FI62295C - SAOSOM FUNGICIDER ANVAENDBARA HALOGENERADE 1-AZOLYL-1-FLUORPHENOXY-BUTANDERIVAT - 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

ΓβΙ m ^ ANNOUNCEMENT 0 0 0 r JjJjgfgJ (11) UTLÄGGNINGSSKRIFT 62 2 95 (45) Patent Eocidelat ^ v ^ (51) Kv.lk?/lntCI.3 C 07 D 249/08 FINLAND — FINLAND (21) iw «ihtk «Mu.-p« t * «t *» etaint 792996 * '(22) Hakamlspllvf - Anaefcnlnpdtg 26.09 * 79 (23) Overture — Glklghaudaf 26.09-79 (41) Tullut jutkliclul - fcltvlt offwtllf 29 · 03 · 8θ

Mntti.ja registry board NihtMWp · *. moonL | -,. nfl n0

Patent and ocean registration AniAktn utltfd and utl.tkrlfun public er * 4 31. UO. od (32) (33) (31) Pyr «» «ty« uolkeu * - B «« lr4 prlorltut 28.09 · 78

Federal Republic of Germany-Förbundsrepubliken Tyskland (DE) P 28U2137.6 (71) Bayer Aktiengesellschaft, Leverkusen, Federal Republic of Germany-Förbunds-republiken Tyskland (DE) (72) Wolfgang Kramer, Wuppertal, Karl Heinz Buchel, Wuppertal, Paul , Federal Republic of Germany Förbundsrepubliken Tyskland (DE) (7 ^ +) Oy Kolster Ab (5 ^) Halogenated 1-azolyl-1-fluorophenoxy - butane derivatives useful as fungicides - Sllsom fungicider användbara halogenerade 1 - azolyl-1-flu The present invention relates to novel halogenated 1-azolyl-1-fluorophenoxy-butane derivatives of the formula F-CH3 Q- <j! HA- |: -CH2 Y (I) CH3 which can be used as fungicides.

O

wherein A is a CO or CH (OH) group, B is a nitrogen atom or a CH group, and Y is a halogen atom, and their physiologically acceptable salts.

62295

It is known that 1-azolyl-1-chlorophenoxy-butane derivatives such as 4-chloro-1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazole-1- yl) - or - (imidazol-1-yl) -butan-2-one and 4-bromo-1- (4-chlorophenoxy) -3,3-dimethyl-1- (imidazol-1-yl) -butan-2-yl had good fungicidal properties (cf. DT-OS 26 32 602 and DT-OS 26 32 603). However, their good effect, especially at low application rates and concentrations, is not always completely satisfactory.

The new halogenated 1-azolyl-1-fluorophenoxy-butane derivatives of the formula I have strong fungicidal properties.

The compounds of the formula I in which A represents a CH (OH) group have two asymmetric carbon atoms and can therefore exist as geometric isomers (erythro and threo forms).

The novel halogenated 1-azolyl-1-fluorophenoxy-butane derivatives of the formula I are prepared by administering a bromoetherketone of the formula

\ V J / -0 ~ CH "C0" C_CH2Y UD

CH3 where Y is as defined above, reacts with an azole of formula

-O

\ N

(III) wherein B is as defined above, in the presence of an acid scavenger and a diluent, and the ketone derivatives thus obtained are optionally reduced in a known manner by means of a complex borohydride, optionally in the presence of a diluent.

The halogenated 1-azolyl-1-fluoro-phenoxy-butane derivatives according to the invention can be converted into salts with ulcers.

3,62295

The active compounds according to the invention surprisingly have a considerably greater fungicidal effect, in particular on leaf molds, than the 1-azolyl-1-chlorophenoxy-butane derivatives known from the prior art, for example 4-chloro-1- (4-chlorophenoxy) -3.3 -dimethyl-1- (1,2,4-triazol-1-yl) - or - (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 by their nature closest compounds. The cowardly active ingredients of the invention thus enrich the prior art.

Of the compounds of formula I according to the invention, those in which Y is chlorine or bromine are preferred, and A and B are as defined above.

If 1-bromo-4-chloro-3,3-dimethyl-1- (4-fluorophenoxy) butan-2-one and 1,2,4-triazole are used as starting materials, the reaction can be illustrated by the following diagram: fX \ I 3 + Hli £ base F - ((> -O-CH-CO-C-CH_Cl -—-> \ = ^ rj * i „32, _k CH,> -O-CH-CO-C-CH 2 C1 .N CH-

O

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 reaction the flow is shown using the following diagram:

Ch3 OH C | H3 f / (^) Vo-CH-CO-C-CH2C1 NaBH ^ F- / l ^ J) Vo-CH-CH- <J-CH2Cl '-' N. CH, '-' / N . CH3 O Of 4 62295

The bromoether ketones of formula II are also novel compounds. They can be prepared according to known methods by reacting, for example, fluorophenol with a bromoketone of the formula CH, I 3

Br-CH -CO-C-CH Y (IV) CH3 wherein Y is as defined above.

The remaining active hydrogen atom is then exchanged for bromine in the usual manner (cf. also the preparation examples).

Examples of starting materials of the formula II are: 1-bromo-4-chloro- (4-fluorophenoxy) -3,3-dimethylbutan-2-one, and 1,4-dibromo- (4-fluorophenoxy) -3.3 -dimethyl-butan-2-one.

Suitable salts of the formula I are those formed with physiologically acceptable acids. These include, in particular, hydrohalic acids such as hydrochloric acid and hydrobromic acid, especially hydrochloric acid, mixed phosphoric acid and nitric acid, as well as mono- and bifunctional carboxylic acids and hydroxycarboxylic acids such as acetic acid, citric acid, citric acid, sorbic acid, sorbinic acid

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

The reaction is carried out in the presence of an acid scavenger. Any commonly used inorganic or organic acid scavengers such as 5,62295 alkali metal carbonates, for example sodium carbonate, potassium carbonate and sodium hydrogen carbonate, or lower tertiary alkylamines, cycloalkylamines or arylalkylamines, for example N-ethylamine, for example triethylamine, can be added. dicyclohexylmethylamine, Ν, Ν-dimethylbenzylamine, further pyridine and diazabicyclooctane. A corresponding excess of azole of formula III is mainly used.

Reaction temperatures can vary widely. Generally, work is in the range of about 0 to 150 ° C, primarily in the range of 60 to 120 ° C.

In the preparation of the compounds according to the invention, 1 to 2 moles of azole and 1 to 2 moles of acid-binding agent are used per mole of compounds of the formula II. To isolate the compounds of formula I, the solvent is distilled off, the residue is taken up in an organic solvent and washed with water. The organic phase is dried over sodium sulfate and the solvent is removed in vacuo. The residue is purified by distillation or recrystallization.

The reduction is performed in the presence of a diluent. Suitable diluents include alcohols such as methanol, ethanol, butanol and isopropanol, and ethers such as diethyl ether and tetrahydrofuran. The reaction is generally carried out at 0 to 30 ° C, preferably at 0 to 20 ° C. In this case, about 1 mole of a borohydride such as sodium borohydride or lithium borohydride is used per 1 mole of the corresponding ketone compound. To isolate the compounds of formula I, for example, the residue is taken up in dilute hydrochloric acid, then made alkaline and extracted with an organic solvent, or diluted with water only and shaken with an organic solvent. The final preparation takes place in the usual way.

The compounds according to the invention have a strong antimicrobial action and can be used for controlling harmful microorganisms. The active ingredients are suitable for use as plant protection products.

In plant protection, fungicides are used to control the following species: Plasmodiophoromycetes, Oomycetes, Chytridio-mycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deutero-mycetes.

Because plants tolerate the active ingredients well at the concentrations necessary to control plant diseases, above-ground parts of plants, plant and cereal seeds, and soil can be treated.

As plant protection agents, the active compounds according to the invention can be used with particularly good success in controlling Erysip species. It should be emphasized that the active compounds according to the invention not only have a protective effect, but also have a systemic effect. Thus, it is possible to protect plants from fungal diseases by introducing the active ingredient through the soil and the roots or seeds into the above-ground parts of the plants.

The active ingredients can be made into conventional mixtures such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural products or synthetic substances impregnated with the active ingredient, small capsules in polymeric substances and in boxes, spirals, etc., and in ULV cold and warm mist museums.

These mixtures are prepared in a known manner, for example by mixing the active ingredients with diluents, i.e. with liquid solvents, with liquefied gases under pressure and / or with solid carriers, optionally using surfactants, i.e. emulsifiers and / or dispersants and / or foaming agents. If water is used as a diluent, organic solvents can also be used as co-solvents. Liquid solvents are mainly: aromatic, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, butyl alcohols, such as cyclohexane; 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 water; liquefied gaseous diluents or carriers mean liquids which are gaseous at normal temperature and pressure, for example aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; suitable solid carriers are: natural stone powders such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or rock flour (diatomaceous earth) and synthetic stone powders such as finely divided silicic acid, alumina and silicates; suitable solid carriers for granules are: for example crushed and fractionated natural stones such as calcite, marble, pumice, sea wax, dolomite as well as synthetic granules of inorganic or organic flours as well as granules of organic material such as sawdust, coconut and coconut; suitable emulsifying and / or foaming agents are: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfonates, alkyl sulfonates, alkyl sulfonates, alkyl sulfonates, suitable dispersants are, for example: lignin sulphite waste liquors and methylcellulose.

Carboxymethylcellulose, naturally occurring or synthetic powdered, granular or latex-like polymers such as acacia, polyvinyl alcohol, polyvinyl acetate can be used as binders in the mixtures.

Dyes such as inorganic pigments can also be used, for example iron oxide, titanium oxide, ferrocyanine blue and organic dyes such as alizarin, azole metal phthalate 8 62295 cyanine dyes and trace elements such as iron, manganese, boron, copper, cobalt, cobalt, cobalt .

The compositions generally contain from 0.1 to 95% by weight of active ingredient, in particular from 0.5 to 90%.

The active compounds according to the invention can be in mixtures or in various forms of use in admixture with other known active substances, such as, for example, fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, avian pesticides, growth agents, plant nutrients and soil improvers.

The active ingredients can be used as such, in the form of mixtures or in preparations prepared from them by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. The application takes place in the usual manner, for example by pouring, dipping, spraying, sprinkling, spraying, steaming, injecting, slurrying, brushing, dusting, sprinkling, dry-wetting and wet-covering, mud-coating or frosting.

When plant parts are treated with n, the concentration of the active ingredient in the Tito applications can vary widely. They are generally in the range from 1 to 0.001% by weight, in particular in the range from 0.5 to 0.001% by weight.

For the treatment of seeds, an amount of active ingredient of 0.001 to 50 g per seed is generally required, in particular 0.01 to 10 g.

For treatment as treatment, active ingredient concentrations of 0.00001 to 0.1% by weight are required, mainly 0.0001 to 0.02% at the site of action.

Example A

Shoot treatment test / grain leaf mold / protection (leaf-destroying mycosis)

To obtain a suitable active ingredient preparation, 0.25 parts by weight of active ingredient in 25 parts by weight of dimethylformamide and Q, Q6 parts by weight of emulsifier (alkyl-aryl-polyglycol ether) are taken and 975 parts by weight of water are added. The concentrate is diluted with water to the desired final concentration of the spray solution.

To study the protective effect, spray young young single-leaf barley shoots, Ämsel variety, with the active ingredient preparation.

9,62295

After drying, the barley shoots are pollinated with spores of Erysiphe graminis var.

After the plants have been 6d at 21-22 ° C and the humidity has been 90-90%, it is estimated how many leaf marks have entered the plant. The degree of contamination is expressed as a percentage of contamination of untreated control plants. In this case, 0% means no contamination at all and 100% the same degree of contamination as untreated control plants. The active substance is more effective / the lower the leaf mold contamination.

The active substances, the concentrations of the active substances in the spray solution and the degree of contamination are shown in the table below.

Table A

Shoots treatment test / grain leaf mold / protection

Active ingredients Percentage concentration of the active ingredient in the control weight group treated with the spray solution as a percentage _ fHs C1 ~ ^) "°"? H ~ C0 "?“ CIfcCl 0.00025 100 CH,

NJj S03 H

(known) SO5H

f «3 F - @ - ° - <j * -co-C- ^ Cl 0.00025 37.5 (i) X0» »xl / 2 (§J§)

SOsH

OT, Q-p-O-CB-TO-C-CHCl 0.00025 50.0 δ * ™ X 1/2 | SjQ)

(known) SO, H

10 62295

Table A (continued)

9HS

F - ^ - O-CH-CO-f-CH * Cl 0.00025 10.0

A

(6) ^ * 1/2 3 ©

S03H

Example B

Barley leaf test (Erysiphe graminis var.hordei) / systemic (fungal disease of barley shoots)

The active ingredients are used as a powdered seed treatment agent. They are prepared by diluting the active ingredient with a mixture of equal parts by weight of talc and diatomaceous earth, so as to result in a fine powder mixture with the desired concentration of active ingredient.

For seed treatment, the barley seeds are shaken with the diluted active ingredient in a sealed glass bottle. The seed is sown using 3 x 12 grains in flower pots to a depth of 2 cm in a soil mixture with one volume of Fruhstorf homogeneous soil and one volume of quartz sand. Germination and emergence from the soil take place under favorable conditions in the orchard. 7 days after sowing, when the barley seedlings have developed their first leaves, they are pollinated with fresh spores of Erysiphe graminis var. typical leaf hunters.

The degree of contamination is expressed as a percentage of contamination of untreated control plants. Thus, 0% means that no contamination has occurred and 100% means the same degree of contamination as in the untreated control group. The lower the degree of leaf mold contamination, the more effective the active ingredient.

The active ingredients, the concentrations of the active ingredients in the grain treatment agent, their application rate and the percentage of leaf mold contamination are shown in the following table.

11 62295

Table B

Barley leaf mold (Erysiphe graminis var.hordei) / systemic test

Active ingredients Active ingredient Coating agent Untreated concentration Application rate Control group Coating agent- g / kg seeds Percentage of contamination sa as a percentage by weight _ <j> H CH,.

Cl - ^^ O-CH-CH-C-CH * Br / N CH,

V-N

(known) 25 10 50.0 _ OH CH, F- ^ j \ * O-CH-CH-C-CHg Br J CH, \\

\-OF

(7) 25 10 12.5

Preparation Examples ✓ Example 1 CH, F - 0 - CH - CO - C - CHjCl ÖCH,

SO, H

x 1/2 QO

SO, H

12,62295 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 moles) of 1,2,4-triazole and heated for 6 h with a reflux condenser. The solvent is distilled off under a water-jet vacuum, the residue is taken up in 700 ml of methylene chloride, the organic phase is extracted twice with 1.5 l of water and dried over sodium sulfate. The solvent is distilled off under a water-jet vacuum and the residual oil is dissolved in 200 ml of acetone. 18 g (0.1 mol) of 1,5-naphthalenedisulphonic acid dissolved in 100 ml of acetone are added and the precipitate formed is filtered off with suction.

47 g (55.7% of theory) of 4-chloro-3,3-dimethyl-1- (4-fluorophenoxy) -1- (1,2,4-triazol-1-yl) -butan-2 are obtained. -one-naphthalene di-sulfonate- (1,5), m.p. is 200 ° C.

Preparation of starting material CH, F _ - 0 - CH - CO - C - CH * Cl

Br CHS

10 g »2 g (0.617 mol) of 1,4-dichloro-3,3-dimethylbutan-2-one are added dropwise at reflux to a solution of 56 g (0.5 mol) of p-fluorophenol and 85 g of potassium carbonate in 700 ml. acetone. Stir for 6 h with a reflux condenser, suction filter and distill off the solvent. 101.5 g (83% of theory) of 4-chloro-3,3-dimethyl-1- (4-fluorophenoxy) -butan-2-one are obtained, which is dissolved without purification in 600 ml of methylene chloride. 66.3 g (0.415 moles) of bromine are then added dropwise at room temperature so that the color disappears. After stirring for a further 30 minutes, the solvent is distilled off under a water-jet vacuum and 100 ml of pentane are added, whereupon the residue crystallizes out. 114 g (85% of theory) of 1-bromo-4-chloro-3,3-dimethyl-1- (4-fluorophenoxy) -butan-2-one are obtained, m.p. is 74 ° C.

CHS

C1CH2 - CO - c - CH2Cl

CH] 13 62295 1050 g (7.8 moles) of 78% 4-chloro-3,3-dimethylbutan-2-one are dissolved in 6 l of methylene chloride and 450 g are introduced into the solution at 10-11 ° C for 6 h. chlorine. It is then stirred for a further 30 minutes, the excess hydrogen chloride is taken off with nitrogen gas and the reaction mixture is distilled off using a 60 cm packed column. 832 g (63% of theory) of 1,4-dichloro-3,3-dimethyl-butan-2-one are obtained, b.p. 50-54 ° C / 0.1 Torr with a purity of 75%.

Example 2 OH CHS 'F - O-OT-CH-C-CH 2 Cl

A

25 g (0.053 mol) of 4-chloro-3,3-dimethyl-1- (4-fluorophenoxy) -1- (1,2,4-triazol-1-yl) butan-2-one naphthalene di sulfonate (Example 1) dissolved in 400 ml of methanol is added portionwise 4.75 g (0.12 mol) of sodium borohydride and stirring is continued for 15 h at room temperature. While cooling, 15 ml of conc. Hydrochloric acid are carefully added dropwise, stirred for 2 h at room temperature and half of the solvent is distilled off under water-jet heat. The reaction solution is added to 400 ml of saturated sodium hydrogen carbonate solution, extracted with 300 ml of methylene chloride, the organic phase is separated off, washed twice with 100 ml of water each time, dried over sodium sulfate and the solvent is evaporated off. The residue crystallizes on addition of 100 ml of diisopropyl ether. 9.1 g (36.4% of theory) of 4-chloro-3,3-dimethyl-1- (4-fluorophenoxy) -1- (1,2,4-triazol-1-yl) -butan-2 are obtained. -oli, m.p. is 87-90 ° C. The following compounds of formula: 14 62295 / “\ CHs

F "(Q)" ° "CH-A-C-CH2Y

\\ J

N— 'y

. (Example no A 'BY Melting point ° C

3 CO N Br 180 (x £ NDS) 4 CHOH N Br 100 5 CO CH Br 241 (x ^ NDS) 6 CO CH Cl 254 (x | NDS) 7 CHOH CH Br 116 8 CHOH CH Cl 115 NDS = 1.5 -naftaliinidisulfonihappo