DD263764A5 - METHOD FOR PRODUCING SUBSTITUTED AZOLYL-METHYL-CYCLOPROPYL-CARBINOL DERIVATIVES - Google Patents

Abstract

The invention relates to a process for the preparation of substituted Azolylmethyl-cyclopropyl-carbinol derivatives for use as plant growth regulators and fungicides. The aim of the invention is the provision of new compounds with strong plant growth-regulating and strong fungicidal activity. According to the invention, novel substituted azolylmethyl-cyclopropyl-carbinol derivatives of the formula (I) are prepared in which, for example: Ar is optionally substituted aryl or heteroaryl, R 1 is hydrogen, alkyl, alkenyl, alkynyl, trialkylsilyl and the like. a, R2 is halogen, cyano, thiocyano, alkylcarbonyloxy, alkylcarbonylthio and the like. a., R2 also also hydrogen, if Ar is optionally substituted heteroaryl and Y is nitrogen or a CH group and their acid addition salts and metal salt complexes. Formula (I)

Description

Process for the preparation of substituted azolylmethyl- o-cyclopropyl-carbinol perivat'jn

Field of application of the invention

The present invention relates to a process for the preparation of novel substituted azolylmethyl-cyclopropylcarbinol derivatives and their use as plant growth regulators and fungicides.

Characteristic of the known technical solutions

It has already become known that certain diazolyl derivatives have fungicidal and plant growth-regulating properties (cf. EP-OS 044 605). For example, 1,3-di- (1,2,4-triazolinyl) ~ 2- (2-chlorophenyl) -propan-2-ol, 1,3-di- (1,2,4-triazol-1-yl) -2- (3-chlorophenyl) -propane-2-oil, 1,3 Di- (1,2,4-triazole-1-yl) -2- (4-chlorophenyl) -propan-2-ol and α, 3-ol (l, 2,4-triazol-1-yl) Use -2-phenyl-propane-2-ol for regulating plant growth and controlling fungi. The effect of these substances, however, is not always satisfactory, especially at low application rates and consonants.

Object of the invention

The aim of the invention is the provision of new compounds which have a stronger plant growth-regulating and fungicidal activity.

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Explanation of the nature of the invention

The invention has for its object to find new compounds' with the desired properties and processes for their preparation *

There have now been new substituted Azolylmethyl-cyclopropylcarbinol derivatives of the formula

_ ₂ . 263

Ar-C CR ²

CH ₀

• ² (D.

in which N

Ar is optionally substituted aryl or optionally substituted heteroaryl,

R ^{1 is} hydrogen, Alk; Alkenyl, alkynyl, trialkylsilyl, optionally substituted phenylalkyl or an acyl radical,

2 R is halogen, cyano, thiocyano, alkylcarbonyloxy, alkylcarbonylthio or the groupings -X-R and

4 5 10 -NR R, in which

R ^{3 is} alkyl, cycloalkyl, alkenyl, alkynyl, hydroxyalkyl, alkylthioalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aryl, optionally substituted aralkyl or the radical of the formula

-CH ₂ -CH ₂ -O-Y ^ ⁰ is S,

4 5 R and R independently of one another represent hydrogen

or alkyl or

4 5 R and R together with the nitrogen atom to which they are attached, optionally

substituted cycloaliphatic ring which may contain further heteroatoms,

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X represents oxygen , sulfur, an SO or a SO_ group,

and

R also represents hydrogen when Ar is optionally substituted heteroaryl,

and

for nitrogen or a CH group su'lit,

and their acid addition salts and metal salt complexes found.

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

a) in a first stage Arylcyclopropyl-Kei-.one the formula

V,

Ar-CO-C-R

in which

Ar and R have the abovementioned meaning ₍

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with dimethyloxosulfonium methylid of formula (CH ₃ ) 2 SO CH ₂ (III)

in the presence 'of a diluent and the resulting aryl-cyclopropyl-oxiranes of the formula

Ar-CCR ²

in which

2 Ar and R have the abovementioned meaning, in a second step with azoles of the formula

10 HN ⁷ "y

 Y = l

(V)

in which

Y has the meaning given above,

in the presence of a diluent and in the presence of a base, or

b) Azolyl keto compounds of the formula

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2 6 3 '16

"2 Ar-C-CH-R

L ¹

¹ N

in which

2 R, Ar and Y have the abovementioned meaning, with dimethyloxosulfonium methylid of the formula

C + CJ ₂ ) ⁰ S0 ° CH ₂ (III)

in the presence of a diluent, odei

c) Azolylmethyl-thio-cyclopropyl-carbinol derivatives of the formula

OH _ Ar-i VSJ _(Ia)

N '

N in which

3 Ar, R and Y are as defined above,

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with oxidizing agents, if appropriate in the presence of a diluent, or

d) hydroxyl compounds of the formula

• \ / 2

Ar-C C R

CH ₂ (Ib)

I- j

in which

Ar, R and Y are as defined above,

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

in which ^ (l

Ar, R and Y are as defined above

and

Z stands for a Baserest,

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with a halogen compound of the formula

R-HaI (VII)

in which

R is alkyl, alkenyl, alkynyl, trialkylsilyl, optionally substituted phenylalkyl

or an acyl radical is and

Shark stands for halogen,

in the presence of a diluent;

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 new substituted azolylmethyl-cyclopropyl-carbinol derivatives of the formula (I) and their acid addition salts and metal salt complexes have strong plant growth-regulating and fungicidal properties.

Surprisingly, the substances according to the invention exhibit a better plant growth-regulating and fungicidal activity than the constitutionally similar diazolyl derivatives 1,3-di- (1,2,4-triazol-1-yl) -2- known from the prior art. 2-chlorophenyl) -propan-2-ol, 1,3-di- (1- _i- 2,4-triazol-1-yl) -2- (3-chlorophenyl) -propa-2-ol, 1, 3 Di-d, 2,4-triazol-1-yl) -2- (4-chlorophenyl) -propan-2-ol and 1,3-di- (1,2,4-triazol-1-yl) -2 -phünyl-pro-

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-B-

pan-2-ol, which are suitable for the same indications.

The substituted azolylmethyl-cyclopropane-carbinol derivatives according to the invention are generally defined by the formula (I). In this formula are preferable

Ar for possibly single or multiple, the same

or differently substituted phenyl, wherein as

/ Substituents are preferably mentioned: halogen;

Alkyl, alkoxy and alkylthio each having 1 to 4 carbon atoms; Haloalkyl, haloalkoxy and haloalkylthio having in each case 1 to 2 carbon atoms and 1 to 5 identical or different halogen atoms, such as fluorine and chlorine atoms; and in each case optionally substituted by alkyl having 1 to 2 carbon atoms and / or halogen-substituted phenyl or phenoxy; furthermore for naphthyl as well as for a optionally mono- or polysubstituted by identical or different substituents 5- to 6-membered heteroaromatic compounds with nitrogen, oxygen and / or sulfur as heteroatoms, whereby as substituents preferably the abovementioned phenyl substituents come into question;

R is hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkenyl and alkynyl each having

2 to 4 carbon atoms, trialkylsilyl having 1 to 4 carbon atoms in each alkyl part, alkylcarbonyl having 1 to 4 carbon atoms in the alkyl part, and optionally mono- or polysubstituted,

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identical or different substituted phenylalkyl having 1 to 2 carbon atoms in the alkyl moiety, wherein as substituents preferably the phenyl substituents already mentioned in Ar come into question,

R is fluorine, chlorine, bromine, cyano, thiocyano, alkyl

carbonyloxy having 1 to 4 carbon atoms in the alkyl part, alkylcarbonylthio having 1 to 4 carbon atoms in the alkyl part, o ^ er for the groupings -XR ³ and -NR ⁴ R ⁵ , wherein

R is preferably straight-chain or branched alkyl having 1 to 18 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, straight-chain or branched alkenyl 1 to 2 carbon atoms, straight-chain or branched alkynyl having 2 to 18 carbon atoms, hydroxy

alkyl having 1 to 18 carbon atoms, alkylthioalkyl having 1 to 6 carbon atoms in the alkylthio group and 1 to 6 carbon atoms in the alkyl group, carboxyalkyl having 1 to 18 carbon atoms in the alkyl part, alkoxycarbonylalkyl

with 1 to 6 carbon atoms in the alkoxy part and 1 to 6 carbon atoms in the alkyl part, and in each case optionally mono- or polysubstituted, identically or differently substituted phenyl or phenylalkyl having 1 or 2

Carbon atoms in the alkyl moiety, wherein as substituents in each case preferably the phenyl substituents preferably mentioned in Ar, or

₃ q R is the radical of the formula -CH ₂ -CH ₃ -O-fO ^ ,

5 R and R independently of one another are preferably for

Hydrogen or straight-chain or branched

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tes alkyl having 1 to 4 carbon atoms or

R 5 and R 4, together with the nitrogen atom to which they are attached, are preferably oxygen, for a given case represented by alkyl of 1 to 4 carbon atoms or alkylcarbonyl of 1 to 4 carbon atoms in the alkyl moiety of the 5- or 6-membered ring , Sulfur and / or nitrogen may contain as further heteroatoms, and

X is preferably oxygen, sulfur, an SO or a S0_ group, and

2 R ^- also represents hydrogen, when Ar is an optionally substituted 5- or 6-membered heteroaromatic, and

Y is preferably nitrogen or a CH group.

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

Ar is phenyl which is optionally monosubstituted to trisubstituted, in particular monosubstituted or disubstituted by identical or different substituents, the substituents being: fluoro, chloro, methyl, isopropyl, tert-butyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, and

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2 63 rf 4

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each optionally substituted by fluorine, chlorine and / or methyl-substituted phenyl or phenoxy; furthermore represents naphthyl as well as in each case optionally monosubstituted or disubstituted by identical or different substituents furyl, thienyl, pyridinyl or pyrimidinyl, where as substituents, the above-mentioned phenyl substituents come into question;

2 R is hydrogen, methyl, ethyl, n-propyl, isopropyl, η-butyl, isobutyl, allyl, propargyl, trimethylsilyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, isobutylcarbonyl, and optionally monounsaturated to trisubstituted, in particular monosubstituted or disubstituted, benzyl which is monosubstituted or differently substituted, wherein as substituents preferably the phenyl substituents already mentioned for Ar are possible,

R is fluorine, chlorine, bromine, cyano, thiocyano, methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy, methylcarbonylthio, ethylcarbonylthio, n-propylcarbonylthio, isopropylcarbonylthio, n-butylcarbonylthio, isobutylcarbonylthio or for the

3 4 5 groupings -X-R or -NR R, in which

R is straight-chain or branched alkyl having 1 to 12 carbon atoms, cycloalkyl having 5 to 7 carbon atoms, straight-chain or branched alkenyl having 2 to 12 carbon atoms, straight-chain or branched

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Alkynyl of 2 to 12 carbon atoms, hydroxyalkyl of 1 to 12 carbon atoms, alkylthioalkyl of 1 to 4 carbon atoms in the alkylthio group and 1 to 4 carbon atoms in the alkyl group, carboxyalkyl of 1 to 12

Carbon atoms in the alkyl moiety / alkoxycarbonylalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, and in each case optionally monosubstituted to trisubstituted, in particular monosubstituted or disubstituted,

phenyl or benzyl which is substituted by identical or different substituents, suitable substituents being the particularly preferred phenyl substituents already mentioned above for Ar,

15 or

R is the radical of the formula -CH ₂ -CH ₂ -O- ^ CN,

5 R and R independently of one another represent hydrogen,

Methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl or

5 R and R together with the nitrogen atom to which

they are each bonded, optionally substituted by methyl, ethyl, methylcarbonyl or ethylcarbonyl piperidinyl, piperazinyl or Movpholinyl, and

X represents oxygen, sulfur, an SO or a S0 ~ group, and also

R is also hydrogen when Ar is for a

the above-mentioned optionally substituted heteroaromatic, and

Y is nitrogen or a CH group.

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2 6 .1 7 $ 4

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Preferred compounds according to the invention are also addition products of acids and those substituted azolylmethyl-cyclopropyl-carbinol derivatives of the formula (I),

1 2 in which Ar, R, R and Y have the meanings which have already been mentioned as preferred for these radicals.

The acids which may be added include, preferably, 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-naphalindisulfonic acid or camphorsulfonic acid.

Other preferred compounds of the invention are addition products of salts of metals of II. To IV. Main and I and II and IV to VIII. Subgroup of the Periodic Table and those substituted Azolylmethyl-cyclopropyl-carbinol derivatives of

1 2

Formula (I) in which Ar, R, R and Y have those meanings which have already been mentioned as preferred for these radicals. Here, salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Suitable anions of these salts are those which are derived from those acids which lead to physiologically acceptable addition products. Particularly preferred such acids in this context are the hydrohalic acids, e.g. the hydrochloric acid and the hydrobromic acid, and also phosphoric acid, nitric acid and sulfuric acid.

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If, for example, 1- (4-chlorobenzoyl) -1-ethylthio-cyclopropane and dimethyloxosulfonium methylide are used as starting materials and 1,2,4-triazole as the reaction component, the course of the process (a) according to the invention can be represented by the following equation become:

V-7

/ ^ \ Y

Cl- (Cy-CO-C-SC ₂ H ₅

(CH) SOCH

r-7

H-N

? ^H

-C-SC ₂ H ₅

CH.

If, for example, 1- (4-chlorophenoxy) -2- (1,2,4-triazol-1-yl) propiophenone and dimethyloxosulphonium methylene are used as starting materials, the course of process (b) according to the invention can be represented by the following equation be reproduced:

2 (CH-), ^ü S0 ° CH.

I! ν

• 2 (CH ₃ J ₂ SO

OH

-Cl

IN

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For example, using 1- (4-chlorophenyl) -1- / T- (ethylthio) -1-cyclopropyl-7-2- (1,2,4-triazol-1-yl) -1-ethanol and hydrogen peroxide in glacial acetic acid as starting materials, Thus, the course of the method according to the invention (c) can be represented by the following equation:

oh ST7

H_O ₂ / glacial acetic acid

T2

N ^lj

For example, use is made of 1- (4-chlorophenyl) -1- / T- (ethylthio) -1-cyclopropyl7-2- (1,2,4-triazol-1-yl) -1-ethanol and sodium hydride as starting materials and iodomethane as Reaction component, the course of the process (d) according to the invention can be represented by the following equation:

OH V7

+ NaH

- H.

+ CH ₃ J

- NaY

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63 76

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The aryl-cyclopropyl ketones to be used as starting materials for the process (a) according to the invention are generally defined by the formula (II). In the di-formula, Ar and R preferably have the 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 substituents.

The aryl-cyclopropyl ketones of the formula (II) are not yet known. They can be prepared by adding aryl halo-propyl ketones of the formula

Ar-CO-CH-CH ₂ CH ₂ -HaI "(VIII)

Quay ¹

in which

Ar has the meaning given above, Hal ^{1 is} halogen and Hal 6 is bromine or chlorine, with compounds of the formula

HR ⁶ (IX)

in which

R for cyano, thiocyano, alkylcarbonyloxy,

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263 76i

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Alkylcarbonylthio or the groupings -XR ³ and -NR ⁴ R ⁵ , in which R ^{3 is} alkyl, cycloalkyl, alkenyl, alkynyl, hydroxyalkyl, alkylthioalkyl,

Carboxyalkyl, alkoxycarbonylalkyl,

optionally substituted aryl, optionally substituted aralkyl or the radical of the formula -CH ₂ -CH ₂ - (W ⁰ ^,

4 5 10 R and R independently of one another

Is hydrogen or alkyl or

5 R and R together with the nitrogen atom,

to which they are attached, represent an optionally substituted cycloaliphatic ring, the other

May contain heteroatoms,

and

X is oxygen, sulfur, an SO or an SO 2 group,

in the presence of a diluent and in

Reacting the presence of a base, or

ß) directly in the presence of a diluent and in the presence of a base.

In the compounds of the formula (VIII) Ar is preferably of 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. Hal ¹ preferably represents fluorine, chlorine or bromine, and Hal preferably represents chlorine or bromine.

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63 76

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The aryl-halopropyl-ketones of the formula (VIII) are known or can be prepared by methods known in principle in a simple manner (cf .. DE-OS 25 21 104, DE-OS 23 20 355 and DE-OS 23 51 948). Thus, for example the aryl halogenpropylketone of formula (VIII) in which Hal ¹ is fluoro are prepared by reacting the corresponding compounds of formula (VIII) in which Hal ¹ represents bromine, luoriden with alkali Metal If as Sodium or potassium fluoride, in the presence of an inert organic diluent, such as benzene, and in the presence of a macrocyclic ether, such as 18-crown-6 (see Preparation Examples).

In the compounds of formula (IX)

R is preferably cyano, thiocyano, alkylcarbonyloxy having 1 to 4 carbon atoms in the alkyl part, alkylcarbonylthio having 1 to 4 carbon atoms

in the alkyl part or for the groupings -XR

4 5 3 4 5

and -NR R, in which R , R, R and X preferably have those meanings which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention preferably for these radicals.

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

If one proceeds in the above process for the preparation of Ary] -cyclopropyl-ketones of the formula (II) by the method (ß), we obtain those compounds of the formula

2 (II) in which R is halogen.

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63 76 4

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In the above process for the preparation of the arylcyclopropyl ketones of the formula (II), suitable diluents for working both by the variant (to) and by the variant (β) are all organic solvents which are inert under the reaction conditions. Preference is given to using alcohols such as methanol, ethanol, methoxyethanol, propanol or tert-butanol, furthermore ketones such as acetone and 2-butanone, furthermore nitriles such as acetonitrile, furthermore esters such as ethyl acetate, furthermore ethers such as dioxane, aromatic hydrocarbons such as benzene or toluene, and also amides, such as dimethylformamide.

Suitable bases for the preparation of arylcyclopropyl ketones of the formula (II), both when working according to the variant (o.sub.E) and according to the variant (.beta.), Are all customarily usable inorganic and organic bases. These include, preferably, alkali metal carbonates, such as sodium and potassium carbonate, alkali metal hydroxides, such as sodium and potassium hydroxide, alkali metal alkoxides, such as sodium and potassium methoxide, ethylate and tert-butoxide; Alkali hydrides, such as sodium hydride, and lower tertiary alkylamines, cycloalkylamines and aralkylamines, in particular triethylamine.

The reaction temperatures in the practice of the above process for preparing the arylcyclopropyl ketones of the formula (II) can be varied within a substantial range both in the variant ((c) and in the variant [P) . In general, one works with tempera

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doors between 0 ° and 200 ⁰ C, preferably between 2O ⁰ C and 150 ⁰ C.

In the preparation of aryl-cyclopropyl ketones of the formula (II) according to the above process variant {qL) , preferably 1 to 2 mol of compound of the formula (IX) and 1 are added to 1 mol of aryl-halopropyl ketone of the formula (VIII) to 2 moles of base. The isolation of the compounds of formula (II) is carried out in the usual manner.

The arylcyclopropyl ketones of the formula (II) are not only of interest as starting materials for the preparation of the compounds of the formula (I) according to the invention, but moreover represent valuable intermediates for the synthesis of other substances.

The dimethyloxo required in each case as reaction component in process (a) and (b) according to the invention. Sulfonium methylid of the formula (III) is known (see J. Am. Chem. Soc., 82, 1363-1364 (1965)). It is processed in the above reaction in a freshly prepared state, by generating it in situ by reaction of trimethyloxosulfonium iodide with sodium hydride or sodium amide, in particular with potassium tert-butoxide or Natriuuunethylat, in the presence of a diluent.

The azoles of the formula (V) required as starting materials for the second stage of process (a) according to the invention are generally known compounds of organic chemistry.

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The aryl cyclopropyl oxiranes of the formula (IV) occurring as intermediates in process (a) according to the invention are not yet known. They are generally interesting intermediates.

The azolyl keto compounds to be used as starting materials for process (b) according to the invention are generally defined by the formula (VI). In this formula (VI)

2, R / Ar and Y are preferably those radicals 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 substituents.

The azolyl-keto compounds of formula (VI) are only partially known (see DE-OS 23 48 663).

The azolyl-keto compounds of the formula

¹⁵ Ar-C-CH-R ⁷

(J (VIa)

N

in which

Ar for optionally substituted aryl or

optionally substituted heteroaryl

Y is nitrogen or a CH group and

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R is halogen, cyano, thiocyanato, alkylcarbonyl oxy, alkylcarbonylthio or the groupings -XR ⁸ and -NR ⁴ R ⁵ ,

wherein

X for oxygen, sulfur, an SO- or

SO ₂ group stands,

R ^{8 is} alkyl, cycloalkyl, alkenyl, alkynyl, hydroxyalkyl, alkylthioalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aralkyl or the

Remainder of the formula -CH _o -CH "-0 -t ^x ° ⁿ | stands,

5 R and R are independently hydrogen

or alkyl, or

5 R and R together with the nitrogen atom to which they are attached, for a gege

optionally substituted cycloaliphatic ring, which may contain other heteroatoms,

and

R is also hydrogen when Ar is optionally substituted heteroaryl,

are new.

The azolyl-keto compounds of the formula (VIa) can be prepared by reacting ketones of the formula

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O Ar-C-CH ₂ -R ⁷ (X)

in which

7 Ar and R have the abovementioned meaning,

with hydroxymethylazoles of the formula

HO-CH ₂ -N

in which

Y has the meaning given above,

in the presence of a diluent and in the presence of a catalyst.

In the azolyl-keto compounds of the formula (VIa), Ar and Y 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. R is preferably fluorine, chlorine, bromine. Cyano, thiocyano, alkylcarbonyloxy having 1 to 4 carbon atoms in the alkyl part, alkylcarbonylthio having 1 to 4 carbon atoms in the alkyl part or for the grouping

8 4 5 gene -XR and -NR R, in which

X preferably represents oxygen, sulfur, an SO ₂ or an SO ₂ group,

R is preferably straight-chain or branched alkyl having 1 to 18 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, straight-chain or branched alkyl

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branched alkenyl having 2 to 18 carbon atoms, straight or branched alkynyl having 2 to 18 carbon atoms, hydroxyalkyl having 1 to 18 carbon atoms, carboxyalkyl having 1 to 18 carbon atoms in the alkyl part, alkylthioalkyl having 1 to 6 carbon atoms in the alkylthio group and 1 to 6 carbon atoms in the Alkyl group, alkoxycarbonylalkyl having 1 to 6 carbon atoms in the alkoxy moiety and 1 to 6 carbon atoms in the alkyl moiety, as well as optionally mono- or polysubstituted, identically or differently substituted phenylalkyl having 1 or 2 carbon atoms in the alkyl moiety, wherein as substituents preferably the phenyl substituents preferably mentioned in Ar Come question

15 or

R ^{8 represents} the radical of the formula -CH ₂ -CH ₂ -Of ⁰ ^,

and

 ° o 5 R and R preferably have those meanings which have already been mentioned in connection with the description of the compounds of formula (I) according to the invention preferably for these radicals, and also stands

R is also preferably hydrogen, when Ar is an optionally substituted 5- or 6-membered heteroaromatic.

The ketones of the formula (X) required as starting materials in the preparation of the aryl ketone compounds of the formula (VIa) are known or can be prepared by methods known in principle.

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203764

The hydroxymethylazoles of the formula (XI) which are additionally required as starting materials in the preparation of the aryl-keto compounds of the formula (VIa) by the above process are known (cf., EP-OS 0 006 102 and Chem. Heterocycl., Comp. 1980 , 189 ).

Suitable diluents for the above process for preparing the azolyl-keto derivatives of the formula (VIa) are preferably inert organic solvents. These include preferably alcohols such as methanol and phenol, ethers such as tetrahydrofuran and dioxane, furthermore aromatic hydrocarbons such as benzene and toluene, and also halogenated aliphatic and aromatic hydrocarbons such as methylene chloride, chloroform, chlorobenzene and dichlorobenzene.

The process for producing the azolyl-keto derivatives of the formula (VIa) is carried out in the presence of a catalyst. It is possible to use all commonly used acidic and especially basic catalysts and their buffer mixtures. These include, preferably, Lewis acids, e.g. Boron trifluoride, boron trichloride, tin tetrachloride or titanium tetrachloride; organic bases such as pyridine and piperidine, and in particular piperidine acetate.

The reaction temperatures can be varied within a substantial range when carrying out this process. In general, it works between 20 and 16O ⁰ C, preferably at the boiling point of the solvent.

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In carrying out this process, 1 to 1.5 mol of hydroxymethylazole of the formula (XI) and catalytic to 0.2 molar amounts of catalyst are used per mole of ketone of the formula (X).

The A.olyl-keto derivatives of the formula (VI) represent interesting Zv / _s .enprodukte and show in appropriate expenditure charges or concentrations also fungicidal and plant growth-regulating properties.

The azolylmethyl-thiocyclopropylcarbinol derivatives of the formula (Ia) to be used as starting materials for process (c) according to the invention are compounds according to the invention.

Possible reaction components in the process (c) according to the invention are all oxidizing agents customary for such reactions. Preferably verwenbar are hydrogen peroxide and peracids, such as m-chloroperbenzoic acid and peracetic acid.

The hydroxy compounds of the formula (Ib) to be used as starting materials for process (d) according to the invention are likewise compounds according to the invention. Their conversion to the corresponding alcoholates is carried out in a well-known manner by reacting with suitable strong bases, such as alkali metal amides or hydrides, quaternary ammonium hydroxides or phosphonium in an inert solvent such as dioxane, at room temperature.

Accordingly, Z in the compounds of the formula (Ic)

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preferably an alkali metal atom, such as sodium and potassium, or quaternary ammonium or phosphonium ion.

The halogen compounds required in the process (d) according to the invention also as starting materials are generally defined by the formula (VII). 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 hydrogen. Hal is preferably chlorine or bromine.

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

Suitable diluents for the first step of the process (a) inert organic solvents in question. These include, preferably, ethers, such as tetrahydrofuran or dioxane, aliphatic and aromatic hydrocarbons, in particular benzene, toluene or xylene; and dimethyl sulfoxide.

The reaction temperatures can be varied within a substantial range when carrying out the first step of process (a) according to the invention. In general, one works between 0 and 100 ⁰ C, preferably between 10 and 60 ⁰ C.

Eei the implementation of the first step of the process (a) is preferably used for 1 mol of aryl cyclopropyl ketone of the formula (II) 1 to 3 mol

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Dimethyloxosulfonium-methylid of formula (III), generated in situ from trimethyloxosulfonium iodide in dimethyl sulfoxide and potassium tert-butoxide. The isolation of the intermediates of formula (IV) is carried out in a generally customary manner.

Suitable diluents for the second step of the process (a) inert organic solvents in question. 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 second stage of process (a) according to the invention is carried out in the presence of a base. All commonly used inorganic and organic bases are suitable. These include, preferably, alkali carbonates, e.g. Sodium and potassium carbonate; Alkali hydroxides, e.g. sodium hydroxide; Alkali alcoholates, e.g. Sodium and potassium methylate and ethylate; Alkali hydrides, e.g. sodium hydride; and lower tertiary alkylamines, cycloalkylamines and aralkylamines, in particular triethylamine.

The reaction temperatures can be varied within a relatively wide range when carrying out the second step of the process (a) according to the invention. In general, one works at temperatures between 0 ⁰ C and 200 ⁰ C, preferably between 6O ⁰ C and 150 ⁰ C.

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In carrying out the second step of the process (a) is preferably used for 1 mol of oxirane of the formula (IV) 1 to 2 moles of azole and 1 to 2 moles of base. The isolation of the end products takes place in a generally customary manner.

The reaction conditions when carrying out the process (b) according to the invention correspond to those for carrying out the first stage of process (a).

When carrying out the process (c) according to the invention, about 1 to 5 mol of oxidizing agent are employed per mole of the compounds of the formula (Ia) according to the invention. 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 -3O ⁰ C to + 3O ⁰ C, formed preferably the compounds of formula (I) according to the invention with the -SO grouping. When excess of oxidizing agent and higher temperatures (10 to 8O ⁰ C) are preferably formed the compounds of formula (I) according to the invention with the -SO ₂ ~ grouping. The isolation of the oxidation products is carried out in the usual manner.

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

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or carbon tetrachloride; and hexamethylphosphoric triamide.

The reaction temperatures can be varied within a substantial range when carrying out process (d) according to the invention. In general, one works between 0 and 12O ⁰ C, preferably between 20 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 stage, preferably 1 to 2 moles of halogen compound of the formula (VII) are employed 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 of the formula (Ib), the latter being converted into the alkali metal alcoholate by means of alkali metal hydride or alkali metal amide in a suitable organic solvent and the latter immediately treated with a calogen compound without isolation Reacting formula (VII), wherein the exit of alkali halide, the compounds of formula (I) according to the invention are obtained in one operation.

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According to a further preferred embodiment, the preparation of the alcoholates and the reaction with a halogen compound of the formula (VII) in a two-phase system, such as aqueous sodium or potassium hydroxide / toluene or methylene chloride, with the addition of 0.01-1 mol of a phase Transfer catalyst, such as ammonium or phosphonium compounds carried out, wherein the alcoholates are reacted with the in the organic phase halides in the organic 'phase or at the interface.

The acid addition salts of the compounds of formula (I) can be readily prepared by conventional salt formation techniques, e.g. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g. Hydrochloric acid, and in a known manner, e.g. by filtration, isolated and optionally purified by washing with an inert organic solvent.

The metal salt complexes of the compounds of formula (I) can be readily 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. by filtration, isolate and optionally purified by recrystallization.

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

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For the mode of action of plant growth regulators applies according to previous experience that an active substance 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 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-regulating substances can be used, for example, for inhibiting the vegetative growth of the plants. 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. 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 a high growth of the plants is undesirable.

Also important is the use of growth regulators to inhibit grain elongation. This reduces or completely eliminates the risk of cropping before harvesting. In addition, growth regulators in cereals can

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The use of growth regulators for stalk shortening and stalk reinforcement makes it possible to apply higher quantities of fertilizer in order to increase the yield without the risk of the grain being stored.

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 can often achieve a promotion of vegetative growth. This is of great benefit when harvesting the vegetative plant parts. Promoting vegetative growth can, however, simultaneously promote generative growth by producing more assimilates to produce more or more fruits.

Increases in yield can in some cases be achieved by interfering with plant metabolism without causing changes in vegetative growth

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to make noticable. Furthermore, 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. For example, it may be possible to increase the sugar content in sugar beet, sugarcane, pineapple and citrus fruits, or to increase the protein content in soya or cereals. It is also possible, for example, to reduce the degradation of desirable ingredients, e.g. Sugar in sugar beet or cane, with growth regulators before or after harvesting. In addition, the production or the discharge of secondary plant ingredients can be positively influenced. 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 in the breeding and production of hybrid seed a

20 has great significance.

Through the use of growth regulators, the branching of the plants can be controlled. On the one hand, by breaking the Apikaidominanz the development of side shoots are promoted, which can be very desirable, especially in ornamental crops, also in conjunction with a growth inhibition. 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.

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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 major role in the mechanical harvesting of cotton but is also important in other crops such as e.g. in viticulture to facilitate the harvest of interest. Defoliation of the plants may also be done to reduce the transpiration of the plants before transplanting.

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 flowers can be promoted to a desired extent ("thinning") to break the alternation. Alternating means the peculiarity of some types of fruit to bring very different yields endogenously from year to year. Finally, it is possible with growth regulators to reduce the forces required to detach the fruits at the time of harvest, to facilitate mechanical harvesting or to 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. Farther

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For example, growth regulators may in some cases improve fruit colouration. In addition, growth regulators can also be used to concentrate mature maturity. This creates the conditions for e.g. in the case of tobacco, tomatoes or coffee a complete mechanical or manual harvesting can be carried out 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. As pineapples or ornamental plants in nurseries, germinate, sprout or flower at a time when they usually do not show willingness to do so. Delaying bud sprouting or seed germination using growth regulators may be desirable in areas prone to frost to prevent damage from late frosts.

Finally, growth regulators can be used to induce plant resistance to frost, dryness or high soil salinity. This makes it possible to cultivate plants in areas which are normally unsuitable for this purpose.

The active compounds according to the invention also have a strong microbicidal action and can be used practically for controlling unwanted microorganisms. The active substances are suitable for use as pesticides.

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Crop protection fungicides are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

The good plant tolerance of the active ingredients in

The concentrations necessary to combat plant diseases allow the treatment of above-ground parts of plants, of planting and seed and of the soil.

As plant protection agents, the active compounds according to the invention can be used with particularly good success for controlling cereal and rice diseases and also Venturia species, such as Venturia inaequalis

 In addition, the substances of the invention show a broad

15 and good in vitro fungicidal spectrum of activity.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, ultrafine encapsulations in polymeric materials and in seed coating compositions, as well as ULV formulations.

These formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, that is to say liquid solvents, liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as extender

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can e.g. also organic solvents can be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzoic, chloroethylene 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. By liquefied gaseous diluents or carriers are meant those liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. As solid. Carriers are suitable: e.g. ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates. Suitable solid carriers for granules are: e.g. crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules

inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. Suitable emulsifying and / or foam-forming agents are: e.g. nichtiono-

and anionic emulsifiers, such as polyoxyethylene

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26376i

Fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates. Suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-type polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate may be used in the formulations.

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

15 are used.

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

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

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,

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Emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules. The application is done in the usual way, e.g. by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume 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 compounds according to the invention as plant growth regulators, the application rates can be varied within a substantial range. In general, from 0.01 to 50 kg, preferably from 0.05 to 10 kg, are used per hectare of soil.

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

Even when using the substances according to the invention as fungicides, the application rate can be varied within a substantial range, depending on the nature of the 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 wt .-%. In the seed treatment, in general, amounts of active ingredient of 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g, needed. When loading

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soil concentration, active substance concentrations of O ₁ 0001 to 0.1% by weight, preferably from 0.0001 to 0.02 %, are required at the site of action «

Working Example

The invention will be explained in more detail below with reference to some examples.

ι For the following examples is the manufacture and use of the compounds produced ·

- 42 -

Production Examples Example 1

^V (1-1)

(Method a)

1st stage

Cl- (C J) -C C SC

(IV-D

To a mixture of 6.4 g of sodium hydride (80% strength) and 44.2 g of trimethylsulfoxonium iodide is added dropwise at 10 ⁰ C 170 ml of dry dimethyl sulfoxide and allowed to stir for one hour at room temperature. 40 g (0.167 mol) of 1- (4-chlorobenzoyl) -1-ethylthio-cyclopropane in 50 ml of dimethyl sulfoxide are then added dropwise. The reaction mixture is stirred for two days at room temperature. Then pour on 500 g of ice, extract more

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corn with ethyl acetate, the combined organic phases with water, dried over sodium sulfate and concentrated. This gives 40.5 g (95.5% of theory) of 1- ^ T- (4-chlorophenyl) -oxiranylZ-i-ethylthio-cyclopropane as an oil, which is reacted further directly.

2nd stage

? ^H V

To a boiling mixture of 33.5 g of 1,2,4-triazole and 22 g of potassium carbonate in 150 ml of acetonitrile is added dropwise a solution of 40.5 g (0.16 mol) of 1- ^ T- (4-chlorophenyl) - OxiranylZ-i-ethylthio-cyclopropane (see Ex.IV-1) in 50 ml of acetonitrile and the reaction mixture heated under reflux for eight hours. It is allowed to cool, mixed with 400 ml of water and the crystalline product is filtered off with suction. After recrystallization from ethanol / water to obtain 26.5 g (51% of theory) of 1- (4-chlorophenyl) -1- / T- (ethylthio) -1-cylcopropyl7-2- (1,2,4-triazole -1-yl) -1-ethanol of melting point 165 ° C.

C1- (G) ^-CO- C-SC-H

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2 * 3764

- 44 -

To a solution of 100 g (0.338 mol) of 4-chlorophenyld-bromo-3-chloropropyl) ketone and 21 g of ethylthiotin 200 ml of dimethylformamide is added dropwise at ^{0 0} C to 1O ⁰ C, a solution of 38 g of potassium hydroxide in 250 ml of methanol. The mixture is stirred for one hour at room temperature and one hour under reflux. It is then concentrated in vacuo and the residue taken up in a mixture of water and methylene chloride. The organic phase is separated, washed with water, dried over sodium sulfate and concentrated in vacuo. The residue is distilled under high vacuum. This gives 70.1 g (86% of theory) of 1- (4-chlorobenzoyl) -1-ethylthio-cyclopropanone of boiling point Kp _{n 1} ,. - 127 ° C.

Example 2

(1-2)

(Method b)

19.7 g (0.06 mol) of 1- (4-chlorophenoxy) -2- (1,2,4-triazol-1-yl) -propiophenone are added in portions to a solution of dimethylsulfoxonium methylide in 70 ml of dimethyl sulfoxide / prepared from 27 , 6 g (0.125 mol) of trimethylsulfoxonium iodide and 14.03 g (0.125 mol) of potassium tert-butoxide. ·

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The mixture is stirred for 6 hours at 6O ⁰ C, then thinned with 1000 ml of water, the deposited oil was taken up in chloroform, dried over sodium sulfate, concentrated and purified by chromatography (silica gel F 60 Merck / eluent: chloroform). The remaining oil crystallizes on stirring with acetonitrile. This gives 1.7 g (8% of theory) of 1- (4-chlorophenoxy) -, 1- ^ T-hydroxy-1-phenyl-2- (1, 2, 4-triazol-1-yl) _7- cyclopropane of melting point 170 ^° C.

10 Preparation of the precursor

29.4 g (0.12 mol) of UJ- (4-chlorophenoxy) acetophenone and 11.9 g (0.12 mol) of 1,2,4-triazol-1-yl-methyl alcohol in 200 ml of toluene 10.8 g (0.18 mol) of acetic acid and 1.8 ml (0.018 mol) of piperidine are added in succession and the mixture is boiled on a water separator until the amount of water separated remains constant. The toluene solution is then washed with water, dried over sodium sulfate, concentrated and the oily residue is purified by chromatography (silica gel F 60 Merck / mobile phase chloroform). This gives 20.8 g (53% of theory) of 1- (chlorophenoxy) -2- (1,2,4-triazol-1-yl, propiophenone of melting point 126 ⁰ C.

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2 63 76

A solution of 154.6 g (1 mol) of & thet; chloroacetophenone in 250 ml of butanone is added to a oily solution of 129 g (1 mol) of 4-chlorophenol, 140 c; (1 mol) of potassium carbonate and 2 g of potassium iodide in 800 ml of butanone are added dropwise, and the mixture is refluxed for a further 12 hours after completion of the addition. The resulting reaction mixture is filtered and evaporated. This gives 179 g (73% of theory) of iü - (4-chlorophenoxy) acetophenone of melting point 97 ° C.

Ex iel 3

-έ-ΛΤ-so-c "

CH, ^{2 5} 11-3)

if ^{> N} N

(Method c)

5 g (0.0155 mol) of 1- (4-chlorophenyl) -1- / T- (ethylthio) -1-cyclopropyl / -2- (1,2,4-triazol-1-yl) -1-ethanol ( see Example 1) are mixed with 3.3 g of m-chloroperbenzoic acid (80-90% strength) in 40 ml of methylene chloride at room temperature overnight and then one hour under reflux.

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26376t

- 47 -

flowed. It is then washed twice with 20 ml of 5% aqueous sodium hydroxide solution and twice with water. The organic phase is dried over sodium sulfate and concentrated in vacuo. The residue is recrystallized from glycol monomethyl ether acetate. This gives 3 g (57% of theory) of 1- (4-chlorophenyl) -1- / T- (ethylsulfinyl) -1-cyclopropyl-7-2- (1,2,4-triazol-1-yl) -1-ethanol of boiling point 185 ⁰ C.

Example 4

10 ^ _x _ ^ _ww

(1-4)

(Method c)

3.2 g (0.01 mol) of 1- (4-chlorophenyl) -1- / T- (ethylthio) -1-cyclopropyl-7-2- (1,2,4-triazol-1-yl) -1-ethanol (see Example 1) are dissolved in 20 ml of glacial acetic acid and stirred with 4 ml of 30% hydrogen peroxide at 7O ⁰ C for six hours. It is then crosslinked with 100 ml of ice water, neutralized with concentrated aqueous sodium hydroxide solution and the crystalline solid is filtered off with suction. This gives 3.4 g (96% of theory) of 1- (4-chlorophenyl) - / T-ethylsulfonyl) -1-cyclopropyl7-2- (1,2,4-triazol-1-yl) -1-ethanol from Melting point 215 ⁰ C.

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Following the methods described in the above examples and the information on the processes according to the invention, the substances of the formula (J) listed in Table 1 below are also prepared.

Le A 23 363

table

Verb no.

1-5 1-6 1-7 1-8

1-9

1-10

1-11

1-12 1-13

Ar

OR ¹ Ar C

Λ *

N'I

R ¹

-R

(I)

N -O-

- (CH ₂ J ₃ CH ₃

Cl> -O - (()) - Cl

CH -0- <

• -C1

S-

-S-CH.

Cl

-Cl

melting point

.39

129 136 128

167 211 137

183

\O

Table 1 (continued)

Verb Ar no.

1-15 1-16

1-17 1-18 1-19 1-20 1-21 1-22 1-23

1-24 1-25

Cl

CH

Il

CH

CH

N CH

-O-SCH.

SCH.

-SC ₂ H ₅ -S (CH ₂ ) ₂ -CH ₃ -S- (CH ₂ ) ₂ -CH ₃ -S-CH ₂ -CH = CH ₂

-S

melting point

121 124

159 153 185 158 131 133 134

141-143 145

T abelle Ί (continued)

Verb no.

1-26 1-27 1-28 1-29 1-30

1-31 1-32 1-33 1-34 1-35

Cl- (O) - H

CH

Cl

Cl

-Cl

'-Cl

CH

N-N N-CH.

CH

SCH.

melting point

94

208 265 119 181

213 122 148 113 156

Os. Co

ro T able 1 (continued)

Verb.

No.

1-36 1-37 1-38 1-39 1-40 1-41 1-42 1-43 1-44 1-45

Ar

Cl

F-

- H

N -SC ^2H 5 CH If N -S (CH

CH

-O-

CH- O- (C)) - Cl

melting point

126 161

130 140

171 144 184 141 227

ro > ro

Table 1 (continued)

Verb no.

1-46 1-47 1-48 I-4S 1-50 1-51 1-52 1-53 1-54

Ar

CH

Cl

-SC ₂ H ₅

- ©

Cl

CH -S-

-Cl-Cl-Cl

SCH.

melting point

122 137 179 144 168 177 245 123 163

ul

> Tabel le 1 (continued)

u, verb. P ¹ no. melting point / * C7 or refractive index Z ⁿ n-7

1-55 1-56 1-57

CH-SCH.

N ~ ^SC 2 ^H 5

CH

160 159

1-58 1-59 1-60 1-61

Cl

N -S- (CH "), -CH-,

N -SC ₃ H ₅

N -SC ₃ -H ₇ -n

N -SC ₃ -H ₇ -n

136

1, 5420 1.5102 1.5610

ul

On. Co

tr · Table 1 (continued)

ro

to verb

u, ^no

Melting point / ° c7bzw.

-20 - refractive index / η _β _ /

1-62 1-63 1-64 1-65 1-66 1-67 1-68 1-69 1-70

Cl

Oh-

-SC ₄ H ₉ -n

-S-CH ₂ -CH = C (CH ₃ )

-SC ₃ H ₇ -ISO

-SC ₂ H ₅ -

-S-CH ₂ -CH = C (CH ₃ ) ₂

-SC ₃ H ₇

-SC ₂ H ₅

-S-CH ₂ -C ₃ H ₇ -IsO

86

1.5790 1.5698

128

110 1.5598

112

1.5563 1.5700

UI UI

ro Table 1 (continued)

£ verb. Ar ω no.

Melting point / ° c7bzw. Refractive index / n __ /

1-71

1-72 C

1-73 C

1-74 C

1-75 Cl- (O) -

1-76 C

1-77 C

1-78 C

1-79 C

CH

-S- (CH ₂ )

CH ₃ -CH-CH ₂ -CH ₃

CH (CH ₃ ) ₂

(CH ₂ ) 5-

N -SO-C ₄ H ₉ -n

1.5430 176 166 104 137 147 130 141 oil

Table 1 (continued)

Verb. Ar

No.

Melting point / ^o c7bzw. Refractive index / n __ /

1-80 1-81 1-82 1-83 1-84 1-85 1-86

^cl - \ 2 /

ci- (Ö}

Cl- (O)

Ci (C?

1-87 Cl- (O) -

1-88 Cl- (O) -

CH

CH-SO-CH ₂ -f JH-CH ₃

-O

-SO (CH ₂ J ₃ -CH ₃

-S- <H

-S- (H

146 113 147 130 149 111 153 191 142

.fcfc.

tr ¹ Table 1 (Continued)

to verb

, , No.

Melting point / ° C / resp. Refractive index / ^ _D _7

1-89

1-91 1-92

1-93 1-94

1-95 1-96 1-97

CI (O) -

1-90 Cl- (O) -

CI (O) -

SO- (CH ₂ ) ₁ ^

SO ₂ - (CH ₂ ) ₁ T-

-SO-CH

H N -SO-CH ₃ H N -SO ₂ -C ₃ H ₇ -n CH ₃ H N -SO ₂ -CH-C ₂ H ₅ H N -SO ₂ -CH (CH ₃ ) ₂ H N -SO ₂ -CH ₂ -CH (CH ₃ J ₂

oil 91 75

128

117

159

(1 diastereomer)

(Diastereomer mixture)

Os. CO

1-98

CuO

-SO ₂ - (CH ₂ J ₅ -CH ₃

140

ro Table 1 (continued)

Verb. Ar

^No

Melting point / ° C / bzv. Refractive index / n _D _7

1-99 Cl- ^ O) -

1-100 Cl- ^ o) -1-101 C

1-102 C 1-103 C 1-104 1-105 1-106 1-107

CH

165

176

S-CH ₂ -CH ₂ -SC ₂ H ₅ 95 S-CH ₂ -COOCH ₃ 118 SC H ₂ -CH ₂ -OH 138 SO- (CH ₂ J ₃ -CH ₃ oil S-CH (CH ₃ J ₂ 191 S-CH (CH ₃ J ₂ 155 Cl 121

Table 1 (continued)

Verb. Ar

No.

Melting point / ^o c7bzw. Refractive index / n _D _ /

1-108 1-109 1-110 1-111 1-112 1-113 1-114 1-115 1-116

CH

CH

CH

-SO ₂ CH ₃ 162 -S-CH (CH ₃ J ₂ 136 -F 162 -F 105 -SCH ₃ 108 -SCH ₃ 167 -SC ₄ H ₉ -H 134 -SC ₄ H ₉ -H 125 -F 123

OJ CTL OJ

Table 1 (continued)

Verb Ar no.

Melting point / ^o c7bzw.

~ -20- refractive index / n _D _ /

1-117 Br- (O) -1-118 1-119 1-120 1-121

1-122

1-123 1-124

C]

CI (O

Cl

SC ₂ H ₅

-Cl

SCH.

-F

SC ₂ H ₅

SC ₄ H _g -n

SO-C ₄ H ₉ -n

168 127 127 111 119

139

170 resin

Os. CO.

CK *.

(T Table 1 (continued)

¹ ^ verb. Ar! No.

Melting point / ° c7bzw

Refractive index ^ ή _β _7

1-125

Cl

HN

-SO ₂ -C ₄ H ₉ -n

159

1-126

H N -SCH.

142

1-127

CL

ci <O

HN -SO ₂ CH ₃

σ »tu

I-12 NC

Cl Cl- (O

HN -S-CH ₂ -CH ₂ -CH ₃

1-129

1-130

Cl Cl- (O

Cl

CI (O

HN -SC ₂ H ₅

HN -S-CH (CH ₃ )

Os. CO

It "CD

Table 1 (continued)

Verb Ar no.

1-131 1-132 1-133 1-134 1-135 1-136

1-137 CH ₃ - (O

1-138

-S-CH.

-SO ₂ CH ₃

-Cl

-F

SC ₂ H ₅

SCH.

Melting point / ° c7bzw

Refraction ir.dex / n _n / /

83

127 125 146

ι ιο

Ov

ro Table 1 (continued)

Verb. Ar melting point I ° c7hzv. Refractive index / n /

1-139

CH.

1-140 CH. 1-141 1-142

-S-CH (CH ₃ ) -S-CH ₂ -CH ₂ -CH ₃ -S-CH ₂ -CH (CH ₃ ) -S- (CH ₂ ) 3 -CH ₃

Table T (continued)

Verb.

No.

Ar

1-143

1-145

1-147

1-148

1-149

1-150

1-14 4 _f _ / q \ _

1-146 Cl- (O / -

C1

CH

-SO ₂ CH ₃ -SO ₂ -CH (CH ₃ J ₂

-SO-CH (CH ₃ )

-F

-SO-CH.

-Cl

-0

Melting point / ° c7bzw. Refractive index / n _Q _7

189 177 141

176 189 109 133 104

Ui I

Table 1 (continued?

Verb no.

Ar melting point / ° c7

1-151 Cl 1-152 1-153

1-154 1-155

1-156 1-157 1-158 1-159

Cl

\ t

CH.

H H H H H H

N N N N N N

N N

SO- (CH ₂ ) ₂ -CH ₃

SO ₂ -CH ₂ -CH ₃

SO ₂ -CH ₂ -CH ₃

SO ₂ -CH (CH ₃ J ₂

-SO-CH (CH.

SO ₂ -CH ₃

-S-CH

140 135

112 137 131

160 127 125

116

1-160

-SO ₂ -CH (CH ₃ ) ₂

149

Table 1 (continued)

Verb.

No.

Ar

Melting point / ° c7

1-161 ch, - <O> -

1-162

1-163

1-164

1-165 CH ₃ O- (O

1-166

-S-CH ₂ -CH (CH ₃ )

-S- (CH ₂ J ₃ -CH ₃

-S-CH ₂ -CH ₃

127 115 123 107 111 119

Table T (continued)

Verb no.

Ar melting point / ° C / resp. Refractive index / n __ /

1-167 1-168

1-169 1-170

1-171 1-172

1-173 1-174

1-175

O)-

Cl

O)-

O)-

egg

Cl

Cl

-SC ₃ H ₇

-S-C (CH ^),

-SC ₃ H ₇

-SC ₃ H ₇

l _r 5630 1 cn 00 75 I 75 1.5630 1.5660 1.5582 106 110

1.5420

Ov.

tj ¹ Table 1 (continued)

^ J verb, oj no.

Ar

Melting point / ° c7

1-176

1-177

O)-

-S-CH (CH ₃ )

-S-CH (CH ₃ )

118 80

- 70 -

Cl-U J) -CO-C-O

Further examples of the preparation of starting materials of the formula (II)

Example (II-2)

(II-2)

To a solution of 29.6 g (0.1 mol) of 4-chlorophenyl (1-bromo-3-chloropropyl) ketone and 9.4 g of phenol in 60 ml of dimethylformamide is added 14 g of potassium carbonate and heated to 50 ⁰ three hours C. then added dropwise at room temperature 8.4 g of potassium hydroxide in 40 ml of methanol and heated three hours 6O ⁰ C. The mixture is concentrated in vacuo and taken up in a water / methylene chloride mixture to the organic phase is separated, washed with water , dried over sodium sulfate and concentrated in vacuo. The residue is distilled under high vacuum.

This gives 20.7 g (76.1% of theory) of 1- (4-chlorobenzoyl) 1-phenoxy-cyclopropane of boiling point Kp _Q. * - 170-80 ⁰ C.

Example (II-3)

NCH ₃

To a mixture of 10.4 g of N-methylpiperazine and 14 g of potassium carbonate in 30 ml of dimethylformamide is added dropwise a solution of 29.6 g (0.1 mol) of 4-chlorophenyl (1

Le A 23 363

bromo-3-chloropropyl) ketone in 30 ml of dimethylformamide at room temperature. The mixture is stirred for three hours and then added dropwise a solution of 9 g of potassium hydroxide in 30 ml of methanol. The reaction mixture is stirred for one hour at 50 ⁰ C and concentrated in vacuo. The residue is taken up in ethyl acetate / water, the organic phase separated, washed with water, dried over sodium sulfate and concentrated in vacuo. The residue is chromatographed on silica gel with chloroform / ethanol (97: 3). This gives 14 g (50.3% of theory) of 1- (4-chlorobenzoyl) -1- (4-methylpiperazin-iyl) -cyclopropane as a reddish oil, which can be used directly.

Example (II-4)

Cl- (O) -CO-C-P

(II-4)

Dissolve 20 g (0.085 mol) of 4-chlorophenyl (1-fluoro-3-chloro-propyl) ketone in 150 ml of tert-butanol and added in portions with 15 g of potassium tert-butoxide. The mixture is stirred for 2 hours at 40 ⁰ C and concentrated in vacuo. The residue is taken up in methylene chloride and water. The organic phase is separated, dried over sodium sulfate and concentrated in vacuo. The residue is distilled under high vacuum. This gives 14.4 g (85% of theory) of 1- (4-chlorobenzoyl) -1-fluoro-cyclopropane of boiling point Kp _{n 1} = 75 ⁰ C.

υ, ι

Le A 23 363

2 * 3 7 * 4

- 72 Preparation of starting materials of the formula (VIII)

-CO-CH-CH ₂ CH ₂ Cl F

A mixture of 68 g of 4-chlorophenyl (1-bromo-3-chloro-propyl) -ketone, 27.5 g of dried potassium fluoride, 11 g of 18-crown-6 and 200 ml of dry benzene is refluxed for 8 hours. Then 200 ml of water are added, the organic phase is separated, washed several times with water, dried over sodium sulfate and concentrated in vacuo. The residue is stirred with mineral spirits with the addition of a little toluene. After filtering off the resulting solid and drying, 28.5 g (53% of theory) of 4-chlorophenyl (1-fluoro-3-chloropropyl) ketone of melting point 53 ° C.

(VIII-2)

A solution of 483 g (2.23 mol) of 4-chlorophenyl-3-chloropropyl-ketone in 1200 ml of methylene chloride is added dropwise at 20 ⁰ C with a solution of 358 g of bromine in 350 ml of methylene chloride. One leaves after one hour

Le A 23 363

- 73 -

764

stir and then concentrate in vacuo. The residue is mixed with 300 ml of petroleum ether and stirred until the crystallization is complete. It is cooled to 1O ⁰ C and filtered off the precipitate. This gives 582 g (88.3% of theory) of 4-chlorophenyl (1-bromo-3-chloropropyl) ketone of melting point 73 ⁰ C.

Analogously to the methods described in Examples (II-1) to (II-4) and according to the stated process conditions, the precursors of the formula (II) listed in Table 2 below are also prepared.

Le A 23 363

table

Bsp.Nr. Ar

II-5 II-6 II-7 II-8 II-9 11-10 11-11 ΙΪ-12 11-13

egg

Cl

Cl

Ar-CO-C-R

-S- (CH ₃ J ₃ CH ₃

-S-CH.

-C (CH ₃ J ₃

> -Cl> -Cl> -Cl

-o (C J) -Ci

-Cl

-J

SCH.,

(ID

Physical. constant

^{= 133} ° ^c

^k po, oi = ¹²⁰ ° ^c

zähfl. oil

= ¹⁶⁰ ° ^C

= 173 ° C

^{= 143} ° ^C

^κ ρ · ο, οι ^{= 146} ° ^c

Mp. = 86 ⁰ C mp. = 98 ° C

> Table 2 (continued) Example no. Ar

11-14 11-15 11-16 11-17

F-

F-

F-

F-

SCH.

-0- (O) -Cl

11-18 11-19

-SC ₂ H ₅ -S- (CH ₂ J ₃ CH ₃

11-20 11-21 11-22 11-23

• @ -

-SC ₂ H ₅

-O Cl

-O-

Cl

Physical. constant

= 102 ° C = 125-130 ⁰ C.

Kp. _{0 1} = 145-150 ⁰ C

Bp. _{0 1} = 165-173 ° C

- ⁵⁵ ° ^C

cn I

Mp = 86 ° C

Mp = 77 ° C

= 147-155 ° C

0.07

= 154 ° C

i * Table 2 (continued)

Bsp.Nr. Ar

11-24 11-25 11-26 11-27 11-23 11-29 II-3Ü 11-31 11-32

Cl <

Cl

Cl

CH ₃ O

-CK _? -n

Physical. constant

Kp._ = 163-170 ⁰ C υ, 1

Mp 104 ⁰ C ^K P-0.06 ^{= 122} ° ^C

^{= 118} ° ^C

= ⁵⁵ ° ^C

= 138 ° C / mp. 73 ° C

= 69 ° C.

= 98 ° C = 88 ° C

CTi I

$ 637 4

- 77 -

Following the method described in Example 1 and according to the specified process conditions, the intermediates of the formula (IV) listed in Table 3 below are also prepared.

5 Table 3

V ₂

Ar-c-c-ir

Bsp.Nr. Ar R Physical. constant

IV-2 Cl- (CJ) - -O \ U> toughened oil

IV-3 Cl- ^ O) -S- (CH ₂ J ₃ CH ₃ "

IV-4 Cl- (O) - F ^K P'0.2 ^{= 83} ° ^C

IV-5 Cl-

IV-7 Cl-t

IV-8 ClH

IV-9 Cl-

iv-10 Ci- (Cj) - -s- <O) oil

SCH ₃ 3 ^ 3 ₂ -CH ₃ Oil ep u S-CH ₂ -CH = CH ₂ oil S- (CH ₂ ) S- (CH ₂ ) oil oil oil

Le A 23 363

Table 3 (continued) Example no. Ar Physical. constant

IV-11 IV-.2 IV-13 IV-14 IV-15 IV-16 IV-17 IV-18 IV-19 IV-20 IV-21 IV-22 IV-23 IV-24 IV-25

Ko) -

-Cl oil oil

oil

Mp 81 ⁰ C

Mp 97 ⁰ C

Kp.π -> = ⁸³ ° ^C

• 0,

N I

-SCH

N-CH 3

oil oil oil

3 -SC ₂ H ₅

-S- (CH ₂ ) ₃ -CH ₃ oil

oil

-O- / 0) ~ Cl Fp 72 ⁰ C

oil

oil

Le A 23 36-

- 79 -

Table 3 (continued) Example no. Ar

physikal. constant

IV-26 IV-27 IV-28 IV-29 IV-30 IV-31 IV-32 IV-33 IV-34 IV-35

O)-

-SCH ₃ oil -SC ₂ H ₅ oil -S- (CH ₂ I ₃ -CH ₃ oil Mp 94 ⁰ C -o © -ci Mp 91 ⁰ C F oil -SC ₂ H ₅ oil 7q \ oil

-o - @ - ci

oil

Mp 62 ⁰ C

According to Example 2 and according to the specified process conditions, the intermediates of the formula (VI) listed in Table 4 below are recovered:

Le A 23

- 80 -

table

VI-2 να-3 VI 4 VI-5 VI-6 VI-7 να-8 VI-9 VJ-10

"2

Bsp.Nr. Ar

Ar-C-CH-R CH ₀

1 *

Y R

N -S-CH- (Q) -Cl

Cl

N -S- (O) -Cl

N -S

CH

N -O-U J) -Cl

¹ B

(VI)

physical constant

Mp. 1O2 ^C C mp. 69 ^P C mp. 102 ^c C mp. 117 ⁰ C mp. 1 <^ ^C C mp. 153 ° C mp. 139 ^C C mp. 156 ⁰ C mp. 128 ^C C

Le A 2 3 36

-bl-

Table 4 (continued)

Bsp.Nr. ' Ar.

Y R melting point (refractive index

VI-II VI-12

VI-14 VI-15 VI-16 VI-17

Cl

N -S- (O

-S- C ₂ H ₅

-S- C ₃ H ₇

-S- C ₂ H ₅

-S- C ₃ Ii ₇

N -SC ₄ H ₉

N -S-CH (CH ₃ )

102

50 1.5632

58 1.5742

1.5762

Cl

Le A 23

- 82 -

use Examples

In the following examples of use, the compounds indicated below are used as reference substances:

(A)

j VlH ₂ -C-CH ₂ -N

Cl

ι.

(B) (N-CH ₂ -C-CH ₂ -N

Cl

(C)

D-

OH I

CH ₂ -C-CH ₂ -N

ι-Ν

(C)

Cl

(known from EP-OS 0 044 605)

Le A 23

2 * 3 7 6-4

- 83 -

Example A Growth inhibition in rice

Solvent: 30 parts by weight Dimethylformamide Emulsifier: 1 part by weight Polyoxyethylene sorbitan monolaurate

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 filled with water to the desired concentration.

Rice is grown in climatic chambers in small pots of vermiculite up to a size of the 1st leaf of 1 - 2 cm. At this stage, the pots are placed in the prepared solutions of the drug to a height equal to half the height of the pot.

After the development of the 3rd leaf, the length of all plants is determined and calculated as a percentage of the length of the control plants. It means 100% growth as in the control plants, values below 100% growth inhibition and values above 100% growth promotion.

In this test, the active compounds (.1-1), (1-6), (1-3) and (1-5) according to the invention show a strong growth inhibition.

Le A 23 363

263 76

- 84 -

Example B Growth in cotton

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

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 filled with water to the desired concentration.

Cotton plants are grown in the greenhouse until fully unfolding the 5th leaf. At this stage, the plants are sprayed dripping wet with the active ingredient preparations. After 3 weeks, the growth of the plants is measured and the growth inhibition calculated as a percentage of the growth of the control plants. 100% plant growth means stagnation of growth and 0% growth corresponding to that of control plants.

In this test, the active compounds (1-4), (1-3) and (1-5) according to the invention show greater growth inhibition than the compound (A) known from the prior art.

Le A 23 363

2 6 3 7-6

- 85 -

Example C Growth inhibition in soybeans

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 specified amounts of solvent and emulsifier and filled with water to the desired concentration.

Soybean plants are grown in the greenhouse until full deployment of the first succeeding leaf. At this stage, the plants are sprayed dripping wet with the active ingredient preparations. After 3 weeks will be at all. Plants measured the growth and calculated the inhibition of growth as a percentage of the growth of the control plants.

100% growth inhibition means the stoppage of growth and 0% growth corresponding to that of the control plants.

In this test, the active compounds (1-4) and (1-3) according to the invention show greater growth inhibition than the compound (D) known from the prior art.

Le A 23 363

- 86 -

Example D Growth inhibition in barley

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 specified amounts of solvent and emulsifier and filled with water to the desired concentration.

Barley plants are grown in the greenhouse up to the 2-leaf stage. At this stage, the plants are sprayed dripping wet with the WirkstoffZubereitungen. After 3 weeks, the growth in all plants is measured and the growth inhibition in percent of the growth of the control plants is calculated. 100% growth inhibition means the stoppage of growth and 0% growth corresponding to that of the control plants,

In this test, the active compounds (1-4), (1-3) and (1-5) according to the invention show greater growth inhibition than the compounds (A), (B), (C) and (D) known from the prior art ).

Le A 23 363

- 87 -

Example E

Venturia test (apple) / protective /

Solvent: 4.7 parts by weight of acetone Emulsifier: 0.3 parts 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 until dripping wet. After the spray coating has dried on, the plants with an aqueous conidia suspension of the apple scab (Venturia inaequalis) and then remain are inoculated at 20 ⁰ C and 100% relative humidity in an incubation for 1 day.

The plants are then placed in a greenhouse at 20 ⁰ C and a relative humidity of about 70%.

12 days after the inoculation the evaluation takes place.

In this test, the compound of the invention (1-1) shows better efficacy than the known reference substance (C).

Le A 23 363

Claims (3)

A process for the preparation of substituted azolylmethyl-cyclopropyl-carbinol derivatives of the formula Ar CR CHO 2 il 26376A - 83 - in which Ar is optionally substituted aryl or optionally substituted heteroaryl, R R 1 is halogen, cyano, thiocyano, alkylcarbonyloxy, alkylcarbonylthio or the groupings -X-R 3 and -NR 4 R 5, wherein R is alkyl, cycloalkyl, alkenyl, alkynyl, hydroxyalkyl, alkylthioalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aryl, optionally substituted aralkyl or the radical of the formula -CH 2 -CH 2 -O- ^ 0S, 4 5 R and R independently represent hydrogen or alkyl or R 5 together with the nitrogen atom to which they are attached represent an optionally substituted cycloaliphatic ring which is widely available and X is oxygen, sulfur, an SO or SO 2 group, and Le A 23 363 R is also hydrogen if Ar is optionally substituted heteroaryl, and Y is nitrogen or a CH group, as well as their acid addition salts and Metallbalz complexes, characterized in that ti) in a first stage aryl cyclopropyl ketones of the formula V 2 Ar-CO-C R (II) in which Ar and R have the abovementioned meaning, with dimethyloxosulfonium-methylide or formula (CH3) 2 ^ + S0Cf CH2 (III) in the presence of a diluent and the resulting aryl-cyclopropyl-oxiranes of the formula Ar CCR * (IV) in which Ar and R have the abovementioned meaning, in a second stage with azoles of the formula in which Y has the abovementioned meaning, in the presence of a diluent and in the presence of a base, or b) azolyl-keto compounds of the formula 0 Ar-C- CH-R2 CHO LJI ¹ N in which R, Ar and Y are as defined above to have, Le A 23 363 - Il - with dimethyloxosulphonium methylid of the formula) ₂ ° ⁺ SO ₂ CH ₂ (II) in the presence of a diluent, oüar c) Azolylmethyl-thio-cyclopropyl-carbinol derivatives of the formula ./) OH ^ ₇ Ar-C 0 SR ³ (Ia) CH. in which Ar, R ^{3 has} 10 Ar, R and Y are as defined above with oxidizing agents, if appropriate in the presence of a diluent, or d) hydroxy compound. the formula V7 ₂ Ar-C CR ^z 15 in which Le A 23 363 26376A - 33- Ar, R and Y are as defined above, with strong bases in the presence of a diluent and the resulting alcoholates of the formula OZ Ar-C C- R ² CH- ^ - ^ N-Y (Ic) in which 2. Pf lanzenwachstumsregul iereooe and fungicidal gowns, characterized Jurch a content between 0.5 and 90 wt .- / i of at least one substituted Azolylmethy1-cyclopropy 1-carbinol-derivative of the formula (I) or a Säureadd itions-Sn I /. or hstalan 1 z -complex of a substituted azolylmethyl-cyclopropyl-carbinol derivative of Forniel (I) 2
Ar, R and Y are as defined above have and Z is a base radical, 10 with a halogen compound of the formula R-HaI (VII) in which R is alkyl, alkenyl, alkynyl, trialkylsilyl, optionally substituted phenylalkyl or an acyl-Rt ^ t and Shark stands for halogen, 'Le A 23 363 26376t in the presence of a confi gation nut; and, if appropriate, an acid or a metal salt is added to the compounds of the formula (1) thus obtained. 3. Use of substituted Azclylmethy1-cyclopropy1-carbinol derivatives of the formula (I) or of their Säiireadditions salts and metal salt complexes, characterized in that they are used for Regulierunrj the P lanzenwachs tuin and for combating fungi.