DD146292A5 - FUNGICIDAL AGENTS - 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

Berlin, January 30, 1980

5 ^ ο j AP C 07 D / 215 826 _ & Λ.% 9 _{56 116 1 ±}

Fungicidal agent

Field of application of the invention

The present invention relates to fungicidal compositions containing novel 1-azolyl-1-fluoro-phenoxy-butane derivatives, a process for their preparation and their use as fungicides.

Characteristic of the known technical solutions

It has already become known that 1-azolyl-l-chlorophenoxy-butane derivatives, such as. As 4-chloro-l- (4-chlorophenoxy) -3,3-dimethyl-l- (l, 2,4-triazol-1-yl) - or - (imidazoll-yl) -butan-2 -on and 4-3rom-l- (4-chlorophenoxy) -3,3-dimethyl-1- (imidazol-1-yl) -butan-2-ol have good fungicidal properties, (see DE-OS 2,632,602) and DE-03 2 632 603). Their good effect, however, is not always quite satisfactory, especially at low application rates and concentrations.

Object of the invention

The aim of the invention is the provision of new agents with improved fungicidal activity, a broad spectrum of activity and good plant tolerance.

Explanation of the essence of the invention

The invention is based on the object, new 1-azolyl-l ·

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Fluorphenoxy-butane derivatives find that have an improved fungicidal activity and are suitable as active ingredients in crop protection agents.

There were new halogenated l ~ Azolyl ~ l-fluorophenoxy-butane derivatives of the general formula

-O - CH - A - C - CH "Y, _. ι <- K ¹ -)>

CH B ^ό

(Γ

NJ

in which

A. Stands for a keto group or a CH (OH) group,

B is a nitrogen atom or a GH group, and

Y is halogen,

and their physiologically acceptable salts found. They have strong fungicidal properties.

Those compounds of formula (I) in which A is the CH (OH) group have two asymmetric carbon atoms; They can therefore be present in the two geometric isomers (erythro and threo form), which can be obtained in different proportions. In both cases they are present as optical isomers. All isomers are claimed according to the invention.

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The halogenated 1-azolyl-l-fluorophenoxybutane derivatives of the formula (I) are obtained by reacting bromo ether ketones of the formula

CH,

O - CH - CO - C - CH_Y (II).

I i

br

in which .

Y has the meaning given above, with azoles of the formula

H - N L (III),

in which

B has the meaning given above,

in the presence of an acid binder and in the presence of a diluent, and optionally the resulting ketone derivatives in a conventional manner with complex borohydrides, optionally in the presence of a diluent, reduced.

Furthermore, the halogenated 1-azolyl-l-fluorophenoxy-butane derivatives obtainable according to the invention can be converted into the salts by reaction with acids.

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Surprisingly, the active compounds according to the invention show a considerably higher fungicidal activity, in particular against mildews, than the 1-azolyl-1-chlorophenoxybutane derivatives known from the prior art, such as 4-chloro-1- (4-chlorophenoxy) -3 , 3-dimethyl-1- (l, 2,4-triazol-1-yl) - or - (imidazol-1-yl) -butan-2-one and 4-bromo-1- (4-chlorophenoxy) - 3,3 <limethyl-1- (imidazol-1-yl) -butan-2-ol, which are the most obvious chemically and operatively. The erfindungsgernäßen agents thus represent an enrichment of the art.

Of the compounds of the formula (I) according to the invention, preference is given to those in which Y.sup.1 is chlorine or bromine and A and B. are as defined in the definition of the invention.

If 1-bromo-4-chloro-3,3-dimethyl-1- (4-fluorophenoxy) -butan-2-one and 1,2 ₍ 4-triazole as starting materials are used, the course of the reaction can be represented by the following formula scheme :

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CH.

-O-CH-CO-C-CH ₂ Cl

CH.

br

base

- HBr

CH.

-O-CH-CO-C-CH ₀ Cl

I ²

CH.

Using 4-chloro-3,3-dimethyl-l ~ (4-fluorophenoxy) -1- (1,2,4-triazol-1-yl) -butan-2-one and sodium borohydride as starting materials, the reaction sequence represented by the following formula scheme:

CH.

-CH-CO-C-CH ₀ Cl

II ²

CH "

OH CH.

-CH-CH-C

CH

CH ₂ Cl

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The bromo ether ketones to be used as starting materials are generally defined by the formula (II). In this formula, Y_ is preferably chlorine and bromine.

The Brometherketone of formula (II) are not yet known, but can be obtained by known methods by z. For example, fluorophenol with a bromoketone of the formula

Cl-L

Br - CH _p - CO - C - CHYY (IV),

CH ₃

in which

Y has the meaning given above,

implements. The remaining active hydrogen atom is then exchanged in the usual way for bromine (see also the l-lerstellungsbeispiele).

As examples of the starting materials of the formula (II) may be mentioned:

1 _A Bromo-4-chloro- (4-fluorophenoxy) -3,3-dimethyl-butan-2-one 1,4-Dibromo (4-fluorophenoxy) -3,3-dimethyl-butan-2-one

Suitable salts for the compounds of the formula (I) are salts with physiologically tolerated acids.

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115

These include preferably the hydrohalic acids, such as. As hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, phosphoric acid, nitric acid, mono- and bifunctional carboxylic acid and hydroxycarboxylic acids, such as. Acetic acid, citric acid, sorbic acid, lactic acid, 1,5-naphthalene disulfonic acid.

Suitable inert diluents for the reaction according to the invention are inert organic solvents. These include preferably ketones, such as diethyl ketone, in particular acetone and methyl ethyl ketone; Nitriles, such as propionitrile, in particular acetonitrile; Alcohols, such as ethanol or isopropanol; Ethers, such as tetrahydrofuran or dioxane; aromatic hydrocarbons, such as toluene and 1,3-dichlorobenzene, benzene; Formamides, in particular dimethylformamide; and halogenated hydrocarbons, such as methylene chloride, carbon tetrachloride or chloroform.

The reaction is carried out in the presence of an acid binder. It is possible to add all customary inorganic or organic acid binders, such as alkali metal carbonates, for example sodium carbonate, potassium carbonate and sodium bicarbonate, or lower tertiary alkylamines, cycloalkylamines or aralkylamines, for example triethylamine, Ν, Ν-dimethylcyclohexylamine, dicyclohexylmethylamine, Ν, Ν-dimethylbenzylamine,

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pyridine and diazabicyclooctane. Preferably, a corresponding excess of the azole of formula (III) is used. -

The reaction temperatures can be varied within a substantial range. In general, from about O to about 150 C, preferably at 60 to 120 ⁰ C.

When carrying out the process according to the invention, preference is given to 1 mol of the compounds of the formula (II) for 1 to 2 mol of azole and 1 to 2 mol of acid binder. To isolate the compounds of formula (I), the solvent is distilled off, the residue taken up with an organic solvent and washed with water. The organic phase is dried over sodium sulfate and freed from the solvent in vacuo. The residue is purified by distillation or recrystallization

 *

For the reduction according to the invention, suitable diluents for the reaction according to the invention are polar organic solvents. These include, preferably, alcohols, such as methanol, ethanol, butanol, isopropanol and ethers, such as diethyl ether or tetrahydrofuran. The reaction is generally carried out at 0 to 30 C, preferably at 0 to 20 C. For this purpose, about 1 mol of a borohydride, such as sodium borohydride or lithium borohydride, is employed per mole of the corresponding keto compound. To isolate the compounds of formula (I), the residue is z. B. in dilute

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215 826

Hydrochloric acid was added, then made alkaline and extracted with an organic solvent, or mixed with water and shaken out with an organic solvent »Further workup is carried out in the usual manner.

The active compounds according to the invention have a strong microbicidal action and can be used practically for controlling unwanted microorganisms. The active ingredients are to be used for pesticide use.

Crop protection fungicides are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

The good plant tolerance of the active ingredients in the necessary concentrations for controlling plant diseases allows treatment of above-ground parts of plants, planting and seed and the soil.

As plant protection agents, the active compounds according to the invention can be used with particularly good success for controlling Erysiphe species. It should be emphasized that the active compounds of the invention not only have a protective effect, but are also systemically effective. So it is possible to protect plants against fungal attack, if the active ingredient on the soil and the root or on the seed the upper

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earthly parts of the plant feeds.

The active compounds can be converted into the usual formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active ingredient-impregnated natural and synthetic substances, microencapsulations in polymeric substances and in seed coating compositions, furthermore in formulations with fuel assemblies, such as smoking cartridges, cans, spirals and others, as well as ULV-KaIt and warm mist formulations.

These formulations are prepared in a known manner, for. Example, by mixing the V / irkstoffe with extenders, that is liquid solvents, liquefied gases under pressure and / or solid carriers, gegebebenfalls using surface-active agents, emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender z. B. organiacha solvents can be used as auxiliary solvent. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, Clioräthylene or methylene chloride, aliphatic © hydrocarbons, such as cyclohexane or paraffins, for. As 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 dimethyl sulfoxide, and

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Water; with liquefied gaseous extenders or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, eg. B. aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers are: z. Natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as fumed silica, alumina and silicates; As solid carriers for granules are: z. B. crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours, and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-producing agents are in question: z. Nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylarylpolyglykol ether, alkyl sulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; as dispersants in question: z. As lignin-sulphite liquors and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-type polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate may be used in the formulations.

It can dyes such as inorganic pigments, eg. For example, iron oxide, titanium oxide, ferrocyan blue and organiabe Dye

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such as alizarin, azole metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90 %. '

The active compounds of the invention may be present in the formulations or in the various forms of application in admixture with other known active compounds, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellents, growth factors, plant nutrients, and soil conditioners.

The active compounds can be used as such, in the form of their preparations or the use forms prepared therefrom by wet dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. The application is done in the usual way, for. By pouring, dipping, spraying, spraying, misting, vaporizing, injecting, silting, spreading, dusting, spreading, dry pickling, wet pickling, wet pickling, slurry pickling or encrusting.

In the treatment of parts of plants, the drug concentrations can be varied in the use forms in a wider range. They are generally between 1 and 0.0001 wt .-%, preferably between 0.5 and 0.001 %.

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In the seed treatment, in general, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are required.

For the treatment of soil, active compound concentrations of 0.00001 to 0.1 by weight are -.%, Preferably from ₁ O oool to 0.02%, on-site VVirkungsr required.

Executed by η cj sbeis pi el

The invention will be explained in more detail below with reference to some embodiments:

Example A "

Sprout Treatment Test / Mildew / Protective (Leaf-destroying Mycosis)

To prepare a suitable preparation of active compound, 0.25 part by weight of active compound in 25 parts by weight of dimethylformamide and 0.06 part by weight of emulsifier (alkylaryl polyglycol ether) are added and 975 parts by weight of water are added. The concentrate is diluted with water to the desired. Final concentration of the spray mixture.

To test for protective activity, the monocled barley seedlings of the variety Amsel are sprayed with the preparation of active compound dewatered. After drying, the barley plants are dusted with spores of Erysiphe graminis var.hordei.

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After 6 days Vervveilzeit of the plants at a temperature of 21 to 22 ⁰ C and a humidity of 80 to 90 % is evaluated, the stocking of plants with mildew pustules. The level of infestation is expressed as a percentage of the infestation of the untreated control plants. O % means no infestation and 100 % the same degree of infestation as in the untreated control. The lower the powdery mildew case, the more effective the active substance is.

Active ingredients, active ingredient concentrations in the spray mixture and infestation levels are shown in the following table:

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215 §26

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Table A

Sprout Treatment Test / Cereal Mite / Protective

drugs

Active substance concentration in the spray mixture in infestation in % of

untreated control

CH.

Cl- / OV ° -CH-C0-C-CH _o Cl

χ / 2

(known)

SO ₃ H

0-CH-CO-C-CH ₀ Cl

• I * I ²

N ^ ₁₁ CH.

χ / 2

SO ₃ H

SO ₃ H

0.00025

0,00025 100

37.5

CH

^C1 - \ O) -0-CH-CO-C-CH ₂ Cl 0.00025

CH

SO ₃ H

(known) χ / 2 [O

50.0

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Continuation Table A

Ci-length

! ³

0-CH-CO-CCH ₀ Cl N '

(6)

"0.00025

XJ ^CH 3

x 1/2

SO ₃ H

SO ₃ H 10,0 -17-

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Example B

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

(fungal cereal disease)

The application of the active ingredients is carried out as a powdered seed treatment agent. They are prepared by stripping the respective active ingredient with a mixture of equal parts by weight of talc and diatomaceous earth to a finely powdered mixture with the desired active ingredient concentration.

For seed treatment, barley seed is shaken with the stretched-out active ingredient in a sealed glass bottle. The seed is sown with 3 x 12 seeds in flower pots 2 cm deep in a mixture of one part by volume of Fruhstorfer unit earth and one part by volume of quartz sand. The germination and the casserole are done under favorable conditions in the greenhouse. 7 days after sowing, when the barley plants have unfolded their first leaf, they are dusted with fresh spores of Erysiphe graminis var. Hordei and at 21 to 22 ⁰ C and 80 to 90 % rel. Humidity and 16-hour exposure further cultivated. Within 6 days the typical mildew pustules develop on the leaves.

The degree of infestation is expressed as a percentage of the infestation of the untreated control plants. Thus, 0 % means no infestation and 100 % the same degree of infestation as in the untreated control. The active ingredient is so

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the more effective the lower the mildew is.

Active ingredients, active substance concentrations in the seed treatment agent, as well as the application rate and the percentage of powdery mildew are shown in the following table:

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ί 5 C26

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Table B

Barley mildew (Erysiphe graminis var.hordei) / systemic test

drugs

Wirkstoffkonzen- Beizmitteltration in pickling expenses amount medium in weight -.% In g / kg

seeds

Infestation in % of

acted in control

OH CH,

i

-O-CH-CH-C-CH ₂ Br

(known)

25

50.0

OH CH.

-O-CH-CH-C

CH ₂ Br

CH.

25

10

12.5

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Her division sbeis pi ele:

example 1

F -

0 - CH ~ CO I

• - u '

IJ

Cl!

C - CH ₂ Cl CH.

x 1/2

57 g (0.177 mol) of 1-bromo-4-chloro-3,3-dimethyl-1- (4-fluorophenoxy) -butan-2-one are dissolved in 600 ml of absolute acetonitrile, 24.2 g (0.35 mol) The solvent is distilled off in a water-jet vacuum, the residue is taken up in 700 ml of methylon chloride, the organic phase is extracted twice with 1.5 l of water and dried over sodium sulfate distilled off and the residual oil is taken up in 200 ml of acetone, 18 g (0.1 mol) of 1,5-naphthalenedisulfonic acid dissolved in 100 ml of acetone are added, and the resulting precipitate is filtered off with suction to give 47 g (55.7 %). dor theory) 4-0ίι1θΓτ3,3-dimethyll- (4-fluorophenoxy) -1- (2,3,4-triazol-1-yl) -butan-2-one-naphthalenedisulfonat- (l, 5) of melting point 200 C ,

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^ am - 2i -

Production of the Ausqanqsproduktes

- 0 - CH-CO - C- CFUCl

br

100.2 g (0.617 mol) of 1,4-dichloro-3,3-dimethyl-butan-2-one are heated at the boiling point to a solution of .56 g (0.5 mol) of p-fluorophenol and 85 g of potassium carbonate in 700 ml acetone dripped. "It is stirred for 6 hours under reflux, filtered off with suction and distilled off the solvent to give 101.5 g (83 % of theory) of 4-chloro-3,3-dimethyl-1- (4-fluorophenoxy) -butan-2 663 g (0.415 mol) of bromine are then added dropwise at room temperature in such a way that discoloration occurs, stirring is continued for 30 minutes, the solvent is distilled off in a water-jet vacuum and 100 ml of pentane are added , the residue crystallized. This gives 114 g (85% of theory) of l-8rom-4-chloro-3,3-dimethyl-l- (4-fluorophenoxy) -butan-2-one of melting point 74- ⁰ C.

ClCH ₂ - CO-C -

^CH 3

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1050 g (7.8 mol) of 78 ^ 4-chloro-3,3-dimethyl-butane ~ 2-0n are dissolved in 6 1 of methylene chloride and at 10 to 11 ⁰ C for 6 hours 450 g of chlorine introduced. The mixture is then stirred for 30 minutes, expelled with nitrogen, the excess hydrogen chloride and distilled da3 reaction mixture above a 60 cm packed column. This gives 832 g (63 % of theory) of 1, 4-dichloro-3,3-dimethyl-butan-2-one of 3i <75% purity.

Example 2

OH

- 0 - CH - CH - C - Cl - UCl

¹ I

Butan-2-one of boiling point 50 to 54 C / o, l Torr with a

To 25 g (0.053 mol) of 4-chloro-3,3-dimethyl-1- (4-fluorophenoxy) -1- (1,2,4-triazol-1-yl) -butan-2-one-naphthalenedisulfonate (Example 1), dissolved in 400 ml of methanol, are added in portions 4.75 g (0.12 mol) of sodium borohydride and stirred for 15 hours at room temperature. Under cooling, 15 ml of concentrated hydrochloric acid are carefully added dropwise, stirred for 2 hours at room temperature and the solvent is distilled off in half under water pump vacuum. The reaction mixture is added to 400 ml of saturated sodium bicarbonate solution, extracted with 300 ml of methylene chloride, the organic phase separated, washed twice with 100 ml of water, over

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21si82i

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Dried sodium sulfate and concentrated by distilling off the solvent. The residue crystallizes after addition of 100 ml of diisopropyl ether. This gives 9.1 g (36.4 % of theory) of 4-chloro-3,3-dimethyl-1- (4-fluorophenoxy) -1- (1,2,4-triazol-1-yl) butane 2-ol of melting point 87 to 90 ^° C. "

Analogously, the following compounds of the formula

CH,

I ³

F - / Γη - O - CH - AC - CH ₀ Y

·. ι

_u B CH.

vj

receive: A B Y melting point ( ⁰ C) Example no. CO N ' br 180 (χ - NDS) 3 CHOH N br 100 4 CO CH br 241 (χ - NDS) 5 CO CH Cl 254 (χ - NDS) 6 CHOH CH br 116 7 CHOH CH Cl 115 8th

NDS = 1,5-naphthalenedisulfonic acid

- 24 -

Claims (4)

30. 1. 1980 AP C 07 D / 215 - 24 - 'Invention claim 1. Fungicidal agent, characterized by a content of 1-azolyl-l-fluorophenoxy-butane derivative of the general formula ^CH 3 - O - CH - A - C - CrUY (I), CH. _JJ in which A is a keto group or a CH (OH) group, B is a nitrogen atom or a CH group, and
Y is halogen, and their physiologically acceptable salts in addition to extenders and / or surface-active agents. 2. A method for combating Pilzan, characterized in that 1-azolyl-l-fluorophenoxy-butane derivative according to point 1 is allowed to act on fungi or their habitat. - 25 - 30. 1. 1980 AP C 07 D / 215 826 - 25 - 3. Use of 1-azolyl-l-fluorophenoxy-butane derivatives according to item 1, characterized in that they are used for controlling fungi. 4. A process for the preparation of fungicidal agents, characterized by mixing 1-azolyl-l-fluorophenoxy-butane derivatives according to item 1 with extenders and / or surface-active agents.