FI77458B - NYA MICROBICIDES ARYLFENYLETTERDERIVAT, FOERFARANDE FOER DERAS FRAMSTAELLNING OCH DERAS ANVAENDNING. - Google Patents

Description

77458

The present invention relates to substituted arylphenyl ether derivatives of the formula I shown below and to their acid additions, as well as to their acid adducts. The invention further relates to the preparation of these compounds and to agrochemicals containing at least one compound of the formula I as active ingredient: the preparation and use of these substances and to a process for controlling or preventing plant diseases caused by phytopathogenic microorganisms.

The arylphenyl ether derivatives of the invention have the formula I.

". „..A Vjj where Y represents a group -CH = or -N =,

Ra and Rb independently of one another denote hydrogen, halogen, C1-C3-alkyl, C1-C3-alkoxy or nitro;

Ar represents unsubstituted or mono- or polysubstituted phenyl by halogen, C1-Cy-alkyl, C1-C7-alkoxy, nitro and / or C1-4; U and V independently represent C 1 -C 12 alkyl optionally substituted by halogen or C 1 -C 6 alkoxy or together form one of the following alkylene silos \> St * / * R 6 V- \ '' · | -t-R5 \ "/ y— \ Where 2 77458

R1 and R2 independently of one another denote hydrogen, C1-C12-alkyl, C1-C12-alkyl substituted one or more times by halogen, phenyl, phenyl substituted one or more times by halogen and / or C1-C3-alkyl or -CH2- Z-R7, wherein Z represents oxygen or sulfur and R7 represents hydrogen, C1-C8-alkyl, C1-C2-alkoxy-substituted C1-C8-alkyl, C3-C4-alkenyl, 2-propynyl, 3-halo-2-propynyl , phenyl, phenyl, benzyl, substituted one or more times by halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, nitro and / or CF 3, or halogen, C 1 -C 3 alkyl and / or C 1 -C 3 benzyl mono- or polysubstituted by alkoxy? R 3, R 4 and R 5 independently of one another denote hydrogen or C 1 -C 4 alkyl, the total number of carbon atoms in the radicals R 3, R 4 and R 5 not exceeding 6 and R 8 denotes hydrogen or C 1 -C 3 alkyl? including acid addition salts and metal complexes of these compounds.

The substituent Ar as an optionally substituted phenyl has, for example, the formula

R

V \.

R 1 e wherein R c, R d and R e are independently hydrogen, halogen, C 1 -C 7 alkyl, C 1 -C 7 alkoxy, nitro or CF 3.

The term alkyl itself or as part of another substituent, depending on the number of carbon atoms indicated, means, for example, the following groups: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl and their isomers, such as isopropyl, isobutyl, tert-butyl, sec-butyl, isopentyl, etc. Alkenyl is, for example, propenyl (1), alkyl, butenyl (1), butenyl (2) or butenyl (3). Halogen in this and the following means fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.

Il 3 77458

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

The salts according to the invention are, in particular, addition salts, depending on the intended use, with physiologically innocuous inorganic or organic acids.

Inorganic and organic acids which are not physiologically innocuous for use in plant protection as microbicides are, for example, hydrohalic acids, e.g. hydrochloric, bromic or hydroiodic acid, sulfuric acid, phosphoric acid, sulfuric acid, nitric acid, optionally halogenated fatty acids, benzenesulfonic acid and methanesulfonic acid.

The metal complexes of the formula I consist of a basic organic molecule and an inorganic or organic metal salt, e.g. halides of copper, manganese, iron, zinc and other metals, nitrates, sulphates, phosphates, tartrates, etc. In this case, metal cations can be present at all possible levels.

The compounds of the formula I are oils, resins or solids which are stable at room temperature and which are characterized by very valuable physiological, such as microbicidal, e.g. plant fungicidal properties. They can therefore be used in the agricultural sector or in nearby areas to control phytopathogenic microorganisms.

An important group for the plant protection of microbicides consists of compounds of the formula I in which Y represents the group -CH = or -N =; Ra and R6 independently of one another denote hydrogen, halogen, C1-C3-alkyl, C1-C3-alkoxy or nitro; Ar represents a group wherein X / R 1 mmm e 4 77458, and R 8 independently of one another denote hydrogen, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, nitro or CF 3; U and V independently of one another denote C 1 -C 4 alkyl, or together form one of the following alkylene bridges R 1 R 2 Κ 3ν> / Α R 6 V- / - \. R 1 and R 2, wherein R 1 and R 2 independently of one another are hydrogen, C 1 -C 4 alkyl, one or more halogen-substituted C 1 -C 2 alkyl, phenyl, one or more times halogen and / or C 1 -C 6 alkyl-substituted phenyl or a group -C 1-4 -RR 4, wherein Z represents oxygen or sulfur and R 4 represents hydrogen, C 1 -C 8 alkyl, C 1 -C 2 alkoxy-substituted substituted C 1 -C 6 alkyl, C 1 -C 6 alkenyl, 2-propionyl, 3-halo-2-propynyl, phenyl, halogen, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, nitro and / or phenyl, benzyl or mono- or polysubstituted by halogen, C 1 -C 4 alkyl and / or C 1 -C 6 alkoxy substituted one or more times by CF 4;

R 9, R 6 and R 8 independently represent hydrogen or C 1 -C 4 alkyl, the total number of carbon atoms in the radicals R 9, R 4 and R 1 - not exceeding 6 and R 8 represents hydrogen or C 1 -C 6 alkyl; Including acid addition salts and metal complexes of these compounds. This subgroup is referred to herein and hereinafter as Group Ia.

> 1 77458

A preferred group of agriculturally useful microbicides comprises those compounds of formula I, including their salts and metal complexes, wherein Y represents -CH = or -N =; R 9 and R 5 independently represent hydrogen, halogen or C 1 -C 4 alkyl; Ar stands for group

R

R ,, | c dyN._ X. /

R

e wherein and R e independently represent hydrogen, halogen, C 1 -C 4 or C 1 -C 4 alkyl; and the residues U and V have the meanings given in formula I? this group ni-10 is measured as group Ib.

In subgroup Ib, preference is given to those compounds of the formula I as microbicides in which U and V independently of one another denote C1-C4-alkyl or together form one of the following alkylene groups R1 R2 / - (or i -j-s 15 in which R1, R2> R R 1, R 2 and R 2 independently of one another denote hydrogen or C 1 -C 4 alkyl, the total number of carbon atoms in the radicals R 1, R 2 and not exceeding 6, this group being called the group Ie.

Another preferred group of agriculturally preferred microbicides comprises those compounds of formula I wherein Y represents -CH = or -N =; the residue Ar has the meanings given in connection with formula I; R 1, R 2, R c, R 2 and R 6 independently represent hydrogen, 6 77458 chlorine, bromine, fluorine, methyl, methoxy or nitro; U and V independently represent C 1 -C 4 alkyl or together form one of the alkylene groups mentioned in connection with formula I, in which R 1, R 6, R 0, R 4, R 2 and R 1, R 6 4 o 5 5 independently of one another denote hydrogen or C 1 -C 4 alkyl or R 4 represents a group -CH 2 -COR-C 1-4 alkyl, wherein R 4 represents C 1 -C 4 alkyl, C 2 -C 4 alkyl substituted by C 1 -C 4 alkoxy, C 1 -C 4 alkyl; -C 1-6 alkenyl or phenyl; this group is hereinafter referred to as Id.

Of the microbicides of subgroup Id, those in which U and V together form an unsubstituted or simply substituted ethylene or propylene bridge are preferred; this group is hereinafter referred to as Ie.

Thus, for example, the following substances are among the very preferred agriculturally useful individual substances: 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-dioxolane, 2- (p- (phenoxy) -phenyl) -2- (1- (1H-1,2,4-triazolyl) -methyl) -4-ethyl-1,3-dioxolane.

11 7 77458

The compounds of formula I can be prepared as follows:

A) of formula II

Me-t / I (II), \ =.

The compound of formula 5, wherein Me represents hydrogen or a metal cation, is condensed of formula III

R

la • 4 »· / T \

Ar-O—> - CH0-X

X

b with a compound according to ----- v, wherein X represents a nucleofugic starting group, or

B) formula IV

R Ia • t · · / ^ / 1

Ar-O- ·> -C-CH -N (IV) \ l. ' Il 2 \ =.

K 0

In the compound of formula 10, the carbonyl group of formula V is converted

V

0y \ (V) 1 t

U V ------

or 8 77458 C) for the preparation of compounds of formula I in which U and V together represent a group of the formula -CH 2 -CH (CH 2 ZR 2) - and denote a non-hydrogen residue r 1, are condensed with each other according to the formulas

R

/ * = I?

Ar_0 '\ / 7C \ 7 ^ H2 ~ \ J (VI) and x2-r7 (VII), \ eH2-CH-CH2-X1

Compounds of formula 5 wherein one of the residues and X2 represents a hydroxy or mercapto optionally present in the form of a salt, e.g. of the formula -Z-Me, and the other represents a nucleophilic starting group X or both X1 and X2 represent hydroxy groups, or D) condensed together and IX

R

Ar-X3 (VIII) and) - CH2-i / (IX), * f * c / \ K ii ° u ..... v, wherein one of X 1 and X 2 represents a group -Ο-Me, wherein Me is hydrogen or preferably a metal lycation, and the other represents a residue to be exchanged for aryloxy, or

E) of formula X.

R

· = N

Ar-O-C-O- · 7 ^ --- C - ΟΗ, -Ν7 | (X) "-t · 7 / \ 2 \ = i o Too \ 1 1

Ö u ----- V

II

9 77458 is decarboxylated intramolecularly and, if desired, the compound obtained according to the process is converted into another compound of the formula I and / or the free compound obtained according to the process is converted into an acid addition salt, an acid addition salt obtained according to the process into a free compound or another acid addition salt or or an acid addition salt obtainable according to the process into a metal complex.

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

Nucleofugic starting groups include, for example, reactive esterified hydroxy groups, such as with hydrohalic acid, e.g. fluoro, chloro, bromo or hydroiodic acid, or lower alkane, optionally substituted benzene or halosulfonic acid, e.g. methane, ethane, benzene, , hydroxy groups esterified with p-toluene or fluorosulfonic acid.

Formula II

Me- / I (II), Ύ = ·

wherein Y is -CH = or -N = and Me is suitably a metal atom, especially an alkali metal atom, of formula III

R

Ia / * \

Ar-O- / --- pr-CH - X (III),

Too \ 1 1

With a compound according to claim 25, wherein the radicals Ar, Rfl, R1, U

and V is as defined in formula I and X is halogen, in particular chlorine, bromine or iodine, or benzenesulfonyloxy, p-tosyloxy, trifluoroacetyloxy or suitably lower alkylsulfonyloxy, such as e.g. mesyloxy, are suitably carried out in relative proportions. in a polar but reaction-inert organic solvent, e.g., N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, acetonitrile, benzonitrile, or the like. Such solvents may 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, etc.

If X represents chlorine or bromine, then alkali iodide (such as Na 2 or 15 KJ) may be added as appropriate to accelerate the reaction. Elevated temperatures of 0 to 220 ° C, preferably 80 to 170 ° C are preferred. Suitably, the reaction mixture is heated to reflux.

In those cases where in formula II Me represents 20 hydrogen, the process is carried out in the presence of a base. Examples of such bases are inorganic bases of alkali and alkaline earth metals, such as oxides, hydroxides, hydrides, carbonates and bicarbonates, as well as, e.g., tert-amines, such as triethylamine, triethylenediamine, piperidine, pyridine, 4-dimethylamine 4-pyrrolidyl-pyridine, etc.

In these and subsequent manufacturing variations, the intermediates and final products can be isolated from the reaction medium, and, if desired, purified by any of the generally conventional methods, e.g., extraction, crystallization, chromatography, distillation, etc.

The conversion of a carbonyl group in compounds of formula IV to a group of formula V takes place by reaction with an orthocarboxylic acid tri-C 1 -C 4 alkyl group in which the C 1 -C 4 alkyl groups are optionally substituted by halogen or C 1 -C 6 alkoxy. , or in the presence of an acid containing 11 to 77458 of at least 2 moles of a monohydric alcohol of the formula U-OH (Va) to give compounds of the formula I in which U and V denote the same, optionally substituted C 1 -C 4 alkyl groups, or by reaction with a diol of the formula 5 Vb HO-U ----- V-OH (Vb) to give compounds of the formula I in which U and V together form an alkylene bridge as defined at the beginning, in which case the radicals Ar, Y, R, cl R , U and V are the meanings given in connection with formula I.

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

According to a preferred embodiment of the ketalization, both reagents are heated under reflux for several hours together with an azeotrope former in a conventional organic solvent. Suitable azeotropes are, for example, benzene, toluene, xylene, chloroform or carbon tetrachloride, in which case the addition of a strong acid, such as p-toluenesulfonic acid, may be advantageous in order to complete the reaction. Useful organic solvents in this case are, for example, aromatic hydrocarbons, such as benzene, toluene, xylene, etc., saturated hydrocarbons, such as n-hexane, or saturated halogenated hydrocarbons, such as, for example, 1,1,1-trichloroethane.

Other methods of ketalization can also be used, e.g. by reacting ketone IV ketalized with the formulas Va or resp. Of the alkanols according to Vb, i.e. with an alcohol or phenol other than diols, and this is re-ketalized by reaction with excess alkanol.

Va vast, with diol Vb to give compound (I). The starting product can be prepared, for example, by means of a method variant A), D) and E).

12 77458

The preparation of compounds of formula I in which the substituents U and V according to method C) together denote the group -CH 2 -CH (CH 2 ZR 7) - takes place, for example, by reaction of a compound of formula VI with a compound of formula VII wherein X 1 represents -ZH and X 2 group X. The reaction is conveniently carried out in reaction inert organic solvents. Suitable for this purpose are, for example, N, N-dimethylformamide, N, N-dimethylacetamide, hexamethylphosphoric triamide, dimethylsulfoxide, 4-methyl-10-3-pentanone, etc. Mixtures of other reaction-inert solvents, e.g. aromatic hydrocarbons, such as benzene, can also be used. , with xylene, etc. In many cases, it may be advantageous to work in the presence of a base to accelerate the rate of the reaction.

Such bases are, for example, alkali metal hydrides or alkali metal carbonates. In certain cases, it may also be advantageous to first convert compound VI into a suitable metal salt in a known manner. This is preferably done by the reaction of compound VI with a Na compound, e.g. sodium hydride, sodium hydroxide, etc. This salt of formula VI is then 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, i.e. at the boiling point of the solvent, in order to improve the reaction rate.

Compounds of formulas VI and VII in which X 1 is a group X and X 2 is a group -ZH may also be reacted in a similar manner.

In the condensation reactions of formulas VI and VII, where X 1 and X 2 represent hydroxy, to products of formula I wherein Z represents 30 oxygen, the reagents can be heated in a suitable solvent under reflux, azeotropically distilling off the water formed at the same time. Solvent-35 I come into question aromatic hydrocarbons such as toluene or alcohol HO-R ^ themselves. This reaction is conveniently carried out in the presence of a strong acid, e.g. p-toluenesulphonic acid.

Variation D) starts from compounds of formulas VIII and IX in which the group represents -OMe and X 1 represents a nucleofugic starting group or vice versa, X 1 represents a nucleofugic starting group and X 1 forms a group -OMe. In this case, the radicals R, R, U, V, Y and Ar have in connection with formula I.

cl D

meanings presented; We appropriately denote hydrogen. The reaction is preferably carried out under the conditions described in connection with method A).

In variant E) a decarboxylable compound of formula X is obtained by ketalizing a compound of formula XI as described in connection with variant B)

R

Ia 0 il / -y

Ar-O-C-O- · '> -C-CH -N (XI), S f 2 V!

which in turn can be obtained by reacting a compound of formula Ar-OH XII with a difunctional derivative of carbonic acid, e.g. phosgene, halo formic acid lower alkyl ester or dialemplyl or diphenyl carbonate, and further reacting with a compound of formula XIII

4? S · «» HO— (> -C-CH, - <Bill)

X

With a compound of claim 20, is heated dry or in a high boiling solvent such as a high boiling ether, e.g. diphenyl ether or ethylene glycol dimethyl ether at a temperature of about 120-220 ° C.

14 77458

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

Thus, for example, the compounds obtainable according to the process can be recetalized to other compounds of the formula I. For example, in compounds of formula I wherein U and V represent the same, optionally substituted C 1 -C 4 alkyl radicals U, by reaction with 1 mole of another optionally substituted C 1 -C 4 (Cc) alkylanol of formula V-OH (Vc) , the group U is replaced by a group V or by reaction with a diol of formula Vb both groups U are replaced by a divalent residue. The re-ketalization takes place in a conventional manner, for example in the presence of an acidic condensing agent, such as a mineral, sulfonic or strong carboxylic acid, e.g. hydrochloric or hydrobromic acid, sulfuric acid, p-toluenesulfonic acid or trifluoroacetic acid, preferably by azeotropic distillation.

20 Furthermore, according to the method,

to the carbocyclic aryl moieties of the compounds optionally with additional substituents on the residue Ar and / or the groups R

3.

resp. Thus, halogen can be attached, for example, by reacting with halogen in the presence of a Lewis acid such as iron, zinc, boron or antimony halide or by treatment with N-chlorosuccinimide.

Furthermore, the nitro groups can be reduced, for example, with the aid of suitable complex hydrides, e.g. lithium aluminum hydride, to amines, these are diazotized, e.g. with nitric acid, and the diazonium group formed is replaced in a conventional manner by halogen or alkoxy. Likewise, halogen can be replaced by alkyl by reacting with an alkyl metal compound, e.g., alkyllithium or alkylmagnesium halide.

35 If the compounds of formula I are obtained as bases, they can then be converted into inorganic or organic acids.

II

is 77458 to the corresponding salts or, preferably, equimolar amounts of metal salts to the metal complexes of the formula I. Conversely the salts of the formula I can be converted, for example by reaction with alkali (hydrogen) carbonate or alkali hydroxide, into the free bases of the formula I.

The starting ketals of formula III can be prepared from the underlying formula of formula XIV

.h / T x

Ar-O- · ^ y- CO-CH3 (XIV)

T

From the methylaryl ketone of Rb by reaction with the desired diol in an inert solvent, e.g., a halogenated hydrocarbon (such as methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, etc.) and halogenation simultaneously or thereafter. To speed up the reaction, the addition of p-toluenesulfonic acid may be preferred.

Ketones of formula IV can be prepared by halogenating the starting ketones of formula XIV

R

ia • 4 ·

Ar-O- ^ ^ -CO-CH2-Hal (XV) Ύ * b and by further reacting a compound of formula XV with azole of formula II according to variant A. In this case, Hai suitably denotes chlorine or bromine.

Ketals III, VI, IX and X are obtained according to variant B, e.g. by reacting the starting ketone of formula IV with a suitable alcohol or diol.

The described method variations are part of the invention.

'6 77458

The starting materials of the formulas III, IV, VI, X and XI, which have been specially developed for the preparation of the compounds of the formula I according to the invention, are new and are also the subject of the invention.

In all the ketone ketalization reactions described with a substituted α, β- or α, γ-diol, mixtures of diastereomers of the resulting ketal are formed primarily. Correspondingly, the starting ketones generally form diastereomeric mixtures of the final products I. The compounds 10 of the formula I can exist, for example, in both of the following diastereomeric forms: X '"Ar' ° 0Ra c / C 'A-types ® f? -? F • · · ·> · .." sv ·.

/ -Ξ A Ή (XVI) ch2zr7 (XVII) r3

The Type A configuration is referred to herein as "trans" isomers

'"Ft- /" I

\ 'K == ^. . .. * b Λ -? ? LJ ... M "··.

4 H (XIX) R3 (XVIII) CH2ZR?

The symbols have the following meanings in space structures: 15 ... = behind the drawing plane = inside the drawing plane ► = above the drawing plane.

tl 17 77458

The type B configuration is referred to as the "cis" isomers, respectively. Separation of the two diastereomers can take place, for example, by fractional crystallization or chromatography (thin, thick layer, column chromatography, high pressure liquid chromatography, etc.). Both isomers have different biological effects. Mixtures of diastereomers are generally used for practical purposes.

The invention relates to all isomeric compounds of the formula I, their salts and metal complexes.

The process for the preparation of the compounds of formula I is described in its variations A, B, C, D and E as part of the invention.

Some of the starting materials and intermediates used in Methods A, B, C, D and E are known, others may be prepared according to methods known per se.

15 Some are new; their preparation is explained here.

1- (β-aryl) -ethylimidazolyl ketals in which aryl represents substituted phenyl or naphthyl are disclosed in the following references as fungicides and bactericides: U.S. Patent Nos. 3,575,999, 3,936,470, 20,101,664, 4,101,666, 4,156 008.

Surprisingly, it has been found that the compounds of the formula I have a microbicide spectrum against phytopathogenic fungi and bacteria which is very suitable for practical purposes.

Thus, they have highly advantageous (curative) curative, preventive and systemic phytotherapeutic properties and can be used to protect crops. The active compounds of the formula I can be used to prevent or eliminate microorganisms present in plants or parts of plants (fruits, flowers, leaves, stems, tubers, roots) of various crops, so that later growing parts of the plant are also spared such microorganisms.

The active ingredients then act in particular against phytopathogenic fungi belonging to the following groups: Ascomycete (enclosed fungi) (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Uncinula); Basidiomycetes (e.g. fungi Hemileia, Rhizoctonia, Puccinia); Fungi imperfecti (incomplete fungi) (e.g. Botrytis, Helminthosporium, 5 Fusarium, Septoria, Cercospora and Alternaria). In addition, the compounds of the formula I act systemically. They can also be used as pickling agents to treat seeds (fruits, tubers, grains) and plant seedlings to protect them from fungal infections and against phytopathogenic fungi in the soil. The compounds according to the invention are characterized in particular by good plant tolerability.

The invention therefore also relates to microbicidal agents and to the use of the compounds of the formula I for controlling phytopathogenic microorganisms, in particular plant-damaging fungi, for preventing plant infection.

In addition, the present invention also encompasses the preparation of agrochemicals, which is characterized by thoroughly mixing the active substance with one or more groups of substances described herein. The invention also relates to a process for the treatment of plants, which process is characterized in that the compounds of the formula I or novel substances are used.

Target crops for the indication areas mentioned herein include, for example, the following plant species within the scope of the invention: cereals (wheat, barley, rye, oats, rice, sorghum and relatives); beets: (sugar and fodder beet); seed, stone and berry fruits: (apple, pear, plum, peach, 30 almonds, cherries, strawberry, raspberry and blackberry); legumes: (beans, lentils, peas, soybeans); oilseeds: (oilseed rape, mustard, poppy, olives, sunflowers, coconut, castor, cocoa, peanuts); cucumbers: (pumpkin, cucumbers, melons); fiber plants: (cotton, flax, 35 hemp, jute); citrus fruits: (oranges, lemons, grapefruits, mandarins); vegetables: (spinach, lettuce, teaspoon ι »77458 asparagus, cabbage, carrots, onions, tomatoes, potatoes, peppers); bay plants: (avocado, cinnamon, camphor) or plants such as corn, tobacco, nuts, coffee, sugar cane, tea, vines, hops, banana and natural-5 plants, and ornamentals (Compositae).

The active compounds of the formula I are customarily used in the agricultural sector in the form of compositions and can be applied simultaneously or sequentially with the other active ingredients to the area to be treated, to the plants or to the plant parts. These other active substances may be used in the context of plant protection products as fertilizers, trace element mediators and other preparations which affect plant growth.

They may also be selective herbicides, insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, together with possibly other carriers, surfactants or other spreading aids customary in the art.

In all preparations, suitable carriers or additives may be solid or liquid and correspond to non-toxic substances appropriate in the art of preparation, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners or binders.

In agriculture, a suitable method for applying an active compound of the formula I or an agrochemical to an infected plant is foliar application (foliar application). The number of applications and the amount of application are then adapted to the infection pressure of the corresponding pathogen (fungal species). However, the active compounds of the formula I can penetrate the plant through the soil and the root system (systemic effect) by wetting the plant growth site with a liquid composition or applying the substances in solid form to the soil, e.g. in the form of granules (land application). However, the compounds of the formula I can also be applied to the seed grains (Coating) in such a way that the grains are moistened with a liquid composition of the active ingredient or coated with a solid composition. In addition to this, other applications are possible in special cases, such as the target treatment of plant stems or buds.

The compounds of the formula I are then used in unchanged form or, preferably, in combination with customary auxiliaries in agrochemical production and are therefore prepared, for example, into emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, powdered powders, spray powders, granules, e.g. by encapsulation in polymeric substances in a known manner. The methods of application, such as spraying, atomizing, dusting, spreading, spreading or pouring, are then selected as well as the quality of the substances according to the desired objectives and the prevailing conditions. Favorable application rates are generally from 50 g to 5 kg of active substance (AS) per hectare; suitably 100 g to 2 kg AS / ha, in particular 200 g to 600 20 AS / ha.

Agrochemical preparations, i.e. Substances, preparations or compositions containing an active ingredient of the 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 ingredients with diluents, such as solvents, solid carriers and optionally surfactants.

Suitable solvents are: aromatic hydrocarbons, preferably fractions C8 to C18, such as xylene mixtures or substituted naphthalenes, phthalic acid esters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane and paraffins, alcohols esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar

II

21 77458 solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils, such as epoxidized coconut oil or soybean oil, or water.

5 For solid carriers, for example dusting or dispersible powders, natural stone powders, such as calcite, talc, kaolin, montmorillonite or attapulgite, are generally used. Highly dispersed silica or highly dispersed absorbent polymers can also be added to improve physical properties. Suitable granular, adsorptive granulate carriers are porous types, such as pumice, crushed brick, sepiolite or bentonite, and non-sorbent carriers, such as calcite or sand. In addition to this, several substances of pre-granulated inorganic or organic nature can be used, such as, in particular, dolomite or comminuted plant residues.

Suitable surfactants are, depending on the nature of the active ingredient to be prepared according to the formula I, non-ionic, cationic and / or anionic surfactants which have good emulsifying, dispersing and wetting properties. Surfactants also mean mixtures of surfactants.

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

Soaps include alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids, such as oleic or stearic acid.

Na or K salts, or corresponding salts of natural fatty acid mixtures, which can be prepared, for example, from coconut or tallow oil. Fatty acid methyl laurine salts should also be mentioned.

35 However, so-called synthetic surfactants are most often used, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates.

Fatty sulphonates or sulphates generally exist as alkali, alkaline earth or optionally substituted ammonium salts and have an alkali residue having 8 to 22 carbon atoms, the alkyl also containing the alkyl part of acyl residues, e.g. lignin sulphonic acid, dodecyl sulfuric acid poester or natural fatty acids Na or Ca salts of an alcohol sulfate mixture. These also include the sulfonic acid salts of sulfuric acid esters and fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain a fatty acid residue having 2-sulfonic acid groups and 8 to 22 carbon atoms. Alkylarylsulfonates are, for example, the Na, Ca or triethanolamine salts of dode-15-alkylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or naphthalenesulfonic acid-formaldehyde condensation product.

Corresponding phosphates, such as, for example, the salts of the phosphoric acid ester of the product p-nonylphenol- (4-14) -ethylene oxide addition-20, are also contemplated.

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

Other suitable nonionic surfactants include water-soluble polyethylene oxide addition products containing polypropylene glycol having from 20 to 250 ethylene glycol ether groups and from 10 to 100 propylene glycol ether groups to polypropylene glycol, ethylenediaminopolypropylene glycol on alkyl, ethylene glycol and alkyl polypropyl and alkyl polyethyl. Said compounds usually contain 35 to 5 ethylene glycol units per propylene glycol unit.

Il 23 7745 8

Examples of nonionic surfactants include nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, are also suitable.

Cationic surfactants are in particular quaternary ammonium salts which contain at least one alkyl residue having 8 to 22 carbon atoms as substituents and lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals as other substituents. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethyl-ammonium chloride or benzyldi (2-chloroethyl) ethylammonium bromide.

In agrochemical manufacturing technology, conventional surfactants have been described e.g. in "Mc Cutcheon's Detergents and Emulsifiers Annual" MC 20 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%, in particular from 0.1 to 95%, of the active compound of the formula I, 9-1%, in particular 99.8-5% of solid or liquid additive, of which 0-25%, in particular 0.1-25% of surfactant.

When rather concentrated substances are preferred as a commodity, the end consumer usually uses diluted substances.

Agrochemicals may also contain other additives such as stabilizers, antifoams, viscosity modifiers, binders, adhesives and fertilizers or other active ingredients to produce specific effects.

35 Such agrochemicals are part of the present invention.

24 77458

Experimental Description In the experiments described below, the following prior art compounds A to N were compared to compounds X1 to X25 of the invention to show that para-phenoxy substitution of a phenyl residue in the azole derivatives of this application is necessary to significantly increase fungicidal activity compared to similar compounds. the phenyl position of said phenyl residue is hydrogen, methoxy or phenyl.

1. Compounds tested 1.1 Compounds according to the prior art

A

N. «. X o 'N0 Χ · -Α USP-4,160,838, Ϊ —— I e.g. IIj. compound

B CH 2 -O- (V-tCt-CH 2 -I

<f N0 - S USP-4,160,838, • -1 e.g. XIV compound C CH »-0— {-fir-Ctlr — K j or> 0 · USP-4,160,838, I-- e.g. XX Fifth compound NCHj / 1

D CHj-0 — t I

flT> D - I USP-4,160,838 »_J Compound No. 31 of Table I ··· ··

E CHj-0 — f ^ · - ^ r-CH * - \ I

\ ./ ςΓΊη —A USP-4,156,008, J_I Compound No. 13 of Table I SCaH »F CHj-0 — f 1 \ · / </> —A USP-4,101,666, JI e.g. XXXI third compound SCH * 0I1 11 25 77458 0 CHj-O- ^ j - 0Γ xO.-S USP-4,160,838, • · esii? .. XXI Fifth compound "'Cy' _ 'C /' * 7VCH2 '-'" O USP - *, 479.00 », YY Compound No. 1.1 j ··. · - ·. Ma ·

! s s ___ / N__c_ch2 - / ^ I

\ ✓ \ / \ T ^>. 1 USP-4,479,004, γ f. «Ft Compound No. 6.1» - - · NCH 2 OCH | K * \ ✓ * * \ / * USP-4,479,004 / ** · *** 9 i Compound No. 2.2 • ——- 0

HjC ^ NC2H5 1 'Ό »SP - *. * /». 004 YY Compound No. 3.1 • · u - \ / 6h3, · - · ^ »a · M ./ \ __./ V__c_ru, _✓" \ ✓ \ / V USP-4,479,004, ... ... 9 ^ γ * “Compound No. 4.6 • · \ /

HjC ^ SCHj * "O ^ - *. '79.0 ° * Y Y Compound No. 4.23 • ·

V

HsC ^ NCjHt 26 7 7 4 5 8 1.2 Compounds according to this application x, »NCiH5 X2 Br ~ · ^ ^» - 0- · ^ 1

% «. y <j> «« N

• · VCHj ^ CHj X3 Cl- · ^ ✓ * "7c \ k: H2" s \ 1 \ ./ N ... py —h »· VCHj / 1 x * --i J— * t XCzH5 / 1 X5 Cl- · ^ ^ »- 0- · ^ ✓ ·" 7C ^ CH ^ "Nv, i N ... '% ·'» -Η ♦ - · XC2Hs. / C1 «« - (‘ν- ^ Ος-ΐΒ, χ i

x.-. ' γ «-H

NCHj XCH »

II

...... / 1 27 7745 8

X8 Cl— £ ^ -0- ^ ✓ • "7cC" ch * ", \ I

·· · * · ··>> - '> NCH2CH2CHj .-. # »# JJ. ·

X9 CFj- '> -0- <J

··· ··. y · * Β •.

SC2Hs ^ CHj t ·· · - ·) ί * ·

X10 CH2O - ^ / * ° “\ s -pC ^ K2- \ I

·· m y (j) • j] «'> XCHj / 1

xii r— ^ V-o— ^ V — c — chj-n I

Ali \ / u \ / \ I

·· ·· Q Ό * MN

• I

HjC ^ \ η3 / C1 · - · f- · ^ J} «*

X12 Cl- · ^ \ -o- · ^ V — C — CH2-K I

\ / \ / 2 \ 1 I ·· · «· O p. · Ν ♦» CHi VCiH, ...... / 1 X13 Cl- · '> -0- <) .- C-CH, - < ^ j ·· «at. pr a ·!) • - <SCH2OCHi / 1 t- ·. ··· JJ ··

X14 Cl- ^ 0— 'y ^ Cr-CHi-S ^ I

·· ·· «Ϋ γ ··». ♦ \ h20CjH7 28 774 5 8

Xl 5 <) -0- (i ·· ·· O o · «> I <\ h2oh ..... / 1

Xl 6 F — f> · - ° - · ν 1

\ m · ·· γ * -S

• - - »SCH2OCH2CH-CH2 / CHs ··· 1» · ^ ··

X17 Cl- () -O-. (I

·· · «· Q O · · Ν CHj • ·· ··· ··

X18 Cl- · ^ v S- ^ Cr-CHi-i ^ I

'·· / x · * · (f y «» N

> '-'> \ 2Hs f »· |« · ··

X19 CF2- ^ 0— ^ 5 "-rCr" CH2-N ^ I

... ... rf Y • H

vc2h5 / C1 · »· ··· ··

X20 Cl-^ O-E; -rCr-CHt-11

\ ./ \ ./ <p ^. «H

• I> CH ^ \ 2Η5 • · \ / # / H, X22 οι - <;;;> - ο - <;;) .- ^ - α, Ι-χ (; ι * Λ,

II

29 77458 ...... / 1 X23 F— () -0- (VC-CHi-H '* j * ·· ··· ψ Ό \ mt • i \ / CBi XCHj X2i T -. () - -0 -. () '- 7Cr <H! - <"·]

- ... y y.-A

V \ „, / Hj X25 Cl- /) -0- () · -τΜΗι- · (j

... y '> y \ .J

V \ „, 2. Test methods 2.1 Residual protective effect against Puccinia qraminis in wheat

Six days after sowing, the wheat seedlings were sprayed with a spray solution prepared from a wettable powder of the active ingredient (200, 20 and 2 ppm of active ingredient). After 24 hours, the treated seedlings were infected with a fungal uredosporisus pension. After incubation for 48 hours at about 25 ° C and 95-100% relative humidity, the infected plants were kept in a greenhouse at about 22 ° C. Evaluation of rust spots formation was performed 14 days after infection. The size and number of typical leaf spots after the experiment were used as a criterion to evaluate the efficacy of the tested substances.

30 77458 2.2 Effect against Cercospora arachidicola in peanut seedlings.

Three-week-old peanut seedlings were sprayed with a spray solution prepared from a wettable powder of the active ingredient (200, 20 and 2 ppm of active ingredient). After about 12 hours, the treated seedlings were sprayed with a fungal conidiosporisus pension. The infected seedlings were then incubated for about 24 hours at 90% relative humidity and then transferred to a greenhouse at about 22 ° C. The amount of fungal infection was assessed after 12 days. The size and number of typical leaf spots present after the experiment were used as a criterion to evaluate the efficacy of the tested substances.

2.3 Residual protective effect against Erysiphe qramin on barley Approximately 8 cm long barley seedlings were sprayed with a spray solution prepared from a wettable powder of the active ingredient (200, 20 and 2 ppm of active ingredient). After 3-4 hours, the treated seedlings were dusted with fungal conidiospores. Infected barley seedlings were transferred to a greenhouse at 22 ° C and fungal infection was assessed after 10 days. After the experiment, the size and amount of typical fungal growth on the leaves were considered a criterion for evaluating the efficacy of the tested substances.

2.4 Residual protective effect against Venturia inaequalis in omega shoots

Apple tree seedlings with new shoots 10-20 cm long were sprayed with a spray solution prepared from a wettable powder of the active ingredient (200, 20 and 2 ppm of active ingredient). After 24 hours, the treated seedlings were sprayed with a fungal conidiosporis suspension. The seedlings were then incubated for 6 days at 90-100% relative humidity and kept for another 10 days in a greenhouse at 20-24 ° C. The amount of fruit lupus intent 31 77458 infection was estimated 15 days after infection. The size and number of typical leaf spots present after the experiment were considered a criterion for evaluating the efficacy of the tested substances.

2.5 Evaluation scale

Labeling% activity 1> 95 (complete inhibition) 3 80-95 (acceptable inhibition) 6 50-80 (insufficient inhibition) 9 <50 (no inhibition)

For each test concentration in the above experiments, three parallel experiments were performed, each entry in the following tables representing the average of the three experimental results.

32 77458 3. Results 3.1 Results of the prior art compounds * Phytotoxic effects observed

Test 2.1 Test 2.2 Test 2.3 Test 2.4

Puccinia Cercoapora Eryaiphe Vanturia

Compound 200/20/2 ppm 200/20/2 ppm 200/20/2 ppa 200/20/2 ppm A 999 999 999 999 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 C 5 * 99 699 1 * 99 999 H 699 299 115 699 I 999589399999 K 369168336699 L 369 669 336 369 H 999 999 999 999 N 136 999 339 999

II

33 77458 3.2. Results of the compounds of this application

Test 2.1 Test 2.2 Test 2.3 Test 2.4

Puccinia Carcoapora Eryaiphe Venturla

Compound 200/20/2 ppm 200/20/2 ppm 200/20/2 ppm 200/20/2 ppm XI 199 126 113 159 X2 12 9 111111111 X3 116 116 111116 X4 119 119 111119 X5 111113 111113 X6 113 111113 113 X7 111 111 113111 X8 111112 113 112 X9 113 113 11112 8 X10 119 119 1113 6 6 XII 111111113 111 X12 113 113 113 116

Xl 3 111112 112 113 X14 111113 13 3 111 X15 336 169 369 336

Xl 6 111111136 112

Xl 7 12 3 111112 113

Xl 8 1 1 6 1 3 9 1 1 1 2 2 6

Xl 9 11112 6 11116 9 X20 1 1 2 1 3 6 1 1 3 1 3 9 X21 1 5 9 1 2 8 1 1 1 1 1 6 X22 111 113 113 113 X23 1 1 6 1 1 9 1 3 3 1 1 6 X24 113 111 111 116 X25 1 1 1 1 1 1 1 1 3 6 9 9 4. Conclusion

In the phytofungicide experiments 2.1 to 2.4 described above, the phenoxyphenyl derivatives X1 to X25 had significantly better activity than the structurally closest, prior art phenyl derivatives A to N.

34 77458

The following examples further illustrate the invention without limiting it. Temperatures are in degrees Celsius, pressures are in mbar. Percentages and parts refer to weight, h stands for hours.

Preparation Examples:

Example 1: Preparation of 2 - [((phenoxy) -phenyl) -2- [1- (1H-1,2,4-triazolyl) methyl) -4-methyl-1,3-dioxane • CH 3 • ·

I I

· - · · - · 0 0 · = N

<> - »- <> —Y — V i« · »• S · · = · N = · a) Intermediate / VCH3 * I (xx) / '% ° \ / ° \ /' 0 \ / - C Preparation of -CH2Br • = · · = · 2 - [(phenoxy) -phenyl) -2-bromomethyl-4-methyl-1,3-dioxane 10 parts 2- (p- (phenoxy) -phenyl) -2-oxy -1-Bromoethane and 4 parts of 1,3-butanediol are heated in 40 ml of absolute toluene in the presence of 0.2 parts of catalytically active p-toluenesulfonic acid under reflux for 3 hours, the water formed being separated in a water separator. After cooling to room temperature, the reaction mixture is washed twice with 20 ml of water each time, dried over sodium sulfate, filtered, the solvent is evaporated off and the crude product is recrystallized from isopropanol. Colorless crystals, m.p. 96-106 °.

b) Preparation of the final product 3.3 parts of 1,2,4-triazole sodium salt and a catalytically effective amount of potassium iodide are mixed in 40 ml of 11 35 77458 dimethyl sulphoxide prepared according to 2- (p- (phenoxy) phenyl) -2-bromomethyl With 4-methyl-1,3-dioxane in 10.2 parts for 30 h at an internal temperature of + 120 ° C. After cooling to room temperature, 300 ml of water are added, the mixture is extracted three times with 30 ml of ethyl acetate each time, the combined extracts are washed twice with 20 ml of water each time, dried over sodium sulphate, filtered and the solvent is evaporated, the oily residue is purified by column chromatography ( silicon-10 l / ethyl acetate). After evaporation of the eluent, an oily residue crystallizes after the addition of petroleum ether. Brownish crystals, m.p. 99.5 to 101 ° C.

Example 2: / ch2och3 · - · · - · i <!) · = Ιι

Cl- () -0 -. () --— 0 —— CH -—— I (3.226) • S · · s · · = ·

X

Preparation of 2 - [(4-chloro-2-methylphenoxy) phenyl) -2- (1-imidazolyl-15-methyl) -4-methoxymethyl-1,3-dioxolane 16 parts of 2- (p- (4-chloro- 2-Methylphenoxy) -phenyl) -2- (1-imidazolylmethyl) -4-hydroxymethyl-1,3-dioxolane is dissolved in 150 ml of Ν, Ν-dimethylformamide and stirred, under nitrogen and with stirring, 1.9 part of a 55% sodium hydride dispersion and heated to 80 ° for 2 h. After cooling to room temperature, 6.3 parts of methyl iodide are added dropwise over 1 h with stirring, the reaction mixture is heated to 60 DEG C. for 2 h and diluted with 800 ml of ice water and extracted three times with 300 ml of ethyl acetate each time. The combined extracts are washed twice with 50 ml of water each time, dried over sodium sulfate, filtered and the solvent is evaporated. The residue is purified by column chromatography (silica gel / acetone-ethyl acetate 36 7745 8 (1: 1)). After evaporation of the propellant mixture, the diastereomeric mixture is crystallized by treatment with hexane. Beige crystals; mp. 92-106 °.

Example 3: / C2H5 NO .- / c 3 _ / '· (I /' \ 4NcA_cH - / '(3'263) CF3 "\ / \ / - C CH2 \ _l 5 2-fp- (2- Preparation of nitro-4-trifluoromethylphenoxy) phenyl) -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane 8.3 parts of 2- (p-hydroxyphenyl) -2- (1-imidazolylmethyl) ) -4-Ethyl-1,3-dioxolane is dissolved in 300 ml of dimethyl sulfoxide and mixed with 1.84 parts of ground potassium hydroxide, raising the temperature from 23 ° to 36 ° C. Heat to 70 ° for 2 hours. 7.4 parts of 4-chloro-3-nitrobenzotrifluoride in 100 ml of dimethyl sulfoxide are added dropwise with stirring at 70 [deg.] C. and the mixture is stirred for 3 h at 70 [deg.] C. After cooling to room temperature, the reaction mixture is poured onto water, which 2000 ml and extracted twice with 200 ml of diethyl ether each time, the combined extracts are washed twice with 70 ml of water each time, dried over sodium sulphate and the solvent is evaporated off, the oily residue is purified by column chromatography (silica gel). i / ethyl acetate). After evaporation of the vehicle, the diastereomeric mixture remains as a viscous mass.

Example 4: ___ / CH2CH3 · - · · - · n n · = · S) .- 0- () · —VI — ch2-n (j (3-12)

^. =. · = · · = N

ci

II

37 77458 Synthesis of 2- [3- (3-chlorophenoxy) -phenyl) -2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane 1.2 parts of imidazole sodium salt and a catalytically effective amount of potassium iodide are mixed in 50 ml. di-5-methylformamide together with 2- (p- (3-chlorophenoxy) -phenyl) -2-bromomethyl-4-ethyl-1,3-dioxolane in 4 parts for 17 h at an internal temperature of 125 °. After cooling, 150 ml of water are added to the brown reaction mixture, the mixture is extracted three times with 50 ml of ethyl acetate each time, the combined extracts are washed twice with 50 ml of water each time, dried over sodium sulfate, filtered and the solvent is evaporated, the oily crude product is via acetone / ethyl acetate (1: 1). After evaporation of the propellant, an oily residue crystallizes after the addition of petroleum ether. Slightly yellowish crystals, m.p. 69-71.

Example 5: ___ / CH2CH3 S ~ \ _ / "% C11 (3.7) cl" \ / ° '\ / - ° CT2 \ m \ • SS9 * B * (2-fp- (4-chlorophenoxy) -phenyl) - Preparation of 2- (1-imidazolylmethyl) -4-ethyl-1,3-dioxolane 20 a) Synthesis of intermediates a) / CH2CH3 C1- <> '° - \) - C-CH3 • = · · = · 38 774 5 8 Preparation of 2 - [(4-chlorophenoxy) phenyl) -2-methyl-4-ethyl-1,3-dioxolane 37 parts of 4- (p-chlorophenoxy) acetophenone and 18 parts of 1,2-butanediol are heated in 400 ml. absolute 5 toluene with 2 parts of catalytically active p-toluenesulfonic acid for 14 h in a water separator under reflux. After cooling to room temperature, the reaction mixture is washed twice with 400 ml of water each time, dried over sodium sulfate, filtered, the solvent is evaporated off and the crude product is chromatographed on a 1 m silica gel column for purification with ligroin / hexane / ethyl acetate / toluene (5 : 3: 1: 1). The product is obtained as a slightly yellowish oil, nD: 1.5527.

6) / CH2CH3 * - «t- · · - · n 0

/> \ A \ υ \ / U

Preparation of C1- [trans-CH2-Br • = · · S · 15 2- [2- (4-chlorophenoxy) -phenyl] -2-bromomethyl-4-ethyl-1,3-dioxolane 36.8 part of the 2- (p- (4-chlorophenoxy) phenyl) -2-methyl-4-ethyl-1,3-dioxolane prepared in a) is heated in 350 ml of chloroform until boiling. Under illumination with a 20 150 watt spot lamp, 19.4 parts of bromine dissolved in 50 ml of chloroform are added dropwise, followed by heating under reflux for 2 h. After cooling to room temperature, the reaction mixture is washed twice with 200 ml of water each time, dried over sodium sulfate, filtered and the solvent is removed in a water-jet vacuum. For purification, the crude product is chromatographed on a 1 m long silica gel column with toluene. The product is obtained in the form of 23 yellow oil. ηβ: 1.5805.

Il 39 7 7 4 5 8 b) Synthesis of the final product 4.4 parts of imidazole sodium salt and a catalytically effective amount of potassium iodide are mixed in 80 ml of dimethylformamide together with 14.7 parts of 2- (p- ( 4-chlorophenoxy) phenyl) -2-bromomethyl-4-ethyl-1,3-dioxolane for 17 h at a bath temperature of 125 ° C. After cooling to room temperature, the reaction mixture is poured onto 600 ml of water, extracted three times with 200 ml of ethyl acetate each time, the combined organic phases are washed twice with 200 ml of water each time, dried over sodium sulphate, filtered and the solvent is evaporated . the oily residue is chromatographed on a 50 cm column of silica gel with acetone / ethyl acetate (1: 1). After evaporation of the propellant, the product is obtained in the form of a brown oil; ηβ: 1.5750.

Example 6: / CH2CH3 • »

· - · · - · 0 0 • —N

A \ A \ \ / / V (1.9) <) - ° - <) - C-CH2 <• = · IB · N = · 2-fp- (phenoxy) -phenyl) -2- (1H-1, Synthesis of 2,4-triazolylmethyl) -4-ethyl-1,3-dioxolane 17 parts of 2- (p- (phenoxy) -phenyl) -3-bromomethyl-4-ethyl-20'-1,3-dioxolane, 8, 4 parts of potassium carbonate, 4.2 parts of 1,2,4-triazole and a catalytically effective amount of sodium iodide are stirred in 100 ml of dimethyl sulfoxide for 24 h at an internal temperature of 125 °. After cooling to room temperature, the reaction mixture is poured onto 600 ml of water, extracted three times with 200 ml of ethyl acetate each time, the combined extracts are washed twice with 200 ml of water each time, dried over sodium sulfate, filtered and the solvent is evaporated. The oily residue is chromatographed on a 50 cm long silica gel column 40 7 7 4 5 8 with chloroform / ether (1: 1). After evaporation of the propellant, an oily residue crystallizes after the addition of petroleum ether. White crystals; mp. 81.5 to 83.5 °.

Example 7:

/ N

Synthesis of 2- (p-phenoxyphenyl) -1- (1H-1,2,4-triazolylmethyl) -1,3-dioxane 14 parts 2- (p-phenoxyphenyl) ) -2-bromomethyl-1,3-dioxane, 7.2 parts of potassium carbonate, 3.6 parts of 1,2,4-triazole and a catalytically effective amount of potassium iodide 10 are stirred in 100 ml of dimethyl sulfoxide for 20 h at 140 °: n internal temperature. After cooling to room temperature, 600 ml of water are added, the mixture is extracted three times with 200 ml of ether each time, the purified extracts are washed twice with 200 ml of water each time, dried over sodium sulfate, filtered and the solvent is evaporated off. through a long silica gel column with chloroform / ether (1: 1). After evaporation of the propellant, the residue crystallizes after the addition of petroleum ether. White crystals, m.p. 129-130 °.

20 Example 8:

/ C ^ OH

· —— · ·. i P / = O S (-O- (1 - 23) -, ([. Synthesis of 4-hydroxymethyl-1,3-dioxolane

II

41 77458 4.5 parts of 2- (p-phenoxyphenyl) -2-bromomethyl-4-hydroxymethyl-1,3-dioxolane, 2.2 parts of potassium carbonate, 1.1 parts of 1,2,4-triazole and catalytically active an amount of potassium iodide is stirred in 50 ml of dimethyl sulfoxide for 4 h at an internal temperature of 140 °. After cooling to room temperature, 600 ml of water are added, the mixture is extracted twice with 200 ml of ethyl acetate each time, the combined extracts are washed twice with 200 ml of water each time, dried over sodium sulphate, filtered and the solvent is evaporated, the oily residue is chromatographed on a 50 cm silica gel column. via acetone. After evaporation of the propellant, an oily residue crystallizes after the addition of petroleum ether. Beige crystals, m.p. 111-122 °.

Example 9: Synthesis of ___ / h2ch2ch3 7 α · 17> [2- (phenoxy) -phenyl) -2- (1H-1,2,4-triazolylmethyl-4-n-propyl-1,3-dioxolane 10, 3 parts of 1- (p-phenoxyphenyl) -2- (1,2,4-triazol-1-yl) -ethanone nitrate, 6.1 parts of 1,2-pentanediol, 6.9 parts of p-toluenesulfonic acid, 20 parts 1-Pentanol and 200 parts of xylene are heated for 6 days in a water separator under reflux and, after cooling to room temperature, washed twice with 200 ml of dilute sodium hydroxide solution each time and twice with 200 ml of water each time. , the oily residue is chromatographed on a 1 m column of silica gel with ethyl acetate, and after evaporation of the propellant 42 7 7 4 5 8 the oily residue slowly crystallizes.

68.5 to 71 °.

Example 10: / CH 3 <> ° - <J / V “2 - K) (5'73) ° \ Λ • - · \ H5 2 - ((2'-methyl-4'-phenoxy) -phenyl) -2 Preparation of - (1-imidazolylmethyl-5H) -4-ethyl-1,3-dioxolane a) Starting material / CH 3 • s · · = · /) · - 0 - (J-CCH Br V / \ -SU 2 0 2 -methyl-4-phenoxy-phenacyl bromide.

To 36.6 parts of 2-methyl-4-phenoxyacetophenone in 160 ml of acetic acid is added 25.9 parts of bromine at 35 ° within 1 hour. At the end of the dropwise addition, stir for 1 hour at room temperature, then pour into 1 liter of ice water and extract twice, each time with 100 ml of ether. The combined organic extracts are washed thoroughly with water, dried over sodium sulfate, filtered and the solvent is evaporated and the crude product is triturated with hexane.

Brown crystals, m.p. 60-61 °.

b) The intermediate Λ • S · · = · \) - 0) -A 'ch2 ”Br o o \ / • - ·

\ HS

2 - ((2-methyl-4'-phenoxy) -phenyl) -2-bromomethyl-4-ethyl-

II

43 7 7 4 5 8 Preparation of 1,3-dioxolane.

85.4 parts of the 2-methyl-4-phenoxy-phenacyl bromide prepared in a) and 25.2 parts of 1,2-butanediol are heated in 250 ml of absolute toluene using 1 part of 5 catalytically active p-toluenesulfonic acid under reflux for 24 hours using a water separator. After cooling to room temperature, the reaction mixture is washed three times with 250 ml of water each time, dried over sodium sulfate, filtered and the solvent is evaporated off. The product is obtained as a reddish-10 light oil.

c) Synthesis of the final product 9.5 parts of 2 - ((2'-methyl-4'-phenoxy) -phenyl) -2-bromomethyl-4-ethyl-1,3-dioxolane prepared in b), 2.4 parts of imidazole 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 °. After cooling to room temperature, 300 ml of water are added, the mixture is extracted three times with 150 ml of ethyl acetate each time, the combined extracts are washed neutral with water, dried over sodium sulfate, filtered, the solvent is evaporated off and the oily residue is chromatographed on ethyl acetate on a 50 cm silica gel column. The product is obtained as a reddish oil, ηβ: 1.5550.

Example 11: • - - · • - · · - · A A · 3εΝ <> - ° - <> Vci.2- <| Preparation of (1,1) • as · · SS · fjs · 2- (p- (phenoxy) -phenyl) -2- [1- (1H-1,2,4-triazolyl) -methyl) -25 1,3-dioxolane 11 parts of 2- (p- (phenoxycarbonyloxy) phenyl) -2-) -1- (1H-1,2,4-triazolyl) methyl) -1,3-dioxolane are heated in 200 ml of ethylene glycol diethyl ether until long (about 10 hours) at 130 ° until the formation of carbon dioxide is la-30 jugs. The solvent is then distilled off under reduced pressure. After cooling to room temperature, the oily crude product is dissolved in 500 ml of diethyl ether, washed twice with 100 ml each time, dried over water / sodium sulphate, filtered and the solvent is evaporated off. The remaining crystals are purified by recrystallization from ethyl acetate / cyclohexane in the presence of activated carbon. White crystals are obtained, m.p. 100-102 °.

Example 12; • ss · ch2-o-ch2- (\ -ci • -

• - · · 8 · O Π · sN

<> -0- <I n.24 / 1.25)

\ / \ S 2 \ I

Preparation of A and B-Dias-10 stereoisomers of 2- (p- (phenoxy) -phenyl) -2- (1H-1,2,4-triazolylmethyl) -4- (p-chlorobenzyloxymethyl) -1,3-dioxolane.

14.1 parts of 2- (p- (phenoxy) -phenyl) -2- (1H-1,2,4-triazolylmethyl) -4-hydroxymethyl-1,3-dioxolane in 100 ml of dioxane are added dropwise with stirring and passing nitrogen at room temperature to 1.8 parts of a 55% sodium hydride dispersion in 100 ml of abs. dioxane and heated at 80 ° for 3 hours. After cooling to room temperature, added dropwise with stirring to a half hour si-- saber 8.6 parts of p-chlorobenzyl bromide in 50 parts of abs. diok

the reaction mixture is heated at 50 [deg.] C. for 3 hours,, after cooling to room temperature, diluted with 1200 ml of ice-water and extracted three times with 200 ml of ethyl acetate each time. The combined extracts are washed twice with 70 ml of water each time, dried over sodium sulfate, filtered and the solvent is evaporated off. The remaining diastereoisomer mixture is separated by column chromatography (silica gel / ethyl acetate). After evaporation of the ethyl acetate, diastereoisomer B is present

fixed; mp. 83-85 °. Diastereoisomer A remains on drying to dryness under high vacuum to a viscous light brown oil, n = 1.5865.

In a similar manner, the following end products of formula I can be prepared (unless otherwise indicated, as diastereomeric mixtures with different mixing ratios).

Il 45 7745 8

In the following table, the symbol A denotes the A-type diastereomer, and B the B-type diastereomer, respectively.

Table 1: Compounds of formula • - · \ o ,, and their isomeric forms:

Comp. r Y Salt Physics. standard 10 1

Well.

1.1 H N m.p. 100-102 ° 1.2 H N HNO 3 1.3 H CH - 1.4 CH 3 N m.p. 85-92 ° 1.5 CH3 N HCl 1.6 CH3 N CuCl2 1.7 CH CH - 1.8 CH3 N Mn (NO3) 2 1.9 C2H5 N - m.p. 81.5T83.5 ° 1.10 c2h5 n hno3 1.11 C2H5 N ZnCl2 1.12 C2H5 N Mn (NO3) 2 1.13 C2H5 N FeCl3 - - 1-14. CH "* light brown oil. · '1.15 C2H5 CH CuCl2 1.16 C3H7' n 'CH - 1.17 C3H7" n N "m.p. 68.5-71 ° 1.18 C3H7_n N ZnCl2 1.19 C3H7_n N HCl

Table 1 continues: «77458 - * ------------ ^ Salt Physics. standard no.

1.20 at C.H. OF

* 4 9

1.21 C.H-n CH

1.22 CH, C1 N

1.23 CH 2 OH N - m.p. 111-122 ° • - ·

/ \ 0 A

1.24 CH2OCH2- ^ Cl N - tough oil, nD = 1.5865 Å

* »S * • - ·

1.25 CH2OCH2 ~ · ^ / * - c1 N Sp. 83-85 ° B

· = * • - *

1.26 CH2 ° ~ '\ / * “CH3 N m.p. 107-109 ° A

• =: ·

1.27 CH2O * * / * ~ CH3 N "Sp * 90_9A ° B

• s · 1.28 CH 2 OH CH - m.p. 118-123 °

1.29 CH2OCH3 CH

1.30 C_Hc N 1 / 2CuSO.

2 5 k

1.31 CH2OC2H5 N

1.32 CH2OCH3 N

1.33 CH2OCH2CH2OCH3 N

II

Table 2: Compounds of formula 47 7 7 4 5 8) "° - \ χ · —7 ° ^ —ch2- <Ϊ <XXII> • = · · = · 0 0 Y = ·» · / \ R11 * 12 , including isomeric forms:

Comp. R12 Y Salt Physics. standard

Well,

2.1 CH3 C2H5 CH

2.2 CH3 C2H5 N

2.3 CH3 C2H3 CH HN03 2.4 CH3 C2H5 N HN03

2.5 CH3 C3H7_n CH

2.6 CH3 C3H7-n N

2.7 CH3 C3H7 ~ n N HNOs 2.8 CH3 C3H7 -n N Mn (NO3) 2

2.9 CH3 CH3 CH

2.10 CH3 CH3 CH CuCl2 2.11 CH3 C2H5 CH Mn (NO3) 2 2.12 CH3 C2H5 CH CuCl2 2.13 CH3 C2H5 N CuCl2 2.14 CH3 C2H5 N ZnCl2 2.15 CH3 C2H5 N Mn (NO3) 2 2.16 CH3 C2H5 N FeCl3 - 2.17 CH3 3 = 1.5643 2.18 CH3 CH3 N HNO3 2.19 C2H5 CH3 CH MnCl2 2.20 C2H5 CH3 N MnCl2 2.21 C ~ H CH0 CH H „S0.

2 5 3 2 4 2.22 C2H5 CH3 CH ZnCl2

Table 2 continues; «77458

Comp. Rjj R12 Y Salt

Well.

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2 3 2 5 2 4

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2.28 C2H5 C3H7-n N

2.29 C2H5 C3H7-i N

2.30 C2H5 C3H2 -n CH

2.31 C2H5 C3H2 -n N HCl 2.32 C2H5 C2H5 N Mn (NO3) 2 2.33 CH3 C2H5 N (C00H) 2 2.34 CH3 C2H5 CH (C00H> 2

2.35 CH3 c3H7 ~ i N

2.36 CH, C, H, -i N H, SO.

3 3 7 2 4

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Compounds of Rn * 12, including isomeric forms:

Comp. R ,, R10 R., R1Q Y Salt Physics. constant li 1/1 / io

Well.

5.1 CH3 C2H5 2-C1H CH - 5.2 CH3 C2H5 2-C1 HN - 5.3 CH3 C2H5 2-C16-C1 CH HNO3 5.4 CH3 C2H5 2-CH3 HN HNO3 5.5 CH3 c3H7_n 2-Cl H CH - 5.6 CH3 C3H? - n 2-C1 HN -

5.7 CH3 C3H7_n 3_cl H N

5.8 CH3 c3H7_n 3_cl 6 ~ C1 N Hn (NO3) 2 5.9 CH3 CH3 2-C1 H CH - 5.10 CH3 CH3 2-C1 6-C1 CH CuCl2 5.11 CH3 C2H5 2-C1 H CH Mn (NO3) 2 5.12 CH3 C2H5 2 -CH3 6-CH3 CH CuCl2 5.13 CH3 CH3 2-CH3 HN HNO3 m.p. 158-160 ° 5.14 CH3 CH3 2_CH3 HN HBr SP · 192-204 ° 5.15 CH3 C2H5 2-CH3 HN ΜηΟΊΟ ^ 5.16 CH3 C2H5 2-NO2 HN FeCl3 5.17 CH3 CH3 2-Cl HN - 5.18 CH3 CH3 2-C1 5-Cl N HN03 5.19 C2H5 CH3 3-C1 H CH MnCl2 5.20 C2H5 CH3 2-CH3 HN MnCl2 5.21 CH CH_ 2-CH_ HN CuCl z 5 J j 5.22 C2H5 CH3 2-C1 5-C1 N ZnCl2 5.23 C2H5 C2H5 2-Br H CH - 5.24 H C2H5 2-OCH3 6-0CH3 CH -

II

Table 5 continues: 83 7745 8

Combine R11 R12 R17 Ri8 Y Salt Phys. standard

Well.

5.25 H H 2-C1 H N -

5.26 H H 2-Cl H CH

5.27 H H 2-Cb 6-C} CH

5.28 H H 2 -Cl H N Mn (NO 3) 2

5.29 H H 2 -Cl 6 -Cl N

5.30 H CH3 2-C1 H N - 5.31 H CH3 2-C1 H N HNO3

5.32 H CH3 2-C1 6-C1 N

5.33 H CH3 2-C1 H CH - 5.34 H CH3 2-OCH3 6-OCH3 CH "5.35 H CH3 3-C1 HN - 5.36 H CH3 2-CH3 HN HNO3 mp 132-134 ° 5.37 H CH3 3_ch3 HN - 5.38 H C2H5 3-CH3 H CH CuCl2

5.39 H C.H 2 -CH 6-CH. OF

2 5 3 3 5.40 H C2H5 2-CH3 H N HNO3 m.p. 108-110 °

5.41 H C2H5 2-Br 5-Br N

5.42 H C2H5 2-C1 H N 1¾2 1.5620 5.43 H C3H7-n 2_Cl H N -

5.44 H C3H7_n2_Cl1-C1N

5.45 H C3H7_i 2-CH3 hn 5.46 H C3H7_i 2 “cH3 H CH - 5.47 H C3H7-1 2-0CH3 b-OCH 2-C1 6-C1 N HCl

5-51 H H 2 -OCH 3> -OCH 3 CH

5.52 C2H5 C3H2-i2-CH3 H N

Table 5 continues: 84 7 7 4 5 8

Comp. R ^ 2 R ^ y R18 ^ Salt Physics. standard

Well.

5.53 H C2H5 2-OCH3 6-OCH3 N

5.5AH C2H5 2-0CH3 6-OCH3 N - 5 · 55 H 'H / 2-OCH3 6-OCH3 N - 5.56 CH3 C2H5 3-Cl HN (COOH> 2 5.57 CH3 C2H5 2-CH3 6-CH3 CH (COOH) 2 5.58 CH3 c3H7 "i-2-C1 HN - 5.59 CH" C-H2-C16-C1 N H.SO.

3 3 7 2 A

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2 A

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2 A

5.67 - (CH 2) - 2-Cl H CH ZnClO 2 A 2 5.68 H H 2 -CH 3 H CH m.p. 103-106 ° 5.69 CH CH 2 -CH H CH - J J J 50 5.70 H C 3 H 7 -n 2-CH 3 H CH 1 ¾ 1.5476; 5.71 H CH2OCH3 2-CH3 H CH - resin 5.72 H CH 2 -CH H CH - 3 3 50 5.73 H C2H5 2-CH3 H CH - 1,5557 5.7AH CH-OH 2-CH_ H CH - 2 J 50 5.75 H CH OCH 2-CH HN - ^ 1/5482 2 3 3 5.76 H C2H5 2-CH3 HN 1.5502 5.77 HH 2-CH HN - m.p. 103-105 * J 50 5.78 H c3H7_n 2_CH3 HN "n 1'5467 5.79 H CH2OH 2-Cl H CH - 5.80 H C_H 2 -Br H CH - 2 5 50 5.81 H C2H5 2-C1 H CH -" d 1, 5765

II

Table 5 continues: 85 7 7 4 5 8

Rj ^ 2 Rjg Y Salt Physics. standard

Well.

5.82 H CH2OCH3 2-C1 H CH - 5.83 H CH2OCH3 2-C1 HN - 5.84 J1 CH2OH 2-Br H CH - 5.85 H CH2OCH3 2-Br H CH - 5.86 CH3 CH3 2-Br HN - 5.87 H CH2OCH3 2-Br HN - 5.88 H CH2OH 3 -NO2 H CH - 5.89 H C3H7_n 3 -NO2 HN - 5.90 H C2H5 2-Br HN - 5.91 H C2H5 3-NO2 H CH - 5.92 H CH3 3-NO2 H CH - 5.93 H C2H5 3-NO2 HN - 5.94 H CH3 3 -NO2 HN - 5.95 H CH2OH 3-CH3 H CH - 5.96 H CH2OCH3 3-CH3 HN - 5.97 H C2H5 2-NO2 H CH - 5.98 H CH2OCH3 2-NO2 H CH - 5.99 H CH OCH 2 -NO HN - 1 3 * 20 5 5.100 H C2H5 3-CH3 H CH1¾ '1.5692 5.101 H CH2OCH3 3-CH3 H CH - 5.102 H. C2H5 3-CH3 HN - v ^ · 1.5577 5.103 H CH2OH 2 -NO 2 H CH - 5.104 H C 2 H 5 2 -NO 2 HN - 86 77458

Table 5 continues:

Ybd. Rjj Rj2 Rj8 Y Salt Physics. standard

Nr.

Sit-, n 5.105 2-CH 2 H 2 -CH 2 5 -CK 2 CH - mass, 1.5463 /

5.106 H c3Vn 2 ~ CH3 H N - oil, n22 1.5461 A

5.107 H C3H7-n 2-CH3 H N - Visc. oil; "22 1-5468 B

Hari: -.

5.108 H C2H5 3-CH3 H N si, r ^ ° ^ 5638 hart- ςη 5.109 H C2H5 3-CH3 H CH - 31, ¾0 1.5732 5.110 H C2H5 2_C2H5 H N HN ° 3 m.p. 132-134 ° 5.111 H C2H5 2-CH3 H CH (C00H> 2 mp 115-118 ° 5.112 H C2H5 2-C2H5 H N Mjy; nj2 1.5642

5.113 H C2H5 3-CH3 H N - oil; τξ2 1.5631; A

5.114 H C2H5 3-CH3 HN 31jyJ τξ2 1.5633 3 · 113 H ^ 2H5 2 ~ ° 2H5 H CH - brown resin 5.116 H CH3 2-C2H5 H CH HN ° 3 mp 105-119 ° 5.117 H CH3 2_G2H5 H CH viscous oil 5.118 H CH3 2 * C2H5 HN HNO-j mp 136-138 °

II

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Examples for the preparation of agrochemicals containing liquid active ingredients of the formula I (% =% by weight) 13. Emulsion concentrates a) b) c) 5 active ingredients from farms 1-10 25% 40% 50%

Ca-dodecylbenzenesulfonate 5% 8% 6% castor oil polyethylene glycol ether 5% ter (30 moles ethylene oxide) tributylphenoyl polyethylene 12% 4% glycol ether (30 moles ethylene oxide) cyclohexanone 20% 20% 20% % Of such concentrates can be prepared by diluting with water emulsions of the desired concentrate.

14. Solutions a) b) c) d) active ingredient from Tables 1-10 80% 10% 5% 95% ethylene glycol monomethyl ether 20% - - - polyethylene glycol MG 400 - 70% 20 N-methyl-2-pyrrolidone-20 % epoxidized coconut oil - 1% 5% petrol (boiling range 160-190 ° C) - - 94% (MG = molecular weight)

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

15. Granules a) b) active ingredient from Tables 1-10 5% 10% kaolin 94% highly dispersed silicic acid 1% - 30 attapulgite - 90%

The active ingredient is dissolved in methylene chloride, sprayed onto the support and the solvent is then evaporated off in vacuo.

Il 109 77458 16. Dusts a) b) active ingredient from Tables 1-10 2% 5% highly dispersed silicic acid 1% 5% talc 97% 5 kaolin - 90%

Thorough mixing of the active ingredient over the carrier provides a useful dusting agent.

Examples for the preparation of agrochemicals containing active substances of the formula I (% = 10% by weight) 17. Spray powders a) b) c) active substance from Tables 1-10 25% 50% 75%

Na-lignin sulfonate 5% 5%

Na-lauryl sulfate 3% to 5% Na-diisobutylnaphthalene - 6% 10% sulfonate octylphenol polyethylene glycol - 2% - ether (7-8 moles of ethylene oxide) highly dispersed silicic acid 5% 10% 10% 20 kaolin 62% 27% -

The active ingredient is mixed well with the additives and ground in a very suitable mill. An spray powder is obtained which can be diluted with water to suspensions of arbitrary concentration.

25 18. Emulsion concentrates active substance from Tables 1-10 10% octylphenol polyethylene glycol ether 3% (4-5 moles of ethylene oxide)

Ca-dodecylbenzenesulfonate 3% 30 castor oil polyglycol ether 4% (35 moles ethylene oxide) cyclohexanone 30% xylene mixture 50% 110 77458 Emulsions of the desired concentration can be prepared from this concentrate by dilution with water.

19. Dusting agent a) b) active ingredient from Tables 1-10 5% 8% 5 talc 95% kaolin - 92%

A ready-to-use dusting agent is obtained by mixing the active ingredient with the carrier and grinding in a suitable mill.

20. Compressed granulate 10 active ingredient from tables 1-10 10%

Na-lignin sulfonate 2% carboxymethylcellulose 1% kaolin 87%

The active ingredient is mixed with additives, ground and moistened with water. This mixture is compressed and then dried in a stream of air.

21. Coating granulate active ingredient from Tables 1-10 3% polyethylene glycol (M G 200) 3% 20 kaolin 94% (MG = molecular weight)

The finely ground active ingredient is spread evenly in a mixer on kaolin moistened with polyethylene glycol. In this way, a dust-free coating granulate is obtained.

25 22. Suspension concentrate active ingredient from Tables 1-10 40% ethylene glycol 10% nonylphenol polyethylene glycol 6% ether (15 moles ethylene oxide) 30 N-lignin sulfonate 10%

II

111 77458 carboxymethylcellulose 1% 37% aqueous formaldehyde solution 0.2% silicone oil 75% aqueous 0.8% 5 emulsion water 32%

The finely ground active ingredient is mixed thoroughly with the additives. A suspension concentrate is thus obtained, from which suspensions of any concentration can be prepared by diluting with water.

Biological examples:

Example 23: Action against Puccinia graminis in wheat t a) Residual protective effect “15 Wheat plants were sprayed 6 days after sowing with a spray broth (0.006% of active ingredient) of the active ingredient spray powder. After 24 hours, the treated plants were infected with a summer spore suspension of the fungus. After 48 hours of incubation at 95-100% relative humidity at 20 and about 20 ° C, the infected plants were placed in a greenhouse at about 22 ° C. Evaluation of the development of rust vesicles occurred 12 days after infection.

b) Systemic impact

5 days after sowing, the wheat plants were sprayed with a spray liquor made of powdered active ingredient (0.006% of active ingredient based on soil volume). After 48 hours, the treated plants were infected with the fungus summer H? 77458 with spore suspension. After 48 hours of incubation at 95-100% relative humidity and about 20 ° C, the infected plants were placed in a greenhouse at about 22 ° C. Evaluation of the development of rust vesicles occurred 12 days after infection.

The compounds in Tables 1-10 showed good activity against Puccinia fungi. Untreated but infected control plants showed 100% Puccinia disease. Among other things, compounds Nos. 1.9, 1.17, 1.24, 1.26, 2.17, 3.1, 3.2, 3.6 -3.8, 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 would prevent , 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 and 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 in residual-protective treatment up to 0-5% of fungal infection. In addition, Compound No. 6.8 showed a complete systemic effect (0% infection) even when diluted to 0.006%.

Example 24: Action against Cercospora arachidicola in peanuts Peanut plants 10-15 cm tall were sprayed with a spray broth (0.02% of active ingredient) of the active ingredient spray powder and 48 hours later they were infected with a fungal conidiosuspension. Infected plants were incubated for 72 hours at about 21 ° C and high humidity and then placed in a greenhouse until typical leaf spots appeared. The evaluation of the fungicidal effect took place 12 days after infection and was based on the number and size of spots present.

Il 113 77458

Compared to untreated but infected control plants (number and size of spots = 100%), peanut plants treated with the active ingredients of Tables 1-10 showed a marked reduction in Cercospora disease. Thus compounds 1.1, 1.4, 1.9, 1.14, 1.17, 1.24 to 1.27, 2.17, 3.1, 3.2, 3.6, 3.7, 3.11, 3.51, 3.52, 3.54, 3.55, 3.57, 3.78, 3.85, 3.86, 3.127, 3.13 ?, 3.155, 3.156, 3.162, 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, 5.71, 5.73, 5.75 - 5.78, 5.105 - 5.110, 5.113 - 5.118, 6.1, 6.8 , 6.93, i 6.94, 7.33, 7.34 and 8.72 in the above experiment almost completely (0-5%) the formation of spots. !

Example 25; Action against Erysiphae graminis in barley a) Residual protective effect Approximately 8 cm high barley plants were sprayed with the active ingredient by spraying with a spray broth (0.02% of active substance). After 3-4 hours, the treated plants were sprayed with fungal conidia. Infected barley plants were placed in a greenhouse at about 22 ° C and fungal infestation was assessed after '10 days · b) Systemic effect For barley cones about 8 cm high, the active ingredient was sprayed with powdered spray broth (0.006% active substance by volume of soil). In doing so, care was taken to ensure that the spray liquor did not come into contact with the above-ground parts of the plant. After 48 hours, the treated plants were sprayed with conidia. Infected barley plants were placed in a greenhouse at about 22 ° C and fungal disease was assessed after 10 days.

114 77458

The compounds of formula I showed a good residual-protective effect against Erysiphe fungi. Untreated but infected control plants showed 100% Erysiphe disease. Among the compounds shown in Tables 1-10, compounds Nos. 1.1, 1.4, 1.9, 1.IA, 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, 3.5 A, 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, 3,231, 3,232 - 3,234, 3,263, 3,267, 3,274, 3,279, 3,287,3,292, 3,311, 3,314, 3,340, 3,348, 3,378, 3,383-3,388, 4.2, 4.15, 4.23, 4.50, 4.57, 4.59, 4.66 , 4.77, 4.78, 4.81, 4.89 - 4.94, 4.113, 4.116, 4.137, 4.139, 4.140, 4.141, 4.146, 4.148, 4.150, 5.13, 5.14, 5.36, 5.40, 5.70, 5.71, 5.73, 5.75 - 5.78, 5.106 - 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 to less than 5% barley fungal disease.

Compound No. 4.50 also showed this effect in soil treatment (systemic effect) and dilution to 0.006%.

Example 26; Residual-protective effect against Venturia inaegualis in apple cultures Apple cuttings with new shoots 10 to 20 cm long were sprayed with a spray broth (0.06% of active ingredient) of the active ingredient spray powder. After 24 hours, the treated plants were infected with a fungal conidia suspension. The plants were then incubated for 5 days at 90-100% relative humidity and further placed in a greenhouse at 20-24 ° C for 10 days. Scabies infection was assessed 15 days after infection. Compounds Nos. 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 - 3.387, 4.15, 4.23, 4.50, 4.59, 4.66, 4.78, 4.81, 4.89, 4.90 - 4.94, 4.113, 4.116, 4.137 - 4.141, 4.146 - 4.150, 5.13, 5.14, 5.36, 5.40, 5.70, 5.73, 5.75, 5.76, 5.106 - 5.110, 5.112 - 5.114, 5.118, 6.1, 6.8, 6.93 and io.7 'and others

II

1.5 77458 would prevent illness to less than 10%. Untreated but infected tumors showed 100% Venturi disease.

Example 27: Action against Botrytis cinerea in beans

Residual-protective effect Approx. 10 cm tall bean plants were sprayed with an active ingredient spray powder (0.02% active substance). After 48 hours, the treated plants were inoculated with a conidia suspension of fungi. After incubation of infected plants for 3 days at 95-100% relative humidity and 21 ° C, fungal disease was assessed. In several cases, the compounds shown in Tables 1-10 inhibited fungal infection very well. At concentrations of 0.02%, for example, compounds 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 to 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 (morbidity 0-5%). Botrytis disease in untreated but infected bean plants was 100%.

Claims (9)

116 77458 1. Formula I „., .. Α._ώ * k <! wherein Y represents -CH = or -N =, Ra and Rjj independently represent hydrogen, halogen, C1-C3 alkyl, C1-C3 alkoxy or nitro; Ar represents unsubstituted or mono- or polysubstituted phenyl by halogen, C1-C7-alkyl, C1-C7-alkoxy, nitro and / or CF3; O and V independently represent C 1 -C 4 alkyl optionally substituted by halogen or C 1 -C 6 alkoxy. . or together form one of the following alkylene bridges; \ s r3v / r <· v.—> - <. ] 4_ * s> „>. s% r 1 and R 2 independently of one another denote hydrogen, C 1 -C 12 alkyl, C 1 -C 12 alkyl substituted one or more times by halogen, phenyl, phenyl substituted one or more times by halogen and / or C 1 -C 3 alkyl or -CH 2 -Z-R7, wherein Z represents oxygen or sulfur and R7 represents hydrogen, C1-C8-alkyl, C1-C2-alkoxy-substituted C1-C8-alkyl, C3-C4-alkenyl, 2-propynyl, 3-halo-2 -propynyl, phenyl, phenyl, benzyl substituted by halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, nitro and / or CF 3, or II 117 77458 by halogen, C 1 -C 3 alkyl and / or C 1-4 Benzyl mono- or polysubstituted by -C3-alkoxy; R 3, R 4 and R 5 independently of one another denote hydrogen or C 1 -C 4 alkyl, the total number of carbon atoms in the radicals R 3, R 4 and R 5 not exceeding 6 and R 8 denotes hydrogen or C 1 -C 3 alkyl; as well as acid addition salts and metal complexes of these compounds. 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-dioxane or a salt thereof. 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-dioxolane or a salt thereof. 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 or a salt thereof. Compound according to Claim 1, characterized in that it is 2- [4- (p-chlorophenoxy) -2-chlorophenyl] -2- [1- (1H-1,2,4-triazolyl) -methyl] -4-ethyl-1,3-dioxolane or a salt thereof. A process for the preparation of compounds of formula I / K j / 1 'ί ** -0 - <„) —f — k X 12- <1 wherein Y represents a group -CH = or -N =, Ra and Rb independently of one another denote hydrogen, halogen, C 1 -C 3 alkyl, C 1 -C 3 alkoxy or nitro; "<77458 Ar denotes unsubstituted or phenyl mono- or polysubstituted by halogen, C1-C7-alkyl, C1-C7-alkoxy, nitro and / or CP3? U and V independently of one another optionally denote by halogen or C1-C6-alkoxy substituted C 1 -C 12 alkyl or together form one of the following alkylene silos \ / 2 V / 4 R 6 V-x / 1 - or * \ H / * 'wherein R 1 and R 2 independently represent hydrogen, alkyl, C 1 -C 12 alkyl, phenyl, phenyl substituted one or more times by halogen and / or C 1 -C 3 alkyl or -CH 2 -Z-R 7 substituted one or more times by halogen, where Z represents oxygen or sulfur and R 7 denotes hydrogen, C1-C8-alkyl, C1-C2-alkoxy-substituted C1-C8-alkyl, C3-C4-alkenyl, 2-propynyl, 3-halo-2-propynyl, phenyl, halogen, C1-C3-alkyl , Phenyl, benzyl, or halogen substituted one or more times by C1-C3-alkoxy, nitro and / or CF3 benzyl mono- or polysubstituted by C1-C3-alkyl and / or C1-C3-alkoxy; R 3, R 4 and R 5 independently of one another denote hydrogen or C 1 -C 4 alkyl, the total number of carbon atoms in the radicals R 3, R 4 and R 5 not exceeding 6 and R 8 denotes hydrogen or C 1 -C 3 alkyl; and for the preparation of acid addition salts and metal complexes of these compounds, characterized in that A) a compound of formula II Me-1 / f Ύ—, in which Me represents hydrogen or a metal cation, is condensed, of formula III II 119 77458 R 4? n Ar '° ", \ / --- CH2" X t? / X? b U ..... with a compound of formula V, wherein X represents a nucleofugic group, or B) of formula XV R la · = Ν Ar '° “\ y — C-CH -K (IV) V s 2 V. s in the compound of formula I is converted to a group of formula VX / o (V) II u ----- V, or C) to prepare compounds of formula I wherein U and V together represent a group of formula -CH 2 -CH (CH 2 ZR 7) - and R71 represents a non-hydrogen residue R7, condensing with one another the compounds of the formulas VI and VII R (VI) and X2 "r7 (VH), * b bi2- £ H-CH2-X1, in which one of the residues Χχ and X2 optionally represents in salt form hydroxy or mercapto, e.g. of formula -Z-Me, and the other represents a nucleophilic starting group X, or both X 1 and X 2 represent hydroxy groups, or D) condensing each other of formulas VIII and IX 120 77458 R Ar-X (VIII) and X -S * --- CH V f (IX), • t * / \ V! Compounds according to I, in which one of the radicals X3 and X4 denotes the group -Ο-Me, in which Me is hydrogen or preferably a metal cation, and the other denotes a radical which can be exchanged for aryloxy, or E) The compound of formula OCO -. ^ ^ --- CH, - / (X) 0 10 0 Rv t I *> u ----- v is decarboxylated intramolecularly and, if desired, the compound obtained according to the process is converted into another compound of formula I and / or converting the free compound obtained by the process to an acid addition salt, the acid addition salt obtained by the process to the free compound or another acid addition salt, or the free compound obtained by the process to the acid addition salt of the process to a metal complex, wherein the substituents of formulas II-X have The meanings given in connection with I, Z denote oxygen or sulfur and Me denotes hydrogen or a metal cation. Method for controlling or preventing infection by phytopathogenic microorganisms in crops, characterized in that the compound of the formula I according to Claim 1 is applied to the plant or to its growth site. The use of compounds of the formula I as claimed in claim 1 for controlling and / or preventing infection by microorganisms in plants. Il 121 7 7458 Use according to Claim 8, characterized in that the microorganisms are phytopathogenic fungi.