NO792970L - HALOGENATED 1-AZOLYL-1-FLUORPHENOXY-BUTANE DERIVATIVES, AND THEIR USE AS FUNGIZIDES - Google Patents

Abstract

1. A-zolyl-1-fluorophenoxy-butane derivatives of the general formula see diagramm : EP0009707,P10,F1 in which A represents a keto group or a CH(OH) group, B represents a nitrogen atom or a CH group and Y represents chlorine or bromine, and their physiologically acceptable salts.

Description

The invention relates to new 1-azolyl-1-chlorophenoxy-butane derivatives and their use as fungicides.

It is already known that 1-azolyl-1-chlorophenoxy-butane derivatives, such as e.g. 4-chloro-1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)- or -(imidazol-1-yl)-butan-2-one and 4-trirom-1-(4-chlorophenoxy)-3,3-dimethyl-1-(imidazol-1-yl)-butan-2-ol has good fungicidal properties (compare DOS

26 32 602 and 26 32 603. However, their good effect, especially at low amounts and concentrations used, is not always completely satisfactory. New halogenated 1-azolyl-1-fluorines have been found phenoxy-butane derivatives of the general formula

in which

A means a keto group or a CH(OH) group,

B means a nitrogen atom or a CH group, and

Y means halogen,

and their physiologically tolerable salts. They have strong fungicidal properties.

The compounds of formula (I) in which A means the CH(OH) group have two asymmetric carbon atoms; they can therefore exist in the two geometric isomers (erythro- and threo-form) which appeared in different amounts. In both cases, they exist as optical isomers. All isomers are covered by the invention.

The halogenated 1-azolyl-1-fluorophenoxy-butane derivatives of formula (i) are obtained, whereas bromether ketones of formula

in which

Y has the above meaning,

in the presence of an acid-binding agent and in the presence of a diluent react with azoles of formula

in which

B has the above meaning,

and optionally the ketone derivatives thus formed are reduced in a manner known per se with complex boron hydrides, optionally in the presence of a diluent.

Furthermore, the obtained halogenated 1-azolyl-1-fluoro-enoxy-butane derivatives can be converted into the salts by reaction with acids.

Surprisingly, the active substances according to the invention show a considerably higher fungicidal effect, especially against powdery mildew types, than the 1-azolyl-1-chlorophenoxy-butane derivatives known from the state of the art, such as 4-chloro-1-(4-chlorophenoxy)-3, 3-dimethyl-1-(1,2,4-triazol-1-yl)-resp. -(imidazol-1-yl)-butan-2-one and 4-bromo-1-(4-chlorophenoxy)-3,3-dimethyl-1-(imidazol-1-yl)-butan-2-ol, which are chemically and functionally the closest compounds. The active substances according to the invention thus entail a

enrichment of the technique.

Of the compounds according to the invention with formula (i), those are preferred in which Y means chlorine or bromine and A and B have the meaning indicated above.

If one uses 1-bromo-4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-butan-2-one and 1,2,4-triazole as starting material, the course of the reaction can be reproduced by the following formula core:

If 4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-1-(1,2,4-triazol-1-yl)-butan-2-one and sodium borohydride are used as starting materials, the course of the reaction can be reproduced by the following formula core:

The bromether ketones that can be used as starting materials are generally defined by formula (II). In this formula, Y preferably means chlorine and bromine.

The brometherketone with formula (II) is not yet known, but can be obtained according to known procedures by e.g. reacts fluorophenol with a bromoketone of formula

in which

Y has the above meaning,

The still remaining active hydrogen atom is then exchanged in the usual way for bromine. (Also compare the manufacturing examples.)

As examples for the starting material with formula (II), the following should be mentioned: 1-bromo-4-chloro-(4-fluorophenoxy)-3,3-dimethyl-butan-2-one 1,4-dibromo-w|4 -fluorophenoxy)-3,3-dimethyl-butan-2-one.

Salts for the compounds of formula (i) include salts with physiologically tolerable acids. This preferably includes the halogen hydrogen acids, which e.g. the hydrochloric acids and hydrobromic acids, especially hydrochloric acid, phosphoric acid, nitric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such as e.g. acetic acid, citric acid, sorbic acid, lactic acid, 1,5-naphthalene disulfonic acid.

For the turnover, preferably inert organic solvents are used as diluents. These preferably include ketones, such as diethyl ketone, especially acetone and methyl ethyl ketone; nitriles such as propionitrile, especially acetonitrile; alcohols such as ethanol or isopropanol; ethers, such as tetrahydrofuran or dioxane; aromatic hydrocarbons, such as toluene and 1,3-dichlorobenzene, benzene; formamides, such as especially dimethylformamide; and halogenated hydrocarbons such as methylene chloride,. carbon tetrachloride or chloroform.

The turnover is carried out in the presence of an acid binder. You can add all commonly used inorganic or organic acids, such as alkali carbonates, for example sodium carbonate, potassium carbonate and sodium bicarbonate, or as lower tertiary alkylamines, cycloalkylamines or aralkylamines, for example triethylamine, N,N-dimethylcyclohexylamine, dicyclohexylmethylamine, N,N-dimethylbenzyl-

amine, further pyridine and diazabicyclooctane. Preferably, a corresponding excess of azole with formula is used

(III).

The reaction temperatures can be varied within a large range. Usually you work between approx. 0 to approx. 150°C, preferably at 60 to 120°C.

When carrying out the method according to the invention, preferably 1 to 2 mol of azole and 1 to 2 mol of acid binder are used for 1 mol of the compound of formula (II). To isolate the compound of formula (i), the solvent is distilled off, the residue is taken up with an organic solvent and washed with water. The organic phase is dried over sodium sulfate and freed of solvent in vacuum. The residue is purified by distillation or recrystallization.

For the reduction, polar organic solvents are used as diluents for the turnover. These preferably include alcohols, such as methanol, ethanol, butanol, isopropanol and ethers, such as diethyl ether or tetrahydrofuran. The reaction is usually carried out at 0 to 30°C, preferably at 0 to 20°C. For this purpose, on 1 mol of the corresponding keto compound approx. 1 mole of a borohydride, such as sodium borohydride or lithium borohydride.

For isolation of the compound of formula (i), the residue is taken up e.g. in dilute hydrochloric acid, then made alkaline and extracted with an organic solvent, or simply mixed with water and shaken out with an organic solvent. Further processing takes place in the usual way.

The active substances according to the invention have a strong microbicidal effect and can be used in practice to combat unwanted microorganisms. The active substances are suitable for use as plant protection agents.

Fungicides in plant protection are used to combat plasmodioforomycetes, Oomycetes, chytridiomycetes, zygomycetes, ascomycetes, basidiomycetes, deuteromycetes.

Good plant compatibility of the active substances

in the concentrations necessary to combat plant diseases, enables the treatment of plant parts above ground,

of plants and fruit and the soil.

As a plant protection agent, the active substances according to the invention can be used with particularly good results.

taken to combat the Erysiphe types. It should be emphasized that the active substances according to the compound not only exert a protective effect, but are also effective systemically.

Thus, it succeeds in protecting plants against fungal attacks when the active substance is applied over the soil and the rats, or over the seed to the parts of the plant above the soil.

The active substances can be transferred in the

equal formulations such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active-substance-impregnated natural and synthetic substances, finely encapsulated in polymeric substances and in sleeve compounds for fruit and vegetables, further in formulations with burning rates such as rok cartridges, boxes,

spirals and the like, as well as ULV cold and warm mist formulations. These formulations are prepared in a known manner, e.g. by mixing the active substances with wetting agents, i.e. liquid solvents, pressurized liquefied gases and/or solid carriers, possibly using surface-active agents, i.e. emulsifiers and/or dispersants and/or foam-producing agents. In the case of using water as a sedative, it can e.g. organic solvents are also used as auxiliary solvents. Liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylene or methylene chloride, aliphatic hydrocarbons,

such as cyclohexane or paraffins, e.g.•petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsulfoxide, as well as water. By liquid gaseous sedatives or carriers, such are meant

liquids that are gaseous at normal temperature and at normal pressure, e.g. aerosol propellants such as halogenated hydrocarbons such as butane, propane, nitrogen and carbon dioxide; as solid carriers it comes into question: e.g. natural rock flour, such as kaolins, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flour such as highly dispersed silicic acid, alumina and silicates; as solid carriers for granules it comes into question: e.g.

broken and fractionated natural stones such as calcite, marble, pitnpesten, sepiolite, dolomite as synthetic granules of inorganic and organic flour as well as granules of organic material such as sawdust, coconut shells, and corn cobs and tobacco stalks; as an emulsifying and/or foam-producing agent it comes into question: e.g. nonionic and anionic emulsifiers,

such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkyl aryl polyglycol ether, alkyl sulphonates, alkyl sulphates, aryl sulphonates and egg white hydrolysates; as dispersants it comes into question: e.g. lignin sulphite liquor and methyl cellulose.

Adhesives can be used in the formulations

such as carboxymethyl cellulose, natural and synthetic powdered granular or latex polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments can be used, e.g. iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azole metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations usually contain between

0.1 and 95% by weight of active substance, preferably between 0.5 and $0$.

The active substances according to the invention can be present in the formulations or in the various forms of application in a mixture with other known active substances such as fungicides, bactericides, insecticides, acaricides,

nematicides, herbicides, protectants against birds

infestation, growth substances, plant nutrients and soil structure-k improvers.

The active substances can be used as such

in the form of their formulations or thereof by further

dilution prepared application forms, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. The application takes place in the usual way, e.g.

by pouring, dipping, spraying, showering, misting, pre-evaporation, injecting, slurrying, ironing, sputtering, stroking, dry pickling, wet pickling, wet pickling, mud pickling or incrustation.

When processing the plant parts, the active substance concentrations in the application forms can be varied over a large area. They are usually between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

When treating fruit, effective amounts of substances from 0.001 to 50 g per kg of fruit, preferably 0.01 to 10 g.

When treating the soil, it is necessary to have active substance concentrations of from 0.00001 to 0.1% by weight, preferably from 0.001 to 0.02% of the active substance type.

Example A

Slat treatment sample / corn meal dew / protective

(leaf-destroying mycosis)

For the production of an appropriate

active substance preparation, you take 0.25 parts by weight of active substance in 25 parts by weight of dimethylformamide and 0.06 parts by weight of emulsifier (alkyl-aryl-polyglycol ether) and add 975 parts by weight of water. The concentrate is diluted with water to the desired final concentration and spray liquid.

For research on protective effect

the single-leaved young barley plants of the thrush type are sprayed with the effective substance preparation, moist with dew. After drying, the barley plant is pollinated with spores of Erysiphe graminis var.hordei.

After 6 days residence time of the plants at

a temperature of 21 - 22°C and a humidity of 80 - 90% is considered the attack of plants with powdery mildew pustules. After the degree of attack, the attack of untreated control plants is expressed in %. Thereby, 0% means no attack and 100% the same degree of attack as in untreated controls. The active substance is all the more effective the less the mildew attack is.

Active substances, active substance concentrations in the spray liquid and degrees of attack are shown in the following table.

Example B

Barley powdery mildew sample (Erysiphe graminis var.hordei) / systemic

(fungal corn sprout disease)

The use of the active substances takes place as a powdered fruit treatment agent. They are produced by grinding the active ingredient with a mixture of equal parts by weight of talc and diatomaceous earth into a finely powdered mixture with the desired active ingredient concentration.

For seed treatment, barley seed is shaken with the diluted active substance in a closed glass bottle. Fro-goods is sown with 3 x 12 grains in flowerpots 8 cm deep in a mixture of 1 part by volume fruhstorfer unit soil and 1 part by volume quartz sand. Germination and germination take place under favorable conditions in greenhouses. 7 days after sowing, when the barley plants have unfolded their first leaves, they are fertilized with fresh spores of Erysiphe graminis var.hordei and further cultivated at 21-22°C and 80-90% rel. humidity, and 16 hours of lighting. In the course of 6 days, the typical powdery mildew pustules form on the leaves.

The degree of attack is expressed as a percentage of the attack of untreated control plants. Thus, 0% means no attack and 100% the same degree of attack as in untreated controls. The active substance is all the more effective the less the mildew attack.

Active substances, active substance concentrations in the crop treatment agent as well as its amount used and percentage of powdery mildew attack are shown in the following table.

First Uling's examples Example 1

In J

F-(C^j)-O-CH-CO-C-CH2Cl

Br CH3

100.2 g (0.617 mol) 1,4-dichloro-3,3-dimethyl-butan-2-one is added dropwise at boiling temperature to a solution of 56 g (0.5 mol) p-fluorophenol and 85 g potassium carbonate in 700 ml of acetone. It is allowed to stir for 6 hours under reflux, the solution is sucked off and distilled. 101.5 g (83% of the theoretical) of 4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-butan-2-one is obtained, which is dissolved crudely in 600 ml of methylene chloride. Then, at room temperature, 66.3 g (0.415 mol) of bromine are added dropwise so that decolorization occurs. After stirring for 30 minutes, the solvent is distilled off in a water jet vacuum and 100 ml of pentane is added,

as the residue crystallizes. 114 g (485% of the theoretical) 1-bromo-4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-butan-2-one of melting point 74°c• are obtained

1050 g (7.8 mol) of 78% 4-chloro-3,3-dimethyl-butan-2-one are dissolved in 6 l of methylene chloride and at 10 to 11°C, 450 g of chlorine are introduced over the course of 6 hours. It is then stirred for 30 minutes, excess hydrogen chloride is expelled with nitrogen and the reaction mixture is distilled over a 60 cm packed column. 832 g (63% of the theoretical) of 1,4-dichloro-3,3-dimethyl-butan-2-one with a boiling point of 50-54°C/0.l dry with a purity of 75% are obtained.

Example 2

To 25 g (0.053 mol) of 4-chloro-3,3-dimethyl-1-(4-fluoro-enoxy)-1-.'(.1,2,4-triazol-1-yl)-butan-2- on-naphthalene disulfonate (Example 1), dissolved in 400 ml of methanol, add 4.75 g (0.12 mol) of sodium borohydride in portions and then stir for 15 hours at room temperature. While cooling, 15 ml of concentrated hydrochloric acid are carefully dropped in, stirred for 2 hours at room temperature and the solvent is distilled off to 1/2 in a water jet vacuum. The reaction mixture is added to 400 ml of saturated sodium bicarbonate solution, extracted with 300 ml of methylene chloride, the organic phase is separated, washed twice with 100 ml of water each time, dried over sodium sulphate and evaporated by distilling off the solvent. The residue crystallizes after the addition of 100 ml of diisopropyl ether. 3.1 g (36.4% of the theoretical) of 4-chloro-3,3-dimethyl-1-(4-fluorophenoxy)-1-(1,2<J4-triazol-1-yl)- butan-29ol of melting point 87-90°C.

Analogously, the following compounds with formula are obtained

Claims (3)

1. 1-azolyl-1-fluorophenoxy-butane derivatives with fungicidal properties, and with the general formula in which A means a keto group or a CH(OH) group, B means a nitrogen atom or a CH group, and Y means halogen, and their physiologically tolerable salts. 2. Fungicidal agent, characterized by a content of at least one 1-azolyl-1-fluorophenoxy-butane derivative according to claim 1. 3. Use of 1-azolyl-1-fluorophenoxy-butane derivatives according to claim 1 for combating fungi.