DE3723230A1 - Novel triazole derivatives, their preparation and their use - Google Patents

Abstract

The novel compounds of the formula <IMAGE> (the substituents being defined in the description) can be obtained by customary processes and used for the control of phytopathogenic fungi.

Description

The invention relates to new triazole derivatives, their Manufacture by conventional methods and their use in the control of phytopathogenic fungi.

The new compounds have the formula

wherein

R for C₁-C₄ alkyl and X₁, X₂
X₃ and X₄ independently of one another for fluorine, chlorine, bromine, iodine or hydrogen,
X₁ also represents C₁-C₄-alkyl or C₁-C₆-alkoxy.

At least two of the radicals X₁ to X₄ are preferred Hydrogen, R n-propyl.

The production takes place according to processes known per se, by using a carbamic acid chloride of the formula

wherein

X₁ to X₄ and R have the above meaning,
reacted with triazole.

Triazole as such or in the form of its alkali salts, preferably the sodium salt with which Reacted carbamic acid chloride II,  preferably in an inert solvent, e.g. B. Dimethylformamide, at temperatures between room temperature and the boiling temperature of the reaction mixture.

The starting materials are made according to methods known per se manufactured, e.g. B. According to the reaction scheme:

Phenols of formula III, wherein X₁ to X₄ is hydrogen can mean from phenol by reaction with a Trifluoromethylsulfonyl halide or by reacting 4-hydroxythiophenol with trifluor (chlor / bromine / iodine) methane be preserved. The halogenation then leads to such  Phenols of the formula III in which at least one of the Radicals X₁ to X₄ is halogen.

The compounds of formula I are suitable for use in biocidal preparations. The effect should be emphasized against phytopathogenic fungi.

The treatment of plants can be protective or curative respectively. Can be fought z. B. powdery mildew like Erysiphe graminis on cereals (barley, wheat), Erysiphe cichoracearum on cucumber, Oidium sp. on begonias and other ornamental plants, piricularia on rice; Rust fungi (Puccinia) on cereals, rust (Puccinia, Phragmidium) on ornamental plants; Helminthosporium; Pellicularia.

For use in crop protection, the new Connect in the usual way with auxiliary and / or Carriers to common forms of Pesticides processed, e.g. B. too Solutions, solution or emulsion concentrates, Suspension powders, dusts, emulsions. The concentrates If necessary, wash with water before use diluted so that spray liquors with an active ingredient content between about 0.005 and 1 percent by weight. When using as a low-volume or Ultra-low-volume formulation can reduce the drug content also be significantly higher (up to 20 or 50 Percent by weight). The application can be by leaf or Soil treatment take place.

If desired, the compounds of the invention can be used as salts.  

Examples of formulations according to the invention:

1. Suspension powder

20 parts by weight of a compound of formula I.
20 parts by weight of kaolin
5 parts by weight of sodium sulfate
2 parts by weight of chalk
9 parts by weight of calcium lignin sulfonate (dispersant)
1 part by weight of diisobutylnaphthalene sodium sulfonate (wetting agent)
43 parts by weight of pebble

The ingredients are ground and the agent becomes suspended in so much water for use that the drug concentration is about 0.005 to 0.5 Weight percent.

2. Emulsion concentrate

15 parts by weight of a compound of formula I.
10 parts by weight of dodecylbenzenesulfonic acid triethylamine salt
75 parts by weight of dimethylformamide

The preparation of the compounds according to the invention is explained in more detail in the examples below:

example 1 1- {N- [2- (4-Trifluoromethylmercapto-phenoxy) ethyl] -N- (n-propyl) amidocarbonyl} -1,2,4-triazole a) Preparation of (4-trifluoromethylmercapto-phenyl) - (2-bromomethyl) ether

To the refluxing mixture of 19.4 g (100 mmol) 4-trifluoromethylmercapto-phenol), 60 ml Water, 30 ml of dioxane and 28.2 g (150 mmol) With good stirring, 1,2-dibromoethane becomes the solution of 4.4 g (110 mmol) sodium hydroxide in 25 ml water slowly added dropwise. Then the so obtained Mix for a further 4 hours while stirring at reflux cooked.

The reaction mixture is then extracted three times with 100 ml of methylene chloride. The combined methylene chloride phases are shaken twice with 100 ml of 0.5N sodium hydroxide solution and then three times with 100 ml of water. The organic phase is dried and concentrated to a residue.
Crude yield: 18.2 g (60% tq)
This crude product is purified by chromatography on a short silica gel column using methylene chloride as the mobile phase.
Pure yield: 17.5 g (58% of theory) of oily (4-trifluoromethylmercapto-phenyl) - (2-bromo-ethyl) ether.

b) Preparation of [2- (4-trifluoromethylmercaptophenoxy) - ethyl] - (n-propyl) amine

The mixture of 14.0 g (46.5 mmol) of product of step a), 100 ml of toluene and 10 g of n-propylamine is boiled under reflux for 20 hours. Then allowed to cool and shaken several times with 100 ml of water. The organic phase is then concentrated to a residue.
Crude yield: 13.0 g (100% tq).
This crude product is purified by chromatography on a silica gel column using ethyl acetate as the mobile phase. The pure product remains in the column and is isolated by elution with methanol.
Pure yield: 11.5 g (88% of theory) of oily [2- (4-trifluoromethylmercapto-phenoxy) ethyl] - (n-propyl) amine.

c) Preparation of the carbamic acid chloride

The solution of 11.5 g (41.2 mmol) in 50 ml of toluene is added dropwise to the solution of 15 g of phosgene in 200 ml of toluene, cooled to 3-5 ° C., with thorough stirring. A white precipitate is formed. After one hour, the mixture is warmed to room temperature, after another to 70 ° C. At this temperature, stirring is continued for 3 hours; a clear solution emerges during this time. This is concentrated to residue in vacuo.
Yield: 14.0 g (99% of theory) of an oily product.

d) Preparation of the title compound

3.2 g of 60% sodium hydride (66.7 mmol) are added to the solution of 4.65 g (67.3 mmol) of 1,2,4-triazole in 100 ml of absolute dimethylformamide. The mixture thus obtained is stirred at 30 ° C. until no more hydrogen is released. Then the solution of 23.0 g (67.2 mmol) of N- [2- (4-trifluoromethylmercapto-phenoxy) ethyl] -N- (n-propyl) carbamic acid chloride in 50 ml of absolute dimethylformamide is added. The mixture thus obtained is stirred at 130 ° C. for 4 hours. The solid portion of the reaction mixture is then suctioned off and the filtrate is concentrated to residue in vacuo. The crude product (23.5 g) thus obtained is purified by chromatography on a silica gel column using ethyl acetate as the mobile phase. The initially oily residue slowly becomes crystalline.
Pure yield: 20 g (53.4 mmol); 79% of theory Th., Mp 59-62 ° C
Elemental analysis corresponds to the theoretical values.

According to the invention can also be manufactured will:

(Compounds of Formula I)

Claims (5)

1. Compounds of the formula whereinR for C₁-C₄ alkyl and X₁, X₂,
X₃ and X₄ independently of one another for fluorine, chlorine, bromine, iodine or hydrogen,
X₁ also represents C₁-C₄-alkyl or C₁-C₆-alkoxy. 2. 1- {N- [2- (4-trifluoromethylmercaptophenoxy) ethyl] -N- (n-propyl) amidocarbonyl) -1,2,4-triazole. 3. Fungicidal agent, characterized by a content of a compound according to claim 1 or 2, in addition usual auxiliaries and / or carriers. 4. Use of compounds according to claim 1 or 2 in the control of phytopathogenic fungi. 5. Process for the preparation of compounds of the formula whereinR for C₁-C₄ alkyl and X₁, X₂,
X₃ and X₄ independently of one another for fluorine, chlorine, bromine, iodine or hydrogen,
X₁ also represents C₁-C₄-alkyl or C₁-C₆-alkoxy, characterized in that a caraminic acid chloride of the formula whereinX₁ to X₄ and R have the above meaning,
with triazole or with an alkali salt of triazole.