120118-14-1

Basic information

• Product Name: 4-Chlor-2-cyano-5-(4-methylphenyl)imidazol
• Synonyms: 4-chloro-5-(4-tolyl)-imidazole-2-carbonitrile;4-Chlor-2-cyano-5-(4-methylphenyl)imidazol;1H-Imidazole-2-carbonitrile, 4-chloro-5-(4-methylphenyl)-;4-Chloro-5-(p-tolyl)imidazole-2-carbonitrile;4-Chlor-2-cyano-5-(4-Methylphenyl)iMidazole;4-Chloro-5-(p-tolyl)-1H-iMidazole-2-carbonitrile;5-Chloro-4-(4-methylphenyl)-1H-imidazole-2-carbonitrile
• CAS NO: 120118-14-1
• Molecular Formula: C₁₁H₈ClN₃
• Molecular Weight: 217.65
• Mol File: 120118-14-1.mol
• Article Data: 5

Chemical Properties

• Boiling Point: 410.891°C at 760 mmHg
• Flash Point: 202.3°C
• Appearance: /
• Density: 1.362g/cm³
• Vapor Pressure: 0mmHg at 25°C
• Refractive Index: 1.635
• Storage Temp.: under inert gas (nitrogen or Argon) at 2-8°C
• CAS DataBase Reference: 4-Chlor-2-cyano-5-(4-methylphenyl)imidazol(CAS DataBase Reference)
• NIST Chemistry Reference: 4-Chlor-2-cyano-5-(4-methylphenyl)imidazol(120118-14-1)
• EPA Substance Registry System: 4-Chlor-2-cyano-5-(4-methylphenyl)imidazol(120118-14-1)

Safety Data

• Hazardous Substances Data: 120118-14-1(Hazardous Substances Data)

Usage

Uses

4-Chloro-2-cyano-5-(4''-methylphenyl) imidazole is a metabolite of Cyazofamid (C987600). Cyazofamid is a imidazole fungicide for use on food crops.

InChI:InChI=1/C11H8ClN3/c1-7-2-4-8(5-3-7)10-11(12)15-9(6-13)14-10/h2-5H,1H3,(H,14,15)

Synthetic route

4(5)-hydroxy-5(4)-(4'-methylphenyl)-2-hydroxyiminomethylimidazole-3-oxide → 5-chloro-4-(4-methylphenyl)-1H-imidazole-2-carbonitrile (120118-14-1)

Conditions	Yield
With thionyl chloride In ethyl acetate for 3h; Reflux;	75%

5-(4'-methylphenyl)imidazole-2-carboxylic acid → 5-chloro-4-(4-methylphenyl)-1H-imidazole-2-carbonitrile (120118-14-1)

Conditions	Yield
Multi-step reaction with 4 steps 1: thionyl chloride / 5 h / 85 °C / Cooling with ice 2: ammonia / methanol / 36 h / 0 °C 3: thionyl chloride / 12 h / 85 °C 4: N-chloro-succinimide / acetonitrile / 3 h / 25 °C View Scheme

5-(4'-methylphenyl)imidazole-2-carboxylic acid ethyl ester → 5-chloro-4-(4-methylphenyl)-1H-imidazole-2-carbonitrile (120118-14-1)

Conditions	Yield
Multi-step reaction with 3 steps 1: ammonia / methanol / 36 h / 0 °C 2: thionyl chloride / 12 h / 85 °C 3: N-chloro-succinimide / acetonitrile / 3 h / 25 °C View Scheme

C11H11N3O → 5-chloro-4-(4-methylphenyl)-1H-imidazole-2-carbonitrile (120118-14-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: thionyl chloride / 12 h / 85 °C 2: N-chloro-succinimide / acetonitrile / 3 h / 25 °C View Scheme

5-(4-methylphenyl)-1H-imidazole-2-carbonitrile → 5-chloro-4-(4-methylphenyl)-1H-imidazole-2-carbonitrile (120118-14-1)

Conditions	Yield
With N-chloro-succinimide In acetonitrile at 25℃; for 3h; Time;	0.18 g
With sulfuryl dichloride In N,N-dimethyl acetamide; acetonitrile at 20 - 25℃;	104 g

para-methylacetophenone (122-00-9) → 5-chloro-4-(4-methylphenyl)-1H-imidazole-2-carbonitrile (120118-14-1)

Conditions	Yield
Multi-step reaction with 3 steps 1: selenium(IV) oxide / 1,4-dioxane; water / 5 h / 50 - 110 °C 2: hydroxylamine hydrochloride / water; methanol / 2 h / Reflux 3: thionyl chloride / ethyl acetate / 3 h / Reflux View Scheme
Multi-step reaction with 4 steps 1.1: dihydrogen peroxide; bromine / cyclohexane / 4 h / 20 °C 2.1: dimethyl sulfoxide / 4 h / 120 °C 3.1: hydroxylamine sulfate / methanol / 6 h / Reflux 4.1: thionyl chloride / N,N-dimethyl-formamide / 3 h / 25 °C 4.2: 3 h / 25 °C / Cooling with ice View Scheme
Multi-step reaction with 3 steps 1.1: acetic acid; bromine / 7 h / 42 °C 2.1: hydroxylamine / methanol / 12 h / 50 °C 3.1: ammonia / methanol / 32 h / 0 °C 3.2: 10 h / 88 °C 3.3: 2.5 h / 28 °C View Scheme

4-methylphenylglyoxal (1075-47-4) → 5-chloro-4-(4-methylphenyl)-1H-imidazole-2-carbonitrile (120118-14-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: hydroxylamine hydrochloride / water; methanol / 2 h / Reflux 2: thionyl chloride / ethyl acetate / 3 h / Reflux View Scheme

4-(bromoacetyl)toluene (619-41-0) → 5-chloro-4-(4-methylphenyl)-1H-imidazole-2-carbonitrile (120118-14-1)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: dimethyl sulfoxide / 4 h / 120 °C 2.1: hydroxylamine sulfate / methanol / 6 h / Reflux 3.1: thionyl chloride / N,N-dimethyl-formamide / 3 h / 25 °C 3.2: 3 h / 25 °C / Cooling with ice View Scheme

C11H11N3O3 → 5-chloro-4-(4-methylphenyl)-1H-imidazole-2-carbonitrile (120118-14-1)

Conditions	Yield
Stage #1: C11H11N3O3 With thionyl chloride In N,N-dimethyl-formamide at 25℃; for 3h; Stage #2: With sulfur dichloride at 25℃; for 3h; Cooling with ice;

2,2-dibromo-1-(4-methylphenyl)ethanone (13664-98-7) → 5-chloro-4-(4-methylphenyl)-1H-imidazole-2-carbonitrile (120118-14-1)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: hydroxylamine / methanol / 12 h / 50 °C 2.1: ammonia / methanol / 32 h / 0 °C 2.2: 10 h / 88 °C 2.3: 2.5 h / 28 °C View Scheme

1-hydroxy-4-(4'-methylphenyl)-2-methylimidazole-3-oxide → 5-chloro-4-(4-methylphenyl)-1H-imidazole-2-carbonitrile (120118-14-1)

Conditions	Yield
Stage #1: 1-hydroxy-4-(4'-methylphenyl)-2-methylimidazole-3-oxide With ammonia In methanol at 0℃; for 32h; Stage #2: With thionyl chloride at 88℃; for 10h; Stage #3: With N-chloro-succinimide In acetonitrile at 28℃; for 2.5h; Temperature;

1-hydroxy-4-(4-methylphenyl)-3-oxide-1H-imidazole-2-carboxaldehyde oxime → 5-chloro-4-(4-methylphenyl)-1H-imidazole-2-carbonitrile (120118-14-1)

Conditions	Yield
Multi-step reaction with 2 steps 1: sodium metabisulfite / N,N-dimethyl acetamide; acetonitrile / 4 h / 80 - 105 °C 2: sulfuryl dichloride / N,N-dimethyl acetamide; acetonitrile / 20 - 25 °C View Scheme

5-chloro-4-(4-methylphenyl)-1H-imidazole-2-carbonitrile (120118-14-1) + dimethylamino sulfonyl chloride (13360-57-1) → 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide (120116-88-3)

Conditions	Yield
With potassium carbonate In ethyl acetate for 3h; Reflux;	96.2%
With potassium carbonate In ethyl acetate for 6h; Solvent; Reflux;	94%
With potassium carbonate In cyclohexane; ethyl acetate Concentration; Solvent; Reflux;	86%
With potassium carbonate In ethyl acetate Reflux;
With potassium carbonate In ethyl acetate at 75℃; for 10.5h;	68 g

isoxazole-4-sulfonyl chloride (80466-79-1) + 5-chloro-4-(4-methylphenyl)-1H-imidazole-2-carbonitrile (120118-14-1) → 4-chloro-1-(3,5-dimethylisoxazol-4-yl-sulphonyl)-5-(4-tolyl)-imidazole-2-carbonitrile (200708-06-1)

Conditions	Yield
With potassium carbonate In dichloromethane; water; acetonitrile

Upstream product

• 13664-98-7 2,2-dibromo-1-(4-methylphenyl)ethanone 
• 619-41-0 4-(bromoacetyl)toluene 
• 1075-47-4 4-methylphenylglyoxal 
• 122-00-9 para-methylacetophenone 

Downstream Products

• 120116-88-3 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide 
• 200708-06-1 4-chloro-1-(3,5-dimethylisoxazol-4-yl-sulphonyl)-5-(4-tolyl)-imidazole-2-carbonitrile 

Relevant articles and documents

PROCESS FOR THE PREPARATION OF 2-CYANOIMIDAZOLE COMPOUNDS

It is an object of the present invention to provide a novel and advantageous process for commercially preparing of 2-cyanoimidazole compounds. More particularly, it relates to an efficient method of preparation of cyazofamid synthetic precursor by simultaneous conversion of aldoxime group to the corresponding cyano-derivative and reducing of N-oxygenated-imidazole ring to imidazole under mild conditions using reducing agent selected from the group consisting of metal salts of sulfur-containing derivatives in the presence of a polar organic solvent.

A 2 - cyano - 4 - chloro - 5 - (4 - methyl phenyl) imidazole synthesis method

The invention relates to a synthetic method for 2-cyano-4-chloro-5-(4-methylphenyl)imidazole. The synthetic method comprises the following steps: (1) by taking p-methylacetophenone as a raw material, carrying out a halogenating reaction under a light condition to obtain a compound I; (2) dissolving the obtained compound I in a solvent, stirring the mixture to react at a certain temperature, and performing cooling and suction-filtering to obtain a compound II; (3) dissolving the obtained compound II in a solvent and carrying out a reaction with glyoxal and hydroxylamine sulphate at a certain temperature to obtain a compound III; and (4) dissolving the obtained compound III in a solvent, carrying out a reaction with sulfoxide chloride in an ice bath in a manner of raising the temperature to room temperature and keeping the temperature for the reaction, dropwise adding sulfur chloride, and after reaction, washing the product to obtain a compound IV which is 2-cyano-4-chloro-5-(4-methylphenyl)imidazole. The synthetic method is good in atom economy, simple and convenient in process operation and high in product yield and industrial application value.

4-chloro-2-cyano-N, N-dimethyl-5-P-tolyl-imidazole-1-sulfonamide synthesis method

The invention discloses a method for synthesizing 4-chloro-2-cyano-N,N-dimethyl-5-p-methylphenylimidazole-1-sulfamide. The method is characterized in that 2-carbonyl-2-P-benzyl acetaldehyde is used as a raw material and reacted with glyoxylic acid to synthesize an imidazole ring, and then ammoniation, dehydration, chlorination and sulfonylation are performed, so that 4-chloro-2-cyano-N,N-dimethyl-5-p-methylphenylimidazole-1-sulfamide is finally synthesized. The purity of 4-chloro-2-cyano-N,N-dimethyl-5-p-methylphenylimidazole-1-sulfamide prepared by adopting the synthesizing method reaches over 98.0%, and the total yield reaches over 44.5%. The method is cheap and readily available in raw materials, simple, mild in reaction conditions and low in environmental pollution, and produces little wastewater. The method is mainly applied to synthesis of 4-chloro-2-cyano-N,N-dimethyl-5-p-methylphenylimidazole-1-sulfamide serving as a pesticide bactericide.