DD274164A5 - FUNGICIDES AND PLANT REGULATING AGENTS - Google Patents

Abstract

The invention relates to fungicidal and plant growth-regulating agents containing as active ingredient new hydroxyethyl-azolyl derivatives of the formula (I) in which the substituents R, R 1, R 2, m, Y, X have the meaning given in the description. They are used to combat fungi and to regulate plant growth. Formula (I)

Description

The present invention relates to fungicidal and plant growth-regulating agents containing as active ingredient new hydroxyethylazolyl derivatives · They are used in crop protection for the control of Plasmodio-phoromycetes, Oomycetes, Chytridiomyeetes, Zygomycetes, Ascomycetea, Baaidiomycetes and Deuteromycetea.

Characteristic of the known state of the art

It is already known that numerous Hydroxyalkylaaoiyl derivatives have fungicidal properties (see, EP-OS 0 040 and EP-OS 0 061 835). Thus, for example, 1- (4-chlorophenoxy) -2-cyclopropyl-1-bis (1,2,4-triazol-1-yl) -propan-2-ol can be used to combat fungi. The effectiveness of this substance is very good; however, plant tolerance and efficacy leave much to be desired in some cases.

Object of the invention

The invention provides the new hydroxyethylazolyl derivatives which have strong fungicidal and plant growth-regulating properties.

Explanation of the essence of the invention

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

There have now been new hydroxyethyl-azolyl derivatives of the formula

2 7 4 ί 6 4

(I)

in which R is hydrogen, alkyl or acyl,

R is halogen, optionally substituted phenyl or the group -Z-R, wherein

Z is oxygen, sulfur, SO or SO ₂ 20

R is optionally substituted phenyl,

R ^ 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, haloalkoxy having 1 or 2 carbon atoms and 1 to 5 halogen atoms, haloalkylthio having 1 or 2 carbon atoms and 1 to 5 halogen atoms, alkoximinomethyl having 1 to 4 carbon atoms in the alkoxy group, optionally 1s by alkyl with 1 or 2 Carbon atoms and / or halogen substituted

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tuiertes phenyl or is optionally substituted by alkyl having 1 or 2 carbon atoms and / or halogen-substituted phenoxy,

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

X is nitrogen or a CH group and

Y is oxygen, sulfur, SO or SO ₂ ,

as well as their acid addition salts and metal salt complexes 1 found.

Furthermore, it was found that hydroxyethyl azoly1 derivatives of the formula (I) and their acid addition Sal ze

and Metal 1 salt complex gets when you get 20

a) oxiranes of the formula

25 ₂

² ^ ⁷ ^ \ (II)

^m 0 CH ₂

in which

1 P ·

R »R» Y and m are as defined above

have, with azoles of the formula

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if

X (III)

in which 10

X has the meaning given above

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

or

b) Azolyl derivatives of the formula

CHo C - ^ - R

'2

CH ₂ (IV)

(IN

-X

in which

R and X have the meaning given above, "30

with phenyl derivatives of the formula

"2 - - ^<V)

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35

274

in which 5

R and m are as defined above and Y is oxygen or sulfur,

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

or

c) hydroxyethyl-azolyl derivatives of the formula

OR

R '

^m CHp (Ia)

2C I ^ά

if

25 in which

R, R ¹ , R * " ¹ , X and m have the abovementioned meaning,

with oxidizing agents, if appropriate in the presence of a thinner,

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274

or

d) Hydroxyethyl-azolyl derivatives of the formula

OH

Y-CH ₂ -C-

in

CH

(Ib)

in which

R ₁ R, X, Y and m have the abovementioned meaning,

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

0R ^f

R '

Y-CH ₂ -C-

CH

-R ^J

(Ic)

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in which 5

R *, R ^, X, Y and m are as defined above, and

R ^ is a cationic radical of a base, 10

with halogen compounds of the formula

R ⁵ - Hal (VI)

15 in which

R ^{5 is} alkyl or acyl and

Shark stands for halogen, 20

in the presence of a diluent,

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

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

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2741 <4

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

Surprisingly, the substances according to the invention have a better fungicidal and plant growth-regulating activity than constitutionally similar previously known compounds of the same direction of action,

The hydroxyethyl-azolyl derivatives according to the invention are generally defined by the formula (I). In this formula are preferable

R is hydrogen, alkyl having 1 to 6 carbon atoms or alkyl carbonyl having 1 to 6 carbon atoms in the alkyl group,

R is fluorine, chlorine, bromine, phenyl optionally substituted by 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 carbon atoms or group -Z-R, wherein

represents oxygen, sulfur, SO or SO ₂ and

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R 1 represents phenyl which is optionally substituted by 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,

R ^{2 is} fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methoximinomothyl, phenyl optionally substituted by fluorine, chlorine and / or methyl or optionally fluorine, chlorine and / or methyl-substituted phenoxy,

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

* X is nitrogen or a CH group and Y is oxygen, sulfur, SO or SO ₂ .

If m stands for the numbers 2 or 3, the radicals which represent R 1 can be identical or different.

Particular preference is given to those compounds of the formula (I) in which

R is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, nr.''-ethylcarbonyl or isobutyl-carbonyl,

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R * represents fluorine, chlorine, bromine, optionally monosubstituted to trisubstituted by identical or different phenyl, substituted by fluorine, chlorine, bromine, trifluoromethyl, methyl, ethyl, methoxy and / or ethoxy, or represents the group -Z-R ^ in which

Z is oxygen, sulfur, SO or SO ₂ and

R is optionally monosubstituted to trisubstituted, identically or differently, by fluorine, chlorine, bromine, trifluoromethyl, methyl, ethyl,

Methoxy and / or ethoxy substituted phenyl,

R ^{2 is} fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methoximinomethyl, phenyl optionally substituted by fluorine, chlorine and / or methyl or optionally fluorine, chlorine and / or methyl substituted phenoxy,

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

X is nitrogen or a CH group and

Y is oxygen, sulfur, SO or SO ₂ .

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Preferred compounds of the invention are also addition products of acids and those hydroxyethyl-azolyl derivatives of the formula (I) in which R _# R ₁ R ^, X, Y and m have the meaning .i, which already preferably for these radicals or these Called index

were. 10

The acids which may be added include, preferably, hydrohalic acids, e.g. hydrochloric acid and hydrobromic acid, especially hydrochloric acid, furthermore phosphoric acid, nitric acid, sulfuric acid, mono- and bifunctional carboxylic acid and hydroxycarboxylic acids, e.g. 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 according to the invention are addition products of salts of metals of II. To IV. Main and the I. and II., And IV to VIII. Subgroup of the Periodic Table of the Elements and those hydroxyethyl-azolyl derivatives of Fcrmel (I), in R, R, R, X, Y and m have the meanings already mentioned as preferred for these radicals and this index

3Q were,

Here are the salts of copper, zinc ,. Manganese, magnesium, tin, iron and nickel are particularly preferred. Anions of these salts are those in Be-35

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274 16

Trachti derived from those acids which lead to physiologically acceptable addition products, Particularly preferred such acids are in this context, the hydrogen halides, such. the hydrochloric acid and the hydrobromic acid, and also phosphoric acid, nitric acid and sulfuric acid.

As examples of hyaroxyethyl-azolyl derivatives of the formula (I), mention may be made of the substances listed in the table below.

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274

30

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Table 1

OR

Y-CH ₂ -C-

2,4-CT,

2.W ₂ ^- 4-CH ₃

4-CF ₃

4-OCF ₃

4-OCH ₃

4-SCH ₃

2,4,6-Cl ₃

4-Cl

4-Cl

4-Cl

4-Cl

4-Cl

4-Cl

4-Cl

4-Cl

HHHHHHHHH CH ₃

CH-

CH

-R ^J

(I)

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

O O O O O O O O O O

35

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7416

Table 1 (continued)

4

4-C ₄ H ₉ -U H H 2-Cl, 4-CH ₃ H H H H 4-Cl -CO-CH H 4-Cl " ^C 2 ^H 5 H 4-F CH ₃ H 2,4-Cl ₂ H 2,4-F ₂ H 4-CH ₃ H 4-CF ₃ H 4-OCFq CH 4-0CH ₃ 4-SCH ₃ 2,4,6-Cl ₃ 4-Cl 4-Cl 4-Cl

4-Cl

4-Cl

4-Cl

4-Cl

4-Cl

CH

N N N

N N

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

Cl

0 0 0 0 0 0 S S S S S S S S S S

Cl

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274

Table 1 (continued)

4-C ₄ H ₉ -U 2-Cl, _4-CH3

4-Cl

4-Cl

4-F

2,4-Cl ₂

2,4-F ₂

4-CH ₃

4-CF ₃

4-0CF ₃

4-OCH ₃

2,4,6-Cl ₃

4-Cl

4-Cl

4-Cl

4-Cl

4-Cl

4-Cl

HHH -CO-CH ₃

" ^C 2 ^H 5 CH _{3 h}

HHHHHHHH CH ₃

^RJ

Cl

Cl Cl Cl Cl Cl

Cl Cl Cl Cl Cl Cl Cl

Cl Cl

Cl

Y s

S S S S S S

so so so so so so so

so

so

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Table 1 (continuation)

4-C ₄ H ₉ -L H H 2-Cl, 4-CH ₃ H H - H H 4-Cl -CO-CH H 4-Cl " ^C 2 ^H 5 H 4-F CH ₃ H 2,4-Cl ₂ H 2,4-F ₂ H 4-CH ₃ H 4-CF ₃ CH 4 OCF ₃ 4-0CH ₃ 2,4,6-Cl ₃ 4-Cl 4-Cl 4-Cl

4-Cl

4-Γ1

-L I

CH

Cl

Cl Cl Cl Cl Cl

Cl Cl Cl Cl Cl Cl Cl

Cl Cl

Cl

so

so be it like that

SO ₂ SO ₂ SO ₂ SO ₂ SO ₂ SO ₂ SO ₂ SO ₂ SO ₂ SO

so

so-

so

so-

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274

10

Table 1 (continued)

^R m R X R ¹ Y H N Cl so 4-C ₄ H ₉ -t. H N Cl so 2-Cl, 4-CH-, H N Cl so H N Cl so 4-Cl -CO-CH ₃ N Cl so 4-Cl -CoH ₅ N Cl so 4-F CH ₃ N F so

If 2- (1-chloro-cyclopropyl) -2- (4-chlorophenoxymethyl) -oxirane and 1,2,4-triazole are used as starting materials, the course of process (a) according to the invention can be illustrated schematically by the following formula:

-CH-

⁺ (ΓΊ

-CH-

OH

-CH-

ίί

Cl

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274 U 4

If 2- [1- (2-chlorophenoxy) -eyelopropyl] -2 - [(1,2,4-triazol-1-yl) methyl] oxirane and 4-chlorothiophenol are used as starting materials, the course of the process (b) according to the invention are illustrated by the following equation:

Cl

S-CH ₂ C-

X U

Using 1 ~ (4-chlorophenylmercapto) -2- [1- (2-chlorophenoxy) cyclopropyl] -3- (l, 2,4-triazol-1-yl) -propan-2-ol as starting material and aqueous hydrogen peroxide in glacial acetic acid as the oxidizing agent, the course of the process (c) according to the invention can be illustrated by the following formula scheme:

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274 f 6 4

Cl

H ₂ O ₂ ZH ₂ OCH ₃ COOH

SO ₂ -CH ₂ "

OH

CH ₂

Using 2- (1-chloro-1-propyl) -1- (4-chlorophenoxy) -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 (ei) according to the invention can be illustrated schematically by the following formula:

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2 7 4 U 4

Cl

ONa

CH-

+ NaH

-Cl

+ CH ₃ J

- NaY

OCH

The oxiranes required as starting materials in process (a) according to the invention are represented by the formula

(II) generally defined. In this formula, R, R , Y 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 as being preferred for these radicals and for this index.

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The oxiranes of the formula (II) are not yet known, they can be prepared by

e) cyclopropyl ketones of the formula

10 / ^ ν_ _ΓΗ γ ^^ τΛ

R '

^m O (VII)

in which 15

R *, R 1, Y and m have the abovementioned meaning,

either 20

α) with DimethyloKosulfonium-methylid of the formula

^ (CH ₃ J ₂ SOCH ₂ (VIII)

or

ß) with dimethylsulfonium methylid of formula 30th

δ® δ ^θ (CHg) ₂ S CH ₂ (IX)

in the presence of a diluent, 35

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The in process (e) required as starting materials cyclopropyl ketones of the formula (VII) are also not yet known, they can be prepared by

f) haloketones of the formula 10

Hal'-CH ₇ -C - ^ - R ¹ (X)

² Il

in which

R ^{1 has} the meaning given above and

Hal 'is chlorine or bromine, with phenyl derivatives of the formula

/ V- _Y 1 _H (γ)

m 25

in which

R, Y and m are as defined above,

in the presence of an acid binder and optionally in Gegenwa. ': Reacting a diluent and then optionally oxidized,

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The haloketones of the formula (X) required as starting materials in process (f) are known in some cases. They can be produced by one

g) ketones of the formula

¹⁰ CH ₃ -C - ^ - R ¹ (XI)

in which 15

R has the meaning given above,

with chlorinating agents or brominating agents in

Reacting the presence of a diluent, 20

The ketones of the formula (XI) required as starting materials in process (g) are known or can be synthesized by methods which are known in principle

(cf., Synthesis 1977, 189). 25

Suitable chlorinating and brominating agents in process (g) are all chlorinating and brominating reagents customary for such reactions. Sulfuryl chloride, suiduryl bromide, chlorine and bromine are preferably suitable.

As diluents commercial, in the process (g) all customary for such reactions inert organic solvents in question. Preferably used are halogenated aliphatic hydrocarbons, such as methylene chloride, chloroform and carbon tetrachloride.

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The reaction temperatures can be varied in the process (g) within a certain range. In general, one works at temperatures between -10 ⁰ C and + 60 ⁰ C, preferably between ^{0 0} C and + 40 ⁰ C.

When carrying out the process (g), as in the other processes described in this application, the process is generally carried out under atmospheric pressure. However, it is also possible to work under increased or reduced pressure.

In carrying out the process (g) is used for 1 mol of ketone of the formula (XI) is generally a stoichiometric amount or a slight excess of chlorinating or brominating agent. The workup is carried out by conventional methods. In general

mine proceeds so that the reaction mixture is washed successively with dilute aqueous sodium bicarbonate solution and water, then dried and concentrated.

The phenyl derivatives required as reaction components in process (f) are represented by the formula (V).

* F · ο ι

In this formula, R, Y 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 as being preferred for these radicals and for this index. The phenyl derivatives of the formula ( V) are well known compounds of organic chemistry,

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Suitable acid binders for carrying out the process (f) are all customary acid acceptors. Preference is given to using alkali metal carbonates and bicarbonates, such as sodium carbonate, potassium carbonate or sodium bicarbonate, and also alkali metal hydroxides and alcoholates, such as sodium hydroxide, potassium hydroxide. Sodium methylate or potassium . butoxide also _t tertiary aliphatic or aromatic amines, such as triethylamine, Ν, Ν-dimethyl-eyelohexyl-amine, Ν, Ν-dimethyl-benzylamine and pyridine, and also cyclic amines, such as 1,5-diaza-bicyclo C4,3.0] non-5-ene (DBN), 1, e-diaza-bicycloC5, 4.0] undec-7-ene (DBU) un '1, 4-diaza-bicyclo [2, 2. 2] octane (DABCO),

Suitable diluents for carrying out process (f) are all inert organic solvents

? 0 ·

Preferably, aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, ethers, such as dimethyl are preferred and dibutyl ethers, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioctane, ketones such as acetone, methylethyl, methyl isopropyl and methyl isobatyl ketone, esters such as methyl acetate and ethyl acetate, nitriles such as acetonitrile and propionitrile and pyridine, and also strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide,

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274 (64

The reaction temperatures can be varied within a wider range in the process (f). In general, one works at temperatures between ^{0 0} C and 150 ⁰ C, preferably between 20 ° C and 130 ⁰ C.

When carrying out the process (f), use is made

1 mole of haloketone of the formula (X) generally 1 to 1.5 moles of phenyl derivative of the formula (V) and 1 to

2 moles of acid binder. The work-up is carried out by customary methods. The procedure is generally such that, if appropriate, the reaction mixture is concentrated after precipitation of precipitated salts, the residue is taken up in a water-immiscible organic solvent, the resulting solution is washed, dried and then concentrated.

The dimethyl-oxo-sulfonium-methylid of the formula (VIII) required as reaction component in the process (e) is known (cf., J, Am, Chem, Soc. T7, 1363-1364 (1965)) processed above in a freshly prepared state by placing it in situ

nc

by reaction of trimethyloxosulfonium iodide with sodium hydride or sodium amide, potassium tert-butoxide or sodium methoxide, in the presence of a diluent.

The ^u in the method (s) also as a reaction component in dimethylsulphonium methylide of the formula (IX) is likewise known (see, Heterocycles

35

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8, 397 (1977)). It is also used in the above reaction when freshly prepared by, for example, in situ from, for example, trimethylsulfonium halide or trimethylsulfonium methylsulfate, in the presence of a strong base, such as sodium hydride, sodium amide, sodium methoxide, potassium tert-butoxide, or * ^ Potassium hydroxide, in the presence of a diluent, such as tert-butanol or dimethyl sulfoxide produced.

Suitable diluents for carrying out process (e) are inert organic solvents.

Preferably used are alcohols, such as tert-butanol, ethers, such as tetrahydrofuran or dioxane, furthermore aliphatic and aromatic hydrocarbons, such as benzene, toluene or xylene, and strongly polar solvents, such as dimethyl sulfoxide or acetonitrile,

The reaction temperatures can be varied within a substantial range when carrying out the process (e). In general, one works between O ⁰ C and

100 ⁰ C, preferably between 10 ⁰ C and 60 ⁰ C, 25

In carrying out the process (e) is used for 1 mol of cyclopropyl ketone of the formula (VII) is generally 1 to 3 moles of dimethyloxosulfonium methylid of the formula. (VIII) or, on Dimethylsul fonium-methyl id of the formula (IX), The isolation of the oxiranes of the formula (II) is carried out by customary methods.

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Suitable acid binders for carrying out process (a) according to the invention are all customary acid acceptors. All acid binders which have already been mentioned in connection with the description of process (f) may preferably be used

 10

Suitable diluents for carrying out the process (a) according to the invention are all customary inert organic solvents.

Preference is given to using nitriles, in particular acetonitrile; aromatic hydrocarbons, such as benzene, toluene and dichlorobenzene; Formamides, in particular dimethylformamide, and hexamethylphosphoric triamide.

The Reaktxonstemperaturen can be varied in carrying out the process (a) according to the invention in a wider range. In general, one works at temperatures between ^{0 0} C and 200 ⁰ C, preferably

between 50 ° C and 150 ⁰ C. 25

When carrying out process (a) according to the invention, it is preferable to use 1 mol of oxirane of the formula (II), 1 to 4 mol of azole of the formula (III) and 1 to 2 mol of base. The isolation of the final products

takes place in the usual way.

The azolylderivatives required as starting materials for carrying out the process (b) according to the invention

vates are generally defined by the formula (IV), In

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of 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 azolyl derivatives of the formula (IV) are not yet known, they can be prepared by

h) Azolyl ketones of the formula

¹⁵ I N-CH ₂ -C - ^ - R ¹ (XII)

in which 20

R and X have the meaning given above,

ent TQ jer

<x) with dimethyloxosulfonium methyl id of the formula

(CH ₃ J ₂ SOCH ₂ (VIII)

or

&) with dimethylsulfonium magnesium of the formula

35 δ ^Θ δ ^θ

(CH ₃ ) ₂ S CH ₂ (IX)

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in the presence of a diluent, 5

The in the implementation of the method (h) required as starting materials Azolylketone are also not yet known, they can be producedi by

i) halo ketones of the formula

Hal'-CHo-C ^ - R ¹ (X)

² Il

in which

R ^{1 has} the meaning given above and 20

Hai 'stands for chlorine or bromine,

with azoles of formula 25

if I! (in)

in which X has the meaning given above »

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

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In carrying out the process (i), the reaction conditions correspond to those of the process (f),

The process (h) is carried out analogously to that of the process (e),

The phenyl derivatives required as reaction components in carrying out the process (b) according to the invention have already been dealt with in connection with the description of process (f) *

In carrying out the process (b) according to the invention, it is possible to use all customary acid binders and diluents. Preference is given to using those acid binders and solvents which have already been mentioned as preferred in connection with the description of process (a).

The reaction temperatures can also be varied within a substantial range when carrying out process (b) according to the invention. In general, one works at temperatures between 0 and 200 ⁰ C, preferably between 50 and 150 ⁰ C,

In carrying out the process (b) according to the invention is used for 1 mole of azolyl derivative of the formula (IV) is generally an equivalent amount or an excess of phenyl derivative of the formula (V) and 2 to 4 moles of acid binder. The work-up is carried out by customary methods. In general, raan proceeds in this way

35

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that the reaction mixture is filtered, the filtrate is concentrated by stripping off the diluent and " ¹ the remaining residue is purified in a conventional manner φ

The hydroxyethy1-azolyl derivatives required for the process (c) according to the invention as starting materials

Formula (Ia) are compounds of the invention.

Suitable reaction components in process (c) according to the invention are all oxidants customary for such reactions. Preference is given to using hydrogen peroxide and peracids, such as m-chloroperbenzoic acid and acetic acid.

When carrying out the process (c) according to the invention, m, based on 1 mol of the compounds of the formula (Ia) according to the invention, contains about 1 to 5 mol of oxidizing agent. When using 1 mole of oxidizing agent, such as m-chloroperbenzoic acid in methylene chloride or hydrogen peroxide in acetic acid or acetic anhydride at temperatures between -30 ⁰ C to +90 ⁰ C, formed preferably the compounds of formula (I) according to the invention, in which Y is a - SO grouping stands. When excess of oxidizing agent and temperatures between 10 ⁰ C and 90 ° C are preferably formed compounds of the formula (I) according to the invention, in which Y stands for a -S02 ~ group- ^JU pierung. The isolation of the oxidation products is carried out in the usual way,

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The hydroxyethyl-azolyl derivatives of the formula (Ib) which are required for starting materials of the process (d) according to the invention are likewise compounds according to the invention; their conversion into the corresponding alcoholates is carried out in a generally known manner by mixing 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 in the compounds of the formula (Ic) is preferably an alkali metal cation, such as a sodium or potassium cation, or a quaternary ammonium phosphonium cation.

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

20

generally defines formula (VI). In this 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 water.

Hai is preferably chlorine or bromine,

The halogen compounds of the formula (VI) are known or can be prepared by methods known in principle, 30

Suitable diluents for carrying out the process (d) according to the invention are inert organic solvents, which preferably include ethers, such as diethyl ether or dioxane; aromatic hydrocarbons, such as benzene, in certain cases also chlorinated

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Hydrocarbons, such as chloroform, methylene chloride or carbon tetrachloride; and hexamethylphosphoric triamide,

The reaction temperatures can be varied in a wider 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 the process (d) according to the invention, hydroxy compounds of the formula (Ib) are first reacted with strong bases to give the corresponding alcoholates of the formula (Ic). In the subsequent step, it is preferable to use 1 to 2 moles of a halogen compound of the formula (VI) per mole of an alcoholate of the formula (Ic).

To isolate the end products, the reaction mixture is freed from the solvent and the residue is mixed 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 ^{u of} the formula (Ib), the latter being converted into the alkali metal alcoholate by means of alkali metal hydride or alkali metal malide in a suitable organic solvent and the latter immediately without isolation with a halogen compound of the formula (VI), wherein under "* ° exit of alkali metal halide, the compounds of formula (7) according to the invention are obtained in one operation.

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274 I A4

According to a further preferred embodiment, the preparation of the alcohols and the reaction with a halogen compound of the formula (VI) 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 a phase Transfer catalyst, such as ammonium or Phosproniumverbindungen carried out, wherein in the organic phase or at the interface, the alcoholates reacted with the halides in the organic phase

become . 15

The Hydroxyethy1-azolyl derivatives of the formula (I) obtainable by the process according to the invention can be converted into acid addition salts or metal salt complexes

become »20

For the preparation of acid addition salts of the compounds of the formula (I), preference is given to those acids which have already been mentioned as preferred acids in connection with the description of the acid addition salts according to the invention,

The acid addition salts of the compounds of the formula (I) can be prepared in a simple manner by customary salt formation methods, e.g. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g. Hydrochloric acid, can be obtained and in known manner ». by filtration, isolated and optionally by washing with an inert

to be cleaned with organic solvents, 35

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For the preparation of metal salt complexes of the compounds of 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 formula (I) can be readily obtained by conventional methods, e.g., B, by dissolving the metal salt in alcohol, e.g. Ethanol and adding to compounds of formula (I). Metal salt complexes can be prepared in a known manner, e.g. by filtration, isolate and optionally by Umkristal1isat ion clean.

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

Fungicides are used in crop protection for the control of Plasmodiophorom> cetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

By way of example but not limitation, some pathogens of fungal and bacterial diseases, which fall under the above-enumerated generic terms, called!

Xanthomonas species, such as Xanthomonas oryzaej Pseudomonas species, such as? Seudomonas lachrymansj Erwinia species, such as Erwinia amylovoraj

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274

Pythium species, such as Pythium ultimum; Phytophthora species, such as Phytophthora infestansj Pseudoperonospora species, such as Pseudoperonospora humuli or Pseudoperonospora cubensej Plosmopara species, such as Plasmopara viticolaj Peronospora species, such as Peronospora pisi or P. brassicae;

Erysiphe species, such as Erysiphe graminis; Sphaerotheca species, such as SphaeroLheca fuligineaj Podosphaera species, such as Podosphaera leucotrichaj Venturia, such as Venturia inaequalisj Pyrenophora species, such as Pyrenophora teres or P. graminea;

(Conidia form Drechslera, Syn: Helmiivthosporium) j Cochliobolus species, such as Cochliobolus sativusj (conidia form: Drechslera, Syn: Helminthosporium) j

20 ·

Uromyces aryls, such as Urornyces appendiculate-us J Puccinia species, such as Puccinia recondita; Ti 1 letia species, such as TilleLia caries;

Usilago species, such as Ustilago nuda or Ustilago avenae;

Pel 1icularia species, such as Pel 1icnlaria sasakiij

Pyricularia species, such as Pyricularia oryzaej

Fusarium species such as Fusarium culmorumj Botrytis species such as Botrytis cinereaj Septoria species such as Septoria nodorumj Leptosphaeria species such as Leptosphaeria nodorumj ^JU Cercospora species such as Cercospora canescensj Alternaria species such as Alternaria brassicaej Pseudocercosporella species such as Pseudocercosporella herpotrichoides,

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274 U 4

The good plant tolerance of the active ingredients in the necessary concentrations for controlling plant diseases allows treatment of above-ground parts of plants, Pflan2- and seeds and the soil.

The active compounds according to the invention are particularly suitable for controlling cereal and rice diseases, such as rust, mildew, Cochliobolus sativus, Pyrenophora teres and Leptosphaeria nodorum on cereals, or Pyricularia oryzae on rice. Furthermore, they can be against

Sphaerotheca to use cucumbers «15

In addition, the active compounds according to the invention also have lance growth regulators. he end properties.

The active compounds according to the invention mature into the metabolism of the plants and can therefore be employed as growth regulators.

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

^{ώΟ can} also exert several different effects on plants. The effects of the substances depend essentially on the time of application, based on the stage of development of the plant and on the active substance applied to the plants or their surroundings.

Amounts and type of application. In any case, growth regulators are intended to influence crops in some desired manner.

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274 ί 6 4

For example, plant growth regulating substances can be used to inhibit vegetative growth of the plants. Such growth inhibition is inter alia in grasses of economic interest, because it can reduce the frequency of grass clippings in ornamental gardens, parks and sports facilities, at roadsides, at airports or in orchards, Also of importance is the inhibition of the growth of herbaceous and woody Plants on roadsides and near pipelines or overland pipelines, or more generally in areas where heavy growth of plants is undesirable.

Also important is the use of growth regulators to inhibit grain elongation. This poses the danger of the plants "stooping"

20 ·

reduced or completely eliminated before harvest.

In addition, growth regulators in cereals can cause a stalk reinforcement, which just counteracts all camps. The use of growth regulators for stalk shortening and stalk augmentation makes it possible to apply higher amounts of fertilizer in order to increase the yield without the risk of the grain being stored.

An inhibition of the vegetative growth enables a denser planting in many crops, so that additional yields relative to the soil surface can be obtained. An advantage of the smaller plants thus obtained is that the culture is easier to process and

can be harvested

 35

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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,

Stimulation of vegetative growth can often be achieved with growth regulators. This is of great benefit when the vegetative parts of plants are harvested. However, a demand of vegetative growth can simultaneously lead to a demand for generative growth, in that more assimilates are formed so that more or more fruits are produced,

Increases in yield can in some cases by a

20.

In addition, growth regulators can be used to achieve a change in the composition of the plants, which in turn can lead to an improvement in the quality of the harvested products. For example, it is possible to control the content of the plant To increase sugar in sugar beets, sugarcane, pineapple and citrus fruits or to increase the protein content in soy or cereals. It is also possible, for example, to inhibit the degradation of desirable ingredients, such as sugars in sugar beets or sugar cane, with growth regulators before or after harvest. In addition, the production or effluent of secondary plant ingredients may be positively affected. As an example, be the

^ Stimulation of latex flow in gum trees called.,

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274/6

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

The use of growth regulators Branching of plants can be controlled "On the one hand, the development of side shoots can be promoted by breaking the apical dominance, which can be very desirable, especially in ornamental plants in conjunction with a ¹ inhibition of growth, but the other hand, it is also possible that Growth of side shoots inhibit. For this effect, for example, there is great interest in tobacco growing or in the planting of tomatoes. 20

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 a role in the

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

decrease.

Likewise can be controlled with growth regulators the fruit case. On the one hand, a premature fruit drop can be prevented. On the other hand, however, the fruit fall or even the fall of the bleed up to a

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desired dimensions ("thinning") to break the alternation. Alternating means the peculiarity of some fruits, endogenous to bring very different yields from year to year, Finally, it is possible with growth regulators at the time of harvest to reduce the forces required to detach the fruit to allow a mechanical harvesting or a facilitate manual harvesting.

With growth regulators can also be an acceleration or deceleration of the ripeness of the crop before or after the harvest reach This is of particular advantage because this can bring about an optimal adaptation to the needs of the market. In addition, growth regulators may in some cases improve the * color fruit colouration. In addition, with growth regulators, a temporal concentration of the maturity can be achieved, thus creating the conditions for, for example, in tobacco, tomatoes or coffee a complete mechanical or manual

Harvesting can be done in one operation.

Furthermore, by using growth regulators, the seed or bud dormancy of the plants can be influenced so that the plants such as z. B. pineapples or ornamental plants

^ ® in nurseries, germinate, sprout or flower at a time when they usually do not show any willingness to do so. Delaying bud sprouting or seed germination by growth regulators may be desirable in areas prone to frost to prevent damage from late frosts.

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2 7 4 ί 6 4

Finally, growth regulators can be used to induce plant resistance to frost, dryness or high salinity in 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 the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, ultrafine encapsulations in polymeric substances and in seed coating compositions, as well as ULV formulations, 15

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

optionally with the use of surfactants, ie emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender, e.g. also organic solvents as auxiliary

Suitable solvents include: aromatics, such as xylene, toluene or alkylnaphthaines, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene

chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. 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

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274 ί 6 4

liquefied gaseous diluents or carriers are meant liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide j as solid carriers are eligible! e.g. ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as fumed silica, alumina and silicates; as solid carriers for granules are: for example, broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic meals and granules of organic Mtt.erial such as flour, coconut shells, corncobs and tobacco stalks ^ ls emulsifier

and / or foaming agents come in question! e.g.

nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers,... * *, B, alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates, and protein hydrolysates

Dispersants are suitable: e.g. Lignin-sulphite waste liquors and methyl cellulose,

In the formulations, adhesives such as carboxymethylcellulose, natural and synthetic powdery,

granular or latex-form polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids, other additives may be used

be mineral and vsgetabile oils. 35

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10

274 i 6 4

- 45 -

Dyes such as inorganic pigments, e.g. 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 are used

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

The active compounds according to the invention may be present in the formulations in a mixture with other known active compounds such as fungicides, insecticides, acaricides and herbicides and mixtures with fertilizers and others

Growth regulators

 20

The active compounds can be used as such, in the form of their formulations or the application forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, foams, suspensions, wettable powders, pastes,

pe

soluble powders, dusts and granules; be applied. The application is done in the usual way, e.g. by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to use the active ingredients * according to the ultra-low-volume method.

TO ·

drive or 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.

35

Le A 25 325

When using the substances according to the invention as fungicides, the application rate can be varied within a substantial range, depending on the type of application. Thus, the active ingredient concentrations in the treatment of parts of plants in the use forms are generally between 1 and 0.0001 wt .-%, preferably between 0.5 and 0.001%. 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, drug concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required on the effector.

When using the compounds of the invention as plant growth regulators Au.fwandmengon in eAnem larger area can be varied, Ini generally used per hectare of soil area from 0.01 to 50 kg, preferably 0 _Λ 05 to 10 kg of active ingredient.

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

Ausführungabeispiele

The preparation and the use of the active compounds according to the invention are evident from the following examples.

- 47 -

2 7 4 I έ 4

Production Examples 5

Example 1

(I-1) 10

In a mixture of 29 g (0.42 mol) of 1,2,4-triazole, 19 g (0.14 mol) of potassium carbonate and 100 ml of acetonitrile under nitrogen atmosphere, a solution of 27.9 g (0.11 mol) 2- (l-Chlorcyc1 opropy1) -2- (4-chloro-phenoxymethyl) -oxi ran added dropwise in 50 ml of acetonitrile, iWi the reaction mixture is refluxed, After completion of the addition is heated for a further 3 hours under reflux, then sucks from the solid residue and the filtrate concentrated under reduced pressure. The remaining residue is taken up in ethyl acetate, the resulting solution is washed with water, dried over sodium sulfate and concentrated under reduced pressure. The product thus obtained is purified by chromatography on silica gel with chloroform / ethanol = 97! 3 as the eluent. 13.7 g (39% of theory) of 2- (1-chlorocyclopropyl) -1- (4-chlorophenoxy) -3- (1,2,4-triazol-1-yl) are thus obtained. Propan-2-ol in the form of an oil.

¹ H-NMR (80 MHz, CDCl 3):

δ = 0.5-1.4 (m, 4H), 4.1-4.4 (m, 3H), 4.75 (s, 2H), 6.8-7.25 (m, 4H), 8.0 (s, 1H), 8.17 (s, IH).

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Production of starting products

Cl- <f 7-0-CH ₂ - -C - ^ - ^C1 (II-l)

-CH ₂

In a mixture of 3.9 g (0.13 mol) of sodium hydride (δΟ '/ - ig) and 27 g (0.12 mol) of trimethyl-oxosulfonium iodide 90 rril absolute dimethyl sulfoxide are added dropwise at 10 ⁰ C under nitrogen atmosphere and with stirring , The mixture is stirred for a further 1 hour at room temperature, then cooled to 10 ^° C. and a solution of 27 g (0.11 mol) of 1-chlorocyclopropyl-4-chlorophenoxymethyl ketone in 40 ml of absolute dimethyl sulfoxide is added dropwise. The reaction mixture is initially heated for 48 hours stirred at 20 ° C, then heated to 40 ° C for 1 hour and then poured onto water. The resulting mixture is extracted with ethyl acetate. The organic phase is with. Water, dried over sodium sulfate and concentrated under reduced pressure, thus obtained in this way 27.9 g (98./. Of theory) of 2- (1-chlorocyclopropyl) -2- (4-chlorophenoxymethyl) oxirane in the form of a oil,

¹ H-NMR (60 MHz, CDCl 3):

δ = 0.75-1.4 (m, 4H), 2.8 (d, IH), 3.05 (d, IH), 4.25 (d, IH), 4.58 (d, IH) , 6.8 - 7.4 in, 4H).

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274 t 6 4

- 49 -

^C1 (VII-I)

A solution of 51 g (0.33 mol) of 1-chloro-1-chloroacetyl-eyelopropan in 250 ml of acetonitrile is added successively to 49 g (0.38 g) of 4-chlorophenol and 70 g (0.51 mol) of potassium carbonate. The mixture is refluxed for 8 hours, then filtered and concentrated by stripping off 3% of solvent. The residue is taken up in ethyl acetate, washed successively with dilute, aqueous sodium hydroxide solution and water, dried over sodium sulfate and the solvent is removed under reduced pressure. The residue is subjected to distillation. Obtained in this way 27 g (33 '/. Of theory) of 1-chloro-cyclopropyl-4-chlorophenoxy-methyl ketone in the form of a liquid of boiling point 125 127 ⁰ C / 0.1 mbar.

ClCHp-C - ^ - ^C1 (XI)

² Il

At room temperature, 40.5 ml (0.5 mol) of sulfuryl chloride are added slowly with stirring to a solution of 54 g (0.46 mol) of 1-acetyl-1-chloro-cyclopropane in 250 ml

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7 4 16

Methylench ¹ .id eingetrcpft It is first stirred for 14 hours at room temperature and then 30 minutes at 30 ° C, The reaction mixture is then washed sequentially with saturated aqueous sodium bicarbonate solution and with water. Thereafter, the organic phase is dried over sodium sulfate and concentrated under reduced pressure, to obtain in this way 51.5 g (74V of theory) of 1-chloro-l-chloroacetyl-cyclopropane in the form of an oily substance,

¹ H-NMR (60 MHz, CDCl 3): 6 = 1.2-1.9 (m, 4H); 4.8 (s, 2H)

Example 2

S-CH ₂ -

OH

(f

CH ₂

(1-2)

A mixture of 15 g (0.05 mol) 2- [1- (2-chlorophenoxy) cyclopropyl] -2 - [(l, 2,4-triazol-1-yl) methyl] oxirane, 7.5 g (0, D5 mol) of 4-chloro-lhiophenol, 0.75 g (0.13 mol) of potassium hydroxide powder and 45 ml of acetonitrile are heated under reflux. The reaction mixture is filtered and the filtrate is concentrated by stripping off the solvent under reduced pressure. The remaining product is subjected to a chromatographic purification, giving 22 g (98% of theory) of 1-

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(4-chlorophenylmercapto) -2- [1- (2-chlorophenoxy) -eyelopropyl-3- (1,2,4-tr ^; azol-1-yl) -propan-2-ol in the form of an oily product,

¹ H-NMR (80 MHz, CDCl ₃ ):

6 = 0.3-1.3 La, 4H), 3.3b (d, IH), 3.58 (d, IH), 4.30 (s, IH), 4.77 (a, 2H), 7.0-7.5 (m, 8H), 8.08 (s, IH), 8.5 (s, IH).

Preparation of starting materials: 15

CH ₂ "

CH-

'- ^(IV " ⁿ

In a mixture of h g (0.2 mol) of sodium hydride (80 / i-ig) and 42 g (0.19 mol) of trimethyloxosulfonium iodide are added dropwise at 10 ° f under nitrogen atmosphere and with stirring 135 ml of absolute dimethyl sulfoxide. The reaction mixture stirred vird i hour at room temperature, then cooled to ⁰ IU C and treated dropwise with a solution of 47 g (0.17 Mo. ¹⁾ 1 - (2-chlorophenoxy) -

cyclopropyl '1 _t 2 , 4-triazol-1-yl) methyl ketone in 50 ml of absolute dimethyl sulfoxide. The mixture is stirred for a further 48 hours at room temperature and then heated for 1 hour at 40 ⁰ C, then poured into the reaction mixture

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274U4

Water and extracted with ethyl acetate. The United

organic phases are washed with water and concentrated by evaporation over sodium sulfate by stripping off the solvent under reduced pressure, This gives 40.2 g (81% of theory) of 2- [1- (2-chlorophenoxy) cyclopropyl] -2 - [(1,2,4-triazol-1-yl) -methyl! Oxirane in the form of an oily product,

¹ H-NMR (60 MHx, _CDCl3) ί

δ = 0.6-1.6 (m, 4H), 2.6 (d, IH), 2.78 (d, IH), 4.34 (d, IH), 4.75 (d, IH) , 6.9-7.5 (m, 4H), 8.0 (s, IH), 8.45 (s, IH),

20 I N-CH ₂ -C - ^ - O- \) (XII-I)

N = ^

Into a mixture of 38.5 g (0.28 mol) of potassium carbonate, 58.4 g (0.85 mol) of 1,2,4-triazole and 140 ml of acetonitrile is added a solution of 62 g (0.25 mol) of 1 Chloroacyl- (2-chlorophenoxy) -eyelopropan added dropwise in 60 ml of acetonitrile, wherein the reaction mixture is refluxed. The Reaktjonsgemisch is heated for a further 8 hours under reflux, then filtered and concentrated by evaporation of the solvent under reduced pressure. Take up the remaining residue in ethyl acetate, wash with water. Dry over sodium carbonate.

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274 t

- 53 -

sulphate and then the solvent is removed under reduced pressure. The remaining product is chromatographed with chloroform / ethanol = 99: 1 as eluent Bn silica gel, thus obtaining 47 g of theory) of 1- (2-chlorophenoxy) -eyelopropyl- (1,2,4-triazol-1-yl ) methyl ketone in the form of an oily

¹⁰ dukes.

-H-NMR (60 MHz, CDCl _3): δ = 1.15-1.85 (m, 4H), 5.34 (s, 2H), 6.80-7.60 (m, 4H), 7 , 90 (s, IH), 8.07 (s, IH).

Cl CHO C-

Into a mixture of 61.7 g (0.29 mol) of 1-acetyl-1- (2-chlorophenoxy) -cyclopropane and 0.4 g of dibenzoyl perdene at 20 ° C with stirring and cooling 48 g

Added dropwise (0.35 mol) of sulfuryl chloride. The mixture is stirred for a further 4 hours at 20 ° C and exposed the reaction mixture simultaneously with a 200 W light bulb. Subsequently, the reaction mixture is treated with a mixture of ELisigester and toluene. It will be with water

^, dried over sodium sulfate and concentrated by evaporation of the solvent under reduced pressure. The remaining product is subjected to a vacuum distillation, giving 62.3 g (87% of theory) of 1-chloroacetyl-1- (2-chloro)

° phenoxy) -eyepropan.

Kp = 117-122 ⁰ C / 0.2 mbar Le A 2 5 325

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16

CH ₃ -C - ^ - Ο- < ^Ν > (XI-I)

Cl

In a mixture of 100 g (0.83 mol) of 5-chloropentan-2-one and 400 ml of methylene chloride is added dropwise at 10 ⁰ C with stirring, a solution of 134 g (0.84 mol) of bromine in 130 ml of methylene chloride. After complete addition, the Reaktionsgernisch is stirred for 15 minutes and then poured onto 500 nl of water. The organic phase is separated, washed successively with 5% aqueous sodium carbonate solution and washed with water, then dried over sodium sulfate and concentrated by evaporation of the solvent under reduced pressure. The residue is taken up in 200 ml of dimethylformamide and the resulting solution is added dropwise at 60 ° C in a mixture of 230 g of potassium carbonate, 106 g (0.83 mol) of 2-chlorophenol and 400 ml of dimethyl formamide, the reaction mixture is first 4 hours at 60 ° C and then stirred at 90 ° C for 4 hours , Then it sucks from the solid

Residue from, the solvent is removed under reduced pressure and the remaining residue is taken up in a mixture of ethyl acetate and toluene, the organic phase is washed with water, dried over sodium sulfate and by evaporation of the solvent under

The residue which remains is subjected to vacuum distillation, giving 92.5 g (53% of theory) of 1-acetyl-1- (2-chlorophenoxy) -cyclopropane in the form of a liquid

of boiling point 81 ⁰ C / 0.2 mbar, 35

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274 U 4

Example 3

SO ₂ -CH ₂ -

OH

CH

A solution of 10 g (23 rulol) of 1- (4-chlorophenylmercapto) -2- [1- (2-chlorophenoxy) cyclopropyl] -3- (1,2-triazol-1-yl) -propane 2-ol in 50 ml Eisossig is heated to 80 ° C and treated dropwise with stirring with 20 ml of 35% hydrogen peroxide solution. The reaction mixture is heated for 4 hours at 90 ° C and then poured onto water. The solid product is filtered off with suction, taken up in methylene chloride, washed successively with dilute, aqueous sodium hydroxide solution and water, dried over sodium sulfate and concentrated by evaporation of the solvent under reduced pressure. This gives 6.4 g (60% of theory) of 1- (4-chlorophenylsulfonyl) -2- [1- (2-chlorophenoxy) -eyepropyl] -3- (1,2,4-triazole) l-yl) propan-2-ol,

¹ H-NMR (200 MHz, CDCl 3):

6 = 0.30-0.95 (m, 4H), 3.65 (d, IH), 3.87 (d, IH), 4.85 (d, IH), 5.11 (d, IH) , 7.0-7.4 (m, 4H), 7.55 (d, 2H), 7.80 (d, 2H), 8.0 (s, IH), 8.44 (s, IH).

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According to the methods given in Examples 1 to 3 and in the description, the substances listed by formula in Table 2 below are also prepared.

10 15 20 25 30 35

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table

OR

Y-CH

CH

Example no. Connection no. ^R m R rl Y X Melting point ( ⁰ C) 4 1-4 1-5 4-F 2,4-Cl ₂ H H Cl 0 0 N N *) 123 6 1-6 2-CH ₃ , 4-Cl H ^ 3 0 N 125 7 1-7 4-CH = N-OCH ₃ H ^ 3 0 N 88 8th 1-8 4-Cl H -O 0 N 140 9 1-9 4-Cl H  <3 ^ 0 N resin

Table 2 (continued)

LTi OJ Ul

Example no. Connection no. 10 1-10 11 1-11 12 1-12 13 1-1-3 14 1-14 15 1-15 16 1-16

17

1-17

2,4-Cl ₂

4-OCF ₃

2-CH ₃ , 4-Cl

4-CH = N-OCH ₃

4-F

CF ₃

4-CH ₃

4-0CF ₃

Melting point ( ⁰ C)

resin

resin

140

113

142

158

137

148

Tabe ll 2 (continued)

Example no. Connection no. 18 1-18 19 1-19 20 1-20 21 1-21 22 1-22 23 1-23 24 1-24 25 1-25

4-CF ₃

4-CH ₃

2-Cl

4-F

2-Cl

2-CH ₃ , 4-Cl

4-Cl 4-CH = N-OCH ₃

0 0 0

Melting point ( ⁰ C)

127

resin

resin

124

136

resin

118

resin

Table 2 (continued)

Example, no.

Connection no.

Melting point ( ⁰ C)

26 27 28 29

1-26

1-27

1-28

1-29

2,4-Cl ₂

2-Cl, 4-0CF ₃

4-OCF

4-Cl

Hp. R ζ

113

108

*) The compound disclosed in Example 4 is characterized by the ¹ H-NMR spectrum (360 MHz, CDCl ₃ characterization:

δ = 0.55-0.70 (ra, 2H), 0.80-0.95 (m, IH), 1.10-1.20 (m, IH) 4.10 (s, IH), 4 , 16 (d, IH), 4.30 (d, 1ΙΓ ;, 4.75 Cd, IH), 4.80 (d, IH), 6.80-7.05 (m, 4H), 3.02 (s, IH), 8.30 (s IH).

274 ί 6 4

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In the following use examples, the compound of the formula given below was used as a comparison substance:

OH

(A) = Cl

0-CH ₂ -C-

(i

(Known from EP-OS 0 040 345).

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2 7 4 ί 6 4

Example A 5

Sphaerotheca test (cucumber) / protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 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 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

20 ·

Dripping wet. After the spray coating has dried on, the plants are pollinated with conidia of the fungus Sphaerotheca fuliginea.

The plants are then at 23 to 24 ° C and at

a relative humidity of about 75 V. in the

Greenhouse set up.

10 days after the inoculation the evaluation takes place

30 ·

In this test, the compound of the formula (1-1) according to the invention has a markedly better action than the comparison substance (A),

Le A 25 325

- 63 -

27 4 \ 6 4

At game B 5

Leptosphaeria nodorum test (wheat) / protective

Solvent: 100 parts by weight of dimethylformamide Emulsifier: 0.25 part by weight of alkylarylpo.'yglyki * 1 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 active compound preparation ^r dewy,

After drying of Sprιtzbelagas the plants

sprayed with a spore suspension of "Leptosphaeria nodorum." The plants remain in an incubation cabin for 48 hours at 20 ° C. and 100 * / relative humidity, 25

The plants are placed in a greenhouse at a temperature of ca, 15 ⁰ C and a relative humidity of about 80%,

10 days after the inoculation, the evaluation is carried out, whereby 0% corresponds to an efficiency which corresponds to that of the untreated control, while an efficiency of lOOX means that no infestation exists

is. 35

In this test, the compound (I-1) according to the invention shows a significantly better activity than the comparison substance (A), Le A 25 325

- 64 -

Example C 5

Growth in soybeans

Solvent! 30 parts by weight of dimethylformamide emulsifier: 1 part by weight of polyoxyethylene sorbitan monolaur st

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

Soybean plants are grown in the greenhouse until full deployment of the first follower sheet. At this stage, the plants are sprayed dripping wet with the active ingredient preparations. After two weeks, the growth is measured for all plants and the growth is calculated as a percentage of the growth of the control plants. 100% growth means growth equal to that of control plants and 0% growth arrest. Values over 100% indicate a growth promotion, while values below 100% indicate a growth inhibition.

In this test, the compound (ΤΙ) according to the invention shows a very good growth-inhibiting effect. 30

Le A 25 325

274 ί 6 4

In game D 5

Growth in cotton

Solvent: 30 parts by weight of dimethylformamide emulsifier: 1 part by weight of polyoxyethylene sorbitan

monolaurate

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 filled with water to the desired concentration,

Cotton plants are grown in the greenhouse until the fifth leaf is fully unfolded. At this stage, the plants are sprayed dripping wet with the active ingredient preparations. After two weeks, the growth is measured in all plants and the growth is calculated as a percentage of the growth of the control plants, lOOtf growth means a growth corresponding to that of the control plants and Q'A the stoppage of growth, values above 100% indicate a growth requirement , while values show under lOOtt a growth inhibition.

In this test, the compound of the invention (I-

1) a very good growth-inhibiting effect. 30

Le A 25 325

Claims (3)

1 to 4 carbon atoms, haloalkyl with 1 or 1 * Fungicides and Pflanzenwuohsregulierende agents, characterized in that they contain as active ingredient at least one hydroxyethyl-azolyl derivative of the formula (I) OR / -V ' ν ι <7-Y-CH ₀ -C * - R m CH ₉ (I), (Γ in which R is hydrogen, alkyl or acyl s'; eht, R is halogen, optionally substituted phenyl or the group -Z-R, wherein Z is oxygen, sulfur, SO or SO ₂ and R is optionally substituted phenyl, 2. Fungicidal and p.flanzenwuchsregulierende agent according to claim 1, characterized in that they contain as active ingredient a hydroxyethyl-azolyl derivative of the formula (I), in which R is hydrogen, alkyl having 1 to 6 carbon atoms or alkylocarbonyl having 1 to 6 carbon atoms in the alkyl group, R represents fluorine, chlorine, bromine, phenyl optionally substituted by 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, or represents the grouping -ZR, wherein .68- 27 4) 64 Z is oxygen, sulfur, SO or SO ₂ and R 'is phenyl which is optionally substituted by 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, ο
R is fluorine, chlorine, bromine, methyl, ethyl, isopropyl, tert-butyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methoximinomethyl, phenyl optionally substituted by fluorine, chlorine and / or methyl or optionally fluorine, chlorine and / or methyl substituted phenoxy, m is the numbers 0, 1, 2 or 3, X is nitrogen or a CH group and Y is oxygen, sulfur, SO or SO ₂ , 2 carbon atoms and 1 to 5 halogen atoms, haloalkoxy having 1 or 2 carbon atoms and 1 to S 2741 <4 -67- Halogen atoms, HalogenAlkylthio having 1 or 2 carbon atoms and 1 to ¹ J halogen atoms, Alkoximinomet-hyl having 1 to 4 carbon atoms in the alkoxy group, optionally substituted by alkyl having 1 or 2 carbon atoms and / or halogen-substituted phenyl or optionally alkyl by 1 or 2 Carbon atoms and / or halogen substituted phenoxy, and m is the numbers 0, 1, 2 or 3, X is nitrogen or a CH group and Y is oxygen, sulfur, SO or SO ₂ , and their acid addition salts and metal salt complexes in addition to customary auxiliaries and carriers. 2
R is halogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio with ² 7 4 ί 6 -OD- claims Use of hydroxyethylazolyl derivatives of the formula (I) according to Claim 1 or of acid addition salts and metal salt complexes, characterized in that they are used to combat fungi and to regulate plant growth.