DD274163A5 - FUNGICIDES AND PLANT GROWTH-CONTROLLING AGENTS - Google Patents

Abstract

The invention relates to fungicidal and plant growth-regulating agents containing as active ingredient new Azolylmethyl-cyclopropyl derivatives of the formula (I) in which the substituents R, R1, Zm and X have the meaning given in the description. They are used to combat fungi and to regulate plant growth. Formula (I)

Description

Fungicidal and plant growth regulating agents Field of application of the invention

The present invention relates to fungicidal and plant growth-regulating agents containing as active ingredient new Azolylmethylcyclopropyl-Dorivate »

They are used in crop protection for the control of Plasmodiophoromycetes, Oomycetes, Chyt ridyomycetes, Zygoniycetes, Ascomycetes, Basidiomycetes and Denteromycetes.

Characteristic of the known state of the art

It is already known that certain Azolylmethyl-cyclopropyl-carbinol derivatives have fungicidal and plant growth-regulating properties (see ₀ ΕΞΡ-OS O 180 136). So z. B. 1- (4-chlorophenyl) -1- (1-chlorocyclopropyl) -2- (1, 2,4-triazol-1-yl) -ethan-1-ol and 1- (4-fluorophenyl) - (1 -chloro-cyclopropyl) -2- (l, 2,4-triazol-1-yl) -ethan-1-ol for the control of fungi and for the regulation of plant growth. The effectiveness of these substances is good; However, it leaves in some cases to be desired at low application rates.

Furthermore, it is known that certain substituted by cycloalkyl hydroxyethyl-azolyl derivatives have fungicidal properties (cf., EP-OS 0 015 756). However, the effectiveness of these substances is not always fully sufficient.

Object of the invention

The invention provides the novel azolylmethyl-cyclopropyl derivatives having fungicidal and plant growth-regulating properties.

fJarlequnq the essence of the invention

The object of the invention is to provide fungicidal and plant growth-regulating agents,

There have now been new Azolylmelhyl-cyclopropyl derivatives of the formula

in which

R is halogen, alkyl, optionally substituted phenyl

2 or the group -YR, where Y is oxygen, sulfur, SO or SO ₃ , and

R is optionally substituted phenyl,

R is hydrogen, alkyl or acyl, X is nitrogen or a Cl-I group,

Z is halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio with

1 to 4 carbon atoms, haloalkyl with 1 or

2 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 halogen atoms, halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 halogen atoms, optionally substituted by alkyl having 1 or 2 carbon atoms and / or halogen-substituted phenyl or optionally by Alkyl substituted with 1 or 2 carbon atoms and / or halogen-substituted phenoxy and

m is the numbers 0, 1, 2 or 3,

as well as their acid addition salts and Hetallsalz complexes found »

Furthermore, it has been found that azolylmethyl-cyclopropyl derivatives of the formula (I) and their acid addition salts and metal salt complexes are obtained when 25

a) Propanol derivatives of the formula

C VCH ₂ -C - ^ - R (II)

shark

in which 35

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-A-

R, Z and m are as defined above and Hal is chlorine, bromine or iodine,

with azoles of the formula H

in which X has the meaning given above,

in the presence of an acid binder and in the presence of a diluent,

or

b) oxiranes of the formula

* ^ - ^ H ₂ -C ^ R (IV)

^m 0 CH ₂

in which 30

R, Z and m are as defined above

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274

with azoles of the formula 5

^ X

(111)

in which X has the meaning given above »

in the presence of an acid binding agent and in the presence of a diluent,

or

c) Azolylmethyl ketones of the formula

N = N Il ^ - ^

I is N-CH ₂ -C - ^ - R (V)

in which R and X have the abovementioned meaning, with organometallic compounds of the formula

3H ₂ MgX ¹ (VI)

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in which 5

Z and m have the meaning given above

and X ^{1 is} chlorine, bromine or iodine,

in the presence of a diluent, or

d) Azolylmethyl-cyclopropyl-carbinol derivatives of

Formula 15

OH

(Ia)

in which

R, X, Z and m have the abovementioned meaning,

with strong bases in the presence of a diluent and the resulting alcoholates of the formula 30

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OR ³

H - C ^ - R (Ib)

ζ ''

CH ₂ L

CH.

in which

R, X, Z and m are as defined above

and

R ^ is a cationic radical of a base, with Halogonverbindungen the formula

R ⁴ -hal (VII)

in which

R ^{4 is} alkyl or acyl and Hal 'is halogen, in the presence of a diluent,

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and optionally subsequently added to the compounds of formula (I) thus obtained, an acid or a metal salt.

Finally, it has been found that the novel azolylmethylcyclopropyl derivatives of the formula (I) and their acid addition salts and metal salt complexes have strong fungicidal and plant growth-regulating properties.

The substances of the invention contain an asymmetrically substituted carbon atom, they can therefore be obtained in optical isomeric forms. The present invention relates to both the individual isomers and their mixtures.

Surprisingly, the inventive Substances have better fungicidal and plant growth regulation

effectiveness as the constitutionally most similar prior art compounds of the same direction of action,

The azolylmethyl-cyclopropyl derivatives according to the invention are represented by the formula (I); Formula are preferred

,

are generally defined by the formula (I). In this

R is fluorine, chlorine, bromine, alkyl having 1 to 6 carbon atoms, optionally halogen,

Haloalkyl having 1 or 2 carbon atoms and 1

to 5 halogen atoms, alkyl having 1 to 4 carbon atoms and / or alkoxy having 1 to 4 carbon atoms substituted phenyl or for the

Grouping -Y-R, wherein 35

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Y is oxygen, sulfur, SO or SO ₂ *> and

R 1 is optionally halogen, haloalkyl of 1 or 2 carbon atoms and 1 to 5 halogen atoms, alkyl of 1 to 4 carbon atoms and / or alkoxy of 1 to 4 carbons

is substituted phenyl,

R ^{1 is} hydrogen, alkyl having 1 to 6 carbon atoms or alkylcarbonyl having 1 to 6 carbon atoms in the alkyl group,

X is nitrogen or a CH group,

Z is fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, phenyl optionally substituted by fluorine, chlorine and / or methyl or optionally fluorine, chlorine

and / or methyl substituted phenoxy and 25

m for the numbers ü, 1, 2 or 3,

When m is 2 or 3, the radicals Z may be the same or different, 30

Particularly preferred are those compounds of the form & l (I) in which

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represents fluorine, chlorine, bromine, methyl, ethyl, optionally monosubstituted to trisubstituted, identically or differently phenyl which is substituted by fluorine, chlorine, bromine, trifluoromethyl, methyl, ethyl, methoxy and / or ethoxy, or represents the grouping -YR ² , wherein

Y is oxygen, sulfur, SO or SO ₂ and

R represents optionally monosubstituted to trisubstituted by identical or different substituents by Fljor, chlorine, bromine, trifluoromethyl, methyl, ethyl, methoxy and / or ethoxy-substituted phenyl,

R ^{1 is} hydrogen, methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropyl-carbonyl, n-butylcarbonyl and isobutyl-carbonyl acetylene,

X is nitrogen or a CH group,

Z is fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, optionally

phenyl which is substituted by fluorine, chlorine and / or methyl or phenoxy which is optionally substituted by fluorine, chlorine and / or methyl and

m is the numbers 0, 1, 2 or 3,

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Preferred compounds according to the invention are also addition products of acids and those Azolylr.iethylcyclopropyl derivatives of the formula (I) in which R, R ¹ , X, Z and m have the meanings which have already been mentioned as preferred for these radicals or this index.

χ

Acids which may be added preferably include hydrohalic acids, e.g. the hydrochloric acid and the hydrobromic acid, in particular the hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acids and hydroxycarboxylic acids, such. Acetic, maleic, succinic, fumaric, tartaric, citric, salicylic, sorbic and lactic acids and sulfonic acids, e.g. p-toluenesulfonic acid, 1,5-naphthalenedisulfonic acid or camphorsulfonic acid,

Other preferred compounds of the invention are addition products of salts of metals of II, IV to main and I. and II., And IV, to VIII. Neben-

group of the Periodic Table of the Elements and those azolylmethyl-cyclopropyl derivatives of the formula (I) in which R, R, X, Z and m have the meanings which have already been mentioned as preferred for these radicals and this index.

Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred here. Suitable anions of these salts are those which are derived from those acids which belong to

lead physiologically acceptable addition products. 35

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Particularly preferred such acids in this context are the hydrohalic acids, e.g. the hydrochloric acid and .ie hydrobromic acid ι also phosphoric acid, nitric acid and sulfuric acid.

As examples of Azolylmathyl-cyclopropyl derivatives of the formula (I) may be mentioned the substances listed in the following table.

Table Ie

(I)

^Z m R ¹ X R 25 4-Cl H N Cl 2,4-Cl ₂ · ·· Cl 2,4-F ₂ "1 Il Cl 4-CH ₃ ·· Cl 30 4-CF ₃ Il Il Cl 4-OCF ₃ Il ·· Cl 4-0CH ₃ Il - · Cl 35 4-UCH ₃ ·· Il Cl

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Ta belle (continued)

-m

2,4,6-Cl ₃ 4-Cl 4-Cl 4-Cl 4-Cl

4-Cl 4-Cl 4-Cl 4-Cl

35

4-Ο-Λ - / Il 4-C ₄ H, Il 2-Cl, 4-CH ₃ 11 _ -CO-CH ₃ 4-Cl ~ ^C 2 ^H 5 4-Cl CH ₃ 4-F H 4-Cl Le A 25,297

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If 1-chloro-2- (1-chlorocyclopropyl) -3- (4-fluorophenyl) -propan-2-ol and 1,2,4-triazole are used as starting materials, the course of the process (a) according to the invention can be characterized by following formula scheme are illustrated!

F-

Cl

-HCl KOC (CH ₃ )

If 2 - [(4-fluorophenyl) -methyl 3-2- (1-chlorocyclopropyl) -oxirane and 1,2,4-triazole are used as starting materials, the course of the process (b) according to the invention can be illustrated by the following formula scheme ;

C- Cl + HN

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10152025

If (1,2,4-triazol-1-ylmethyl) - (1-chlorocycloprop-1-yl) ketone and 4-fluorobenzyl magnesium bromide are used as starting materials, the course of the process (c) according to the invention can be are illustrated by the following equation scheme:

u>

-CH ₂ -C-

-Cl + F

H ₂ -MgBr

MgO / HBr

Using 1- (4-fluorophenyl) -2- (1-chlorocyclopropyl) -3- (1,2,4-triazol-1-yl) -propan-2-ol and sodium hydride as starting materials and iodomethane as the reaction component the course of the process (d) according to the invention are illustrated by the following formula scheme!

30 35

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274 f 6

+ CH ₃ I - NaI

ONa

H ₂ -C-

CH-

The propanol derivatives required as starting materials in process (a) according to the invention are generally defined by the formula (II). In this formula, R, Z and m preferably have those meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention preferably for these radicals or this index. Hai is preferably chlorine or bromine.

The propanol derivatives of the formula (II) are not yet known. They can be prepared by cyclopropyl ketones of the formula

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274 f 6 3

Hal "-CH ₂ -C ^ x R (VIII)

in which

R has the meaning given above and 10

Shark "stands for chlorine or bromine»

with organometallic compounds of the formula 15

H ₂ -MgX ¹ (VI)

in which 20

X, Z and m are as defined above

in the presence of a diluent.

in the preparation of propanol derivatives according to the

Cyclopropyl ketones of the formula (VIII) required as starting materials are known in some cases. They can be prepared by adding ketones of the formula

CH ₃ -C - ^ - R (IX)

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in which 5

R has the meaning given above,

with chlorinating agents or brominating agents in

Reacting the presence of a diluent. 10

The ketones of the formula (IX) required as starting materials in the preparation of cyclopropyl ketones of the formula (VIII) are known or can be synthesized by methods which are known in principle (cf. Synthesis 1977, 189).

Suitable chlorinating and brominating agents in the above process for the preparation of cyclopropyl ketones of the formula (VIII) are all chlorination and bromination reagents customary for such reactions. Preferably, usable are sulfuryl chloride, sulfuryl bromide and bromine.

Suitable diluents in the preparation of cyclopropyl ketones of the formula (VIII) according to the above process are all inert organic solvents customary for such reactions. Preferably used are halogenated aliphatic hydrocarbons, such as methylene chloride, chloroform and carbon tetrachloride.

The temperatures in the above process for the preparation of cyclopropyl ketones of the formula (VIII) within a certain. Range can be varied. In general carried out at temperatures between -10 ⁰ C and +60 ⁰ C, preferably between O ⁰ C and +40 ⁰ C.

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In carrying out the above process for the preparation of Cylcopropylketonen of formula (VIII) is generally carried out under atmospheric pressure. However, it is also possible to work under elevated or reduced pressure.

1 "In carrying out the above process for the preparation of cyclopropyl ketones of the formula (VIII) is generally used for 1 mol of ketone of formula (IX) is a Btöchiometrische amount or a slight excess of chlorinating or brominating agent In general, the procedure is followed by washing the reaction mixture successively with dilute, aqueous sodium bicarbonate solution and with water, then drying and

tight, 20

The organometallic compounds of the formula (VI) required as reaction components in the above process for the preparation of propanol derivatives of the formula (II) are known or can be synthesized by methods known in principle. Thus, compounds of the formula (VI) are obtained by reacting benzyl halides the formula

-CH ₇ -X ¹ (X)

_z <* - ^{7 Z}

in we3 sooner

X ¹ , Z and m are as defined above, 35

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with magnesium in the presence of an inert diluent, such as diethyl ether, at temperatures between ^{0 0} C and 50 ° C.

The benzyl halides of the formula (X) are generally known compounds of organic chemistry,

Suitable diluents in the above process for the preparation of propanol derivatives of the formula (II) are all customary for such reactions inert organic solvents. Preferably usable are ethers, such as diethyl ether, tetrahydrofuran and dioxane.

The reaction temperatures can in carrying out the above process for Her. "'. El development of propanol derivatives of the formula (II) can be varied within a certain range. In general, the reaction is carried out at temperatures between -80 ⁰ C and +50 ⁰ C, preferably between -80 ⁰ C and 40 ⁰ C.

In carrying out the above process for the preparation of propanol derivatives of formula (II), mar generally operates under normal pressure. However, it is also possible to increase or decrease the pressure

work

 30

In carrying out the above process for the preparation of propanol derivatives of the formula (II) is used for 1 mol of cyclopropyl ketone. The formula (VIII) im

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al lgemoinen 1 to 1.2 mol of mstallorganischer Verbin- ® tion of the formula (VI), which is conveniently prepared immediately before and further processed in situ. The workup is carried out by conventional methods. In general, the procedure is carried out by first acidifying and adding water, and then separating off the organic phase. washes and narrows after drying.

The azoles of the formula (III) required as reaction components in carrying out the process (a) according to the invention are generally known compounds of organic chemistry.

When SHurebindemittel come in carrying out the process according to the invention da) all customary inorganic and organic bases in question. Preference is given to using alkali metal carbonates, such as sodium and potassium carbonate, and also alkali metal hydroxides, such as sodium and potassium hydroxides, alkali metal alcoholates, such as sodium and potassium methoxide and ethylate, and potassium tert-butoxide, and also lower tertiary alkylamines, cycloalkylamine. ? and aralkylamines, especially triethylamine.

As Verduunungsmi ttel come bt> i the implementation of the method (ε.) All the usual inert

3G Organic Solvents in Revenues. Preference is given to using nitriles, such as acetonitrile, furthermore aromatic hydrocarbons, such as benzene, toluene and dichlorobenzene, and also formamides, such as dimethylformamide, and strongly polar solvents, such as dimethyl sulfoxide and hexamethylphosphoric triamide ,

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The Reakt ionstemperaturer. can be varied in carrying out the process (a) according to the invention within a substantial range. In general, one works at temperatures between ^{0 0} C and 200 ⁰ C, preferably between 60 ° C and 150 ⁰ C.

T _he process of the invention (a) as well as methods according to the invention (b), and (d) is performed (c) is generally under normal pressure, but it is jeweiIs.auch, possible to operate under elevated or reduced

Pressure to work, 15

When carrying out process (a) according to the invention, 1 to 4 mol of azole of the formula (III) and 1 to 3 mol of acid binder are generally employed per mole of propanol derivative of the formula (II). In some cases, it is expedient to work under a protective gas atmosphere. The workup is carried out by conventional methods. In general, the procedure is to concentrate the reaction mixture by stripping off the diluent, to take up the remaining residue in a water-immiscible organic solvent, to wash the organic phase and to concentrate it after drying. The remaining product may optionally be subjected to further purification procedures.

The oxiranes required as starting materials in the process (b) according to the invention are generally defined by the formula (IV). In this formula, R, Z and m preferably have those meanings which have already been mentioned as preferred in connection with the description of the substances of the formula (I) according to the invention for these radicals or this index.

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The oxiranes of For.nel (IV) are not yet known. They can be prepared by adding propanol derivatives of the formula

C> -CHO-C - ^ - R (II)

shark

in which

R, Z, Hal and m are as defined above,

with bases in the presence of a diluent.

Suitable bases in the preparation of oxiranes of the formula (IV) according to the above process are all customarily suitable for such reactions inorganic and organic bases. Preferably usable

are all those bases which have already been mentioned as preferred acid binders in connection with the description of process (a) according to the invention,

The reaction temperatures may be varied within a certain range in the production of oxiranes by the above method. In general, one works at temperatures between ^{0 0} C and 100 ⁰ C, preferably between 20 ° C and 60 ⁰ C.

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In carrying out the above method for producing

Position of oxiranes of the formula (IV) is generally carried out under atmospheric pressure. However, it is also possible to work under increased or reduced pressure.

In carrying out the above process for the preparation of oxiranes of the formula (IV) is used in general for 1 mol of propanol derivative of the formula (II) 1 to 3 KoI of base. The workup is carried out by customary methods, 15

Suitable acid binders and diluents for carrying out the process (b) according to the invention are all acid binders and diluents customarily used for such reactions

Preferably, all those acid binders and diluents which have already been used in connection with the description of process (a) according to the invention as preferred acid binders and

Diluents were called. 25

When carrying out process (b) according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, one works at temperatures between ^{0 0} C and 200 ⁰ C, preferably between 60 ° C and 150 ⁰ C.

In carrying out the process (b) according to the invention is used for 1 mol of oxirane of the formula (IV) in

general 1 to 2 moles of azole of formula (III) and 35

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1 to 2 moles of acid binder. The workup is carried out by conventional methods.

The azolyl methyl ketones required as starting materials in the process according to the invention (c) are generally defined by the formula (V). In this formula, R and X preferably have those meanings which have already been mentioned as preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention.

The azolylmethyl ketones of the formula (V) are not yet known. They can be prepared by cyclopropyl ketones of the formula

Hal "-CH ₂ -C - ^ - R (VIII)

in which

R and Hal "are as defined above, 25

with azoles of the formula

ff Il (HD

N

in which

X has the meaning given above, 35

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2 7 4

in the presence of an acid binder and optionally in the presence of a diluent,

Suitable acid binders and diluents in the preparation of azolylmethylketones of the formula (V) according to the above process are all acid binders and diluents customarily used for such reactions. Preferably all acid binders which have already been used in connection with the description of the process according to the invention (a) have been mentioned as preferred acid binders. Preferred diluents are ketones, such as acetone, and nitriles, such as acetonitrile.

The reaction temperatures can be used in the production of

Azolylmethyl ketones of the formula (V) can be varied within a substantial range according to the above method. In general, one works at temperatures between ^{0 0} C and 120 ⁰ C, preferably between 20 ° C and

100 ⁰ C

 25

The above process for the preparation of Azolylmothylketonen of formula (V) is generally carried out under atmospheric pressure.

In carrying out the above process for the preparation of azolylmethyl-ketones of the formula (V) is used for 1 mol of cyclopropyl ketone of the formula (VIII) im

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general 1 to 4 moles of azole of the formula (III) and 1 to 3 moles of SäurebindemiLLeI. The Aufung Lung EriolgL after usual MeLhoden.

The organometallic compounds of the formula (VI) which are required as reaction components in the process (c) according to the invention have already been mentioned in connection with the description of the process for the preparation of the propanol derivatives of the formula (II),

When carrying out the process (c) according to the invention, suitable diluents are all customary inert organic solvents. Preferably usable are ethers, such as diethyl ether, tetrahydrofuran and dioxane.

The reaction temperatures can also be varied within a substantial range when carrying out process (c) according to the invention. In general, temperatures between -80 ⁰ C and +60 ⁰ C, preferably between -70 ⁰ C and +50 ⁰ C.

When carrying out process (c) according to the invention, 0.8 to 1 mol of organometallic compound of the formula (VI), which is expediently prepared immediately before and further processed in situ, are generally employed per mole of azolylmethyl ketone of the formula (V) , The workup is carried out by conventional methods.

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The azolylmethyleye 1-propyl derivatives of the formula (Ia) required as starting materials in process (d) according to the invention are compounds according to the invention. Their conversion into the corresponding alcoholates is carried out in a generally known manner by reacting with suitable strong bases, such as alkali metal amides or hydrides, quaternary ammonium hydroxides or phosphonium hydroxides in an inert diluent, such as dioxane, at room temperature. Accordingly, R ³ in the compounds of the formula (Ib) is preferably an alkali metal cation, such as a sodium or potassium cation, or a quaternary ammonium or Phosphoniumkat ion.

The in the process according to the invention (d) also required as starting materials halogen compounds are

^ the formula (VII) generally defined. In dioser formula, R preferably has the meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention for the substituent R, with the exception of the meaning of hydrogen. Hal preferably represents chlorine, bromine or iodine.

The halogen compounds of the formula (VII) are known or can be prepared by methods known in principle.

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Suitable diluents for carrying out the process (d) according to the invention are inert organic solvents. These preferably include ethers, such as diethyl ether or dioxane; aromatic hydrocarbons, such as benzene, in some cases also chlorinated hydrocarbons, such as chloroform, methylene chloride or carbon tetrachloride; and hexamethylphosphoric triamide ·

The reaction temperatures can be varied within a substantial range when carrying out the process (d) according to the invention. In general, it works between O ⁰ C and 120 ⁰ C, preferably between 20 ° C and 100 ⁰ C.

When carrying out process (d) according to the invention, hydroxy compounds of the formula (Ia) are first reacted with strong bases to give the corresponding alkoxides of the formula (Ib). In the subsequent stage, 1 mol of an alkoxide of the formula is employed (Ib) preferably 1 to 2 moles of halogen compound of the formula (VII)

25

on. Z.ur isolation of the final products, the reaction mixture is freed from the solvent and the residue with water and an organic solvent. The organic phase is separated, worked up in the usual manner and purified.

In a preferred embodiment, it is expedient to proceed by starting from a hydroxy compound of the formula (Ia), the latter in an appropriate organic solvent by means of alkali metal hydride

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or Alkalimetal1-amide converted into the alkali metal alcoholate and the latter without isolation immediately with a halogen compound of the formula (VII), wherein _{it he} exit of alkali metal halide compounds of formula (I) according to the invention are obtained in one operation

 10

According to a preferred embodiment, it is expedient to prepare the alkoxides and to react them with a halogen compound of the formula (VII) in a two-phase system, for example aqueous sodium hydroxide or potassium hydroxide / toluene or methylene chloride, with addition of 0.01-1 mol of one phase Transfer catalyst, such as ammonium or phosphonium compounds carried out, wherein in the organic phase or at the interface, the alkoxides

be reacted with the halides in the organic phase,

The azolylmethyl-cyclopropyl derivatives of the formula (I) obtainable by the processes according to the invention can be

be converted into acid addition salts or metal salt complexes.

For the preparation of acid addition salts of the compounds of formula (I) are preferably those acids in question; which have already been mentioned as preferred acids in connection with the description of the acid addition salts according to the invention.

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The acid addition salts of the compounds of the formula (I)

can be conveniently prepared by standard salt formation techniques, e.g. by dissolving a compound of formula (I) in a suitable inert solvent, adding the acid, e.g. Hydrochloric acid, obtained and known in the art, e.g. by filtration, isolated and, if appropriate, purified by washing with an inert organic solvent.

For the preparation of metal salt complexes of the compounds of the formula (I), preference is given to those salts of metals which have already been mentioned as preferred metal salts in connection with the description of the metal salt complexes according to the invention.

The metal salt complexes of the compounds of the formula (I)

- ...

can be easily obtained by conventional methods, e.g. by dissolving the metal salt in alcohol, e.g. Ethanol and adding to compounds of formula (I). Metal salt complexes can be prepared in known manner, e.g. filtered off, isolated and given

if cleaned by recrystallization,

The active compounds according to the invention have a strong microbicidal action and can be used as fungicides

 JO

Fungicides are used in crop protection for the control of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes,

Deuteromycetes, 35

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By way of example but not limitation, some pathogens of fungal and bacterial diseases, which fall under the above-enumerated generic terms, gena.int:

Xanthomonas species, such as Xanthomonas oryzaej Pseudomonas species, such as Pseudomonas lachrymans; Erwinia species, such as Erwinia amylovoraj Pythium species, such as Pythium ultimumj Phytophthora species, such as Phytophthora infestans; Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubense; Plasmopara species, such as Plasmopara viticolaj peronospora species, such as Peronospora pisi or P, brassicae J

Erysiphe species, such as Erysiphe graminisj Sphaerotheca species, such as Sphaerotheca fuligineaj

Podosphaera species, such as Podosphaera leucotrichaj Venturia species, such as Venturia inaequalisj Pyrenophora species, such as Pyenophora Leres or P, gramineaJ

(Conidia form: Drechslera, Syn: Helminthosponum) j Cochliobolus species, such as Cochliobolus sativus; (Conidia form: Drechslera, Syn: Helminthosporium) j Uromyces species, such as Uromyces appendiculatus ', Puccinia species, such as Puccinia recondits;

Tilletia species, such as Tilletia caries; Ustilago species, such as Ustilago nuda or Ustilago avenaej Pel 1icularia species, such as Pellicularia sasakii; Pyricularia species, such as Pyricularia oryzaej

Fusarium species, such as Fusarium culmorumj 35

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Boylrix species, such as Botrytis cinerea; Septoria species, such as Septoria nodorum; LeptoGphaeria species such as Leptosphaer i a nodorum. "Cercospora species such as Cercospora canescens; Alternaria species such as Alternaria brassicae; Pseudocerco Bporella species such as Pseudocercosporella

Good compatibility of the active substances in the concentrations necessary to combat plant diseases allows the treatment of aboveground parts of plants, of planting and seed and of the soil.

The active compounds according to the invention are particularly suitable for controlling cereal and rice diseases, such as Pseudocercosporella, as well as for controlling Uromyces and Bot.rytis in fruit, wine and vegetable cultivation.

They can be used with particular success against Pyricularia on rice and against Leptosphaeria nodorum, Pyrenophora teres and rust and mildew in cereal crops. In addition, the substances according to the invention show a good in vitro action,

In addition, the active compounds according to the invention also possess

plant growth-regulating properties. 30

The active compounds according to the invention intervene in the metabolism of the plants and can therefore be used as growth regulators.

"For the mode of action of plant growth regulators applies according to previous experience that an active ingredient

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27 4 U 3

can also exert several different effects on plants. The effects of the substances depend essentially on the time of application in relation to the stage of development of the plant and on the amounts of active substance applied to the plants or their surroundings and on the mode of application. In any case, growth regulators are intended to influence crops in some desired manner.

Plant growth regulators can be used, for example, to inhibit the vegetative growth of plants.

be set. Such growth inhibition is of economic interest among grasses, among other things, because this can reduce the frequency of grass clippings in ornamental gardens, parks and sports facilities, on roadsides, at airports or in orchards. From

Significance is also the inhibition of the growth of herbaceous and woody plants on roadsides and in the vicinity of pipelines or overland lines or more generally in areas where a strong increase of the plants

is undesirable, 25

Also important is the use of growth regulators to inhibit grain elongation. This reduces or completely eliminates the risk of plants being "stooped" before harvesting. In addition, growth regulators in crops can produce a straw boost which also counteracts storage. The use of growth regulators for stalk shortening and stalk augmentation makes it possible to apply higher quantities of fertilizer in order to increase the yield without the risk of the grain being stored,

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An inhibition of vegetative growth allows a denser planting in many crops, so that more yields can be achieved relative to the soil surface. An advantage of the smaller plants thus obtained is that the culture can be more easily processed and harvested,

An inhibition of the vegetative growth of the plants can also lead to increased yields, that the nutrients and assimilates benefit the flower and fruit formation to a greater extent than the vegetative plant parts.

With growth regulators promotion of vegetative growth can often also be achieved. This is of great benefit when the vegetative plant parts are harvested. Promoting vegetative growth may also, at the same time, promote generative growth by producing more assimilates so that more or more fruits are produced

arise, 25

In some cases, increases in yield can be achieved by interfering with the plant metabolism, without causing any changes in vegetative growth. It can also be used with growth regulators

a change in the composition of the plants can be achieved, which in turn can lead to an improvement in the quality of the harvested products. So it is possible, for example, the sugar content in sugar beet,

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2 7 4 f <S

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It is also possible, for example, to inhibit the degradation of desirable ingredients, such as Z ₁ B. sugar in sugar beets or sugar cane, with growth regulators before or after harvesting. In addition, the produc-

tion or the discharge of secondary plant constituents. An example is the stimulation of latex flow in gum trees.

Under the influence of growth regulators, parthenocarp fruits may develop. Furthermore, the sex of the flowers can be influenced. Also, a sterility of the pollen can be produced, which is a great in the breeding and production of hybrid seed

Meaning has 20

Through the use of growth regulators, the branching of the plants can be controlled. On the one hand, the development of lateral shoots can be promoted by breaking apicaidin dominance, which is particularly evident in ornamental plants.

,

zenbau also in connection with a growth inhibition can be very desirable. On the other hand, it is also possible to inhibit the growth of the side shoots. For this effect there is e.g. great interest in growing tobacco or planting tomatoes.

Under the influence of growth regulators, the foliage of the plants can be controlled so that the leaves are exfoliated at a desired time. Such defoliation plays in the

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mechanical harvesting of cotton plays a big role

But it is also of interest in other crops such as viticulture to facilitate the harvest. A defoliation of the plants can also be done to prevent the transpiration of the plants before transplanting

lower

 10

Likewise can be controlled with growth regulators the fruit case. On the one hand, premature fruiting can be prevented. On the other hand, however, the loss of fruit or even the falling of the bleeds can be demanded to a desired extent ("thinning out") in order to break the alternance. Alternating means the peculiarity of some types of fruit to bring very different yields endogenously from year to year. Finally, it is possible to use growth regulators for the time being.

at the point of harvest to reduce the forces required to detach the fruit in order to enable mechanical harvesting or facilitate manual harvesting;

With growth regulators can also accelerate or delay the ripeness of the crop before or after harvest reach. This is of particular advantage because it can bring about an optimal adaptation to the needs of the market. In addition, growth regulators may in some cases improve fruit colouration. In addition, with growth regulators, a temporal concentration of maturity can be achieved. Thus, the conditions are created that, for example, in the case of tobacco, tomatoes 25

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or coffee a complete mechanical or manual harvesting can be done in one operation.

By using growth regulators, the seed or bud rest of the plants can also be influenced, so that the plants, such as. B ₁ Pineapples or ornamental plants in nurseries to germinate, sprout or flower at a time when they would normally be unwilling to do so. Delaying bud sprouting or germination of seeds by growth regulators may be desirable in areas prone to frost to avoid damage from late frosts.

Finally, with growth regulators, a resistance of the plants against frost, drought or high Saiz

·

salary of the soil. This makes it possible to cultivate plants in areas that are normally unsuitable for this purpose.

The active compounds can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, as well as ULV formulations.

These formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, ie liquid solvents, liquefied gases under pressure and / or solid support

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f) *

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2 7 i U 3

optionally with the use of surfactants, ie emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as extender, for example, organic solvents can also be used as auxiliary solvents. The liquid solvents are substantially Fung: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphttic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water with liquefied gaseous extenders or carriers are liquids which are gaseous at normal temperature and under atmospheric pressure, For example, aerosol propellants, such as Halogenkohlenwas & erstoffe and butane, propane, nitrogen and carbon dioxide ', as solid ^Λ carriers are: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, Attapulgit, Montmr.ri 1 ioni t or diatomaceous earth U.N d synthetic rocks, such as fumed silica, alumina and silicates; as solid carriers for granules come into question! eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours, as well as

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2 7 4 ί 4 3

Granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foaming agents. ' e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylarylpolyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and protein hydrolysates J as dispersants are suitable: for example, lignin-sulphite liquors and methylcellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex polymers may be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids. Further additives may be mineral and vegetable oils.

Dyes such as inorganic pigments, for example, iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.

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The active compounds according to the invention can be present in the formulations in a mixture with other known active substances such as fungicides, insecticides, acaricides and herbicides and mixtures with fertilizers and other growth regulators.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules. The application happens in the usual way _; eg by pouring, squirting. It is also possible to apply the active ingredients according to the ultra-low-volurae method or to inject the active ingredient preparation or the active ingredient itself into the soil. It can also be the seed of the plants to be treated.

When using the substances according to the invention as fungicides, the application rate depending on the type of application in

2S rt be a substantial range varii <?, The Wirkstoifkonzentrat ion -Y, in the treatment of parts of plants in the use forms, in general, between 1 and 0.0001 wt.. ^ VO ugsweise between 0.5 and 0.001 y, _t In the seed treatment, in general, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, needed. When treating the soil, Wirkstoffkonzentrat ions of 0.00001 to 0.1 parts by weight, preferably from 0.0001 to 0.02 % , required at the site of action,

35

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When using the compounds of the invention as plant growth regulators, the amounts used can be varied within a coarser range "in general are used per hectare of soil surface O Ol ₁ to 50 kg, preferably 0.05 to 10 kg on active ingredient.

When using the substances according to the invention as plant growth regulators, the application is made in a preferred period vorgonominen whose exact delimitation depends on the climatic and vegetative conditions.

Exportuno.sbc isp leIe

üie preparation and the use of the active compounds according to the invention is apparent from the following examples.

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Hers te 1l u nqsbei games 5

Eeίspi el 1

_{χ 7 β (} (1-1)

ίο ^χ '

(Method a):

Under a nitrogen atmosphere, 65 g (0.94 mol) of 1,2,4-triazole and 71 g (0.63 mol) Kai ium-tert-butoxide are initially charged in 160 ml of absolute dimethylformamide and to 80 ° C.

^After heating at this temperature, a solution of 70.6 g (0.26 mol) of 1-chloro-2- (1-chlorocyclopropyl) -3- (4-fluorophenyl) -propan-2-ol in 90 is added dropwise while stirring ml of absolute dimethylformamide added. It is nachgellhrt for 6 hours at 100 ⁰ C and then concentrated by removing the diluent under reduced pressure. The residue is taken up in ethyl acetate, washed with water and, after drying over sodium sulfate, the solvent is removed under reduced pressure. The remaining product is passed through a silica gel column with chloroform

^ O as eluent chromatographed. This gives 28.2 g (39 % of theory) of 1- (4-fluorophenyl) -2- (1-chi (r-cyclopropyl) -3- (1,2,4-triazole-l-) yl) -propan-2-ol in the form of a solid substance of melting point 111 ⁰ C.

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Production of precursors: 5

274 ί 6 3

(HI)

A solution of 65.7 g (0.35 mol) of 4-fluorobenzyl bromide in 430 ml of absolute diethyl ether is added dropwise at room temperature to a mixture of 9.3 g (0.38 mol) of magnesium turnings in 185 ml of diethyl ether. The mixture is heated for 30 minutes under reflux and the resulting solution is then added dropwise at -78 ⁰ C with stirring in a solution of 47.8 g (0.32 mol) of 1-chloro-l-chloroacetyl-cyclopropane in 300 ml of absolute diethyl ether. The reaction mixture is stirred at -78 ⁰ C for 4 hours. Then allowed to warm slowly to ^{0 0} C and then added dropwise a solution of 31 ml of acetic acid in 300 ml of diethyl ether. The resulting reaction mixture is poured onto 1.200 ml of water. The organic phase is separated, washed with aqueous sodium hydrogen sulfite solution and with water, dried over sodium sulfate and concentrated under reduced pressure. This gives 70.6 g (86% of theory) of l-chloro-2- (l-chloro-cyclopropyl) -3- (4-fluoro-phsnyl) -propan-2-ol in the form of an oily product ¹ H NMR (200 MHz, CDCl _3): δ = 0.6-1.2 (m, 4H); 3.05 (d, IH) J 3.15 (d IH); 3.75 (d, IH); 4.03 (d, IH); 7.0 (t, 2H); 7.22-7.37 (m, 2H).

ClCH ₇ -C - ^ - Cl

H

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At room temperature, 40.5 ml (0.5 mol) of sulfuryl chloride are slowly added with stirring to a solution of 54 g

Dropped (0.46 mol) of 1-acetyl-l-chloro-cyclopropane in 250 ml of methylene chloride. The mixture is stirred first at room temperature for 14 hours and then at 30 ° C. for 30 minutes. The reaction mixture is then washed successively with saturated aqueous sodium bicarbonate solution and with water. Thereafter, the organic phase is dried over sodium sulfate and concentrated under reduced pressure. This gives 51.5 g (74 % of theory) of 1-chloro-1-chloroacetyl-cyclopropane in the form of an oily substance.

¹ H-NMR (60 MHz, CDCl _3): δ = 1.2-1.9 (m, 4H); 4.8 (s, 8H)

The compound of formula 20

-Cl

(1-1)

can also be prepared by the process (c) according to the invention by reacting (1,2,4-triazol-1-yl-methyl) - (1-chloro-cycloprop-l-yl) -ke> ^ on with 4-fluoro benzyl magnesium bromide in the presence of diethyl ether,

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Preparation of the starting material of formula:

-CH ₂ -CCl (VI)

A solution of 60 g of 1-acetyl-1-chloro-cyclopropane in 50 ml of acetone is added dropwise to a solution of 50 g of potassium carbonate and 35 g of 1,2,4-triazole in 200 ml of acetone under a nitrogen atmosphere while stirring. The mixture is heated under reflux for 8 hours, then concentrated by evaporation of the Verdünnuigsmittelsä under reduced pressure, the residue is taken up in a mixture of ethyl acetate and toluene, washed with water, dried over sodium sulfate and concentrated under reduced pressure. This gives 38.9 g of (1,2,4-triazol-1-yl-methyl) - (i.-chlorocycloprop-1-yl) ketone in the form of a solid substance of melting point 79 ⁰ C.

¹ H-NMR (200 MHz, _CDCl3): 6 = 1.50 (m, 2H), 1.78 (m, 2H), 5.62 (s, 2H), 7.98 (s, IH), 8.14 (s, IH).

Following the methods given in Example 1 and in the description, the azolylmethyl-cyclopropyl derivatives of the formula (1) listed in the table below are also prepared.

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table

Example no.

3 4 5 6 7 8 9

10 11

2-F

2,4-F ₂ 2-Cl 3,4-Cl ₂

4-Cl

2,4-Cl ₂ 4 -CH ₃ 3,4-F ₂ 4-F

H H H H H H H H H

(1)

X R Melting point ( ⁰ C) N Cl 103 N Cl 117 N Cl 108 N Cl 80-92 N Cl 81 N Cl 97 N Cl 159 N Cl 132 N Cl 98 CH Cl 171

In the following examples of use, the compounds of the formulas given below were used as dancing chips *.

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- 4P -

OH

(A) = F

CH-

274U3

OH

CH-

-Cl

OH

Cl

CH,

-Cl

(Known from EP-OS 0 180 136),

(D) = Cl

OH

I A

CH-

(Known from EP-OS 0 015 756).

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27 4 ί 6 3

Game A 5

Botrytis-fest (bean) / protective

Solvent: 4.7 parts by weight of acetone emulsifier! 0.3 part by weight of alkylaryl polyglycol ether

To prepare a suitable active ingredient preparation, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test for protective efficacy, young plants are sprayed with active ingredient preparation to dripping wet. After the spray coating has dried, 2 small pieces of agar covered with Botrytis cinerea are placed on each leaf. The inoculated plants are placed in a darkened, moist chamber at 20 ° C. 3 days after the inoculation, the size of the lesions on the leaves is evaluated.

In this test, the compound (1-1) according to the invention has a significantly better activity than the comparison substances (A) and (C)

 30

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2 7 4

Example B 5

Uromyces test (bush bean) / protective

Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To prepare a suitable active compound preparation is mixed 1 part by weight of active compound with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration,

To test for protective activity, young plants are sprayed with the preparation of the active ingredient up to the dripping point After the spray coating has dried on, the plants are inoculated with an aqueous uredospore suspension of the bean rust pathogen (Uromyces appendiculatus) and remain in a dark moist chamber for one day

20 to 22 ° C and 100 '/. relative humidity. 25

The plants are then grown under intense lighting for

9 days at 20 to 22 ° C and a relative humidity of 70 to 80 V, in the greenhouse

on gesv.el It

 30

10 days after the inoculation the evaluation takes place.

In this test, the compound (1-1) according to the invention has a significantly better activity than the comparison substances (A), (B) and (C).

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Step Example l ⁿ _ 5

Venturia test (apple) / protective

Solvent! 4.7 parts by weight of acetone emulsifier! 0.3 part by weight of alkylaryl polyglycol ether

To prepare a suitable active compound preparation, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of the active ingredient until dripping wet. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the apple scab pathogen (Venturia inaequalis) and then remain for 1 day at 20 ° C. and 100 % relative atmospheric humidity in an incubation booth.

The plants are then placed in the greenhouse at 20 ° C and a relative humidity of about 70 Ά .

12 days after the inoculation the evaluation takes place,

In this test, the compound (1-1) according to the invention shows a significantly better action than the comparison substances (A) and (C)

 35

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Be i game D F,

Pseudocercospila herpotri choides test (wheat) / protective

Solvent! 100 parts by weight of dimethylformamide emulsifier: 0.25 part by weight of alkylarylpolygly-

kolether

To prepare a suitable preparation of active compound ***, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

on t «· ·

* ^u To test for protective efficacy, spray young plants with the preparation of active ingredient in a dewy manner. After the spray coating has dried on, the plants are planted on the stem base with spores of Pseudocercosporella

herpotrichoides inoculated

 25

The plants are placed in a greenhouse at a temperature of about, 10 ⁰ C and a relative humidity of about, 80 Y. ,

21 days after the inoculation the evaluation takes place,

In these. Test shows the compound (1-1) according to the invention a very good activity,

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2741

Example E 5

Erysiphe test (barley) / seed treatment

The application of the active ingredients is carried out as a dry dressing. They are prepared by stripping the respective active ingredient with rock flour to a fine powdery mixture, which ensures a uniform distribution on the seed surface.

For dressing, shake the seed for 3 minutes with the mordant in a sealed glass bottle.

The barley is sown with 3x12 grain 2 cm deep into a standard soil, 7 days after sowing, when the young plants have unfolded their first leaf, they will _m it. Spores of Erysiphe graminis f. sp. hordei pollinated,

The plants are placed in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80 % in order to favor the development of powdery mildew pustules,

7 days after the inoculation the evaluation takes place.

In this test, the compound of the invention (1-1) shows a much better effect than the comparison substance (A).

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274 f 6 3

Example F 5

Leptosjjhaer ia nodorum test (wheat) / protective

Solvent: 100 parts by weight of dimethylformamide emulsifier: 0.25 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the * concentrate is diluted with water to the desired concentration,

To test for protective activity, young plants are sprayed with the preparation of the active ingredient in a dewy manner. After the spray coating has dried, the plants are sprayed with a spore suspension of Leptosphaeria nodorum. The plants remain at 20.degree. C. and 100 V. relative humidity for 48 hours an incubation cabin,

"The plants are placed in a greenhouse at a temperature of about 15 ⁰ C and a relative humidity of about 80 '/ .

10 days after inoculation the evaluation takes place. 30

In this test, the compound (1-1) according to the invention shows a significantly better activity than the comparison substance (D),

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274 I 63

Example G 5

Pyrenophora Leres-TesL (barley) / protective

Solvent! 100 parts by weight of dimethylformamide emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

For the purpose of sealing a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrated solution is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound in a dewy manner. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Pyrenophora Leres. The plants remain 48 hours at 20 ° C and 100 * /. relative humidity in an incubation cabin>

The plants are placed in a greenhouse at a temperature of about 20 ° C and a relative humidity of about 80 Y.

7 days after the inoculation the evaluation takes place. 30

In this test, the compound of the invention (1-1) shows a much better effect than the comparison substance (D).

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Claims (2)

claims in which R is halogen, alkyl, optionally substituted 2 phenyl or the group -Y-I? stands in which Y is oxygen, sulfur, SO or SO ₂ and 2
R is optionally substituted phenyl, R is hydrogen, alkyl or acyl, X is nitrogen or a CH group, Z is halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, halogenoalkyl with 1 O'jer 2 carbon atoms and 1 to 5 halogen atoms, halogenoalkoxy with 1 or 2 carbon atoms and 1 to 5 halogen atoms, halogenoalkylthio with 1 or 2 carbon atoms - 57 - atoms and 1 to 5 halogen atoms, phenyl optionally substituted by alkyl having 1 or 2 carbon atoms and / or halogen, or phenoxy optionally substituted by alkyl having 1 or 2 carbon atoms and / or halogen, and m is the numbers O ₁ 1, 2 or 3, and their addition salts and Hetallsalzkomplexe addition to conventional excipients and carriers. 2. Use of Azolylmethyl-cyclopropyl derivatives of the formula (I) according to claim 1 bzvi <, whose acid addition salts and fietallsalzkomplexen, characterized in that they are used for controlling fungi and for regulating plant growth.