CS241522B2 - Method of new arylphenylethers derivatives production - Google Patents

Description

The present invention relates to a process for the preparation of the novel substituted arylphenyl ethers derivatives of formula (I) below, as well as their acid addition salts and their copper complexes. The novel arylphenyl ether derivatives are used to combat phytopathogenic fungi in plant protection.

New valuable arylphenyl ethers derivatives

according to the invention correspond to the general formula Ar-O- ja K _b O V -c—- ó l CH _Z ~ / srN (1) in which

Y is —CH = or —N =,

R _a and R _b are each independently hydrogen, halogen, C 1 -C 3 alkyl or methoxy,

U and V are, independently of one another, an alkyl group having 1 to 3 carbon atoms or together are an alkylene bridge of the formula

R 1 R 2 y

R 1 represents a hydrogen atom or a C 1 -C 3 alkyl group,

R ₂ represents a group of the formula -CH ₂ -Z-R 2, wherein

Z is oxygen because sulfur and R ₇ is an alkyl group having 1-3 carbon atoms, alkenyl having 3 to 4 carbon atoms, methoxyethyl, phenyl skujpinu, chlorine or · methyl substituted phenyl, benzyl, chlorine or · methyl substituted a benzyl group; and

Ar represents a group of the formula

whereas

R _c , R _d and R _e are each independently hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 3 alkoxy, trifluoromethyl or nitro, and also include acid addition salts of the compounds of formula (I) and complexes of the compounds of formula I with copper.

The term "alkyl" alone or as a component. Depending on the number of said carbon atoms, the substituents are, for example, the following groups: methyl, ethyl, propyl, butyl, etc., and their isomers, such as isopropyl, isobutyl, tert-butyl, sec-butyl, etc.

The term "alkenyl" means, for example, 1-propenyl, allyl, 1-butenyl, 2-butenyl or 3-butenyl.

Halogen is herein to be understood as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.

The present invention relates to a process for the preparation of the free compounds of the formula I, their addition salts with inorganic and organic acids as well as their complexes with copper salts.

Salts are in particular addition salts with physiologically acceptable inorganic or organic acids. (in accordance with the purpose of use).

Suitable physiologically acceptable inorganic and organic acids are, for example, hydrohalic acids, for example hydrochloric acid, hydrobromic acid or hydroiodic acid, sulfuric acid, phosphorous acid, phosphoric acid, nitric acid or halogenated fatty acids, such as acetic acid, trichloroacetic acid. and oxalic acid or sulfonic acids such as benzenesulfonic acid and methanesulfonic acid.

The complexes of copper and the compounds of formula I consist of a basic organic molecule and an inorganic or organic salt of copper, for example, halides, nitrate, sulfate, phosphate, tartrate, copper. The copper cation may be present in the various moieties belonging to it.

The compounds of formula (I) are stable oils, resins or solids at room temperature, which have very valuable fungicidal properties in plant protection. The compounds can therefore be used in agriculture and related fields to combat phytopathogenic microorganisms.

One of the fungicide groups that is important for use in plant protection is represented by the compounds of formula (I) wherein:

Y is —CH = or —N =,

R a _and R _b independently represent a hydrogen atom, a halogen atom, an alkyl group having from 1 to 3 carbon atoms or a methoxy group,

U and V are independently C 1 -C 3 alkyl or together are an alkylene bridge of the formula

Ri Rz

M where

R ₁ represents a hydrogen atom or a C 1 -C 3 alkyl group,

R ₂ represents a group of formula -CH ₂ -Z-R ₇ wherein

Z is oxygen or sulfur,

R ₇ is C 1 -C 3 alkyl, C 3 -C 4 alkenyl, methoxyethyl, phenyl, chloro or methyl substituted phenyl, benzyl, or chloro or methyl substituted benzyl, and

whereas

R _c , R _d and R _e are each independently hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 3 alkoxy, trifluoromethyl or nitro, as well as their acid addition salts and complexes thereof with copper.

A preferred group of agriculturally useful fungicides are compounds of formula I, including their salts and complexes with copper, in which Y is -CH = or --N = · R _a and R _b are independently hydrogen, halogen or alkyl having 1 to And Ar represents a group of the formula

where

R _c , R _d and R _e are each independently hydrogen, halogen, trifluoromethyl or C 1 -C 3 alkyl, and

U and V have the meanings given in formula I.

241322

This group will be referred to as Group Ib.

Another preferred class of agriculturally useful fungicides are those compounds of formula I wherein Y is —CH— or —N—, Ar is as defined for Formula I, R _a , R b, R _c > Rd and R _e are independently of each other. hydrogen, chlorine, bromine, fluorine, methyl, methoxy or nitro, U and V are each independently an alkylene group represented by formula (I), wherein R ₁ is hydrogen or (C 1 -C 3) alkyl and R ₂ is -CH ₂ -O-R ₇ wherein R ₇ is an alkyl group having 1-3 carbon atoms, alkoxy of 1-3 carbon atoms substituted with alkyl of 2-4 carbon atoms, alkenyl having 3, a, Z 4 carbon atoms or phenyl group.

This * group will be referred to as * group Id in the following.

Thus, for example, the following compound belongs to the agriculturally particularly useful individual substances:

2- [p- (3 ‘, 4‘-dichlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methoxymethyl-1,3-dioxolane.

According to the invention, the compounds of the formula I, their acid addition salts and their complexes with copper are prepared by preparing a compound of the formula I in which U and V together represent a group of the formula -CH ₂ -CH (CH ₂ ZR ₇₎ 'j - and R ₇ ' denotes a radical R ₇ different from hydrogen, at a temperature of 40 to 130 ° C and preferably in a polar organic solvent which is inert under the reaction conditions, the compounds of the general formula VI and the general formula VII condense with each other

and

X ₂ -R ₇ (VII) wherein one of X ₁ and X ₂ is an optionally present hydroxy or mercapto group in the form of a salt, for example a group of the formula —Z — Me, wherein Z and Me are as defined above, and the other represents a nucleophilic leaving group X, or both X _b and X _{2 are} deprotected by hydroxy, and

Ar, R _a , R _d , X, Y and R ₇ have the meanings given in formula I, whereupon the optionally obtained free compound is converted by reaction with an organic or inorganic acid into an acid addition salt, the obtained acid addition salt optionally with reaction with carbonate , the alkali metal bicarbonate or hydroxide is converted to the free compound or the optionally obtained free compound or the acid addition salt obtained is converted by reaction with a copper salt into a copper complex.

The metal cations Me are, for example, alkali metal cations, for example lithium, sodium or potassium, or alkaline earth metal cations, such as magnesium, calcium, strontium or barium cations.

Nucleophilic leaving groups are, for example, reactively esterified hydroxy groups, such as hydroxy groups esterified with hydrohalic acid, for example hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydroiodic acid, lower alkane, optionally substituted with benzene or halosulfonic acid, for example methane, ethane, benzene. , p-toluene- or fluorosulfonic acid.

Preparation of compounds of formula I in which the substituents U and V together represent a group -CH ₂ -CH (CH ₂ ZR ₇ j, the process according to the invention is carried out by reacting the compound of formula VI * becného a compound of formula VII, wherein X _x is -ZH group and X ₂ represents a group X. the reaction is preferably carried out in organic solvents which are inert to the reactants. For this purpose, are, for example, N, N-dimethylformiamid, N, N-dimethylacetamide, hexamethylphosphoric triamide, dimethylsulfoxide, 4 methyl-3-pentanone, etc. Mixtures with other solvents which are inert to the components of the reaction mixture, for example aromatic hydrocarbons such as benzene, toluene, xylene, etc. may also be used.

In many cases, it may also be advantageous to work to accelerate the reaction in the presence of a base. Such bases are, for example, alkali metal hydrides or alkali metal carbonates. In many cases, it may also be advantageous to convert the compound of formula VI to a suitable metal salt in a manner known per se.

This is preferably done by reacting the compound of formula VI with a sodium compound, for example sodium hydride, sodium hydroxide, etc. Then, the salt of formula VI is reacted with a compound of formula VII. In many cases, it is also possible to work at an elevated temperature, preferably at a temperature of 80 to 130 ° C or at the boiling point of the solvent, to increase the reaction rate.

In an analogous manner, compounds of formulas VI and VII may also be mentioned in re241522, in which X ₁ is X and X ₃ is -ZH.

In the condensation reaction of compounds of formulas VI and VII in which X 1 and X 1 _; are hydroxy, which leads to products of formula I in which Z is oxygen, the reactants can be heated in suitable solvents to reflux, while the water formed is distilled off from the reaction mixture by azeotropic distillation. Aromatic hydrocarbons, such as toluene alcohol HO-R ₇ , can be used as solvents. The reaction is conveniently carried out in the presence of a strong acid, for example p-toluenesulfonic acid.

The compounds obtained by the process according to the invention can be converted into other compounds of formula I by known methods.

Thus, for example, the compounds obtained can be recetalized to other compounds of formula I. For example, in compounds of formula I in which U and V are the same and are optionally substituted alkyl radicals of 1 to 12 carbon atoms, optionally substituted C 1 -C 12 alkainol

V-OH (Vc) group U by one group V or by reaction with a diol of formula Vb both groups U by a bivalent radical. Recalculation is carried out in a conventional manner, for example in the presence of an acidic condensing agent such as mineral acid, sulfonic acid or strong carboxylic acid e.g. hydrochloric or hydrobromic acid, sulfuric acid, p-toluenesulfonic acid or trifluoroacetic acid, preferably under distillation or under azeotropic distillation, to remove easily boiling reaction products.

Further, carbocyclic aryl groups can be used. parts of the compounds obtained according to the invention optionally additionally introduce substituents into the radical Ar and / or R _n or R b. Thus, for example, halogen can be introduced by reaction with a halogen in the presence of a Lewis acid, such as ferric, zinc, boric or antimony trichloride or N-chlorosuccinimide.

Further, nitro groups can be reduced, for example, with suitable complex hydrides, for example lithium aluminum hydride, to amines, which are then diazotized, for example by treatment with nitrous acid, and the diazoinium formed can then be replaced by halogen or alkoxy. Likewise, halogen can be replaced by reaction with a metal alkyl derivative, for example an alkyl lithium or alkyl magnesium halide, an alkyl group.

When the compounds of the formula I are obtained in the form of bases, they can be converted into the corresponding salts by treatment with inorganic or organic acids or they can be converted into metal complexes of the formula I by treatment with preferably equimolar amounts of metal salts. Conversely, the salts of formula I can be converted, for example, by reaction with an alkali metal carbonate or bicarbonate or an alkali metal hydroxide into the free bases of formula I.

The ketones of formula (IV) may be prepared by halogenation of methylarylketones of formula (XIV)

and further reacting compounds of formula XV with an azole of formula II

Me

where Me is metal,

Y is —CH = or —N— a

Hal is preferably chlorine or bromine, while

Ar, Ra _and R. have the above meanings.

The ketals of formula VI are obtained by reacting the starting ketone with a suitable alcohol or diol.

The described process variant is also part of the invention.

In ketalization reactions of a ketone with a substituted α, β- or α, γ-diol, predominantly mixtures of diastereomers of the resulting ketal are formed. Correspondingly, mixtures of diastereomers of the end products of formula I are generally formed from the starting ketones. The compounds of formula I may exist, for example, in the following diastereomeric forms.

ΛΓ-Ο,

.CH,

CfyZR? H (XVl) ββ

here and in the next part of the description as the "trans" -isomer.

The type A configuration is denoted

Ar-O.

a- f = ^R b vN ^ \ d ^C

Ar-0

types B

CH _from ZRy (xím ^r k.

ď Ό

Ή (Xi /) y = r N

The symbols in the spatially represented patterns have the following meanings:

...... = for

- = 7 = V = in front of the plane shown

The type B configuration is accordingly referred to herein as the " cis " isomer.

Separation of the two diastereomers can be carried out, for example, by fractional crystallization or by chromatography (thin layer chromatography, dilution chromatography, column chromatography, high pressure liquid chromatography, etc.). Both of these isomers show different biological activity. Generally, mixtures of diastereomers are used for practical purposes.

Some of the starting materials and intermediates used in the process of the present invention are known compounds, others can be prepared by methods known per se 1- (4-aryl) ethylimidazolyl ketals in which aryl is substituted phenyl or * naphthyl are cited as fungicides and bactericides in the following publications:

U.S. Pat

575 999,

936 470,

101 664,

101 666 a

156 008.

Surprisingly, it has been found that the compounds of formula I have a very favorable spectrum of microbicidal activity against phytopathogenic fungi and bacteria for practical requirements and further possess antifungal and / or anticulsive properties which establish their usefulness as drug active ingredients.

Thus, these compounds have very advantageous curative, preventive and systemic properties in plant protection and can be used to protect crop plants. The active compounds of the formula I can control or destroy the microorganisms present on plants or parts of plants (such as fruits, flowers, leaves, stems, tubers and roots) of various useful plants, while remaining protected from such microorganisms later grown parts of plants.

The active substances are particularly active against phytopathogenic fungi belonging to the following groups:

Ascomycetes, such as

Venturia,

Podosphaera,

Erysiphe,

Monilinia,

Uncinula,

Basidiomycetes such as

Hemileia,

Rhizoctonia,

Puccinia,

Fungi imperfecti, such as · are they? Botrytis, F.

Helminthosporium,

Fusarium,

Septoria,

Cercospora and Alternaria.

In addition, the compounds of the formula I are also active systemically. They can also be used as a dressing agent for the treatment of seeds (fruits, tubers, grains) and plant seedlings to protect against fungal infections as well as against phytopathogenic fungi occurring in the soil. The active compounds according to the invention are particularly well tolerated by crop plants.

The invention therefore also relates to microtoicidal compositions as well as to the use of the compounds of the formula I for combating phytopathogenic microorganisms, in particular fungi which are harmful to plants or preventively prevent the attack of plants.

In addition, the present invention also encompasses the production of agrochemical compositions which consist in mixing the active ingredient thoroughly with one or more of the substances described herein or a group of substances described herein.

The invention also relates to a process for the treatment of plants which is characterized by the application of the compounds of the formula I and of the novel compositions.

Suitable crop plants for the areas of indication described herein are, for example, the following plant species in the context of the present invention:

cereals such as wheat, barley, rye, oats, rice, sorghum and related plants, beets such as sugar beet, fodder beet, fruit trees, fruit bearing kernels, seeds and berries, for example:

apple, pear, plum, peach, almond, cherry, strawberry, raspberry, blackberry, legume, such as bean, lentils, peas, soybean, oilseed rape, mustard, poppy, olive, sunflower, coconut, castor, cacao, • groundnuts, cucurbits such as pumpkins, cucumbers, melons.

fibrous plants such as cotton, flax, hemp,

·. citrus fruit trees, such as orange, lemon, lemon, mandarin, various vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes,. . ·.

potatoes, peppers, laurel plants (such as avocado Porsea gratissima), cinnamon, camphor,.

or · other plants such as maize, tobacco, butternut, coffee, sugarcane, teas, grapevine, hops, banana and rubber, as well as ornamental plants (Compositae).

The active compounds of the formula I are used in agriculture usually in the form of compositions and can be applied simultaneously or sequentially with other active compounds, namely

241322 either to the treated area, plants, or part of the plants. These · other active substances, in the case of plant protection products, are represented as fertilizers, with trace element preparations, or · other preparations which affect plant growth. However, they can also be selective herbicides, insecticides, fungicides, bactericides, non-maicides, molluscicides or mixtures of several of these preparations, together with, if appropriate, other customary carriers, surfactants or other additives which improve the application possibilities.

In all of these compositions, suitable carriers and additives may be solid or liquid substances and correspond to non-gray substances which serve their purpose in the corresponding compositions; such as, for example, regenerated minerals, solvents, dispersing agents, wetting agents, adhesives, thickeners or binders.

One preferred method used in agriculture to apply the active compound of the formula I or the agrochemical composition to the infected plant is to apply to the leaves of the plants. The number of applications and the amount used depend on the state of infection for the respective disease agent (fungus species). However, the active compounds of the formula I can also be fed to the plant via soil via the root system (systemic effect) by watering the place where the plant grows, or by incorporating the substances in solid form into the soil, for example in the form of granules. soil application). However, the compounds of formula I can also be applied to plant seeds (Couting) by either impregnating the seeds with a liquid preparation of the active substance or by providing a layer of solid preparation. In addition, in other cases, other modes of application are possible, such as the deliberate treatment of plant stems or buds.

The compounds of the formula I are used in unchanged form or preferably together with auxiliaries customary in the preparation of agrochemical preparations and are therefore processed into emulsion concentrates, paint pastes, sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dust granules , for example, into encapsulated polymers in a known manner. Application procedures, such as spraying, fogging, dusting, sprinkling, coating or watering, as well as the type of formulation, are selected appropriately according to the desired objectives and conditions. A favorable application rate is generally between 50 g to 5 kg of active ingredient per hectare, preferably from 100 g to 2 kg of active ingredient per hectare, in particular 200 g to 600 g of active ingredient per hectare.

Agrochemical compositions containing the active compound of the formula I and optionally a solid or liquid additive and concentrates or other preparations of this type are prepared in a known manner, for example by thoroughly mixing and / or grinding the active compounds with fillers, such as solvents , solid carriers and optionally; surfactants (surfactants).

Suitable solvents are aromatic hydrocarbons, preferably fractions containing 8 to 12 carbon atoms, such as xylemp or substituted naphthalenes, phthalic acid esters such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffin hydrocarbons, alcohols and glycols, as well as their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol, monomethyl ester or ethylene glycol monoethyl ether, ketones such as cyclothexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimeithyl formamide; and optionally epoxidized vegetable oils, such as epoxidized coconut oil or soybean oil, or water.

As solid carriers, for example for bust and dispersible powders, natural stone flours are generally used; such as limestone, talc, kaolin, montmorillonite or attapulgite. Highly dispersed silicic acid or highly dispersed absorbent polymers may also be added to improve physical properties. Suitable granular adsorptive carriers for granules are porous types, such as pumice, brick, sepiolite or bentonite, and non-sorptive carrier materials, for example limestone or sand. · In addition, can be used in a large number of pre-granulated materials of inorganic or organic origin ^1, as especially dolomite or pulverized plant residues ·.

Depending on the type of active compound to be treated, non-ionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties are suitable as surface-active compounds. Surfactants are also understood as meaning mixtures of surfactants; ·

Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surfactants.

Soaps include the alkali metal, alkaline earth metal, higher fatty acid (C10 -C22) salts or the corresponding optionally substituted ammonium salts, such as sodium or potassium salts of oleic acid or stearic acid, or mixtures of natural fatty acids, which are obtained, for example, from coconut oil or from tallow oil. The fatty acid salts of methyl taurine must also be mentioned.

However, so-called synthetic surfactants are used more frequently, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

Fatty sulfonates or fatty sulfates are

4 1 5 2 3

1S are generally present as alkali metal, alkaline earth metal or optionally substituted ammonium salts and contain an alkyl radical of 8 to 22 carbon atoms, the alkyl also comprising an alkyl portion of the acyl radicals, such as the sodium or lignin sulphonic acid salt, dodecylsulphuric acid ester or a mixture of sulfated fatty alcohols made from natural fatty acids. Also included are salts of sulfuric acid esters and sulfonic acids of fatty alcohol adducts with ethylene oxide. The sulfonated bemmidimidazole derivatives preferably contain 2 sulfo groups and a C 8 -C 22 fatty acid residue. Alkylarylsulfonates are, for example, the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or the naphthalenesulfonic acid-formaldehyde condensation product.

Also suitable are corresponding phosphates, such as salts of the phosphoric acid ester of the p-nonylphenol adduct with ethylene oxide (4 to 14).

Suitable nonionic surfactants are, in particular, polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon residue and 6 to 18 carbon atoms in the an alkyl radical of alkylphenols.

Other suitable nonionic surfactants are the water-soluble polyethylene oxide adducts of polypropylene glycol, ethylenediaminopolypropylene glycol and an alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. Said compounds usually contain from 1 to 5 e-units per propylene glycol unit. thylene glycol.

Examples of inionic surfactants include nooylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene adducts with polyethylene oxide, tributylphenoxypolyethoxyethanol, polyethylene glycol, and octylphenypolyethoxyethanol.

Also suitable are fatty acid esters derived from polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are in particular quaternary ammonium salts which contain, as a substituent on the nitrogen atom, at least one alkyl radical of 8 to 22 carbon atoms and which contain, as further substituents, lower or halogenated alkyl radicals, benzyl radicals or lower hydroxyalkyl radicals. These salts are preferably in the form of halides, methylsulfates or ethylsulfates, for example, stearyltrimethylammonium chloride or benzl-di- (2-chloroethyl) ethylammonium bromide.

Surfactants useful in the manufacture of the agrochemical compositions of the invention are described, inter alia, in the following publications: "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ringwood, New Jersey, 1980 Sisely and Wood, "Encyclopedia of Surface Active Agents" Chemical Publishing Co., Inc. | New York, 1980.

Agrochemical preparations generally contain from 0.1 to 99% of active compound of the formula I, in particular from 0.1 to 95% of active compound of the formula I, from 99.9 to 1%, in particular from 99.8 to 5% of solid or liquid additives, and up to 25%, in particular 0.1 to 25% of surfactants.

While concentrated formulations are preferred as commercial products, generally dilute formulations are used for the final use.

The agrochemical compositions may also contain other additives such as stabilizers, anti-foaming agents, viscosity regulators, binders, adhesives, as well as fertilizers or other active ingredients to achieve particular effects.

The following examples serve to illustrate the invention in greater detail without restricting it. Percentages and parts refer to weight.

Examples:

He did

2- | p- (4-chloro-2 inethylfenoxy ^j) phenyl j-2- (1-imidazolylmethyl) -4-methoxymethyl-l, 3-dioxolane

(3,226)

17 parts of 2- [p- (4-chloro-2-methylphenoxy) phenyl] -2- (1-imidazolylmethyl) -4-hydroxymethyl-1,3-dioxolane are dissolved in 150 parts of Ν, Ν-dimethylformamide and introducing a stream of nitrogen into the solution while stirring, 1.9 parts of a 55% sodium hydride dispersion are added and the reaction mixture is heated at 80 ° C for 2 hours. After cooling to room temperature, 6.3 parts of methyl iodide are added dropwise with stirring over 1 hour, the reaction mixture is heated at 60 ^DEG C. for 2 hours and then diluted with 800 ml of ice-water and extracted three times with 300 ml of ethyl acetate. The combined extracts were washed three times with 50 ml of water each time, dried over sodium sulfate, filtered and the solvent was evaporated.

The residue was purified by silica gel column chromatography using a 1: 1 mixture of acetone and ethyl acetate as eluent. After evaporation of the solvent mixture, the mixture of diastereomers is crystallized by addition of hexane. Beige crystals of m.p. 92 DEG-106 DEG C. are obtained.

Example 2

Preparation of 2- (p- (phenoxy) phenyl) -2- (1H-1,2,4-triazolyl-ethyl) -4- (p-chlorobenzyloxymethyl) -1,3-dioxolane A- and B-diastereomer <3

(1.25 / 1.25)

14.1 parts of 2- [p- (phenoxy) phenyl] -2- (1H-1,2,4-triazolylmethyl) -4-hydroxymethyl-1,3-dloxolan in 100 ml of absolute dioxane were stirred and introduced with nitrogen dropwise at room temperature to 1.8 parts of a 55% dispersion of sodium hydride in 100 ml of absolute dioxane, and the reaction mixture was heated at 80 ° C for 3 hours. -chlorobenzyl bromide in 50 parts of absolute dioxane, the reaction mixture is heated at 50 ° C for 3 hours, cooled to room temperature, diluted with 1,200 ml of ice-water and extracted three times with 200 ml of ethyl acetate each time. The mixture of diastereomers was separated by column chromatography on silica gel using ethyl acetate as eluent, and after evaporation of ethyl acetate diastereomer B solidified, m.p. 83-85 ° C. Mer A remains as a viscous, light brown oil after drying under high vacuum. n _D ²⁶ = 1.5865.

Example 2a

Preparation of 2- [p- (3,4-dichloropheno (xy) phenyl) -2- (1H-1,2,4-triazolylmethyl) -4-methoxymethyl-1,3-dioxolane

11 parts of a 20% potassium hydride dispersion are added under stirring under nitrogen atmosphere and the reaction mixture is heated at 65 ° C for 1 hour. After cooling to room temperature, 7.8 parts of methyl iodide in 50 ml of tetrahydrofuran was added dropwise and the reaction mixture was heated at 40 degrees Celsius for 9 hours. The reaction mixture is stirred during the dropwise addition and heating. The reaction mixture is then poured onto 1000 ml of ice-water and extracted twice with 200 ml of diethyl ether each time. The combined ether extracts were washed twice with 50 ml of water each time, dried over sodium sulfate, filtered and the diethyl ether removed in vacuo. The residue was purified by silica gel column chromatography using a 1: 1 mixture of acetone and ethyl acetate as eluent. After evaporation of the solvent mixture, the diastereomer mixture crystallizes by addition of hexane. White crystals of m.p. 48-60 ° C are obtained.

Example 2b

Preparation of 2- [p- (4-chloro-2-methylphenoxy) phenyl] -2- (1H-1,2,4-triazolylmethyl) -4-methoxymethyl-1,3-dioxolane

parts of 2- [p- (4-chloro-2-methylphenoxy) phenyl] -2- (1H-1,2,4-triazolylmethyl) -4-hydroxymethyl-1,3-dioxolane in 50 ml of dimethylacetamide under stirring and under an atmosphere of 21.1 parts of 2- [p- (3,4-dichlorophenoxy) -phenyl] -2- (1H-1,2,4-triazolylmethyl) -4-hydroxy-methylmethyl-1,3-dioxolane are dissolved in 200 ml. ml of nitrogen at room temperature is added dropwise to 1.5 parts of a 55% dispersion of sodium hydride in 100 ml of dimethylacetamide and the reaction mixture is heated at 90 DEG C. for 2 hours. 2 parts of methyl bromide in 50 ml of dimethylacetamide are added, the reaction mixture is heated at 100 DEG C. for 2 hours, cooled to room temperature, diluted with 1400 ml of ice-water, extracted three times with 50 ml of ethyl acetate each time and dried. The residue was purified by column chromatography on silica gel using a mixture of acetone and ethyl acetate in ethyl acetate. 1: 1 as eluent After evaporation of the solvent mixtures, the mixture of diastereomers is crystallized by treatment with ligroline (b.p. 60-90 ° C). Yellowish crystals of m.p. 101-103 ° C are obtained.

Example 2c

Preparation of 2- [p- (4-chloro-3-methylphenoxy) phenyl] -2- (1H-1,2,4-triazolylmethyl) -4-methoxymethyl-1,3-dioxolane-chloro- ₃ ^{: H2} \ J ^CH 3

Dissolve 24.1 parts of 2- [p- (4-chloro-3-methylphenoxy) phenyl] -2- (1H-1,2,4-triazolylmethyl) -4-hydroxymethyl-1,3-dioxolane in 200 ml of diethylglycol dimethyl ether and 12.5 parts of a 20% potassium hydride dispersion are added under nitrogen atmosphere introduced into the reaction solution with stirring, and the mixture is heated at 60 DEG C. for 1 hour, after cooling to room temperature, 3.5 parts are added dropwise with stirring over 10 minutes. The reaction mixture is then heated at 130 DEG C. for 4 hours and, after cooling to room temperature, poured onto 1200 ml of ice-water and extracted three times with 50 ml of ethyl acetate each time. It is then dried over sodium sulphate, filtered and the solvent is evaporated and the residue is purified by column chromatography on silica gel (acetone / ethyl acetate 1: 1). a solvent mixture of diastereomers was induced to crystallize by addition of hexane. Yellow-brownish crystals of m.p. 88 DEG-93 DEG C. are obtained.

The following reaction products of the formula I can also be prepared in an analogous manner (unless otherwise stated, mixtures of diastereomers with different ratios j are obtained):

In the tables below, A is a diastereomer A and B is a type B diastereomer.

Table 1

Compounds of formula

fyo (XXl)

(including isomeric forms): Y salt physical data merge- nina number Rio 1.24 ^{CH2- 0CI 't} 2 ^^ ~ Cl N - viscous oil; n _D ²⁶ = 1.5865 A 1.25 CH 2 OCH 2 - Cl N - mp 83-85 ° C B 1.26 N - mp 107-109 ° C A 1.27 ch ₂ o-^ J ^ -ch ₃ N - mp 90-94 ° C B 1.29 CH ₂ OCH ₃ CH _ 1.31 CH2OC2H5 N - 1.32 CH ₂ OCH ₃ N - 1.33 CH2OCH2CH2OCH3 N -

cú + - »ca Ό \ i— (t

Ř — l 'ti &

»Tí w

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Table 4

(including its isomeric forms):

Rh Rj ₂ nina no. r ₁₇ ^R 18 Y salt physical data 5.71. H ₂ CH ₂ OCH ₃ 2-CH3 H CH - resin 5.75 H CH ₂ OCH ₃ 2-CH3 H N - oil, n _D ⁵⁰ 1.5482 5.82 H CH ₂ OCH ₃ 2-C1 H CH - 5.83. H ₂ CH ₂ OCH ₃ 2-C1 H N - 5.85 H CH ₂ OCH ₃ 2-Br H CH - 5.87 H CH2 OCH3 2-Br H N - 5.96 H CH ₂ OCH ₃ 3-CH3 H N - H, CH9OCH3 2-N H CH - 5.99 H CH2 OCH3 2-NO ₂ H N - 5.101 H CH 9 OCH 3 3-CH3 H CH - Examples of fungicidal compositions which contain liquid active ingredients of formula I (% - ° / o weight): 3. Emulsion concentrate and) (b) C) the active substance of Tables 1 to 4 25% 40 'θ / ο 50% calcium salt of dodecylbenzene- sulfonic acids 5% 8 '% 6% polyethylene glycol ether ricino- (36 moles of ethylene- oxide j 5 θ / ο - - tributylphenoylpolyethylene- -glycol ether (30 moles of ethyl- lenoxide) - .12% 5 ° / o · cyclohexanone - 15% 20% mixture of xylenes 65% 25 θ / ο 20% Of such concentrates, can by dilution with water to prepare emulsions every required concentration. 4. Solutions and) (b) C) (d) the active substance of Tables 1 to 4 80% 10% 5% 95 '% ethylene monomethylether glycol 20 θ / ο - - - polyethylene glycol (molecular weight 400) - 70% - - N-methyl-2-pyrrolidone - 20 '% - - epoxidized coconut oil - - 1% 5% '

petrol (boiling point 160 degrees Celsius)

-190%

22nd

These solutions are suitable for application in the form of minimal drops.

5. Granulate

aj (b) the active substance of Tables 1 to 4 5% 10% kaolin 94% - high-disperse silicic acid 1% attapulgit - 90%

The active substance is dissolved in methylene chloride, sprayed onto the carrier and dissolved in the solvent.

the dough is then evaporated in vacuo. 6. Dust and) (b) the active substance of Tables 1 to 4 2% 5% high disperse silicic acid 1% 5% talc 97 «/ o .— kaolin - 90%

By thoroughly mixing the carrier substances with the active substance, a directly usable dust is obtained.

Examples of fungicidal compositions containing solid active ingredients of the formula I (% = ‘0 / q by weight)

7. Wettable powder

and) (b) C) the active substance of Tables 1 to 4 25% 50% 75% Ligninsulfonic acid sodium salt selins 5% 5% - sodium lauryl sulfate 3% - 5 o / o natriumdiisobutylnaftalen- sulfonate - 6 o / o 10% octylphenolpolyethylene glycol- ether (7 to 8 moles of ethylene oxide) . - 2 o / o - high dispersive acid siliceous 5% 10% 10 O / o kaolin 02% 27 o / o - The active ingredient is well mixed with others- calcium dodecylbenzenesulfonic acid with the ingredients and the mixture is well ground in acid 3 o / o suitable mill. A wettable powder is obtained. castor oil polyglycol ether check that can be diluted with water to suspension (35 moles of ethylene oxide) 5 ° / o of each desired concentration. cyclohexanone 30% a mixture of xylenes 50% 8. Emulsion concentrate From this concentrate may be diluted the active substance of Tables 1 to 4 10 ‘« / o water to prepare emulsions of each octylphenolpolyethylene glycol ether 3% concentration. (4 to 5 moles of ethylene oxide) 9. Dust. and) (b) the active substance of Tables 1 to 4 5 o / o 8% talc 95 «/ o - kaolin - 92%

241322

The active ingredient is mixed with the carrier and ground in a suitable mill. A dust is obtained which can be directly applied.

10. Granules obtained by extrusion active ingredient from Tables 1 to 4 10% sodium lignin sulphonate 2% carboxymethylcellulose 1% kaolin 87%

The active ingredient is mixed with the additives, the mixture

is ground and moistened with water. This mixture was extruded on an extruder and then dries in a stream of air. 11. Coated granulate the active substance of Tables 1 to 4 3% polyethylene glycol (molecular weight 200] 3% kaolin 94% Finely ground active substance in mission-

or evenly applied to kaolin moistened polyethylene glycol. In this way a non-dusted coated granulate is obtained. 12. Suspension concentrate the active substance of Tables 1 to 4 40% ethylene glycol nonylphenolipolyethylene glycol ether 10% (15 mol of ethylene oxide i 6% ligninsulfonic acid sodium salt 10% k-arb ox y methyl cell 1 axis 1% 37% aqueous formaldehyde solution silicone oil in the form of 75% aqueous 0.2% emulsion 0.8% water 3? %

The finely divided active ingredient is intimately mixed with the remaining ingredients. A suspension concentrate is obtained from which suspensions of each desired concentration can be prepared by dilution with water.

Examples illustrating biological activity:

In all of the examples described below which illustrate biological activity (Examples 19 to 23J), the following products A to D, which are known on the market, were also tested for comparison at the same time as the Residual Protective Effect against Puccinia Compound Infestation% Number:

A = 'Maneb' = manganese ethylene bis-dithiocarbamate

B = 'Manganozinc' - manganese-zinc ethylene bis-dithioicarb amate

C - 'Fentin Acetate' = triphenylcinacetate

D "Forpet" = N-trichloromethylthiophthalimide.

Example 19

Effect against rust (Puccinia graminis) on wheat

(a) Residual protective effect

Wheat plants are sprayed 6 days after sowing with a dispersion made of a wettable powder (active ingredient concentrate), with the active ingredient concentration in the spray suspension being 0.06%, and after 24 hours, the treated plants are infected with the uredospore suspension of the fungus. 95-100% relative humidity and at a temperature of about 20 ^L C, the infected plants are placed DO- greenhouse at about 22 ° C. evaluation of the rust-development is made 12 days after infection.

b) Systemic effect

5 days after sowing, the wheat plants are covered with a suspension made of a wettable powder of the active substance (concentration 0.006% active substance based on soil volume). After 48 hours, the treated plants are infected with a uredoispor fungus suspension. After incubation for 48 hours at 95-100% relative humidity and at a temperature of about 20 ^{° C} , the infected plants are placed in a greenhouse at η · η ice of about 22 ° C. Assessment of rust development is performed 12 days after infection

The compounds of Tables 1 to 4 show good activity against Puccinia. Not treated. but flax control plants are 100% infected with Puccinia,

The results are shown in the following table:

graminis compound infestation% number

1.24 0—1 3.233 0 1.26 0—4 3.340 0—2 3.78 0—3 3.348 0—1 3.83 0—2 AND 90—95 3.176 0—3 (B) 92—97 3.177 0-4 C 90—95 3.226 0—4 D 90—93 3.227 0—3 control '100% 3.231 0

25:

Example 20

Activity against Cercospora arachidicola on groundnut plants Up to 15 cm high groundnut plants are sprayed with a spray suspension (0.02% active ingredient) which was made from a wettable powder of the active ingredient. After 48 hours, the plants are infected with a conidia suspension of the fungus. Infected plants are incubated for 72 hours at a temperature of about 21 degrees Celsius and high humidity 26.

chu and then placed. 'in the greenhouse until' lypic 'stains appear on the leaves. The assessment of the fungicidal effect is carried out for 12 days. after. infection, based on the number and size of the spots occurring.

Compared to untreated but infected control plants (number and size of spots = 100%), peanuts which have been treated with the active ingredients of Tables 1 to 4 show a significantly reduced attack by Cercospora. Individual results are shown in the following table:

Effect against Cercospora arachidicola:

compound attack% compound attack% number number 1.24 0 3.231 0 1.25 0 3.233 0 1.26 0—2 3.348 0—2 1.27 0—1 5.71 0-2 3.55 0 5.75 0. 3.78 0 AND 93—98 3.155 5—9 (B) 95—100 3.176 0 C 93—96 3.177 0—1 D 94—98 3.226 0—3 control 100 ALIGN! Example 21 pour suspension (concentration 0.006% effective (based on the volume of soil) that was Effect against powdery mildew (Erysiphe gra- made of wettable powder effective. minis) on barley substances. Doing so makes sure that the suspension did not come into contact with above-ground grate parts aj Residual protective effect tench. After 48 hours, the treated plants were treated dusted with conidia mushrooms., Infected grate- About 8 cm high barley plants Barley lines are placed in a greenhouse at temperature sprayed with a suspension (with a concentration of 0.02% 22 ° C and after 10 days the active substance], which was made of sponge. readable powder effective substances. Pd 3 to 4 The compounds of formula I show good During the hours the treated plants are dusted with coni dual protective effect against powdery mildew diemi mushrooms. Infected barley plants are Erysiphe graminis). Untreated, then placed in a greenhouse at about 22 ° C but infected control plants statement- degrees Celsius and after 10 days eating 100% grass powdery mildew. sponge. Test results are. summarized in the following- Table: bj Systemic effect: About 8 cm tall barley plants Action against powdery mildew (Erysiphe gramini: AT compound attack% compound attack% number number 1.24 0-5 3.227 0—3 1.25 0 3.231 4-5 1.26 0 3.233 3-5 1.27 0—3 3.340 10 3.55 0 3.348 10-15 3.78 0 5.71 0 3.176 5—6 5.75 0 3.177 0-3 AND 98—100 3.226 0 (B) 100 ALIGN! C 97—100 D 96—100 control 100 ALIGN!

Example 22

Residual protective effect against apple scab (Venturia inaequalisj on apple shoots)

Apple seedlings with 10-20 cm long fresh shoots are sprayed with a suspension (concentration of 0.06% active ingredient) which was made of a wettable powder against Venturia inaequalis:

compound attack number% of active substance. After 24 hours, the treated plants are infected with a fungal conidia suspension. The plants are then incubated for 5 days at 90-100% RH and placed in a greenhouse at 20-24 ° C for a further 10 days. Scab infestation is evaluated 15 days after infection. The results of the test are shown in the following table:

compound infestation% number ·

1.24 5- -8 5.75 8—11 1.26 9- -13 AND 100 ALIGN! 3.55 0 (B) 100 ALIGN! 3.176 8- -14 C 100 ALIGN! 3.177 5- -9 D 100 ALIGN!

3.233 6—11

Effect against Botrytis cinerea:

Untreated but infected shoots show 100% infestation with Venturia inaequalis.

Compound number%

Example 23

Effect against gray mold (Botrytis cinerea) on bean

Residual protective effect

About 10 cm tall bean plants are sprayed with a suspension (0.02% active ingredient, which was made from a wettable powder of the active ingredient. After 48 hours, treated plants are infected with a fungal conidia suspension. After incubating the infected plants for 3 days at 95 ° C. up to 100% relative air humidity and a fungus infestation is carried out at 21 ^DEG C. The compounds of Tables 1 to 4 suppress fungal infections very strongly in many cases.

3.55 5—10

3.226 5—7

3.231 5—10

5.71 0—5

5.75 0

Plants that have been treated with compounds A, B, C, or D, as well as untreated control plants, show 100% infection with Botrytis cinerea.

None of the comparative products A to D that are commercially available achieved a remarkable fungicidal effect at the low test concentrations used in these tests. In all tests, the infestation reached more than 90% and thus practically did not differ from untreated control plants.

Claims (4)

Subject A process for the preparation of novel arylphenyl ethers derivatives of general formula I (O OF THE INVENTION Y is —CH = or —N =, R _a and R _b are each independently hydrogen, halogen, C 1 -C 3 alkyl or methoxy, U and V are independently C 1 -C 3 alkyl or together are alkylene of formula Rd R _z H in which <7 2 4153 2 29? where R 1 represents a hydrogen atom or a C 1 -C 3 alkyl group, R ₂ represents a group of formula -CH ₂ -Z-R _7, wherein Z is oxygen or sulfur; R ₇ is C 1 -C 3 alkyl, C 3 -C 4 alkenyl, methoxyethyl, phenyl, chloro or methyl substituted phenyl, benzyl or chloro or methyl substituted benzyl, and Ar represents a group of the formula 3ft Ar, Y, R _a and R _b have the meanings given above, whereupon the optionally obtained free compound is converted by reaction with an organic or inorganic acid into an acid addition salt, the acid addition salt optionally converted by reaction with an alkali metal bicarbonate, carbonate or hydroxide optionally, the free compound, or the acid addition salt obtained, is optionally converted by reaction with a copper salt into a copper complex. 2. The process of item 1, for producing compounds of formula I wherein R _c , R _d and R _e are each independently hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 3 alkoxy, trifluoromethyl or nitro, as well as their acid addition salts and complexes with copper, characterized in that at temperatures from. 40 to 130 ° C, and preferably in a polar organic solvent that is inert under the reaction conditions to produce compounds of formula I wherein U and V together are -CH ₂ -CH (CH ₃ ZR ₇ ') - and R ₇ 'represents a radical R ₇ different from hydrogen, the compounds of the general formula VI and the general formula VII condense with each other X2-R7 (VII) wherein one of X, _X and X ₂ is an optionally present in salt form or with hydroxy meirkaptoskupinu, for example a group of formula -Z-Me and the other is a nucleophilic odštěplteiniou group X, or both X and X _b represent ₂ hydroxy groups, Me is hydrogen or a metal cation and wherein Y is -CH 3 or -N-, R _a and R _b are each independently hydrogen, halogen, C 1 -C 3 alkyl or methoxy, U and V are independently C 1 -C 3 alkyl or together are alkylene of the formula wherein: R 1 represents a hydrogen atom or a C 1 -C 3 alkyl group, R ₂ represents a group of formula - CH ₂ -Z-R _7, wherein Z represents oxygen or sulfur and R ₇ is an alkyl group having 1-3 carbon atoms, alkenyl having 3 to 4 carbon atoms, methoxyethyloyou, phenyl, chlorine or methyl-substituted phenyl, benzyl, or chloro- or methyl-substituted benzyl group and Ar represents a group of the formula wherein R _c , R _d and R _e are each independently hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 3 alkoxy, trifluoromethyl or nitro, as well as their acid addition salts and complexes with Copper, characterized in that at temperatures from 40 to 130 ° C and preferably in a polar organic solvent which is inert under the reaction conditions, to produce compounds of the formula I in which U and V together represent a group of the formula -CH ₂ —CH (CH 2 ZR ₇ *) - and R ₇ 'represents a radical R _{7 other} than hydrogen, the compounds of the general formula VI and the general formula VII condense with each other and X 2 -R 7 (VII) wherein one of X ₁ and X ₂ is optionally a hydroxyl group or a mercapto group present in the form of a salt, for example a group of formula -Z-Me, and the other is a nucleophilic leaving group X, or X ₁ , thus X ₂ represents hydroxyl groups, and Me represents a hydrogen atom or a metal cation and Ar, R _a , R _b and R ₇ and Y are as defined above, whereupon any compound obtained is converted into an acid addition salt or a copper complex. Process according to either of Claims 1 or * 2, characterized in that the corresponding compounds of the general formulas (VI) and (VII) are used as starting materials to give compounds of the general formula (I) in which: Y is - CH or --N =, R _a and R e are each independently hydrogen, halogen or C 1 -C 3 alkyl, Ar represents a group of the formula wherein R _c , R j and R _e are each independently hydrogen, halogen or C 1 -C 3 alkyl; and U and V have the meaning given in point 1 or 2. Process according to either of Claims 1 and 2, characterized in that the corresponding compounds of the general formulas (VI) and (VII) are used as starting materials to give 2-β- (3 ', 4'-dichlorophenoxyphenyl) -2 - [1- (1H-1,2,4-triazolyl) methyl] -4-methoxymethyl-1,3-dioxolane.