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

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

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

Method for synthesizing high-purity difenoconazole

The invention discloses a method for synthesizing high-purity difenoconazole, which comprises the following steps: 1) carrying out acylation reaction on 3,4'-dichlorodiphenyl ether to obtain an intermediate I; 2) performing cyclization reaction on the intermediate I to obtain an intermediate II; 3) brominating 1,2,4-triazole to prepare a 1,2,-4-triazole bromide; 4) carrying out bromination reaction on the intermediate II and 1,2,4-triazole bromide to obtain an intermediate III and triazole, and carrying out condensation reaction on the intermediate III and 1,2,4-triazole under the action of potassium hydroxide to obtain a difenoconazole crude product; and 5) refining the difenoconazole crude product to obtain a difenoconazole refined product. The method is low in cost, high in quality andhigh in yield, dibromo and hydrolysis byproducts are hardly generated, and the product content and appearance quality of the difenoconazole refined product are improved.

APPLICATION OF TETRAHYDROBENZAZOLE IN PREPARATION OF AGRICULTURAL FUNGICIDE OR FUNGICIDE COMPOSITION AND PREPARATION METHOD THEREOF

An application of tetrahydrobenzazole in the preparation of an agricultural fungicide or a fungicide composition and a preparation method therefor. A 4-((-(2-chloro-4-(4-chlorophenoxy)phenyl)-4-methyl-1,3-dioxapentan-2-yl)methyl)-4H-1,2,4-triazole(tetrahydrobenzazole) compound has application in agricultural fungicides, having the structural formula shown in formula I is provided. Also, the embodiments transform waste that can usually only be treated as a hazardous organic waste solid, accounting for 35-40% of the production process of an agricultural fungicide difenoconazole, into a useful pesticide, significantly reducing discharge of hazardous organic waste solids, and alleviating environmental protection pressure on manufacturers. The preparation method of the embodiments can also increase the yield of difenoconazole and reduce costs.

Preparation method of difenoconazole nitrate

The invention discloses a preparation method of difenoconazole nitrate. The preparation method comprises the following steps: carrying out a microwave reaction on 2-(bromomethyl)-2-(2- chloro-4-(4-chlorophenoxy)phenyl)-4-methyl-1,3-dioxolame and 1H-1,2,4-triazole in the existence of an acid binding agent, a catalyst and a solvent; carrying out distillation to obtain a crude product of difenoconazole, and dissolving the crude product; dissolving the crude product of difenoconazole, and adding nitric acid to form a salt; and carrying out filtration and drying to obtain a finished product of difenoconazole nitrate. The preparation method of difenoconazole nitrate, disclosed by the invention is more mild in reaction condition, short in reaction time, low in solvent dosage, simple in step, green, environment-friendly and suitable for industrial production, and both the yield and content of a final product are relatively high.