94361-06-5

Basic information

• Product Name: Cyproconazole
• Synonyms: SHANDON;CYPROCONAZOLE;ALTO;1H-1,2,4-Triazole-1-ethanol, .alpha.-(4-chlorophenyl)-.alpha.-(1-cyclopropylethyl)-;(2RS,3RS:2RS,3RS)-2-(Chlorophenyl)-3-cy- clopropyl-1-(1H-1,2,4-triazol-1-yl)butan- 2-ol;2-(4-Chlorophenyl)-3-cyclopropyl-1-(1,2,4-triazol-1-yl)butan-2-ol;cyproconazole (ISO) (2RS,3RS2RS,3SR)-2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol;Alto 100
• CAS NO: 94361-06-5
• Molecular Formula: C15H18ClN3O
• Molecular Weight: 291.78
• Product Categories: CO - CZPesticides;Conazoles;Alpha sort;C;CAlphabetic;Fungicides;Pesticides&Metabolites;Pharmaceutical intermediate
• Mol File: 94361-06-5.mol
• Article Data: 13

Chemical Properties

• Melting Point: 108℃
• Boiling Point: >250℃
• Flash Point: >100 °C
• Appearance: /
• Density: 1.32
• Vapor Pressure: 1.05E-09mmHg at 25°C
• Refractive Index: 1.6330 (estimate)
• Solubility: Soluble in acetone, ethanol, xylene, and dimethyl sulfoxide.
• PKA: 12.59±0.29(Predicted)
• Water Solubility: 140 mg l-1(25 °C)
• BRN: 8396421
• CAS DataBase Reference: Cyproconazole(CAS DataBase Reference)
• NIST Chemistry Reference: Cyproconazole(94361-06-5)
• EPA Substance Registry System: Cyproconazole(94361-06-5)

Safety Data

• Hazard Codes: Xn,N
• Statements: 22-50/53-63
• Safety Statements: 36/37-60-61-36
• RIDADR: UN3077 9/PG 3
• WGK Germany: 3
• RTECS: XZ4803250
• HazardClass: 9
• Hazardous Substances Data: 94361-06-5(Hazardous Substances Data)

Usage

Uses

Used in Agricultural Industry:
Cyproconazole is used as a fungicide for the control of cereal and sugar beet foliar diseases such as Septoria, rust, powdery mildew, Rhyncosporium, Cercospora, and Ramularia. It is also utilized in fruit trees, vines, coffee, banana, turf, and vegetables to manage Venturia, powdery mildew, rust, Mycosphaerela, Monilia, Mycena, Sclerotinia, and Rhizoctonia.
Used in Wood Preservation Industry:
Cyproconazole is used as a wood preservative treatment to prevent decay from fungi in above-ground applications. It is applied as a surface treatment or through pressure treatment for above-ground uses, including siding, plywood, millwork, shingles, and lumber.
Used in Horticulture:
Cyproconazole is used to inhibit demethylation in fungal sterol synthesis, making it effective for the control of fungal diseases in greenhouse and field-grown roses.
Used in Chemical Synthesis:
Cyproconazole's chemical properties as a colorless, crystalline solid with no odor make it suitable for use in various chemical synthesis processes where its antifungal properties can be leveraged for specific applications.

Physical and chemical properties

It appears as colorless crystals with the melting point of 106 to 109 °C, the boiling point of> 250 °C and the vapor pressure at 20 ° C of 0.03470 mPa. It has a relative density of 1.259 with water solubility at 25 ℃ of 1.4g/kg, acetone> 2300g/kg, dimethyl sulfoxide> 180g/kg, ethanol> 230g/kg and xylene: 1200g/kg. It has a Ko819 (±195) (pH 7). Under 70 °C, it can be stable up to 15 days. The DT50 of the soil surface was 21 days under the sunlight; pH value is at the range of 3~9. It is stable under 59 ℃. The soil adsorption coefficient K was 4.1 (loam, pH 6.4, organic matter content: 2.3%), 16 (soil sandy soil, pH 5.1, organic matter content: 3.9%).

Fungicide

Cyproconazole is a kind of triazole agricultural fungicide with the mechanism of action being inhibition of sterol demethylation with prevention and treatment effect. Currently it has been widely used in pesticides, being effective in the treatment of powdery mildew, rust fungi, Rhizopus, Cercospora, Acipenseris and Scleroderma in cereal crops, coffee, sugar beet and fruit trees. It is effective in the treatment of following plant diseases such as the rust diseases of cereals and coffee, powdery mildew diseases of cereals, fruit trees and grape, leaf spot of peanuts and beet, apple scab and white rot disease cereal eye spot, leaf spot and reticulosis of peanuts. Its persistence in the treatment of wheat rust disease is about 4 to 6 weeks and of powdery mildew is 3 to 4 weeks. The spraying method is as follows: spray, the dosage is 80g/ha for cereal crops, 20-50g/ha for coffee, 40-60g/ha for beets and 10 g/ha for fruit tree. For example, we can apply 40~100g/ha for prevention of cereals and coffee rust, cereal, fruit powdery mildew and so on. Cyproconazole can be mixed with other fungicides for better control of cereal eye disease, leaf spot and leaf net blotch disease. Analytical method: The product was analyzed by GLC or HPLC. The residue was assayed by GLC. Allowable residue: The residual amount of the parent compound in the cereal crop is 0.03 mg/kg.

Toxicity

Male rats had acute oral LD50 of 1020 mg/kg, female rats of 1333 mg/kg; male mice of 200 mg/kg and female mice of 218 mg/kg. Rats, rabbits acute percutaneous LD50> 2g/kg; rats acute inhalation LC50 (4 hours)> 5.65mg/L ? air. (1 year) and 1 mg/(kg ? d) in rats (2 years). No irritation to rabbit skin and eyes, no mutagenic effect, no skin allergies to guinea pigs. Low toxicity to birds, quail acute oral LD50 of 150mg/kg; LC50 of duck in 8 days feeding test is 1197mg/kg, while the value for quail is 816mg/kg. Fish poisoning LC50 (96 hours): carp 18.9mg/L, rainbow trout 19mg/L, blue gills 21mg/L. Bees LD50> 0.1mg/bee (contact),> 1mg/kg (oral). Daphnia LC50 (48 hours) was 26 mg/L.

Preparation

1-(4-chlorophenyl)-2-cyclopropyl-1-propanone was reacted with sodium hydride and methyl iodide to give 1-(4-chlorophenyl)-2-cyclopropyl-1-acetone, followed by reaction with CH3(CH2) 11S + (CH3)2CH3SO3-to produce ethylene oxide derivatives, and finally condensed with 1H-1, 2, 4-triazole, leading to the formation of Cyproconazole.

Trade name

ALTO?; ALTO?, ELITE; ATEMI?; ATEMI-50-SL?;EVIPOL?; FLINT?; NOAH GOLD?; SAN-619 F?; SENTINEL?; SN 108266?

Potential Exposure

Triazole fungicide used to control fun- gus on cereals, coffee beans; anthracnose and other diseases on turfgrass; used against rust and leaf spot disease.

Metabolic pathway

Cyproconazole is a mixture of diastereiosomers and the preferential mammalian metabolism of one isomer has been observed. Pathways of metabolism in plants and mammals are quite similar. Metabolism primarily involves oxidation of the terminal methyl group to alcohols and carboxylic acids and/or hydroxylation at the 3-position. Loss of the alkyl cyclopropyl moiety or the triazolyl ring also occurs.

Degradation

Cyproconazole is stable and decomposition was <5% after 2 years. It was stable in aqueous solutions (at pH 1-9) for 35 days (50 °C) or 14 days (80 °C). It is slowly hydrolysed in hydrochloric acid or sodium hydroxide. 14C-Labelled cyproconazole was applied at a rate equivalent to 100 g ha-1 to the surface of a 2 mm layer of loam soil. The samples were exposed to natural sunlight for up to 72 days on open dishes or in flasks fitted with plugs to trap volatile products. Samples were extracted at intervals and analysed. After 37 days exposure on dishes, 50% of the applied cyproconazole remained whereas 85% remained after 72 days in the flasks. In the dishes, unextractable residues amounted to 13-20% of the applied radiolabel after 20 days or more exposure, whereas in the flasks it reached a maximum of 6% after 15 days. The products identified in the dishes were: 1-(4-chlorophenyl)-2-(1H -1,2,4-triazol-l-yl)- ethanone (2, 5%), 3-cyclopropyl-1-(1H-1,2,4-triazol-l-yl)butanone(4,4%), 2-(2- or 3-hydroxy-4-chlorophenyl)-3-cyclopropyl-1-(1H -1,2,4-triazol-1-yl)- butan-2-ol (3 4%), and 4-chlorobenzoic acid 5 (Scheme 1) (PSD, 1991). Degradation in the flasks was similar but occurred to a lesser extent. No volatde products were trapped and recoveries of radiolabel were 94- 102%.

Incompatibilities

The triazoles are sensitive to heat, fric- tion, and impact. Sensitivity varies with the type substitu- tion to the triazole ring. Metal chelated and halogen substitution of the triazol ring make for a particularly heat sensitive material. Azido and nitro derivatives have been employed as high explosives. No matter the derivative these materials should be treated as explosives .

InChI:InChI=1/C15H18ClN3O/c1-11(12-2-3-12)15(8-20,19-10-17-9-18-19)13-4-6-14(16)7-5-13/h4-7,9-12,20H,2-3,8H2,1H3

Upstream product

• 58905-19-4 1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)ethanone 
• 593-71-5 Chloroiodomethane 
• 75-11-6 diiodomethane 
• 74-97-5 chlorobromomethane 
• 74-95-3 1,1-dibromomethane 
• 94361-26-9 2-(4-chlorophenyl)-3-cyclopropyl-1,2-butylene oxide 
• 41253-21-8 sodium triazole 
• 36982-56-6 (2-bromoethyl)cyclopropane 
• 288-88-0 1,2,4-Triazole 
• 38674-38-3 1-cyclopropylchloroethane 
• 937-20-2 p-chlorophenacyl chloride 
• 123989-29-7 1-(p-chlorophenyl)-2-cyclopropyl-2-methylethan-1-one 
• 123989-28-6 1-(4-chlorophenyl)-2-cyclopropyl-1-propanol 
• 104-88-1 4-chlorobenzaldehyde 

Downstream Products

• 1527518-39-3 3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)-2-(4-(trimethylstannyl)phenyl)butan-2-ol 
• 1527518-42-8 2-(biphenyl-4-yl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol 
• 1527518-43-9 3-cyclopropyl-2-(4'-fluorobiphenyl-4-yl)-1-(1H-1,2,4-triazol-1-yl)butan-2-ol 
• 1527518-44-0 3-cyclopropyl-2-(4-(naphthalen-1-yl)phenyl)-1-(1H-1,2,4-triazol-1-yl)butan-2-ol 
• 1527518-46-2 3-cyclopropyl-2-(2'-methoxybiphenyl-4-yl)-1-(1H-1,2,4-triazol-1-yl)butan-2-ol 
• 43121-43-3 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one 
• 82657-04-3 bifenthrin 

Relevant articles and documents

AN IMPROVED PROCESS FOR PREPARATION OF AN AZOLE FUNGICIDE

The present invention relates to improved process for the preparation of a fungicide of the class of azoles. The present invention specifically relates to an improved process for the preparation of (2RS,3RS;2SR,3SR)-2-(4-chlorophenyl)-3-cyclopropyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol having the following Formula I.

Method for preparing cyproconazole with 2,4'-dichloroacetophenone being raw material

The invention relates to the field of organic synthesis and especially relates to a method for preparing cyproconazole with 2,4'-dichloroacetophenone being a raw material. The method includes: a) performing a nucleophilic substitution reaction on the 2,4'-dichloroacetophenone and 1,2,4-triazole or 1,2,4-triazole salt to obtain 1-(4-chlorophenyl)-2-(1H-1,2,4-triazole-1-yl)ethyl ketone; b) performing a nucleophilic addition reaction on the 1-(4-chlorophenyl)-2-(1H-1,2,4-triazole-1-yl)ethyl ketone with one or more of a 3-halogenated-1-butylene Grignard reagent, a 3-halogenated-1-butylene organozinc reagent, a 1-halogenated-2-butylene Grignard reagent and a 1-halogenated-2-butylene organozinc reagent, thus generating 2-(4-chlorophenyl)-3-methyl-1-(1H-1,2,4-triazole-1-yl)-4-pentene-2-ol; c) performing a ring forming reaction on the 2-(4-chlorophenyl)-3-methyl-1-(1H-1,2,4-triazole-1-yl)-4-pentene-2-ol with one or more Simmons-Smith reagents prepared from dihalogenated methane, thus preparing the cyproconazole. The preparation method is short in route, gentle in reaction and high in yield. The reactions are free of dangerous reagents, so that the method is suitable for large scale industrial production.

Through 1 - chloro -2 - (4 - chlorophenyl) -3 - methyl -4 - pentene -2 - alcohol preparation triabimefron method

The invention relates to the field of organic synthesis, in particular to a through 1 - chloro - 2 - (4 - chlorophenyl) - 3 - methyl - 4 - pentene - 2 - ol preparation triabimefron method, comprises the following steps: (1) 2, 4' - dichloro ethanone deprotecting reagent or organic zinc reagent nucleophilic addition reaction, generating 1 - chloro - 2 - (4 - chlorophenyl) - 3 - methyl - 4 - pentene - 2 - ol, 2 - (4 - chlorophenyl) - 2 - (d - 3 - en - 2 - yl) - ethylene oxide or a mixture of both; (2) step (1) the product obtained with the halogeno methane ring 1 - chloro - 2 - (4 - chlorophenyl) - 3 - cyclopropyl-d - 2 - ol, 2 - (4 - chlorophenyl) - 2 - (1 - cyclopropyl-ethyl) - ethylene oxide or a mixture of both; (3) step (2) product with 1, 2, 4 - triazole or 1, 2, 4 - three nitrogen zuozuo salt undergo nucleophilic substitution reaction to obtain triabimefron. The invention provides a method for preparing triabimefron short route, high yield, the reaction process does not use a foul smell of sulfur reagent, not with the use of toxic reagent, also without the use of a noble metal catalyst, suitable for large-scale industrial production.

In order to 1 - (4 - chlorophenyl) -2 - (1 H - 1, 2, 4 - triazole -1 - yl) ethanone synthetic triabimefron method

The invention relates to the field of organic synthesis, in particular to a using the intermediate 1 - (4 - chlorophenyl) - 2 - (1 H - 1, 2, 4 - triazole - 1 - yl) ethanone synthetic triabimefron method, comprises the following steps: (1) 2, 4' - dichloro ethanone with 1, 2, 4 - triazole or 1, 2, 4 - three nitrogen zuozuo salt undergo nucleophilic substitution reaction to obtain 1 - (4 - chlorophenyl) - 2 - (1 H - 1, 2, 4 - triazole - 1 - yl) ethyl ketone; (2) 1 - (4 - chlorophenyl) - 2 - (1 H - 1, 2, 4 - triazole - 1 - yl) ethanone with 1 - cyclopropyl halogenated ethane Grignard reagent, 1 - cyclopropyl halogenated ethane organic zinc reagent or a mixture thereof a nucleophilic addition reaction triabimefron. The present invention provides a method of synthesis of triabimefron short route, mild reaction, high yield, the reaction process does not use a foul smell of sulfur ylide reagent, does not need to use dangerous [...], also will not produce a large amount of phosphorus-containing waste water, suitable for large-scale industrial production.

Novel preparation method of cycloazole alcohol

The invention relates to the field of organic synthesis, in particular to a novel preparation method of cycloazole alcohol. The method includes following steps: (1), allowing 2, 4'-dichloroacetophenone to be in nucleophilic addition reaction with 1-cyclopropyl halogenated ethane Grignard reagent or 1-cyclopropyl halogenated ethane organic zinc reagent to generate 1-chloro-2-(4-chlorphenyl)-3-cyclopropyl butyl-2-alcohol or 2-(4-chlorphenyl)-2-(1-cyclopropy ethyl)-ethylene oxide or a mixture of the two; (2), enabling the product of the step (1) to be in nucleophilic substitution reaction with 1,2, 4-triazole or 1, 2, 4-triazole salt to obtain cycloazole alcohol; or enabling 1-chloro-2-(4-chlorphenyl)-3-cyclopropyl butyl-2-alcohol to react with alkali to generate 2-(4-chlorphenyl)-2-(1-cyclopropy ethyl)-ethylene oxide, then being in ring-opening reaction with 1, 2, 4-triazole or 1, 2, 4-triazole salt to obtain cycloazole alcohol. The preparation method is short in path, high in yield, needless of sulfur reagent with foul odor, highly toxic reagent and noble metal catalyst expensive in price in the process of reaction and suitable for large-scale industrial production.

Preparation method for cyproconazole

The invention discloses a preparation method for cyproconazole. The preparation method comprises the following steps: (1) dropwise adding dimethylsulfide to dimethyl sulfate and acetonitrile solution,to obtain solution A; (2) adding sodium methylate to the solution A, and dropwise adding acetonitrile solution of Alpha-methyl-4-chlorphenylcyclopropyl methyl ketone, after mixing, to obtain solutionB; (3) performing decompression treatment on the solution B, adding water and ethyl acetate for extracting, treating to obtain epoxide; (4) mixing triazole and the epoxide in N,N-dimethylformamide solution, adding sodium hydride, treating to obtain solution C; and (5) performing chloroform extraction on the solution C, after treatment, to obtain the cyproconazole. The preparation method is simplein process, and lower in production cost.

Preparation method of cyproconazole

The invention relates to a preparation method of cyproconazole as shown in the chemical structural formula I. According to the preparation method, 4-chlorobenzaldehyde is selected as a raw material to undergo a Grignard reaction to obtain a key intermediate 1-(4-chlorophenyl)-2-cyclopropyl-1-propanol; and 1-(4-chlorophenyl)-2-cyclopropyl-1-propanol undergoes an oxidation reaction, and then Sulfur ylide reaction and ring-opening reaction are successively carried out to prepare cyproconazole. Preparation reaction is as shown in the specification, wherein an oxidizing agent is selected from N-halosuccinimide, 1,3-dihalo-5,5-dimethyl hydantoin or ketone-alkoxy-aluminium; a sulfur ylide reagent is prepared by carrying out a reaction between (CH3)2S and (CH3)2SO4 under the action of KOH in isobutanol; DBU is 1,8-diazabicyalo[5.4.0]C11-7-en; and NMP is N-methylpyrrolidine.

Synergistic Active Compound Combinations Comprising Phenyltriazoles

The present invention relates to novel active compound combinations comprising, firstly, at least one known compound of the formula (I) in which R1 and R2 have the meanings given in the description. and at least one further known active compound from groups (2) to (27) listed in the description, which combinations are highly suitable for controlling animal pests such as insects and unwanted acarids and also phytopathogenic fungi.

Synergistic Fungidical Active Substance Combinations

The present invention relates to novel active substance combinations which contain spiroxamine, which is known, a known azole and a known carboxamide and which are very suitable for controlling undesired phytopathogenic fungi.

Fungicide mixture

A composition comprising effective amounts ofa) a carbamate of the formula I where T is CH or N, n is 0, 1 or 2 and R is halogen, C1-C4-alkyl or C1-C4-haloalkyl, it being possible for the radicals R to be different if n is 2, andc) a compound III selected from the group consisting of the oxime ether carboxylate IIIa, the oxime ether carboxamide IIIb and the methoxyacrylate IIIc and optionally an oxime ether (II) and/or an azole (IV) as defined in the specification which exhibits a synergistically enhanced fungicidal effect is described.