111992-18-8

Basic information

• Product Name: 2-(5-Amino-2,4-Dichlorophenyl)-4-(Difluoromethyl)-2,4-Dihydro-5-Methyl-3H-1,2,4-Triazol-3-One
• Synonyms: 1-(5-amino-2,4-dichlorophenyl)-4-difluoromethyl-3-methyl-1H-1,2,4-triazol-5-one; 1-(5-amino-2,4-dichlorophenyl)-4-difluoromethyl-4,5-dihydro-3-methyl-1,2,4-triazol-5(1H)-one; 1-(5-amino-2,4-dichlorophenyl)-4,5-dihydro-4-difluoromethyl-3-methyl-1,2,4-triazol-5(1H)-one; 3-acetyl-5-amino-1,2,4-oxadiazole; triazol-5(1H)-one
• CAS NO: 111992-18-8
• Molecular Formula: C₁₀H₈Cl₂F₂N₄O
• Molecular Weight: 309.12
• Mol File: 111992-18-8.mol
• Article Data: 7

Chemical Properties

• CAS DataBase Reference: 2-(5-Amino-2,4-Dichlorophenyl)-4-(Difluoromethyl)-2,4-Dihydro-5-Methyl-3H-1,2,4-Triazol-3-One(CAS DataBase Reference)
• NIST Chemistry Reference: 2-(5-Amino-2,4-Dichlorophenyl)-4-(Difluoromethyl)-2,4-Dihydro-5-Methyl-3H-1,2,4-Triazol-3-One(111992-18-8)
• EPA Substance Registry System: 2-(5-Amino-2,4-Dichlorophenyl)-4-(Difluoromethyl)-2,4-Dihydro-5-Methyl-3H-1,2,4-Triazol-3-One(111992-18-8)

Safety Data

• Hazardous Substances Data: 111992-18-8(Hazardous Substances Data)

Usage

General Description

2-(5-Amino-2,4-Dichlorophenyl)-4-(Difluoromethyl)-2,4-Dihydro-5-Methyl-3H-1,2,4-Triazol-3-One is a chemical compound that belongs to the triazol class of compounds. It is a derivative of 1,2,4-triazole and contains a dichlorophenyl group, a difluoromethyl group, and an amino group. 2-(5-Amino-2,4-Dichlorophenyl)-4-(Difluoromethyl)-2,4-Dihydro-5-Methyl-3H-1,2,4-Triazol-3-One is used in pharmaceutical research and development, particularly in the synthesis of potential drugs for the treatment of various medical conditions. The precise pharmacological and toxicological properties of this compound are still under investigation, and it has not yet been approved for any specific medical or industrial use.

Synthetic route

4,5-dihydro-3-methyl-4-difluoromethyl-1-(2,4-dichloro-5-nitrophenyl)-1,2,4-triazole-5(1H)-one → 2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one (111992-18-8)

Conditions	Yield
With iron; ammonium chloride In ethanol; water for 4h; Reflux;	94%
With palladium on activated charcoal; hydrogen In methanol at 50 - 60℃; under 3000.3 - 3750.38 Torr; Autoclave;	94.5%
With iron; ammonium chloride In ethanol; water Reflux;
With palladium on activated charcoal; hydrogen In methanol at 60℃; under 3750.38 Torr; for 2h;	31.9 g
With iron; acetic acid In water at 25 - 35℃; for 2h;	2 g

2-(5-azido-2,4-dichlorobenzene)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one → 2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one (111992-18-8)

Conditions	Yield
With 5%-palladium/activated carbon; hydrogen In methanol under 760.051 Torr; for 10h; Reagent/catalyst; Solvent; Pressure;	92%

2,4-Dichloroaniline (554-00-7) → 2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one (111992-18-8)

Conditions

Yield

Multi-step reaction with 5 steps 1.1: hydrogenchloride; sodium nitrite / water / 1.5 h / -9 - 0 °C / Inert atmosphere 1.2: -9 - 20 °C / Inert atmosphere 1.3: 0.58 h / Inert atmosphere 2.1: triethylamine; diphenyl phosphoryl azide / toluene / 2 h / Reflux 3.1: potassium hydroxide; tetrabutylammomium bromide / tetrahydrofuran / Reflux 4.1: sulfuric acid; nitric acid / 25 °C 5.1: ammonium chloride; iron / water; ethanol / 4 h / Reflux View Scheme

4,5-dihydro-1-(2,4-dichlorophenyl)-3-methyl-1,2,4-triazol-5(1H)-one (79604-49-2) → 2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one (111992-18-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: potassium hydroxide; tetrabutylammomium bromide / tetrahydrofuran / Reflux 2: sulfuric acid; nitric acid / 25 °C 3: ammonium chloride; iron / water; ethanol / 4 h / Reflux View Scheme
Multi-step reaction with 3 steps 1: potassium hydroxide; tetrabutylammomium bromide / tetrahydrofuran / 18 h / 0 - 20 °C 2: nitric acid; sulfuric acid / 0.5 h / 25 °C 3: acetic acid; iron / water / 2 h / 25 - 35 °C View Scheme

4,5-dihydro-3-methyl-4-difluoromethyl-1-(2,4-dichlorophenyl)-1,2,4-triazol-5(1H)-one → 2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one (111992-18-8)

Conditions	Yield
Multi-step reaction with 2 steps 1: sulfuric acid; nitric acid / 25 °C 2: ammonium chloride; iron / water; ethanol / 4 h / Reflux View Scheme
Multi-step reaction with 2 steps 1: fuming sulphuric acid; nitric acid / 40 - 50 °C 2: palladium on activated charcoal; hydrogen / methanol / 50 - 60 °C / 3000.3 - 3750.38 Torr / Autoclave View Scheme
Multi-step reaction with 2 steps 1: fuming sulphuric acid; nitric acid / 2 h / 50 °C 2: palladium on activated charcoal; hydrogen / methanol / 2 h / 60 °C / 3750.38 Torr View Scheme
Multi-step reaction with 2 steps 1: nitric acid; sulfuric acid / 0.5 h / 25 °C 2: acetic acid; iron / water / 2 h / 25 - 35 °C View Scheme
Multi-step reaction with 3 steps 1: iodine; fuming sulphuric acid / 10 h / 20 °C / Cooling with ice 2: sodium azide; copper(l) iodide; L-valine; sodium hydroxide / dimethyl sulfoxide / 60 °C / Inert atmosphere 3: 5%-palladium/activated carbon; hydrogen / methanol / 10 h / 760.05 Torr View Scheme

2-(2-(2,4-dichlorophenyl)hydrazono)propanoic acid (103998-84-1) → 2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one (111992-18-8)

Conditions	Yield
Multi-step reaction with 4 steps 1: triethylamine; diphenyl phosphoryl azide / toluene / 2 h / Reflux 2: potassium hydroxide; tetrabutylammomium bromide / tetrahydrofuran / Reflux 3: sulfuric acid; nitric acid / 25 °C 4: ammonium chloride; iron / water; ethanol / 4 h / Reflux View Scheme
Multi-step reaction with 4 steps 1: triethylamine / toluene / 2 h / Reflux 2: potassium hydroxide; tetrabutylammomium bromide / tetrahydrofuran / 18 h / 0 - 20 °C 3: nitric acid; sulfuric acid / 0.5 h / 25 °C 4: acetic acid; iron / water / 2 h / 25 - 35 °C View Scheme

1-o-chlorophenyl-3-methyl-4-difluoromethyl-1,2,4-triazol-5-one → 2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one (111992-18-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: antimony(III) chloride; iron(III) chloride; silica gel; chlorine / 8 - 10 °C 2: fuming sulphuric acid; nitric acid / 40 - 50 °C 3: palladium on activated charcoal; hydrogen / methanol / 50 - 60 °C / 3000.3 - 3750.38 Torr / Autoclave View Scheme

1-(2-chlorophenyl)-3-methyl-1,2,4-triazolin-5-one (109913-40-8) → 2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one (111992-18-8)

Conditions	Yield
Multi-step reaction with 4 steps 1: potassium hydroxide; tetrabutylammomium bromide / tetrahydrofuran / 75 - 85 °C 2: antimony(III) chloride; iron(III) chloride; silica gel; chlorine / 8 - 10 °C 3: fuming sulphuric acid; nitric acid / 40 - 50 °C 4: palladium on activated charcoal; hydrogen / methanol / 50 - 60 °C / 3000.3 - 3750.38 Torr / Autoclave View Scheme

1-phenyl-3-methyl-1H-1,2,4-triazol-5-one (22863-24-7) → 2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one (111992-18-8)

Conditions	Yield
Multi-step reaction with 5 steps 1: toluene; water / 110 °C 2: potassium carbonate; tetrabutylammomium bromide / 1 h / 120 °C 3: chlorine / N,N-dimethyl-formamide / 1 h / 5 - 8 °C 4: fuming sulphuric acid; nitric acid / 2 h / 50 °C 5: palladium on activated charcoal; hydrogen / methanol / 2 h / 60 °C / 3750.38 Torr View Scheme

1-phenyl-3-methyl-1,2,4-triazol-5-one tetrabutylammonium → 2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one (111992-18-8)

Conditions	Yield
Multi-step reaction with 4 steps 1: potassium carbonate; tetrabutylammomium bromide / 1 h / 120 °C 2: chlorine / N,N-dimethyl-formamide / 1 h / 5 - 8 °C 3: fuming sulphuric acid; nitric acid / 2 h / 50 °C 4: palladium on activated charcoal; hydrogen / methanol / 2 h / 60 °C / 3750.38 Torr View Scheme

4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1-phenyl-1H-1,2,4-triazole → 2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one (111992-18-8)

Conditions	Yield
Multi-step reaction with 3 steps 1: chlorine / N,N-dimethyl-formamide / 1 h / 5 - 8 °C 2: fuming sulphuric acid; nitric acid / 2 h / 50 °C 3: palladium on activated charcoal; hydrogen / methanol / 2 h / 60 °C / 3750.38 Torr View Scheme

2-(2,4-dichloro-5-bromophenyl)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one → 2-(5-amino-2,4-dichlorophenyl)-4-(difluoromethyl)-2,4-dihydro-5-methyl-3H-1,2,4-triazol-3-one (111992-18-8)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: magnesium; iodine / tetrahydrofuran / 1.33 h / 37 - 45 °C / Inert atmosphere 1.2: 2 h / -10 - 20 °C 2.1: sodium azide; copper(II) sulfate / methanol / 6 h / 20 °C 3.1: 5%-palladium/activated carbon; hydrogen / methanol / 10 h / 760.05 Torr View Scheme

Upstream product

• 111992-17-7 4,5-dihydro-3-methyl-4-difluoromethyl-1-(2,4-dichloro-5-nitrophenyl)-1,2,4-triazole-5(1H)-one 
• 554-00-7 2,4-Dichloroaniline 
• 79604-49-2 4,5-dihydro-1-(2,4-dichlorophenyl)-3-methyl-1,2,4-triazol-5(1H)-one 
• 111992-16-6 4,5-dihydro-3-methyl-4-difluoromethyl-1-(2,4-dichlorophenyl)-1,2,4-triazol-5(1H)-one 
• 103998-84-1 2-(2-(2,4-dichlorophenyl)hydrazono)propanoic acid 
• 109913-40-8 1-(2-chlorophenyl)-3-methyl-1H-1,2,4-triazol-5(4H)-one 
• 22863-24-7 1-phenyl-3-methyl-1H-1,2,4-triazol-5-one 

Downstream Products

• 122836-35-5 sulfentrazone 
• 128621-34-1 2-chloro-3-[2,4-dichloro-5-(4-difluoromethyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl)phenyl]propionic acid 
• 1009091-52-4 C₁₈H₁₀Cl₂F₂N₄O₃ 
• 1009091-56-8 C₁₈H₁₄Cl₂F₂N₄O₃ 
• 1009091-70-6 C₁₇H₁₂Cl₃F₂N₅O₂ 
• 1009091-69-3 C₁₇H₁₃Cl₂F₂N₅O₂ 
• 1009091-60-4 C₁₈H₁₆Cl₂F₂N₄O₃ 

Relevant articles and documents

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The invention relates to a preparation method of sulfonyl carfentrazone-ethyl, which takes 2, 4-dichloroaniline as an initial raw material, and comprises the following steps of: 1, carrying out nitration reaction on a benzene ring of the 2, 4-dichloroaniline; as the N-difluoromethyl substituted triazolinone ring is formed, nitration and reduction reactions on the benzene ring can be carried out before the N-difluoromethyl substituted triazolinone ring is formed, and the N-difluoromethyl substituted triazolinone ring does not need to be placed in reaction environments such as mixed acid nitration and nitro reduction in the presence of concentrated sulfuric acid and concentrated nitric acid, so that the generation of byproducts is reduced, and the synthesis yield of the compound is improved; the production cost of the compound is reduced; and moreover, the problem that an N-difluoromethyl substituted triazolinone ring is unstable under certain nitrification conditions is also avoided, so that the nitrification and reduction methods have more choices, and a more advanced sulfonyl carfentrazone-ethyl production process is favorably developed.

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The invention discloses a method for synthesizing a sulfentrazone midbody and sulfentrazone. The method comprises the following steps: preparing the sulfentrazone midbody (III) from 1-phenyl-3-methyl-1H-1,2,4-triazole-5-ketone used as a raw material in an aprotic solvent in the presence of a compound (A) or a compound (B) and alkali, performing difluoro methylation to obtain a midbody (IV), performing chlorination, nitration and reduction, and further performing methyl sulfone chloride sulfonylation to obtain a final product, namely, N(2,4-difluoro-5-(4-difluoro methyl-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazole-1-yl) phenyl) sulfamide. The method has the main beneficial effects that due to an adopted catalytic hydrogenation process, the nitroreduction is not only high in chemical selectivity, but also is more environment-friendly, efficient, safe and reliable, as triphenylphosphine, polyethylene glycol or crown ether is used as a catalyst which takes the place of a conventional used catalyst such as DMF (Dimethyl Formamide) in the sulfonylation reaction, less side reaction is caused, and the yield is high. The overall process is simple and convenient, the reaction condition is gentle, the yield is high, the product quality is high, and the industrial production is facilitated.

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