CA1271760A - Azolylmethylcycloalkanes, their preparation and fungicides containing them - Google Patents

Abstract

ASTRACT OF THE DISCLOSURE:

Azolylmethylcycloalkanes of the formula

Description

1~7176{) The present invention relates to novel azolyl-methylcycloalkanes, processes for their preparation and fungicides which contain these compounds.
The use of azole compounds, such as azolymethylcarbinols or azolylmethylketones (German Laid-Open Application DOS 2,431,407 and French Patent 2,249,616), as fungicides has been disclosed. However, their action is unsatisfactory.
It has now been found that azolylmethylcyclo-alkanes of the formula (I):

H~

L ~ ~ ~
m ~C~ (I) , 2 ~N~

N

where A and B are identical or different and are eachhydrogen, unsubstituted or fluoro-substituted alkyl of 1 to 4 carbon atoms, naphthyl, furanyl, thienyl, pyridyl, biphenyl or phenyl, where the phenyl radical can be substituted by halogen, nitro, alkyl, alkoxy or haloalkyl, each of 1 to 4 carbon atoms, phenoxy or phenylsul.fenyl, D
and E are .identica.l. or d:iffercnt and ar~ cacll hydrogen or halogen, Z is Cll or N, m can be 1, 2, 3 or 4 and n can be 0, 1 or 2, their plant-tolerated addition salts with acids, and metal complexes, have good fungicidal properties.
The compounds of the formula (I) where A and B are hydrogen are already known. Of course, the present invention as claimed hereinafter is restricted to the 't 1.271760 - la -compounds of the same formula (I) where A and B not hydrogen.
The novel compounds of the formula (I) contain chiral centers and are generally obtained in the form of reacemates. While the novel azolylmethylcyclopropanes of the formula (I), where m is 1, n is O and B is not H, can be ~1 ~ 2~760 synthesized diastereoselectively by a simple procedure, in general mlxtures of the erythro and threo forms are obtained. In this case, the diastereomers of the novel com-05 pounds can be separated by, for example, solubllity dif-ferences or column chromatography, and can be isolated in the pure form. From the pure diastereomer pairs, it is posslble to obtain pure enantiomers by a conventional method. Both these and their mixtures (racemates) are embraced by the present invention. Tb prepare funglcidal agents, elther the pure diastereomers or enantiomers or thelr mlxtures can be used.
A and B are each, for example, methyl, ethyl, propyl, isopropyl, butyl, sec.butyl, isobutyl, tert.-butyl, trifluoromethyl, l-naphthyl, 2-naphthyl, p-biphenyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 4-fluorophenyl, 4-bromophenyl, 2~4-dl-chlorophenyl, 3,4-dlchlorophenyl, 3,5-dichlorophenyl,

2,6-dichlorophenyl, 3-chloro-4-methylphen~yl, 2-methoxy-phenyl, 3-methoxyphenyl, 2,4-dimethoxyphenyl, 3,4-dimeth-oxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 4-tert.-butoxy-phenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert.-butylphenyl, 4-phenoxyphenyl, 3-phenoxyphenyl,

3-phenoxyphenyl, 3-nitrophenyl, 4-nitrophenyl, 3-trifluoro-methylphenyl, 4-trifluoromethylphenyl, 4-phenylsulfenyl-phenyl, hetaryl, e.g. 3-furanyl, 2-furanyl, 3-thlenyl, 2-thienyl, 3-pyridyl or 4-pyridyl.
D and E are each, for example, fluorlne, chlorine, bromlne or hydrogen.
Examples of acid addltlon qalts are the hydro-chlorldes, bromldes, sulfates, nltrates, phosphates, oxalates and dodecylbenzenesulfonates. The activity of the salts ls attrlbutable to the catlon, so that any desired anion may be chosen. For practlcal reasons, however, non-phytotoxic anions are used.
The salts are prepared by reactlng an azolylmethyl-cycloalkane wlth an appropriate acid.

.~1 7 ~ 0 - 3 - O.Z. 0050/36402 Metal complexes are those obtained from a compound of the formula I and a salt of a metal, for example o~
copper, zinc, tin, manganese, iron, cobalt or nickel, with an inorganic acid, e.g. hydrochloric acid, sulfuric acid, 05 phosphoric acid or hydrobromic acid. The metal compl~xes are prepared by reacting an azolylmethylcycloalkane with an appropriate metal salt.
The novel compounds of the formula I can be prepared by a process in which a cycloalkane of the formula II

H~

m [ ~A~C~

where A, B, D, E, m and n have the above meanings and L is a leaving group which can be substituted nucleophilically, such as chlorine, bromine, methyl-, trifluoromethyl-, 2,2,2-trifluoroethyl-, nonafluorobutyl-, 4-methylphenyl-,

4 bromophenyl-, 4-nitrophenyl- or phenylsulfonyloxy, is reacted a) with an azole of the formula III
t - Z~
I ~ ~ ~ Ma (III), where Me is a hydrogen atom or, preferably, a metal atom such as sodium or potassium, or b) when L ls a hydroxyl group, with a compound of the formula IV
o T ' Z\ 11 /Z
/ \ , I (IV)~
~ ' where Y is carbon or sulfur.

127~760 _ 4 _ O.Z. 0050/36402 Process a), Me denoting a metal atom, is preferred.
Reaction a), Me denoting hydrogen, is carried out in the presence or absence of a solvent or diluent and with or without the addition o~ an inorganlc or organic base or 05 of a reaction accelerator at from 10 to 120C. Preferred solvents and diluents include ketones, e.g. acetone, methyl ethyl ketone or cyclohexanone, nitriles, e.g. aceto-nitrile, esters, e.g. ethyl acetate, ethers, e.g. diethyl ether, tetrahydrofuran or dio~ane, sulfoxides, e.g. di-methyl sulfoxide, amides, e.g. dimethylformamide, dimethyl-acetamide or N-methylpyrrolidone, and sulfolane, as well as mixtures of these.
Examples of suitable bases, which may also be used as acid acceptors in the reaction, are alkali metal hydroxides, such as lithium hydroxide, sodium hydroxide or potassium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate, or an excess of 1,2,4-triazole, imidazole, pyridine or 4-dimethylaminopyridine. However, other conventional bases may also be used.
Preferred reaction accelerators are metal ha]ides, e.g. sodium lodide or potassium lodide, quaternary ammonium salts, e.g. tetrabutylammonium chloride, bromide or iodide or benzyltriethylammonium chloride or bromide~
25 and crown ethers, e.g. 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6 or dicyclohexanone-18-crown-6.
The reactions are carried out ln ~eneral at ~rom lO
to 120C, under atmospheric or superatmospheric pressure, continuously or batchwise.
Reaction a), Me denoting a metal atom, is carried out in the presence or absence of a solvent or diluent and with or without the addition of a strong inorganic or organic base or of a reaction accelerator, at from -10 to +120C.
Preferred solvents or diluents include amides, such as dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone and hexamethyl-1~7~L760

- 5 - O~Z. 0050/36402 phosphorotriamide, sulfoxides, e.g. dimethyl sulfoxide, and finally sulfolane.
Examples of suitable bases, whlch may also be used as acid acceptors in the reaction, are alkali metal hydrides, 05 such as llthium hydride, sodium hydride or potassium-hydride, alkali metal amides, such as sodium amide or potassium amide, and sodium tert.-butoxide, potassium tert.-butoxide, llthium-trlphenylmethyl, sodium-triphenyl-methyl, potassium-trlphenylmethyl, naphthalene-lithium, naphthalene-sodium and naphthalene-potassium.
Suitable solvents or diluents for reaction b) are polar organic solvcents, such as nitriles, e.g. aceto-nitrile, sulfoxldes, e.g. dimethyl sulfoxide, formamldes, e.g. dimethylformamide, ketones, e.g.acetone, ethers, e.g.
diethyl ether or tetrahydrofuran, and in particular chloro-hydrocarbons, e.g. methylene chloride and chloroform.
The reaction is carried out in general at from O to 100C, preferably from 20 to 80C. Where a solvent is present, the reaction is advantageously carried out at the boiling point of the particular solvent.
In carrying out process b), about 1 mole of carbonyl--bis(1-(1,2,4-triazole)) or carbonyl-bis(l-imidazole) or preferably about 1 mole of sulfonyl-bis(1-(1,2,4-tri-azole)) or sulfonyl-bis(1-imidazole) i5 employed per mole of the compound of the formula II where L i8 OH, or the stated sulfonyl compound is produced in sltu.
The resulting compounds of the ~ormula I are isolated by a conventiona~ method, purifled lf required and, lf desired, converted with an acid to a salt, or with a metal salt to a complex.
The starting compounds of the formula II, in which L
is a leaving group which can be substituted nucleo-philically, can be prepared, using a method of synthesis which is known ln principle, by reacting a compound of the formula II where L is OH with a halide carrier, such as hydrogen chloride, hydrogen bromide, thionyl chloride, thionyl bromide~ acetyl bromide, phosphorus tribromide or ~:717~0

- 6 - O.Z. 0050/36402 the phenylphosphine-bromlne complex or sulfonyl chlorldes, such as methane-, trifluoromethane-, nonafluorobutane-, 2,2,2-trifluoroethane-, 4~methylbenzene-, 4-bromobenzene-, 4-nitrobenzene- or benzenesulfonyl chloride, ln the pre-05 sence or absence of an inert solvent and of an organic orinorganic base, where the latter may also serve as the solvent (Houben-Weyl-M~ller, Methoden der organlschen Chemie, Vol. 5/3, Stuttgart 1964, page 760 et seq.;
Vol. 5~4, Stuttgart 1960, page 354 et seq.; Vol. 9, Stutt-gart 1955, pages 388 and 663; and J. org. Chem. 35 (1970),3195)-Hydroxymethylcycloalkanes of the formula II where Lis OH are obtained ln accordance with the following dia-gram:

~'~7~766~

_ 7 - O.Z. 0050/36402 C ~ O

S ~ - J

~1 2~ ~7 ~ \c I

~ ca\ .

C~
J
E E

~L~7~760 - 8 - o.z. oo50/36402 Process A
Nitriles of the formula V where R is CN can be sub-~ected to solvolysis under acidic or alkaline conditlons at from 20 to 120C in the presence of a solvent to give 05 the corresponding carboxylic acid derivatives V in which R
is not CN (e.g. R=COOH~, these being converted by a con-ventional method to the alcohols II, where L is OH, by reduction with a complex hydr~de, e.g. lithium alumlnum hydride or sodium borohydride, in the case o~ an an-1~ hydride, or with hydrogen in the presence of a catalyst,under atmospheric or superatmospheric pressure, by a multistage (Processes Cl, C2) or single-sta~e (Process C3) procedure.
Process B
The nitrile V in which R is CN can be redu~ed with dlisobutyl aluminum hydride (Synthesis 1975, 617) to the aldehyde VII (R=CHO) which can be further reduced with a complex hydride, e.g. sodium borohydride or lithium aluminum hydride, or with hydrogen in the presence of a catalyst (cf. C2) to give the alcohol II in which L is OH.
The cycloalkylcarboxylic acid derivatives V, in which D and E are each hydrogen, are prepared by a conventional method, by bisalkylation of a carboxylic acid derivative VIII with a bifunctional compound IX in which L is a leavlng group which can be substituted nucleophilically.

VIII ~ (C/2) ~ C~ ) L IX V -(D,~

This reaction is preferably carried out under phase--transfer conditions (Rocz. Chem. 40 (1966), 1647 and Przen. Chem. 46 (1967), 393), but can also be carried out ~7~760 - 9 - O.Z. 0050/36402 in the presence of a strong base, for example a metal hydride or metal amide (J. Amer. chem. Soc. 69 (1947), 2902).
Cyclopropyl derivatives of the formula XI, where A
05 and B have the above meanings, R is a nitrile or ester group or an aldehyde group which may or may not be acet-alized and D and E are each hydrogen, may furthermore pre-ferably be obtained by cyclopropanation of ~,~-unsaturated nitriles or aldehyde or carboxylic acid derlvatives of the formula X, where A, B and R have the above meanings.

li:
> D

~I
Trimethylsulfoxonium salts are particularly suitable for the reaction, these being reacted with an ~ un-saturated carboxylic acid derivative X in an inert solventin the presence of a strong base, for example an alkali metal alcoholate, such as potasslum tert.-butylate. If a stereochemlcally pure olefin X ls used as the starting material, the pure diastereomeric cyclopropane is obtained (Z. Naturforsch. 18 [b] (1976), 976; and Chem. Ber. 98 (1965), 3721. Other processes for the preparation o~ cyclo-propanes by lntramolecular reaction or by reactlon of olefins wlth reagents whlch trans~er methylene groups, e.g. diazomethane, or by the Slmmons-Smlth method have been described (Houben-~eyl-M~ller, Methoden der orga-nlschen Chemle, Stuttgart 1971, Vol. 4/3, pages 32-148).
Cyclopropyl derivatlves of the formula XI, where A
and B have the above meanings, R ls a nitrile or ester group or an aldehyde group which may or may not be acetalized, and D and E independently of one another are each hydrogen or halogen, with the exception of those com-~L27~7{;0 - 10 - O.Z. 0050f36402 pounds in which D and E are simultaneously hydrogen, are obtained by reacting an ~ unsaturated aldehyde or carb-oxylic acid derivative X with a mono- or dihalocarbene, which as a rule is produced in situ by well-known pro-05 cesses (cf. for example Houben-Weyl-Muller, Methoden der organischen Chemie, Stuttgart 1971, Vol. 4/3, page 150 et seq.) or by a reaction carried out under phase-transfer catalysis (Llebigs Ann. 758 (1972), 148; Synth. Commun. 3 (1973), 305; and Tetrahedron 33 (1977), 363).
The following examples and directions illustrate the preparation of the novel compounds and their precursors.

1-(4-chlorophenyl)-1-(1,2,4-triazol-1-ylmethyl)-cyclo-15 butane (compound 1) 4.1 g of 1,2,4-triazole in 15 ml of N,N-dimethylfor-mamide were added to o.66 g of sodium hydride (80%
strength dispersion in mlneral oil) in 15 ml of N,N-di methylformamide at room temperature, under nitrogen. The 20 mixture was stirred for 30 minutes, after which 5.1 g of [1-(4-chlorophenyl)-cyclobut-1-yl]-methyl methanesulfonate in 15 ml of N,N-dimethylformamide were added dropwise, and the mixture was stlrred for 24 hours at room temperature and for 12 hours at 100C, then hydrolyzed with water and 25 extracted with ethyl acetate. 2.6 g of 1-(4-chlorophenyl)--1-(1,2,4-triazol-1-ylmethyl)-cyclobutane of meltln~; point 124-125C were obtained.
Preparation of the startlng material 15.6 g of 1-(4-chlorophenyl)-cyclobutane-1-carboxylic 30 acid, dissolved in 80 ml of absolute tetrahydrof`uran, were added dropwise to 7.68 g of lithium aluminum hydride in 250 ml of absolute tetrahydrofuran at room temperature, under nitrogen. The mixture was stirred for 1 hour under reflux and for 12 hours at room temperature, after which 35 lt was hydrolyzed with ice water, acidified with 10%
strength sulfuric acid and extracted with methylene

7 ~ 7 ~ 0 - 11 - O.Z. 0050~36~02 chlorlde. The extract was dried and the solvent was eva-porated to give 11.5 g of 1-(4-chlorophenyl)-1-hydroxy-methylcyclobutane of meltlng point 53-54C. 11.4 g of 1-(4-chlorophenyl)-1-hydroxymethylcyclobutane were 05 dissolved ln 105 ml of pyridine in the absence of moisture, and 7.8 g of methanesulfonyl chlorlde were added dropwise at 0-5C. Stirring was continued for 2 hours at thls temperature, after which the suspenslon was poured into ice water and extracted with methylene chloride, the combined organic phases were washed with water and dried, the solvent was removed and the product was recrystallized from cyclohexane. 5.1 g of [1-(4-chlorophenyl)-cyclo-but-l-yl]-methyl methanesulfonate of melting point 66-70C were obtained.

1-(4-chlorophenyl)-1-(imidazol-1-ylmethyl)-2-(4-biphenyl-yl)-cyclopropane hydrochloride (compound 38) 4.8 ml of methanesulfonyl chloride in 15 ml of methylene chlorlde were added dropwise to 16.5 g of 1-(4-chlorophenyl)-1-hydroxymethyl-2-(4-biphenylyl)-cyclo-propane in 150 ml of methylene chloride and 8.6 ml of tri-ethylamine at 20C. The mixture was stirred ~or 2 hours at room temperature, after which it was washed with dilute sodium bicarbonate solutlon and then with water and dried over magnesium sulfate, and the solvent wa~ distilled o~
under reduced pressure.
The solid residue was taken up in 50 ml of dimethyl sulfoxide, 1 g of potassium iodide was added and the mixture was added dropwise, at room temperature and under nitrogen, to a solutlon prepared from 4.1 g of imidazole and 2.4 g of sodlum hydride (80% strength dispersion in mineral oil) in 150 ml of dimethylformamide at 15C.
Stirring was carried out for 24 hours at room temperature, after which the reaction solution was poured into water and extracted with methylene chloride, the organic phase ~271760 ~ 12 - 0.~. 0050~36402 washed with water and dried over magnesium sulfate, and the solvent was evaporated off to give a syrup. m is was taken up in warm acetone, and a saturated solution of hydrogen chloride in dilsopropyl ether was added. 14.5 g 05 of 1-(4-chlorophenyl)-1-(imidazol-1-ylmethyl)-2-(4-bi-phenylyl)-cyclopropane crystallized out as the monohydro~
chloride; mp. 212-214C.
Preparation of the starting materials a) 48 g of 4-phenylbenzaldehyde and 39.9 g of 4-chlorobenzyl cyanide were stirred with 3 g of sodium methylate in 400 ml of ethanol for 1 hour at 30C. The precipitate formed was filtered off under suction and washed with a little isopropanol and then with petroleum ether. 82.5 g of Z-1-(4-chlorophenyl)-2-(4-biphenylyl)-acr ylonitrile of melting point 194-198C were obtained.
b) 34 g of potassium tert.-butylate were introduced, a little at a time, lnto a solution of 80 g of 1-(4-chloro-phenyl)-2-(4-biphenylyl)-acrylonitrile and 80 g of tri-methylsulfoxonium iodide in 750 ml of dimethyl sulfoxide, while cooling at 15C and under nitrogen. Stirring was continued for 1 hour at room temperature, after which the mixture was poured onto water and extracted with methylene chloride, the organic phase was washed with water and dried over magnesium sulfate, the solvent was evaporated off under reduced pressure and the resldue was taken up ln warm ethanol. 78.6 g of 1-(4-chlorophenyl)-2-(4-biphenyl-yl)-cyclopropyl cyanide of melting point 129-131C
crystallized from this solution.
c) 75 g of this product were taken up in a mixture of 500 ml of dlethyl ether and 100 ml of tetrahydrofuran, and 300 ml of a 1.2 molar solution of diisobutyl aluminum hydride in toluene were added dropwise at from 0 to 4C, under nitrogen. The mixture was stirred for 1.5 hours at room temperature and then poured onto 2 liters of 10%
strength aqueous tartaric acid solution, a further 2 liters of diethyl ether were added, and the organic ~7~76(~

- 13 - O.Z. 0050~36402 phase was separated off, washed with water and dried over magnesium sulfate. On evaporating down the solution, a precipitate formed; this was filtered off under suction, washed wlth water and a little petroleum ether and re-05 crystallized from methanol to give 73 g of 1-t4-chloro-phenyl)-2-(4-biphenylyl)-cyclopropylcarbaldehyde of melting point 188-190C.
d) 73 g of this product ln a mixture of 1 liter of methanol and 1 liter of methylene chlorlde were stirred with 6 g of sodium borohydride for 2 hours, after which the solvent was evaporated off under reduced pressure,the residue was taken up in methylene chloride, the solution was washed with water, dried over magnesium sulfate and evaporated to dryness, and the residue was recrystallized from toluene to give 68 g of 1-(4-chlorophenyl)~l-hydroxy-methyl-2-(4-biphenylyl)-cyclopropane of melting point 168-170C.
The compounds in the following table for which a melting point is given were prepared analogously. The other compounds may be prepared analogously.

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E~ v 1 - 20 - O.Z. 0050/36402 The novel compounds, and their salts and metal com-plex compounds, have an excellent action on a broad spec-trum of plant-pathogenic fungi, especially from the Ascomy-cetes and Basidiomycetes classes. Some of them have a 05 systemic action and may be used as soil and foliar fun-gicides.
The fungicidal compounds are of particular interest for combating a large number of fungi in various crops or their seed, especially wheat, rye, barley, o~ats, rice, Indian corn, cotton, soybeans, coffee, sugarcane, fruit, ornamentals in horticulture, and vegetables, such as cucum-bers, beans and Cucurbitaceae.
The novel compounds are particularly suitable for ccmbating the following diseases: Erysiphe graminis in cereals, Erysiphe cichoriacearum in Cucurbitaceae, Podosphaera leucotricha in apples, Uncinula necator in grapes, Puccinia species in cereals, Rhizoctonia solani in cotton, Ustilago specles in cereals and sugarcane, ~enturia inaequalis (apple scab), Septoria nodorum in wheat, Botrytis cinerea in grapes and strawberries, Cerco-spora musae in bananas, Pseudocercosporella herpo-trichoides in wheat and barley, Hemileia vastatrix in coffee, and Piricularia oryzae in rice.
The compounds are applied by spraying or dusting the plants, or treating the seed with the active ingredients.
Application may be effected before or after infection of the plants or seed by the flm~l.
The novel active lngredients can be converted into the conventional ~ormulatlons, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application depends entirely on the purpose for which the agent is to be used; at all events, it should ensure a fine and uniform distribution of the active ingredients.
The formulations are prepared in the conventional manner, for example by diluting the active ingredient with sol-vents and/or carriers, ~ith or without the addition of 7 ~ 0 - 21 - O.Z. 0050/36402 emulsifiers and dispersants and, where water is used as the dlluent, wlth or without an organic auxiliary solvent.
Suitable auxiliaries are, essentially, solvents, for example aromatics, e.g. xylene and benzene, chloroaro-05 matics. e.g. chlorobenzene, paraffins, e.g. petroleum frac-tions, alcohols, e.g. methanol and butanol, amines, e.g.
ethanolamine, and dimethylformamide and water; carriers, for example natural rock powders, e.g. kaolin, alumina, talc and chalk, and synthetic rock powders, e.g. highly disperse silica and silicates, emulsifiers, for example non-ionic and anionic emulsifiers, e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates, and dlspersants, for example lignin, sulfite waste liquors and methylcellulose.
m e fungicidal agents generally contain from 0.1 to 95, preferably from 0.5 to 90, wt% of active ingredlent.
The application rates depend on the effect desired, and range from 0.1 to 3 kg of active ingredient per hectare~ or more.
m e novel compounds may also be used for protecting materials. For instance the following wood- and finish--discolorlng fungl, soft-rot fungl and wood-destroylng f mgl may be combatted wlth the agents according to the inventlon: Pullularla (Aureobasidium) pullulans, Sclero-phoma pityophila, Ceratocystls spec., Paecilomyces variotii, Hormiscium spec., Stemphylium spec., Phoma violacea, Cladosporium herbarum, Trlchoderma vlrlde, Chaetomium globosum, Hul-nicola gri~ea, Merulius lacrlmans, Coniophora puteana, Lentinus lepideus, Lenzltes trabea, Polystictus versicolor, Stereum hirsutum, and Fomes annosus.
The novel active lngredients may also be employed for protecting materials in formulations, such as solutions, emulsions, pastes and oil disperslons. The formulations generally contaln from Ool to 95, and preferably from 0.25 to 50, wt% of active ingredient. The application rates 7 ~ 7 ~

- 22 - O.Z. 0050/36Ll02 depend on the effect desired, and range from 0.5 to 8 g of active lngredient per m2 of wood surface to be protected, or from 50 to 4~000 g~m3 of wood. Paints contain for instance from 0.5 to 5 wt% of active ingredient. To 05 protect wood-base materials, the active ingredients may be added to the adhesive as an emulsion, or mixed with ~t, for example in amounts of from 2 to 6 wt%. The active ingredients are applied to the wood for example by painting, spraying, immersion, pressure impregnation, or dlffusion. To prepare water-repellant finishes, suitable substances such as zinc stearate, aluminum stearate and waxes may be added to the oily wood preservatives. To achieve color effects, inorganic or organic pigments may be incorporated lnto the formulations.
The agents and the ready-to-use formulations made therefrom, e.g., solutions, emulsions, suspensions, powders, dusts, pastes or granules, are applied in known manner, for example by spraying, atomizing, dusting, scattering, seed-disinfecting, or watering.
I. 20 parts by weight of the compound of Example 2 are well mixed with 3 parts by weight of the sodlum salt of diisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mtxture ln water, a spray liquor is obtained.
II. 3 parts by weight of the compound of Example 6 are intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the actlve ingredient.
III. 30 parts by weight of the compound of Example 18 are intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which have been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

7 ~

- 23 - O.Z. 0050/36402 IV. 40 parts by weight of the compound of Example 19 are intlmately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable 05 aqueous dispersion. Dilution in water gives an aqueous dis persion.
V. 20 parts of the compound of Example 21 are intimately mlxed wlth 2 parts of the calcium salt of dodecylbenzene-sulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acld-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.
VI. 90 parts by weight of the compound of Example 17 are mixed with 10 parts by welght of N-methyl-alpha-pyrroli-done. A solution ls obtalned which ls suitable for applica-tion in the form of very flne drops.
VII. 20 parts by weight of the compound of Example 18 are dissolved in a mlxture consistlng of 80 parts by welght of xylene, 10 parts by welght of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of olelc acid-N-monoethanol-amide, 5 parts by welght of the calcium salt of dodecyl-benzenesulfonic acld, and 5 parts by weight of the adduct of 40 moles of ethylene oxlde and 1 mole of castor oil. By pouring the solution into water and uniformly distrlbuting it therein, an aqueous dlspersion is obtained.
VIII. 20 part~ by welght of the compound Or Example 21 are dlssolved ln a mlxture conslstlng o~ 40 parts by welght of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of lsooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. ~y pouring the solution into water and finely dlstri-buting lt thereln, an aqueous dlsperslon ls obtained.
IX. 10 parts by weight of the compound of Example 24, 20 parts by weight of polyoxyethylene sorbitan mono-7 ~ 7 ~ `

- 24 - O.Z. 0050~36402 laurate, 20 parts by weight of methanol and 50 parts by weight of water are stlrred to give a solution containing 10 wt% of the active ingredlent. More dilute solutions may be prepared by addlng water.
05 X. To prepare a solvent-containing wood preservative containing 1% of active ingredient, 1 part (by welght) of compound 17 is dissolved~ with slight heating, in 55 parts of a gasoline fraction rlch in aromatics. 10 parts of an alkyd resin are then added, and the mixture made up to 100 parts, at room temperature, with mineral spirit.
Solvent-containing wood preservatives containing up to 5 wt% of active ingredient may be prepared in a similar manner.
In these application forms, the agents according to the invention may also be mixed and applled with other active ingredients, e.g., herbicides, lnsecticides, growth regulators, other fungicides and fertilizers. When mixed with other fungicides~ the spectrum of fungicldal action is in many cases increased. With a number of these fungi-cidal mixtures, synergistic effects also occur, i.e., theeffectiveness of the combination product is greater than the combined ef'fects of the individual components.
Examples of fungicides which may be combined with the active ingredients according to the invention are as follows:
sulfur dithiocarbamate~ and derlvatives thereo~, such as ferric dimethyldithiocarbamate zinc dimethyldithiocarbamate manganese ethylenebisdithiocarbamate zinc ethylenebisthiocarbamate tetramethylthiuram disulfide manganese-zinc ethylenediamine-bisdithiocarbamate zinc-(N,N'-propylene-bisdithiocarbamate) ammonia complex of zinc-(N,N'-ethylene)-bisdithiocarbamate and ~71760 - 25 - O.Z~ 0050~36402 N,N'-polyethylene-bls-(thiocarbamoyl)-disulflde ammonla complex o~ zinc-(N,N'-propylene-bisdithio-carbamate) and 05 N,N'-polypropylene-bis-(thiocarbamoyl)-disulfide nitro derivatives, such as dinitro~ methylheptyl)-phenylcrotonate 2-sec-butyl-4,6-dinitrophenyl-3,5-dimethylacrylate 2-sec-butyl-4,6-dlnitrophenylisopropylcarbonate diisopropyl 5-nitroisophthalate heterocyclic structures, such as 2-heptadecyl-2-lmidazoline acetate 2~4-dichloro-6-(o-chloroanllino)-s-triazine 0,0-diethylphthalimidophosphorothionate 5-amino-1-[bis-(dimethylamino)-phosphynyl]-3-phenyl-1,2,4--triazole 2,3-dicyano-1,4-dlthiaanthraquinone 2-thlo-1,3-dithlo-(4,5-b)-quinoxaline methyl l-(butylcarbamoyl)-2-benzimidazole carbamate 2-methoxycarbonylaminobenzimldazole 2-[~uryl-(2)]-benzimidazole 2-rthiazolyl-(4)]-benzlmidazole N-(1,1,2,2-tetrachloroethylthlo)-tetrahydrophthalimide N-trichloromethylthiotetrahydrophthalimide N-trichloromethylphthalimide N-dichloro~luoromethylthio-N',N'-dimethyl-N-phenyl--sulfuric acid diamide 5-ethoxy-3-trlchloromethyl-1,2~3-thiadlazole 2-thiocyanomethylthlobenzthiazole 1,4-dichloro-2,5-dimethoxybenzole 4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone pyrldlne-2-thlo-1-oxlde

8-hydroxyqulnollne and its copper salt 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin 2,3-dlhydro-5-carboxanllido-6-methyl-1,4-oxathlin-4,4-di-oxlde ~2~7~(3 ~ 26 - O.Z. 0050~36402 2-methyl-5,6-dihydro-4-H-pyran-3-carboxanilide 2-methyl-furan-3-carboxanilide 2,5-dimethyl-~uran-3-carboxanilide 2,4,5-trlmethyl-furan-3-carboxanilide 05 2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide N-cyclohexyl-N-methoxy~2,5-dimethyl-furan-3-carboxamide 2-methyl-benzoic acid anilide 2-iodobenzoic anilide N-formyl-N-morpholine-2,2,2-trichloroethylacetal piperazlne-1,4-diylbis-(1-(2,2,2-trlchloroethyl)-formamide l-(3,4-dichloroanllino)~ ormylamino-2,2,2-trichlorethane 2,6-dimethyl-N-trldecyl-morpholine and its salts 2,6-dimethyl-N-cyclododecyl-morpholine and its salts N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-di-methylmorpholineN-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyl]--l-H-1,2,4-triazole l-t2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-yl--ethyl]-1-H-1,2,4-triazole N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imldazol--ylurea 1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)--2-butanone 1-t4-chlorophenoxy)-3,3-dimethyl-1-(1~l-1,2,4-triazol-1-yl) -2-butanol alpha-(2-chlorophenyl)-alpha-(4-chlorophenyl)-5-pyrimldlne-methanol 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine bls-(p-chlorophenyl)-3-pyridinemethanol 1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene 1,2-bis-(3-methoxycarbonyl)-2-thioureido)-benzene and various fungicides, such as dodecylguanldine acetate 3-[2-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutar-imlde ~ll2717~i0 - 27 - O.Z. 0050/36402 hexachlorobenzene D,L-methyl-N-(2,6-dimethylphenyl)-N-(2-furoyl)-alanate methyl D,L-N-(2,6-dimethylphenyl)-N-(2-methoxyacetyl)--alanate 05 N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyro-lactone methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate 5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxa-zolidlne 3-(3,5-dichlorophenyl)-5-methyl-5-methoxymethyl-1,3-oxa-zolidln-2,4-dione 3-(3,5-dichlorophenyl)-1-isopropyl-carbamoylhydantoin N-(3,5-dlchlorophenyl)-1,2-dimethyl-cyclopropane-1,2-di-carboximide.
To increase the spectrum of action - particularly with regard to combatting wood-destroying or wood- or finlsh-discoloring fungi -, the active ingredients may be combined wlth the following compounds:
organotin compounds, such as tributyltin oxide and tri-butyltin benzoate methylene bis-thiocyanate alkyl-dimethyl-benzylammonium chloride cetyl-pyridlnium chloride chlorinated phenols, such as tetra- and pentachlorophenol tetrachloroisophthallc acid dinitrile 2-halobenzolc acid anilide N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide N,N-dimethyl-N'-phenyl-(N'-fluorodichloromethylthio)--sulfamide N-phenyl-N,N'-dimethyl-N'-fluorodichloromethyl-thio-sulfonyl-diamide methyl benzimidazole-2-carbamate 2-thiocyanomethyl-thiobenzothiazole copper naphthenate copper 8-oxyquinoline 12~

- 28 - O.Z. 0050/36402 alkali metal and metal salts of N'-hydroxy-N-cyclohei~yl-diazenium oxide.
For the following experirnents, prior art fungicidal active ingredients were used for comparison purposes, 05 viz., 1-(2,4-dichlorophenyl)-2-(imidazolyl)-ethan-1-ol (comparative compound A), disclosed in French 2,249,616, (2,4-dichlorophenyl)-1,2,~-triazol-1-yl methyl ketone (comparative compound B) and tert.-butyl-1,2,4-triazol-1--yl methyl ketone (comparative agent C) disclosed in 10 German Laid-Open Application DE-OS 24 31 407.
Experiment 1 Action on wheat mildew Leaves of pot-grown wheat seedlings of the "Jubilar"
variety were sprayed with aqueous liquors, the solids of 15 which consisted of 80~ (by weight) of active ingredient and 20% of emulsifier, and dusted, 24 hours after the sprayed-on layer had dried, with pores of wheat mildew (Erysiphe graminls var. trltici). The plan'cs were then placed in a greenhouse at 20 to 22C and 75 to 80%
20 relative humidity. The extent of mildew spread was determined after 7 days.
The results of the experiment show that novel active lngredlents 1, 3, 6, 17, 18, 19, 20, 21, 22, 28, 30 and 35, applied for example as 0.006 or 0.0015% suspensions, ~5 had a better fungicidal action (e.g~, 90%) than prior art compounds A and C (e.g., 70%).
Experiment 2 Action on leaf rust of wheat Leaves of pot-grown wheat seedlings of the "Jubilar"
30 variety were dusted with spores of rust (Puccinia recon-dita~. The pots were then placed in a high humidlty (90-95%) chamber at from 20 to 22C for 24 hours. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue. The infected plants were 35 then sprayed to run-off with aqueous liquors, the solids comprising 80~ of active lngredlent and 20% of emulsifier.

7~0 - 29 - O.Z. 0050/36402 After the spray coating had drled, the test plants were set up in a greenhouse at from 20 to 22C and from 65 to 70% relative humidity. After 8 days, the degree of develop-ment of the rust fungi on the leaves was determined.
05 The results of this experiment show that novel active ingredients 1, 6, 17, 18, 19, 20, 21, 22, 28, 29, 30, 35, 37 and 38, applled for example as 0.025 or 0~06% suspensions, had a better fungicidal action (e.g., 97%~ than prior art compounds A, B and C (e.g., 70%).
Experiment 3 Action on Botrytis cinerea in pimientos Pimiento seedllngs of the "Neusiedler Ideal Elite"
variety were sprayed, after 4 to 5 leaves were well developed, to runoff with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% of emulsi-fier. After the sprayed-on layer had dried, the plants were sprinkled with a conidial suspension of the fungus Botrytis cinerea, and placed at 22 to 24C in a chamber of high humidity. After 5 days, the disease had spread to such a great extent on the untreated plants that the necroses covered the ma~or portion of the leaves.
The results of thls experiment show that novel actlve ingredients 6, 17, 19, 20, 22, 27, 29, 30, 31, 33, 38 and 42, applied for instance as 0.05% suspensions, had a better funglcidal action (e.g., 97%) than prlor art compounds A, B and C (e.g., 70%).
Experiment 4 Action on cucumber mildew The leaves of pot-grown cucumber seedllngs of the "Chinesische Schlange" variety were sprayed at the 2-leaf stage with a spore suspension of cucumber mlldew (Erysiphe cichoracearum). After about 20 hours, the plants were sprayed to runoff with aqueous emulsions consistlng (dry basis) of 80% of active ingredient and 20% of emulsifier.
After the sprayed-on layer had dried, the plants were set up in the greenhouse at from 20 to 22C and a relative 127~L7C~0 _ 30 _ o.z. 0050/36402 humidity of 70 to 80%. To assess the action of the novel compounds, the extent of fungus spread was determined after 21 days.
The results of this experiment show that novel active 05 ingredients 3, 4, 19, 20, 21, 22, 25, 27, 28, 29, 30, 31, 32, 33, 35, 37, 38, 39 and 41, applied for example as 0.025% suspensions, had a very good fungicidal action (e.g., 97%).
Experiment 5 Action on soft-rot and mold fungi The active ingredients were dissolved in acetone and added, in amounts of 40 ppm, tG a liquid 50% malt extract agar. The agar was poured into Petri dishes and allowed to solidify. The funglcide-containing nutrient agar was then centrally inoculated with Chaetomiwm globosum, a fungus which causes mold and soft rot, and Trichoderma viride, a green wood mold. After the dishes had been incubated for 5 days at 25C, the development of the fungus colonies on the nutrient medium was assessed against a control (no active lngredient added).
m e results of this experiment show that novel active lngredients 19, 20, 21 and 22, applied for instance at a rate of 40 ppm, had a very good fungicidal action (e.g., 97%).
Experiment 6 Fungicidal actlon on wood-destroyln~ fun~i To determlne the activity on the wood-destroying fungi Coniophora puteana and Polystictus versicolor, pine sapwood blocks measuring 50x25x15 mm were coated at a rate of 100 g/m2 of wood surface with oily wood preservative formulatlons containlng 1~ of actlve ingredient. After the treated blocks had been stored for 4 weeks, they were placed, together wlth untreated blocks, ln glass dlshes contalnlng the fungi Coniophora puteana or Polystictus versicolor in a nutrient agar. m e dishes were then incubated in an atmospheric laboratory at 22c and a 2 7 ~

- 31 - O.Z. 0050/36402 relative humidity of 70%. After 3 months, the fungus mycelium attaching to the blocks was removed and the blocks were dried. The degree of wood destruction was then ascertained.
05 The results obtained show that novel active ingre-dients 17, 18, 19, 20, 21 and 22, applied for example as 1% formulatlons, had a very good fungicidal action (e.g., 100%).

Claims (9)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. An azolylmethylcycloalkane of the formula:

(I) where:
A and B are identical or different and are each unsubstituted or fluoro-substituted alkyl of 1 to 4 carbon atoms, naphthyl, furanyl, thienyl, pyridyl, biphenyl or phenyl, where the phenyl radical can be substituted by halogen, nitro, alkyl, alkoxy or haloalkyl, each of 1 to 4 carbon atoms, phenoxy or phenylsulfenyl, and D and E are identical or different and are each hydrogen or halogen, Z is CH or N, m can be 1, 2, 3 or 4 anc n can be 0, 1 or 2, its addition salts with acids, and metal complexes.

2. 1-(4-Chlorophenyl)-1-(imidazol-1-ylmethyl)-2-phenyl-cyclopropane hydrochloride.

3. 1-(4-Chlorophenyl)-1-(1,2,4-triazol-1-ylme-thyl)-2-phenyl-cyclopropane hydrochloride.

4. 1-(4-Chlorophenyl)-1-(imidazol-1-ylmethyl)-2-(4-chlorophenyl)-cyclopropane.

5. A process for the manufacture of an azolylmethylcycloalkane of the formula (I) as defined in claim 1, wherein a cycloalkane of the formula:

(II) where A, B, D, E, m and n have the meanings given in claim 1 and L is a leaving group capable of nucleophilic substitution, is reacted a) with a compound of the formula (III):

(III) where Me is a hydrogen atom or a metal atom and Z has the meanings given in claim 1, in an inert solvent and - when Me is hydrogen - in the presence of a base, or b) with a compound of the formula (IV):

(IV) where Z has the meanings given in claim 1 and Y is carbon or sulfur, in an aprotic solvent, and the compound obtained is, if desired, converted into an addition salt with an acid, or a metal complex.

6. A process for combatting fungi, wherein an azolylmethylcycloalkane of the formula (I) or a plant-tolerated addition salt thereof with an acid, or a metal complex thereof is applied onto the fungi, or the materials, areas, plants or seed threatened by fungus attack.

7. A process for combatting fungi, wherein a compound as defined in claim 2, 3 or 4 is applied onto the fungi, or the materials, areas, plants or seed threatened by fungus attack.

8. A fungicidal composition comprising an effective amount of an azolylmethylcycloalkane of the formula (I) as defined in claim 1 or a plant-tolerated addition salt thereof with an acid, or a metal complex thereof, in admixture with an agriculturally acceptable diluent or carrier.

9. A fungicidal composition comprising an effective amount of a compound as defined in claim 2, 3 or 4 or a plant-tolerated addition salt thereof with an acid, or a metal complex thereof, in admixture with an agriculturally acceptable diluent or carrier.