NO780316L - 2,4-DICHLOROPHENYL-TRIAZOLYL-ETHANE ONERS (OLES), AND THEIR USE AS FUNGICIDES - Google Patents

Description

2,4-dichlorophenyl-triazolyl-ethan-ones (ols),

as well as their use as fungicides.

The invention relates to new 2,4-dichlorophenyl-triazolyl-ethan-one(s), as well as their use as fungicides.

It is already known that especially 3,3-dimethyl 1-1-phenoxy-1-triazolyl-butan-2-ones and -ols have a good fungicidal effect (cf. DOS 2.201.063 and 2.32<*>1.010). However, their effect is not always satisfactory, especially at low amounts and concentrations used.

It has been found that the new 2,4-dichlorophenyl-triazoly-1-ethan-ones (-ols) of the general formula:

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

X means halogen, alkyl or optionally substituted

phenyl and

n means integers from 0 to 3

and their physiologically tolerable salts 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 can appear in different proportions. In both cases, they are available as optical isorners. All isorners re-

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understood by the invention.

One obtains 2, *4-dichlorophenyl l-triazoly 1-ethan-ones (-ols)

• with formula (I) when l-bromo-2-( 2 , *J-dichlorophenyl 1)-1-phenoxy-ethan-2-one with formula:

where X and n have the above meaning,

is reacted with 1,2,4-triazole in the presence of a diluent and an acid binder 1, and optionally the resulting 1,2,4-triazolyl-ethanones are reduced in a manner known per se with complex borohydrides, optionally in presence of a diluent.

Furthermore, the 2,<*>1-dichlorophenyl-triazolyl-ethan-one(s) obtainable according to the invention can be transferred into the salts by reaction with acids.

Surprisingly, the active substances according to the invention show a considerably higher fungicidal effect, especially against grain diseases, than the 3,3-dimethyl-1-phenoxy-1-triazolyl-butan-2-ones and -ols known from the state of the art, which are chemically and functionally closest compounds.

The active substances according to the invention thus mean an enrichment of the technique.

If 1-bromo-1-('4-chlorophenoxy)-2-(2,'1-dichlorophenyl)-ethan-2-one and 1,2,k,-triazole are used as starting materials, the course of the reaction can be reproduced by the following formula core: using 1 ( 4-chlorophenoxy )-2-( 2 ,-^-dichlorophenyl)-1-(1, 2 , k-triazol-1-yl)-ethan-2-one and sodium borohydride as starting materials, can the course of the reaction is reproduced by the following formula core: The 1-bromo-2-(2,4-dichlorophenyl)-1-phenoxy-ethan-2-ones which can be used as starting materials are generally defined by formula II.

In this formula, X preferably means the halogens fluorine, chlorine, bromine and iodine, straight or branched alkyl with 1 to *J carbon atoms, and optionally substituted phenyl with halogen, especially chlorine. The index n preferably means whole numbers from 0 to 2.

As starting substances with formula II, the following should be mentioned, for example:

1-bromo-l-phen ok sy-2-(2,*l-dichlor ny l)-ethano-2-one 1-bromo-l- (*l-chlorophenoxy)-2-(2,*l -dichlorophenyl)ethan-2-one 1-bromo-1- (*J- fluorophenoxy )-2 - ( 2 , *J -dichlorophenyl)-ethan-2-one 1-bromo-1-( h -brom en oksy )-2-(2,yl-dichlorophenyl)-ethan-2-one 1-brorn-1-(it-iodophenoxy)-2-(2,<i>J -dichlorophenyl)-ethan-2-one l-bromo-l-(2,<*>l-dichlorophenoxy)-2-(2,<*>l-dichlorophenyl)-ethan-2-one l-brom-l(2,6-dichlorophenoxy-(2- (2,<*>1-dichlorophenyl)-ethan-2-one l-brorn-1-(2,5-dichlorophenoxy)-2-(2,<i>J-dichlorophenyl)-ethan-2-one 1- bromo-1-(3-fluorophenoxy)-2-(2,4-dichlorophenyl)-ethan-2-one, 1-bromo-1-(3-chlorophenoxy)-2-(2,4-dichlorophenyl)-ethano-2- on l-bromo-l(3-bromophenoxy)-2-(2,<i><-dichlorophenyl)-ethano-2-one 1-bromo-l - ( 2-chlor or ph enoxy ) - 2 - (2 , *l -dichloroph eny 1) - et an-2-one 1-bromo-l (*J - me ty 1 f enoxy ) - 2-( 2 , k -dichloroph eny 1) -ethano-2-one l-bromo -1-(*1-ethylphenoxy)-2-(2,*1-dichlorophenyl)-ethan-2-one 1-bromo-1-(3-methylphenoxy)-2-(2,yl-dichlorophenyl)ethane -2-one 1-bromo-1-(2-methylphenoxy)-2-(2,iJ -dichloropheny 1)-ethan-2-one 1-br om-1-(2-isopropylphenoxy)-2-(2,^-dichlorophenyl)'-ethan-2-one 1-bromo-1-( ^ -k 1 or-2-methyl lf en oxy ) -2- ( 2 , ;l-dichlorpheny 1)-et an-2-one 1-bromo-1 - (*l-bromo-2-methylphenoxy )-2-(2,yl-dichlorophenyl)-ethane -2-on

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1-bromo-1-C4-fluoro-2-methylphenoxy)-2-(2,']-dichlorophenyl.)'-ethan-2-one 1-bromo-1-(k-iod-2-methylphenoxy ) - 2-(2,'4-dichlorophenyl)-ethan-2-one 1-bromo-1-(2,3-dimethylphenoxy}-2-(2,k-dichlorophenyl)-ethan-2-one 1- bromo-l - (*J-bi ph eny lox y ) - 2- ( 2,4-dichloro ph eny 1) -ethano-2-one l-bromo-l ( 4-V -chloro bi ph eny ly lox y ) -2 - ( 2 , *4-dichlorophenyl)-ethan-2-one 1-bromo-1-(i4-2',yl'-dichlorobiphenylyloxy)-2-(2,4-dichlorophenyl)-ethan-2-one 1- bromo-l - ( 4-2 , k ' - dichlorophen y loxy ) - 2 - ( 2 , *t-di ch lor fe ny 1)-ethan-2 -one 1-bromo-l - ( k- A ' - bromodiphenyl ly oxy ) - 2-( 2 , *J-dichlorophenyl 1)-et an-2-one 1-bromo-1-(4-2-chlorobiphenylyloxy)-2-(2,k-dichlorophenyl)-ethane- 2-Mon

The 1-brorn-2-(2,*1-dichlorophenyl)-1-phenoxy-ethan-2-ones of formula II that can be used as starting materials are not known, but can however be prepared according to known methods, since known phenols of formula: in which X and n have the above meaning is reacted with a bromoacetophenone of formula:

The still remaining active hydrogen atom is then exchanged in the usual way for bromine.

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

For the turnover according to the invention it comes

preferably inert organic solvents 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 and dioxane, aromatic hydrocarbons such as toluene and 1,3-dichlorobenzene, benzene, formamide such as dimethylformamide in particular, 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 acid binders such as alkali carbonate, for example sodium carbonate, potassium carbonate and sodium hydrogen carbonate, or as a lower tert. alkylamines, cycloalkylamines or aralkylamines, for example triethylamine, N,N-dimethylcyclohexylamine, dicyclohexylmethylamine, N,N-dimethylbenzylamine, further pyridine and diazabicyclooctane. Preferably, a corresponding excess of triazole is used.

The reaction temperatures can vary within a large range. Usually you work between approx. 0 to approx. 150°C, preferably from 60 to 120°C, in the presence of a solvent such as acetone or methyl ethyl ketone.

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 a vacuum. The residue is purified by distillation or recrystallization.

For the reduction according to the invention it comes

as diluents for the turnover of said polar organic solvents. 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 compound with formula II, approx. 1 mole of a borohydride such as sodium borohydride or lithium borohydride. To isolate the compound of formula I, the residue is taken up e.g. in

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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.

As examples of particularly effective representatives of the active substances according to the invention, in addition to those in the preparation examples and the examples in Table 1, the following should be mentioned: l-(2-chlorophenoxy)-2-(2,4-dichlorophenyl)-l-( 1,2,4,-triazol-1-yl)-ethan-2-one resp. -beer

1-(2-isopropylphenoxy)-2-(2,4-dichloropheny1)-1-(1,2,4-triazol-1-yl)-ethan-2-one resp. -beer

1-(2-methylphenoxy)-2-(2,*)-dichlorophenyl)-1-(1,2,4-triazol-1-yl)-ethan-2-one'resp. -beer

1-(2-chloro-H-methylphenoxy)-2-(2,4-dichlorophenyl)-1(1,2,k-triazol-1-yl)-ethan-2-one resp. -beer

The active substances according to the invention have a strong fungitoxic effect. They do not damage cultivated plants in the concentrations necessary to combat fungi. Of

for these reasons they are suitable for use as a plant protection agent to combat fungi. Fungitoxic agents in plant protection are used to combat plasmodiophoromycetes, oomycetes, chytridiomycetes, zygomycetes, ascomycetes, basidiomycetes, duteromycetes.

The active substances according to the invention have a broad spectrum of action and can be used against parasitic fungi that attack plant parts above the ground or attack the plants from the ground, as well as against seed-borne disease agents. A particularly good effect occurs against parasitic fungi on plant parts above ground.

As a plant protection agent, the active substances according to the invention can be used with particularly good results to combat true powdery mildew fungi, for example to combat cucumber powdery mildew (Erysiphe cichoriacearum), apple powdery mildew (Podosphaera leucotricha) and grain powdery mildew, as well as against other grain diseases, for example grain rust.

As a plant protection agent, the active substances according to the invention can be used for seed and soil treatment and for the treatment of plant parts above ground.

The active substances according to the invention can be transferred in the usual formulations such as solutions, emulsions, suspensions, powders, pastes and granules. These are produced in a known manner, e.g. by mixing the active substances with emulsifiers, i.e. liquid solvents, pressurized liquid 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 drying agent, it can e.g. organic solvents are also used as auxiliary solvents. As a liquid solvent, these are essentially: aromatics such as xylene, toluene, benzene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffin, e.g. petroleum fractions, alcohols, such as butanol or glycol, as well as 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, as well as water, by liquefied gaseous suspending agents or carriers are meant such liquids as is gaseous at normal temperature and under normal pressure, e.g. aerosol propellants such as dichlorodifluoromethane or trichlorofluoromethane, as solid carriers: 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, aluminum oxy and silicates, as emulsifiers, non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl-polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates, as well as egg white hydrolysates, as dispersants: e.g. lignin, sulphite liquor and methyl cellulose.

The active substances according to the invention can be present in the formulation in the mixture with other known active substances such as fungicides, insecticides, acaricides, nematicides, herbicides, protective substances against bird attacks, growth substances; plant nutrients and soil structure improvers.

The formulation usually contains between 0.1 and

95% by weight active substance and preferably between 0.5 and 90%.

The active substances can be used as such i

form of their formulations or the application forms 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 way, e.g. by pouring, spraying, showering, spraying, spreading, dry pickling, wet pickling, wet pickling, mud pickling or incrustation.

When used as foliar fungicides, the active substance concentration in the application forms can be varied over a large range. They are usually between 0.1 and 0.00001% by weight, preferably between 0.05 and 0.0001%.

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

For soil treatment, the necessary active

substance quantity from 1 to 1000 g/m^ soil, as in particular 10 to 200 g.

The many-sided application possibilities can be seen from the following examples.

Example A

Slat treatment sample/grain powdery mildew/protective

(leaf-destroying mycosis)

For the preparation of a suitable active substance preparation, 0.25 parts by weight of active substance are taken in 25 parts by weight of dimethylformamide, and 0.06 parts by weight of emulsifier alkylaryl-polyglycol ether and 975 parts by weight of water are added. The concentrate is diluted with water to the desired final concentration in the spray liquid.

For research on protective effect, syringes

rnan one-leafed barley seedlings of the Amsel type with the effective substance preparation dewy. 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 2l-22°C and a humidity of 80-90%, the attack of plants with powdery mildew pustules is assessed. The degree of attack is expressed in % of attack of untreated control plants. Hereby, 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 powdery mildew attack.

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

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Example B

Spros treatment sample/grain rust/protective

(leaf destroying mycosis)

For the preparation of a suitable active substance preparation, 0.25 parts by weight of active substance are taken up in 25 parts by weight of dimethylformamide and 0.06 parts by weight of emulsifier alkylaryl polyglycol ether and 975 parts by weight of water are added. The concentrate is diluted with water to the desired final concentration in the spray liquid.

To investigate the protective effect, one-leaf wheat seedlings of the Michigan Amber type are inoculated with an uredospore suspension of puccinia recondita in 0.1% water agar. After drying the spore suspension, the wheat plants are sprayed with the active substance preparation moist with dew and set up for incubation for 24 hours at approx. 20°C and 100% humidity in a greenhouse.

After 10 days of residence of the plants at a temperature of 20°C and a humidity of 80-90%, the attack of the plants with rust pustules is assessed. The degree of attack is expressed in % of the attack of untreated control plants. Hereby, 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 rust attack.

Active substances, active substance concentration in spray liquids and the degree of attack are shown in the following table.

Example C

Podosphaera sample (apple)/protective

The amount of active substance required for the desired active substance concentration in the spray liquid is mixed with the indicated amount of solvent and the concentrate is diluted with the indicated amount of water containing the aforementioned additives.

With the spray liquid, young apple seedlings that are in the 4th to 6th leaf stage are sprayed until droplet moisture. The plants remain for 24 hours at 20°C and a relative humidity of 70% in the greenhouse. They are then inoculated by pollination with conidia of the apple powdery mildew producer (Podosphaera leucotricha) and brought into a greenhouse with a temperature of from 21 to 23°C and a relative humidity of approx. 70%.

Ten days after inoculation, the infestation of the seed plants is determined. Formed assessment values are converted into % attack. 0% means no attack, 100% means that the plant is completely attacked.

Active substances, active substance concentrations and results appear in the following table.

Example D

Erysiphe test (cucumber)/protective

The amount of active substance required for the desired active substance concentration in the spray liquid is mixed with the indicated amount of solvent and the concentrate is diluted with the indicated amount of water containing the aforementioned additives.

With the spray liquid, young cucumber plants with approximately three leaves are sprayed until the moisture level drops to a drop. The cucumber plants remain for drying 2*4 hours in the greenhouse. They are then pollinated for inoculation with conidia of the fungus Erysiphe cichoriacearum. The plants are then set up at 23-24°C in greenhouses with a relative humidity of approx. 75%.

After 12 days, the attack of the cucumber plants is determined.

The formed assessment values are converted into % attack. 0% means no attack, 100% means the plates are completely attacked.

Active substances, active substance concentrations and results appear in the following table.

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Manufacturing examples

Example 1

To 1*19 g (2.13 mol) 1,2,4-triazole in 1500 ml acetonitrile

2*1*1.6 g (0.62 mol) 1-bromo-1 (4-chlorophenoxy)-2-(2,*1-dichlorophenyl)-ethan-2-one are added at boiling temperature. It is heated *I0 hours under reflux. The solvent is then distilled off in a vacuum, the residue is taken up in 1000 ml of methylene chloride and shaken with three

times 500 ml of water. The aqueous phase is shaken again with 500 ml of methylene chloride. The combined methylene chloride phases are dried over sodium sulfate and evaporated by distilling off the solvent in a vacuum. The residue is dissolved in 300 ml of acetone and mixed with 100 g of 1,5-naphthalenedisulfonic acid hexahydrate in 200 ml of acetone. You get 270 g (*11.3% of the theoretical) 1,(*1-chlorophenoxy)-2-(2,*1-dichlorophenyl 1)-1-(1,2,*!-triazole-1 -y 1) ethan-2-one-naphthalene-disulfonate-(1,5) with melting point 198°C

Example 2

According to Example 1, 1-(4-chlorophenoxy)-2-(2,4-dichloro-phenyl)-1-(1,2,4-triazol-1-yl)-ethan-2-one-naphthalene disulfonate formed (1.5)' is released by the addition of sodium bicarbonate solution, the base is taken up in acetic acid and transferred by ethereal hydrochloric acid into the hydrochloride, which after a longer period of time crystallizes out in ether. One obtains quantitatively 1-(4-chlorophenoxy)-2-(2,4-dichlorophenyl)-1-(1,2,4-triazol-1-yl)ethan-2-one hydrochloride with melting point 138-140°C .

Example 3

226 g (0.42 mol) 1-(4-chlorophenoxy)-2-(2,4-dichlorophenyl)-1-(1,2,4-triazol-1-yl)-ethan-2-one-naphthalene disulfonate- (1.5) (Example 1). slurried in 500 ml of methylene chloride, mixed with 100 ml of saturated sodium bicarbonate solution and stirred for 5 hours. The > isolated organic phase is dried over sodium sulphate and evaporated in vacuo. The residue is taken up in 1.5 1 methanol, added at approx. 0 to 5°C 17 g (0.45 mol) sodium borohydride in portions of

about. lg and let it stir for 15 hours at room temperature. 200 ml of concentrated hydrochloric acid are then added dropwise at 0°C and stirred again for 15 hours at room temperature. The reaction mixture is then stirred into 1000 ml of saturated sodium bicarbonate solution, the aqueous phase is shaken with twice 500 ml of methylene chloride and the organic phase with twice 200 ml of water. The combined organic phases are dried over sodium sulfate and evaporated in vacuo by distilling off the solvent. The remaining oil is dissolved in 800 nil of ether and mixed with an excess of dry hydrogen chloride. 113.5 g (64% of the theoretical) 1-(4-chlorophenoxy)-2-(2,4-dichlorophenyl)-1-(1,2,4-triazol-1-yl)ethan-2- ol hydrochloride as a mixture of isomers of a melting point of 157-172°C.

Analogous to the above example, the following compounds are obtained in Table 1.

Claims (2)

1. 2,4-dichloropheny1-triazoly1-ethan-ones (-ols) with fungicidal properties and the general formula: in which A means a keto group or a CH(OH) grouping X means halogen, alkyl or optionally substituted phenyl and n means integers from 0 to 3 and their physiologically tolerable salts. 2. Fungicide mite1 characterized by a content of at least one 2,4-dichlorophenyl-1-triazoly1-ethan-one(-ol), according to claim 1. 3- Use of 2,H-dichlorophenyl-triazolyl-ethan-ones (-ols), according to claim 1, for combating fungi.