 g of a toluene solution (concentration: 50 wt%) of pyrazole compound (a) (optical purity: 95.4% ee) and 0.06 g of sodium bis (2-ethylhexyl) sulfosuccinate. While stirring, 64.9 g of water was added to the resulting mixture. While stirring the obtained mixture, the pressure in the flask was reduced to 30.3 kPa, and toluene was removed over 3 hours.
  • a toluene solution
  • Example 3 303.5 g of water and 1 g of seed crystals were charged into a 500-mL flask equipped with a stirrer equipped with three blades, a baffle, a cooling tube, and a thermometer. The flask was kept warm with warm water adjusted to 43 ° C. While stirring the mixture in the flask, the pressure in the flask was reduced to 7.3 kPa, and the mixture was refluxed. The temperature of the mixture in the flask at this time was 40.6 ° C.
  • Example 4 300.3 g of water and 1 g of seed crystals were charged into a 500-mL flask equipped with a stirrer equipped with three blades, a baffle, a cooling tube, and a thermometer. The flask was kept warm with warm water adjusted to 45 ° C. While stirring the mixture in the flask, the pressure in the flask was reduced to 5.3 kPa, and the mixture was refluxed. The temperature of the mixture in the flask at this time was 35 ° C.
  • crystals of a pyrazole compound exhibiting a controlling effect against plant diseases can be produced industrially advantageously.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
PCT/JP2013/083807 2012-12-25 2013-12-11 ピラゾール化合物の結晶の製造方法 WO2014103812A1 (ja)

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BR112015015120A BR112015015120A2 (pt) 2012-12-25 2013-12-11 processo para produzir cristal de composto pirazol

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9765032B2 (en) 2014-02-07 2017-09-19 Sumitomo Chemical Company, Limited Method for producing (R)-1,1,3-trimethyl-4-aminoindane
WO2021085263A1 (ja) * 2019-11-01 2021-05-06 住友化学株式会社 ３－（ジフルオロメチル）－１－メチル－ｎ－（１，１，３－トリメチル－２，３－ジヒドロ－１ｈ－インデン－４－イル）－１ｈ－ピラゾール－４－カルボキサミドの結晶

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JPH06505252A (ja) * 1991-01-28 1994-06-16 モンサント・カンパニー ３−ジフルオロメチルピラゾールカルボキサミド殺菌剤
JPH07291884A (ja) * 1994-04-28 1995-11-07 Dai Ichi Kogyo Seiyaku Co Ltd 粉末状高融点２，２−ビス［４′−（２″，３″−ジブロモプロポキシ）−３′，５′−ジブロモフェニルプロパンの製造方法
JP2002226464A (ja) * 2001-01-30 2002-08-14 Sumitomo Pharmaceut Co Ltd トリアリール類縁体およびその利用
JP2012025735A (ja) * 2010-06-24 2012-02-09 Sumitomo Chemical Co Ltd 植物病害防除組成物及び植物病害防除方法

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JPH06505252A (ja) * 1991-01-28 1994-06-16 モンサント・カンパニー ３−ジフルオロメチルピラゾールカルボキサミド殺菌剤
JPH07291884A (ja) * 1994-04-28 1995-11-07 Dai Ichi Kogyo Seiyaku Co Ltd 粉末状高融点２，２−ビス［４′−（２″，３″−ジブロモプロポキシ）−３′，５′−ジブロモフェニルプロパンの製造方法
JP2002226464A (ja) * 2001-01-30 2002-08-14 Sumitomo Pharmaceut Co Ltd トリアリール類縁体およびその利用
JP2012025735A (ja) * 2010-06-24 2012-02-09 Sumitomo Chemical Co Ltd 植物病害防除組成物及び植物病害防除方法

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9765032B2 (en) 2014-02-07 2017-09-19 Sumitomo Chemical Company, Limited Method for producing (R)-1,1,3-trimethyl-4-aminoindane
WO2021085263A1 (ja) * 2019-11-01 2021-05-06 住友化学株式会社 ３－（ジフルオロメチル）－１－メチル－ｎ－（１，１，３－トリメチル－２，３－ジヒドロ－１ｈ－インデン－４－イル）－１ｈ－ピラゾール－４－カルボキサミドの結晶

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