DE3522440A1 - Substituted azolylmethyl cyclopropyl carbinol derivatives - Google Patents

Abstract

Novel substituted azolylmethyl cyclopropyl carbinol derivatives of the formula <IMAGE> in which Ar represents optionally substituted aryl or optionally substituted heteroaryl, R<1> represents hydrogen, alkyl, alkenyl, alkynyl, trialkylsilyl, optionally substituted phenylalkyl or an acyl radical, R<2> represents halogen, cyano, thiocyano, alkylcarbonyloxy, alkylcarbonylthio or the groups -X-R<3> and -NR<4>R<5>, in which R<3> represents alkyl, cycloalkyl, alkenyl, alkynyl, hydroxyalkyl, alkylthioalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aryl, optionally substituted aralkyl or the radical of the formula <IMAGE> R<4> and R<5> independently of one another represent hydrogen or alkyl or R<4> and R<5> together with the nitrogen atom to which they are bonded represent an optionally substituted cycloaliphatic ring which can contain further hetero atoms, and X represents oxygen, sulphur, an SO or an SO2 group, and R<2> furthermore also represents hydrogen if Ar represents optionally substituted heteroaryl, and Y represents nitrogen or a CH group, and their acid addition salts and metal salt complexes, a plurality of processes for the preparation of these novel active substances and their use as plant growth regulators and fungicides. Novel intermediates and their preparation.

Description

The present invention relates to new substituted Azolylmethyl-cyclopropyl-carbinol derivatives, several Process for their preparation and their use as Plant growth regulators and fungicides.

It has already been known that certain diazolyl Derivatives fungicidal and plant growth regulating Possess properties (cf. EP-OS 0 044 605). So For example, 1,3-di- (1,2,4-triazol-1-yl) - 2- (2-chlorophenyl) propan-2-ol, 1,3-di- (1,2,4-triazol-1- yl) -2- (3-chlorophenyl) propan-2-ol, 1,3-di- (1,2,4-triazole- 1-yl) -2- (4-chlorophenyl) propan-2-ol and 1,3-di- (1,2,4- triazol-1-yl) -2-phenyl-propan-2-ol to regulate the Use plant growth and fungus control. However, the effect of these substances is, in particular at low application rates and concentrations, not always quite satisfactory.

There have now been new substituted azolylmethyl-cyclopropyl-carbinol derivatives of the formula in which

Ar for optionally substituted aryl or optionally substituted heteroaryl,

R ^{1 represents} hydrogen, alkyl, alkenyl, alkynyl, trialkylsilyl, optionally substituted phenylalkyl or an acyl radical,

R ^{2 represents} halogen, cyano, thiocyano, alkylcarbonyloxy, alkylcarbonylthio or the groupings -XR ³ and -NR ⁴ R ⁵ , in which

R ³ for alkyl, cycloalkyl, alkenyl, alkynyl, hydroxyalkyl, alkylthioalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aryl, optionally substituted aralkyl or the rest of the formula stands,
R ⁴ and R ⁵ independently of one another represent hydrogen or alkyl or

R ⁴ and R ⁵ together with the nitrogen atom to which they are attached represent an optionally substituted cycloaliphatic ring which may contain further heteroatoms,

X represents oxygen, sulfur, an SO or an SO ₂ group,
and
R ² also stands for hydrogen if Ar stands for optionally substituted heteroaryl,
and
Y represents nitrogen or a CH group,
as well as their acid addition salts and metal salt complexes.

It was also found that substituted azolylmethyl cyclopropyl-carbinol derivatives of the formula (I) as well as their acid addition salts and metal salt complexes get when one

a) in a first stage aryl-cyclopropyl-ketones of the formula in which
Ar and R ^{2 have} the meaning given above,
with dimethyloxosulfonium methylide of the formula

in the presence of a diluent and the resulting aryl-cyclopropyl-oxiranes of the formula in which
Ar and R ^{2 have} the meaning given above,
in a second stage with azoles of the formula 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 in which
R ² , Ar and Y have the meaning given above,
with dimethyloxosulfonium methylide of the formula

in the presence of a diluent,
or

c) Azolylmethylthio-cyclopropyl-carbinol derivatives of the formula in which
Ar, R ³ and Y have the meaning given above,
with oxidizing agents if appropriate in the presence of a diluent, or

d) hydroxyl compounds of the formula in which
Ar, R ² and Y have the meaning given above,
with strong bases in the presence of a diluent and the resulting alcoholates of the formula in which
Ar, R ² and Y have the meaning given above and
Z represents a base residue,
with a halogen compound of the formula

in which
R represents alkyl, alkenyl, alkynyl, trialkylsilyl, optionally substituted phenylalkyl or an acyl radical and
Hal stands for halogen,
in the presence of a diluent;
and optionally then adding an acid or a metal salt to the compounds of formula (I) thus obtained.

Finally it was found that the new ones were substituted Azolylmethyl-cyclopropyl-carbinol derivatives of the formula (I) as well as their acid addition salts and metal salt complexes strong plant growth regulating and fungicidal properties have.

The substances according to the invention surprisingly show a better plant growth regulating and fungicidal Effectiveness than the constitutionally similar, from which Prior art diazolyl derivatives 1,3-di- (1,2,4-triazol-1-yl) -2- (2-chlorophenyl) propan-2-ol, 1,3-di- (1,2,4-triazol-1-yl) -2- (3-chlorophenyl) propane- 2-ol, 1,3-di- (1,2,4-triazol-1-yl) -2- (4-chlorophenyl) propane- 2-ol and 1,3-di- (1,2,4-triazol-1-yl) -2-phenyl-propan-2-ol,  which can be used for the same indications are.

The substituted azolylmethyl-cyclopropane according to the invention Carbinol derivatives are general by the formula (I) Are defined. In this formula are preferably

Ar for single or multiple, if necessary, the same or differently substituted phenyl, where as The following may preferably be mentioned as substituents: halogen; Alkyl, alkoxy and alkylthio each with 1 to 4 Carbon atoms; Haloalkyl, haloalkoxy and Haloalkylthio, each with 1 to 2 carbon atoms and 1 to 5 same or different Halogen atoms such as fluorine and chlorine atoms; such as each optionally by alkyl with 1 to 2 Carbon atoms and / or halogen substituted Phenyl or phenoxy; continue for naphthyl as well for one, if necessary, single or multiple, the same or different substituted 5- to 6- membered heteroaromatics with nitrogen, oxygen and / or sulfur as heteroatoms, where as Substituents preferably those mentioned above Phenyl substituents come into question;

R ^{1 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 for optionally Phenylalkyl with 1 to 2 carbon atoms in the alkyl part which is mono- or polysubstituted by one or more substituents, the phenyl substituents already mentioned for Ar preferably being suitable as substituents,

R ² for fluorine, chlorine, bromine, cyanio, thiocyano, alkylcarbonyloxy with 1 to 4 carbon atoms in the alkyl part, alkylcarbonylthio with 1 to 4 carbon atoms in the alkyl part, or for the groups -XR ³ and -NR ⁴ R ⁵ , in which

• R ^{3 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 having 2 to 18 carbon atoms, straight-chain or branched alkynyl having 1 to 18 carbon atoms, hydroxyalkyl having 1 to 18 carbon atoms, Alkylthioalkyl with 1 to 6 carbon atoms in the alkylthio group and 1 to 6 carbon atoms in the alkyl group, carboxyalkyl with 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 for each optionally one or more times is the same or different substituted phenyl or phenylalkyl having 1 or 2 carbon atoms in the alkyl part, the preferred substituents in each case being the phenyl substituents preferably mentioned in Ar, or
  R ³ for the rest of the formula stands,
  R ⁴ and R ⁵ independently of one another preferably represent hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms or
• R ⁴ and R ⁵ together with the nitrogen atom to which they are attached are preferably a 5-membered or 6-membered ring which may be substituted by alkyl having 1 to 4 carbon atoms or alkylcarbonyl having 1 to 4 carbon atoms, the oxygen, sulfur and / or can contain nitrogen as further heteroatoms, and
  X preferably represents oxygen, sulfur, an SO or an SO ₂ group, and
  R ² also stands for hydrogen if Ar stands for an optionally substituted 5- or 6-membered heteroaromatic, and
  Y preferably represents nitrogen or a CH group.

Those compounds of the Formula (I) in which

Ar for single to triple if necessary, in particular single or double, same or different substituted phenyl, being as a substituent may be mentioned: fluorine, chlorine, methyl, isopropyl, tert-butyl, methoxy, methylthio, trifluoromethyl, Trifluoromethoxy, trifluoromethylthio, and  in each case optionally by fluorine, chlorine and / or Methyl substituted phenyl or phenoxy; Farther for naphthyl as well as for simple in each case or doubly, identically or differently substituted Furyl, thienyl, pyridinyl or pyrimidinyl stands, with the above mentioned as substituents Phenyl substituents come into question;

R ² for hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, allyl, propargyl, trimethylsilyl, methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, n-butylcarbonyl, isobutycarbonyl, and for optionally simply to triple, in particular single or double, identical or differently substituted benzyl, the preferred substituents being the phenyl substituents which are already preferred for Ar,

R ² for fluorine, chlorine, bromine, cyano, thiocyano, methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, isopropylcarbonyloxy, n-butylcarbonyloxy, isobutylcarbonyloxy, methylcarbonylthio, ethylcarbonylthio, n-propylcarbonylthio, isopropylcarbonylthio, n-butylcarbonylthio, n-butylcarbonylthio, n-butylcarbonylthio for n-butylcarbonylthio, ³ or -NR ⁴ R ⁵ , in which

R ³ for straight-chain or branched alkyl with 1 to 12 carbon atoms, cycloalkyl with 5 to 7 carbon atoms, straight-chain or branched alkenyl with 2 to 12 carbon atoms, straight-chain or branched alkynyl with 2 to 12 carbon atoms, hydroxyalkyl with 1 to 12 carbon atoms, alkylthioalkyl with 1 up to 4 carbon atoms in the alkylthio group and 1 to 4 carbon atoms in the alkyl group, carboxyalkyl with 1 to 12 carbon atoms in the alkyl part, alkoxycarbonylalkyl with 1 to 4 carbon atoms in the alkoxy part and 1 to 4 carbon atoms in the alkyl part, and for each optionally from one to three times, in particular once or phenyl or benzyl which is substituted twice, in the same way or differently, where the particularly preferred phenyl substituents already mentioned above for Ar are suitable as substituents, or

R ³ for the rest of the formula stands,

R ⁴ and R ⁵ independently of one another represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl or

R ⁴ and R ⁵ together with the nitrogen atom to which they are attached each represent piperidinyl, piperazinyl or morpholinyl, optionally substituted by methyl, ethyl, methylcarbonyl or ethylcarbonyl, and

X represents oxygen, sulfur, an SO or an SO ₂ group, and also

R ^{2 is} also hydrogen if Ar is one of the optionally substituted heteroaromatics mentioned above, and

Y represents nitrogen or a CH group. Preferred compounds according to the invention are also addition products of acids and those substituted azolylmethyl-cyclopropyl-carbinol derivatives of the formula (I) in which Ar, R ¹ , R ² and Y have the meanings which have preferably already been mentioned for these radicals.

The acids that can be added preferably include Hydrohalic acids, such as. B. the hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, also phosphoric acid, Nitric acid, sulfuric acid, mono- and bifunctional Carboxylic acids and hydroxycarboxylic acids, such as. B. acetic acid, Maleic acid, succinic acid, fumaric acid, tartaric acid, Citric acid, salicylic acid, sorbic acid and Lactic acid and sulfonic acids, such as. B. p-toluenesulfonic acid, 1,5-Naphalindisulfonic acid or camphorsulfonic acid.

In addition, preferred compounds according to the invention are addition products from salts of metals of the II. To IV. Main group and of I. and II. And IV. To VIII. Subgroup of the periodic table and those substituted azolylmethyl-cyclopropyl-carbinol derivatives of the formula (I), in which Ar, R ¹ , R ² and Y have those meanings which have preferably already been mentioned for these radicals. Salts of copper, zinc, manganese, magnesium, tin, iron and nickel are particularly preferred. Anions of these salts are those which are derived from acids which lead to physiologically tolerable addition products. Particularly preferred such acids in this context are the hydrohalic acids, such as. B. the hydrochloric acid and hydrobromic acid, also phosphoric acid, nitric acid and sulfuric acid.

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 process (a) according to the invention can be represented by the following formula will:

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

For example, 1- (4-chlorophenyl) -1- [1- (ethylthio) -1-cyclopropyl] -2- (1,2,4-triazol-1-yl) -1-ethanol and hydrogen peroxide in glacial acetic acid are used as starting materials , the course of process (c) according to the invention can be represented by the following formula:

For example, if 1- (4-chlorophenyl) -1- [1- (ethylthio) -1-cyclopropyl] -2- (1,2,4-triazol-1-yl) -1-ethanol and sodium hydride are used as starting materials and iodomethane as a reaction component, the course of process (d) according to the invention can be represented by the following formula:

Formula (II) provides a general definition of the arylcyclopropyl ketones to be used as starting materials for process (a) according to the invention. In this formula, Ar and R ² preferably have the meanings which have already been mentioned preferably for these substituents in connection with the description of the substances of the formula (I) according to the invention.

The aryl-cyclopropyl ketones of the formula (II) are not yet known. They can be prepared by using arylhalopropyl ketones of the formula in which
Ar has the meaning given above,
Hal 'represents halogen and
Hal ″ stands for bromine or chlorine,
α) with compounds of the formula

in which
R ^{6 represents} cyano, thiocyano, alkylcarbonyloxy, alkylcarbonylthio or the groupings -XR ³ and -NR ⁴ R ⁵ , in which

R ³ for alkyl, cycloalkyl, alkenyl, alkynyl, hydroxyalkyl, alkylthioalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aryl, optionally substituted aralkyl or the rest of the formula stands,
R ⁴ and R ⁵ independently of one another represent hydrogen or alkyl or
R ⁴ and R ⁵ together with the nitrogen atom to which they are attached represent an optionally substituted cycloaliphatic ring which may contain further heteroatoms,
and
X represents oxygen, sulfur, an SO or an SO ₂ group,
in the presence of a diluent and in the presence of a base, or
β) heated directly in the presence of a diluent and in the presence of a base.

Ar is preferably in the compounds of the formula (VIII) for those meanings that are already related with the description of the invention Substances of formula (I) were preferably mentioned for Ar. Hal 'preferably represents fluorine, chlorine or bromine, and Hal ″ is preferably chlorine or bromine.  

The aryl halopropyl ketones of the formula (VIII) are known or can be done in principle known procedures produce in a simple manner (cf. DE-OS 25 21 104, DE-OS 23 20 355 and DE-OS 23 51 948). So can, for example, the aryl-halopropyl ketones of the formula (VIII), in which Hal 'represents fluorine by using the appropriate compounds of formula (VIII), in which Hal ′ represents bromine, with alkali metal fluorides, such as sodium or potassium fluoride, in the presence an inert organic diluent, such as for example benzene, and in the presence of a macrocyclic Ethers, such as 18-Krone-6 (see manufacturing examples).

In the compounds of formula (IX)

R ⁶ preferably for 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 groups -XR ³ and -NR ⁴ R ⁵ , in which R ³ , R ⁴ , R ⁵ and X preferably have those meanings which have already been mentioned preferably in connection with the description of the substances of the formula (I) according to the invention for these radicals.

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

If the above process for the preparation of aryl-cyclopropyl-ketones of the formula (II) is carried out by the method (β), the compounds of the formula (II) in which R ^{2 is} halogen are obtained.

In the above process for producing the arylcyclopropyl Ketones of formula (II) come as diluents both when working according to the variant (α) as well as variant (β) all under the reaction conditions inert organic solvents in question. Alcohols, such as methanol, are preferably usable. Ethanol, methoxyethanol, propanol or tert-butanol, also ketones, such as acetone and 2-butanone, also nitriles, like acetonitrile, furthermore esters, like ethyl acetate, over it in addition ethers, such as dioxane, aromatic hydrocarbons, such as benzene or toluene, and also amides, such as dimethylformamide.

The bases used in the production of arylcyclopropyl ketones of formula (II) both when working after variant (α) as well as variant (β) all commonly used inorganic and organic Bases into consideration. These preferably include alkali carbonates, such as sodium and potassium carbonate, alkali hydroxides, such as sodium and potassium hydroxide, alkali alcoholates, such as sodium and potassium methylate, ethylate and t-butylate; Alkali hydrides, such as sodium hydride, as well as lower tertiary alkylamines, cycloalkylamines and Aralkylamines, such as in particular triethylamine.

The reaction temperatures can when carrying out the above process for producing the arylcyclopropyl ketones of formula (II) both in variant (α) and also varied in a larger range in variant (β) will. Generally one works at temperatures  between 0 ° and 200 ° C, preferably between 20 ° C and 150 ° C.

In the production of aryl-cyclopropyl-ketones Formula (II) according to process variant (α) above is preferably set to 1 mole of aryl halopropyl ketone of formula (VIII) 1 to 2 moles of compound of the formula (IX) and 1 to 2 moles of base. Isolation of the connections Formula (II) is carried out in the usual way.

The aryl-cyclopropyl-ketones of the formula (II) are not only as starting materials for the production of the invention Compounds of formula (I) of interest, but also provide valuable intermediates for the synthesis of other substances.

That in processes (a) and (b) according to the invention in each case Dimethyloxosulfonium required as reaction component methylide of the formula (III) is known (cf. J. Am. Chem. Soc. 87, 1363-1364 (1965)). It will be at the processing the above implementation in a freshly prepared state, by doing it in situ by reacting trimethyloxosulfonium iodide with sodium hydride or sodium amide, especially with potassium tert-butoxide or sodium methylate, produced in the presence of a diluent.

The also for the second stage of the invention Process (a) as starting materials required azoles Formula (V) are generally known compounds of organic Chemistry.  

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

Formula (VI) provides a general definition of the azolyl keto compounds to be used as starting materials for process (b) according to the invention. In this formula (VI), R ² , Ar and Y preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.

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

The azolyl keto compounds of the formula in which
Ar represents optionally substituted aryl or optionally substituted heteroaryl,
Y represents nitrogen or a CH group and
R ^{7 represents} halogen, cyano, thiocyanato, alkylcarbonyloxy, alkylcarbonylthio or the groupings -XR ⁸ and -NR ⁴ R ⁵ ,
wherein
X represents oxygen or sulfur an SO or SO ₂ group,
R ⁸ for alkyl, cycloalkyl, alkenyl, alkynyl, hydroxyalkyl, alkylthioalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aralkyl or the rest of the formula stands,
R ⁴ and R ^{5 are} independently hydrogen or alkyl, or
R ⁴ and R ⁵ together with the nitrogen atom to which they are attached represent an optionally substituted cycloaliphatic ring which may contain further heteroatoms,
and
R ⁷ also represents hydrogen if Ar represents optionally substituted heteroaryl,
are new.

The azolyl keto compounds of the formula (VIa) can be prepared by using ketones of the formula in which
Ar and R ^{7 have} the meaning given above,
with hydroxymethylazoles of the formula 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 for these radicals in connection with the description of the substances of the formula (I) according to the invention. R ⁷ preferably represents 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 the groups -XR ⁸ and -NR ⁴ R ⁵ , in which
X preferably represents oxygen, sulfur, an SO or an SO ₂ group,
R ^{8 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 having 2 to 18 carbon atoms, straight-chain or branched alkynyl having 2 to 18 carbon atoms, hydroxyalkyl having 1 to 18 carbon atoms, carboxyalkyl 1 to 18 carbon atoms in the alkyl part, alkylthioalkyl with 1 to 6 carbon atoms in the alkylthio group and 1 to 6 carbon atoms in the alkyl group, alkoxycarbonylalkyl with 1 to 6 carbon atoms in the alkoxy part and 1 to 6 carbon atoms in the alkyl part, and for optionally single or multiple, similar or differently substituted phenylalkyl having 1 or 2 carbon atoms in the alkyl part, the preferred substituents being the phenyl substituents preferably mentioned in Ar, or R ⁸ for the rest of the formula stands, and
R ⁴ and R ⁵ preferably have those meanings which have preferably been mentioned for these radicals in connection with the description of the substances of the formula (I) according to the invention, and also stands
R ^{7 is} also preferably hydrogen if 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 keto compounds of the formula (VI a ) are known or can be prepared by methods which are known in principle.

The hydroxymethylazoles of the formula (XI) which are also required as starting materials in the preparation of the aryl-keto compounds of the formula (VI a ) by the above process are known (cf. EP-OS 00 06 102 and Chem. Heterocycl. Comp. 1980, 189).

As diluents for the above process Preparation of the Azolyl Keto Derivatives of the Formula (VIa) preferably inert organic solvents in question. These preferably include alcohols such as methanol and Phenol, furthermore 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, choroform, Chlorobenzene and dichlorobenzene.

The process for the preparation of the azolyl keto derivatives of the formula (VIa) is in the presence of a catalyst carried out. You can use all commonly used acidic and especially basic catalysts and their buffer mixtures. These include preferably Lewis acids, such as. B. 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 carried out this method varies over a wide range will. Generally one works between 20 and 160 ° C, preferably at the boiling point of the particular Solvent.  

When carrying out this procedure, one sets on 1 mol of ketone of the formula (X) 1 to 1.5 mol of hydroxymethylazole of formula (XI) and catalytic to 0.2 molar Amounts of catalyst.

The azolyl keto derivatives of the formula (VI) represent interesting ones Intermediate points represent and show in corresponding Application rates or concentrations also fungicidal and plant growth regulating properties.

The starting materials for process (c) according to the invention Azolylmethyl-thiocyclopropylcarbinol to be used Derivatives of the formula (Ia) are according to the invention Links.

The reaction components in the invention Process (c) all usual for such reactions Oxidizing agents into consideration. Preferably used are hydrogen peroxide and peracids like m- Chloroperbenzoic acid and peracetic acid.

The starting materials for process (d) according to the invention Hydroxy compounds of the formula to be used (Ib) are also compounds according to the invention. Your Conversion to the corresponding alcoholates takes place in generally known manner by using with appropriate strong bases, such as alkali metal amides or hydrides, quaternary ammonium hydroxides or phosphonium hydroxides in an indifferent solvent, such as for example dioxane, at room temperature.

Accordingly, Z is in the compounds of the formula (Ic)  preferably for an alkali metal atom such as sodium and Potassium, or for quaternary ammonium or phosphonium ion.

Formula (VII) provides a general definition of the halogen compounds also required as starting materials in process (d) according to the invention. In this formula, R preferably represents 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 ¹ , with the exception of the meaning of hydrogen. Hal preferably represents chlorine or bromine.

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

The diluents used for the first stage of the invention Process (a) inert organic solvents in question. These preferably include ethers such as Tetrahydrofuran or dioxane, aliphatic and aromatic Hydrocarbons, such as in particular benzene, toluene or xylene; and dimethyl sulfoxide.

The reaction temperatures can be carried out the first stage of process (a) according to the invention can be varied over a wide range. In general operating between 0 and 100 ° C, preferably between 10 and 60 ° C.

When performing the first stage of the invention Process (a) is based on 1 mol of aryl-cyclopropyl ketone of formula (II) preferably 1 to 3 moles  Dimethyloxosulfonium methylide of the formula (III), generated in situ from trimethyloxosulfonium iodide in dimethyl sulfoxide and potassium tert-butoxide. The insulation the intermediates of formula (IV) are generally given usual way.

As a diluent for the second stage Process (a) according to the invention is an inert organic solvent in question. Nitriles are preferably usable, such as in particular acetonitrile; aromatic hydrocarbons, such as benzene, toluene and dichlorobenzene; Formamides, such as especially dimethylformamide; such as Hexamethylphosphoric triamide.

The second stage of the process (a) according to the invention is carried out in the presence of a base. Come here all commonly used inorganic and organic bases. These preferably include Alkali carbonates such as e.g. B. sodium and potassium carbonate; Alkali hydroxides, such as. B. sodium hydroxide; Alkali alcoholates, such as B. sodium and potassium methylate and ethylate; Alkali hydrides, such as. B. sodium hydride; as well as lower tertiary alkylamines, cycloalkylamines and Aralkylamines, such as in particular triethylamine.

The reaction temperatures can be carried out the second stage of process (a) according to the invention can be varied over a wide range. In general one works at temperatures between 0 ° C and 200 ° C, preferably between 60 ° C and 150 ° C.  

When performing the second stage of the invention Process (a) is preferably set to 1 mol Oxirane of formula (IV) 1 to 2 moles of azole and 1 to 2 moles Base one. The end products are generally isolated usual way.

The reaction conditions when carrying out the invention Process (b) correspond to that for the Carrying out the first stage of the procedure (a).

When carrying out process (c) according to the invention, about 1 to 5 mol of oxidizing agent are employed per mol 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 -30 ° C to + 30 ° C, the compounds of formula (I) with the -SO grouping are preferably formed. If there is an excess of oxidizing agent and higher temperatures (10 to 80 ° C.), the compounds of the formula (I) with the —SO ₂ grouping are preferably formed. The oxidation products are isolated in a conventional manner.

As a diluent when performing the Process (d) according to the invention inert organic solvents in question. These preferably include ethers, such as diethyl ether or dioxane; aromatic hydrocarbons, like benzene; in some cases also chlorinated Hydrocarbons such as chloroform, methylene chloride  or carbon tetrachloride; and hexamethylphosphoric triamide.

The reaction temperatures can be carried out process (d) according to the invention in a larger one Range can be varied. Generally one works between 0 and 120 ° C, preferably between 20 and 100 ° C.

When carrying out the method according to the invention (d) one first sets hydroxy compounds of the formula (Ib) with strong bases to the corresponding alcoholates of the formula (Ic). In the next stage after that 1 mol of an alcoholate of the formula (Ic) is preferred 1 to 2 moles of halogen compound of the formula (VII) a.

The reaction mixture is used to isolate the end products freed from the solvent and the residue with Water and an organic solvent are added. The organic phase is separated off in a conventional manner worked up and cleaned.

In a preferred embodiment, expediently proceed in such a way that one of a hydroxy compound of formula (Ib), the latter in a suitable organic solvents using alkali metal hydride or alkali metal amide in the alkali metal alcoholate transferred and the latter immediately without isolation with a Halogen compound of formula (VII) is implemented, wherein with leakage of alkali halide the invention Compounds of formula (I) in one operation be preserved.  

According to another preferred embodiment expediently 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 solution / toluene or methylene chloride, under Addition of 0.01-1 mol of a phase transfer catalyst, such as ammonium or phosphonium compounds, performed, being in the organic Phase or at the interface with the alcoholates implemented in the organic phase halides will.

The acid addition salts of the compounds of formula (I) can be made in a simple manner using conventional salt formation methods, e.g. B. by dissolving a compound of formula (I) in a suitable inert solvent and adding the acid, e.g. B. hydrochloric acid obtained be and in a known manner, for. B. by filtering, isolated and optionally by washing with a inert organic solvents can be cleaned.

The metal salt complexes of the compounds of the formula (I) can be obtained in a simple manner by customary methods be so. B. by dissolving the metal salt in Alcohol, e.g. B. ethanol and adding to compounds of formula (I). One can know metal salt complexes in known Way, e.g. B. by filtering, isolating and optionally clean by recrystallization.

The active substances according to the invention reach into the metabolism of the plants and can therefore act as growth regulators be used.  

For the mode of action of plant growth regulators Experience has shown that an active ingredient also several different effects on plants can exercise. The effects of the substances depend essentially from the time of application related to the stage of development of the plant as well as from the on the plants or their surroundings applied amounts of active ingredient and the type of application. In any case growth regulators are supposed to regulate the crops in certain influence as desired.

Plant growth regulating substances can, for example used to inhibit the vegetative growth of the plants will. Such growth inhibition is under other with grasses of economic interest, because this can reduce the frequency of grass cuts in ornamental gardens, Park and sports facilities on the side of the road Airports or in orchards. From It is also important to inhibit the growth of herbaceous plants and woody plants on and around roadsides of pipelines or overland lines or more generally in areas where there is a strong growth of plants is undesirable.

The use of growth regulators is also important to inhibit the longitudinal growth of cereals. Hereby there is a risk of the plants bending reduced or completely eliminated before harvest. In addition, growth regulators in cereals can be a  Culm reinforcement that also cause storage counteracts. The application of growth regulators for shortening the stalk and reinforcing the stalk allows higher Spread fertilizer amounts to increase the yield, without the risk of the grain being stored.

An inhibition of vegetative growth enables many cultivated plants a denser planting, so that additional yields are achieved based on the floor area can be. An advantage of the smaller ones achieved in this way Planting is also that the culture works more easily and can be harvested.

An inhibition of the vegetative growth of the plants can also lead to increased yields in that the nutrients and assimilates to a greater extent the Blossom and fruit formation benefit as the vegetative Plant parts.

With growth regulators, one can often also Achieve vegetative growth. This is of great use if the vegetative parts of the plant be harvested. Promoting vegetative growth can also promote the lead to generative growth in that more assimilates are formed so that more or larger fruits arise.

In some cases, yield increases can be achieved through a Interference in plant metabolism can be achieved without changes in vegetative growth  to make noticable. Can also use growth regulators achieved a change in the composition of the plants be, which in turn leads to a quality improvement of the Crop products can result. For example, it is possible the sugar content in sugar beet, sugar cane, Pineapple as well as in citrus fruits or increase the protein content to increase in soy or cereals. Is too it is possible, for example, to break down desired ingredients, such as B. sugar in sugar beets or sugar cane, with growth regulators before or after harvest inhibit. In addition, the production or the drain of secondary phytonutrients. One example is the stimulation of the latex flow called with rubber trees.

Under the influence of growth regulators, it can become Formation of parthenocarpic fruits come. Furthermore, the gender of the flowers can be influenced. Can too a sterility of pollen is generated, which at the breeding and production of hybrid seeds is of great importance.

By using growth regulators control the branching of plants. On the one hand can by breaking the apical dominance the development of Side shoots are promoted, especially in ornamental plant growing also in connection with an inhibition of growth can be very desirable. On the other hand, it is also possible to inhibit the growth of the side shoots. For this effect exists e.g. B. great interest in tobacco growing or when planting tomatoes.  

Under the influence of growth regulators Leaves of the plants are controlled so that a Defoliate the plants at a desired time is achieved. Such defoliation is an example the mechanical harvesting of cotton is a big one Role is also in other cultures such. B. in Viticulture to facilitate the harvest of interest. A Defoliation of the plants can also be made about the transpiration of the plants before transplanting belittling.

The fall can also be controlled with growth regulators Taxes. On the one hand, premature fruiting can occur be prevented. On the other hand, it can also the fruiting or even the falling of the flowers until are promoted to a desired extent ("thinning"), to break the alternance. Under alternance one understands the peculiarity of some types of fruit, endogenously very different from year to year Bring yields. Finally, it is possible with Growth regulators at harvest time To reduce peeling of the fruit required forces to enable mechanical harvesting or to facilitate manual harvesting.

Acceleration can also be achieved with growth regulators or delaying the ripening of the crop or reach after harvest. This is special Advantage, because this allows an optimal adaptation to the Market needs. Farther  In some cases, growth regulators can change the color of the fruit improve. It can also use growth regulators also a temporal concentration of the Maturity can be achieved. This creates the prerequisites created for z. B. with tobacco, tomatoes or coffee a full mechanical or manual harvest in can be carried out in one operation.

By using growth regulators, the Plant seed or bud rest are affected, so that the plants such. B. pineapple or ornamental plants in nurseries, germinate at a time, sprout or bloom, at which they are usually unwilling to do so demonstrate. A delay in the sprouting of Buds or the germination of seeds with the help of growth regulators may be desirable in areas at risk of frost to avoid damage from late frosts.

Finally, resistance to growth regulators the plants against frost, drought or high salinity of the soil are induced. This will make the Cultivation of plants possible in areas that are usually unsuitable for this.

The active compounds according to the invention also have a strong one microbicidal action and can be used to control used by unwanted microorganisms will. The active ingredients are for use as pesticides suitable.  

Fungicidal agents are used in crop protection to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

The good plant tolerance of the active ingredients in those necessary to combat plant diseases Concentrations allowed treatment from above ground Parts of plants, of seedlings and des Floor.

The pesticides according to the invention can be used Active substances with particularly good success for combating of cereal and rice diseases as well as Venturia Species such as Venturia inaequalis can be used. In addition, the substances according to the invention show a wide range and good fungicidal spectrum of activity in vitro.

The active ingredients can be in the usual formulations are transferred, such as solutions, emulsions, suspensions, Powders, foams, pastes, granules, aerosols, Very fine encapsulation in polymeric substances and in coating compositions for seeds and ULV formulations.

These formulations are prepared in a known manner e.g. B. by mixing the active ingredients with extenders, i.e. liquid solvents, under pressure standing liquefied gases and / or solid carriers, optionally using surfactants Agents, i.e. emulsifiers and / or Dispersing agents and / or foaming agents. If water is used as an extender  can e.g. B. also organic solvents as auxiliary solvents be used. As a liquid solvent essentially come into question: aromatics, like Xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or Paraffins, e.g. B. petroleum fractions, alcohols, such as butanol or glycol and their ethers and esters, ketones, such as Acetone, methyl ethyl ketone, methyl isobutyl ketone or Cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. With liquefied gaseous extenders or carriers are meant such liquids, which in normal Temperature and under normal pressure are gaseous, for. B. Aerosol propellants, such as halogenated hydrocarbons as well Butane, propane, nitrogen and carbon dioxide. As fixed Carriers come into question: z. B. natural stone powder, such as kaolins, clays, talc, chalk, quartz, Attapulgite, montmorillonite or diatomaceous earth and synthetic Rock powder, such as highly disperse silica, Alumina and silicates. As solid carriers for Granules are possible: B. broken and fractionated natural rocks such as calcite, marble, pumice, Sepiolite, dolomite and synthetic granules inorganic and organic flours and granules organic material such as sawdust, coconut shells, Corn cobs and tobacco stalks. As an emulsifying and / or Foaming agents are possible: z. B. non-ionic and anionic emulsifiers, such as polyoxyethylene  Fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, Aryl sulfonates and protein hydrolyzates. As a dispersant come into question: z. B. lignin sulfite and Methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g. B. 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 be used.

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

The active compounds according to the invention can be used in the formulations in a mixture with other known active ingredients are present, such as fungicides, insecticides, acaricides and Herbicides, as well as in mixtures with fertilizers and others Growth regulators.

The active ingredients as such, in the form of their formulations or the application forms prepared from it, such as ready-to-use solutions, emulsifiable concentrates,  Emulsions, foams, suspensions, wettable powders, pastes, soluble powders, dusts and granules will. The application happens in the usual way, e.g. B. by pouring, spraying, spraying, scattering, dusting, Foaming, brushing, etc. It is further possible the active ingredients according to the ultra-low-volume Apply procedures or drug preparation or inject the active ingredient into the soil yourself. The seeds of the plants can also be treated.

When using the compounds of the invention as Plant growth regulators can reduce the application rates can be varied over a wide range. In general 0.01 to 50 kg is preferably used per hectare of soil 0.05 to 10 kg.

When using the substances according to the invention as plant growth regulators applies that the application in one preferred period is made, its exact Differentiation between climatic and vegetative conditions judges.

Even when using the substances according to the invention as fungicides The application rate can vary depending on the type of application can be varied over a wide range. That's how they are Active substance concentrations in the treatment of Plant parts in the application forms in general between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight. In the seed treatment in general amounts of active ingredient from 0.001 to 50 g per kg Seed, preferably 0.01 to 10 g, is required. During treatment  of the soil are active ingredient concentrations of 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02%, required at the site of action.

The production and use of the invention The following examples show substances.  

Manufacturing examples example 1

(Method a)

1st stage

To a mixture of 6.4 g sodium hydride (80%) and 44.2 g of trimethylsulfoxonium iodide are added dropwise at 10 ° C. 170 ml of dry dimethyl sulfoxide and leave for one hour stir at room temperature. Then moved dropwise with 40 g (0.167 mol) of 1- (4-chlorobenzoyl) - 1-ethylthio-cyclopropane in 50 ml of dimethyl sulfoxide. The The reaction mixture is stirred for two days at room temperature. Then enjoy on 500 g of ice, extracted several times  with ethyl acetate, washes the combined organic Phases with water, dries over sodium sulfate and constricts a. 40.5 g (95.5% of theory) 1- [1- (4- Chlorophenyl) oxiranyl] -1-ethylthio-cyclopropane as an oil, that will be implemented directly.

2nd stage A solution of 40.5 g (0.16 mol) of 1- [1- (4-chlorophenyl) is added dropwise to a boiling mixture of 33.5 g of 1,2,4-triazole and 22 g of potassium carbonate in 150 ml of acetonitrile ) -oxiranly] -1-ethylthio-cyclopropane (cf. Ex. IV-1) in 50 ml of acetonitrile and the reaction mixture is heated under reflux for eight hours. The mixture is allowed to cool, 400 ml of water are added and the crystalline product is filtered off with suction. After recrystallization from ethanol / water, 26.5 g (51% of theory) of 1- (4-chlorophenyl) - 1- [1- (ethylthio) -1-cylcopropyl] -2- (1,2,4- triazol-1-yl) - 1-ethanol melting at 165 ° C.

Manufacture of the starting product

A solution of 38 g of potassium hydroxide is added dropwise at 0 ° C. to 10 ° C. to a solution of 100 g (0.338 mol) of 4-chlorophenyl- (1-bromo-3-chloropropyl) ketone and 21 g of ethylthiol in 200 ml of dimethylformamide 250 ml of methanol. The mixture is stirred for one hour at room temperature and for one hour under reflux. It is then concentrated in vacuo and the residue is taken up in a mixture of water and methylene chloride. The organic phase is separated off, washed with water, dried over sodium sulfate and concentrated in vacuo. The residue is distilled in a high vacuum. 70.1 g (86% of theory) of 1- (4-chlorobenzoyl) -1-ethylthio-cyclopropanone with a boiling point of _0.15 = 127 ° C. are obtained.

Example 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 dimethylsulfoxide [prepared from 27.6 g (0.125 mol) trimethylsulfoxonium iodide and 14.03 g (0.125 mol) potassium tert-butoxide].

The mixture is stirred at 60 ° C. for 6 hours, then with Diluted 1000 ml of water, the separated oil in chloroform added, dried over sodium sulfate, concentrated and chromatographic (silica gel F 60 Merck / mobile solvent: Chloroform). The remaining oil crystallizes on stirring with acetonitrile. You get 1.7 g (8% of theory) of 1- (4-chlorophenoxy) -1- [1-hydroxy-1-phenyl-2- (1,2,4-triazol-1-yl)] cyclopropane melting point 170 ° C.

Production of the preliminary product

29.4 g (0.12 mol) of ω- (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 were added in succession and the mixture was boiled on a water separator until the amount of water removed remained 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 solvent chloroform). 20.8 g (53% of theory) of 1- (chlorophenoxy) -2- (1,2,4-triazol-1-yl) propiophenone with a melting point of 126 ° C. are obtained.

A solution of 154.6 g (1 mole) ω-chloroacetophenone in 250 ml of butanone is dissolved in a boiling solution of 129 g (1 mole) 4-chlorophenol, 140 g (1 mole) potassium carbonate and 2 g of potassium iodide dropped in 800 ml of butanone, and that After the addition has ended, the mixture is stirred for a further 12 hours cooked under reflux. The reaction mixture obtained is filtered and evaporated. 179 g are obtained (73% of theory) on ω- (4-chlorophenoxy) acetophenone from the melting point 97 ° C.

Example 3

(Method c)

5 g (0.0155 mol) of 1- (4-chlorophenyl) -1- [1- (ethylthio) - 1-cyclopropyl] -2- (1,2,4-triazol-1-yl) -1-ethanol (cf. Example 1) with 3.3 g of m-chloroperbenzoic acid (80-90%) in 40 ml methylene chloride at room temperature overnight and then one hour under reflux  touched. Then twice with 20 ml 5% aqueous sodium hydroxide solution and washed twice with water. The organic phase is dried over sodium sulfate and concentrated in vacuo. The backlog will recrystallized from glycol monomethyl ether acetate. Man receives 3 g (57% of theory) 1- (4-chlorophenyl) -1-] 1- (ethylsulfinyl) -1-cyclopropyl] -2- (1,2,4-triazol-1-yl) - 1-ethanol from the boiling point 185 ° C.

Example 4

(Method c)

3.2 g (0.01 mol) of 1- (4-chlorophenyl) -1- [1- (ethylthio) -1- cyclopropyl] -2- (1,2,4-triazol-1-yl) -1-ethanol (cf. Example 1) are dissolved in 20 ml of glacial acetic acid and with 4 ml 30% hydrogen peroxide stirred at 70 ° C for six hours. 100 ml of ice water are then added, neutralized with concentrated aqueous sodium hydroxide solution and sucks off the crystalline solid. 3.4 g are obtained (96% of theory) 1- (4-chlorophenyl) -] 1- (ethylsulfonyl) - 1-cyclopropyl] -2- (1,2,4-triazol-1-yl) -1-ethanol from Melting point 215 ° C.  

The substances of the formula (I) listed in Table 1 below are also prepared by the methods described in the preceding examples and the details of the processes according to the invention.

Further examples for the preparation of starting materials of the formula (II) Example (II-2)

14 g of potassium carbonate are added 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 and the mixture is heated for three hours 50 ° C. 8.4 g of potassium hydroxide in 40 ml of methanol are then added dropwise at room temperature and heated at 50 ° C. for three hours. The mixture is concentrated in vacuo and taken up in a water / methylene chloride mixture. The organic phase is separated off, washed with water, dried over sodium sulfate and concentrated in vacuo. The residue is distilled in a high vacuum. 20.7 g (76.1% of theory) of 1- (4-chlorobenzoyl) -1-phenoxy-cyclopropane with a boiling point of _0.15 = 170-80 ° C. are obtained.

Example (II-3)

To a mixture of 10.4 g of N-methylpiperazine and 14 g of potassium carbonate dripped in 30 ml of dimethylformamide a solution of 29.6 g (0.1 mol) of 4-chlorophenyl- (1-  bromo-3-chloropropyl) ketone in 30 ml of dimethylformamide Room temperature. The mixture is left to stir for three hours and then drops a solution of 9 g of potassium hydroxide in 30 ml of methanol. The reaction mixture is one hour stirred at 50 ° C and concentrated in vacuo. The residue is taken up in ethyl acetate / water, the organic Phase separated, washed with water, over sodium sulfate dried and concentrated in vacuo. The Residue is over silica gel with chloroform / ethanol (97: 3) chromatographed. 14 g (50.3% of the Theory) 1- (4-chlorobenzoyl) -1- (4-methyl-piperazin-1- yl) -cyclopropane as a reddish oil that goes straight on can be used.

Example (II-4)

20 g (0.085 mol) of 4-chlorophenyl- (1-fluoro-3-chloropropyl) ketone are dissolved in 150 g of tert-butanol and 15 g of potassium tert-butoxide are added in portions. The mixture is stirred for 2 hours at 40 ° C and concentrated in vacuo. The residue is taken up in methylene chloride and water. The organic phase is separated off, dried over sodium sulfate and concentrated in vacuo. The residue is distilled in a high vacuum. 14.4 g (85% of theory) of 1- (4-chlorobenzoyl) -1-fluoro-cyclopropane with a boiling point of _0.1 = 75 ° C. are obtained.

Preparation of starting products of the formula (VIII)

A mixture of 68 g of 4-chlorophenyl- (1-bromo-3-chloropropyl) ketone, 27.5 g of dried potassium fluoride, 11 g of 18-crown-6 and 200 ml of dry benzene is heated under reflux for 8 hours. Then 200 ml of water are added, the organic phase is separated off, 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 suctioning off the resulting solid and drying, 28.5 g (53% of theory) of 4-chlorophenyl- (1-fluoro-3-chloropropyl) ketone with a melting point of 53 ° C. are obtained.

A solution of 483 g (2.23 mol) of 4-chlorophenyl-3-chloro propyl ketone in 1200 ml of methylene chloride is at 20 ° C. dropwise with a solution of 358 g bromine in 350 ml Methylene chloride added. Allow to stir for an hour  and then concentrated in a vacuum. The backlog will mixed with 300 ml of petroleum ether and until complete the crystallization stirred. It is cooled to 10 ° C and sucks off the precipitation. 582 g (88.3% of theory) 4-chlorophenyl (1-bromo-3-chloropropyl) ketone from the melting point 73 ° C.

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

The intermediates of the formula (IV) listed in Table 3 below are also prepared by the method described in Example 1 and under the specified process conditions.

The intermediates of the formula (VI) listed in Table 4 below are obtained in accordance with Example 2 and in accordance with the specified process conditions:

Examples of use

In the following examples of use, the compounds specified below are used as comparison substances:

(known from EP-OS 0 044 605)  

Example A Inhibition of growth in rice

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

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amounts of solvent and emulsifier and fill with Water to the desired concentration.

Rice is grown in climate chambers in small pots with vermiculite tightened to a size of the 1st leaf of 1-2 cm. At this stage, the pots are raised to a height that corresponds to half the height of the pot, in the prepared Active ingredient solutions provided.

After the development of the 3rd leaf, the length of all Plants determined and as a percentage of the length of the control plants calculated. It means 100% growth like in the control plants, values below 100% inhibited growth and values over 100% support growth.

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

Example B Inhibition of growth in cotton

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

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amounts of solvent and emulsifier and fill with Water to the desired concentration.

Cotton plants are grown to the full in the greenhouse Unfolding of the 5th following sheet attracted. In this Stage the plants are dripping wet with the active ingredient preparations sprayed. After 3 weeks, the increase of the plants measured and the inhibition of growth in percent of the growth of the control plants. Mean it 100% inhibition of growth and growth arrest 0% growth corresponding to that of the control plants.

The active compounds according to the invention show in this test (I-4), (I-3) and (I-5) have a stronger growth inhibition than the compound (A) known from the prior art.  

Example C Inhibition of growth in soybeans

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

For the preparation of a suitable active ingredient preparation you mix 1 part by weight of active ingredient with specified amounts of solvent and emulsifier and fills with water to the desired concentration.

Soybean plants are grown to the full in the greenhouse Unfolding of the first following sheet attracted. In this Stage the plants are dripping wet with the active ingredient preparations sprayed. After 3 weeks, everyone Plants measured the growth and inhibited growth in Percentage of control plant growth calculated. 100% growth inhibition means that growth has stopped and 0% growth corresponding to that of the control plants.

The active compounds according to the invention show in this test (I-4) and (I-3) a stronger inhibition of growth than that from known compound (D).  

Example D Inhibition of barley growth

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

For the preparation of a suitable active ingredient preparation you mix 1 part by weight of active ingredient with specified amounts of solvent and emulsifier and fills with water to the desired concentration.

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

The active compounds according to the invention show in this test (I-4), (I-3) and (I-5) have a stronger growth inhibition than the compounds (A) known from the prior art, (B), (C) and (D).  

Example E

Venturia test (apple) / protective /
Solvent: 4.7 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amounts of solvent and emulsifier and diluted the concentrate with water to the desired concentration.

To test for protective efficacy one splashes young plants with the active ingredient preparation up to Dripping wet. After the spray coating has dried on the plants with an aqueous conidia suspension of Apple scab pathogen (Venturia inaequalis) inoculated and then remain at 20 ° C and 100% relative for 1 day Humidity in an incubation cabin.

The plants are then in the greenhouse at 20 ° C and a relative humidity of approx. 70%.

Evaluation is carried out 12 days after the inoculation.

In this test, the compound according to the invention shows (I-1) a better efficacy than the known comparison substance (C).

Claims (15)

1. Substituted azolylmenthyl-cyclopropyl-carbinol derivatives of the formula in which
Ar represents optionally substituted aryl or optionally substituted heteroaryl,
R ^{1 represents} hydrogen, alkyl, alkenyl, alkynyl, trialkysilyl, optionally substituted phenylalkyl or an acyl radical,
R ^{2 represents} halogen, cyano, thiocyanio, alkylcarbonyloxy, alkylcarbonylthio or the groupings -XR ³ and -NR ⁴ R ⁵ , in which
R ^{3 represents} alkyl, cycloakyl, alkenyl, alkynyl, hydroxyalkyl, alkythioalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aryl, optionally substituted aralkyl or the rest of the formula stands,
R ⁴ and R ⁵ independently of one another represent hydrogen or alkyl or
R ⁴ and R ⁵ together with the nitrogen atom to which they are attached represent an optionally substituted cycloaliphatic ring which may contain further heteroatoms, and
X represents oxygen, sulfur, an SO or an SO ₂ group, and
R ² also stands for hydrogen if Ar stands for optionally substituted heteroaryl, and
Y represents nitrogen or a CH group,
as well as their acid addition salts and metal salt complexes. 2. Process for the preparation of substituted azolyl-methyl-cyclopropyl-carbinol derivatives of the formula in which Ar represents optionally substituted aryl or optionally substituted heteroaryl,
R ^{1 represents} hydrogen, alkyl, alkenyl, alkynyl, trialkylsilyl, optionally substituted phenylalkyl or an acyl radical,
R ^{2 represents} halogen, cyano, thiocyano, alkylcarbonyloxy, alkylcarbonylthio or the groupings -XR ³ and -NR ⁴ R ⁵ , in which
R ³ for alkyl, cycloalkyl, alkenyl, alkynyl, hydroxyalkyl, alkylthioalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aryl, optionally substituted aralkyl or the rest of the formula stands,
R ⁴ and R ⁵ independently of one another represent hydrogen or alkyl or
R ⁴ and R ⁵ together with the nitrogen atom to which they are attached represent an optionally substituted cycloaliphatic ring which may contain further heteroatoms, and
X represents oxygen, sulfur, an SO or an SO ₂ group, and
R ² also stands for hydrogen if Ar stands for optionally substituted heteroaryl, and
Y represents nitrogen or a CH group,
and of their acid addition salts and metal salt complexes, characterized in that
a) in a first stage aryl-cyclopropyl-ketones of the formula in which
Ar and R ^{2 have} the meaning given above,
with dimethyloxosulfonium methylide or formula in the presence of a diluent and the resulting aryl-cyclopropyl-oxiranes of the formula in which
Ar and R ^{2 have} the meaning given above,
in a second stage with azoles of the formula 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 in which
R ² , Ar and Y have the meaning given above,
with dimethyloxosulfonium methylide of the formula in the presence of a diluent, or c) Azolylmethylthio-cyclopropyl-carbinol derivatives of the formula in which
Ar, R ³ and Y have the meaning given above,
with oxidizing agents if appropriate in the presence of a diluent, or d) hydroxy compounds of the formula in which
Ar, R ² and Y have the meaning given above,
with strong bases in the presence of a diluent and the resulting alcoholates of the formula in which
Ar, R ² and Y have the meaning given above and
Z represents a base residue,
with a halogen compound of the formula in which
R represents alkyl, alkenyl, alkynyl, trialkylsilyl, optionally substituted phenylalkyl or an acyl radical and
Hal stands for halogen,
in the presence of a diluent; and optionally adding an acid or a metal salt to the compounds of formula (I) thus obtained. 3. Plant growth regulating and fungicidal agents, characterized by a content of at least a substituted azolylmethyl-cyclopropyl- carbinol derivative of the formula (I) or an acid addition Salt or metal salt complex of a substituted one Azolylmethyl-cyclopropyl-carbinol derivative of formula (I). 4. Use of substituted azolylmethyl-cyclopropyl- carbinol derivatives of the formula (I) or of their acid addition salts and metal salt complexes to regulate plant growth and Fighting mushrooms. 5. Aryl-cyclopropyl-ketones of the formula in which
Ar represents optionally substituted aryl or optionally substituted heteroaryl and
R ^{2 represents} halogen, cyano, thiocyano, alkylcarbonyloxy, alkylcarbonylthio or the groupings -XR ³ and -NR ⁴ R ⁵ , in which
R ³ for alkyl, cycloalkyl, alkenyl, alkynyl, hydroxyalkyl, alkylthioalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aryl, optionally substituted aralkyl or the rest of the formula stands,
R ⁴ and R ⁵ independently of one another represent hydrogen or alkyl or
R ⁴ and R ⁵ together with the nitrogen atom to which they are attached represent an optionally substituted cycloaliphatic ring which may contain further heteroatoms, and
X represents oxygen, sulfur, an SO or an SO ₂ group, and
R ² also stands for hydrogen if Ar stands for optionally substituted heteroaryl. 6. Process for the preparation of aryl-cyclopropyl-ketones of the formula in which
Ar represents optionally substituted aryl or optionally substituted heteroaryl and
R ^{2 represents} halogen, cyano, thiocyano, alkylcarbonyloxy, alkylcarbonylthio or the groupings -XR ³ and -NR ⁴ R ⁵ , in which
R ³ for alkyl, cycloalkyl, alkenyl, alkynyl, hydroxyalkyl, alkylthioalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aryl, optionally substituted aralkyl or the rest of the formula stands,
R ⁴ and R ⁵ independently of one another represent hydrogen or alkyl or
R ⁴ and R ⁵ together with the nitrogen atom to which they are attached represent an optionally substituted cycloaliphatic ring which may contain further heteroatoms, and
X represents oxygen, sulfur, an SO or an SO ₂ group, and
R ² also represents hydrogen if Ar represents optionally substituted heteroaryl,
characterized in that arylhalopropyl ketones of the formula in which Ar has the meaning given above,
Hal 'represents halogen and
Hal ″ stands for bromine or chlorine,
α) with compounds of the formula in which
R ^{6 represents} cyano, thiocyano, alkylcarbonyloxy, alkylcarbonylthio or the groupings -XR ³ and -NR ⁴ R ⁵ , in which
R ³ for alkyl, cycloalkyl, alkenyl, alkynyl, hydroxyalkyl, alkylthioalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aryl, optionally substituted aralkyl or the rest of the formula stands,
R ⁴ and R ⁵ independently of one another represent hydrogen or alkyl or
R ⁴ and R ⁵ together with the nitrogen atom to which they are attached represent an optionally substituted cycloalipathic ring which may contain further heteroatoms,
and
X represents oxygen, sulfur, an SO or SO ₂ group,
in the presence of a diluent and in the presence of a base,
β) heated directly in the presence of a diluent and in the presence of a base. 7. Aryl-cyclopropyl-oxiranes of the formula in which
Ar represents optionally substituted aryl or optionally substituted heteroaryl and
R ^{2 represents} halogen, cyano, thiocyano, alkylcarbonyloxy, alkylcarbonylthio or the groupings -XR ³ and -NR ⁴ R ⁵ , in which
R ³ for alkyl, cycloalkyl, alkenyl, alkynyl, hydroxyalkyl, alkylthioalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aryl, optionally substituted aralkyl or the rest of the formula stands,
R ⁴ and R ⁵ independently of one another represent hydrogen or alkyl or
R ⁴ and R ⁵ together with the nitrogen atom to which they are attached represent an optionally substituted cycloaliphatic ring which may contain further heteroatoms, and
X represents oxygen, sulfur, an SO or an SO ₂ group, and
R ² also stands for hydrogen if Ar stands for optionally substituted heteroaryl. 8. Process for the preparation of aryl-cyclopropyloxiranes of the formula in which
Ar represents optionally substituted aryl or optionally substituted heteroaryl and
R ^{2 represents} halogen, cyano, thiocyano, alkylcarbonyloxy, alkylcarbonylthio or the groupings -XR ³ and -NR ⁴ R ⁵ , in which
R ³ for alkyl, cycloalkyl, alkenyl, alkynyl, hydroxyalkyl, alkylthioalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aryl, optionally substituted aralkyl or the rest of the formula stands,
R ⁴ and R ⁵ independently of one another represent hydrogen or alkyl or
R ⁴ and R ⁵ together with the nitrogen atom to which they are attached represent an optionally substituted cycloaliphatic ring which may contain further heteroatoms, and
X represents oxygen, sulfur, an SO or an SO ₂ group, and
R ² also stands for hydrogen if Ar stands for optionally substituted heteroaryl,
characterized in that arylcyclopropyl ketones of the formula in which
Ar and R ^{2 have} the meaning given above,
with dimethyloxosulfonium methylide of the formula in the presence of a diluent. 9. Azolyl keto compounds of the formula in which
Ar represents optionally substituted aryl or optionally substituted heteroaryl,
Y represents nitrogen or a CH group and
R ^{7 represents} halogen, cyano, thiocyano, alkylcarbonyloxy, alkylcarbonylthio or the groupings -XR ⁸ and -NR ⁴ R ⁵ ,
wherein
X represents oxygen, sulfur, an SO or SO ₂ group,
R ⁸ for alkyl, cycloalkyl, alkenyl, alkynyl, hydroxyalkyl, alkylthioalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aralkyl or the rest of the formula stands,
R ⁴ and R ^{5 are} independently hydrogen or alkyl, or
R ⁴ and R ⁵ together with the nitrogen atom to which they are attached represent an optionally substituted cycloaliphatic ring which may contain further heteroatoms, and
R ⁷ also represents hydrogen if Ar represents optionally substituted heteroaryl. 10. Process for the preparation of azolyl-keto compounds of the formula in which
Ar represents optionally substituted aryl or optionally substituted heteroaryl,
Y represents nitrogen or a CH group and
R ^{7 represents} halogen, cyano, thiocyano, alkylcarbonyloxy, alkylcarbonylthio or the groupings -XR ⁸ and -NR ⁴ R ⁵ ,
wherein
X represents oxygen, sulfur, an SO or SO ₂ group,
R ⁸ for alkyl, cycloalkyl, alkenyl, alkynyl, hydroxyalkyl, alkylthioalkyl, carboxyalkyl, alkoxycarbonylalkyl, optionally substituted aralkyl or the rest of the formula stands,
R ⁴ and R ⁵ independently of one another represent hydrogen or alkyl or
R ⁴ and R ⁵ together with the nitrogen atom to which they are attached represent an optionally substituted cycloaliphatic ring which may contain further heteroatoms, and
R ⁷ also represents hydrogen if Ar represents optionally substituted heteroaryl,
characterized in that ketones of the formula in which
Ar and R ^{7 have} the meaning given above,
with hydroxymethylazoles of the formula in which
Y has the meaning given above,
in the presence of a diluent and in the presence of a catalyst.