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.

A 4-chloro-2-cyano-N, N-dimethyl-5 - (4 the [...] -methyl-phenyl) - 1H-imidazole-1-sulfonamide synthesis method

The invention discloses a synthesis method of 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide (cyazofamid). According to the synthesis method, methylacetophenone is taken as a raw material, selenium dioxide is used for oxidation to prepare an intermediate, namely 2-carbonyl-2-p-benzyl aldehyde, then N,N-dimethylformamide and the like are taken as solvents, thionyl chloride is taken as a chlorinating agent and reducing agent for preparing the intermediate, and then intermediate further reacts with N,N-dimethyl sulfonamide chloride to synthesize the cyazofamid. Compared with the prior art, the synthesis method has the advantages that the reaction period is shortened, the post-treatment process is simplified and the synthesis method is suitable for mass industrial production.