120116-88-3

Basic information

• Product Name: CYAZOFAMID
• Synonyms: RANMAN;MILDICUT;IKF-916;DOCIOUS;CYAZOFAMID;4-CHLORO-1-(DIMETHYLAMINOSULFONYL)-5-(P-TOLYL)IMIDAZOLE-2-CARBONITRILE;Fenamidone, Pestanal;cyazofamid (bsi, pa iso)
• CAS NO: 120116-88-3
• Molecular Formula: C₁₃H₁₃ClN₄O₂S
• Molecular Weight: 324.79
• EINECS: 203-625-9
• Mol File: 120116-88-3.mol
• Article Data: 10

Chemical Properties

• Melting Point: 152.7°
• Boiling Point: 498.2°Cat760mmHg
• Flash Point: 4 °C
• Appearance: /
• Density: 1.38g/cm³
• Vapor Pressure: 0mmHg at 25°C
• Refractive Index: 1.634
• Storage Temp.: -20°C
• PKA: -6.61±0.70(Predicted)
• CAS DataBase Reference: CYAZOFAMID(CAS DataBase Reference)
• NIST Chemistry Reference: CYAZOFAMID(120116-88-3)
• EPA Substance Registry System: CYAZOFAMID(120116-88-3)

Safety Data

• Hazard Codes: F,Xn,N
• Statements: 11-38-48/20-63-65-67-20/21/22-50/53-52/53
• Safety Statements: 36/37-62-36-61-60-16
• RIDADR: UN1294 3/PG 2
• WGK Germany: 3
• Hazardous Substances Data: 120116-88-3(Hazardous Substances Data)

Usage

Description

Cyazofamid, an imidazole fungicide, is a chemical compound characterized by its dimethylsulfamyl, cyano, chloro, and 4-tolyl substituents at positions 1, 2, 4, and 5 respectively. It is primarily used for controlling Oomycete and Plasmodiophora diseases on crops such as potatoes and tomatoes. Cyazofamid is known to be a skin and eye irritant and exhibits moderate toxicity to birds, most aquatic organisms, honeybees, and earthworms.

Uses

Used in Agricultural Industry:
Cyazofamid is used as an agricultural fungicide for controlling Oomycete and Plasmodiophora diseases on food crops, specifically targeting potato and tomato plants. Its application helps in reducing the impact of these diseases, ensuring a healthier and more productive crop yield.
Used in Food Crop Protection:
Cyazofamid is used as a protective agent for food crops against fungal infections, particularly those caused by Oomycete and Plasmodiophora pathogens. By incorporating Cyazofamid into the crop management strategy, farmers can minimize the damage caused by these diseases, leading to improved crop quality and increased food security.

InChI:InChI=1/C13H13ClN4O2S/c1-9-4-6-10(7-5-9)12-13(14)16-11(8-15)18(12)21(19,20)17(2)3/h4-7H,1-3H3

Synthetic route

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

C13H14N4O2S → 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide (120116-88-3)

Conditions	Yield
With N-chloro-succinimide In acetonitrile at 20℃; for 4h; Time;	95%

5-(4'-methylphenyl)imidazole-2-carboxylic acid → 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide (120116-88-3)

Conditions	Yield
Multi-step reaction with 5 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 5: potassium carbonate / ethyl acetate / 6 h / Reflux View Scheme

5-(4'-methylphenyl)imidazole-2-carboxylic acid ethyl ester → 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide (120116-88-3)

Conditions	Yield
Multi-step reaction with 4 steps 1: ammonia / methanol / 36 h / 0 °C 2: thionyl chloride / 12 h / 85 °C 3: N-chloro-succinimide / acetonitrile / 3 h / 25 °C 4: potassium carbonate / ethyl acetate / 6 h / Reflux View Scheme

C11H11N3O → 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide (120116-88-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: thionyl chloride / 12 h / 85 °C 2: N-chloro-succinimide / acetonitrile / 3 h / 25 °C 3: potassium carbonate / ethyl acetate / 6 h / Reflux View Scheme

para-methylacetophenone (122-00-9) → 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide (120116-88-3)

Conditions	Yield
Multi-step reaction with 4 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 4: potassium carbonate / ethyl acetate / 3 h / Reflux View Scheme
Multi-step reaction with 4 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 4.1: potassium carbonate / ethyl acetate / Reflux View Scheme

4-methylphenylglyoxal (1075-47-4) → 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide (120116-88-3)

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

2,2-dibromo-1-(4-methylphenyl)ethanone (13664-98-7) → 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide (120116-88-3)

Conditions	Yield
Multi-step reaction with 3 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 3.1: potassium carbonate / ethyl acetate / Reflux View Scheme

1-hydroxy-4-(4-methylphenyl)-3-oxide-1H-imidazole-2-carboxaldehyde oxime → 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide (120116-88-3)

Conditions	Yield
Multi-step reaction with 3 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 3: potassium carbonate / ethyl acetate / 10.5 h / 75 °C View Scheme

4(5)-(4-tolyl)-1H-imidazole (670-91-7) → 4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulfonamide (120116-88-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: potassium carbonate / ethyl acetate / 6 h / 77 °C 2: copper(l) iodide; dipotassium peroxodisulfate / N,N-dimethyl-formamide / 12 h / 110 °C 3: N-chloro-succinimide / acetonitrile / 4 h / 20 °C View Scheme

Upstream product

• 120118-14-1 5-chloro-4-(4-methylphenyl)-1H-imidazole-2-carbonitrile 
• 13360-57-1 dimethylamino sulfonyl chloride 
• 122-00-9 para-methylacetophenone 
• 1075-47-4 4-methylphenylglyoxal 
• 13664-98-7 2,2-dibromo-1-(4-methylphenyl)ethanone 
• 670-91-7 4⁽⁵⁾-(4-tolyl)-1H-imidazole 

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.

Synthesis method of cyazofamid

The invention discloses a synthesis method of cyazofamid. The synthesis method of cyazofamid comprises the following steps: synthesizing 2,2-halogenated-4'-methyl acetophenone; synthesizing 1-hydroxy-4-(4-methyl phenyl)-2-oxime imidazole-3-oxide; synthesizing 2-cyan-4-chlorine-5-(4'-methyl phenyl)imidazole; adding methanol into 1-hydroxy-4-(4-methyl phenyl)-2-oxime imidazole-3-oxide, performing ice-water bath reaction, adding sulfoxide chloride, performing temperature-rising reaction, adding acetonitrile and N-chlorosuccinimide, and performing reaction; and synthesizing cyazofamid: adding 2-cyan-4-chlorine-5-(4'-methyl phenyl)imidazole, anhydrous potassium carbonate, ethyl acetate and N,N-dimethylsulfamoyl chloride into a reaction kettle, and performing refluxing reaction. The synthesis method of cyazofamid has the advantages of rich raw material source, easily available raw materials, low cost, mild reaction condition, no need of special equipment, high economic property, high total yield and good industrialized prospect.

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.