119446-68-3

Basic information

• Product Name: Difenoconazole
• Synonyms: SCORE;1-((2-(2-chloro-4-(4-chlorophenoxy)phenyl)-4-methyl-1,3-dioxolan-2-yl)methyl)-1h-1,2,4-triazole;DIFENOCONAZOL;DIFENOCONAZOLE;DIVIDEND;1h-1,2,4-triazole,1-((2-(2-chloro-4-(4-chlorophenoxy)phenyl)-4-methyl-1,3-diox;4-triazole,1-((2-(2-chloro-4-(4-chlorophenoxy)phenyl)-4-methyl-1,3-dioxolan-2-yl)methyl)-1h-2;cga169374
• CAS NO: 119446-68-3
• Molecular Formula: C₁₉H₁₇Cl₂N₃O₃
• Molecular Weight: 406.26
• Product Categories: Alpha sort;ConazolesPesticides&Metabolites;D;DAlphabetic;DID - DIN;Fungicides;Pesticides
• Mol File: 119446-68-3.mol
• Article Data: 10

Chemical Properties

• Melting Point: 76°C
• Boiling Point: 220°C
• Flash Point: 284.6 °C
• Appearance: colorless solid
• Density: 1.4916 (rough estimate)
• Vapor Pressure: 5.09E-12mmHg at 25°C
• Refractive Index: 1.6140 (estimate)
• Storage Temp.: 0-6°C
• PKA: 2.94±0.12(Predicted)
• Water Solubility: 3.3 mg/L (20 ºC)
• Merck: 13,3160
• BRN: 9073356
• CAS DataBase Reference: Difenoconazole(CAS DataBase Reference)
• NIST Chemistry Reference: Difenoconazole(119446-68-3)
• EPA Substance Registry System: Difenoconazole(119446-68-3)

Safety Data

• Hazard Codes: Xn,N
• Statements: 22-41-43-50-20/22
• Safety Statements: 26-36/37/39-61
• RIDADR: UN 3077 9 / PGIII
• WGK Germany: 3
• RTECS: XZ4380000
• Hazardous Substances Data: 119446-68-3(Hazardous Substances Data)

Usage

Description

Difenoconazole is a kind of triazole-type fungicide. It is a broad-spectrum triazole fungicide. It takes effect through acting as the inhibitor of sterol 14α-demethylase, blocking the biosynthesis of sterol. Through inhibiting the sterol biosynthesis process, it inhibits the mycelia growth and germination of pathogens by spores, ultimately suppressing the proliferation of fungi. Difenoconazole has been extensively used in a wide range of crops in many countries due to its ability to control various fungal diseases. It is also one of the most important and widely-used pesticides for disease control in rice.

Uses

Different sources of media describe the Uses of 119446-68-3 differently. You can refer to the following data:
1. Agricultural fungicide.
2. Pestanal is an fungicide that exhibits a broad spectrum of activities against a wide variety of fungi including members of the Aschomycetes, Basidomycetes and Deuteromycetes families.
3. Difenoconazole is a fungicide with broad-range activity, protecting yield and quality by foliar application or seed treatment. It provides long-lasting and curative activity against Ascomycetes, Basidiomycetes and Deuteromycetes. It is used against disease complexes in grapes, pome fruit, stone fruit, potatoes, sugar beet, oilseed rape, banana, ornamentals and various vegetable crops. It is also used as a seed treatment against a range of pathogens in wheat and barley.

Definition

ChEBI: A member of the class of dioxolanes that is 1,3-dioxolane substituted at position 2 by 2-chloro-4-(4-chlorophenoxy)phenyl and 1,2,4-triazol-1-ylmethyl groups. A broad spectrum fungicide with novel broad-range activity used as a spray or seed treatment. It is moderately toxic to humans, mammals, birds and most aquatic organisms.

Agricultural Uses

Fungicide: For suppression of fungi diseases in crops and seeds.

Trade name

CGA 169374?; DIVIDEND?; DIVIDEND? EXTREME FUNGICIDE; HELIX?; SCORE?; TECHNICAL CGA-169374?

Metabolic pathway

There is limited published information on the metabolism of difenoconazole. It is slowly dissipated in soils, and metabolism in plants involves rupture of the triazole linkage or oxidation of the phenyl ring followed by conjugation.

Degradation

Difenoconazole is stable to hydrolysis and is thermally stable to 150 °C. DT50 of difenocoazole in natural sunlight was 145 days.

References

Kwok, Iris M‐Y., and R. Thomas Loeffler. "The biochemical mode of action of some newer azole fungicides." Pest Management Science 39.1 (1993): 1-11. Wang, K., J. X. Wu, and H. Y. Zhang. "Dissipation of difenoconazole in rice, paddy soil, and paddy water under field conditions." Ecotoxicology and environmental safety 86 (2012): 111-115.

InChI:InChI=1/C19H17Cl2N3O3/c1-13-9-25-19(27-13,10-24-12-22-11-23-24)17-7-6-16(8-18(17)21)26-15-4-2-14(20)3-5-15/h2-8,11-13H,9-10H2,1H3

Synthetic route

2-(bromomethyl)-2-(2-chloro-4-(4-chlorophenoxy)phenyl)-4-methyl-1,3-dioxolane → difenconazole (119446-68-3)

Conditions	Yield
With potassium hydroxide In dimethyl sulfoxide; N,N-dimethyl-formamide at 140 - 145℃;	97.2%

C19H19Cl2N4O3(1+)*Br(1-) → difenconazole (119446-68-3)

Conditions	Yield
Stage #1: C19H19Cl2N4O3(1+)*Br(1-) With hydrogenchloride; sodium nitrite In water at 5 - 20℃; for 2h; Stage #2: With water at 40℃; Temperature; Alkaline conditions;	95%

1,2,4-Triazole (288-88-0) + 2-(bromomethyl)-2-(2-chloro-4-(4-chlorophenoxy)phenyl)-4-methyl-1,3-dioxolane → difenconazole (119446-68-3)

Conditions	Yield
With potassium carbonate; potassium iodide In N,N-dimethyl-formamide at 185℃; for 0.25h; Solvent; Temperature; Reagent/catalyst; Microwave irradiation;	92.6%
With trimethyldodecylammonium chloride; potassium hydroxide In 1-methyl-pyrrolidin-2-one at 130℃; Reagent/catalyst;	83%
With potassium carbonate In 1-methyl-pyrrolidin-2-one at 163℃; for 5.5h; Temperature;	27 g

2-(2,4-dichlorophenyl)-2-bromomethyl-4-methyl-1,3-dioxolane + 4-chloro-phenol (106-48-9) + potassium 1,2,4-triazolate → difenconazole (119446-68-3)

Conditions	Yield
Stage #1: 2-(2,4-dichlorophenyl)-2-bromomethyl-4-methyl-1,3-dioxolane; potassium-1H-1,2,4-triazol With potassium carbonate In dimethyl sulfoxide at 150℃; for 8h; Green chemistry; Stage #2: 4-chloro-phenol With potassium carbonate In toluene for 10h; Reflux; Green chemistry;	166.8 g

1-(2,4-dichlorophenyl)ethan-1-one (2234-16-4) → difenconazole (119446-68-3)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: dihydrogen peroxide; sodium carbonate; bromine / dichloromethane / 20 - 40 °C / Green chemistry 2.1: toluene-4-sulfonic acid / toluene / 4 h / Reflux; Green chemistry 3.1: potassium carbonate / dimethyl sulfoxide / 8 h / 150 °C / Green chemistry 3.2: 10 h / Reflux; Green chemistry View Scheme

1,3-Dichlorobenzene (541-73-1) → difenconazole (119446-68-3)

Conditions	Yield
Multi-step reaction with 4 steps 1.1: 4 h / 60 °C / Ionic liquid; Green chemistry 2.1: dihydrogen peroxide; sodium carbonate; bromine / dichloromethane / 20 - 40 °C / Green chemistry 3.1: toluene-4-sulfonic acid / toluene / 4 h / Reflux; Green chemistry 4.1: potassium carbonate / dimethyl sulfoxide / 8 h / 150 °C / Green chemistry 4.2: 10 h / Reflux; Green chemistry View Scheme

difenoconazole nitrate → difenconazole (119446-68-3)

Conditions	Yield
With sodium hydroxide In water; toluene at 60℃; pH=8 - 9; Large scale;

4-((2-(2-chloro-4-(4-chlorophenoxy)phenyl)-4-methyl-1,3-dioxolan-2-yl)methyl)-4H-1,2,4-triazole → difenconazole (119446-68-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: potassium hydroxide / water / 11 h / 97 °C 2: hydrogen bromide / 4.5 h / 55 °C 3: potassium carbonate / 1-methyl-pyrrolidin-2-one / 5.5 h / 163 °C View Scheme

3,4'-Dichlorobiphenyl ether (6842-62-2) → difenconazole (119446-68-3)

Conditions	Yield
Multi-step reaction with 4 steps 1: aluminum (III) chloride / 1,2-dichloro-ethane / 10 - 50 °C 2: sulfuric acid / 1,2-dichloro-ethane / Reflux 3: 1-bromo-1,2,4-triazole / 5 - 10 °C 4: potassium hydroxide / dimethyl sulfoxide; N,N-dimethyl-formamide / 140 - 145 °C View Scheme

1-(2-chloro-4-(4-chlorophenoxy)phenyl)-ethan-1-one (119851-28-4) → difenconazole (119446-68-3)

Conditions	Yield
Multi-step reaction with 3 steps 1: sulfuric acid / 1,2-dichloro-ethane / Reflux 2: 1-bromo-1,2,4-triazole / 5 - 10 °C 3: potassium hydroxide / dimethyl sulfoxide; N,N-dimethyl-formamide / 140 - 145 °C View Scheme

difenconazole (119446-68-3) → difenoconazole nitrate

Conditions	Yield
With nitric acid In benzene at 20℃; for 2h; Solvent; Temperature;	84.1%

difenconazole (119446-68-3) → 2-{2-[2-chloro-4-(4-chlorophenoxy)-phenyl]-4-methyl-[1,3]dioxolan-2-ylmethyl}-2,4-dihydro[1,2,4]triazole-3-thione (186259-71-2)

Conditions	Yield
Stage #1: difenconazole With isopropylmagnesium chloride In tetrahydrofuran at 40℃; for 1.5h; Stage #2: With sulfur In tetrahydrofuran at 0℃; for 1h; Stage #3: With hydrogenchloride; water In tetrahydrofuran	59%

hydrogen sulfide (7783-06-4) + difenconazole (119446-68-3) → 2-[2-chloro-4-(4-chloro-phenoxy)-phenyl]-2-[(5-mercapto-1,2,4-triazol-1-yl)-methyl]-4-methyl-1,3-dioxolan

Conditions	Yield
With 1-methyl-pyrrolidin-2-one
With 1-methyl-pyrrolidin-2-one
With 1-methyl-pyrrolidin-2-one
With 1-methyl-pyrrolidin-2-one
With 1-methyl-pyrrolidin-2-one

dimethylsulfoximine (1520-31-6) + difenconazole (119446-68-3) → C21H22Cl2N4O4S

Conditions	Yield
With TEMPO; 3,6‐di‐tert‐butyl‐9‐mesityl‐10‐phenylacridin‐10‐ium tetrafluoroborate; oxygen In acetonitrile at 37℃; for 21h; Sealed tube; Irradiation; regioselective reaction;

Upstream product

• 106-48-9 4-chloro-phenol 
• 57-55-6 propylene glycol 
• 136815-80-0 1-[2-chloro-4-(4-chloro-phenoxy)-phenyl]-2-[1,2,4]triazol-1-yl-ethanone 
• 873012-43-2 2-(bromomethyl)-2-(2-chloro-4-(4-chlorophenoxy)phenyl)-4-methyl-1,3-dioxolane 
• 119851-28-4 1-(2-chloro-4-(4-chlorophenoxy)phenyl)-ethan-1-one 
• 6842-62-2 3,4'-Dichlorobiphenyl ether 
• 541-73-1 1,3-Dichlorobenzene 
• 2234-16-4 1-(2,4-dichlorophenyl)ethan-1-one 
• 288-88-0 1,2,4-Triazole 

Downstream Products

• 186259-71-2 2-{2-[2-chloro-4-(4-chlorophenoxy)-phenyl]-4-methyl-[1,3]dioxolan-2-ylmethyl}-2,4-dihydro[1,2,4]triazole-3-thione 

Relevant articles and documents

Triazole compound containing dioxolame and preparation method of intermediate of triazole compound

The invention relates to a preparation method of a dioxolane-containing triazole compound and an intermediate thereof, and the method comprises the following steps: reacting a compound shown as a formula (V) with a compound shown as a formula (IV) in the presence of Lewis acid to prepare a compound shown as a formula (III); reacting the compound shown in the formula (III) with a compound shown in the formula (II) to prepare the compound shown in the formula (I). According to the technical scheme, a triazole group is introduced into 1H-1, 2, 4-triazole-1-acetic acid, generation of an isomer 1, 3, 4-triazole byproduct is avoided, the reaction yield is increased, and the method has the advantages of being simple and convenient in process route, few in reaction step, simple in process, low in production cost, environmentally friendly, green and safe; the post-treatment of the product only needs a simple solvent crystallization process, a nitric acid salifying method and a high-temperature distillation method do not need to be adopted, the requirements on equipment are reduced and the cost is reduced under the condition of improving the yield and content of the product, and the method is suitable for industrial production.

Method for converting 4 - H difenoconazole isomer into 1 - H-difenoconazole (by machine translation)

A method for converting 4 - H-difenoconazole isomer into 1 - H-difenoconazole isomer to obtain an alcohol, 2) reaction of the alcohol and hydrobromic acid to obtain a bromide; 3) separating 1 difenoconazole and 4 - H) 1 - H) from the mixture of 4 - H-difenoconazole and 1 - H-difenoconazole isomer; 4) completely converting 4 - H-difenoconazole isomer into 4 - H-phenylene difenoconazole.) isomer is obtained by dissolving 1) difenoconazole and difenoconazole as a mixture in the presence of a base and a transition metal catalyst to obtain a mixture of difenoconazole and difenoconazole -4 4 - H 1 - H. The method not only can effectively reduce the solid waste problem 4 - H difenoconazole isomer, but also can convert the difenoconazole product into 1 - H difenoconazole product, so that the cost is reduced, the product yield is increased, and the economic benefit is improved. (by machine translation)

Synthetic process of difenoconazole

The invention discloses a synthetic process of difenoconazole, comprising the steps of synthesizing 2,4-dichloroacetophenone through ionic liquid acylation using m-dichlorobenzene as a raw material; then synthesizing alpha-bromo-2,4-dichloroacetophenone through a green bromination method; subjecting the alpha-bromo-2,4-dichloroacetophenone and 1,2-propanediol to cyclization to generate a ketal compound that is 2-(2,4-dichlorophenyl)-2-bromomethyl-4-methyl-1,3-dioxolane; subjecting the ketal compound and 1,2,4-triazole potassium to condensation to generate 1-[[2-(2,4-dichlorophenyl)-4-methyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole; and finally subjecting the 1-[[2-(2,4-dichlorophenyl)-4-methyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole and parachlorophenol to etherification to obtain the difenoconazole. The process has advantages of easily available raw materials, a high reaction conversion ratio, few byproducts, capability of being friendly to production environment and a low cost.