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

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

Downstream Products

• 1009091-52-4 C₁₈H₁₀Cl₂F₂N₄O₃ 
• 1009091-56-8 C₁₈H₁₄Cl₂F₂N₄O₃ 
• 1009091-70-6 C₁₇H₁₂Cl₃F₂N₅O₂ 
• 1009091-69-3 C₁₇H₁₃Cl₂F₂N₅O₂ 
• 1009091-60-4 C₁₈H₁₆Cl₂F₂N₄O₃ 
• 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 

Relevant articles and documents

Preparation method of sulfonyl carfentrazone-ethyl

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.

Method for synthesizing Sulfentrazone

The invention relates to a method for synthesizing Sulfentrazone. The method is characterized by comprising the steps of liberating o-chlorophenylhydrazine from o-chlorophenylhydrazine hydrochloride, which serves as a raw material, by an alkali, subjecting o-chlorophenylhydrazine to a reaction with trimethyl orthoacetate and potassium cyanate so as to obtain 1-o-chlorophenyl-3-methyl-1H-1,2,4-triazol-5-one, and then, subjecting 1-o-chlorophenyl-3-methyl-1H-1,2,4-triazol-5-one to N-alkylation, chlorination, nitration, reduction and sulfonylation, thereby obtaining the Sulfentrazone, wherein a composite catalyst and a solvent, i.e., dichloroethane are adopted in a chlorination reaction. The method for synthesizing the Sulfentrazone, disclosed by the invention, has the advantages that the o-chlorophenylhydrazine hydrochloride serves as the raw material, so that the steric hindrance of an intermediate product can be low, and the yield of the product is increased; and meanwhile, in the chlorination reaction, the composite catalyst is adopted, thus, the orientation effect on all atoms is good, and the solvent is dichloroethane, so that the recycling of the solvent is facilitated.

NOVEL FORM OF SULFENTRAZONE, PROCESS FOR ITS PREPARATION AND USE THEREOF

The invention describes a new crystalline form of sulfentrazone and its preparation process. The invention also describes the analyses of the crystal through various analytical methods and the use of the crystal to prepare stable agrochemical formulation. The novel crystal form is particularly suitable for use in herbicidal compositions and in the control of unwanted plant growth.