DD223350A5 - METHOD OF CONTROLLING PHYTOPATHOGENIC FUNGI - Google Patents

Abstract

The invention relates to novel α- (aryl (alkylene) m) -α (CR1R2- (CHR3) n -R4) -1H-1,2,4-triazole and -1H-imidazole-1-ethanol compounds in which m is 0 or 1, n is 0, 1 or 2, R 1 is a hydrocarbon radical more closely defined in the description and R 4 is a C 3-7 cycloalkyl group optionally substituted by C 1-5 alkyl and R 2 and R 3 are as defined in the description, and Aether and esters of these ethanols, the preparation of these compounds, their use as a fungicide in agriculture, as well as preparations containing these new compounds.

Description

-7-

AP A Ol N / 265 725 64 147 12

Field of application of the invention

The invention relates to fungicidal preparations containing as active ingredient α, α-disubstituted-1H-azole-1-ethanols or more precisely, α-aryl and α-aralkyl-α- (cycloalkyl-alkyl) -H-azole-1-ethanols , which can be used because of their fungicidal activity in agriculture.

Well-known technical solutions

GB-PS 2064520A discloses a-phenyl-a- (C ₃ _g cycloalkyl-C _{1 3} alkyl) - Hl-2,4-triazol-l-ethanols having fungicidal activity. According to this patent are the (cycloalkyl-alkyl) Meanings preferably C, _fi cycloalkyl-methyl; specific examples are given for the a -cyclohexyl and a-cyclopentylmethyl meanings.

Object of the invention

It is an object of the invention to enrich the state of the art with new agricultural compounds.

Because of the invention

The invention is based on the object, methods for controlling phytopathogenic fungi using new a-aryl and a-aralkyl-a- (cycloalkyl-alkyl) -lH-azol-l-ethanols, as well as fungicidal agents such new compounds included, develop.

It has been found that α-aryl or a-aralkyl-a- (cycloalkyl-alkyl) -

AP A 01 N / 265 725'7 " ^la " 64 147 12

IH-azole-1-ethanols wherein the alkyl group linking the cycloalkyl group to the ethanol radical is substituted or branched at the carbon atom adjacent to the C (OH) group have surprisingly favorable fungicidal properties, especially when the cycloalkyl group is cyclopropyl.

The invention thus relates to the use of novel a-Caryl (alkylene)] -

) -R ₄ I-IH-I, 2,4-triazole and -IH-imidazole-1

ethanols

Ri is unsubstituted or substituted by halogen, C-,, alkoxy, phenyl-C-,., Alkylthio or phenylthio substituted C, -alkyl, wherein any phenyl groups by C, cAlkyl, halogen, halogenated C. j-alkyl, C -, -.rAlkoxy or halogenated C,, alkoxy may be substituted:

for alkenyl or C _? , Alkynyl, unsubstituted or substituted by halogen: or

for cycloalkyl, unsubstituted or substituted by C-, C-alkyl:

or - '"*

phenyl, unsubstituted or substituted by substituents of the series halogen and C-, c-A

stands,

AP A Ol N / 265 725 64 147 12 - 2 -

R ₂ and R _{3 are} independently of one another, represent H or one of the meanings given for R,

wherein R ₁ and R ₂ may be linked together to form a C _{3 to} C ₇ cycloalkyl radical, m is 0 or 1, and

η is 0.1 or 2, and R ₄ represents a C _3-7 CyClOaIkylgruppe, unsubstituted or substituted by C | ₅ alkyl substituted _,

and ethers and esters of these ethanols (hereinafter referred to as "inventive compounds") as a fungicide.

The aryl part in the α-Caryl (alkylene) radical of the compounds according to the invention is suitably an optionally substituted aromatic hydrocarbon (for example naphthyl, preferably phenyl) or an optionally substituted heteroaromatic ring bonded via a ring carbon atom (for example a 5- or 6-membered ring) 1 or heteroatoms of the series 0, N and S, preferably furyl, thienyl and pyridyl).

Examples of particularly suitable a-Caryl (alkylene) _m ] groups are phenyl, benzyl or aC, gAlkylbenzyl, optionally mono- or disubstituted in the PhenyTrest by NO ₂ ; Halogen; optionally halogenated C, _g alkyl, C ₂ _j.Alkeny1, C ₂ _ ₅ alkynyl or Cj ^ alkoxy; optionally substituted phenyl or phenoxy. Further examples of particularly suitable a-aryl groups are the heteroaromatic radicals 3-pyridyl and also 2-thienyl and 2-furyl, optionally monosubstituted

tuier.t by halogen or lower alkyl (e.g., 5-Cl-2-thienyl and 5-tert-butyl-2-furyl).

-3- 130-3959

The α-Caryl (alkylene)! Group preferably means in the aromatic radical R, R and R ₇ substituted phenyl, benzyl or α-C, 1-alkylbenzyl, wherein R ₅ and R _{5 are the} same or different and are hydrogen ; Halogen; optionally halogenated C cAlkyl "C- (alkenyl, _C2 alkynyl or C-], .Alkoxy; optionally substituted phenyl or phenoxy; or represent the NCL group, and R ₇ is H, halogen or C.rAlkyl.

Susceptible C, -Alkylsubstituenten of the compounds according to the invention suitably contain 1 to 4, preferably 1 to 2, but especially 1 carbon atom. The same applies to substituents of the compounds according to the invention which contain such C 1-8 -alkyl groups.

Any cycloalkyl groups of the compounds according to the invention are in particular 3- to 5-membered, preferably 3-membered.

Any halogen substituents of the compounds according to the invention stand for F, Cl, Br or I.

Preferred C ₂ alkenyl and C ₂ alkynyl meanings of R, are CH ₂ -CH = CH ₂ and CH ₂ -C = CH; Examples of suitable halogenated derivatives thereof are in particular monohalogenated groups such as CHp-C = CCl and

Preferred C ₁ , alkenyl and C 1 -alkynyl-β meaning of R ₁ . and R- are CH = CHp, C = CH; Examples of suitable halogenated derivatives thereof are in particular monohalogenated derivatives such as CCl = CHp.

Examples of favorable phenyl substituents R and Rg are CH. ,, F, Cl, Br, I, CH ₃ O, CGH _5, CF ₃ O and C ₂ H _5, especially CH _3, C ₅ H _5, and preferably Cl. In general, these phenyl substituents are preferably in the 2,4-position (eg 2,4-diCl) or more preferably in the 4-position (monosubstituted).

Ry is preferably H

 η is preferably 0 or 1.

If the hydroxy group of the compounds according to the invention is etherified, these are e.g. C 1-6 alkylC 1-10 alkenyl, C 1-6 alkynyl or aralkyl ethers such as methyl, allyl, propargyl or benzyl ether.

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If the hydroxy group is esterified, these are e.g. Esters of aliphatic carboxylic acids, such as acetates.

The compounds according to the invention have 1 or more chiral centers

on. These compounds are generally in the form of the racemate, the

Diastereomerengemisches and possibly additionally the cis / trans mixture

receive. However, such mixtures may, if desired, either

completely or partially in the individual isomers or the desired

Isomer mixtures are separated by known or analogous to known methods.

A preferred class of compounds according to the invention are accordingly compounds of the formula I.

T _{R I}

^R 7 ₂

(CHR ₃ ) _n -R ₄

, wherein R ^, R ^, R ^, R ₄ . R5, Rg, R _7, m and η have the above meanings and Y is CH or N, and Rg is H or C, -alkyl,

and ethers and esters thereof.

The compounds of the invention may be in free basic form, in salt form, as an acid addition salt with an organic or inorganic acid, e.g. as the hydrochloride, or as the alkoxide, e.g. as a sodium ethoxide, and as a metal complex, e.g. with a metal ion of the groups Ib, Ua, Hb, VIb, VIIb and VIII of the Periodic Table, such as Cu (II) or Zn (JIj and with an anion such as chloride, sulfate and nitrate exist.

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The compounds according to the invention can be prepared by reacting a compound of the formula II

wherein M is hydrogen, a metal or a trialkylsilyl group, and Y has the above meaning,

with the corresponding 2-CAryl (alkylene ^ -S-CCR ^ -tCHR ^ R ^ -oxirane compound (in which R-, R ₂ , R- ,, R *, m and η have the above meanings) or a reactive derivative thereof, and any subsequent etherification or esterification of the thus-obtained ethanol compounds.

Accordingly, the compounds of the formula I are obtained by reacting a compound of the formula II with a compound of the formula III

6 wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _g> R ₇ , r _{m and} d η above meanings

own, or

with a reactive derivative thereof, and, if desired, subsequently etherifying or esterifying the resulting ethanol compounds.

The inventive method can analogously to the preparation of azole-1-ethanols of an azo! and an oxirane known methods.

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If M i.n of the formula II is hydrogen, the reaction with the oxirane compound is conveniently carried out in the presence of a base.

If M in the formula II is a metal, this is conveniently an alkali metal, e.g. N / A.

If M in the formula II is a trialkylsilyl group such as the trimethylsilyl group, the reaction is conveniently carried out in the presence of a base such as NaH.

The process according to the invention is advantageously carried out in a solvent which is inert under the reaction conditions, such as dimethylformamide. A suitable reaction temperature is between room temperature and reflux temperature of the reaction mixture, conveniently at elevated temperature, e.g. between 70 ° and 110 °.

The term "reactive derivatives" as used in connection with the above-defined 2- [aryl (alkylene)] -2- (CHR.,) R 1 -oxiranes, such as the compounds of formula III, includes all oxirane derivatives obtained by reaction with an azole Formula II lead to the inventive ethanol compounds. Several examples of such reactive derivatives are known to those skilled in the art; a suitable example of this is an oxirane-corresponding halohydrin (where the halogen is, for example, Cl or Br).

The reaction conditions at which compounds of the formula II can be reacted with reactive derivatives of the above defined 2- [aryl (alkylene)] -2-CCR- [R ₂ "(CHR ₃ ) Rj-oxiranes are also known.

-7- 130-3965

The reaction of a compound of the formula II with a halohydrin corresponding to the oxirane of the formula III can be carried out as described for the reaction with the oxirane, but expediently using an additional equivalent of a base.

Ester and ether derivatives of the ethanol compounds according to the invention can be obtained by known esterification or etherification methods starting from the corresponding ethanols.

The novel compounds are obtained in the form of the free base or as a salt (acid addition salt or alkoxide) or metal complex.

The salts or metal complexes can be prepared from the corresponding compounds in free form, and vice versa.

From the reaction mixture, the end product can be isolated and purified by methods known per se.

As far as the preparation of the starting compounds is not described, they are known or can be prepared analogously to known methods.

The novel compounds in free form or in a salt form suitable for agriculture (acid addition salt or alkoxide), or in the form of a metal complex, are suitable as fungicides for controlling phytopathogenic fungi. The good fungicidal effect goes u.a. from in vivo tests against Uromyces appendiculatus (bean rust) on runner beans as well as against other rust fungi (Hemileia, Puccinia) on coffee, wheat, pelargonium and snapdragon and against Erysiphe

-8th- . 130-3965

cichoracearum on cucumber and against other powdery mildew fungi (E. graminis f.sp. tritici, E. graminis f.sp.horsei, Podosphaera leucotricha, Uncinula necator) on wheat, barley, apples and vine at test concentrations of .0008 bis 0.05%. Other interesting effects are i.a. in vitro against Ustilago maydis at concentrations of 0.8 to 200 ppm, in vivo against Rhizoctonia solani at concentrations of 10 to 160 ppm, calculated on the volume of the substrate. Since the tests also show good plant tolerance and good systemic behavior, the compounds according to the invention are accordingly suitable for the treatment of plant and seed, and the soil for controlling phytopathogenic fungi, for example for combating Basidiomycetes, Ascomycetes, Deuteromycetes, in particular Basidiomycetes of the order Uredinales (rust fungi) such as Puccinia spp, Hemileia spp, tlromyces spp; of Ascomycetes of the order Erysiphales (powdery mildews) such as Erysiphe spp, Podosphaera spp and Uncinula spp. and the order Pleosporales like Venturia spp; as well as Phoma, Rhizoctonia, Helminthosporium, Pyricularia, Pelicularia (= Corticium), Thielaviopsis and Stereum spp. Various of the compounds of the invention, e.g. the compound according to Example 1, also have a good botryticidal activity.

The amount of the compound of the invention used depends on various factors; Such factors are, for example, the nature of the compound according to the invention, the subject of the treatment (plant, soil, seed), the type of treatment (casting, spraying, spraying, dusting, pickling), the purpose of the treatment (prophylactic or therapeutic), the type of treatment treating fungi and the application time.

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In general, satisfactory results are obtained when the compound of the invention is used in the case of a plant or soil treatment in an amount of about 0.0005 to 2, advantageously from about 0.01 to 1 kg / hectare; e.g. 0.04 to 0.125 kg of active ingredient / ha in crops such as cereals, or concentrations of 1 to 5 g of active ingredient / hl in crops such as fruits, vines and vegetables (with an application volume of 300 to 1000 l / ha, depending on the size or leaf volume of the cultures, which corresponds to an amount of application of about 10 to 50 g of active ingredient / ha).

The treatment may be repeated if desired, e.g. in an 8 to 30-day interval. When the compound of the present invention is used in a seed treatment, satisfactory results are generally obtained when the compound is used in an amount of about 0.05 to 0.5, preferably about 0.1 to 0.3, g / kg of seed.

The term "soil" includes any wax medium, i. Soil, be it natural or artificial.

The novel compounds can be used in a large number of crops, for example in soybean, coffee, ornamental plants (including geranium, rose), vegetables (including pea, cucumber, celery, tomato and bean plants), sugar beets, sugar cane, cotton, flax, corn , Grapevine, kernels and drupes (apples, pears, plums), and are particularly suitable for use in cereals (eg wheat, oats, barley, rice), especially in wheat and apples.

Compounds of the invention which are particularly suitable for agricultural use are compounds of the formula I which have 1 or more of the following structural elements:

Y is N

m is 0

η is 0, C is H or CH.

R ₁ is CH ₃

^X 2

-ΊΟ- 130-3959

R. is cyclopropyl

R _g is in 4-position

R. is H or 2-Cl

 ο

The invention also includes fungicidal compositions containing as fungicide an inventive compound in free form or in an acceptable salt form for agriculture or as a metal complex and an inert, agriculturally acceptable diluent. They are obtained by known methods, for example by mixing a compound of the invention with a diluent and optionally additional excipients such as surface-active substances.

By diluents is meant liquid or solid, agriculturally acceptable materials which are suitable for rendering the active substance in a more easily or better applied form, or for diluting it to a useful or desired efficiency. Examples of such diluents are talc, kaolin, diatomaceous earth, xylene or water.

In particular, formulations which are used in the form of a spray, e.g. water-dispersible concentrates or wettable powders. may contain surface-active compounds such as wetting or dispersing agents, e.g. the condensation product of formaldehyde with naphthalene sulfonate, an alkylaryl sulfonate, a lignin sulfonate, a fatty alkyl sulfate, an ethoxylated alkylphenol or an ethoxylated fatty alcohol.

In general, the formulations contain from 0.01 to 90% by weight of active ingredient, from 0 to 20% for a fungicide, acceptable surfactants and from 10 to 99.99% of diluent.

Concentrated forms of formulations, e.g. Emulsion concentrates generally contain between about 2 and 90, most often between about 5 and 70 percent by weight of active.

" ^11- 130-3959

Applications of such compositions generally contain from 0.0005 to 10% by weight of a compound of the invention as an active ingredient. For example, typical spray suspensions may contain from 0.0005 to 0.05, preferably from 0.001 to 0.02, weight percent of active ingredient.

In addition to the usual diluents and surface-active substances, the formulations according to the invention may contain further auxiliaries for special purposes, e.g. Stabilizers, deactivators (for solid formulations on active surface supports), adjuvants to improve plant adhesion, corrosion inhibitors, anti-foaming agents and dyes. In addition, other fungicides, with similar or complementary fungicidal activity, e.g. Sulfur, chlorothalonil, dithiocarbamates such as manpozeb, maneb, zineb, propineb, trichloromethanesulfenylphthalimides, and analogs thereof such as captan, captafol and folpet, benzimidazoles such as benomyl, or other beneficial actives such as e.g. Insecticides to which formulations are attached.

Examples of agriculturally applicable fungicidal formulations are described below:

a) Wettable powder formulation

10 parts of a compound according to the invention are ground with 4 parts of synthetic, fine silica, 3 parts of sodium lauryl sulfate, 7 parts of sodium ligninsulfonate and 66 parts of finely divided kaolinite and 10 parts of diatomaceous earth until the average particle size is less than 5 microns. The spray liquid obtained can be used as a spray for the foliage, as well as for the rooting.

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b) granule formulation

On 94.5 parts by weight of quartz sand in a drum mixer, 0.5 parts by weight of a binder (a non-ionic surfactant id) are sprayed on and the whole is mixed thoroughly. 5 parts by weight of a compound of the invention are then added thereto and vigorously mixed to obtain a granular formulation having a Tei Ichenbereich of 0.3 to 0.7 mm. The granules can be added to the soil in which the plants are to be treated or raised.

c) Ejnuisionstconzentrat

10 parts by weight of a compound according to the invention are mixed with 10 parts by weight of an emulsifier and 80 parts by weight of isopropanol. This concentrate can be diluted with water to the desired concentration.

d) seed coating or seed treatment

45 parts by weight of a compound according to the invention are mixed with 1.5 parts of diamylphenol decaglycol ether, 2 parts of spindle oil, 51 parts of finely ground talc and 0.5 part of rhodamine 8. The mixture is milled in a contraplex mill at 10,000 spins / minute until the average particle size is less than 20 microns. The dry powder thus obtained has good adhesiveness and can be added to the seed, e.g. by mixing for 2 to 5 minutes in a slowly rotating kettle.

In the following examples, which illustrate the invention in more detail, but are not intended to limit its scope in any way, all temperatures in degrees Celsius. Rf values are on silica gel.

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end products

Example 1 : ^ - {^ Chiorghenyl- ^ c ^ c ^ ogrogY ^ JidHlli ^. ^ Tr1-l-1-butan-2-o2 (Diastereomeric mixture)

Level 1 :

7.6 g of 1- (4-chlorophenyl) -2-cyc1-propyl-1-propanone are dissolved in 120 ml of dry toluene, mixed at room temperature with 28.6 g of dodecyldimethylsulfonium methylsulfate and the suspension is stirred for 15 minutes. Then it is provided with 6.3 g of powdered KOH and stirred at 35 ° for 18 hours. After cooling, the reaction mixture is poured onto ice, a little dimethylformamide added and extracted with diethyl ether. The organic extracts are washed 3 times with water, then with saturated aqueous NaCl solution, dried over magnesium sulfate and evaporated in vacuo. The residue is an OeI which, in addition to dodecylmethylsulfide and dodecene-1, contains 25% of 2- (4-chlorophenyl) -2- (1-cyclopropyl-ethyl) -oxirane.

Level 2 :

The crude oxirane reaction product is added dropwise to a mixture of 4.2 g of 1,2,4-triazole kept at 90 ° and 15.4 g of K ₂ CO ₃ in 80 ml of dry dimethylformamide and the mixture is stirred at 90 ° for 2 hours.

After cooling, the reaction mixture is poured onto ice, extracted with diethyl ether, the organic extracts washed with water and saturated aqueous NaCl solution, dried over MgSO ₄ and freed from solvent in vacuo. The title compound is obtained after chromatography on silica gel with hexane / ethyl acetate as a colorless, thick syrup (Diastereomerengemisch), which slowly crystallized on standing. By recrystallization from hexane / CH-Cler, the product is obtained in the form of colorless crystals of mp. 100-101 °. Rf values in thin-layer chromatogram (silica gel plate, eluent ethyl acetate):

"O

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Diastereomer A: Rf 0.30 Diastereomer B: Rf 0.38

Repeated chromatography on silica gel with diethyl "ether-acetone" (99: 1) and diethyl ether-ethyl acetate 99: 1 to 90:10, and crystallization from hexane / CHpClp, the isomer mixture is separated into the pure diastereomers:

Example IA: Diastereomer A: mp 109-110 °. Example IB: Diastereomer B: mp 125-127 °.

Example IC

To a mixture of 2.0 g of p-toluenesulfonic acid monohydrate in 50 ml of toluene which has been concentrated to a volume of 5 ml is added, with stirring at room temperature, a solution of 2.9 g of 2- (4-chlorophenyl) -3-cyclopropyl-1 - (lH-l, 2,4-triazol-1-yl) -butan-2-ol (diastereomer mixture) in 35 ml abs. Toluene was added dropwise and allowed to stand for 15 hours. After the addition of 20 ml of ether, the crystallizate formed in toluene is stirred for a further 30 minutes, then filtered off, washed with ether and dried under high vacuum at 60 °, mp 170-171 °.

Analogously to the process according to Example IC, the following acid addition salts of the same triazole compound are prepared:

ID) hydrogen oxalate, mp 180-182 ° IU). Hydrochloride, mp 190-200 °.

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Example 2 : 2; [4

Starting from 1- (4-chlorophenyl) -2-cyclopropyl-2-methylpropan-1-one, the procedure is initially analogous to that in Example 1 (stages 1 and 2). However, purification of the title compound takes place by crystallization from hexane, giving colorless crystals of mp 88-90 ° (= racemate of the title compound).

Example 3

The procedure is analogous to Example 1 (stage 2) and the following compounds of the formula I are obtained by reacting an azole with the desired oxirane (Table A, Table B).

TABLE A (m = 0) Ex. R ₁

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(CHR ₃ ) _n R ₄ R ₅ , R ₆ , R ₇ : Y m.p.

3.1

CVJ π CH ₃ 3 Il Cycio propy! 4 Cyclo- ρropy 1 H 5 Il H 6 (I CH ₃ 7 Il It 8 9 C ₂ H ₅ CH ₃ H H 10 CH ₃ H 11 CH ₃ H . 12 13 CH ₃ CH ₃ CH ₃ CH ₃ 14 CH ₃ CH ₃ 15 CH ₃ CH ₃ 16 CH ₃ H 17 CH ₃ H 18 19 ι ro πί rc rc CJ CJ CH ₃ H 20 CH ₃ H 21 CH ₃ CH ₃ 22 CH ₃ CH ₃ 23 CH ₃ H 24 CH ₃ CH ₃ 25 CH ₃ CH ₃ 26 CH ₃ H 27 CH ₃ CH ₃ 28 CH, CH,

CycTo-4-C1propyl

Il N Il N Il N 84-86 ° Il CH 171.5-173.5 ° Il N Il CH Il N 4-CH ₃ S N Il CH 4-CH ₃ N Il N M CH 4-CH ₃ O N Il CH 2,4-DICL N 113-117 ° CH Il N 141-142 ° 2-CH ₃ -4 -CH ₃ S N. 4-CH ₂ = CH N ti ν CH M H 4-HC = C N Il Ν Il CH 4-CH ₂ = CCI N Il N Il CH

- 17 - 130-3959

TABLE A (continued) '. '

Ex. R ₁ . R ₂ (CHR ₃ ) _n .R ₄ 'R ₅₅ R ₅₅ R ₇ , Y m.p.

3.29 2-CH ₃ -cyclo-2-CH ₃ -cyclo-4-Cl-N-propyl; propyl

3.30 "CH ₃

3.31 "·" H

3.32 CH ₂ -C = C-Br C

3.33 "CH

3.32 CH ₇ -C = C-Br C, H _c ^l '' - C, H _C

3.34 CH ₂ -C = CJ CH ₃ -

3.35 CH ₂ -S-CH ₃ CH ₃

3.36 "CH ₃ CH ₂ .3.37" CH ₃ CH ₂

3.38 "C ₃ H ₅ 'CH ₂

3.39 "CH ₃ CH _2. "

3.40 CH ₂ -O-CH ₃ CH ₃

3.41 CH ₃ H - C ₅ H ₉ ^

3.42 -CH ₁ H-C, H _V

011

3.43 CH ₃ CH ₃ CH ₂ C ₃ H ₅

3.44 CH ₃ H - C ₃ H ₅

3.45 CH ₃ H -. ^C 3 ^H 5

(1) C ₃ H ₅ = cyclopropyl; (2) C ₅ H _g = cyclopentyl; (3)

(4) Oiastereomer mixture; (5) Oiastereomer A.

Il N 95-96 ° (4 Il CH N 147-141 (5 ti N Il N Il N 2,6-Dicl N 2,6-diCH ₃ N 2,6-diCH ₃ N 4-Cl-2,6-diCH ₃ N 2,4-DICL N 4-Cl H 4-Cl N 4-Cl N 4-Cl CH 4-Cl CH

Ex. ^R l H ( ^CHR 8 \ n R ₅₅ R ₅₅ R ₇ Y 3:46 CH ₃ H CH ₂ 4-Cl N 3:47 CH ₃ CH ₃ CH ₂ 4-Cl N 3:48 C ₃ H ₅ H CH ₂ 4-Cl H - 3:49 CH ₃ H CH (IC ₃ H ₇ ) 4-Cl

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Example 4 ': 2- (4-Chlorophenyl) -2- (1-cyclopropylcyclopropyl H- (IH-1,2,4- triazol-1-yl) -ethan-2-ol (racemate)

Level 1 ;

To a stirred under N ^ atmosphere suspension of 5.1 g of 80 percent sodium hydride in 50 ml of abs. Tetrahydrofuran (THF) at room temperature first 13.3 g of dimethyl sulfoxide (DMSO) and then within 20 minutes 13.5 g of 4-chlorophenyl (1-cyclopropyl-cyclopropyl) ketone in 50ml abs. THF dripped. The resulting green suspension is added in portions with 15.0 g of trimethylsulfonium iodide and stirred for 16 hours at room temperature and 3 hours at 50 °. The reaction mixture is cooled to 0-5 °, some water is added dropwise and - after the exothermic reaction has subsided - the product is extracted with ether. The organic phase is washed three times with water and once with brine, dried over magnesium sulfate and evaporated in vacuo at 60 °. The residue consists mainly of 2- (4-chlorophenyl) -2- (1-cyclopropylcyclopropyl) oxirane.

Level 2 :

The crude oxirane from stage 1 is reacted analogously to the method described in example 1, stage 2 with 1,2,4-triazole. This gives, after chromatography on silica gel and crystallization from hexane / CH-Cl- the pure title compound with the mp. 110-112 ° (racemate).

-19-. 130-3959

Example 5 :. 2- (4-chloro-phenyl) -3-cyclopropyl-2-methoxy-3-methyl-1- (1H- 1,2,4-triazol-1-yl) -butane

, 0.8 g of sodium hydride 80% are placed in 25 ml of dimethylformamide '. At room temperature, a solution of 7.64 g of 2- (4-chlorophenyl) -3-cyclopropyl-3-methyl-1- (1H-l, 2,4-triazol-1-yl) butan-2-ol is added dropwise 50 ml of dimethylformamide and then stirred for 30 minutes at 40 °. Then 3.76 g of methyl iodide are added dropwise at 5 °. The mixture is stirred for 18 hours at 20 °, then poured into 1 l of water and extracted with methylene chloride. The water-washed organic phases are dried over magnesium sulfate and concentrated on a rotary evaporator. The title compound is obtained after column chromatography on silica gel (ether / triethylamine = 10: 2) in the form of white crystals with a melting point of 87-89 °.

Example 6 : 2- (4-Chlorophenyl) -3-cyclopropyl-2-allyloxy-3-methyl-1- (1H-'l , 2,4-triazol-1-yl) -butane

The title compound is obtained analogously to the process according to Example 5, using allyl bromide instead of CH ₃ I and the reaction mixture is stirred for 18 hours at 70 ° (instead of at 20 °). Mp 58-60 ° (white crystals).

Example 7 : 2- (4-Chlorophenyl) -3-cyclopropyl-2-benzyloxy-3-methyl-1- (1H- 1,2,4-triazol -1-yl) -butane

The title compound is obtained analogously to the method of Example 6, using benzyl bromide instead of allyl bromide, mp 130-132 ° (white crystals).

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Example 8 : 2- (4-Chlorophenyl) -cyclopropyl -acetoxy-S-methyl-1- (1H-1,2,4-triazo1-1-yl) -butane

The title compound is obtained analogously to the procedure of Example 5, using acetyl chloride instead of CH-J, the reaction mixture being stirred at 70 ° for 24 hours; it crystallizes from diethyl ether, mp 117-119 ° (yellow crystals).

intermediates

Example 9 : 1- (4-Chloro-phenyl) -2-cyclopropyl-propane! -One

15 g of 4-chlorophenyl (cyclopropylmethyl) ketone, dissolved in 80 ml of DMF abs., Are added dropwise to a stirred under N ^ atmosphere suspension of 2.6 g of 80-prozentigem sodium hydride in 30 ml of DMF and the mixture hours at 25-35 ° further stirred. For this purpose, within 15 minutes, at room temperature, with cooling 15.3 g of CH ~ J are added dropwise and the mixture, after stirring for 15 minutes at 25-30 °, mixed with cold water and taken up in ether. After washing the organic extracts with water and saturated aqueous NaCl solution, dry over MgSO 4. and evaporation, the crude title compound is purified by chromatography on silica gel with hexane / ethyl acetate (98: 2).

The 4-chlorophenyl cyclopropyl methyl ketone used as the starting compound can be prepared from the corresponding alcohol by Jones oxidation with CrO ₃ in aqueous FLSO 4 / acetone solution.

Example 10 : 1- (4-chloro-phenyl) -cyclopropyl-methyl-propane-1-one

The procedure is analogous to Example 9, but can be reacted per equivalent of 4-chlorophenyl (cyclopropylmethyl) ketone with 2.4 equivalents of NaH and 3 equivalents of CH ^ J. The with hexane / ethyl acetate (99: 1) at

20 silica gel chromatographed title compound has: n _Q = 1.5390.

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Example 11 : 4-Chlorophenyl- (1-cyclopropyl-cyclopropyl) -ketone

To a stirred under ^ atmosphere suspension of 4 g of 80 percent sodium hydride in 40 ml of abs. THF are under gentle reflux within 40 minutes 23.3 g of 4-chlorophenyl (cyclopropylmethyl) ketone in 250 ml abs.

THF was added dropwise and stirred for 45 minutes under reflux. 15.8 ml of phenylvinyl sulfoxide are then added dropwise at 20.degree. C. with the aid of a syringe (exothermic reaction) and the mixture is stirred at 20.degree.-30.degree. For 2 hours. The resulting intermediate (sulfoxide) is then cyclized by stirring for 18 hours under reflux to the title compound.

The reaction mixture is then cooled to 0-5 ° and, after dropwise addition of 200 ml of water, extracted with ether. The organic phase is washed three times with water and once with brine, dried over magnesium sulfate and evaporated in vacuo at 60 °. Chromatography on silica gel with hexane-ethyl acetate (99: 1) gives the pure product:

n [j ^O = 1.56O5.

The title compound according to Example 11 can also be obtained by replacing in the above example, the phenyl vinyl sulfoxide by the corresponding sulfone or by a Oimethylvinylsulfoniumsalz.

Example 12

20. The title compound of Example 9 can also be prepared starting from 4-chlorobenzyl cyanide by reaction with cyclopropyl methyl ketone in the presence of NaH, reduction of the thus obtained 1- (4-chlorophenyl) -1-cyano-2-cyclopropyl propene -1 with Mg / CH-jOH / NH ^ Cl to give l- (4-chlorophenyl) -l-cyano-2-cyclopropyl-propane, followed by oxidation by Q ^ of this cyano compound under alkaline conditions in the presence of a phase transfer catalyst. Depending on the situation (price, environment, etc.), the method according to this example may be preferred.

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Biological effect / fungicidal application

1. Test results in the greenhouse

The following test results (obtained using the test methods described in GB 2064520A) illustrate the surprisingly favorable fungicidal activity of the compounds according to the invention. The standard used is a- (cyclohexylmethyl) -a- (p-methylphenyl) -1H-1,2,4-triazole-1-ethanol (Example 2Z-22 in GB 2064520A). The results are expressed as EC 90, i. as a concentration allowing 90% control of the infestation after spray application.

connection 1* 2 3.16 3.18 - default according to example Fungus / Culture 5 3 1 <1 38 Erysiphe / Cucumber 3 4 5 3 > 900 Erysiphe / Wheat 6 5 5 3 126 Podosphaera / apples 4 6 15 2 46 Uncinula / vines <1 <] <1 1 ^ 30 Uromyces / bean 39 32 77 36 > 9OO Septoria / Wheat

* Mixture of diastereomers 2. Control of infestation under field conditions

The fungicidal action of the compound according to Example 1 (mixture of diastereomers) was further investigated under field conditions: 62 g of active ingredient / ha allow more than 90% control of powdery mildew and rust in cereals; and 2.6 g / hl allow up to 99% control of powdery mildew in vines.

Further investigations suggest an effect of the compound according to Example 1 the

- equal to or better than that of propiconazole against powdery mildew in cereals and cucumbers and against rust in cereals and coffee, or - equal to or better than fenarimol against powdery mildew in apples and vines and against Venturia in apples, or

- better than Triadimefon against u.a. Grates in coffee.

Claims (5)

-23- AP A Ol N / 265 725. 64 147 12 Claim for invention 1. A method for controlling phytopathogenic fungi, characterized in that one of their habitat. Fungicidally effective amount of a- [aryl (alkylene) _m ] -a- [CR ₁ R ^ (CHR ₃ ) _n -R ₄ ] -1H -l, 2,4-triazole-1-ethanoles or -IH-imidazol-1-ethanoles, wherein R, for unsubstituted or by halogen, C- ^ alkoxy, phenyl-C, ..alkoxy, phenoxy, C, ^ alkylthio, phenyl-C, -alkylthio. or phenylthio-substituted C, ₅ alkyl, where any phenyl groups can be substituted by C 1 -C 4 alkyl, halogen, halogenated C 1 -C 4 -alkyl, C 1 -C 6 -alkoxy or halogenated C 1 -C 4 -alkoxy; or C ₂ -alkenyl or C-alkynyl, unsubstituted or substituted by halogen; for cycloalkyl, unsubstituted or 'by C, j-alkyl substituted; or
phenyl, unsubstituted or substituted by substituents of the series halogen and C 1 -C 4 alkyl,
stands, R 1 and R 2 are independently of one another H or one of the meanings given for R, where R and R can be linked to one another to form a C 1-6 cycloalkyl radical,
m is 0 or 1, and η is 0, 1 or 2, and R ₄ is a C ^ cycloalkyl group which is unsubstituted or is substituted by ₅ alkyl C] _, or an ether or ester of such an ethanole, in free form or in the form of the acid addition salt, alcoholate or metal complex, appIi ed. AP A Ol N / 265 725 7 64 147 12 2. The method according to item 1, characterized in that a compound of the formal I Γ "" jl OH R wherein R R ₂ , R-, R ₄ , m, η and Y, which have the meaning given in claim 1, R_ and R _{6 are the} same or different and are for water fabric, halogen; optionally halogenated C _1-5 - Alkyl, C 1-6 alkenyl, C _{0 c} alkynyl or C ₁ , alkoxy; ^J ' 2-5 ^J 2-5 IS optionally substituted phenyl or phenoxy; or the NO ^ group stand,
R ₇ is H, C _{1 5} alkyl, or halogen, R _{8 is} H or C 1-4 alkyl,. , and Y has the meaning given in claim 1, or an ether or ester thereof, in free form or in the form of the acid addition salt, alkoxide or metal complex applied. 3. The method according to item 2, characterized in that 2- (4-chlorophenyl) -3-cyclopropyl-l - (! H-l, 2,4-triazol-l-yl) -butan-2-ol, applied. 4. The method according to item 2, characterized in that 2- (4-chlorophenyl) -3-cyclopropyT-3-methyl-l- (IH-I, 2,4-triazol-1-yl) -butan-2- oil, applied. 5. A fungicidal preparation, characterized in that it contains a compound according to any one of items 1 to 4 in free form, or in an agriculturally acceptable acid addition salt, alcoholate or metal complex form, and an inert, agriculturally acceptable diluent ,