210631-68-8

Usage

Uses

Used in Agriculture:
TOPRAMEZONE is used as a herbicide for the treatment of broad-leaved weeds and grass weeds in maize crop protection. It effectively controls these weeds, ensuring the healthy growth of maize crops and increasing agricultural productivity.

InChI:InChI=1/C16H17N3O5S/c1-9-10(15(20)11-8-17-19(2)16(11)21)4-5-13(25(3,22)23)14(9)12-6-7-24-18-12/h4-5,8,21H,6-7H2,1-3H3

Synthetic route

1,4-dioxane (123-91-1) + 3-(3-bromo-2-methyl-6-(methylsulfonyl)phenyl)-4,5-dihydroisoxazole (247922-29-8) + 1-methyl-5-hydroxypyrazole (33641-15-5) → topramezone (210631-68-8)

Conditions	Yield
With carbon monoxide; potassium carbonate; triethylamine; triphenylphosphine; palladium(II) chloride In water	100%
With hydrogenchloride; potassium carbonate; triethylamine; bis(triphenylphosphine)palladium(II) dichloride In water

[3-(4,5-dihydro-1,2-oxazol-3-yl)-4-methylsulfonyl-2-methylphenyl](5-methoxy-1-methylpyrazole-4-yl)methanone → topramezone (210631-68-8)

Conditions	Yield
With hydrogen bromide; methyl(tri-n-octyl)ammonium bromide for 3h; Reagent/catalyst; Reflux;	93.5%

3-(3-bromo-2-methyl-6-(methylsulfonyl)phenyl)-4,5-dihydroisoxazole (247922-29-8) + formyl radical (2597-44-6) + 1-methyl-5-hydroxypyrazole (33641-15-5) → topramezone (210631-68-8)

Conditions	Yield
Stage #1: 3-(3-bromo-2-methyl-6-(methylsulfonyl)phenyl)-4,5-dihydroisoxazole With potassium carbonate In 1,4-dioxane Reflux; Stage #2: 1-methyl-5-hydroxypyrazole With triphenylphosphine; sodium iodide In 1,4-dioxane at 60℃; for 0.5h; Stage #3: formyl radical With palladium on activated charcoal In 1,4-dioxane at 120℃; under 11251.1 Torr; for 20h; Reagent/catalyst; Temperature;	84.4%

3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoic acid (223646-24-0) + 1-methyl-5-hydroxypyrazole (33641-15-5) → topramezone (210631-68-8)

Conditions	Yield
Stage #1: 3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoic acid With pyridine; thionyl chloride In benzene for 3h; Reflux; Stage #2: 1-methyl-5-hydroxypyrazole With triethylamine In 1,4-dioxane at 20℃; for 3h; Stage #3: With potassium carbonate for 6h; Reflux;	81.46%
Stage #1: 3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoic acid With pyridine; thionyl chloride In toluene for 3h; Reflux; Stage #2: 1-methyl-5-hydroxypyrazole With triethylamine In 1,4-dioxane at 20℃; for 3h;	80.5%
Stage #1: 3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoic acid With thionyl chloride for 2h; Reflux; Stage #2: With triethylamine In 1,2-dichloro-ethane at 20 - 30℃; for 0.5h; Stage #3: 1-methyl-5-hydroxypyrazole In 1,2-dichloro-ethane for 4h; Reflux;	20.87%

5-hydroxy-1-methyl-1H-pyrazole hydrochloride + 3-(3-bromo-2-methyl-6-(methylsulfonyl)phenyl)-4,5-dihydroisoxazole (247922-29-8) + carbon monoxide (201230-82-2) → topramezone (210631-68-8)

Conditions	Yield
With potassium carbonate; triethylamine; triphenylphosphine; palladium dichloride In 1,4-dioxane at 130℃; under 7500.75 Torr; for 10h; Inert atmosphere;	70%

5-hydroxy-1-methyl-1H-pyrazole hydrochloride + 3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoyl chloride (223646-31-9) + 2-hydroxy-2-methylpropanenitrile (75-86-5) → topramezone (210631-68-8)

Conditions	Yield
With triethylamine In methanol; chloroform

3-(3-bromo-2-methyl-6-(methylsulfonyl)phenyl)-4,5-dihydroisoxazole (247922-29-8) + carbon monoxide (201230-82-2) + 1-methyl-5-hydroxypyrazole (33641-15-5) → topramezone (210631-68-8)

Conditions	Yield
With potassium carbonate; triphenylphosphine; palladium dichloride In 1,4-dioxane at 130℃; under 11251.1 Torr;

1-methyl-5-methoxy-4-pyrazolecarboxylic acid → topramezone (210631-68-8)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: thionyl chloride / toluene / Reflux 1.2: 5 h / 0 °C 2.1: magnesium / tetrahydrofuran / 5 h / 60 °C / Inert atmosphere 2.2: 1 h / 10 °C / Inert atmosphere 3.1: sodium tungstate (VI) dihydrate; dihydrogen peroxide; acetic acid / 3 h / 60 °C 4.1: methyl(tri-n-octyl)ammonium bromide; hydrogen bromide / 3 h / Reflux View Scheme

N,5-dimethoxy-N,1-dimethyl-1H-pyrazole-4-carboxamide → topramezone (210631-68-8)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: magnesium / tetrahydrofuran / 5 h / 60 °C / Inert atmosphere 1.2: 1 h / 10 °C / Inert atmosphere 2.1: sodium tungstate (VI) dihydrate; dihydrogen peroxide; acetic acid / 3 h / 60 °C 3.1: methyl(tri-n-octyl)ammonium bromide; hydrogen bromide / 3 h / Reflux View Scheme

3-((2-methyl)-6-methylthiophenyl)-4,5-dihydroisoxazole (250592-91-7) → topramezone (210631-68-8)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: N,N,N,N,-tetramethylethylenediamine; n-butyllithium / ethyl acetate; hexane / 3 h / 0 °C / Reflux 1.2: 2 h / 0 - 20 °C 2.1: acetic acid; dihydrogen peroxide / 30 h / 30 °C 3.1: pyridine; thionyl chloride / toluene / 3 h / Reflux 3.2: 3 h / 20 °C View Scheme

3-(2-methyl-6-aminophenyl)-4,5-dihydroisoxazole (250592-89-3) → topramezone (210631-68-8)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: nitroso isopentyl ester; copper / 2 h / 30 °C / Cooling with ice 2.1: N,N,N,N,-tetramethylethylenediamine; n-butyllithium / ethyl acetate; hexane / 3 h / 0 °C / Reflux 2.2: 2 h / 0 - 20 °C 3.1: acetic acid; dihydrogen peroxide / 30 h / 30 °C 4.1: pyridine; thionyl chloride / toluene / 3 h / Reflux 4.2: 3 h / 20 °C View Scheme

3-((2-methyl)-6-nitrophenyl)-4,5-dihydroisoxazole (250592-88-2) → topramezone (210631-68-8)

Conditions

Yield

Multi-step reaction with 5 steps 1.1: 5%-palladium/activated carbon; hydrogen / dichloromethane / 10 h / 25 - 30 °C 2.1: nitroso isopentyl ester; copper / 2 h / 30 °C / Cooling with ice 3.1: N,N,N,N,-tetramethylethylenediamine; n-butyllithium / ethyl acetate; hexane / 3 h / 0 °C / Reflux 3.2: 2 h / 0 - 20 °C 4.1: acetic acid; dihydrogen peroxide / 30 h / 30 °C 5.1: pyridine; thionyl chloride / toluene / 3 h / Reflux 5.2: 3 h / 20 °C View Scheme

2-methyl-6-nitrosobenzaldehyde oxime → topramezone (210631-68-8)

Conditions

Yield

Multi-step reaction with 6 steps 1.1: acetic acid; chlorine / 4 h / Inert atmosphere 1.2: 24 h / 6000.6 - 7500.75 Torr 2.1: 5%-palladium/activated carbon; hydrogen / dichloromethane / 10 h / 25 - 30 °C 3.1: nitroso isopentyl ester; copper / 2 h / 30 °C / Cooling with ice 4.1: N,N,N,N,-tetramethylethylenediamine; n-butyllithium / ethyl acetate; hexane / 3 h / 0 °C / Reflux 4.2: 2 h / 0 - 20 °C 5.1: acetic acid; dihydrogen peroxide / 30 h / 30 °C 6.1: pyridine; thionyl chloride / toluene / 3 h / Reflux 6.2: 3 h / 20 °C View Scheme

2,3-dimethylnitrobenzene (83-41-0) → topramezone (210631-68-8)

Conditions

Yield

Multi-step reaction with 7 steps 1.1: nitroso isopentyl ester; sodium methylate / N,N-dimethyl-formamide / 0.5 h / -40 - -35 °C 2.1: acetic acid; chlorine / 4 h / Inert atmosphere 2.2: 24 h / 6000.6 - 7500.75 Torr 3.1: 5%-palladium/activated carbon; hydrogen / dichloromethane / 10 h / 25 - 30 °C 4.1: nitroso isopentyl ester; copper / 2 h / 30 °C / Cooling with ice 5.1: N,N,N,N,-tetramethylethylenediamine; n-butyllithium / ethyl acetate; hexane / 3 h / 0 °C / Reflux 5.2: 2 h / 0 - 20 °C 6.1: acetic acid; dihydrogen peroxide / 30 h / 30 °C 7.1: pyridine; thionyl chloride / toluene / 3 h / Reflux 7.2: 3 h / 20 °C View Scheme

2,3-dimethyl-4-methanesulfonyl-1-chlorobenzene (250593-01-2) → topramezone (210631-68-8)

Conditions

Yield

Multi-step reaction with 5 steps 1.1: sodium ethanolate; n-Butyl nitrite / N,N-dimethyl-formamide / 2 h / -20 - -15 °C 2.1: N-chloro-succinimide / acetonitrile / 1 h / 45 - 60 °C 2.2: 3 h / 20 °C / 4500.45 Torr / Autoclave 3.1: copper(l) iodide / N,N-dimethyl-formamide / 24 h / 100 °C / Inert atmosphere 4.1: sulfuric acid / 12 h / 100 °C 5.1: thionyl chloride; pyridine / benzene / 3 h / Reflux 5.2: 3 h / 20 °C 5.3: 6 h / Reflux View Scheme

2-methyl-3-chloro-6-methanesulfonylbenzaldehyde oxime → topramezone (210631-68-8)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: N-chloro-succinimide / acetonitrile / 1 h / 45 - 60 °C 1.2: 3 h / 20 °C / 4500.45 Torr / Autoclave 2.1: copper(l) iodide / N,N-dimethyl-formamide / 24 h / 100 °C / Inert atmosphere 3.1: sulfuric acid / 12 h / 100 °C 4.1: thionyl chloride; pyridine / benzene / 3 h / Reflux 4.2: 3 h / 20 °C 4.3: 6 h / Reflux View Scheme

3-[3-chloro-2-methyl-6-methylsulfonylphenyl]-4,5-dihydroisoxazole → topramezone (210631-68-8)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: copper(l) iodide / N,N-dimethyl-formamide / 24 h / 100 °C / Inert atmosphere 2.1: sulfuric acid / 12 h / 100 °C 3.1: thionyl chloride; pyridine / benzene / 3 h / Reflux 3.2: 3 h / 20 °C 3.3: 6 h / Reflux View Scheme

2,3-dimethyl-4-methylsulfanylbromobenzene (250593-00-1) → topramezone (210631-68-8)

Conditions

Yield

Multi-step reaction with 6 steps 1.1: acetic acid; dihydrogen peroxide; sodium tungstate (VI) dihydrate / 2 h / 100 °C 2.1: sodium ethanolate; n-Butyl nitrite / N,N-dimethyl-formamide / 2.5 h / -20 - -15 °C 3.1: N-chloro-succinimide / acetonitrile / 1 h / 45 - 60 °C 3.2: 3 h / 20 °C / 4500.45 Torr / Autoclave 4.1: N,N-dimethyl-formamide / 8 h / 120 °C / Inert atmosphere 5.1: sulfuric acid / 12 h / 100 °C 6.1: thionyl chloride; pyridine / benzene / 3 h / Reflux 6.2: 3 h / 20 °C 6.3: 6 h / Reflux View Scheme

2,3-dimethyl-4-methanesulfonyl-1-bromobenzene (128277-66-7) → topramezone (210631-68-8)

Conditions

Yield

Multi-step reaction with 5 steps 1.1: sodium ethanolate; n-Butyl nitrite / N,N-dimethyl-formamide / 2.5 h / -20 - -15 °C 2.1: N-chloro-succinimide / acetonitrile / 1 h / 45 - 60 °C 2.2: 3 h / 20 °C / 4500.45 Torr / Autoclave 3.1: N,N-dimethyl-formamide / 8 h / 120 °C / Inert atmosphere 4.1: sulfuric acid / 12 h / 100 °C 5.1: thionyl chloride; pyridine / benzene / 3 h / Reflux 5.2: 3 h / 20 °C 5.3: 6 h / Reflux View Scheme

2-methyl-3-bromo-6-methanesulfonylbenzaldehyde oxime → topramezone (210631-68-8)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: N-chloro-succinimide / acetonitrile / 1 h / 45 - 60 °C 1.2: 3 h / 20 °C / 4500.45 Torr / Autoclave 2.1: N,N-dimethyl-formamide / 8 h / 120 °C / Inert atmosphere 3.1: sulfuric acid / 12 h / 100 °C 4.1: thionyl chloride; pyridine / benzene / 3 h / Reflux 4.2: 3 h / 20 °C 4.3: 6 h / Reflux View Scheme

3-(3-bromo-2-methyl-6-(methylsulfonyl)phenyl)-4,5-dihydroisoxazole (247922-29-8) → topramezone (210631-68-8)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: N,N-dimethyl-formamide / 8 h / 120 °C / Inert atmosphere 2.1: sulfuric acid / 12 h / 100 °C 3.1: thionyl chloride; pyridine / benzene / 3 h / Reflux 3.2: 3 h / 20 °C 3.3: 6 h / Reflux View Scheme

3-[3-cyano-2-methyl-6-methylsulfonylphenyl]-4,5-dihydroisoxazole → topramezone (210631-68-8)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: sulfuric acid / 12 h / 100 °C 2.1: thionyl chloride; pyridine / benzene / 3 h / Reflux 2.2: 3 h / 20 °C 2.3: 6 h / Reflux View Scheme

1,2-dimethyl-3-(methylsulfanyl)benzene (66794-10-3) → topramezone (210631-68-8)

Conditions	Yield
Multi-step reaction with 7 steps 1.1: bromine / 1,2-dichloro-ethane / 2 h / 20 - 25 °C 2.1: acetic acid; dihydrogen peroxide; sodium tungstate (VI) dihydrate / 2 h / 100 °C 3.1: sodium ethanolate; n-Butyl nitrite / N,N-dimethyl-formamide / 2.5 h / -20 - -15 °C 4.1: N-chloro-succinimide / acetonitrile / 1 h / 45 - 60 °C 4.2: 3 h / 20 °C / 4500.45 Torr / Autoclave 5.1: N,N-dimethyl-formamide / 8 h / 120 °C / Inert atmosphere 6.1: sulfuric acid / 12 h / 100 °C 7.1: thionyl chloride; pyridine / benzene / 3 h / Reflux 7.2: 3 h / 20 °C 7.3: 6 h / Reflux View Scheme
Multi-step reaction with 7 steps 1.1: chlorobenzene; aluminum (III) chloride; sulfuryl dichloride / 2.33 h / 5 °C 2.1: acetic acid; dihydrogen peroxide; sodium tungstate (VI) dihydrate / 1.17 h / 100 °C 3.1: sodium ethanolate; n-Butyl nitrite / N,N-dimethyl-formamide / 2 h / -20 - -15 °C 4.1: N-chloro-succinimide / acetonitrile / 1 h / 45 - 60 °C 4.2: 3 h / 20 °C / 4500.45 Torr / Autoclave 5.1: copper(l) iodide / N,N-dimethyl-formamide / 24 h / 100 °C / Inert atmosphere 6.1: sulfuric acid / 12 h / 100 °C 7.1: thionyl chloride; pyridine / benzene / 3 h / Reflux 7.2: 3 h / 20 °C 7.3: 6 h / Reflux View Scheme

2,3-dimethyl-4-methylthio-1-chlorobenzene → topramezone (210631-68-8)

Conditions

Yield

Multi-step reaction with 6 steps 1.1: acetic acid; dihydrogen peroxide; sodium tungstate (VI) dihydrate / 1.17 h / 100 °C 2.1: sodium ethanolate; n-Butyl nitrite / N,N-dimethyl-formamide / 2 h / -20 - -15 °C 3.1: N-chloro-succinimide / acetonitrile / 1 h / 45 - 60 °C 3.2: 3 h / 20 °C / 4500.45 Torr / Autoclave 4.1: copper(l) iodide / N,N-dimethyl-formamide / 24 h / 100 °C / Inert atmosphere 5.1: sulfuric acid / 12 h / 100 °C 6.1: thionyl chloride; pyridine / benzene / 3 h / Reflux 6.2: 3 h / 20 °C 6.3: 6 h / Reflux View Scheme

3-[2-methyl-6-bromophenyl]-4,5-dihydroisoxazole → topramezone (210631-68-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: copper(l) chloride / tetrahydrofuran; N,N-dimethyl-formamide / 12 h / 0 °C / Inert atmosphere 2: iron(III) chloride; N-Bromosuccinimide / tetrahydrofuran / 2 h / 50 - 65 °C / Inert atmosphere 3: triethylamine; potassium carbonate; palladium dichloride; triphenylphosphine / 1,4-dioxane / 10 h / 130 °C / 7500.75 Torr / Inert atmosphere View Scheme

C8H8BrNO → topramezone (210631-68-8)

Conditions

Yield

Multi-step reaction with 4 steps 1: iron(III) chloride; N-chloro-succinimide / tetrahydrofuran / 5 h / 60 °C / 7500.75 Torr / Inert atmosphere 2: copper(l) chloride / tetrahydrofuran; N,N-dimethyl-formamide / 12 h / 0 °C / Inert atmosphere 3: iron(III) chloride; N-Bromosuccinimide / tetrahydrofuran / 2 h / 50 - 65 °C / Inert atmosphere 4: triethylamine; potassium carbonate; palladium dichloride; triphenylphosphine / 1,4-dioxane / 10 h / 130 °C / 7500.75 Torr / Inert atmosphere View Scheme

2-bromo-6-methylbenzaldehyde (176504-70-4) → topramezone (210631-68-8)

Conditions

Yield

Multi-step reaction with 5 steps 1: hydroxylamine hydrochloride; sodium hydroxide / tetrahydrofuran; water / 6 h / 30 °C / Inert atmosphere 2: iron(III) chloride; N-chloro-succinimide / tetrahydrofuran / 5 h / 60 °C / 7500.75 Torr / Inert atmosphere 3: copper(l) chloride / tetrahydrofuran; N,N-dimethyl-formamide / 12 h / 0 °C / Inert atmosphere 4: iron(III) chloride; N-Bromosuccinimide / tetrahydrofuran / 2 h / 50 - 65 °C / Inert atmosphere 5: triethylamine; potassium carbonate; palladium dichloride; triphenylphosphine / 1,4-dioxane / 10 h / 130 °C / 7500.75 Torr / Inert atmosphere View Scheme

2-methylphenyl aldehyde (529-20-4) → topramezone (210631-68-8)

Conditions

Yield

Multi-step reaction with 6 steps 1: iron(III) chloride; N-Bromosuccinimide / ethyl acetate / 2 h / 45 °C / Inert atmosphere 2: hydroxylamine hydrochloride; sodium hydroxide / tetrahydrofuran; water / 6 h / 30 °C / Inert atmosphere 3: iron(III) chloride; N-chloro-succinimide / tetrahydrofuran / 5 h / 60 °C / 7500.75 Torr / Inert atmosphere 4: copper(l) chloride / tetrahydrofuran; N,N-dimethyl-formamide / 12 h / 0 °C / Inert atmosphere 5: iron(III) chloride; N-Bromosuccinimide / tetrahydrofuran / 2 h / 50 - 65 °C / Inert atmosphere 6: triethylamine; potassium carbonate; palladium dichloride; triphenylphosphine / 1,4-dioxane / 10 h / 130 °C / 7500.75 Torr / Inert atmosphere View Scheme

3-[2-methyl-6-(methylsulfonyl)phenyl]-4,5-dihydroisoxazole → topramezone (210631-68-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: iron(III) chloride; N-Bromosuccinimide / tetrahydrofuran / 2 h / 50 - 65 °C / Inert atmosphere 2: triethylamine; potassium carbonate; palladium dichloride; triphenylphosphine / 1,4-dioxane / 10 h / 130 °C / 7500.75 Torr / Inert atmosphere View Scheme

Upstream product

• 123-91-1 1,4-dioxane 
• 247922-29-8 3-(3-bromo-2-methyl-6-(methylsulfonyl)phenyl)-4,5-dihydroisoxazole 
• 33641-15-5 1-methyl-5-hydroxypyrazole 
• 33641-16-6 5-hydroxy-1-methyl-1H-pyrazole hydrochloride 
• 223646-31-9 3-(4,5-dihydroisoxazol-3-yl)-4-methylsulfonyl-2-methylbenzoyl chloride 
• 75-86-5 2-hydroxy-2-methylpropanenitrile 
• 250593-01-2 2,3-dimethyl-4-methanesulfonyl-1-chlorobenzene 
• 250593-00-1 2,3-dimethyl-4-methylsulfanylbromobenzene 
• 128277-66-7 2,3-dimethyl-4-methanesulfonyl-1-bromobenzene 
• 66794-10-3 1,2-dimethyl-3-(methylsulfanyl)benzene 
• 176504-70-4 2-bromo-6-methylbenzaldehyde 
• 529-20-4 2-methylphenyl aldehyde 
• 201230-82-2 carbon monoxide 
• 95-47-6 o-xylene 

Relevant academic research and scientific papers

Preparation method of topramezone

The invention relates to a preparation method of topramezone. The method comprises: carrying out reaction on a compound I (3-[3-bromo-2-methyl-6-(methylthio)-phenyl]-4, 5-dihydroisoxazole) and a compound II (1-methyl-5-hydroxypyrazole) in the atmosphere of a copper catalyst, a ligand, an organic solvent, an alkali and a CO gas to prepare the topramezone, wherein the reaction temperature is controlled to be 25-120 DEG C, and the reaction time is 18-24 hours. The preparation method is simple and convenient to operate, the catalyst is cheap, the production cost is greatly reduced, the product yield is high, and the preparation method can be used for industrial production of topramezone.

Preparation method of topramezone

The invention relates to a preparation method of topramezone. Themethod comprises the following steps of: (1) carrying out oxidation reaction on a compound 5 and an oxidant under the action of a catalyst to obtain a compound 6; (2) carrying out Grignard reaction on the compound 6, magnesium and carbon dioxide to obtain a compound 7; and (3) carrying out condensation reaction on the compound 7 and1-methyl-5-hydroxy pyrazole to obtain topramezone. The structural formula of the compound 5, the structural formula of the compound 6, the structural formula of the compound 7 are described in descriptions of the invention. The preparation method of topramezone has the advantages of few by-products, high purity and yield of topramezone, low wastewater treatment difficulty, low cost, no toxic or side effect in the production process and suitability for industrial production.

Preparation method and application of topramezone

The invention discloses a preparation method and application of topramezone, and the preparation method comprises the following steps: taking 2-methylbenzaldehyde, a bromination reagent, a catalyst, hydroxylamine hydrochloride, an alkali, ethylene gas, a sulfonylation reagent and a preset solvent as reaction raw materials, and preparing 3-[3-bromo-methyl-6-(methylsulfonyl) phenyl]-4, 5-dihydroisoxazole through a first reaction process; taking diethyl malonate, triethyl orthoformate, nickel sulfate, monobasic saturated carboxylic acid, methylhydrazine, a hydrocarbon solvent, an ethanol solutionand hydrochloric acid as reaction raw materials, and carrying out a second reaction process to prepare 1-methyl-5-hydroxypyrazole; and taking the 3-[3-bromo-methyl-6-(methylsulfonyl) phenyl]-4, 5 dihydroisoxazole,-1-methyl-5-hydroxypyrazole, triethylamine, potassium carbonate, palladium chloride, triphenylphosphine, 1, 4-dioxane, water, a saturated NaHCO3 solution and a hydrochloric acid solutionas reaction raw materials, and carrying out a third reaction process to prepare the topramezone. The problems that a sulfur-containing intermediate can emit odor and the raw materials are difficult to obtain in the existing process are solved.

PROCESS FOR PREPARATION OF HETEROARYLKETONES

The present invention relates to a process for preparation of heteroarylketones of formula (I). The invention relates to an efficient process for the preparation of heteroarylketones for formula (I) which find use as herbicides. (I)

Topramezone intermediate and topramezone preparation method

The invention relates to the field of organic synthesis, in particular to a topramezone intermediate and a topramezone preparation method. The topramezone preparation method comprises the following steps: 3-[3-halogen-2-methyl-6-(methylsulfonyl)phenyl]-4, 5-dihydroisoxazole and cyanide are subjected to a substitution reaction to obtain 3-[3-cyano-2-methyl-6-(methylsulfonyl)phenyl]-4, 5-dihydroisoxazole; hydrolysis reaction is performed on 3-[3-cyano-2-methyl-6-(methylsulfonyl)phenyl]-4, 5-dihydroisoxazole under the action of acid or alkali to obtain 2-methyl-3-(4, 5-dihydroisoxazole-3-yl)-4-methylsulfonyl benzoic acid; and 2-methyl-3-(4, 5-dihydroisoxazole-3-yl)-4-methylsulfonyl benzoic acid and 1-methyl-5-hydroxypyrazole are condensed and rearranged to generate topramezone. According to the topramezone intermediate and the topramezone preparation method provided by the invention, the use of an expensive palladium catalyst and a dangerous butyl lithium reagent is avoided, the yield isrelatively high, the cost is reduced, the process is simplified, the defects in the prior art are overcome, and the industrial value is achieved.

Improved method for preparing topramezone

The invention discloses an improved method for preparing topramezone and belongs to the technical field of chemical synthesis. The improved method takes 3-nitro-o-xylene as a raw material and is characterized in that the topramezone is obtained through oximation reaction, ethylene cyclization, palladium carbon reduction, diazotization, aldehydelation, oxidation and condensation rearrangement reaction; under optimal conditions, the total yield is 33.7 percent, the raw material is cheap and easy to obtain, the treatment is convenient in the whole process, the yield is relatively high, and a certain significance in industrialized production is realized.

Preparation method of topramezone

The invention discloses a preparation method of topramezone. The particularly comprises the steps of carrying out cyclization, methylation, hydrolysis, amidation, Grignard reaction, oxidation and demethylation on 2-(alkoxymethylene)malonate as a raw material, so as to obtain a target product, wherein the yield of the target product reaches 61.8%-63.2%. According to the preparation method, the raw materials such as a palladium/platinum catalyst which is high in cost and difficult to recycle, a virulent rearrangement catalyst and high-cost methylhydrazine are not adopted, and the preparation method which is low in cost, easy in operation, low in pollution and accordant with large-scale industrial production requirements is provided.

NOXIOUS ARTHROPOD CONTROL AGENT CONTAINING AMIDE COMPOUND

An object of the present invention is to provide a compound having the controlling activity on a noxious arthropod, and a noxious arthropod controlling agent containing an amide compound of formula (I): wherein X represents a nitrogen atom or a CH group, p represents 0 or 1, A represents a tetrahydrofuranyl group or the like, R1, R2, R3, R4, R5, R6 and R7 represent a hydrogen atom or the like, n represents 1 or 2, Y represents an oxygen atom or the like, m represents any integer of 0 to 7, and Q represents a C1-8 chain hydrocarbon group optionally having a phenyl group or the like, has the excellent noxious arthropod controlling effect.

Crystalline form of [3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)phenyl]-(5-hydroxy-1-methyl-1H-pyrazol-4-yl)methanone

The present invention relates to crystalline forms of [3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)phenyl]-(5-hydroxy-1-methyl-1 H-pyrazol-4-yl)methanone, which is also known under the common name topramezone. The invention also relates to a process for the preparation of these crystalline forms and formulations for plant protection which comprise one of these crystalline forms of topramezone.

Method and novel intermediate products for producing isoxazolin-3-yl-acylbenzenenes

The present invention describes a process for preparing isoxazoles of the formula I where: R1is hydrogen, C1-C6-alkyl, R2is hydrogen, C1-C6-alkyl, R3, R4, R5are each hydrogen, C1-C6-alkyl or R4and R5together from a bond, R6is a heterocysclic ring, n is 0, 1 or 2; which comprises preparing an intermediate of the formula VI where R1, R3, R4and R5are each as defined above, followed by halogenation, thiomethylation, oxidation and acylation to give compounds of the formula I. Furthermore, the invention describes novel intermediates for preparing the compounds of the formula I and novel processes for preparing the intermediates.