DK157866B - 1-ARYLOXYPHENYL-2-AZOLYL-ETHANONE DERIVATIVES OR ACID ADDITIONAL SALTS OR COMPLEXS WITH INORGANIC OR ORGANIC METAL SALTS THEREOF AND A PROCEDURE TO COMPLETE OR MAKE A RESISTANCE OR PROCEDURES - Google Patents

Description

in

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The present invention relates to novel 1-aryloxy-phenyl-2-azolyl-ethanone derivatives of formula I or their acid addition salts or complexes with inorganic or organic metal salts as well as a process for controlling or protecting culture plants from attack by phytopathogenic microorganisms.

From US Patent No. 3,575,999, No. 3,936,470, No.

No. 4,160,838; antimicrobial action.

It has been found that the compounds of the invention have a surprisingly good effect in low concentrations of use against phytopathogenic microorganisms compared to the known compounds, as will be further illustrated below.

The 1-aryloxyphenyl-2-azolyl-ethanone derivatives of the invention are characterized in that they have the general formula U.

/ \

R O V

| a I I

Ar-O- -CO (I) * b cv "Q" wherein Y means -CH = or -N =, R ' means hydrogen, halogen, C1-6 alkyl, C3-3 alkoxy or nitro,

Ar means unsubstituted or with halogen, C1-7 alkyl, C1-7 alkoxy, nitro and / or CF3 mono- to trisubstituted phenyl or naphthyl, U and v each independently means with halogen or C1-6 alkoxy monosubstituted C1- 2 'alkyl or 25 together form an alkylene bridge of the formula

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2 wherein and individually hydrogen, C 1-6 alkyl, is substituted one to three times with halogen substituted C 1-6 alkyl, phenyl, one to three times with halogen and / or C 1-6 alkyl substituted phenyl or the group -CH 2 -Z-R 7 where Z represents oxygen or sulfur and R 7 represents hydrogen, C 1-6 alkyl, with C 1-6 alkoxy monosubstituted C 1-6 alkyl, C 1-4 alkenyl, 2-propynyl, 3 -halo-2-propynyl, phenyl, with halogen, C1-6 alkyl, C1-6 alkoxy, nitro and / or CF3 a phenyl, benzyl substituted three times, or with halogen, C1-6 alkyl and / or C Cgg alkoxy substituted by three to three times benzyl, R,, and R ^ each represent hydrogen or C ^4 alkyl alkyl, however, R R, R ^ and Rg together contain not more than 6 C atoms and R R is hydrogen or C1-3 alkyl, or is acid addition salts or complexes with inorganic or organic metal salts thereof.

The method of the invention for the control or protection of culture plants against attack by five topogenic microorganisms is characterized by applying a compound of formula I or its acid addition salts or metal complexes to the plant 20 or its growing site.

The substituent Ar has as optionally substituted phenyl or naphthyl the formula vix R "<r ~>

v> - or Rj— X. - S

Wherein R_, Rj and R are each independently hydrogen, halogen, C Q 6 C C _7 alkyl, C ^ _7 alkoxy, nitro or CF ^.

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3

By alkyl as such or as a constituent of another substituent, the following groups, for example, are understood to mean, for example, the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl and the isomers thereof, e.g. isopropyl, isobutyl, tert-butyl, sec-butyl, isopentyl, etc. For example, alkenyl means propenyl (1), allyl, butenyl (1), butenyl (2) or butenyl (3). Halogen means here and hereinafter fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.

The invention relates to both the free compounds of formula I and their acid addition salts with inorganic and organic acids as well as their complexes with metal salts.

The salts in question are, in particular, addition salts, depending on the purpose of use, physiologically harmless inorganic or organic acids.

When used as plant protection microbicides, physiologically harmless inorganic and organic acids are, for example, hydrogen halide acids, e.g. hydrochloric acid, hydrogen bromic acid or hydrogen iodide acid, sulfuric acid, phosphoric acid, phosphoric acid, nitric acid, optionally halogenated fatty acids such as acetic acid, trichloroacetic acid and oxalic acid, sulfonic acids such as benzenesulfonic acid and methanesulfonic acid.

Metal complexes of formula I consist of the organic basic molecule and an inorganic or organic metal salt, e.g. halides, nitrates, sulphates, phosphates, tartrates, etc. of copper, manganese, iron, zinc and other metals. The metal cations may be present in the different possible valences for that metal.

The compounds of formula I are at room temperature stable oils, resins or solids which are distinguished by extremely valuable physiological such as microbicides, e.g. plant fungicide, properties. The connections can therefore 4

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used in the agricultural sector and related fields to control phytopathogenic microorganisms.

An important group of the compounds of the invention for use in the field of plant protection are those wherein Y, R &lt; 1 &gt; have the above meanings, Ar * means the group of the formula "wherein R, R, and R , halogen, C ^-C ^ alkyl, C ^-C ^ alkoxy, nitro or CFg, U and V each represent C ^-C ^₂ alkyl or together form an alkylene bridge of the formula * · K, s ~ ^ where R ^, R2 ^ R ^, R ^ r Rg and Rg have the above meanings as well as their acid addition salts and metal complexes.

15 This subgroup is referred to here and hereafter as group 1a.

A preferred group of compounds of the invention which j.

are useful for use in the plant protection field, are in compounds of formula I wherein Y, Ra and R 2 have the above-mentioned meanings, Ar means the group j R

Rd ic e! in

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wherein R 1, R 1 and R 1 each represent hydrogen, halogen, C 1 -C 6 CFg or C 1 -C 4 alkyl, and U and V have the meanings given above, as well as salts and metal complexes thereof. compounds. This group is referred to as Ib.

Among the compounds of subgroup Ib, as microbicides are preferred those compounds of formula I wherein U and V each represent C 1 -C 3 alkyl or together form an alkylene bridge of formula · · ··· 10 wherein r 1, R 2, R 9, R 4 and R 5, respectively, represent hydrogen or C 1 -C 4 alkyl, where R 9, R 2 and R 2. together contain no more than 6 carbon atoms. This group is called Ic.

Another preferred group of microbicidal compounds which may be advantageously used in the plant protection field are 15 compounds of formula I wherein Y means -CH = or -N =, Ar has the meaning given under formula I, Ra, R 2, R, R and R 5 each represents hydrogen, chlorine, bromine, fluorine, methyl, methoxy or nitro, and U and V each represent C 1-3 alkyl or together form one of the alkylene bridges listed in Formula I wherein R 1, R 2, R 1, R 2, R 1, and R 2 each represent hydrogen or C 1-3 alkyl, or -CH 2 -OR 3, where R 1 2 ”alkoxy substituted C2-4 alkyl, C3-4 alkenyl or phenyl. This group is called Id.

Among the compounds of subgroup Id, especially those in which U and V together form an unsubstituted or monosubstituted ethylene or propylene bridge are particularly preferred. This group is called le.

Examples of particularly preferred compounds for use in the field of plant protection may be mentioned, for example:

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2- [p- (Phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methyl-1,3-dioxane, 2- [p- (phenoxy) ) -phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxane, 2- [p- (phenoxy) -phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methyl-1,3-dioxane and * 2- [p- (phenoxy) phenyl] -2- [1- (1H-1) , 2,4-triazolyl) methyl] -4-ethyl-l, 3-dioxane.

Another group of advantageous compounds of formula I 10 are those in which Y means -CH = or -N =, Ra and each means hydrogen, halogen or C 1-6 alkyl, Ar means the group R ",

C

Rj ") G>

D »I

e wherein R R, R,, and R 'each independently mean hydrogen, halogen, CF,, C ^-Cg alkyl or C ^-C ^ alkoxy, and D and V have the meanings set forth in Formula I. This group is called If.

Of the compounds of Group If, because of their pronounced effect, compounds of formula I, 20 wherein U and V are each independently preferred are C 1-6 alkyl, optionally with halogen or C 1-6 alkoxy monosubstituted C 2-4 alkyl or together form an alkylene bridge of formula V? Wherein R 1, R 2, R 3, R 4 and R 5 each represent hydrogen or C 1 -C 4 alkyl, wherein R 3, R 4 and R 5 together contain no more than 6 carbon atoms. This group is designated Ig.

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7

Of the compounds of subgroup If, because of their particularly pronounced microbicidal activity, those compounds of formula I in which U and V together form an alkylene group of formula CH2OR} 5 / - where R} represents C C 1 -C 4 alkoxy substituted C 2 -C 4 alkyl, C 3 -C 4 alkenyl or 2-propynyl. This group is called Ih.

Another very interesting group of active compounds 10 of formula I are those wherein Y means -CH =, R &lt; 2 &gt; and R &lt; 2 &gt; individually means hydrogen, methyl, chlorine or bromine,

Ar means

'Yt> - · ““ I: SL

R

e wherein R c, R 2 and R 2 each represent hydrogen, fluorine,

15 chlorine, bromine, methyl, methoxy, GF 2 or nitro, U and V

each optionally means with C 1 -C 2 alkoxy or chloro substituted C 1 -C 2 alkyl or together form one of the alkylene groups listed in Formula I, wherein R 2, R 2, R 3, R 4, R 5 and R is hydrogen or C 1 -C 3 alkyl, or R 2 represents -CH 2 OR, where R 1 is C 1 -C 8 alkyl, with C 1 -C 4 alkoxy substituted C 2 -C 3 alkyl or C 3 -C 4 alkenyl .

This group is denoted li.

Examples of particularly preferred compounds of subgroup If can be mentioned:

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2- [p- (Phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methyl-5-methyl-1,3-dioxolane, 2- [ p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -1,3-dioxane, 2- [p- (phenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane, v 2- [p- (2,4-dimethylphenoxy) -phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane , 2- [p- (3-chlorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane, 2- [p- (4-chlorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane, 2- [p- (3-trifluoromethylphenoxy) -phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane, 2 - [p- (4-chloro-3-methylphenoxy) -phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane, 2- [p- (3,4-dichlorophenoxy) -phenyl ] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane, 2- [p- (2,5-dichlorophenoxy) phenyl] -2- (1-imidazolylmethyl) -20 4-ethyl-1 , 3-dioxolane, 2- [p- (3,4-dichlorophenoxy) -phenyl] -2- (1-imidazolylmethyl) -4-methoxymethyl-1,3-dioxolane, 2- [p- (4-fluorophenoxy) - phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane, 2- [p- (4-fluorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-methyl-5-methyl-1,3-dioxolane. and their acid addition salts.

Another preferred subgroup Ij is constituted by the compounds of formula i wherein Y means -CH = or -N =, R & 30 and each independently means hydrogen, halogen or alkyl and wherein Ar means unsubstituted or with C 1 -C 2 alkyl , C 1 -C 4 alkoxy, CF 2 or halogen substituted phenyl, and U and V have the meanings set forth in Formula I.

Among the compounds of subgroup Ij, particular mention should be made of compounds of formula I wherein Y means -CH = or -N =,

Ra * b where to go? means hydrogen, methyl, chlorine or

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9 is bromine, and wherein Ar is unsubstituted or with halogen, methyl or CF 2 substituted phenyl, and U and V each represent C 1 -C 8 alkyl, optionally with halogen or C 1 -C 4 alkoxy substituted C 2 -C 3 alkyl or together form an alkylene bridge of formula v * - wherein R 1, R 2, R 3 F R 2 and R 1 J. each represents hydrogen or C 1-4 alkyl, with R 3, R 4 and R 2 taken together containing at most 4 carbon atoms. This group is called Ik.

A further preferred group of compounds of formula I are those wherein Y is -CH = or -N =, R and R, ab are hydrogen, Ar is unsubstituted or with halogen, methyl substituted phenyl, and U and V together form a group with the formula

frost

y ^ or Λ wherein R ”represents C ^-C ^ alkyl such as methyl or ethyl, or hydroxymethyl or methoxymethyl or ethoxymethyl. This group is called II.

Among the compounds of subgroup Ij, the following are particularly preferred: 2- [p- (phenoxy) -phenyl] -2- [1- (1H-1,2,4-triazole) -methyl] -1,3-dioxane, 2- [p- (4-chlorophenoxy) -phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane, 2- [p- (4-chloro-2-methyl-phenoxy) -phenyl] - 2- (1-imidazolyl

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Methyl) -4-methoxymethyl-1,3-dioxolane, 2- [p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-hydroxymethyl 1,3-dioxolane, 2- [p- (4-fluorophenoxy) -phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane, 2- [p- (4-fluorophenoxy) - phenyl] -2- (1-imidazolylmethyl) -4-hydroxymethyl-1,3-dioxolane, 2- [p- (4-fluorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) ) -methyl] -1,3-dioxane 10 and their acid addition salts.

The compounds of formula I can be prepared by a) condensing a compound of formula

^ = N Me-N I

NY = J (ii) wherein Me means hydrogen or a metal cation, with a compound of the formula

Raw

Ar-O- v> - CHO-X (III) \

¾ o ---- V

wherein X represents a nucleofuge cleavage group, or b) in a compound of the formula

R

a

, - v ^ = N

Ar-O - <^ VS.-C-CH -N (IV)> 2> r = 1 "b transfers the carbonyl group into a group of the formula

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11

NRX

/ \ (v>??

U ---- V

or c) for the preparation of compounds of formula I wherein U and V together form a group of formula -CH 2 -CH (CH 2 ZR 2) 5 and represents a hydrogen-different group R 7, condensing compounds of formula

R

, a

/ = N

Ar-O-A —CH2-Nn I (VI) and X2-R? (VII) C \ Y = 1 ftb CH2-CH-CH2-X1 wherein one of the groups X1 and X2 optionally represents hydroxy or mercapto, e.g. of the formula -Z-Me and the other means a nucleophilic cleavage group X, or both X 1 and X 2 represent hydroxy groups, or d) condenses compounds of the formula | a ατ-χ3 (VIII) and V <f77> ^ c <-cV <J (ιχ) oo "bi-4 15 wherein one of the groups X ^ and X ^ represents a group -O-Me, where Me means hydrogen or preferably a metal cation and the other means one with aryloxy interchangeable group, or, e) intramolecularly decarboxylates a compound of the formula

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12

R

a

Ar-O-C-O- Λ ^ _C _CH0-N / (X) I \ 2 Νϊ = '

0 I I

Rk --- V

and, if desired, converting a prepared compound into another compound of formula I and / or converting a manufactured free compound into an acid addition salt, a prepared acid addition salt to the free compound or another acid addition salt, or converting a manufactured free compound or a prepared acid addition salt to a metal complex.

Metal cations Me are, for example, alkali metal cations, e.g. lithium, sodium or potassium cations, or alkaline earth metal cations, e.g. magnesium, calcium, strontium or barium cations.

Nucleofuge cleavage groups are, for example, reactive esterified hydroxy groups, e.g. hydroxy groups esterified with a hydrogen halide acid, e.g. with hydrogen fluoride, hydrogen chloride, hydrogen bromide or hydrogen iodide acid, or a lower alkanoic, optionally substituted benzene or halogen sulfonic acid, e.g. with methane, ethane, benzene, p-toluene or fluorosulfonic acid.

The reaction of an azole of the formula

Me-N I (II)

\ Y = I

wherein Y means -CH = or -N =, and Me preferably means a metal atom, especially an alkali metal atom, having a compound of the formula

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13 R I a

Ar-O-S? V-C-CH0 ~ X (III) \ _L /? \ 2 ^ = f- ^ o o

i I I

Rb U --- V

wherein Ar, R &, R4, D and V have the meanings set forth in Formula I and X represents, for example, halogen, especially chlorine, bromine or iodine, or benzenesulfonyloxy, p-tosyloxy, trifluoroacetyloxy or preferably lower alkylsulfonyloxy such as f. eg. mesyloxy, is preferably carried out in a relatively polar, though reaction-inert, organic solvent, e.g. Ν, Ν-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, acetonitrile, benzonitrile and others. Such solvents can be used in combination with other reaction inert solvents such as aliphatic or aromatic hydrocarbons, e.g. benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene, nitrobenzene and others.

When X means chlorine or bromine, alkaline metal iodide such as sodium iodide or potassium iodide may conveniently be added to promote the reaction. Advantageously, temperatures of 0-220 ° C, preferably 80-170 ° C, are used. The reaction mixture is conveniently heated at reflux.

In the cases where Me in formula II means hydrogen, the process is carried out in the presence of a base. Examples of such bases include inorganic bases such as oxides, hydroxides, hydrides, carbonates and hydrogen carbonates of alkali metals and alkaline earth metals as well as e.g.

25 tertiary amines such as triethylamine, triethylenediamine, piperidine, pyridine, 4-dimethylaminopyridine and 4-pyrrolidylpyridine.

In this and the following processes, the intermediates and final products can be isolated from the reaction medium and, if desired, purified using one of the usual

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14 methods, e.g. extraction, crystallization, chromatography and distillation.

The conversion of the carbonyl group into compounds of formula IV into the group of formula V is carried out by reacting with an orthocarboxylic acid tri-C 1 -C 4 alkyl ester whose C 1 -C 2 alkyl groups are optionally substituted by halogen or C C1-4 alkoxy, or in the presence of an acid having at least two 100 moles of a monovalent alcohol of formula U-OH (Va) to give compounds of formula I wherein O and V are identical, optionally substituted C ^-C ^ alkyl groups, or by reaction with diol of formula HO-UV-OH (Vb) to give compounds of formula I wherein U and V together represent one of the alkylene bridges defined above. Ar, Y, R &, R 2, U and V have the meanings given under the formula I.

This ketalization reaction can be carried out analogously to known ketalization reactions, e.g. analogous to the preparation of 2-bromomethyl-2,4-diphenyl-1,3-dioxolane 20 [Synthesis, 1974 (I), 23].

In the preferred embodiment of the ketalization, the two reactants are refluxed for several hours together with azeotropes in one of the usual organic solvents. As an azeotroping agent, for example, benzene, toluene, xylene, chloroform or carbon tetrachloride may be used, as it may be advantageous to add a strong acid, e.g. p-toluenesulfonic acid, to promote the reaction. Ordinary organic solvents are in this case e.g. aromatic hydrocarbons, e.g.

30 benzene, toluene, xylene, etc., saturated hydrocarbons such as n-hexane, or saturated halogenated hydrocarbons, e.g. 1,1,1-trichloroethane.

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15

The catalysis may also be carried out by other means, e.g. reacting a ketone IV which is ketalized with one of the alcohols or diols of the formula Va or Vb different alcohol or diol, and recalibrating it by reaction with excess of the alkanol Va or diol Vb to (I).

The starting product may be prepared, for example, according to one of processes a), b) and e).

The preparation of process c) of compounds of formula I wherein the substituents U and V together bond) -CH 2 -CH (CH 2 ZR 2) - is carried out, for example, by reacting a compound of formula VI with a compound of formula VII, wherein represents a group -ZH, and means a group X. The reaction is preferably carried out in organic solvents which are inert to the reaction. Suitable solvents are, for example, N, N-dimethylformamide, Ν, Ν-dimethylacetamide, hexamethylphosphoric triamide, dimethylsulfoxide, 4-methyl-3-pentanone, etc. Mixtures with other solvents which are inert in the reaction may also be used. eg. with aromatic hydrocarbons such as benzene, toluene, xylene, etc. In many cases it may be advantageous to work in the presence of a base to increase the reaction rate. As bases, for example, alkali metal hydrides or alkali metal carbonates may be used. In some cases, it may also be advantageous to first convert compound VI in a known manner to a suitable metal salt.

This is preferably accomplished by reacting VI with a sodium compound, e.g. sodium hydride, sodium hydroxide, etc. Then this salt of VI is reacted with the compound of formula VII. In order to increase the reaction rate, in many cases it is also possible to operate at elevated temperature, e.g. 80-130 ° C, or at the boiling point of the solvent.

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Analogously, compounds of formulas VI and VII can also be reacted wherein X 1 is a group X and is a group -ZH.

In the condensation reaction to form compounds 5 of formula I wherein Z represents oxygen, of compounds of formulas VI and VII wherein X and X 2 are hydroxy, the reactants can be heated under reflux in a suitable solvent, whereby the resulting water can be simultaneously distilled off apoptropically from the reaction mixture. As 10 solvents may be used aromatic hydrocarbons such as toluene or the alcohol HO-R 2 itself. The reaction is conveniently carried out in the presence of a strong acid, e.g. p-toluenesulfonic acid.

In the practice of process d) 15 is preferably based on compounds of formulas VIII and IX, wherein X3 represents a group -OMe and X1 represents a nucleofuge cleavage group and / or vice versa X4 means the nucleofuge cleavage group and X ^ means the group -OMe. R 1, R 2, U, V, Y and Ar have the meanings given under the formula I and Me 20 preferably represents hydrogen. The reaction is advantageously carried out using the conditions described in process a).

In process e), the compound of formula X which is to be decarboxylated and which can be prepared by catalysing a compound of formula XI is heated in the same manner as described in b),

Ra o / - —II / ^

Ar-O-C-O - <^ N ^ -C-CH 2 -N ^ J (XI)

Rb which can again be obtained by reaction with a compound of formula Ar-OH (XII) with a difunctional carbonic acid derivative, e.g.

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17 with phosgene, a halo formic acid low alkyl ester or a di-lavallyl or diphenyl carbonate, and further reacting with a compound of the formula \ "H" + "C" CH2 "N \ Y = I (xiii)" b The heating may be carried out in dry state or in a high boiling solvent such as a high boiling ether, e.g. diphenyl ether or ethylene glycol dimethyl ether, to approx. 120-220 ° C.

The compounds prepared can be converted in known manner to other compounds of formula I.

Thus, for example, one may recketalize prepared compounds for other compounds of formula I. In compounds of formula I wherein U and V mean the same, optionally substituted C 1 -C 4 alkyl groups U, for example, by reacting with 1 mole of another , optionally substituted C 1 -C 4 alkanol of formula v-OH (Vc), substituting a group U with a group V or by reaction with a diol of formula Vb, both groups U are replaced by a divalent group. The ketalization is carried out in the usual manner, e.g. in the presence of an acidic condensing agent such as a mineral acid, a sulfonic acid or a strong carboxylic acid, e.g. hydrochloric acid, hydrogen bromic acid, sulfuric acid, p-toluenesulfonic acid or trifluoroacetic acid, advantageously during distillative or azeotropic distillative removal of easily volatile reaction products.

Further, in the two aryl portions of the compounds prepared, additional substituents, e.g. in the group Ar or groups Ra or the phenylene group can be introduced.

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Thus, halogen can be introduced e.g. by reaction with a halogen in the presence of a Lewis acid, such as an iron, zinc, boron or antimony halide, or by treatment with N-chlorosuccinimide.

Furthermore, nitro groups can be reduced, e.g. by suitable complex hydrides, such as with lithium aluminum hydride, for amines which are diazotized e.g. with nitric acid, upon which the diazonium groups formed can be exchanged in the usual manner with halogen or alkoxy. Furthermore, halogen can be exchanged with alkyl by reaction with an alkyl metal compound, e.g. with an alkyl lithium or alkyl magnesium halide.

When the compounds of formula I are formed in the form of bases, these can be converted to the corresponding salts with inorganic or organic acids or to metal complexes using preferably equimolar amounts of metal salts.

Conversely, salts of the compounds of formula I can be converted to the free bases of formula I e.g. by reaction with alkali metal hydrogen carbonate or alkali metal hydroxide.

The starting ketones of formula III can be prepared from methyl aryl ketones of formula Ia

Ar-Q - <^ I ^ -CO-CH3 (XXV) ¾ by reaction with the desired alcohol or diol in an inert solvent, e.g. a halogenated hydrocarbon such as methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, etc., and simultaneous or subsequent halogenation. To accelerate the reaction, p-toluenesulfonic acid may advantageously be added.

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19

The ketones of formula IV can be prepared by halogenating starting ketones XIV to form XV

R

[a

Ar-O - ^ ‘‘ - CO-CH₂-Hal (XV)

Rb which is reacted analogously to process a) with a 5 azole of formula II. In this case, halogen preferably means chlorine or bromine.

Ketals III, VI, IX and X are prepared analogously to process b) by reacting the starting ketone with a suitable alcohol or diol.

The starting compounds of formulas III, IV, VI, X and XI, developed specifically for the preparation of the compounds of formula I, are novel compounds.

In all of the described ketization reactions for a ketone 15 with a substituted α, β or α, γ-diol, predominantly mixtures of diastereomers of the formed ketal are formed. Similarly, from the starting ketones, diastereomeric mixtures of the final products are usually formed from the compounds of formula I, for example, in the following two diastereomeric forms:

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20

Ar-0 R .. Ar-0 _

MVCI

Rb O '' 'N0 R, Oy S0 I_I. I i / "-H" · «

# R

CH2ZR7 3 (XVI) (XVII)

The type A configuration is referred to herein as "trans" isomers.

Ar-0 π „Ar-0 R

V / R / = N \ / a>. = N

<> ~ y / <.i -> - y / A = <^ CH2> CIi2

"" A B t A

Lit in CH2ZR7 R3 (XVIII) (XIX) 5 The symbols in the spatial structures have the following meanings: ..... = behind the plane of the paper = in the plane of the paper ► = in front of the plane of the paper.

The type B configuration is similarly referred to as the "cis" isomer. The separation of the two diastereomers can be carried out, for example, by fractional crystallization or by chromatography, such as thin layer chromatography, thick layer chromatography, column chromatography, liquid high pressure chromatography, etc.

The two isomers have different biological effects. For practical purposes, the diastereomer mixtures are usually used.

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21

The invention encompasses all isomeric compounds of formula I, as well as their salts and metal complexes.

Some of the starting compounds and intermediates used by processes a, b, c, d and e are known compounds and others can be prepared in a manner known per se. Some are new and their preparation is described here.

Compounds of formula I exhibit, for practical purposes, a particularly favorable microbicide spectrum against phytopathogenic fungi and bacteria. Thus, they have highly beneficial curative, preventive and systemic herbal therapeutic properties and can be used to protect cultural plants. Microorganisms on plants or plant parts (fruits, flowers, foliage, stems, tubers, roots) in various utility cultures can be completely or partially eradicated with the active compounds of formula I, since later grown plant parts are also protected against these microorganisms.

Effective compounds are particularly effective against phytopathogenic fungi belonging to the following groups: Ascomyceter 20 (e.g. Venturia, Podosphaera, Erysiphe, Monilinia and Un-cinula), Basidiomyceter (e.g. the genus Hemileia,

Rhizoctonia and Puccinia), Fungi imperfecti (e.g. Botrytis, Helminthosporium, Fusarium, Septoria, Cercospora and Alter-nafia). In addition, the action of the compounds in question is systemic. They can also be used as a pesticide car propagating material for sowing (fruits, tubers, grains) and plant cuttings for protection against fungal infections as well as against phytopathogenic fungi occurring in the soil. The active compounds in question are distinguished by their excellent tolerance to the plants.

Thus, the compounds of the invention can be used in microbicidal agents to control phytopathogenic microorganisms, especially plant-damaging fungi, or for preventive protection against microorganism attacks on plants.

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For example, as target cultures for the indicated ranges indicated herein, the following plant species apply: Cereals, such as wheat, barley, rye, oats, rice, sorghum and related cereals, beets such as sugar beet and fodder beets, kernel, stone and berries such as apple, pear, plum, the research, almond, cherry, strawberry, raspberry and blackberry, legumes such as beans, lentils, peas and soy, oilseed crops such as canola, mustard, poppy, olive, sunflower, coconut , castor, cocoa and peanuts, cucumber plants such as pumpkin, cucumbers and melons, fiber plants such as cotton, flax, hemp and jute, citrus fruits such as oranges, lemons, grapefruit and mandarins, vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes and peppers, laurel plants such as avocado, cinnamon and camphor, or plants such as corn, tobacco, nuts, coffee, sugar cane, tea, grapes, hops, banana and natural rubber plants and ornamental plants (cow mpositer).

Active compounds of formula I are usually used in the agricultural sector in the form of preparations and may be applied simultaneously or before or after on surfaces, plants or plant parts to be treated, together with other active compounds. These other active compounds may be, by plant protection agents, fertilizers, agents containing trace elements or other preparations for influencing plant growth. It may also be selective herbicides, insecticides, fungicides, bactericides, nematodicides, molluscicides or mixtures of several of these compositions, together with any other carriers, surfactants or other application-promoting additives commonly used in the formulation technique.

In all the compositions, suitable carriers and additives may be solid or liquid and correspond to the nontoxic substances useful in the formulation technique concerned, such as e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, adhesives, thickeners or binders.

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An agricultural preferred method of applying an effective compound of formula I or an agrochemical to an infested plant is application to the foliage (leaf application). The number of applications and the amount used depend on the severity of the infestation of the disease causing (fungal variety). However, the active compounds of formula I can also penetrate into the plants via the soil through the root network (systemic effect), saturating the growing site of the plants with a liquid preparation or incorporating the substances in solid form into the soil, e.g. in the form of granules (soil application). However, the compounds of formula I may also be applied to seed (coating) by either saturating the grains with a liquid composition containing the active compound or coating with a solid composition. In addition, in special cases it is possible to make other types of application, e.g. targeted treatment of the plant stem or buds.

The compounds of formula I are used in unchanged form or preferably together with the aids commonly used in the agrochemical formulation technique and are processed in a manner known per se, e.g. for emulsion concentrates, irradiated pastes, spray-ready or dilute solutions, diluted emulsions, spray powders, soluble powders, dusting agents, granules, by encapsulation in e.g. polymeric substances. The method of application, such as spraying, misting, spraying, sprinkling, sprinkling or pouring, is selected in the same way as the nature of the agent, taking into account the desired results and the given conditions. Favorable amounts of application are usually in the range of 50 g to 5 kg of active compound per day. ha, preferably from 100 g to 2 kg of active compound per hectare. ha, especially from 200-600 g of active compound per hectare. ha.

The agrochemical preparations, viz. the agents, preparations or compositions containing the active compound.

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Formula I and optionally a solid or liquid additive are prepared in a known manner, e.g. by thoroughly mixing and / or grinding the active compounds with excipients such as e.g. solvents, 5 solid carriers and optionally surfactants.

As solvents, for example, aromatic hydrocarbons, preferably Cg-C ^₂, carbohydrates, such as e.g. xylene mixtures or substituted naphthalene, 10 phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols, and ethers and esters thereof such as ethanol, ethylene glycol, ethylene glycol monomethylhexyl, ethyl ether, ethyl ether, solvents such as N-methyl-2-pyrrolidone, dime thylsulfide oxide or dimethylformamide, and optionally epoxidized plant oils such as epoxidized coconut oil or soybean oil, or water.

As solid carriers, e.g. For dusting agents and dispersible powders, natural stone flour, such as calcite, talc, kaolin, montmorillonite or atta pulgite, are generally used. To improve the physical properties, high-dispersion silicic acid or high-dispersive absorbent polymers can also be added. Porous types can be used as granular adsorbent granular carrier, e.g. pumice, crushed bricks, sepiolite or bentonite, and as non-absorbent carriers e.g. calcite or sand. In addition, a large number of pre-granulated materials of inorganic or organic nature can be used, such as in particular dolomite or finely divided plant residues.

As surfactants, depending on the nature of the active compound of formula I to be formulated, nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties can be used. Tensides must also be understood

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2-g surfactant mixtures.

Suitable anionic surfactants may be so-called water-soluble soaps as well as water-soluble synthetic surfactants.

For example, as soaps, alkali metal / alkaline earth metal or optionally substituted ammonium salts of higher fatty acids (C cio C₂ ^ r som as e e e ^ · Na Na Na ~ Na Na K K K K K K K K K K K K K K K K K K K K K K K K K K K K K) which can be extracted from coconut oil or tallow oil, for example, and fatty acid methyl laurine salts can also be used.

However, so-called synthetic surfactants are often used, especially fatty sulfonates, fatty sulfates, sulfonated benzumidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or fatty sulfates are generally present as alkali metal, alkaline earth metal or optionally substituted ammonium salts and contain an alkyl group of 8-22 carbon atoms, the alkyl also comprising the alkyl portion of the acyl group. eg. The Na or Ca salt of lignin sulfonic acid, of dodecyl sulfuric acid ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. These include the salts of the sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2-sulfonic acid groups and a fatty acid group of 8-22 carbon atoms. Alkylarylsulfonates are e.g. The Na, Ca or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid formaldehyde condensation product.

Furthermore, similar phosphates may also be used, e.g. salts of the phosphoric acid ester of a p-nonylphenol (4-14) ethylene oxy adduct.

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As non-ionic surfactants, poly-glycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkyl phenols, which may contain 3-30 glycol ether groups and 8-20 carbon atoms in the (aliphatic) hydrocarbon group and 6-18, are used primarily. carbon atoms in the alkyl group of the alkyl phenols.

*

Other suitable nonionic surfactants are the water-soluble 20-250 ethylene glycol ether groups and 10-100 propylene glycol ether groups containing polyethylene oxide adducts with polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol having 1-10 carbon atoms in the alkyl chain. The said compounds usually contain 1-5 ethylene glycol units per liter. propylene glycol unit.

Examples of nonionic surfactants include nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxy-polyethoxyethanol, polyethylene glycol, and octylphenoxypolyethoxyethanol.

Further, fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate can be used.

The cationic surfactants are primarily quaternary ammonium salts containing as N substituents at least one alkyl group of 8-22 carbon atoms and as additional substituents containing lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl groups. The salts are preferably present as halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyldi (2-chloroethyl) ethylammonium bromide.

The surfactants commonly used in the agrochemical formulation technique are described, inter alia, in the following publications:

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27 "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.

The agrochemicals generally contain 0.1-99, in particular 0.1-95% by weight of active compound of formula I, 99.9-1%, especially 99.8-5% solid or liquid additive, including 0-25, especially 0.1-25% surfactant.

While as a commodity, concentrated agents are usually preferred, the end consumer usually uses diluted agents.

The agrochemicals may also contain other additives such as stabilizers, antifoam agents, viscosity regulators, binders, adhesives, as well as fertilizers and other active compounds to achieve particular effects.

The invention is further illustrated by the following examples. Percentages and parts are by weight.

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Preparation Examples

Example 1

Preparation of Λ CH,

PY

O, -v ° v P> = N

- (C (CH) -N) - 2- [p- (Phenoxy) -phenyl] -2- [1- (1H-1,2,4-triazolyl) -methyl] - 4-Methyl-1,3-dioxane (a) Preparation of the intermediate of the formula rV "30 0 -Λ ° v P <XX) -0- ^ ~ \ - ^ C - CH2Br 2- [p- (Phenoxy) - phenyl] -2-bromomethyl-4-methyl-1,3-dioxane 10 parts 2- [p- (phenoxy) phenyl] -2-oxo-1-bromethane and 4 parts 1,3-butanediol in 40 ml absolute The toluene is heated under reflux for 3 hours in the presence of 0.2 parts of catalytically acting p-toluenesulfonic acid, removing the formed water by means of a water separator. After cooling to room temperature, the reaction mixture is washed with twice 20 ml of water, dried over sodium sulfate. , filter, the solvent is evaporated and the crude product is recrystallized from isopropanol.

Colorless crystals are obtained with m.p. 96-106 ° C.

b) Preparation of the final product.

3.3 parts of 1,2,4-triazole sodium salt and a catalytic amount of potassium iodide are stirred in 40 ml of dimethyl sulfoxide together with 10.2 parts of the 2- [p- (phenoxy) phenyl] -2- bromomethyl-4-methyl-1,3-dioxane for 30 hours at an internal temperature of 120 ° C. After cooling to room temperature 25, 300 ml of water extracted with three times 30 ml of ethyl acetate are added, the combined extracts washed twice.

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29 ml of water, dried over sodium sulfate, filtered and the solvent evaporated. The oily residue is purified by column chromatography (silica gel / ethyl acetate). After evaporation of the eluent, the oily residue 5 crystallizes after the addition of petroleum ether. Brownish crystals are obtained with m.p. 99.5-101 ° C.

Example 2

Preparation of CH ~ OCHL s 2 3

_ _ Γ ~ ί / = N

C1 ~ νγ ~ 0 ~ / - ~ c ~ -CH2- (3.226) CH3 10 2- [p- (4-Chloro-2-methylphenoxy) phenyl] -2- (1-imidazolylmethyl) - 4-Methoxymethyl-1,3-dioxolane-16 parts 2- [p- (4-chloro-2-methylphenoxy) -phenyl] -2- (1-imidazol-yl) -4-hydroxymethyl-1,3-dioxolane are dissolved in 150 ml of N, N-dimethylformamide and 1.9 parts of 55% sodium-hydride dispersion are added under nitrogen and stirring and heated for 2 hours to 80 ° C. After cooling to room temperature, 6.3 parts of methyl iodide are added dropwise with stirring over one hour, the reaction mixture is heated for 2 hours to 60 ° C and diluted with 800 ml of ice water, then extracted with three times 300 ml of ethyl acetate.

The combined extracts are washed with twice 50 ml of water, dried over sodium sulfate, filtered and the solvent evaporated. The residue is purified by column chromatography (silica gel / acetone-ethyl acetate (1: 1)). After evaporation of the eluent mixture, the diastereomer mixture is crystallized by treatment with hexane. Beige colored crystals with m.p. 92-106 ° C.

Example 3

The preparation of

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30 CE

/ 25 | ° 2 j- (

I \ 9 / = N

CT3 + O - CH2 N2 (3.263) 2- [p- (2-Nitro-4-trifluoromethylphenoxy) -phenyl] -2- (1- "imidazolylmethyl) -4-ethyl-1,3- dioxolane 8.3 parts of 2- (p-hydroxyphenyl) -2- (1-imidazolylmethyl) -4-5 ethyl-1,3-dioxolane are dissolved in 300 ml of dimethyl sulfoxide and 1.84 parts of ground potassium hydroxide are added, raising the temperature from 23 to 36 ° C. After heating for 2 hours to 70 ° C, 7.4 parts of 4-chloro-3-nitrobenzotrifluoride are added dropwise with stirring at 70 ° C in 100 ml of dimethyl sulfoxide and stirred at 70 ° C for 3 hours. After cooling to room temperature, the reaction mixture is poured into 2000 ml of water and extracted twice with 200 ml of diethyl ether. The combined extracts are washed with twice 70 ml of water, dried over sodium sulfate and the solvent is evaporated. The oily residue is purified by column chromatography (silica gel / ethyl acetate). After evaporation of the eluent, the diastereomer mixture is obtained with m.p. 96-102 ° C.

Example 4

Preparation of CH9CH,

r Y

o-20 p-O- ^ 3 - C-CH 2 -N (^ I (3.12)

Cl 2- [p- (3-Chlorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4- ethyl-1,3-dioxolane 1.2 parts imidazole sodium salt and a catalytic amount of potassium iodide are stirred in 50 ml of dimethylformamide together with 4 parts 25 of 2- {p- (3-chlorophenoxy) phenyl] -2-bromomethyl-4-ethyl-1,3-dioxolane for 17 hours at an internal temperature of 125 ° C. After cooling, add 150 ml of water to the brown reaction mixture, then extract with three times 50 ml of ethyl acetate,

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. The combined extracts are washed with twice 50 ml of water, dried over sodium sulfate and filtered, and the solvent is evaporated. The crude crude product is chromatographed over a 35 cm silica gel column using a mixture of acetone and ethyl acetate (1: 1). After evaporation of the eluent, the oily residue crystallizes after the addition of petroleum ether. Slightly yellow crystals are obtained with m.p. 69-71 ° C.

Example 5

Preparation of CH cH

i— (2 3

00 = N

C--φ-ο-φ - c - CH₂-N ^ (3,7) 2-Iβ- (4-chlorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3 -dioxolane (a) Preparation of intermediates (a) Preparation of CHOCH_ rf ci-O'O'O'- -CH3 2- [p- (4-Chlorophenoxy) phenyl] -2-methyl-4-ethyl1-1, 3-dioxolane 37 parts of 4- (p-chlorophenoxy) -acetophenone and 18 parts of 1,2-butanediol in 400 ml of absolute toluene are heated in the presence of 2 parts of 20 catalytically active p-toluenesulfonic acid for 14 hours under reflux on a water separator. After cooling to room temperature, the reaction mixture is washed with twice 400 ml of water, dried over sodium sulfate, filtered, then the solvent is evaporated and the crude product is purified by chromatography over a 1 m silica gel column using ligroin / hexane / ethyl acetate / toluene (5: 3 : 1: 1) The product is obtained in the form of 22 a slightly yellowish oil nQ = 1.5527.

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32 β) Preparation of CH_CH_ r-rs o o

C1 - C3- CH2-Br> 2- [p- (4-Chlorophenoxy) -phenyl] -2-bromomethyl-4-ethyl-1,3-dioxolane 5 36.8 parts of the 2 - [p- (4-chlorophenoxy) phenyl] -2-methyl-4-ethyl-1,3-dioxolane is heated to boil in 350 ml of chloroform. Under illumination with a 150 watt lamp, 19.4 parts of bromine dissolved in 50 ml of chloroform are added dropwise and then heated for 2 hours under reflux. After cooling to room temperature, the reaction mixture is washed with twice 200 ml of water, dried over sodium sulfate and filtered, and the solvent is removed under water jet vacuum.

The crude product is purified by chromatography over a 1 m silica column using toluene. The product is obtained in form 23 15 of a yellow oil, ηβ = 1.5805.

b) Preparation of the final product 4.4 parts of imidazole sodium salt and a catalytic amount of potassium iodide are stirred in 80 ml of dimethylformamide together with 14.7 parts of the 2- [p- (4-chlorophenoxy) phenyl] - 2-Bromomethyl-4-ethyl-1,3-dioxolane for 17 hours at a bath temperature of 125 ° C. After cooling to room temperature, the reaction mixture is poured into 600 ml of water, then extracted with three times 200 ml of ethyl acetate, the combined organic phases are washed with twice 200 ml of water, dried over 25% sodium sulfate and filtered and the solvent is evaporated. The oily residue is chromatographed over a 50 cm silica gel column using acetone / ethyl acetate (1: 1). After evaporation of the eluent, the product is obtained in the form of a brown oil, ηβ = 1.5750.

Example 6

The preparation of

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33 CHOCHO or V_ch2-n ^ J (1.9) 2- [p- (Phenoxy) -phenyl] -2- (1H-1,2,4-triazolylmethyl) -4-ethyl-1,3-dioxolane [p- (phenoxy) -phenyl) -3-bromomethyl-4-ethyl-1,5-dioxolane, 8.4 parts of potassium carbonate, 4.2 parts of 1,2,4-triazole and a catalytic amount of sodium iodide are stirred. 100 ml of dimethyl sulfoxide for 24 hours at an internal temperature of 125 ° C. After cooling to room temperature, the reaction mixture is poured into 600 ml of water, extracted with three times 200 ml of 10 ethyl acetate and the combined extracts washed with twice 200 ml of water, dried over sodium sulfate and filtered and the solvent is evaporated. The oily residue is chromatographed over a 50 cm silica gel column using chloroform / ether (1: 1). After evaporation of the eluent, the oily residue crystallizes after the addition of petroleum ether. White crystals are obtained with m.p. 81.5 to 83.5 ° C.

Example 7

Preparation of Λ

O 0 = N

20 - ~ C - CH2 "N" * (f6 · 1) 2- [p- (Phenoxy) -phenyl] -2- (1H-1,2,4-triazolylmethyl) -1,3-dioxane - [p-phenoxyphenyl] -2-bromomethyl-1,3-dioxane, 7.2 parts potassium carbonate, 3.6 parts 1,2,4-triazole and a catalytic amount of potassium iodide are stirred in 100 ml of dimethyl sulfoxide for 20 hours. at an internal temperature of 140 ° C. After cooling to room temperature, 600 ml of water extracted with three times 200 ml of ether are added to the combined extracts

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34 is washed with twice 200 ml of water, dried over sodium sulfate and filtered and the solvent is evaporated. The oily residue is chromatographed over a 50 cm silica gel column using chloroform / ether (1: 1). After evaporation of the eluent, the residue crystallizes after the addition of petroleum ether. White crystals are obtained with m.p. 129-130 ° C.

Example 8

The preparation of

CH-OH

1- (oo 10ΟΌ - CH₂ ~N \ ^C1-23) 2- [p- (Phenoxy) -phenyl] -2- (1H-1,2,4-triazolylmethyl) -4-hydroxymethyl-1, 3-dioxolane 4.5 parts 2- [p-phenoxyphenyl] -2-bromomethyl-4-hydroxymethyl-1,3-dioxolane, 2.2 parts potassium carbonate, 1.1 parts 1,2,4-15 triazole and a catalytic the amount of potassium iodide is stirred in 50 ml of dimethyl sulfoxide for 4 hours at an internal temperature of 140 ° C. After cooling to room temperature, 600 ml of water are added, the mixture is extracted twice with 200 ml of ethyl acetate, the combined extracts washed with twice 200 ml of water, dried over sodium sulfate and filtered, and the solvent is evaporated. The oily residue is chromatographed over a 50 cm silica column using acetone. After evaporation of the eluent, the oily residue crystallizes after the addition of petroleum ether. Beige colored crystals with m.p. 111-122 ° C.

Example 9

Preparation of d

00 = N

ζ ^ -Ο-ζ-y - c - CH2-NC ^ (1.17)

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2- [p- (Phenoxy) -phenyl] -2- (1H-1,2,4-triazolylmethyl) -4-n-propyl-1,3-dioxolane, 10.3 parts of the nitrate of 1- (p -phenoxyphenyl) -2- (1,2,4-triazolyl-1-yl) -ethanone, 6.1 parts 1,2-pentadiol, 6.9 parts 5-p-toluenesulfonic acid, 20 parts 1-pentanol and 200 parts xylene heated for 6 days under reflux on a water separator and, after cooling to room temperature, the mixture is washed with twice 200 ml of dilute sodium hydroxide solution and twice 200 ml of water. The organic phase is dried over sodium sulfate, filtered and the solvent is evaporated.

The oily residue is chromatographed over a 1 m silica gel column using ethyl acetate. After evaporation of the eluent, the oily residue crystallizes slowly. Beige colored crystals with m.p. 68.5 to 71 ° C.

Example 10

Preparation of ch3.

Q '° C-A-cH2 - «Λ <5 · 73» - oo C2H5 2 - [(21-Methyl-41-phenoxy) -phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1, 3-dioxolane 2 © a) Preparation of the starting compound / CH3 + CH2Br o 2-Methyl-4-phenoxy-phenacyl bromide

To 36.6 parts of 2-methyl-4-phenoxy-acetophenone, 25.9 parts of bromine in 160 ml of acetic acid at 35 ° C are added dropwise over 25 1 1/2 hours. After drip is completed, the mixture is stirred for 1 to 36 hours

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at room temperature, then pour it into 1 liter of ice water and extract with 2 x 100 ml of ether. The combined organic extracts are washed thoroughly with water, dried over sodium sulfate, filtered, the solvent is evaporated and the crude product is digested with hexane. Brown crystals are obtained with m.p. 60-61 ° C.

b) Preparation of the intermediate CH3 O "0" O-A "" cb2'Br o o

U

C 2 H 5 2 - [(2'-Methyl-41-phenoxy) -phenyl] -2-bromomethyl-4-ethyl-1,3-dioxolane.

85.4 parts of the 2-methyl-4-phenoxyphenacyl bromide prepared above under (a) and 25.2 parts of 1,2-butanediol are heated at reflux in 250 ml of absolute toluene in the presence of 1 part of catalytically acting p-toluenesulfonic acid in 24 hours of water separator. After cooling to room temperature, the reaction mixture is washed with 3 x 250 ml of water, dried over sodium sulfate, filtered and the solvent evaporated. The product is available in the form of a reddish brown oil.

c) Preparation of the final product.

9.5 parts of the 2 - [(2'-methyl-20 -4'-phenoxy) phenyl] -2-bromomethyl-4-ethyl-1,3-dioxolane, 2.4 parts of imidazole prepared above in b) and 4.0 parts of potassium tert.-butylate are stirred in 50 ml of dimethyl sulfoxide for 30 hours at an internal temperature of 110 ° C. After cooling to room temperature, 300 ml of water are then extracted with ethyl acetate (3 x 150 ml), the 25 mixed extracts are washed neutral with water, dried over sodium sulfate and filtered, the solvent is evaporated and the oily residue is chromatographed over a

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37 50 cm silica gel column with ethyl acetate. The product is obtained in form 50 of a reddish oil having n ^: 1.5550.

Example 11

The preparation of

1-1 ._N

. Island Island /-

5 O \ / - ^ C-CH2 ~ \ d-D

2- [p- (Phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -1,3-dioxolane 11 parts 2- [p-phenoxycarbonyloxy) phenyl] 2- [1- (1H-1,2,4-triazolyl) methyl] -1,3-dioxolane is heated in 200 ml of ethylene glycol-diethyl ether to 130 ° C until carbon dioxide evolution has ceased (about 10 hours). Then the solvent is distilled off under reduced pressure. After cooling to room temperature, the crude crude product is taken up in 500 ml of diethyl ether, washed with 2 x 100 ml of water, dried over sodium sulfate and filtered and the solvent is evaporated. The remaining crystals are purified by recrystallization from ethyl acetate / cyclohexane in the presence of activated carbon. White crystals are obtained with m.p. 100-102 ° C.

Example 12 Preparation of the A and B diastereomers of _ / CH2 - ° - CH2 - <Q - C1. (1.24 / 1.25) 2- [p- (Phenoxy) -phenyl] -2- (1H-1,2,4-triazolylmethyl) -4- (p-chlorobenzyloxymethyl) -1,3-dioxolane 14.1 parts 2- [p- (phenoxy) phenyl] -2- (1H-1,2,4-triazolylmethyl) -25 -4-hydroxymethyl-1,3-dioxolane in 100 ml of absolute dioxane is added dropwise with stirring and under nitrogen

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At room temperature to 1.8 parts 55% sodium hydride dispersion in 100 ml of absolute dioxane and heated to 80 ° C for 3 hours. After cooling to room temperature, 8.6 parts of p-chlorobenzyl bromide in 5 50 parts of absolute dioxane are added dropwise with stirring over 1/2 hour, the reaction is heated for 3 hours to 50 ° C, cooled to room temperature, diluted with 1200 ml of ice water and extracted. with 3 x 200 ml ethyl acetate. The combined extracts are washed with 2 x 70 ml of water, dried over sodium sulfate and filtered, then the solvent is evaporated. The residual diastereomer mixture is separated by column chromatography (silica gel / ethyl acetate). After evaporation of the ethyl acetate, the dispersion B is obtained in solid form with m.p.

83-85 ° C. After drying in high vacuum, the diastereomer A is a cool 26 light brown oil with n 1: 1.5865.

Analogously, subsequent end products of formula I are prepared (unless specifically mentioned diastereomer mixtures with different mixing ratios): In the following tables, the symbol A means a diastereomer of type A and B correspondingly a diastereomer of type B.

Table 1

Compounds of formula f ~ \ -o- f ~ \ - c - CH 2 -n ^ (XXI-) \ = y \ == s q x0 Y = 1 s R 10 which also includes isomeric forms.

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39

Table 1

Conn. No. Y Salt Physically constant

1.1 Η N m.p. 100-102 ° C

1.4 CH3 N - m.p. 85-92 ° C

1.9 C2H5 N - m.p. 81.5 to 83.5 ° C

1.17 C3H7 "n N - Mp 68.5-71 ° C

1.23 CH2 OH N - m.p. 111-122 ° C

1.24 CH2OCH2- · ^ / * _ c1 n - Cool oil; rr6 = 1.5865 A

• = · ^

1.25 CHOOCH- / \ -ci N Mp. 83-85 ° C B

2 2 \ / · = ·

1.26 CH2 ° C / CH3 N - mp 107-109 ° C A

• = · · - ·

1.27 CH2 ° "* \ / * ~ GH3 n" Mp 90-94 ° C B

e = ·

1.28 CH2 OH CH - m.p. 118-123 ° C

Table 2; Compounds of formula \> - ° - \> ~ 7V: h2'V (XXII) / \ R11 * 12 which also include the isomeric nuclei.

Conn. No. R1] L R12 Y Salt Physical constant 2.17 CH3 CH3 N - oil, n33 = 1.5643

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DK 157 866 B

59

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Table 5: Compounds of Formula 60

DK 157866 B

! 18 · - · 5 · - «6 · = Ν

· () - ° - <) - 7 ° s- “X

· = · 3 · * · 7 {yr (J γ = · 17 / \ R11 12 which also includes the isomeric forms.

Conn. R R R RY Salt Physical constant - No. 11 12 17 18

5.13 CH3 CH3 2_CH3 h n hn03 Mp. 158-160 ° C

5.14 CH3 CH3 2-CH3 Η N HBr Mp. 192-204 ° C

5.36 H CH3 2_CH3 h n hn03 SltlP · 132-134 ° C

5.40 H C 2 H 5 2-CH 3 h n hn03 Mp. 108-110 ° C

5.42 H C-H_ 2-C1 Η N n22 = 1.5620

Z D D

5.68 Η H 2-CH, H CH '- m.p. 103-106 ° C

J 50 5.70 H C3H7 "n 2-CH3 H CH n £ = 1.5476 5.73 H C-Hc 2-CH- H CH n + ° = 1.5557 2 5 3 50 5.75 H CH2OCH3 2-CH3 Η N n ^ = 1.5482 5.76 H C2H5 2-CH3 Η N n ^ ° = 1.5502

5.77 Η H 2-CH- Η N - m.p. 103-105 ° C

J 5D

5.78 H C3H7_n 2_CH3 h N n ^ = 1.5467 5.81 HC, Hc 2-C1 H CH n ^ ° = 1.5765 2 5 20 5 5.100 H C2H5 3 CH3 Η N n ^ 2 = 1.5577

Table 5 (continued) 61

DK 157 866 B

Conn. R11 R12 R1? R18 Y salt Physical constant no.

5.105 2-CH0 H 2-CH, 5-CH, CH - Cool mass,

• J J -> I-Q

n £ U = 1.5463 5.106 H C, H_-n 2-CH, Η N - Oil, ό / 3 99

n ^ = 1.5461 A

5.107 H CQH_-n 2-CH, Η N - Viscous. oil, • j / * 5 '99

n = 1.5468 B

5.108 H C „Hr 3-CH, Η N - Resin, 2 b j cn n £ u = 1.5638 5.109 H C, H, - 3-CH, H CH - Resin, 2 b 3 5o n ^ U = 1.5732

5.110 H C2H5 2-C2H5 Η N HN03 Mp. 132-134 ° C

5.111 H C 2 H 5 2-CH 3 H CH (COOH) 2 Mp. 115-118 ° C

5.112 H C2H5 2-C2H5 Η N - Oil, n22 = 1.5642 5.113 H C0H, 3-CH, Η N - Oil, Δ O O 99

n = 1.5631; A

5.114 H C-H, - 3-CH, Η N - Oil, 2 b b on n ^ = 1.5633

5.116 H CH3 2-C2H5 H CH HN03 Mp. 105-119 ° C

5.118 H CH3 2-C2H5 Η N HN03 Mp. 136-138 ° C

Table 5 (continued) 62

DK 157866 B

Forb.R ^ R12 R17 Rlg Y Salt Physical constant »no.

5.119 H C2H5 2-CH3 H CH HCl Snip. 166-171 ° C

5.120 H C2H5 2-CH3 H CH H2SO4 Mp. 136-138 ° C

MHH

5.121 H C2H5 2-CH3 H CH CH3SO3H Mp. 98-106 ° C

5.122 H C2 H5 2-CH3 H CH HN03 Mp. 96-98 ° C

5.123 H C2H5 2-C2Hc H CH HN03 Mp. 134-137 ° C

5.124 H C2H5 2-CH3 H CH A, n ^ 3 1.5780 23 5.125 H C2H5 2-CH3 H CH B, ¾ 1.5631 5.126 H C H -n 2-CH3 5-CH3 N - n ^ 3 1.5580

5.127 H C2H5 2-CH3 5-CH3 N - m.p. 73-75 ° C

5.128 H CH3 2-CH3 5-CH3 N - m.p. 93-95 ° C

5.129 CH3 CH3 2-CH3 5-CH3 N - m.p. 59-62 ° C 23 5.130 H CH3 2-CH3 5-CH3 CH - 1.5751

5.131 H C H, 2-CH 3-CHO N HNOO m.p. 103-105 ° C

2 5 3 3 3

5.132 H C2H5 2-CH3 3-CH3 CH HNO3 Mp. 126-128 ° C

5.133 H C2H5 · 2-CH3 Η N HN03 Mp. 108-110 ° C

63

t. DK 157866B

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Table 7 Compounds of formula

DK 157866B

64 R; L4 \ ^ 13. · = Ν troiI> / \ / 2 V \ r, E22 E23 E13 * E14 H] which also includes the isomeric forms.

Conn. R "" R "_ R". R, c R, Y Salt Physical. Constant 22 23 24 15 16 - No. _

7.3 CH, CH, Η Η Η N Mp. 122-124 ° C

J J ΛΛ 7.7 CH3 CH3 H Cl 6-C1 - Oil, n ^ = 1.5782

7.21 CH3 CH3 C3H? -N Η Η N Mp. 119-121 ° C

7.27 Η Η H F Η N '- m.p. 105-107 ° C

7.33 Η Cl H Cl H CH Mp. 116-118 ° C

7.34 H H H Cl Η N Mp. 101-103 ° C

DK 157866 B

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70

Formulation Examples of Agrochemicals Containing Liquid Active Compounds of Formula I (% = wt%) A. Emulsion Concentrates a) b) c)

Active compound from Tables 1-10 25% 40% 50% 5 Ca-dodecylbenzenesulfonate 5% 8% 6%

Castor oil polyethylene glycol ether 5% - (36 moles of ethylene oxide)

Tributylphenoyl-polyethylene glycol ether (30 moles of ethylene oxide) - 12% 4% Cyclohexanone - 15% 20%

Xylene blend 65% 25% 20%

From such concentrates, emulsions of any desired concentration can be prepared by dilution with water.

B. Solutions a) b) c) d) Active Compound from Tables 1-10 80% 10% 5% 95%

Ethylene glycol monomethyl ether 20% -

Polyethylene Glyxol 400 - 70% - - N-Methyl-2-pyrrolidone - 20% - -

Epoxidized Coconut Oil - 1% 5% Gasoline (Boiling range 160 ~ 190 ° C) - - 94%

The solutions are suitable for use in the form of small droplets.

C. Granules a) b)

Active compound from Table 1-10 5% 10% 25 Kaolin 94% High-dispersion silicic acid 1%

Attapulgit - 90%

The active compound is dissolved in methylene chloride, after which the solution is sprayed onto the carrier and the solvent is then evaporated in vacuo.

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71 D. Dust a) b)

Active compound from Table 1-10 2% 5% High-dispersion silicic acid 1% 5%

Talc 97% - 5 kaolin - 90%

By thoroughly mixing the carriers with the active compound, ready-to-use dusting agents are obtained.

Formulation Examples of Agrochemicals Containing Solid Active Compounds of Formula I (% -% by weight) E. Spray Powder a) b) c)

Active compound from Tables 1-10 25% 50% 75%

5% 5% of lignin sulfonate

NaLauryl Sulfate 3% - 5%

Na-diisobutylnaphthalenesulfonate - 6% 10% Octylphenol polyethylene glycol ether - 2% (7-8 moles of ethylene oxide) High dispersant silicic acid 5% 10% 10%

Kaolin 62% 27%

The active compound is thoroughly mixed with the additives and thorough grinding is performed on a suitable mill. A spray powder is obtained which can be diluted with water to suspend any desired concentration.

F. Emulsion Concentrate

Active compound from Tables 1-10 10% Octylphenol polyethylene glycol ether 3% (4-5 moles ethylene oxide)

Ca-dodecylbenzenesulfonate 3%

Castor oil polyglycolther (35 moles of ethylene oxide) 4% Cyclohexanone 30%

Xy lenb 1 and ing 5 0%

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72

By diluting the concentrate with water, emulsions of any desired concentration can be prepared.

G ·, Dust a) b)

Active compound from Table 1-10 5% 8% 5 Talc 95%

Kaolin - 92%

Ready-to-use dusting agents are obtained by mixing the active compound with the carrier and grinding on a suitable mill.

10 H. Extruded granules

Active compound from Table 1-10 10%

Na-lignin sulfonate. 2%

Carboxymethyl cellulose 1%

Kaolin 87% The active compound is mixed with the additives, then ground and wetted with water. The mixture is extruded and then dried in an air stream.

j. Omhylningsgranulat

Active Compound from Tables 1-10 3% 20 Polyethylene Glycol 200 3%

Kaolin 94%

The finely ground active compound is uniformly applied to kaolin moistened with polyethylene glycol in a blender.

In this way, dust-free casing granules are obtained.

25 K. Suspension Ion Concentrate

Active compound from Table 1-10 40%

Ethylene glycol 10%

Nonyphenol polyethylene glycol ether 6% (15 moles ethylene oxide) 30 N-lignin sulfonate 10%

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73

Carboxymethyl cellulose 1% 37% aqueous formaldehyde solution 0.2%

Silicone oil in the form of a 75% aqueous emulsion 0.8% 5 Water 32%

The finely ground active compound is thoroughly mixed with the additives. Thus, a suspension concentrate is obtained from which, by dilution with water, suspensions of any desired concentration can be prepared.

10 Biological Examples

Example I

Effect against Puccinia graminis on wheat a) Residual protective effect

Wheat plants are sprayed 6 days after sowing with single-spray liquid made from spray powder containing the active compound (0.06% effective compound). After 24 hours, the treated plants are infected with an uredo-spore suspension of the fungus. After incubation for 48 hours at a relative humidity of 95-100% and approx. At 20 ° C, the infected plants are placed in a greenhouse at 22 ° C. The black rust attack is assessed 12 days after infection.

b) Systemic action 5 days after sowing, a wheat liquid is sprayed into wheat plants made from a spray powder containing the active compound (0.006% effective compound, based on soil volume). After 48 hours, the treated plants are infected with an uredospores suspension of the fungus. After an incubation period of 48 hours at a relative humidity of 95-100% and approx. At 20 ° C, the infected plants are placed in a greenhouse at approx. 22 ° C. The black rust attack is assessed 12 days after infection.

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74

Compounds from Table 1-10 have a good effect against Puccinia fungi. Untreated but infected control plants exhibit a Puccinia attack of 100%. Among others, Compounds Nos. 1.9, 1.17, 1.24, 1.26, 2.17, 3.1, 3.2, 3.6-3.8, 5 3.12, 3.26, 3.51, 3.52, 3.54, 3.55, 3.70, 3.75, 3.78, 3.83, 3.85, 3.86, 3.127 , 3.133, 3.155, 3.156, 3.160, 3.162, 3.164, 3.168, 3.171, 3.172, 3.176, 3.177, 3.193, 3.212, 3.213, 3.220, 3.226, 3.227, 3.231-3.234, 3.263, 3.267, 3.274, 3.279, 3.287, 3.292 3.311, 3.314, 3.340, 3.348, 3.373, 3.376, 3.384, 3.386, 4.2, 4.15, 4.23, 4.50, 4.55, 4.57, 4.66, 4.70, 4.77, 4.78, 4.81, 4.89-4.94, 4.113, 4.116, 4.136, 4.138-4.147, 5.13, 5.14, 5.36, 5.40, 5.70, 5.71, 5.76, 5.78, 5.105, 5.113, - 5.117, 6.8, 6.82, 6.93, 7.7, 7.33 and 8.66 for residual protective treatment against the fungal attack to 0-5%. In addition, Compound # 6.8 exhibits complete systemic effect (0% attack) even at a dilution of 0.006%.

Example II

Effect against Cercospora arachidicola on peanut plants

Peanut plants with a height of 10-15 cm are sprayed with a 20 spray liquid (0.02% effective compound) prepared from a spray powder containing the active compound, and 48 hours later the plants are infected with a conidial suspension of the fungus. The infected plants are incubated for 72 hours at ca. 21 ° C and high humidity, after which they are left in a greenhouse until typical leaf spots appear. The fungicidal effect is assessed 12 days after infection based on the number and size of the spots occurring.

Compared to untreated but infected control plants 30 (number and size of spots = 100%), peanut plants treated with active compounds listed in Table 1-10 exhibit a greatly reduced Cercospora attack. Thus, Compounds Nos. 1.1, 1.4, 1.9, 1.14, 1.17, 1.24-1.27, 2.17, 3.1, 3.2, 3.6, 3.7, 3.11, 3.51, 3.52, 3.54, 3.55, 35, 3.57, 3.78, 3.85, 3.86, 3.127, 3.133, 3.155, 3.156, 3.162,

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75 3.171, 3.172, 3.176, 3.177, 3.212, 3.213, 3.220, 3.221, 3.226, 3.231, 3.232, 3.233, 3.234, 3.267, 3.292, 3.314, 3.348, 3.384-3.388, 4.15, 4.23, 4.50, 4.57, 4.59, 4.66 , 4.89-4.94, 4.113, 4.116, 4.136-4.148, 5.13, 5.14, 5.36, 5.40, 5.70, 5 5.71, 5.73, 5.75-5.78, 5.105-5.110, 5.113-5.118, 6.1, 6.8, 6.93, 6.94, 7.33, 7.34 and 8.72 in the above experiment almost completely (0-5%) the appearance of stains.

Example III

Effect against Erysiphae graminis on barley 10 a) Residual protective effect

Barley plants with a height of approx. 8 cm is sprayed with a spray liquid (0.02% effective compound) made from a spray powder containing the active compound. After 3-4 hours, the treated plants are pollinated with conidia of the 15 fungus. The infected barley plants are recommended in greenhouses at approx. 22 ° C and the fungal attack is evaluated after 10 days.

b) Systemic effect

For approx. 8 cm tall barley plants are poured a spray liquid (0.006% effective compound, calculated on the soil volume) made from a spray powder containing the active compound.

Care shall be taken to ensure that the spray liquid does not come into contact with the plant parts above the soil surface. After 48 hours, the treated plants are pollinated with conidia of the fungus. The infected barley plants are recommended in a greenhouse at 25 approx. 22 ° C and the fungal attack is evaluated after 10 days.

The compounds of formula I have a good residual protective effect against Erysiphae fungi. Untreated but infected control plants show a 100% Erysiphae attack. Among other compounds from Tables 1-10, Compounds Nos. 1.1, 1.4, 1.9, 1.14, 1.17, 1.23 to 1.27, 2.17, 3.1, 3.2, 3.6 to 3.8, 3.11, 3.12, 3.26, 3.51, 3.52, 3.54 , 3.55, 3.70, 3.75, 3.78, 3.85, 3.86, 3.103, 3.127, 3.133, 3.156, 3.160, 3.162, 3.164, 3.168, 3.171, 3.172, 3.174, 3.176, 3.177, 3.193, 3.212, 3.213, 3.220, 3.221, 3.226 , 3.227,

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76 3.231 / 3.232 to 3.234, 3.263, 3.267, 3.274, 3.279, 3.287, 3.292, 3.311, 3.314, 3.340, 3.348, 3.378, 3.383 to 3.388, 4.2, 4.15, 4.23, 4.50, 4.57, 4.59, 4.66, 4.77, 4.78 , 4.81, 4.89 to 4.94, 4.113, 4.116, 4.137, 4.139, 4.140, 4.141, 5 4.146, 4.148, 4.150, 5.13, 5.14, 5.36, 5.40, 5.70, 5.71, 5.73, 5.75 to 5.78, 5.106 to 5.114, 6.1, 6.8, 6.17, 6.79, 6.80, 6.82, 6.93, 7.3, 7.7, 7.21, 7.33, 7.34, 8.66, 8.69, 8.72 and 10.7 the fungal attack on barley to less than 5%. Compounds # 4.50 also exhibit this effect in the soil treatment (systemic effect) and a dilution of 0.006%.

Example XV

Residual protective effect against Venturia inaequalis on apple-shoots Apple cuttings with 10-20 cm long fresh shoots are sprayed with a spray liquid (0.06% effective compound) made from a spray powder containing active compound. After 24 hours, the treated plants are infected with a conidial suspension of the fungus. Then, the plants are incubated for 5 days at a relative humidity of 90-100%, after which they are left for 10 days in a greenhouse at 20-24 ° C. The scab attack is assessed 15 days after the infection. Compounds no.

1.4, 1.9, 1.17, 1.24, 1.26, 2.17, 3.1, 3.6, 3.7, 3.11, 3.52, 3.55, 3.85, 3.86, 3.156, 3.160, 3.164, 3.172, 3.176, 3.177, 3.213, 3.221, 3.233, 3.314, 3.383 to 3,387, 4.15, 4.23, 4.50, 4.59, 4.66, 4.78, 4.81, 4.89, 4.90 to 4.94, 4.113, 4.116, 4.137 to 4.141, 4.146 to 4.150, 5.13, 5.14, 5.36, 5.40, 5.70, 5.73, 5.75, 5.76 , 5.106 to 5.110, 5.112 to 5.114, 5.118, 6.1, 6.8, 6.93 to 10.7 reduce the disease incidence to less than 10%. Untreated but infected 30 shots have a Venturia attack of 100%.

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77

Example y

Effect against Botrytis cinerea on beans Residual protective effect

Ca. 10 cm tall bean plants are sprayed with a spray liquid 5 (0.02% effective compound) made from a spray powder containing the active compound. After 48 hours, the treated plants are infected with a conidial suspension of the fungus. After incubating the infected plants for 3 days at a relative humidity of 95-100% and 21 ° C, the fungal attack is assessed. In many cases, the compounds of Tables 1-10 greatly inhibit fungal infection. At a concentration of 0.002%, e.g. Compounds Nos. 1.1, 1.4, 1.9, 1.17, 3.6, 3.7, 3.12, 3.51, 3.55, 3.86, 3.226, 3.231, 3.267, 3.311, 4.15, 4.50, 4.59, 4.66, 4.78, 4.90, 4.93, 4.113, 5.13, 5.36, 5.40, 5.70, 5.71, 5.73, 5.75, 5.76, 5.78, 6.1, 6.8, 7.3, 7.33 and 8.72 fully effective (disease attack 0-5%). The botrytis attack on untreated but infected bean plants is 100%.

Comparative Example 20 The effect of a number of known compounds A to N is compared to the effect of a large number of the compounds of the invention XI to X25. The test compounds used are as follows:

Known Comparative Compounds A 'S ^ 7ava ,,' <* i · - · B CH3-0- () · —C — CH2 — j - · <j> <j> · * Ν

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78 c> 7VH2- <i · «· p p · * Ν xch3 .- / C1 d γΗ2 - \. 1. * - · · *«

e ch3-o- (c-ch2-I

- (f <ρ - N

XC2H5 · - · · * ·

F CH3-0- () · - £ —CH2 — ίζ I

· = · Ϋ <p · «=» xch2oh • · \ / H - c — CHa - / = j

· = · · = · P p · —N

• - · 0-0 · 7ν- <] nch2och3 K Ό'-Ό-γψ ^ ΐ I "§ h3c / nc2h5 'ΟΟλ * <• - · \ / 6h3 79

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M. () · - (i • · \ / *

Hat / XCH3

K / ~ 's --- K' \ - c-CHa- / H

\ / \ / vT ^ 2 \ 1 · = · · = · η O · = Ν • * \ / Η3 </ NC3H7

Compounds of the Invention XI · () - ° - () · ^ Η- <"]

♦ o · tv * Π p teJJ

NC2Hs X2 Br- () .- 0 -. (Vs-CBa- ^ i · * · · * · pp · βΝ nch3 / η3 X3 ci -. () .- 0 -. () .- 0 ^, - ^ i · = · *** pp · * Ν \ h3 ../1

X4. () .- 0 -. (V-c-cHa-itf I

te * txtp p · = $ xc2h5 XS Cl- () .- 0 -. () .- 7c-ch! -8 (K i · = · · «= * (p. =] tf

Nc2H5

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80 ../1 -,.

X6 Cl- () .- 0 -. (W-CH2-1 <i · »· · * · Π o» afj 9 9 NCH3 X7 Br- () .- 0- (V-C-CHa-S ^ i

·*· ·· ISLAND ISLAND

\ h3 / 1 · - · · - · Ke «

X8 Cl - () - ° -v) -7C; -CH2- / I

X. ·. ·· (j> X (j) Χ · * Ν \ h2ch2ch3

X9 CF3- () -0- () · -C-CH2- / I

· «· · * · <Jf X» «H

• .... i. - «NC2Hs / η3 X10 CHaO- (). 0 -. () ._ C_CH! -» (i

• * t 9X9 O p t »N

• »nch3 .- / 1 XI1 F— ^ \ -0— ^ —c — CH2- /]

\ ./ /? / N? \ -A

HsC '' NCH3

...... X

XI2 Cl - ^ .- 0— ^ —C — CH2-l / ί

\ ./ \ .A

9 '' 'ί 9 CH ^ \ 2H5 81

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/ 1> - · »- · 11“ ·

XI3 Cl-f v “0_ * v / *“ ^ c — CHZ-N ^ I

\ '. \ =. ^ x <j) * 4 • .. · nch2och3. / C1 XI4 Cl- · ^ y * "0" · ^ 1

\ = V \ =. <j) <j) * “N

\ h2OC3H7 X15 · () - 0- () .- ^ - CH2- <i

• «· ·· p o *“ N

\ h2oh ...... / C1

XU F- () -0- () .- c-ch2- <I

· * · · * · P π · * Κ xch2och2ch-ch2 / X3 X17 ci- () -0- () - 7crC "= - <i

· * · · = · P p ** N

/ Ha X'8 cl- <) - ° - <i · = »· * · p p · = Ν \ 2Η5 · - · ♦ ·· · κ ·

XI9 CF3— ^) · ° ° * () · - ^ C ^ CH2-N ^ I

· = · · * · (J) (j) · = Ν NC2H5 / C1 · - · · «· · * ·

X20 Cl -. (> -0 -. (I

· »· · = · O O *« = N

CH2 NC2H5

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82 x21 cl- <i · * · · * · p π · * Ν • · \ / ^ CHa X22 Cl- ') -0- (> vBeCB «- <B i ·« · · »· Q p · * Ν \ / xCH3 / 1 i ·· · - «N * ·

X23 F— () - ° - (^ - ^ Cr-CH 2 -N ^ I

<jf N (j) «-R

• ♦ \ / CH3 nch3 i «· · - · N» ·

X24 T- {) -0- () - * r-Wz- \ I

. «· Y <j> •» N

* N / \ h3 / CHs s x25 «- <;> - ο - <;> ^ * <i V \ *

The following test methods are used.

2.1 Residual protective effect against Puccinia graminis on wheat_

Wheat plants are sprayed 6 days after sowing with a 10 spray liquid made from a spray powder containing the active compound (200/20 and 2 ppm active compound). After 24 hours, the treated plants are infected with an uredospores suspension of the fungus. After incubation for 48 hours at ca. At 25 ° C with a relative humidity of 95-100%, the infected plants are left in a greenhouse at approx. 22 ° C. The assessment of the rust attack 83

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should be done 14 days after infection. The size and number of typical leaf spots present after the test period serve as a criterion for assessing the efficacy of the test compounds.

5 2.2 Effect against Cercospora arachidicola on peanut plants_ 3 week old peanut plants are sprayed with a spray liquid (200, 20 and 2 ppm active compound) prepared from a spray powder containing the active compound.

10 The treated plants are sprayed after approx. 12 hours with a conidial spore suspension of the fungus. The infected plants are incubated for approx. 24 hours at a relative humidity of 90% and then placed in a greenhouse at approx. 22 ° C. The prevalence of fungal infection is assessed after 12 days prior to 15 runs. The size and number of typical leaf spots occurring at the end of the trial period are used as a criterion for assessing the efficacy of the test compounds.

2.3 Residual protective effect against Erypsiphe graminis on barley_ 20 Barley plants with a height of approx. 8 cm is sprayed with a spray liquid (200, 20 and 2 ppm effective compound) made from a spray powder containing the active compound.

The treated plants are pollinated after 3-4 hours with conidia of the fungus. The infected barley plants are recommended 25 in a greenhouse at approx. 22 ° C and the fungal attack is evaluated after 10 days. The size and number of typical fungal growth on the leaves after the end of the experimental period is used as a criterion for assessing the effect of the test compounds.

30 2.4 Residual protective effect against Venturia inaequalis on apple shoots_ Apple cuttings with 10-20 cm long fresh shoots are sprayed with

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84 a spray liquid (200, 20 and 2 ppm active compound) made from a spray powder containing the active compound. After 24 hours, the treated plants are sprayed with a conidia spore suspension of the fungus.

5 Then, the plants are incubated for 6 days at a relative humidity of 90-100% and then left for a further 10 days at 20-24 ° C in a greenhouse. The prevalence of the scab attack is assessed 15 days after infection. The size and number of typical leaf spots occurring at the end of the test are used as a criterion for assessing the efficacy of the test compounds.

2.5 Rating Scale; Assessment - Effect in% s es number 1> 95 (complete control) 3 80-95 (acceptable control) 15 6 50-80 (insufficient control) 9 <50 (no control)

Each test concentration is used in the tests described above: a three parallel tests, and each test number in the following table is an average value of three test results.

85

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results

Results obtained with known comparative compounds ________ * = phytotoxic effects are observed

Connect Test 2.1 Test 2.2 Test 2.3 Test 2.4 Puccinia Cercospora Erysiphe Venturis 200/20/2 ppm 200/20/2 ppm 200/20/2 ppm 200/20/2 ppm A 999 999 9 9 9 999 B 999 999 999 999 C 399 999 689 999 D 1 * 99 999 1 * 69 599 E 3 * 99 999 1 * 69 999 F 999 999 999 999 G 5 * 99 6 99 1 * 99 999 H 699 299 115 699 I 999589399999 K 369 168 336 699 L 369 669 336 369 M 999 999 999 999 N 136 999 339 999 86

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Results obtained with the compounds of the invention

Connect Test 2.1 Test 2.2 Test 2.3 Test 2.4 Puccinia Cercospora Erysiphe Venturis 200/20/2 ppm 200/20/2 ppm 200/20/2 ppm 200/20/2 ppm XI 199 126 113 159 X2 129 111 111 111 X3 116 116 111 116 X4 119 119 111 119 X5 111113 111113 X6 113 111113 113 X7 111 111 113111 X8 111112 113 112 X9 113 113 111128 X10 119 119 1113 6 6 XII 111 111 113 111 XI2 113 113 113 116 XI3 111112 112 113 XI4 111113 133 111 X15 336 1 6 9 369 336 XI6 111111136 112 XI7 123 111112 113 XI8 116 139 111 226 XI9 111126 111169 X20 112,136 113 139 X21 159 128 111 116 X22 111113113113 X23 116 119 133 116 X24 113111111116 X25 111 111 113 699

It is evident from the results set forth above that the compounds of the invention have a substantially better effect than the closely related known compounds.

Claims (32)

Ar - 0- <f \ -C 4 (I) In ch9-n ^ »b Y = 1 wherein Y means -CH = or -N =, R &apos; R &apos; individually means hydrogen, halogen, C -alkyl, C- g g alkoxy or nitro, Ar means unsubstituted or halogen, C - ^^ alkyl alkyl, C _ _ - alkoxy, nitro and / or CF ^ mono- to trisubstituted phenyl or naphthyl, U and V each optionally means with halogen or C C _ al alkoxy monosubstituted C ^ _ ^ 2 alkyl alkyl or together form an alkylene bridge of the formula R R R R in R--p V'Λ / / R \ or ^HN wherein R 1 and R 2 each represent hydrogen, C 1-6 alkyl, one to three times substituted with halogen substituted C 1-6 alkyl, phenyl, one to three times with halogen and / or C 1-8 alkyl substituted phenyl or the group -Cl 2 -ZR 2, where Z means oxygen or sulfur, and R means hydrogen, C1-6 alkyl, with C1-6 alkoxy monosubstituted C1-6 alkyl, C8-20 alkenyl, 2-propynyl, 3-halo-2-propynyl, phenyl, with halogen, C1-6 alkyl, C - β-alkoxy, nitro and / or CF₂ a phenyl, benzyl substituted three times, or with halogen, Cjg alkyl alkyl and / or Cggko alkoxy substituted three times benzyl, Rg, R₂ and Rg each hydrogen or C 1 -C 6 alkyl, although R 9, R 2 and R 9 together contain not more than 6 C atoms, and R 9 represents hydrogen or g-alkyl, or are acid addition salts or complexes with inorganic or organic metal salts thereof. . DK 157866 B Compounds according to claim 1, characterized in that Ar means the group R Rc Γ 1 d Rc or Ea - S = <R e e · - -i in which Rc, R 2 and Rg are each independently hydrogen, halogen, C C-CC alkyl, C ^-C ^ alkoxy, nitro or CF3, U and V each represent C ^-C ^ alkyl or together form an alkylene bridge of the formula R-ι R0 Ro R <WK, - ^ - R5 or ^^^ H ^, where R ^, R2, R ^ / R5 and Rg have the meanings specified in claim 1. Compounds according to claim 2, characterized in that Ar represents the group of formula R 'r *. c Rd $ h- Ré wherein R ', R' and R 'each represent hydrogen, halogen, C u 6 Or C ^-C ^ alkyl. Compounds according to claim 3, characterized in that U and V each represent C 1 -C 4 alkyl or together form an alkylene group of formula DK 157866 B E'1 R'2 R3 / R4 or X * X wherein R R,, R £, R3, R4 and R R - each independently means hydrogen or C ^-C ^ alkyl, wherein R ^, R ^ and R ^ together contain at most 6 C atoms, Ar represents the group of formula R R e wherein R ”, R £ and R" each independently means hydrogen, halogen or C ^-C ^ alkyl, - Compounds according to claim 2, characterized in that Ar has the meanings given in claim 2, wherein R, a 10 R ^, Rc, Rd °? R 1 independently means hydrogen, chlorine, bromine, fluorine, methyl, methoxy or nitro, U and V each represent C 1 -C 4 alkyl or together form one of the alkylene bridges mentioned in claim 1, wherein R 1, R 2, R 3 , R4, R ,. and Rg each represents hydrogen or C ^-C ^ alkyl, or R ^ 15 represents -CCI ^ -OR ^ wherein R ^ represents C ^-C ^ alkyl, with alkoxy substituted C₂-C4 alkyl, C3 -C4 alkenyl or phenyl. Compounds according to Claim 1, characterized in that Ra and R 2 each represent hydrogen, halogen or C 1 -C 4 alkyl, or a salt thereof, Ar represents the group III RC R 11t e wherein R , R "and R", respectively, represent hydrogen, halogen, C1-C0 CF2 / C1-C3-alkyl or C1-C4-alkoxy. Compounds according to claim 1, characterized in that R &apos; and R &lt; a &gt; individually represent hydrogen, halogen or C1 -C4 -alkyl, Ar means the group RIII R5 c R5. and R ™ each independently means hydrogen, halogen, CF3, C ^-C ^ alkyl or C --C C alkoxy, U and V each represent C ^-Cg alkyl, optionally with halogen or C ^. -C 1 -alkoxy monosubstituted C 2 -C 4 alkyl or together form an alkylene bridge of the formula R 1 R 1 R 5 R 2, or 3 yY 4 10 / R 5 wherein R 1, R 2 f R 3, R 4 and R 5 each represent hydrogen or C 1 -C1 -alkyl, wherein R3, R4 and R4 together contain not more than 6 C atoms. Compounds according to claim 1, characterized in that R 1 and R 2 are each independently hydrogen, halogen or C 1 -C 4 alkyl, Ar represents the group of the formula R c VN-e wherein R 1, R 2 and R ™ is independently hydrogen, halogen, CF3, C ^-C ^ alkyl or C ^-C ^ alkoxy, and the U and V group form an alkylene group of formula CH-ORi DK 157866 B wherein R 'is C, r C -alkyl, with C 1 -C 4 alkoxy substituted / 14 X Δ C 2 -C 4 alkyl, C 3 -C 4 alkenyl or prop-2-ynyl. Compounds according to claim 1, characterized in that Y means -CH =, R and R, each means 5 hydrogen, methyl, chlorine or bromine, Ar is as defined in claim 2, wherein R, R, and R each represents od θ hydrogen, fluorine, chlorine, bromine, methyl, methoxy, CF 2 or nitro, U and V each optionally means with C 1 -C 2 alkoxy or chloro substituted C 1 -C 2 alkyl or together 10 forms one of the alkylene groups listed under formula I wherein R 1, R 2, R 3, R 4, R 2. and Rg each represents hydrogen or C ^-C ^ alkyl, or R ^ represents -CH₂OR7 wherein RR represents C C-Cg alkyl, with C ^-C ^ alkoxy substituted C₂-C3 alkyl or C3-C4 alkenyl. Compounds according to claim 1, characterized in that R 1 and R 2 are each independently hydrogen, halogen or C 1 -C 3 alkyl and Ar is unsubstituted or with C 1 -C 3 alkyl, C 1 -C 3 alkoxy, CF 3 or halogen substituted phenyl. Compounds according to claim 1, characterized in that R &apos; and R < a &gt; individually represent hydrogen, methyl, chlorine or bromine, and Ar is unsubstituted or with halogen, methyl or CF3 substituted phenyl, and U & V each represent C C 1 -C 2 alkyl, optionally with halogen or C 1 -C 2 alkoxy substituted C 2 -C 3 alkyl or together form an alkylene bridge of the formula 3 ^ <R 5 or V wherein r 2, R 10, R 9, R 2 and R 9 are each independently hydrogen or C 1 -C 4 alkyl, with R 9, R 2 and Rg together contain a maximum of 4 C atoms. DK 157866B Compounds according to Claim 1, characterized in that R 1 and R are hydrogen, Ar means unsubstituted or with halogen or methyl substituted phenyl, and U and V taken together represent a group of the formula RIU 5 or wherein R 1 represents C 1 -C 4 -alkyl, hydroxy-methyl or C Compound according to claim 1, characterized in that it is 2- [p- (phenoxy) -phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methyl -1,3-dioxane or a salt thereof, 2- [p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3 -dioxane or a salt thereof, 2- [p- (phenoxy) -phenyl] -2- [1- (1H-1,2,4-triazolyl) -methyl] -4-methyl-1,3, -dioxolane or a salt thereof, 2- [p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane or a salt thereof , 2- [p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-methyl-5-methyl-1,3-dioxolane, 2- [ p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -1,3-dioxane or a salt thereof, 2- [p- (phenoxy) phenyl ] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane or a salt thereof, 2- [p- (2,4-dimethylphenoxy) phenyl] -2- (1-imidazolylmethyl) -4- ethyl 1,3-dioxolane or a salt thereof, 2- [p- (3-chlorophenoxy) -phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane or a salt thereof, 2 - [p- (4-chlorophenoxy) phenyl] -2- (1-imidazolylmethyl ) -4-Ethyl-1,3-dioxolane or a salt thereof, 2- [p- (3-trifluoromethylphenoxy) -phenyl] -2- (1-imidazolyl-methyl) -4-ethyl-1,3-dioxolane or a salt thereof, 2- [p- (4-chloro-3-methylphenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane or a salt thereof, 2- [p- (3,4-dichlorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane or a salt thereof, 2- [p- (2,5-dichlorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1/3-dioxolane or a salt thereof, 2- [p- (3,4-dichlorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-methoxymethyl -1,3-dioxolane or a salt thereof, 2- [p- (4-fluorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane or a salt thereof, - [p- (4-fluorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-methyl-5-methyl-1,3-dioxolane or a salt thereof, 2- [p- (4-chloro-2) -methyl-phenoxy) -phenyl] -2- (1-imidazolyl-methyl) -4-methoxymethyl-1,3-dioxolane, 2- [p- (phenoxy) -phenyl] -2- [1- (1H- 1,2,4-Triazolyl) -methyl] -4-hydroxy-methyl-1,3-dioxolane, 2- [p- (4-fluoro) -phenoxy) -phenyl] -2- (1-imidazolylmethyl) -4-hydroxy-methyl-1,3-dioxolane or 2- [p- (4-fluorophenoxy) -phenyl] -2- [1- (1H-1) , 2,4-triazolyl) methyl] -1,3-dioxane. Compound according to claim 1, characterized in that it is 2- (p- (phenoxy) -phenyl] -2- [1- (1H-1,2,4-triazolyl) -methyl] -4-ethyl-1 , 3-dioxolane. Compound according to claim 1, characterized in that it is 2- [p- (4'-chlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4 ethyl-l, 3-dioxolane. Compound according to claim 1, characterized in that 2- [p- (phenoxy) -phenyl] -2- [1- (1H-1,2,4-triazolyl) -methyl] -4-methyl-1, 3-dioxane. Compound according to claim 1, characterized in that it is 2- [p- (31,4'-dichlorophenoxy) phenyl] -2- [1- (1H - 1,2,4-triazolyl) methyl] -4-methoxymethyl-1,3-dioxolane. DK 157866B A compound according to claim 1, characterized in that it is 2- [p- (3 ', 4'-dichlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane. Compound according to claim 1, characterized in that it is 2- [p- (phenoxy) -2'-methoxyphenyl] -2- [1- (1H-1,2,4-triazolyl) -methyl] - 4-ethyl-l, 3-dioxolane. Compound according to claim 1, characterized in that it is 2- [p- (4'-chlorophenoxy) -2'-methylphenyl] -2- [1- (1H-1,2,4-triazolyl) -methyl ] -4-methyl-l, 3-dioxolane. 10 21. Compound according to claim 1, characterized in that it is 2- [p- (41-chlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl 1,3-dioxolane - copper sulphate complex. Compound according to claim 1, characterized in that it is 2- [p- (4-chlorophenoxy) -21-methylphenyl] -2- - [1- (1H-1,2,4-triazolyl) methyl] -4-ethyl-1,3-dioxolane. A compound according to claim 1, characterized in that it is 2- [p- (phenoxy) -21-chlorophenyl] -2- [1- (1H - 1,2,4-triazolyl) methyl] -4- ethyl-l, 3-dioxolane. 20 .24. Compound according to claim 1, characterized in that it is 2- [p- (4-chlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4,5- dimethyl-l, 3-dioxolane. A compound according to claim 1, characterized in that it is 2- [p- (4-bromophenoxy) phenyl] -2- [1- (1H-1,2,4-25-triazolyl) methyl] -4 ethyl-l, 3-dioxolane. Compound according to claim 1, characterized in that it is 2- [p- (phenoxy) -2'-methylphenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4- ethyl-l, 3-dioxolane. DK 157866B A compound according to claim 1, characterized in that it is 2- [p- (41-chlorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane. A compound according to claim 1, characterized in that it is 2- [p- (3'-chlorophenoxy) phenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane. A compound according to claim 1, characterized in that it is 2- [p- (phenoxy) -2'-methylphenyl] -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane. A compound according to claim 1, k; characterized in that it is 2- [p- (4'-chlorophenoxy) -2'-methylphenyl] -2- (1-imidaz olylmethyl) -4-methyl-1,3-dioxolane. Compound according to claim 1, characterized in that it is 2- [p- (41-fluorophenoxy) -21-methylphenyl] -2-15 - (1-imidazolylmethyl) -4-methyl-1,3-dioxolane, 32 ,. Compound according to claim 1, characterized in that it is 2- [p- (phenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4-hydroxymethyl-1 , 3-dioxolane. A compound according to claim 1, characterized in that it is 2- [p- (4'-chlorophenoxy) phenyl] -2- [1- (1H-1,2,4-triazolyl) methyl] -4 methoxy-methyl-l, 3-dioxolane. A method for controlling or protecting cultured plants from attack by phytopathogenic microorganisms, characterized in that a compound according to claims 1 to 5 or 13 is applied to the plant or its growing site.