SU793357A3 - Fungicidic composition - Google Patents

Abstract

Imidazole derivatives have the following formula <IMAGE> in which X is identical or different and denotes halogen, lower alkyl, nitro or lower haloalkyl, n is 1 or 2 and Y denotes alkoxy lower alkyl, lower alkenyloxyalkyl, lower phenoxyalkyl, substituted lower phenoxyalkyl or benzyl, with the proviso that Xn denotes trifluoromethyl in the 2 position and chlorine in the 4 position when Y represents benzyl. The compounds may be present as complexes of metal salts. A fungicide contains as at least one active component a compound of the formula I. The compounds of the formula I are obtained by reacting imidazole with a halide which donates the radical <IMAGE>

Description

The reaction is carried out in an inert solvent in the presence of an alkaline condensing agent, such as sodium carbonate, potassium carbonate, sodium hydroxide, sodium methyl alcohol, trimethylamine, triethylamine, pyridine or piperidine. Chloroform, dichloromethane benzene, toluene can be used as an inert solvent. xylene, chlorobenzene, acetonitrile, acetone, dimethyl sulfoxide, tetrahydrofuran, dimethylformamide or dioxane. A temperature in the range of usually is sufficient. to the boiling point of the reaction solvent / temperatures from 40 ° C to the boiling point are preferred. Usually the reaction proceeds 1-Sp. Upon completion of the reaction, the reaction mixture is washed with water and dried.

If necessary, washing and drying are carried out after changing the solvent. The solvent is then distilled off in order to obtain the desired compound.

The metal complexes of the present invention: can be prepared by the following reaction. / N-C X / Y (AB is an organic or inorganic metal salt, A is a divalent or trivalent metal atom. B is the anionic component of salt, and e corresponds to the valency of metal atom A in the metal salt DB). Chlorides, copper sulfates, zinc chloride, and zinc acetate are used as metal salts. When carrying out the reaction to obtain metal complexes, the imidazole derivative is dissolved in an inert solvent, and the metal salt is added thereto, the reaction proceeds while stirring the mixture. The reaction is usually carried out at room temperature for several minutes. As an inert solvent, any solvent can be used that expands the immobilized imidazole derivatives and is miscible with water. The proposed method uses ethyl acetate, methanol, acetonitrile, dioxane, or tetrahydrofuran. At the end of the reaction, the reaction mixture was poured into n-hexane or water, and the precipitated crystals were separated from the mixture by filtration, and thus a metal complex was obtained.

Take p1. (2-Bromophenyl) -2-ethoxypropanimidoyl-imidazole (compound M 3),

11 g of 2-bromo-2 (ethoxy) -propionanilide is reacted with 8.4 g of phosphorus pentachloride in 50 ml of chloroform by heating the solution under reflux for 30 minutes. Then, chloroform and phosphorus oxychloride, which is formed as a by-product, are removed by distillation and the residue in 40 ml of acetonitrile. 2.8 g of imidazole and 4.1 g of triethylamine are added to the solution and the mixture is then heated under reflux for 3 hours. Upon completion of the reaction, the acetonitrile is distilled off and the residue is dissolved in 30 ml of dichloromethane. The solution is washed several times with water and dried over anhydrous magnesium sulphate. After distillation

0 dichloromethane, the remaining oily product is purified by chromatography on silica gel with dichloromethane and obtain 4 g of the target compound (p. 1.5870).

5 Example2. (2,4-Dichlorophenyl. -Nyl) -2-propoxypropanimidoyl-3-imidazole (compound No. 9). 7.5 g of 2, 4-dichloro-2- (propoxy) propioanilide is reacted with 5, bg of phosphorus chloride in 40 ml of chloroform by heating the solution with a reflux condenser for 30 minutes. Then chloroform and phosphorus oxychloride formed as a by-product are removed by distillation under reduced pressure and the residue is dissolved in 40 ml of acetonitrile. To the solution, 1.9 g of imidazole and 2.7 g of triethylamine are added, the mixture is boiled with reverse fridge for 3h. Upon completion of the reaction, the reaction mixture is treated as in Example 1, and 4 g of the desired product are obtained with mp. 68-89 ,. Froze - (2,4-Dichlororphenyl) -3-propoxypropanimidoyl-imidazole (compound 36). 6.9 g of 2,4-dichloro-3 (nponokcn) propioanilide and 8 g of triethylamine are dissolved in 30 ml of chloroform and 3.7 g of phosgene are introduced into the solution at a temperature from 0 to 10 ° C with ice cooling. After raising the temperature to. The room solution is stirred for 2 hours and then 2 g of imidazole is added to it. The mixture was heated under reflux for 2 hours. Upon completion of the reaction, the resulting reaction mixture is cooled to room temperature, washed with water and dried over anhydrous magnesium sulphate. Upon removal of chloroform from the solution by distillation, 7.7 g of the title compound are obtained (p 1.5688. EXAMPLE 4. 1 - {N - (4-ChLOR-2 trifluoromethylphenyl) -2-propoxy-acetimidoyl-3-imidazole (compound W 37). 12.6 g of 4-chloro-2-trifluoromethyl-2- (propoxy) acetanilyl and 12.9 g of triethylamine are dissolved in 80 ml of chloroform and then a solution of 6.4 g of phosgene in 30 ml of chloroform is added dropwise to the mixture. The solution is stirred for 1 h at room temperature. After the reaction was complete, chloroform was removed by distillation. The remaining residue was dissolved in n-hexane, the solution was washed with water and dried over anhydrous magnesium sulfate. After removal of n-hexane by distillation, the residue is purified by silica gel chromatography to give 9.8 g of the desired compound with a melting point of 66-66.5 C. EXAMPLE 5. I- {N - {4-Chloro -2-tr fluoromethylphenyl) -3-ethoxypropanimido -imidazole (compound No. 46.). 6.5 g of 4-chloro-2-trifluoromethyl-2- (ethoxy) propioanilide are reacted with 4.9 g of p-chloride of phosphorus in 30 ml of chloroform and refluxed for 1 hour. Then, chloroform and phosphorus pentachloride are removed by distillation under reduced pressure. 3.2 ml of imidazole and 30 ml of acetonitron are added to the residue, the mixture is heated for 30 minutes under reflux. Upon completion of the reaction, the acetonitrile is removed by distillation and the residue is dissolved in dichloromethane. The solution is washed with water and dried with anhydrous magnesium sulphate. After removing the solvent from the solution by distillation, the residue is purified by chromatography on an alumina column to give 3 / 5g of the desired product (m.p. 61-62 C). Example 6 Bis- {1- K- (2.4 -dichlorophenyl) -2-propoxypropanimidoylDimidazole copper chloride (compound No. 57). 1 g of (2,4-dichlorophenyl) -2-propoxypropanimidoyl 3 -imidazole is dissolved in 5 ml of methanol, and 0.5 g of anhydrous chloric copper is added to the solution. The mixture is stirred for 5 minutes at room temperature and then poured into 100 ml of water in order to precipitate the crystals. The crystals separated by filtration are washed with water and then with n-hexane. The crystals are dried under reduced pressure to obtain 1 g of the target complex (mp. 165-.). In tab. 1 and 2 show the compounds obtained and their physical constants. 1 a b l i d a 1.

Continued table. one

Continued table. one

b l and C a 2.

T a

Continued table. 2

Continuation of table 2 ..

Continued table. 2

Claims (1)

Claim A fungicidal composition containing an active principle based on imidazole derivatives and an additive selected from. groups carrier, diluent and excipient, which is due to the fact that ’, in order to enhance fungicidal activity, it is. contains as a derivative of imidazole a compound of the general formula: / = \ // ⁿ -Q- " ^z '\ _γ where X is the same or different substituent selected from the group consisting of chloro, fluoro, bromo, alkyl-C ^ -Cg, nitro or trifluoromethyl. η is 1 or 2, the Y-group of the formula R ^ -I-Rg where alkylene, R. alkyl C ₃ -C _{5 |} Cg, or Y is allyloxyethyl, 2-methyl-4-chlorophenoxymethyl, phenoxyethyl or benzyl, provided that X _p represents trifluoromethyl at position 2 and chlorine. At position 4, if Y is benzyl, Z is copper chloride, copper sulfate , zinc chloride, zinc acetate, ha is 0 or 1, in an amount O, 5-80 wt.%. Priority by feature. 03/31/77 at X-chlorine, fluorine, bromine, alkyl C <- Cg ·, nitro, trifluoromethyl; ^ n - numbers 1 or 2> V-benzyl. 07/27/77 at the Ύ-group '. R ^ —O — Rg, where Rf is alkylene C —C ₄ , R <, is alkyl C ( Cg, or 'V-allyloxyethyl ,, phenoxyethyl, 2-methyl-4-chlorophenoxymethyl.